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ISBN 978-967-5770-06-7

Proceedings of International Conference on Advances in Renewable Energy Technologies (ICARET 2010)


6-7 July 2010, Putrajaya, Malaysia
ICARET2010-035

Flowsheet Modelling of Biomass Steam Gasification


System with CO2 Capture for Hydrogen Production
Abrar Inayat, Murni M Ahmad*, M I Abdul Mutalib, Suzana Yusup
Department of Chemical Engineering
Universiti Teknologi PETRONAS, Bandar Seri Iskandar
Tronoh, Perak, Malaysia
*e-mail: murnim@petronas.com.my
AbstractThere exists high potential for hydrogen production
in Malaysia from biomass due to abundant agriculture waste.
Biomass steam gasification with in situ carbon dioxide capture
has good prospects for the production of hydrogen rich gas.
This work focuses on the mathematical modeling of the
flowsheet design for hydrogen production from biomass via
steam gasification with in situ carbon dioxide absorption by
CaO, carried out using MATLAB. The effects of temperature,
steam/biomass ratio and sorbent on the purity and yield of
hydrogen in the product gas stream are predicted using the
model. Based on the results, the maximum hydrogen purity
predicted is 0.81 mole fraction at 950 K at outlet of the gasifier
unit and it can be enhanced to 99.99 % using a scrubber and a
pressure swing adsorption unit. At 950 K with steam/biomass
ratio 3.0 and sorbent/biomass ratio, the hydrogen yield
obtained 95.40 g/kg of biomass. Between the temperature
range of 800 to 1300 K, hydrogen yield is predicted to increase
from 76.5 to 97.3 g/kg of biomass. It is observed that the
increase in hydrogen yield is larger when increasing the
steam/biomass ratio compared to when increasing
temperature, within the selected ranges. The mass conversion
efficiency (MCE) showed linear co relation with temperature.
The results are compared with the literature and show good
agreement.
Keywords-hydrogen; biomass; flowsheet; modelling;

I.

INTRODUCTION

Due to the energy crises of the fossil fuel and


environmental problems the production of hydrogen as a
clean and sustainable fuel is now attractive [1]. Biomass
gasification research is recently increasing attention as
renewable energy source for the hydrogen production [2]. In
2006 the hydrogen world demand was calculated 50
MT/year with 10% expansion yearly [3]. The potential for
hydrogen production from biomass in Malaysia is logical
due to the abundance of biomass available estimated at
21.625 t th-1 y-1 [4-5]. Different gasification agents used for
biomass gasification, such as air-steam, oxygensteam and
pure steam [6-7]. The use of pure steam as gasification agent
is not only in favor of more hydrogen but also economical
than other conventional gasifying agents and pyrolysis [811]. Furthermore, hydrogen can be increased in the product
gas by integrating it with CO2 capture step using CaO as
sorbent [12].
There were several research works have been reported
based on experimental and modeling approach applying CO2

capture using CaO in air-steam and steam gasification


process.
Initially, Mahishi et al. [13] performed an experimental
work using CaO as sorbent with pure steam in a micro
reactor. They predicted hydrogen concentration of 66 vol %
in the product gas. They argued on the dual role of the CaO
as sorbent and catalyst, as the important factor leading to
higher hydrogen production. Acharya et al. [14] investigated
hydrogen production through steam gasification of biomass
in presence of CaO. They reported the hydrogen
concentration more than 54.43 % based on experimental
work at steam/biomass of 0.83, CaO/biomass of 2.0 and
temperature 670 C.
In line with the above findings, Florin et al. [15]
developed a thermodynamic equilibrium model for hydrogen
production from biomass coupled with CO2 capture step in a
dual fluidized bed gasifier. They investigated the influence
of temperature, pressure, steam/biomass and sorbent/biomass
ratios on hydrogen concentration. Using the modeling
results, they predicted that hydrogen concentration could be
increased from 50 to 80 vol% in the product gas by using
CaO as sorbent. There was another equilibrium model
reported for steam gasification with CO2 adsorption using
CaO as sorbent implemented in the ASPEN PLUS process
simulator [16]. Using gasification integrated with absorption
system and gas cleaning unit, they predicted that
concentration of hydrogen increased by 19% compare to
conventional gasification process. Abu-Zahra et al. [17]
presented a new concept of integrated process for hydrogen
production. Using syngas as a feed stock, simulation result
shows 95% hydrogen in product gas. They designed
flowsheet with water gas shift reactor, scrubber and
membrane separation unit. Emun et al. [18] developed a
simplified flowsheet model but for coal gasification using
gasifier, gas cleaning and cooling units applied in ASPEN
PLUS process simulator. Few authors also proved
experimentally and through modeling results that CO2
capture step is in favor of more hydrogen production [19-20]
The objective of the present work is to develop a
simplified process for enriched hydrogen production from
biomass in Malaysia. The effect of process parameters i.e.
temperature, steam/biomass ratio and addition of CaO on
hydrogen concentration and yield in the steam gasification
process with CO2 capture was also studied. The flowsheet
model incorporates the gasification, adsorption kinetics
model and material balance. The flowsheet model

incorporates the gasification and adsorption kinetics models


and material balances. The developed model is used as a
platform to investigate the feasible operating conditions for
the production of hydrogen rich gas from biomass using a
single-pass fluidized bed gasifier. This study has been
carried out for single pass fluidized bed gasifier using
MATLAB.
II.

TECHNICAL APPROACH

A. Process Devalopment
A simplified process has been developed for enriched
hydrogen gas production from biomass using pure steam as
gasification agent and CaO as CO2 sorbent. The block
diagram of the process is shown in Fig 1. The whole process
is consists of four sections, feed treatment, steam generation,
gasification and gas cleaning section. The detail of each
section is described in next headings. The process flow
diagram (PFD) is shown in Fig 2.

consisting of drying and size reduction. Drying used to


remove the moisture from the biomass either from flue gases
or by steam but steam drying is preferred due to very low
emissions and safer [24]. Usually drying removes the
moisture contents from 10-15 % in the biomass [25]. The
best condition of biomass for fluidized bed gasifier is that the
biomass must well grind as well [26]. So to achieve such
best condition for biomass feed to gasifier a dryer and ball
mill used to remove moisture from the biomass and fine
grinding respectively shown in Fig 2.
C. Steam Generation
The process design includes a steam generation system
that produced steam by a general steam generator.
Furthermore steam is super heated until 523 K by super
steam heaters. The steam is supplied to the gasifier at
atmospheric pressure. The steam generation system is also
shown in fig 2.
D. Gasification
The conversion of biomass to hydrogen takes place in
single pass fluidized bed gasifier through steam gasification
process integrated with CO2 capture. There are few
assumptions were considered in flowsheet development
modeling for gasification process are as follows.

Figure 1. Block diagram of the process.

The operating conditions and process parameters for the


flowsheet modeling are assumed, which are also close to
many commercial and research scale biomass gasification
processes [12, 16, 21-23]. The assumptions are as follows:

Biomass feed rate: 72 g/hr.

The gasifier operates under steady state conditions


and atmospheric pressure.
The reactions proceed adiabatically and at constant
volume.
There is no tar formation in this process.

In the modeling framework, biomass is assumed as char


and six major reactions [6-7, 21], given in Table I, are
assumed to occur in the gasifier. The base reaction kinetic
models along with validation and the preliminary results on
the effect of different variables on the product gas
compositions are presented in an earlier work [27].

Steam/biomass ratio range: 1 to 3.5 for hydrogen purity


and from 2 to 5 for hydrogen yield

The total moles and the moles of hydrogen in product gas


are calculated using the kinetics model [27]. The mole
fraction of hydrogen in product gas calculated from equation
(1).

Sorbent/biomass ratio: 1.0 for both hydrogen purity


and hydrogen yield profiles.

(1)

B. Feed Treatment
Pretreatment of biomass for gasifier is generally

Mass and energy balances calculated by the equations (2)


and (3) respectively [28].

Temperature range: 800 to 1300 K

Figure 2. Block diagram of the process.

(2)

K the hydrogen starts decreases. This observation can be


explained due to the exothermic and reversible behavior of
water gas shift reaction. Along with water gas shift reaction
the carbonation reaction also becomes slower due to highly
exothermic behavior.

(3)

Where mi is the inlet mass (g), mo is the out mass (g) and
E is the energy flowrate (kj/h). The variation in the hydrogen
yield can be used to investigate the effect of temperature and
steam/biomass ratio on the hydrogen production from
biomass steam gasification. The definition of hydrogen yield
is defined using equation (4) [21].
=

)(4)

( )/

The mass conversion efficiency (MCE) is one of the


mass performance parameter. The MCE of gasifier is
calculated by using equation (5) [29].
(%) =

TABLE I.
No
1
2
3
4
5
6

100
(

(5)

RECTIONS INVOLVED IN PROCESS [6-7, 21]

Name
Char Gasification
Methanation
Boudouard
Methane Reforming
Water Gas Shift
Carbonation

Reaction
C + H2O CO + H2
C + 2H2 CH4
C+ CO2 2C
CH4 + H2O CO + 3H2
CO + H2O CO2 + H2
CO2 + CaO CaCO3

H (kj/mol)
+131.5
-74
+172
+206
-41
-178.3

E. Gas Cleaning
The product gas produced by the gasification process
contained hydrogen, carbon monoxide, carbon dioxide,
methane, steam and fly ash. To get pure hydrogen as end
product, there were several steps involved in product gas
cleaning with different units like filter, scrubber and pressure
swing adsorption as shown in Fig 2. Fly ash was removed
from the system by filter. It is assumed that the product gas
contained 13% fly ash of biomass feed rate [30].
Furthermore the steam was removed by passing through
scrubber with fresh water [31]. Along with the steam there
are also some others product gases will be also absorbs in
water which was calculated by chart of solubility of gases in
water at atmospheric pressure and different temperature [32].
The scrubber is also used to cool down the product gas.
Finally pressure swing adsorption (PSA) unit applies to get
pure hydrogen (99.99%). As the advantages of PSA that it
remove the impurities at any level and produced high purity
hydrogen as product [33].
III.

RESULTS AND DISCUSSION

A. Effect of Variabales on Hydrogen Purity


Temperature is one of the important variables in biomass
fluidized bed gasifier. The effect of temperature on the
hydrogen mole fraction versus temperature change from 800
to 1300 K is shown in Fig 3. The figure shows that the
hydrogen mole fraction is more than 0.80. This is might be
due to pure steam gasification process along with CO2
capture step in the system. These results can be explained by
the Le Chateliers principle on the endothermic reforming
reactions of char and CH4 that are promoted by the
increasing temperature.
The figure also shows that the maximum hydrogen mole
fraction obtained at 950 K. It is also observed that after 950

Figure 3. Effect of temperature on hydrogen mole fraction.


Steam/biomass ratio: 3.0, Sorbent/biomass ratio: 1.0.

There is another very important variable in steam


gasification process i.e. steam/biomass ratio. To study the
effect of steam/biomass ratio on hydrogen concentration a
three-dimensional surface plot predicted along with effect of
temperature shown in Fig 4. The figure shows that with
increasing steam/biomass ratio the mole fraction of H2
increases. As steam is the only gasification agent being used,
so the reactions involving steam i.e. methane reforming and
water gas shift, are highly dependent on steam feed rate.

Figure 4. Effect of temperature and steam/biomass ratio on hydrogen


mole fraction. Sorbent/biomass ratio: 1.0.

It is observed that at 800 K with lower steam/biomass


ratio, i.e. 1.0, the hydrogen mole fraction is 0.73, and at high
temperature 1300 K with same steam/biomass ratio (1.0), the
hydrogen amount is almost 0.80 mole fraction. In addition,
the surface plot shows that the highest hydrogen mole
fraction achieved is 0.81 mole fraction that occurs at 950 K
and at steam/biomass ratio of 3.0.
The presence of sorbent (CaO) in system increased the
hydrogen mole fraction in product gas by absorbing the CO2
present in the system. The difference of H2 and CO2 mole
fraction in product gas by using CaO as sorbent and without
CaO is show in Fig 5. Also Fig 5 shows that hydrogen can be
increased from 0.65 to 0.83 and CO2 can decreased from
0.31 to 0.09 by using CaO as sorbent. The amount of sorbent
influenced a lot on the production of hydrogen, as sorbent

used to increase H2 and decrease CO2 in product gas


composition.

Figure 6. Mass balance at gasifier. Temperature: 950 K, Steam/biomass


ratio: 3.0, Sorbent/biomass ratio: 1.0.

Figure 5. Effect of CaO on hydrogen and carbon dioxide. Temperature:


950 K, Steam/biomass ratio: 3.5, Sorbent/biomass ratio: 1.5.

B. Mass Balance of the Process


Mass balance calculated to evaluate the process
performance. The operating condition for mass balance are
selected base on the discussion in previous section i.e. 950 K
temperature,
3.0
steam/biomass
ratio
and
1.0
sorbent/biomass ratio.
Fig 6 shows the calculation result of mass balance on
gasifier. It is observed that hydrogen yield obtained 95.4035
g/kg of biomass. It is also observed that the feed rate of
steam is 216 g/hr and at the out let of gasifier the steam
flowrate is 182 g/hr, which shows that only 15 % steam
consumed in the gasification reactions.

Which also showed that more than 80 % steam used to


fluidize the biomass inside the gasifier. Several authors
already has been reported that the product gas of gasifier
contains more than 60 % of unreacted steam [34]. Fiorenza
et al. [35] also reported less than 20 % steam conversion in
the fluidized bed gasifier. Corella et al. [36] reported
unreacted steam from the outlet of the fluidized bed gasifier
as a weakness of the steam gasification process and there is
need of more attention to solve this problem. It is also
observed that 108.7421 g/hr of CaCO3 obtained from the
gasifier, which can be regenerated.
The overall mass balance of the flowsheet is shown in
Fig 7. It is assumed that the biomass is pretreated and fed to
the gasifier. The figure shows that after the gasifier 9.7 g/hr
fly ash removed through filter. Furthermore the steam in the
product gas removed through scrubber with fresh water.
Mean while very little amount of the H2, CO and CH4 also
absorbs in the water and exit through scrubber. It is also
observed that high amount of CO2 i.e. 8.3691 g/hr also

Figure 7. Overall mass balance of flowsheet. Temperature: 950 K, Steam/biomass ratio: 3.0, Sorbent/biomass ratio: 1.0.

absorbs in water.
So the scrubber not only help to remove steam from the
system and to cool down the temperature, it also helps to
decrease the more amount of CO2 in the product stream.
Finally, the PSA unit separates the rest amount of CO, CO2
and CH4 from H2. The result showed 6.8659 g/hr of pure H2
(99.99 %) at the end of process.
Furthermore the effect of Temperature and
steam/biomass ratio are also on hydrogen yield is shown in
Fig 8. The figure shows that both variables are in favor for
hydrogen yield.
The Fig 8 shows that at 800 K and steam/biomass ratio of
2.0, hydrogen yield is 78.5 g/kg of biomass. Taking same
temperature but with higher amount of steam/biomass ratio
i.e. 5.0, hydrogen yield obtained 96 g/kg of biomass. It is
observed that the difference due to increase of steam/biomass
ratio at same temperature is 17.5. On the other hand, at high
temperature 1300 K and low value of steam/biomass ratio
i.e. 2.0, hydrogen yield is 88.5 g/kg of biomass. But at the
same temperature (1300 K) with high steam/biomass ratio
i.e. 5.0, hydrogen yield is obtained 97 g/kg of biomass. The
difference observed in hydrogen yield is 8.5.

Figure 9. Effect of temperature on mass conversion efficiency.


Steam/biomass ratio: 3.0, Sorbent/biomass ratio: 1.0.

C. Comparison with Literature


The results of current study are compared with literature.
The results on hydrogen purity from the current flowsheet
modeling are compared with Mahishi et al. [13] experimental
and Florin et al. [12] modelling results on biomass steam
gasification with CO2 capture. The comparison along with
operating condition and basis is shown in Table II. It has
been observed that the results of this study showed good
agreement with the literature.
TABLE II.
Basis

COMPARISON FOR HYDROGEN PURITY


This Study

Approach
Modelling
Gasification
Steam
Temperature (K)
950
Pressure (atm)
1
Steam/biomass ratio
2.0
Sorbent/biomass ratio
1.0
H2 mole fraction
0.77
Deviation error with current study

Figure 8. Effect of temperature and steam/biomass ratio on hydrogen


yield. Sorbent/biomass ratio: 1.0.

So the values of differences for both cases shows that the


influence of steam feed rate at lower temperature is more
significant than at high temperature for the steam gasification
process. This is because the endothermic forward water gas
shift reaction is favored at low temperature as mentioned
earlier. Fig 8 also shows that the influence of steam/biomass
ratio is more than temperature influence on hydrogen yield.
This is might be due to the pure steam gasification process.
The effect of temperature on MCE is shown in Fig 8. It
has been observed linear co relation between temperature
and MCE, which means as temperature increase the MCE
increases as well. The figure shows 76 % MCE at 950 K and
more than 95 % at 1300 K. This is might be due to
endothermic behavior of overall process, as mentioned
before that steam gasification is endothermic process, so
according to Le Chateliers principle by increasing
temperature the endothermic process moves in forward
direction.

Mahishi et al.
[13]
Experimental
Steam
950
1
1.0
1.0
0.68
0.130

Florin et al.
[12]
Modelling
Steam
950
4.94
2.0
0.50
0.72
0.078

For hydrogen yield, the comparison has been done with


Lv et al. [37] experimental work carried out conventional
gasification with catalyst and Shen et al. [20] modeling
results on air steam gasification. The comparison results with
operating conditions are shown in Table III. The results
showed that current study predicts more hydrogen compare
to others conventional methods. The comparison also proved
that the hydrogen yield is higher in steam gasification system
with CO2 capture step rather than other conventional
gasification processes even with usage of catalyst.
TABLE III.

COMPARISON FOR HYDROGEN YIELD

Basis

This Study

Lv et al. [36]

Approach

Modelling

Gasification

Steam

Temperature (K)
Pressure (atm)
Steam/biomass ratio
Sorbent/biomass ratio
H2 (g/kg of biomass)

950
1
3.0
1.0
95.4

Experimental
Air-Steam +
Catalyst
873
1
5.8
72

IV.

Shen et al.
[20]
Modelling
Air-Steam
1123
0.98
0.6
62

CONCLUSION

A simplified flowsheet has been designed for the


enriched hydrogen gas production from biomass steam

gasification integrated with CO2 capture. The flowsheet


mainly consist of four sections i.e. pretreatment, steam
generation, gasification, and gas cleaning. The effect of
process parameters temperature and steam/biomass ratio was
studied on hydrogen production. Both temperature and
steam/biomass ratio is the important variables, as the
hydrogen production increased by increasing both. Initially
hydrogen increases with increasing of temperature but at
very high temperature, hydrogen purity decreases due to the
exothermic and reversible behavior of water gas shift
reaction. By capturing CO2, the hydrogen purity increased as
CO2 is removed from the system. In addition CO2 can also be
removed from the product gas in scrubber through fresh
water. It is observed that 950 K and 3.0 steam/biomass ratio
provides the maximum hydrogen mole fraction in the
product gas i.e. 0.82 and hydrogen yield obtained 95.4035
g/kg of biomass at same conditions. Mass conversion
efficiency increases by increasing temperature due to the
overall endothermic process of steam gasification.
Additionally, it was observed that steam/biomass ratio has
the higher impact on hydrogen yield rather than temperature.
The study provides a useful simulation tool for the design
and optimization of a future experimental work.

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

ACKNOWLEDGMENT
The authors gratefully acknowledge the financial support
from Petroleum Research Fund of PETRONAS and
Universiti Teknologi PETRONAS, Malaysia.

[23]

[24]

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