International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

www.elsevier.com/locate/ijhydene

Exergy analysis of hydrogen production via steam methane reforming

Adam P. Simpson a,∗ , Andrew E. Lutz b
a Department of Mechanical Engineering, Stanford University, Building 520, Stanford, CA 94403, USA
b Sandia National Laboratories, P.O. Box 969, MS-9053, Livermore, CA 94551-09069, USA

Received 1 November 2006; received in revised form 10 July 2007; accepted 13 August 2007
Available online 23 October 2007

Abstract
The performance of hydrogen production via steam methane reforming (SMR) is evaluated using exergy analysis, with emphasis on exergy
flows, destruction, waste, and efficiencies. A steam methane reformer model was developed using a chemical equilibrium model with detailed
heat integration. A base-case system was evaluated using operating parameters from published literature. Reformer operating parameters were
varied to illustrate their influence on system performance. The calculated thermal and exergy efficiencies of the base-case system are lower
than those reported in literature. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions and heat
transfer. A significant amount of exergy is wasted in the exhaust stream. The variation of reformer operating parameters illustrated an inverse
relationship between hydrogen yield and the amount of methane required by the system. The results of this investigation demonstrate the utility
of exergy analysis and provide guidance for where research and development in hydrogen production via SMR should be focused.
䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Exergy analysis; Hydrogen production; Steam methane reforming

1. Introduction The objective of this paper is to apply exergy analysis to

the production of hydrogen via natural gas SMR with em-
Hydrogen has been proposed and aggressively pursued over phasis on exergy flows, destruction, waste, and efficiency.
the past decade as a possible alternative fuel. Hydrogen is an Exergy analysis is a critical evaluation tool that provides
attractive energy carrier because it can be combusted, similar insight into a system beyond what first-law energy conser-
to gasoline and natural gas, or converted to electricity in a vation considers. Specifically, exergy analysis allows for the
fuel cell without any carbon emissions at the point of use. location, cause, and true magnitude of wastes and losses in
The major disadvantage is that hydrogen must be produced a system to be determined [2]. Such information can then
from other naturally occurring species—typically from fossil be used to make design improvements that optimize re-
hydrocarbons or water. source use.
Currently, 80–85% of the world’s total hydrogen produc- The analysis presented in this paper uses system compo-
tion is derived via steam methane reforming (SMR) of natural nent models, a chemical equilibrium reformer model, and
gas [1]. Most of the remaining hydrogen production is accom- detailed heat integration to perform exergy analysis. Exergy
plished via coal gasification and water electrolysis (at a smaller analysis of a base-case SMR system quantifies the perfor-
scale). Hydrogen production requires the investment of energy mance of the system and demonstrates the utility of exergy
and capital. Over the past several years hydrogen production analysis. Comparisons between the base-case performance
has become more efficient and less expensive, however it re- results and literature are made to illustrate the importance
mains energy intensive and costly when compared to gasoline of using a chemical equilibrium model with detailed heat
production. integration. Variations in the operating parameters illus-
trate the system’s performance sensitivity and provide guid-
∗ Corresponding author. ance for where research and development efforts should be
E-mail address: simpsona@stanford.edu (A.P. Simpson). concentrated.
0360-3199/$ - see front matter 䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.08.025
4812 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

2. SMR description 1 and 40 atm. A detailed overview of hydrogen membrane sep-

aration technologies is given in Adhikari and Fernando [3].
Fig. 1 shows a simplified diagram of a SMR system. SMR
is accomplished by first reacting methane and steam over a 3. Model description
high-temperature catalyst. The reaction is endothermic and typ-
ically achieved over a nickel-based catalyst operating at ele- The model developed for this investigation uses a library of
vated temperatures (900–1200 K) and pressures (5–25 bar). Due component models developed in Simulink [4]. The key com-
to the endothermic reaction, heat must be provided to the re- ponents of the developed model are the chemical equilibrium
former. Fig. 1 shows the heat coming from an external source. reformer, heat transfer blocks for detailed heat integration, the
In practice, the required heat is typically provided through com- expansion valve, and the hydrogen separation membrane. A di-
bustion of additional methane and/or from using the available agram of the model developed for this investigation is shown in
energy in the separated exhaust stream through combustion or Fig. 2. The purpose of this model is to investigate the steady-
simple heat exchange. The ideal global reformation reaction is state production of hydrogen via natural gas reforming; the
given in Eq. (1). The chemical composition of the syngas is model is not applicable to start-up operations.
determined by kinetics in a real reformer, but our model as- The hydrogen production process begins by compressing the
sumes fast enough kinetics to achieve chemical equilibrium. natural gas and pumping the inlet water to the reforming oper-
Depending on the steam-to-carbon ratio (S/C ratio) and the re- ating pressure. For simplicity the natural gas is represented by
former operating temperature and pressure, there may also be pure methane, CH4 . In practice, the natural gas must be desul-
significant amounts of CH4 , H2 O, and CO2 in the product gas furized before entering the reformer to avoid contamination
(syngas). of the catalyst, which requires additional work that is not ac-
counted for in this investigation. The pumped water is heated to
CH4 +H2 O(g)−→CO+3H2 HR =+251 MJ/kmolCH4 . (1) steam before entering the reformer and mixing with methane.
This heating is achieved through heat exchange with the shift
The syngas exiting the reformer is passed through a reactor (WGS-W/S HE), H2 cooling heat exchanger (W/S HE
water–gas shift (WGS) reactor that converts the CO in the 1), pre-shift heat exchanger (W/S HE 2), and exhaust stream
syngas to CO2 and H2 using the available H2 O in the syngas heat exchanger (W/S HE 3).
or additional H2 O to system. Although the shift reaction in The reformer model can be broken into three parts: (1)
Eq. (2) is exothermic, the net reaction of (1) and (2) is en- methane/steam mixing, (2) reformation, and (3) combustion of
dothermic. In practice, the shift reaction takes place over two the retentate/air/methane stream to provide heat for the refor-
reactors that operate between 473–673 K and 400–450 K. mation. The retentate stream is the gas that is not separated
in the hydrogen separation membrane. The mixing is modeled
as an adiabatic and constant pressure process with the mixed
CO+H2 O(g)−→CO2 +H2 HR =−41.2 MJ/kmolCO . (2)
stream entering the reformer at the reformer operating temper-
ature. The reforming model replaces the global reaction shown
The final step in SMR is the separation of the hydrogen from in Eq. (1) with a calculation of the chemical equilibrium com-
the syngas exiting the WGS reactor, which is mostly H2 , H2 O, position, which produces a more realistic estimate of the syn-
and CO2 . This separation process can be accomplished through gas composition. The equilibrium computation incorporates a
a number of techniques. The three most common methods are: temperature and pressure dependence, without requiring infor-
(1) pressure-swing-adsorption (PSA) to separate the H2 , (2) mation on the specific reactions, flow characteristics within
PSA to separate the CO2 followed by condensation of the re- the reformer, or catalyst material. It is assumed that the syn-
maining H2 O, and (3) a membrane to separate the H2 . Both gas exits the reformer at the reformer operating temperature
PSA separation techniques are relatively mature technologies and pressure. The heat required by the reformation is provided
that are energy intensive and provide various degrees of end by combustion of the retentate/air/methane stream (combus-
stream H2 purity (up to > 99%). Hydrogen membrane sepa- tion stream). Methane addition into the combustion stream is
ration is a promising and developing technology that is also only required when there is not enough energy available in the
capable of producing high end stream H2 purity (>99%). Metal- retentate stream to provide the total heat for the system. The
lic membranes operate at temperatures between 573–873 K reformer exhaust stream exits at the reformer operating tem-
and with a pressure difference across the membrane between perature and the environmental pressure.
Heat integration is an essential part of this investigation be-
cause the performance of a SMR system depends largely on the
Heat and Work amount of methane required by the system. The heat exchang-
ers are modeled using a prescribed effectiveness and minimum
CH4 H2
temperature difference between inlet and outlet streams. It is
Reformer Shift Reactor H2 Separation assumed that there are no pressure losses across the heat ex-
H 2O Exhaust changers. If a minimum temperature difference is not achieved
in any of the heat exchangers, methane is added to the com-
Fig. 1. Simplified schematic of SMR system. bustion stream in order to attain the prescribed temperature
 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820 4813

Fig. 2. Detailed schematic of SMR system. Dashed line represents system boundary.

difference. Any excess thermal energy in the exhaust stream 4. Operating parameters and evaluation methods
following all heat transfer is wasted.
The WGS reactor is modeled as a single stage shift reactor Table 1 provides a complete list of the base-case operating
that operates at constant temperature and pressure. The heat parameters. The reformer operating parameters are based on
produced during the WGS reaction is used to heat the pumped the operating parameters of a DOE demonstration SMR facility
water. The modeled WGS reactor only considers H2 , H2 O, CO, at the city of Las Vegas, NV [4,5]. The S/C ratio was adjusted
and CO2 , and the reaction is assumed to go to equilibrium. so that no additional methane was required in the combustion
Following the WGS reactor, the hydrogen-rich gas stream is stream. The WGS reactor operating temperature represents an
heated by the exhaust stream to the operating temperature of average between the high- and low-temperature shift reactors
the hydrogen separation membrane. reported in literature [6]. The membrane operating temperature
The hydrogen separation membrane is modeled as an isother- is an averaged metallic membrane temperature taken from Ad-
mal metallic membrane that produces a pure hydrogen stream hikari and Fernando [3]. The dead state chemical composition
(product stream) with a prescribed effectiveness. The mem- represents atmospheric air and gives liquid water zero chemi-
brane effectiveness is defined as the molar percentage of the cal exergy. More information on the treatment of liquid water
inlet hydrogen that is transferred to the product stream. The re- chemical exergy can be found in Szargut et al. [7], Moran [8],
tentate stream exits the membrane at the membrane operating and Bejan et al. [2].
temperature and pressure. The product stream exits the mem- The performance of a SMR system is traditionally evaluated
brane at the membrane operating temperature and the environ- by the thermal efficiency of the system. The thermal efficiency
mental pressure. To ensure that the prescribed effectiveness is of the system is based on a first-law energy balance and is
achieved, the pressure of the product side of the membrane is shown in Eq. (3).
adjusted (pumped down) such that the pressure of the pure hy-
drogen stream is less than the hydrogen partial pressure of the ṁH2 · LHVH2
Thermal = . (3)
retentate stream. The product stream exits the membrane (or ṁCH4 · LHVCH4 + ẆCompressor + ẆPump
compressor if necessary) and is cooled to the environmental
temperature through heat exchange with the pumped water be- Exergy analysis focuses on a system’s exergy flows, destruc-
fore exiting the SMR system. The retentate stream is expanded tion, waste, and efficiency. The steady-state exergy flows into
across a valve to the environmental pressure before being mixed and out of the system are defined in Eqs. (4) and (5), and the
with air and additional methane (if needed) for combustion in exergy destruction and un-used exergy are defined in Eqs. (6)
the reformer. and (7). For a steady-state system, the exergy destruction is the
4814 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

Table 1 delivered into the system. Given this definition and through
Base-case operating parameters manipulation of Eqs. (4) through (7), the exergy efficiency of
Dead state the system can be written in terms of the amount of un-used
T 298 K exergy and the amount of exergy into the system. Both forms
P 1 atm of the exergy efficiency definition are given in Eq. (8).
O2 20.34 mol%
N2 76.52 mol% Exergy
H2 O 3.103 mol%
CO2 0.0370 mol % ĖH2 ṁH2 · ĖH2
= =
Inlet fuel (CH4 ) ĖIn ṁCH4 · ĖCH4 + ẆCompressor + ẆPump
T 298 K
P 1 atm ĖUn-used
=1− . (8)
Inlet water ĖIn
T 298 K
P 1 atm Exergy analysis can be also applied to individual compo-
nents within the system. The exergetic performance of a com-
Inlet air
T 298 K
ponent is measured by the amount of exergy destroyed within
P 1 atm the component and its exergy efficiency. Component exergy de-
O2 20.34 mol% struction and exergy efficiency definitions are given for the kth
N2 76.52 mol% component in Eqs. (9) and (10).
H2 O 3.103 mol%
 
CO2 0.0370 mol % ĖDestruction,k = ĖIn,k − ĖOut,k , (9)
Reformer 
T 973 K ĖOut,k ĖDestruction
P 10 atm Exergy =  =1−  . (10)
S/C ratio 3.2 –
ĖIn,k ĖIn,k

Shift reactor 5. Base-case results and discussion

T 573 K
P 10 atm
Table 2 lists the global thermal and exergy efficiencies and
Membrane molar flow ratios of the SMR system operating with the base-
T 723 K
PH2 ,Permeate 1 atm
case parameters listed in Table 1. The thermal efficiency of
PRetentate 10 atm the system is in good agreement with the 68% thermal effi-
H2 purity 100 % ciency reported from the Las Vegas test site [5]. The exergy
Membrane 90 % efficiency is 4% less than the thermal efficiency of the system.
Other parameters This is due to the combined influence of hydrogen having a
s,Compressor 70 % smaller exergy content (116.69 MJ/kg) than its lower heating
s,Pump 85 % value (119.96 MJ/kg) and methane having a larger exergy con-
Heat exchange 90 % tent (51.72 MJ/kg) than its lower heating value (50.01 MJ/kg).
THE−Inlet/Outlet 5 K
Combustor 0.97 –
Note that Eq. (8) takes on the same form as Eq. (3), except
with exergy substituted for lower heating value.
Table 3 lists the global exergy flows of the SMR system. The
third column of Table 3 breaks-down the global exergy flows
difference between the total amount of exergy into and out of by their percentage of the total exergy into the system; Fig. 3
the system. The destroyed exergy measures the lost available displays these percentages graphically. The compression and
energy that is unrecoverable. The un-used exergy of the sys- pump work represent a small fraction of total exergy into the
tem is defined as the sum of the amount of exergy destroyed system. Methane is the dominant exergy input. The majority of
within the system and the amount of exergy wasted in the ex- the exergy out of the system is carried by the hydrogen. The un-
haust stream. The exergy of the exhaust stream is theoretically used exergy is mostly destroyed exergy, due to irreversibilities
recoverable. within the system.
The total exergy destroyed within the system is calculated
ĖIn = ĖCH4 + ẆCompressor + ẆPump , (4)
by either Eq. (6) or by summing all the individual component
ĖOut = ĖH2 + ĖExhaust , (5) irreversibilities, which are calculated by Eq. (9). Table 4 lists
the exergetic performance of each component within the SMR
ĖDestruction = ĖIn − ĖOut , (6) system operating with the base-case parameters. The third col-
umn breaks-down the component exergy destructions by their
ĖUn-used = ĖDestruction + ĖExhaust . (7)
percentage of the total exergy destruction. The majority of the
The exergy efficiency of a SMR system is defined as the ratio exergy destruction occurs in the reformer, mostly due to the
of exergy recovered in the hydrogen stream to the total exergy high irreversibility of combustion, and in the water-to-steam
 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820 4815

Table 2 pump exergy efficiency is the result of defining water to have a

Base-case global efficiencies and flow ratios zero exergy content at the environmental temperature and pres-
Efficiencies sure. When Eq. (10) is used to evaluate the pump, it reduces
Thermal 66.65 % to the exergy out of the pump divided by the work into the
Exergy 62.69 % pump. The change in the exergy of the water through the pump
Molar flow ratios is mostly due to its increase in enthalpy (its increase in entropy
H2 produced 2.25 mol/molCH4 is small), which results in the pumps exergy efficiency being
Air combustor 4.43 mol/molCH4 approximately equal to its isentropic efficiency.
CH4 added 0.0 mol/molCH4 The exergy efficiency of the system, as defined in Eq. (8),
can be evaluated as a function of the un-used exergy within
the system. Fig. 4 illustrates the un-used exergy break-down
Table 3 by component as a percentage of the total un-used exergy. Of
Base-case global exergy flows the total un-used exergy, 81% is destroyed within the system
Exergy (kJ/molCH4 ) Percent of total EIn (%) and 19% is wasted in the exhaust stream. Strictly first-law
Exergy in 845.34 100.00
analysis of the SMR system would lead to the misconception
ECH4 829.76 98.16 that most of the energy is wasted in the exhaust stream. The
Wfuel compressor 10.55 1.25 un-used exergy break-down illustrates the utility of exergy anal-
Wpump 0.06 0.01 ysis. A design engineer could use these results to make de-
Wmembrane comp 4.97 0.59 sign improvements that could decrease the amount of un-used
Exergy out 589.60 69.75
E H2 530.02 62.70
exergy.
EExhaust 59.58 7.05 The majority of the exergy destruction occurs in the reformer.
Exergy destroyed 255.74 30.25 To examine possible approaches for reducing the amount of ex-
Exergy un-used 315.32 37.31 ergy destroyed within the reformer, the reformer model needs
to be broken-down into its components: fuel/steam mixer, ref-
ormation/heat transfer, and combustion. The exergy destroyed
in the fuel/steam mixer is unavoidable and is already minimized
in this model because it is assumed to occur adiabatically and
at constant pressure. To reduce the amount of exergy destroyed
in the reformation/heat transfer process, the temperature of the
heat source (combustion product gases) and the reformation
temperature could be better matched. This could be achieved by
diluting the combustion stream with excess air. This, however,
increases the amount of exergy destroyed in the combustor and
decreases the amount of available energy in the exhaust stream
that can be used to produce steam for the reformer. The amount
of exergy destroyed in the combustor can be reduced by op-
erating with less excess air (closer to a stoichiometric amount
of air). However, operating with less excess air increases the
temperature of the product gases, which increases the amount
of exergy destroyed in the reformation/heat transfer process.
Fig. 3. Distribution of exergy flows into and out of the modeled SMR system. There is therefore a trade-off between the amount of excess air
in the combustion stream and the amount of exergy destroyed in
the reformation/heat transfer and combustion processes. Vary-
heat exchangers. The membrane heat exchanger, membrane, ing the excess air in the model shows that operating with less
and shift reactor contribute a small percentage to the total ex- excess air reduces the total amount of exergy destroyed in the
ergy destruction. reformer. This is because the decrease in the amount of ex-
The fourth column in Table 4 lists each component’s indi- ergy destroyed in the combustor is greater than the increase in
vidual exergy efficiency calculated using Eq. (7). With the ex- the amount of exergy destroyed in the reformation/heat trans-
ception of the combustor, third water-to-steam heat exchanger, fer process. Furthermore, operating with less excess air also
and pump, the exergy efficiency of each component is high. reduces the amount of exergy destroyed in the retentate/air/fuel
The relatively low combustor efficiency of 76.3% is typical of mixer.
combustors due to the large amount of entropy produced dur- Following the reformer, the next largest destroyers of exergy
ing uncontrolled chemical reactions, in accordance with pub- are the heat exchangers, expansion valve, and retentate/air/fuel
lished data [6,10]. The third water-to-steam heat exchanger has mixer. Heat exchangers inherently destroy exergy due to heat
the worst heat exchange component efficiency due to the large transfer across a finite temperature difference. To minimize
temperature difference between the inlet and outlet water/steam the exergy destruction within a heat exchanger, the tempera-
stream and the reformer combustion exhaust stream. The low ture differences between the two streams should be as small
4816 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

Table 4
Exergy destruction break-down by component

Exergy destroyed (kJ/molCH4 ) Percent of total ED (%) Component Exergy (%)

Pump 0.01 0.00 85.05

Compressor 1.84 0.72 99.78
Water/Steam HE 60.13 23.51 –
W/S HE 1 6.69 2.62 98.77
W/S HE 2 23.69 9.26 97.68
W/S HE 3 29.76 11.64 84.57
Reformer 134.97 52.78 89.90
M/S mixing 8.70 3.40 99.08
Reformation 33.31 13.03 97.30
Combustion 92.95 36.35 76.28
Membrane HE 8.87 3.47 99.23
Membrane separation 7.65 2.99 99.22
Shift-W/S HE 4.99 1.95 99.48
Expansion valve 18.30 7.16 95.74
R/A/M Mixer 18.98 7.42 95.38

Total exergy destroyed 255.74

In Fig. 4, the exergy of the exhaust is separated into

two forms: thermo-mechanical (T-M) and chemical. The
T-M exergy associated with the exhaust stream is due to
the temperature being higher than the environmental tem-
perature. A portion of the T-M exergy could be transformed
into work by adding a bottoming cycle to the system. If all
of the T-M exergy was recovered from the exhaust stream,
the system exergy efficiency would increase from 62.7
to 66.2%.
The chemical exergy of the exhaust stream is the amount
of work that could be extracted from the stream if it was
brought into chemical equilibrium with the environment. Al-
though the exhaust stream is in equilibrium with itself and
comprised of stable species, the extraction of its chemical ex-
ergy is difficult, if not impossible. Theoretically, a reactor could
be used that would produce only environmental species while
extracting work. Each specie would then need to be brought
to its environmental concentrations (partial pressures). This
Fig. 4. Un-used exergy break-down. Total un-used exergy = 315.32 kJ/
could theoretically be achieved through a series of species-
molCH4 . specific membranes that would diffuse each species to its en-
vironmental partial pressure while extracting diffusive work. If
both the T-M and chemical exergy of the exhaust stream were
as possible. Heat exchangers could be integrated into the utilized, the exergy efficiency of the system would increase
SMR system to better match the inlet and outlet tempera- to 69.7%.
tures of the streams. In place of an expansion valve, a turbine The thermal and exergy efficiencies presented in this pa-
could be used to extract work, which could then be used per are lower than those given in the limited number of other
to provide power for the fuel compressor and water pump. thermodynamic SMR analysis papers. Table 5 summarizes the
Adiabatic stream mixing is highly irreversible, resulting in thermal and exergy efficiencies of SMR systems reported in lit-
exergy destruction. The retentate/air/fuel mixer destroys more erature. The variance in reported thermal and exergy efficiencies
exergy than through the entropy production of mixing alone be- can be attributed to a number of differences between the models
cause the inlet retentate stream enters the mixer at an elevated and their operating parameters. The present paper is unique for
temperature (the membrane operating temperature), which re- combining an equilibrium reformer model with detailed heat
sults in further exergy destruction due to heat transfer. This integration. The implementation of an equilibrium reformer
could be remedied by matching the temperatures of the two with detailed heat exchange significantly influences the perfor-
streams more closely. These design recommendations based mance of a SMR model through the amount of hydrogen pro-
on exergy analysis would not be identified by first-law analysis duced and the amount of additional methane required in the
alone. combustor.
 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820 4817

Table 5
Comparisons of SMR thermal and exergy efficiencies from literature

Author Reference Number Thermal (%) Exergy (%) Notes

Rosen [6] 86 78.5 Detailed system analysis with heat-integration. Uses global
reformation model with PSA CO2 separation and metha-
nation
Lambert et al. [11] – 76.62a Purpose of paper was to analyze SMR with oxygen enriched
combustion. Uses equilibrium reformer model. Separation
method is not described
Sorin et al. [12] – 79.88 Only analyzes natural gas reformation to syngas. Reforma-
tion heat is provided by combustion of extra fuel
Simbeck [1] 65.3, 76.2 – Purpose of paper was to determine hydrogen production
costs. Details of SMR were not described
Lutz et al. [9] 89b , 81c – First law based analysis. Analyzes both a global and equi-
librium reformer. Reformer heat is provided by combus-
tion of retentate stream exiting membrane. Does not use
detailed heat-integration
Bargigli et al. [13] 77d 71d Purpose of paper was to use a multi-criteria approach to
compare hydrogen production pathways through energy,
exergy, and emergy analysis
a Uses slightly different exergy efficiency definition.
b Maximum thermal efficiency using global reaction model going to equilibrium.
c Maximum thermal efficiency using equilibrium reformer model.
d Values taken from National Renewable Laboratory report.

S/CRatio = 3.2, P reform = 10 atm, S/CRatio = 3.2, P reform = 10 atm,

T shift = 573 K,T membrane = 723 K,EQ Ratio =0.97. T shift = 573 K,T membrane = 723 K,EQ Ratio =0.97.
70 2000
Thermal Efficiency Exergy In
Exergy (kW /reformer mole CH4)

Exergy Efficiency 1800 Exergy Out

65
H2 Exergy
1600
Exhaust Exergy
60 1400 Destroyed Exergy
Efficiency (%)

Un-Used Exergy
55 1200
1000
50
800
45 600
400
40
200
35 0
850 900 950 1000 1050 1100 1150 1200 1250 1300 850 900 950 1000 1050 1100 1150 1200 1250 1300
Reformer Temperature (K) Reformer Temperature (K)

Fig. 5. Influence of reformer operating temperature on system efficiencies and global exergy flows.

6. Parametric study results at 974 K. The behavior of the efficiency curves can be explained
through evaluation of the global exergy flows. As the reformer
This section examines the influence that the reformer oper- temperature increases, the amount of hydrogen produced in-
ating temperature, pressure, and S/C ratio has on system effi- creases until it plateaus at approximately 1175 K. This behav-
ciencies and global exergy flows. The global exergy flows are ior is consistent Le Chatelier’s Principle, which states that if a
measured in units of kW per mole of methane into the reformer dynamic equilibrium is disturbed by changing the conditions,
as opposed to per mole of total methane required (reformer the position of equilibrium moves to counteract the change.
methane plus combustor methane). The results were calculated Since the global reaction is endothermic, higher temperature
by varying one operating parameter while holding all other pa- shifts the equilibrium position towards the products in order
rameters constant at their base-case values. to absorb more heat. The increase in hydrogen production in-
Fig. 5 illustrates the effects that the reformer temperature has creases the system efficiencies. However, at temperatures above
on system efficiencies and global exergy flows. The thermal 974 K, additional methane is required by the system to make
and exergy efficiencies of the system reach maximum values of up for the decreased heating value of the reformate stream. As
66.67% and 62.73%, respectively, when the reformer operates the reformer temperature increases above 974 K, the amount of
4818 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

S/CRatio =3.5, P reform= 10atm, additional methane increases at a faster rate than the amount
T shift= 573 K,Tmembrane =523K, EQRatio = 1.0. of hydrogen produced, which decreases the efficiency of the
100 system. This effect was not shown in Lutz et al. [9], because
ThermalEfficiency - Present Study
90 Thermal Efficiency-Lutz el al. the heat integration in their model did not include a prescribed
80 heat exchanger effectiveness or minimum inlet/outlet stream
temperature difference.
70
Fig. 6 compares the parametric thermal efficiency re-
Efficiency (%)

60 sults presented by Lutz et al. [9] to the present results. The

50 thermal efficiency results presented by Lutz et al. [9] were
40 calculated operating with a reformer pressure of 10 atm, a S/C
ratio of 3.5, an equivalence ratio of 1.0, and a membrane and
30
WGS temperature of 573 K. The operating parameters for the
20 model developed in this study were adjusted to match those
10 used in Lutz et al. [9]. The two efficiency curves exhibit the
0 same behavior until 975 K. The horizontal shift in thermal effi-
750 800 850 900 950 1000 1050 1100 1150 1200 ciencies reported by Lutz et al. [9] is due to the difference be-
Reformer Temperature (K) tween the designs of the two models. The departure of the two
Fig. 6. Comparison between the results presented by Lutz et al. [9] and the curves above 975 K illustrates the effects of using detailed heat
present paper. integration.

S/C Ratio = 3.2,T reform=973 atm, S/C Ratio = 3.2,T reform = 973 atm,
T shift = 573 K,T membrane = 723 K,EQ Ratio = 0.97. T shift = 573 K,T membrane = 723 K,EQ Ratio = 0.97.
70 2000 Exergy In
Thermal Efficiency
Exergy (kW /reformer mole CH4)

Exergy Out
Exergy Efficiency 1800 H2 Exergy
65 1600 Exhaust Exergy
Destroyed Exergy
1400
Efficiency (%)

Un-Used Exergy
60 1200 Fuel Comp Power
Mem Comp Power
1000 Methane Exergy In
55 800
600
50 400
200
45 0
2 4 6 8 10 12 14 16 18 20 22 2 4 6 8 10 12 14 16 18 20 22
Reformer Pressure (atm) Reformer Pressure (atm)

Fig. 7. Influence of reformer operating pressure on system efficiencies and global exergy flows.

T reform = 973 K, P reform = 10 atm, T reform = 973 K, P reform = 10 atm,

Tshift = 573 K, T membrane = 723 K, EQ Ratio = 0.97. Tshift = 573 K, T membrane = 723 K, EQ Ratio = 0.97.

68 1600
Exergy In
Exergy (kW /reformer mole CH4)

66 1400 Exergy Out

64 H2 Exergy
1200 Exhaust Exergy
62 Destroyed Exergy
Efficiency (%)

60 1000 Un-Used Exergy

Thermal Efficiency
58 Exergy Efficiency
800
56 600
54
400
52
50 200

48 0
2 2.5 3 3.5 4 4.5 5 5.5 6 2 2.5 3 3.5 4 4.5 5 5.5 6
Steam to Carbon Ratio Steam to Carbon Ratio

Fig. 8. Influence of reformer steam-to-carbon ratio on system efficiencies and global exergy flows.
 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820 4819

S/C Ratio = 3.2, T reform = 973K, P reform = 10 atm, S/C Ratio = 3.2, T reform = 973K, P reform = 10 atm,
T membrane = 723 K,EQ Ratio =0.97. T membrane = 723 K,EQ Ratio =0.97.
68 1400 Exergy In
Exergy Out

Exergy (kW /reformer mole CH4)

67
1200 H2 Exergy

66 Exhaust Exergy
1000 Destroyed Exergy
65 Un-Used Exergy
Efficiency (%)

64 800

63 600
62
400
61
Thermal Efficiency 200
60 Exergy Efficiency
59 0
480 500 520 540 560 580 600 620 640 660 680 480 500 520 540 560 580 600 620 640 660 680
Shift Temperature (K) Shift Temperature (K)

Fig. 9. Influence of shift temperature on system efficiencies and global exergy flows.

The influence that reformer operating pressure has on sys- The influence that the WGS temperature has on system effi-
tem efficiencies and global exergy flows is shown in Fig. 7. ciencies and global exergy flows is shown in Fig. 9. The ther-
The thermal and exergy efficiencies reach maximum values mal and exergy efficiencies reach maximum values of 66.66%
of 66.81% and 62.85%, respectively, when the reformer op- and 62.70%, respectively, when the WGS takes place at 572 K.
erates at 6.8 atm. As the pressure decreases below 6.8 atm, At temperatures below 572 K, the efficiencies decrease with
the equilibrium syngas composition shifts to higher hydrogen temperature because the system’s requirement for additional
concentrations and the required fuel compressor and pump methane is greater than the increase in hydrogen yield. At tem-
power decreases. These effects are out-weighed by the addi- peratures above 572 K, the system no longer requires addi-
tional methane and membrane compressor power required at tional methane and the decreases in system efficiencies are due
lower pressures. Together, these effects lead to a slight decrease to the decrease in hydrogen yield. The decrease in hydrogen
in thermal and exergy efficiency as the pressure is decreased yield with increasing temperature is consistent with Le Chate-
below 6.8 atm. As the pressure increases from 6.8 to 9.9 atm, lier’s Principle—the WGS reaction, Eq. (2), is exothermic and
the efficiencies only decrease by approximately a half of a per- at higher temperatures the equilibrium shifts to reactants to
cent due to the trade-off between hydrogen yield, compression absorb more heat.
(fuel and membrane) and pumping power, and the amount of
additional methane required by the system. At pressures above 7. Conclusion
9.9 atm, the system no longer requires additional methane. As
the pressure increases above 10 atm, the relatively sharp de- This investigation uses exergy analysis to evaluate the per-
crease in system efficiency is due to the decrease in hydro- formance of hydrogen production via SMR. The key compo-
gen yield. The shift in syngas equilibrium composition with nents of the SMR model are a chemical equilibrium reformer
pressure is consistent with Le Chatelier’s Principle. Since the model, an expansion valve, a hydrogen separation membrane,
global reformation reaction increases the total number of moles, and heat transfer components for detailed heat integration. The
as the reformer pressure increases, equilibrium shifts towards global thermal and exergy efficiencies of the base-case system
reactants (less hydrogen). are 66.7% and 62.7%, respectively. The majority of the exergy
Fig. 8 illustrates the effects that reformer S/C ratio has on destruction occurs within the reformer, mostly due to the high
system efficiencies and global exergy flows. The thermal and irreversibility of combustion and heat transfer, and in the water-
exergy efficiencies of the system increase significantly with the to-steam heat exchangers. Of the 37.3% of exergy not utilized
S/C ratio until approximately 3.2, because excess water shifts within the system (un-used exergy), 81% is destroyed within
the equilibrium towards products. At S/C ratios above 3.2, the the system and 19% exits in the exhaust stream.
efficiencies increase only slightly with excess steam because The variation of reformer operating parameters demonstrates
additional methane is required, which counter-balances the in- the importance of using a chemical equilibrium model and de-
creased hydrogen yield. There is an optimum S/C ratio above tailed heat integration. The model identifies optimal conditions
3.2 and before the additional methane required begins to reduce for temperature and S/C ratio. In general, the optimal effi-
the system’s efficiencies; however, the profile is relatively flat ciency maximizes hydrogen yield without requiring additional
and would be hard to identify in practice. The thermal and ex- methane for combustion. This occurs at approximately 974 K
ergy efficiencies reach maximum values of 66.97% and 63.00%, for the nominal conditions. The efficiency increases with ex-
respectively, when operating with a reformer S/C ratio of 4.1. cess steam, but the benefit is marginal above a steam-to-carbon
4820 A.P. Simpson, A.E. Lutz / International Journal of Hydrogen Energy 32 (2007) 4811 – 4820

ratio of 3.2. The equilibrium model is less useful in determin- [4] Lutz A. IV.C.2 Power parks system simulation. DOE Hydrogen Program;
ing the optimal reformer operating pressure because kinetics 2004 Progress Report.
limit real reformer operating pressures. However the equilib- [5] Wait MF. R&D of a PEM fuel cell, hydrogen reformer, and vehicle
refueling facility (Las Vegas Energy Park). Presented at the 2005
rium model does show that system efficiencies significantly hydrogen and fuel cells merit review meeting, Washington, DC, May;
decrease at pressures above 10 atm due to decreased hydrogen 2005.
yield. [6] Rosen MA. Thermodynamic investigation of hydrogen production
Exergy analysis provides insight into the performance of by steam-methane reformation. Int J Hydrogen Energy 1991;16(3):
the modeled SMR system that would elude purely first-law 207–17.
[7] Szargut J, Morris DR, Steward FR. Exergy analysis of thermal, chemical,
analysis. Research and development efforts should be fo- and metallurgical processes. New York, NY: Hemisphere; 1998.
cused on reducing exergy destruction within the reformer [8] Moran MJ. Availability analysis: a guide to efficient energy use. New
and heat exchangers, as well as utilizing the exhaust stream York, NY: ASME Press; 1989.
exergy. [9] Lutz A, Bradshaw R, Keller J, Witmer D. Thermodynamic analysis
of hydrogen production by steam reforming. Int J Hydrogen Energy
2003;28:159–67.
References [10] Brzustowski TA. Toward a second-law taxonomy of combustion
processes. Energy 1980;5:743–56.
[1] Simbeck DR. Hydrogen costs with CO2 capture. Presented at the 7th [11] Lambert J, Sorin M, Paris J. Analysis of oxygen-enriched combustion
international conference on greenhouse gas control technologies (GHGT- for steam methane reforming SMR. Energy 1997;22(8):817–25.
7), Vancouver, British Columbia, Canada, September 6–10; 2004. [12] Sorin M, Lambert J, Paris J. Exergy flows analysis in chemical reactors.
[2] Bejan A, Tsatsaronis G, Moran M. Thermal design and optimization. Trans IChemE 1998;76(A).
New York, NY: Wiley; 1996. [13] Bargigli S, Raugei M, Ulgiati S. Comparison of thermodynamic and
[3] Adhikari S, Fernando S. Hydrogen membrane separation techniques. Ind environmental indexes of natural gas, syngas and hydrogen production
Eng Chem Res 2006;45:875–81. processes. Energy 2004;29:2145–59.