BIOMASS GASIFICATION

(Lecture-6)

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 Lecture-6 Page-2

BIOMASS GASIFICATION
(Lecture-6)
 Biomass Feedstock for Gasification
 biomass feedstocks are classified based on several factors, such as : moisture content,
material, and form as shown in Table-1.
 biomass is broadly divided into three groups: dry, wet, and others
 dry biomass is classified as woody or herbaceous and wet biomass as sludge/excreta,
common food, or other
 each classification has three sub-categories: waste, unutilized, and produced

Table-1: Classification of Biomass Feedstocks

 among these, dry woody/herbaceous biomasses are used as feedstocks for BG plants in
Japan
 woody biomasses contain waste woods (construction wastes and timber off cuts) and
unutilized woods (forest thinning, remaining timbers, and damaged trees) composed of
cedar, cypress, pine, etc.
 short-rotation woody crops (eucalyptus, willow, etc.) are categorized as produced woods
 energy crops such as willow may be cultivated in land fallow and used as biomass
 for unutilized herbaceous biomass, crop residues such as rice/wheat straw and rice husks
 while for produced herbaceous biomass, grasses such as Napier grass, sorghum, and
Miscanthus are usable
 above all, rice husks contain abundant silica
 the ash byproduct from gasifiers has potential use in nanomaterials

 Chemistry of Gasification
 the reactions taking place in the gasifier can be summarized as given below:
Partial oxidation:
C + O2 ↔ CO ΔH = − 268 kJ/mol (1)
Complete oxidation:
C+O2 ↔ CO2 ΔH = − 406 kJ/mol (2)
Water gas phase reaction:
 Lecture-6 Page-3

C + H2O ↔ CO + H2 ΔH = 118 kJ/mol (3)

Boudouard reaction:
C + CO2 ↔ 2CO ΔH = 170.7 kJ/mol (4)
 the heat required for water gas phase and Boudouard reactions is provided by complete
and partial oxidation reactions, and complete oxidation provides around 60% of the heat
requirements during gasification
 in addition to the previous reactions that are common in combustion and gasification,
hydrogen, steam, and carbon monoxide undergo further reactions as shown below:
Water gas shift reaction:
CO + H2O ↔ CO2 + H2 ΔH = − 42 kJ/mol (5)
Methane formation:
CO + 3H2 ↔ CH4 + H2O ΔH = − 88 kJ/mol (6)
 the water gas shift and methane formation reactions are in equilibrium and the governing
parameters are: pressure, temperature, and concentration of reaction species
 the possible gasification reaction may also be summarized and shown by the following
diagram

 Overall Steps Involved in Biomass Gasification

 the main steps involved can be categorized as upstream processing, the gasification
process in the gasifier and the downstream processing as shown in Figure-1
Upstream Processing
 upstream processing includes processing of the biomass to make it suitable for
gasification operations
 size reduction is needed to obtain appropriate particle sizes
 drying is needed to achieve appropriate moisture so that the process can work efficiently
 densification also may be necessary due to the low density of biomass
Gasification
 this is the second step where the gasification process is carried out under specified
conditions in order to achieve optimum product yield, i.e. the producer gas
 different types of gasifiers are used for the purpose

Down Stream Processing

 Lecture-6 Page-4

 this is the third step where the cleaning (purification ) of the gaseuos products take place
as per the desired sopecifications
 unit operations are applied foe the purpose

Figure-1: Processes involved in overall biomass gasification.

 The Biomass Gasification Process (Mechanisms of Gasification)
 the biomass gasification process consists in the conversion of a solid/liquid organic
compound in a gas/vapor phase and a solid phase
 the principal reactions of gasification are endothermic and the necessary energy for their
occurrence is, generally, granted by the oxidation of part of the biomass, through an allo-
thermal or an autothermal phase
 in the auto-thermal process, the gasifier is internally heated through partial combustion,
while in the allo-thermal process the energy required for the gasification is supplied
externally
 considering the auto-thermal system, gasification can be seen as a sequence of several
stages
 a simplified schematic representation of the gasification is demonstrated in Figure-2
 the main steps of the gasification process are:
i. oxidation (exothermic stage)
ii. drying (endothermic stage)
iii. pyrolysis (endothermic stage)
iv. reduction (endothermic stage)

Figure-2: Main stages of the gasification process.

 Lecture-6 Page-5
 Oxidation
 in order to obtain the thermal energy required for the endothermic reaction and to
maintain the operative temperature, the oxidation of part of the biomass is necessary
 the oxidation is carried out in conditions of lack of oxygen with respect to the
stoichiometric requirement
 despite the partial oxidation involving all carbonaceous species (tars included), it is
possible to simplify the system considering that only char and the hydrogen contained
in the gas produced participate in the partial oxidation
 the main reactions that take place during the oxidation phase are given in Figure-2
and also discussed in the chemistry of biomass gasification
 as evident, the main product of this step is the thermal energy necessary for the whole
process, while the combustion product is a gas mixture of CO, CO2 and water
 in this mixture nitrogen can be present if the biomass oxidation is performed with air,
otherwise nitrogen is practically absent if only oxygen is used
 Drying
 drying consists in the evaporation of the moisture contained in the feedstock
 the amount of heat required in this stage is proportional to the feedstock moisture
content
 generally, the heat required derives from the other stages of the process
 drying can be considered complete when a biomass temperature of 150 °C is achieved
 Pyrolysis
 pyrolysis leads to the thermochemical decomposition of the matrix carbonaceous
materials
 the cracking of chemical bonds takes place with the formation of molecules with a
lower molecular weight
 by pyrolysis, it is possible to obtain different fractions: a solid, a liquid/condensed gas
and non-condensed gas
 the solid fraction, which can range from 5–10 wt% for fluidized bed gasifiers to 20–
25 wt% for fixed bed gasifiers, has a high carbon content and is characterized by a
high heating value
 the solid fraction includes the inert materials contained in the biomass in the form of
ashes and a high carbon content fraction, called “char”
 the liquid fraction, usually called "tars", varies according to the gasifier type, such as
lower than 1 wt% for downdraft gasifiers, 1– 5 wt% for bubbling bed gasifiers, 10–20
wt% for updraft gasifiers and
is constituted by complex organic substances, condensable at relatively low
temperatures
 the gaseous fraction is typically 70–90 wt% of the fed material and is a mixture of
gases that are non-condensable at ambient temperature
 the gaseous fraction is called "pyrolysis gas" and consists mainly of hydrogen, carbon
monoxide, carbon dioxide and light hydrocarbons such as methane and other C2, C3
hydrocarbons; minor constituents are acid or inert gases
 the pyrolysis reactions take place with a temperature in the range 250–700 °C
 they are endothermic and, as in the drying step, the heat required comes from the
oxidation stage of the process

 Lecture-6 Page-6
 Reduction
 the reduction step involves all the products of the preceding stages of pyrolysis and
oxidation
 the gas mixture and the char react with each other resulting in the formation of the
final gaseous mixture
 main reactions occurring in the reduction step have been shown in ‘Chemistry of
Biomass Gasification’ and also demonstrated in Figure-2
 Conceptual diagram with respect to the mechanism of gasification demonstrated in
multiple steps fixed-bed (a) updraft and (b) downdraft gasifiers

Figure-3: Conceptual diagram of multiple steps in fixed-bed (a) updraft and (b)
downdraft gasifiers

 Factors Affecting the Gasification Process

 the biomass gasification units may be divided into small-, medium-, and large-scale
biomass gasification and power generation units
 pretreatment of biomass is needed which includes size reduction, size screening,
separation of magnetic materials, and storing as wet biomass
 then prior to gasification, drying and storing as dry material are accomplished to reduce
the moisture content
 feedstock type and feedstock preparation are important factors affecting the yield and
quality of produced gaseous mixture or the syngas
 shredding and drying are two processes conducted to prepare the biomass raw material
for gasification process
 the main parameters affecting the gasification are: equivalence ratio (ER), biomass
characteristics, moisture content, moisture content, Superficial velocity, Operating
temperature, gasifying agent, residence time, pressure, catalyst, effect of biomass/steam
ratio
 Lecture-6 Page-7

 Equivalence Ratio (ER)

 the equivalence ratio (ER), Φ is defined as the ratio of the actual air supplied to that
of the stoichiometric/theoretical air used for gasification, i.e.
Actual Air supplied to the System for Combustion
Φ
Theoretica l/Stoichio metric requiremen t of Air for Combustion
 the efficiency,  of a gasifier is defined as
Chemical energy output in the dry Producer Gasat15 0 C

Energy input from the Biomass
 it may be seen from the following Figure-4 that total energy in the gaseous phase
increases with the increase of equivalence ration, Φ .

Figure-4: Producer gas composition with variable stoichiometric variation.

 increasing ER decreases the heating value of the produced gas due to decreasing H2
and CO concentration and increasing CO2 concentration
 higher ER helps in reducing tars and provides more O2 to react with volatiles
 typical values of ER ranges between 0.2 and 0.4.
 it was reported that increasing ER decreases the concentration of combustible gases
CO, CH4, and CnHm, however H2 increases till the value goes to 0.4 and then it
decreases
 increasing ER improves the reaction temperature and carbon conversion, and reduces
the tar yield

 Biomass Characteristic
 biomass characteristic is a major factor affecting produced gases during gasification
 the physical properties that may have major effect are: absolute and bulk density, and
particulate size
 Lecture-6 Page-8
 the chemical composition parameters that are of major importance to define the
quality including volatile matter, moisture content, fixed carbon, ash content, and
gross calorific
 the ultimate analysis comprises the carbon, oxygen, nitrogen, and sulfur of the dry
biomass on a weight% are also highly significant
 Moisture Content
 the moisture content can be determined by complete drying of biomass sample
 the moisture content is calculated by subtracting the sample weight after drying from
fresh sample weight
 maximum allowable moisture content in downdraft gasifier is 40% on dry weight
basis
 updraft gasifier can handle biomass with higher moisture content
 the higher moisture content in biomass will increase the consumed energy for drying,
and will reduce the pyrolysis of biomass
 as a general rule, increasing moisture content decreases the conversion
 Superficial Velocity
 it is the ratio of the biogas production rate at normal conditions and the narrowest
cross-sectional area of gasifier
 lower superficial velocity is linked with high yield of char, and large quantities of
unburned tars, which may deactivate catalyst, plug lines, and destroy compressors
 higher superficial velocity results in reduced amount of char and low overall process
efficiency
 Operating Temperature
 operating temperature affects conversion, tar content, gas composition, gas heating
value, and char conversion
 in order to select the optimum temperature, gasifier type, and biomass source is
considered
 generally, temperature higher than 800°C should be used to obtain high conversion
and low tar content in the produced biogas
 low temperature is associated with low tar content, low H 2 and CO content in the
produced biogas
 increasing temperature will increase gas yield, hydrogen, heating value, and ash
agglomeration
 the ash agglomeration problem can be overcome by keeping the temperature below
750°C
 Gasifying Agent
 gasifying agents in use are air, steam, steam/oxygen mixture, and CO2
 they affect the heating value of the produced gas
 the heating value increases with increasing steam content of the gasifying agent,
whereas heating value decreases as air increases in the gasifying agent
 the steam/oxygen mixture represents a zero nitrogen-gasifying agent which increases
the heating value and allows liquefying the produced gas after proper treatment
 Residence Time
 it has a significant impact on the composition and produced tars in biomass
gasification
 oxygen-containing compounds may be decreased by increasing the residence time
 Lecture-6 Page-9
 increasing residence time decreases yield of one and two atomic ring compounds,
 Pressure
 in gasification processes, either atmospheric or and higher pressures are commonly
used
 selection of the optimum pressure depends on the application of the produced gaseous
product
 if it is used for production of methanol or synthetic auto-fuels, higher pressures are
preferred to improve the process yield and to reduce tar content
 for generating burnable gases, atmospheric pressure should be used
 high pressure applications are recommended for large scale gasification
 however, atmospheric pressure is recommended for small-scale gasification
 high pressure gasification is still not well developed and further research is needed to
commercialize such processes
 Catalyst
 The type of the catalyst is an important factor affecting gasification quality and the
product
 catalyst affects the composition of the syngas by manipulating the percentage volume
of hydrogen, carbon dioxide, methane, and carbon monoxide
 optimum quantity of catalyst plays a significant role in minimizing the gas content of
carbon dioxide and maximizing the useful gases in the gaseous products such as
hydrogen, carbon monoxide, and methane

 Technologies of Biomass Gasification

 Introduction
 gasification process converts biomass, a low-energy density material, into a gaseous
product mixture containing mainly CO, H2, CH4 and CO2 .
 gasification is a partial oxidation process and it is commonly operated at 800–900 0C.
 in some cases, steam is also used as the gasification agents
 the gaseous products from the gasifier can be utilized in gas engines or gas turbines
for the generation of electricity
 gasifier reactors are simple in construction, however the chemistry and physics
involved in their operation is not well understood
 gasifiers designs are generally categorized into three types: downdraft, updraft and
fluidized bed
 all of the gasification processes oxidize part of the biomass to generate energy and to
carry out the process
 the selection of the gasifier depends on the end use and quantity of the producer gas
required
 in fixed bed gasifier the biomass fuel is fixed or stable on the bed and does not move
 fixed-bed biomass gasifiers are classified into two category: down draft and updraft
 Downdraft Gasifier
 in downdraft gasifier, fuel is fed near the top of the reactor
 the schematic diagram of the system is shown in Figure-5
 air can be introduced alongwith the fuel or at some intermediate level below
 hot producer gas alongwith char and ash exit the bottom of the reactor vessel
 a slight vacuum is usually applied at the gasifier exit to withdraw producer gas
 Lecture-6 Page-10
 the four different zones of drying, pyrolysis, combustion and reduction occur
sequentially from the top to the bottom of the gasifier, respectively
 the top section of the gasifier acts as a surge vessel for fuel to br dried before entering
the pyrolysis zone
 since the top of the downdraft gasifier is at ambient temperature and pressure, fuel
feeding is quite simple

Figure-5: Downdraft gasifier.

 radiant and combustive heat transfer from the lower pyrolysis and the combustion
sections provide the heat for drying
 water vapor from the drying zone flows downwards towards the pyrolysis and
combustion section where a portion is reduced to hydrogen
 however, majoririty of water vapour remains in the final producer gas
 a small amount of air may be added in the drying section to facilitat the downward
flow of gas, thereby sweeping out excess moisture
 the dried solid fuel moves downward by gravity into the pyrolysis zone and is heated
such that volatile matter is evolved
 resulting gas flows through the reduction zone on an ash support grate before before
exiting the reactor
 gaseous products of the pyrolysis reactions are drawn downwards alongwith the char
into the combustion zone of the gasifier
 a portion of the pyrolysis products and char are burned in the combustion zone as free
oxygen becomes available
 at this point, an oxidizer gas, such as air or oxygen is injected
 reactions with oxygen results in steep rise of temperature upto 1000 – 1200 0C ,
depending on the moisture content of the fuel
 some downdraf reactor reactor designs employ a restriction, commonly known as a
throat section, to increase the velocity of gas to promote heat and mass transfer
 Lecture-6 Page-11
 Updraft Gasifier
 updraft gasification system has been shown by Figure-6
 air is injected near the bottom of the reactor (in the combustion zone) with the
resulting producer gas flowing upwards through the interstitial spaces in the solid fuel
 the producer gas exit the top of the reactor where incoming biomass fuel is added
 hence the updraft producer gas exits at lower temperatur (130 – 150 0C) than that of
the downdraft reactor due to the drying of the solid fuel

Figure-6: Updraft gasifier.

 however, the gas is heavily contaminated by pyrolysis products (primarily tar, oils
and partculate) from the incoming fuel
 Since the producer gas exits at the top, special precautions are taken to avoid air in-
leakage with the incoming biomass
 the updraft gasification process is similar to that of the downdraft mode in that the
major reaction stages are present: drying, pyrolysis, combustion and reduction
 however, with respect to the solids, the order of these stages is changed
 most of the miosture evaporated from the fuel solids and products of the pyrolysis
reactions exit the top of the reactor with the producer gas
 the charged solid migrates below to the reduction zone
 heated combustion gases enter the reduction zone providing the required energy for
the endothermic reactions
 finally, the remaining char reacts with oxygen or airinjected into the bottom of the
reactor vessel
 ash is extracted from the bottom of the reactor
 Fluidized-Bed Gasifier
 shcematically, the fluidized-bed gasifier is shown in Figure-7
 it makes the use of an inert medium such as sand to mix the solid fuel with the
 Lecture-6 Page-12
gas phase
 depending on the specific reactor design and average bed media particle size, the
superficial gas velocity typically ranges from 0.5 – 1.0 m/s
 air is injected in the bottom of the reactor vessel through a distributor comprising of a
perforated plate and series of nozzles such that the bed material is suspended in a
fluid-like state as evident from the Figure – 7, below:

Figure-7: Fluidized-Bed Gasifier

 gas bubbles form at the distributor, increasing in size as they rise upward toward the
bed surface due to the decreasing hydrostatic presuure
 air within the bubbles exchanges with combustion and pyrolysis gases formed in the
dense phase as the fuel is converted to producer gas
 fly ash, char, and inert bed materials are ejected from the dense phase bed as gas
bubbles erupt on the surface
 the turbulent fluidized medium promotes high heat-transfer rates, and as a result the
bed-temperature is maintained in an essentially isothermal state
 the maximum temperature obtained during gasification is only 800 0C – 900 0C which
is less than the temperature that of the fixed bed design (downdraft, updraft)
 this is combined with the low gas residence time which increases the yields of tars,
oils, and light hydrocarbons
 the tar/oil concentration in the producer gas is higher than that derived from the
downdraft gasifier
 fuel is pneumatically conveyed into the bottom of the dense-phase bed

 Entrained Flow Gasifier

 entrained flow gasifier is a comparatively new design with high efficiency
 it is normally employed for large-scale gasification of coal, biomass, and refinery
residues
 however, fuel particles should be highly pulverized for this kind of gasifier, and
hence it is problematic when biomass is used as a feedstock
 Lecture-6 Page-13
 on the other hand, gasification in these gasifiers takes place above 1000 0C which
helps in cracking tar
 they are basically classified into two families, namely, top-fed gasifier and side-fed
gasifier as shown in the Figure-8, below:

Figure-8: Top-fed entrained flow gasifier. (B) Side-fed entrained flow gasifier.

 top-fed entrained flow gasifiers are vertically aligned cylindrical shaped vessels
 finely refined fuel particles and gasifying media come in the form of a jet from the
top end of the reactor (Figure-8A)
 an inverted burner results in their combustion followed by gasification
 Lecture-6 Page-14
 product gas is taken out from the side of the lower section, whereas slag is deposited
at the bottom of the reactor
 in side-fed gasifier, pulverized fuel and gasifying agent are fed through nozzles
present in the lower part of the reactor (Figure-8B)
 this design results in appropriate mixing of fuel and oxygen
 the product gas is collected from the top and the slag from the bottom of the vessel
 other important issues that process designs need to deal with are slagging, fouling,
and corrosion
 these issues arise out of the inorganic species present in the biomass and are,
therefore, dependent to a large part on the biomass composition

 Advantages and Disadvantages of Various Biomass Gasification

Technologies (Gasifiers) used
 Fixed Bed
 Illutrated in the Table-2, below:
Table-2: Advantages and Disadvantages of Fixed Bed Gasifiers

 Entrained Flow Gasifier

 Reflected by the following Table-3:

Table-3: Advantages and Disadvantages of Entrained Flow Gasifiers

 Lecture-6 Page-15
 Fluidized Bed Gasifier
 Summarized in the Table-4, below:

Table-3: Advantages and Disadvantages of Fluidized Bed Gasifiers

Energies 2009, 2, 556-581; doi:10.3390/en20300556
OPEN ACCESS

energies
ISSN 1996-1073
www.mdpi.com/journal/energies

Review

Thermochemical Biomass Gasification: A Review of the Current

Status of the Technology
Ajay Kumar 1, David D. Jones 2 and Milford A. Hanna 2,3,*
1
Department of Biosystems and Agricultural Engineering, Oklahoma State University, Stillwater,
OK 74078, USA; E-Mail: [email protected]
2
Department of Biological Systems Engineering, University of Nebraska-Lincoln, Lincoln, NE
68583, USA; E-Mail: [email protected]
3
Industrial Agricultural Products Center, University of Nebraska-Lincoln, Lincoln, NE 68583, USA

* Author to whom correspondence should be addressed; E-Mail: [email protected];

Tel.: +1-402-472-1634; Fax: +1-402-472-6338

Received: 13 May 2009; in revised form: 15 July 2009 / Accepted: 16 July 2009 /
Published: 21 July 2009

Abstract: A review was conducted on the use of thermochemical biomass gasification for
producing biofuels, biopower and chemicals. The upstream processes for gasification are
similar to other biomass processing methods. However, challenges remain in the
gasification and downstream processing for viable commercial applications. The
challenges with gasification are to understand the effects of operating conditions on
gasification reactions for reliably predicting and optimizing the product compositions, and
for obtaining maximal efficiencies. Product gases can be converted to biofuels and
chemicals such as Fischer-Tropsch fuels, green gasoline, hydrogen, dimethyl ether, ethanol,
methanol, and higher alcohols. Processes and challenges for these conversions are also
summarized.

Keywords: review; thermochemical conversion; gasification; biomass; syngas; biofuel;

chemical; combined heat and power
Energies 2009, 2 557

1. Bioenergy and the Role of Biomass Gasification

The demand for energy sources to satisfy human energy consumption continues to increase. Prior to
the use of fossil fuels, biomass was the primary source of energy for heat via combustion. With the
introduction of fossil fuels in the forms of coal, petroleum and natural gas, the world increasingly
became dependent on these fossil fuel sources. Currently, the main energy source in the world is fossil
fuels. The use of plastics and other chemicals which are derived from these fossil fuels also have
increased. These tremendous increases have led to many concerns. Although it is not known how much
fossil fuel is still available, it is generally accepted that it is being depleted and is non-renewable.
Given these circumstances, searching for other renewable forms of energy sources is reasonable. Other
consequences associated with fossil fuel use include the release of the trapped carbon in the fossil fuels
to the atmosphere in the form of carbon dioxide which has led to increased concerns about global
warming. Also, fossil fuel resources are not distributed evenly around the globe which makes many
countries heavily dependent on imports.
Biomass combines solar energy and carbon dioxide into chemical energy in the form of
carbohydrates via photosynthesis. The use of biomass as a fuel is a carbon neutral process since the
carbon dioxide captured during photosynthesis is released during its combustion. Biomass includes
agricultural and forestry residues, wood, byproducts from processing of biological materials, and
organic parts of municipal and sludge wastes. Photosynthesis by plants captures around 4,000 EJ/year
in the form of energy in biomass and food. The estimates of potential global biomass energy vary
widely in literature. The variability arises from the different sources of biomass and the different
methods of determining estimates for those biomasses. Fischer and Schrattenholzer estimated the
global biomass potential to be 91 to 675 EJ/year for the years 1990 to 2060 [1]. Their biomass included
crop and forestry residues, energy crops, and animal and municipal wastes. Hoogwijk estimated these
to be 33 to 1135 EJ/year [2]. Biomass included energy crops on marginal and degraded lands,
agricultural and forestry residues, animal manure and organic wastes. Parikka estimated the total
worldwide energy potential from biomass on a sustainable basis to be 104 EJ/year, of which woody
biomass, energy crops and straw constituted 40.1%, 36% and 16.6%, respectively [3]. Only about 40%
of potential biomass energy is currently utilized. Only in Asia, does the current biomass usage slightly
exceed the sustainable biomass potential. Currently, the total global energy demand is about
470 EJ/year. Perlack estimated that, in the United States, without many changes in land use and
without interfering with the production of food grains, 1.3 billion tons of biomass can be harvested
each year on a sustainable basis for biofuel production [4]. 1.3 billion tons of biomass is equivalent to
3.8 billion barrels of oil in energy content. US equivalent energy consumption is about 7 billion barrels
per year [5]. However, harvesting, collecting and storage of biomass adds another dimension of
technical challenges to the use of biomass for production of fuels, chemicals and biopower [6].
Two main ways of converting biomass energy (solid fuel) into biofuels and biopower are
biochemical conversion and thermochemical conversion processes. Biochemical conversions convert
the biomass into liquid or gaseous fuels by fermentation or anaerobic digestion. Fermentation of the
biomass (starch and cellulose) produces primarily ethanol. Anaerobic digestion leads to the production
of gaseous fuel primarily containing methane. The details of biochemical conversions are outside the
intended scope of this manuscript.
Energies 2009, 2 558

Thermochemical conversion technologies include combustion, gasification and pyrolysis. While

combustion of biomass is the most direct and technically easiest process, the overall efficiency of
generating heat from biomass energy is low. Gasification has many advantages over combustion. It can
use low-value feedstocks and convert them not only into electricity, but also into transportation fuels.
In the upcoming years, it will serve as a major technology for complementing the energy needs of the
world [7]. Use of advanced technologies such as gas turbines and fuel cells with the syngas generated
from gasification results in increased efficiency [8]. For complete combustion of solid fuels, excess air
is needed, and high combustion temperatures generate more NOx and other emissions, as compared
with the combustion of products by gasification. During combined cycles for combined heat and power
generation, contaminants in the syngas such as sulfur and nitrogen species and trace elements are
removed efficiently resulting in much lower emissions [9]. Moreover, liquid and gaseous fuels are
more of interest because of their ease of handling and operations, and their applications as
transportation fuels.
High oxygen content in biomass reduces the energy density of the biomass. The production of
hydrocarbons, similar to petroleum transportation fuels, requires the removal of oxygen from the
carbohydrate structure. The oxygen may be removed in the forms of CO2 and H2O. Thermochemical
conversion of biomass to syngas is an attractive route to extract the oxygen from carbohydrate
structures to produce intermediate compounds having C1 (CO and CH4), which can be further
synthesized into hydrocarbons by catalysis or fermentation. Other thermochemical schemes of
decarboxylation (CO2 removal) and dehydration (H2O removal) from carbohydrates result in higher
hydrocarbons (higher than C2) having undesired properties which require further conversion to be
compatible with transportation fuels [10].
Thermochemical conversion technologies have certain advantages and disadvantages over
biochemical conversion technologies. The main advantages are that the feedstock for thermochemical
conversion can be any type of biomass including agricultural residues, forestry residues, non-
fermentable byproducts from biorefineries, byproducts of food industry, byproducts of any
bioprocessing facility and even organic municipal wastes; and the product gases can be converted to a
variety of fuels (H2, Fischer-Tropsch (FT) diesels, synthetic gasoline) and chemicals (methanol, urea)
as substitutes for petroleum-based chemicals; the products are more compatible with existing
petroleum refining operations. The major disadvantages are the high cost associated with cleaning the
product gas from tar and undesirable contaminants like alkali compounds, inefficiency due to the high
temperatures required, and the unproven use of products (syngas and bio-oil) as transportation fuels.
However, research on the optimization of gasifier operating conditions and heat recovery, syngas
cleaning, bio-oil stabilization, and efficient product utilization can make the process important for
sustainable production of biofuels. With life cycle assessment, Wu concluded that use of cellulosic
biofuels (ethanol via gasification and fermentation, FT diesel and dimethyl ether (DME) from biomass,
etc) in light duty locomotives results in significant savings of fossil fuel resources and reduction in
green house gases [11]. Co-production of cellulosic biofuels and power generation by GTCC
consumes the least fossil fuel resources and results in the greatest reduction in green house gas (GHG)
emissions on a per-mile basis, of the thermochemical conversion techniques.
There have been substantial efforts to generate both gaseous and liquid fuels from coal gasification
during the 1970s oil embargo. However, after that the continued low price of petroleum resources
Energies 2009, 2 559

halted the major research, development and commercialization of these technologies. Biomass
gasification differs from coal gasification. Biomass is a carbon-neutral and sustainable energy source
unlike coal. Because biomass is more reactive and has higher volatiles content than coal, biomass
gasification occurs at a lower temperature. Lower temperature reduces the extent of heat loss,
emissions and material problems associated with high temperatures. Biomass also has low sulfur
content, which results in lower SOx emission. But the high alkali contents in biomass, like sodium and
potassium, cause slagging and fouling problems in gasification equipment [12].
The main steps involved in the gasification process can be categorized as upstream processing,
gasification and downstream processing (Figure 1).

Figure 1. Processes involved in biomass gasification.

Preprocessing Gasification Gas clean-up Gas utilization

of biomass & reforming

Size reduction, Heating, Cleaning of tar Gas turbine,

Drying, Chemical from syngas, Gas burner,
Preparation of reactions, Reforming of Fuel cell,
gasifying agents Catalysis the syngas, Combined heat
Catalysis and power
(CHP)
Upstream Gasification Downstream processing
processing

2. Upstream Processing

Upstream processing includes processing of the biomass to make it suitable for gasification
operations. Size reduction is needed to obtain appropriate particle sizes. Drying is needed to achieve
appropriate moisture so that the process can work efficiently. Densification also may be necessary due
to the low density of biomass.

2.1. Size reduction

Smaller particles have larger surface areas per unit mass and larger pore sizes which facilitate faster
rates of heat transfer and gasification [13]. Lv observed that smaller particles resulted in more CH4,
CO, C2H4 and less CO2 which led to higher gas yields, gas energy content (LHV) and carbon
conversion efficiency (Ceff) [14]. Rapagna reported increases in gas yield and gas compositions of CO,
CH4 and CO2, when the particle size was reduced from largest (1.090 mm) to smallest (0.287 mm) [15].
By decreasing the particle size from 1.2 mm to 0.075 mm, it was observed that H2 and CO contents as
well as gas yield and carbon conversion efficiencies increased whereas the CO2 decreased [16]. Higher
gas yields and energy efficiencies were attributed to the increased heat transfer in smaller size particles
due to the larger surface area.
Energies 2009, 2 560

Hammer-mills, knife mills and tub grinders are typical instruments used for reducing the particle
sizes of agricultural and forestry residues. Hammer mills are used both for dry agricultural and dry
forestry residues. Tub grinders are small, mobile hammer-mills. Screens are used in the mills to assure
the ground particles have certain maximum size [17]. Energy consumption during size reduction
depends on the moisture content, initial size of biomass, biomass properties, and screen size of the mill
and properties of the mill. Mani conducted tests of grinding performance on corn stover, barley straw,
wheat straw and switchgrass, and found that the corn stover consumed the least specific energy during
hammer mill grinding [18]. On the other hand, switchgrass used the most specific energy probably
because of its fibrous nature.

2.2. Drying

Biomass collected from farm and forest lands may contain high moisture. Drying is needed to
obtain a desired range of water content for the gasification processes. Drying is an energy intensive
process which may decrease the overall energy efficiency of the process. However, in case of
gasification, waste heat can be utilized to decrease the moisture content of the biomass which will
increase the overall efficiency of the process. Perforated bin dryers, band conveyor dryers and rotary
cascade dryers have been used to dry biomass [17]. In the case of generating combined heat and power,
biomass moisture should be as low as possible to increase the overall efficiency and decrease the net
cost of electricity. However, for low moisture raw biomass (less than 10%) drying stage may not be
needed [19].

3. Gasification

Gasification is the heart of the process. The main operating parameters of the gasifier include type
and design of gasifier, gasification temperature, flow rates of biomass and oxidizing agents (air or
steam), type and amount of catalysts, and biomass type and properties.

3.1. Types of gasifier

Gasifiers are categorized based on types of bed and flow. The gasifier bed can be a fixed-bed or a
fluidized bed. Fixed bed gasifier can be classified further as updraft (countercurrent) or downdraft
(concurrent). In the updraft gasifier, the feed (biomass) is introduced from the top and moves
downwards while gasifying agents (air, steam, etc.) are introduced at the bottom of the grate so the
product gas moves upwards. In this case, the combustion takes place at the bottom of the bed which is
the hottest part of the gasifier and product gas exits from the top at lower temperature (around 500 °C).
Because of the lower exit temperature, the product gas contains large amounts of tar. In a downdraft
gasifier, both the feed and product gas moves downward and the product exits from the bottom at a
higher temperature, i.e., around 800 °C. In this case, most of tars are consumed because the gas flows
through a high temperature region. However, heat needs to be recovered from high temperature
product gas to increase the energy efficiency. These two types of gasifiers, updraft and downdraft,
have been used most extensively in the past.
Energies 2009, 2 561

In the fluidized bed gasifier, the feed is introduced at the bottom, which is fluidized using air,
nitrogen and/or steam and the product gas then moves upward. There are more particulates in the
product gas from this gasifier [20]. Fluidization of the bed enhances the heat transfer to the biomass
particle leading to increases in reaction rates and conversion efficiencies. Fluidized beds also are able
to tolerate a wide variation in fuel types and their characteristics. A fluidized bed can be either a
bubbling fluidized bed or a circulating fluidized bed. In case of the bubbling fluidized bed gasifier, the
flow rate of the fluidizing agent is comparable to the minimum fluidizing velocity. Uniform
temperature across the bed can be maintained by fluidization resulting in uniform product gases. The
fluidizing mediums used are generally silica or alumina materials which have high specific heat
capacity and can operate at high temperature. Catalysts also can be added as fluidizing agents which
can increase the conversion efficiency and reduce tar formation. However, fluidized catalysts are more
susceptible to attrition and poisoning. There is a need for robust catalysts that are effective at high
temperature (800 °C or more) in the fluidized medium. Some of the catalysts that have been
investigated are discussed in detail in the in-bed catalyst section. Circulating fluidized beds have
higher flow rates of the fluidizing agents which move most of the solid and ungasified particles to an
attached cyclone separator, from which the solids are re-circulated to the gasifier bed. The higher flow
of gasifying agent increases the heat transfer and conversion rate of the biomass.
The advantages and disadvantages of each type of gasifiers have been summarized by
Warnecke [21]. Gasifiers also can be categorized by the method of heat source provided for the
endothermic gasification reactions. Heat can be supplied to the gasifier indirectly or directly. In a
directly-heated gasifier, part of biomass is allowed to combust inside the gasifier. The combustion then
raises the temperature and provides the required heat for the endothermic gasification reactions. In the
case of an indirectly heated gasifier, biomass or ungasified char is combusted in a separate chamber
and heat exchanger tubes conduct the heat from the combustion chamber to the gasification
chamber [12].

3.2. Gasification process

Gasification takes place at high temperature in the presence of an oxidizing agent (also called a
gasifying agent). Heat is supplied to the gasifier either directly or indirectly which raises the
gasification temperature of 600–1,000 °C. Oxidizing agents are typically air, steam, nitrogen, carbon
dioxide, oxygen or a combination of these. In the presence of an oxidizing agent at high temperature,
the large polymeric molecules of biomass decompose into lighter molecules and eventually to
permanent gases (CO, H2, CH4 and lighter hydrocarbons), ash, char, tar and minor contaminants. Char
and tar are the result of incomplete conversion of biomass.
The overall reaction in an air and/or steam gasifier can be represented by Equation 1, which
proceeds with multiple reactions and pathways. Equations 2–8 are common reactions involved during
gasification. Among these, Equations 4–7 occur when steam is available during gasification. Many
authors have studied the degradation kinetics of various biomass feedstocks (rice husk, pine chips,
wheat straw, rapseed straw, pigeon pea stalk, etc.) using thermogravimetric analyses (TGA). TGA
provides the weight loss of any material with change in temperature. The weight loss (or thermal
degradation) in a nitrogen atmosphere occurred in mainly three stages; with the first stage being
Energies 2009, 2 562

dehydration (below 125 °C), the second stage being active pyrolysis (125–500 °C) and the third stage
being passive pyrolysis above 500 °C. The dehydration reflects loss of water, the active pyrolysis
reflects the loss of the hemicellulose, cellulose and part of lignin, and the passive pyrolysis reflects the
slow and continuous loss of residual lignin. The temperature ranges of these stages and the kinetic
parameters of the degradations depend primarily on the rate of heat transfer, the composition of the
biomass, and the degree of the oxidizing environment [22–25].
CHxOy (biomass) + O2 (21% of air) + H2O (steam)
(1)
= CH4 + CO + CO2 + H2 + H2O (unreacted steam) + C (char) + tar

2C + O2 = 2CO (partial oxidation reaction) (2)

C + O2 = CO2 (complete oxidation reaction) (3)

C + 2H2 = CH4 (hydrogasification reaction) (4)

CO + H2O = CO2 + H2 (water gas shift reaction) (5)

CH4 + H2O = CO + 3H2 (steam reforming reaction) (6)

C + H2O = CO + H2 (water gas reaction) (7)

C + CO2 = 2CO (Boudourd reaction) (8)

3.3. Effects of gasification operating conditions on the product properties

To obtain the desired product gas composition, the least amount of impurities, and to increase the
net energy conversion efficiency, the gasification operating conditions need to be optimized. The
following section describes the effects of the main operating conditions on the quantity and
composition of the product gas and its impurities.

3.3.1. Biomass flow rate, type and properties

Overfeeding of biomass can lead to plugging and reduced conversion efficiencies whereas starve-
feeding results in less gas yield. Hence, an optimum biomass flow rate is desired for the gasification
system to maximize energy efficiency. Optimum biomass flow rate is dependent primarily on the
design of the gasifier and the properties of the biomass.
The main constituents of lignocellulosic biomass are cellulose, hemicellulose and lignin. Cellulose
is a linear polymer of D-glucose (a six-carbon sugar) linked with β-1,4 linkages; hemicellulose is a
branched polymer with both five carbon and six-carbon sugars, and lignin is a randomly constructed
and highly aromatic cross-linked macromolecule. Herbaceous crops and wood contain 60–80% (db)
cellulose and hemicellulose, and 10–25% lignin [5]. The composition of these polymers in the biomass
affects the product composition. Hanaoka observed that at 900 °C, carbon conversion efficiencies of
cellulose, xylan and lignin were 97.9%, 92.2% and 52.8%, respectively [26]. The product
compositions from gasification of xylan and lignin were similar. Cellulose resulted in higher CO
Energies 2009, 2 563

(35 vs. 25 mol %) and CH4 (6 vs. 5 mol %) but lower CO2 (27 vs. 36 mol %) and H2 (29 vs. 33 mol %)
yields than those of xylan and lignin. Barneto observed that composting of biomass increased the
lignin content in the compost, which resulted in up to 20% increased H2 production at a slow heating
rate as compared to the original biomass at a fast heating rate [27].
Co-firing of biomass with coal also is being studied. Kumabe observed that by varying the ratio of
coal to biomass for the gasification, the extent of the water gas shift reaction was maximal at the ratio
of 0.5 which they attributed to the synergy between the coal and biomass [28]. With increase in
biomass ratio, they observed increases in gas and CO2 yields, decreases in char, tar and H2 but CO, and
hydrocarbons (HCs) were unchanged. Gasification of coal with biomass reduces problems associated
with high ash and sulfur contents of the coal [29].

3.3.2. Air flow rate (equivalence ratio, ER or superficial velocity, SV)

Equivalence ratio (ER) and superficial velocity (SV) are measures of the air (or oxygen) flowrate.
ER is the ratio of air flow to the airflow required for stoichiometric combustion of the biomass, which
indicates extent of partial combustion. The SV is the ratio of air flow to the cross-sectional area of the
gasifier which removes the influence of gasifier dimension by normalization [30]. Hence, both ER and
SV are directly proportional to the airflow. Air flow influences the gasification products in different
ways. Air supplies the O2 for combustion (and fluidization in the case of fluidized bed) and effects the
residence time. By varying amount of the O2 supply, air flow rate controls the degree of combustion
which in turn, affects the gasification temperature. Higher airflow rate results in higher temperature
which leads to higher biomass conversion and a higher quality of fuel. But, an excess degree of
combustion, on the other hand, results in decreased energy content of the gas produced because a part
of biomass energy is spent during combustion. Higher airflow also shortens the residence time which
may decrease the extent of biomass conversion.
With an increase in ER (from 0.20 to 0.45), Narváez observed an increase in gas yield, a decrease in
lower heating value (LHV) of the gas and decreased contents of H2, CO, CH4 and C2H2 and tar [31].
Lv reported that with an increase in ER from 0.19 to 0.27, the H2 content varied a little but gas yield
increased and then decreased with an optimal ER of 0.23 [32]. Wang found that with an increase in ER
from 0.16 to 0.26, the bed and freeboard temperatures increased resulting in a higher yield and higher
heating value (HHV) of the gas, an increase in cold gas efficiency from 57% to 74%, an increase in H2
content from 8.5% to 13.9%, and an increase in CO content from 12.3% to 14% [33]. Kumar observed
increases in gas yields, carbon conversion and energy efficiencies with an increase in ER from 0.07 to
0.25 [34]. All authors reported increases in gas yields with increases in ER (from 0.0 to 0.45).
However, contradictory results of decreases in H2 and CO yields with increases in ER also have been
reported [35]. The increase in gas yield with increase in ER implies that an increased airflow increases
conversion rate. Some of the contradictory results on the effects of ER on the contents of H2, CO and
CH4 (%) is logical because the percentage compositions of individual gases depend on both the yield
of individual gases and the overall gas yield. If the increase in overall gas yield is more pronounced
than the increase in individual gas yield, then the percentage composition of individual gas decreases,
even though the individual gas yield may actually have increased. Effects of ER on the product gas
composition also depend upon other factors such as temperature and steam to biomass ratio. During
Energies 2009, 2 564

steam gasification, at high temperature, the H2 yield is more pronounced than the increase in gas yield
which results in an increase in H2 content.

3.3.3. Steam flow rate (steam to biomass ratio, S/B)

Supplying steam as a gasifying agent increases the partial pressure of H2O inside the gasification
chamber which favors the water gas, water gas shift and methane reforming reactions (Equations 5–7),
leading to increased H2 production. However, the gasification temperature needs to be high enough
(above 750–800 °C) for the steam reforming and water gas reactions to be favorable [34,36,37].
Catalysts can lower the operating temperature needed for the above reactions to occur. Higher S/B also
leads to higher biomass conversion efficiency [38].
Reduction in tar also is observed at higher steam to biomass ratios, which is attributed to steam
reforming of the tar with an increased partial pressure of steam. Narváez found that with an increase in
H/C ratio (H and C from incoming biomass, moisture and steam) from 1.6 to 2.2, H2 content increased,
LHV increased from 4 to 6 MJ/Nm3 and tar content decreased from 18 to 2 g/Nm3 [31]. By varying
S/B from 0 to 4.04, Lv observed that with S/B higher than 2.7, the gas composition did not change
significantly but, with S/B between 0 and 1.35, CO yield decreased, and CH4, CO2 and C2H4 yields
increased [32]. With S/B of 1.35 and 2.70, the CO and CH4 yields decreased and CO2 and H2 yields
increased which implied higher steam reforming reactions. Turn observed that increasing S/B from 1.1
to 4.7 decreased CO, CH4, C2H2 yields, and increased H2 and gas yields [35]. H2 increased from 46 to
83 g per kg dry and ash-free (daf) biomass. Since the temperature of the steam supplied to the gasifier
is lower than the gasification temperature, a significant amount of heat is needed to raise the steam
temperature which, in turn, may lower the temperature of the gasifier bed. Hence an S/B ratio above a
threshold, steam had negative effects on the product.
Increasing the temperature of the gasifying agents led to an increase in the heating value of the fuel
gas, and reduces the tars, soot and char residues [36]. A preheater is recommended before the
introduction of gasifying agents (steam and air) to the gasifier to facilitate higher gasification
bed temperature.

3.3.4. Gasification temperature profile

Gasification temperature is one of the most influential factors affecting the product gas composition
and properties. Higher temperature results in increased gas yield because of higher conversion
efficiency. Since, the reactions (Equations 5–8) occur simultaneously, the contents and ratios of H2,
CO, CO2 and CH4 in the product gas are affected by temperature and partial pressures of reactants.
At temperatures above 750–800 °C, the endothermic nature of the H2 production reactions (steam
reforming and water-gas reactions) results in an increase in H2 content and a decrease in CH4 content
with an increase in temperature. At temperatures above 850–900 °C, both steam reforming and the
Boudouard reactions (Equations 6–8) dominate, resulting in increases in CO content. High temperature
also favors destruction and reforming of tar (Equations 9–10) leading to a decrease in tar content and
an increase in gas yield [31,34,37,39,40]. Gupta and Cichonski observed significant increases in H2
above 800 °C for S/B between 0.5 and 1.08 [37]. Maximal H2 yield was obtained at 1,000 °C for a
feedstock consisting of paper, and 900 °C feedstocks consisting of cardboard and wood pellets.
Energies 2009, 2 565

González observed that in air gasification contents of H2, CO increased from 700 to 900 °C, whereas
contents of CH4 and CO2 decreased [40]. They also observed that the CO/CO2 ratio linearly increased
from 0.85 at 700 °C to 2.7 at 900 °C in two segments. At 700–800 °C, the slope was 0.0067 and then
almost doubled to 0.113 at higher than 800 °C which showed the predominance of the Boudouard
reaction at higher temperatures. It was also observed that higher temperatures (700 to 950 °C)
increased the gas yield and overall energy content of the gas [38,41]. Kumar observed that an increase
in temperature (furnace set point from 750 to 850 °C), led to increases in energy and carbon
conversion efficiencies and percent gas compositions of H2 [34]. Turn found that with an increase from
750 to 950 °C, H2 increased from 31% to 45%, CH4 and CO remained fairly constant, CO2 decreased
and gas yield increased [35]. Boateng reported that with an increase in gasification temperature from
700 to 800 °C, gas yield, gas HHV, energy efficiency, carbon conversion efficiency and H2 content
increased and CH4, CO and CO2 contents decreased [42]. The decrease in CO content may have been
due to the comparatively lower temperature (than 850–900 °C) for the Boudouard reaction
to predominate.
CnHx = nC + x/2 H2 (9)

CnHx + mH2O = nCO + (m + x)/2 H2 (reforming reaction) (10)

4. Downstream Processing

The product gas from biomass gasification needs to be processed further for effective utilization.
The processes involved are, overall, termed as downstream processing. Cleaning of tar and other
contaminants from product gas, biopower generation, reforming and conversion to biofuels constitute
the downstream processing operations. The product gas contains particulates, tar, alkali compounds,
and nitrogen and sulfur containing compounds which typically need to be removed before the product
gas is used. Reforming reactions change the gas composition of the product gas as desired for the
specific syngas utilization. For example, high H2 content is desired for fuel cell applications, and
specific ranges of CO/H2 are desired for producing other fuels and chemicals from syngas. Tolerable
amounts of the contaminants in the syngas depend on the syngas applications. Combustion systems can
work with relatively high amounts of tar but hydrocarbon conversion catalysts and fuel cells need
syngas with low levels of tar.

4.1. Syngas cleaning

4.1.1. Particulate removal

The product gas stream from the gasifier typically contains particulates. The particulates consist of
unconverted biomass material (ash and char) and bed material. Ash materials are the mineral
components of the biomass; char is the unconverted portion of the biomass which is less reactive,
resulting in decreased carbon conversion efficiency, and the fines from the bed material also are
entrained with the gas stream. Particulate deposition in the downstream equipment causes plugging
and results in higher wear.
Energies 2009, 2 566

Cyclone separators are widely and routinely used to separate the larger particulates (above 5 μm in
diameter) at the initial cleaning stage with little pressure drop. These are inexpensive to build and
operate. The design methodology for cyclone separators is available [43–45]. Generally, multiple
cyclones are used to increase separation efficiency. Wet scrubbers, various barrier filters and
electrostatic precipitators subsequently separate smaller particulates.
Wet scrubbers remove particulates using liquid sprays (usually water) on the gas stream. These can
remove 95–99% of over 1 μm particle size and 99% of over 2 μm with pressure across the venturi of
2.5 to 25 kPa [46]. However, wet scrubbers are used at less than 100 °C which results in loss of
sensible heat. Hotter gas is desired, especially, for many applications such as in gas turbines and
reforming reactions.
Electrostatic precipitators (ESP) apply electrical voltage to charge and then separate particulates.
The separation efficiency depends on particulate resistivity, and sulfur and alkali contents. Because of
its large size and high capital cost, it is suited for large-scale operations.
Barrier filters allow the gas to pass through various porous media collecting the particulates of
0.5 to 100 μm. Because of the smaller pore size, it increases the pressure differential across the filter.
Common types of barrier filters are (a) metal or ceramic porous candle filters, (b) bag filters, and (c)
packed bed filters. Candle filters can operate at high temperature (ceramic more than metallic) which
makes them attractive for hot gas cleaning. Ceramic filters have been tested in a gasifier operated at
about 700 °C gas temperature. Bag filters are constructed of woven material which collect smaller
particles of even sub-micron size, and can operate at temperatures of about 350 °C. Packed bed filters
use bed materials such as ceramic spheres and sawdust to capture the particulates as gas flows through
it [47].

4.1.2. Alkali removal

Significant amounts of alkali compounds (CaO, K2O, P2O5, MgO, Na2O, SiO2, SO3) are present in
biomass. These alkali compounds can vaporize at temperatures above 700°C during gasification which,
when condensed (below about 650 °C), form particles (<5 μm) in the downstream equipment (gas
turbine, heat exchanger), stick to the metal surfaces, and result in corrosion. Moreover, alkali salts
inactivate the catalysts used in tar cracking, reforming and converting syngas into hydrocarbons.
Removal of alkali can be performed by cooling the gas and then passing it through barrier filters. Hot
gas removal of alkali compounds holds promise, particularly for high temperature applications.
However, research on hot gas alkali removal is still in the experimental stage [47]. Turn reported that a
bauxite filter at 650–725 °C removed most of the Na and K compounds [48].

4.1.3. Nitrogen compounds

When gasified, the nitrogen content of the biomass (0.5–3%) results primarily in ammonia (60–65%)
and molecular nitrogen. Unlike coal gasification, conversion to hydrogen cyanide is very low in
biomass gasification [49]. If not removed, combustion of part of ammonia (occurring at temperatures
above 1,000 °C, typical of combustion) results mostly in NOx formation. If cold product gas is desired,
ammonia can be removed by wet scrubbing. Hot gas cleaning for ammonia can be performed by
Energies 2009, 2 567

destructing ammonia at higher temperature using dolomites, nickel-based catalysts and iron-based
catalysts [50].

4.1.4. Sulfur compounds

Most biomass contains very little sulfur (<0.5%), which, during gasification, is converted to H2S
and SO2. Because of the low sulfur content in biomass, as compared to coal, the gas sulfur content in
the gas is low enough to meet the needs of most applications. But for a few applications, such as
methanol synthesis, even a low sulfur level can irreversibly inactivate the catalysts. Fuels cells and
some tar catalysts also are sensitive to sulfur. SO2 in syngas can be removed by wet scrubbing. SO2 and
H2S are the predominant sulfur compounds in the exit gas, in the cases of coal combustion and
gasification, respectively. Limestone, dolomite or CaO are used for SO2 and H2S removal because of
their low cost and wide availability. Calcination processes are advantageous for SO2 removal whereas
cleaning at 600–900 °C and regeneration of sorbents is the best scrubbing process for H2S removal
from hot gas [51].

4.1.5. Tar removal

Tar is a generic term used for all organic compounds found in the product gas with the exception of
gaseous hydrocarbons. Tar is the part of the biomass which does not decompose completely into
lighter gases. Removal of tar is one of the biggest technical challenges facing the commercialization of
gasification technology [52]. The high-temperature product gas from a gasifier contains tar. If not
removed, the tar condenses on the wall of the downstream equipment such as heat exchangers,
combustion engine, reactors or fuel cells [53]. Measurement of tar has been improved over the years to
maintain consistency among different tar measurement techniques [54,55].
The primary organic compounds in tar can be grouped as mixed oxygenates, phenolic ethers, alkyl
phenolics, heterocyclic ethers, poly-aromatic hydrocarbons (PAH) and larger PAH. The composition
shifts from larger molecules (e.g., larger PAH) to smaller molecules (e.g. mixed oxygenates) with
increased reaction severity [46,47]. During gasification, reaction severity can be increased by
increasing the temperature, flow of oxidizing agents or amount of catalysts.
Tar is less problematic for combustion of product gas because tar also can combust and add to the
calorific value of the fuel, although less readily and at higher temperatures. Other applications, wherein
the gas stream is cooled, result in condensation of the tar. Tars also are detrimental to catalysts used for
conversion of syngas and fuel cell applications.
Tar removal techniques are categorized as: (a) primary removal techniques and (b) secondary
removal techniques. Primary removal techniques refer to techniques that reduce the tar content in the
syngas and are employed inside the gasifier without the need of a secondary reactor. Primary removal
methods include design and optimization of the gasification operating conditions, and addition of
catalysts in the gasifier bed (called in-bed catalysts). Secondary tar removal techniques use a separate
reactor to destruct and reform the tar content below acceptable level in the product gas. Secondary tar
cleaning techniques are divided further into wet and hot gas cleaning. Devi reviewed the methods for
removing tar from syngas, with a focus on primary tar removal methodologies [56].
Energies 2009, 2 568

Effects of operating conditions (A primary removal technique)

Numerous studies have shown that the gasification operating parameters, primarily gasification
temperature profile, ER, type of gasifying agent, S/B, total gasifying agent to biomass ratio, and feed
rate are effective in reducing the amount of tar in the syngas. Effects of the operating conditions on the
amount of tar in the product gas have been described in the previous section. In general, higher
temperature, ER, and S/B results in product gas with less tar due to their contributions to destruction of
tar. Yamazaki found that, in a downdraft gasifier, a higher SV of 0.7 m/s resulted in higher amount of
tar as compared to a lower SV of 0.4 m/s [30]. According to them, higher SV resulted in shorter
residence time and channeling which may have led to higher amounts of tar. However, a SV of 0.4 to
0.6 m/s were able to produce gas suitable for use in internal combustion engines. Particle yield also
increased with increasing SV. Various gasifier designs, such as secondary injection of air or oxygen
into the gasifier and two-stage gasification systems, also can result in lower tar contents [56].

In-bed catalyst (A primary removal technique)

The addition of catalysts such as dolomite, limestone, olivine, alkali carbonates, Ni-based catalysts,
metal-oxide catalysts, zeolite or char in the gasifier bed, either with or without sand along with the
biomass feed, help reduce tar and increase the extent of reforming reactions in the gasifier, thereby
increasing overall carbon conversion efficiency.
Rapagna compared the performances of sand, dolomite and olivine particles as bed materials in a
bubbling fluidized bed lab-scale gasifier [57]. They observed that the gas yield increased by more than
50%, tar was reduced by 20 times and char was reduced by 30% when dolomite or olivine was used as
a bed material as compared to using sand. However, methane content was almost the same which
indicated that the olivine and dolomite catalyzed tar destruction, but not methane reforming.
Mechanical strengths of olivine and sand were similar but dolomite resulted in more fines. Asadullah
found the amount of tar was negligible when using Rh/CeO2/SiO2 catalysts as compared to 30, 113 and
139 g/m3 observed for commercial steam reforming catalyst G-91, dolomite and non-catalyst systems,
respectively, in the bed for low temperature (823–973 K) fluidized-bed gasification [58,59].
Deactivation was not severe in the 20 h test probably because carbon conversion efficiency was high
leaving less char in the bed.
In-bed catalysts reduce tar content but complete tar removal (satisfactory for downstream
processing) is not achieved without the use of secondary reactors [52]. Also, it should be noted that the
optimized operating conditions, gasifier designs and the application of in-bed catalysts for tar
reduction using primary methods may not be optimum conditions for yield, composition, and energy
content of the syngas. Therefore, the process efficiencies also need to be considered in determining the
best operating conditions and gasifier design for obtaining desired product composition.

Wet cleaning (A secondary removal technique)

Cold gas cleaning uses water scrubbing and venturi scrubbing to condense the tar compounds from
the syngas and simultaneously removing the particulates. It has been demonstrated that tar
concentrations below 20–40 mg/Nm3 can be achieved using a venturi scrubbing system [53]. This
Energies 2009, 2 569

technology has been used extensively in coke-oven and gas processing industries, whose details can be
found in Baker [46]. The exit gas temperature from wet cleaning methods is 35–60 °C, which results in
loss of sensible heat and water condensate which requires treatment before disposal.
The use of barrier filters and cyclone separators have not been effective for tar removal since tar
aerosol particles are less than 1μm in size and are sticky in nature which makes them difficult to
remove from walls of the cyclone and filter. Electrostatic precipitator (ESP) wet scrubbers can remove
most of the tar up to about 150 °C but are more expensive. The tar collected using these physical
techniques can be burned to produce heat or re-injected into a gasifier. Bergman developed a wet
scrubbing (scrubbing liquid was other than water which was regenerated and recycled) based cleaning
technology called “OLGA” [52]. Tar components, which condensed above 25 °C, were heavy poly-
aromatic hydrocarbons (PAH) (≥4 rings), light PAH (2–3 rings) and heterocyclic compounds. By
removing these three tar components selectively, based on their dew points, the dew point of the
resulting tar was less than normal temperature. Hence, the cleaned syngas can be acceptable for most
syngas applications.
The disadvantages of wet cleaning are: (a) that since the product gases are at a high temperature,
reducing the temperature, during wet cleaning, decreases the net energy efficiency of the process, (b)
that the waste water needs to be treated extensively before discharge which is a capital-intensive
process, and (c) if the product gas is used for high temperature applications, there will be a net loss of
energy in cooling and heating the product gas stream [53].

Reforming for secondary tar removal and increased H2 production

The drawbacks of wet cleaning have encouraged extensive research on hot gas cleaning
technologies. The aim of hot gas cleaning is to crack the tar using high temperature. Without a catalyst,
the temperature required for tar cracking is above 850 °C which reduces efficiency, causes material
problems and produces soot [12]. Hot gas cleaning also results in increased hydrogen production in the
product gas because the destruction of tar yields hydrogen, and the higher temperature and catalysts
provide favorable conditions for reforming and shift reactions [53]. Non-catalytic reforming performed
by Wang at 800–950 °C indicated that supplying air to the reformer decreased the HHV of the product
gas by partial combustion and dilution of the reformed gas [33]. With an increased ER from 0.15 to
0.21, tar concentration decreased from 5.7 to 1.0 Ng/m3. Supplying steam (up to S/B of 0.5) to the
reformer increased the HHV and cold gas efficiency of the reformed gas. H2, and CH4 contents
increased but CO and tar contents decreased with increasing S/B into the reformer. Supplying steam
or/and air to the secondary reactor, in presence of catalysts, enables the tar to react and form CO, H 2,
CO2 and CH4.
Tar removing catalysts are grouped into mineral and synthetic catalysts. The mineral-based
catalysts are naturally occurring minerals and inexpensive. They also have fewer disposal problems.
Calcined rocks (calcined dolomite, magnesite and calcite), olivine, clay materials and iron ores are
mineral-based catalysts. Among these, calcined rocks are the most efficient catalysts. However,
calcined rocks are suited only for fixed-bed secondary reactors as they erode in fluidized bed reactors.
Olivine has more mechanical strength for attrition but is less efficient than dolomite. Clay materials
generally do not withstand temperatures of 800–900 °C, whereas iron ores are rapidly deactivated.
Energies 2009, 2 570

Fluid catalytic cracking (FCC), char, alkali metal-based, activated alumina, and transition metal-based
(Pt, Zr, Rh, Ru, Fe, and Ni) catalysts are synthetic catalysts. Transition metals (Ni, Rh, etc.), as well as
other synthetic catalysts, are relatively expensive as compared to the mineral catalysts. FCC deactivate
rapidly, alkali metals agglomerate in the bed, and transition metals, although very active (8–10 times
than dolomite), need gas with low levels of sulfur, tar and char [60].
Numerous efforts have been made to design catalysts for destructing tar and increasing the extents
of reforming reactions at the same time. Using calcined dolomite (120 g per kg/h of biomass) in the
gasification fluidized bed and a nickel based catalyst (weight hourly space velocity, WHSV of 2.7 to
10.7 h-1) in a secondary fixed-bed reactor, Lv observed that decreasing WHSV had a positive impact
on H2 content and H2/CO. CH4 content decreased by half, H2 content increased up to 49% (v/v), and
H2/CO increased up to 3.32 at a WHSV of 2.7 h-1 [39]. WHSV was defined as the ratio of biomass
flow rate to catalyst mass in the secondary reactor. With an increase in catalytic reactor temperature
(650 to 850°C), H2 content increased, CH4 CO2, C2 yields decreased but CO content remained the
same. Maximal H2 yield was 130.28 g H2/kg biomass.
Wang found that activity of Ni/dolomite catalysts in the secondary catalytic reactor were
comparable to commercial steam reforming catalysts [61]. Ni/dolomite catalysts are relatively cheaper
than steam reforming catalysts and have anticoking properties. With a space time of 0.02 kg of
catalyst (m3/h) and a temperature of 850 °C, the catalysts were able to convert 98% of the tar while
increasing H2 content. By comparing commercial steam reforming catalysts for naphtha and natural
gas, Aznar and Corella concluded that catalysts for naphtha were more effective in destructing tar than
catalysts for natural gas reforming [62,63]. A 2 g/m3 level of tar did not poison the catalysts. Operating
conditions such as temperature, space time (mass of catalyst per unit flow rate of product gas), catalyst
particle size and gas compositions affected tar conversion efficiencies. Inaba compared two types of
supports for production of hydrogen over Ni catalysts [64]. They found that metal oxides produced
large quantities of dark-colored tar while zeolite-based support produced carbon deposition without tar
formation. Higher temperatures led to higher rates of gasification and H2 production, and decreased
depositions of tar and char on the catalysts. Nordgreen reported improved gas yield, decreased tar
(most pronounced decline was for toluene), increased CO, CO2, H2 yields and decreased CH4 yield by
using elemental iron as a tar removal and reforming catalyst in a secondary reactor [65]. Corella
concluded that the performances of expensive Ni-based monoliths were comparable to cheaper
dolomite for tar elimination [66]. The development of more robust and efficient catalysts can improve
the tar conversion efficiency. Resistance to coking and sulfur poisoning were reported after adding
WO3 as sulfur-resistant promoter to Ni/MgO-CaO catalysts supported on dolomite [67]. Kimura found
that a co-impregnation method resulted in higher performance of the catalysts for steam reforming of
tar (Ni/CeO2/Al2O3) than sequential impregnation (Ni/Al2O3 and Ni/CeO2/Al2O3) due to strong
interaction between Ni and CeO2 [68].

4.2. Conversion of syngas to biofuels, bioproducts and biopower

Syngas, primarily a mixture of CO and H2, is a building block for synthesizing a variety of fuels and
chemicals [69]. The main routes of converting syngas to fuels and chemicals, and generating
biopower follow.
Energies 2009, 2 571

4.2.1. Biopower

The product gas from biomass gasification can be used to produce heat and electricity using a
combined heat and power (CHP) system called integrated gasifier combined cycle (IGCC or BIGCC,
Biomass-fired IGCC). The main advantages of producing heat and electricity using gasification over
direct combustion are (a) fuel-gas based technologies such as gas engines or gas turbines can achieve
higher efficiencies than combustion efficiency, (b) the overall efficiency of gasification is higher
because gaseous fuels, having improved combustion characteristics, burn more efficiently than solid
fuel, and (c) production of gas provides an opportunity to remove contaminants that ultimately produce
NOx and SOx emissions [9,70,71]. With an overall efficiency of 35%, 7 billion tons of globally
available biomass, with an energy content of 124 EJ, could produce 44 EJ of electricity [72].
Several demonstration and commercial CHP plants have been developed around the world as
alternatives to the use of fossil fuel for electricity production [72]. Most remarkable and first BIGCC
was demonstrated at Varnamo, Sweden producing 6 MW of electricity and 9 MW of heat primarily
from wood chips. This facility operated between 1993 and 1999, and was closed due to unfavorable
economic conditions. The 8,500 h of gasification runs and about 3,600 h as a fully operational
integrated plant provided valuable experiences. The demonstration proved that the producer gas from a
high-pressure circulating bed gasifier could be cleaned using hot cleaning technique and could be
burned in a gas turbine under stable conditions even with low-energy of 3.8 MJ/kg. More research
initiatives are underway to restart the demonstration plant for increased H2 production using municipal
wastes [73]. Yin reported that a circulating fluidized-bed (CFB) gasifier attached to gas engines and a
capacity of 150 t/d of rice husk, located in China, reliably provided 1 MW of electricity at a rice mill
with an overall electrical efficiency of 18% with a payback period of less than 2 years [74]. Wu
reported that after 8,000 h of operation, the overall efficiency improved to 28% for demonstration plant
of BIGCC at the scale of 5.5 MWe [75]. The operating and capital costs were estimated to be
0.079 USD/kWh and 1,200 USD/kW with a biomass price of 35.7 USD/ton.
With an increase in size of the gasification system, the cost of electricity production decreases.
Brammer and Bridgwater estimated the cost of electricity (coE) was 8.67 Euro c/kWh for a 2 dt/h
system at cost of €30/dt with a rotary dryer reducing the moisture from 50% to 10% [18]. Craig and
Mann estimated cost of electricity production to be 0.0655 to 0.0820 USD/kWh, depending on the
gasifier design, including high or low pressure, and directly or indirectly heated [76]. Uddin and
Barreto, and Rhodes and Keith found that biomass-fired cogenerations systems such as BIGCC, with
carbon capture, were energy efficient, emission efficient and cost competitive with natural gas
cogeneration systems with carbon capture [77,78]. Tiffany concluded that, for ethanol production from
corn, the use of biomass (corn stover and fermentation byproduct such as distillers grains and corn
syrup) to produce heat and/or electricity might require high capital cost but the profitability of the
process was more resilient to the change in prices of commodities (corn, oil, natural gas, electricity),
and these were competitive with the conventional natural gas and purchased electricity [79]. However,
issues related to biomass collection and utilization, and commercialization of CHP-BIGCC need to be
resolved. High capital costs associated with first generation large-scale gasification of biomass, the
technical risks involved, and the unproven technologies of tar cleaning are the main hindrance to the
Energies 2009, 2 572

commercialization efforts. The heating value of the product gas needs to be increased, especially in air-
blown gasification, to power gas turbines [7,80].
CHP generation from biomass is especially beneficial for rural electrification in developing
countries where diesel is the primary fuel. Abe, in a case study of Cambodia, estimated that with the
current technology, the cost of electricity from gasification of locally available biomass (agricultural
residue, planted trees) was lower than the cost of electricity from diesel engine at the scale of
13.3 kWh electricity usage per household [81]. Gasification has potential to provide electricity to more
than 60% of the villages which currently are without electricity. However, the major challenges in the
commercialization of small-scale gasification systems are to effectively clean the product gas, at this
scale, for proper operation of gas engines; to design the system flexible enough to operate using
varying biomass qualities; and to decrease the capital cost [82,83].

4.2.2. Hydrogen

H2 can be used as a transportation fuel in fuel-cell based automobiles, as a zero-emission fuel. It

should be realized that H2 is not an energy carrier, but rather an energy source. Hence, sources of
energy are needed to produce hydrogen. H2 has the highest energy content on a mass basis. Use of H2
in fuel cells has gained attention because of its high efficiency (around 60%) as compared to efficiency
of IC engines (20–38%). However, more research is needed in the areas of production, storage,
transportation and utilization of H2 for its viable use as an energy carrier [84,85]. Currently, the total
production of H2 is about 9 million tons, 95% of which is produced by steam reforming of natural gas.
The H2 is used for the production of chemicals and intermediate products with 95% being used to
produce ammonia (50%), petroleum products (37%), and methanol (8%) [86,87].
Biomass gasification results in H2 production. As described in the previous sections, changes in
gasifier and reformer operating conditions influence the H2 content of the product gas. Higher
temperature, ER, S/R and catalysts all lead to higher H2 production. However, additional reforming
reactions may be needed to further increase the H2 content in the product gas.

4.2.3. Catalytic synthesis of methanol and higher alcohols

Methanol, produced in large quantity, is used for making various fuels and chemicals. Currently, it
is used primarily for making formaldehyde, dimethyether, MTBE (methyl tert-butyl ether, additive for
gasoline) and acetic acid. Methanol also is used for converting fats and oil to biodiesel. CO, H2, CO2
and H2O are used to produce methanol using methanol synthesis reactions in the temperature range of
220 to 300 °C and pressures of 50 to 100 bars using Cu/ZnO catalysts (Equations 11 and 12) [12].
CO + H2O = H2 + CO2 (11)

CO2 + 3H2 = CH3OH + H2O (12)

Optimum operating conditions such as temperature, pressure and space velocity (ratio volumetric
flow and reactor volume) for the maximal selectivity of methanol from syngas depend heavily on the
composition of the syngas. Using a commercial Cu/ZnO/Al2O3 catalyst, Gerber showed that methanol
Energies 2009, 2 573

yield was affected by ratio of H2 to CO+CO2 but methanol selectivity was more affected by the
CO2/CO ratio [88]. Removal of CO2 improved both the selectivity and yield of methanol.
In Europe, a number of efforts have been made to produce methanol from biomass. In France and
Sweden, methanol production by pressurized biomass gasification was developed and tested [83].
However, the low cost of petroleum-based feedstocks (natural gas and coal) have been detrimental to
use of biomass for this application. Recently, increase in the price of fossil fuels and increased
awareness about the global warming have led to amplified research efforts for biomass utilization for
production of biofuels and chemicals.
Syngas can be converted to higher alcohols using catalysts. After a survey, Gerber reported that
catalysts for mixed alcohol synthesis are not commercially available except for one available for
methanol synthesis [88]. By comparing 10 catalysts from different classes, they observed that
Rh/Mn/Fe/SiO2 catalysts and two modified FT based catalysts had high STY (space-time yields,
g/Lcat/h) of C2+ oxygenates (predominantly C2 to C5 alcohols, acetic acid, acetaldehyde, and ethyl
acetate) with a maximum of 170–400 and 50–830, respectively. Rhodium catalysts seemed to be the
best for C2+ oxygenate selectivity and STY. Modified FT catalysts were best for best C2 alcohol
selectivity and total liquid STY. Further testing of Rh based catalysts, with different promoters and
temperature condition, showed that iridium gave maximum STY of oxygenates of 880 followed by
lithium and nickel. Selectivity to C2+ alcohols were best by iron and rhenium followed by carbon [89].

4.2.4. Fischer-Tropsch Synthesis (FTS) diesel and gasoline

The Fischer Tropsch (FT) process is a method to produce alkanes from syngas in the presence of Fe,
Co and Ru-based catalysts as represented by Equation 13. Co and Fe are more practical to use because
of the high cost of Ru. Co also is comparatively more expensive than Fe, but due to its higher activity
and longer life, it is the preferred FT catalyst. Co-based catalysts in slurry phase reactors give high wax
production from syngas, which is then selectively cracked to diesel fuel [90]. The process takes place
at 20 to 40 bars and 180–250 °C. The FT product needs to be hydrocracked with H2 to reduce the
double bonds of unsaturated hydrocarbons producing hydrocarbons in the diesel fuel range. Larger
(higher than C5) hydrocarbons are desired for use as liquid fuels. FT products are free of sulfur. The
yield of FT diesel is estimated to be 120 L/mt biomass with a prediction of ultimately reaching
210 L/mt. The research challenge for the FT synthesis process is to narrow the range of resulting
hydrocarbons. The chain lengths of FT products vary from 1 to 50 producing hydrocarbons ranging
from methane, gasoline range, diesel range, naphtha, kerosene, to heavy waxes.
CO + H2 = CnHm + H2O (13)
During World War II, Germany produced these fuels from coal based syngas. Currently, Sasol in
South Africa and Shell in Malaysia produce FT fuels from coal and natural gas, respectively. To date,
there is no commercial demonstration of FT fuel production from biomass.
Contaminants in biomass-derived syngas need to be removed to suit the FT synthesis process.
Around 2.1:1 H2/CO ratio is desired for FT synthesis depending on selectivity. As syngas from
biomass gasification has less H2/CO ratio, shift reactions are required to increase the H2 content
suitable for the FT process. Higher partial pressures of CO and H2 are desired for higher selectivity for
Energies 2009, 2 574

longer chain hydrocarbons. Other gas components also may reduce the partial pressures of CO and H 2,
thereby reducing the liquid selectivity. Hot gas cleaning does not seem very beneficial for FT process
because this process operates at lower temperature (200 °C) [12,91]. Detailed reviews of the reactors
used in FT process can be found elsewhere [90].
Many authors have suggested that by using FT catalysts on zeolite based supports the selectivity of
the product can be narrowed to gasoline range hydrocarbons. The bifunctional catalysts allows two
simultaneous reactions (syngas to methanol over the metallic function and methanol to hydrocarbons
over acidic function) to take place. With Cr2O3-ZnO/ZSM5 as bifunctional catalysts, Ereña observed
that conversion of CO increased with pressure (10–50 atm), temperature (300–425 °C) and space time
(7.23–62.22 h-1) and decreased with CO/H2 molar ratio (0.33–2.0) [92]. The gasoline fraction (C5+)
increased with space time and CO molar ratio and decreased with pressure and temperature. Methanol
content was less than 0.01 wt% in the product, which indicated that the reaction rate was limited by
methanol synthesis. The product distribution was nearly constant with 70–75 wt% CO, 22–28%
hydrocarbons and a small amount of water.
Cr2O3-ZnO, with an atomic ratio of 2.0, was the best catalytic mixture for high CO conversion and
high gasoline fraction. Cr/Zn > 2.0 decreased CO conversion. Higher Zn gave higher gas production,
especially methane and light paraffins because Zn favored hydrogenation reactions over the gasoline
formation reactions. Zeolite, with Si/Al ratio of about 154, was most suitable for production of
gasoline range hydrocarbons [93].

4.2.5. Fermentation of syngas to ethanol

Fermentation of synthesis gas (Equations 14 and 15) is an attractive process to produce ethanol as a
transportation fuel because the biological catalysts are more specific resulting in less side products [94].
Henstra summarized the micro-organisms used for the fermentation of syngas [95]. Since the
fermentation takes place at lower temperature as compared to catalytic conversion of the synthesis gas
to liquid fuels, the wet gas cleaning can be used for removal of impurities from the product gas.
Moreover, ethanol (blended with gasoline) has been used successfully as a transportation fuel in many
countries, most notably in US and Brazil with existing transportation infrastructure and automobile
engines. As compared to the biochemical conversion with hydrolysis and fermentation processes,
gasification and fermentation have potential to use a much wide variety of feedstock producing ethanol.
6CO + 3H2O = C2H5OH + 4CO2 (14)

6H2 +2CO2 = C2H5OH + 3H2O (15)

Datar demonstrated using the producer gas, generated from gasification of switchgrass, to produce
ethanol by fermentation [96]. During their 20-day fermentation study, they alternately used bottled gas
(clean gases) from days 0 to 8.5 and days 11.4 to 14.5 and producer gas for the rest of the days. They
observed that after introducing producer gas, the H2 utilization stopped but the CO utilization
continued forming primarily ethanol. At the end of the run, ethanol concentration reached 5 g/L.
The major challenge with this process was to increase rate and yield of fermentation by increasing
gas to liquid mass transfer rate of CO and H2 [97,98], and to search for a right microbe having
increased ethanol yield and high resistance to the contaminants in the syngas [95,99,100]. Sensible
Energies 2009, 2 575

heat from product gas during wet gas cleaning also needs to be recovered to increase the net energy
efficiency of the overall process.

5. Conclusions

Biomass gasification is a promising technology to displace use of fossil fuels and to reduce CO2
emission. Among other alternative energy conversion pathways, it has great potential because of its
flexibility to use a wide range of feedstock, and to produce energy and a wide range of fuels and
chemicals. Recently, the focus of its application has changed from production of combined heat and
power to production of liquid transportation fuel. The technical challenges in commercialization of
fuels and chemicals production from biomass gasification include increasing the energy efficiency of
the system and developing robust and efficient technologies for cleaning the product gas and its
conversion to valuable fuels and chemicals.

Acknowledgements

This project was supported in part with Hatch funds through the Agricultural Research Division of
the Institute of Agriculture and Natural Resources at the University of Nebraska.

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 Chapter 21

Review of Biomass Thermal Gasification

Review of Biomass Thermal Gasification

Mohammed Abed Fattah Hamad,

Mohammed
Aly MoustafaAbed Fattah
Radwan andHamad,
Ashraf Amin
Aly Moustafa Radwan and Ashraf Amin
Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/66362

Abstract
Gasification of biomass is one of the most attractive methods for producing hydrogen
rich gas. Syngas production from biomass is an attractive solution for energy crisis. The
production of energy from biomass reduces the dependence of developing countries on
fossil fuels, as ample biomass is available in the developing countries and is renewable.
Downdraft gasifiers are fixed bed gasifiers where the gasifying agent and biomass are
flowing downwards, developed for high-volatile fuels such as wood or biomass gasifica-
tion. Cocurrent flow regime throughout the oxidation and reduction zones reduces the
tars and particulates in syngas, which will reduce the necessity of complicated cleaning
methods compared to updraft gasifiers especially if the gas is used as a burnable gas in a
small community. It is important to ensure homogenous distribution of gasifying agent
at the downdraft gasifier throat. This chapter presents latest trends in gasification of bio-
mass using downdraft gasification.

Keywords: gasification, hydrogen, agriculture waste, catalysts, downdraft gasifier

1. Introduction

Gasification of biomass is one of the most attractive methods for producing hydrogen
rich gas. Syngas production from biomass is an attractive solution for energy crisis. The
production of energy from biomass reduces the dependence of developing countries on
fossil fuels; as ample biomass is available in the developing countries and is renewable.
Downdraft gasifiers are fixed bed gasifiers where the gasifying agent and biomass are
flowing downwards, developed for high volatile fuels like wood or biomass gasification.
Cocurrent flow regime throughout the oxidation and reduction zones reduces the tars and
particulates in syngas, which will reduce the necessity of complicated cleaning methods
compared to updraft gasifiers especially if the gas is used as a burnable gas in a small

©©2016
2017 The
The Author(s).
Author(s). Licensee
Licensee InTech.
InTech. This
This chapter
chapter is distributed
is distributed under
under thethe
termsterms of the
of the Creative
Creative Commons
Commons
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,
distribution,
and andin
reproduction reproduction
any medium,inprovided
any medium, provided
the original worktheisoriginal
properlywork
cited.is properly cited.
488 Biomass Volume Estimation and Valorization for Energy

community. It is important to ensure homogenous distribution of gasifying agent at the

downdraft gasifier throat [1–3].
Gasification is a process under development to utilize the energy conserved in biomass.
Gasification can be used as a source of energy in rural and off-grid areas to fill the power gaps.
The limited supply and the increasing demands of fossil fuels have led the world to investigate
alternative energy sources. Renewable energy sources have been studied widely, and biomass
appears as the most promising renewable energy source. Biomass can be used to overcome
the depletion of fossil fuels and to reduce the environmental impact of the conventional fuels
such as greenhouse gas emissions using one of these four technologies: direct combustion,
thermochemical processes, biochemical processes, and agrochemical processes. Biomass is
the third energy source after coal and oil. Biomass covers 35% of the energy demand of the
developing countries corresponding to 13% of the world energy demand. Biomass is widely
available in quantities enough to meet the world energy demand [1–7].

The oldest way to generate energy is to burn biomass. Due to environmental and technical
difficulties associated with burning biomass, innovative processes should be developed to
utilize biomass [5, 8–10]. Developing more effective techniques to utilize biomass will reduce
the disposal problem and create profits. Hydrolysis, pyrolysis, gasification, and hydrogena-
tion are the principal processes for biomass conversion in the literature [7, 11]. Gasification
represents efficient and environmentally friendly method for producing the syngas as a bio-
fuel from different sources of biomass [12–14], and to produce second-generation biofuels
such as methanol, ethanol, and hydrogen [8, 10, 12, 15]. Gasification can be defined as the
partial (incomplete) combustion of biomass, and gasification could extract up to 60–90% of
the energy stored in biomass [16, 17]. To develop second-generation biofuels, economical and
Feasible clean technologies of syngas are required. [15]. However, economical gasification
of biomass may produce burnable gases, which can be used to provide heat requirements
instead of LPG [12]. Gasifiers were developed to replace biomass burners. Gasifiers will pre-
vent the necessity of on-site power generation [18, 19]. Gasification is the conversion of bio-
mass into a combustible gas and charcoal by partial oxidation of biomass at temperature
range of 800–900°C [6, 19, 20].
The charcoal is finally reduced to H2, CO, CO2, O2, N2, and CH4 [6, 8–10, 21]. Char gasification
starts at temperatures above 350°C [7]. The products of gasification consist of the following
components: ash, volatile alkali metals, tars, and syngas. Tars represent a challenge for the
commercialization of gasification product as an alternative fuel [22]. Frequently using tar may
result in complete shutdown and repair of the industrial unit [18, 22]. Tars set and amount
vary considerably based on reaction conditions and gasifier type [18]. Gas produced from
gasifier can be cleaned by removing tars either physically or chemically [18]. Physical removal
can be achieved using bag filters or wet scrubbers. Chemical removal methods depend on
converting tars to lighter hydrocarbons either using thermal conversion or catalytic conver-
sion processes [18, 22].

Gasification of such material may help in reducing the gap between electricity requirements
and available energy sources. Decentralized power regeneration units will help to fill power
gap in rural and off-grid locations [4]. Yet, it is still difficult to develop a decentralized power
 Review of Biomass Thermal Gasification 489
http://dx.doi.org/10.5772/66362

generation unit based on biomass energy which can be used to fill the gap in energy needs in
rural areas and farms [4]. Technical difficulties prevent further commercialization of gasifica-
tion units in accordance to lower conversion efficiency [23, 24]. Leung et al. [25] proposed a
governmental support to accomplish faster steps toward gasification units commercializa-
tion. However, all over the world, biomass energy has been widely incorporated in the power
generation system; U.S. started partial and full conversion of conventional power plants to
biomass [24]. Throughout this chapter, we will discuss the latest trends in agricultural waste
gasification. Our goal is to provide a full description of the process starting from basic under-
standing and ending by design of a gasification unit.

2. Chemistry of gasification

The reactions taking place in the gasifier can be summarized as indicated below [3, 4, 21]:
Partial oxidation:

C + __21  O 2 ↔ CO ΔH = − 268 kJ/mol (1)

Complete oxidation:

C+O 2 ↔ CO 2  ΔH = − 406 kJ/mol (2)

Water gas phase reaction:

C + H 2 O ↔ CO + H 2  ΔH = 118 kJ/mol (3)

Boudouard reaction:

C + CO 2 ↔ 2CO ΔH = 170.7 kJ/mol (4)

The heat required for water gas phase and Boudouard reactions is provided by complete and
partial oxidation reactions, and complete oxidation provides around 60% of the heat require-
ments during gasification [3, 17]. In addition to the previous reactions that are common in
combustion and gasification, hydrogen, steam, and carbon monoxide undergo further reac-
tions as shown below [3, 24]:

Water gas shift reaction:

CO + H 2 O ↔ CO 2 + H 2  ΔH = − 42 kJ/mol (5)

Methane formation:

CO + 3 H 2 ↔ CH 4 + H 2 O ΔH = − 88 kJ/mol (6)

490 Biomass Volume Estimation and Valorization for Energy

The water gas shift and methane formation reactions are in equilibrium and the governing
parameters are: pressure, temperature, and concentration of reaction species.

3. Gasifier design

The unit design is a very important factor in determining the syngas quality and heating value
[15]. The gasifier will hold two processes: conversion of biomass to charcoal and then conver-
sion of charcoal to hydrogen and carbon monoxide. The mixture of hydrogen and carbon
monoxide can be used for direct heating in rural areas [16]. Leung et al. [25] identified four
types of gasifiers: updraft, open core, downdraft, and circulating fluidized bed (CFB) gasifi-
ers. The maximum efficiency of the updraft, downdraft, and CFB gasifiers may reach to 75%,
the maximum energy output is 10E6, 4E6, and 40E6 kJ/h, respectively. According to Chopra
and Jain [13], the fixed bed gasifiers can be further divided into: updraft, Imbert downdraft,
throatless downdraft, cross draft, and two-stage gasifiers. The fixed-bed gasifier is suitable for
producing low heating value gas for small and medium applications [13, 26]. The downdraft
gasifier is distinguished by a simple design, high carbon conversion, long residence time, low
cost, low pressure, relatively clean gas, and low gas velocity. The downdraft gasifier is suit-
able for producing low heating value burnable gas or for generating electricity of small-scale
systems in the range of 10 kW up to 1 MW [12, 26–28].

3.1. Design of downdraft gasifiers

Downdraft gasifiers are fixed bed gasifiers where the gasifying agent and biomass are flowing
downwards, developed for high volatile fuels like wood or biomass gasification. Cocurrent
flow regime throughout the oxidation and reduction zones reduces the tars and particulates in
syngas, which will reduce the necessity of complicated cleaning methods compared to updraft
gasifiers especially if the gas is used as a burnable gas in a small community [12, 17]. It is impor-
tant to ensure homogenous distribution of gasifying agent at the downdraft gasifier throat.
Bhavanam and Sastry [24] provided design procedures for different types of downdraft gas-
ifiers. The gasification reaction in a downdraft gasifier undergoes several steps, starting with
drying step at 100°C, followed by pyrolysis step between 200 and 300°C resulting in release of
around 70% of biomass weight as volatile matter and tars [16, 24]. After pyrolysis, the remain-
ing biomass and volatile matter react with the incoming oxygen in the combustion step. Finally,
various reactions take place in the reduction zone including carbon and steam reaction to pro-
duce CO and hydrogen, water-gas shift reaction, and CO and steam to form methane and
carbon dioxide [24]. The four gasification reaction steps are illustrated in Figure 1. However,
a limited experience has been gained in the field of biomass gasification while it represents
an attractive renewable energy route [16]. Table 1 illustrates the design specifications for two
types of downdraft gasifiers: Imbert and stratified downdraft gasifiers. Table 1 is developed
based on extensive discussion in Bhavanam and Sastry [24].

Imbert downdraft gasifier is a cylindrical chamber of varying inner diameter across cham-
ber length. The upper part of the cylindrical chamber is loaded with biomass according to
 Review of Biomass Thermal Gasification 491
http://dx.doi.org/10.5772/66362

Figure 1. Different reaction zones in downdraft gasifier.

Design considerations Imbert Stratified

Biomass Material Uniform woody Small size

Moisture content <20% <20%

Ash content <5% –

Reactor type Packed bed supported on a No-throat cylindrical packed

throat bed with open top

Biomass feeding Hopper Open top

Gas feeding Nozzle in the combustion Enters from top mixed with
zone biomass

Produced gas Tar oils <1% T = 700°C Less tar

Maximum capacity 500 kW Easy to scale up

Table 1. Design consideration for Imbert and stratified downdraft gasifiers.

requirement. Air nozzles, attached to distribution manifold, permit air to be drawn into bio-
mass to improve mixing of gasifying agent and biomass. A charcoal balance is established
around the nozzles. Below the air nozzles, a classical Imbert hearth forms the reduction
part. Insulating the reduction hearth reduces the amount of tars in the produced syngas and
increases gasification efficiency. The hot gases are forced to go through the hot zone due to
hearth constriction. The char bed on the grate removes the dust, which should be cleaned
eventually to prevent clogging, and dropping in airflow or channeling [17].

Stratified or open-top downdraft gasifier is a uniform diameter gasifier, usually made of a cylin-
drical vessel with a hearth near the bottom. The stratified gasifier is an improved, easy to
492 Biomass Volume Estimation and Valorization for Energy

design gasifier compared to Imbert downdraft gasifier. The open-top helps in maintaining
uniform access of gasifying agent to the pyrolysis zone, which prevents localized heating.
Biomass is added through the open-top to the top layer of gasifier. The length of the gasifier
can be divided into four reaction zones: unreacted biomass zone at which air enters, the flam-
ing pyrolysis zone at which air reacts with biomass, adiabatic char gasification zone at which
gases from flaming pyrolysis zone reacts with charcoal, and finally the unreacted charcoal
zone that is located just above the grate which acts as a buffer for ash and charcoal. The strati-
fied downdraft gasifier can be mathematically modeled easily as a plug flow reactor at which
air and biomass are uniformly mixed. With such simple design, it is expected that stratified
downdraft gasifier will replace the Imbert downdraft gasifier in commercial applications [17].
Wander et al. [29] illustrated the design of 12 kg/h downdraft stratified gasifier for sawmill
dust gasification. The reactor is a cylindrical body of 270 mm internal diameter and 1100 mm
of height made of SAE 1020 steel. Internal rods are used to mix the sawdust in the reduction
zone. Ash box is used to reduce the ash content of the produced syngas. The reactor is insu-
lated using 50 mm of rock wall. Air was introduced from the open top as a gasifying agent and
a secondary air was used to provide air required for internal burner. A gas chromatography
was used to analyze the gas samples and three water condensers in an ice bath were used to
measure tars and humidity content.
Zainal et al. [30] developed a downdraft gasifier for the gasification using around 50 kg/h
of wood chips. The temperature in the combustion zone may reach 1000°C, which reduces
the tar content of produced syngas. The gasifier is made of mild steel pipe with a diameter
of 0.6 m and a height of 2.5 m. A cone structure is used inside the gasifier above the combus-
tion zone with an inclination of 60° to facilitate the wood material movement. The air supply
was accomplished using a 40 mm diameter stainless-steel pipe with eight 10 mm diameter
nozzles. The air is preheated by positioning the supply tube inside the gasifier. The heating
value of the produced syngas was in the range of 4.65–5.62 MJ/Nm3 depending on operating
conditions.

Panwar et al. [31] developed an open-top downdraft gasifier for wood gasification to provide
the heat requirement for the food processing industry. The downdraft gasifier was lined with
ceramic and designed for a wood input of 60 kg/h equivalent to 180 kW. The gasifier body is
made of mild steel. The air distribution system consists of six air tuyeres of 20 mm in diam-
eter. A cyclone was used to remove solid particulates from produced syngas. The complete
combustion of the syngas is achieved in a premixed burner to provide heat needed for the
food processing industry unit. Note that 30 kg of charcoal and 10 kg of wood were used to
provide hear required for gasifier start up.
Sheth and Babu [1] showed a design of an Imbert downdraft gasifier for wood waste gasifica-
tion with a total height of 1.1 m. The diameter of pyrolysis zone and reduction zone are 0.31
and 0.15 m, respectively. The gasifier has throated combustion zone, a bed of char supported
by a grate follows the combustion zone. The air is supplied through two nozzles in the oxida-
tion zone. The high temperature in the combustion zone ensures cracking of tars into volatiles
and water. The diameter of pyrolysis, reduction, and oxidation zones is 310, 150, and 53 mm,
respectively. The grate is movable to unclog it for removing ash.
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Vervaeke et al. [32] illustrated the design of a small-scale pilot plant downdraft gasifier equiv-
alent to 100 kW of electricity generation. The downdraft unit used in this study is a pilot scale
of the Xylowatt gasifier. The downdraft gasifier is a batch gasifier with a capacity of 90–105
kg. The gasification system consists of downdraft gasifier and inside it are ash collection con-
tainer, cyclone, filter, and a scrubber.
Lv et al. [33] developed a downdraft gasifier to produce hydrogen from biomass using air and
oxygen/steam as gasifying agents. Total 5 kg of char were supported on the grate to reduce
tar content and to act as a catalyst to upgrade syngas. Biomass is pine wood blocks used in
cubes cut into 3 cm × 3 cm × 3 cm. The gasifier height is 1.3 m and the diameter is 35 cm. The
gasifying agent is preheated in a chamber inside the gasifier. Gas is cleaned using triple-stage
spray shower filled with steel wire rings. The internal diameter of the gasifier is calculated
according to the power output. The height is calculated based on batch operation time. The
internal diameter is calculated in meters using the following equation [26]:

1.27 ∗ FCR 0.5

D = (_________
SGR )
(7)

where FCR is the fuel consumption rate (kg/h) and SGR is the specific gasification rate (kg/h/m2).
The height can be determined in meter using the following equation [26]:

SGR × t
H = _______
ρ (8)

where t is the operation time (h) and ρ is the feedstock bulk density (kg/m3).
The power output P0 can be calculated in kW from the following equation [26]:

FCR × HHV × η
P0 = _____________
3.6
(9)

where HHV is the higher heating value of the feedstock in MJ/kg and η is the efficiency of the
gasifier usually around 0.7. The amount of air needed during operation can be calculated in
Nm3/h from the following equation [26]:

ε × FCR × SA
AFR = __________
ρ (10)
a

where ε is the equivalence ratio, FCR is the fuel consumption rate, SA is the stoichiometric
amount of air required for chemical reaction, and ρa is the density of air (1.18 kg/m3). Finally,
the size of the air nozzle, which is required for uniform air distribution, can be calculated in
mm2 from the following equation [26]:

AFR × 10 3
A = ________
ν × 3.6
(11)

where ν is the inlet velocity of air (m/s).

494 Biomass Volume Estimation and Valorization for Energy

4. Factors affecting on the gasification process

Zhou et al. [34] discussed the ongoing gasification projects taking place in China. The biomass
gasification units were divided based on scale: small-, medium-, and large-scale biomass gas-
ification and power generation units. Pretreatment of biomass includes size reduction, size
screening, separation of magnetic materials, and storing as wet biomass. Then prior to gasifi-
cation, drying and storing as dry material are accomplished to reduce the moisture content
to 10–15% [35]. Feedstock type and feedstock preparation are important factors affecting the
yield and quality of produced syngas. Shredding and drying are two processes conducted to
prepare the biomass raw material for gasification process [14]. The main parameters affecting
the gasification are clarified below:
Equivalence ratio (ER): The equivalence ratio is the air/biomass ratio divided by the theoreti-
cal air/biomass ratio. Increasing ER will decrease the heating value of the produced gas due
to decreasing H2 and CO concentration and increasing CO2 concentration. Higher ER helps
in reducing tars and provides more O2 to react with volatiles. Typical values of ER ranges
between 0.2 and 0.4 [24]. Guo et al. [36] reported that increasing ER decreases the concentration
of combustible gases (H2, CO, CH4, and CnHm). The heating value was higher than 4 MJ/Nm3
when ER is kept lower than 0.4. Increasing ER improves the reaction temperature and carbon
conversion, and reduces the tar yield. For a downdraft stratified gasifier, Wander et al. [29] sug-
gested an equivalence ratio of 0.3:0.35 kg-O2/kg-wood. A higher ratio is required when higher
heat loss is expected, an equivalence ratio of 2:2.4 kg-air/kg-wood is optimum for producing
a syngas with low heating value of 4–6 MJ/Nm3. For woody material in a downdraft gasifier,
Zainal et al. [30] suggested an equivalence ratio of 0.268–0.43 with 0.38 showed optimum value
(corresponding to a heating value of 5.62 MJ/Nm3). While Sheth and Babu [1] defined that the
optimum equivalence ratio for wood gasification in Imbert downdraft gasifier is 0.205.
Effect of biomass characteristics: Biomass characteristic is a major factor affecting produced syn-
gas quality. The physical properties that may have major effect are: absolute and bulk density,
and particulate size. The chemical composition parameters that are of major importance to
define the syngas [17] quality including volatile matter, moisture content, fixed carbon, ash
content, and gross calorific value and the ultimate analysis comprises the carbon, oxygen,
nitrogen, and sulfur of the dry biomass on a weight% [19].
Moisture content: The moisture content can be determined by complete drying of biomass sam-
ple. The moisture content is calculated by subtracting the sample weight after drying from fresh
sample weight. Maximum allowable moisture content in downdraft gasifier is 40% on dry weight
basis. Updraft gasifier can handle biomass with higher moisture content. The higher moisture
content in biomass will increase the consumed energy for drying, and will reduce the pyrolysis
of biomass. As a general rule, increasing moisture content decreases the conversion [1, 24].
Superficial velocity: The superficial velocity is the ratio of the syngas production rate at normal
conditions and the narrowest cross-sectional area of gasifier. Lower superficial velocity is
linked with high yield of char, and large quantities of unburned tars, which may deactivate
catalyst, plug lines, and destroy compressors. On the other hand, higher superficial velocity
results in reduced amount of char and low overall process efficiency [24].
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Operating temperature: Operating temperature affects conversion, tar content, gas composi-
tion, gas heating value, and char conversion. To select the optimum temperature, gasifier
type, and biomass source should be considered. Usually, temperature higher than 800°C
should be used to obtain high conversion and low tar content in the produced syngas [24].
Low temperature is associated with low tar content, low H2 and CO content in the produced
syngas [12]. Increasing temperature will increase gas yield, hydrogen, heating value, and ash
agglomeration. To overcome the ash agglomeration problem, practical temperature does not
exceed 750°C [24].

Gasifying agent: Gasifying agents in use are air, steam, steam/oxygen mixture, and CO2.
Gasifying agent affects the heating value of the produced syngas. The heating value
increases with increasing steam content of the gasifying agent, while heating value
decreases as air increases in the gasifying agent [24]. The steam/oxygen mixture repre-
sents a zero nitrogen-gasifying agent which increase heating value and allow liquefying
the produced gas after proper treatment [37]. Using almond shells, the lower heating value
was 5.9–6.7, 6.3–8.4, and 10.9–11.7 MJ/Nm3 using the gasifying agent: 35 wt.% O2 enriched
air, 50 wt.% O2 enriched air, and steam/oxygen mixture, respectively. Campoy et al. [38]
reported a heat value of syngas produced from gasification to have an average value of 4–6
and 9–13 MJ/Nm3 using air and oxygen/steam mixture, respectively. In addition to lower
efficiency compared to air/steam mixture, enriched oxygen-air requires high capital cost for
oxygen [38]. The addition of steam will shift toward the reforming reaction and heteroge-
neous gasification reactions.
Residence time: Residence time has a remarkable impact on the composition and produced
tars. Increasing residence time decreases the fraction of oxygen-containing compounds,
decreases yield of one and two atomic ring compounds, and increases three and four ring
compounds [24].

Pressure: Atmospheric and higher pressures are commonly used in gasification process.
Selecting the optimum pressure depends on the application of the produced syngas. If the
syngas is used for producing methanol or synthetic auto-fuels, higher pressures are preferred
to improve the process yield and to reduce tar content. For generating burnable gases, atmo-
spheric pressure should be used [12]. High pressure applications are recommended for large-
scale gasification, while atmospheric pressure is recommended for small-scale gasification
[35]. High pressure gasification is still not well developed and further research is needed to
further commercialize such process [39].

Catalyst: Catalyst type is a very important factor affecting gasification quality and produced
syngas. Catalyst affects the composition of the syngas by manipulating the percentage vol-
ume of hydrogen, carbon dioxide, methane, and carbon monoxide. Optimum catalyst should
play a role in minimizing the gas content of carbon dioxide and maximizing the gas content
of hydrogen, carbon monoxide, and methane [40]. The catalyst type and loading on the gas-
ification of cotton stalks and saw dust were studied. The catalysts selected are USY zeolite,
dolomite, CaO, granulated slag, red brick clay, olivine, and cement kiln dust. The results
demonstrate that the cement kiln dust and calcium hydroxide are more effective for increas-
ing the gas yield and decreasing the char yield [8, 10].
496 Biomass Volume Estimation and Valorization for Energy

Effect of biomass/steam ratio: Biomass/steam ratio affects hydrogen content in the produced
syngas. Contradictory reports are found in literature, while Lv et al. [41] reported a positive
effect on hydrogen content when biomass/steam ratio increases. Lv et al. [33] reported a nega-
tive effect of biomass/steam ratio increase on syngas hydrogen content. This variation can be
understood by considering that biomass/steam ratio effect is altered according to the entire
system configuration.
Lower values of biomass/steam ratio shift the reaction to produce more solid carbon and
methane, since number of moles of steam increases in the feed. While at higher values of
biomass/steam ratio, Co and H2 are increased in the syngas as carbon and methane produced
are decreased consequently.

5. Cost of biomass gasification process

The cost of any industrial process is governed by the capital cost and the running cost.
Selection of best gasifier type depends on cost of fabrication, ease of manufacture, tar content,
lower heating value, feedstock elasticity, and application of syngas [26]. The fixed bed gasifi-
ers are more suitable for small- and medium-scale applications, while fluidized bed gasifiers
are suitable for large-scale applications (equivalent to >15 MW) [25]. For example in China
rice hulls, fluidized bed gasifiers are used in a production scale equivalent to 1–1.2 MW while
downdraft gasifiers are used in a production scale equivalent to 60–200 kW [42]. The capital
cost of the gasifier is divided into three items: gasifier and gas cleaning system cost, fuel gas
utilization equipment cost, and fitting and system construction cost [25]. Cleaning systems
and removing tars will add a significant cost to the produced syngas, which reduce the fea-
sibility of using syngas in internal combustion engines [12]. Optimizing tar content can be
achieved by varying the operating conditions and feedstock [43].

Upgrading using catalytic treatment represents the most economical and efficient method for
syngas upgrading since it provides a way for removing tars and other particulates and con-
verting tars to hydrocarbons [12]. Downdraft gasifier represents a reasonable cost production
method for generating syngas with low tar content [29]. Especially small gasifiers that has
proven economic feasibility [27].Wu et al. [44] recommended implementing biomass gasifica-
tion depending on the low biomass price. By comparing different technologies to generate
electricity based on 1 MW scale, Wu et al. [44] mentioned that the capital cost of fluidized bed
gasifier system for biomass gasification-power generation system is 60–70% of the capital cost
of coal power station and much lower compared to the capital cost of conventional power
station. For producing combustible gases, Bridgwater et al. [45] reported that for syngas pro-
duced from fluidized bed, updraft, and downdraft gasifiers: hydrogen volume percentage
is 9, 11, and 17%, respectively; CO volume percentage is 14, 24, and 21%, respectively; and
a heating value of 5.4, 5.5, and 5.7 MJ/Nm3, respectively. The downdraft represents the ideal
solution to produce combustible (burnable) gases for household uses.
Biomass gasification economics are very sensitive to the scale of produced MW [44]. Leung
et al. [25] mentioned two disadvantages of small- and medium-size gasifiers: capital cost
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limitation that may prevent incorporating important processes like tar removal, and the envi-
ronmental demands imposed by new regulations which is difficult to be met by different bio-
mass gasification technologies. Wu et al. [44] identified 160 kW as a critical scale of biomass
gasification unit, less than 160 kW biomass gasification units loses the economical attraction.
Note that 1–5 MW was recommended as the most competitive size for biomass gasification
unit. Lower than a unit capacity of 160 kW, the price of kWh increases sharply from 0.4 to 1.8
Yuan RMB/kWh for very small capacities. For unit with capacities higher than 160 Wh, the
price will decrease gradually as the unit size increases. At the 600 kW capacity, the price will be
around 0.3 Yuan RMB/kWh; while the price may reach 0.25 for a unit capacity of 1000 kW [44].
It is recommended to conduct gasification at pilot plant scale to mimic large scale to figure out
the approximate industrial process scale economics [38]. The steam enhances the reforming
and heterogeneous gasification reactions, the temperature inside the gasifier should be kept
enough to support such reactions [38]. Combining gasification unit with heat and power gen-
eration systems will improve the economics of the process [3]. Gasification units combined
with heat and power generation systems are expected to have an overall efficiency of 85%
compared to a maximum efficiency of 35–55% for conventional power station, in addition to
a substantial saving in carbon emissions. Total 1000 kg/year of carbon are saved for each MW
when gasification units hybrid with heat and power generation systems [3].
Downdraft gasifiers are economically competitive even to conventional LPG heating unit.
Panwar et al. [31] found that replacing LPG heating system with a downdraft wood gasifica-
tion system could save $13,850 US for 3000 h of operation. The payback period of the gasifica-
tion system was only 1100 h. According to the extensive study of literature, the recommended
gasification process consists of the following steps [13, 17, 19]:
1. Straw collection and preparation (milling and pelletization of straws).
2. Belt conveyor for feeding of the gasifier.

3. Downdraft gasifier.

4. Blower for suction of air and gas produced.

5. Gas cleaning and separation of tars.

6. Gas holder for storage of gas.

7. Gas distribution net.

8. Gas application devices.

9. Gas metering devices.

6. Preliminary techno-economic studies of downdraft gasifier

The aim of this chapter is to illustrate a detailed design of biomass gasification system to
generate syngas for household applications. The stratified gasifier is selected based on the
498 Biomass Volume Estimation and Valorization for Energy

Figure 2. Gasification system for producing burnable gas.

following parameters: easiness in design and scaling up, and production of syngas with tar
content lower than that of Imbert gasifier [16–18, 26]. The gasification system comprises of
a downdraft burnable syngas gasifier followed by a gas cleaning and distributing system.
Throughout this chapter, the design specification of the downdraft gasifier is presented. This
system can be used to convert solid agricultural waste to a syngas that is a burnable gas used
to provide energy requirements for small communities, as shown in Figure 2.
The energy (household) requirements: for 50 families.

The gas demand per day is: 500 m3/day.

The syngas gas will be produced on two batches: Morning and afternoon (each one will last
for 250 m3/batch).
The first batch will take place from 7 to 10 am.

The second batch will take place from 2 to 5 pm.

The storage unit will hold around 200 m3 gas and accordingly will provide heating require-
ments during the period of nonoperation.
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The system consists of the following units: biomass shredding, grinding unit, gasification
unit, air controlling system, air heating and gas precooling unit, cyclone (acts like cyclone to
remove dust), gas cooler, water filter (scrubbing unit), gas distribution system, control sys-
tem, cork filter, and storage tank.

No. Object Cost, Egyptian pounds

1 Gasifier with control system 30,000

2 Gas cleaner 10,000

3 Belt conveyor 15,000

4 Milling and pelletization of biomass 50,000

5 Gas holder 15,000

6 Gas distribution system 100 × 500 60,000

7 Gas stoves 100 ×350 35,000

8 Gas meters 100 ×400 40,000

9 Erection 10,000

10 Contingency (10%) 26,000

Total 2,90, 000

$ = 8.5 Egyptian pounds.

Assume that:
Cost of material = 300 L.E/ton
Cost of preparation = 100 L.E/ton
Cost of raw materials = 0.25 ×400 × 360 = 36 000 L.E/year
Labors required = 2 ×1500 = 3000 L.E/month = 3000 ×12 = 36000 L.E/year
Income gas production = 500 m3/day
≈60 kg L.P.G/day
= 60 × 360 = 21,600 Kg/year
= 21,600 × 7 = 151,200 L.E/year
Profit = income − raw material − depreciation
Profit = 151,200 – 36,000 – 36,000 – 29,000 = 49,400
Return on Investment = profit/initial cost
Return on Investment = (49,400/290,000)×100 = 17%
Therefore, the payback period is about 6 years based on the international prices of L.P.G.

Cost of equipment for gasification system.

The cost of land required for erection of the plant is not included in this calculation of the
feasibility study.

7. Conclusions

Gasification represents a viable solution to overcome the energy shortage by developing

commercial gasification units in rural and off-grid areas. An integrated system comprising a
500 Biomass Volume Estimation and Valorization for Energy

gasification-electrical generation method represents an ideal solution from the technical and
economical points of view.

However, due to the wide varieties of available biomass feedstock, it is recommended to

manipulate different systems in each location depending on the feedstock, produced syn-
gas, and energy demands. Downdraft gasifier is recommended for small-scale applications
in rural areas. The co-current nature of air and biomass flow reduces the tar content and
increases CO and H2 in the produced syngas. The syngas produced from downdraft gasifier
can be used after a simple purification process in thermal applications. From a cost study, the
payback period of a gasification system is around 5 years.

Acknowledgements

The authors would like to express deepest thanks for the Science and Technology Development
Fund (STDF Egypt) for financing and supporting the development of the thermal gasification
of biomass.

Author details

Mohammed Abed Fattah Hamad*, Aly Moustafa Radwan and Ashraf Amin

*Address all correspondence to: [email protected]

National Research Centre, Cairo, Egypt

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 Progress in Energy and Combustion Science 46 (2015) 72e95

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs

Review

New concepts in biomass gasification

Steffen Heidenreich a, *, Pier Ugo Foscolo b
a
Pall Filtersystems GmbH, Werk Schumacher Crailsheim, Zur Flügelau 70, D-74564 Crailsheim, Germany
b
Department of Industrial Engineering, University of L'Aquila, Via Campo di Pile, 67100 L'Aquila, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Gasification is considered as a key technology for the use of biomass. In order to promote this technology
Received 28 January 2014 in the future, advanced, cost-effective, and highly efficient gasification processes and systems are
Accepted 29 May 2014 required. This paper provides a detailed review on new concepts in biomass gasification.
Available online 2 July 2014
Concepts for process integration and combination aim to enable higher process efficiencies, better gas
quality and purity, and lower investment costs. The recently developed UNIQUE gasifier which integrates
Keywords:
gasification, gas cleaning and conditioning in one reactor unit is an example for a promising process
Biomass
integration. Other interesting concepts combine pyrolysis and gasification or gasification and combustion
Gasification
Process intensification
in single controlled stages. An approach to improve the economic viability and sustainability of the
Process combination utilization of biomass via gasification is the combined production of more than one product. Poly-
Polygeneration generation strategies for the production of multiple energy products from biomass gasification syngas
offer high efficiency and flexibility.
© 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2. Advanced process integration and combination concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.1. Compact UNIQUE reactor concept e integrated gasification, gas cleaning and conditioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.1.1. The UNIQUE gasifier concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.1.2. In bed primary catalytic reduction of tar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.1.3. In bed abatement of detrimental trace elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.1.4. Tar and dust abatement by catalytic filter candles in the gasifier freeboard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.2. Combination of pyrolysis and gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.2.1. First approach e multi-stage gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.2.2. Second approach e use of pyrolysis and gasification at different locations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.3. Combination of gasification and combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.3.1. Dual fluidized bed process with internal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.3.2. Gasification with partial combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.3.3. Implementation of gasification in coal fired power plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3. Polygeneration strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.1. Combined heat and power production (CHP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.2. SNG, heat and power production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.3. Biofuels, heat and power production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.4. Hydrogen and heat production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4. New gasification concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.1. Plasma gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.2. Supercritical water gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

* Corresponding author. Tel.: þ49 7951 302 172.

E-mail address: [email protected] (S. Heidenreich).

http://dx.doi.org/10.1016/j.pecs.2014.06.002
0360-1285/© 2014 Elsevier Ltd. All rights reserved.
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 73

5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

1. Introduction whereas using pure oxygen or steam as an oxidant leads to

significantly higher heating values of the gas of 10e18 MJ/m3 [4,5].
Global warming and climate change concerns result in efforts to Biomass comprises a broad range of different kinds of bio ma-
reduce CO2 greenhouse gas emissions by increasing the use of terials, such as wood, forest and agricultural residues, waste from
renewable energies and increasing the energy efficiency. Besides wood and food industry, algae, energy grasses, straw, bagasse,
solar and wind energy, biomass is considered as a main renewable sewage sludge etc. The use of different kinds of biomass results in
energy source. In the renewable energy mixture of solar, wind and different challenges and solutions for transportation, storage and
biomass energy, biomass can be used as adjustable, controlled feeding of the biomass, for operation of the gasifier and for cleaning
energy which will be supplied in increased amount when wind and of the produced syngas. Most commonly used types of biomass
solar energy supply is low. gasifiers are fixed bed and moving bed, fluidized bed and entrained
Since the discovery of the mankind how to make fire, biomass flow gasifiers. Fluidized bed and entrained flow gasifiers provide an
has been the main energy source for thousands of years and still intensive contact between the gas and the solid biomass which
today it contributes in the range of more than 10% to the world results in high reaction rates and conversion efficiencies. Fixed bed
energy supply and ranks as the fourth source of energy in the world gasifiers typically have a lower heat and mass transfer and often
[1]. In rural agricultural areas, biomass is still the main energy generate higher amounts of tar and char. However, operation and
resource for heating and cooking and often it is the only available design of fixed bed gasifiers are simpler and they are preferably
energy source there. In developing countries in Asia and Africa used in small size. Performance data of the mentioned gasifier
more than one-third of the total energy consumption is based on types are given in Table 1.
biomass. A big advantage of biomass is that it is available at every Depending on the use of the syngas, its cleaning needs to be very
place all over the world which is in contrast to coal or natural gas. efficient. Catalytic synthesis reactions or the use in fuel cells for
For example, in India which has very large coal reserves of more examples require high purity of the syngas. Main impurities in the
than 250 billion tons, the coal deposits are just located in the state syngas are fly ash particles and tar. Other impurities in the syngas
of Bihar and northeast. Transportation costs play a major role in the are typically sulphur compounds (e.g. H2S, COS), hydrogen chloride,
distribution of the coal. Biomass in contrast is uniformly and widely alkalines, and ammonia. Tar formation is a main problem in
distributed over the country [2]. biomass gasification. Tar condensation at lower temperatures can
Gasification is a key technology for the use of biomass. It offers a cause clogging or blockage of pipes, filters, catalyst units or engines.
high flexibility in using different kind of feedstock materials as well Tar formation also lowers the syngas yield and the heating value of
as in the generation of different products. In principal, all different the gas. Tar removal has been the subject of many researches
types of biomass can be converted by gasification into syngas leading to the development of primary and secondary measures for
mainly comprising hydrogen, carbon monoxide, carbon dioxide tar reduction. Overviews on this topic are recently given e.g. by Han
and methane. From this syngas, all kinds of energy or energy car- and Kim [13], by Aravind and de Jong [14] and by Shen and Yosh-
riers e heat, power, biofuels, hydrogen, biomethane e as well as ikawa [15].
chemicals can be provided. Synthesis of FischereTropsch (FT) In order to promote the utilization of biomass gasification,
diesel, dimethyl ether (DME), methanol and methane are estab- advanced concepts are required which have to maximize the syn-
lished technical processes. The use of the available biomass re- gas yield, optimize the gas quality, increase the gas purity, increase
sources needs to be highly efficient and sustainable. Gasification the overall process efficiency and improve the economic viability
offers a high potential and a high process efficiency for the use of by decreasing system and production costs.
biomass [3]. Gasification of biomass is performed by partial This paper aims to provide a detailed review on such new
oxidation of the carbon contained in the biomass at high temper- concepts in biomass gasification. Process integration and combi-
ature using a controlled amount of an oxidant which can be air, nation, polygeneration strategies as well as new gasification con-
pure oxygen or steam. The composition and properties of the cepts are presented as follows (see also Table 2):
syngas depend on the biomass feedstock, the gasifier type and the
operation conditions of the gasifier, such as the used oxidant, the  An interesting example for process integration is the recently
temperature and the residence time in the gasifier. Gasification developed UNIQUE gasifier concept which integrates gasifica-
with air leads to a syngas with a heating value of 4e7 MJ/m3 tion, gas cleaning and conditioning in one reactor unit. This

Table 1
Performance data of most commonly used gasifier types.

Gasification technology Gasification temperature/ C Cold gas Char conversion/% Tar content in raw References
efficiency/% producer gas/g/m3N

Fluidized bed (FB) gasifier 800e900 <70 <70 10e40 [6]

Circulating fluidized bed (CFB) gasifier 750e850 50e70 70e95 5e12 [7,8]
Fixed bed downdraft gasifier Max. bed temp.: 900e1050 30e60 <85 0.015e0.5 [9,10]
gas exit temp.: 700
Fixed bed updraft gasifier Max. bed temp.: 950e1150 20e60 40e85 30e150 [9,11,12]
gas exit temp.: 150e400
74 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

Table 2
Overview of the presented gasification concepts.

Concept Characteristics Benefits Current state

UNIQUE gasifier Integrates gasification, gas cleaning Compact design with decreased Lab-scale testing of the concept
and conditioning in one reactor unit requirements for footprint as well successful.
as reduced investment costs
Multi-stage gasification combining Separate and combine pyrolysis and High process efficiencies and high Realization of concepts from
pyrolysis and gasification gasification in single controlled quality syngas with low tar 100 kW to 6 MW successful.
stages concentration
Combination of pyrolysis and Produce concentrated oil-char Transportation of the biomass as Start of a 5 MW demonstration
gasification at different locations slurries by decentralized pyrolysis well as biofuel production becomes plant
plants and gasification of the more economical
slurries and production of biofuels
in a large centralized plant
Combination of gasification with a Gasification is combined with a Tar reduction by partial oxidation Used in multi-stage gasification
partial oxidation stage subsequent partial oxidation stage processes of small scale
Indirect biomass co-filing in coal biomass is gasified and the Easy and cost-effective way to Used in large scale
fired boilers produced gas is co-fired in a boiler reduce fossil CO2 emissions
with coal
Polygeneration e combined heat Combined production of heat and High overall process efficiency Used in scales up to a few MW
and power power
Polygeneration e combined SNG, Combined production of SNG, heat High overall process efficiency; Tested in smaller scale; large scale
heat and power and power high flexibility possible; application planned
transportation fuel
Polygeneration e combined Combined production of biofuels, High overall process efficiency; Tested in smaller scale; large scale
biofuels, heat and power heat and power high flexibility possible; application planned
transportation fuel
Polygeneration e combined Combined production of hydrogen High overall process efficiency; First tests in smaller scale started
hydrogen and heat and heat renewable hydrogen production
Plasma gasification Gasification is performed in a Decomposition of any organic Mainly used for waste treatment
plasma material into its elemental
molecules
Supercritical water gasification Gasification is performed in Wet and liquid biomass can be Lab-scale testing and research
supercritical water treated without pre-drying

concept offers a compact design with decreased requirements 2. Advanced process integration and combination concepts
for footprint as well as reduced investment costs.
 New advanced multi-stage gasification concepts separate and 2.1. Compact UNIQUE reactor concept e integrated gasification, gas
combine pyrolysis and gasification in single controlled stages. cleaning and conditioning
This enables to achieve high process efficiencies and a syngas
with low tar concentration. On the other hand, the complexity of In existing gasification plants, abatement of particulate (char, fly
the process is increased by combining different reactors. ash) and tar (high molecular weight hydrocarbons) content of the
 A special approach performs pyrolysis and gasification at raw syngas is normally done by filtration and scrubbing: in this way
different locations. The concept aims to produce concentrated the clean fuel gas is made available at temperatures close to
oil-char slurries by decentralized pyrolysis plants and gasifica- ambient, and the most immediate option for power generation is
tion of the slurries and production of biofuels in a large gas engine. Such process configuration does not allow high electric
centralized plant. In this way, transportation of the biomass as conversion efficiencies: reported values are close to 25% [16], that is
well as biofuel production becomes more economical. what is also obtainable with modern combustion plants coupled
 Other concepts combine gasification with a combustion stage. In with steam turbines. This penalizes notably the overall economic
this way unreacted char can be combusted to increase the balance of the plant, which would benefit of a higher share of
overall process efficiency. electricity against heat production, due also to the incentives for
 By combination of gasification with a partial oxidation stage, tar green electricity offered in most countries. In addition, tar separa-
can be converted. tion is sometimes not as effective as it should be, reduces the gas
 Indirect biomass co-firing in coal fired boilers by gasification of yield, and generates waste streams difficult to dispose or recycle
the biomass is an easy and cost-effective way to reduce fossil properly.
CO2 emissions. High temperature gas cleaning and catalytic conditioning is
 Polygeneration strategies for the production of more than one the focal point to promote more efficient industrial applications
product in a combined process can significantly improve process of biomass gasification for energy and chemicals: gas treat-
efficiency, economic viability and sustainability of the use of ments should be strictly integrated with biomass conversion
biomass. Combined heat and power production is a classic and carried out at a close temperature range, to preserve the
example for a polygeneration process, but also new approaches, thermal energy content of the biomass gas. This is even more
such as combined SNG, heat and power production, or biofuels, true in the case of steam gasification and its coupling with a
heat and power production as well as hydrogen and heat pro- high temperature fuel cell or downstream catalytic processes,
duction attract increasing interest. to avoid loss by condensation of the significant amount of
 New gasification concepts, such as plasma and supercritical water vapour contained in the gas stream, useful to reform
water gasification, provide interesting advantages for special CH4, shift CO towards H2 and prevent carbon deposition on the
kinds of biomass. catalytic surfaces.
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 75

The application of such fundamental process integration con-

cepts not only allows to realize more simple, efficient and cost
effective gasification plants, but offers the opportunity to overcome
some major obstacles still preventing a large market diffusion of
such technologies, specifically at the small to medium scales (less
than 10 MWth) amenable to vast economic contexts of developed
and developing countries. It needs to be stressed that the integra-
tion of a biomass steam gasifier with a high temperature fuel cell
(more specifically, a solid oxide fuel cell) appears most suitable to
realize very efficient bio-energy systems at relatively small scale. It
is almost universally recognized that power generation by means of
a fuel cell can compete in terms of efficiency with large IGCC in-
stallations; high temperature fuel cells are able to utilize the major
fuel species obtained from the biomass gasification process (H2, CO,
CH4). Although they are much more resistant to contaminants than
low temperature fuel cells, provision should be made however to
drastically reduce the fuel gas content of alkali and sour gas
compounds.
Recent developments in innovative catalysts, sorbents and high Fig. 1. The UNIQUE concept for integration of gasification with hot gas cleaning and
temperature filtration media offer the opportunity to integrate in conditioning in one reactor vessel [20].
one reactor biomass gasification and gas cleaning and conditioning
processes needed to obtain a clean fuel gas from biomass that
As a result, this arrangement (integration of catalytic filtration
would allow immediate and efficient conversion into power (high
and biomass gasification in one reactor vessel) allows for the con-
temperature fuel cells; micro gas turbines; combined, strictly in-
version of tar, elimination of trace elements and an efficient
tegrated heat and power plant schemes) and further catalytic gas
abatement of the particulate, delivering high purity syngas, suitable
processing addressed to second generation bio-fuels (liquid fuels,
to assure a high share of power generation even in small- to
hydrogen) and chemicals, allowing to implement diversified poly-
medium-scale (few MWth) combined heat and power production
generation strategies.
and power plants, and to increase the overall economic revenue.
The UNIQUE gasification technology, developed by means of
The UNIQUE concept for hot gas cleaning and conditioning provides
joint R&D efforts by several research organizations and private
a concrete contribution to the target of reducing the cost of elec-
companies throughout Europe, did provide the opportunity to
tricity obtained by means of advanced biomass energy systems.
develop technical innovations addressed to existing and new in-
dustrial installations. Their effectiveness was tested at real indus-
trial conditions, over a significant range of scales, from lab facilities 2.1.2. In bed primary catalytic reduction of tar
to output slip streams of industrial gasifiers. Both authors of this As it is well known, the main problems to improve industrial
paper are directly connected to the developments of the so called viability of biomass gasification processes are related to the pres-
UNIQUE gasifier: although such a circumstance may well explain ence of tar in the product gas. Steam reforming of high molecular
why it is described in some details within this survey about inno- weight hydrocarbons is considered the most appropriate way for
vative biomass gasification concepts, it should be mentioned here their elimination [24], however chemical kinetics of the gaseous
that additional, complementary reviews stress in their conclusions phase homogeneous reactions are satisfactory at high tempera-
the potential of hot gas cleaning for efficient tar reforming, espe- tures, above 1200  C, due to high activation energies, in most cases
cially since the particulate filter combined with a catalyst can be a greater than 250e350 kJ/mol. With the use of catalysts, steam and
key component of the gasifier itself [17]. dry reforming reactions become an effective way to remove tar
components from the fuel gas at lower temperatures, compatible
2.1.1. The UNIQUE gasifier concept with those adopted in gasification processes.
This new concept for a compact integration of biomass gasifi- One of the most important advantages of a fluidized bed gasifier
cation and hot syngas cleaning and conditioning systems was is given by the possibility to utilize a low cost mineral bed material
originally outlined in patents [18,19], deeply investigated in its catalytically active for such reactions, in presence of steam as a
different technical aspects by means of a collaborative R&D Euro- gasification agent [25,26]. The catalyst to be utilized should be at
pean project [20] and applied in further developments [21] and the same time efficient in the reforming of hydrocarbons, has high
industrial testing campaigns. selectivity for syngas, and high resistance for attrition and carbon
Catalytic filter elements for particle and tar removal (see e.g. formation. It should also satisfy the requirement of relatively low
Refs. [22,23]) are directly integrated into the freeboard of a fluid- cost, because the formation of ash and char obliges to discharge
ized bed steam gasifier. Fig. 1 shows schematically the principle of used material and reintegrate the bed inventory continuously with
this new gas cleaning concept. Remarkable system simplification is a fresh/regenerated charge. A detailed analysis of the performance
achieved by housing the whole gas conditioning system in the of primary tar removal catalysts applied at lab to industrial scale is
gasifier, reducing thermal losses, equipment and plant space, and beyond the scope of this work; a comprehensive review of the
allowing for a very compact unit: the activity of catalysts and sor- primary measures (including gasification conditions and gasifier
bents is increased, while keeping high the thermal efficiency of the design in addition to bed additives) for tar elimination in biomass
whole conversion process as no cooling step is included, and gasification processes has been published by Devi and co-authors
avoiding particle entrainment in the product gas at the reactor [27], and a more general and recent examination of different stra-
outlet. As a result, some major advantages of traditional primary tegies for tar reduction in the biomass product gas via mechanical,
and secondary hot gas treatments are combined together, without catalytic and thermal methods [28] also provides quantitative and
their well-known respective drawbacks (catalyst clogging by solid comparative figures about catalytic hot gas conditioning performed
particles, loss of gas chemical and thermal energy, etc.). within the gasifier bed itself.
76 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

A large number of investigations deals with dolomite, (Ca,Mg) qualitatively (by visual comparison of liquid samples collected in
CO3, or olivine, (Mg,Fe)2SiO4. Calcined dolomite, limestone or the tar condensers) and quantitatively in Fig. 2, as a function of the
magnesite have been found able to increase the gas hydrogen gasification temperature, in relation to fully similar tests with sand
content [29e33]. Olivine shows a slightly lower activity in biomass (catalytically neutral) and olivine. The Feeolivine material has a
gasification and tar reforming, but higher attrition resistance than double effect on tar destruction: on one hand, it acts as a catalyst for
dolomite [34e36]. Adding calcined dolomite to the fluidized bed tar and hydrocarbon reforming; on the other hand, it is also active
inventory of the gasifier allows to reduce the tar content in the dry in relation to water gas shift reaction, at high temperature.
product gas from two digit numbers down to 1e2 g/Nm3, while When 10 wt% Feeolivine was utilized in a pilot gasifier instead
with olivine the corresponding average value is 5e7 g/Nm3. of olivine, the gas yield increased on average by 40% and the
Ni-based reforming catalysts show higher activity and selec- hydrogen yield by 88%; correspondingly, the methane content in
tivity for tar conversion to hydrogen-rich gas, increasing noticeably the syngas was reduced by 16% and tar production per kg of dry ash
the gas yield at the expense of char and tar, but suffer from (i) free (daf) biomass by 46% [43]. Complete characterization and
mechanical fragility, (ii) rapid deactivation mostly due to sulphur, micro-reactor reactivity data are also available for Feeolivine ma-
chlorine, alkali metals, coke, (iii) metal sintering, altogether terials containing up to 20 wt% of iron [44] and definitively confirm
resulting in limited lifetime [37]. Ni-based catalysts are also very the interest of addition of iron on olivine.
effective to reduce the NH3 content in the product gas. Very positive
results with respect of all points just mentioned were obtained by 2.1.3. In bed abatement of detrimental trace elements
impregnation of olivine with nickel [38]. The mechanism of the Studies were performed on high temperature separation of H2S,
active phase formation in Ni-olivine under biomass gasification HCl and other detrimental trace elements, like alkalis, and heavy
conditions is well understood [39] and the large scale preparation metals, by means of appropriate sorbents to be added to the flu-
controlled. The positive features of natural olivine (mechanical idized bed inventory of the UNIQUE gasifier [45,46]. Thermody-
resistance and activity in tar reforming) are combined with those of namic process models assuming Gibbs free energy minimization
nickel catalysts (high activity in reforming of hydrocarbons), were utilized to investigate the fate and removal of sour gases and
without the disadvantages encountered with commercial products. alkali species in the biomass gasification process, as a function of
The Ni-olivine catalyst showed very good resistance to attrition and different composition of inlet streams and gasifier temperature
coke formation, with an order of magnitude reduction in the tar [47,48]. To confirm theoretical findings, experimental tests were
content of the product fuel gas, when utilized instead of a bed made performed on conventional and innovative synthetic solid sorbents
entirely of olivine, in a pilot scale (100 kW thermal) dual fluidized suitable to be utilized at the operating conditions of the gasifier and
bed gasifier as primary catalyst for tar destruction and methane able to assure very low concentration levels of these contaminants
reforming [26]. The major drawback to an extensive utilization of in the gas phase, comparable with threshold values recommended
Ni-olivine in the fluidized bed of biomass gasifiers is represented by for solid oxide fuel cells and production of biofuels by chemical
existing stringent constraints on nickel manipulation and syntheses (see also the following Section 3 about polygeneration
discharge, Ni being a heavy metal. Its use would increase consid- strategies).
erably the cost of disposal of contaminated biomass ash. Contaminants are typically removed in downstream equipment.
It is well known that olivine samples with similar general Adding suitable sorbents to the fluidized bed inventory of the
composition and phase structure may show different catalytic ac- gasifier (see Fig. 1) allows for an additional beneficial effect: the
tivity depending on the degree of integration of iron into their improvement of catalyst activity for tar reforming in the filtering
respective crystalline structure [40]. Calcination of iron-bearing elements placed in the freeboard of the gasification reactor.
olivines in air leads to the oxidation of iron and formation of iron
free oxides, the presence of which affects the olivine activity. The 2.1.3.1. Sour gases. The experimental evidence indicates that Ni-
amount of iron oxides formed is dependent on calcination time and catalysts are suitable to convert tarry fuel gases into a clean syn-
temperature [40,41]. Recently, using an optimized impregnation gas even if hydrogen sulphide is present: with H2S concentrations
method, the Fe content of olivine was enriched with an additional below 100 ppmv, as it is the case of most biomass gasification
10 wt% (corresponding to a total iron weight percentage of about processes, the catalyst activity is slightly reduced, however the
16 wt%), and catalytic biomass gasification experiments were per- remaining activity is constant, even after substantial operation
formed at bench scale [42]. The abatement of tar content is shown time, and complete conversion of naphthalene (a key tar

Fig. 2. Effect of bed material and gasification temperature on tar content. Reproduced from Virginie et al. [42].
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 77

phase on a support are the strategies commonly explored to over-

come these problems.
Experimental work done at real conditions for the H2S removal
or with simulated coal gas has led to the conclusion that fuel gas
composition does not have a large influence on the desulphuriza-
tion performance, except for the minimum residual H2S level. The
thermodynamic equilibrium is worse when CO, CO2, H2O are pre-
sent [54]. With CeO2, it is indicated that the presence of H2O has no
negative impact [55], and this seems to be true also with CuO-
eAl2O3 sorbents [56].
Data of H2S sorption experiments on packed beds of Ca- and Cu-
based sorbents (Fig. 4) show that these are not suitable to reduce
the H2S concentration below 1 ppmv at 700e900  C. The sorbent
composition has an influence on the achievable H2S reduction: slag
lime, which contains several oxides beside calcium oxide, achieves
the best H2S reduction (down to 50 ppmv) of all Ca-based sorbents.
In order to meet the requirement of 1 ppmv H2S, a new sorbent
was synthesized according to thermodynamic predictions indi-
cating that stabilized, Ba-based sorbents should be effective; the
“CaBa” sorbent was prepared from a mixture of 10 mol-% BaCO3 and
90 mol-% CaCO3.
The CaBa sorbent allowed to achieve H2S concentrations lower
than 0.5 ppmv (the detection limit in these experiments) in the
temperature range of 800e900  C [46]. The stabilization effect was
confirmed by the XRD spectra showing the occurrence of a BaS
phase. At temperatures below 760  C the H2S concentration in the
effluent stream raises up to 175 ppmv due to carbonation of the
sorbent: the CaBa sorbent regeneration could therefore be possible
by cooling the saturated sorbent under non-oxidizing atmosphere.
The sorption data also showed that the CaBa sorbent is able to
reduce the HCl gas content below 1 ppmv over the temperature
range 800e900  C [46]. The formation of BaCl2 phases is confirmed
by the XRD spectra.
Fluidized bed gasification tests at pilot scale (100 kWth) done at
Vienna University of Technology with the CaBa sorbent, confirmed
the tendency toward lowered H2S content in the product gas.
However, such tests show only qualitative trends; the operating
conditions, like sorbent particle size and amount charged into the
Fig. 3. KCl concentration in the gaseous stream leaving the sorbent sample: a) 800  C; gasifier, still need to be optimized.
b) 900  C [46].

2.1.3.2. Alkali species. Alkalis and heavy metals cause fouling and
corrosion by condensing. As a result of the potassium and chlorine
component) has been demonstrated with model gases treated by a
content of biomass, KCl is the most important compound released
catalytic filter in these condition [49e51]. Of course, the presence of
during biomass gasification. Aluminosilicates have shown the
H2S at such levels is expected to determine serious problems for
downstream chemical syntheses and at the fuel cell anode, espe-
cially for fuel cell operation at temperatures below 1000  C [14]: for
most applications of the product gas the utilization of appropriate
sorbents is therefore required, the development of which is
described below in this chapter.
An additional issue is that of separation of the sorbents from the
remaining constituents of the gasifier bed inventory, with the aim
to perform regeneration and cyclic utilization of them: classifica-
tion based on particle size appears as the most appropriate means.
Calcium based sorbents have been recognized for a long time as
effective media to capture H2S at high temperature; the sulphida-
tion of both, calcined and uncalcined limestone, has been studied
extensively [52,53]. However, thermodynamic limitations, espe-
cially in presence of a considerable content of steam in the gas
phase, can hardly allow to reach H2S concentrations as low as those
required by SOFC. Alternative systems are all characterized by
drawbacks of different nature, spanning from reduction of sorption
capacity with temperature (iron oxide), metal vaporisation (zinc
oxide), oxide reduction by H2 and CO (copper oxide) [14]. Combi-
nations of different metal oxides and high dispersion of the active Fig. 4. H2S concentration in the gaseous stream leaving the sorbent sample [46].
78 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

ability to reduce the alkali concentration to the ppb-level under

gasification conditions [57]. In addition, aluminosilicates rich in
alumina remove chlorine [57] and heavy metals like zinc [58]. Al-
kalis contaminated gases have high condensation temperatures, so
that the attention is often focused on the analysis of the sorbent
capacity more than on the gas purity at the outlet of the sorption
treatment, the latter being rarely determined in a direct way and
more often back-calculated from the sorbent conversion.
The thermodynamic calculations of KCl sorption on alumino-
silicates show that the alkalis concentration in the gasifier derived
gases can be limited to values of 100 ppbv to 4 ppmv depending on
the biomass type. Although KCl is the most abundant of all alkali
species in the syngas, NaCl is the alkali species with the highest
concentration in the cleaned gas. Thus, the condensation temper-
ature decrease depends on the residual NaCl concentration in the
cleaned gas. This ranges from 530 to 630  C, resulting in a drasti-
cally reduced risk of fouling and corrosion downstream the gasifier,
specifically when a SOFC is operated (at temperatures of about
800  C).
Fig. 5. Scheme of the continuous fluidized bed biomass gasification plant: (a) Tar in
The sorption experiments reported in Ref. [46] were performed the condensate samples determined by total organic carbon (TOC) analysis; (b) Tar
at packed bed conditions and atmospheric pressure. The inlet gas fraction sampled in 2-propanol, according to the Technical Specification CEN/TS 15439
stream was laden with KCl by overflowing a KCl source set at analysed by GCMS or HPLC/UV. Adapted from Rapagn
a et al. [60].
700  C; the KCl gas concentration was about 20 ppmv, determined
by the change in weight of the KCl source at the end of each
experiment. At a space velocity of 9800 h1 no evidence of kinetic fluidized bed and without filter candle. The dry gas yield
limitation was observed. The results of the KCl sorption tests improvement obtained with the catalytic filter candle and quanti-
confirm that aluminosilicates are suitable sorbents for KCl removal fied in the bench scale tests is in the range 70e100%, and the total
below 100 ppbv at 800e900  C (Fig. 3). carbon in the permanent gaseous phase per kg of biomass is
Fluidized bed gasification tests at atmospheric pressure in increased on average by 30% as a result of tar conversion in smaller
presence of bauxite for the removal of the most abundant alkali molecules. This substantial increase in the gas yield is partially
halides, i.e. KCl (and NaCl), confirmed the suitability of alumino- counterbalanced by a reduction in the LHV of the fuel gas by
silicate sorbents for the removal of alkali halides released during 13e16%.
gasification processes [59]. These materials (bauxite, bentonite, Fig. 7 shows the characterization of tar samples obtained from
kaolinite and naturally occurring zeolites) are easily available, bench gasification runs with catalytic candles, compared to the
cheap and without environmental implications for their disposal reference test without candle [62]. The experimental rig is always
when exhausted. that schematized in Fig. 5; all tests were performed with a fluidized
bed of olivine particles; in the catalytic tests, the product gas is
2.1.4. Tar and dust abatement by catalytic filter candles in the made to percolate through an Al2O3 based catalytic filter candle
gasifier freeboard positioned in the gasifier freeboard. Test I is characterized by a
Laboratory tests at real process conditions (a 400 mm high gasification time of 6 h, while the overall duration of Test II is 20 h
filter candle segment integrated in the freeboard of a 100 mm ID (three consecutive periods called a, b and c, with intermediate char
gasifier electrically heated) and proofs of concept at the Güssing burning steps). The catalytic filter candle used in Test II contained
dual fluidized bed gasification plant, run by Biomasse Kraftwerk additional catalyst integrated in the hollow cylindrical space within
Güssing GmbH & Co. KG (a prototype candle inserted in the the porous candle structure. Tar samples were collected in 2-
gasifier freeboard and processing a slip stream of raw syngas) propanol according to the UNI CEN/TS 15439 protocol and ana-
confirmed that nickel-based catalytic filters of different design can lysed by HPLC/UV. Quantitative determination was carried out by
be used successfully in integrated high temperature reforming of using calibration curves of pure standard tar compounds: phenol
tar and removal of particles from biomass gasification product. (Ph-OH), toluene (Tol), styrene (Styr), indene (Ind), naphthalene
Fig. 5 shows the arrangement of the bench scale facility used for (Nap), biphenyl (Bph), diphenyl ether (DphE), fluorene (Fle),
the lab tests [60], while Fig. 6 shows a sketch and the P&I flow- phenanthrene (Phe), anthracene (Ant), fluoranthene (Fla) and
sheet of the test module realized in Güssing [61]; in the latter case, pyrene (Pyr) [55]. Among different tar species, toluene appears as
the filter candle is cleaned periodically from the dust cake by the prevailing compound after the catalytic reforming treatment.
means of a rather conventional back pulsing system for rigid hot In the reference test (without candle) less than 60% of the
gas filter elements. Nitrogen is used as the blowback gas for hydrogen content of the biomass was found in the product gas as
regeneration, properly preheated to overcome possible conden- H2, while in each test with the catalytic candle this value greatly
sation problems. exceeded 100% as a result of enhanced hydrocarbon reforming re-
Both types of test showed that the particulate content of the actions with steam. To quantify the reforming activity of the cata-
cleaned gas is practically brought to zero, making it compatible lytic candle, the values of steam conversion detected
with the most sophisticated applications (fuel cells): in the Güssing experimentally were compared with corresponding thermody-
test the reference values were 56.3 and 23.6 g/Nm3, respectively for namic equilibrium values calculated at the test respective condi-
the dust and char content of the raw gas in the gasifier freeboard. tions for biomass steam gasification: in the latter case, char and
Tar content reduction is as high as 95%; at bench scale a greater hydrocarbons are completely converted and concentrations of
methane conversion was obtained (with a maximum value of 40%; carbon monoxide and dioxide, hydrogen and steam in the fuel gas
at plant scale methane content decreased only from 10.1 to 8.1%). are fixed as a result of equilibrium attained for the wateregas shift
The reference values are in both cases those obtained with olivine (WGS):
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 79

Fig. 6. Sketch and P&I flow-sheet of the test module realized in Güssing for gas filtration inside the gasifier freeboard [61].

C21H30O14 þ 7H2O / 21CO þ 22H2 downstream equipment for gas conditioning treatments, where
energy from additional sources is often required [64].
CO þ H2O 4 CO2 þ H2 Pressure drop measurements through the catalytic filter candle
fitted in the reactor freeboard were performed on the empty sys-
where the empirical formula chosen for biomass (C21H30O14) agrees tem (without the particulate bed in it) at different temperature
with the composition of almond shells utilized in the experimental levels, and as a function of the filtration velocity (Fig. 9A). The data
tests. reported here are generally higher than those exhibited by a non-
As shown in Fig. 8, the water conversion obtained experimen- catalytic filter of the same structural characteristics, the reduction
tally is quite close to equilibrium values in almost all tests with a of porosity brought about by impregnation and the presence of
catalytic candle. This is a noteworthy result, as low water conver- more rough surfaces being the main reasons for this effect [63]. The
sion is often considered as a drawback for steam gasification [63]. figure shows an increase of pressure drop with temperature at the
In the catalytic candle, methane and tar steam reforming takes same filtration velocity, mainly ascribable to the increase of gas
place together with WGS: from the experimental results and viscosity. On the other hand, data in Fig. 9B were obtained during
thermodynamic calculations it is estimated a corresponding ther- different gasification runs (about 800  C) and show the increase of
mal energy demand of the order 0.5 MJ/kg of biomass. The pressure drop with time due to the build-up of a dust cake on the
enhancement of the reforming reactions inside the gasifier vessel filtration surface. Two different filtration velocities are considered:
allows to optimize the supply of this thermal load, provided by the pressure drop measured at the beginning of each test (clean
gasification itself, with respect to alternative process layouts with filter candle) is quite compatible with that reported previously in

Fig. 7. Characterization of tar samples from gasification tests. Reference: test without filter candle; Test I: with catalytic filter candle and S/B ¼ 0.84; Test II: with catalytic filter
candle and S/B ¼ 1.1. Reproduced from Rapagna
et al. [62].
80 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

Fig. 8. Experimental and theoretical water conversion values. Test I: without filter candle; Tests IIeX: with a catalytic candle in the reactor freeboard [63].

Fig. 9A at the corresponding filtration velocity (and temperature). pyrolysis products (liquid and solid) to a centralized large gasifi-
After substantial gasification time, the data points seem to reach a cation plant in order to produce biofuels.
plateau suggesting that the thickness of the powder cake tends to a
stable value; in industrial applications, pressure drop across the
2.2.1. First approach e multi-stage gasification
filter candle is controlled by a periodic blowback of clean gas, as
Multi-stage gasification processes perform pyrolysis and gasifi-
was shown in Fig. 6. As a whole, the operation of the filter candle in
cation controlled in separated zones in the gasifier or in single
the gasifier freeboard appears to be a promising option for hot gas
cleaning toward tar and particulate. However, the overall technical
feasibility is not yet proven as the long term behaviour at industrial
conditions is still an outstanding issue: innovative ceramic porous
structures resistant to the gasifier freeboard environment and
temperature peaks were recently developed by Pall Filtersystems
GmbH and fully assessed at laboratory scale [65] and tests are in
progress at the Güssing plant to verify the long term reliability
required by commercial applications.

2.2. Combination of pyrolysis and gasification

Gasification as a thermochemical process to convert carbona-

ceous material into gas by using a gasifiying agent comprises
several overlapping process steps, such as heating and drying, py-
rolysis, oxidation and gasification. The overlapping of these process
steps makes it impossible to control and optimize the different
steps separately in a one-stage gasifier. Moreover, interaction be-
tween volatiles and char can have negative impact on the reactivity
and gasification of the char [66]. Thus, char gasification should be
performed in the absence of the volatiles in order to increase the
gasification efficiency. Modern, advanced gasification concepts
separate the pyrolysis and the gasification steps in single controlled
stages which are combined in a multi-stage gasification process.
High gas purity with low levels of tar and high process efficiencies
with high char conversion rates are possible.
There are two different approaches which have been followed.
The first one combines pyrolysis and gasification directly in a two or
three stage gasification process. The different stages can be com-
bined in one unit with separated pyrolysis and gasification zones or
in separate reactor units combined in a series. The second approach Fig. 9. (A) Pressure drop across the catalytic filter candle with the reactor empty of
particles; temperature levels:(C) 20  C, (▫) 300  C, ( ) 450  C, (B) 600  C, ( ) 800  C.
performs pyrolysis and gasification at different locations. In this (B) Pressure drop across the catalytic filter candle, as a function of time on test;
concept pyrolysis aims to concentrate biomass at decentralized filtration velocity: (B) 2.3 cm/s, (D) 2.2 cm/s, (C) 1.8 cm/s, (▫) 1.7 cm/s. Reproduced
small pyrolysis plants for an economical transport of the biomass from Rapagna
et al. [63].
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 81

combined reactors. This enables conversion of the biomass under

optimized operating conditions for the single steps. Main reason for
the development and use of a multi-stage gasification process is
that a clean syngas with low tar content can be achieved.
Furthermore, the overall process efficiency and the product quality
and quantity can be enhanced compared to a one-stage gasification.
Several gasification processes according to the multi-stage
gasification concept separating pyrolysis and gasification zones
have been developed recently. Some examples are the 75 kWth
Viking gasifier developed at the Danish Technical University [67],
the FLETGAS process developed at the University of Sevilla in Spain
[6] and the LT-CFB (low temperature circulating fluid bed) gasifi-
cation process developed by Dong Energy company from Denmark
[68].
The Viking gasifier (see Fig. 10) is a two-stage process with a
screw pyrolysis reactor followed by a fixed bed downdraft gasifi-
cation reactor. The outlet of the pyrolysis reactor is directly com-
bined to the gasification reactor. Between the pyrolysis and the
Fig. 11. Principle scheme of the three-stage FLETGAS gasification process [73].
gasification zone air is added to partially oxidize the pyrolysis
products. By the partial oxidation and by passing the char bed, the
tar content in the syngas is reduced to less than 15mg=mN 3 . The
produced gas contains about 32% H2, 16% CO, 20% CO2, 30% N2, and a gas coming from the second stage flows through the char bed
small amount of CH4 of about 2%. The higher heating value of the which serves as a catalyst for further tar reduction. The char pro-
gas is about 6:6mg=mN 3 [67]. A cold gas efficiency of 93% has been duced in the first stage is directly transported from the first stage to
reported for the process [69]. The Viking gasifier has recently been the third stage via a gas seal solid transport part [70,71]. Some
upscaled to a 200 kWe gasifier and work is in progress for a 500 kWe modelling work [6] has been performed showing the advantages of
gasifier [3]. the process compared to one-stage fluidized bed gasification. A
The FLETGAS process (see Fig. 11) is a special designed three- significant decrease of the tar concentration to 10mg=mN 3 , char
stage gasification process. In the first stage, devolatilization in a conversion of 98% and gasification efficiency of 81% compared to tar
fluidized bed reactor takes place with low conversion of tar and concentration of 31g=mN 3 , char conversion of 59% and gasification
char at temperatures between 700 and 750  C. Air and steam can be efficiency of 67% for the one-stage fluidized bed gasification has
added in this stage at reduced amount to keep the temperature low been shown which is an interesting result of this new concept. The
to have just the devolatilization. High amount of reactive tar is composition of the gas was calculated on a dry basis with: 55 %N2,
produced. In the second stage, the tar is reformed with steam at 13% CO, 15% CO2, 4% CH4, 8% H2, and 2% C2H6. The higher heating
high temperature of 1200  C. In the third stage, the char generated value was calculated with 6:4MJ=mN 3 . Some experimental work
in the first stage is gasified in a moving bed downdraft reactor. The [72e74] has also been performed to develop the process. The pro-
cess is still under development at pilot scale [6]. Besides the proof of
the concept by operation of a pilot unit a techno-economical
assessment would also be needed to prove the economical
benefit of this concept. A drawback seems to be the high complexity
of the reactor set-up.
Fig. 12 shows the schematic principle of the LT-CFB gasifier. The
gasifier has two stages. The first stage is a circulating fluidized bed
pyrolysis reactor operated at about 650  C. The second stage is a
bubbling fluidized bed reactor operated at about 730  C for the
gasification of char. Gasification of char is possible at this low
temperature since the residence time in the gasifier is high. The
gasifier is autothermally operated by using air as an oxidizing
medium. Sand and ash are recirculated from the bottom of the
gasifier to the pyrolysis reactor carrying the heat for the pyrolysis of
the biomass. Additionally, the char gas is redirected to the pyrolysis
reactor. In between the two reactors, a cyclone is installed to
separate char and sand from the gas. Char and sand enter the
gasifier and pyrolysis and char gas are cleaned in a second cyclone
from the ash [68]. After testing the process in a 100 kWth [75] and a
500 kWth unit [3], a 6 MWth demonstration plant has been built and
is in operation since 2012 in a power plant owned by Dong Energy
where the produced gas is co-fired with coal [68]. The LT-CFB
gasification process has been developed for the use of more diffi-
cult biomass feedstocks, such as straw, manure fibres, sewage
sludge and different organic wastes [3]. Cold gas efficiencies of
87e93% have been achieved in tests with the 500 kWth unit [3]. A
gas composition of 3.5% H2, 16.3% CO, 14.5% CO2, 59% N2, 4.3% CH4
and higher heating values between 5:2 and 7MJ=mN 3 have been
Fig. 10. Scheme of the Viking gasifier [67]. achieved [76]. It is reported that the two-stage process is robust, the
82 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

company in Germany [78e80]. Fig. 13 shows the Carbo-V process

schematically. The first process stage is a pyrolysis reactor, called
low temperature gasifier. The second process stage is a combustion
chamber where the pyrolysis gas and recycled char from the
deduster is oxidized with pure oxygen. The third process stage is a
gasification reactor. The char produced in the pyrolysis reactor is
gasified in this stage by using the combustion gas from stage 2 as a
reacting agent. Since the reactions in the third stage are strongly
endothermic, this stage is also called chemical quenching [79]. The
process has been demonstrated in a 1 MWth plant in long-term
operation for the production of biofuels. A cold gas efficiency of
82% and an almost tar free gas has been reported for the process
[80]. The gas composition was 34.6% H2, 36.8% CO, 22.6% CO2, 1.7%
N2, 0.4 CH4, and 3.9% H2O [81]. An upscale of the process to a
45 MWth plant was commissioned and a test program was started
but not completed due to insolvency of Choren in 2011 [82]. Main
reasons for the stop of the 45 MW plant have been seen in problems
related to the scale-up of the new technology. This extended the
commissioning of the plant far beyond the planned schedule and
Fig. 12. Simplified principal scheme of the LT-CFB gasifier.
increased the costs so that the investors decided to stop their
funding [83,84]. The technology has been acquired by the German
company Linde in 2012 [85]. Linde reported about 1 year after the
acquisition of the Carbo-V technology that they have refined the
process to a level that demonstration with a partner can commence
[86]. Forest BtL Oy from Finland has recently bought a licence from
Linde for using the Carbo-V process in a new BtL (Biomass to Liquid)
plant with a gasification capacity of 480 MW. Forest BtL Oy selected
the Carbo-V technology since this multi-stage gasification process
offers a high fuel conversion to syngas and a high syngas quality
[87].
An overview of the described multi-stage gasification processes
is given in Table 3. It can be concluded that very low tar concen-
trations in the producer gas are achieved by the different multi-
stage gasification processes. Also higher char conversion and gasi-
fication efficiencies are achieved compared to one-stage gasifica-
tion processes (see Table 1). The complexity of the gasification
Fig. 13. The Carbo-V gasification process [79]. process is increased by combining different reactors. However, this
can be compensated by a simpler subsequent gas cleaning process.

construction is cheap and requires low maintenance. Alkalines are

maintained in the ash due to the low process temperature [77]. 2.2.2. Second approach e use of pyrolysis and gasification at
However, the produced gas has a high tar content ð > 4:8g=mN 3 Þ different locations
[76]. Thus, use of the gas in engines, fuel cells or for biofuel pro- A special concept to use pyrolysis and gasification at different
duction is not possible without further gas cleaning. locations has been developed under the name bioliq process by the
Besides the recent new developments, there has been so far one Karlsruhe Institute of Technology (KIT) [88e90]. In the bioliq
multi-stage gasification process separating pyrolysis and gasifica- concept (see Fig. 14), biomass is concentrated into an oil-char slurry
tion in different reactors which has been built and operated in large in multiple decentralized small pyrolysis plants. The concentrated
scale e the three-stage Carbo-V process developed by the Choren oil-char slurry is then transported to a large central process plant

Table 3
Overview of multi-stage gasification processes.

Number Process stages Cold gas Tar content Gas Higher

of stages efficiency/% in the producer composition heating
gas/mg/m3N value/MJ/m3N

2  Screw conveyor pyrolysis reactor 93 <15 32% H2 6.6

 Downdraft fixed bed gasifier 16% CO
 Partial oxidation by air addition between the 2 stages 2% CH4
3  Fluidized bed pyrolysis reactor 81 10 8% H2 6.4
 Steam reformer 13% CO
 Moving bed downdraft gasifier 4% CH4
2  CFB pyrolysis reactor 87e93 >4800 3.5% H2 5.2e7
 BFB gasifier 16.3% CO
4.3% CH4
3  Pyrolysis reactor 82 Tar free 34.6% H2 High
 Partial combustion chamber 36.8% CO
 Entrained flow gasifier 0.4% CH4
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 83

be tested and stable atomization and gasification have to be proven

for these different slurries.
An economical assessment of the bioliq concept has shown that
the production of gasoline and olefins from biomass by this process
is not competitive compared to current market prices. Only sub-
sidies, e.g. from tax reduction and CO2 certificates, could currently
enhance the competitiveness of the biofuels [91].

2.3. Combination of gasification and combustion

Concepts which combine gasification with a combustion stage

aim on one hand at increasing the overall process efficiency by
combining combustion of unreacted char for additional heat pro-
duction or on the other hand for the conversion of tar by partial
combustion to achieve a product gas with a lower tar
concentration.
Fig. 14. Schematic principle of the bioliq concept.
A third concept is to implement the gasification process for co-
firing of the product gas in a coal combusted power plant. This
for gasification of the slurry and synthesis of biofuels. The concept option reduced the requirements with regard to the gas purity
is based on the use of low-grade lignocellulosic biomass, such as significantly and needs no additional gas cleaning and conditioning
straw or forest residues. The energy density of the oil-char slurry is equipment downstream of the gasifier. Thus, the process set-up can
increased by about ten times compared to the initial energy density be kept very simple and cost-effective.
of straw. Thus, transportation of the oil-char slurry is much more
economical than that of the untreated biomass [91]. 2.3.1. Dual fluidized bed process with internal combustion
A demonstration plant of the bioliq process has recently been Biomass gasification is globally an endothermic process, so that
built at KIT in Germany [92]. The process comprises the following 4 it requires providing thermal energy to the reactor. This can be
process steps: 1) Fast pyrolysis to produce the oil-char slurry in a done in different ways that in most practical applications involve
separate decentralized pre-step, 2) Gasification of the slurry to burning part of the gasification products, including sometimes
produce syngas, 3) Hot syngas cleaning and conditioning, 4) Syn- auxiliary fuels made available by downstream purification treat-
thesis of the biofuel. ments. In this context, air is the most common gasification agent
Fast pyrolysis has been chosen since short reaction times give utilized in gasification plants: the excess of thermal energy avail-
higher yields of pyrolysis oil [93]. The slurry is gasified in a 5 MWth able in industrial installations allows to heat up the air stream to
Lurgi entrained flow gasifier at an operating pressure of 8 MPa [92]. the gasifier above ambient temperature and to close the energy
Even if entrained flow gasifiers are widely used for gasification of balance satisfactorily. The ratio between biomass and air fed to the
water based coal slurries or refinery residues, the gasification of gasifier, commonly related to what would be needed by a stoi-
such pyrolysis oil-char slurry is new and part of several experi- chiometric biomass combustion process, is expressed as a fraction
mental investigations related to the atomization of the oil-char of it and called equivalence ratio. In the case of fluidized bed gas-
slurry as well as to the modelling of the gasification of the slurry ifiers, the air flow rate should also comply with an adequate
[94]. fluidization regime.
The syngas is cleaned in a completely dry hot gas cleaning A major drawback of this simple and cost effective arrangement
process [95]. First the syngas is filtered at 800  C in a special is contamination with nitrogen of the product gas, with N2 molar
designed ceramic hot gas filter, where the filter elements are hor- fraction values of 50% and more, resulting in a substantial reduction
izontally installed [96]. In a typical hot gas filter design, filter can- of the gaseous fuel heating value (LHV) down to 4e5 MJ/Nm3, still
dles closed at one end are installed vertically hanging in a acceptable for generating power with internal combustion engines,
tubesheet [97]. An advantage of the design with horizontally although unsuitable for more sophisticated and efficient energy
installed filter elements is a more compact design of the filter with applications (fuel cells) and chemical syntheses. To avoid this
a smaller footprint and size of the filter vessel. A problem can be the problem, air could be replaced by oxygen (enriched air) and steam
regeneration of the filter elements which requires a very efficient mixtures, with the additional benefit to enhance tar reforming
backpulse system to remove the dust cake also from the top side of reactions and char gasification. However, this choice implies oxy-
the horizontally installed filter elements. Downstream of the filter, gen (enriched air) availability. With small to medium size biomass
chloride and sulphur gas components, such as HCl and H2S, are gasification units (operating at ambient pressure) and readily
removed by sorbents and tars are catalytically reformed in a available gas separation systems, air enrichment would be mainly
following step. accomplished by selective nitrogeneoxygen sorption systems
Open issues which need to be addressed by further research are requiring feed gas compression, that is compression of a volumetric
how storage (storage conditions and duration) influences the gaseous stream up to 5 times larger than the oxidant used in the
properties and composition of the bio-oil and accordingly the at- gasification process, with a substantial penalty of the whole energy
omization and the gasification behaviour of the oil slurry. Due to the efficiency.
composition, bio-oil generally tends to change during its storage. Bio With fluidized bed gasification systems, a more efficient
oil from pyrolysis of biomass is a mixture of different components, arrangement is obtained by physically separating gasification and
such as furfural, phenols, aldehydes, ketones, esters, ethers etc. [98], combustion reactions and utilizing the mineral particle bed (sand,
having a quite high content of oxygen and water. Depending on the olivine) to transfer heat between them. Fig. 15 illustrates thermal
biomass feedstock, oxygen content is usually in the range of 35e40% and mass fluxes within the system [100], while Fig. 16 shows
and the water content is between 15 and 30% [99]. schematically the application of this principle to biomass gasifica-
Furthermore, the properties of different oil-char slurries coming tion [101]. This is realized by means of dual fluidized bed (DFB)
from different locations and different biomass feedstocks have to systems. Relevant DFB biomass gasifiers and their major features
84 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

the utilization of steam as an additional gasification agent that

improves gas quality (lower tar content). In comparison to more
traditional installations, the complexity of plant layout and opera-
tion is increased, however the syngas quality is also increased
remarkably, opening the way to more diversified utilization options
and to polygeneration strategies.
The capacity of the Güssing plant is about 8 MW (electrical
output of 2 MWe and district heating output of approximately
4.5 MWth). This dual fluidized bed reactor was developed at the
Institute of Chemical Engineering of Vienna University of Tech-
nology (TUV) in cooperation with AE Energietechnik, and known
internationally under the name FICFB (fast internally circulating
fluidized bed) gasification system [103e105]. The construction of
the Güssing plant was started in September 2000, and electricity
was first generated in April 2002; since then, the plant has been
Fig. 15. Heat and mass fluxes in a dual fluidized bed (DFB) gasification system [100]. operating regularly, and the present utilization index is above
7000 h/year. A number of literature references about dual fluidized
bed systems for biomass gasification can be found in Koppatz et al.
have recently been reviewed by Kaushal et al. [102] and Goransson
[101]. Recently, the TUV FICFB CHP technology has been applied in a
et al. [17].
number of gasification installations in Austria, Germany and
The well-known CHP plant in Güssing is the prototype industrial
Sweden.
application of dual fluidized bed biomass gasification: the gasifier is
The gas cleaning (Fig. 17 [103]) has been investigated and
a bubbling bed fluidized by steam, where the biomass feedstock is
developed by RENET Austria (Energy from Biomass Network of
devolatilized, and organic vapours and char are properly steam
Competence): it is made in three different and integrated ways.
reformed to obtain permanent gases (CO, CO2, H2, CH4); the gran-
Fine hydrated lime is injected into the system to obtain a primary
ular bed material is continuously circulated by means of a chute
reduction of tar to less than 1 g/Nm3, which allows enhanced re-
(and a loop seal) to a fast circulating bed fluidized by air, where any
covery of sensible heat from the product gas stream; particulate
non-gasified fuel particles transported along with the bed material
filtration is operated smoothly at about 150  C; the fuel gas is then
are fully burnt, together with additional fuel properly injected,
contacted with biodiesel (RME) in a scrubbing column, to reach a
determining an increase in temperature of the particulate solid of
tar content of about 20mg=mN 3 and a temperature of about 50  C.
50e100  C above that in the gasifier; solid and gaseous phases are
Exhausted biodiesel is used as an additional fuel in the combustion
then separated at the top of the riser/combustor in a cyclone-type
section of the gasifier, and condensed water recycled to the gasi-
device, and hot particles are brought back to the gasification
fication section, so that disposal of liquid streams is avoided.
chamber by means of a second loop seal that avoids gas mixing
Finally, the dual fluidized bed gasification system is well suited
between gasifier and combustor, to provide the heat required by
to exploit the advantages brought about by a reduction of CO2
the gasification reactions. By adjusting properly the solid circula-
content in the product gas by absorption on basic oxides [106]: the
tion rate, steady state behaviour is obtained at the desired gasifi-
use of a CO2 sorbent minimizes carbon oxides and enhances the
cation temperature. As a result, air and steam can be used as
equilibrium conversion of catalytic tar and CH4 steam reforming
gasification agents while keeping a very low nitrogen concentra-
allowing to clean the gaseous fuel and improve the H2 yield. The
tion in the fuel gas, permitting LHVs of about 12e14 MJ/Nm3 and
practical feasibility has been demonstrated by adding calcined
limestone or dolomite to the reactor bed inventory. The sorbent
circulates between the gasifier e CO2 capture bubbling bed, and the
combustor e calciner riser: in the reactor chamber devoted to
biomass gasification and CO2 capture, the endothermic gasification
and the exothermic solid carbonation processes combine well
together and their coupling reduces the amount of the solid cir-
culation rate required to sustain thermally devolatilization and
gasification reactions. On the other hand, the riser provides the
calcined solid sorbent and the remaining thermal loading. When
oxygen (instead of air) is utilized for combustion reactions in the
riser, a CO2 stream is easily obtained (by steam condensation),
available for storage and sequestration.
The thermodynamic constraints of the reaction between CO2
and CaO impose, at ambient pressure, a temperature level for
gasification somewhat lower (650e700  C) than the usual one
(800e850  C). However, the experimental evidence at pilot and
industrial scale [107,108] does not show substantial increase of tar
content in these conditions. The H2 yield in the dry product gas is
increased up to 70%.

2.3.2. Gasification with partial combustion

Thermal treatment of tar is one method for the reduction of tar
concentration in biomass gasification gas [28,13]. At high temper-
ature, the stability of tar is reduced and tar can be converted or
Fig. 16. Scheme of the DFB reactor system [101]. cracked into lighter gases. However, thermal reduction of tar is a
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 85

Fig. 17. Fuel gas cleaning with dry dust precipitation and wet RME scrubbing in Güssing [103].

quite complex process and the result depends highly on the process The influence of the hydrogen concentration on the presence of
parameters. For example, it has been shown that just heating a tar free radicals in the partial combustion process has been studied by
containing gas by an external heat source to a temperature of van der Hoeven et al. [111]. Their investigation showed that a
900e1150  C leads to polymerization reaction of light tar compo- higher hydrogen concentration has positive influence on tar
nents and to the formation of soot instead of the cracking of the tars cracking due to increased reaction rates, higher amounts of free
[109]. radical generated, and longer residence times of the radicals.
Partial combustion has been attracting increasing interest of Svensson et al. modelled soot formation during partial oxidation
researchers in recent years as a method to achieve thermal tar of gasifier product gas [112]. They simulated different gas compo-
conversion. Air/fuel ratio, hydrogen concentration, methane con- sitions and used naphthalene as a tar component. The simulation
centration, temperature and free radicals produced during the results showed decrease of soot formation with increasing the
combustion influence the cracking or polymerization reactions of hydrogen concentration in the gas as well as an increase of soot
the tar components. formation in the case of increased methane concentration. This is in
Houben et al. [109] investigated tar reduction by partial com- qualitative agreement with the experimental results by Houben
bustion by using naphthalene as model tar component at a very low et al. [109]. However, the influence of the hydrogen concentration
concentration of 2:6mg=mN 3 in a mixed gas stream of hydrogen, on the soot formation was very low in the simulation which re-
methane and nitrogen. It has been shown that without oxygen quires further investigations. In all simulated cases soot was formed
addition polyaromatic hydrocarbons (PAH) and soot were formed. and could not significantly be reduced expect when no naphtha-
Also, if too much oxygen was added, PAH and soot were formed. For lene was added to the gas. In this latter case about 50% less soot was
a very low air to fuel ratio of l ¼ 0.2, the partial combustion reduced formed compared to the base case where naphthalene was added
the tar content by more than 90%. For l > 0.2, the tar concentration in an amount of 0.5 mol% of the total incoming gas flow.
increased. Thus, an optimum was found in the amount of air added Ahrenfeldt et al. [113] showed higher tar reduction with
for the reduction of the naphthalene. For l > 0.4, polymerization to increasing air ratio for the partial oxidation of real gas from the
higher tar rings and sooting prevailed. It has also been found that pyrolysis of wood pellets. They showed complete conversion of
hydrogen and methane have an influence on tar reduction. phenol for l > 0.3 and temperatures above 950  C. For lower air
Hydrogen acts as an inhibitor for the formation of soot. With ratios higher temperatures were required to get the same result.
increasing hydrogen concentration, the amount of higher tar ring Above 900  C phenol and other primary tars were converted into
components decreased. At hydrogen concentrations higher than low molecular weight PAH, primarily naphthalene. The tar con-
20% nearly all naphthalene was converted to benzene or permanent centration in the raw pyrolysis gas was quite high (above 200 g/
gases. For higher methane concentrations and very low hydrogen kgwood).
concentrations, polymerization to higher tar ring components and Investigations of Brandt et al. [114] showed a minimum of the
soot formation was observed. tar concentration at an air ratio of l ¼ 0.5 for partial oxidation of gas
Naphthalene as model tar component doesn't simulate the tar from the pyrolysis of straw. For higher air ratios the tar concen-
composition of real gases correctly. Real tar is composed of a lot of tration slightly increased. The tests were performed at 800 and
different components and has typically high concentrations of 900  C. The tar reduction was nearly comparable for both tem-
benzene and toluene which are the most stable tar species and peratures. Composition of the tar downstream of the partial
require high temperatures above 1200  C for their effective oxidation reactor as well as soot formation has not been
reduction (see e.g. Ref. [110]). At the same time, high temperatures investigated.
favour the formation of coke. Zhang et al. [110] showed that coke Su et al. [115] investigated the partial oxidation of gas from the
formation starts at 900  C having a maximum at 1100  C. pyrolysis of rice straw. Maximum tar reduction has been achieved
86 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

at an air ratio of l ¼ 0.34 at a temperature of 900  C. Phenolic Based on the successful operation in Lahti, the concept of indi-
compounds were completely converted for l > 0.2. It is reported rect co-firing of biomass by gasification using a CFB Foster Wheeler
that oxygen increases the reaction rate and can promote the for- gasifier similar to the one in Lahti has been applied at the coal fired
mation of free radicals for initial tar cracking reactions. For air ratios Ruien power plant of Electrabel in Belgium [128e131]. The gasifier
above 0.278 only PAHs e naphthalene, fluorine, phenanthrene and was commissioned in December 2002 and commercial operation
pyrene e can be found in the gas. Higher air ratios lead to formation started in May 2003. The gasifier is installed at the boiler of unit 5 of
of higher PAHs. This agrees with the results of Houben [109] (see the power plant. Unit 5 has a power output of 190 MWe on coal. No
above). pre-treatment (drying, grinding) of the biomass as well as no
Partial combustion for tar reduction has already been applied cleaning and conditioning of the produced gas are required. The
successfully in some recent multi-stage gasification concepts, such quality of the gas is sufficient to be burned in two burners, which
as the Viking gasifier (described in Section 2.2) for which a tar are installed below the coal burners in the boiler. Wood residues
reduction by partial combustion by a factor of 100 has been re- from the local wood industry as well as fresh wood chips are used
ported [67] or the newly developed Fraunhofer ISE gasification as a feedstock. About 9% of the coal is substituted by gas from the
process for production of synthesis gas with tar contents below biomass gasification and 120 000 t/year CO2 emissions are saved
50mg=mN 3 [116]. The partial combustion in these multi-stage [131].
gasifiers aims to increase the temperature of the pyrolysis gas In the Netherlands, an 85 MWth CFB Lurgi gasifier is in operation
required for the subsequent endothermic char gasification reaction. for indirect co-firing of biomass since 2002 at unit 9 (net produc-
In a single stage gasification process, a partial combustion stage tion capacity: 600 MWe and 350 MWth) of the Amer power station
downstream of the gasifier is typically not used since the high of Essent in Geertruidenberg [132,133]. Low quality demolition
temperature required for an efficient conversion of tars reduces the wood is mainly used as a feedstock. About 90 000 t biomass was
energy efficiency of the process. Additionally, it reduces the syngas gasified in 2010 generating an electric capacity of about 33 MWe
yield. [133].
In Austria, a 10 MWth, CFB biomass gasifier designed by Austrian
2.3.3. Implementation of gasification in coal fired power plants Energy was installed for indirect co-firing of biomass with coal at
Co-firing of biomass in coal fired power plants is a simple way to the Zeltweg power plant (137 MWe, 344 MWth) [134,135]. The
substitute fossil fuels by renewable ones [117e119]. At the first gasifier was commissioned in 1997 and shut down in April 2001
sight, the easiest and least expensive way is direct co-firing of due to shut down of the power plant. Mainly bark and wood chips
biomass in the boilers. Up to about 3% of biomass on energy basis were gasified.
can be directly co-fired with minimal additional investment costs After 2003, the interest in the concept of indirect co-firing of
[1]. However, the properties of biomass as fuel are quite different biomass by gasification declined. However, recently the interest
compared to coal. Biomass has lower ash content, higher oxygen in this concept increased again and new biomass gasifiers were
content, higher content of volatiles, lower density and heating installed at coal fired power plants. In Denmark, Dong Energy
value, grinding is more difficult due to fibre structures and some installed a 6 MWth LT-CFB biomass gasifier (see Section 2.2),
have high alkali and/or halogen content [120]. Thus, direct co-firing which is in operation since 2011, at its Asnaes power plant [68].
of biomass can result in several problems, especially if higher Straw is mainly used as a feedstock. In Finland, the so far world's
amounts of biomass shall be co-fired. These problems are mainly largest biomass gasifier has been inaugurated in March 2013
related to the different properties of the biomass ashes due to high [136]. The gasifier, a 140 MW CFB gasifier designed and supplied
alkaline and chlorine contents. Main problems which are reported by Metso, was installed at the 560 MWth coal fired power plant
are corrosion, slagging and fouling in the boiler as well as in the of Vaskiluodon Voima Oy in Vaasa [137]. Between 25 and 40% of
heat exchanger and in the piping, poisoning of DeNOx catalysts and the coal consumption of the plant will be substituted by
performance problems in electrostatic precipitators [121e124]. biomass.
One approach to overcome these problems is indirect co-firing Indirect co-firing of biomass by gasification is a concept which is
of biomass by biomass gasification. Biomass is gasified in a well proven by long-term operating experience in large coal fired
gasifier and the produced gas is co-fired in a coal fired boiler [125]. power plants, as mentioned above. This concept has several ad-
Up to 10% of the thermal capacity of the boiler can be co-fired vantages which can be summarized as follows:
without the need of reconstruction of the boiler and auxiliary de-
vices. For higher ratios major changes of the boiler would be - Easy and cost-effective way to reduce fossil CO2 of coal fired
required [117]. power plants
The first power plant where this concept has been used was the - Purity and quality of the produced gas can be low to be burned
Kymija €rvi power plant in Lahti (Finland) [126,127]. The power plant in the boiler. Thus, no high efficient gas cleaning and condi-
has an electrical power production capacity of 167 MW and a dis- tioning or cooling equipment is required and the investment
trict heat production capacity of 240 MW. A Foster Wheeler CFB costs are lower than in cases where high gas quality and purity
(circulating fluidized bed) gasifier was started-up at the beginning are needed.
of 1998. Depending on the feedstock and its moisture content the - High flexibility in using a broad range of biomass feedstocks,
capacity of the gasifier is 40e70 MWth (nominal capacity 50 MWth). including low quality biomass as well as RDF (refuse derived
Raskin et al. [127] reported on the successful operation of the plant. fuels).
Wood chips, wet and dry waste wood, saw dust, bark, shredded - Biomass which generates problems in direct co-firing, e.g. straw,
tires, plastics as well as recycled fuels were successfully gasified. can be used.
The recycled fuels comprised mainly paper, cardboard and wood, - Compared to direct co-firing, no drying or grinding is required.
and about 5e15% plastics. It was demonstrated that the concept of - High biomass conversion; residual fine char particles and tars
indirect co-firing of biomass by gasification is a successful way to are burnt in the boiler.
generate heat and power by using different types of biomass and a - No operating dependency on availability of biomass; biomass
way to operate an existing coal fired boiler with only small modi- can be substituted by fossil fuel.
fications. The power plant could be operated in a flexible way by - No influence on the operating availability of the power plant by
adjusting the amount and the type of biomass which was co-fired. possible problems with the gasifier.
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 87

- Less coal ash pollution than in direct co-firing (coal ash is often reported. In all cases gas engines are used for electricity generation
used in concrete production). Less biomass ash enters the boiler showing increased efficiency of newer gas engine types. The pro-
since coarser ash particles are removed in the cyclone of the CFB duced heat is used for district heating.
gasifier and returned into the gasifier where they accumulate An approach to increase the amount of generated electricity is
and are removed as bottom ash. If higher percentages of applied in the 15 MWth plant in Ulm in Germany where in addition
biomass are co-fired or higher coal ash purity is needed, a hot to 2 gas engines an organic Rankine cycle (ORC) is installed for
gas filter [97] can additionally be used to remove fine ash par- electricity production [146]. By using ORC, some of the heat
ticles from the produced gas without energy loss due to cooling. (10e15% of the heat) [9] can be additionally converted into elec-
tricity. Combining gas engines with ORC, biomass to electricity ef-
3. Polygeneration strategies ficiencies of more than 40% are achievable.
Another approach to increase the electricity efficiency, is the
Polygeneration is an approach to improve the economic and integrated gasification combined cycle (IGCC) process, where a gas
sustainability of the utilization of biomass via gasification. Poly- turbine and a steam turbine are combined to generate electricity.
generation refers to the combined production of at least two The IGCC process has been used for coal gasification since the mid-
products. The goal is to maximize the transformation efficiency of 1990s, showing electricity efficiencies of up to 46% for plant sizes of
the energy and material of the feedstock into products. Syngas from 200e300 MW [147,148]. Theoretical investigations (see e.g. Ref.
biomass gasification can be converted into a broad range of prod- [149]) show that even overall electrical efficiencies of up to 53%
ucts, e.g. electricity, heat, gaseous or liquid fuels or chemicals. As an could be possible with an IGCC process. For biomass, the IGCC
additional advantage, polygeneration offers flexibility with regard process has been applied in the 18 MWth (6 MWel and 9 MWth for
to changes of market demands. For example, a polygeneration district heating) demonstration plant in V€ arnamo in Sweden
process for the combined production of biofuels, heat and power [150,151]. The plant was operated from 1993 to 1999 when the
could be used as a back-up power plant. If the current electricity demonstration program was completed. The plant had a net elec-
consumption increases, the production of biofuels can be switched trical efficiency of 32% and a total net efficiency of 83% [150]. Since
to the production of power. small steam turbines have a low electrical efficiency [152], an IGCC
However, higher flexibility comes with higher capital invest- process is only interesting for larger scales.
ment costs as well as higher operation and maintenance costs. A technology for electricity generation which has already gained
Combined heat and power production is a classical example for a high interest is the fuel cell technology. Fuel cells offer the ad-
a polygeneration process. Newer approaches aim to combine SNG vantages of very high electrical efficiencies, an environmental
(synthetic natural gas) or hydrogen and heat production, or bio- friendly operation and they can be used from some hundreds of
fuels, and heat and power production. kilowatts down to 1 kW for very small scale applications. Solid
Oxide Fuel Cells (SOFCs), which operate at high temperatures with
3.1. Combined heat and power production (CHP) hydrogen, carbon monoxide and methane and their mixtures as
fuel [14] are specifically considered as a good option to be com-
Power production is generally coupled with the production of bined with biomass gasification. For application as CHP, the high
heat. If the heat can be used, the overall process efficiency can be exhaust temperature of the SOFC is an advantage to use the heat.
significantly increased. Whereas electricity can be easily trans- However, even if the biomass gasification syngas composition is
ported and distributed, heat has to be produced close to the user. generally well suitable as fuel for a SOFC, it has to be cleaned to
For this reason, decentralized heat and power production by achieve the high requirements of the fuel cell with regard to im-
smaller units is preferred, and larger units of several hundreds of purities. Aravind and de Jong [14] gave a very comprehensive
MW as typically used for power production are not an option. literature review of the different contaminants in the raw syngas,
Interesting ways to use the heat are for example CHP plants of a few their influence on the performance of a SOFC and techniques to
MW coupled to district heating systems, CHP plants below 1 MW remove them. They concluded that it is possible to clean the syngas
for heating large public or commercial buildings, public swimming to meet the requirements of a SOFC. They proposed a gas cleaning
pools, hospitals, hotels or apartment buildings, or CHP plants set-up comprising a series of fixed bed reactors and 2 ceramic hot
installed at pulp and paper plants, at saw mills etc. where biomass gas filters.
waste can directly be used to produce electricity, heat or steam for Many performance models and theoretical analyses of the
the local plant. Combined heat and power production by biomass combination of SOFCs and biomass gasifiers show the high poten-
combustion is already widely used [138]. However, CHP by biomass tial of this combination with electrical efficiencies from 34 to 45%
gasification offers some advantages, such as higher biomass to and CHP efficiencies from 74 to 80% [153e157].
power efficiency [3,139], and higher flexibility concerning the used A further increase of the electrical efficiency is possible by
feedstock as well as the applied electricity generation process [140]. combining a SOFC and an additional Micro-Gas Turbine (MGT) with
First CHP applications by biomass gasification started at the a biomass gasifier. By adding the MGT, the excess fuel in the exhaust
beginning of the 1990s [141]. CHP biomass gasification plants with gas from the SOFC can be used to generate additional electricity.
capacities of a few MW of biomass input have demonstrated several The combination of a SOFC and an MGT with a biomass gasifier
years of successful operation showing the overall reliability of the offers a very efficient power production solution for small decen-
technology and the achievable high process efficiency. Some ex- tralized CHP plants. Recent modelling studies of Bang-Møller et al.
amples are the 5.2 MWth Harboøre plant (start-up in 1993) [3,142,9] [158] showed an electrical efficiency of 58% and a CHP efficiency of
and the 26 MWth Skive plant (start-up in 2006) [9] in Denmark, the 87.5% for an optimized process using the two stage Viking gasifier
8 MWth plant in Güssing (start-up in 2002) [143], the 2 MWth plant combined with a SOFC and an MGT. Morandin et al. [159] have
in Wiener Neustadt (in operation from 2003 to 2007) [144,145], the recently modelled nine different system configurations using either
8.5 MWth plant in Oberwart (start-up in 2008) [9] and the 15 MWth an internally circulating fluidized bed gasifier or the Viking two
plant in Villach (in operation from 2010 to 2013) in Austria as well stage gasifier and different combinations as CHP unit, just a SOFC, a
as the 15 MWth plant in Ulm (start-up in 2012) in Germany [146]. In SOFC combined with a steam cycle and a SOFC combined with an
most of the plants just mentioned, overall process efficiencies of MGT. Their thermo-economic analysis showed that the combina-
about 90% and biomass to electricity efficiencies from 25 to 31% are tion of a fast internally circulating fluidized bed gasifier with a
88 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

pressurized operated SOFC and MGT is the most promising aims to remove particulates, tars, alkali and sulphur components.
configuration with an electrical efficiency of 65%. The removal of these components has to be very efficient in order to
However, combination of SOFC and biomass gasification has not protect downstream catalysts from poisoning. Conditioning of the
been demonstrated on full scale and for long-term operation yet. gas comprises typically a wateregas shift to adjust the needed H2/
Experimental investigations have only been performed with single CO ratio of 3 or more for the methanation reaction. After the
cells or very small stacks, and for short test durations of about methanation, water and CO2 as well as unreacted hydrogen and
5e150 h (see e.g. Refs. [160e162,69,163]). Only one test has been impurities of ammonia are removed from the SNG to achieve the
performed for longer test duration of 1200 h [164]. required gas quality, for example to deliver the SNG to the gas grid.
Based on the published experimental results, the following More details of the process are given in the literature (see e.g. Refs.
conclusions can be drawn: [165e167]).
In the last 10 years, the production of SNG from biomass gasi-
 SOFCs can successfully be operated by using cleaned biomass fication syngas has gained increasing interest and has been inves-
gasification syngas. General feasibility of the combination of tigated by some research groups such as the Energy Research
biomass gasification with a SOFC is shown. However, demon- Center of the Netherlands (ECN) and the Paul-Scherrer Institute
stration on full scale and for long-term operation is still missing. (PSI) in Switzerland [165].
 The cell performance depends on the syngas composition and Recently, the feasibility to produce SNG from biomass gasifica-
fluctuations of both can be correlated [161]. tion syngas has been demonstrated in a 1 MW scale at the Güssing
 The risk of carbon deposition increases with higher concentra- plant [168]. ECN operates a 0.8 MWth SNG pilot unit [169]. A
tion of methane and tars. However, carbon deposition can be thorough investigation by Wirth and Markard showed that Bio-SNG
prevented by addition of steam. plants require a size of 20 MW or larger to be economical since the
 However, if steam content is too high, the risk of nickel oxida- process including gasification, gas cleaning, catalytic methanation
tion of the anode is increased resulting in cell performance and CO2 separation is complex and expensive [170].
degradation [163]. The first commercial Bio-SNG plant of a size of 100 MW will be
 Inefficient particle removal from the syngas causes ash deposits built in the GoBiGas project in Go €teborg in Sweden [171,172]. In the
and prevents a smooth long-term operation [160]. For this first phase of the project, a 20 MW plant has been erected. In the
reason fly ash and char particles have to be removed efficiently second phase a 80 MW plant will be built which shall start oper-
from the syngas. ation in 2016. There are further plans for large commercial Bio-SNG
 Besides particle removal, efficient removal of gaseous impu- plants, e.g. the 200 MW Bio2G project of EOn in Sweden [173].
rities, such as tars, sulphur compounds, alkalines, chlorides and Finally, there is the question whether the effort to produce SNG
ammonia, is important to prevent poisoning of the anodes [14]. from the syngas is valuable. If the SNG is used for domestic heating
 Attention has to be taken on the syngas composition. Higher and cooking, it would be a shorter chain to use the syngas directly
concentrations of methane, propane and higher hydrocarbons in instead of having an additional production step to produce SNG and
the biomass syngas increase the rate of internal reforming, if no to increase the costs and drop the process efficiency. The reason
separate external reformer unit is used, and cause thermal stress why the additional step to produce SNG is taken is that the existing
which may result in cracking of the cells [161]. distribution system for natural gas can easily be used for SNG which
is a big advantage and justifies the higher effort. In areas where no
Finally, it can't be concluded which one of the available tech- natural gas distribution system is available it would be more
nologies for combined heat and power production should be fav- beneficial to use the cleaned syngas directly for household heating
oured. It depends on case specific conditions which CHP technology and cooking like it has already been practised e.g. in China in rural
is preferred. One important condition beside investment costs, areas [174]. However, a risk of the direct use of the syngas is the
earnings or incentives for heat and power supply and availability toxicity of the CO contained in the gas.
and cost of biomass is the local annual heat demand. Gas engines Compared to domestic heating by wood combustion, Bio-SNG is
are well proven and have a relatively high electrical efficiency at less efficient and about twice the wood quantity would be required
relatively low investment costs. SOFCs and the combination of to produce the same quantity of heat [175]. Also power production
SOFCs with MGTs are promising technologies which offer very high by using Bio-SNG is less efficient than using the syngas from
power generation efficiencies even at very small size. However, biomass gasification directly.
long-term testing on full scale size is still missing and will be an However, Bio-SNG as renewable fuel for transportation can have
important topic for future investigations. an efficiency advantage. Felder and Dones [176] showed in their
evaluation of the ecological impact of Bio-SNG that the preferential
3.2. SNG, heat and power production use of SNG is as a transport fuel for cars to substitute oil based fuels.
Fahlen and Ahlgren [177] concluded in their study that it is more
SNG from biomass is considered as a renewable clean fuel economical to use Bio-SNG as vehicle fuel than to use it for power
substitute for fossil fuels in heating, CHP and transportation sys- and heat production. Ahman [178] showed in his assessment of Bio-
tems. Bio-SNG is also regarded as a flexible renewable energy car- SNG as a transport fuel that Bio-SNG can be produced cost effi-
rier. The existing natural gas pipeline system offers the advantage ciently already at low to medium scale plants of 20e100 MW
for an easy transportation and storage of the SNG. Gas heaters, whereas the production of liquid biofuels require larger scale plants
boilers and engines as well as natural gas cars and buses are to be competitive. Additionally he stated that the production effi-
available as established clean technologies for the use of SNG. ciency of Bio-SNG is higher than for DME, methanol or Fischere-
Several methanation processes were developed in the past for the Tropsch diesel.
production of SNG from coal gasification syngas. One of these Production of Bio-SNG in a polygeneration plant offers several
processes is e.g. the well-known Lurgi process using a series of process possibilities with high overall process efficiencies of up to
adiabatic fixed bed reactors. A comprehensive review on metha- 90%. For example, excess heat of the process can be used for district
nation technologies has been given by Kopyscinski et al. [165]. heating [177] or part of the excess heat can be transformed in a
Before the methanation reaction can be performed, the pro- Rankine cycle to co-produce power [179]. The integration of SNG
duced syngas has to be cleaned and conditioned. The gas cleaning and electricity via biomass gasification in a district heating system
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 89

offers economic benefit and reduces CO2 emission [180]. Poly- low hydrogen concentration and a high effort of hydrogen
generation of Bio-SNG can offer a high flexibility on market de- purification.
mands by adjusting the requested amounts of Bio-SNG, heat and In order to separate and purify the hydrogen from the syngas
power or just balancing the demands by producing the Bio-SNG as pressure swing adsorption or membranes can be used. To achieve
an energy storage. high hydrogen content in the syngas a reforming stage and addi-
In a polygeneration system there is also the possibility to tionally a water gas shift stage typically follows the gasifier.
operate the gasifier with the aim to produce a syngas with a higher Toonssen et al. [187] modelled 10 process configurations with
content of methane and to separate this methane directly from the and without heat recovery based on different gasifiers. They
syngas avoiding the need of a subsequent methanation process. The calculated exergy efficiencies between 45 and 50% for the cases of
remaining syngas can then be used for heat and power generation hydrogen production without heat recovery and between 62 and
for example. 66% with heat recovery. The hydrogen yield for the different gas-
ifiers was between 97 and 106 g per kg of dry biomass. Bhatta-
3.3. Biofuels, heat and power production charya et al. [188] calculated in their model for an oxygen blown
gasification process a similar hydrogen gas yield of 102 g per kg dry
Comparable to Bio-SNG, biofuels, such as FT diesel, DME and biomass.
methanol, are considered as renewable clean fuel substitutes for Tock and Marechal [189] compared in their thermo-economic
fossil transportation or heating fuels. Additionally, liquid biofuels modelling the hydrogen production from natural gas and from
generate less emissions than oil based fuels. biomass with regard to energy efficiency optimization by poly-
Since the use of liquid fuels for cars and trucks is state of the art, generation of hydrogen, heat and power and including CO2 capture.
and accordingly an expanded infrastructure of oil based re-fuelling They concluded that the system performance is improved by pro-
stations exists globally, liquid biofuels can be relatively easily cess integration maximizing the heat recovery and valorizing the
introduced and used in the market. This is the main advantage for waste heat. They calculated an energy efficiency of 60% for
the use of liquid biofuels for transportation compared to SNG or hydrogen production by biomass gasification compared to 80% ef-
hydrogen from biomass. ficiency for hydrogen production by steam reforming of natural gas.
Polygeneration of liquid biofuels, heat and power offers as main Shabani et al. [190] investigated hydrogen production by gasi-
advantages high process flexibility and process efficiencies up to fication of rice husk combined with heat recovery for electricity
about 90% [3] which is similar to the polygeneration of Bio-SNG, generation by 2 Rankine cycles. They used a GE gasifier operated at
heat and power described in the previous section. The advantage 1200  C and 3 MPa with oxygen as gasification medium in their
of a polygeneration versus a stand-alone production has been model. Hydrogen efficiency of 40% and net electrical efficiency of
concluded from several technoeconomic analyses. 3.25% has been calculated if CO2 is not compressed for capture and
Narvaez et al. [181] showed in a recent case study that a poly- storage. With CO2 capture and storage the net electrical efficiency
generation plant for the production of methanol and power has a drops to 1.5%.
better performance and higher flexibility compared to the separate Abuadala and Dincer [191] modelled a quite complex integrated
stand-alone production plants. Furthermore, they showed savings system for polygeneration of hydrogen, heat and power. They
of the syngas consumption as well as the possibility to compensate considered a system comprising steam gasification of saw dust, a
a decrease of the catalyst activity by an increase of the syngas feed coupled SOFCeSOEC (solid oxide electrolyser cell), steam reformer,
rate for the methanol production route and using the unreacted water gas shift reactor, compressors, gas turbine and burner. They
syngas afterwards for power production. concluded that their results give an indication for hydrogen pro-
Haro et al. [182] concluded in their assessment of 12 different duction costs which are quite favourable and have potential for
process concepts based on DME as intermediate and considering practical applications.
ethanol, methyl acetate, DME, H2 and electricity as final products Beside the aforementioned theoretical studies, an experimental
that the highest internal rate of return is given by a concept of investigation of an efficient integrated process to produce hydrogen
producing methyl acetate, DME and electricity and that the poly- is developed in the frame of the UNIfHY research project funded by
generation is more profitable than a single product plant. the European Commission [21]. The system developed in this
Meerman et al. [183] concluded in their study that the eco- project comprises a UNIQUE gasifier (described in Section 2.1), a
nomics of a flexible polygeneration FT-liquid facility is better than water gas shift reactor and a pressure swing adsorption unit. Purge
its stand-alone counterpart. gas is recirculated to the gasifier to be used as a heat source for the
Djuric Ilic et al. [184] showed in their study that polygeneration endothermic reactions in the process. It is predicted that the pro-
of biofuels with co-production of heat and power has a higher cess with the integration of several subsystems will achieve high
reduction of greenhouse gas emissions than the stand-alone pro- hydrogen conversion efficiencies of higher than 66% [21].
duction of biofuels.
Comparing the production costs of biofuels to fossil fuels, 4. New gasification concepts
different techno-economic analysis have shown that biofuels have
to be supported by tax or CO2 incentives in order to be competitive 4.1. Plasma gasification
(see e.g. Refs. [185,91]). The production costs decrease with
increasing size of the production plant [186]. In a plasma, gas molecules are ionized by electric discharges. A
plasma is highly reactive due to the electrons, ions and the high
3.4. Hydrogen and heat production energy density in the gas. To generate a plasma, direct current (DC)
discharge, alternating current (AC) discharge, radio frequency (RF)
Hydrogen generated from biomass can be an interesting envi- induction discharge or microwave discharge are typically used.
ronmental friendly and renewable energy carrier mainly for the use Thermal and cold plasmas can be distinguished. Cold plasmas are
in fuel cells in stationary as well as transportation applications. generated at vacuum pressure whereas thermal plasmas are ach-
Gasification of biomass produces a syngas rich in hydrogen if steam ieved at atmospheric pressure. As plasma gases argon, nitrogen,
or oxygen and steam are used as a gasification agent. If air is used as hydrogen, water vapour or gas mixtures are used. The temperatures
a gasification medium, the nitrogen dilutes the syngas leading to a of thermal plasmas can be 5000 K and higher. Thermal plasma
90 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

gasification units often use DC or AC arc plasma torch generators.

Fig. 18 shows 2 different DC arc plasma torch generator concepts
[192]. Generators up to 10 MW power are commercially available
[193]. Fig. 19 shows as an example a plasma gasification reactor
where the reactor chamber is connected to a non-transferred DC
arc plasma torch generator [194].
The very high temperatures of thermal plasmas enable an effi-
cient decomposition of any organic material into its elemental
molecules. For this reason plasma gasification has gained interest
for the treatment of toxic organic wastes as well as for rubber and
plastic waste. Inorganic matter is recovered as a vitrified slag. En-
ergy can be generated from the gasification of the waste. For
example, a plasma gasification plant in Utashinai (Japan) is in
operation since 2002 gasifying up to about 300 tons per day of
municipal solid waste and automobile shredder residues and pro-
ducing 7.9 MWh electricity with a net production of 4.3 MWh
delivered to the grid [192].
Even if the main application for plasma gasification is waste
treatment, the use of plasma gasification has gained attraction for
syngas production from biomass. Gasification of injected biomass
in the plasma takes place within milliseconds without any inter-
mediate reaction at the very high temperatures [195]. Advantages
of plasma gasification are syngas with high hydrogen and CO
content, low CO2 content, low tar concentration, high heating value,
useable for wet biomass, such as sewage sludge [196,197], no in-
fluence of particle size and structure of the biomass.
Disadvantages are the high electricity consumption to operate
the plasma, high investment costs, and lower efficiencies.
Plasma gasification of biomass has been investigated by several
researchers recently. Hlina et al. [198] have investigated the gasi-
fication of wood saw dust, wood pellets, waste plastics and oil from
the pyrolysis of waste tires in a DC electric arc plasma with a torch Fig. 19. Scheme of a plasma gasification reactor [194].
input power of about 100 kW. A mixture of water vapour with a
small amount of argon was used as plasma gas. CO2 or water vapour Tang and Huang [200] investigated a lab-scaled RF plasma
was added as an oxidizing medium. For all 4 feedstocks, a syngas of reactor for biomass pyrolysis operated at low pressure
high quality with about 90 vol% H2 and CO was produced. They (3000e8000 Pa). They produced two products, a gas of 66 wt% of
evaluated the efficiency of the process by comparing the low the biomass feed as well as char. The gas was a mixture of H2, CO,
heating value of the produced gas to the torch input power. Due to CO2 CH4, light hydrocarbons and almost no tars. The energy loss of
the high electricity input the efficiency of the process is low. For the this lab reactor was quite high and the energy input to the biomass
gasification of the pyrolysis oil the energy efficiency of the process feedstock accordingly low.
is even negative. A comparison between DC arc plasma gasification and conven-
Rutberg et al. [199] evaluated plasma gasification of wood for tional air gasification has been modelled based on non-
combined heat and power production. By using an AC air plasma stoichiometric chemical equilibrium for different feedstocks by
with a power input of 2.2e3.3 MJ/kg they produced a syngas with Janajreh et al. [194]. Air gasification showed a higher efficiency than
13.8e14.3 MJ/kg. By calculations they showed the potential to plasma gasification. They calculated an average process efficiency
achieve a net electric energy conversion of 46%. of plasma gasification of about 42% compared to a process effi-
ciency of 72% of air gasification. The difference is caused by the high
energy consumption of the plasma.
Plasma gasification of distiller grains residues has been inves-
tigated in a 10 kW plasmatron reactor by Shie et al. [201]. A syngas
with 50e55 vol% H2, 40e44 vol% CO, 2e3 vol% CO2 and 1.4e2.5 vol%
CH4 was achieved.
In order to overcome the high energy consumption and high
investment costs of DC plasmas, several researchers have investi-
gated the use of microwave plasmas for gasification of carbona-
ceous feedstocks (see e.g. Refs. [202e205]). All these investigations
were performed on small lab-scale with power inputs from 1 to
5 kW. Gasification of glycerol from biodiesel production in a mi-
crowave plasma was performed by Yoon et al. [203]. They produced
a hydrogen rich syngas with 57% H2 and 35% CO without any oxy-
gen feed. The carbon conversion was 80% in this case. Feeding ox-
ygen decreased the hydrogen content and the heating value of the
gas and increased the CO2 content and the carbon conversion. Quite
Fig. 18. Scheme of a DC non-transferred arc plasma torch (left) and of a DC transferred similar results were also reported for the gasification of coal and
arc plasma torch (right). Adapted from Tang [192]. charcoal [204].
 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95 91

Even if lab studies showed that a syngas with high hydrogen enhance the conversion rate and the hydrogen yield. Several cata-
content can be achieved by microwave plasma gasification, the lysts have been tested for supercritical water gasification of
possibility of an upscale to technical gasifiers with high through- biomass including the typical reforming catalysts, such as Ni and
puts seems very unlikely. Ru, activated carbon, Pt-based catalysts, alkali metal based mate-
rials, such as trona, KOH, NaOH, K2CO3. Overviews are recently
4.2. Supercritical water gasification given e.g. in the papers of Elliott [218], Guo et al. [216], and Azadi
and Farnood [219].
Conversion and gasification of organic hydrocarbons in super- The energy efficiency of the supercritical water gasification of
critical water has already been fundamentally investigated since biomass has been studied by different researchers. Marias et al.
the mid of the 1970s. In the last 10 years interest in supercritical [220] modelled the gasification of vinasse in supercritical water.
water gasification of biomass increased and progress has been They showed that the best gasification efficiency of their process of
made in the investigation of technical processes. Several review about 87% was achieved at a reaction temperature of 600  C. By
papers on supercritical water gasification of biomass have been thermodynamic modelling of a supercritical water gasification
published giving overview of the fundamentals and reactions as process for hydrogen production from wet biomass, Lu et al. [221]
well as details and problems of the process (see e.g. Refs. showed an energy and exergy efficiency of their process of more
[206e208]). Furthermore, several studies on the usability of than 40%. Energy loss results from heat transfer mainly in the heat
different feedstocks, such as e.g. agricultural wastes, leather wastes, exchanger, the cooler, the preheater and the reactor. High heat
switchgrass, sewage sludge, algae, manure, olive mill wastewater transfer efficiency increases the energy efficiency of the system. As
and black liquor, have been performed (see e.g. Refs. [209e215]). an alternative to very efficient heat exchangers, oxygen can be
Water in its supercritical condition e above its critical point of added to the process in a small amount to make the process
p ¼ 22.12 MPa and T ¼ 374.12  C (see Fig. 20) e has unique prop- energetically self-sustainable with only a small loss of the heating
erties as solvent and as reactant. Solubility of organic materials and value of the produced syngas [222]. A polygeneration process for
gases is significantly increased and materials which are insoluble in the production of methanol and power by supercritical water
water or water vapour can be dissolved whereas solubility of gasification of glycerol has been studied by Gutierrez Ortiz et al.
inorganic material is decreased. [223]. Power was produced by a turbine and a fuel cell in their
Main components in the produced gas are H2, CH4 and CO2. CO study. They calculated an overall net energy efficiency of their
content is typically low since CO reacts further by water gas shift proposed process of 38% for a gasification temperature of 1000  C.
and methanation reaction [209]. Tar and coke formation is inhibi- Even if progress has been made in supercritical water gasifica-
ted by fast solution of the formed gas components in the super- tion of biomass in recent years and this technology seems to be very
critical water. At reaction temperatures below 450  C, CH4 is the interesting especially for wet biomass, technical solutions still need
main component in the produced gas, whereas at reaction tem- to be developed for large-scale production.
peratures above 600  C hydrogen is dominant [216]. At tempera-
tures above 600  C, water is a strong oxidant and reacts with the 5. Conclusions
carbon and releases hydrogen [217].
Main advantages of biomass gasification in supercritical water Biomass is one of the main renewable energy sources beside
are: wet biomass can be treated without pre-drying, even liquid wind and solar energy. In contrast to wind and solar energy,
biomass waste can be treated e e.g. olive mill wastewater [214], renewable energy production from biomass can be adjusted to
production of hydrogen-rich gas, high gasification efficiency, low current consumption need. Gasification is a key technology for the
tar formation. Main disadvantages are: high investment costs due use of biomass offering high flexibility and efficiency. New
to the need of special corrosion and high pressure and high tem- knowledge and more efficient and cost-competitive industrial ap-
perature resistant materials, and high energy need to heat up the plications are required for the long run, showing evidence of
water to the reaction temperature. promising developments and cross-fertilization with sectors other
The use of catalysts can reduce the reaction temperature and than energy, which may provide ideas, experiences, technology
thus the equipment and operating costs. Furthermore, they can contributions, new approaches, innovative materials and skills.
The detailed survey of this paper showed some very interesting
new concepts and strategies in biomass gasification. These con-
cepts and strategies aim to promote the application of biomass
gasification in the future. New advanced process integration and
combination concepts enable higher process efficiencies, better gas
quality and purity, and lower investment costs. Polygeneration
biomass gasification facilities for the production of more than one
product in combined processes achieve a highly efficient use of
biomass. Furthermore, these facilities offer the flexibility to pro-
duce electricity when it is needed and if it is not needed to produce
biofuels or chemicals from the syngas. This flexibility is not free of
charge. It is coupled to higher investments in both the reactors as
well as in the power generation equipment. However, back-up
power plants are needed at all and the required investments can
be made in polygeneration plants.
In this frame, the development of innovative catalysts, sorbents
and high temperature filtration media was shown to represent a
fundamental requirement to increase yield and purity of the
biomass gasification product, to allow efficient conversion into
power (high temperature fuel cells; gas turbines; combined, strictly
Fig. 20. Schematic phase diagram of water. Adapted from Yakaboylu et al. [213]. integrated heat and power plant schemes) and further catalytic
92 S. Heidenreich, P.U. Foscolo / Progress in Energy and Combustion Science 46 (2015) 72e95

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 Chapter 1

Biomass
Biomass Gasification:
Gasification: An
An Overview
Overview of
of Technological
Technological
Barriers
Barriers and
and Socio-Environmental
Socio-Environmental Impact
Impact

Xiang Luo, Tao Wu,

Xiang Luo, Tao Wu, Kaiqi Shi,
Kaiqi Shi, Mingxuan Song
Mingxuan Song and
and
Yusen Rao
Yusen Rao

Additional
Additional information is available
information is available at
at the
the end
end of
of the
the chapter
chapter

http://dx.doi.org/10.5772/intechopen.74191

Abstract
Biomass gasification has been regarded as a promising technology to utilize bioenergy
sustainably. However, further exploitation of biomass gasification still needs to over-
come a significant number of technological and logistic challenges. In this chapter, the
current development status of biomass gasification, especially for the activities in China,
has been presented. The biomass characters and the challenges associated with biomass
collection and transportation are covered and it is believed that biomass gasification
coupled with distributed power generation will be more competitive in some small com-
munities with large amount of local biomass materials. The technical part of biomass
gasification is detailed by introducing different types of gasifiers as well as investigating
the minimization methods of tar, which have become more and more important. In fact,
applying biomass gasification also needs to deal with other socio-environmental barriers,
such as health concerns, environmental issues and public fears. However, an objective
financial return can actually accelerate the commercialization of biomass gasification for
power and heat generation, and in the meantime, it will also contribute to other technical
breakthroughs.

Keywords: biomass gasification, gasifiers, tar removal, socio-environmental impact

1. Introduction

Fossil fuel is on the verge of depletion in this century. Scientists and governments around
world are looking for new energy resources which could be used safely and efficiently
with enough amount for deployment and security. Bioenergy is a renewable energy, which

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
4 Gasification for Low-grade Feedstock

is stored in the organic form in the chemical state and supports human beings’ daily life
since our ancestor apes knew how to use fire to cook. In these millions of years, bioenergy
was mostly used in small scale like household cooking. Now, people have realized that effi-
cient exploitation of biomass resource can actually reduce their dependency over fossil fuel.
Biomass gasification has been regarded as an effective pathway to utilization of bioresource.
It takes biomass as raw materials and employs pyrolysis or thermal cracking under anoxic
conditions. This is an energy conversion process including a group of complex chemical reac-
tions that large organic molecules degrade into carbon monoxide, methane and hydrogen and
other flammable gases in accordance with chemical bonding theory. Biomass feedstock with
the gasification agent is heated inside an integrated gasifier. With temperature increase, bio-
mass goes through dehydration, volatilization and decomposition. Eventually, the produced
gases are used for central gas supply and power generation. This technology has already been
developed over several decades and progressively achieved commercialization all over the
world, especially in Sweden, Germany, Canada, the United States, India and China. In the
early stage, downdraft gasifier had been implemented at a large scale in China and India due
to its relatively low tar production. Recently, the development of circulating fluidized bed
(CFB) gasifier makes it adaptable for both biomass quality and the raw particle size. Besides,
CFB is also easy for scale-up and ash cleaning.

China, as a large agricultural country, produces a large number of crop straw, poultry manure,
agricultural by-products and other plant biomass every year. Thus, research and development
on key technologies and integrated peripherals of biomass gasification become very neces-
sary. China has already developed various gasifiers, the size of which range from 400 KW to
10 MW. However, compared with fossil fuel, biomass has lower bulk density and energy den-
sity, which make it uneconomic for collection and transportation. Therefore, biomass gasifica-
tion coupled with distributed power generation in small communities with abundant biomass
resource would be the way out in future [1].

In recent years in China, the yield of domestic waste has increased every year and exceeds
400 million tonnes per year. Chinese government’s 13th five-year plan proposed that the pro-
portion of waste harmless treatment should be no less than 70% by 2020. But waste landfill
is still the primary method used to deal with waste in rural areas. Compared with landfill,
gasification has advantages of lower environmental impacts and does not consume land
resource. When contrasting gasification with incineration, the gasification technology has
better quality of gaseous emissions with much lower capital input, which makes gasifica-
tion more suitable for distributed deployment in rural area. Therefore, there will be a great
demand for deployment of waste gasification treatment plants in Chinese rural areas, and
more and more people are now focusing on the development of more efficient small-scale
gasifiers with capacity under 300 tonne/day. The relevant equipment has also been deployed
in Iran, Thailand, Burma and Laos. However, several technical barriers are still there such as
effective removal of tar with low cost, environmental influence, accuracy control of gasifier
inner temperature, solidification of fly ash and so on.

Therefore, this chapter introduces both technological and logistics challenges of biomass gas-
ification via introducing biomass characters and gasifier technologies. The details of tar mini-
mization and socio-environmental impacts of biomass gasification are also presented as main
contents to help understand the primary barriers for the deployment of biomass gasification.
 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 5
http://dx.doi.org/10.5772/intechopen.74191

2. Biomass characteristics and general conversion

2.1. Composition of biomass and its common characteristics

Biomass includes all the living or recently living organisms, like land plants, grasses, water-
based vegetation and manures [2], and these organisms consist of a number of major elements
such as C, H, O, N, P and S. The classification of biomass into different categories is based on
their properties. One feasible way is based on the appearances and the growth environment
of biomass: woody plants, herbaceous plants/grasses, aquatic plants, manures and wastes [2].
Biomass could also be divided into two types: low moisture content and high moisture con-
tent. The low moisture content biomass can be used in thermo-chemical processes (i.e., gasifi-
cation, combustion and pyrolysis), while the high moisture content plants are more suitable to
be used in some wet processing technologies (i.e., fermentation and anaerobic digestion) [3].
Such high moisture contents would consume a large amount of energy for the drying process
if employed as resources for thermo-chemical processing.
Biomass is derived from solar energy via photosynthesis. Under a good illumination condi-
tion, carbon dioxide in the atmosphere can be converted into organic materials or, in another
way, the solar energy is stored as chemical energy, which existed as chemical bonds in the
organisms [4]. The said chemical energy is released when these bonds are broken either via
thermo-chemical or wet processing. This is an ongoing energy transfer from the sun and hence
the sustainability of biomass resource could be ensured. As we have known, the total energy
captured annually in biomass is more than that of the annual energy consumption globally
[5]. On the other hand, biomass is clean as it is carbon neutral. On the view of carbon network,
the net emission of carbon dioxide into the environment during the harvesting of energy from
biomass is zero. The final products of conversion of biomass (CO2 and H2O) are originally
absorbed into the plants from the atmosphere during photosynthesis. The conversion of bio-
mass also has less harmful releases such as NOx and SOx compared with fossil fuels [6].
However, the characters of biomass also create many barriers during its actual application.
On the aspect of species diversity, biomass usually does not behave as steady as fossil fuels,
which causes a lot of difficulty during project planning stage including gasifier type, plant size
and the way of energy output. On the other hand, the varieties of biomass resource also lead
to different heating values and moisture contents. Compared with other energy carriers, bio-
mass has much lower heating values. Taking wood and wheat straw as examples, their lower
heating values are only 18.6 and 17.3 MJ/kg, respectively, while the lower heating value of
coal is as high as 23–28 MJ/kg [2, 7]. The reason for this disparity is that the oxygen content of
biomass carbohydrates is very high while the combustible elements such as C and H are low.
In addition, the intrinsic moisture content in biomass is also very high, which requires more
energy for drying before further processes take place [3]. Hence, use of biomass requires the
complexity in material handling, pre-treatment and the design of processing facilities [3]. For
the purpose of transportation and collection, biomass is unlike any other renewable resources
(solar, wind, hydropower) where it is able to be stored directly and transported somewhere
else. However, biomass is highly dispersed in regional distribution and the low volumetric of
biomass makes it a bit more difficult for the collection and transportation. Therefore, small-
scale gasification unit operated in small communities with abundant biomass resource or
domestic waste would be the way out in future.
6 Gasification for Low-grade Feedstock

2.2. General conversion technologies of biomass except gasification

For the utilization purpose, the conversion technologies of biomass could be classified in three
categories: mechanical extraction; thermo-chemical conversion; and biological conversion,
as illustrated in Figure 1 [3, 8]. Among them, direct combustion, gasification and pyrolysis
are considered as the thermo-chemical processes; fermentation and anaerobic digestion are
regarded as biological conversion.

2.2.1. Direct combustion

The direct combustion of biomass is widely applied in small-scale cooking and domestic
heating by converting chemical energy stored in biomass into heat [9]. In modern industrial
technology, combustion is also employed in large-scale applications to produce mechanical
power and electricity with the aid of boilers, steam turbines and turbo-generators. The tem-
perature range of biomass combustion is within 800–1000 ° C. Materials with the moisture con-
tent higher than 50 wt% are not suitable for combustion processes [3]. The net efficiency of
electricity generation from biomass combustion varies between 20 and 40% [8]. The efficiency
could be improved either by scaling up the system to over 100 MWe or co-firing with coal
(<10 wt% by weight) [10].

2.2.2. Pyrolysis

Pyrolysis is a thermo-chemical process, in which biomass decomposes into fuel gas, bio-oil
and solid char in the absence of oxygen. The selectivity leading to different types of products
could be controlled by manipulating the operating conditions (temperature and residence
time). Low temperatures (<500 ° C) and long residence time favor the production of solid char

Figure 1. The main processes for the biomass conversion technologies [3].
 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 7
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(up to 35 wt% yield), while high temperatures (700–1100 ° C) and short reaction time favor the
production of gases (up to 80 wt% yield) [11]. Bio-oil production is normally favored at 500 ° C,
with very short retention time (<1 s) [12].

2.2.3. Fermentation

Fermentation is a bio-chemical process which is used for the production of about 80% of
the world’s ethanol [13]. The main process of fermentation involves using microorganisms
to convert sugars into ethanol under a warm and wet environment. The sugar is typically
obtained from the mechanical handling (crushing and mixing with water) of sugar-rich
crops, such as sugar cane and sugar beet. However, the high cost of sugar-rich crops has
diminished its proportion of utilization in fermentation. The starch-based biomass is also
commonly used for ethanol production. However, it requires an extra step to convert starch
into sugar by enzymatic reactions.

2.2.4. Anaerobic digestion

Anaerobic digestion involves using anaerobic microorganisms to convert biomass into bio-
gas (CH4 and CO2 as the main gaseous products) by means of decomposition. Under the
anaerobic environment, the organic material in biomass is decomposed into usable-sized
molecules, such as sugar, as the first step. The sugar molecules is then converted into organic
acids and further decomposed to CH4 gas. This process has been proven as a commercially
feasible technology and is widely applied in the rural areas of China.

3. Technologies of biomass gasification

Gasification process converts biomass, a low-energy density material, into a gaseous product
(LHV at 4–11 MJ/N/m3), which is a mixture of CO, H2, CH4 and CO2 [10]. Gasification is a par-
tial oxidation process and it is commonly operated at 800–900 ° C for biomass gasification [2].
In some cases, steam is also used as the gasification agents. The gaseous products from the
gasifier can be utilized in gas engines or gas turbines for the generation of electricity. In terms
of economics, it has also been proven that the performance of a biomass gasification plant
with a combined cycle gas turbine (CCGT) is comparable to that of a conventional coal power
plant [7], if not better.

3.1. Types of gasifiers

The gasifier, as the principle component of a gasification plant, actually provides a space for
biomass and gasification agent being mixed to a certain extent, in some cases with catalysts
or additives [14]. The different selection of gasifiers is actually responsible for keeping steady
the production of syngas regarding the variations of biomass. Literature shows that gasifiers
could be categorized into three main types: fixed bed gasifiers, fluidized gasifiers and the
entrained flow gasifiers [15].
8 Gasification for Low-grade Feedstock

3.1.1. Fixed bed gasifier

Fixed bed gasifiers is the traditional approach applied for biomass gasification and generally
operated around 1000 ° C. An alternative name for the fixed bed gasifier is “moving bed reac-
tor”. This is due to the movement of the biomass material in the main flow direction with very
slow flowrate. The fixed bed gasifiers could be principally classified as updraft (countercur-
rent) and downdraft (co-current) due to the different airflow direction [14].
In an updraft gasifier (shown in Figure 2), the biomass material is fed from the top of the reac-
tor, while the gasification agent enters from the bottom. The gasification agent flows through
the bed of ash and biomass. The gas generated is exhausted through the top. For the reaction,
the gasification agent meets the bottom char at first and achieves a complete combustion and
raises temperature to c.a. 1000 ° C with production of H2O and CO2. This hot gas dries the
incoming biomass near the top of the vessel and provides heat for pyrolysis of the descending
biomass as well as percolates through the unreacted char bed to produce H2 and CO [15]. In
this gasification system, the product gas is withdrawn from the low temperature zone; thus,
the product would be contaminated with significant amount of tars. If the product is used
for further downstream applications like fuel in combustion engine electricity generator, a
set of cleaning processes for tar removal is essential. However, the cleaning processes require
intensive operation and establishment; therefore, the application of updraft gasification is not
suitable for internal combustion engines [1].

Figure 2. Schematic of updraft gasifier [16].

 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 9
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For the downdraft gasifier (shown in Figure 3), both biomass and gasification agent flow into
the vessel from the top. At the “throated” area, where air or O2 is fed into system with homo-
geneously distribution. The temperature could rise to around 1200–1400 ° C, which leads to
both combustion and pyrolysis of the fuel. The produced hot gases will then be reduced to H2
and CO as the main components after passing the hot char bed and will leave the gasifier unit
at temperatures of about 900–1000 ° C. The tar content of the product gas is lower than that of
the updraft gasifier, but the particulate content of the gas is higher [16]. Hence, the downdraft
gasifier is suitable for downstream applications like internal combustion engines electricity
generator. However, the product is withdrawn at a relatively high temperature; it needs to be
cooled to acceptable range before further usage.

3.1.2. Fluidized gasifier

In the fluidized gasifier, the gasification agent enters the bed at a relatively fast rate from
the bottom of the vessel and exits from the top. This kind of gasification features uniform
temperature distribution in the bed zone. The consistency of temperature is obtained by
the application of air-fluidized bed material, which ensured the intimate mixing of fuel,
hot combustion gas and bed material. Currently, three main types of fluidized gasifiers are
widely used [15], bubbling fluidized bed (BFB), circulating fluidized bed (CFB) and dual
fluidized bed (DFB).

Figure 3. Schematic of downdraft gasifier [16].

10 Gasification for Low-grade Feedstock

BFB gasifier applies inlet from the bottom and moves the bed of fine-grained materials. The
bed temperature is maintained at 700–900 ° C by manipulating the ratio of fed biomass and
gasification agent [16]. The flowrate of gasification agent is set to be slightly greater than the
minimum velocity of fluidization of the bed material. The biomass is decomposed into char
and gas products with a low tar percentage.
The CFB gasifier consists of two principle units: the gasifier unit and the circulation unit, as
shown in Figure 4. The bed material and char in this type of gasifier is circulated between the
reaction chamber and the cyclone separator, where ash and hot gas could be separated. The bed
material is fully fluidized and leaves from the first unit, and then it is sent back by the second
unit. The solids are moving in the solid circulation loop in greater extent of fluidization with
higher residence time. Moreover, its operation pressure is also relatively higher.
Dual fluidized bed (DFB) gasifiers consist of two separated fluidized beds which are used
for pyrolysis process and combustion process [14]. The first bed is operated as a pyrolysis
reactor and it is heated by the second reactor with hot circulated bed material. The second
reactor provides heat by burning char provided from the first reactor. The bed material
plays an important role as a heat transfer medium, which prevents the dilution of the hot
gas product.

3.1.3. Entrained flow gasifier

Entrained flow gasifiers are generally classified into two types: top-fed gasifier and side-fed
gasifier (shown in Figure 5), which is according to how and where the fuel and gasifica-
tion agent is fed. This type of gasifier is suitable for integrated gasification combined cycle
(IGCC) plants. It is extensively applied in large-scale gasification and is widely employed for
coal, biomass and refinery residues. The gasification temperature of this kind of gasifier could
reach 1400 ° C with a pressure range of 20–70 bar [14]. This high temperature could accelerate
tar cracking and mitigate severe tar issue of biomass gasification. However, this kind of high

Figure 4. Schematic diagram of circulating fluidized bed gasifier (CFB) [17].

 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 11
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Figure 5. Schematic diagram of an entrained flow gasifier (side-fed) [17].

temperature gasification requires a finely fed biomass material (<0.1–0.4 mm), which makes
this process unsuitable for most biomass materials (such as wood). Therefore, this process is
not considered in detail.

3.2. Tar removal

Tar is a major inherent problem in biomass gasification; it can cause a lot of issues such as
equipment blockages, lower system efficiency, poor quality gas output and increased main-
tenance. Tar consists of a group of very complicated mixtures with more than 200 compo-
nents. Several key components include benzene, toluene, single-ring aromatic hydrocarbon,
naphthalene and so on. The formation of tar was due to lower temperature of gasification. It
was confirmed that increased temperature of gasification could reduce the content of tar in
the outflow and it was believed that higher temperature can promote the cracking of tar [18].
Currently, there are a lot of methods that could be employed for tar minimization, and they
can be divided into two categories depending on where the removal technology is applied.
Firstly, tar could be removed inside the gasifier by choosing an appropriate operation param-
eter or using a catalyst. Previous research indicates that both particle size and surface area-
volume ratio of loading feedstock have a significant effect on tar yields [19, 20]. It showed that
the gasification of pine saw dust only produced 0.4 wt% of tar at 700 ° C when the particle size
was smaller than 75 micron. While if particle size increased to the range of 600–1000 micron,
the tar yield would be higher than 10 wt% even at 900 ° C. From the view of thermal kinetics,
the gasification of larger size of particles needs to overcome greater resistance of thermal con-
ductivity; in other words, it needs more time to complete heat transfer and the devolatiliza-
tion of biomass materials. On the other hand, small particle size also can contribute to a fast
diffusion of the gasification agent and shorten time duration of the whole process. However,
12 Gasification for Low-grade Feedstock

the small size of feedstock particle required much more energy input during the biomass
pre-preparation process. In addition, it is also effective by applying an optimal design of gas-
ification reactor. A collaborative project between Switzerland and India demonstrated that an
open-top fixed bed would produce much less tar and particulates than a closed-top fixed bed
[15]. The reason behind this is that the open-top fixed bed could introduce dual air from the
top and nozzles actually increase the residence time for degrading tar.
Secondly, in many processes, tar is removed as a downstream step after gasification, includ-
ing mechanical method, thermal cracking and catalysis. The details of some common tech-
nologies have been listed in Table 1. Wet gas cleaning method has been accepted at an early
stage. Its equipment investment is relatively low and the operation is also easy to handle. But
this technology would also create a lot of waste water and bring serious environmental issues.
Therefore, dry gas cleaning method becomes more widespread via various types of filters,
rotating particle separators and dry cyclones. Although the dry method avoids waste water
issues, its efficiency of tar removal is not good enough if compared with wet method. On the
other hand, the replacement, renewal or disposal of filter materials reduces the financial effec-
tiveness of the entire gasification system. This similar situation could also be applied to ther-
mal cracking method and higher operation temperature requires much more energy input.

In the recent two decades, catalytic cracking has attracted more and more attention and has
already become the central branch of research. Catalytic cracking is more like a downstream
catalytic reforming unit and could easily degrade comparative stable tar to a significant
extent. The previous research indicated that the catalytic cracking unit could promote gas
yield by 10: 20 vol% and increase the heating value by c.a. 15% [23]. Ni-based catalyst is
applied most widely and especially preferred for hydrogen or syngas production. Nickel has
a very good catalytic activity and a preferable price advantage. While the application of Ni
catalysts needs to avoid extremely high heavy-tar content flue gas, which will form a seri-
ous carbon deposition over the catalyst surface and lead to a quick deactivation. The other
transition metal-based catalysts, such as co, Fe and cu, also have similar issues. Thus, some
applications used the two-stage catalytic reforming process: the first stage used dolomite to

Method Technique used Details/examples

Wet gas cleaning Usage of mechanical device Electrostatic precipitator, wet cyclone, wet scrubber
[21] or equipment

Dry gas cleaning Usage of mechanical device Cyclone, rotary partial separator, fabric filter, ceramic filter,
[21] or equipment activated carbon adsorber, sand filter

Thermal Application of high Maximum tar destruction was found at 1250 ° C and 0.5 s
cracking [21, 22] temperature with long
residence time

Catalytic Usage of appropriate catalyst Tar cracking catalysts are divided into five major groups, namely
cracking [21] Ni-based, non-Ni-based, alkali metal-based, acid catalysts, basic
catalysts and activated carbon-based catalysts

Table 1. Post-gasification tar removal methods [15].

 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 13
http://dx.doi.org/10.5772/intechopen.74191

reduce the concentration of tar to a certain level and then the second stage employed transi-
tion metal-based catalysts bed for near-completed removal of tar. But this kind of two-stage
reforming process would increase operational cost clearly. In the research scale, some people
applied noble metal catalysts and achieved highly catalytic activity as well as better carbon-
resistant ability. However, high cost and low accessibility still restrain the wide utilization of
noble metal-based catalysts before the technical breakthrough of catalyst regeneration. Alkali
metal catalyst is an alternative with good catalytic performance and also exhibits outstand-
ing coke resistance. It is due to this that alkali metal could suppress directly decomposition
of hydrocarbon by avoiding quick adsorption of tar components. But alkali metal evaporates
under high temperature gasification condition. In many practical process, biomass ash has
been reused as an alkali catalyst because most biomass contains abundant alkali metal ele-
ments and it is believed that this type of natural catalyst with properties of low cost and
disposability should attract special attention

In the future, the development of novel and economic catalysts is still a promising option for
tar elimination. At this stage, the biggest barrier for the catalyst development is the unclear
mechanism of complex tar reformation. Therefore, employing model tar components for the
study of coke formation mechanism is still very important and will be an effective way out.
For the catalyst synthesis, composite catalysts with different components should be consid-
ered. It is also favored that if the developed catalyst could be applied under a low temperature
condition (400–600 ° C), it will minimize cost effectively in a practical operation by using waste
heat. In addition, the practical application of the catalyst also requires solving many scale-up
issues, such as variation of temperature and pressure, impurities, fly ash and catalyst collapse

4. Socio-environmental impact

Biomass gasification could exploit an abundant variety of waste materials as feedstock such as
agricultural residues and food waste. It actually achieves resource recovery and mitigates CO2
emission as an environmental benefit. However, power generation from biomass gasification
poses several key hazards and socio-environmental impacts.

4.1. Health and safety hazard

One of the major risks is the potential emission of toxic producer gas and particulates. The
production of CO, SOx, NOx and volatile organics involves incomplete combustion and oxi-
dation of trace elements in feedstock [24]. As one of the most dangerous constituent, CO can
permeate into human blood system and combine with hemoglobin to stop oxygen adsorption
and distribution. Long-term exposure to CO causes asthma, lung inflammation, schizophre-
nia and cardiac defects. Toxic gases like SOx, NOx and volatile organics could also destruct
inhalation, ingestion and dermal system of human [25]. Hence, the entire gasification process
should prevent leakage and an efficient gas clean-up system is essential. In recent years, the
hazard of particles emission (PM2.5) attracts public attention increasingly, due to its carci-
nogenicity. PM2.5 particles can adsorb many soluble organic compounds including alkanes,
14 Gasification for Low-grade Feedstock

carboxylic acid and aromatic compounds, which will damage human organs like lung and
liver [26]. For control of these particles’ emission, an efficient gas clean-up system with con-
ditioning unit is necessary, as well as avoiding insufficient combustion and gasification. In
addition, ashes and condensate from biomass gasification also contribute to environmental
problems if they are not disposed properly. Especially the toxic condensate with high content
of tar is very difficult to deal with and has higher risk of hazards.

Besides the risk of health hazards and environment, gasification is also confronted with risk
of fire and explosion. Because the gasification system is normally operated at relatively high
temperature and pressure, it also produces flammable gas mixture with a great portion of
hydrogen gas. However, explosion is not easy to be created even air leakage into the gasifica-
tion system, which could raise a partial combustion. This will only lead to lower quality and
higher temperature of producer gas [1], unless there is a large amount of air which enters with
feedstock from the feeding system or massive leakage of flammable outlet gas occurs.

4.2. Social impact

The development of bioenergy will need a lot of land for energy-growing crops. This require-
ment will clash with other applications of farmland, like food and other cash crops. The com-
petition with food agriculture must be intensive. The food shortage is still a big global issue
nowadays. According to the data of World Hunger Education Service, the world’s hungry
population was 925 million in 2010. Besides this, the world population is still growing by rate
of 1.2%. The natural disasters and climate change also affect agriculture. These three factors
will decide that the demand of the farmland in the future will expand. Thus, transferring
farmland for energy crop planting in a large scale would be difficult, especially in Europe.

4.3. Ethical issues

The bioethics report by Nuffield council points out that deployment of bioenergy should
not violate the human right which is reflected in the Universal Declaration of Human Right
(UDHR). In the UDHR, it states that every people can share and enjoy the protection of the
moral and the any product from any scientific, literary or artistic which is owed by them.
There are a lot of ethical issues referring bioenergy, like human rights, solidarity and sustain-
ability. Biofuel production application will require land use, water supply and labor from
local community. Destruction to the land and local ecosystem cannot be avoided. Also, land
displaced for energy crops will not only bring food price increases; some local residents may
face migration. All these could be regarded as the actions, which violate the human rights of
citizens and non-citizens.

5. Conclusion

The commercialization of biomass gasification is still at the early stage of development and
leaves a lot to be desired on the technology aspect. In particular, large-scale utilization of
biomass still needs to overcome the challenge of biomass collection and transportation, due
 Biomass Gasification: An Overview of Technological Barriers and Socio-Environmental Impact 15
http://dx.doi.org/10.5772/intechopen.74191

to its low energy density. However, in some small communities, with large amount of local
biomass materials, using biomass to replace polluting fossil fuels is a competitive way for
providing reliable and clean power and heat.
This chapter provides the current technique status and development condition in China. It
concludes that the gasification of biomass waste with distributed power generation would
be a potential market. The properties of biomass feedstock have been analyzed and both
advantage and disadvantage of biomass utilization were pointed out. Consequently, highly
dispersed property and the low volumetric of biomass limit its large-scale application. Apart
from that, this chapter also detailed some common types of gasifiers, except some emerg-
ing technologies, for meeting special requirements such as supercritical water gasification
(SCWG) for wet biomass and plasma gasification for toxic organic waste. The tar issue, one of
the most baffling problems in biomass gasification, is introduced briefly as well as its removal
technologies. In our view, the socio-environmental impact is not the primary factor for restric-
tion of biomass gasification development, while an objective financial return can actually
attract investors and accelerate commercialization; in the meantime, it will also contribute to
other technical breakthroughs.

Author details

Xiang Luo1,2*, Tao Wu1,2, Kaiqi Shi1,2, Mingxuan Song3 and Yusen Rao3
*Address all correspondence to: [email protected]
1 A Key Laboratory of Clean Energy Conversion Technologies, The University of
Nottingham Ningbo China, Ningbo, China
2 New Materials Institute, The University of Nottingham Ningbo China, Ningbo, China
3 Department of Chemical and Environmental Engineering, The University of Nottingham,
Nottingham, UK

References

[1] Asadullah M. Barriers of commercial power generation using biomass gasification gas:
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[2] McKendry P. Energy production from biomass (part 1): Overview of biomass. Biore-
source Technology. 2002;83:37-46
[3] McKendry P. Energy production from biomass (part 2): Conversion technologies. Biore-
source Technology. 2002;83:47-54
[4] Fallot A, Saint-André L, Le Maire G, Laclau J-P, Nouvellon Y, Marsden C, Bouillet J-P,
Silva T, Piketty M-G, Hamel O. Biomass sustainability, availability and productivity.
Revue de Métallurgie Paris. 2009;106:410-418
16 Gasification for Low-grade Feedstock

[5] Field CB, Behrenfeld MJ, Randerson JT, Falkowski P. Primary production of the bio-
sphere: Integrating terrestrial and oceanic components. Science. 1998;281:237-240

[6] Gan M, Fan X, Chen X, Ji Z, Lv W, Wang Y, Yu Z, Jiang T. Reduction of pollutant emis-

sion in iron ore sintering process by applying biomass fuels. ISIJ International. 2012;
52:1574-1578
[7] Demirbas A. Combustion characteristics of different biomass fuels. Progress in Energy
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[8] Demirbaş A. Biomass resource facilities and biomass conversion processing for fuels and
chemicals. Energy Conversion and Management. 2001;42:1357-1378
[9] Faaij A. Modern biomass conversion technologies. Mitigation and Adaptation Strategies
for Global Change. 2006;11:335-367
[10] van den Broek R, Faaij A, van Wijk A. Biomass combustion for power generation. Bio-
mass and Bioenergy. 1996;11:271-281
[11] Lan P. Investigation of Hydrogen Production from Steam Reforming of Bio-oil and
Catalytic Deactivation by Carbon Deposition, East China University of Science and
Technology, East China University of Science and Technology; 2011. pp. 121

[12] Bridgwater AV, Meier D, Radlein D. An overview of fast pyrolysis of biomass. Organic
Geochemistry. 1999;30:1479-1493

[13] Lin Y, Tanaka S. Ethanol fermentation from biomass resources: Current state and pros-
pects. Applied Microbiology and Biotechnology. 2006;69:627-642

[14] Ruiz JA, Juárez MC, Morales MP, Muñoz P, Mendívil MA. Biomass gasification for elec-
tricity generation: Review of current technology barriers. Renewable and Sustainable
Energy Reviews. 2013;18:174-183
[15] Sikarwar VS, Zhao M, Clough P, Yao J, Zhong X, Memon MZ, Shah N, Anthony EJ,
Fennell PS. An overview of advances in biomass gasification. Energy & Environmental
Science. 2016;9:2939-2977

[16] McKendry P. Energy production from biomass (part 3): Gasification technologies. Biore-
source Technology. 2002;83:55-63

[17] Basu P. Biomass Gasification and Pyrolysis. Boston: Academic Press; 2010
[18] Maschio G, Lucchesi A, Stoppato G. Production of syngas from biomass. Bioresource
Technology. 1994;48:119-126
[19] Luo S, Xiao B, Hu Z, Liu S, Guo X, He M. Hydrogen-rich gas from catalytic steam gasifi-
cation of biomass in a fixed bed reactor: Influence of temperature and steam on gasifica-
tion performance. International Journal of Hydrogen Energy. 2009;34:2191-2194

[20] Mahapatra S, Dasappa S. Influence of surface area to volume ratio of fuel particles on
gasification process in a fixed bed. Energy for Sustainable Development. 2014;19:122-129
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[21] Anis S, Zainal ZA. Tar reduction in biomass producer gas via mechanical, catalytic
and thermal methods: A review. Renewable and Sustainable Energy Reviews. 2011;
15:2355-2377
[22] Fagbemi L, Khezami L, Capart R. Pyrolysis products from different biomasses: Appli-
cation to the thermal cracking of tar. Applied Energy. 2001;69:293-306
[23] Corella J, Orío A, Aznar P. Biomass gasification with air in fluidized bed: Reforming of
the gas composition with commercial steam reforming catalysts. Industrial and Engi-
neering Chemistry Research. 1998;37:4617-4624

[24] San Miguel G, Domínguez MP, Hernández M, Sanz-Pérez F. Characterization and poten-
tial applications of solid particles produced at a biomass gasification plant. Biomass and
Bioenergy. 2012;47:134-144
[25] Kampa M, Castanas E. Human health effects of air pollution. Environmental Pollution.
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[26] Lewtas J. Air pollution combustion emissions: Characterization of causative agents and
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Research/Reviews in Mutation Research. 2007;636:95-133
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 Chapter 7

Biomass Gasification: A Review of Its Technology, Gas

CleaningGasification:
Biomass Applications,Aand TotalofSystem
Review Life Cycle Gas
Its Technology,
Analysis Applications, and Total System Life Cycle
Cleaning
Analysis
Kenji Koido and Takahiro Iwasaki
Kenji Koido and Takahiro Iwasaki
Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.70727

Abstract
Gasification technology presents one option for energy-conversion technique from woody
biomass contaminated by radionuclides released in March 2011 during the Fukushima
Dai-ichi Nuclear Power Plant accident. The gasification process converts carbonaceous
materials into combustible gases, carbon dioxide, and residues. Owing to their small-
scale distributed configuration, woody biomass gasification plants are suitable for gasify-
ing Japan’s biomass and have been installed increasingly in Japan recently. This chapter
reviews current trends of gasification and life cycle assessment (LCA) of total systems,
including gas cleaning.

Keywords: biomass gasification, gas cleaning, desulphurisation, radioactive materials,

life cycle assessment

1. Introduction

Lignin is a crosslinked macromolecular material based on a phenylpropanoid monomer

structure. Vascular plant species such as fern-related plants, gymnosperms, and angiosperms
have lignin structures. Woody plants such as softwoods and hardwoods are composed,
respectively, of 25–35% and 20–25%. Recently, small-scale woody biomass power generation
plants have been installed increasingly in Japan. Such plants are suitable for gasifying Japan’s
biomass because of their small-scale, distributed characteristics.
To utilise small-scale biomass more effectively, biomass plants must be installed near energy
source and demand sites in order to shorten transport distances. This is especially effective
for small-scale woody biomass plants. Here small scale is defined as a plant scale of at most

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
© 2018 The
Attribution Author(s).
License Licensee InTech. This chapter is distributedwhich
(http://creativecommons.org/licenses/by/3.0), underpermits
the terms of the Creative
unrestricted Commons
use, distribution,
Attribution
and License
reproduction (http://creativecommons.org/licenses/by/3.0),
in any medium, provided the original work is properlywhich permits unrestricted use,
cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
162 Lignin - Trends and Applications

2 MWe. Power generation in such small-scale plants requires biomass gasification tech-
nology in order to obtain higher thermal efficiency. Gasification is a process that converts
carbonaceous materials into carbon monoxide, hydrogen, carbon dioxide, and gaseous
hydrocarbons (producer gas). Producer gas can be supplied as fuel to internal combustion
engines and power generators. To maximise the efficiency of woody biomass conversion,
producer gas should be utilised not only for power generation but also for thermal produc-
tion from the producer gas’ sensible heat. Cogeneration system for heat and power produc-
tion is called combined heat and power (CHP).

Recently, many kinds of biomass gasification combined heat and power (BGCHP) systems
have been developed (mainly in Europe). These micro/small-scale CHP systems can be con-
nected and integrated to achieve an appropriate plant scale according to the biomass supply
and heat and power demands. Further description of BGCHP is presented in section 2.4.

Woody biomass in Fukushima was contaminated by radionuclides released between 12 and

31 March 2011 due to the Fukushima Dai-ichi Nuclear Power Plant accident. To safely utilise
the contaminated woody biomass in Fukushima as biomass gasification (BG) fuel, the radio-
activity of products and by-products such as offgas and ashes in ash bins and on filters must
be investigated.

This chapter reviews current trends of gasification and life cycle assessment (LCA) of total
systems, including gas cleaning. Previously, there have been no reviews of small-scale gas-
ification process for hydrogen production and CHP and no critical review of LCA of BG pro-
cesses. Gas cleaning is one of the most important processes in BG systems for controlling
contaminants in producer gases and preserving the catalysts of fuel cells and gas engines.

2. Gasification technology

A biomass gasifier is comprised of four reaction zones, i.e. drying, pyrolysis, combustion,
and reduction. The produced gas (syngas) contains impurities to be cleaned utilising a bag
filter, activated carbon, scrubber, etc. This chapter describes the fates of two contaminants,
radionuclides and sulphur, during the gasification process. The radioactivity of caesium-137
(137Cs) and caesium-134 (134Cs) in fly ash over a bag filter was observed using a germanium
semiconductor detector. The fate of sulphur was also reviewed because sulphur often triggers
fuel cell catalyst poisoning and gas engine erosion. The LCA of a total system based on the
energy profit ratio and environmental impact is then reviewed.

2.1. Biomass feedstock

Biomass feedstocks are classified based on several factors: moisture content, material, and form,
as presented in Table 1. Biomass is broadly divided into three groups: dry, wet, and other. Dry
biomass is classified as woody or herbaceous and wet biomass as sludge/excreta, common
food, or other. Each classification has three sub-categories: waste, unutilised, and produced.
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 163
http://dx.doi.org/10.5772/intechopen.70727

Moisture Classification Wastes Unutilised Produced

Dry Woody Construction wastes, Forest thinnings, Short-rotation woody crops
Timber offcuts Remaining forest (eucalyptus, willow, etc.)
timbers, Damaged
trees

Herbaceous Crop residues (rice Grasses (Napier grass,

/ wheat straw, rice sorghum, Miscanthus etc.)
husk)

Wet Sludge /Excreta Sewage sludge,

Livestock excreta

Common food Food-processing

wastes, Kitchen wastes

Other Other Molasses, Waste Landfill gas Cultivated maize, Cultivated

food oil sugar cane

Table 1. Classification of biomass feedstocks.

Among these, dry woody/herbaceous biomasses are used as feedstocks for BG plants in
Japan. For instance, woody biomasses contain waste woods (construction wastes and timber
offcuts) and unutilised woods (forest thinnings, remaining timbers, and damaged trees) com-
posed of cedar, cypress, pine, etc. Short-rotation woody crops (eucalyptus, willow, etc.) are
categorised as produced woods. Energy crops such as willow are expected to be cultivated in
land fallow and used as biomass because non-food-producing farmlands have been recently
abandoned in Japan [1].
For unutilised herbaceous biomass, crop residues such as rice/wheat straw and rice husks
[2] are available, while for produced herbaceous biomass, grasses such as Napier grass, sor-
ghum, and Miscanthus are usable. Above all, rice husks contain abundant silica. The ash by-
product from gasifiers has potential use in nanomaterials [3].

2.2. Gasifier

There are various kinds of gasifiers (e.g., fixed-bed, fluidised, pressurised, etc.). This chapter
describes the simplest fixed-bed gasifiers. Fixed-bed gasifiers have a long history and have
established confidence through experience with small-scale biomass gasification reactors [4].
Figure 1 schematically illustrates fixed-bed updraft and downdraft gasifiers. The flows of
biomass and producer gases are counter-current for updraft and co-current for downdraft.
The gasification reaction is comprised of four main reaction zones. Heat released during the
combustion process is used for drying, pyrolysis, and reduction processes in the gasifier.
For both gasifier types, biomass fuels are supplied into each gasifier followed by a drying
process. The dried biomass is then pyrolysed to release volatiles and gases. These products
are combusted partially or completely using air fed with heat released from the combustion
process. The gases, tars, and chars resulting after combustion are reduced in the reduction
zone. The positional relationship of these processes is shown schematically in Figure 2.
164 Lignin - Trends and Applications

Figure 1. Schematic of updraft and downdraft fixed-bed gasifiers [5].

2.3. Gasification mechanisms

Gasification proceeds through many kinds of simultaneous or consecutive complex reactions.

Reactions corresponding to each reaction zone are shown in this section. Figure 3 represents
several main reaction pathways in biomass gasification reactions. The reactions for each path-
way (or reaction zone) are presented in Table 2 based on the literature [7, 8].

2.3.1. Drying

Biomass moisture at ordinary temperatures becomes water vapour during the drying process
at about 100–250 °C. The conversion occurs owing to heat transfer between hot gases from the
oxidation and biomass in the drying zone [4]. First, the moisture on the biomass surface evap-
orates followed by inherent moisture evaporation. The vapour produced is used for reduction
reactions in the reduction zone, including the water-gas reaction.

Figure 2. Conceptual diagram of multiple steps in fixed-bed (a) updraft and (b) downdraft gasifiers [6].
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 165
http://dx.doi.org/10.5772/intechopen.70727

Figure 3. Biomass gasification pathway proposed based on Ref. [10, 11].

2.3.2. Pyrolysis

In the absence of oxygen, volatiles with weaker molecular bonds begin to be thermally decom-
posed at 200–240 °C; this continues up to 400 °C. The volatiles are vaporised to produce gases,
tars, and chars. The chars are also pyrolysed with gas production and weight loss of about 30% [9].
Pyrolysis takes place owing to heat transfer from radiation, convection, and conduction to the bio-
mass as shown in Figure 3a. The pyrolysis reactions are represented as Reaction (R1) in Table 2.

Name of reaction Chemical reaction No.

∆ H ( (kJ/mol) ∆ G ( (kJ/mol)
0 0
r 298) r 298)

Pyrolysis CxHyOz → aCO2 + bH2O + cCH4  (R1)

+ dCO + eH2 + fC2+ + char  + tar

Partial oxidation C + 0.5 O2 → CO −111 (R2)

Complete oxidation C + O2 → CO2 −394 (R3)
Steam-tar reforming CnHm + 2nH2O → (2n + m/2) H2 + nCO2 (R4)

Hydrogenating gasification C + 2H2 ↔ CH4 123.7 168.6 (R5)

Boudouard equilibrium C + CO2 ↔ 2CO 205.3 140.1 (R6)
Water-gas shift (WGS) CO + H2O ↔ CO2 + H2 −41.47 −28.5 (R7)

Heterogeneous WGS C + H2O ↔ CO + H2 130.4 89.8 (R8)

Steam reforming of methane CH4 + H2O ↔ CO + 3H2 172.6 118.4 (R9)

Dry reforming of methane CH4 + CO2 ↔ 2CO + 2H2 −74.9 −50.3 (R10)

Ethylene 2CO + 4H2 ↔ C2H4 + 2H2O −104.3 −111.6 (R11)
Ethane 2CO + 5H2 ↔ C2H6 + 2H2O −172.7 −212.7 (R12)

Propane 3CO + 7H2 ↔ C3H8 + 3H2O −165.1 −293.2 (R13)

Butane 4CO + 9H2 ↔ C4H10 + 4H2O −161.9 −376.7 (R14)
H2S formation S + H2 ⇄ H2S (R15)

H2S-COS equilibrium H2S + CO ⇄ COS + H2 (R16)

Table 2. Chemical reactions occurring in biomass gasification (gasifying agent: steam).

166 Lignin - Trends and Applications

2.3.3. Oxidation

Heat is released during the oxidation of gases and of gaseous volatiles and chars produced
in pyrolysis under supplied air. The heat is used for drying, pyrolysis, and other endo-
thermic reactions [4]. Partial oxidation (R2) and complete oxidation (R3) occur. Reaction
temperatures are around 600–900 °C for partial oxidation and around 800–1400 °C for
complete oxidation. Partial oxidation releases 111 kJ/mol of heat while complete oxidation
releases 394 kJ/mol.

2.3.4. Reduction

During the reduction process, the char and tar produced from oxidation release gases at around
600–950 °C via several reactions. The typical reactions include the heterogeneous water-gas
shift (HWGS: C + H2O → H2 + CO) and water-gas shift reaction (WGS: CO + H2O ⇆ CO2 + H2).
Via the endothermic HWGS reaction, char or tar reacts with water vapour (derived from bio-
mass and air) to produce CO and H2 at temperatures greater than 750 °C. The WGS reaction
is an exothermic reversible reaction and has an equilibrium point for CO, H2O, CO2, and H2
concentrations. The higher the reaction temperature, the greater the amount of gaseous prod-
ucts produced on the equation’s right-hand side. Reduction is a totally endothermic reaction
because the water-gas reaction is dominant.

2.4. Combined heat and power gasification

Gasification power generation systems are different in terms of gasifier type, gas cleaner for
dust/tar/hydrogen sulphide removal (as described in sections 3.2 and 3.3), heat exchanger type,
and power generator type (gas turbine, internal combustion engine, fuel cell, etc.). A BGCHP
requires seven elemental processes: (i) pretreatment, (ii) storage, (iii) gasifier, (v) gas cleaner,
(iv) gas cooler, (vi) gas engine, and (vii) power generator, as shown in Figure 4. BGCHP is a
process that cogenerates heat and power from syngas produced in the gasifier. Figure 4 shows
a simplified schematic of BGCHP. Generally, biomass power generation from direct combus-
tion has an efficiency of ca. 30% at most. However, via BGCHP, a total efficiency of ca. 85% is
attained with thermal-load-following operation.

There are many kinds of small-scale gasifiers manufactured by European companies such as
in Germany (e.g., Burkhardt [12], Spanner [13], Entrade [14], etc.), Finland (e.g., Volter [15]),
and Sweden (e.g., Cortus Energy AG [16]).

2.5. Biohydrogen production via gasification

Biohydrogen via thermochemical conversion is obtained by gasifying woody biomass fol-

lowed by a gas cleaning process. Biomass gasification typically yields producer gases such
as H2 (14–25%), CO (15–24%), CO2 (12–15%), CH4 (2.0–2.5%), H2S (<100 ppmv), and COS (50
ppmv) [6]. For H2 production, gas cleaning is required for gases other than H2. Generally, CO
is converted into H2 and CO2 with steam by a shift converter packed with nickel or nickel
oxide catalysts.
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 167
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Figure 4. Flow diagram of power generation from biomass gasification.

3. Gas cleaning

3.1. Contaminants

Contaminants in syngas generally include particulate matter, condensable hydrocarbons

(i.e. tars), sulphur compounds, nitrogen compounds, alkali metals (primarily potassium and
sodium), hydrogen chloride (HCl), and radioactive nuclides. In this review, the sulphur com-
pounds and radioactive nuclides in Fukushima, Japan are the focus.

Syngas (CO + H2) has many uses ranging from heat and/or power applications (e.g., CHP) to
many kinds of synthetic fuels and chemicals as shown in Figure 5. During production, each
contaminant triggers process inefficiencies, including not only corrosion pipe blockages but
also rapid and permanent deactivation of catalysts [17].

Figure 5. Different syngas transformation routes for synthesising fuels and other chemicals [18].
168 Lignin - Trends and Applications

Contaminant levels depend on feedstock impurities and the syngas generation method used.
The level of cleaning required may also be influenced substantially by end-use technology
and/or emission standards [17]. Table 3 shows the syngas cleaning requirements for some
typical end-use applications.

3.2. Sulphur

There are several gas cleaning technologies: absorption, adsorption, conversion, and biologi-
cal transformation. Wiheeb et al. has described the adsorption process of H2S. Table 4 pres-
ents a summary of the characteristics of sulphur removal technologies [19]. In gasification
processes, absorption and adsorption are employed well as gas/bag filter and scrubber pro-
cesses, respectively.

3.2.1. Fate of sulphur during gas cleaning over adsorbents

The fate of sulphur during the gasification of lignin slurry was investigated by Koido et al. [20]. In
their study, hydrogen sulphide removal from bio-synthesis gas over a nickel oxide catalyst sup-
ported by calcium aluminate (NiO/CaAl2O4) was investigated at high temperatures. They inves-
tigated the sulphur balance of the process at different operating temperatures (T = 750–950 °C),
moisture contents of the lignin slurry (MC = 73–90 wt%), and catalyst loadings (CL = 0.00–0.61 g-
catalyst/g-feedstock). The sulphur balance was 0.79, 0.04, 0.003, and 0.378 mmol/g-lignin for the
gas, char, water-soluble fraction, and NiO/CaAl2O4 catalyst surface, respectively.

3.3. Radionuclides

3.3.1. Introduction

Radionuclides including 134Cs and 137Cs were released into the environment after the Fukushima
Dai-ichi Nuclear Power Plant accident in March 2011. After the accident, decontamination was

Contaminants Applications

Methanol synthesis FT synthesis (μL Gas turbine (μL−1) IC engine (mg m−3)
(mg m−3) L−1)
Particulate (soot, dust, char, ash) <0.02 Not-detectable <0.03 (PM5) < 50 (PM10)

Tars (condensable) –a <0.01b — —

Tars (heteroatoms, BTX) <0.1 <1 — <100

Alkalis — <0.01 <0.024 —

Nitrogen (NH3, HCN) <0.01 <0.02 <50 —

Sulphur (H2S,COS) <1 <0.01 <20 —

Halides (primarily HCl) <0.1 <0.01 1 —

Data are not available in the original literature.

a

b
All values are at STP unless explicitly specified.

Table 3. Syngas cleaning requirements for some typical end-use applications [17].
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 169
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Classification [19] Technology [19] Characteristics [19] Reference

Absorption (wet Conventional • Absorption has been used in petroleum and Taheri
desulphurisation) absorption process gas industries to remove H2S and CO2 from et al., [21]
sour natural gas and refinery gas.
• The removal is called gas sweetening, which
involves transferring of H2S from a gaseous
phase (feed) into a liquid phase (solvent).
• The conventional process has higher sulphur
removal but requires strict pH control of
chemical concentrations and wastewater
treatment, which could cause corrosion
problems.

Membrane reactor • Membranes can be used to purify biogas. Dolejš

• Membranes are not usually used for selective et al., [22]
removal of H2S, but rather to upgrade biogas
to natural gas standards.

Adsorption (dry Carbonaceous • Activated carbon has a high specific surface Kazmierczak-
desulphurisation) adsorbents area of more than 1000 m2/g. Razna et al., [23]
• The surface area, pore volume, and surface
chemistry promote numerous catalytic
reactions.

Metal oxide adsorbents • The removal of H2S at high temperature has Abdoulmoumine
received much attention owing to its potential et al., [24]
in reducing H2S concentration to 10 ppm.
• Metal oxide: FeO, Cu2O, MnO, ZnO CoO,
NiO and MoO, alkaline earths (CaO, SrO, and
BaO), and alkalis (Li2O, K2O and Na2O).
• The process has higher thermal efficiency
through sensible heat utilisation and easy
treatment of wastewater but requires either
catalyst exchange or regeneration.

Conversion Claus process • The Claus process is used in oil and natural Ibrahim
gas refining facilities and removes H2S by et al., [25]
oxidising it to elemental sulphur.
• Removal efficiency is about 95% using two
reactors and 98% using four reactors.

Selective catalytic • The selective catalytic oxidation of H2S into Tasdemir

oxidation elemental sulphur is one of the treatment et al., [26]
methods employed for the removal of H2S
from Claus process tail gas.
• The catalytic oxidation of H2S can be
performed above or below the sulphur dew
point (180 °C).

Liquid redox sulphur • Liquid-phase oxidation systems convert Kim

recovery H2S into elemental sulphur through redox et al., [27]
reactions by electron transfer from sources
such as vanadium or iron reagents.

Biological Biological methods • Microorganisms have been used for the Tóth
transformation removal of H2S from biogas. et al., [28]
• Ideal microorganisms would have the ability
to transform H2S to elemental sulphur.

Table 4. Characteristics of each sulphur removal technology [20].

170 Lignin - Trends and Applications

implemented in resident areas, and was completed over all residential area surfaces at the end
of March 2017 [29, 30]. However, for utilisation of Fukushima’s forest resources, which are
contaminated by radioactive nuclides, utilisation of woody biomass as fuel for bioenergy pro-
duction from gasification (such as heat, power, hydrogen, etc.) in the near future is a possible
option. For this purpose, the mass balance of radionuclides must be revealed.
In particular, 137Cs is almost distributed in argilliferous soils and fallen leaves in Fukushima.
Of all the local 137Cs in 2015, 87% was distributed in soil with 10% in fallen leaves in Japanese
cedar forests, while 87% was distributed in soils with 11% in fallen leaves in Quercus serrata
forests [31]. Moreover, 3% of 137Cs was in Japanese cedar timbers (bark: 0.5%; boards: 0.4%;
branches: 0.7%; and leaves: 0.6%), while 2% of 137Cs was found in Quercus serrata timber (bark:
0.7%; boards: 0.2%; branches: 0.5%; and leaves: 0.1%) [31].
The radioactivity of gasification pellet fuel, products, and by-products was measured to clar-
ify the fate of 134Cs and 137Cs from Fukushima’s woody biomass during the biomass gasifica-
tion process.

3.3.2. Material and methods

The measured samples were woody pellet fuel, gasification residue in ash bins (main ash),
soot on ash filters (fly ash), and exhaust gas, which are produced from woody BGCHP sys-
tems (E3 unit, Entrade Energy) at the Spa Resort Abukuma in Nishigo village, Fukushima.
The woody pellets are comprised of a mixture of Japanese cedar and Quercus serrata obtained
from the Yamizo Mountains. Using these pellets, the radioactivity of products/by-products
for each BGCHP process was observed. The exhaust gas was filtered by means of a high-
volume air sampler (Shibata Scientific Technology Ltd., HV-500RD) for 30 min at suction flow
rate of 500 L/min.
A germanium semiconductor detector (CANBERRA GC4020) was used to detect the radio-
activity arising from radionuclides such as 134Cs and 137Cs. To minimise measurement errors,
each measurement was taken over 3 h for the pellet fuels, the gasification residues, and the
soot on filters, while 12 h for the filter of high-volume air sampler. Each radioactivity concen-
tration was calculated by dividing the measured radioactivity by the sample mass/volume.
The solid samples were placed into a vessel (100 mL) and measured.

3.3.3. Results and discussion

For 137Cs, the radioactivity levels of solid samples were 20.6 Bq/kg (standard error, SE: 1.01 Bq/kg)
for the woody pellets, 1333 Bq/kg (SE = 10.4 Bq/kg) for residue, and 5432 Bq/kg for soot from
bag filters as presented in Table 5. The offgas radioactivity was not detectable when the limit
of detection (LOD) was 0.002 Bq/m3. All of the by-products were smaller than the criterion.
For 134Cs, the solid sample radioactivity levels were less than 4.10 Bq/kg for the woody pellets,
207 Bq/kg (SE = 7.58 Bq/kg) for residue, and 849 Bq/kg for soot from bag filters as presented in
Table 5. The offgas radioactivity was not detectable. All of the by-products were smaller than
the criterion. In this study, the biomass gasification plant was capable of keeping the radioac-
tive nuclides (in the residue and the filters) within the plant. However, radionuclides should
be monitored periodically.
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 171
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Sample 137
Cs 134
Cs Sample amount

Mean SE a
LOD b
Mean SE a
LOD b

Woody pellet (Bq/kg) 20.6 1.01 3.50 < 4.10 na 3.55 70.5 g

Residue (Bq/kg) 1333 10.4 15.0 207 7.58 15.4 39.6 g

Bag filter (Bq/kg) 5432 na 43.0 849 na 46.8 11.6 g

Offgas (Bq/m3) nd na 0.002 nd na 0.003 14.9 m3

SE = standard error.
a

b
LOD = limit of detection.
na = not available.
nd = not detectable.

Table 5. Radioactivity levels in the E3 biomass gasification process.

4. Life cycle assessment of the biomass gasification process

Life cycle assessment (LCA) is a methodology that examines products and services “from
cradle to grave” with a view to understanding system-wide environmental impacts. A cradle-
to-grave LCA study of a product considers all life cycle stages from extraction or primary pro-
duction of materials and fuels (‘cradle’) through production and use of the product to its final
disposal (‘grave’). The framework has been standardised by the International Organisation as
ISO 14,044:2006 [32].
Recent studies concerning biomass gasification are summarised in Table 6. Recent LCA stud-
ies concerning biomass gasification are categorised into four groups: (i) biomass-based hydro-
gen (bio-H2) production [33–38], (ii) biomass gasification combined heat and power (CHP)
[39–44], (iii) other energy systems [45–48], and (iv) dynamic LCA [49]. This chapter covers the
review of the LCA studies about biomass gasification.

4.1. Biomass gasification for hydrogen production

To evaluate the environmental performance of H2 production via indirect gasification of

short-rotation poplar, a LCA was implemented using process simulation for normal BG pro-
cesses [33] and for BG with CO2 capture by pressure swing adsorption [34]. From a life-cycle
perspective, H2 from poplar gasification generally arose as a good alternative to conventional,
fossil-derived H2 produced via steam methane reforming.
Moreno and Dufour [35] examined the environmental feasibility of four Spanish lignocellu-
losic wastes (vine and almond pruning, and forest wastes coming from pine and eucalyptus
plantation) for the production of H2 through gasification via LCA methodology using global
warming potential, acidification, eutrophication and the gross energy necessary for the pro-
duction of 1 Nm3 of hydrogen as impact categories.
Kalinci et al. [36] performed LCA for stages from biomass production to the use of the pro-
duced hydrogen in proton exchange membrane fuel cell vehicles. Two different gasification
 172
Lignin - Trends and Applications
Study Methodology Economic Environmental impact category
impact
Location FU System Products EC AC EP GWP HT LU OD PO RC WC ET PM IR
boundary
Susmozas et al. 1 kg of H2 produced from the Cradle-to- Bio-H2 from BG with X X X X X X X
[33] plant with 99.9 vol% purity gate CCS

Susmozas et al. EU 1 kg of H2 produced from the Cradle-to- Bio-H2 from indirect X X X X X X X

[34] plant with 99.9 vol% purity gate BG with CO2 capture

Moreno and Cradle-to- H2, CO2, other X X X X

Dufour [35] gate emissions, wastes

Kalinci et al. Cradle-to- Bio-H2 X X

[36] gate

Iribarren et al. 1 m3 stp of purified H2 Cradle-to- Bio-H2 X X X X X X X

[37] gate

El-Emam, et al. 1 TJ of produced energy Cradle-to- Bio-H2 X

[38] gate

Elsner et al. Poland Cradle-to- CHP X

[39] gate

Adams and UK 1 MJ (or kWh) of energy Cradle-to- Small-scale BG CHP X X X X X X X

McManus [40] produced gate

Patuzzi et al. South- Thermal efficiencies Cradle-to- Small-scale BG CHP X

[41] Tyrol, Italy gate

Oreggioni et al. EU Cradle-to- Small-scale BG CHP X X X X

[42] gate

Klavina et al. Latvia 1 kg of untreated forest Cradle-to- Small-scale BG CHP X X X X X X X X

[43] residue woodchips gate

Kimming et al. EU 1 y supply of heat and power Cradle-to- Small-scale BG CHP X X X X

[44] to a modern village of 150 gate
households
Study Methodology Economic Environmental impact category
impact
Location FU System Products EC AC EP GWP HT LU OD PO RC WC ET PM IR
boundary
Sreejith et al. State of 1 MJ energy content in the Cradle-to- Producer gas X X X
[45] Kerala in gaseous fuel gate generated from
India coconut shell
gasification

Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System…
Parvez et al. Cradle-to- Heat and syngas X X
[46] gate produced from
gasification

Kalina [47] Poland Cold/hot gas efficiency Cradle-to- Integrated BG dual X X

gate fuel combined cycle
power plant

Wang et al. [48] Harbin, 1 y operation Cradle-to- Building cooling X X X X

China gate heating and power

Yang and Chen China 1 MJ of primary energy Cradle-to- Producer gases (CO2, X X
[49] produced in a BG plant grave H2, CO and CH4)
(dynamic LCA) from BG

Abbreviation: CCS: carbon dioxide capture; na: not available; CHP: combined heat and power; BG: biomass gasification; EC: energy consumption; AC: acidification; EP:
eutrophication; GWP: global warming potential; HT: human toxicity; LU: land use; OD: ozone depletion; PO: photochemical oxidation; RC: resource consumption; WC:
water consumption; ET: ecotoxicity; PM: particulate matter; IR: ionising radiation.

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Table 6. Recent life cycle assessment studies on biomass gasification.

173
174 Lignin - Trends and Applications

systems, a downdraft gasifier and a circulating fluidised bed gasifier (CFBG), are considered
and analysed for H2 production using actual data taken from the literature. Functional unit
was 1 MJ/s H2 production. Then, the costs of GHG emissions reduction are calculated.

Iribarren et al. [37] assessed environmental and thermodynamic performance of H2 produc-

tion via BG through a LCA and an exergetic analysis. The case study involves poplar gasifica-
tion in a low-pressure char indirect gasifier, catalytic tar destruction, cold wet gas cleaning,
syngas conversion and hydrogen purification. The system boundary covers from poplar cul-
tivation to H2 purification.

El-Emam et al. [38] focused on efficiency and environmental impact assessments of steam
biomass gasification and gasification-solid oxide fuel cell (SOFC) integrated system for power
and H2 production. The environmental assessment is performed based on the carbon dioxide
produced from the system with respect to the generated useful products.

4.2. Biomass gasification for CHP

Experimental and numerical analyses of a CHP installation (75 kWe of electrical power) was
investigated by Elsner et al. [39], which is equipped with a biomass downdraft gasifier, gas
purification system, and gas piston engine. The economic analysis was performed taking into
account policies and regulations in the Polish energy market sector. They revealed that it is
more profitable to consume the generated power and heat for its self-consumption rather than
selling it on the market.

Using the techniques of LCA and net energy analysis, the study by Adams and McManus [40]
quantified the energy, resource, and emission flows, to assess the net energy produced and
potential environmental effects of BG using wood waste. The paper conducted a case study
that uses waste wood from a factory for use in an entrained flow gasification CHP plant.
Overall, small-scale biomass gasification is an attractive technology if the high capital costs
and operational difficulties can be overcome, and a consistent feedstock source is available.

Patuzzi et al. [41] did an investigation resulting in an overview of the actual state-of-the-art of
small-scale biomass gasification technology in Italy in terms of energy efficiency of the plants,
effectiveness of the adopted solutions and characteristics of the products and by-products. In
the study by Oreggioni et al. [42], a combined heat and power via BG, CHP with pre-com-
bustion adsorptive carbon capture unit, and CHP with post combustion absorptive carbon
capture unit were environmentally assessed.

Klavina, et al. [43] performed environmental performance analysis of biochar from wood-
chip pyrolysis, and woodchip CHP through midpoint category impact comparison using
LCA. Kimming et al. [44] conducted a simplified LCA over four scenarios for supply of the
entire demand of power and heat of a rural village. Three of the scenarios are based on utilisation
of biomass in 100 kWe CHP systems and the fourth is based on fossil fuel in a large-scale plant.

4.3. Biomass gasification for other energy systems

Sreejith et al. [45] investigated the suitability of coconut shell-derived producer gas as a substi-
tute for coal gas from an environmental perspective using LCA. Thermochemical gasification in
 Biomass Gasification: A Review of Its Technology, Gas Cleaning Applications, and Total System… 175
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an air-fluidised bed with steam injection is the gaseous fuel production process. The study indi-
cates that coconut shell-derived producer gas life cycle is capable of saving 18.3% of emissions
for global warming potential, 64.1% for ozone depletion potential, and 71.5% for nonrenewable
energy consumption. The analysis of energy and exergy consumptions is 62.9% for producer
gas life cycle, while it is only 2.8% for coal gas life cycle.

In the study of Parvez et al. [46], air, steam, and CO2-enhanced gasification of rice straw
was simulated using Aspen Plus™ and compared in terms of their energy, exergy, and
environmental impacts. The maximum exergy efficiency occurred in 800–900 °C. For CO2-
enhanced gasification, exergy efficiency was found to be more sensitive to temperature than
CO2/Biomass ratios. In addition, the preliminary environmental analysis showed that CO2-
enhanced gasification resulted in significant environmental benefits compared with steam
gasification.

Kalina [47] presents theoretical study of the concept of a small-scale combined cycle system
composed of natural gas fired micro turbine and Organic Rankine Cycle, integrated with
thermal gasification of biomass. The main issues addressed in the paper are configuration of
the ORC technology and allocation of generated electricity between natural gas and biomass.
Energy and exergy allocation keys are demonstrated. An initial cash flow calculations are
presented in order to assess financial performance of the plant.

Wang et al. [48] proposed a combined methodology of optimisation method and life cycle
inventory for the biomass gasification based building cooling, heating, and power (BCHP) sys-
tem. The system boundary of life cycle models includes biomass planting, biomass collection-
storage-transportation, BCHP plant construction and operation, and BCHP plant demolition
and recycle. Economic cost, energy consumption and CO2 emission in the whole service-life
were obtained. Then, the optimisation model for the biomass BCHP system including vari-
ables, objective function and solution method are presented.

Prior to large-scale crop-residue gasification application, the lifetime environmental perfor-

mance should be investigated to plan sustainable strategies. As traditional static LCA does
not include temporal information for dynamic processes, Yang and Chen [49] proposed a
dynamic life cycle assessment approach, which improves the static LCA approach by consid-
ering time-varying factors, e.g., greenhouse gas characterization factors and energy intensity.
Results show that the crop residue gasification project has high net global warming mitigation
benefit and a short global warming impact mitigation period, indicating its prominent poten-
tial in alleviating global warming impact.

5. Conclusions

After the nuclear power plant accident in Fukushima, nearby forests were contaminated by
the released radionuclides. Gasification technology can gasify the contaminated woody bio-
mass and produce syngas and ash. Current trends in biomass gasification technologies and
the subsequent gas cleaning process including desulphurisation and separation of radioactive
substances were reviewed.
176 Lignin - Trends and Applications

Life cycle assessment of the total gasification system is receiving increasing attention. It analy-
ses the energy profit ratio and environmental impacts of a process of interest (e.g. greenhouse
gas emission, acidification potential, photochemical oxidation, eutrophication potential, land
competition, etc.).

The radioactivity of the syngas produced was quite low, and that of ash was high (within
acceptable levels), implying that the gasification technology can be utilised as an option for
energy conversion of contaminated woody biomass in Fukushima.

Acknowledgements

The author thanks all those involved in preparing this chapter, including Mr. Tachihara
and Dr. Moritz for providing plant data. The authors acknowledge financial aid from
Fukushima prefecture for overseas collaboration on renewable energy research and
development.

Author details

Kenji Koido* and Takahiro Iwasaki

*Address all correspondence to: [email protected]

Faculty of Symbiotic Systems Science, Fukushima University, Fukushima, Japan

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 Journal of Energy Chemistry 25 (2016) 10–25

Contents lists available at ScienceDirect

Journal of Energy Chemistry

http://www.journals.elsevier.com/
journal-of-energy-chemistry/
journal homepage: www.elsevier.com/locate/jechem

Review

Biomass gasification technology: The state of the art overview

Antonio Molino a,∗, Simeone Chianese b, Dino Musmarra b
a
ENEA, National Agency for New Technologies, Energy and Sustainable Economic Development, UTTRI SS 106 Ionica, km 419+500, 75026 Matera, Italy
b
Department of Civil and Building Engineering, Design and Environment (DICDEA), Second University of Naples (SUN)-via Roma 9, 81031 Aversa (CE), Italy

a r t i c l e i n f o a b s t r a c t

Article history: In the last decades the interest in the biomass gasification process has increased due to the growing atten-
Received 20 May 2015 tion to the use of sustainable energy. Biomass is a renewable energy source and represents a valid alternative
Revised 22 September 2015
to fossil fuels. Gasification is the thermochemical conversion of an organic material into a valuable gaseous
Accepted 25 September 2015
product, called syngas, and a solid product, called char. The biomass gasification represents an efficient pro-
Available online 28 November 2015
cess for the production of power and heat and the production of hydrogen and second-generation biofuels.
Keywords: This paper deals with the state of the art biomass gasification technologies, evaluating advantages and dis-
Gasification advantages, the potential use of the syngas and the application of the biomass gasification. Syngas cleaning
Biomass though fundamental to evaluate any gasification technology is not included in this paper since; in the authors’
Syngas opinion, a dedicated review is necessary.
Gasification technology © 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.
Biofuel
Power and heat generation

1. The biomass gasification process the feedstock, the gasification technology and the operational condi-
tions [1–3].
The biomass gasification process consists in the conversion of a The char produced is a mixture of unconverted organic fraction,
solid/liquid organic compound in a gas/vapor phase and a solid phase. largely carbon, and ash. The amount of unconverted organic frac-
The gas phase, usually called "syngas", has a high heating power and tion mainly depends on the gasification technology and the oper-
can be used for power generation or biofuel production. The solid ational conditions. On the other hand, the amount of ash depends
phase, called "char", includes the organic unconverted fraction and on the biomass treated. The LHV of the char ranges from 25 to
the inert material present in the treated biomass. This conversion 30 MJ/kg [4], depending on the amount of unconverted organic
represents a partial oxidation of the carbon in the feeding material fraction.
and is generally carried out in the presence of a gasifying carrier, The principal reactions of the gasification are endothermic and the
such as air, oxygen, steam or carbon dioxide. Biomass gasification is necessary energy for their occurrence is, generally, granted by the ox-
considered as a way to increase the use of biomass for energy pro- idation of part of the biomass, through an allo-thermal or an auto-
duction allowing widespread biomass utilization. The development thermal phase. In the auto-thermal process, the gasifier is internally
of biomass gasification processes is pushed up by the growing aware- heated through partial combustion, while in the allo-thermal process
ness of the possible effects of fossil fuels on the climate and by the the energy required for the gasification is supplied externally [5,6].
continuous increase in oil prices. Considering the auto-thermal system, gasification can be seen as a
The syngas produced is a gas mixture of carbon monoxide (CO), sequence of several stages. A simplified schematic representation of
hydrogen (H2 ), methane (CH4 ) and carbon dioxide (CO2 ) as well as the gasification is reported in Fig. 1. The main steps of the gasification
light hydrocarbons, such as ethane and propane, and heavier hydro- process are:
carbons, such as tars, that condense at temperatures between 250
and 300 °C. Undesirable gases, such as sulphidric (H2 S) and chloridric
(1) Oxidation (exothermic stage).
acid (HCl), or inert gases, such as nitrogen (N2 ), can also be present in
(2) Drying (endothermic stage).
the syngas. Their presence depends on the biomass treated and on the
(3) Pyrolysis (endothermic stage).
operational conditions of the gasification process. The lowest heating
(4) Reduction (endothermic stage).
value (LHV) of the syngas ranges from 4 to 13 MJ/Nm3 , depending on

An additional step, consisting in tar decomposition, can be also

∗
Corresponding author. Tel: +390835974736; Fax: +390835974210. included in order to account for the formation of light hydrocarbons
E-mail address: [email protected] (A. Molino). due to the decomposition of large tar molecules.

http://dx.doi.org/10.1016/j.jechem.2015.11.005
2095-4956/© 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 11

Fig. 1. Main stages of the gasification process.

1.1. Oxidation derives from the other stages of the process. Drying can be consid-
ered complete when a biomass temperature of 150 °C is achieved, as
The oxidation of part of the biomass is necessary to obtain the discussed by Hamelinck and co-workers [187].
thermal energy required for the endothermic processes, to maintain
the operative temperature at the required value. The oxidation is car-
ried out in conditions of lack of oxygen with respect to the stoichio- 1.3. Pyrolysis
metric ratio in order to oxidize only part of the fuel. Despite the par-
tial oxidation involving all carbonaceous species (tars included), it is This phase consists in the thermochemical decomposition of the
possible to simplify the system considering that only char and the matrix carbonaceous materials; in particular, the cracking of chemi-
hydrogen contained in the syngas participate in the partial oxidation cal bonds takes place with the formation of molecules with a lower
reactions. The main reactions that take place during the oxidation molecular weight. By pyrolysis it is possible to obtain different frac-
phase are the following: tions: a solid, a liquid/condensed and a gaseous fraction [7–10].
The solid fraction, which can range from 5–10 wt% for fluidized
C + O2 → CO2 H = –394 kJ/mol Char combustion (1)
bed gasifiers to 20–25 wt% for fixed bed gasifiers [7–10], has a
high carbon content and is characterized by a high heating value.
C + 1/2O2 → CO H = –111 kJ/mol Partial oxidation (2) This fraction includes the inert materials contained in the biomass
in the form of ashes and a high carbon content fraction, called
“char”.
H2 + 1/2O2 → H2 O H = –242 kJ/mol Hydrogen combustion The liquid fraction, usually called "tars", varies according to the
(3) gasifier type, such as lower than 1 wt% for downdraft gasifiers, 1–
5 wt% for bubbling bed gasifiers, 10–20 wt% for updraft gasifiers and
The main product of this step is the thermal energy necessary for
is constituted by complex organic substances, condensable at rela-
the whole process, while the combustion product is a gas mixture
tively low temperatures [10,47,188,189].
of CO, CO2 and water. In this mixture nitrogen can be present if the
The gaseous fraction is typically 70–90 wt% of the fed material
biomass oxidation is performed with air, otherwise nitrogen is prac-
[10,188] and is a mixture of gases that are incondensable at ambient
tically absent if only oxygen is used.
temperature. The gaseous fraction is called "pyrolysis gas" and con-
sists mainly of hydrogen, carbon monoxide, carbon dioxide and light
1.2. Drying hydrocarbons such as methane and other C2 , C3 hydrocarbons; minor
constituents are acid or inert gases.
Drying consists in the evaporation of the moisture contained in The pyrolysis reactions take place with a temperature in the range
the feedstock. The amount of heat required in this stage is propor- 250–700 °C. They are endothermic and, as in the drying step, the heat
tional to the feedstock moisture content. Generally, the heat required required comes from the oxidation stage of the process.
12 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Table 1. Gasifiable biomass [13].

Supply sector Type Example

Forestry Dedicated forestry Short rotation plantations (e.g., willow, poplar, eucalyptus)
Forestry by-products Wood blocks, wood chips from thinnings
Agriculture Dry lignocellulosic energy crops Herbaceous crops (e.g., miscanthus, reed canary grass, giant reed)
Oil, sugar and starch energy crops Oil seeds for methylesters (e.g., rape seed, sunflower)
Sugar crops for ethanol (e.g., sugar cane, sweet sorghum)
Starch crops for ethanol (e.g., maize, wheat)
Agricultural residues Straw, pruning of vineyards and fruit trees
Livestock waste Wet and dry manure
Industry Industrial residues Industrial waste wood, sawdust from sawmills
Fibrous vegetable waste from paper industries
Waste Dry lignocellulosics Residues from parks and gardens (e.g., prunings, grass)
Contaminated waste Gemolition wood
Organic fraction of municipal solid waste
Biodegradable landfilled waste, landfill gas
Sewage sludge

The pyrolysis process can be schematized with the following over-

all reaction [11]:
Biomass →
← H2 + CO + CO2 + CH4 + H2 O(g ) + Tar
+ Char (Endothermic ) (4)
When the feedstock is made of biomass, since cellulose is its
main component (typically 50% of the weight), in this reaction the
biomass can be indicated with the chemical formula of cellulose [12]:
C6 H10 O6 .
Several complex phenomena are involved in the pyrolysis process.
They include heat transfer, product diffusion from biomass pores to-
wards gas phase bulk and reactions in series. At low temperatures the
kinetic of the reactions may be the limiting step, while at higher tem-
peratures the limiting step may become the heat transfer or the prod-
uct diffusion. For cellulose, the pyrolysis reactions occur between 600
and 700 °C.
Fig. 2. Influence of temperature process on the syngas characteristics.

1.4. Reduction
increase the oxidation of char (reducing the solid residue of the pro-
The reduction step involves all the products of the preceding cess) and reduce the formation of tar. On the other hand they in-
stages of pyrolysis and oxidation; the gas mixture and the char re- crease the risk of ash sintering and reduce the energy content of the
act with each other resulting in the formation of the final syngas. The syngas.
main reactions occurring in the reduction step are: The reduction temperature is a key parameter of the overall pro-
C + CO2 ↔ 2CO H = 172 kJ/mole Boudouard reaction (5) cess, determining the characteristics of the solid residue and those of
the syngas. These effects are summarized in Fig. 2.
The influence of temperature on the entire gasification process
C + H2 O ↔ CO + H2 H = 131 kJ/mole Reforming of the char
has led to the development of multiple technological solutions, each
(6) one characterized by a different syngas composition and a different
amount of solid residue.
CO + H2 O ↔ CO2 + H2 The typical temperature range in which gasification processes
H = –41 kJ/mole Water gas shift reaction (7) have been developed at full scale is 800–1100 °C, while in the pro-
cesses that use oxygen for the gasification step, the process tempera-
tures are in the range 500–1600 °C.
C + 2H2 ↔ CH4 H = –75 kJ/mole Methanation (8)
Reactions (5 and 6) are endothermic, while Reactions (7 and 8) 2. Gasifiable biomass and their pre-treatments
are exothermic; however, the contribution of both Boudouard Re-
action (5) and char reforming (6) makes the reduction step glob- The 2009/28/EC European Directive defines biomass as “the
ally endothermic, and then the whole step requires energy from the biodegradable fraction of products, waste and residues of biological
oxidation reactions. Reactions (5–8) are chemical equilibrium reac- origin from agriculture (including vegetal and animal substances),
tions and therefore products and reactants can coexist and maintain forestry and related industries, including fisheries and the aquacul-
their concentration ratios as defined by the laws of thermodynamic ture, as well as the biodegradable fraction of industrial and munic-
equilibrium. In general, it can be stated that the endothermic Reac- ipal wastes”. Examples of gasifiable biomass are shown in Table 1
tions (5 and 6) are favored (condition of equilibrium shifted toward [13] and they are composed of cellulose, hemicellulose, lignin and
the formation of products) when temperature increases, while Re- proteins [14,15]. Cellulose and hemicellulose are made of saccharides
actions (7 and 8) are favored at low temperatures. The temperature that bond to form long polymeric chains, which are the fibers of the
at which the reduction step is carried out has a fundamental role in biomass; lignin (a phenolic polymer) acts as the glue of the fibers, and
determining the composition of the syngas, and therefore its char- therefore, has a key role in ensuring the structural protein stiffness.
acteristics (lower heating value, presence of tar). High temperatures The proteins are mainly present in herbaceous species.
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 13

Fig. 3. Influence of temperature process on the syngas characteristics.

Table 2. Composition of hardwood, softwood and straw (wt% on dry basis) [13,193,194] a function of the moisture content in some types of biomasses [16]
Biomass type Cellulose Hemi-cellulose Lignin while Table 3 reports the typical LHV values for the main fuels, as a
comparison term.
Hardwood 42–48 27–38 16–25
Softwood 40–45 24–29 26–33
Straws 36–40 21–45 15–20 3. Biomass gasification products

The biomass gasification end products may be distinct in a solid

phase and a gas/vapor phase. The solid phase, ash, consists in the in-
Table 2 reports the composition of some woody biomasses [13]. ert materials present in the feedstock and the un-reacted char. The
The knowledge of biomass physical-chemical properties is fun- char in the ashes is a very low percentage of the total ash amount,
damental for its use as sustainable resource for energy produc- generally lower than 1 wt%, the transformation of the carbon matrix
tion. Biomasses diversify for various parameters such as moisture, in gas being the objective of the overall process [17,18].
chemical composition, ashes and inorganic substance content. The The gas/vapor phase, syngas, may be divided in a gas phase and
elements mainly present, in decreasing order of abundance are: a condensable phase. The gas phase is a gas mixture that contains
carbon, oxygen, hydrogen, nitrogen, calcium, potassium, silicon, mag- the gases that are incondensable at ambient temperature, CO, H2 ,
nesium, aluminum, sulphur, iron, potassium, chloride, sodium and CO2 , light hydrocarbons, CH4 and some C2 –C3 . If air is used in the
manganese [201]. oxidization step as a gasifying carrier, then inert N2 is present in
Syngas composition is not largely affected by biomass type, how- the gas phase. Minor components are NH3 and inorganic acid gases
ever if straw is used as feedstock an increase of hydrogen content can (H2 S and HCl and some minor gaseous compounds [182–184] (RIF)).
be observed while the lower heating value (LHV) of the produced gas The amounts of minor components depend on the biomass compo-
degreases. Using softwood as feedstock, the highest LHV can be found sition. The amount of syngas may range in 1–3 Nm3 /kg on a dry ba-
[188,190]. sis, with a LHV spanning over 4–15 MJ/Nm3 . These values may be
The highest and the lowest char contents can be found for soft- highly affected by the gasification technology chosen and the oper-
wood biomass and straw biomass, respectively, otherwise the higher ating variables [19,20]. Particular considerations are required for the
dust content can be observed for straw. The higher tar content can be condensable phase, tar, since it is made of several organic compounds
found for hardwood biomass [188,190–192]. that, once condensed, may be considered as bituminous oil. The Eu-
The moisture content is one of the most important parameters ropean board for standardization [21] has defined tar as: "all the or-
and critically affects the energy balance of the biomass gasification ganic compounds that are present in the syngas excluded the gaseous
process. Fig. 3 shows the trend of the Lower Heating Value (LHV) as hydrocarbons from C1 to C6 " and has defined the main procedure

Table 3. Lower calorific value of the main fuels [16].

Fuel LHV (MJ/kg) Bulk density (kg/m3 ) Energy density by volume (MJ/Nm3 )

Wood chips (30% MC) 12.5 250 3100

Log wood (stacked-air dry: 20% MC) 14.7 350–500 5200–7400
Wood (solid-oven dry) 19 400–600 7600–11,400
Wood pellets 17 650 11,000
Miscanthus (bale-25% MC) 13 140–180 1800–2300
House coal 27-31 850 23,000–26,000
Anthracite 33 1,100 36,300
Heating oil 42.5 845 36,000
Natural gas (NTP) 38.1 0.9 35,200
LPG 46.3 510 23,600
14 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Table 4. Tar type classification [28].

Tar type Type name Peculiarity Characteristic compounds

1 GC-undetectable Very heavy tars, cannot be detected by GC Determined by subtracting the GC-detectable tar fraction from total
gravimetric tar
2 Heterocyclic aromatics Tars containing hetero atoms, highly water Pyridine, phenol, cresols, quinoline, isoquinoline, dibenzophenol
soluble compounds
3 Light aromatic (1 ring) Usually light hydrocarbons with single ring; do Toluene, ethylbenzene, xylenes, styrene
not pose a problem regarding condensability and
solubility
4 Light PAH compounds (2-3 rings) 2 and 3 rings compounds; condense at low Indene, naphthalene, methylnaphthalene, biphenyl, acenaphthalene,
temperature even at very low concentration fluorene, phenanthrene, anthracene
5 Heavy PAH compounds (4-7 rings) Larger than 3-ring, these components condense Fluoranthene, pyrene, chrysene, perylene, coronene
at high-temperature at low concentration

Fig. 4. Simplified mechanism of tar formation [29].

for their analysis. A large number of scientific papers have been hemicellulose, which are made of a lot of oxygen atoms, determine
devoted to tar characterization [22–24,185] and to tar formation primary tars containing oxygenated organic compounds (alcohols,
[25–27]. carbon acid, ketones, aldehydes, etc.). On the other hand the pyrol-
Tars are a complex mixture of condensable hydrocarbons whose ysis of lignin gives rise mainly to aromatic compounds, mostly bi- or
composition depends on the biomass feedstock, the gasification tech- tri-functional substituted phenols (cresol, xylenol, etc.). In the oxida-
nology used and on the operating parameters chosen. Various re- tion step, the increase in temperature, above 500°C, and the presence
search groups give different definitions of tars but there is general of an oxidant (oxygen, air or steam), may allow for the transformation
consensus [28] on dividing them into five classes, as reported in of primary tars, which begin to rearrange (via dehydration, decar-
Table 4, according to their molecular weight. boxylation, and decarbonylation reactions) forming more gas and a
Tar compounds belonging to class 1 are not known, they have series of molecules known as secondary tars. Secondary tars are alky-
a very high molecular weight and cannot be detected by gas chro- lated mono- and di-aromatics including hetero-aromatics like pyri-
matography. Tar compounds grouped into class 2 include oxygenated dine, furan, dioxin, and thiophene [30]. A further increase in temper-
condensable compounds that are highly water-soluble. Tar com- ature, over 800 °C, may lead to the formation of tertiary tars. Tertiary
pounds grouped in the classes 3–5 are aromatic compounds with an tars are also known as recombination or high-temperature tars. Ter-
increasing number of aromatic rings; class 3 includes single ring com- tiary tars are mainly made of aromatic and polynuclear aromatic hy-
pounds, while PAH compounds are included in the classes 4 and 5. drocarbons (PAH), e.g., benzene, naphthalene, phenanthrene, pyrene,
In any case tar composition and classification are a major issue in and benzopyrene. Compounds in tertiary tars are not present in the
gasification process. The European Commission defined a standard- biomass gasified and they are the results of the decomposition and
ized protocol to collect and to measure the tars produced by biomass recombination of secondary tars in the reducing environment of the
gasification [21]. syngas. Tertiary tars and primary tars do not coexist, and tertiary tars
In a gasification process, the tars are formed in a series of com- appear when primary tars are completely converted into secondary
plex reactions, which are highly dependent on the reaction condi- tars [29].
tions. Tars stem from the pyrolysis step and are subject to recombi- A schematic representation of tar types as a function of tempera-
nation and decomposition (Fig. 1). The reaction paths are complex ture is reported in Fig. 5.
and not completely understood; they include a large number of reac- The formation of tertiary tars and their decomposition in smaller
tions in series or parallel to one another. A possible simplified mech- compounds is a complex scientific problem on which several research
anism of tar formation [29] is shown in Fig. 4, which considers tars groups are working to define the reaction path and to develop a ki-
as the end products of three main macro-phenomena and classifies netic model that describes the experimental results. However, the re-
primary, secondary and tertiary tars. sults obtained are often conflicting and unable to describe neither
Primary tars arise directly during the pyrolysis step and the large variety of compounds in the tars nor their dependence on
mainly depend on the biomass gasified. In particular cellulose and the process conditions [31–46]. The general approach is to treat the
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 15

Fig. 5. Tar types as function of temperature [29].

tar compounds as a certain number of lumped classes and to define a consequent increase in the energy content. In many cases the tor-
a reaction path for a single compound, which is considered as rep- refaction process is performed with a system of pelletization to in-
resentative of the total amount of the classes. A lot of papers can be crease the bulk density of the material [50–52].
found in the scientific literature [42], in which this approach is used The roasted pellets have an amount of energy per unit volume of
to overcome the difficulty in describing the large number of reactions 14,000–18,500 MJ/Nm3 , which is significantly greater than the pellets
involving the numerous compounds found in the tar mixture. How- produced by conventional material, such as wood-pellets, which are
ever, to the best of our knowledge, at this moment any defined re- between 8,000 and 11,000 MJ/Nm3 [51]. This type of pre-treatment
action path for tar formation and decomposition does not exist. Dis- consists of a combination of torrefaction and pelletization and was
crepancies among authors [42,43] exist even for the description of introduced by the Energy Research Centre of the Netherlands (ECN).
the formation of the simplest PHA compounds: naphtalene, consid-
ered as representative of two ring aromatic compounds. 4.2. Hydro thermal upgrading (HTU)
The simplest way to describe tar decomposition/recombination is
the following reaction: The HTU consists in the production of an oil, like crude oil, named
“bio-crude” oil, by the decomposition of biomass in water. The pre-
α Cn Hm → β Cn−x Hm−y + δ H2 (Endothermic ) Tarcracking (9) treatment is conducted, essentially, in two stages. The first one con-
sists in treating the biomass with water at temperatures of 200–
Cn Hm → nC + (x/2 ) H2 (Endothermic ) Carbon formation (10) 250 °C and a pressure of about 30 bars. The second one is an in-
crease both in temperature and pressure in a period of time variable
Cn Hm + nH2 O → (n + x/2 ) H2 + nCO from 5 to 10 min, in which the conversion of the biomass takes place
by bringing the water at pressures of 120–180 bar and temperatures
(Endothermic ) Steam reforming (11) of 300–350 °C [53,54]. Bio-crude is a mixture of different hydrocar-
bons, with a LHV between 30 and 36 MJ/kg that can be employed
Cn Hm + nCO2 → (x/2 ) H2 + 2nCO as a co-fuel in the coal power plants or in the chemical industry to
(Endothermic ) Dry reforming (12) produce chemicals or synthetic fuels with diesel-like properties [54].
The combination of gasification and biomass hydro thermal upgrad-
where, Cn Hm represents a generic tar while Cn-x Hm-y are representa- ing could be an optimal treatment strategy although further studies
tive of hydrocarbons with a weight lower than that of tars. and R&D on HTU are required [55,56].
The presence of tars in the syngas may be considered, as stated
by Reed already in 1997 [47], as the Achilles’ heel of biomass gasifi- 5. Gasification technologies
cation affecting the final use of the syngas itself: energy production
and/or chemical utilization. Tars removal or their conversion is the The reactors used on an industrial scale to gasify a pre-treated
great technical challenge to overcome and develop a successful ap- biomass, usually called gasifiers, essentially differ from one another
plication of biomass-derived gas. Different approaches are being fol- for:
lowed by researchers [41,48,49,195]:
(1) Mode of contact between the feed material and the gasifying
• End of pipe tar syngas clean-up process; agent.
• In bed thermal tar cracking; (2) Mode and rate of heat transfer.
• In bed catalytic tar reforming. (3) Residence time of the fed material into the reaction zone.
Different technological solutions can be implemented in order to
4. Biomass-pre-treatment obtain different plant configurations; in particular, the mode of con-
tact of the biomass with the gasification agent may be in counter-
The pre-treatment of biomass has the primary objective to ensure current, or co-current, or cross flow, and the heat can be transferred
that the gasification process is conducted using a feedstock material from the outside or directly in the reactor using a combustion agent;
that is homogeneous by size and composition. Other pre-treatments the residence time can be in the order of hours (static gasifiers, rotary
aim at reducing the initial moisture content that, in general, must not kiln) or min (fluidized bed gasifiers).
exceed 25–30 wt%; among these the main pre-treatments, besides The main reactors used in the biomass gasification process are:
drying, are torrefaction and hydrothermal upgrading (HTU).
(1) Entrained flow reactor.
(2) Fixed bed.
4.1. Torrefaction
(3) Fluidized bed.
(4) Rotary kiln reactor.
Torrefaction is a thermochemical process which is carried out at
(5) Plasma reactor.
a temperature between 200 and 300 °C in the absence of oxygen. At
these temperatures some chemical reactions take place; the biomass A brief description of the different reactors is reported below in
loses both the rigid fibrous structure and the moisture content, with order to highlight the main advantages and disadvantages.
16 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Fig. 7. Fixed bed reactor: (a) updraft, (b) downdraft.

Fig. 8. Fluidized bed reactor: (a) bubbling, (b) circulating.

Using biomass powder as fuel during entrained flow gasification

may give an extra cost due to its low bulk density, which might be
reduced by an initial torrefaction process [59].
Fig. 6. Entrained flow reactor. Table 5 shows the main advantages and disadvantages of these
types of reactors [60–62].

5.2. Fixed bed reactor

5.1. Entrained flow reactor
The main technological solutions based on the fixed-bed reactor
In an entrained flow reactor the feed fine fuel (0.1–1 mm par- are the updraft and the downdraft reactor (Fig. 7a and b). In the up-
ticles) and the gasifying agent are injected in co-current (Fig. 6). draft reactor the solid moves downwards with respect to the gasifica-
The gasifier operates at high temperatures (1300–1500 °C) and pres- tion agent and then the syngas produced moves upward (countercur-
sures (25–30 bar) and water slurries or dry feeds can be used as rent); while in the downdraft reactor, both the solid and the gas are
raw material. A pneumatic feeding is usually used to inject pressur- moved downward (co-current).
ized powder solid fuels into the gasifier, while slurries are atom- Table 6 shows the main advantages and disadvantages of these
ized and subsequently fed as pulverized solid fuel. Entrained flow types of reactors, as reported in the scientific literature [61–65,196].
reactors can be divided in slagging and non-slagging: in the former
the ash leaves the reactor as a liquid slag, and in the latter slag is 5.3. Fluidized bed reactor
not produced (1% is the maximum allowable ash content). Usually a
torrefaction-based pre-treatment is required to reduce the bulk den- The bubbling fluidized bed reactor (Fig. 8a) is made of a bed of in-
sity and moisture content, when biomass fine particles are used as ert granular material (sand) held in a condition of fluidization where
feedstock [52,56–58]. the gasification agent is fuelled bottom-up from the bed through a
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 17

Table 5. Advantages and disadvantages of the entrained flow reactor.

Reactor type Advantage Disadvantage

Entrained flow reactor -Fuel flexibility -Large oxidant requirements

-Uniform temperature -High level of sensible heat in product gas
-High carbon conversion -Heat recovery is required to improve efficiency
-There are not problems of scale-up -Low cold gas efficiency
-Good ability to control the parameters process -Requires the reduction of size and preparation supply
-Short reactor residence time. -Short life of system components, including gasifier vessel refractory
-Very low tar concentration. -High plant cost
-High Temperature slagging operation (vitrified slag). -High maintenance cost

Table 6. Advantages and disadvantages of fixed bed reactors.

Reactor type Advantage Disadvantage

-High content of tar in the syngas

-High thermal efficiency -Energy content of tar> 20%
-Good contact between the solid material and the oxidizing agent -Low production of CO and H2 . -requires a subsequent treatment of
the tar cracking
-Can handle materials of different sizes -Limited flexibility to load and process (the treated material should
have properties homogeneous)
Fixed bed “Updraft” -Can handle materials with high humidity -Reduced starting difficulties and temperature control
-Reduced entrainment both of dust and that of Ashes -Need for installation of mobile grates to avoid the formation of
preferential paths in the fixed bed
-Simple construction -According to catalysts, they may be not usable since syngas energy
may be lower than that necessary for the activation, requiring
external energy supply -Poisoning deactivation of catalysts may be
possible
-Robust technology -Low specific capacity
-There are no problems of scale-up -Need for uniform sizes in input (pellets no larger than 100 mm)
-Training of sintered slag on the grid
Fixed bed “Downdraft” - High carbon conversion -Requires materials with a low moisture content
-Low production of tar -Limited flexibility to load and process (the treated material must
have the same characteristics)
-Limited entrainment of ash and dust -Low coefficient of heat transfer
-High solid residence time -Difficulty starting and controlling the temperature
-Simple construction -Poisoning deactivation of catalysts may be possible
-Reliable technology -Limited possibility of scale-up (the dimensions of the reactor are
limited by problems of temperature control)

distribution grid, with a velocity between 1 and 3 m/s. In these con-

ditions, the bed of inert solid behaves like a liquid, and is continu-
ously stirred by the presence of gas bubbles whose mobility ensures
uniform conditions both of exchange of matter and heat between the
solid and the gas. The extent of the grid region can significantly af-
fect the mass and heat transfer between the gasification agent and
the bed solids [66]. The various phases of the gasification process
occur within the bed, although a part of the gasification reactions
can be completed in the freeboard, i.e., the upper part of the reac-
tor that is not reached by the fluidized bed, where only the gas phase
is present. In recirculating bed reactors (Fig. 8b), the gasification pro-
cess is divided into two stages; in the first, generally consisting of a
bubbling fluidized bed, the reactions of combustion generating the
heat necessary for gasification occur, and in the second there is a
high-speed gas (5–10 m/s) to allow the dragging of the solid, where
the reactions of pyrolysis and gasification take place. At the outlet of
Fig. 9. Rotary kiln reactor.
the reactor a cyclone is also present; it allows for the separation of
the solid, which is, generally, re-circulated to the bubbling fluidized
bed. At present, the fluidized bed is the most promising technology in vantages of these types of reactors, as reported in the scientific liter-
biomass gasification as much as for tar conversion: it has high mix- atures [3,58,62,68].
ing capabilities, with a high mass and heat transfer rate, which se-
cures constant temperatures all over the gasifier, and moreover cat- 5.4. Rotary kiln reactor
alysts can be used as part of the gasifier bed, affecting tar reforming
[197–200]. Furthermore Puadian and co-workers [67] demonstrated Rotary kilns (Fig. 9) consist in a slightly tilted (1%–3%) cylindrical
that the biomass injection point is extremely important, as these ben- chamber that slowly rotates around its own axis. The gas–solid con-
efits are enhanced when the biomass is fed deep inside the fluidized tact takes place due to the rotation of the drum that, by continuously
bed; this results in the greatest product gas yield, due to the increased stirring, exposes the new solid surfaces to the gasification agent. The
exposure to the catalytically active bed environment. conditions for the exchange of matter and heat between the solid and
Fluidized bed reactors have advantages and disadvantages de- the gas are not very effective, and then, the residence time (reaction
pending on the various technological solutions: bubbling fluidized volumes) is higher than those with the other gasification technolo-
bed or dragged bed. Table 7 shows the main advantages and disad- gies. The efficiency of solid-gas contact may be improved with the
18 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Table 7. Advantages and disadvantages of fluidized bed reactors.

Reactor type Advantage Disadvantage

-High mixing and gas-solid contact

-High carbon conversion
-High thermal loads -Loss of carbon in the ashes
-Good temperature control (temperature distribution along the -Dragging of dust and ashes
reactor)
-Can handle materials with different characteristics -Pre-treatment need with heterogeneous materials
Bubbling fluidized bed -Good flexibility both of load and process -Need to have a relatively low process temperature to avoid
phenomena of de fluidization of the bed (temperature lower than
the softening point of the solid residues)
-Suitable for highly reactive fuels such as biomass and municipal
waste pre-treated
-Low level of tar in the syngas -Restrictions on the size
-Ease of start-up, shutdown and control -High investment costs and maintenance costs
-Possibility to use catalysts, even on a large scale (thanks to the
good temperature control)
-No moving parts
-Good ability to scale-up
-Possibility of casting the ashes
-Loss of carbon in the ashes
Circulating fluidized bed -Lower tar production -Requires the reduction of size and preparation supply (the solid
material must be finely pulverized, with dimensions lower than
100 mm)
-High conversions -Restricted solid-gas contact
-Flexible load - Need for special materials
-Reduced residence times -Technology complex and difficult to control.
-Good ability to scale-up -Security issues
-High start-up costs and investment costs

Table 8. Advantages and disadvantages of the rotary kiln reactors.

Reactor tyoe Advantage Disadvantage

-Significant difficulty in starting and temperature controlling

-Low sensitivity to changes in composition, humidity and size of the fed -Presence of movement part and their problems with leakage and wear
-Maximum loading flexibility -Consumption of refractory quite high
-High conversion -Low capacity of heat exchange
Rotary kiln -Suitable for waste that can melt -High content of dust and tar
-There are problems of scale-up -Low efficiency heat
-Simplicity of construction and high reliability of operation -Limited flexibility process
-Reduced investment costs -High maintenance costs

installation of barriers inside the drum that increase the handling of control of the temperature of the process independently from
the solid material and improve the contact with the gaseous stream. any fluctuations in the quality of the solid and of the gasifica-
The most used configuration is the one in countercurrent: the ma- tion agent, accepting a wide variation in the flow rate, moisture
trix to be gasified is fed into the top of the reactor and the oxidizing content, size and elemental composition of the material to be
agent in the bottom of the reactor. Table 8 shows the main advantages treated.
and disadvantages of these reactors, as reported in the scientific lit- (2) Application to the gas produced by a gasification upstream
eratures [69–71]. process, when the main objective is to maximize the produc-
tion of a synthesis gas with a high content of light components,
5.5. Plasma technology removing the tar initially present (the plasma process has a
function of clean syngas without altering the energy content).
The plasma is an ionized gas stream at high temperature (up to
Table 9 shows the main advantages and disadvantages of this type
10,000 °C) obtained from the application of an electric discharge, typ-
of reactor, as reported in the scientific literature [72].
ically indicated as "arc". The device on which the electrodes are in-
stalled is called "flashlight"; the electrodes used are usually in copper,
but it is also possible to use carbon electrodes (Fig. 10). 5.6. Gasification technology comparison
The plasma process consists in an atomic degradation of the mat-
ter; consequently if it is applied to the treatment of an organic The main “bottlenecks” of the biomass gasification technology can
matrix (waste/biomass) and in the presence of an oxidizing agent be summarized in: feed material, syngas quality and development
(air/oxygen/steam), the energy flow, supplied from the plasma, deter- status. An entrained flow reactor requires specific features of the feed
mines the rise in temperature necessary for the reactions that make fuel, in terms of particle size (0.1–1 mm), moisture content (< 15 wt%)
up the gasification process, while in the absence of an oxidizing agent and a constant composition, while biomass feedstock with light or
the plasma process is similar to the pyrolysis at higher temperature. without pre-treatment can be supplied to a plasma gasifier and a ro-
The use of plasma technologies for the thermal treatment of or- tary kiln reactor. Fluidized and fixed bed reactors are more flexible
ganic matrices can occur in two patterns: than an entrained flow reactor operating with larger particle sizes
(20–100 mm) and a wider range of moisture contents (5%–55%), how-
(1) Direct application to the solid to be treated, in adequate size, ever a feedstock with low ash melting temperatures should be used.
when the main goal is the thermal destruction. The applica- In terms of syngas quality, the best gasifier is the plasma reactor; en-
tion of the plasma process directly to the matrix allows for the trained flow gasifiers also ensure a very low tar content with a better
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 19

Table 9. Advantages and disadvantages of plasma reactors.

Reactor type Advantage Disadvantage

-Presence of nanoparticles in the syngas

-Presence of moving parts with their maintenance problems
-Production of vitrified completely inert and non-leachable slag, -Consumption of refractory
which include heavy metals
-Non continuous process
-The waste products, being non-leachable, can be recovered and -Heat Schock for the start-up and shout-down
used directly as a building material
Plasma reactor -Reduced flow rate of the syngas -Necessity of auxiliary fuel for obtain an homogeneous temperature
inside the reactor
-Content extremely limited polluting compounds in syngas -Frequent changing of the electrodes
-Extremely short reaction times -Safety problems
-There are not problems of scale-up -Solidification of molten material in the ducts
-High plant, operational and exercise costs

and high capital and maintenance costs; rotary kiln gasifiers are char-
acterized by good efficiency, low capital costs and high maintenance
costs; plasma gasifiers show low efficiency versus high capital and
maintenance costs.

6. End use of thermochemical biomass conversion products

Roskilly et al. [75] define biofuels as any type of combustible sub-

stance derived from biomass conversion. Biofuels have raised a great
interest over the past ten years due to the growing attention to cli-
mate change and to renewable energy sources. The use of biofuels for
energy conversion allows reducing greenhouse gas emissions, thanks
to the CO2 neutral conversion, and fossil fuel dependence [76–78]. For
these reasons, the industrial production of bioethanol and biodiesel
has greatly increased in the last decade [79] with 100 billion of liters
and 60 billion of liters, in 2010, respectively [80,81]. These produc-
tion levels have been reached by first generation biofuels, mainly
bio-ethanol and bio-oil whose production technologies can be con-
sidered as mature; on the contrary, first generation biofuels that use
food products to produce fuels (e.g. ethanol from corn) have prob-
lems of sustainability and security of feedstock. The production of
second-generation bio-fuels, that use no-food biomass such as in-
digenous wood, grass species, forestry residues and municipal solid
waste (MSW) is not fully developed as a technology and further im-
provements are required.
The gasification process and other biomass conversion technolo-
gies such as pyrolysis, and combustion, can provide several primary
products, charcoal, liquid, fuel gas and heat that can be processed
Fig. 10. Plasma reactor. for obtaining secondary products as electricity, gasoline, diesel,
methanol, chemicals and ammonia [82]. A schematic representation
of the thermochemical processing and products is shown in Fig. 11.
quality syngas than a fluidized and fixed bed reactor. In turn the syn- This figure, starting from the version proposed by Bridgwater [82] has
gas from a fluidized bed gasifier has a better quality than the syngas been updated to include novel processes and products.
produced by a fixed bed reactor. The syngas from a rotary kiln reactor Primary products can be directly used as combustible substances
has the worst quality [73]. Entrained flow gasifiers are very promising in power plants for heat and power production (CHP); primary prod-
in terms of commercialization, showing a great potential for scale-up ucts, after a more or less advanced purification step, may be used in
and, consequently, low capital costs, thanks to economies of scale; facilities with high energy efficiency such as gas turbines [83], inter-
fluidized bed gasifiers are a consolidated technology for biomass gasi- nal combustion engines [75], solid oxide fuel cells (SOFC), molten car-
fication, with good established heat and power applications; plasma bonate fuel cells (MCFC) [84].
gasifiers are used for power production, but they are mainly focused Secondary products include the electricity and the heat obtained
on municipal waste, with a little experience with biomass. Fixed bed using the primary products and chemical compounds such as gaso-
and rotary kiln gasifiers are not widespread because of the low syngas line, diesel, methanol, and some chemicals that can be used as fuels
quality. for energy conversion or as reagents in chemical processes.
It is not possible to carry out a real gasification technology cost A brief description of the different uses of primary and secondary
analysis because the data available in the literature refer to gasifiers gasification processes/products is given in the following.
with various plant scales, development phases and technical con-
cepts, however some general considerations are possible [73,74]: en- 6.1. Electricity and heat production
trained flow gasifiers have high efficiency versus high pre-treatment
costs (if decentralized) and moderate capital and maintenance costs; 6.1.1. Steam cycle
fixed bed gasifiers have moderate efficiency and limited capital and The combustion of syngas or cracking oil in a boiler is a simple use
maintenance costs; fluidized bed gasifiers show both high efficiency of the thermochemical primary products as fuels in a conventional
20 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Fig. 11. Thermochemical biomass processing and products.

steam cycle [85,186]; using these fuels does not increase the impact 100 mg/Nm3 , Particulate = 50 mg/Nm3 , Metals = 0.025–0.1 ppmw,
on the environment [86]. A lot of power plant applications are fuelled H2 S = 20 ppmv) are required [95,96,98–100]. In particular, compar-
by syngas or by cracking oil without any particular problem, however ing syngas characteristics for GT and ICE it is possible to highlight that
the overall electricity energy efficiency is low and varies from 15% gas turbines need a higher purity syngas in terms of tar and particu-
up to 35% in plants with a boiler energy size higher than 150 MWth late contents.
[87,88]. Higher energy efficiency may be reached if cogeneration units The main problem is that in the current market, the engines are
for heat re-use are applied. designed for gasoline and diesel, and therefore a modification of the
injection system is necessary [101,102]. In internal combustion en-
6.1.2. Co-combustion gines the syngas can be also used for co-combustion, mixed with bio-
The primary products obtained by the thermochemical conver- gas derived from the anaerobic digestion of organic waste [103].
sion of biomass may be added to conventional fuels (coal, heavy oil or
biomass) in power plants for co-combustion processes [90]. This use 6.1.5. High temperature fuel cells
does not imply any technical problem and the overall electrical effi- High temperature fuel cells are electrochemical systems for elec-
ciency of these plants (about 35%) [89] is not affected if fuel replace- tricity production via chemical energy conversion [104]. The key ad-
ment by biomass primary products is limited to 5–15 wt% [90,91]. vantage of these systems is that an electric conversion efficiency
greater than 40% can be easily obtained [105]; moreover high tem-
perature fuel cells can be fed with a mixture of H2 and CH4 or directly
6.1.3. Combustion in gas turbines
by syngas. The syngas usage in high temperature fuel cells, without
Fuel combustion in gas turbines (GT) may reach a higher elec-
any combustion processes, has a lower impact on the environment.
trical conversion efficiency, up to 40%, than conventional steam cy-
Molten carbonate fuel cells (MCFCs) and solid oxide fuel cells
cles, even in low size plants (<50 MWth) [87,88,92–94]. However,
(SOFCs) are the main fuel cells technologies that can be fed with syn-
in order to avoid the rapid deterioration of the blades of the tur-
gas. The great advantage is the flexibility of the fuel that can be made
bines because of the high temperature of the flue gas, an accu-
of carbon monoxide or carbon dioxide in addition to hydrogen and
rate cleaning (Tars = 10 mg/Nm3 , Particulate = 2.4 mg/Nm3 , Met-
methane. In MCFC a nickel catalyst is required for the reforming re-
als = 0.025–0.1 ppmw, H2 S = 20 ppmv) and a calorific value greater
action and the H2 S content in the gas must be lower than 10 ppmv to
than 4 MJ/Nm3 are required [95,96].
avoid catalyst poisoning deactivation. SOFC can only tolerate 1 ppmv
The energy conversion in the gas turbine may be increased by
of H2 S. For both technologies tars and particulate have to be removed.
adding an additional energy recovery system (steam cycle–Integrated
Furthermore, the high temperature, in the range 700–1000 °C, pro-
Gasification Combined Cycle–IGCC) that allows for an overall energy
motes a higher energy recovery than in MCFC [106].
efficiency in the range 30%–60% [87,88]. Furthermore, the gas turbine
In any case, both molten carbonate fuel cells and solid oxide fuel
may be coupled to tri-generative systems or to heat re-use in order to
cells can be fuelled by syngas, after a cleaning phase [106], and to
improve the energy use in terms of fuel utilization, which can reach
the best of our knowledge no one other technology have reached full
70%–90% [97].
scale application.

6.1.4. Combustion in internal combustion engines 6.2. Secondary products

The syngas produced by biomass thermochemical conversion may
be fed to internal combustion engines (ICE) obtaining an overall elec- The use of biofuels for energy conversion allows reducing green-
trical energy conversion in the range 35%–45% [88]. However, a high house gas emissions, thanks to the CO2 neutral conversion, and fossil
calorific value (>4 MJ/Nm3 ) and a low pollutant contents (Tars = fuel dependence [77,78].
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 21

Gaseous and liquid biofuels can be easily used instead of fossil fu- where, n is an integer. Methane (for n = 1 in reaction (14)) is consid-
els (transport, energy, heat and chemical production). Thermal treat- ered as an unwanted compound.
ments directly produce gaseous and/or liquid biofuels. The latter can The most significant parameter for Fischer–Tropsch synthesis is
also be produced through conversion processes starting from syngas. the H2 /CO ratio, for which the optimal value required by the process is
Gaseous biofuels are mainly methane and hydrogen, the others ∼2 (or higher) [136]. In the syngas produced by biomass gasification,
(CO and light hydrocarbon) being generally in a negligible amount the characteristic H2 /CO ratio is ∼1 (or lower). Typically, the water
[75,107]. The main liquid biofuels are gasoline and diesel; they are ob- gas shift reaction is favored by an increase in the H2 /CO ratio. Among
tained by the direct thermal conversion of biomass and ethanol and the catalysts adopted in the FT synthesis, iron has a higher water-gas-
of methanol and dimethylether after syngas conversion [108–110]. shift activity than the others, therefore an iron-based catalyst is the
The industrial production of liquid biofuels (bioethanol and most appropriate to obtain a H2 /CO ratio useful for biomass gasifi-
biodiesel) has greatly increased in the last decade [79]. In particular, cation syngas [135,137–139]. Cobalt-based catalysts are more active
from 2001 to 2010, the world bioethanol production tripled reaching than iron, but their water-gas-shift activity is lower [135].
about 100 billion of liters in 2010 [80,81]; at the same time the world FT synthesis is characterized by a process temperature in the
biodiesel production increased by an order of magnitude, reaching range of 693–893 °C and an operative pressure in the range of 1–
about 60 billion liters in 2010 [80,111]. 30 atm. Increasing temperature and pressure lead to a higher con-
version rate but high temperatures favor methane production. The
6.2.1. Secondary liquid bio-fuels formation of methane is minimized by working at temperature of
Ethanol can be produced from biomass-derived syngas through about 693–753 °C. The methane produced by the synthesis and the
two processes: syngas fermentation and syngas thermochemical cat- methane contained in the biomass syngas can be converted into
alyst conversion [112–114]. H2 through catalytic dehydrogenation, with the advantage that CO2
Syngas fermentation is led by acetogenic bacteria. This process emissions are reduced if FT synthesis and catalytic dehydrogenation
presents a greater flexibility in terms of biomass type and is more cost are coupled [140].
effective [112,114]. Acetogens are anaerobic bacteria able to trans- Several research centers are studying new catalysts like carbon
form CO and/or CO2 and H2 into acetyl-CoA through the reductive nanotubes containing acidic functional groups and zeolites to pro-
acetyl-CoA pathway [115]. The well-kwon acetyl-CoA pathway was duce biodiesel from syngas via FT synthesis [141,142].
first characterized by Ljungdahl and Wood [116]; for this reason it Bio-dimethylether is obtained from methanol via catalytic dehy-
is also known as the Wood-Ljungdahl pathway. CO2 fixation con- dration using catalysts based on silica-alumina [83,129,143,144]. DME
sists of a methyl branch (also called “Eastern”) and a carbonyl branch is also produced directly from syngas using bifunctional catalysts
(also called “Western”). Six electrons reduce one molecule of CO2 to such as copper-ZSM-5 zeolite [145–147] or hybrid copper-allumina
a methyl group in the methyl branch, while another CO2 molecule is based catalysts [148]. Several research centers showed that it is pos-
reduced to CO in the carbonyl branch; the combination of the methyl sible to obtain an increasing of DME production with lanthanum ox-
group with CO and the enzyme acetyl-CoA synthase results in acetyl- ide [149] or niobium–allumina [150]. An innovative, one-step process
CoA. The reduction of CO2 is catalyzed by the enzyme CO dehydro- for DME production is based on the “reactive dividing-wall column”
genase [117]. Ethanol can be produced through two systems: directly where it is possible to combine the unit of reactive distillation with
from acetyl-CoA in a two-step reaction via acetaldehyde, or via ac- the “dividing-wall column” technology in one single process [151–
etate and subsequent reduction to acetaldehyde [112]. 153].
Syngas thermochemical catalyst conversion into bioethanol can At atmospheric pressure Bio-DME has a gaseous state, but due to
be obtained using several catalysts. Rhodium-based catalysts are its high capacity to liquefy at low pressure, as liquefied petroleum gas
ideal catalysts for their C2+ alcohols high selectivity but because (LPG), it is used as a liquid biofuel [154,155].
of their cost researchers focus on more affordable substitutes, such According to Park and Lee [154] the engine performance improves
as copper-based catalysts [118–122]. If copper-based catalysts are with bio-dimethylether combustion thanks to its higher cetane num-
used, promoters are required to minimize the undesired reactions ber than biodiesel. Moreover HC and CO emissions are lower than in
and maximize the ethanol production. Alkali, transition metals and biodiesel combustion. An exhaust gas recirculation can be adopted to
their oxides are common promoters [121]. The main reaction occur- reduce the NOx emission from DME combustion.
ring in long chain hydrocarbons synthesis follows the general scheme Laksmono and co-workers [131] studied thermal cracking and cat-
[123,124]: alytic cracking as methods to exploit the tars from biomass gasifica-
tion as fuels for internal combustion engines. They found that using
nCO + 2nH2 → Cn H2n + OH + (n–1 )H2 O (13) thermal cracking, biodiesel production was around 75 wt% of feed at a
temperature of about 953 °C; using catalytic cracking in the presence
where, n is an integer ranging from 1 to 8 (for ethanol n = 2).
of zeolite, magnesium oxide, and aluminum oxide catalysts biodiesel
Temperature is a fundamental parameter to control alcohol pro-
production was 62–75 wt%, 55–66 wt%, 67–71 wt%, respectively.
ductivity. High production of C2 –C3 alcohols can be achieved in the
interval 833–858 °C; this temperature range minimizes the forma-
6.2.2. Gaseous products
tion of unwanted by products [125].
The biomethane production from biomass thermochemical con-
The methanol production is carried out via catalyst conversion, in
version begins by syngas production. The syngas is compressed and
particular copper- or nichel-allumina-based catalysts [83,126–129].
fed to the catalytic methanation stage, where the exothermal reac-
The main processes to produce biodiesel from syngas are based
tions due to catalyst systems, such as nickel-allumina catalyst occur
on the Fischer–Tropsch (FT) synthesis [130–133]. The well-assessed
[156–162]. Biomethane can also be produced by a membrane tech-
FT process, when applied to a biomass syngas, can be defined as the
nology, using a multistage configuration process, in which the syngas
indirect liquefaction of the biomasses in the presence of a catalyst
is compressed and fed to some polymer permeation modules in se-
[134]. Indeed, the syngas obtained by steam/air biomass gasification
ries [163,164].
is cleaned and then fed to the Fischer–Tropsch reactor where the re-
The great advantage of the production of biomethane is the pos-
action between H2 and CO occurs to produce hydrocarbons of varying
sibility to plug it directly into the natural gas grid, upgraded to nat-
molecular weight. According to Schulz [135], the main reaction occur-
ural gas quality [163]. By 2020 the German government intends to
ring in the FT process follows the scheme:
increase the biomethane injection in the pipeline system to 6 billion
(2n + 1 ) H2 + nCO → Cn H(2n + 2 ) + nH2 O (14) m3 /y [165]. Moreover biomethane can be used as transport biofuel
22 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

Fig. 12. Status of applications for market potential and technology reliability derived from Maniatis [172].

Table 10. European biomass gasification plants [173].

Site gasification plant Input Product Output Technology

Skive, Denmark Lignocellulosics; wood pellets Heat; power 11 MWth; 5,5 MWel CHP conversion
Harboøre, Denmark Lignocellulosics; wood chips Heat; power 3,5 MWth; 1 MWel CHP conversion
Barrit, Denmark Lignocellulosics; wood chips Heat; power 140 kWth; 35 kWel CHP conversion
Kgs. Lyngby, Denmark Lignocellulosics; wood chips Heat; power 140 kWth; 35 kWel CHP conversion
Cumbria, United Kingdom Lignocellulosics – 1 MWel CHP conversion
Mossborough, United Kingdom Lignocellulosics; wood chips – 250 kWel CHP conversion
Neunkirchen, Austria Lignocellulosics; waste wood, clean wood, biomass Heat; power 620 kWth; CHP conversion
300 kWel;
Güssing, Austria Lignocellulosics; wood chips Heat; power 4.5 MWth; CHP conversion
2.0 MWel
Oberwart, Austria Lignocellulosics; wood chips Heat; power 1–6 MWth; CHP conversion
2.7 MWel
Neumarkt, Austria Cleanwood, biomass Heat; power 580 kWth; CHP conversion
240 kWel
Sulzbach-Laufen, Germany Other; wastewood, biomass Heat; power 280 kWth; CHP conversion
130 kWel
Neufahrn bei Freising, Germany Lignocellulosics; waste wood, clean wood Heat; power 250 kWth; 110 kWel CHP conversion
Langballig, Germany Lignocellulosics; wood chips Heat; power 280 kWth; 70 kWel CHP conversion
Carlow, Ireland Lignocellulosics; wood chips Heat; power 140 kWth; 35 kWel CHP conversion
Wila, Switzerland Lignocellulosics; dried chips from waste wood Heat; power 425 kWth; CHP conversion
350 kWel;
Stans, Switzerland Lignocellulosics; dried chips from demolition wood Heat; power 1.2 MWth; 138 kWel CHP conversion
Geertruidenberg, Netherlands Wastewood; demolitionwood Heat; power; gas for 30 MWel Co-firingconversion
coal-fired boiler
Buggenum, Netherlands Biomass /biomasscoalblends Power 280 MWth Co-firingconversion
Lahti, Finland Lignocellulosics; wood chips, wood waste, plastic waste Fuel gas 40–90 MWth Co-firingconversion
Värö, Sweden Lignocellulosics; bark Heat 35 MWth Co-firingconversion
Varkaus, Finland Other; wood fibre, plastic, aluminium FT-liquids; heat; 14 t/d; 50 MWth Synthesisconversion
aluminium
Groningen, Netherlands Other; from biodiesel and oleochemicals Methanol 200 000 t/a Synthesisconversion

for gas-operated cars or for electric cars [166–168]. For example, in the main low temperature shift catalysts. They must be operated at a
the Swedish city of Västerås biomethane has been adopted as vehicle temperature of about 200 °C [171].
fuel in the local public transport system [169]. Hydrogen can be used as the chemical basis for ammonia pro-
The typical path to produce hydrogen from syngas is the catalyzed duction or as a fuel for fuel cells. A schematic representation of the
Water-Gas Shift Reaction [170]: market potential and the technological reliability of the products of
biomass gasification is shown in Fig. 12; this figure, starting from
CO + H2 O ↔ CO2 + H2 (15) the version proposed by Maniatis [172], has been updated to include
novel processes.
Two kinds of catalyst can be used: high temperature and low tem-
perature shift catalysts. 7. Status of the European biomass gasification plants
Chromium-supported iron-based catalysts are the main high tem-
perature shift catalysts. They must operate at a temperature in the In the last decades, the presence of the gasification process in the
range 350–400 °C to achieve a CO outlet concentration in the range European market has increased. In Europe there are 22 gasification
2–4 vol%, in a single adiabatic fixed bed [171]. plants and 7 companies have the know-how for their construction
Using a dual fixed bed system, CO conversion can be improved. [173]. Sixteen are power generation or combined heat and power gen-
If copper-based catalysts are used in the second bed, the CO outlet eration plants, four are co-combustion plants and two plants are ded-
concentration can reach the range 0.1–0.3. Copper-based catalysts are icated to the production of chemicals, as show in Table 10.
 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25 23

Table 11. Italian biomass gasification plants [174].

Site gasification plant Input Output (kWe)

Rossano calabro (CS) Olive pomace 4,200

Belluno (BL) Wood chips 1000
Parma (PA) Kenaf 1000
Vistarino (PV) Wood chips 1000
Gadesco pieve delmona (CR) Biomass chopped/biomass chips 960
Alessandria (AL)a Biomass forestry 640
Vigevano (PV) Wood chips 500
Caluso (TO) Agriculture waste, biomass forestry, food industry waste 400
Oltrepo pavese (PV) Wood chips 320
Castel san pietro (BO) Pruning wastes, corns stocks, wood chips 250
Orzinuovi (BS) Biomass forestry 250
Verbania (VB)a Biomass forestry 250
a
Experimental plant.

Table 12. Biomass gasification plants in Europe with an operation time greater than the internal combustion engines, using biomass as co-feeding mate-
7000 h/y [176–180].
rial [181].
Site Thermal output (MW) Running (h/y)

a
Harboore (Denmark) 20 8000
Gussing (Austria)b 8 7000–8000 8. Conclusions
Skive (Denmark)c 20 7500f
Lahti (Finland)d 40 7000 Gasification technology can be a good solution for energy produc-
Buggenum (the Netherlands)e 600 7500 tion from renewable sources, but in order to eliminate the causes that
a,b,c
Biomass gasification plant. hinder its development on a large scale other efforts are necessary.
d,e
Co-combustion plant fuelled with carbon and biomass. Several technological problems exist, first of all the compatibility be-
f
Cumulative hours in the 2008–2009 biennium.
tween the engines and syngas. The optimal operation of engines cou-
pled with gasification plants requires a high quality standard fuel, but
In Italy several gasification plants exist, they have low capacity due to the high concentration of pollutants, such as tar, ammonia and
and are power generation plants, as show in Table 11 [174]. sulphidric/chloridric acids, the syngas quality is often not sufficient.
The biomass gasification plants operating in Europe produce elec- Furthermore, gasification companies provide little information about
tricity in combined heat and power (CHP) configuration; these plants the cleaning section of plants and the engine is not guaranteed for
often do not produce more than 1 MWe. On the other hand, larger a long period of time. Moreover, economic profitability strongly de-
plants are often co-combustion plants and only few biomass gasifi- pends on the biomass market price, even if gasification plants often
cation plants are able to produce biofuels such as methanol or others obtain considerable financial incentives from governments.
biofuels via Fischer Tropsch process [175]. A Best Practics in biomass gasification process is the heat recov-
In several cases there is no information about the yearly running ery of power production flue gas. To achieve the highest energetic ef-
time for these plants, and, when this information is available it is dis- ficiency heat and power production systems (CHP) or tri-generative
couraging. The biomass gasification plants with long running times processes are combined with electrical, heat and cool production
per year are reported in the Table 12. The data in this table show that (CCHP).
about 700 MW are running for biomass gasification in Europe; these Syngas is not only an energetic carrier for power production but
plants have an operation time greater than 7000 h/y [176–180]. also an intermediate product for liquid and gaseous biofuel produc-
Although this paper is focused on biomass gasification, accord- tion. Liquid biofuels, such as biodiesel and bioethanol, can be stored
ing to the authors it can be useful to present a short overview of the and used as transport fuels; gaseous biofuels, such as biomethane,
waste gasification plants (Table 13) in Europe at present. It is possi- can be injected directly in the natural gas distribution grid. A high
ble to see that in several cases the gasification stage is a pre-stage overall efficiency of biomass power production–Organic Rankine Cy-
for the successive complete combustion. In this way the combustion cle or heat, cool and power production–is the key for the success of
stage, burning the syngas, is cleaner and more efficient than the direct such a plant.
combustion of wastes and it is possible to use a reduced excess air. Due to the high syngas purity, required to save the catalyst in
Only few gasification plants, SchwarzePumpe, Rudersdorf, Freiburg, the biofuel synthesis, only few pilot or industrial plants for the pro-
Lahiti, Greve and Norrsundet are pure-gasifier which produces syn- duction of liquid or gaseous biofuels from syngas are functioning at
gas usable in combustion devices for the power production such as present.

Table 13. Waste gasification plant running in Europe [181].

Site Input Technology

Averoy, Norway MSW Gasificat. + combustion

Hurum, Norway MSW and industrial waste Gasificat. + combustion
Sarpsborg, Norway MSW and industrial waste Gasificat. + combustion
Forus, Norway MSW Gasificat. + combustion
Karlsruhe, Germany MSW and commercial waste Pyrolysis + gasification
Minden, Germany MSW and commercial waste Gasificat. + combustion
SchwarzePumpe, Germany plastics, RDF, wood, sewage, sludge, lubricants,coal RDF Gasification
Rudersdorf, Germany plastics, RDF, wood, sewage, sludge, lubricants,coal RDF Gasification
Freiberg, Germany sewage sludge + MSW Pyrolysis and entrained flow gasification
Lathi, Finland biomass fuels (up to 40% RDF) Circulating fluidized-bed boiler with gasification
Greve-in-Chianti, Italy pelletised RDF Gasification
Norrsundet, Sweden MSW and industrial waste Gasification
24 A. Molino et al. / Journal of Energy Chemistry 25 (2016) 10–25

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