international journal of hydrogen energy 33 (2008) 5430–5438

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Hydrogen-rich gas production from biomass

steam gasification in an updraft fixed-bed gasifier
combined with a porous ceramic reformer

Ningbo Gaoa,b, Aimin Lia,b,*, Cui Quana, Fan Gaoa

a
School of Environmental & Biological Science & Technology (SEBST), Dalian University of Technology,
Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, Dalian 116024, China
b
School of Energy & Power Engineering, Dalian University of Technology, Dalian 116024, China

article info abstract

Article history: This paper investigates the hydrogen-rich gas produced from biomass employing an
Received 12 May 2008 updraft gasifier with a continuous biomass feeder. A porous ceramic reformer was
Received in revised form combined with the gasifier for producer gas reforming. The effects of gasifier temperature,
3 July 2008 equivalence ratio (ER), steam to biomass ratio (S/B), and porous ceramic reforming on the
Accepted 3 July 2008 gas characteristic parameters (composition, density, yield, low heating value, and resi-
Available online 11 September 2008 dence time, etc.) were investigated. The results show that hydrogen-rich syngas with
a high calorific value was produced, in the range of 8.10–13.40 MJ/Nm3, and the hydrogen
Keywords: yield was in the range of 45.05–135.40 g H2/kg biomass. A higher temperature favors the
Biomass hydrogen production. With the increasing gasifier temperature varying from 800 to 950  C,
Gasification the hydrogen yield increased from 74.84 to 135.4 g H2/kg biomass. The low heating values
Porous ceramic reforming first increased and then decreased with the increased ER from 0 to 0.3. A steam/biomass
Hydrogen production ratio of 2.05 was found as the optimum in the all steam gasification runs. The effect of
porous ceramic reforming showed the water-soluble tar produced in the porous ceramic
reforming, the conversion ratio of total organic carbon (TOC) contents is between 22.61%
and 50.23%, and the hydrogen concentration obviously higher than that without porous
ceramic reforming.
ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.

1. Introduction and other greenhouse gases. One of the attractive ways to

utilize biomass energy is hydrogen production. Hydrogen has
In the past decades, renewable biomass resources such as good properties as a fuel for internal combustion engines in
short-rotation woody crops, herbaceous biomass, and agri- automobiles. It is used as a clean power source for fuel cells.
cultural residues have received increasing attention as an Also, its use could be advantageous as a clean energy carrier
interesting renewable energy source [1]. As a source of for heat supply and transportation purposes [2].
renewable energy, biomass energy has significant environ- Biomass gasification process has emerged as a clean and
mental benefits including lower emissions of carbon dioxide efficient way of producing hydrogen. It is a well-known

* Corresponding author. School of Environmental & Biological Science & Technology (SEBST), Dalian University of Technology, Key
Laboratory of Industrial Ecology and Environmental Engineering, 2 Linggong Road, MOE, Dalian 116024, China. Tel./fax: þ86 411 8470
7448.
E-mail address: [email protected] (A. Li).
0360-3199/$ – see front matter ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.07.033
 international journal of hydrogen energy 33 (2008) 5430–5438 5431

technology that can be classified depending on the gasifying

agent: air, steam, steam–oxygen, air–steam, oxygen-enriched 2. Experimental
air, etc. [3]. Several biomass gasification reactor designs have
been developed and evaluated and can be generally classified The original material (pine sawdust) used as the feedstock for
into three categories, they are fixed bed [4], fluidized bed [5] gasification was obtained from a timber mill in Dalian City,
and moveable bed [6]. These gasifiers are conducted widely by China. The particle size of this pine feedstock is between 0.2
many researchers in biomass gasification [7]. and 0.4 mm. The results of proximate analysis and ultimate
Several advantages of steam as gasification agent are: analysis of biomass sample used for the experiment are
producing a gaseous fuel with relatively higher H2 content, shown in Table 1. The carbon (C), hydrogen (H), nitrogen (N)
eliminating the need for an expensive oxygen plant when and sulphur (S) analyses of pine sawdust were performed on
oxygen is employed as gasification agent, reducing the a CHNS/O analyzer (Elementar, VarioEL III), and the ash
diluting effect of N2 from air and producing higher heating content obtained by carrying the samples at oxygen (O) was
value syngas [8]. Much has been published in the literature on calculated by difference to 100%. The proximate analysis of
experimental investigations into the biomass steam gasifi- the samples was carried out according to standard norms. The
cation processes. Turn et al. [9] investigated hydrogen moisture, ashes and volatile matter were measured according
production from biomass gasification using a bench scale to the ASTM standard test method no. E871, D1102 and E872.
fluidized bed gasifier. Lv et al. [3] discussed biomass air–steam The fixed carbon was calculated by difference to 100%. The
gasification in a fluidized bed. Different effects such as higher heating value (HHV) was measured with oxygen bomb
temperature, steam to biomass ratio (S/B), equivalence ratio calorimeter.
(ER) and biomass particle size were investigated. Chaudhari The experimental apparatus setup that was used to
et al. [10] studied hydrogen production via steam gasification perform steam gasification experiments is shown in Fig. 1. It
of two biomass derived chars in a fixed bed. Higher concen- consists of a fixed-bed gasifier with a continuous biomass
tration hydrogen was produced by the simple steam gasifi- feeding system, a steam reformer with porous ceramic
cation process. Two distinct strategies converting packing layer, a steam/gas feeding line, a cooling system for
thermochemically biomass to hydrogen are gasification fol- the separation of water and tar, and various measurement/
lowed by shift conversion and catalytic steam reforming of analysis devices.
the whole oil or its fraction [11]. Many researchers carried out The gasifier and reformer are two same stainless steel
biomass gasification and catalytic reforming on different cylindrical tubes (1500.0 mm long and 87.5 mm i.d.), they were
reactor. Rapagn et al. [12] investigated catalytic biomass placed inside two same externally electrical furnaces (3.3 kW,
steam gasification in a bench scale plant consisting of 220 V, 15 A) which provided the heat for reaction and steam
a fluidized bed gasifier and a secondary catalytic fixed-bed reform. The internal configuration of reformer fixed-bed
reactor. Kimura et al. [13] discussed the different catalytic reactor is as same as gasifier; in particular, a porous ceramic
performance of Ni/CeO2/Al2O3 catalysts in steam gasification layer (200 mm in length and 87 mm in diameter) was located
of biomass. A Ni/olivine catalyst was tested by Świerczyński in the middle of the reformer. Table 2 shows the chemical
et al. [14] in a fixed-bed reactor in toluene steam reforming as composition and physical properties of porous ceramic filled
a tar destruction model reaction for a fluid bed biomass steam in the reformer. Two porous ceramics with same physical
gasification. Recently, Tomishige et al. [15,16] have investi- structure were employed in the reformer and each was
gated the gasification of biomass with steam using different 100 mm in length and 87 mm in diameter. Two K-type ther-
catalysts (Rh/CeO2/SiO2, Ni/CeO2/Al2O3) in fluid bed reactor. mocouples with a diameter of 0.3 mm were mounted through
And they found that these catalysts showed effectiveness in the wall of the reactor and measured the temperatures at the
the steam or air gasification and reforming of biomass, and reactor centerline. Oxygen and steam were employed as
high resistance to coke deposition and high stability was gasification agents for the tests. The steam of 120  C was
showed in the reforming process. generated in an electrical heated boiler, and the steam flow
Although many researchers had experimentally studied rate was controlled with a voltage regulator which controlled
hydrogen production by biomass gasification and the the voltage of boiler. All experiments were carried out at
reforming of product gas and tars, these gasification studies atmospheric pressure.
were conducted on batch-type reactor, fluidized bed gasifier or The original feed was fed under gravity to the top of the
bubbling fluidized bed, and most reforming processes were gasifier by a continuous feeding system composed of a screw
carried out with catalyst. Only a few studies explore
hydrogen-rich gas production from continuous biomass
steam gasification in an updraft gasifier and the product gases Table 1 – proximate analysis and ultimate analysis of
pine sawdust
and tars reforming with porous ceramic. In this work,
continuous biomass feed for updraft fixed-bed steam gasifier Proximate analysis Ultimate analysis
was investigated, a novel method of a porous ceramic (wt.%) (wt.% daf)
reformer combined with gasifier was proposed to reform Moisture content 3.93 C 44.75
gases and crack tars produced in biomass steam gasification, Fixed carbon 18.88 H 6.31
in which a porous ceramic rather than catalyst as filling Volatile 76.85 O (difference) 47.21
Ash 0.34 N 1.68
material in the secondary reformer was employed, and the
S 0.05
properties of regenerative heat and trapping for tars and soot
Higher heating value (MJ/kg, db) 18.47
carbon were utilized for tar and gas reforming.
5432 international journal of hydrogen energy 33 (2008) 5430–5438

Fig. 1 – Diagram of the fixed-bed biomass gasification system: (1) steam boiler; (2) oxygen tanker; (3) valve; (4) electric
furnaces; (5) fixed-bed gasifier; (6) screw feeder; (7) biomass hopper; (8) thermocouple; (9) secondary reformer; (10) porous
ceramic layer; (11) purification and drying device; (12) condenser; (13) tar collector; (14) PID temperature controller.

feeder and a variable speed motor. The gasifier and the a thermal conductivity detector and a double injector con-
reformer were preheated to the desired temperature using nected to three 5 m length, 3 mm diameter columns with
the external electrical furnaces by passing air flowing. When helium as carrier gas. The first column was 5A 100:120 chro-
the desired temperature was reached, the airflow was turned matographic column for giving H2, O2, N2, CO, CH4 concen-
off and switched to the desired gas (steam or oxygen) at the trations; the second column is TDX-01 yielded CO2
desired flow rate. As the reactor temperature was stabilized, concentration, the third column is GDX-102 chromatographic
the feeder was turned on at the desired rotate speed and the column as it was used for C2H4, C2H6 and some light hydro-
test begun. Generally, after the commencement of the carbons detection. The contents of total carbon (TC), total
feeding, it took about 20 min to obtain a steady state. For each organic carbon (TOC) and inorganic carbon (IC) in water-
run, three samples were taken in the stable state at an interval soluble tars were carried out using a TOC analyzer (Shimadzu
of 5 min. To verify the validity of data, all experiments were 5050 TOC-VCPH, Japan).
performed two times.
Products (gas and liquids) exiting the gasifier passed
a stainless steel cylindrical tube (500.0 mm long and 30 mm 3. Results and discussion
i.d.) for preventing the product gas temperature decrease, and
then the products were introduced into secondary reformer The effect of reaction temperature, equivalence ratio, steam to
for tar reforming. After left the reformer, the gasification biomass ratio and porous ceramic was studied. In the present
products passed through a heat exchange system. The volume study, all the temperatures of reformer were set as same as the
of dry gas produced was measured by means of a volumetric temperatures of gasifier. As a comparison, the effect of
gas-meter. reforming without porous ceramic was investigated in the
To clean the gas and separate it from the condensable same operating condition of varying steam to biomass ratio.
fraction, two stages of traps were setup. First, the gases
leaving the secondary reformer made direct contact with 3.1. Effect of reaction temperature
a countercurrent water-cooled heat exchanger, and the tar
condensed from producer gas was collected in a vial. Second, The effect of reaction temperature on biomass steam gasifi-
the producer gas pass through a tube filled with CaCl2 for the cation is investigated. Reactions were performed at four
sake of steam removal and gas purity. Gases were collected reaction temperatures from 800 to 950  C in 50  C increments.
using a gasbag only after 10 min of gasification. The operating conditions and test results are presented in
The product gas was collected periodically through a gas Table 3 and Fig. 2. It can be observed from Fig. 2 that hydrogen
syringe and analyzed off-line by gas chromatography (GC). concentration increased from 39 to 55% with the temperature.
The gas fraction composition, mainly H2, CO, CH4, CO2, C2H4, Moreover, an increasing trend of H2 was shown with the
and C2H6, was identified using a gas chromatograph with increasing reactor temperature. Carbon monoxide has
 international journal of hydrogen energy 33 (2008) 5430–5438 5433

60
Table 2 – The chemical composition and physical
properties of porous ceramic
Chemical composition Physical 50
(wt.%) properties H2

Gas composition (vol%)

CO
SiO2 26 Density (kg/m3) 2100 40 CH4
Al2O3 60 Specific heat (kJ/(kg K)) 850–1050 CO2
MgO 11 Softening temperature 1600 30 C2H4
( C) C2H6
Fe2O3 1 Heat conduction 1.4–2
coefficient (20–1000  C, 20
W/(mK))
Na2O þ K2O þ CaO 1.1–1.5 Thickness of Wall (mm) 0.45
10
TiO2 þ BaO 0.8 Porosity (%) 80
Surface Area (m2/m3) 805
0
800 850 900 950
a smaller decrease from 27 to 20% between 800 and 950  C. Temperature (°C )
Methane and carbon dioxide decreased from 10 to 6% and
Fig. 2 – Effect of reaction temperature on gas composition.
from 21 to 17%, respectively. As the steam gasification incor-
porated a series of complex reactions, which is presented as
follows, the results of gas composition varied with the oper-
ating conditions. the conversion of char to gas through the selection of a suit-
able reaction temperature.
Boudouard reaction : C þ CO2 4 2CO þ 172 kJ=mol; (1)
Fig. 3 shows the molar ratios of H2/CO and CO/CO2 in the
production gas. The molar ratio of H2/CO increases with an
increase reaction temperature, while the CO/CO2 molar ratio
Water gas ðprimaryÞ reaction : C þ H2 O 4 CO þ H2
decreases slightly. The molar ratio of H2/CO between the
þ 131:5 kJ=mol; (2)
values of 1 and 2 (1 < H2/CO < 2) should be useful for the
chemical industry to synthesise products such as methanol
and virgin naphtha [17]. In this study, the molar ratio of H2/CO
Methanation reaction : C þ 2H2 4 CH4  74:8 kJ=mol; (3)
is between 1.5 and 2.7 (1.5 < H2/CO < 2.7). The H2 may be
formed in three paths: the first one is derived from the fast
Steam reforming reaction : CH4 þ H2 O 4 CO þ 3H2 pyrolysis at the commencement of biomass introduced into
reactor, the second is produced through the endothermal char
þ 206 kJ=mol; (4)
reactions [8], the third one is produced through the further
cracking reaction of heavier hydrocarbons and tars trapped by
Water gas shift reaction : CO þ H2 O 4 CO2 þ H2  41 kJ=mol: the porous ceramic. The higher molar ratio of CO/CO2 strongly
influences the calorific content of the producer gas. With
(5)
reaction temperature increase, the molar ratio varies between
Higher temperature favors the products in reactions (1), (2) 0.9 and 1.3 (0.9 < CO/CO2 < 1.3), and the LHV of production gas
and (4) (endothermic reactions), and the reactants in reactions shows a decreasing trend (as showed in Table 3).
(3) and (5) (exothermic ones). Therefore, endothermic reac-
tions were strengthened with a higher reaction temperature,
3
and caused an increment of H2. To enhance H2 yield, a balance H2/CO
H2/CO and CO/CO2 ratio (mol/mol)

should be established between the maximum H2 yields and CO/CO2

2.5

2
Table 3 – Experimental results of different reaction
temperature
Reactor and reformer temperature 800 850 900 950
1.5
Wet feed rate (kg/h) 0.48 0.48 0.48 0.48
Dry feed rate (kg/h) 0.44 0.44 0.44 0.44 1
Steam rate (kg/h) 0.67 0.67 0.67 0.67
Steam to biomass ratio 1.4 1.4 1.4 1.4
0.5
Gas density (kg/Nm3) 0.68 0.63 0.61 0.53
Gas yield (m3/kg daf biomass) 2.14 2.51 2.47 2.74
Low heating value (MJ/Nm3) 12.25 10.10 11.51 10.02 0
800 850 900 950
Residence time (s) at reactor 7.11 4.67 4.15 3.25
temperature Reaction temperature (°C)
Hydrogen yield (g H2/kg biomass, 74.84 99.55 102.77 135.40
Fig. 3 – Effect of reaction temperature on H2/CO and CO/CO2
dry basis)
molar ratio.
5434 international journal of hydrogen energy 33 (2008) 5430–5438

3.2. Effect of equivalence ratio 50

H2
The equivalence ratio (ER) is a crucial parameter in the
40 CO
biomass steam gasification when the oxygen or air was CH4

Gas composition (vol%)

employed in the processes. The equivalence ratio is defined as CO2
the amount of air added relative to the amount of air required C2H4
30
for stoichiometric combustion. Since the presence of nitrogen C2H6
dilutes the produce gas and decrease the gas quantity, oxygen
was employed as gasification agents. Based on the ultimate 20
analysis of pine sawdust, the stoichiometric pure oxygen
demand was calculated as 3.21 Nm3 oxygen/kg dry pine
sawdust. 10
Table 4 and Fig. 4 show the operating condition and test
results with varying ER. The equivalence ratio was increased
0
from 0 to 0.30 at a constant feed rate. As shown in Fig. 4, 0.00 0.05 0.10 0.15 0.20 0.25 0.30
hydrogen concentration decreased from 44.45 to 23.56% with ER
the varying ER. On the contrary, the concentration of carbon
Fig. 4 – Effect of equivalence ratio on gas composition.
dioxide increased sharply from 23.70 to 48.74% with the
increasing ER. Carbon monoxide first increased and then
decreased. The increased ER influences the gas composition
from two sides. One is higher ER supplies more oxygen, as
a result, the temperature of reaction zone increased and the
2H2 þ O2 4 2H2 O þ 484 kJ=mol: (8)
reaction of gasification is strengthened. The other is higher ER
bring on the low heating value of producer gas decline due to As more oxygen was fed, less H2 and other combustible
more H2 and CO is consumed. gases through oxidization reaction. Although these
Fig. 5 shows the change of H2/CO and CO/CO2 molar ratios exothermic oxidation reactions lead to release more heat to
in the product gas with the equivalence ratio. It is indicated the gasification process, and optimize quality of product gases
that the yield of H2 became more less. The molar ratio of H2/ to some extent [17], as more CO2 and less combustible gases
CO decreases from 2.1 to 1.2, while the ratio of CO/CO2 production which result in the LHV decrease. So, a suitable
changes between 1.1 and 0.4. It can be inferred that, when ratio would be existed in the gasification process. An optimum
oxygen was not introduced into reactor and only steam as the value of ER was found to be 0.05 in this study. Gas yield
gasification media (ER ¼ 0), the reactions (2) and (5) would be declined from 2.51 to 1.89 m3/kg daf biomass with increasing
the primary reactions in the gasification process, however, as ER. Hydrogen yield also declined from 99.55 to 45.05 g H2/kg
ER increased, more oxygen was supplied to the system, reac- biomass with ER.
tions (6)–(8) participate in the gasification process. In Table 4,
the LHV first increased and then decreased with the increased 3.3. Effect of steam/biomass ratio
ER from 0 to 0.3.
C þ O2 4 2CO þ 246:4 kJ=mol; (6) The steam/biomass ratio (S/B) has been studied at 1.05, 2.05,
2.53 and 3.47 at the temperature 850  C. The varying steam/

C þ O2 4 CO2 þ 408:8 kJ=mol; (7)

2.5
H2/CO
CO/CO2
H2/CO and CO/CO2 ratio (mol/mol)

Table 4 – Experimental results of different equivalence

ratio 1.5
Equivalence ratio 0 0.05 0.1 0.3
Reactor temperature ( C) 850 850 850 850
Wet feed rate (kg/h) 0.48 0.48 0.48 0.48 1
Dry feed rate (kg/h) 0.44 0.44 0.44 0.44
Steam rate (kg/h) 0.67 0.67 0.67 0.67
Steam to biomass ratio 1.4 1.4 1.4 1.4 0.5

Gas density (kg/Nm3) 0.63 0.68 0.75 0.83

Gas yield (m3/kg daf biomass) 2.51 2.24 2.07 1.89
Low heating value (MJ/Nm3) 10.10 12.67 11.44 8.10 0
0 0.05 0.1 0.3
Residence time (s) at reactor 4.67 6.93 5.05 3.62
temperature ER
Hydrogen yield (g H2/kg biomass, 99.55 79.07 64.02 45.05
Fig. 5 – Effect of equivalence ratio on H2/CO and CO/CO2
dry basis)
molar ratio.
 international journal of hydrogen energy 33 (2008) 5430–5438 5435

4
Table 5 – Experimental results of different steam/biomass
ratio
3.5

H2/CO and CO/CO2 ratio (mol/mol)

Steam to biomass ratio 1.05 2.05 2.53 3.47
Reactor temperature ( C) 850 850 850 850 3
Wet feed rate (kg/h) 0.48 0.48 0.48 0.48
Dry feed rate (kg/h) 0.44 0.44 0.44 0.44 2.5
Steam rate (kg/h) 0.50 0.98 1.21 1.66 H2/CO
3 2 CO/CO2
Gas density (kg/Nm ) 0.59 0.56 0.54 0.47
Gas yield (m3/kg daf biomass) 1.83 1.99 1.77 1.77
1.5
Low heating value (MJ/Nm3) 11.36 11.33 12.22 11.94
Residence time (s) at reactor 7.72 5.12 4.64 3.67
1
temperature
Hydrogen yield (g H2/kg biomass, 77.99 89.80 83.34 95.89
0.5
dry basis)

0
1.05 2.05 2.53 3.47
biomass ratio was controlled by keeping the biomass feed rate S/B
while changing steam rate. Oxygen was not introduced in
Fig. 7 – Effect of steam to biomass ratio on H2/CO and CO/
gasifier. The operating conditions and test results are shown
CO2 molar ratio.
in Table 5 and Fig. 6.
It can be seen that the gas composition displayed
increasing trend with the S/B increasing from 47.61 to 60.59%,
carbon monoxide levels has a slight change in the range of S/B Fig. 7 shows the molar ratio of H2/CO and CO/CO2 in
from 1.05 to 3.47, while carbon dioxide decreased from 26.71 to product gas. As the steam increases, H2 and CO generation
14.47%. As water gas (primary) reaction (2) and water gas shift increases and CO2 decreases. The molar ratio of H2/CO
reaction (5) take a key role in the steam gasification process, increases with the steam/biomass ratio increase. The H2/CO
hydrogen production was raised. Although some researchers and CO/CO2 molar ratio changes slightly between 2.91 and
[9,18] reported different phenomena with our results, that is, 3.47 and between 0.61 and 1.20, respectively. It can be inferred
with the increase of the S/B, H2 and CO2 contents increased that the water–gas shift reaction favors H2 production, and
while CO concentration dropped, different biomass species, porous ceramic may be promote water–gas reaction and tar
the type and structure of reactor and reformer, operating and heavier hydrocarbon cracking when the products pass
conditions and gasification agents lead to different results. In though the pore embedded in ceramic.
our study, the porous ceramic reformer for tars in the product Although, on the basis of experiments, higher S/B produce
gas reforming may take a distinct effect in the gasification larger amount of hydrogen yield, as a byproduct, higher water
process. The difference of gasifier with and without porous content was produced in the gasification processes. As we
ceramic reformer was studied in the next section in detail. The know, the separation steam from producer gas easily by
concentration of methane and other hydrocarbons (C2H4, condensation and dryness, however, more energy was
C2H6) holds a relative smooth varying with S/B. The gas yield consumed to produce excess steam as well as consumed in the
exhibited a trend of first increase and then decrease. As the process of condensation [19]. So, it may be necessary to select an
increasing S/B, more steam was introduced into reactor, optimal steam/biomass ratio according to different operating
which led to the decrease of gas residence time (s) in reactor. condition. In this study, the optimal value of S/B was found to be
2.05 under the operating condition shown in Table 5.

60
3.4. Effect of porous ceramic reforming

50
H2 Tar production in biomass gasification is a very important
Gas composition (vol%)

CO problem for the reason of blocking pipeline of gasifier and

40 CH4 polluting environment. As the filling material, porous ceramic
CO2
was filled in the secondary reformer for tar cracking. When
C2H4
30 C2H6 producer gas passed through porous ceramic layer, tar pres-
ence in producer gas was introduced simultaneously into the
reformer, and was decomposed into small molecule such as
20
H2, CO, CO2, etc. In this process, due to plenty of through pores
embedded in the porous ceramic, steam reforming reaction (4)
10
and water gas shift reaction (5) could be improved for the
products sufficient contact.
0 Table 6 shows the content of TC (total carbon), TOC (total
1.0 1.5 2.0 2.5 3.0 3.5
organic carbon) and IC (inorganic carbon) in the water-soluble
S/B
tars in the process of reforming with or without porous
Fig. 6 – Effect of steam to biomass ratio on gas composition. ceramic. Since the tar in organic phase is too little to be
5436 international journal of hydrogen energy 33 (2008) 5430–5438

Table 6 – The comparison of TOC in tars produced from 60

two types of reforming
Steam/biomass 1.05 2.05 2.53 3.47 50

Gas comopsition (vol%)

ratio
Without porous TC (mg/l) 899.13 806.50 789.39 755.50
40
ceramic TOC (mg/l) 766.88 699.38 694.37 692.25
reforming IC (mg/l) 132.25 107.19 95.01 63.21
30
With porous TC (mg/l) 511.96 558.13 599.00 399.13
ceramic TOC (mg/l) 440.13 489.38 537.38 344.50
reforming IC (mg/l) 58.71 68.66 61.59 54.67 20

TOC conversion (%) 33.24 20.20 13.74 42.34

10

0
measured, only the dissolved tars in the water phase were 1.0 1.5 2.0 2.5 3.0 3.5
detected when using porous ceramic reforming. The content S/B
of TOC in tars varies in the range of 693.25–766.88 mg/l without porous ceramic reforming porous ceramic reforming
without ceramic reforming, while change between 344.50 and H2 CO CH4 H2 CO CH4
537.38 mg/l with ceramic reformer. The conversion of TOC is CO2 C2H4 C2H6 CO2 C2H4 C2H6

roughly between 22.61 and 50.23% in the two types of

Fig. 9 – Effect of porous ceramic filter on gas composition.
reforming process. Fig. 8 shows the appearance comparison of
two types of tars produced from porous ceramic reforming
and without porous ceramic reforming. It can be seen that, for
In addition, the presence of inorganic compositions of
porous ceramic reforming, it is hardly found the heavy tars in
porous ceramic, for example MgO [20], Fe2O3 [21], Na2O [22],
the organic phase, and the main composition is the water-
K2O [23], CaO [24], TiO2 [25] and BaO [26], etc. may take some
soluble tars, while the mixing of organic phase tars and the
catalyst or support roles in the tars and heavy substances
dissolved tars in the water phase was observed for without
cracking, the water gas shift reaction (4) and steam reforming
porous ceramic reforming. This may be explained as follows:
reaction (5), which may enhance H2 production. The steam
the porous ceramic in the reformer promoted reaction (9)
introduced into the gasifier may have some improved func-
when the steam and gasification gas entered the pores
tion in the process of char conversion gas. Due to the larger
embedded in porous ceramic. And then, the heavy oil vapours,
contact area and the good regenerative heat of porous
C1–C5 hydrocarbons, naphthalin, gas oils and aromatic
ceramic, the reforming reaction may be promoted. Therefore,
compounds were decomposed to yield a mixture of small
the production of H2 with porous ceramic reforming is higher
mole gases (H2, CO, CO2, etc.).
than the reforming without porous ceramic. The further
Steam porous ceramic reforming of tars / H2 þ CO þ CO2 detailed catalyst supported with porous ceramic for biogas
þ hydrocarbon þ .; DH > 0 and tar reforming will be investigated in future.
Fig. 9 presents the comparison of gas composition in the
two modes, that is, with and without porous ceramic
reforming. The gas concentration of hydrogen for porous
ceramic reforming is higher than the one which is filled
nothing in the reformer. The maximum H2 concentration was
found at the higher value 60.59% for porous ceramic reforming
than the value 43.37% for without porous ceramic reforming

Table 7 – Experimental results of different steam/biomass

ratio without porous ceramic reforming
Steam to biomass ratio 1.05 2.05 2.53 3.47
Reactor temperature ( C) 850 850 850 850
Wet feed rate (kg/h) 0.48 0.48 0.48 0.48
Dry feed rate (kg/h) 0.44 0.44 0.44 0.44
Steam rate (kg/h) 0.5 0.98 1.21 1.66

Gas density (kg/Nm3) 0.69 0.72 0.73 0.73

Gas yield (m3/kg daf biomass) 2.12 2.27 2.33 2.06
Low heating value (MJ/Nm3) 13.40 12.89 12.87 12.67
Residence time (s) at reactor 7.25 4.87 4.07 3.53
Fig. 8 – The appearance comparison of tars produced from temperature
Hydrogen yield (g H2/kg biomass, 82.35 84.93 86.08 75.41
two types of reforming: (a) without porous ceramic
dry basis)
reforming; (b) porous ceramic reforming.
 international journal of hydrogen energy 33 (2008) 5430–5438 5437

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