Article

Cite This: Energy Fuels 2017, 31, 10924-10932 pubs.acs.org/EF

Air-Blown Entrained-Flow Gasification of Biomass: Influence of

Operating Conditions on Tar Generation
Ludwig Briesemeister,*,† Michael Kremling,† Sebastian Fendt,† and Hartmut Spliethoff†,‡
†
Department of Mechanical Engineering, Institute for Energy Systems, Technical University of Munich, Boltzmannstraße 15, 85748
Garching, Germany
‡
ZAE Bayern, Walther-Meißner-Straße 6, 85748 Garching, Germany

ABSTRACT: The formation of tars in gasifiers based on fluidized- or fixed-bed technology is a major problem in biomass
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gasification. By pretreating biomass using hydrothermal carbonization (HTC), entrained-flow gasification becomes applicable.
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Oxygen-blown entrained-flow gasifiers (EFGs) operate at very high process temperatures, leading to an almost tar-free syngas.
However, in decentralized small-scale units, preferably air is used as the gasification agent, which, in turn, causes lower gasifier
temperatures. The specific impacts of air-blown gasification conditions and fuel properties of biocoal from HTC on tar formation
require particular attention. Therefore, in this work, tar formation under air-blown gasification conditions is investigated using
solid-phase adsorption at an electrically heated EFG with temperatures of 900−1300 °C and different air/fuel equivalence ratios
λ. Furthermore, tars are measured in the hot syngas of an industrial-like autothermal EFG. HTC biocoals of various feedstocks
(beech, biogenic residuals, municipal waste, and green waste), raw biomass (corn cobs), and fossil fuel (Rhenish lignite) are used
as fuels. The results show that the main influencing parameter on tar loading in the syngas is the temperature, whereas the
residence time and λ have less impact. However, in autothermal operation, the choice of λ controls the gasifier temperature and,
thus, effectively affects the resulting tar loading. Identified tar compounds are mainly light polycyclic aromatic hydrocarbons, of
which naphthalene is the most frequently occurring. At 1300 °C, tar loading is reduced to less than 0.2 g/Nm3, which allows for
direct syngas use in internal combustion engines.

1. INTRODUCTION whereby the latter is preferable in decentralized applications for

On the basis of the findings of the Intergovernmental Panel on heat and power generation.10 To reach the high fuel quality
Climate Change (IPCC), the massive exploitation of fossil fuels required for the application of EFGs, biomass is thermally
since the start of industrialization and the associated release of pretreated by torrefaction7,11,12 or hydrothermal carbonization
greenhouse gases have caused an increase in global temper- (HTC).8,13,14 A short overview of recent activities concerning
atures.1 To limit negative consequences, such as rising sea levels entrained-flow gasification of biomass is given by Schneider et
or glacial melting, the European Union aims at a reduction of al.15
greenhouse gas emissions by 80−95% by 2050 compared to The generation of tars from biomass gasification is well-
1990.2 As a result of the inherent CO2 balance of biomass, its investigated. A common definition considers hydrocarbons
utilization for heat and power production has the potential of larger than benzene (>C6) as tars.16 During pyrolysis, tars are
contributing to this goal. For the conversion of lignocellulosic formed from the macromolecules of the fuel. Thermal
biomass, state-of-the art solutions in decentralized applications degradation of cellulose, hemicellulose, and lignin produces
are direct combustion and gasification in combination with heat primary tar compounds, such as levoglucosan and furfurals, that
and power generation. Most biomass gasifiers are fixed- or are further decomposed to phenolics and olefins.3 A further
fluidized-bed-type because of the comparable low fuel quality temperature increase favors the formation of aromatic and
requirements of these technologies. However, dependent upon polycyclic aromatic hydrocarbons (PAHs) by recombination of
specific fuel properties and gasifier design, the syngas of both the primary and secondary tars. PAHs can have high dew points
types is polluted with tar compounds that result in high- of up to 500 °C.17
maintenance and gas-cleaning costs. Typical tar loading in the In the literature, different methods for measuring tars are
syngas is between 1 g/Nm3 (downdraft) and 100 g/Nm3 used. The two most frequently applied methods are the tar
(updraft) for fixed-bed gasifiers and around 10 g/Nm3 for protocol,16 which is based on gravimetric measurement of tars,
fluidized-bed gasifiers.3 Entrained-flow gasifiers (EFGs) operate and the solid-phase-adsorption (SPA) method.18 The SPA
at higher process temperatures, which provoke thermal cracking method is capable of detecting heterocyclic and aromatic tar
of tars and produce syngas that is often considered tar-free.4,5 compounds as well as PAHs, whereby the measurement of
Thus far, EFGs are mainly used to convert fossil coals for high-volatile compounds and very large PAHs is restricted. To
large-scale synthesis processes, which require the utilization of improve the SPA method, recent research aims at the utilization
pure oxygen as a gasifying agent as well as an operation at
elevated pressures.5 Recently, the entrained-flow gasification of Received: June 23, 2017
biomass is investigated for both pressurized operation using Revised: August 30, 2017
oxygen6,7 and air-blown operation at atmospheric pressure,8,9 Published: August 30, 2017

© 2017 American Chemical Society 10924 DOI: 10.1021/acs.energyfuels.7b01801

Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

Figure 1. Simplified flow sheets of BabiTER (left) and BOOSTER (right).

of a combination of different adsorption materials, which cally heated EFG. Furthermore, gasification in an industrial-like
additionally allows for the measurement of volatile compounds, autothermal EFG is applied to evaluate the transferability of the
such as benzene.19,20 aforementioned results.
As a result of the large number of different occurring species,
tars are classified in the literature to describe their nature and 2. EXPERIMENTAL SECTION
evolution in a comprehensive way. Evans and Milne use a Figure 1 shows the two different gasification test rigs used for the
classification based on the temperature-dependent occurrence experiments. On the left side, the baby high-temperature entrained-
of the individual tar compounds, which differentiates between flow reactor (BabiTER) consists of an electrically heated ceramic tube
primary, secondary, and tertiary tars.21,22 Another system (1) 1.48 m long with an inner diameter of 40 mm. It is designed for
developed at the Energy Research Centre of the Netherlands atmospheric pressure and allows for gasification experiments in varying
(ECN) assigns tars as a result of their chemical composition to gas atmospheres at well-defined temperatures. Mass flow controllers
five classes depending upon the size and number of their (MFCs) adjust nitrogen and oxygen flows, so that the overall
composition of the gasification agent is like air. Three individually
aromatic ring structures.23,24 controlled heating zones ensure a constant temperature along the
In general, the most important influencing factors on tar reaction zone. Tar samples are taken after a constant plug-flow
evolution are temperature, pressure, gasifying agent, stoichi- residence time of 1 s by varying the mass flows of the fuel and the
ometry, residence time, and catalytic effects.25 Increasing gasification agent.
temperatures cause a reduction of the total tar loading as a The biomass pilot-scale entrained-flow gasifier (BOOSTER) on the
result of the conversion of oxygen-containing tars, such as right is designed for autothermal operation with a thermal fuel input of
phenols, cresols, and furans, that only exist up to 800 °C.26 At around 100 kW. The system uses a pneumatic dense-phase conveying
higher temperatures, tars consist mainly of aromatic com- system for supplying the fuel that is inserted with a swirl burner (2)
together with preheated air (3). A refractory contained in the reactor
pounds, such as benzene, naphthalene, and phenanthrene.26
vessel (5) builds the reaction chamber (4), which has an inner
Many authors are investigating the influences of the process diameter of 250 mm and a total length of 2.3 m. At the end of the
conditions on tar composition and loading in the syngas of reactor, the syngas is water-quenched (6), filtered (8), and burnt in a
fixed- and fluidized-bed gasifiers, whereas only few works flare (10). A regulation valve (9) maintains a constant system pressure
address the tar formation under EFG conditions. Yu et al. of 0.2 barg. Tar samples are withdrawn 1.9 m downstream from the
investigate the gasification of cellulose, hemicellulose, and lignin burner mouth through a heated sampling port (7). A constant thermal
between 800 and 1100 °C and identify PAHs as the fuel input of 70 kW is used for the experiments. More information on
predominant species in EFG.27 Here, increases in both both test rigs can be found in other papers.7,8,29
temperature and stoichiometric oxygen ratio reduce the tar The applied SPA method for tar analysis was developed and
successfully used in the context of fluidized-bed gasification by
loading. Hernández et al. investigate the gasification of marc of Mayerhofer.4,30,31 A similar sampling probe for SPA measurements is
grape using air, steam, and mixtures of both in an EFG at used for BabiTER and BOOSTER trials, as shown in Figure 2. Syngas
temperatures up to 1200 °C.28 However, a detailed analysis of is withdrawn from the hot reaction zone, and a glass fiber filter
the tar evolution in autothermal EFG with pretreated biomasses removes particles. After a constant flow is ensured, a syngas volume of
and temperatures relevant for industrial EFG is only known to
the authors from the work of Kremling et al.7 Herein, applied
reaction conditions are representative of oxygen-blown gas-
ifiers.
In this work, tar loading and composition are investigated
under air-blown gasification conditions using different biocoals
from HTC, raw biomass, and lignite. Tars are measured using
the SPA method to obtain quantitative information on tar
loading and composition.18 Separate influences of gasification
temperature and stoichiometry are evaluated using an electri- Figure 2. Schematic of SPA sampling.

10925 DOI: 10.1021/acs.energyfuels.7b01801

Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

Table 1. Calibrated Tar Compounds with ECN Classification and Minimum Detection Limit
class species abbreviation ctar,min (mg/Nm3) class species abbreviation ctar,min (mg/Nm3)
2 phenol pho 18.01 4 naphthalene naph 12.65
2 cresol (o) cre (o) 16.40 4 biphenyl bip 13.16
2 cresol (m) cre (m) 17.64 4 fluorene fluo 13.77
3 toluene tol 13.21 4 anthracene ant 14.42
3 xylene (o) xyl (o) 12.41 4 phenanthrene phen 14.68
3 styrene styr 13.43 5 fluoranthene fluor 15.68
4 indene ind 12.72 5 pyrene pyr 15.92

Table 2. Chemical and Physical Properties of the Fuels

HTC compost HTC beech HTC green waste HTC municipal waste Rhenish lignite corn cobs
(HCo) (HBe) (HGW) (HMW) (RL) (CC)
Ultimate Analysis (wt %, ar)
C 59.96 55.62 60.74 35.28 60.30 44.73
H 3.67 4.25 5.28 2.74 3.79 5.52
N 0.68 0.35 0.70 1.85 0.67 0.27
S 0.57 0.31 0.38 1.48 0.52 0.14
O (calculated) 20.15 25.56 26.61 11.06 17.48 39.57
Proximate Analysis (wt %, ar)
moisture 11.32 8.51 2.29 11.13 13.32 8.51
volatile yield 55.11 56.03 59.71 45.10 46.19 73.53
ash 3.66 5.40 3.99 36.46 3.92 1.25
fixed carbon (fc) 29.91 30.07 34.01 7.31 36.56 16.71
Lower Heating Value (MJ/kg, ar)
LHVfuel 22.00 20.34 22.75 13.21 22.06 16.13
Particle Size Analysis (μm)
d50 53.1 87.3 56.2 52.2 56.5 220.8
Ash Composition (wt %)
Na2O 9.4 1.0 1.2 0.6 3.9 2.4
MgO 12.7 0.7 0.8 5.3 15.7 3.0
Al2O3 2.6 4.8 4.5 8.0 2.6 1.7
SiO2 5.4 56.7 29.2 27.1 2.2 11.4
P2O5 0.6 1.2 3.5 5.5 0.8 4.6
SO3 17.4 1.2 3.1 2.9 17.1 0.8
K2O 1.9 1.6 1.8 1.4 3.0 59.7
CaO 36.8 14.3 40.1 34.1 32.3 0.0
TiO2 0.3 0.3 0.3 0.6 0.2 0.1
Fe2O3 2.3 5.0 4.0 3.9 7.6 0.2
traces 10.6 13.3 11.6 10.6 14.6 16.2

100 mL is drawn over an amino-phase column (Supelco-Supelclean species detected by the GC−FID are also considered and indicated as
LC-NH2, 3 mL/500 mg) within 60 s using a syringe. Before and after not identified (n.id.). Their concentrations in the syngas are
sampling, the SPA columns are cooled, thus ensuring complete approximated by a mean calibration factor and are therefore perceived
adsorption of the tars.32 To avoid condensation of tars, everything is as semi-quantitative values. As a result of the utilization of only one
electrically heated to above 200 °C in the sampling line. SPA stage (amino phase), high-volatile compounds cannot be detected
Tar samples are eluted from the amino phase using dichloro- completely.19 Thus, the given total tar loadings represent minimum
methane and analyzed in a gas chromatograph equipped with a flame values. However, particularly, tar compounds with high tar dew points
ionization detector (GC−FID, Agilent model 7890A).30 An Agilent are measured almost completely, which provides the technically most
HP-5 column (30 m, 320 μm, 0.25 μm) is used with H2 as the mobile decisive information. The benzene signal is ignored in the data
phase. Each GC analysis is repeated 3 times, and averaged values are evaluation and is therefore not considered in the given tar-loading
used. The GC−FID is calibrated for 14 tar species frequently values.
occurring in biomass gasification. Table 1 shows calibrated species, The fuels used for the investigations cover a wide range of different
their classification according to the ECN system, and the minimum input materials. Four fuels represent HTC biocoals based on a mixture
detection limit ctar,min for each compound. The calibration method is of biogenic residues for composting (HCo), beech wood (HBe), green
based on an external standard. Therefore, a representative mixture of waste (HGW), and municipal waste (HMW). HCo, HBe, and HGW
the 14 tar species is dissolved in dichloromethane, thus representing a were produced in a HTC demonstration plant by SunCoal Industries.
stock solution. For the quantitative calibration, various dilutions from Applied HTC conditions were around 210 °C at 20−21 bar with a
1:10 to 1:833 of the stock solution in dichloromethane are used, residence time of 3 h. The Spanish company Ingelia delivered HMW.
representing tar loadings of 0.0024−0.4816 g/Nm3 of each species in After HTC treatment, the fuels were mechanically dewatered,
the syngas. Measurement errors of the SPA analysis are around 7% for thermally dried, and ground to reach the final water content and
all species.4 particle size. Rhenish lignite (RL) was purchased as filter dust directly
The given values for the tar loading of all calibrated species are from the manufacturer and required no further processing. In this
quantitative and indicated as identified (id.). In addition, unknown work, it represents a well-known fossil fuel. Corn cobs (CC) represent

10926 DOI: 10.1021/acs.energyfuels.7b01801

Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

an untreated biomass with a high share of cellulose and hemicellulose gasified under EFG conditions at 1200 °C, the overall tar
delivered by JRS Rettenmaier. Table 2 summarizes the chemical and loading level is quite low.28 In this work, tars are measured by
physical properties of all fuels. means of a liquid chromatography method. Tar loading is
reduced from 15.3 to 1 g/Nm3 by increasing λ from 0.19 to
3. RESULTS 0.67. Besides the incomplete representation of benzene,
A detailed investigation of the individual influences of toluene, and xylene (BTX) by the SPA method, especially
stoichiometry and temperature on tar evolution is carried out the HTC pretreatment of the biomass seems to provoke a
for HBe, HGW, and RL in BabiTER. Stoichiometry is varied in significant reduction of the tar amount.
terms of the air/fuel equivalence ratio λ between 0.3 and 0.5. To provide a more detailed view, Figure 4 shows the
Therefore, λ is calculated by the ratio of the actual oxygen input influences of the operating parameters on tar composition.
ṁ O2 to the oxygen required for stoichiometric combustion
ṁ O2,stoic (eq 1).
ṁ O2
λ=
ṁ O2,stoic (1)
The temperature is varied between 900 and 1300 °C to cover a
wide range of conditions relevant for air-blown EFG.
Furthermore, 900 °C represents the upper limit of applicable
temperatures in fluidized-bed gasifiers, thus allowing for good
comparability of the results. Figure 3 shows the influences of λ

Figure 3. Influence of the temperature and λ on tar loading in

BabiTER.

and temperature on total tar loading subdivided into identified

and unknown species. Both increasing temperatures and λ
cause a decrease of the tar loading, whereby the temperature
effect is much stronger. By increasing λ, a part of the tar
reduction results from the syngas dilution by additional
nitrogen of air. This effect represents the actual impact of air-
blown gasification on syngas and is therefore not removed from
the data by recalculation. Figure 4. Influence of the temperature and λ on tar composition in
When the fuels are compared, RL has the lowest tar loading, BabiTER for HGW (top), HBe (middle), and RL (bottom).
especially at low λ. Lignite is known to release few tar during
pyrolysis.33 HBe causes the highest values with more than 1 g/
Nm3 at 900 °C. The most probable reason for the comparably Here, the ECN classification system is used considering the
high tar loadings of the HTC fuels is remaining lignin structures calibrated tar compounds listed in Table 1. Tars of all classes
that do not convert completely during HTC.34,35 Lignin has occur, but those of class 4 are the dominant species for all fuels.
low reactivity under gasification conditions and still decom- Looking at the results for RL, the temperature increase
poses at temperatures around 900 °C.36 At 1100 and 1300 °C, significantly reduces the amount of aromatic hydrocarbons,
lignin is completely converted and the resulting tars are whereas the amount of class 2 tars is almost constant. An
thermally cracked. In comparison to the results of a similar increase in λ reduces tars of classes 3 and 4, particularly at lower
investigation by Hernández et al., in which raw biomass is temperatures. The effect on class 4 tars is mainly caused by a
10927 DOI: 10.1021/acs.energyfuels.7b01801
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Energy & Fuels Article

Table 3. Detailed Results of Tar Measurements in BabiTER

operating conditions tar loading (mg/Nm3)
fuel T (°C) λ tol xyl (o) ind cre (o) nap flu fluor pyr phen id. n.id. total
RL 900 0.3 60 31 0 37 235 24 0 0 0 388 0 388
0.4 40 0 0 34 170 25 0 0 0 268 0 268
0.5 45 0 0 36 180 25 0 0 0 286 88 374
1100 0.3 20 0 0 36 80 26 0 0 0 163 102 265
0.4 0 0 0 34 64 26 0 0 0 124 51 175
0.5 0 0 0 35 32 27 0 0 0 94 71 165
1300 0.3 0 0 0 39 0 28 0 0 0 67 42 109
0.4 0 0 0 34 0 26 0 0 0 60 37 97
0.5 0 0 0 34 0 25 0 0 0 59 72 131
HBe 900 0.3 52 33 33 0 406 26 91 101 105 847 231 1078
0.4 47 38 47 0 450 26 0 0 44 652 302 953
0.5 43 33 39 0 324 24 60 61 72 656 243 898
1100 0.3 33 0 0 0 162 0 29 65 22 310 276 586
0.4 0 0 0 0 0 0 0 0 0 0 67 67
0.5 27 0 0 0 60 0 0 0 0 87 106 194
1300 0.3 20 0 0 0 0 0 0 0 0 20 48 69
0.4 19 0 0 0 0 0 0 0 0 19 23 42
0.5 19 22 0 0 0 0 0 0 0 40 24 64
HGW 900 0.3 75 40 51 34 482 26 0 0 50 758 285 1043
0.4
0.5 42 29 0 35 256 24 0 0 0 386 132 518
1100 0.3 31 0 0 39 201 25 0 0 0 295 175 470
0.4 0 0 0 34 66 26 0 0 0 125 63 189
0.5 0 0 0 35 44 24 0 0 0 103 72 174
1300 0.3
0.4
0.5 0 0 0 35 0 27 0 0 0 61 71 133

reduction in naphthalene, whose reactivity under EFG methodology as described for BabiTER. Before sampling, a
conditions develops strongly between 1000 and 1300 °C.37 stable operating point is awaited to ensure thermal equilibrium
The behavior of HGW is similar to RL, but the amount of class of the refractory. As the main operating parameter, λ is varied
4 tars is more than twice as high. For HGW and RL, the only between 0.35 and 0.6. Besides the measurement of tars, for the
identified tar species at 1300 °C are fluorene and cresol (o). BOOSTER trials, also the dry syngas composition is measured
Unlike HGW and RL, HBe produces no tars of class 2, but at using an online gas analyzer (Sick S700). The syngas
low temperatures, class 5 tars, namely, fluoranthene and pyrene, composition represents averaged values over a period of at
are identified. Although their concentrations are comparably least 10 min in stable operation. A more detailed description of
low, these large PAHs have high dew points and can cause the experimental procedure is given in a previous paper.8 That
severe problems in further processing steps of the syngas. The paper presents measurement values for HGW in BOOSTER,
existence of class 5 tars is in accordance with observations from which are considered here for reasons of comparability.
other authors gasifying raw beech under comparable con- Figure 5 shows the dry syngas compositions in BOOSTER
ditions.7 Therefore, the aforementioned presumption of for all fuels. By increasing λ, the evolution of the syngas is
incomplete conversion of the biomass structure during HTC mainly influenced by the increasing temperature as well as
is confirmed. A further temperature increase to 1300 °C causes additional oxygen and nitrogen. An increasing temperature
complete conversion of class 4 and 5 tars, so that toluene and causes an increase of char conversion and affects the syngas
xylene (o) are the only remaining species. composition by the water-gas shift reaction.5 Additional oxygen
Table 3 summarizes the detailed results of the tar is consumed by the combustion of the volatiles, which, in turn,
measurements for the BabiTER trials. The calibrated species increases the temperature. The general behavior is similar to
cresol (m), phenol, and styrene are not detected in the test results considering the equilibrium of the water-gas shift
series because their secondary cracking reactions are already reaction.38 In contrast to oxygen-blown processes, the share of
completed at temperatures around 850 °C.21 Furthermore, nitrogen increases by increasing λ. By only considering
neither anthracene nor biphenyl occurs, which is why these chemical equilibrium, methane would not be present as a
species are not listed in the table. In comparison to the results result of the high temperatures reached. However, as a result of
of Hernández et al.,28 measured xylene values are rather low, kinetic limitations of the methane conversion,39 it still reaches
which indicates a possible underestimation as a result of the use significant values, especially at low λ.
of the SPA method. A significant share of the n.id. compounds Syngas from raw biomass (CC) has the highest methane
probably is acenaphthylene, which is reported by Hernández et content, whereas lignite produces only few methane. The HTC
al. for similar reaction conditions.28 fuels show an intermediate methane level. This can be
The autothermal test series in BOOSTER involves all fuels attributed to the reduction of the volatile yield in comparison
listed in Table 2. Tar sampling and analysis follow the same to the raw fuel.40 As a result of the very high ash content in the
10928 DOI: 10.1021/acs.energyfuels.7b01801
Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

cause lower gasifier temperatures as a result of their low LHV

and, in the case of HMW, a high ash content. The measured
inner wall temperatures of HMW are up to 100 °C lower than
for, e.g., HBe or HGW. Furthermore, on the basis of an ash-free
consideration, both fuels have very high volatile yields. Because
during pyrolysis tars form from the complex volatile matter, this
is an additional reason for the comparable high tar loadings. By
increasing λ, tars are efficiently reduced, so that, for all fuels,
except for HMW, the tar loading is below 0.2 g/Nm3 at λ = 0.4.
Similar values are reported by Kremling et al. for oxygen-blown
operation in the case of lignite or pretreated biomass as fuels,
whereas raw biomass causes tar loadings of up to 3.5 g/Nm3.7
In BOOSTER, the tar loadings of HBe, HGW, and RL are
comparable to the results at λ ≥ 0.4 and T ≥ 1100 °C in
BabiTER. Therefore, the considerably longer residence times
achieved in BOOSTER do not seem to have a crucial effect on
the tar loading if compared to other parameters, such as the
temperature.26 Calculated tar dew points range between ≤ −20
and 55 °C, whereby the tar dew point mostly correlates to the
tar loading. However, for CC at λ = 0.35, tar loading is much
smaller than for HMW, but at the same time, the dew point is
higher. For HMW, total tar loading decreases with increasing λ,
but initially, the dew point increases. The reason for these
observations is the formation of phenanthrene, which is
exclusively present for these trials and has a high dew point
of 340 °C. For all other trials, the only identified species are
naphthalene and toluene.
Because only class 3 and 4 tars occur in BOOSTER, a
detailed consideration of the influences on tar classes is not
shown. Instead, Figure 7 shows the tar loading of all occurring
species for HMW, which is the most problematic fuel in terms
of tar-related issues. Most of the tar consists of naphthalene.
Phenanthrene is increasingly formed until λ = 0.45 and
decreases after that.
Besides the variation of λ, previously published results show
that the addition of water steam has the potential to improve
the performance of an autothermal EFG in terms of the fuel
conversion and the cold gas efficiency.8,42 To investigate its
influence on tar loading, the addition of water steam is applied
for RL, HBe, and HGW in BOOSTER. Therefore, we use the
steam addition ratio Π, which is calculated as the steam mass
flow ṁ st related to the fuel mass flow ṁ f (eq 2).
ṁ st
Π=
Figure 5. Influence of λ on the syngas composition in BOOSTER. ṁ f(ar) (2)

fuel, the process temperatures for HMW are low, which leads to Steam addition is applied for a constant λ = 0.4, meaning that
low methane conversion. Moreover, low temperatures promote the supplied air flow is constant for a given fuel and the
the reduction of CO in favor of CO2 by the water-gas shift additional steam mass flow increases with Π. Similar to the
reaction. results from these fuels without steam addition, the only
Figure 6 shows the results of the tar measurements for all identified tar species are toluene and naphthalene. Figure 8
fuels. Besides tar loading, the figure shows corresponding tar shows tar loadings and tar dew points. In comparison to air-
dew points calculated with the ECN tar dew point calculator blown gasification, the addition of steam tends to increase both
considering the identified species.41 Because the utilization in a the tar loadings and the tar dew points slightly. The reason for
gas engine is the most probable application of the syngas from this is probably the reduced temperature as a result of the
air-blown EFG, condensation of tars is a critical issue,17 whereas moderating effect of the steam,8 which results in decreased
gaseous tar species are less problematic. Tar dew points shown naphthalene conversion.
as −20 °C involve calculated values of −20 °C and below. All tar dew points are below 15 °C, therefore, from a
As expected, the highest tar loading occurs for low λ and technical point of view, the effect of steam addition on tar
therefore at the lowest temperatures. Tar loading is strongly evolution is negligible. An increase in tar loading by steam
dependent upon the fuel type, and CC and HMW have the addition is also reported by Hernández et al. for the gasification
highest values. In comparison to the other fuels, CC and HMW of marc of grape.28
10929 DOI: 10.1021/acs.energyfuels.7b01801
Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

Figure 6. Influence of λ on tar loading in BOOSTER.

Figure 7. Influence of λ on detailed tar composition for HMW in

BOOSTER.

Figure 9. Relationship between the methane content in the syngas and

total tar loading in BOOSTER.

function of the dry methane content for all fuels. Overall, an

increasing methane content seems to indicate an increase in tar
loading, but the effect is particularly dependent upon the
different fuel properties. CC, for instance, produces much
methane but only few tars, whereas HMW reaches comparably
high tar loadings already at around 2 vol % CH4.
For RL, there is no clear trend. Therefore, by considering
only the methane content, a reliable statement on tar evolution
is not possible. Nevertheless, for a given fuel, it provides
valuable information on the stability of the process and an
estimation of operating limits, where tar evolution becomes
critical.
In autothermal gasification, the fuel quality and operating
Figure 8. Influence of steam addition on tar loading in BOOSTER at parameters greatly influence the gasifier temperature. Because
constant λ = 0.4. the temperature is considered the most prevailing influence
parameter on tar generation, a correlation between both values
is also examined for the BOOSTER trials. Therefore, the
Finally, simplified correlations are investigated on the basis of temperature T3 serves as a reference value (see Figure 1). It is
the experimental results from the BOOSTER trials. In measured for all trials and represents the inner wall temperature
industrial gasifiers, a sophisticated tar measurement is often halfway down the reaction zone. Figure 10 shows the
not available and online monitoring of the process is desirable. relationship of total tar loading as a function of the wall
Therefore, in the literature, easily measurable variables are temperature for all BOOSTER trials. Here again, increasing
considered indicators of tar evolution. Examples of these are temperatures clearly reduce tar loading, but the absolute
acetylene and benzene43 as well as ethane or methane.44 In this amount is fuel-dependent. As already observed from the
work, the methane content in the syngas is measured for all BabiTER trials, the temperature range for strong tar develop-
trials, and its suitability as a tar indicator is therefore examined. ment is below 1000 °C. However, for fuels such as RL that only
Figure 9 shows an overview of the total tar loadings as a produce few tars, tar loading does not increase much, even at
10930 DOI: 10.1021/acs.energyfuels.7b01801
Energy Fuels 2017, 31, 10924−10932
Energy & Fuels Article

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
ORCID
Ludwig Briesemeister: 0000-0002-2444-615X
Michael Kremling: 0000-0002-8616-430X
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This work was supported by the German Federal Ministry for
Economic Affairs and Energy (BMWi) in the framework of the
project “FLUHKE” (FKZ 03KB074B). The authors thank the
students involved in this work (Roland Balint and Martijn van
Figure 10. Relationship between the gasifier wall temperature (T3) Stiphout). The support of the Technical University of Munich
and total tar loading in BOOSTER. (TUM) Graduate School is gratefully acknowledged.

comparably low temperatures, and a temperature correlation is

■ NOMENCLATURE
BabiTER = baby high-temperature entrained-flow reactor
only of limited significance. BOOSTER = biomass pilot-scale entrained-flow gasifier
It is worth noting that the wall temperature T3 does not CC = corn cobs
represent the gas temperature, which, in fact, can be ECN = Energy Research Centre of the Netherlands
significantly higher. In addition, pyrolysis and tar formation EFG = entrained-flow gasifier
already occur in the flame region in the upper part of the fc = fixed carbon
reactor. Therefore, the crucial temperatures probably exceed FID = flame ionization detector
those measured at T3 by far. GC = gas chromatograph
HBe = hydrothermal carbonized beech wood
4. CONCLUSION AND OUTLOOK HCo = hydrothermal carbonized residues for composting
This study focuses on tar generation during entrained-flow HGW = hydrothermal carbonized green waste
gasification of HTC biocoal, raw biomass, and lignite HMW = hydrothermal carbonized municipal waste
specifically for the use of air as a gasification agent. Tar HTC = hydrothermal carbonization
measurements using the SPA method are performed in an id. = identified
electrically heated EFG (BabiTER) as well as in an industrial- IPCC = Intergovernmental Panel on Climate Change
like autothermal EFG (BOOSTER). Identified tar compounds LHV = lower heating value
are mainly light PAHs, of which naphthalene is the MFC = mass flow controller
predominant species. Therefore, the majority of the tars are n.id. = not identified
formed by recombination of primary and secondary pyrolysis PAHs = polycyclic aromatic hydrocarbon
products. Of all studied operating parameters, the temperature RL = Rhenish lignite
shows the greatest effect on tar evolution, whereas the SPA = solid-phase adsorption
residence time and λ have less influence. In the BabiTER
trials, the measured tar loading of more than 1 g/Nm3 at 900
°C decreases to less than 0.2 g/Nm3 with a temperature
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