Energy 93 (2015) 1321e1327

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Energy
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Characteristics of rice husk tar secondary thermal cracking

Ming Zhai*, Xinyu Wang, Yu Zhang, Peng Dong**, Guoli Qi, Yudong Huang
Harbin Institute of Technology, Harbin, Heilongjiang 150001, China

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

Article history: A two-stage xed bed pyrolysis system for rice husk tar high-temperature thermal cracking was
Received 22 May 2015 designed. Pyrolysis of rice husk and high-temperature thermal cracking of the rice husk tar were
Received in revised form separated. High-temperature ue gas was used to promote rice husk pyrolysis, and then high-
4 October 2015
temperature secondary thermal cracking tar started in the high-temperature environment. The char-
Accepted 11 October 2015
acteristics of secondary thermal cracking of rice husk tar were investigated. Results show that rice husk
Available online xxx
tar yield is 18 mg/kg of dry rice husk, or 11.7 mg/Nm3 at 1200
C, and no tar is collected at 1300
C. At the
temperature of 1200
C and residence time of 0.5 s, the rate of decline of tar reaches the maximum. The
Keywords:
Rice husk tar
oxy-organics content in the tar at 700
C reaches the maximum 24.5% and becomes zero at 1100
C. The
High-temperature pyrolysis naphthalene content in the tar reaches the maximum 26.4% at 800
C. With the increase in temperature,
Secondary thermal cracking all the tar converts into non-condensable gas and char nally.
Tar yield 2015 Elsevier Ltd. All rights reserved.
Cracking rate

1. Introduction
Biomass tar is a complex mixture of condensable hydrocarbons,
which is generated from the process of biomass chemical conver-
sion [1]. It is generally dened as an organic matter with a mo-
lecular weight larger than benzene, including oxygen-containing
and complex polyaromatic hydrocarbons [2]. The denition on
biomass tar is made mostly from condensing temperature of tar
and molecular weight, which is mainly conrmed according to the
research scope and condition of the investigators, or based on
specic requirements [3,4]. However, there is no uniform denition
on tar. Any organic matter that is generated by organic materials
under heated condition or partial oxidation (gasication) effect can
be considered as tar [5]. Also, it is usually believed that the tar is
mainly composed of large molecular aromatic hydrocarbons.
Currently, more than 100 species have been analyzed while it is still
hard to dene all of the components. What can be ensured is that
the number of the main components is more than 20. Most of the
components are derivative of benzene and PAH (polycyclic aro-
matic hydrocarbon). More specically, there are seven types of
benzene with its component greater than 5%, namely benzene,
naphthaline, methylbenzene, dimethylbenzene, styrene, phenols,
and indene [6].
* Corresponding author. Tel.: 86 18646218082.
** Corresponding author. Tel.: 86 451 86413171.
E-mail addresses: zhaiming@hit.edu.cn (M. Zhai), dongp@hit.edu.cn (P. Dong).
Broido proposed the formation and variation model of tar in the
process of biomass pyrolysis [7]. According to Broido-Shazadeh
model [7,8], biomass pyrolysis generates gaseous product (pyroly-
sis gas), liquid product (tar and water) and solid product (semi-char
and ash) after pyrolysis. It is dened as the rst reaction. The tar
generated will continue to produce gas, char, and secondary tar in
the pyrolysis reaction under a high-temperature environment. The
process is dened as the secondary reaction. Kinetic model [9],
product yields and kinetics [10], particle pyrolysis [11] and heat of
reactions [12] for the process were studied, but till now, no state-
ment has been widely accepted in the secondary reaction. The
secondary pyrolysis of volatile matter involves a series of compli-
cated chemical reactions. Generally, it is a process where chemical
bond, which is supported by thermal decomposition and free
radical theory, breaks, recombines, and lowers the average molec-
ular weight of reactant. Under the condition of many pyrolytic re-
actions, experimental data show that light gas was the prominent
product generated in the process of secondary pyrolysis. Hence, the
simplest secondary reaction path volatile matter / light gas has
been adopted widely. However, under such conditions, especially
high temperature, and long residence time, semi-char will also
become an important product of the secondary reaction, and
signicantly inuence the distribution of pyrolysis product. On the
other hand, the tar obtained from high-temperature pyrolysis was
signicantly different from the liquid obtained after cooling the
primary volatiles [13]. According to the constituents of products of
these two liquids, tar generated from conventional pyrolysis is the
secondary product formed in the further disaggregation and

http://dx.doi.org/10.1016/j.energy.2015.10.029
0360-5442/ 2015 Elsevier Ltd. All rights reserved.
1322 M. Zhai et al. / Energy 93 (2015) 1321e1327
condensation of volatile matter, namely the so-called secondary tar
[3,14].
Tar blocks and contaminates the burning line, lter, engine, and
turbine. The tar yield of using circulating uidized beds for biomass
pyrolysis and gasication is 1e30 g/Nm3 [15]. The tar yield of other
forms of gasication equipment, such as downdraft gasiers and
updraft gasiers, is 0.1e150 g/Nm3 [14,16]. In terms of most
biomass pyrolysis and gasication application equipment, the
required content of tar should be less than 0.05 g/Nm3 [17]. Hence,
tar removal has become an urgent problem that must be resolved in
the process of biomass pyrolysis and gasication technology. At
present, biomass limited oxygen combustion is adopted in most
biomass pyrolysis and gasication processes, but the tar content of
product gas generated is high.
Tar can be reduced by thermal cracking that requires heating the
tar to a high temperature or exposing the tar to catalysts at lower
temperatures [3]. It is believed that biomass high-temperature
pyrolysis is the most effective method to reduce tar content
[18,19]. However, since the addition of oxygen to increase tem-
perature will reduce the energy content of the gas product, most
conventional biomass gasication processes operate below 900
C,
even if the reactors can operate at a higher temperature. Moreover,
since biomass pyrolysis and high-temperature thermal cracking of
tar usually occur in one-stage gasier, it is difcult to control the
temperature and residence time, which are the main factors
affecting the tar content in product gas. Another issue is tar sam-
pling for analysis. CST (Cold solvent trapping) and SPME (solid
phase microextraction) adsorption are widely used in practice for
tar online sampling in pyrolysis gas [20e22]. The CST method is
more convenient for sampling tar from the gas with a high content
of tar [20], but SPME adsorption is more precise and quicker,
simpler and easier to operate [22]. For online tar sampling in the
pyrolysis gas, both of the methods have their strengths and
weaknesses.
To overcome these issues mentioned above, this paper designed
a two-stage xed bed pyrolysis system for rice husk tar thermal
cracking. High-temperature pyrolysis of rice husk and high-
temperature thermal cracking of tar were separated. First, high-
temperature ue gas was used to promote rice husk pyrolysis;
then high-temperature secondary thermal cracking tar started in
the high-temperature environment. Although propane was used as
the fuel for combustion in the experiment, it could be replaced by
product gas generated from pyrolysis and gasication of the
biomass itself for industrial application [23]. This option has more
energy cost, but there is less energy loss of tar condensing and post-
reduction and no risk of inactivation of catalysts. The objective of
the work is focused on the characteristics of rice husk tar secondary
thermal cracking. The temperature and residence time for the py-
rolysis and secondary thermal cracking were monitored and
controlled separately. The tar in the gas was condensed and
collected; then the moisture was removed from the tar for GCeMS
analysis. The inuences of temperature and residence time on
compositions of the gaseous product and the tar, and the cracking
rate and yield of the tar were investigated. The operating conditions
for thermal cracking to reduce rice husk tar will be provided.
Table 1
Proximate and ultimate analysis of rice husk.
Moistureada(%) Volatilead(%) Ashad(%) Fixed carbonad(%)
5.08 0.15 63.05 0.60 14.98 0.20 16.89d
a
ad: air-dry basis.
b
daf: dry, ash free basis.
c
Qnet,d: net caloric value, dry basis.
d
By difference.
2. Materials and methods
2.1. Material for the experiment
Rice husk typically found in Heilongjiang province, China's
largest rice-growing area where the rice production was 1.5  107 t
in 2014, was chosen as the raw material. Rice husk, an agricultural
biomass resource, is composed of ber, lignin, extractives and ash.
Moreover, it is recognized that the product gas made from pyrolysis
or gasication of the biomass-derived material is carbon neutral.
For example, one ton of CO2 will be mitigated by combustion of
2700 m3 of the gas made from rice husk char, which expresses the
benet of the carbon neutrality [24]. Rice husk is easy to collect
since it primarily accumulates in rice processing plants. The rice
husks in this paper are from a rice processing plant of Harbin, the
capital city of Heilongjiang. The proximate and ultimate analysis of
rice husk is shown in Table 1.
2.2. Experimental setup
The two-stage xed bed pyrolysis system which is illustrated in
Fig. 1 mainly consists of a primary burner, a secondary burner, a
xed bed reactor for pyrolysis, a high-temperature cracking reactor
for the tar, a condenser, and a mixing chamber. Considering high-
temperature ame was generated in the burners, stainless steel
mesh was wired on the inner wall, and refractory concrete and
construction aggregate were applied inside. Thermal insulation
material was covered outside the burners. Propane and air supplied
to the burner were tangential. An observation window was set on
the end face of each burner for observing the ignition and burning
condition. The xed bed reactor was made of stainless steel with
the inner diameter of 148 mm and the length of 700 mm for rice
husk pyrolysis. Stainless steel featured by refractory concrete was
installed on its inner wall. The primary burner and the secondary
burner were the same, but ceramic tubes with small diameter were
lled in the tail part of the secondary burner to increase the heat
accumulation of fuel gas in the tail region. The high-temperature
cracking reactor made of stainless steel with ceramic heat accu-
mulator was for tar secondary thermal cracking into incondensable
gas. Several high-temperature cracking reactors were made with
the lengths and diameters from 0.5 to 2 m and 448 to 4219 mm
respectively.
2.3. Experimental procedures
Dry rice husk in its original size (2e10 mm) with the amount of
1.5e2 kg was fed to the grid plate initially, and valve 10 was open
and valve 9 was closed. Propane and air sufciently combusted in
both of the burners. The ue gas analyzer was used to measure the
oxygen content of the ue gas and adjust the proportion of propane
and air to ensure there was no oxygen in the ue gas (O2 is less than
0.2%). When the temperatures at the exit of the burners were sta-
ble, valve 9 was opened and valve 10 was closed so that the high-
temperature ue gas generated from the primary burner entered
the xed bed reactor for the pyrolysis of rice husk. The temperature
Cdafb(%) Hdaf(%) Odaf(%) Ndaf(%) Sdaf(%) Qnet,dc(kJ/kg)
46.18 0.50 6.08 0.15 45.02d 2.62 0.08 0.10 0.03 14,556 120
 M. Zhai et al. / Energy 93 (2015) 1321e1327
22 10
Flue
gas
400~1200 C
11
12
13
14
Flue 15
16
gas
400~1300 C
20 0.5~4s
17
18
31
20~30 C
32
1 and 25: propane; 2 and 27: air tanks; 3, 4, 26 and 29: pressure gages; 5, 6, 23 and 24: regulators;
7: primary burner; 28: secondary burner; 8: fixed bed reactor; 9, 10 and 19: valves; 11-16, 30, 31
and 32: thermal couples; 17: condenser; 18: water pump; 20: deposition tank; 21: grid plate; 22:
exhaust tube; 33: high-temperature cracking reactor
Fig. 1. Two-stage high-temperature pyrolysis system.
at the exit of the primary burner was monitored and controlled
from 400 to 1200
C. The temperatures from the top to the bottom
of the xed bed reactor increased gradually and then reach a con-
stant which meant the end of the pyrolysis at a certain layer in the
xed bed. Then, the mixture of volatile matter and high-
temperature ue gas entered into the high-temperature cracking
reactor for secondary thermal cracking. The temperature at the exit
of the secondary burner was monitored and controlled from 400 to
1600
C. The ue gas from the secondary burner mixed directly
with the pyrolysis gas in the xed bed reactor. The volatile con-
densable matter converted into non-condensable gas. The tem-
perature at the exit of the secondary burner was set higher than
that at the exit of the xed bed reactor. The temperature in the
high-temperature cracking reactor decreased rst, and when the
reaction in the xed bed reactor nished, the temperature in the
high-temperature cracking reactor would increase. Gas mixture
exhausted from the high-temperature cracking reactor entered the
condenser to 20e30
C. The condensed tar ew into the deposition
tank, and the non-condensable gas was discharged into the atmo-
sphere. The tar condensed in the condensing tube of the condenser
was dissolved by acetone and collected and calculated to determine
the total mass of the tar condensed.
The residence time of the pyrolysis gas in the cracking reactor
can be determined by the length of the cracking reactor divided by
the ow rate of the gas in the creaking reactor. Therefore, pre-tests
were done to determine the ow rate of the gas in the creaking
reactor by installing different sizes of the high-temperature
cracking reactors at a certain operating condition. The total reac-
tion time was about 30 min that depended on the operating
conditions.
2.4. Measurement devices
S type thermocouples, with a range of temperature measure-
ment from 0 to 1600
C, were adopted to measure the exit tem-
perature of the burner. Rotameters were taken to measure the ow
of air and fuel gas. The Testo350 ue gas analyzer was used to
measure the composition of the ue gas at the exit of the burner.
1323
Rice husk 1.5~2.0kg
6
7
8 3 4
400~800 C
5
21
1
2
9
23
33
28 29 26
30 24
400~1600 C
19 25
27
The GCeMS analysis technology was applied to analyze the rice
husk tar and gas composition. GCeMC analysis was conducted on
condensed tar after high temperature thermal cracking at 700, 900,
1000 and 1200
C respectively. The HP5973GCeMS gas
chromatograph-mass spectrometer was adopted. Chromatographic
conditions were as follows. HP-5 trace analysis chromatographic
column was 30 m  0.25 mm  0.25 mm capillary column; carrier
gas was high-purity helium with ow rate of 1.0 mL/min with initial
pressure of 7.89 psi, mean velocity of 36 cm/s, split ratio of 5:1,
column temperature of 55
C, and equilibrium time of 0.5 min; the
heating rate was 10
C/min to increase to 300
C with residence
time of 22 min and injector temperature of 320
C. Mass spectrum
conditions were as follows. Ionization source was EI with electron
bombardment energy of 70 eV, mass range m/z from 15 to 650 amu
and scanning time of 3 min.
3. Results and discussions
In this section, a heating rate of rice husk was 20
C/min and the
average pyrolysis temperature of 700
C was considered. The rice
husk tar generated in the xed bed reactor began secondary ther-
mal cracking in the high-temperature cracking reactor after the rice
husk pyrolysis. The characteristics of the pyrolysis product, the
gaseous product, tar cracking rate and tar's composition were
investigated.
3.1. Composition of the pyrolysis product
Fig. 2 is the mass of each component of rice husk pyrolysis
product under the condition of 0.5 s residence time and different
temperatures. The liquid yield increases rst and decreases with
the rise of temperature, reaching the maximum at 500
C. It is
mainly contributed by the production of bio-oil. According to Die-
bold [25], cellulose pyrolyzes predominantly to levoglucosan which
vaporizes above 500
C, thus contributing primarily to gas and
liquid yields. Lignin also makes some contribution to the liquid
yield. With the increase of temperature, the liquid decreases
signicantly at 800
C with a tar output of 1.8 g/kg of dry rice husk.
1324 M. Zhai et al. / Energy 93 (2015) 1321e1327
Fig. 2. Composition of pyrolysis product.
When the temperature reaches 1000
C, the tar content will be
reduced to 800 mg/kg of dry rice husk, or 522 mg/Nm3. When the
temperature reaches 1200
C, the tar yield will be 18 mg/kg of dry
rice husk, or 11.7 mg/Nm3. Within the temperature between 1000
and 1200
C, the tar content has reached milligram level. Brandt
et al. [26] obtained 21 mg/kg of dry material cracked under the
condition of 0.5 s and 1250
C. Compared with that, the results are
similar to Brandt's results. At the temperature of 1300
C, no tar is
collected. It can be observed that temperature plays a signicant
role in affecting the cracking of liquid product. The yield of the gas
product increases signicantly with temperature from 400 to
700
C and reaches 79.5% at 800
C. Then, the rise of gas yield slows
down, reaching the maximum of 81% at 1300
C. It is contributed to
the fact that part of gasication of carbon residue has resulted in a
slight increase of gas.
Although the temperature required is higher than that for most
conventional biomass reactors, the main advantages of the second
thermal cracking are the tar reduction, the pyrolysis thoroughness,
and the process simplicity. Unlike physical cleaning, the tar need
not be condensed so that there is no heat loss for condensing.
Moreover, the solid product (rice husk char) of the pyrolysis at high
Fig. 3. Composition of gaseous product.
Fig. 4. Variation of tar cracking rate.
temperature is good-quality material for gasication due to its high
reactivity and large specic surface area [27].
3.2. Composition of the gaseous product
Fig. 3 shows that the components of product gas vary with the
cracking temperature. The volume fraction of CO2 is the calculation
value without the CO2 generated by ue gas. With the increase of
temperature, the volume fraction of CO2 decreases gradually, which
is mainly due to the fact that CO2 is primarily released by resolving
the carboxyl group of the rice husk or the organic steam at the
lower temperature. The volume fraction of H2 increases gradually
when the cracking temperature is lower than 800
C, and the vol-
ume fraction of CO and CH4 increases rst and then decreases.
According to the Broido-Shazadeh model, the condensable vapor
undergoes secondary reactions, cracking the vapor into secondary
gases, tar and char [7,8]. CO and CH4 are mainly generated by the
organic stream from the process of secondary reaction under the
higher temperature. The secondary reaction that organic stream
occurs includes decarboxylation, decarbonylation, dehydrogena-
tion, cyclization, aromatization, polymerization, et al. The fraction
 M. Zhai et al. / Energy 93 (2015) 1321e1327 1325

of CmHn is zero at low temperatures. When the temperature is
greater than 800
C, the volume fraction of CH4 begins to increase,
and CmHn also increases gradually. The reason is that under the
high-temperature environment, thermal cracking of tar generates
H2, CH4 and CmHn. Therefore, high-temperature thermal cracking of
tar will produce gas rich in hydrogen. If the dilution of the product
gas by the ue gas is considered, high temperature may have a
negative effect of reducing the heating value of the product gas,
because additional oxygen may be required for heat generation.
3.3. Tar cracking rate
The experiment was conducted by selecting the temperature
range from 900 to 1200
C and residence time from 0.5 to 4 s. The
yield of the liquid product after pyrolysis was 105 g per kilogram of
dry rice husk, which was regarded as the initial value for compar-
ison. Fig. 4 shows the variation of tar cracking rate with time under
different temperatures. The increase of temperature and residence
time can signicantly reduce the tar content. Under the tempera-
ture of 900
C, when residence time is from 0.5 s to 4 s, the tar
content decreases gradually. At 4 s, the residue tar content is 60 g/
kg of dry rice husk, and the tar cracking rate is 42.9%. Under the
temperature of 1000
C, when residence time is from 0.5 to 3 s, the
tar content decreases signicantly. The cracking rates at 3 s and 4 s
are almost the same, which are about 70%. Under the temperature
of 1100
C, when residence time is from 0.5 to 4 s, the tar content
decreases signicantly. The tar cracking rate reaches 84.8% at 4 s.
Particularly, under the temperature of 1200
C, when residence
time is 0.5 s, the tar content decreases signicantly. The tar cracking
rate reaches 99.98% at 0.5 s, which means 18 mg/kg of dry rice husk.
Since the residence time can be short for tar reduction, the
process of the second thermal cracking can be applied in an
entrained bed. The previous work [23,28] done by the authors
presented a scheme for using a two-stage cyclone gasier (an
entrained bed) for high-temperature rice husk pyrolysis and gasi-
cation. The scheme uses part of the product gas for combustion in

Table 2
Recognizable compounds in the tar at different secondary cracking temperatures.

No. Retention Name Molecular Molecular 700
C 900
C 1000
C 1200
C

time (min) formula weight a b
RC (%) RSD (%) RC (%) RSD (%) RC (%) RSD (%) RC (%) RSD (%)

1 9.173 Phenol, 4-ethyl- C8H10O 122 1.033 3.12 e e e e e e

2 9.400 Naphthalene C10H8 128 e e 2.332 2.56 e e e e
3 10.811 4-Hydroxy-3-methylacetophenone C9H10O2 150 1.182 2.89 e e e e e e
4 11.028 Naphthalene, 2-methyl- C11H10 142 e e 3.412 2.30 6.996 2.10 e e
5 11.268 Naphthalene, 1-methyl- C11H10 142 e e 3.645 3.42 5.989 3.21 e e
6 11.320 Phenol, 2-methoxy-4-propyl- C10H12O2 164 1.213 4.22 e e e e e e
7 11.920 Naphthalene, 2,3-dimethyl- C12H12 156 1.374 5.12 e e e e e e
8 12.189 Biphenyl C12H10 154 1.015 3.07 1.915 3.54 4.696 3.12 e e
9 12.714 Naphthalene, 1,6-dimethyl- C12H12 156 e e 1.212 2.33 e e e e
10 12.755 Naphthalene, 2,6-dimethyl- C12H12 156 e e 1.365 2.65 e e e e
11 13.107 Biphenylene C12H8 152 e e 8.688 2.89 13.042 3.76 e e
12 13.137 Acenaphthylene C12H8 152 e e e e e e 3.724 2.78
13 13.540 4-Methyl-5-penta-1,3-dienyltetrahydrofuran-2-one C10H14O2 166 1.378 2.01 e e e e e e
14 13.544 1-Isopropenylnaphthalene C13H12 168 e e 2.009 2.82 3.751 3.94 e e
15 13.939 Pyridine, 4-(2-(pyridyl-4)ethenyl)-, trans- C12H10N2 182 2.281 2.07 e e e e e e
16 13.942 Dibenzofuran C12H8O 168 1.290 3.09 4.209 4.02 8.744 4.59 e e
17 14.520 Cyclopropane, 1methyl-2-pentyl- C9H18 126 1.085 4.32 e e e e e e
18 14.522 L-Valine, N-[(9H-uoren-9-ylmethoxy)carbonyl]- C20H21NO4 339 e e 1.277 4.44 e e e e
19 14.737 Fluorene C13H10 166 7.221 2.15 6.872 3.14 12.135 4.77 6.357 2.45
20 14.985 1H-Phenalene C13H10 166 e e 1.735 3.11 e e e e
21 15.178 Dibenzofuran, 4-methyl- C13H10O 182 1.412 3.00 2.181 2.97 2.476 5.80 e e
22 15.338 3-(2-Naphthyl)acrylaldehyde C13H10O 182 e e 1.568 2.55 e e e e
23 15.683 n-Hexadecanoic acid C16H32O2 256 1.141 5.05 e e e e e e
24 16.057 8,11-Octadecadienoic acid, methylester C19H34O2 294 1.152 2.98 e e e e e e
25 16.058 9H-Fluorene, 1-methyl- C14H12 180 e e 1.849 4.00 e e 2.478 3.52
26 16.256 1-Heptene, 2-isohexyl-6-methyl- C14H28 196 e e 4.716 3.88 e e e e
27 16.508 1,10 -Biphenyl, 4-ethenyl- C14H12 180 e e 1.802 4.25 e e e e
28 16.544 9H-Fluoren-9-one C13H8O 180 e e e e e e e e
29 16.948 Anthracene C14H10 178 2.433 4.07 10.193 4.66 6.340 4.00 20.881 3.45
30 16.953 Phenanthrene C14H10 178 e e e e 18.783 4.39 7.095 1.58
31 17.055 Fluoranthene, 2-methyl- C17H12 216 1.573 5.06 e e e e e e
32 18.125 Anthracene, 9-methyl- C15H12 192 e e 1.045 2.87 e e e e
33 18.142 Anthracene, 1-methyl- C15H12 192 e e e e e e 1.092 1.99
34 18.204 Phenanthrene, 2-methyl- C15H12 192 1.139 5.90 e e e e 2.035 2.11
35 18.279 Pentadecanoic acid, 14-methyl-,methylester C17H34O2 270 e e 4.714 3.17 3.908 3.38 e e
36 18.361 4H-Cyclopenta[def]phenanthrene C15H10 190 e e 1.691 2.56 e e 9.801 5.01
37 18.872 5,16[10 ,2']:8,13[100 ,2'']-Dibenzen odibenzo C32H24 408 e e 1.526 4.11 e e e e
[a,g]cyclododecene, 6,7,14,15-tetrahydro-
38 18.890 1,2,4,8-Tetramethylbicyclo[6.3.0]undeca-2,4-diene C15H24 204 e e e e e e 2.371 4.34
39 18.915 Benzenamine, 4-methoxy-N-(3-pyridinylmethylene)- C13H12N2O 212 e e 1.095 3.99 e e e e
40 19.747 Fluoranthene C16H10 202 2.500 3.14 4.774 3.69 6.041 2.19 17.519 4.06
41 19.941 9-Octadecenoic acid (Z)-, methylester C19H36O2 296 e e 1.311 5.77 e e e e
42 20.247 Pyrene C13H10 202 e e e e 7.098 2.88 11.108 3.47
43 21.129 Pyrene, 2-methyl- C17H12 216 e e e e e e 3.024 3.09
44 21.295 11H-Benzo[a]uorene C17H12 216 4.806 3.45 e e e e 3.132 3.55
45 23.100 Cyclopenta[cd]pyrene C18H10 226 e e e e e e 6.257 4.97
46 23.224 Triphenylene C18H12 228 e e e e e e 3.124 4.23
a
RC: relative content.
b
RSD: relative standard deviation.
1326 M. Zhai et al. / Energy 93 (2015) 1321e1327
an external burner to generate a high-temperature anaerobic ue
gas, as well as to provide heat for pyrolysis and gasication. The
process and the gasesolid ow eld in the gasier were simulated
[28]. Heat self-sufcient of the process can be achieved by using
15.4%e20.5% of the total product gas for combustion [23].
3.4. Composition of the tar
The main recognizable compounds in the tar at the secondary
cracking temperature of 700
C, 900
C, 1000
C and 1200
C are
presented in Table 2. The relative contents of the compounds above
1% are selected. Fig. 5 shows the inuence of temperature on the
number of species of the tar.
Phenol components generated at 700
C disappear at a higher
temperature. The contents of the main components in the tar such
as anthracene, phenanthrene, pyrene, uoranthene and their de-
rivatives that are aromatic or polycyclic aromatic hydrocarbons
increase with the cracking temperature. The reason is that other
components in the tar convert to aromatic or polycyclic aromatic
hydrocarbons on the one hand. On the other hand, it is more
difcult to crack aromatic components than other components, so
the contents of aromatic or polycyclic aromatic hydrocarbons in-
crease compared with other components.
The contents of naphthalene, biphenyl, biphenylene, dibenzo-
furan and their derivatives increase with the temperature below
1000
C. The results are similar to that of Devi et al. [1]. When the
temperature is above 1000
C, the contents mentioned all decrease
signicantly, which implies that high temperature has an adverse
effect on the presence of these compounds. The reason is that the
compounds with hydroxyls, CeO bonds or C]O bonds are not
stable at high temperature and the bonds break. The bonds of
heterocyclic compounds with N or S also tend to break at high
temperature due to their thermolability.
With the increase of temperature, the species in the tar de-
creases gradually. At the temperature of 700
C, the tar is mainly
composed of oxy-organics and monocycle organics, and there are
129 types in total. When the temperature reaches 1200
C, the
composition of tar is primarily consisting of tricyclic and tetracyclic
organics, and the amount of tar and species decreases sharply.
Fig. 6 refers to the variation of the compounds in the tar at
different temperatures. The content of oxy-organics at 700
C
reaches 24.5%, and it almost becomes zero at 1100
C. The acids in
the tar decreased with temperature due to decarbonylation
Fig. 5. Number of species of the tar various with temperature.
reactions [29]. The content of naphthalene is few at 700
C and
reaches the maximum 26.4% at 800
C. The content of naphthalene
decreases gradually with temperature, and it becomes zero at
1200
C. The relative content of uorene is zero at 700
C. The
content of uorene increases slowly with temperature, but sharply
at 1000e1100
C. It is because with the decline of naphthalene and
oxy-organics, part of which polymerizes into isomer of uorene
and phenanthrene with greater molecular weight, while the other
part cracks into non-condensable gas. The content of uorene de-
clines rapidly at 1100e1200
C, as part of the uorene cracks into
non-condensable gases, while the other part polymerizes into tet-
racyclic aromatic hydrocarbons. There is hardly any tar content,
such as PAHs, at 700
C. With the increase of temperature, the mass
and components of the tar decrease gradually, PAHs in the tar in-
crease and then all tar converts into non-condensable gas and char
nally. It can be inferred that decarbonylation and carbonization
reactions occurred, as the chemical bonds rupture and recombi-
nation at higher temperatures.
4. Conclusions and recommendations
The motivation of this paper is the potential application of
secondary high-temperature thermal cracking to reduce tar con-
tent in the pyrolysis gas. A two-stage xed bed pyrolysis system for
rice husk tar high-temperature thermal cracking was designed.
Rice husk pyrolysis and secondary thermal cracking for the tar were
separated in the two-stage xed bed pyrolysis system. The objec-
tive of the work is focused on the characteristics of rice husk tar
secondary thermal cracking. The inuences of temperature and
residence time on compositions of the gaseous product and the tar,
and the cracking rate and yield of the tar were investigated.
The increase of temperature and residence time of secondary
thermal cracking remarkably reduces tar content in the pyrolysis
gas. Rice husk tar yield is 18 mg/kg of dry rice husk, or 11.7 mg/Nm3
at 1200
C, and no tar is collected at 1300
C. When the temperature
is higher than 800
C, the volume fraction of CH4 begins to rise, and
CmHn increases gradually. At the temperature of 1200
C and resi-
dence time of 0.5 s, the rate of decline of tar reaches the maximum.
The oxy-organics content in the tar at 700
C reaches the maximum
24.5% and becomes zero at 1100
C. The naphthalene content in the
tar reaches the maximum 26.4% at 800
C. With the increase in
temperature, all the tar converts into non-condensable gas and char
Fig. 6. Variation of compounds in the tar.
 M. Zhai et al. / Energy 93 (2015) 1321e1327
nally. From the results of this study, the tar in the pyrolysis gas can
be cracked completely at high temperature (~1300
C) with a short
residence time (~1s).
Recommendations for future study are to establish a pilot scale
of the entrained bed gasier proposed [28] and investigate the
characteristics of the pyrolysis and gasication in the gasier for
reducing the tar content.
Acknowledgment
This work was supported by National Natural Science Founda-
tion of China (Grant No.: 51206032), China Postdoctoral Science
Foundation (Grant No.: 2013M531037) and Heilongjiang Post-
doctoral Financial Assistance (Grant No.: LBH-Z12101).
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