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international journal of hydrogen energy 35 (2010) 49704980

Available at www.sciencedirect.com

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Thermodynamic analysis of hydrogen production from

biomass gasification

M.K. Cohce*, I. Dincer, M.A. Rosen

Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario,
Canada L1H 7K4

article info abstract

Article history: An investigation is reported of the thermodynamic performance of the gasification process
Received 19 June 2009 followed by the steam-methane reforming (SMR) and shift reactions for producing
Received in revised form hydrogen from oil palm shell, one of the most common biomass resources. Energy and
26 August 2009 exergy efficiencies are determined for each component in this system. A process simula-
Accepted 31 August 2009 tion tool is used for assessing the indirectly heated Battelle Columbus Laboratory (BCL)
Available online 7 October 2009 gasifier, which is included with the decomposition reactor to produce syngas for producing
hydrogen. A simplified model is presented here for biomass gasification based on chemical
Keywords: equilibrium considerations, with the Gibbs free energy minimization approach. The
Biomass gasifier with the decomposition reactor is observed to be one of the most critical compo-
Gasification nents of a biomass gasification system, and is modeled to control the produced syngas
Hydrogen yield. Also various thermodynamic efficiencies, namely energy, exergy and cold gas effi-
Thermodynamics ciencies are evaluated which may be useful for the design, optimization and modification
Energy of hydrogen production and other related processes.
Exergy Crown Copyright 2009 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu. All
Efficiency rights reserved.
Oil palm shell

1. Introduction gasification [1]. Such a fuel can be used for various tasks,
including producing hydrogen, which can be used cleanly and
Biomass, a relatively large energy source globally which efficiently as a fuel in combustion engines and fuel cells.
includes wood, municipal solid wastes and agricultural resi- Hydrogen is likely to be an important energy carrier in the
dues, is being investigated in various countries as a potentially future. Presently, it can be produced by the steam reforming of
significant renewable resource. Biomass is derived from solar natural gas, coal gasification and water electrolysis among
energy. Biomass is relatively clean compared to other sources other processes. However these current processes are not
of energy, as it releases no net CO2 emissions when carefully sustainable because they use fossil fuels or electricity from
managed since CO2 is fixed by photosynthesis during biomass non-renewable resources. Hydrogen production can be made
growth and is released during utilization. This form of energy more sustainable if it is produced from sustainable energy
can be converted to gaseous fuel through thermochemical resources. In this regard, alternative thermochemical

* Corresponding author.
E-mail addresses: mehmet.cohce@uoit.ca (M.K. Cohce), ibrahim.dincer@uoit.ca (I. Dincer), marc.rosen@uoit.ca (M.A. Rosen).
0360-3199/$ see front matter Crown Copyright 2009 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu. All rights reserved.
international journal of hydrogen energy 35 (2010) 49704980 4971

(pyrolysis and gasification) and biological (biophotolysis,

water-gas shift reaction and fermentation) processes are 2. Thermodynamic evaluation
practical and can be more sustainable than present processes
[2,3]. Overviews of technologies for hydrogen production from A thermodynamic evaluation of a complex system requires
biomass have been reported [48]. Many researchers are consideration of its components and their characteristics,
focusing their research on the gasifier portion of this process, chemical reactions and thermal losses. Recently, biomass
as gasification appears to be more favorable for hydrogen gasification in indirectly heated steam gasifiers has received
production than pyrolysis [9]. much attention for the conversion of biomass to combustible
The gasifier is the most important component in any gas [38,39]. In our simulation, we consider the energy effi-
biomass gasification system [10]. Gasification, which is char- ciency of the gasification reaction as the total energy of the
acterized by partial oxidation, is utilized in numerous clean desired products divided by the total energy of the process
energy processes including hydrogen production via biomass inputs [28]. For this analysis, the products are taken to be
gasification. Currently, 8085% of the worlds total hydrogen a mixture of H2O, N2, H2, CO2, CH4, CO, NH3 and H2S. Char is
production is derived from natural gas via steam-methane assumed to consist of solid carbon (C) and tar is not taken into
reforming (SMR) [11]. Much research has been reported on the account in the simulation.
production of hydrogen by SMR [1215], with many studies Simulations are preformed with the Aspen Plus simulation
concentrating on analysing the reforming reactor [16]. Gasifier software, which is utilized in a wide range of industrial
modelling and simulation, using programs such as Aspen applications [18]. A Fortran subroutine is applied to control
Plus, have been ongoing [1719]. Some researchers predict process yields. In Aspen Plus, streams represent mass or
biomass gasification in supercritical water to be a promising energy flows. Energy streams may be defined as either work or
technology for hydrogen production for it allows the utiliza- heat streams, of which the latter also contain temperature
tion of wet biomass [20,21]. Recent research has focused on information to avoid infeasible heat transfer. Mass streams
determining energy and exergy efficiencies [2225] and are divided by Aspen Plus into three categories: mixed, solid,
improving understanding and data availability with experi- and non-conventional (for substances like biomass). Mixed
mental studies. In this study, the gasifier, the most significant streams contain mixtures of components, which can be in
part of the system, is analyzed in detail. gaseous, liquid and solid phases. The solid phase component
Exergy analysis is a tool for understanding and improving in this simulation is solid carbon (C). Thermodynamic prop-
efficiency [4], and is used throughout this investigation in erties are defined in the Aspen Plus libraries for chemical
addition to energy analysis. Extensive exergy analyses have components. Components present in the mixed and solid
been reported using devices, technologies and systems, in stream classes may participate in phase and chemical equi-
a variety of fields. Some examples include exergy assessments librium, and are automatically flashed by Aspen Plus at stream
of power plants for transportation and power generation, temperature and pressure. Non-conventional components are
chemical and metallurgical processing facilities and building defined in Aspen Plus by supplying standard enthalpy of
systems [26,27]. Exergy-based assessments and comparisons formation and the elementary composition (ultimate and
have also been performed of such energy technologies as proximate analyses) of the components may also be defined.
hydrogen production [2833], electricity generation with fuel Biomass is characterized in this manner here. Although Aspen
cells and other technologies, for instance, coal-fired and Plus calculates enthalpies and entropies for conventional
nuclear [34,35], and larger energy systems [36,37]. components, ambient temperature and pressure, which are
The aim of the present work is to investigate hydrogen required in evaluations of exergy, are not readily available in
production by thermochemical biomass gasification using the result output. A property termed availability by Aspen Plus
energy and exergy methods, and to evaluate the potential of is calculated for conventional components, but this does not
hydrogen production from biomass. A parametric analysis of include chemical exergy. For these reasons, the EES program is
factors influencing the thermodynamic efficiency of biomass used to calculate total exergy (physical and chemical) for each
gasification is carried out. Energy and exergy assessments are stream in this simulation.
performed and the effects are determined on both system The following simplifying assumptions are made in the
efficiency and hydrogen yield of varying parameters of the simulation:
fractioned syngas. The system considered has two parts, and
both include syngas production as an input for producing  Char only contains solid carbon and ash, and there is no tar
hydrogen in the hydrogen plant. The manner is assessed by yield.
which hydrogen production is changed by fractioning the  The process occurs at steady state and isothermally, and
syngas streams and by importing methane from external residence time is not considered. Also catalysis is not
sources. The focus of this research is on the gasifier since it used.
requires the most improvement in terms of energy and exergy  The ZNO-bed and the pressure swing adsorption (PSA)
utilization. The significance of the present work is its focus on system are not included in the energy and exergy
green energy sources and increasing the efficiency of systems calculations.
for hydrogen production. It is anticipated that the results will  All gases behave ideally.
assist efforts to optimize and enhance the environmental  Air is considered on a volume basis as 79% nitrogen and 21%
performance of energy systems. The use of computer simu- oxygen.
lation yields a better understanding of the overall system, and  A heat stream is used as a heat carrier in Aspen Plus instead
is a particularly useful tool in support of design. of sand.
4972 international journal of hydrogen energy 35 (2010) 49704980

2.1. Balances X  
exch xi exch
i  RT0 ln xi (8)
Mass and enthalpy values are evaluated with Aspen Plus. For
Here, xi is the mole fraction and exch
i the standard chemical
a general steady-state process, we can write mass and energy
exergy of component i. Standard chemical exergy values used
balances, respectively, as
here are taken from model 2 in Szargut et al. [26].
m _o
m (1) The entropy balance for a steady-flow reacting system can
i o be written as

X X X Q_ j X X
E_ in E_ out (2) _ i si 
m _ o so S_ gen 0
m (9)
i o _Tj

An overall exergy balance can be written for a steady-state The exergy destroyed due to irreversibility can be expressed
process as follows: as follows:
X  X  X 
_ i
Ex _ j
Ex _
Ex (3) _ dest T0 S_ gen
Ex (10)
in out dest

where The physical exergy of biomass is zero when it is entering

X  the system at temperature T0 and pressure P0. Thermody-
_ i
Ex _ air Ex
Ex _ drybio Ex
_ biomoist Ex
_ st Ex
_ meth (4) namic properties are needed for the calculation of the chem-
ical exergy of biomass. Since such properties for oil palm shell
X  biomass are not available, a correlation factor for solid
_ j
Ex _ prodg Ex
Ex _ unconcarb Ex
_ st Ex
_ exh W
_ turb (5)
out biomass (for O/C < 2) is used based on statistical correlations
developed by Szargut et al. [29]:
These values are available in Table 1
Both physical and chemical exergy inlet and outlet values 1:044 0:0160H=C  0:3493O=C1 0:0531H=C 0:0493N=C
are determined for the Gasification, Combustion, SMR, HTS 1  0:4124O=C
and LTS product gases, are used to assess exergy destructions. (11)
Some components possess only physical exergy. The specific The specific chemical exergy for biomass can then be
flow exergy associated with a specified state is expressible by determined as
the sum of specific physical and specific chemical exergy:
biosolid bLHVbio (12)
exprodg exph exch (6)
Although the magnitude of the physical exergy of biomass
The physical exergy defined as is small, it is calculated in this simulation after the drying
process. The calculation is performed using the heat
exph h  ho  T0 s  so (7)
capacity of dry biomass which is described by Gronli and
and the chemical exergy contribution can be calculated for an Melaaen [37]:
ideal gas mixture as follows:
Cpbio 1:5 103 T (13)

where Cp(bio) is the heat capacity and T is the temperature of

the biomass.
The change in specific entropy in Eq. (7) can be written for
Table 1 Exergy results for the overall hydrogen plant for biomass as
Case 1.
Exergy flow Percentage of total Cp;i
Ds dT (14)
rate (kJ/h) exergy inlet T0 T

Inputs Equation (14) can be used to calculate the physical exergy

Wet biomass 2,397,523 81.0 with Eq. (7) at the specified temperature.
Water 8,469 3.0
The heat capacity of solid carbon is determined using
Air 3,432 1.0
Aspen Plus property data and substituted into Eq. (7) to find
Methane (CH4) 527,500 16.0
Purchased electricity 0 0.0 entropy values, which are used for the thermal exergy calcu-
Total 2,936,924 100.0 lation in Eq. (7).

Outputs and destructions

Hydrogen 653,052 22.3 2.2. Energy, cold gas and exergy efficiencies for BCL
Electricity 46,800 1.5 gasification
Exhaust 303,573 10.3
Water 49,850 1.7 Tables 2 and 3 show the properties and gas composition of the
Total output 1,053,265 35.9 main streams and the overall system performance based on
Exergy destruction 1,883,658 64.1
the simulation results. The latter can be expressed with the
Total output 2,936,923 100.0
and destruction
cold gas efficiency. This measure is the ratio of the chemical
energy of the produced gas to that of the biomass feed energy
international journal of hydrogen energy 35 (2010) 49704980 4973

Table 2 Properties and composition of the main streams in the H2 plant.

Quantity Stream

COMP Outlet SMR outlet HTS Outlet LTS outlet PSA inlet Off-gas

T ( C) 43.5 850 518 241 43 40
P (bar) 31 28 27 26.5 25.2 1
Flow rate (kg/h) 52.06 121.23 121.23 120.90 70.695 69.70

Dry gas composition (% vol)

H 2O 0.0 49.0 38.0 34.0 0.0 0.0
H2 46.0 28.0 40.0 43.0 65.60 26.58
CO 30.0 15.0 4.00 1.0.0 0.40 0.30
CO2 14.0 6.0 17.0 21.0 32.15 72.32
CH4 10.0 0.01 1.00 1.0 1.85 0.8

content. The cold gas energy efficiency of the BCL hydrogen where Ex _ in respectively are the exergy destruc-
_ dest and Ex
i i
plant is determined as tion rate and the exergy input rate for component i.
The steambiomass ratio (STBR) can be expressed as
m_ prodg LHVprodg
hcg (15)
_ drybio LHVdrybio
m m_ st
STBR (20)
_ drybio
Hydrogen is the desired product in this simulation, so the
production efficiency can be described as the system effi- Also, the ratio of exergy destruction xdest for a component
ciency in general. Energy efficiency h and exergy efficiency j can be evaluated by dividing its exergy destruction by the total
values are often evaluated for steady-state processes, and can exergy provided to the system. Here, we can write
be written here as follows:
_ dest
Ex i
xdest P (21)
E_ prodg W_ turb Ex _ i
hsys (16)
_Eair E_ drybio E_ biomoist E_ st E_ meth
_ dest is the exergy destruction for each component
where Ex i
and Exi in is the exergy flow of all input material streams.
_ prodg W
Ex _ turb
jsys (17)
_ air Ex
Ex _ drybio Ex
_ biomoist Ex
_ st Ex
_ meth

where E_ prodg is the rate of product energy output, Ex_ prodg is the
3. Case study
rate of product exergy output and W _ turb is the turbine work
rate. Also the energy efficiency of component i may be written Heating and drying are endothermic processes that require
as follows: a source of heat. Heat can be supplied by an external source
via indirect heating. In gasification, indirect heating allows us
E_ out i
hi 1  (18) to have indirectly heated gasification. More often, a small
E_ in
amount of air or oxygen, typically not more than 25% of the
where E_ out i and E_ in i are the energy output and input rates stoichiometric requirement for complete combustion of the
for component i. Similarly, the exergy efficiency for compo- fuel, is input for the purpose of partial oxidation, which
nent i may be written as releases sufficient heat for drying and pyrolysis as well as for
the subsequent endothermic chemical reactions. These
_ dest
ji 1  i
(19) include the carbonoxygen, boudovard, carbonwater and
_ in
Ex i hydrogenation reactions [35].
The system simulated in this paper includes the gasifica-
tion plant and the hydrogen plant. Related energy efficiency
and economic analyses have been performed [38]. In this
Table 3 Simulation results for cases 1 and 2. investigation, the system analyzed by those authors is modi-
Quantity Case 1 Case 2 fied and energy and exergy efficiencies are evaluated for
varied conditions (e.g., water streams and the amount of
Biomass flow rate (wet) (kg/h) 166.67 166.67
entered biomass).
Biomass flow rate (dry) (kg/h) 88.40 88.40
Steam input to gasifier (kg/h) 33.17 33.17 In this study, we focus on the gasifier. The R-GIBBS block
Syngas fraction to SMR-COMB 0.196 0.0 reactor uses single-phase chemical equilibrium, or simulta-
CH4 input to SMR-COMB (kmol/h) 0.0 0.475 neous phase and chemical equilibrium, by minimizing the
Hydrogen production rate (kg/h) 5.53 6.91 Gibbs free energy, subject to atom balance constraints. This
Steam-biomass ratio (STBR) 0.38 0.38 block reactor is useful when the temperature and pressure are
Cold gas efficiency, hcg 0.30 0.40
known and the reaction stoichiometry is unknown. The latter
System energy efficiency, hsys 0.24 0.27
System exergy efficiency, jsys 0.22 0.25
reactor and the decomposed (RYIELD) reactor combined have
been used to model the BCL low-pressure indirectly heated
4974 international journal of hydrogen energy 35 (2010) 49704980

In this simulation, however, it is a designed heat stream

Table 4 Proximate and ultimate analyses and other data
for oil palm shell [41]. using just enough heat to supply the gasifier heat demand and
the gas cleaning section (see Fig. 1). At the same time
Proximate analysis (wt% dry basis)
combustion occurs in a third reactor, which is fed with
Volatile matter 73.74
Fixed carbon 18.37 methane gas (CH4) from an external supply and char gener-
Ash 2.21 ated by the gasifier. There are two combustors which operate
at different temperatures; the first combustor runs at
Ultimate analysis (wt% dry basis)
C 53.78 a temperature of 1255 K, while the second runs at 1355 K with
H 7.20 15% excess air.
O 36.30 Fig. 1 shows that the syngas enters the scrubber which is
N 0.00 designed for syngas cleaning. During this process some of the
S 0.51 toxic gas is cleaned and water in the syngas is condensed.
Moisture content (wt %) 5.73
After entering the scrubber the syngas passes to the separator
Average particle size (mm) 0.250.75
(SP1), from which part goes to the SMR-COMB. Note that in
Molecular formula CH1.61O0.51
Lower heating value (MJ/kg) 22.14 this study, the first case has the fraction of the product
stream at 19.6% but the fraction of the product stream is 0%
for the second case. After, the syngas passes through the five-
stage compressor system, which has polytropic efficiency of
gasifier. The feedstock used for this analysis is oil palm shell, 79% for each compressor stage and a mechanical efficiency of
delivered at 50 wt% moisture; the ultimate and the proximate 95%. The syngas is cooled, the preferred method being air
analyses for the feed used in this study are given in Table 4. cooling as it avoids excess pressure losses. After the
The plant capacity is designed to be 2000 dry tonne/day (83.3 t/ compression and cooling processes, the syngas pressure
h), and the lower heating value (LHV) of the dry biomass is increases from 1 to 31 bar while the temperature increases
22.14 MJ/kg. by 43 K. Before reaching the ZnO-Bed, the syngas is heated
In this paper we divide the system into two parts. The first to 653 K because the ZnO-Bed cannot function at a lower
is the gasification plant in Fig. 1, which produces syngas for temperature [40].
the second part of the system, which is the hydrogen plant. In After sulphur cleaning in the ZnO-Bed, the syngas
this assessment, we consider two cases that have been undergoes three main reactions: steam-methane reforming
designed for producing hydrogen via gasification. In the first (for which the main reaction is CH4 H2O $ CO 3H2), high-
case, 19.6% of the produced syngas and the total amount of temperature shift (for which the main reaction is
off-gas are fed to the steam-methane reformer combustion CO H2O $ CO2 H2), and low-temperature shift. The water-
(SMR-COMB) in order to supply heat for the SMR in the gas shift reaction is usually performed in two stages in
hydrogen plant in Fig. 1. Also, in the first case energy and commercial processes: a high-temperature shift (HTS) in the
exergy analyses for the entire system are carried out. In the range of 643693 K and a low-temperature shift (LTS) in the
second case, instead of feeding the SMR-COMB with frac- range of 473523 K [38]. The sulphur-free syngas mixes with
tioned syngas, it is fed by just enough methane gas (CH4) from the steam from the superheater in mixer 1 to drive SMR. The
external sources to enhance the hydrogen yield at the end of reforming condition is fixed at 1123 K and 28 bar because
the simulation. methane conversion decreases at high pressure. After the
As a case study, biomass and flue gas are mixed in the dry syngas enters the water heat boiler (WHB3), it cools to 677 K
reactor in order to evaporate the water, and dry the wood before entering the high-temperature shift reactor (HTS).
from 50% to 5.7% moisture content. After the drying process While reducing carbon monoxide in the shift reactor, the
is completed in the stoichiometric reactors (RSTOIC) in Fig. 1, hydrogen yield increases by almost 7.5%. As shown in Table 2,
the gas passes through the decomposition (RYIELD) reactor. after the HTS, the syngas passes through a heat exchanger
Normally the BCL device is an indirectly heated gasifier (HE6) and superheater, where its temperature reduces to
consisting of two main reactors [38]: the gasifier and the 473 K. The final treatment for the syngas before pressure
combustor. However, in this simulation the BCL unit contains swing adsorption (PSA) is the low-temperature shift reactor
three main reactors which are the decomposer, the gasifier (LTS), where the carbon monoxide is converted and hydrogen
and the combustor. First the biomass is decomposed in the content increased. The outlet of the LTS has the highest
RYIELD reactor (this reactor is used in the Aspen plus simu- hydrogen flow rate (6.51 kg/h here).
lation); this reactor simulates the decomposition of the feed The PSA unit purifies the syngas by separating the
at low temperature (394 K, 1 atm). In this step, biomass is hydrogen from the other components in the shifted gas
converted into its constituent components including carbon stream, mainly CO2 and unreacted CO, CH4 and other
(C), hydrogen (H2), oxygen (O2), sulphur (S), nitrogen (N2) and hydrocarbons. Based on studies and data from industrial
ash, by specifying the yield distribution according to the gas producers, the shifted gas stream must contain at least
biomass ultimate analysis. These components enter the 70 mol% hydrogen before it can be economically purified in
Gibbs reactor (at 1 atm and 1162 K) to produce syngas using the PSA unit. For the present analysis, the concentration of
steam (at 923 K and 1 atm), as seen in Table 5. The heat of hydrogen in the shifted stream prior to the PSA unit is
combustion of the actual indirectly heated gasifier system is between 60 and 65 mol%. Therefore, part of the PSA unit
transferred to the gasifier by recirculating hot inert material, hydrogen product stream is recycled back into the PSA
usually sand. feed. For a 70 mol% hydrogen PSA feed, a hydrogen
international journal of hydrogen energy 35 (2010) 49704980 4975

1 biomass SYNGAS







SP 1 CH4 addition


15 55
16 17 19 51


38 SP3

39 SP2

54 34 23





Q1 47 46


41 25



42 EC2




EC 1 EC3
73 31
30 29 28

72 L6 43
H2-REC 45

P2 P1


Fig. 1 Aspen Plus simulation flow diagram of a process for hydrogen production by biomass indirectly heated gasification.
4976 international journal of hydrogen energy 35 (2010) 49704980

Table 5 Conditions at the gasifier outlet. SMR
Quantity Value 21

Gasifier outlet temperature ( C) 890

Combustor 1 outlet temperature ( C) 982 Q2
Gasifier outlet composition (kg/h)
H2O 38.23 32

H2 3.52 22
CO 31.87
CH4 5.93
CO2 22.98
NH3 0.08 40 54
H2S 0.08
N2 0.70
C (solid) 18.02
Ash 0.77 Split syngas
and off gas AIR from HE2
from HE3

Fig. 2 Aspen Plus simulation flow diagram of a process for

recovery rate of 85% is typical with a product purity of steam-methane reforming with heat supplied by
99.9% by volume [40]. combustion of methane gas (CH4) from external source.
For the SMR-COMB unit, air enters at 298 K and 1 atm and
passes through two heat exchangers (HE2 and HE4). The
temperature of the air rises to 1060 K, while concurrently the
off-gas from the PSA and the fractioned syngas passes
through heat exchanger 5 and heat exchanger 3 at 720 K and the second case, performance improvements are noted, as the
1 atm, and enters the SMR-COMB to supply heat for SMR (Case energy efficiency is found to be 27% and the exergy efficiency
1). In addition heat exchanger 3 and WHB3 produce the steam 25%. The efficiency increase occurs because importing
for the turbine which produces electricity. methane gas from external sources increases the hydrogen
The effects of fractioned syngas on the hydrogen produc- production rate from 5.53 kg/h to 6.91 kg/h after the PSA unit.
tion yield are shown in Fig. 2. That figure shows that the The energy and exergy efficiency values for Cases 1 and 2
steam-methane reformer combustion (SMR-COMB) is differ because of the improvement applied to the system in
supplied with methane gas at a rate of 0.76 kg/h CH4. The Case 2. These differences are not attributable to uncertainties
equivalent thermal contribution of this gas is the same as the associated with computer simulation. The improvements in
19.6% of the fractioned syngas in Case 1. Case 2, as previously noted, include non-fractioned syngas
which passes sequentially through the SMR, HTS and LTS
units in order to increase the hydrogen yield in the reforming
and shift reactions. In Case 1 which used fractioned syngas,
4. Results and discussion 19.6% of the gaseous product cannot pass the SMR, HTS and
LTS processes so less hydrogen is produced, which affects the
We now report the results of the energy and exergy analyses, overall system energy and exergy efficiencies. Also, the cold
including the energy and exergy efficiencies and exergy gas efficiencies differ because the second case has a higher
destructions for each component. The results are reported for productivity rate than the first.
Case 1 in Table 1. It is demonstrated that the inlet and outlet The products from this process are hydrogen and elec-
exergy flows for the hydrogen plant are mainly attributable to tricity, but other energy streams also exit. There are two
the energy and exergy inlet with the biomass and the methane sources of flue gas: the char combustor and the second
gas. The produced electricity also contributes to the system combustor (SMR-COMB). Together, their energy contents
products and efficiency, on energy and exergy bases. Further, account for about 4% of the energy in the dried biomass.
the exergy losses are observed to be due to emissions and The simulated hydrogen production flow rates for Cases 1
internal consumptions associated with chemical reactions, and 2 are shown in Fig. 3. It is seen there that the hydrogen
particularly those related to combustion and gasification. production is affected by fractioned and unfractioned syngas
Note that inlet exergy values are evaluated for fuels on an LHV through the component split 1 (point 13 in Fig. 1). It is observed
basis. for the first case that the hydrogen production rate is lower
Some key results from the simulations for the two cases than for the second case, in which the SMR-COMB unit is fed
are presented and compared in Table 3. In this simulation at with fractioned syngas. At the end of the simulation, there-
1162 K and 1 atm, for the low-pressure indirectly heated fore, the fractioned syngas is prevented from passing through
gasifier (R-GIBBS) with the decomposition reactor (RYIELD), the SMR, HTS and LTS processes, which are where the
the maximum hydrogen production efficiency for the first hydrogen yield is increased. In the second case, the unfrac-
case is found to be 24% while exergy efficiency is 22%, as tioned syngas passes through of the SMR, HTS and LTS units.
determined using Eqs. (16) and (17). These values are relatively The energy and exergy efficiencies of the main components
low because of losses for the gasifier, combustor and SMR. For involving chemical reactions are shown in Fig. 4. The energy
international journal of hydrogen energy 35 (2010) 49704980 4977

Fig. 3 Simulated hydrogen production rates for Cases 1 and 2.

efficiency of the gasifier is approximately 72% while the cor- destructions are very low, leading to high exergy efficiencies
responding exergy efficiency is 66% based on Eqs. (18) and (19). for these devices. It is observed that significant heat is trans-
Normally the energy efficiency at these conditions may be ferred to water to produce steam in heat exchangers, boilers
expected to be around 80%; the value here is lower since the and economizers. The results suggest that the low-pressure
system assessed has unconverted solid carbon as char and indirectly heated gasifier requires improvements in terms of
catalysis is not used to promote the gasifier reactions. In energy recovery.
addition, the fuels are over-oxidized in the gasifier in order to For this system, with its feed rate of 4000 kg per day of wet
attain the required gasification temperature [41], and this biomass to the gasification process, the hydrogen production
process may reduce the gasifier efficiency. The gasifier exergy energy efficiency is 24% (see Table 3). It is determined with the
efficiency is lower than the energy efficiency, mainly due to simulation that 132.7 kg hydrogen can be produced from
chemical reactions and oxidization. Both combustion reactors 4000 kg biomass with an energy rate of 4.5 MW. For the second
operate with high energy and low exergy efficiencies. The case, also with a feed rate of 4000 kg per day of wet biomass to
latter are associated primarily with internal irreversibilities. the gasification process, the hydrogen production energy
For the steam-methane reformer, the energy efficiency is efficiency is improved to 27% (see Table 3). Also, it can be
found to be 83% and the exergy efficiency 77%. These values found that 165 kg hydrogen is produced from 4000 kg biomass
are consistent with those reported in the literature [34,42]. with an equivalent thermal input 5.6 MW.
Note that in the HTS and LTS units, the shift reactions occur It can be seen in Fig. 5 that the reactors with the highest
but there is no combustion. Therefore internal exergy exergy destruction rates based on Eq. (21) are the gasifier

Fig. 4 Energy and exergy efficiencies for main system components for Case 1.
4978 international journal of hydrogen energy 35 (2010) 49704980

Fig. 5 Exergy destruction ratios for main components for Case 1.

(R-GIBBS), in which 34% of the total exergy inlet is destroyed. fractioned syngas in one case, and by external methane gas
This observation implies that the gasifier is an important (CH4) supply in the other. Assessments are required to
component for efficiency system improvement, especially understand better how hydrogen production is affected by
since the biomass can be gas, solid and liquid. The combustion changing this parameter, with the aim of investigating the
reactors are also responsible for large exergy destructions, feasibility of producing hydrogen from biomass and better
mainly due to irreversibilities associated with the combustion understanding the potential of biomass as a renewable energy
reactions. These exergy losses mainly relate to chemical source. As pointed out earlier, detailed energy and exergy
exergy destructions, and for both combustion units 1 and 2 are assessments were performed for just one system (Case 1). For
around 11%. It is also interesting that the dry reactor has Case 2, the improvement of the system performance was
a high exergy destruction rate, which is approximately 4.5% gauged by altering one parameter and observing the impact
due to the 50% moisture content of the inlet biomass. Thus, on hydrogen production and system overall energy and exergy
the heat demand is high for this process, resulting in high efficiencies. The energy and exergy efficiencies and exergy
exergy destruction rates. destruction ratios for the main system components for Case 2
Exergy destruction ratios (on a percentage basis) for Case 1 are similar to those for Case 1, so performance figures are not
are shown in Fig. 5 for the system components and in Fig. 6 for presented for Case 2. Also, the exergy destruction ratios for
components with lower exergy losses. The exergy destruction auxiliary components for Cases 1 and 2 are similar. However,
ratio is the ratio of the exergy destruction for a component to improvements are observed for Cases 1 and 2 in hydrogen
the overall system exergy destruction. The exergy destruction production rate and overall system energy and exergy
ratio in Fig. 5 shows that the HE2 and WHB units are each efficiencies.
responsible for about 1% of the exergy destruction rate, and On a broader scale, the results of this study support the
the SMR, HTS and LTS reactors, which do not include contention by many that biomass may contribute to a future
combustion, also have very low exergy destruction rates. hydrogen economy. Although biomass has the advantage of
There are two cases of note in this assessment. The steam- being renewable if managed properly, it has challenges; large
methane reforming (SMR) heat demand is supplied by quantities of biomass need to be grown and transported to

Fig. 6 Exergy destruction ratio for auxiliary components for Case 1.

international journal of hydrogen energy 35 (2010) 49704980 4979

produce a small amount of hydrogen. Transportation STBR steambiomass ratio

concerns may be alleviated by using pyrolysis of biomass to T temperature, K
produce bio-oil, as opposed to direct gasification. Based on the T0 reference-environment temperature, K
costs and availability of hydrogen production processes, it is W_ work rate, kJ/h
likely that hydrogen will be produced by steam-methane x exergy ratio
reforming or coal gasification during a transition to
Greek symbols
a hydrogen economy. Future advances in water-splitting
j exergy efficiency, %
processes may allow them to replace fossil fuel processes as
h energy efficiency, %
cleaner, long-term energy solutions. Many predictions of how
b correlation factor, %
a hydrogen economy will unfold have been published. For
instance, a roadmap was created that provides an overview of Subscripts
a possible evolution of hydrogen production technologies in bio biomass
the future [43]. The timing of each step in this evolution biomoist biomass moisture
towards a hydrogen economy depends on how quickly tech- cg cold gas
nology advances and other factors. dest destroyed
drybio dry biomass
en energy
5. Conclusions gen generated
i,j index for components
The energy and exergy analyses performed of biomass-based in input
hydrogen production have yielded energy and exergy effi- meth methane gas (CH4)
ciencies and an understanding of the impact on performance out output
of several parameters. The feasibility of producing hydrogen st steam
from biomass and a better understanding the potential of sys system
biomass as a renewable energy source have been attained by turb turbine
considering two methods: 1) the heat required for steam- prodg produced gas
methane reforming is supplied by fractioned syngas, and 2) unconcarb unconverted carbon
the SMR-COMB reactor is provided with externally supplied
methane gas. Oil palm shell is the biomass considered. For the
ch chemical
direct gasification reaction, a BCL-type low-temperature
ph physical
indirectly heated steam gasifier is examined. The thermody-
namic assessments for the two cases demonstrate that the Acronyms
processes have low efficiencies. The simulation confirms for COMB combustion
the system that the second case considered, which indicates COMP compressor
performance improvements, has higher energy and exergy COOL cooling
efficiencies than the first case. EC economizer
HE heat exchanger
HTS high-temperature shift
LTS low-temperature shift
PSA pressure swing adsorption
WHB waste heat boiler
The authors acknowledge the support provided by the Ontario
Research Excellence Fund and the Natural Sciences and
Engineering Research Council of Canada. references

[1] Kruse A, Gawlik A. Biomass conversion in water at 330
410  C and 3050 MPa: identification of key compounds for
Cp specific heat, kJ/kg K indication different chemical reaction pathways. Industrial
Engineering and Chemistry Research 2003;42(2):26779.
E_ energy flow rate, kJ/h
[2] Ni M, Leung DYC, Leung MKH, Sumathy K. An overview of
Ex exergy flow rate, kJ/h hydrogen production from biomass. Fuel Processing
ex specific exergy, kJ/kg Technology 2006;87:46172.
h specific enthalpy, kJ/kg [3] Ntaikou I, Gavala HN, Kornaros M, Lyberatos G. Hydrogen
LHV lower heating value, MJ/kg production from sugars and sweet sorghum biomass using
mi inlet mass, kg Ruminococcus albus. International Journal of Hydrogen Energy
mo outlet mass, kg
[4] Dincer I, Rosen MA. Exergy: energy, environment and
Po reference-environment pressure, kPa
sustainable development. Oxford, UK: Elsevier; 2007.
Q heat, kJ [5] Kelly-Yong TL, Lee KT, Mohamed AR, Bhatia S. Potential of
R universal gas constant, kJ/kmol K hydrogen from oil palm biomass as a source of renewable
S entropy, kJ/K energy worldwide. Energy Policy 2007;35:5692701.
4980 international journal of hydrogen energy 35 (2010) 49704980

[6] Midilli A, Dincer I. Key strategies of hydrogen energy systems [25] Simbeck DR. Hydrogen costs with CO2 capture. Presented at
for sustainability. International Journal of Hydrogen Energy 7th international conference on greenhouse gas control
2007;32(5):51124. technologies (GHGT-7). Vancouver, British Columbia,
[7] Milne TA, Elam CC, Evans RJ. Hydrogen from biomass: state Canada; September 610, 2004.
of the art and research challenges. Report No IEA/H2/TR-02/ [26] Szargut J, Morris DR, Steward FR. Exergy analysis of thermal,
001. Golden, CO, USA: National Renewable Energy chemical and metallurgical processes. New York:
Laboratory; 2002. Hemisphere; 1988.
[8] Luyben WL. Chemical reactor design and control. Hoboken, [27] Edgerton RH. Available energy and environmental
New Jersey: Wiley; 2007. economics. Toronto: D.C. Heath; 1982.
[9] Mahishi MR, Goswami DY. Thermodynamic optimization of [28] Ptasinski KJ, Prins MJ, Pierik A. Exergetic evaluation of
biomass gasifier for hydrogen production. International biomass gasification. Energy 2007;32:56874.
Journal of Hydrogen Energy 2007;32:383140. [29] Szargut J. Exergy method: technical and ecological
[10] Mahishi MR, Sadrameli MS, Vijayaraghavan S, Goswami DY. applications. Boston: WIT Press; 2005.
A novel approach to enhance the hydrogen yield of biomass [30] Berthiaume R, Bouchard C, Rosen MA. Exergetic evaluation
gasification using CO2 sorbent. Journal of Engineering for Gas of the renewability of a biofuel. Exergy International Journal
Turbines and Power 2008;130. paper 0115011. 2001;1:25668.
[11] Rosen MA. Thermodynamic investigation of hydrogen [31] Turpeinen E, Raudaskoski R, Pongracz E, Keiski RL.
production by steammethane reforming. International Thermodynamic analysis of conversion of
Journal of Hydrogen Energy 1999;16:20717. alternative hydrocarbon-based feedstocks to hydrogen.
[12] Simpson AP, Lutz AE. Exergy analysis of hydrogen International Journal of Hydrogen Energy 2003;33:
production via steam methane reforming. International 663543.
Journal of Hydrogen Energy 2007;32:481120. [32] Moran MJ. Availability analysis: a guide to efficient energy
[13] Toonssen R, Woudstra N, Verkooijen AHM. Exergy analysis use. New York: American Society of Mechanical Engineers;
of hydrogen production plants based on biomass 1989.
gasification. International Journal of Hydrogen Energy 2008; [33] Rosen MA, Scott DS. Comparative efficiency assessments for
33:407482. a range of hydrogen production processes. International
[14] Lutz AE, Bradshaw RW, Keller JO, Witmer DE. Thermodynamic Journal of Hydrogen Energy 1998;23:6539.
analysis of hydrogen production by steam reforming. [34] Rosen MA, Scott DS. A thermodynamic investigation of the
International Journal of Hydrogen Energy 2003;28:15967. potential for cogeneration for fuel cells. International Journal
[15] Handbook of heterogeneous catalysis. Weinheim, PA: VCH of Hydrogen Energy 1988;13:77582.
Verlagsgesellschaft Mbh; 1997. [35] Rosen MA. Thermodynamic comparison of coal-fired and
[16] Kotas TJ. The exergy method of thermal plant analysis. nuclear electrical generating stations. Transactions of the
Malabar, Florida: Kreiger; 1995. Canadian Society for Mechanical Engineering 2000;24(1B):
[17] Robinson PJ, Luyben WL. Simple dynamic gasifier model that 27383.
runs in Aspen dynamics. Industrial Engineering and [36] Higman C, Burgt VM. Gasification. Amsterdam: Elsevier; 2003.
Chemistry Research 2008;47:778492. [37] Lover KA. Biomass gasification integration in recuperative
[18] Nikoo MB, Mahinpey N. Simulation of biomass gasification in gas turbine cycles and recuperative fuel cell integrated gas
fluidized bed reactor using ASPEN PLUS. Biomass and turbine cycles. MSc thesis, Department of Energy and
Bioenergy 2008;32:124554. Process Engineering, Norwegian University of Science and
[19] Lu Y, Guo L, Zhang X, Yan Q. Thermodynamic modeling and Technology, Norway; 2007.
analysis of biomass gasification for hydrogen production in [38] Corradetti A, Desideri U. Should biomass be used for
supercritical water. Chemical Engineering Journal 2007;131: power generation or hydrogen production? ASME Journal
23344. of Engineering for Gas Turbines and Power 2007;129:
[20] Lei Y, Feng X, Min S. Parameters optimization of hydrogen 62934.
production from glucose gasified in supercritical water by [39] Li XT, Grace JR, Lim CJ, Watkinson AP, Chen HP, Kim JR.
equivalent cumulative exergy analysis. Applied Thermal Biomass gasification in a circulating fluidized bed. Biomass
Engineering 2007;27:232431. Bioenergy 2004;26:17193.
[21] Feng W, Van der Kooi HJ, Arons JS. Biomass conversions in [40] Spath P, Aden A, Eggeman T, Ringer M, Wallace B, Jechura J.
subcritical and supercritical water: driving force, phase Biomass to hydrogen production detailed design and
equilibria, and thermodynamic analysis. Chemical economics utilizing the BCL indirectly heated gasifier. Report
Engineering and Processing 2004;43:145967. No. TP-51037408. National Renewable Energy Laboratory;
[22] Penninger JML, Rep M. Reforming of aqueous wood pyrolysis 2005.
condensate in supercritical water. International Journal of [41] Babu SP. Biomass gasification for hydrogen production
Hydrogen Energy 2006;31:1597606. process description and research needs. Des Plaines, Illinois:
[23] Penninger JML, Maass GJJ, Rep M. Compressed hydrogen-rich Gas Technology Institute; 2002.
fuel gas (CHFG) from wet biomass by reforming in super [42] Rosen MA. Evaluation of energy utilization efficiency in
critical water. International Journal of Hydrogen Energy 2007; Canada using energy and exergy analyses. Energy
32:14726. International Journal 1992;17(4):33950.
[24] Antal Jr MJ, Allen SG, Schulman D, Xu X, Divilio RJ. Biomass [43] Miller GQ, Penner DW. Possibilities and challenges for
gasification in supercritical water. Industrial Engineering and a transition to a hydrogen economy. Chemical Engineering
Chemistry Research 2000;39:404453. Transactions 2004;4:518.