Available at www.sciencedirect.com
Department of Chemical Engineering, Feng Chia University, 100 Wenhwa Rd., Seatwen, Taichung 407, Taiwan
Green Energy Development Center, Feng Chia University, 100 Wenhwa Rd., Seatwen, Taichung 407, Taiwan
article info
abstract
Article history:
The objective of this study is to investigate the biomass gasification to produce the bio-
hydrogen and syngas in a fluidized bed. a-cellulose and other agriculture waste were
gasified at the temperature of 600e1000 C with respect to different equivalent and steam
13 May 2011
to biomass ratios were studied. The yield of the bio-hydrogen, syngas, and the other
products were analyzed to maximize the yield of bio-hydrogen or the syngas. A kinetic
model to determine the order of the reaction and activation energy is also proposed.
Current results suggested that at the equivalent ratio of 0.2 and 1000 C without steam
Keywords:
achieved the maximum yield of the bio-hydrogen (29.5%) and CO (23.6%). CO2 concentra-
Biomass gasification
tion at this condition is 10.9% only. The yield of the H2 and CO, which is called syngas in the
Hydrogen
industrial, can be further used for the liquid fuel production or gas cleanup to produce
Syngas
hydrogen.
Agriculture waste
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Fluidized bed
1.
Introduction
reserved.
* Corresponding author. Department of Chemical Engineering, Feng Chia University, 100 Wenhwa Rd., Seatwen, Taichung 407, Taiwan.
Tel.: 886 4 2451 7250x3676/3664, fax: 886 4 2451 0890.
E-mail address: acchang@fcu.edu.tw (A.C.C. Chang).
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.05.105
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 4 2 5 2 e1 4 2 6 0
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H2, heating value of 16 MJ/N m3, and gas yield of 1.2 N m3/kg
biomass fed.
The goal of this study is to establish a biomass gasifier for
hydrogen and syngas production. The commercial a-cellulose
was used as the substrate to test the operating parameters.
Gasification temperature, equivalent ratio, and the steam to
the biomass ratio are the key operating parameters. Bagasse
and the mushroom growth bag waste were also used as the
substrate to produce hydrogen and syngas. The composition
and the thermogravimetric properties were also analyzed of
these materials, which are very important to determine the
potential route for the agriculture waste treatment.
2.
2.1.
The schematic design of the biomass gasifier for the lignocellulosic materials or the agriculture wastes for this study is
shown in Fig. 1. This gasifier can be divided into feeding,
gasification, and effluent zones.
The feeding zone consisted of the feed of air (supplied by
a compressor and controlled by a flow meter), steam (supplied
and controlled by a steam generator), and the biomass
(supplied by a substrate holder and controlled by a spiral
feeder).
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Definitions
yi
DT
DTGmax
Ea
ER
Hj
k
k0
LHVH2
LHVtotal dry
LHVH2
n
R
S
SB
t
T
Ti
Tmax
W
x
Ygas
rH2
u
gas
Items
Bagasse
Mushroom
waste
5.16 0.04
92.18 0.07
2.70 0.03
3.69 0.07
86.27 0.29
10.17 0.24
42.80
5.61
50.55
0.53
0.51
N.A.
40.24
5.05
53.09
1.43
0.19
N.A.
2.2.
Experimental procedure
2.2.1.
Start up
To prepare the substrates for the gasification, the feedstocks were naturally dried for several days, grounds, dried
at 65 C, and stored in a sealed container prior the usage.
The moisture content of the substrate is controlled at
2e10% with the particle size less than 0.35 mm. To start
the gasification, the oven temperature, air flow rate, and
steam flow rate were controlled at the designated condition prior feeding the biomass to the gasifier by the spiral
feeder. All equipments were carefully calibrated before the
reaction.
2.2.2.
Experimental run
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inside the tubular reactor and the before cooling down the
oven.
2.3.
where CO, H2, CH4 and CnHm are the concentrations of the gas
products.
Analysis of substrates
3.
The chemical properties of the biomasses in this study were
characterized by proximate analysis (by the standard
procedure of NIEA R205.01C, Republic of China) to determine
the ratios of moisture, combustible content, and ash; ultimate analysis (Elementar, EA, Vario E1) to determine the
elemental composition (C, H, O, N, and S) of the biomasses.
The ash obtaining from the ultimate analysis was further
analyzed by EDS (SEM/EDS, HITACHI S3000H) and inductively coupled plasma-optical emission spectrometer (ICPOES, Perkin Elmer OPTIMA 2000DV) for the composition
analysis.
The basic combustive properties are determined by the
differential scanning calorimetry (DSC, TA Instruments,
SDT2960). The relations of the combustion temperature, energy
change, and weight loss can be determined. The ignition
temperature, the maximum weight loss ratio and the temperature during the heating processes, exothermic band, and the
activation energy of combustion can also be determined.
2.4.
Parameters definition and methods of data
processing
The major operation parameters for this study are the gasification temperature (Tb,) equivalent ratio (ER), and the steam
to biomass ratio (SB) for the biomass. By adjusting the operation parameters, the yield of effluent gas and the composition and the low heating value of the produced gas
LHVtotal dry gas can be obtained. In general, 40e50% of the
cellulose is found in the agriculture materials [14]. Thus,
a-cellulose (Sigma CAS 9004-34-6) was used as the feed at the
first phase of this study. The agriculture wastes such as
bagasse and the mushroom growth bag waste (wood waste)
which were also used in this study.
The definition of the operation parameters are listed as [4]:
- The equivalence ratio (ER)
ER
3.1.
SB
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(2)
- Dry product gas low heating value, LHVtotal dry gas (MJ/N m3)
LHVtotal dry gas 30:0 yCO 25:7 yH2 85:4 yCH4 151:3
4:2
yCn Hm
MJ=N m3
106
(3)
(1)
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min C2) and burn-out characteristic index (Hj) [17]. They are
defined as:
DTGmax
Tmax Ti
(4)
DTGmax
Hj
Ti Tmax
(5)
DTh
DT
The ignition property index expresses the burning conditions, the greater the value the better the performance of
catching fire and combustion stability. A larger value of the
burn-out characteristic index also shows a better combustion
property for cleaner combustion. The results of the all
biomass at different analysis condition are listed in Table 3.
They show that a-cellulose can be burned much easier than
bagasse and wood waste.
In general, it was believed that the biomass combustion to
be the first order reaction [18] and the activation energies for
the a-cellulose, wood waste, and bagasse at different heating
rates are showed in Table 3 [3,16]. This result is agreed with
the literature results that the activation energy of a-cellulose
pyrolysis is higher than 100 kJ/mol. The higher activation
energy of combustion also shows the higher ignition
temperature; which is agreed with the conclusion of the
ignition temperature.
Although it was believed that the biomass combustion is
the first order reaction, the actual order of the reaction and
the activation energy should be depended on the
biomasses. If the reaction kinetic model of the combustion
is defined as the weight loss ratio during the heat process
and the heating rate in the analysis is also an important
factor to define the activation energy; the reaction rate
constant is expressed by the Arrhenius equation and the
order of the reaction can be determined. Thus, the governing equations to develop the kinetic model can be
written as:
dx
k1 xn
dt
k k0 exp
Ea
RT
(7)
W0 W
W0
(8)
T T0 u
dx
dx
u
k0 exp
dt
dT
(6)
(9)
Ea
1 xn
RT
(10)
ln
dx
k0
Ea 1
ln
n 1 x
u
dT
R T
(11)
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Table 3 e The thermogravimetric properties of the biomasses used in this study with different heating rate.
Biomass_ramp
Units
DTGmax
Mg/min
Ti ( C)
Tmax ( C)
DTh( C)
DTh/DT
Hj (105)
Mg/min. C2
S (105)
Mg/min. C2
Ea (kJ/mol)
Cellulose_5 C
Cellulose_10 C
Cellulose_20 C
Bagasse_5 C
Bagasse_10 C
Bagasse_20 C
Mushroom_5 C
Mushroom_10 C
Mushroom_20 C
0.9084
2.6237
5.1921
0.2844
0.6312
0.3838
0.8727
0.5607
1.5165
292.63
303.86
330.99
244.91
239.30
258.89
278.60
292.63
298.25
313.19
329.33
346.27
297.05
305.12
316.42
301.09
316.42
326.10
26.65
24.53
14.44
122.37
105.14
156.55
347.13
337.42
359.83
0.305
0.314
0.205
0.501
0.468
0.569
0.806
0.780
0.796
3.24
8.35
22.10
0.78
1.85
0.82
1.29
0.78
1.96
0.99
2.62
4.53
0.39
0.86
0.47
1.04
0.61
1.56
139.61
150.32
138.27
61.67
69.45
56.77
93.46
91.69
93.21
3.2.
Table 4 e The activation energies and reaction kinetics
parameters of the biomasses for this study.
Substrate
Cellulose
Bagasse
Mushroom
wood
Heating
rate
( C/min)
Ea
(KJ/mol)
k0
(K/min)
20
10
5
20
10
5
20
10
5
157.803
161.501
143.873
58.031
62.464
54.684
108.396
99.822
97.791
1.115
1.138
1.013
1.036
0.912
0.588
2.573
1.671
1.163
1.718E13
3.418E13
9.710E11
3.965E04
1.007E05
8.181E03
1.720E09
1.752E08
9.567E07
Table 5 e Experimental results of the a-cellulose gasification at ER [ 0.2 and SB [ 0 at different temperature.
Reactor temperature ( C)
Parameter
600
Dry effluent gas composition
H2
N2
CO
CH4
CO2
Syngas
Effluent gas flow
rate (L/min)
Ygas (L/min)
Ygas (L/g Biomass)
LHVdry product gas
(MJ/N m3)
(vol%)
5.95
56.97
13.57
1.87
21.64
19.52
8.32
2.32
0.34
7.02
700
1.97
2.49
2.81
0.80
2.81
8.74
48.35
14.58
4.15
24.18
23.32
9.80
3.80
0.56
8.27
800
1.65
3.67
2.17
0.78
1.15
16.08
42.47
12.13
4.21
25.12
28.21
11.16
5.16
0.77
8.30
900
2.29
4.37
2.04
1.21
0.80
24.73
34.30
16.92
4.84
19.22
41.65
13.82
7.82
1.16
9.95
1000
2.40
3.07
2.07
0.81
1.94
29.54
33.28
23.60
2.67
10.90
53.15
14.24
8.24
1.22
10.67
1.75
2.91
1.53
0.77
0.95
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Table 6 e Experimental results of the a-cellulose gasification at 800 Cand SB [ 0 and different equivalent ratios (ER).
Parameter
16.08
42.47
12.13
4.21
25.12
Syngas
Effluent gas flow rate (L/min)
Ygas (L/min)
Ygas (L/g Biomass)
LHVdry product gas (MJ/N m3)
28.21
11.16
5.16
0.77
8.30
13.50
45.42
11.21
3.58
26.30
2.29
4.37
2.04
1.21
0.80
Thus, the yield of the hydrogen and the syngas will be then
decreased.
To discuss the effect of steam onto the gasification, the
results of the a-cellulose gasification at 800 C and equivalent
ratio equals 0.27 with respect to different steam to biomass
ratio fed to the gasifier and the result is shown in Table 7. It is
suggested that with the presence of the steam, the reaction is
toward the reforming and will enhance the yield of hydrogen.
However, with the excess amount of the steam fed to the
reactor, the system loses a lot of energy to heat up the steam,
which is not favored to process of the energy production. This
apparent result is also agreed with the studies by Yan et al. [5]
and Lv et al. [7].
3.3.
0.27
Section 3-2 showed the gasification results of using commercial cellulose gasification. Upon having all the valuable design
parameters, the studies of using real biomass, especially the
agriculture waste, were studied. Bagasse and the mushroom
0.34
1.79
2.49
1.06
0.85
0.98
10.23
51.20
8.38
2.21
27.98
24.71
13.91
5.91
0.88
7.61
2.96
4.45
1.68
0.56
0.49
18.61
15.43
5.43
0.81
6.05
Table 7 e Experimental results of the a-cellulose gasification at 800 Cand ER [ 0.27 at different steam to biomass ratios (SB).
Parameter
13.50
45.42
11.21
3.58
26.30
Syngas
Effluent gas flow rate (L/min)
Ygas (L/min)
Ygas (L/g Biomass)
LHVdry product gas (MJ/N m3)
24.71
13.91
5.91
0.88
7.61
0.5
1.79
2.49
1.06
0.85
0.98
14.28
47.77
6.45
3.73
27.77
20.73
13.23
5.23
0.78
7.07
1
1.75
4.31
2.08
1.11
0.71
18.56
42.58
8.34
3.02
27.51
26.89
14.84
6.84
1.02
7.20
1.5
0.99
1.19
1.40
0.35
1.20
15.69
46.96
7.82
2.21
27.32
23.51
13.46
5.46
0.81
6.55
3.59
5.55
3.61
1.07
2.80
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Fig. 3 e Experimental results of the a-cellulose, bagasse, and mushroom waste gasification at 700e900 C, ER [ 0.27e0.34,
and SB [ 0e0.5.
4.
Conclusions
The establishment of the biomass gasifier to produce biohydrogen and the syngas is studied. The commercial available, a-cellulose, as well as the agriculture wastes, bagasse
and mushroom growth bag waste, were used as the substrates
for the gasifier. The gasification temperature (T ), the biomass
feeding rate, equivalent ratio (ER), and the steam to the
biomass ratio (SB) are the key operating parameters for the
gasifier. The chemical properties of the biomass can be
determined by the thermogravimetric analysis and the
composition and the yield of the gas phase sample after the
gasification is also determined.
For the studies of using agriculture waste as the feed to the
gasifier, the ash content of the materials is a key factor to
operate the gasifier. For the materials with relatively high ash
contents will lead to blockage of the manifold. Pretreatment of
the substrate to remove the ash, design of the manifold, or the
operation procedure of the gasifier should also be addressed to
use the real biomass to the gasifier for the hydrogen production for the future studies.
The gasification of the biomass and/or the agriculture
waste can efficiently generate the hydrogen and the syngas. If
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Acknowledgments
The authors would thank for the financial support for this
study from the Ministry of Education in Taiwan, ROC, and
Feng Chia University (under contract No. FCU-08G27201, FCU09G27102) are highly acknowledged.
references