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Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China
b
Department of Chemical and Biochemical Engineering, The University of Western Ontario,
London, Ont., Canada N6A 5B9
Received 29 May 2006; accepted 10 November 2006
Available online 12 January 2007
Abstract
Biomass gasication is an important method to obtain renewable hydrogen. However, this
technology still stagnates in a laboratory scale because of its high-energy consumption. In order to
get maximum hydrogen yield and decrease energy consumption, this study applies a self-heated
downdraft gasier as the reactor and uses char as the catalyst to study the characteristics of hydrogen
production from biomass gasication. Air and oxygen/steam are utilized as the gasifying agents. The
experimental results indicate that compared to biomass air gasication, biomass oxygen/steam
gasication improves hydrogen yield depending on the volume of downdraft gasier, and also nearly
doubles the heating value of fuel gas. The maximum lower heating value of fuel gas reaches 11.11 MJ/
N m3 for biomass oxygen/steam gasication. Over the ranges of operating conditions examined, the
maximum hydrogen yield reaches 45.16 g H2/kg biomass. For biomass oxygen/steam gasication,
the content of H2 and CO reaches 63.2772.56%, while the content of H2 and CO gets to
52.1963.31% for biomass air gasication. The ratio of H2/CO for biomass oxygen/steam
gasication reaches 0.700.90, which is lower than that of biomass air gasication, 1.061.27. The
experimental and comparison results prove that biomass oxygen/steam gasication in a downdraft
gasier is an effective, relatively low energy consumption technology for hydrogen-rich gas
production.
r 2006 Elsevier Ltd. All rights reserved.
Keywords: Biomass; Oxygen/steam gasication; Hydrogen; Air; Downdraft gasier
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1. Introduction
With the fast economic growth, energy demand in China has increased two-fold in the
past three decades. Various energy resources have been exploited and utilized and biomass is
one of the energy resources that is abundant and has been widely used in China for a long
time [1]. As No.256 Academic Forum of Xiangshan Conference in China pointed out
biomass energy will be a crucial constitution of renewable energy system in the future and
hydrogen production from biomass on a large scale may contribute to a renewable
development of energy and environment [2]. However, due to high-energy consumption in
all the technologies of hydrogen production from biomass, such as biomass fast pyrolysis,
pyrolysis-steam reforming and biomass gasication in super-critical water, progress is
impeded and this technology remaining restricted to a laboratory scale. Therefore, in order
to reduce energy consumption of biomass-derived hydrogen, this study introduces a selfheated downdraft gasier as the reactor to investigate hydrogen-rich gas production from
biomass. Meanwhile, aiming at elevating hydrogen content of gaseous product, steam is
added to the gasifying agent, which is produced by the gasier itself through a novel design.
Meanwhile in order to provide a more suitable gas for puried hydrogen production, oxygen
(95% pure), instead of air, is utilized as the gasifying agent. For comparison, some tests of
air gasication are conducted to verify the benets of oxygen/steam gasication.
As a thermochemical conversion technology, biomass gasication has been studied
extensively and has developed matured. Different gasiers are employed in this process,
including, xed bed [3], moveable bed [4] and uidized bed [5]. The study of biomass
gasication in the above-mentioned gasiers has been conducted extensively by researchers
around the world. The selection of gasier is determined by their different features.
A downdraft gasier is characterized in achieving a higher H2 content of gaseous product;
therefore this investigation chooses it as the gasier.
Quite many researchers investigated hydrogen production from biomass gasication in a
uidized bed [612] and only a few studies explore hydrogen-rich gas production from
biomass air or oxygen/steam gasication in a downdraft gasier [10].
Based on summarizing our previous research on hydrogen-rich gas production from biomass
gasication in a uidized bed [1113], this study mainly explored the potential of hydrogen
production from biomass oxygen/steam gasication in a self-heated downdraft gasier.
2. Experimental section
2.1. Feed materials
The feed material, pine wood blocks, comes from a sawmill in Guangzhou, China. The
blocks are cut into an average size 3 cm 3 cm 3 cm by hand. Its absolute density is
556 kg/m3, while its apparent density is 222 kg/m3. Its ultimate and proximate analysis is
presented in Table 1.
2.2. Apparatus
The gasication system consists of air intake equipment, a downdraft gasier, gas
cleaning part, roots blower, ow meters and off-gas burner,Its schematic diagram is shown
in Fig. 1.
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Table 1
Proximate and ultimate analysis of pine wood blocks
Moisture content (wt% wet basis)
Higher heating value (kJ/kg)
Proximate analysis (wt% dry basis)
Volatile matter
Fixed carbon
Ash
Ultimate analysis (wt% dry basis)
C
H
O
N
S
8
20,540
82.29
17.16
0.55
50.54
7.08
41.11
0.15
0.57
sprinkler
to exhaust burner
thermocouple hole
gas rotameter
Air
Air
water
steam
spray
tower
gas sampling
catalyst inlet
roots blower
ash chamber
gas sampling
Total height of the gasier is 1.3 m and inner diameter is 35 cm. There are ve
thermocouples distributed uniformly along the height of the gasier, while two
manometers are installed on the top and grate, respectively. Near the neck, an air
preheating room is arranged to preheat the gasifying agent. Below the air-preheating
room, a steam generation room is scheduled to produce the steam through a novel design
as Fig. 1 shows. Through the steam generating room, a steam with atmospheric pressure
and 100120 1C is produced. Above the grate, a catalyst room is designed to ll the
catalysts. In the present study, charcoal is applied as tar cracking catalyst.
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Gas cleaning apparatus is composed of triple-stage spray shower and steel wire rings are
lled full in it. The steel wire rings slower gas velocity, and also increases contact area
between gas and water, which is helpful for gas cleaning. At the exit of spray shower, gas
temperature is decreased to about 30 1C and 8090 wt% of tar is diminished.
2.3. Experimental procedure
First open the sealing cover of the gasier and put about 5 kg of charcoal on the grate,
carefully making them distributed uniformly. Then pine wood blocks are placed on
charcoal. A specied quantity of hot water is added into steam generating room for steamgeneration. Afterwards feedstock in the gasier is ignited and induced fan is turned on to
preheat the gasier. Then relling is done with xed weight of wood blocks at a specied
intervals. The whole temperature of the gasier is raised step-by-step and steam is ready
after about 23 h. When temperature at the neck and outer wall of furnace reaches 900 1C
and over 70 1C, respectively, a specied weight of wood blocks is put into the gasier and
gasifying agents are driven into the gasier. Since that, the tests start up and at the interval
of test, the temperature of 5 points is recorded once every 2 min. The gas yield is measured
by a ow meter simultaneously. Usually, the tests arrive at a steady state after 15 min of
startup and then gas sampling is carried out at an interval of 10 min. To assure the
reliability of the experimental results, every operating condition is repeated two times and
the experimental results presented here are average values of there two times.
Kechuang GC-9800T thermal conductivity detector (TCD) and hydrogen ame
ionization detector (FID) are employed to analyze gas composition.
3. Results and discussion
3.1. Temperature distribution in the gasifier
Temperature distribution along the height of the gasier is shown in Fig. 2, on which
Nos. 15 mean the locations denoted in Fig. 1. As Fig. 2 shows, temperature in the gasier
increases along the height from the top. From Fig. 2 it can be found that it needs a longer
time for the drying zone and pyrolysis zone to reach a high-temperature level than the
combustion and reduction zones. This phenomenon can be attributed to two reasons.
First, there are no solids but gases in these two zones, and it is difcult to warm gases.
Second, the gasier has thermal inertia and hence temperature will not be raised to a high
level until the thermal inertia is overcome. On the other hand, the thermal inertia helps the
gasier keep a steady temperature level after the whole temperature goes up. At a steady
state temperature of drying zone is about 300 1C, while temperature of the pyrolysis zone
remains about 600 1C. The steady temperatures of the pyrolysis zone, combustion zone and
reduction zone are 600, 700900 and 800 1C, respectively.
On the temperature curve of the combustion zone, there appears a uctuation, which is
an occasional phenomenon and possibly caused by O2 deagrating because of local
accumulation. This reveals that when the downdraft gasier operates in O2/steam mode,
the ow of O2 should be changed step by step to avoid a sudden O2 accumulation and
assure operation safety at the startup stage of each run. Besides, a multiple-entry air intake
system is necessary to make O2 enter into the gasier uniformly and avoid local
accumulation.
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temperature/C
2177
1.drying zone
2.pyrolysis zone
3.oxidization zone
4.reduction zone
5.catalyst zone
950
900
850
800
750
700
650
600
550
500
450
400
350
300
250
200
150
100
0
10
20
30
40
50
time/min
Because gases and solids move forward in the same direction in the downdraft gasier,
different reactions occur in the different zones. In the drying zone, temperature is about
150300 1C. Therefore, water vaporization mainly occurs in this zone. In the pyrolysis
zone, temperature is about 600 1C, and pyrolysis of biomass happens and produces char,
tar and gas as reaction (1) shows. In the combustion zone, because of the presence of
oxygen, oxidization reactions of biomass pyrolysis products proceed here to provide the
required heat for the whole gasication as reactions (2)(3) present. In all the reactions
presented here, the value of reaction heat refers to temperature 298.15 K:
biomass ! char tar gasesCO2 ; CO; H2 O; H2 ; CH4 ; Cn Hm ;
(1)
(2)
(3)
In the reduction and catalyst zones, secondary reactions of biomass pyrolysis and
oxidization products proceed, e.g. cracking, reforming and tar decomposition as listed in
reactions (4)(10). Nearly all these reactions are endothermic, therefore the temperature of
reduction drops from 800 to about 600 1C in this zone:
tar ! gasesCO2 ; CO; H2 O; H2 ; CH4 ; Cn Hm ;
(4)
CO H2 O CO2 H2 41 kJ=mol;
(5)
(6)
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(7)
C H2 O CO H2 131 kJ=mol;
(8)
(9)
(10)
Table 2
Hydrogen-rich gas yield from biomass oxygen/steam gasication in a downdraft gasier
No.
798
1.50
6.68
4.14
0.22
0.62
886
1.70
6.55
4.50
0.25
0.69
850
1.80
7.22
4.40
0.24
0.61
774
1.00
3.80
1.20
0.26
0.32
934
2.00
7.92
3.20
0.25
0.40
26.42
0.97
36.85
3.52
31.96
0.22
0.05
1.50
35.53
3.06
9.04
30.51
0.65
39.21
3.29
25.75
0.28
0.31
1.62
44.13
2.77
9.88
28.58
1.01
38.66
6.01
24.45
1.01
0.28
1.47
37.51
7.86
11.11
29.91
0.94
42.65
3.58
22.29
0.43
0.21
1.24
33.11
3.14
10.37
27.17
1.16
37.65
4.78
28.89
0.29
0.06
1.32
32.02
5.27
9.75
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Table 3
Hydrogen-rich gas yield from biomass air gasication in a downdraft gasier
No.
930
9.11
7.89
0.25
1108
13.27
11.36
0.25
1093
14.32
11.20
0.28
1015
13.55
10.76
0.27
870
7.98
7.20
0.24
31.40
0.89
29.56
6.23
30.02
1.60
0.30
0.91
25.51
9.85
5.44
28.49
1.61
24.59
6.58
36.41
2.03
0.29
0.88
22.39
11.46
5.05
28.93
1.48
25.53
6.82
34.88
2.07
0.28
0.82
21.18
12.70
4.76
29.16
1.05
25.20
8.21
34.36
1.63
0.39
0.85
22.13
14.23
5.05
35.39
0.91
27.92
4.36
30.11
1.17
0.14
0.94
29.70
7.40
5.17
yield is reached, respectively, when applying oxygen/steam gasication. This implies that
for the given gasier, more hydrogen can be produced applying biomass oxygen/steam
gasication, i.e. the hydrogen ow rate by volume of the gasier can be raised.
This conclusion gets conrmed by Adnan et al.s [10] experimental results. They got an
average hydrogen yield 24 g/kg biomass for biomass air gasication in a downdraft
gasier. Comparing Tables 2 and 3, we can also see that heating value of the gaseous
product is nearly doubled by applying oxygen/steam gasication other than air
gasication.
It is valuable to have a preliminary comparison between the experimental results listed in
Table 2 with other investigations performed in a uidized bed with comparable operating
conditions. In Turn et al. study [7], which uses temperature 800 1C, steam to biomass ratio
1.4 and oxygen/steam gasication, the value of hydrogen yield reaches about 38 g/kg
biomass. This result is lower than run no. 2 listed in Table 2. Besides, in Turn et al.
research [7], the uidized bed is electrically heated. Also in our previous study in a
electrically heated uidized bed [11], with the temperature 800 1C, steam to biomass ratio
1.56, for different equivalence ratios, the average hydrogen yield gets to 49.45 g/kg
biomass, a little higher than that of run no. 2 listed in Table 2. The above comparison
results prove that, for hydrogen production, biomass oxygen/steam gasication in a
downdraft gasier has an advantage over other technical processes in saving energy and
thus correspondingly lowering operational cost.
3.3. Effect of feeding rate on hydrogen yield and hydrogen flow rate
For a specied gasier, accelerating feeding rate is benecial for increasing production
capacity. However, excessively high feeding rate will result in a higher gas yield and a
shorter gas residence, thus degrading gas quality. Therefore, a study is carried out to
investigate its effect on hydrogen yield and hydrogen ow rate. At the condition of air
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gasication, keeping ER at a constant value of 0.27, biomass feeding rate is changed from
7.20 to 11.36 kg/h to conduct the tests. The experimental results are listed in Table 4 and
Fig. 3.
Table 4 indicates that hydrogen content decreases from 31.88% to 27.12% with feeding
rate. This proves that excessively high feeding rate is unbenecial for biomass gasication
cracking and reforming reactions, which leads to a reduction of hydrogen content in gases.
From Table 4 and Fig. 3, it can be found that the temperature increases with feeding rate,
whereas hydrogen yield shows an opposite trend. For hydrogen ow rate, it rsts increases
and then reaches a maximum value of 0.25 kg/h. This is a result caused by co-action of two
factors, increase of feeding rate and decrease of hydrogen content.
Table 4
Effect of feeding rate on hydrogen-rich gas from biomass air gasication in a downdraft gasier
1
9.24
11.52
0.27
910
9.78
12.20
0.27
1025
10.33
12.90
0.27
1035
10.76
13.55
0.27
1015
11.47
14.55
0.27
1090
31.88
1.14
28.77
5.45
31.76
0.94
0.06
0.91
7.04
4.78
31.47
1.10
27.52
5.70
33.39
0.75
0.07
0.88
7.84
4.60
31.17
1.71
25.81
6.01
33.32
1.68
0.30
0.86
8.96
4.82
29.16
1.05
25.20
8.21
34.36
1.63
0.39
0.85
13.13
5.05
27.12
1.07
25.07
9.02
35.62
1.67
0.42
0.78
16.52
5.26
40
0.30
35
0.25
30
25
0.20
20
0.15
No.
15
10
0.10
9.0
9.5
10.0
10.5
11.0
11.5
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ER
Feeding rate (kg/h, wet basis)
O2 (N m3/h) (95%)
Steam (kg/h)
Temperature at the neck (1C)
Steam/biomass (wet basis)
Gas composition (vol%, dry, inert free)
H2
O2
CO
CH4
CO2
C2H4
C2H6
Gas yield (N m3/kg, wet basis)
Tar yield (g/kg biomass, wet basis)
Lower heating value (MJ/N m3)
0.30
4.90
1.50
3.04
905
0.62
0.27
5.40
1.50
3.35
897
0.62
0.25
5.82
1.50
3.61
830
0.62
0.24
6.14
1.50
3.81
810
0.62
0.22
6.68
1.50
4.14
798
0.62
29.20
0.65
35.73
3.02
30.86
0.48
0.06
1.52
2.47
9.15
31.29
0.99
36.25
3.16
27.68
0.51
0.12
1.54
2.62
9.55
31.61
0.75
35.00
4.09
27.74
0.59
0.22
1.60
3.92
9.92
28.74
0.94
38.22
2.32
29.33
0.38
0.07
1.56
1.83
9.10
26.42
0.97
36.85
3.52
31.96
0.22
0.05
1.50
3.06
9.04
50
0.5
45
0.4
40
35
0.3
30
0.2
25
20
0.1
0.22
0.24
0.26
0.28
0.30
No.
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As Table 5 indicates, temperature of oxidization zone slightly rises with ER, from 798 to
905 1C. This reveals that there exists a self-balance mechanism of temperature in the
downdraft gasier. On one hand, a higher value of ER promotes the oxidization reactions,
which reads to more heat release and temperature of the gasier rise. On the other hand,
temperature rise accelerates the rate of reduction reactions, which consume more energy.
Besides, strong oxidization reactions produce more CO2 and steam, which needs more heat
to be reduced in the reduction zone. Therefore, the temperature of the gasier is not very
sensitive to the value of ER at the condition of biomass oxygen/steam gasication. This
analysis is conrmed by other researchers investigation [13].
As stated above, with the variation of ER, temperature level in the gasier is controlled
by the interacting of exothermic and endothermic reactions. Accordingly when the value of
ER is too small, temperature in the gasier is low, which is unfavorable for further
reactions of biomass gasication gas and on hydrogen yield drops. When the value of ER
is too large, oxidization reactions advance strongly, which produces more CO2, but less H2.
Consequently, as Fig. 4 illustrates, with variation of ER, both hydrogen yield and
hydrogen ow rate, have a maximum achievable value 45.16 g/kg biomass (wet basis) and
0.26 kg/h, respectively, when ER is 0.25.
3.5. A comparison of gas composition between biomass air gasification and oxygen/steam
gasification
H2 and CO are two most important gas species in the gaseous products, whose content
and ratio are two indicators to determine gas quality. For experimental results listed in
Tables 2 and 4 and 3 and 5, a coarse comparison of the content of H2+CO and H2/CO
ratio between biomass air gasication and oxygen/steam gasication is conducted. Figs. 5
and 6 show the comparison results.
From Fig. 5, we can nd that at similar values of biomass feeding rates, the content of
H2+CO for oxygen/steam gasication is higher than that of air gasication. This result is
caused by two reasons. First, because of near absence of N2 at the condition of oxygen/
80
78
76
74
72
70
68
66
64
62
60
58
56
54
52
50
48
46
oxygen/steam gasification
air gasification
10
11
12
Fig. 5. A comparison of content of H2+CO between biomass air gasication and oxygen/steam gasication.
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2.0
oxygen/steam gasification
air gasification
1.8
Ratio of H2/CO
1.6
1.4
1.2
1.0
0.8
0.6
0.4
3
10
11
12
Fig. 6. A comparison of H2/CO ratio between biomass air gasication and oxygen/steam gasication.
steam gasication, the gas ow is reduced, which results in a longer residence time and
correspondingly the cracking and reforming reactions of biomass gasication gas advance
to a higher extent to yield more H2 and CO. Secondly, the presence of steam makes a
deeper reforming reactions of biomass gasication gases, thus more H2 and CO is
generated. For a general situation, at the condition of biomass oxygen/steam gasication,
the content of H2+CO is 63.2772.56%, while for air gasication, that value is
52.1963.31%.
From Fig. 6, we can also discover an important phenomenon. That is the ratio of
H2/CO for air gasication is higher than that of oxygen/steam gasication. For former,
that value is 1.061.27, while for the latter, that value is 0.700.90. This can be explained
by that the gassolid reactions (8)(10) are more likely to happen than gasgas reactions
(5)(7) in the downdraft gasier for biomass gasication. In addition, there is a longer gas
residence time for biomass oxygen/steam gasication when operated at similar conditions
with biomass air gasication. Therefore, reaction (10) is strengthened at the condition of
biomass oxygen/steam gasication and this makes CO yield large [14]. Accordingly the
ratio of H2/CO drops less for biomass oxygen/steam gasication compared to that for air
gasication.
4. Conclusions
In the process of biomass gasication in a downdraft gasier, compared to air
gasication, hydrogen yield by volume is improved through application of oxygen/steam
gasication. Further, gas heating value is nearly doubled. The maximum lower heating
value of fuel gas reaches 11.11 MJ/N m3 for biomass oxygen/steam gasication. At the
present operating conditions, the maximum hydrogen yield reaches 45.16 g H2/kg biomass
(wet basis).
The affecting behavior of feeding rate on experimental results indicates that hydrogen
ow rate cannot be raised by simply increasing the feeding rate in a specied downdraft
gasier.
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[12] Lv PM, Chang J, Wang TJ, Fu Y, Chen Y, Zhu JX. Hydrogen-rich gas production from biomass catalytic
gasication. Energy Fuels 2004;18:22833.
[13] Wu CZ, Ma LL. Modern utilization technologies of biomass energy. Beijing: Chemical Industrial Publisher;
2003. p. 9192.
[14] Franco C, Pinto F, Gulyurtlu I, Cabrita I. The study of reactions inuencing the biomass steam gasication
gasication process. Fuel 2003;82:83542.