international journal of hydrogen energy 35 (2010) 2606–2611

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Hydrogen production from biomass combining pyrolysis

and the secondary decomposition

Baofeng Zhao*, Xiaodong Zhang, Li Sun, Guangfan Meng, Lei Chen, Yi Xiaolu
Energy Research Institute of Shandong Academy of Sciences, Jinan 250014, China

article info abstract

Article history: An efficient method of hydrogen production from biomass was studied in this paper. The
Received 1 April 2009 pyrolysis of biomass was combined with the secondary decomposition of gaseous inter-
Accepted 3 April 2009 mediate for hydrogen-rich gas production, with the avoidance of N2 and CO2 dilution to the
Available online 2 May 2009 energy density of gaseous effluents. In order to acquire the optimum conditions for
hydrogen generation, effects of operating parameters on this two-step decomposition of
Keywords: biomass were analyzed through simulation of thermodynamic equilibrium and experi-
Biomass ments using Ni/cordierite catalyst. The results indicate that the operating parameters,
Hydrogen including pyrolysis temperature 923 K, 18 min of residence time, the secondary decom-
Pyrolysis position temperature 1123 K and molar steam to carbon ratio 2, satisfy all the criteria for
Simulation high hydrogen content and energy efficiency. Hydrogen content of above 60% and
Catalytic steam reforming hydrogen yield of around 65 g/kg biomass were achieved with optimized conditions. The
hydrogen-rich gas is preferred for potential utilization in downstream fuel cells for the
implementation of distributed energy supply, and is also practical for pure hydrogen
production.
ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction
In view of growing environmental concerns such as global
warming and the depletion of fossil fuel reserves, hydrogen is
expected to be the most prominent energy resource for the
near future and the implementation of hydrogen economy
has become the common sense of international community
[1,2]. Biomass, which is a renewable, abundant, potentially
sustainable and relatively environmentally friendly source of
energy, has been considered as one of the most probable
source for hydrogen production.
To obtain hydrogen from biomass, pyrolysis and gasifica-
tion are two mainly effective thermo-chemical conversion
methods to produce hydrogen-rich gas, which can be further
steam-reformed to make higher-purity streams for various
fuel cells. Biomass gasification coupled with water gas shift is
the most widely practiced route, with air, steam and oxygen as
gasifying agent [3–7]. In these processes, the influence of
nitrogen and carbon dioxide on the energy density and
hydrogen separation can’t be neglected. And what’s more
important, there is always large content of tar in the gas
product from traditional gasification process. Tar proposes
a serious threaten to downstream fuel cell system, both for
the electrodes and for the pipelines [7–11]. And still there are
some investigations on the reforming of biomass derived
pyrolysis oil to produce hydrogen, which may be limited by
the cost of the bio-oil production [12,13]. It is of great potential
to develop efficient and economically viable hydrogen
production technology based on biomass.
In our previous work [14], one technical route combining
the pyrolysis of solid biomass and the secondary decomposi-
tion of gaseous intermediate is proposed to produce hydrogen

* Corresponding author. Tel.:þ86 531 8559 9028; fax:þ86 531 8296 1954.
E-mail address: zhaobf@sderi.cn (BF Zhao).
0360-3199/$ – see front matter ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.04.011
 international journal of hydrogen energy 35 (2010) 2606–2611 2607

from biomass. With no air introduced in the over-all process,
the energy density of gas product is increased from the
avoidance of N2 and CO2 dilution, resulting in decreased
difficulty in gas separation. The influence of carbon on
hydrogen separation from hydrocarbons was lightened with
increased hydrogen mass content in the reaction network,
which makes the technical route more economic. The aim of
the present work is to find the optimum operating conditions
for maximization of hydrogen production with experiments
and thermodynamic analysis which predicts the technical
and economical feasibility of the process.
2. Experiments
2.1. Experimental apparatus and procedure
Experiments were carried out at an atmospheric pressure in
the whole process. Fig. 1 briefly illustrates the technical flow.
The moving-bed pyrolyzer is composed of one screw
conveyor, with inner diameter of 0.08 m and length of 1.5 m,
which is heated from outside by flue gas from residue carbon
combustion and exhaust heat from the secondary decompo-
sition stage. Pyrolysis temperature can be controlled by
adjusting the heating process. And also the residence time of
feedstock can be controlled by quantitative feeding device.
Rice husk is pyrolyzed into permanent gas (including H2, CO,
CO2, CH4, C2þ, etc), bio-oil, and char at normal heating rates in
the moving-bed pyrolyzer with no air permitted in. Char is let
out at this stage, while the gas and bio-oil are introduced into
second-decomposition reactor, where bio-oil and methane
can be converted to hydrogen via catalytic steam reforming at
high temperature. After condensation and cooling down the
water vapor, a hydrogen-rich gas at normal temperature is
produced and burned at the exit.
The ultimate analysis of char was performed in an
elemental analyzer (Elementar VarioEL III). The gas products
were analyzed on-line by Siemens Model 1080 infrared gas
analyzer.
2.2. Materials
Rice husk was used as a feed material and its ultimate and
proximate analysis are shown in Table 1. As a highly efficient
catalyst for removing tar, the monolithic catalyst using
cordierite as the catalyst carrier with high mechanical
strength, low thermal expansion coefficient and nickel as the
active species [15], was adopted to catalyze the steam
reforming of tar and methane.
3. Thermodynamic calculations
In our previous study [16], assuming the complete thermo-
dynamic equilibrium, the calculations based on the minimi-
zation of Gibbs free energy were used to simulate the biomass
pyrolysis, which indicate that the contents of H2 and CO could
reach the maximum of 51 mol% and 48 mol% respectively in
the gas product of biomass pyrolysis due to the high volatile
content and the high hydrogen to carbon atom ratio of
biomass. And CO could be converted further for higher H2
content. Then, thermo-chemical conversion of biomass based
on pyrolysis is favorable for hydrogen production.

10

4 5

9
1

7
AC
3

AC

11

Fig. 1 – Experimental system combing pyrolysis and the secondary decomposition. (1) Quantitative feeding device;
(2) Moving-bed pyrolyzer; (3) Char collector; (4) Evaporator; (5) Second-decomposition reactor; (6) Condenser; (7) Liquid
collector; (8) Gas flow meter; (9) Vacuum pump; (10) Infrared gas analyzer; (11) Instruments-control and data-acquisition
system.
2608 international journal of hydrogen energy 35 (2010) 2606–2611

follow-up system, the mass fraction of char, consisting of

Table 1 – Ultimate and proximate analyses pf rice husks.
carbon and ash, need to be measured. Fig. 3 shows the
Ultimate analysis Proximate analysis (wt%) distribution of char mass fraction with changes of the
(wt%, dry basis)
temperature and the residence time. In the same pyrolysis
C H O N S Moisture Ash Volatile temperature, char yield only reduced about 2% when the
residence time of feedstock increased from 6 min to 24 min,
39.9 5.1 37.9 2.17 0.12 9.94 14.8 69.3
which indicates volatile matter was mostly released in
6 min and the effect of the increase in reaction time on the
In the moving-bed pyrolyzer, complete thermodynamic
depth of rice husk pyrolysis is negligible. The char yield had
equilibrium would hardly be achieved because of the simul-
a decline trend when pyrolysis temperature increased from
taneous existence of gas and solid inducing kinetic
673 K to 1273 K. Clearly, the rate of char yield decline tends
constraints. The results of thermodynamic equilibrium
to be milder in 923–1273 K. This might be due to the release
calculations on the secondary decomposition should be closer
of a few high boiling point compounds, which remain in the
to those of experiments, as the only gaseous products exist in
char at low temperature.
the second-decomposition reactor. And then the thermody-
As is known, the high carbon content of char makes it
namic equilibrium calculations introduced in the previous
suitable to act as a fuel [17]. The elemental analysis of char
study [16], were used to simulate the effects of temperature
obtained at 923 K of pyrolysis temperature is shown in Table 2.
and steam/carbon molar ratio on the secondary decomposi-
60.87% carbon content of char makes it suitable to act as
tion. Herein, amounts of carbon are total number of moles in
a solid fuel, which can supply the energy needed by the
system minus those of char. The Gibbs reactor of this process
moving-bed pyrolyzer. Though the intensification of
to be simplified for the computations is shown in Fig. 2, which
secondary reactions in pyrolysis process at temperatures
also shows the flow procedure of C, H and O elements. As the
higher than 923 K could induce the increase of H2 content [18],
input of the Gibbs reactor, the amounts of C, H and O elements
it may mean the efficiency decrease in downstream secondary
in permanent gas and bio-oil, was got by their total number of
decomposition reaction. In addition, the much higher
moles in the rice husk minus those of char. In the calculations,
temperature results in energy loss because of the existence of
five species were taken into account: H2, CO, CO2, CH4 and H2O.
char at this stage. So, the pyrolysis temperature of about 923 K
might favor the energy efficiency of the over-all hydrogen
production network and the energy distribution between
4. Results and discussion pyrolysis and the secondary decomposition.

4.1. The first pyrolysis in moving-bed pyrolyzer

4.2. Simulation and experiment of the secondary

The effects of the operating parameters on rice husks
decomposition
pyrolysis are investigated in moving-bed pyrolyzer. The
studied parameters include reaction temperature range of
The residence time of 18 min and the temperature of 923 K
923–1273 K at 50 K interval and residence time of feedstock
were adopted to implement the rice husk pyrolysis, in the
in pyrolyzer varied from 6 min to 24 min. In order to
simulation of the secondary decomposition, temperature and
compute the amounts of C, H and O elements entering the
molar steam to carbon ratio were considered to study the
effects of operating parameters on the secondary
Rice husk
decomposition.

Pyrolyzer 45
t=6 min
t=12 min
Mass fraction of char (mass%)

40 t=18 min
Char (C, ash) Bio-oil Permanent gas t=24 min

35
C, H, O H2O

30

Gibbs reactor
(Second-decomposition reactor) 25

20
H2, CO, CO2, CH4, H2O
623 723 823 923 1023 1123
Temperature, K
Fig. 2 – Gibbs reactors in secondary decomposition process
of rice husks. Fig. 3 – Mass fractions of char of rice husks pyrolysis.
 international journal of hydrogen energy 35 (2010) 2606–2611 2609

approach equilibrium. A large S/C molar ratio induces the

Table 2 – Results of elemental analysis of char.
Element C N
Content (mass.%) 60.87
The results of calculation indicate that CH4 was unnotice-
able. Molar fractions of H2, CO and CO2 in dry gas and the
molar fraction of H2O in all products were shown in Fig. 4,
respectively. With the temperature increasing from 923 K to
1223 K, CO and H2O contents increase while that of CO2
decrease. When S/C molar ratio changes from 0 to 3, contents
of CO2, H2O and H2 increase whereas that of CO decreases.
These gas contents evolutions with the molar steam to carbon
ratio (S/C) and temperature can be explained by the reactions
involved in steam reforming of tar and CH4. The main reac-
tions are as follows:
large molecular hydrocarbonsðþH2 OÞ / H2 þ CO þ CO2
CH4 þ H2O 4 CO þ 3H2 DHq298 ¼ 206.11 kJ mol1
CO þ H2O 4 CO2 þ H2 DHq298 ¼ 41.17 kJ mol1
At normal operating conditions, reactions of tar (Reaction
(1)) are irreversible, whereas the methane reforming reaction
(Reaction (2)) and the shift conversion reaction (Reaction (3))
equilibrium for Reactions (2) and (3) to be shifted towards H2
S H production. With the temperature increasing, H2 content
0.822 0.161 1.671 slightly decreases when S/C molar ratio is higher than 1. One
possible explanation is that in the high temperature area
Reaction (3) happened in the converse direction, because the
increasing of temperature would favor the shift of the reaction
towards endothermic direction. Due to the same reason, CO
content increases while that of CO2 decreases with the
increasing of temperature. In the process of biomass pyrolysis
for hydrogen, the removal of a significant amount of tar is
required to increase hydrogen content. The calculation shows
that H2 content is about 60 mol% in the dry gas for any
temperature considered herein when S/C molar ratio is 2.
Above this S/C molar ratio, H2 content slightly increases but
the thermal cost of the excess steam load makes this mode of
operation unfavorable. Thus, the S/C molar ratio of 2 and the
D
temperature range from 1023 K to 1173 K provide favorable
þCH4 þ C þ Cn Hm (1) operating conditions.
Based on the result of simulation, catalytic steam reform-
ing of tar was performed with the temperature range of
973–1273 K at intervals of 50 K and the S/C molar ratio of 2
(2)
using Ni/cordierite catalyst in second-decomposition reactor.
The effect of temperature on the dry gas composition is
illustrated in Fig. 5 for both experimental and calculated
(3)
results. Comparison between them showed satisfactory
agreement, with a little difference due to the thermodynamic
imbalance of the real system. H2 content remains above
60 mol% and slightly varies when the temperature is higher

0.70 0.40
S/C=0 S/C=2.0
S/C=0.5 S/C=2.5 0.35
Molar fraction of CO (dry)
Molar fraction of H2 (dry)

0.65 S/C=1.0 S/C=3.0

S/C=1.5 0.30

0.60 0.25

0.20
0.55 0.15

0.10
0.50
0.05

0.45 0.00
950 1000 1050 1100 1150 1200 1250 1300 950 1000 1050 1100 1150 1200 1250 1300
Temperature, K Temperature, K

0.30 0.7

0.6
Molar fraction of CO2 (dry)

0.25
Molar fraction of H2 O

0.5
0.20
0.4
0.15
0.3
0.10
0.2

0.05 0.1

0.00 0.0
950 1000 1050 1100 1150 1200 1250 1300 950 1000 1050 1100 1150 1200 1250 1300
Temperature, K Temperature, K

Fig. 4 – Effects of temperature and S/C molar ratio on theoretical equilibrium values of gas composition.
2610 international journal of hydrogen energy 35 (2010) 2606–2611

0.7 higher than 60 vol.%, with relatively few impunities, the

hydrogen-rich gas product can fulfill the requirements of
0.6 downstream fuel cell or the purification of hydrogen for
H2
further utilization [19]. Although CO content in the product
0.5 gas is still above 12%, it can be easily converted to increase
Molar fraction

hydrogen productivity in modern water-gas-shift process.

0.4
These optimum operation parameters were adopted to
increase the hydrogen content in gas product, but they may
0.3
CO2 not be the optimization conditions to the energy distribution
0.2 of overall hydrogen production network. The energy efficiency
and over-all balance for the experimental set-up will be
0.1 CO investigated in further work.
CH4
0.0
1000 1050 1100 1150 1200
Temperature, K 5. Conclusions

Fig. 5 – Comparison of gas composition between
experiment (points) and simulation results (lines).
than 1123 K, which indicates that the temperature of 1123 K
could be the optimum reaction temperature for maximum
hydrogen production. H2 content arrives very close to that of
the equilibrium at this temperature, which may be induced by
the low space velocity of about 1.0  103 h1 and the addition
of overplus steam in the second-decomposition reactor. At the
range of experimental temperature, CO content is about
12 mol% in gas products, which could be converted further for
higher H2 content. And the water-gas-shift reaction favoring
the steady formation of H2 at relatively low temperatures
should be performed following the secondary decomposition.
An efficient technology to produce hydrogen from biomass
was studied, which combines the pyrolysis of rice husks and
the secondary decomposition of gaseous intermediate in
order to extensively promote hydrogen content. Through
experiments and thermodynamic analysis, the optimum
operating conditions, including pyrolysis temperature 923 K,
18 min of residence time, the secondary decomposition
temperature 1123 K and molar steam to carbon ratio 2, were
acquired. Hydrogen content of above 60% and H2 yield of
around 65 g/kg biomass were achieved with these conditions,
which indicates this route is efficient and economically
competitive. The rich-hydrogen gas is suitable for down-
stream fuel cell utilization for the implementation of distrib-
uted energy supply mode in areas with plenty of biomass
resources or for the purification of hydrogen.

4.3. Optimum conditions for maximum hydrogen

production Acknowledgments

The operating parameters of pyrolysis temperature 923 K, The work cited in this paper was funded by National Natural
18 min of residence time, the secondary decomposition Sciences Foundation of China (No. 50676052), National
temperature 1123 K and molar steam to carbon ratio 2 satisfies Hi-Tech Research and Development Program (863) project
all the criteria for high hydrogen content and energy effi- (No. 2006AA05Z117), and Natural Sciences Foundation of
ciency. The experiment was repeated three times in these Shandong Province (No.Y2007F56).
optimum operating conditions and the results were shown in
Table 3. H2 yield of the over-all process reached around 65 g/kg
biomass, which has already exceeded the hydrogen content in references
original biomass (about 47 g/kg biomass). The excess
hydrogen should be coming from water decomposed with
energy from biomass. The average content of hydrogen is [1] Sun Y, Su W, Zhou L. Hydrogen fuel. Beijing: Chemistry
Industry Press; 2005.
[2] Steinberg M, Cheng HC. Modern and prospective
technologies for hydrogen production from fossil fuels.
Table 3 – Results of experiments with optimum International Journal of Hydrogen Energy 1989;14:797–820.
conditions for hydrogen generation. [3] Milne TA, Elam CC, Evans RJ. Hydrogen from biomass, State
of the art and research challenges. Golden, CO, USA: National
Experiment number 1 2 3 Renewably Energy Laboratory. [IEA/H2/TR-02/001].
Gaseous products composition (vol. %) [4] Bari ID, Barisano D, Cardinale M, Matera D, Nanna F,
H2 61.3 60.5 62.1 Viggiano D. Air gasification of biomass in a downdraft fixed
CO 13.37 12.9 12.6 bed: a comparative study of the inorganic and organic
CO2 23 23.6 23.94 products distribution. Energy Fuels 2000;14:889–98.
CH4 1.2 1.31 1.17 [5] Franco C, Pinto F, Gulyurtlu I, Cabrita I. The study of
H2 yield (g/kg) 65.68 63.74 67.09 reactions influencing the biomass steam gasification
process. Fuel 2003;82:835–42.
 international journal of hydrogen energy 35 (2010) 2606–2611
[6] Pengmai L, Chang J, Xiong Z, Huang H, Wu C, Chen Y.
Biomass air-steam gasification in fluidized bed to produce
hydrogen rich gas. Energy Fuels 2003;17:677–82.
[7] Midilli A, Dogru M, Howarth CR, Ayhan T. Hydrogen
production from hazelnut shell by applying air-blown
downdraft gasification technology. International Journal of
Hydrogen Energy 2001;26:29–37.
[8] Milne TA, Evans RJ, Abatzoglou N. Biomass gasifier ‘tars’:
their nature, formation and conversion. Report NREL/TP-570–
25357. Golden (CO, USA): National Renewable Energy
Laboratory NREL; 1998.
[9] Devi L, Ptasinski KJ, Janssen FJJG. A review of the primary
measures for tar elimination in biomass gasification
processed. Biomass & Bioenergy 2003;24:125–40.
[10] Zhang RQ, Brown RC, Suby A, Cummer K. Catalytic
destruction of tar in biomass derived producer gas. Energy
Conversion and Management 2004;45:995–1014.
[11] Huber GW, Iborra S, Corma A. Synthesis of transportation
fuels from biomass: chemistry, catalysts and engineering.
Chemical Reviews 2006;106:4044–98.
[12] Wang D, Czernik S, Chornet E. Production of hydrogen from
biomass by catalytic steam reforming of fast pyrolysis oils.
Energy & Fuels 1998;12:19–24.
2611
[13] Rioche C, Kulkarni S, Meunier FC, Breen JP, Burch R. Steam
reforming of model compounds and fast pyrolysis bio-oil on
supported noble metal catalysts. Applied Catalysis B:
Environmental 2005;61:144–53.
[14] Sun L, Zhang XD, Yi XL, Xu M. Study on efficient hydrogen
production from biomass. In: Proceedings of the ASME Turbo
Expo, GT2006-90593; 2006. p. 363–7.
[15] Xu X, Chen L, Zhang XD, Sun HQ, Xu M, Sun L. Steam
reforming model compounds of biomass gasification tars. In:
The second seminar on biomass energy research of graduate
students in china. China, Guangzhou; 2007.
[16] Zhao BF, Sun L, Zhang XD, Chen L, Zhang J, Meng GF, et al.
Thermodynamic equilibrium analysis of rice husk
pyrolysis. In: Proceedings of ASME Turbo Expo Berlin,
German, GT2008–51052: CD-ROM Publication; 2008.
[17] Katyal S, Thambimuthu K, Valix M. Carbonisation of bagasse
in a fixed bed reactor: influence of process variables on char
yield and characteristics. Renewable Energy 2003;28:713–25.
[18] Morf P, Hasler P, Nussbaumer T. Mechanisms and kinetics of
homogeneous secondary reactions of tar from continuous
pyrolysis of wood chips. Fuel 2002;81:843–53.
[19] Zhu B. Advantages of intermediate temperature SOFCs for
tractionary applications. Journal of Power Sources 2001;93:82–6.