chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

A modified process for overcoming the drawbacks

of conventional steam methane reforming for
hydrogen production: Thermodynamic
investigation

Lin Zhu, Luling Li, Junming Fan ∗

Key Laboratory of Gas Process Engineering, School of Chemistry and Chemical Engineering, Southwest Petroleum
University, Chengdu 610500, Sichuan Province, China

a r t i c l e i n f o a b s t r a c t

Article history: In this novel work, application of CaO sorption enhanced steam methane reforming (SESMR)
Received 14 June 2015 for promoting hydrogen production thermally coupled with chemical looping combustion
Received in revised form 26 August (CLC) instead of furnace for CO2 capture has been investigated to modify the conventional
2015 SMR process. In this novel process, CLC is employed to provide the necessary heat for SESMR,
Accepted 14 October 2015 simultaneously achieving inherent separation of CO2 without extra energy consumed. This
Available online 23 October 2015 unprecedented technique was developed and calculated using Aspen Plus and it has been
found to be favored by operating under conditions of stem to methane ratio (S/C) = 4, CaO
Keywords: to methane ratio (Ca/C) = 1 and reforming pressure of 25 bar. The competitiveness of this
Steam methane reforming novel configuration shows excellent advantages against dominant industrial SMR process
Hydrogen production including promoting H2 purity of product gas to be 92.6% without extra process to separate
Chemical looping combustion impurities from product gas, simultaneously decreasing CO and CO2 concentrations from
Simulation 0.2% and 2.4% to ppm level. The overall energy efficiency of SMR and this suggested pro-
Enhanced reforming CaO cess is calculated equal to 68.02% and 85.50%, respectively; approximately 17.48% of energy
Thermodynamic efficiency is benefited from this novel process. The heat load analysis for reforming pro-
cess suggests that the Ca-based sorption enhanced steam reforming process can achieve
autothermal operation.
© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction CO + H2 O → CO2 + H2 H298 = −41.1 kJ/mol (3)

Steam methane reforming (SMR) is the dominant process for
the industrial hydrogen production over the past decades. The
three main reactions that occur during SMR process are rep-
resented by the following equations (Dittmar et al., 2013):
CH4 + H2 O → CO + 3H2 H298 = 206.2 kJ/mol
CH4 + 2H2 O → CO2 + 4H2 H298 = 164.9 kJ/mol
The reforming reactions (1) and (2) are highly endothermic,
therefore a large amount of heat should be provided by com-
bustion of extra methane in furnace. The conventional type
of reactor adopted in SMR process is a shell and tube type
reactor (Rahimpour et al., 2013), as shown in Fig. 1. In tube,
SMR process takes place under Ni-based catalyst. The shell
(1)
side, where supplemental methane burns, acts as a furnace
providing the necessary heat for SMR process. The reformer
(2) gas produced from reforming process mainly consists of H2

∗
Corresponding author at: Xinndu Avenue 8#, Xindu District, Chengdu City 610500, Sichuan, China. Fax: +86 28 83037323.
E-mail address: junmingfan@hotmail.com (J. Fan).
http://dx.doi.org/10.1016/j.cherd.2015.10.022
0263-8762/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806 793

CH +Steam

Nomenclature

AR air reactor Air+CH

Ca/C the molar ratio of CaO sorbents to methane fed

to reformer
CC CO2 capture
CCS carbon dioxide capture and storage
CLC chemical looping combustion Ni-based
catalyst
En the energy
Ex the exergy
FR fuel reactor
H the enthalpy flow of a material stream
Me metal
MeO metal oxide
Flue gas
n the molar flow rate
Ni/C the molar ratio of NiO to methane fed to
reformer Reformer gas

NiO/C (fuel) the molar ratio of NiO carriers to methane

as fuel fed to FR Fig. 1 – Schematic diagram of conventional SMR process.
S the entropy flow of a material stream
S/C the molar ratio of steam to methane fed to
reformer
Reduced
SMR steam methane reforming CO2+H2O
air
SESMR sorption enhanced steam methane reforming
T temperature in Kelvin
MeO
P pressure in bar
PR-BM Peng Robinson cubic equation of state with
Boston–Mathias alpha function
Fuel Reactor,FR
Q heat CnHm+(2n+m/2)MeO=
Air Reactor,AR
O2+2Me=2MeO
WGS water gas shift (2n+m/2)Me+m/2H2O+nCO2
x the mole fraction of liquid phase
y the mole fraction of vapor phase
H the enthalpy change, kJ/mol Me
S the entropy change

Greek symbols CnHm Air

˛M Methane conversion
 The energy efficiency Fig. 2 – Schematic diagram of chemical looping combustion
ϕ The exergy efficiency (CLC).

Superscripts separate it from flue gas for reducing greenhouse effect,

0L the liquid phase which is the most expensive and complicated step during
0V the vapor phase the overall hydrogen production process. Anheden et al.
demonstrated that the system energy efficiency would
Subscripts decrease 6%–10% when CO2 capture process was involved
0 the environmental situation in the traditional SMR technique (Anheden and Svedberg,
i the component i 1998).
r the reference environment (2) Because H2 purity in reformer gas is not high, additional
ch the chemical operations, like purification, separation and compression,
in inlet would be used to get high purity of H2 , further causing
mix the mixture additional amounts of energy penalty (Zhu et al., 2015).
out outlet
ph the physical
In relation to the problem (1), various techniques for carbon
dioxide capture and storage (CCS), such as pre-combustion,
oxy-fuel and post-combustion, are used to capture CO2 from
(usually, H2 purity <80% (Barelli et al., 2008)), and the flue gas combustion flue gas (Zhu et al., 2015). However, as mentioned
generated from methane combustion is composed by various above, due to high energy penalty as well as expensive equip-
components, such as CO, CO2 , N2 , NOx , H2 O, etc. ment, CO2 conversion in these methods has not high energy
During the industrial operation of SMR process, two major efficiency (Zhu and Fan, 2015). Chemical looping combustion
problems should be highlighted: (CLC) is a novel technology of burning fuels with inherent
separation of CO2 beyond extra energy consumed. As shown
(1) Because of high emission of CO2 , from the environmen- schematically in Fig. 2, CLC is composed of two interconnected
tal perspectives, several techniques should be adopted to fluidized reactors, i.e. a fuel reactor (FR) and an air reactor
794 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806
(AR) (Hong et al., 2006; Zhang et al., 2014a). And a kind of
metal oxide carriers is circulating between AR and FR. The
CLC process involves two steps, i.e., the reduction step and
the oxidation step. In the reduction step, fuel (Cn Hm ) reacts
with a metal oxide carrier. As a result, the metal oxide (MeO)
is reduced to metal (Me) while fuel is completely oxidized to
CO2 and H2 O. In the oxidation step, the reduced metal oxide
(Me) is reoxidized by air, producing heat and reduced air. In
CLC process, the flue gas from FR is never diluted with N2 , and
after water condensation, pure CO2 can be obtained, avoiding
the energy intensive CO2 separation step (Zhang et al., 2014b).
For CLC process, the conventional fuel combustion is
divided into two subreactions, with each being typically car-
ried out in separate reactor, so the heat released from CLC is
theoretically equal to conventional fuel combustion (Lyngfelt,
2014). Furthermore, CLC is also capable of minimizing the for-
mation of NOx due to the indirect contact of fuel and air.
The partial aim of this work is the improvement of con-
ventional SMR technique by considering the conventional
furnace is replaced by using CLC technology, in other words,
the necessary heat for SMR process is provided by CLC rather
than conventional methane-air direct combustion. Therefore,
a possible route for solving the first problem (i.e. eliminating
the energy penalty on CO2 capture from combustion flue gas)
was presented.
Meanwhile, research efforts on promoting H2 purity in
reformer gas have been targeted to two options including
selective permeation through a membrane to separate H2 and
sorption enhanced steam methane reforming (SESMR) as CO2
acceptor, which can be easily understood by applying the Le
Chatelier’s principle, removing either H2 or CO2 benefits H2
purity. However, in comparison to membrane technology, sev-
eral benefits can be obtained from SESMR such as:
(1) Lower operating temperature (673–923 K) can obtain high
purity of H2 (>90%).
(2) A wide range of pressure is adaptable to get high purity of
H2 .
(3) The unfavorable side reaction is minimized.
(4) The capital cost is lower.
Therefore, the concept of SESMR was investigated quite
intensively in recent year. Among the most possible candi-
dates as CO2 acceptor, Ca-based sorption is a predominant
absorbing material for in situ CO2 separation, owing to it is
easy to find, inexpensive and large adsorption ability. In the
case of employing Ca-based sorption, the non-catalytic highly
exothermic carbonation reaction is included in SESMR:
CaO(s) + CO2 (g) → CaCO3 (s) H298 = −178 kJ/mol (4)
The carbonation reaction is strongly exothermic which can
provide in situ energy to the highly endothermic reforming
reaction (Antzara et al., 2015) in that the combined reactions
(1), (3) and (4) are almost thermally neutral, so that no supple-
mental energy is required to heat the reformer.
Because CaO sorbents are effectively consumed in the
reactor, the process is inherently cyclic in operation, requir-
ing sorbents regeneration by calcining CaCO3 . Reaction (5) is
highly endothermic, so large amounts of energy is required
to reach the calcination temperatures which equilibrium
demands (>1173 K, in pure CO2 barosphere, at 1 bar).
CaCO3 → CO2 + CaO H298 = 178 kJ/mol (5)
The concept of Ca-based SESMR process for H2 production
is not new, and its effects have been previously demon-
strated. Deuk et al. developed a mathematical model for steam
methane reforming enhanced by in situ CO2 removal for H2
production (Lee et al., 2004). In another related work in 2012,
Fernandez built a dynamic model to describe the SESMR oper-
ation in the packed bed reactor, observing a high H2 purity
(95%) and 85% of CH4 conversion at high operating pressure,
high steam to methane ratio (S/C) and moderate operating
temperature (Fernandez et al., 2012b). In Tzanetis’s work, the
comparative exergy analysis between sorption enhanced and
conventional steam methane reforming was conducted, and
the advanced sorption enhanced reforming could superiorly
lead to a hydrogen purity increase by 17.3%, simultaneously
the exergy benefit of sorption enhanced reforming was cal-
culated to be 3.2% compared with conventional reforming for
hydrogen production (Tzanetis et al., 2012).
An inherent drawback of the sorption enhanced steam
methane reforming is that the CaO sorbents regeneration
step is highly endothermic, requiring large amounts of energy
to supply the necessary heat for calcination of CaCO3 , and
most publications related to Ca-based SESMR concept do not
mention how to solve the regeneration problem in practice.
Nevertheless, few researchers focused on this issue. Chevron
developed a process of using high temperature combustion
gases to provide the necessary heat for CaCO3 calcination in
calcinator (Stevens et al., 2007). However, due to the dilution
of the outlet flue gas, an additional large amount of energy
should be supplied to separate CO2 from flue gas. Meanwhile,
with this approach, the overall energy efficiency trends to
be decreased because of huge energy consumption required
to capture CO2 . Fernandez designed a novel Ca/Cu chem-
ical looping process by employing CaO sorbents enhanced
reforming integrated with chemical looping combustion pro-
cess. The CaO sorbents as CO2 acceptor were used to promote
H2 purity and the exothermic reduction of CuO to Cu was con-
ducted as the heat resource to calcine CaCO3 in the cyclic
three-step chemical looping process for hydrogen produc-
tion (Fernandez et al., 2012a). In another associated work,
Martínez presented a novel Ca/Cu/Ni chemical looping pro-
cess for hydrogen production, similar to the aforementioned
Ca/Cu process, this suggested process was carried out in the
oxidation-reforming-calcination three-stage reactors. In this
process, the Ni sorbents employed as catalyst in the reform-
ing stage, and during the regeneration stage, air was passed
through to oxidize the reduced metal (oxidation of Ni and Cu to
NiO and CuO, respectively), and the heat released in the oxida-
tion reaction was absorbed by CaCO3 , therefore calcination of
CaCO3 could be achieved by heat released from the reduction
reactions of NiO and CuO sorbents with fuel to their reduced
state (Martínez et al., 2014). These choices like to be promising
in the near-coming decades due to a high energy-efficiency,
lower energy-consumption and zero carbon-emission hydro-
gen production methods seem to be found. However, these
options still suffer from both techno-economic restriction (the
three-step process requires new designs and the present SMR
plant will be fundamentally changed) and limitation of ther-
modynamics of different reactions involved in the scheme,
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806
furthermore the heat exchange efficiency between different
solid carriers is still inefficient in reality.
Inspired by this concept, CLC technique can meet the
requirement of providing the required heat for calcinator
without extra energy demands for CO2 separation, thus
thermally coupling of Ca-based SESMR and CLC is a new
alternative to overcoming the two problems of present SMR
process, i.e. (1) promoting H2 purity in reformer gas and (2)
elimination of energy penalty for capturing CO2 from flue gas.
In this work, we conduct a detailed thermodynamic analysis
of the newly suggested process by conducting the commer-
cial Aspen Plus simulator, and conventional SMR process as
reference system is also investigated for comparison purpose.
2. Process configuration
2.1. Conventional SMR process (reference system)
Fig. 3 shows the simulation flowchart of the conventional
steam methane reforming (SMR) process. The SMR process
begins from compressing methane via three-stage compres-
sors and pumping water to the reforming operation pressure
(25 bar). The pumped water is preheated utilizing the excess
heat from water gas shift reactor, then the steam is gener-
ated by absorbing heat from combustion flue gas. The feed
stream to the reformer, mixture of methane and steam, is pre-
heated prior to entering the reformer. Preheating is performed
in the heat exchanger (EX1), completely utilizing the heat
load of the hot reformer gas. The reforming reactions which
are taken place in the reformer have been shown in Reac-
tion (1)–(3). The steam reforming operates under the condition
of Tr = 900 ◦ C, Pr = 25 bar. Due to highly endothermic SMR, the
furnace should supply continuous heat for maintaining the
operation of reforming. The amount of heat (Q), transferred
from furnace to reformer, is shown by the dashed line in Fig. 3,
which can be realized by burning of the supplemental com-
pressed methane (via C2) and low-pressure air (via C3).
In order to convert undesired CO to CO2 and to increase
H2 production, the reformer gas is further processing in a
water gas shift (WGS) reactor operating at 200 ◦ C and 25 bar.
CO contained in reformer gas is converted to CO2 and H2
by supplemental water (if necessary) or the existing water
in reformer gas. The H2 -rich gas (at the outlet of WGS) is
then cooled down to 40 ◦ C for water condensation and then is
introduced to CO2 capture (CC) unit for obtaining the purified
hydrogen. In this work, MEA scrubbing is adopted for separat-
ing CO2 from product gas.
2.2. Ca-based SESMR thermally coupled with CLC
system
The simulation flow diagram of the Ca-based SESMR thermally
coupled with CLC system is presented in Fig. 4. In general, this
novel designed process consists of three major parts, namely
the CLC system and the SESMR system. In contrast to con-
ventional SMR process, the CLC system instead of furnace
provides necessary heat for calcinator rather than reformer
because the introduce of CaO sorbents can obtain autothermal
operation, thus supplemental heat is not needed for maintain-
ing the normal operation of SESMR.
In the SESMR process, compressed CH4 , mixed with high-
temperature steam and CaO sorbents is introduced to the
reformer. As previously mentioned, Ca-based sorption can
795
achieve in situ CO2 separation in the formation of CaCO3 in
SESMR process, and removal of CO2 can promote water–gas
shift reaction (Reaction (3)) toward its positive direction,
resulting in decrease of CO, and decrease of CO surely accel-
erates the SMR reaction to promote H2 production, so the
reforming process gets enhanced. The generated CaCO3 solids
are separated from gaseous steam in a cyclone (CYC1), and
the gaseous product herein is cooled via a cooler (cooler1) and
water is condensed in a two-phase flash separator (condens1),
meanwhile the high-purity H2 product is generated.
In order to obtain multicycle operation, CaO carriers need
to be regenerated in calcinator (named calcinat in Fig. 4)
by calcining CaCO3 . The operating temperature for CaCO3
decomposition is always kept at 1173 K (at pure CO2 baro-
sphere, 1 bar), and the required calcination energy is supplied
by CLC system marked as the dashed line (named Q) in Fig. 4.
In this work, NiO/Ni is chosen as the suitable oxide carrier
due to its large capacity of transferring oxygen, which is circu-
lating between air reactor (AR) and fuel reactor (FR). In FR, NiO
reacts with the compressed CH4 (via C2), and the outlet stream
of FR mainly consists of Ni, CO2 and H2 O. The pure CO2 can be
obtained after a cyclone (CYC4) and water condensation (con-
dens2). The main reactions involved in FR can be expressed at
Reaction (6):
CH4 + 4NiO → CO2 + 2H2 O + 4Ni H298 = 156.9 kJ/mol
(6)
In general, NiO reduction process is highly endothermic.
However, FR is still operated under adiabatic condition, caus-
ing the required heat for maintaining reactions is completely
coming from the sensible heat of the heated NiO carrier.
Subsequently, the reduced Ni carriers are reoxidized with
compressed air (via C3) in AR. The reaction that occurs in AR
is shown below:
2Ni + O2 → 2NiO H298 = −479.8 kJ/mol (7)
Reaction (7) is intensively exothermic. In AR, the released
heat can be utilized in three aspects including: (1) heating NiO
carrier, supporting the required heat for CH4 reduction in FR;
(2) providing the necessary heat for calcinator; and (3) heating
the flue gas up to the combustion temperature.
The pumped water is first preheated by the excess heat
released from cooler1, and it is further heated by the high-
temperature flue gas from AR to generate superheated steam
via heat exchanger (EX1) prior to being sent to reformer.
3. Process modeling
Both conventional SMR process and Ca-based SESMR ther-
mally coupled with CLC process were developed and
simulated using Aspen Plus. The first step of modeling both
processes is to define the possible species. Commonly, the
overall components taken into consideration are Ni, NiO, CaO,
CaCO3 , CH4 , CO, CO2 , H2 , N2 , H2 O, NO2 , NO, N2 O and O2 .
From numerous methods provided by Aspen Plus, the
PR-BM method uses the Peng Robinson cubic equation of
state with Boston–Mathias alpha function for all thermody-
namics properties, and is recommended for gas processing
application (Fan and Zhu, 2015). Thus, it is used to calculate
the thermodynamic properties of conventional components
defined in Aspen Plus.
796 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806

PRODUCT
CONDENSE
COOLER
CC
COOL-IN COOL-OUT CC-IN
C1
CH4-RE C-CH4-RE
WGS H2O
CO2

HEAT

WGS-IN
EXHAUST REFORMER
C2
EX1 FURNACE

EX2 REFO-IN Q CH4-FUEL

PRE-HEAT
PUMP FURN-IN C3
STEAM REFO-OUT AIR-IN
PUMP-H2O
WATER
FLUE-GAS

Fig. 3 – Simulation flow diagram of the conventional SMR process.

HEAT PRODUCT
COOLER1
CONDENS1
COOL-IN COOL-OUT
C1 CYC1
H2O-1
CH4-RE C-CH4-RE CALCINAT
CACO3
REFORMER
EXHUAST
PREHEAT
PUMP CYC2
CAO
PUMP-H2O EX1
WATER
SE-SMR sy ste m

CONDENS2 CO2-1 Q
CO2-2 FLUEGAS
COOLER2
CO2+H2O
CYC4 AR
AR-IN C3
H2O-2 C2 CYC3
FR AIR-IN
AR-OUT
CH4-FUEL
FR-IN

CLC systea m

Fig. 4 – Simulation flow diagram of the Ca-based SESMR thermally coupled with CLC system.

An equilibrium approach or a rate-based approach can
be used for modeling of a reaction process. The equilibrium
approach is based on the concept of chemical reaction and
phase equilibria (Ravikiran et al., 2011). The reasons for choos-
ing the equilibrium approach is as follows: (1) to give a quick
limit of the operation, by considering the most excellent cat-
alytic activity of catalysts, these catalysts can obtain chemical
and phase equilibrium at a specified operation condition; and
(2) it is useful to evaluate the system performance at opti-
mal operating conditions, and if the optimal performance
has few advantages compared with previous process, fur-
ther investigations are not deserved. The furnace, reformer,
WGS, AR, FR, and calcinator are all modeled using the built-in
RGibbs modules implemented in Aspen Plus with calcula-
tion of the chemical and phase equilibrium by minimizing
the Gibbs free energy of all components expected to obtain
equilibrium.
To separate solid phase from gas phase, a cyclone was used
for separating solids, and without considering of solid size dis-
tribution, the cyclone was simulated by Sep model (the cyclone
efficiency is assumed to be 100%) in Aspen Plus.
For heat exchangers (EX1 and EX2), the Heater model is
employed for simulation of shell and tube heat exchangers
which is formulated using given heat transfer coefficients and
specified minimum temperature approach.
For simplicity, the Sep module embedded in Aspen Plus
is used for modeling CO2 capture unit as MEA wet scrub-
bing in conventional SMR process. The CO2 capture unit is
modeled using Aspen Plus module Sep which can be regarded
as black-box assumptions. In black-box assumptions, the
complicated module for capturing CO2 is represented by
one box which owns one inlet stream and allows two
outlet streams (product and waste). The amount of work
and heat required to perform separation are determined by
the 2nd law efficiency, effectiveness, product stream purity,
and the temperatures and pressures for the inlet stream,
product stream and waste stream. More information about
black-box model for CO2 capture can be found elsewhere
(Simpson and Simon, 2007). The black-box model can cal-
culate the minimum work or heat required for separation,
however the calculated value for separation are generally
far from the actual work load compared with that reported
in literature. To have an idea of energy consumption per
kg of captured carbon dioxide, Table 1 lists the heat and
power consumptions during MEA scrubbing reported by other
work.
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806 797

Table 1 – Heat and power consumptions in MEA scrubbing process.

Units Abu-Zahra Desideri Bolland (Bolland Berstad (Berstad
(Abu-Zahra et al., (Desideri and and Mathieu, et al., 2012)
2007) Paolucci, 1999) 1998)

CO2 captured % 90 86.5 90 90

Power consumption MJ/kg CO2 – 0.32 0.11 –
Heat consumption MJ/kg CO2 4.0 3.95 4.0 3.95

From Table 1, it can be noticed that MEA scrubbing is the 4.1. Methane conversion
relatively costly process, and requires approximately 4 MJ/kg
CO2 of heat at 493 K and at least 0.11 MJ/kg CO2 of work to per- Methane conversion (˛M ) has an essential effect on the system
form the separation, which results in an exergy consumption performance of both systems due to it determines the degree
of 1.69 MJ/kg CO2 (Simpson and Simon, 2007). of the steam reforming, and is defined below:
The amounts of methane and air consumed for combus-
 
tion are calculated using Design Specification Tool embedded nCH4 ,out
˛M = 1− × 100 (8)
in Aspen Plus by computing the necessary enthalpy required nCH4 ,in
for maintaining reforming process in SMR and calcination
process in Ca-based SESMR thermally coupled with CLC where nCH4 ,out and nCH4 ,in denote the molar flow rate of
process. methane at the outlet of the reformer and the inlet of the
The convergence of this model is based on mass and energy reformer, respectively.
balance of each block. In the convergence options of Aspen
Plus, the mass balance tolerance is set to 0.0001. The simula-
4.2. CaO conversion
tion of the circulation of NiO and CaO solid is realized by the
method of “tear stream” of Aspen Plus. The “direct method”
In this novel process, CaO sorbents have an important effect
is chosen as the convergence method, for direct substitution,
on hydrogen purity and heat balance of the reformer, and is
the new value of the tear stream variable is the value resulting
defined as the number of moles of CaO that reacted (moles in
from the previous flowsheet calculation and also can make
inlet minus the moles in the outlet) divided by the moles of
it easy to identify convergence problem in contrast to other
CaO in the feed stream of the reformer:
convergence methods (such as Broyden and Newton).
Simulation processes were performed with the following
 
nCaO,in − nCaO,out
assumptions: ˛CaO = × 100 (9)
nCaO,in

where nCaO,out and nCaO,in denote the molar flow rate of CaO
sorbents at the outlet of the reformer and the inlet of the
(1) The simulations are in a steady state and are not applicable
reformer, respectively.
to start-up operations.
(2) The excessive air number is considered as 1.05 as constant.
4.3. Energy and exergy analysis
(3) Reactions involved in both processes are assumed to be
equilibrium, and the reaction residence time is consid-
Thermodynamic energy and exergy efficiencies of both sys-
ered to be long enough to achieve chemical and phase
tems are investigated. The overall energy efficiency () relates
equilibrium.
the useful energy output (product gas) from the process to the
(4) The heat and pressure losses are assumed to be negligible
necessary energy input (such as methane, power consump-
in all operational units.
tion and CO2 capture energy consuming (in SMR process)) to
(5) The solid size is considered to be equal without size distri-
this process:
bution, and the cyclone efficiency is assumed to be 100%.
(6) Ambient air is assumed to be constituted with 80% N2 and
Enout
20% O2 on a volume basis. = (10)
Enin

The exergy efficiency (ϕ) is defined as the ratio between

the useful exergy output from the process and the necessary
The main modules used to simulate the SMR process and exergy input to this process. The exergy efficiency (ϕ) is defined
the Ca-based SESMR thermally coupled with CLC process as:
in Aspen Plus and their specifications are summarized in
Tables 2 and 3, respectively. Exout
ϕ= (11)
Exin

4. Performance evaluation For a multicomponent material stream, the exergy is

In order to conduct a comparative analysis between the con-
ventional SMR process and this newly designed process, some
thermodynamic performances are focused on including the
composition of product gas, methane conversion, CaO conver-
sion, energy efficiency and exergy efficiency of both systems.
divided into three terms of exergy, namely physical exergy
(Exph ), chemical exergy (Exch ) and mixing exergy (Exmix ).
Together, they give the overall exergy of a material stream as
written by Eq. (12).
ExM = Exph + Exch + Exmix (12)
798 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806

Table 2 – Names and description of main block units used in the conventional SMR process under Aspen Plus.
Module names Block unit names Specification

RGibbs FURNACE Operating temperature: 1273 K

Operating pressure: 3 bar
Excessive air number: 1.05 (as constant)
REFORMER Operating temperature: 1173 K
Operating pressure: 25 bar
S/C molar ratio: 4
WGS Operating temperature: 473 K
Operating pressure: 25 bar
HeatX EX1 Cold outlet temperature: 913 K
EX2 Cold outlet temperature: 623 K
MCompr C1 (three-stage) Discharge pressure: 25 bar
Compressor ratio: 2.924
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
Compr C2 Discharge pressure: 3 bar
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
C3 Discharge pressure: 3 bar
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
Pump PUMP Discharge pressure: 25 bar
Pump efficiency: 0.85
Sep CC CO2 capture efficiency: 90%
Heat consumption: 4 MJ/kg CO2
Power consumption: 0.11 MJ/kg CO2
Heater COOLER Outlet temperature: 313 K

Table 3 – Names and description of main block units added in the Ca-based SESMR thermally coupled with CLC process
under Aspen Plus.
Module names Block unit names Specification

RGibbs AR Operating temperature: 1273 K

Operating pressure: 3 bar
Excessive air number: 1.05 (as constant)
FR Operating pressure: 3 bar
Heat duty: 0 kW (Adiabatic)
REFORMER Heat duty: 0 kW (Adiabatic)
Operating pressure: 25 bar
S/C molar ratio: 4
CALCINAT Operating temperature: 1173 K
Operating pressure: 1 bar
Sep CYC1-CYC4 Cyclone separation efficiency: 100%
Heater COOLER1, COOLER2 Outlet temperature: 313 K
HeatX EX1 Cold outlet temperature: 823 K
MCompr C1 (three-stage) Discharge pressure: 25 bar
Compressor ratio: 2.924
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
Compr C2 Discharge pressure: 3 bar
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
C3 Discharge pressure: 3 bar
Isentropic efficiency: 0.83
Mechanical efficiency: 0.98
Pump PUMP Discharge pressure: 25 bar
Pump efficiency: 0.85

The physical exergy is defined as the maximum work that
can be extracted when the stream changes its operating con-
ditions from the a working state to a state in equilibrium with
the environmental (Ni et al., 2007; Szargut et al., 1987). The
physical exergy is dependent with working temperature and
pressure and can be calculated by Eq. (13) associated with the
simulation results obtained from Aspen Plus.
Exph = (H − H0 ) − T0 (S − S0 ) (13)
where H and H0 represent the enthalpy flow of a material
stream at working state and at environmental state, respec-
tively; S and S0 represent the entropy flow of a material stream
at working state and at environmental state, respectively.
The chemical exergy is defined as the maximum work that
can be obtained when the substance is brought from the envi-
ronmental state to the reference state by reversible process
involving only heat transfer and exchange of substances with
the environment (Xiang et al., 2004). The chemical exergy of
all pure components can be obtained from Kotas’s reference
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806 799

Table 4 – Design specification and input data (taken from

plant value) of conventional SMR process (Rahimpour 40 simulation
et al., 2013). plant

Parameter Value
Feed gas composition (mol %) 30

Mole fraction (%)

CO2 1.72
CO 0.02
H2 5.89 20
CH4 32.59
N2 1.52
H2 O 58.26
Inlet temperature (K) 793.15 10
Inlet pressure (bar) 40
Total feed gas flow (kmol/h) 9129.6
Designed SMR operating temperature (K) 1063.15
0
Designed SMR operating pressure (bar) 41 CO CO H CH N HO
Composition
environmental model, and the chemical exergy of a material
Fig. 5 – Comparison between simulation prediction and
stream is calculated by Eq. (14).
plant data (Rahimpour et al., 2013) (at the conditions shown
  in Table 4: 1063.15 K, 40 bar).

n

n
0L 0V
Exch = F x0,L x0,i Exch,i + x0,V y0,i Exch,i (14)
100 100
i=1 i=1
90 P=25 bar
80 S/C=4
where F denotes the molar flow rate of a material stream; x0,L 80
70
Composition,dry basis (%)

and x0,V denote the liquid and vapor mole fractions, respec-

Methane conversion,%
60
tively; x0,i and y0,i denote the mole fraction of component i in 50
0L 0V 60
the liquid and vapor phases, respectively; and Exch,i and Exch,i 40
denote the standard chemical exergy of component i in liquid
2.5
and vapor phases, respectively. 2.0 40
The last step is to calculate the mixing exergy, which always 1.5
H
CO
has a negative value, and can be estimated by Eq. (15). 1.0
α
20
0.5
Exmix = Hmix − T0 Smix (15) 0.0
800 880 960 1040 1120
T (K)
where Hmix and Smix denote enthalpy and entropy changes
of mixing, respectively. Fig. 6 – Effect of reforming temperature on product gas
composition and methane conversion in conventional SMR
5. Results and discussion process.

5.1. Model verifications
To verify the accuracy of the simulator, a comparison of
reformer gas compositions between plant data and the pre-
dicted value was carried out. It should be noted that this
verification work is to evaluate the differences between the
model value and plant data of traditional SMR process, with-
out referencing to either CLC system or Ca-based SESMR
process. An RGibbs model based on Gibbs free energy mini-
mization principle was developed to simulate the traditional
SMR process. The designed specifications and input data of
conventional SMR process (taken from plant) are presented in
Table 4 (Rahimpour et al., 2013). And the differences between
the model value and plant data of SMR process are shown
in Fig. 5. As shown in this figure, H2 and CO concentrations
are a little higher than the plant data, whereas, the predicted
value of CH4 and H2 O concentrations are slightly lower than
the plant data. The reason is that the predicted reformer
gas compositions are obtained at thermodynamic equilib-
rium condition, that is to say, SMR reactions are reaching
their chemical and phase equilibrium, beyond the practi-
cal industrial SMR. Though, there does exist some errors
between the predicted data and plant value, by using thermo-
dynamic equilibrium method, the maximum errors are still
within acceptable range. Especially, this work is the initial
guess to present the obvious advantages of this novel pro-
cess, so the thermodynamic equilibrium method can obtain
the expected purpose of showing the competitiveness of this
process against the previous SMR system.
5.2. Thermodynamic analysis of conventional SMR
In this section, a parametric sensitivity analysis including
reforming temperature, reforming pressure and S/C (molar
ration of steam to methane) was performed in order to inves-
tigate the main operating conditions.
Fig. 6 presents the effect of reforming temperature in the
range of 773 K–1173 K on H2 concentration and CO2 concentra-
tion of product gas and methane conversion for conventional
SMR. The increase of reforming temperature greatly increases
H2 concentration and methane conversion, meanwhile a
slight increase of CO2 concentration is also observed. As the
reforming temperature increases from 773 K to 1173 K, H2 con-
centration in product gas continuously increases from 42.2%
to 95.7% and CO2 concentration increases to 2.4%, correspond-
ingly an equilibrium methane conversion of 93.76% is reached
at the reforming temperature of 1173 K. Due to the highly
endothermic SMR, higher operating temperature is favored for
converting more methane to H2 and CO as shown in Reac-
tion (1). It can be observed that CO2 concentration basically
800 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806

100
Table 5 – Initial operating conditions in Ca-based SESMR
97.0
thermally coupled with CLC process.
96.5 98
T=1173K Parameters Value

Methane conversion,%
96.0 S/C=4
Composition,dry basis (%)

Reformer reactor pressure/bar 25

95.5 96 S/C 4
95.0 Ca/C 1
Calcinator temperature/K 1173
2.8 94
Calcinator pressure/bar 1
2.6
AR temperature/K 1273
2.4 AR and FR pressure/bar 3
92
H
2.2 Ni/C 1.28
CO
2.0 α Methane fed to FR/kmol/h 30.7
90 Air fed to AR/kmol/h 322.35
10 20
P(bar)
800
Fig. 7 – Effect of reforming pressure on product gas 95
P=25bar
composition and methane conversion in conventional SMR Ca/C=1 600
90
process.
400
85

CO & CO2 , ×10-6

100 100

H2, dry basis (%)

P=25 bar 80 200
T=1173K
90 90
75
Composition,dry basis (%)

20
Methane conversion,%

80
2.5
2.0
1.5
1.0
1 2 3 4
S/C
Fig. 8 – Effect of S/C on product gas composition and
methane conversion in conventional SMR process.
coincides and follow the same trend. This is due to the
increase of CO can shift the water-gas shift reaction in WGS to
its right direction, hence CO2 composition in product gas gets
promoted.
Fig. 7 shows the product gas composition and methane
conversion as a function of the reformer pressure in con-
ventional SMR process. As reforming pressure increases from
5 bar to 25 bar, H2 composition decreases from 97.2% to 95.7%,
and methane conversion correspondingly decreases from
99.68% to 93.76%, during this range, a slight change of CO2
concentration is observed in this investigation. According to Le
Chatelier’s principle, increasing reforming pressure has a neg-
ative effect on methane reforming, and a fraction of methane
remains unreacted in the reformer. However, it is still interest-
ing to operate SMR under high operating pressure because in
industrial applications it is highly desirable in order to reduce
equipment size and operation costs (Rydén and Ramos, 2012).
Fig. 8 shows the product gas composition and methane
conversion as a function of S/C in the conventional SMR pro-
cess. Based on the simulation results, with increasing S/C in
the range of 1–5, H2 content in product gas increases from
76.8% to 96.4%, which corresponds to CO2 content increases
from 1.4% to 2.4%. When S/C ratio is higher than 4, a slower
increase for both H2 content and methane conversion is
depicted in Fig. 8. An increase of S/C enhances the steam
reforming toward its positive direction, whereas a higher
S/C of 5 is not favored for methane conversion due to a
high methane conversion has been reached by equilibrium
70
80
H2
CO 10
65
CO2
70
60 0
1 2 3 4 5
H S/C
60
CO
α Fig. 9 – Effect of S/C molar ratio on product gas
50 compositions (dry basis) under adiabatic reactor (at the
5
conditions shown in Table 5: CaO to methane molar ratio:
Ca/C = 1, 25 bar).
restriction. Furthermore, a higher S/C requires a considerable
amount of heat to produce steam, greatly decrease of the
overall plant efficiency in SMR. Therefore, an S/C ratio of 4
is generally adopted in SMR plants.
5.3. Thermodynamic analysis of Ca-based SESMR
thermally coupled with CLC
In this section, some key parameters, such as S/C, Ca/C (molar
ratio of CaO sorbents to methane fed to reformer), reformer
operating pressure and reformer operating temperature, are
analyzed, and the initial conditions are shown in Table 5. It
should be noted that the molar flow rates of methane fed to
FR, air fed to AR and Ni/C (molar ratio of NiO to methane fed to
reformer) are calculated by a calculator model in Aspen Plus
to reach the expected calcinator temperature of 1173 K.
5.3.1. Effect of S/C
S/C is an important parameter in the Ca-based SESMR ther-
mally coupled with CLC system. The effect of S/C in the range
of 1–5, on reformer gas compositions (dry basis) and tem-
perature is shown in Fig. 9. Increasing S/C ratio from 1 to 5
enhances H2 purity from 64.2% to 93.4% (on dry basis), and CO
and CO2 concentrations increase from 8 ppm to 200 ppm and
from 12 ppm to 700 ppm, respectively, as it can be seen in Fig. 9.
When S/C > 4, the increasing tendency of H2 content in prod-
uct gas begins to level off and sudden increase of CO and CO2
contents is observed. These results show that the excess of
steam improves H2 purity by promoting steam reforming (R1
and R2) and water–gas shift (WGS, R3) reactions toward their
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806 801

90 51000
50800
80 92
P=25bar P=25bar 50600
80 Ca/C=1 50400
S/C=4
70 50200
50000
70
Methane conversion, %

69 49800

CaO conversion, %

H2,dry basis(%)
60

CO & CO2 , ×10-6

49600
60 49400
49200
50
46 49000
50 H2
40 CO 225

40 CO2 150
α 30
23
75
30 α
0
20 0.0 0.5 1.0 1.5 2.0
1 2 3 4 5
Ca/C
S/C
Fig. 11 – Effect of Ca/C molar ratio on product gas
Fig. 10 – Effect of S/C molar ratio on CH4 and CaO
compositions (dry basis) under adiabatic reactor (at the
conversion under adiabatic reactor (at the conditions
conditions shown in Table 5: S/C = 4, 25 bar).
shown in Table 5: Ca/C = 1, 25 bar).
100
80
P=25bar
S/C=4
positive directions, which favors H2 , CO and CO2 production 70
80
(Johnsen et al., 2006; Tavares et al., 1996). However, a higher
60
Methane conversion, %

S/C ratio is not favored by the Ca-based SESMR thermally cou-

CaO conversion, %
pled with CLC process due to a higher carbonation efficiency 50 60

has been obtained. 40

In contrast to conventional SMR, the increase of S/C 40
enhances CO2 production up to 2.4%, as shown in Fig. 8, and 30

CO concentration has a negligible values (below 0.1%) due to 20

20
the lower temperature WGS reactor. However, in the Ca-based α
10
SESMR thermally coupled with CLC process, COx contents are α
within ppm level and further process and equipment for sep- 0 0
0.0 0.5 1.0 1.5 2.0
arating these impurities are unnecessary. It is worthy to note
that S/C range of 3–5 is the likely range of interest to mini- Ca/C

mize carbon formation while reducing the excessive energy
for steam generation (Johnsen et al., 2006) and carbon forma-
tion is not observed in this work.
Fig. 10 shows the effect of the S/C molar ratio in the range
of 1–5 on methane and CaO conversions. As explained above,
increasing S/C enhances SMR and WGS reactions, facilitating
H2 and CO2 production, therefore it promotes the methane
conversion from 31.17% to 83.83%. At the same stage, increas-
ing CO2 can accelerate carbonation reaction (Reaction (4)),
resulting in the promotion of CaO conversion from 31.20% to
83.81%.
It should be noted that increase of S/C enhances both SMR
and carbonation reactions. Whereas, it is necessary to find
a balance between the need of obtaining a high degree of
H2 purity in reformer gas and the overall process efficiency,
causing supplemental energy need to be supplied to generate
steam. Therefore, a molar ratio of S/C of 4 is selected in this
work to achieve energy-efficiency hydrogen production.
5.3.2. Effect of Ca/C
The Ca/C (molar ratio of CaO to methane which is fed
to reformer) is a critical parameter in this novel designed
process, which has a major effect on the degree of CO2 cap-
ture efficiency, CH4 conversion and H2 yield. In a Ca-based
SESMR process, CaO sorbents regenerate through decompo-
sing CaCO3 in the calcinator, then the fresh sorbents react with
CO2 in the reformer to achieve in situ CO2 separation by car-
bonation reaction and the maximum H2 yield by enhancing
SMR and WGS reactions. Importantly, highly exother-
mic carbonation makes it possible to obtain autothermal
Fig. 12 – Effect of Ca/C molar ratio on CH4 and CaO
conversion under adiabatic reactor (at the conditions
shown in Table 5: S/C = 4, 25 bar).
reactions during SESMR process, hence supplemental heat is
not required for supplying steam reforming.
The effect of Ca/C molar ratio on product gas compositions
has been studied at 25 bar and an S/C molar ratio of 4 (see
Table 5) under adiabatic reactor (see Fig. 11).
Though the effect of Ca/C on SESMR system has been
widely discussed by other researchers, these discussions were
carried out at a certain operating temperature (Fernandez
et al., 2012a; Johnsen et al., 2006), and discussions under
autothermal condition in SESMR system are rarely noticed.
As shown in Fig. 11, an equilibrium dry H2 concentration
of 20.2% is reached when no sorbents are added (Ca/C = 0).
When CaO sorbents are added to the reformer, H2 concentra-
tion increases from 20.2% to 92.6% for Ca/C = 0 and Ca/C = 1,
respectively, and increases at a moderate speed from 92.6%
to 92.9% when Ca/C > 1. By contrast, the CO2 and CO concen-
trations initially drop at a fast speed from 0.05 to 17 ppm and
from 270 ppm to 5 ppm, respectively, and reach their minimum
concentrations at Ca/C = 1, then slowly increase. The sensitive
analysis of Ca/C results shows that Ca/C molar ratios of around
1 is optimal to yield a high purity H2 .
The effect of Ca/C on CH4 and CaO conversions is shown in
Fig. 12. The results show that increasing Ca/C (in the range of
0–1) leads to higher methane conversion, which reflects in an
increase from 6.38% (due to the low equilibrium temperature)
to 76.33%. Beyond this range (i.e. Ca/C in the range of 1–2),
802 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806
96.0
95.5
S/C=4
95.0 Ca/C=1
H2, dry basis (%)
94.5
94.0
93.5
93.0
92.5
5 10 15 20
P(bar)
Fig. 13 – Effect of reforming pressure on product gas
compositions (dry basis) under adiabatic reactor (at the
conditions shown in Table 5: S/C = 4, Ca/C = 1).
the methane conversion hardly rises from 76.66% to 77.38%.
The CaO conversion, however, firstly increases to its maxi-
mum value of 1 at Ca/C = 0.5, then rapidly declines to 38.7%
at Ca/C = 2.
In order to obtain high purity of H2 (see Fig. 11), the Ca/C
molar ratio is set to 1.
The reasons may be explained as follows: increasing Ca/C
means more CaO sorbents are introduced to the reformer,
and the heated CaO sorbents particles (from calcinator, at
1173 K) provides excessively sensible heat to the reformer. It
should be further noted that carbonation combined SMR can
obtain autothermal reactions, which cannot upgrade the sys-
tem temperature. However, the reforming temperature will
be increased due to the continuous addition of the heated
CaO particles. SMR reactions are favored at high tempera-
tures, so H2 concentration gets increased. CO2 can be captured
through carbonation in the formation of CaCO3 . With decrease
in CO2 , WGS reaction is promoted toward its positive direc-
tion to eliminate CO, and decrease of CO conversely promotes
SMR reactions to generate H2 . It is interesting that CO and
CO2 concentrations start to rise when Ca/C > 1, which may
cause by that CaO sorbents have reached their maximum
CO2 absorbing efficiency (see Fig. 12). Due to that, extra CaO
sorbents cannot react with CO2 , resulting in the decrease of
CaO conversion. Meanwhile, at high temperature, endother-
mic SMR reactions are favored, resulting in the formation of
H2 , CO and CO2 , so the reformer gas compositions (H2 , CO and
CO2 ) and methane conversion increase. However, this phe-
nomenon is valid for adiabatic operation only, where the rate
of heat transfer is determined by heated CaO sorbents parti-
cles. For isothermal operation the above phenomenon is not
valid, causing the heat transfer is determined for a given tem-
perature, thus the SMR reactions rate cannot be changed by
the transferred heat.
5.3.3. Effect of reforming pressure
It is well known that the SESMR is favored at lower pres-
sure due to the rise in the number of gas moles associated
with the overall reaction which involves SMR and carbona-
tion reactions (Harrison, 2008). However, in order to accelerate
reforming reactions rate and to reduce the reformer reac-
tor volume, the high-pressure performance in the range of
20–50 bar is particularly of interest.
Fig. 13 shows the effect of reforming pressure in the range
of 5 bar–25 bar on product gas compositions under adiabatic
30 90 100
S/C=4
88 Ca/C=1
24
86
Methane conversion, %
90
CO & CO2 , ×10-6
CaO conversion, %
18 84
82
12
H2
CO 80 80
CO2
6
78
α
76 α
0
25 70
5 10 15 20 25
P(bar)
Fig. 14 – Effect of reforming pressure on CH4 and CaO
conversion under adiabatic reactor (at the conditions
shown in Table 5: S/C = 4, Ca/C = 1).
reactor at S/C and Ca/C molar ratio of 4 and 1, respectively.
The H2 purity reaches a maximum value of about 95.8% on a
dry basis at 5 bar, as against 92.6% H2 purity at 25 bar. On the
other hand, the CO2 and CO concentrations decrease over the
whole pressure range from 28 ppm to 17 ppm and from 8 ppm
to 3 ppm, respectively.
In relation to the conversions, Fig. 14 shows the effect of
reforming pressure on methane and CaO conversions. With
increase of reforming pressure, the methane and CaO conver-
sions trend to drop from 88.92% to 76.33% and from 88.90% to
76.31%, respectively. Increasing reforming pressure shifts the
equilibrium toward suppressing CH4 conversion, as indicated
in Reactions (1) and (2), so the higher pressure gives a prod-
uct gas containing less H2 , CO and CO2 . As shown in Fig. 14,
decreasing CO2 indicates that the Ca-based SESMR is affected
by the change of pressure. It is worthy to point out that the
huge excess of steam in the feed (S/C = 4) leads to a high H2
selectivity, resulting few CO and CO2 (within ppm level), as
mentioned earlier. Although carbonation is favored at high
operating pressure, the total carbon loss is not favored at the
same way, due to the drop in methane conversion (Fernandez
et al., 2012a), so the CaO conversion drops by the decrease of
CO2 .
5.3.4. Effect of reforming temperature
As discussed above, these parameters, such as S/C, Ca/C and
reforming pressure, are investigated under adiabatic reactor
to observe the autothermal performance of SESMR, which also
means that the equilibrium cannot be determined by a given
temperature, but by the overall reaction thermal effect. How-
ever, temperature is another vital operating parameter in the
SESMR process because it has a decisive effect on H2 yield.
Especially, for the in situ Ca-based SESMR reaction, it is also
a critical variable to extend the ultimate conversion of CaO as
well as carbonation. In this section, we investigate the effect
of reforming temperature on system performances by setting
a given temperature, unlike the previous adiabatic studies.
Figs. 15 and 16 show the effect of reforming temperature
on product gas compositions and CH4 , CaO conversions under
isothermal reactor at a S/C = 4, Ca/C = 1, 25 bar, respectively.
Due to endothermic SMR reaction is favored at high tempera-
ture, the methane conversion increases from 76.84% to 95.68%
(see Fig. 16) at a fast speed over the whole temperature range
(673 K–1173 K). Although higher reforming temperature leads
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806 803

95 100
14
25

12
S/C=4 80
90 20
Ca/C=1 10
P=25bar

CO & CO , ×10
H , dry basis (%)

60

CO & CH (%)
15

H & CO(%)
8
85

6 10
H 40

80 H CO
4
CO 5 CO
CO 2 CH 20

75 0
0
600 700 800 900 1000 1100 1200 0
1 2 3 4 5
T(K)
NiO/C(fuel)
Fig. 15 – Effect of reforming temperature on product gas
Fig. 17 – Effect of NiO/C (fuel) on gas compositions of FR
compositions (dry basis) under isothermal reactor (at the
outlet stream (dry basis).
conditions shown in Table 5: S/C = 4, Ca/C = 1, 25 bar).

80
95

S/C=4
70 5.3.5. Analysis of fuel reactor
Ca/C=1 For the Ca-based SMSR thermally coupled with CLC system,
60
P=25bar
Methane conversion, %

90 the required heat for maintaining calcination temperature of

CaO conversion, %

50 1173 K is derived from CLC system. Supplemental fuel is first

40
oxidized with NiO in fuel reactor (FR), then the reduced Ni
85
carriers reoxidized with fresh air in AR, simultaneously releas-
30 ing large amounts of heat to supply the heat within system.
20 However, reduction of NiO carriers with fuel is an essential
80
α step for utilizing CLC system. In this section, a sensitive anal-
10
α ysis of parametric NiO/C (fuel), as defined below, on reaction
75 0 performances is studied.
600 700 800 900 1000 1100 1200

T(K)
NiO n
(fuel) = NiO (fuel) (16)
Fig. 16 – Effect of reforming temperature on CH4 and CaO C nCH4
conversion under isothermal reactor (at the conditions
shown in Table 5: S/C = 4, Ca/C = 1, 25 bar). where nNiO and nCH4 (fuel) stand for molar ratio of NiO carriers
and methane as fuel fed to FR.
to higher conversion of methane, the CaO conversion effi- Fig. 17 shows the relationship between NiO/C (fuel) ratio
ciency decreases, as can be seen in Fig. 16. When reforming and the gas compositions of FR outlet stream. According
temperature remains in the range of 673 K–973 K, the CaO con- to this figure, by increasing NiO/C (fuel) ratio, H2 concen-
version shows little change with temperatures, as well as H2 tration first reaches it maximum value of 25.1%, then it
concentration. And CO and CO2 in this temperature range are declines to 0% as it has been decided by the partial oxida-
almost negligible. At temperature higher than 973 K, the CaO tion of methane with NiO carriers (CH4 + NiO → CO + 2H2 + Ni
conversion begins dramatically drop from 79.3% to about 0%, and CH4 + 2NiO → CO2 + 2H2 + 2Ni). Correspondingly, CO com-
correspondingly decrease of H2 purity from 93.7% to 76.2%, position initially keeps constant of around 3% due to partial
and CO and CO2 concentrations are rapidly rising from 0.4% oxidation of methane, then it drops to ppm level when NiO/C
to 13.6 and from 0.4% to 8.8%, respectively. The decrease of CaO (fuel) ratio reaches the stoichiometric number of 4 (shown in
conversion is caused by the carbonation efficiency reduction. Reaction (6)), fully oxidation of CH4 to CO2 and H2 O.
The conversion of CaO is dominantly controlled by operat- As can be expected, the increase of NiO/C (fuel) results
ing temperature, and to achieve high CO2 capture capacity, in the changeable oxidation state from partial oxidation of
the temperature from 773 K to 1023 K is the optimal tempera- methane to complete oxidation of methane, thus CO2 con-
ture range for in situ CO2 capture (Mostafavi et al., 2013). Due centration continuously increases to its maximum value of
to the decrease of CaO conversion efficiency, the enhance- 97.2%, and CH4 composition drops to 0% to maintain the fully
ment effect on SMR reaction declines, so the H2 selectivity oxidation.
decreases, resulting in a drop in H2 purity. On the other hand, When NiO/C (fuel) > 4, as fully oxidation of CH4 has been
higher temperature favors thermodynamically the formation reached at NiO/C (fuel) = 4, more NiO carriers have not any
of CO and CO2 by SMR reactions (R1 and R2), promoting pro- effect on FR reaction performances, hence the gaseous com-
duction of CO and CO2 . positions remain unchangeable.
The results show that operation at reforming tempera- For a complete oxidation of chemical looping combus-
tures in the range of 673 K–973 K is preferred for production of tion system, CO2 is the only desirable product in FR, and a
high purity H2 and for obtaining the maximal CaO conversion NiO/C (fuel) ratio of 4 should be satisfied for obtaining a CO2 -
efficiency. sequence ready stream.
804 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806

Table 6 – System performances of Ca-based SESMR thermally coupled with CLC system and conventional SMR process.
Traditional SMR process Newly designed process

Reforming operating parameters

Reactor type Isothermal operated at 1173 K Adiabatic determined by overall SESMR reactions
Operating pressure/bar 25 25
Product gas (mol%, dry basis)
H2 95.7% 92.6%
CO 0.2% 500 ppm
CO2 2.4% 1700 ppm
CH4 1.6% 7.2%
Flue gas compositions (mol%) AR FR
N2 73.0% 98.8% –
O2 0.9% 1.2% –
CO2 8.7% – 33.3%
H2 O 17.4% – 66.7%
NOx Few – –

Table 7 – Energy and exergy analysis of conventional SMR and Ca-based SESMR thermally coupled with CLC system.
Conventional SMR Newly designed process

Energy (LHV) Exergy Energy (LHV) Exergy

Input (MW) 38.99 37.79 30.15 31.15

Methane 33.89 35.05 29.14 30.14
Wcompressors 1.0 1.0 1.0 1.0
Wpump 0.01 0.01 0.01 0.01
CO2 capture 4.09 1.73 0 0
Output (MW) 26.52 25.39 25.78 25.41
Product gas 26.52 25.39 25.78 25.41
Efficiency 68.02% 67.18% 85.50% 81.57%

after reforming process, WGS operation and CO2 capture

Table 8 – Heat load analysis of reforming process in
conventional SMR and Ca-based SESMR thermally
coupled with CLC process.
Conventional Newly
SMR designed
process
Reaction heat 55.85 −3.22
demands
(MJ/kmol H2 )
Consumption 60.67 51.55
Generation −4.82 −54.77
5.4. Competitiveness analysis of the Ca-based SESMR
thermally coupled with CLC process
To demonstrate the competitiveness of this novel process,
the performances of the Ca-based SESMR thermally coupled
with CLC system were compared with those of a traditional
SMR process. The system performances, flue gas compositions
and system efficiency are compared between conventional
SMR and this novel process. The operating conditions for con-
ventional SMR are S/C = 4, reforming temperature of 1173 K,
reforming pressure of 25 bar. Similar to SMR, this novel pro-
cess is calculated under optimal parameters at conditions:
S/C = 4, Ca/C = 1 and 25 bar, and the feeding conditions for both
processes keep consistent.
The results indicate that the reforming process of this
newly designed process can be operated under adiabatic
reactor in this work, with no supplemental energy pro-
viding to reformer and achieving autothermal reforming,
as against huge energy provided to reformer in conven-
tional SMR process (operated at 1173 K). H2 purity can be
promoted to 92.6% in this novel process without other sep-
aration processes to separate impurities from product gas.
In traditional SMR process, H2 content can be up to 95.7%
unit, increasing the energy penalty and equipment invest-
ment. CO and CO2 concentrations are declined to ppm
level, against that of conventional SMR of 0.2% and 2.4%,
respectively.
More attractiveness of this novel process over present SMR
technology can be shown by the combustion flue gas composi-
tion. In present SMR process, methane and air are combusted
together to provide the required heat for SMR process as fur-
nace. If CO2 from combustion flue gas is captured via chemical
or physical absorbents for ameliorating anthropogenic climate
change, CO2 capture process becomes rather complicated and
requires high energy penalty due to the dilution of N2 . As
shown in Table 6, the flue gas mainly consists of N2 (73.0%),
with small account of CO2 (8.7%) and H2 O (17.4%) in traditional
SMR. It is worthy to note that due to the direct contact of N2
and O2 at high temperature, fewer nitrogen oxides (NOx ) are
generated, which is a poisonous pollutant and also can harm
human beings. The CLC system divides combustion reaction
into two subreactions, with each being typically carried out
in a separate reactor, i.e. AR and FR. In AR, the air is reduced
by Ni carrier, resulting in a reduced air flue gas (composed
by N2 98.8% and O2 1.2%). In FR, methane oxidizes with NiO,
generating CO2 and H2 O (33.3% and 66.7%, respectively), and
after water condensation operation, pure CO2 can be obtained,
saving the expensive equipment and huge energy to capture
CO2 .
The global energy and exergy analyses of both SMR and
Ca-based SEMSR thermally coupled with CLC process are
shown in Table 7. The tabulated data (Table 7) clearly show
that methane is the dominant energy/exergy input to both
systems. The reduction of methane consumption benefits
this newly designed process, as exergy of 31.15 MW in newly
designed process as against exergy of 37.79 MW in conven-
tional SMR. The work consumed for compressors and pump
 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806
makes small contribution to the whole input exergy or energy.
The work consumed for capturing CO2 represents a large
energy input (4.09 MW), which can be calculated by assuming
4 MJ/kg CO2 of heat at 220 ◦ C for regeneration of MEA (Abu-
Zahra et al., 2007; Yang et al., 2012), furthermore a exergy of
1.73 MW is also required for separing CO2 from product gas.
In comparision to conventional SMR, due to the in situ sepa-
rtion of CO2 in reformer, CO2 capture proces is not necessary
in the newly designed process, eliminating the energy penalty
as well as the expensive equipment investment.
The calculated energy and exergy efficiency for conven-
tional SMR is equal to be 68.02% and 67.18%,respectively,
keeping in consistent with the references (Simpson and Lutz,
2007). In the present study energy of about 17.48% or exergy
of about 14.39% is benefited from newly designed process
compard to that of conventional SMR, which indicates the
potential advantages of the suggested process.
According to the aforementioned study, though supple-
mental energy from chemical looping combustion is required
to calcine CaCO3 , the total energy input is declined in this
newly designed process, as shown in Table 7, which is mainly
due to the Ca-based SESMR process can achieve autothermal
reforming, simultaneously lower the reforming temperature.
In the following study, a heat load analysis of reforming pro-
cess for both processes is conducted to investigate the heat
consumption and heat generation, as shown in Table 8.
As shown in Table 8, the reaction heat demands for sus-
taining SMR is predicted to be 60.67 MJ/kmol H2 , as it can be
calculated by the required enthalpy (refereed to Reaction (1))
for achieving the methane conversion of 93.76% (discussed in
Section 5.2). However due to slightly exothermic WGS (Reac-
tion (3)), a heat generation of 4.82 MJ/kmol H2 is calculated,
therefore an overall heat demands of 55.85 MJ/kmol H2 is
still needed for SMR. By contrast, in the Ca-based sorption
enhanced reforming process, the reaction heat consumption
is reduced to 51.55 MJ/kmol H2 due to the lower methane con-
version is observed, as shown in Fig. 10. However the released
heat through carbonation and water gas shift reactions remain
to be 54.77 MJ/kmol H2 , generating heat of 3.22 MJ/kmol H2 in
the overall reaction heat load of SESMR, which can be realized
by summarizing the overall enthalpy of Reactions (1), (3) and
(4).
6. Conclusion
In this work, application of Ca-based sorption enhanced steam
methane reforming (SESMR) for enhancing H2 purity in prod-
uct gas thermally coupled with chemical looping combustion
(CLC) technique for reducing the energy penalty for capturing
CO2 from combustion flue gas was presented to improve the
traditional SMR process.
The performances of some key variables, including CaO to
methane ratio (Ca/C) in the range of 0–2, stream to methane
ration (S/C) in the range of 1–5 and reforming pressure in the
range of 5–25 bar were discussed. The results reveal that the
optimal operating conditions for this newly designed process,
as Ca/C, S/C and reforming pressure are 1, 4, 25 bar, respec-
tively.
H2 purity of product gas in this newly designed process is
calculated to be 92.6%, simultaneously decreasing CO and CO2
concentrations within ppm level and also obtaining separa-
tion of CO2 from combustion flue gas without the extra energy
required. The overall exergy efficiency increases by 14.39
805
percentage points compared to conventional SMR, showing
an attractive competitiveness against SMR.
References
Abu-Zahra, M.R., Niederer, J.P., Feron, P.H., Versteeg, G.F., 2007.
CO2 capture from power plants: part II. A parametric study of
the economical performance based on mono-ethanolamine.
Int. J. Greenh. Gas Control 1, 135–142.
Anheden, M., Svedberg, G., 1998. Exergy analysis of
chemical-looping combustion systems. Energy Convers.
Manag. 39, 1967–1980.
Antzara, A., Heracleous, E., Bukur, D.B., Lemonidou, A.A., 2015.
Thermodynamic analysis of hydrogen production via
chemical looping steam methane reforming coupled with
in situ CO2 capture. Int. J. Greenh. Gas Control 32, 115–128.
Barelli, L., Bidini, G., Gallorini, F., Servili, S., 2008. Hydrogen
production through sorption-enhanced steam methane
reforming and membrane technology: a review. Energy 33,
554–570.
Berstad, D., Anantharaman, R., Jordal, K., 2012. Post-combustion
CO2 capture from a natural gas combined cycle by CaO/CaCO3
looping. Int. J. Greenh. Gas Control 11, 25–33.
Bolland, O., Mathieu, P., 1998. Comparison of two CO2 removal
options in combined cycle power plants. Energy Convers.
Manag. 39, 1653–1663.
Desideri, U., Paolucci, A., 1999. Performance modelling of a
carbon dioxide removal system for power plants. Energy
Convers. Manag. 40, 1899–1915.
Dittmar, B., Behrens, A., Schödel, N., Rüttinger, M., Franco, T.,
Straczewski, G., Dittmeyer, R., 2013. Methane steam reforming
operation and thermal stability of new porous metal
supported tubular palladium composite membranes. Int. J.
Hydrog. Energy 38, 8759–8771.
Fan, J., Zhu, L., 2015. Performance analysis of a feasible
technology for power and high-purity hydrogen production
driven by methane fuel. Appl. Therm. Eng. 75, 103–114.
Fernandez, J., Abanades, J., Grasa, G., 2012a. Modeling of sorption
enhanced steam methane reforming—part II: simulation
within a novel Ca/Cu chemical loop process for hydrogen
production. Chem. Eng. Sci. 84, 12–20.
Fernandez, J., Abanades, J., Murillo, R., 2012b. Modeling of
sorption enhanced steam methane reforming in an adiabatic
fixed bed reactor. Chem. Eng. Sci. 84, 1–11.
Harrison, D.P., 2008. Sorption-enhanced hydrogen production: a
review. Ind. Eng. Chem. Res. 47, 6486–6501.
Hong, H., Jin, H., Liu, B., 2006. A novel solar-hybrid gas turbine
combined cycle with inherent CO2 separation using
chemical-looping combustion by solar heat source. J. Sol.
Energy Eng. 128, 275–284.
Johnsen, K., Grace, J.R., Elnashaie, S.S., Kolbeinsen, L., Eriksen, D.,
2006. Modeling of sorption-enhanced steam reforming in a
dual fluidized bubbling bed reactor. Ind. Eng. Chem. Res. 45,
4133–4144.
Lee, D.K., Baek, I.H., Yoon, W.L., 2004. Modeling and simulation
for the methane steam reforming enhanced by in situ CO2
removal utilizing the CaO carbonation for H2 production.
Chem. Eng. Sci. 59, 931–942.
Lyngfelt, A., 2014. Chemical-looping combustion of solid
fuels—status of development. Appl. Energy 113, 1869–1873.
Martínez, I., Romano, M., Fernández, J., Chiesa, P., Murillo, R.,
Abanades, J., 2014. Process design of a hydrogen production
plant from natural gas with CO2 capture based on a novel
Ca/Cu chemical loop. Appl. Energy 114, 192–208.
Mostafavi, E., Sedghkerdar, M.H., Mahinpey, N., 2013.
Thermodynamic and kinetic study of CO2 capture with
calcium based sorbents: experiments and modeling. Ind. Eng.
Chem. Res. 52, 4725–4733.
Ni, M., Leung, M.K., Leung, D.Y., 2007. Energy and exergy analysis
of hydrogen production by solid oxide steam electrolyzer
plant. Int. J. Hydrog. Energy 32, 4648–4660.
806 chemical engineering research and design 1 0 4 ( 2 0 1 5 ) 792–806
Rahimpour, M.R., Hesami, M., Saidi, M., Jahanmiri, A., Farniaei,
M., Abbasi, M., 2013. Methane steam reforming thermally
coupled with fuel combustion: application of chemical looping
concept as a novel technology. Energy Fuels 27, 2351–2362.
Ravikiran, A., Renganathan, T., Pushpavanam, S., Voolapalli, R.K.,
Cho, Y.S., 2011. Generalized analysis of gasifier performance
using equilibrium modeling. Ind. Eng. Chem. Res. 51,
1601–1611.
Rydén, M., Ramos, P., 2012. H2 production with CO2 capture by
sorption enhanced chemical-looping reforming using NiO as
oxygen carrier and CaO as CO2 sorbent. Fuel Process. Technol.
96, 27–36.
Simpson, A.P., Lutz, A.E., 2007. Exergy analysis of hydrogen
production via steam methane reforming. Int. J. Hydrog.
Energy 32, 4811–4820.
Simpson, A.P., Simon, A.J., 2007. Second law comparison of
oxy-fuel combustion and post-combustion carbon dioxide
separation. Energy Convers. Manag. 48, 3034–3045.
Stevens, J.F., Krishnamurthy, B., Atanassova, P., Spilker, K., 2007.
Development of 50 kW Fuel Processor for Stationary Fuel Cell
Applications. Chevron Techology Ventures, LLC.
Szargut, J., Morris, D.R., Steward, F.R., 1987. Exergy Analysis of
Thermal, Chemical, and Metallurgical Processes.
Tavares, M., Alstrup, I., Bernardo, C., Rostrup-Nielsen, J., 1996.
Carbon formation and CO methanation on silica-supported
nickel and nickel–copper catalysts in CO + H2 mixtures. J.
Catal. 158, 402–410.
Tzanetis, K.F., Martavaltzi, C.S., Lemonidou, A.A., 2012.
Comparative exergy analysis of sorption enhanced and
conventional methane steam reforming. Int. J. Hydrog. Energy
37, 16308–16320.
Xiang, J., Cali, M., Santarelli, M., 2004. Calculation for physical
and chemical exergy of flows in systems elaborating
mixed-phase flows and a case study in an IRSOFC plant. Int. J.
Energy Res. 28, 101–115.
Yang, S., Yang, Q., Li, H., Jin, X., Li, X., Qian, Y., 2012. An integrated
framework for modeling, synthesis, analysis, and
optimization of coal gasification-based energy and chemical
processes. Ind. Eng. Chem. Res. 51, 15763–15777.
Zhang, X., Li, S., Hong, H., Jin, H., 2014a. A hydrogen and oxygen
combined cycle with chemical-looping combustion. Energy
Convers. Manag. 85, 701–708.
Zhang, X., Li, S., Jin, H., 2014b. A polygeneration system based on
multi-input chemical looping combustion. Energies 7,
7166–7177.
Zhu, L., Fan, J., 2015. Thermodynamic analysis of H2 production
from CaO sorption-enhanced methane steam reforming
thermally coupled with chemical looping combustion as a
novel technology. Int. J. Energy Res. 39, 356–369.
Zhu, L., Jiang, P., Fan, J., 2015. Comparison of carbon capture IGCC
with chemical-looping combustion and with calcium-looping
process driven by coal for power generation. Chem. Eng. Res.
Des. 104, 110–124.