Lignocellulose biorefinery product

engineering 5
5.1 Overview
Petroleum refining is a technology that uses fossil fuels as raw materials and chemical
catalysts as a means to achieve conversion of petroleum through once, twice, and deep
processing to get a series of chemical products, which are further used as the basic raw
materials for synthetic fibers, synthetic rubber, plastics, chemical fertilizers and pes-
ticides production. With the gradual depletion of oil resources, the fossil economy is
facing serious challenges. Biorefining has gradually become a new method used to
produce energy and chemical products, which parallels petroleum refining. Biomass
is used as a raw material to produce some middle platform compounds by thermo-
chemical, chemical, or biological methods, which are then processed into bio-fuels
or chemicals. Biorefining offers the possibility of achieving sustainable production
of bioenergy and biomaterials. Biorefining is a new concept in industrial manufactur-
ing, which will become a new manufacturing technology paradigm, becoming more
and more important because of its use of alternative resources and its environmental
benefits (Demirbaş, 2001).
Biorefinery products consist of: heat; electricity; various solid, liquid, and gaseous
energy products; as well as bio-based materials and chemicals. The distinctive char-
acteristics and functions of biomass allows for its use in products that will most likely
replace oil, coal, and natural gas, opening up a future nonfossil fuel energy era. Bio-
mass can produce liquid fuels to replace oil, solid fuels to replace coal, as well as gas-
eous fuel to replace natural gas.
Compared with petroleum refining, biorefining is unique for the following reasons:
(1) Biorefinery feedstock is carbohydrates while petroleum refining involves hydro-
carbons without oxygen molecules and lacking functional groups, thus biorefining
is more economical from the point of view of atom utilization. Therefore, it is
cost-effective due to the avoidance of the high-cost oxidation process. (2) Compared
with the petroleum fuels, biodiesel obtained from biorefining has better oxidation sta-
bility and higher energy density, which can reduce carbon deposits on the engine, so
that operating costs are only half those of the conventional diesel apparatus. (3) In the
petroleum refining process, the resource-rich region is separated from the end market,
which means long-distance transport is required, while biomass resources are usually
found near to the market.
Biorefinery techniques are far from mature. However, with the advances of techno-
logy, a number of bio-based products that are able to replace or partially replace
petroleum-based products – such as fuel ethanol, lactic acid, citric acid, biodiesel
and 1, 3-propanediol – have sprung up. These products can be divided into many groups
according to carbohydrates platform, oil platform, and thermochemical platform.
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126 Lignocellulose Biorefinery Engineering

Crude oil

Pretreatment Biomass

Hydro-
Oil cracking
Gasification/ Other
refining Pretreatment
pyrolysis processing

Farm produce
Gas Enzymatic
Hydrogen
separation hydrolysis

Fuel/ Biochemical
chemicals Synthesis Fermentation
reactions
Energy

Post- Biochemical
Steam and processing products
power
generation Residue
Biofuel
Figure 5.1 Schematic diagram of biorefining and petroleum refining.

Although there are a variety of products from biorefining, many of them are not needed
in large quantities. Therefore, it would be not be economical to prepare all of these
products directly from the basic raw materials. Hence, it is necessary to develop many
platform products, such as succinic acid, fumaric acid, or malic acid, which can then be
economically converted into various chemicals (Wang et al., 2007; Figure 5.1).

5.2 Bioenergy
Solar energy is the source of almost all energy on earth. Biomass is a resource pro-
duced from the conversion of solar energy. The energy basis for modern industrial
development (i.e. coal, oil, and natural gas), evolved from the ancient biomass buried
under the ground through the joint action of microbes and geological chemistry.
Trends in the utilization of energy are biomass ! coal ! oil ! coal ! biomass.
Humans have improved the utilization efficiency of energy by changing their utiliza-
tion methods. Conversion of biomass to bioenergy alternatives of coal, oil, and natural
gas or other fossil fuels is in line with the balance: CO2 þ sunshine ! crops ! bio-
based energy ! CO2, and finally forms a mass cycle with a theoretically zero net
CO2 emission (Figure 5.2).
If biomass completely replaced fossil fuels, CO2 emissions during the production
and transfer of biomass energy such as bioethanol would be equal to those during the
exploitation and transfer of fossil fuels. However, alternative energy can reduce CO2
Product engineering 127

CO2+H2O Solar energy

Photosynthesis

Carbohydrates

Physical transformation Biotransformation Thermochemical conversion

Ethanol
Butanediol Gasification gas
Biomass briquette
Biogas Pyrolysis oil
Hydrogen

Combustion

CO2+H2O

Figure 5.2 Ecological carbon balance of biomass energy.

emission through improving the energy utilization methods and the utilization ratio. In
addition, in the process of biofuels production, N, S, and other impurities are removed
to a great extent. Therefore, it is a type of green energy. It meets the demand for
decreasing CO2 emissions, and creates a low-carbon economy to replace fossil fuels
with biomass energy. Moreover, it can reduce the concentration of pollutants in the
atmosphere, which helps to protect the environment.
The BP Statistical Review of World Energy Report 2011 showed that as of the end
of 2010, oil, natural gas, and coal can only be used for another 46.2, 58.6, and
118 years, respectively, according to the world’s proven reserves and production
(‘BP statistical review of world energy June 2011’, 2011, Available from: www.
bp.com/statisticalreview). China is short of fossil energy resources, especially oil
and natural gas. However, due to the rapid development of the Chinese economy,
energy consumption is increasing sharply, and accounted for 20.3% of total global
energy consumption in 2010; Chinese coal consumption accounted for 48.3% of total
global coal consumption (‘BP statistical review of world energy June 2011’, 2011,
Available from: www.bp.com/statisticalreview). China has surpassed the USA to
become the largest energy consumer in the world. Although the use of new forms
of energy is growing rapidly, coal is still the primary energy form in China, and this
128 Lignocellulose Biorefinery Engineering

is unlikely to change in the short term, resulting in the situation where China’s emis-
sions of SO2 and CO2 rank first and second in the world, respectively. Therefore, look-
ing for environmentally friendly clean energy to gradually replace oil and coal and
meet the large demand for liquid energy is an irreversible quest. We should develop
new kinds of available energy before running out of oil. The ultimate aim of bioenergy
research is to reduce our dependence on oil; thus, our current challenge is to search for
large-scale, economically feasible bioenergy technologies. As is shown by the con-
stant consumption and shrinkage of fossil fuels and their increasing price, we have
to accelerate the pace of study and production of bioenergy. In order to realize the
industrialization of bioenergy, two key factors are essential: first is the determination
and planning of government, favorable legal policy, guaranteed huge investment, and
market demand from consumers; and second is making constant progress in biorefin-
ery technologies and breakthroughs in key technology.
Biomass can be used with oil as a raw material to produce chemical products and
other substances, while other sources of energy cannot. The composition of biomass
from different materials varies widely. For example, the main components of straw
are cellulose, hemicellulose, and lignin; potatoes are mainly composed of starch;
while oil-bearing crops contain fat. However, all in all, the main components of plant
materials contain the following basic substances: carbohydrates (including sugar), starch,
cellulose, hemicellulose, lignin, fat, and protein. Biomass materials contain various sub-
stances, and many oxygen-containing groups like hydroxy, carbonyl, and benzene rings.
Compared with the linear aggregation structure of oil materials with only d(CH2)nd,
biomass is more suitable for chemical modification and producing various chemical prod-
ucts as well as providing more chances for development of new products in addition to the
conversion to bioenergy, such as biofuels (Chen and Wang, 2008).
Using different techniques, biomass can be converted into different products. Bio-
mass can be burned directly or used to generate electricity by gasification; provide gas
resources; be converted into biogas (biogas, biohydrogen), biofuels (bioethanol, bio-
diesel, biobutanol, bio-oil, solid fuel), and also into biological materials and chemicals
(acid, polylactic acid); and so on. The choice of the best pathway depends on the spe-
cific issues of each situation. Oil is processed via heated distillation, catalytic crack-
ing, hydrocracking, and other technologies to produce fuels like gasoline and
ethylene, and chemicals like propylene, based on different market needs. Therefore,
with the development of raw material resources and the utilization of advances in tech-
nology, biomass energy will play an important and indispensable role in human life.

5.2.1 Ethanol
5.2.1.1 Applications and market for fuel ethanol
The most direct and important application for the bioenergy system is to produce eth-
anol through biomass fermentation technology. With the gradual depletion of fossil
resources, more and more countries have regarded the energy supply diversification
strategy that ethanol and other alternative energy sources supply as one of the main
directions for their energy policies. The rise in oil prices, constant progress of fuel
ethanol manufacturing technology, the wide application of flexible fuel vehicles
Product engineering 129

(FFV), the widespread use of renewable fuel ethanol, and expanded sources of raw
materials have brought about reliable technology and economic viability for the fuel
ethanol industry. In addition, the application of fuel ethanol in diesel engines can fur-
ther expand the application range of fuel ethanol, which will provide a broader utili-
zation base for fuel ethanol.
Ethanol is a new kind of green energy as well as a basic chemical raw material that
is widely used in the chemical engineering, food, beverage, military, household che-
micals, pharmaceuticals, and health fields. Moreover, as an excellent fuel (combustion
value reaching 26,900 kJ/kg), ethanol can improve fuel quality. The advantages of
using ethanol fuel include the following: (1) ethanol can replace or partially replace
gasoline as a motor fuel, reduce gasoline consumption, and ease the demand for fossil
fuels, thereby reducing dependence on oil imports and improving national energy
security; (2) as a high-octane gasoline component, the octane number of ethanol is
generally above 120, it can improve the anti-knock properties of spark-ignition inter-
nal combustion engines and make the engine run more smoothly; (3) due to the fact
that ethanol is an aerobic fuel, it can replace methyl tert-butyl ether (MTBE), which is
a pollutant to water, making combustion more complete and decreasing the emission
of air pollutants such as particulate matter and CO by at least one-third, which reduces
energy consumption; (4) it can effectively eliminate carbon deposits on spark plugs,
valves, piston tops, and the exhaust muffler, thereby extending the service life of the
main parts of automobiles. The entire production and consumption of ethanol can
form a clean and nonpolluting closed cycle, which is permanent and endless
(Cardona and Sánchez Toro, 2006).
More than 90% of the ethanol in the world is produced by fermentation of biomass,
so ethanol is a renewable energy source. The exploitation of ethanol fuels has become
more and more important with intensive need for liquid fuels and the huge pressure
this puts on the environment. Attention is paid to ethanol production due to its poten-
tial to decrease oil consumption and reduce environmental pollution, especially after
the introduction of the Kyoto Protocol; the application of ethanol is regarded as an
effective measure to make use of biomass and reduce CO2 emission.

5.2.1.2 The development of ethanol production

and associated problems
The main materials used to obtain fuel ethanol by fermentation processes are raw
sugars, starch, and lignocelluloses, while cassava, sweet sorghum, and corn stalks
are the focus for the development of fuel ethanol production in China. Sweet sorghum
is a saccharine material whose syrup after pressing is mainly used for fermentation;
and cassava is a kind of starch feedstock whose glucose component from starch hydro-
lysis is used for fermentation. Both of these processes produce ethanol from parts of
the biomass materials. However, because sugar and starch are edible, the production
of ethanol from these materials faces the problem of competing for a resource that is a
source of food for humans, and what’s more, the cost of raw materials makes up more
than 40% of the total cost (Li et al., 2011). Therefore, the production of fuel ethanol
faces dual pressures on moral and cost grounds, and this has led to high hopes for
130 Lignocellulose Biorefinery Engineering

cellulose ethanol production. Corn stalks are cellulose materials, and the glucose pro-
duced via hydrolysis of cellulose is used for fermentation. Despite the fact that ligno-
cellulosic raw materials like straw are abundant, their complex structure requires
complicated technology routes, and results in low utilization rates and high energy
consumption for separation, which leads to a higher production cost than sugar and
starchy materials. To fully use lignocellulosic raw materials, the following challenges
must be overcome: technology must be simplified, production costs reduced and
wastewater emissions reduced. At present, many factories produce bioethanol from
straw, cassava, and sorghum. It is necessary to search for new technologies to produce
ethanol from agricultural and forestry wastes instead of corn and thereby improve the
multipurpose utilization, reduce the production cost of bioethanol and enhance com-
petitiveness (Figure 5.3).
In August 2006, the first fuel ethanol production demonstration project from straw
enzymolysis and fermentation with an annual yield of 3000 t was established, based on
the patents of low pressure and nonpollution steam-explosion pretreatment for straws
and cellulase production via solid-state fermentation that was proposed by Prof. Chen.
The technology could produce high-value-added xylo-oligosaccharide besides ethanol,
which conquers the problem of ethanol conversion from xylose and also improves eco-
nomic returns. Such technologies possess proprietary intellectual property rights and
complete technical parameters, which will provide a rich experience for the industrial-
ization of cellulose ethanol production at a level level of 10,000 tons (Chen and Qiu,
2007).
The cost of raw materials, which accounts for 65% of the total cost, is a key
factor for the economic feasibility of the technology. The cost of cellulase and corn

Cellulase storage tank

Dilute sulphuric acid

Seeding tank
Raw material storage
Disintegrator SSCF reactor
Pretreatment reactor

Solid liquid separator

Molecular sieve
Lignin

Rectification
Distillation
Fuel oil

Ethanol

Stillage
Figure 5.3 Process flowchart of fuel ethanol production from corn stalk.
Product engineering 131

stalks severely affects the production cost, which is also one of the key factors that
affect the ethanol cost.
However, there are still many problems to overcome to realize the industrialization
of such a process; among which are how to realize the effective saccharification of
straw cellulose and avoid the mutual inhibition effects between raw materials and
products.

5.2.2 Butanol
5.2.2.1 Applications and market for butanol
Biobutanol or bio-based butanol fuel is a second-generation alcoholic fuel with a
higher energy density and lower volatility compared to ethanol. Butanol’s application
as a replacement for gasoline will outpace ethanol, biodiesel, and hydrogen when its
safety and simplicity of use are seen. Butanol is an important chemical raw material
and organic solvent, which is widely used in industry, medicine, and food. As a better
prospective new biofuel than ethanol, butanol has broad application prospects due to
its good water-insolubility, low vapor pressure, high calorific value, and other char-
acteristics. Butanol can reach a higher mixing rate with gasoline compared to ethanol
fuel and its energy density is closer to gasoline, which is more suitable for the existing
fuel supply and distribution systems. At the same time, butanol is more environmen-
tally friendly when compared to fuels from oil refining and hence decreases the emis-
sion of greenhouse gases during the gasoline refining process.
The butanol fermentation industry began in the early 20th century, and was applied
on a large-scale in World War I. Butanol fermentation has become the second largest
fermentation industry next to ethanol fermentation (Durre, 2011). Because the
fermentation products are a mix of acetone, butanol, and ethanol (acetone–butanol–
ethanol, ABE), the solvent production fermentation is also known as ABE fermenta-
tion. With the development of the petrochemical industry, the chemical method to
produce butanol from petrochemical feedstock has shown more advantages over
the fermentation method based on both cost and productivity. Therefore, butanol
production from the synthesis method had gradually replaced the fermentation method
by the 1960s. However, people paid attention to butanol production via fermentation
again due to the outbreak of the oil crisis in the late 1970s. And in the 1980s, the study of
the genetic system of clostridium-producing solvents made great progress, which played
an important role in improving the grains’ fermentation properties. The most widely
researched subjects were the construction of excellent strains and the improvement
of fermentation and separation technologies.

5.2.2.2 The development of butanol production

and associated problems
Raw material cost accounts for 60–70% of the total cost of butanol, which is an impor-
tant limitation of the industrial development of butanol fermentation. Corn, wheat, and
molasses have been the primary materials for acetone–butanol fermentation for a long
132 Lignocellulose Biorefinery Engineering

time. However, with the constant rise in food and molasses prices and the potential
demand for grains by the increasing world population, choosing cheaper lignocellu-
losic feedstocks like straw has become an effective route for reducing fermentation
cost (Chen et al., 2010). The cellulose and hemicellulose produced after lignocellu-
losic feedstock hydrolysis or acid hydrolysis may be converted into sugars by micro-
bial fermentation. But due to the fact that the composition of lignocellulosic feedstock
materials is more complex than food and the conversion efficiency is relatively low,
lignocellulosic raw materials should be pretreated before fermentation. Researchers
began to study the use of lignocelluloses for acetone–butanol fermentation in
the 1980s.
In addition, for butanol production, the bottleneck lies in the low butanol concen-
tration caused by the inhibition of butanol fermentation products. Therefore, it is nec-
essary to adopt a strategy of continuous fermentation to achieve efficient production
of butanol and the aim of coupling fermentation with separation technologies. In this
way, we may realize the goals of removing the inhibition of butanol fermentation
products and saving separation and energy costs. Our group (Wang and Chen,
2011) constructed a fermentation device coupled with enzymolysis and membrane
recycling, and used steam-exploded wheat straw to produce acetone–butanol, which
realized of a maximum yield of butanol of 0.31 g/(L h), a cellulose and hemicellulose
conversion rate of 72% and 80% respectively, and achieved continuous enzymatic
hydrolysis and fermentation. This illustrates that the use of lignocellulosic raw mate-
rials to produce acetone–butanol by fermentation is feasible. Concerning the problems of
low enzymolysis efficiency and difficulty in degrading cellulose, Prof. Chen used the
hydrolysate of hemicellulose to produce acetone–butanol via fermentation, and the
cellulose was used for butanol fermentation after grading to obtain short fibers.
Meanwhile, the long fibers and lignin within the straw were used for the production of
high-value products. They accomplished an increase in butanol production with an
annual yield of 50,000 tons together with cogeneration of acetone, ethanol, furfural,
polyether polyol, and phenolic resin (Kamm and Kamm, 2007) (Figure 5.4).
Figures 5.5–5.7 show the industrial-scale application of this polygeneration technology.
A straw refinery production line established by the Institute of Process Engineering
and Songyuanlaihe Chemical Co. Ltd started to run in August 2010 with an annual
processing capacity of 300,000 tons. The line is a high value-added way to utilize
straw in which the five-carbon sugars are used to produce butanol, acetone, and eth-
anol; long-cellulose fiber is used to make paper; and short-cellulose fiber and lignin
are used to produce polyether and phenolic resins as well as other products. Using the
lignin and cellulose produced by this production line, another two production lines
with polyether polyol yields of 50,000 tons per year and phenolic resin glue yield
of 20,000 tons per year are going to start operation. After the 300,000 t/y straw refin-
ery line production was put into operation, the total sales reached 1.2 billion yuan
(US$ 192 million) with about 100 million yuan (US$ 16 million) profit.
Although lignocellulose is considered to be the best prospective fermentation sub-
strate, there are many problems in the process of converting lignocellulosic feedstock
into butanol. The current situation is that the major industrial strain of Clostridium still
cannot effectively hydrolyze lignocellulose. Therefore, lignocellulosic feedstock
 Product engineering
Acid hydrolysis residue

Steam
explosion
Cornstalk vessel
Screw press dewaterer
Hydrolysis tank

Pulverizer

Furfural
P-40

Condenser Short-fiber
Vacuum distillation tank Extraction residue
P-21
Alkali
treated
materials Long-fiber
Vacuum distillation tank
Carding machine

Screw extractor P-22 NaOH solution

Alkali extract pot
P-10 Extraction liquor

Electrodialysis
Agitation tank NaOH Ultra filtration membrane
solution
Activated carbon
treatment

Furfural
Lignin

Butyl alcohol fermentation

tank Rectifier

Agitation tank
P-43
Drying machine Centrifuge

Ethanol tower Sewage

Acetone tower Waste liquor
Butanol, acetone and plant
ethanol
Solvents

Butanol tower

Vacuum distillation tank

Figure 5.4 Flowchart of converting hemicellulose into butanol and the comprehensive utilization of corn stover.

133
Figure 5.5 An 80 m3
hydrolysis tank.

Figure 5.6 A 400 m3 fermentation

tank.
Product engineering 135

Figure 5.7 Butanol–acetone distillation tower.

must be pretreated to effectively hydrolyze cellulose and hemicellulose into monosac-

charide, which is suitable for Clostridium to convert to butanol. Meanwhile, many
complex products during the pretreatment period of lignocellulose could inhibit the
fermentation of butanol. More importantly, during the utilization process of lignocel-
lulose, people often use a single technology and use only one component while ignor-
ing the use of other components, resulting in materials waste and environmental
pollution, which is the main reason that the whole biomass industry can not compete
with the petrochemical industry.

5.2.3 Biogas
5.2.3.1 Applications and market for biogas
Energy is the foundation for the progress of human civilization as well as an indispens-
able requirement for the progress of modern society (Demirbaş, 2001). For a long
time, fossil fuels have played the dominant role in the energy structure of China.
Therefore, using cleaner energy utilization technologies is essential in order to protect
the environment and tackle climate changes. Marsh gas is one kind of renewable
resource and using wastes from marsh gas production by anaerobic digestion is a
favorable avenue of exploration toward solving the energy crisis. Therefore, both
Western countries and China have attached importance to marsh gas production
(Chen et al, 2010).
China’s energy consumption increased by 11.9% in 2010, which made China the
world’s largest energy consumer, surpassing the USA. China can be described as
being rich in coal, having less oil and a shortage of gas. Of the fossil fuel reserves
in China, oil and gas account for 5.4 % and 0.6 %, respectively. China’s natural
gas resources and productivity are severely insufficient compared with the rapidly
increasing demand. For example, the natural gas yield was 103.06 billion m3 and
the consumption was 117.38 billion m3, with a 14.32 billion m3 gap between supply
and demand (‘BP statistical review of world energy June 2011’, 2011, Available from:
136 Lignocellulose Biorefinery Engineering

www.bp.com/statisticalreview). With the rapid development of its domestic econ-

omy, the gaps between supply and demand for oil and natural gas will increase and
will influence the sustainable development of China, which could also cause potential
safety hazards for the energy supply of China. Due to the huge gap, energy alternatives
are essential to release the import pressure on oil and natural gas. The effective com-
ponent of marsh gas and natural gas is methane, and the content of methane in purified
marsh gas could reach 95%. Therefore, marsh gas is almost the same as natural gas and
will be an optimal choice to displace natural gas. That is also the reason that both
medium and large marsh gas project construction has been paid much attention by
society. Moreover, construction of marsh gas projects requires a lot of money, which
encourages the government to pursue the application of agricultural waste technolo-
gies (Jiang et al, 2011).
As a molecular functional structure assembly consisting of cellulose, hemicellu-
lose, and lignin, straw has a complex chemical structure and composition, which
results in the mutual disturbance of various components and a low conversion ratio
during plant usage, and hence causes difficulties in high-value utilization. If we could
separate the components effectively and then convert them separately, we could
improve the conversion efficiency of straw by reducing the mutual disturbance, but
also make full use of the different components and increase the comprehensive utili-
zation value (Jin and Chen, 2007). Compared with the usual raw materials like live-
stock manure, straw is widely distributed and abundant and could completely solve
the problems of insufficient raw materials for marsh production. Due to its low water
content, the biogas residue is solid, which could be used as organic manure directly.
Meanwhile, biogas slurry could be used for water content adjustment for the next fer-
mentation, which meets the demand of a circular economy during a cleaner production
process. While the livestock manure has high water content, the biogas residue and
slurry are hard to use and dispose of. Moreover, some biogas residue and slurry are
discharged without treatment, which causes secondary pollution to the environment
and would not solve the environmental pollution problem. Straw can be preserved
for a long time and transferred conveniently, and has a relatively low cost. Biogas pro-
duction from straw refining is an environmentally friendly, clean process that could
realize the complete conversion of straw and the high-value utilization of resources
(Kaparaju et al., 2009a, 2009b).

5.2.3.2 The development of biogas and associated problems

Biogas can decrease energy consumption, reduce pollution, and construct a platform
of rural energy conservation and emission reduction, as well as improving rural health,
solving the problem of household energy consumption of farmers, and protecting the
environment. Thus, biogas project construction has become an essential link that
promotes construction in the countryside and develops a sustainable agricultural cycle.
The existing ecological agricultural modes “Four in One” (a typical one is pig-biogas-
vegetable-heliogreenhouse) and “Three in One” (a typical one is pig-biogas-fruit) are
choices based on the raw materials of human and animal manures. These development
modes cannot satisfy the demand of large-scale and intensive breeding, agricultural
modernization, rural urbanization, and city and countryside integration. Producing
Product engineering 137

biogas from straw has the advantages of abundant materials and wide distribution
without limitations of time and space, which can achieve a complete ecological cycle
and effective utilization of straw. Straw is rich in cellulose, hemicellulose, and lignin
that contain plentiful energy. Therefore, straw can be used as a potential energy
supplier to solve the current security issues related to the energy supply. Through
appropriate pretreatment, bioenergy in the form of biogas could partly satisfy the need
for renewable green energy (Zeng et al., 2007). In this way, biogas not only solves the
problems of agricultural waste pollution of the environment and disposal difficulties,
but also produces biological natural gas that partly displaces fossil resources. And
at last, the aims of low carbon, circular economy development, and clean energy
replacement will be achieved.
The effective constituent of biogas and natural gas is methane. Therefore, biogas is
the optimal choice to displace natural gas. For a long time, agricultural wastes such as
straw have been used as auxiliary ingredients for anaerobic digestion to adjust C/N and
not as the main materials to produce biogas via anaerobic digestion. The reasons are
the following: straw contains a high proportion of lignocellulose, which is hard to
digest using anaerobic bacteria, leading to a low digestion rate, low yield of biogas,
and poor input and output efficiency; straw cannot be digested continuously due to its
nonflowing character; straw materials cannot achieve a high production efficiency due
to their low density, large volume, and difficulties in feeding and ejecting the mate-
rials; and the existing devices are designed for the digestion of wastewater and live-
stock excrement, which are not suitable for straw materials. However, compared with
the usual digestion raw materials such as livestock excrement, straw has the charac-
teristics of being widely available, having convenient collection and storage, and
being cheap in price. Therefore, straw could be a prospective resource for a significant
bioenergy industry if all these problems are solved.
At present, the use of biogas as an alternative to coal and natural gas to generate
electricity and heat or serve as bionatural gas for automobiles has been industrialized
in EU countries (Li et al., 2011). Moreover, biogas utilization has turned into a
win–win situation of energy generation and environmental protection rather than just
simply a service for environmental protection. Despite the current situation, we think
that the economic value of biogas still remains to be exploited. Especially in China, it
is hard to realize the dual benefits of economy and environmental protection without
special project funding and fiscal subsidies from the government. Based on these
problems, we believe that biogas production via the straw refining process should start
from raw materials, the production process, and the products. After that, the issues
involving extracting xylose from straw hemicellulose hydrolyzate, and obtaining
acetic acid and bioethanol from the biogas production process should be studied.

5.2.4 Hydrogen
5.2.4.1 Applications and market for hydrogen
Fossil fuels will be used up in the near future, while hydrogen gas is one of the most
ideal alternative energy sources at present. Due to the fact that hydrogen itself is
renewable and does not generate any kind of pollutants (even CO2 during
138 Lignocellulose Biorefinery Engineering

combustion), using hydrogen gas could realize zero release. Hydrogen has a series of
advantages over other energy-containing substances. The energy density of hydrogen
is 2.68 times higher than that of gasoline; its electricity-storing properties could be
superior to any other method in terms of economic efficiency of technology; its ther-
mal efficiency is 30–60% higher than that of other fossil fuels when converted into
power; for example, hydrogen could be used as the fuel of fuel cells and combined
with fuel cells to provide an effective, clean, non-drive disk assembly and non-noise
technology, whose efficiency would be improved by 100%; hydrogen is fit for pipe-
line transportation and can share the same delivery system as natural gas; and the
delivery cost of hydrogen is the lowest and the loss is the smallest of all the energy
forms. Pint-sized, low-temperature, solid-ion exchange membrane fuel cells could be
used in automobiles and trains. In addition, hydrogen can serve as fuel for engines
directly. At present, hydrogen is used as an alternative to fossil fuels in hydrogen fuel
automobiles and hydrogen fuel cells. Powerful market demand from the oil, chemical
engineering, electricity, and chemical fiber industries should promote the develop-
ment of hydrogen industrialization. We believe that hydrogen will be one of the main
sources of energy in the post-fossil fuel era.

5.2.4.2 The development of hydrogen production

and associated problems
Due to its clean combustion products, high energy density, high thermal conversion
rate, and low transportation cost, hydrogen is regarded as an ideal source of clean
energy and is essential for the modern economy and sustainable development. At pre-
sent, hydrogen production from fossil fuels like coal, oil, and natural gas has begun to
take shape. However, it will not meet the need for sustainable development over the
long haul. High cost is the main problem restricting the industrialization of hydrogen
production. China has abundant materials for hydrogen production. The cost would be
decreased dramatically if industrial wastes, municipal sewage, household refuse, ani-
mal waste, and lignocellulose biomass were used to produce hydrogen after fermen-
tation. Dark fermentation coupled with biohydrogen production technology could
integrate effluent treatment, solar energy utilization, and clean energy production
organically and form a new kind of environmentally friendly industry. Therefore,
hydrogen via fermentation has huge potential either from the aspect of protecting
the environment or exploiting new energy sources and sustainable development
(Kumar et al., 2009). Research on hydrogen is relatively small compared with meth-
ane production via biomass fermentation. Studies by Chen showed that the maximal
hydrogen yield reached 68 ml/g of steam-exploded straw using Clostridium butyricum
to produce hydrogen via simultaneous saccharification and solid-state fermentation
with straws as substrate (Corredor et al., 2008).
How to reduce the hydrogen production cost is a question that perplexes hydrogen
applications, especially biohydrogen production via fermentation; this is also the
problem to solve to make hydrogen more competitive compared with other bioenergy
sources such as biogas and cellulose ethanol (De Vries et al., 2010). Additional prob-
lems include how to improve the conversion rate of hydrogen from glucose and how to
produce hydrogen effectively at the bioreactor level.
Product engineering 139

As two kinds of energy carriers, hydrogen and methane are both important raw mate-
rials for energy production and chemical engineering. More research concerns the pro-
cesses of how to produce hydrogen during methane fermentation and how the
fermentation residue of hydrogen production could be used as a substrate for methane
fermentation. In this way, the benefit of co-production would be much larger than that
of sole production. Furthermore, cheap development and utilization of substrates is
important for reducing the cost of biohydrogen production. Research is needed on both
dark fermentation and light fermentation for hydrogen production from industrial and
agricultural wastewater, municipal sewage, livestock wastewater, and lignocellulose bio-
mass materials, which could decrease production costs and help protect the environment
at the same time.

5.2.5 Biomass briquettes

5.2.5.1 Applications and market for biomass briquettes
Biomass briquette fuel technology is one of the main directions of biomass conversion
and application technologies. Studies showed that the combustion properties were
increased by 20% after the biomass was molded into solid briquettes. Moreover,
the emissions of greenhouse gas, NOx, and SO2 were only one-ninth, one-fifth,
and one-tenth that of coal, respectively. Biomass briquettes have the advantages of
an abundant supply of raw materials, simple technology, convenient operation and
low cost. Due to high thermal efficiency, excellent combustion properties, convenient
delivery properties, and ease of industrialization of biomass briquettes production,
they are fit for utilization on a large scale. Biomass briquettes are also suitable sub-
stitutes for coal in the fields of rural cooking, heating, providing clean fuels for cities,
providing energy for greenhouses, and providing fuels for industrial boilers and power
stations. The productivity and demand for biomass briquettes have recently increased
rapidly. For example, the total production of biomass briquettes was 766,000 tons in
2009, in China alone, which will have reached 20 million tons by 2015. China is a vast
agricultural country whose biomass resources are very rich, which provides a guaran-
tee for the development of biomass briquettes.
Biomass briquettes are molded materials with a certain degree of density, and are
produced as follows. Lignocellulosic raw materials are crushed into particles of appro-
priate size, and then the particles are compressed to rod-like, nubbly, or granulous
materials without either heating or adhesive under the conditions of 50–200 MPa
and 150–300  C (Jin et al., 2013). In recent years, biomass briquettes have developed
rapidly as competitive fuels (Yu et al., 2009) (Figure 5.8).

5.2.5.2 The development of biomass briquette production

and associated problems
The final forms of biomass utilization are gas, liquid, and solid. Conversion of bio-
mass to liquid and gaseous products must go through a chemical reaction process, dur-
ing which a certain amount of energy is lost. Therefore, compared with other
utilization technologies of biomass, biomass briquettes are easier to produce on a large
140 Lignocellulose Biorefinery Engineering

Figure 5.8 Biomass briquettes – pelleted fuel.

scale due to the simple production process and the ease of use of the end-products.
Hence, China has included the research and industrialization of biomass briquettes
in its renewable resources project.
Biomass briquettes are produced through dehydration of collected loose straw, then
grinding and extruding the straws into rod-like, nubbly, globular or granular solid
fuels, especially rod-like and granular ones. The physical and chemical properties
of briquette fuels are different from straws. Biomass briquettes solve the problems
of low bulk density, low energy density, and difficulty of storage and transfer.
The combustion properties of biomass briquettes have greatly improved, increas-
ing from 10–15% of direct burning to 30–40%. Meanwhile, biomass briquettes have
the advantages of high volatility, ease of burning, and low ash content compared with
coal. The combustion gases of biomass briquettes contain only a trace of SO2. There-
fore, biomass briquettes can realize the aim of zero CO2 emission and little pollution
of the environment as a kind of renewable resource.
However, the main problems of biomass briquettes utilization are hearth corrosion
and slag bonding (Zhang, 2007). The most significant characteristic of biomass bri-
quettes is a high Cl content (0.2–3.0%) compared to fossil fuels. The high Cl content
leads to the severe corrosion of hearth and the combustion residues tend to appear as
slagging phenomena similar to that of coal. The mechanism of deposition and corrosion
may be that the volatile alkali metal salts enter the gas phase of the hearth under 700  C
during combustion, and the volatile ash and other fine particles coagulate on the con-
densing surface to form the initial settled layer. With the increase of temperature, a melt-
ing bonding surface appears and a new settled layer is formed on the initial layer when
larger particles fall on the initial settled layer. If the hearth temperature exceeds 780  C,
these deposits form glassy slags (a complex mixture), which could take the boiler out of
operation. Usually, large-scale biomass boilers need to shut down every 10–12 months
for cleaning, and this can take about one week.
Product engineering 141

5.2.6 Bio-oil
5.2.6.1 Applications and market for bio-oil
Bio-oil is a complex mixture of organic fuel containing 25–30% water and a small
amount of fine carbon, whose calorific value is 15.0  16.0 MJ/kg and is more difficult
to ignite and burn out. Bio-oil has the advantages of abundant resources, renewability,
convenient to deliver, and high energy density, which gives it potential as a liquid fuel
and chemical raw material (Wang et al., 2010).
Depending on the sources of bio-oil, it can be divided into three categories. The first
is the liquid products derived from the destructive distillation of biomass, which is
called wood tar. Wood tar is similar to coal tar, and consists of polycyclic aromatic hydro-
carbon and asphaltene. The second category is bio-oil derived from rapid pyrolysis or
liquidation whose major component is liquid fuel. Compared with conventional crude
oil, this kind of bio-oil has some disadvantages, such as unsteady physical and chemical
properties, component changes with time and temperature, high viscosity, and high
oxygen and water content. The third category is the tar produced from the biomass
gasification process, which is an inevitable by-product that will affect the operation
of systems once condensed and coked. Therefore, corresponding measures should be
taken to control the tar yield in order to get syngas with high quality. Table 5.1 shows
the component analysis of bio-oil from straw pyrolysis (Jung et al., 2008).

5.2.6.2 The development of bio-oil production

and associated problems
(1) Commercial value of bio-oil (Zeng et al., 2011).
First, bio-oil can completely dissolve in alcohol. By adding a small amount of alcohol, the
fuel properties could be highly improved, the viscosity decreased, and the stability
enhanced. Compared with ethanol on a commercial level, these blended products are more
environmentally friendly due to the lower price.
Second, bio-oil is insoluble in diesel oil, although it could be emulsified by diesel oil.
Scientists from Canada and Italy have tried to make bio-oil emulsify with diesel oil using
surfactants. The stability, corrosion-preventing ability, viscosity, and quantity of diesel oil
are improved when adding 10–30% bio-oil, and diesel oil of this kind is similar to pure
diesel oil.
Third, the quality of bio-oil can be improved through catalytic reforming, which is sim-
ilar to that of petroleum. Bio-oil can be gasified or converted into manufactured gas, bio-
diesel, or biomethane. Biogas could be used in SO or PEM fuels directly and biodiesel could
be used in petrol engines.
(2) Problems in the application of bio-oil.
The composition and physical and chemical properties of bio-oil are affected by many fac-
tors, such as the raw material sources, water content, reactor types, reaction parameters, and
the production collection methods. But bio-oils derived from different routes still have
commonalities, such as high oxygen content (35–40%), high corrosive ability (pH 2–3),
poor thermal stability (polymerization over 80  C), high viscosity, and low calorific value
(the calorific value of crude bio-oil is 16-20 MJ/Kg and that of engine oil is 42 MJ/Kg).
Such properties restrict the application of bio-oil as an engine fuel. Moreover, due to
142 Lignocellulose Biorefinery Engineering

Table 5.1 Composition of bio-oil from straw pyrolysis

Substance Content (%)a

Levoglucosan 19.30
Furfural 9.29
p-Vinylguaiacol 6.59
Pyrocatechol 6.26
Acetic acid 5.73
Cresol 4.32
4-Methyl-benzaldehyde 4.17
Syringol 4.03
4-Ethyl-phenol 3.89
Guaiacol 3.81
2(5H)-Furanone 3.80
2-Hydroxy-2-cyclopenten-1-one 3.39
Phenol 2.70
3-Methyl-pyrocatechol 2.67
4-Methyl-catechol 2.54
3-Methyl-2-cyclopenten-1-one 1.82
p-Ethylguaiacol 1.72
Vanillin 1.64
Eugenol 1.59
3-Methoxy-pyrocatechol 1.37
Xylenol 0.94
4-Hydroxy-benzaldehyde 0.70

a
Analyzed by the GC–MS of bio-oils from rice straw.
(Jung et al., 2008)

the high oxygen content, bio-oil is easily hardened on contact with air. Therefore, only
after refining could bio-oil have the potential to partially displace fossil fuels and be
used in existing thermal equipment, especially internal combustion engines (Zhang
et al., 2006).
Bio-oil refining technology has been a research hotspot worldwide, and various technol-
ogies have their own drawbacks as well as advantages. Catalytic cracking has the advan-
tages of simple equipment and low cost, but the catalysts are easily coked and deactivated;
emulsification technology is simple, but its cost and energy consumption are high; catalytic
esterification is a useful method for modification, but it results in poor quality bio-oil. The
yield of bio-oil from catalytic hydrogenation and catalytic pyrolysis technologies is low,
with the deactivation of catalysts restricting the development of bio-oil refining technology.
Therefore, the key problems for bio-oil refining technology to resolve are how to develop a
catalyst with high catalytic activity and high stability and now to create a new technique to
improve the yield of bio-oil.

5.2.7 Conclusions
In order to satisfy the need for rapid economic and green development in China, the
key problem is to vigorously develop clean energy resources such as biomass to
Product engineering 143

displace fossil fuels and thereby improve the structure of the energy industry.
Emissions of CO2 and air pollutants would be decreased dramatically by displacing
coal with cleaner fossil fuels such as natural gas. This could also lay the foundation
for low-carbon development in China and provide more buffer time before fossil
fuels diminish. The low-carbon transition of the energy system is a huge opportunity
for China.

5.3 Bio-based chemicals

Biorefining, the conversion of biomass to renewable chemicals and fuels, is important
under the current situation of rising costs and decreasing oil supply. In particular, plant-
derived biomass is a reproducible and low environmental-loading resource, produced
from CO2 and water via photosynthesis using sunlight. Among various biomass resources,
lignocellulose biomass is the most abundant and is nonedible, which makes it a promi-
sing candidate for the sustainable production of chemicals. Figure 5.9 demonstrates the
path for the production of various organic acids from cellulose (Deng et al, 2014).

5.3.1 Oxalic acid

5.3.1.1 Applications and market for oxalic acid
(1) Recovery of noble metals under the action of metals, preparing materials with special
properties.
Oxalic acid can react with many metal ions and generate corresponding oxalate, which
could be dissolved and also generated in water. For example, potassium oxalate is obtained

OH
OH
O HO O
O
HO O
OH
OH n
Cellulose 2

Hydrolysis
OH OH
HO O Ana
ero OH
bic
OH O2 HO
OH
HO O OH OH O
Lactic acid
bic
OH
HO Gluconic acid
a ero OH O2
O An Glucose
O2 O2
OH HO O

O O
O OH
Levulinic acid Glycolic acid
OH OH
Formic acid Acetic acid
Figure 5.9 Organic acids produced from cellulose.
(Deng et al, 2014).
144 Lignocellulose Biorefinery Engineering

only by dissolving oxalic acid and KOH in water and neutralizing while stirring. During the
process of nuclear fuel recycling, transuranic elements can be recycled using oxalic acid as
a precipitator. Therefore, oxalic acid plays an important role in material production, leather
preparation, and tombarthite recovery. Moreover, due to the fact that China is the main pro-
ducing area of tombarthite, the interaction between tombarthite and oxalic acid is a key
aspect of domestic research.
(2) Preparation and application of glyoxylic acid.
Glyoxylic acid is obtained by reducing one carboxyl of oxalic acid into an aldehyde group
through electrochemical catalytic action. Recently, many reports have described glyoxylic
acid synthesis via electrolytic reduction from oxalic acid, but the yields in different reports
are different due to the effects of the shape, structure, and operational mode of the electro-
lytic cells. Many countries have built industrial devices to synthesize glyoxylic acid via
oxalic acid electrochemical reduction. Glyoxylic acid can be used to synthesize cosmetics
and spices, such as allantoin and vanillic aldehyde; in the pharmaceuticals industry,
glyoxylic acid is applied in the production of antihypertension, antiulcer, and tumor inhi-
bition medicines; and in agriculture, glyoxylic acid is mainly used for the synthesis of insec-
ticides, herbicides, fungicides, and plant growth regulators.
(3) Ester compounds of oxalic acid and their applications.
Oxalic acid can react with methyl alcohol, ethyl alcohol, and butanol to generate dimethyl
oxalate, diethyl oxalate, and dibutyl oxalate, respectively. Such esters are usually used as
solvents and raw materials for the production of antibacterial agents, antipyretic com-
pounds, and anticancer intermediates in the pharmaceuticals industry; they play a protective
role in the preparation of superconducting oxides; and they are also used to produce liquid
crystal materials, photosensitive materials, adhesives used during surgical procedures,
herbicides, and so on.

5.3.1.2 The development of oxalic acid production and associated

problems
Traditional preparation technologies for oxalic acid mainly consist of the carbohy-
drate oxidation method, the carbon monoxide coupling method, and the sodium for-
mate method. The carbohydrate oxidation method has the advantages of being a
simple technique and requiring moderate reaction conditions, but the yield is low
and many kinds of NOx substances exist in the tail gas. Moreover, grains are usually
used as the raw materials in the carbohydrate oxidation method, which increases the
production cost and restricts its application. The carbon monoxide coupling method
has the advantages of being a relatively simple catalytic system and having high cat-
alytic activity, which results in products with higher purity. However, the carbon mon-
oxide coupling method requires, and consumes a large amount of, high-purity carbon
monoxide, leading to high investment costs. The sodium formate method is a mature
technology, has a short production period, and high product yields, but its lead ions
would pollute the environment during production. There are also other preparation
methods including nitric acid oxidation of ethylene glycol, propylene oxidation,
glyoxal oxidation, and so on.
A novel technology to produce oxalic acid through the alkali fusion and oxidation
of steam-exploded straw in the alkali fusion system was proposed by Prof. Chen
(Figure 5.10). The basic technology is as follows: 40–60% alkali solution (KOH,
Product engineering 145

Alkali
Materials Steam
fusion and Filter
crushing explosion
oxidation

CaO
Filter precipitate
liquor
refluence

Filter

Precipitation
and
acidification

Figure 5.10 Preparation process of oxalic acid by steam-explosion pretreatment from

lignocellulosic biomass.

NaOH) is added to steam-exploded straws and the mixture is reacted for a period to
form an alkaline steam-exploded straw solution. The solution is filtered and the filter
liquor is collected. Then a certain concentration of CaO solution is added to the liquid
to generate CaC2O4 and CaOH. Then a certain amount of 20–30% H2SO4 is added to
the calcium oxalate and reacted for a certain period under a temperature of 200  C.
After acidification the solution is condensed and crystallized to obtain oxalate crystal
(Chen et al., 2000).
After the steam-exploded straw is washed by water, the hemicellulose exists in the
form of xylose or xylo-oligosaccharide in the hydrolysate. Therefore, the steam-
exploded straw hydrolysate could be used to produce oxalic acid by brown rot fungi
fermentation. Brown rot is a kind of wood rot fungi that is the collection of filamen-
tous fungi leading to the brownness and rot of wood. Brown rot fungi mainly degrade
the cellulose and hemicellulose (and not lignin) within wood. The wood is then
cracked into small pieces and becomes brown and fragile. Therefore, brown rot fungi
play the role of degradation and reduction in the forest ecosystem, which is also an
inevitable part of mass and energy recycling in the forest ecosystem. Research has
found that oxalic acid plays the role of proton donor during the enzymatic or non-
enzymatic hydrolysis process of hydrate. Oxalic acid is the primary metabolite of
brown rot fungi, whose biosynthetic pathway consists of a “short circuit” TCA route,
glyoxysome, and acetic acid recycling route. Brown rot fungi could use the sugars
inside the steam-exploded straw hydrolysate to produce oxalic acid, which then
achieves the resource utilization of biomass wastes.
146 Lignocellulose Biorefinery Engineering

5.3.2 Levulinic acid

5.3.2.1 Applications and market for levulinic acid
One of the key sugar-based building blocks that can be obtained from lignocellulose
biomass is levulinic acid (LA), which has been identified by the US Department of
Energy as a top-platform chemical. Levulinic acid is a five-carbon molecule with car-
boxylic acid and ketone functionalities, and the existence of these two functional
groups provides this compound with interesting reactivity pathways.
As a top-platform chemical, levulinic acid is the building block used to produce a
great number of biochemicals such as succinic acid, resins, polymers, herbicides,
pharmaceuticals, flavoring agents, solvents, plasticizers, and antifreeze agents. In par-
ticular, some levulinic acid derivatives can be used for fuels and oxygenated fuel addi-
tives. For example, esterification of levulinic acid with C1-C2 alcohols produces
levulinic esters that can be used as diesel additives. Elliott and Frye (1999) have also
shown that levulinic acid can be hydrogenated in the presence of a bifunctional
catalyst to produce methyl-tetrahydrofuran (MTHF), which can directly serve as a
gasoline blend stock. Levulinic acid can also undergo hydrogenation to produce valer-
olactone, which has been shown to be a sustainable liquid transportation fuel suitable
for replacing ethanol in gasoline–ethanol blends.

5.3.2.2 The development of levulinic acid production

and associated problems
A substantial amount of attention has been paid to the preparations of bulk chemicals
from renewable biomass resources as substitutes for traditional fossil resources. One
attractive option is the conversion of lignocellulose to levulinic acid (LA), which is
regarded as a promising platform chemical. LA contains two important functional
groups, a ketone group and a carboxylic acid group, which make LA a versatile build-
ing block for various bulk chemicals such as fuel additives, polymer precursors, and
resin precursors.
LA can be produced from glucose, fructose, starch, and lignocellulosic raw materials.
Due to a simplified and low-cost process, the direct conversion of lignocellulosic raw
materials to LA has gained considerable interest around the world. For a long time,
homogeneous acids (HCl, H2SO4, H3PO4, etc.) were the most popular catalysts for
the conversion of lignocellulosic raw materials to LA (Mosier et al., 1999), which
resulted in many problems such as difficult recovery of acid, complicated separation
of products, and serious environmental pollution. Solid superacid, stronger than 100%
H2SO4, is a kind of acid with many advantages over liquid acid; for example, it is easy
to separate from the reaction mixture and easy to regenerate and reutilize (Olah et al.,
2009). Because of these advantages, a number of research studies have appeared on solid
acid-catalyzed production of LA from hexose, obtained from lignocelluloses. However,
the solid superacid catalyzed decomposition of lignocellulose to prepare LA is still little
reported.
Product engineering 147

Microwave
Steam- Washing, Steam- Sieving catalysis
Mechanical Ultrafine
exploded press exploded using 60
pulverization grinding
cornstalk filter cornstalk mesh
High
temperature
catalysis

Levunilic acid
Air Short
production with
classification fiber
polymerization inhibitor
Figure 5.11 Levulinic acid preparation via steam explosion.

Prof. Chen established a process for LA preparation from fractionated straw com-
ponents based on the characteristics of straw (Figure 5.11). LA is prepared from
steam-exploded straw hydrolysate and short-fibers via the catalysis of solid acid
(Chen et al., 2011).
Rice straw was steam exploded at 200  C (1.5 MPa) for 6 minutes by saturated
steam in a 4.5 L reactor. Steam-exploded rice straw was dried at 105  C under vac-
uum, followed by mechanical grinding with a vegetation disintegrator to 60 mesh
(0.25 mm). Solid superacid catalyzed production of LA was conducted in the autoclave.
The solid–liquid ratio of pretreated rice straw to deionized water was 1:15 (w/v). After
being sealed, the reactor was heated to the desired temperature of 150–240  C within
30 minutes and maintained for different times of 0–15 minutes under stirring
(180 rpm). When the reaction ended, the reactor was immediately put into an ice water
bath to decrease the temperature. Then the reaction mixture was filtered and washed
with deionized water, followed by centrifugation (8000 rpm, 20 min). The centrifugate
was collected for the determination of LA.
Solid superacid, S2O82-/ZrO2–SiO2–Sm2O3, could be used as a potential catalyst
for the preparation of LA from rice straw. But the method was highly reliant on
the concentration of solid superacid and the substrate pretreatment method. Steam
explosion combined with superfine grinding could be used as an effective approach
to improve LA yield due to the increase of cellulose accessibility. Under optimum
conditions, LA yield could reach 22.8%, accounting for 70% of the theoretical value.

5.3.3 Furfural
5.3.3.1 Applications and market for furfural
Lignocellulose biomass is an abundant and renewable resource, and the conversion of
the highly functionalized carbohydrates of biomass into valuable chemicals that could
eventually replace those derived from petrochemical resources is very significant
to improve the structure of the energy industry and reduce environmental pollution.
Biomass mainly consists of cellulose, hemicellulose, and lignin. In particular, the
148 Lignocellulose Biorefinery Engineering

conversion of the hemicellulose fraction by chemical catalytic processes or other

physicochemical or thermochemical strategies is of great importance due to the fact
that the biological conversion of hemicellulose is inefficient.
Furfural, derived from hemicelluloses, is used for the production of a wide range of
important non-petroleum-derived chemicals such as furan, tetrahydrofuran, and fur-
furyl alcohol. It is also used to produce fungicide, nematicide and other products in the
plastics, food, pharmaceutical, and agricultural industries. There is no synthetic route
available for furfural production in the chemical industry. Furfural is exclusively
produced from hemicelluloses of lignocellulose biomass. About 250,000 tons of
furfural—probably the only unsaturated, large volume, organic chemical—are pre-
pared from carbohydrate sources annually.
Furfural is an important chemical that possesses a unique advantage because it is
produced from renewable biomass, such as agricultural wastes or forest residues, that
is rich in pentosan polymers. Furfural and its derivatives are considered in many
instances to be strategic chemicals based on their various applications and use. As
a non-petroleum-derived product, furfural has been broadly used as the feedstock
in the manufacturing of furfuryl alcohol, 2-methylfuran, tetrahydrofuran (THF),
2-methyltetrahydrofuran (MeTHF), plastics, pharmaceutics, and agrochemicals.
Resins with excellent thermosetting properties and extreme physical strength can also
be produced by condensation of furfural with formaldehyde, phenol, acetone, or urea.
What is more, furfural and its derivatives have the potential to serve as gasoline blend
stock (López et al., 2014).

5.3.3.2 The development of furfural production

and associated problems
Lignocellulose biomass is a plentiful and renewable resource for chemicals. Despite
this potential, nearly all renewable fuels and chemicals are now produced from edible
resources, such as starch, sugars, and oils. The challenges imposed by notoriously
recalcitrant and heterogeneous lignocellulosic feedstocks have made their production
from non-food biomass inefficient and uneconomical. The commercial furfural pro-
duction process employing mineral acid as a catalyst is inefficient, and suffers from
disadvantages such as furfural loss, equipment corrosion, and high energy consump-
tion. In addition, the high level of pollution caused by the acidic effluent is another key
challenge for the industrial production of furfural.
Furfural is generated by the dehydrogenation and cyclization of pentose, which
is generated from pentosan hydrolysis. The catalysts usually used in furfural pro-
duction are sulfuric acid, hydrochloric acid, phosphoric acid, and others. In the furfu-
ral production process, steam stripping and solvent extraction are simultaneously
adopted to remove furfural from the system over time. At present, the preparation
technologies of furfural include one-stage and two-stage methods. The one-stage
method is the one used by most factories in which the pentosan hydrolysis and dehy-
drogenation and cyclization of pentose are conducted in one hydrolysis kettle. Furfu-
ral technologies have improved greatly over the past few decades from the initial
single-pot cooking technology to many pots in series and continuous production.
Product engineering 149

The widely used technologies include Quaker Oats, Agrifuran, Petrole-chimie, Escher
Wyss, Rosenlew and RRL-J technologies whereby furfural is removed via steam
extraction. The steam consumption of the one-stage method is huge. For example, pro-
ducing 1 ton of furfural requires 18–25 tons of steam. The furfural yield is low in the
one-stage method, reaching 60% at most. Moreover, the one-stage method generates a
large amount of waste residues composed of cellulose, lignin, unreacted hemicellu-
lose, and residual catalysts. The present method of disposing of waste residues is
adopting mixed burning of coal cinder technology to utilize furfural waste residues
as fuels for steam generation. In the two-stage method technology, pentosan hydro-
lysis and the dehydration and cyclization of pentose are separated (Li, 2006).
The combination of steam explosion pretreatment and rinsing proposed by Prof.
Chen could separate rice straw and cornstalk into hydrolysate and steam-exploded
straw or cornstalk, which uses the hydrolysis and primary separation of pentosan.
Then the separated pentose is dehydrated and cyclized to produce furfural in a
two-stage method. The specific process is as follows: raw materials are delivered
to the processing workshop from bunkers and cut into 5 cm lengths; then steam is
passed into the vessel until the pressure is 0.1–0.3 MPa higher than the work pressure
(1.5 MPa) and the pressure is maintained for a certain time; then the bleeder valve is
opened to pop up the materials instantly. The water content of steam-exploded mate-
rials is about 50%. Hydrolysate is prepared with the addition of water (1:3), and the
hydrolysate is rich in hemicellulose degradation sugars. Then the hydrolysate is fil-
tered and condensed to produce concentrated solution that is suitable for furfural pro-
duction. Multiple-effect evaporation is adopted to produce furfural from the
hydrolysate, which helps to condense the hydrolysate rich in hemicellulose degrada-
tion sugars to 13–18% sugar concentration. The concentrated sugar solution is added
into the distilling kettle with the addition of 98% sulfuric acid (at 5%) to produce fur-
fural. Then furfural is recycled by condensation and the same amount of water is added
to achieve a 6% furfural solution. Next the furfural is transferred into the negative
pressure distillation tower to evaporate wastewater, and then crude furfural is obtained
through washing the organic acids (Chen, 2013).

5.4 Bio-based materials

About 80% of chemical products are still based on crude oil. However, bio-based
materials will increasingly gain importance. Bio-based plastics have a history of over
150 years. Key milestones include the invention of cellulose nitrate (celluloid) in the
1860s, man-made cellulose (1890s), cellulose-hydrate films (cellophane) in 1912,
casein protein (milk fiber) in the 1930s, and soy-based plastics in the 1930s. These
materials lost their importance with the rise of the petrochemical industry in the
1950s. Since the 1980s there has been increasing interest in the development of bio-
degradable plastics such as polylactic acid (PLA), polyhydroxyalkanoates (PHAs),
and various types of thermoplastic starch made from bio-based feedstock. The renais-
sance of bio-based plastics and bio-based materials in general has been fueled by
150 Lignocellulose Biorefinery Engineering

progress in biotechnology, high fossil fuel prices, as well as environmental concerns.

Bio-based materials have the potential to reduce nonrenewable energy use as com-
pared to conventional materials, but may come at the cost of additional land use
and related environmental impacts.

5.4.1 Cellulose acetate

5.4.1.1 Applications and market for cellulose acetate
Cellulose acetate is one of the most commercially important cellulose derivatives, and
is widely used as fiber, film, paint, filters, and dialyzers. A major application is in cig-
arette filters to remove particulates during smoking. As fiber, cellulose acetate is used
in textiles because of its relatively low cost, draping quality, softness, comfort, luster,
and natural feel. The material is also used as a substrate for motion picture camera
film. It also finds applications as an ingredient in sheet and molded objects and as
an additive in surface coatings and inks. Its price is around $1.80 per lb.
It is estimated that 1.5 billion pounds of cellulose acetates are manufactured glob-
ally every year. Generally, wood and cotton are the major resources for industrial
acetylation. In recent years, low-cost lignocellulose biomass has become attractive
as a renewable resource, because it is available in large quantities and is routinely cul-
tivated in the world (Cheng et al., 2010).

5.4.1.2 The development of cellulose acetate production

and associated problems
Cellulose acetate is typically made from wood pulp through reactions with acetic acid
and acetic anhydride in the presence of sulfuric acid to form cellulose triacetate. The
triacetate is then partially hydrolyzed to the desired degree of substitution. Recently,
several other synthetic methods have been developed for polysaccharide esterifica-
tion, including the use of ionic liquids. Another recent development is the use of iodine
as a catalyst for the esterification of cellulose and starch in the presence of acetic
anhydride.
People are always concerned about how to get products of a certain degree of sub-
stitution and uniform substitution, therefore the study of cellulose acetate preparation
and the technological difficulties involved is a key topic of current research.
Prof. Chen used waste straw as the crude material, with the straw undergoing acety-
lation reaction after pretreatment by steam-explosion, and then cellulose acetate was
separated from the acetylation products of straw according to their different properties
(Zhang & Chen, 2007). The technological route is shown in Figure 5.12.
The technology used to produce cellulose acetate from acetylation reactions of
straw has the advantages of low cost and simplicity, which is conducive to establish
an ecological industry model in which cellulose acetate is regarded as a flagship prod-
uct (Zhang & Chen, 2007).
Product engineering 151

Steam Glacial Acetic Distilled

explosion acetic acid anhydride Sulfuric acid water

Straw Activation Esterification Precipitation Rinsing Grinding Poaching

Cellulose biodegradable
Acetylized hemicellulose, film
Acetone lignin and some cellulose
extraction
diacetate Separation
Washing Drying
CH2Cl2 Hydrolysis
extraction Cellulose triacetate Cellulose diacetate
Analysis and
purification

Figure 5.12 Preparation of cellulose acetate from straw.

5.4.2 Sodium carboxymethyl cellulose

5.4.2.1 Applications and market for sodium carboxymethyl
cellulose
Sodium carboxymethyl cellulose (CMC) is one of the most important products of cel-
lulose ethers, which are formed by natural cellulose modification as a kind of cellulose
derivate with an ether structure. Due to the fact that the acid form of CMC has poor
water solubility, it is usually preserved as sodium carboxymethylcellulose, which is
widely used in many industries and regarded as monosodium glutamate in industry.
CMC could be used as flocculating agent, chelating agent, emulsifier, thickening
agent, water-retaining agent, sizing agent, and film-forming material, and so on.
CMC is also widely applied in fields such as electronics, pesticides, leather, plastics,
printing, ceramics, and the daily-use chemical industry. Moreover, due to its excellent
properties, wide application, and the developing potential fields, CMC has broad appli-
cation prospects.

5.4.2.2 The development of CMC production

and associated problems
With the development of domestic technology, we have made great progress in the
research and application of cellulose and its derivatives. Due to the fact that the posi-
tion of cellulose as an important source of synthetic organic materials has become
more and more prominent, people have already realized that cellulose has a superior
advantage over limited coal, oil, and natural gas. Cellulose is not only a type of renew-
able resource; it can also be turned into many kinds of functional products. What’s
more, cellulose will have more broad sources once agricultural and forest wastes
are more intensively exploited and utilized, which will promote the development
of the cellulose industry.
Despite the improvement from the water-borne method to the solvent-borne
method, the cellulose materials for CMC production are still concentrated in the linter
and wood pulp, which have a relatively high a-cellulose content and degree of
152 Lignocellulose Biorefinery Engineering

polymerization. Such materials are not abundant and have a high cost; in addition, the
pretreatment processes are also complex and will damage the environment. Therefore,
it is very important to search for cheaper raw materials, to simplify pretreatment tech-
nologies, and to decrease the pretreatment cost. Previous research has indicated that
straw, sugar cane, bamboo, beet, waste velveteen, tobacco, orange peel, paper mill
sludge, and sago could be the raw materials of industrial CMC preparation. These
materials are acid-boiled or alkali-boiled to extract cellulose and then the cellulose
is etherified. The cost of such technology has decreased, but the route is complex
and the pretreatment technology conditions are rigorous.
Prof. Chen’s group adopted a pollution-free steam explosion technology to activate
the straw materials and then introduced a carboxymethylation reaction to the system.
The different components of straw are separated according to the different physical-
chemical properties of the products and the high-value CMC is then produced (Smith
and Klosek, 2001) (Figure 5.13). In this process, the raw materials are cheap and the
technology route is relatively simple, which is of great importance in the respect of
realizing the component separation of straw, saving resources, and making the produc-
tion technology become environmental friendly.

5.4.3 Bio-based desert soil amendment materials

5.4.3.1 Applications and market for bio-based desert soil
amendment materials
Desertification is one of the most severe ecological problems in China. Although the
government has reinforced the management of deserts, desertification is still a big
problem in the country. China started the desert land governance in the 1990s and

Filter
Straw residue Cellulose and
Comb grading
lignin mixture
Filtra-
Steam tion
explosion
Filter
liquor Hemicellulose Parenchyma
macrofiber Staple fiber
hydrolysate cells

Non-acid Alkali Thermochemical

Fermentation treatment
autocatalysis treatment

Crude furfural Fermentation

Etherification SiO2 etc.
products

Refining CMC

Etherification
Carboxymethyl
products
Furfural lignin

Figure 5.13 Preparation of CMC from straw.

Product engineering 153

the preliminary stage was similar to other countries, in which straw was used to pre-
pare sand-protecting barriers. However, it could not solve the problem fundamentally;
actually, it could only supplement desert soil governance. Drought, vegetation dete-
rioration, and poor soil texture are the main driving forces of soil desertification.
Therefore, researchers around the world have realized that the fundamental actions
needed to prevent soil desertification are to improve the soil texture, improve the
water conservation force, and strengthen the vegetation construction. Plenty of studies
have been carried out around these measures and chemical materials were once one of
the research focuses. However, the cost of chemical materials is high and the absorp-
tivity of plants for massive chemical amendments is limited; moreover, a lengthy
period of chemical amendments usage would pollute the underground water, make
the soil harden, and destroy the environment. Under such conditions, there is an urgent
need to find a biodegradable material that could solve the problems effectively and
enhance soil fertility.
At present, most of the domestic practice of treating straw to be used as desert soil
amendment materials is simple mechanical pulverization. Straws, after such simple
pretreatment, are of poor quality, the stacking and retting period is long, and the
fertilizer efficiency is low when returning to the field. Existing research indicates
that the results of using straws as desert soil amendment materials are no less favorable
than those of chemical materials, and straws have advantages like easy acquisition of
materials, being low cost and long lasting, and having multiple functions.

5.4.3.2 Bio-based desert soil amendment materials

China is one of the countries most severely affected by desertification, and the rapid
development of desertification and the significant influence on the social economy
and the environment have attracted much attention. The desert land is mainly distrib-
uted in the arid and semiarid regions and some semihumid regions in north China
including Inner Mongolia, Ningxia, Gansu, Xinjiang, Qinghai, Tibet, Shannxi, Shanxi,
Hebei, Jilin, Liaoning, and Heilongjiang, especially centered on the semiarid region to
the east of Helan Mountain. Desertification is a kind of land deterioration that causes a
decrease in land output and the loss of land resources, presenting a desert landscape due
to the combined effects of human economic activity and the fragile environment in
these areas. At present, the desert area in China is vast and, what’s worse, the rate of
development of desertification is still increasing. The ever-expanding area of desert
land has severely affected our domestic ecological environment and social and eco-
nomic development. It has also caused huge harm in China, by destroying the ecological
balance, decreasing the land productivity, endangering the survival and development of
citizens, and accelerating the degree of poverty. Hence, it is essential to develop
bio-based desert soil amendment materials in order to promote the processes of com-
bating desertification, redeeming the economic loss, and repairing the environment.
Present pretreatment methods to prepare desert soil amendment materials from
straws have disadvantages like unsatisfactory technology, environmental pollution,
and high cost due to additional demand for inorganic fertilizer, humic acid, and nutri-
ents. Based on these facts, the author’s group developed a method to prepare desert
154 Lignocellulose Biorefinery Engineering

soil amendment materials from the fermentation of steam-exploded straws, in which

the steam-exploded straws under pretreatment were solid fermented with wheat bran
to prepare functional materials including biofertilizer and prophylaxis treatment of
plant disease, and then the functional materials were compounded with biodegradable
bacterial cellulose with high water-absorbing qualities. These products not only can
improve the soil microstructure and decrease the amount of active water-retaining
agent required, but also gather plenty of beneficial microorganisms that have func-
tions like water preservation and sustained release of nutritients. Therefore, such
bio-based desert soil amendment materials are propitious to the large-scale applica-
tion of desert land control (Kaparaju et al., 2009a, 2009b).
The technology route for production of desert soil amendment materials is shown
in Figure 5.14. Compared to pulverizing straw via machines, the water absorption and
water-retention rates of steam-exploded straw are increased by 32–40% and
80–100%, respectively. Moreover, after solid-state fermentation the materials func-
tion as a biofertilizer and prophylaxis treatment for plant disease. The organic content
of desert soil amendment materials after solid-state fermentation exceeds 60%, humic
acid content is 15%, the total number of active bacteria is 300 million/g, and the N, P,
and K contents are all higher than 5%.

5.4.4 Lignocellulose board

5.4.4.1 Applications and market for lignocellulose board
With the development of China’s domestic economy, the market for building mate-
rials has turned to quality from an initial emphasis on quantity, and one of the most
active fields in the building materials market has become the production of boards for
construction and structural shapes from lignocellulose.
Due to the low cost of both straw raw material and materials used in its processing,
the cost of lignocellulose board is lower than any other boards of the same type. The
preparation of straw boards has successfully relieved the situation of undersupply of
domestic wood raw materials, which also opens up a new route of straw substitution
for wood materials. Experimental results indicate that producing slabs only from
straws or mixing the straws with composite wood are both available options. More-
over, the success of straw boards could increase farmers’ incomes and broaden income
sources through developing the artificial straw boards. Besides, straw boards also
solve the straws collection problem to some extent, remit the atmospheric pollution

Straw
Filter liquor
Bacterial
Steam fermentation
explosion Appropriate mixture
Filter Complex microbial for bio-based
residue solid fermentation desert soil
amendment materials

Figure 5.14 Preparation of desert soil amendment materials from straw (Chen, 2009).
Product engineering 155

due to straws combustion, and at the same time, decrease the consumption of a forest
resource, thus protecting the environment.

5.4.4.2 The development of lignocellulose board production

and associated problems
The TianBao Project (the natural forest protection project) avoids mass deforestation
and also provides a chance for the application of lignocellusic boards. Producing
boards and building materials from lignocellulose biomass is an effective route for
the high-value utilization of biomass, which could help to maintain the ecological bal-
ance and satisfy the requirements for planks. The structure and properties of straws are
changed by physical, chemical, and biological methods. The degradation could con-
vert hemicellulose and lignin directly and rearrange the hydrogen bonds within the
cellulose to prepare straw materials with new properties and make it easy to produce
a variety of products. The application of modified straws currently focuses on wall
materials in the building industry, e.g., artificial beaverboard; inner packing materials
in the packing industry; and disposable tableware and seeding devices in agriculture.
Straw building material is a kind of “green building material” that has a low weight.
Therefore, it could save forest resources and avoid the severe air pollution caused by
straw combustion if wood was replaced by straw materials. Besides, great contribu-
tions have been made to the ecological environment by replacing packing plastics and
plastic disposable tableware. However, a certain amount of thermosetting resin and
formaldehyde should be added during the production of wall materials, green beaver-
board, inner packing materials, disposable tableware, and seeding devices from
straws, which could not compete cost-wise with other kinds of decorative materials
and plastics, and also causes environmental pollution. Hence, it is attractive to produce
materials without sizing materials economically and environmentally, which could
not only decrease production cost, but also avoid environmental pollution.
There are problems of tackifier contamination, non-uniform gluing, and unsteady
properties during the production of new materials from straws, so it is essential to
improve from the very beginning in order to develop green tackifiers or new technol-
ogies of lignocellulose board production to satisfy the need for industrialization.
Cheng and Logan proposed a new concept for modified straw and developed a set
of methods for straw modification via steam explosion based on straw modification
methods and thermocuring, and then put forward new methods for the clean produc-
tion of ecological materials from modified straws (Cheng and Logan, 2007). The route
is shown in Figure 5.15
Modified straws refer to straws that have changed their structure and properties
through physical, chemical, or biological methods. The degradation of cellulose, hemi-
cellulose, and lignin in the straws helps the formation of thermocuring resin adhesive,
which gives the fiber the characteristic of autohension to satisfy the demand for molding
of the building boards. The modification of straws by steam explosion makes the lignin
active groups increase rapidly, which has similar properties to those of polyphenols
and could be used as a natural adhesive. During this process, hemicellulose is degraded
into soluble sugar, dehydrated sugar, and furfural, and could be reacted with lignin
instead of formaldehyde. During steam explosion, cellulose is not degraded, while
156 Lignocellulose Biorefinery Engineering

Straw

Air-dried
Filter liquor
straws
Steam
explosion
Phanerochaete
Filter residue chrysosporium Modified straws
fermentation Thermocuring

Figure 5.15 Technology route of xylose extraction via steam explosion.

the crystallinity of cellulose is increased. The modification technology mainly consists

of two molding technologies. One is thermocuring, in which the thermofixation process
is directly controlled by controlling the water content to rearrange the cellulose hydro-
gen bond and form the thermoset biological resin adhesive. The other modification
technology is cellulose recombination and molding technology, in which the straw
fibers pass through molding devices and then bond together under certain temperature
and pressure conditions to form boards that can meet the mechanical strength require-
ments for building material. Ecologically friendly materials without synthetic adhesive
are attractive to both the economy and the environment. The route simplifies the pro-
duction process and decreases the cost through reducing the procedure of glue mixing
and the corresponding devices. Moreover, the produced materials can be degraded
completely in nature and they can also be used as feedstuff or manure that has no envi-
ronmental pollution effects. In addition, the strength of the ecological materials is
increased greatly due to the effective modification.
The abundant straw resources can be turned from waste into wealth via straw mod-
ification technology. The thick filamentary products derived from steam explosion
can be used to produce fluting mediums, wall materials, fiber slabs, packing materials,
disposable tableware, and seeding devices through compression and processing.
Experts predict that the annual construction area in China could reach 1.5 billion
m2. If the demand for building boards for a 1 m2 area is 10 m2, the quantity of building
boards required is 15 billion m2; therefore, the market capacity for building boards is
considerable and represents a promising source of future economic growth.

5.5 Food and animal feed

5.5.1 Food
5.5.5.1 Xylose and xylitol
Applications and market for xylose and xylitol
Xylose (C5H10O5) is a type of pentose that is soluble in water and some organic sol-
vents like hot ethanol, while insoluble in diethyl ether. Xylose often exists as a
colorless or white crystal or powder that tastes sweet and refreshing. It exists in the
Product engineering 157

form of a polysaccharide (melting point is 145  C) in plants, especially in product

wastes like straws and ears of rice. Xylitol is produced by catalytic hydrogenation
from xylose. Xylitol is widely used for food additives due to its outstanding features
like anticaries properties and because it can be used by diabetics.
Xylo-oligosaccharide is a kind of oligosaccharide linked by b-1, 4-glycosidic bonds
from 2 to 7 xylose molecules. The main composition of xylooligosaccharide is xylo-
biose and xylotriose; some of them contain side chains like D-arabino-2-hexulosonic
acid or glucuronic acid. The solid form of xylo-oligosaccharide is a milk white or faint
yellow powder with good processing characteristics and storage stability.
Xylitol is a type of sugar alcohol (C5H12O5, white powder or crystal) with five-
carbon molecules and exists widely in vegetables and fruits in nature, while the con-
tent is usually less than 900 mg/g. Xylitol is also an intermediate metabolite of mam-
mals. For example, 5–15 grams of xylitol is produced by a person every day. The
sweetness of xylitol is very close to saccharose, and has the specific property of cool
sensations. Among its many excellent properties, the edible-medicinal one is the most
important. Xylitol has sweetness that is close to saccharose and the sugar cannot be
used by caries bacteria, so xylitol can protect teeth from corrosion. Because xylitol can
absorb lots of heat under dissolution and thus decrease the temperature of the medium,
xylitol crystal tastes cool and, like mint, it can improve food flavor. Xylitol has a spe-
cific metabolic pathway in which insulin is not needed. Therefore, xylitol passes
through the glucuronic acid xylulose pathway and the phosphopentose pathway
and generates ribose phosphate. The key product of this metabolism is glucose-6-
phosphate, and then glycogen is produced to generate energy by oxidative metabo-
lism. Therefore, xylitol can regulate the disturbance of carbohydrate metabolism in
humans. When a lack of insulin occurs, xylitol can pass through the cytomembrane
as usual and provide nutrients and energy for cells. Xylitol can slow the production
of fatty acid in plasma, and does not result in a rise in blood sugar, so xylitol is a ther-
apeutic agent and nutrient for diabetics and also a liver-protecting medicine for liver
infections. Xylitol has good thermal stability and will not react when heated with
amino acids, so it can be mixed with amino acids to produce medicinal nutrients.
Xylitol can also promote the secretion of gastric juice, promote the activity of the
pancreas and the gallbladder, and accelerating corticotrophin releasing hormone, so
it is suitable for the old and the weak.
Prof. Chen and his team have established a new technology to extract xylose via a
steam-explosion method, which is described as follows: the appropriately crushed bio-
mass materials are steam exploded to get steam-exploded straws; then xylitol is
recycled by counter-current extraction and detoxified to eliminate the inhibitors like
formic acid, acetic acid, and furfural; and xylitol is hydrolyzed into xylose by micro-
organisms. In this process, the concentration of xylose can reach 30.12 g/L, and the
extraction rate is more than 80% (Xu & Luo, 2011) (Figure 5.15).

The development of xylose and xylitol production

and associated problems
As is widely known, xylitol is a kind of functional sweetening agent produced via tra-
ditional catalytic hydrogenation. In fact, this technology has the problems of complex
processing, poor security and high cost because of the pure xylose required. Due to the
158 Lignocellulose Biorefinery Engineering

problems existing with the chemical methods, the main technology for xylitol produc-
tion is microbial conversion, in which microorganisms convert xylose into xylitol by
xylose reductase within microbial cells. The advantages of the microbial conversion
technology are as follows. First, it has a high utilization ratio of raw materials. The
chemical method uses only pure xylose as raw materials, thus the xylose (30%) in corn
stover hydrolysate cannot be used. However, the bioconversion method can use the
xylose in corn stover hydrolysate, improving the utilization ratio of raw materials. Sec-
ond, the bioconversion process can reduce the environmental pollution because in this
process raw materials are directly used without pretreatment. Third, bioconversion
consumes less energy. In a traditional chemical process, corncob hydrolysate is con-
centrated and crystallized to obtain xylose and then xylose is redissolved and diluted
before being hydrogenated, re-enriched, and crystallized, which uses a lot of energy. In
the bioconversion process, xylitol is produced through one-stage concentration and
crystallization, thereby decreasing energy consumption. Fourth, the bioconversion pro-
cess needs simpler devices. Xylitol production via the chemical method requires hydro-
gen and this process has to be conducted under high temperature and pressure, placing
high demands on the devices. In the bioconversion process, the main devices are simple
reaction tanks and a few fermentation cylinders. Fifth, the process is safe and easy to
operate. Bioconversion is processed under normal temperature and pressure without
asepsis operation. Sixth, the process can provide better products. The products are more
suitable for food processing because the whole process avoids contact with metal pow-
der catalysts. As mentioned previously, the screening and optimization of new strains
and the foundation of new routes are the key problems for xylitol production in the
future (Fang et al., 2013).

5.5.1.2 Vanillin
Applications and market for vanillin
Vanillin is also called vanillin or 3-methoxy-4-hydroxybenzaldehyde; it is a white to
faint yellow crystalline powder or acicular crystal. The melting point of vanillin is
80–81  C and the boiling point is 285  C. Vanillin is slightly soluble in cold water,
but dissolves well in ethyl alcohol, diethyl, chloroform, glacial acetic acid, and pyr-
idine. Vanillin usually exists in vanilla, clove oil, benzoin extract, and caryophyllus.
Pure vanillin has the rich aroma of butter with no peculiar smell. Pure natural vanillin
is mainly extracted from the pods of vanilla, and the yield is too low to satisfy market
demand (Chen and Wang, 2008). “Biovanillin,” produced from the natural precursors
of vanillin by microorganisms, could displace natural vanillin.
Vanillin is widely applied in industrial production. For example, it is used as a per-
fume or perfume fixing agent in food, toothpaste, fancy soap, and tobacco. Vanillin is
also an important intermediate material in pharmaceutical chemicals. Specifically, it
can be used to produce drugs for hypertension, cardiopathy, dermatosis, ozostomia
and hydragogue. Additionally, vanillin can be an auxiliary material in chemical engi-
neering, an antihardening agent for plastics, and an electroplating brightening agent
for Ni, Cr, and Cd. In agriculture, vanillin can be used as a yield-increasing agent or
ripening agent for sugarcane, as well as a material for the preparation of herbicides and
insect attractants.
Product engineering 159

Vanillin is the main component extracted from the pods of vanilla and is also one of
the most widely used spices. A large demand for vanillin has arisen due to the high
value that many countries put on food security. As an important high-ranking spice,
vanillin is closely related to humans’ daily life and the demand for it has been enlarged
gradually. As a rough estimate, the yield of vanillin worldwide is around 5000–8000
tons and the demand exceeds supply by 3000–4000 tons. Therefore, vanillin produc-
tion has been an attractive proposition. The most frequently used method to prepare
vanillin is to take advantage of lignin and guaiacol, which have the advantages of
being cheap and easily procured materials and use a mature technology.

Development of vanillin production and associated problems

Vanillin production via the bioconversion method has been developed for more than
10 years, and this technology makes use of multiple biological materials including
fungi, genetically engineered bacterium, and extracted enzymes. It is known from
the literature that at the beginning of such research, most studies were biased toward
a theory including various microorganisms and the metabolism routes of vanillin syn-
thesis and degradation in plant cells. Of course, extensive research was conducted at
the cell, enzymology, and gene level and lots of excellent results were obtained. With
the deepening of the research, many researchers turned to the study of the industrial
production of vanillin and the technical routes described were also diverse. However,
there has been no report on the multiple industrialization of vanillin until now. Such
researche in China is still at the initial stages and relative developments have not yet
been reported (Chen, 2013).
The most studied bioconversion method is a two-stage technology where vanillic
acid is produced from ferulic acid and then vanillin is further prepared from vanillic
acid (Prifert et al., 2001) (Figure 5.16).

5.5.2 Animal feed

5.5.2.1 Applications and market for animal feed
With the rapid increase of the population and individual incomes, the composition of
food consumed by Chinese residents has improved greatly, which calls for more edi-
ble animal by-products. Therefore, the demand for animal feed is increasing as a result

O
HO O O

OH

OCH3 OCH3 OCH3

OH OH OH
Ferulic acid Vanillic acid Vanillin
Figure 5.16 Conversion route of vanillin from ferulic acid.
160 Lignocellulose Biorefinery Engineering

of rapid increase in demand for animal foods like meat, eggs, and milk. Meanwhile,
the cultivated land resource in China is decreasing and the natural grassland keeps
vanishing. Under these conditions, it becomes especially important to use existing pre-
cious resources more reasonably and effectively.
Using straw as a feedstuff has a long history in China, and the main crop straws
used are wheat straw, rice straw, corn stalk, sorghum straw, and beanstalk. The nutri-
tional components of the different kinds of straw vary, but all kinds of straw have the
following things in common: the crude protein content is as low as 2–5%; the crude
fiber content is as high as 20–45%; the content of minerals such as Ca and P is low and
unbalanced; and the palatability is poor, leading to a low feed intake by animals. It is
worth noting that after processing treatments such as ensiling, microbiological fer-
mentation, and ammoniating, the feed intake, nutritive value, and digestibility
increases. Hence, the improvement of feedstuff has rewards and economic benefits
beyond adding weight to grass-eating animals.
In the international market, Japan, South Korea, Taiwan, and some Southeast Asian
countries need to import a large amount of forage grass due their lack of biomass
resources. For example, Japan has to import millions of tons of bulk forage grass from
Canada; but in order to decrease the cost of transportation and animal feeding, Japan
has explored opportunities to imported processed feed products derived from crop
straw like cornstalk, rice straw, and beanstalk from China. In the Chinese domestic
market, grass yield has decreases dramatically due to the severe degradation of grass-
land; in order to recover vegetation and protect the ecology, measures such as grazing
prohibition, returning grain acreage to forestry and grassland, and rearing livestock in
pens have been conducted in many places in China, which again leads to the demand
for storing plenty of forage grass. In China alone, the number of cows was 0.14 billion
and sheep 0.27 billion in 2010. Calculated by the ratio of 20% of the animals being
reared in pens, the annual demand for various forage grasses was as much as 0.16 mil-
lion tons. Statistics show that the crude demand per cow for feedstuff is 10 kg/d and
3.3 kg/d for sheep, and the total crude feedstuff demand in China is 0.8 billion tons
per year.
Therefore, feedstuffs made from straw will enjoy a broad development space and
huge market potential if product quality is improved, products are easy to transport
and wrap, and the price is reasonable.

5.5.2.2 The development of animal feed production

and associated problems
The degeneration and desertification of grassland lead to the shortage of animal feed
of high quality, while the development of large-scale farming practices calls for a
large amount of animal feed. There are many reports on feedstuffs made from straw
via microorganisms’ fermentation, but due to the single metabolism of microorgan-
isms and difficulties in degrading the stable macromolecular compound formed by
cellulose, hemicellulose, and lignin within straw, the opportunity for improvement
of nutrients inside the feedstuff is very limited. At present, research is centered on
Product engineering 161

the methods of microbiological fermentation, ensiling, and ammoniating to treat

straw, and these measures cannot realize the efficient conversion of crop straw to
feedstuff of high quality and high nutritive value. In addition, the focus of the indus-
trialization of feedstuff production from straw by steam explosion is only on cornstalk,
and no reports on wheat straw have currently been seen.
Cornstalk is the main source of traditional feedstuffs, but its application is limited
due to its high C/N ratio. Prof. Chen established an ammonium salt presoaking
coupled with steam explosion method to increase the nitrogen content in straw
(Chen & Liu, 2007). Results show that except for urea, the addition of other nitrogen
sources is conducive to the degradation of hemicellulose, producing a large amount of
soluble sugar (Figures 5.17–5.19). The degradation ratio of hemicellulose can reach
over 58% when adding 5% of (NH4)2SO3. The addition of ammonium salts can help
increase the nitrogen content of straw compared to steam explosion without ammo-
nium salts, and the highest nitrogen content can reach 2.3%. The addition of
(NH4)2SO3 is the most efficient way to improve nitrogen content in straw, and the
nitrogen source conversion ratio can be up to 84%. After steam explosion, the biode-
gradability of straw is dramatically improved and the maximum value is 71%. This
novel method has obvious advantages compared to traditional methods aimed at
increasing nitrogen content. Liquid ammonia presoaking can increase nitrogen con-
tent, but the reaction time is long and the ammonia is easily volatilized, leading to
inconvenience for operations. Steam explosion coupled with ammonia presoaking
can significantly increase the nitrogen content of straw, and the recycle cost is high
even though the ammonia can be reused (Chen et al., 2005).

CHC
CC
CL
35

30

25
CHC, CC, CL (%)

20

15

10

0
Water (NH2)2CO (NH4)2SO3 NH4HCO3 NH3.H2O
Additive
Figure 5.17 Hemicellulose, cellulose, and lignin content (% DW) of cornstalk after amination
by steam explosion. Note: water control; CHC, the content of hemicellulose; CC, the content of
cellulose; CL, the content of lignin.
162 Lignocellulose Biorefinery Engineering

16

14

12
Soluble sugars (%)

10

0
Water (NH2)2CO (NH4)2SO3 NH4HCO3 NH3.H2O
Additive
Figure 5.18 Soluble sugars content (% DW) of cornstalk after amination by steam explosion.
Note: water control.
Predicted in vivo digestibility (%)

70

60

50

40
Water (NH2)2CO (NH4)2SO3 NH4HCO3 NH3.H2O
Additive
Figure 5.19 Speculated in vivo digestibility of treated cornstalk by amination coupled with
steam explosion.
Note: water control (Chen & Liu, 2007).

Research into silage feed started years ago. Ensiling is a process coupling anaerobic
fermentation and acidifying, during which the soluble sugar and protein contents are
low, which is unfavorable for animal consumption. Adding cellulase during the ensiling
process can increase the soluble sugar and organic acid contents during fermentation. In
this way, lactic acid fermentation and saccharification processes are synchronized by
Product engineering 163

adding lactic acid bacteria and hydrolase. The soluble sugar produced from enzymolysis
can be used by lactic acid bacteria, and the growth of lactic acid bacteria can inhibit the
growth of other microorganisms. However, the enzyme cost is high in this process. To
solve the problems, Prof. Chen put forward the method of in situ fermentation coupled
with ensiling. Results of this study showed that both cellulase and hemicellulase were
produced during fermentation; nitrogen content was increased from 6.7% to 14.7%
after fermentation; and the cellulose was degraded by 38% and hemicellulose by
21%. Ensiling proceeded, followed by solid-state fermentation. During this process,
lactic acid content increased dramatically, and the pH value decreased rapidly, which
was conducive to the subsequent ensiling of feedstuff (Chen et al., 2005).

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