i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2

Available online at www.sciencedirect.com

ScienceDirect

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

Review Article

Hydrogen production with CO2 capture

Mari Voldsund*, Kristin Jordal, Rahul Anantharaman

SINTEF Energy Research, Sem Sælandsvei 11, NO-7465 Trondheim, Norway

article info abstract

Article history: In view of the abundance of fossil fuels, hydrogen production with CO2 capture could be a
Received 28 October 2015 key transition technology for moving in the direction of a sustainable hydrogen-using
Received in revised form society. An overview of technologies for hydrogen production from fossil fuels with CO2
23 December 2015 capture is provided in this paper: reforming or gasification with subsequent gas separation
Accepted 4 January 2016 by adsorption, absorption, membranes or cryogenic/low-temperature separation; process
Available online 15 February 2016 routes with integrated syngas production and gas separation by wateregas shift mem-
brane reactors, reformer membrane reactors, sorption-enhanced wateregas shift and
Keywords: sorption-enhanced reforming; and processes utilizing the concept of chemical looping.
CO2 capture Furthermore, purity requirements for the produced CO2 and hydrogen are reviewed. Few
Hydrogen production technologies exist that can produce both high-purity hydrogen and CO2 at transport quality
Hydrogen use simultaneously, and the few possible approaches are maximum on the pilot stage. Pro-
Gas separation ducing hydrogen from fossil fuels, while capturing the CO2 for transport and storage is
therefore a matter of matching hydrogen and CO2 separation technologies in a best
possible manner, taking into account the planned transport option for the CO2 and the way
in which the hydrogen will be used. Hydrogen production with CO2 capture can potentially
lead to large CO2 emission reductions in eg. transport sector.
Copyright © 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4971
1.1. Global background: fossil-fuel based hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4971
1.2. Technology background: process routes for hydrogen production with CO2 capture . . . . . . . . . . . . . . . . . . . . . . . . 4972
1.3. Paper aim and strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973
2. Syngas production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973
2.1. Steam reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973
2.1.1. Steamemethane reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973
2.1.2. Partial oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973
2.1.3. Autothermal reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4974

* Corresponding author.
E-mail addresses: mari.voldsund@sintef.no (M. Voldsund), kristin.jordal@sintef.no (K. Jordal), rahul.anantharaman@sintef.no
(R. Anantharaman).
http://dx.doi.org/10.1016/j.ijhydene.2016.01.009
0360-3199/Copyright © 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
4970 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2

2.2. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4974

2.3. Wateregas shift . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4974
2.4. Typical syngas compositions and conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4974
3. Separation technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4975
3.1. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4975
3.1.1. PSA for hydrogen purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4975
3.1.2. PSA for CO2 capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4976
3.2. Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4976
3.3. Membrane separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4977
3.3.1. Hydrogen selective membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4977
3.3.2. CO2 selective membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4977
3.4. Cryogenic/low-temperature separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4977
3.4.1. Cryogenic separation of hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4978
3.4.2. Low-temperature separation of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4978
3.5. Technology performance summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4979
4. Advanced hydrogen production with CO2 capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4979
4.1. Integrated syngas production and gas separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4979
4.1.1. Membrane reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4979
4.1.2. Sorption-enhanced hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4981
4.2. Chemical looping hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4982
4.2.1. Syngas chemical looping process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4982
4.2.2. Direct chemical looping gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4983
4.3. Technology performance summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4983
5. CO2 and hydrogen product purity requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4983
5.1. CO2 purity requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4983
5.2. Hydrogen purity requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4984
6. Large-scale plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
6.1. Ammonia synthesis with CO2 capture by absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
6.2. Hydrogen production for refineries with CO2 capture by absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
6.3. Hydrogen production for refineries with CO2 capture by VSA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
7. Selection of process route . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
7.1. Retrofit versus new plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4985
7.2. Process intensification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4986
7.3. Process integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4986
7.4. Combination of technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4986
7.5. Trade-off . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4987
8. Outlook on production and use of hydrogen in a CCS context . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4987
8.1. Emission reductions in the transport sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4987
8.2. Use of hydrogen in industry and power generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4987
8.3. CO2 emissions between hydrogen production and end user . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4988
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4988
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4988
Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4988
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4988
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2 4971

industry without resorting to hydrogen may be hard to ach-

Abbreviations ieve” [2].
The current global hydrogen production is approximately
ATR Autothermal reforming
7.2 EJ per year. It is largely fossil-fuel based, resulting in
CCS CO2 capture and storage
approximately 500 Mt CO2 per year [3]. The shares of the
CLC Chemical looping combustion
various production methods of hydrogen globally are shown
EOR Enhanced oil recovery
in Fig. 1. Conversion of fossil fuels is responsible for 96%, while
ESA Electric swing adsorption
electrolysis of water is responsible for the remaining 4%.
ETP Energy Technology Perspectives
Natural gas steam reforming holds the largest share of the
FCEV Fuel cell electric vehicle
production from hydrocarbon sources, the second largest part
HDV Heavy duty vehicle
is oil-based, and the remaining part is derived from coal
HHV Higher heating value
gasification.
HT High-temperature
The hydrogen use by sector in 2013 compared to projected
IEA International Energy Agency
use in 2050 in IEAs standard and high-hydrogen 2DSs are
IGCC Integrated gasification combined cycle
shown in Fig. 2. In the standard 2DS, the deployment of fuel
LDV Light duty vehicle
cell electric vehicles (FCEVs) in the passenger light duty ve-
LT Low-temperature
hicles (LDVs) sector begins in earnest in 2025. By 2050 FCEVs
MDEA Methyl diethanolamine
have a share of 13% of the total passenger LDV fleet and 7% of
MEA Monoethanolamine
the total truck stock. In the high-hydrogen 2DS, FCEVs are
MOF Metal-organic framework
PEM Proton exchange membrane
POX Partial oxidation
PSA Pressure swing adsorption
S/C Steam-carbon
SE-SMR Sorption-enhanced steamemethane reformer
SE-WGS Sorption-enhanced wateregas shift
SMR Steamemethane reforming
SMR-MR Steamemethane reformer membrane reactor
TEA Triethanolamine
TSA Temperature swing adsorption
VSA Vacuum swing adsorption
WGS Wateregas shift
WGS-MR Wateregas shift membrane reactor
2DS 2 ! C Scenario
Fig. 1 e Shares of production methods for hydrogen
worldwide [3].

Introduction

Global background: fossil-fuel based hydrogen production

The International Energy Agency (IEA) states in Energy Tech-

nology Perspectives (ETP) 2015 that in order to limit global
temperature increase to 2 ! C (the 2 ! C Scenario e 2DS), energy-
and process-related CO2 emissions should be cut by almost
60% by 2050 compared to 2012. It mentions using hydrogen
based on low-carbon sources as energy carrier as an impor-
tant option to reduce CO2 emissions. Furthermore, it states
that hydrogen production is one of the “sweet spots” for CCS e
it is one of the sectors where the gap is smallest between
current CCS technology costs and the willingness of govern-
ments and firms to invest in climate change mitigation [1].
In ETP 2012 the potential role of hydrogen was studied in
particular by developing two alternative 2DSs: the 2DS high- Fig. 2 e Global hydrogen consumption by sector in EJ in
hydrogen and the 2DS no-hydrogen. It was stated that hydrogen 2013 and anticipated future use in 2050 in the IEA standard
may become especially important in the very long term, and 2DS and high-hydrogen 2DS (see Supplementary
that “completely eliminating fossil fuels in transport and Information for background data).
4972 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
commercially introduced by 2020 and the number of vehicles
by 2050 is doubled compared to the standard 2DS. Hydrogen
use in industry and buildings is not assumed to start before
2050 in the standard 2DS. In the high-hydrogen 2DS,
hydrogen-based steel making and CO2-free hydrogen as
feedstock and energy carrier in the chemical and petro-
chemical sector will play a role in the industry, and fuel-cell
co-generation units will be taken into use in buildings [2].
The development and market introduction of FCEVs ap-
pears to be accelerating. Toyota has launched a FCEV model in
Japan in 2014, Hyundai is planning to begin the sale of FCEVs
in the near future and has had a model available for lease
since summer 2014, and Honda announced plans to launch its
next generation FCEVs in 2016 [3]. The demand for hydrogen
in the transport sector could increase faster that predicted by
IEA even in the high-hydrogen scenario, requiring an even
higher amount of hydrogen production.
On a long term, large-scale hydrogen production by elec-
trolysis of water with abundant electric power from renew-
able sources would be preferable. The hydrogen would be
continuously consumed as fuel for automotive and stationary
fuel cells and as feedstock in the industry. In periods with
excess renewable power, hydrogen could be stored, giving the
possibility to provide load-following electric power
production.
On a shorter term, with increasing but still insufficient
supply of renewable energy, hydrogen production from fossil
fuels with CO2 capture and storage (CCS) may prove to be an
enabler for low CO2-emission hydrogen production. IEA pre-
sents in their Technology Roadmap for Hydrogen and Fuel
Cells [3] suggested pathways to meet the demand for
hydrogen within the high-hydrogen 2DS at lowest cost
(assuming carbon prices for emissions) for US, EU 4 (Germany,
Italy, France, UK) and Japan. In these scenarios renewable
electricity and biomass account for 12e38% of the hydrogen
production in 2050, while fossil sources with CCS account for
58e81%. The share of renewable electricity may prove to be
higher in 2050 than suggested by IEA, and this would be the
preferred scenario. However, even if the shares of renewables
were doubled compared to the IEA pathways, the hydrogen
Fig. 3 e The presently most mature route for hydrogen production from fossil sources with CO2 capture. Solid black lines
represent gasification or autothermal reforming processes, while dashed black lines represents additional streams and
units for the steamemethane reforming process. The preferred sequence of the CO2 capture and hydrogen purification units
in the gas separation part depends on the selected technologies.
production covered by fossil sources with CCS would be
considerable.
Technology background: process routes for hydrogen
production with CO2 capture
With present commercial hydrogen production technologies,
fossil fuel sources are first converted to syngas. The syngas is
typically produced by gasification or reforming, eg. steame-
methane reforming (SMR) or autothermal reforming (ATR),
followed by wateregas shift (WGS). The shifted syngas con-
sists mainly of hydrogen and CO2, but also some unconverted
or partly converted combustible components like CH4 and CO,
and possibly components like H2S, N2 and/or Ar. The CO2 and
the other impurities are separated from the hydrogen in a
hydrogen purification unit.
For a hydrogen production process with CO2 capture, the
gas separation part following the syngas production must be
extended. This is most easily done by including an additional
separation unit. The objective is now to obtain high-purity
hydrogen and CO2 of sufficiently high purity for transport
and storage. This would give three resulting process streams:
one stream with purified hydrogen, one with purified CO2, and
an off-gas containing some hydrogen, CO2, CO, CH4, N2, etc.
A general hydrogen production route with CO2 capture is
shown in Fig. 3. In the case of gasification or ATR, fuel is
oxidized inside the reactor providing heat (the reactor is
internally heated) whereas for SMR, heating is provided by
burning fuel in a furnace (the reactor is externally heated). For
the latter case, a separate stream of fossil fuel is provided to
the reforming furnace, and flue gas is produced. If CO2 in this
case is captured only from the syngas, around 60% of the CO2
from the overall process can be captured. For a higher CO2
capture ratio, a separate CO2 capture unit is required for the
flue gas (post-combustion capture).
The currently most used technology for hydrogen purifi-
cation is pressure swing adsorption (PSA), while the most
mature technology for CO2 capture is absorption with sol-
vents. Alternatively, novel separation technologies such as
different kinds of membranes and sorbents can be used, or
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
low-temperature/cryogenic separation. Furthermore,
advanced technologies for hydrogen production with CO2
capture are under development, such as membrane reactors,
sorption-enhanced hydrogen production, and chemical loop-
ing hydrogen production. The technologies for membrane
reactors and sorption-enhanced reforming and WGS are
developed in the context of process intensification: the syngas
production and gas separation steps are combined to get more
compact and efficient processes where the equilibrium-
limited reactions in the syngas production step are shifted
towards the product side by continuously removing one of the
products. Chemical looping hydrogen production is developed
in the context of CO2 capture.
Paper aim and strategy
The aim of this paper is to provide a general overview and
status of different technology options for fossil-fuel based
hydrogen production for different hydrogen users with CO2
capture. This includes technologies that are commercially
available today, and technologies that are in an R&D phase.
The literature is replete with papers on hydrogen produc-
tion with CO2 capture focussing on specific production routes
and technologies. As regards review papers giving an over-
view of several technologies, a review was made in 2006 by
Damen et al. [4] with the purpose to compare the cost of
hydrogen and electricity production with CO2 capture for
different technology options. The main focus was on absorp-
tion and membrane capture technologies. Further, a tech-
nology review on hydrogen production for chemical and
petrochemical industries was provided by Ritter and Ebner in
2007 [5]. This review included technologies such as membrane
reactors and sorption enhanced reaction processes, but the
perspective of CO2 capture was not incorporated. An extensive
and in-depth description of syngas generation, hydrogen
production and purification technologies was provided in 2010
in the book edited by Liu et al. [6], where CO2 capture is briefly
mentioned. Kenarsari et al. [7] provided in 2013 a review on
CO2 capture technologies with a section about pre-
combustion capture, while Jansen et al. [8] presented in 2015
a dedicated review on the topic pre-combustion capture.
Many of the pre-combustion technologies presented are
relevant for hydrogen production with CO2 capture. However,
the focus is on power production, where the produced
hydrogen does not have to be of high purity. No recent and
comprehensive review has to the authors' knowledge been
provided that gives an overview on all relevant technologies
for production of hydrogen with CO2 capture. The present
paper aims at filling this gap.
CO2 capture as well as hydrogen production from fossil
fuels are vast areas where tremendous research efforts are
being made. The primary strategy in this paper for assembling
knowledge on technology performance and status has there-
fore been to go through recent review papers on the various
technologies, and to complement the findings with additional
knowledge from relevant research papers.
The paper starts with an introduction to syngas produc-
tion, and a review of the relevant separation technologies and
advanced technologies for hydrogen production with CO2
capture. Then current standards and knowledge on
4973
requirements for hydrogen and CO2 purity are listed. There-
after, a review of current large-scale plants are given. This is
followed by a discussion on the selection of process route,
before an outlook on production and use of hydrogen in a CCS
context is given.
Syngas production
A first step in the generation of hydrogen from fossil fuels
(solid, liquid or gaseous) is the production of shifted syngas
(largely consisting of CO2 and H2). Today, syngas is also pro-
duced in large scale as a first step in the synthesis of chemicals
like ammonia and methanol. Different industrial options are
well known, and only briefly described below.
Steam reforming
In steam reforming, gas or liquid fossil fuel is converted to
syngas. Important processes are SMR, partial oxidation and
ATR.
Steamemethane reforming
In SMR, steam and methane react to yield hydrogen and car-
bon monoxide in an equilibrium-limited, highly endothermic
reaction:
CH4 þ H2 O#CO þ 3H2 DHrx ¼ 206 kJ=mol (1)
The reaction is normally carried out at temperatures of
500e900 ! C, pressures of 20e35 atm and steam-to-carbon (S/C)
ratios of 2.5e3.0 [5,9]. High conversion is favoured by high
temperature, low pressure and high S/C ratio (which also
limits carbon deposition) [9]. However, low S/C ratio is
preferred from an energy efficiency and economic point of
view. In modern plants, high temperatures (>900 ! C) are
possible, allowing S/C ratios below 2.5 [10].
SMR is normally performed in externally heated packed
bed reactors, often with a Ni-based catalyst which has suffi-
cient activity and a low cost [9]. The catalyst is sensitive to H2S
poisoning, so if there are considerable amounts of sulphur in
the natural gas, this has to be removed in a desulphurisation
unit prior to the SMR.
If the feed contains ethane and other heavier hydrocar-
bons, a pre-reformer can be used upstream the reformer. A
pre-reformer converts the heavier hydrocarbons into
methane, and also reforms some of the methane into CO and
hydrogen. It operates at lower temperatures than the
reformer: around 400e500 ! C [5].
Partial oxidation
Partial oxidation (POX) of hydrocarbons is a method for pro-
ducing hydrogen from heavy hydrocarbons such as diesel fuel
and residual oil. In principle, any hydrocarbon feedstock that
can be either compressed or pumped may be used for syngas
production with this technology. The reaction occurs when a
fuel is partially burnt with a substoichiometric amount of air
in a reformer. Partial oxidation is an exothermic process and
can be performed both with and without catalyst. The general
reaction equation is:
4974 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
Cm Hn þ m=2O2 #m CO þ n=2H2 (2)
Large-scale uncatalysed reactors typically operate at tem-
peratures in the range of 1150e1500 ! C and pressures between
25 and 80 bar [5,11]. For the catalytic POX process operating
temperatures and pressures are lower (temperature between
780 and 900 ! C and pressure between 25 and 35 atm). Pure or
enriched oxygen supplied by an oxygen plant is commonly
used, in order to avoid processing nitrogen downstream.
However, for ammonia production some nitrogen is desirable,
and the oxygen can be supplied as air [5].
Autothermal reforming
ATR is the combination of non-catalytic POX and SMR.
Methane is reacted with oxygen and steam in a single
chamber:
CH4 þ 1=2H2 O þ 1=4O2 #CO þ 5=2H2 DHrx ¼ 84 kJ=mol (3)
In principle, the heat required for the endothermic SMR
reaction is provided by the exothermic POX reaction. The
temperature of the reaction, and the H2/CO ratio in the prod-
uct can be controlled by varying the steam and oxygen
amounts. The reaction is normally carried out with tempera-
tures in the range of 900e1150 ! C, and ATR reformer pressures
can be between 1 and 80 bar [11]. As for partial oxidation, the
oxygen may be provided in pure form (O2-blown ATR) or as air
(air-blown ATR), depending on whether the syngas will be
used in ammonia synthesis or not.
Gasification
Solid fuels like coal or biomass can be converted to syngas by
gasification. In this process, the fuel is reacted with oxygen
and steam at high temperature and pressure. Some of the
reactions taking place are:
C þ H2 O#CO þ H2 DHrx ¼ 131 kJ=mol (4)
C þ O2 #CO2 DHrx ¼ $394 kJ=mol (5)
C þ 1=2O2 #CO DHrx ¼ $111 kJ=mol (6)
C þ CO2 #2 CO DHrx ¼ 172 kJ=mol (7)
Most commercial gasifiers are entrained-flow gasifiers, and
the most well known examples are GE and Shell Gasifiers. In a
GE gasification system, the gasification temperatures are in
the range 1350e1500 ! C. The pressure can be as high as
100 bar, but is often selected based on the purpose of the gas
product, for instance 85e100 bar in the ammonia industry and
60e70 bar in the methanol industry. Shell gasifiers typically
operates at pressures of 20e40 bar and temperatures of
1440e1600 ! C [12].
Wateregas shift
After reforming or gasification, the produced CO is typically
reacted with steam to produce CO2 and additional hydrogen in
the WGS reaction. This reaction is particularly important for
hydrogen production with CO2 capture, due to the conversion
of CO to CO2, and because the hydrogen yield is maximised.
The reaction is equilibrium-limited and slightly exothermic:
CO þ H2 O#CO2 þ H2 DHrx ¼ $41 kJ=mol (8)
WGS conversion is favoured at low temperatures, while
reaction kinetics are favoured at high temperatures [13].
Similar to the SMR, a high S/C ratio gives high CO conversion,
but results in an efficiency penalty. Since the net amount of
moles does not increase in the reaction, the total pressure
does not influence the CO conversion. However, a high pres-
sure gives a higher reaction rate [14].
The WGS reaction is often conducted in at least two stages:
first a high temperature step (HT WGS) at 320e360 ! C and
10e60 bar where fast reaction is favoured, and the catalyst bed
volume is therefore minimized; then a low temperature step
(LT WGS) at 190e250 ! C and 10e40 bar where a high conver-
sion is favoured. This allows a smaller adiabatic temperature
rise and a better steam management, at the same time as the
amount of catalyst is minimised and high conversion is ob-
tained [14].
The reaction may be performed both with H2S present
(sour WGS) and without (sweet WGS). For the case of sour
WGS, a cobalt-molybdenum catalyst is used. For sweet WGS,
the HT WGS is often carried out with a Fe-based catalyst, while
the LT WGS is often carried out with a Cu-based catalyst [14].
After WGS, the syngas is usually cooled and flashed to
remove water.
Typical syngas compositions and conditions
The composition, temperature and pressure of the resulting
syngas depends on factors such as the selected reforming or
gasification type, the composition of the fuel that has been
used, S/C ratio, the degree and conditions of the shift reaction,
and the purity and flow of the oxygen feed (if used). In general,
syngas originating from natural gas has higher hydrogen
levels and lower CO2 levels than coal derived syngas, and for
syngas from air-blown ATR the level of nitrogen is significant.
Natural gas derived syngas has very low levels of sulfur
compounds, because most sulfur is removed before the
reformer to prevent catalyst poisoning, while coal derived
syngas typically contains more sulfur. Shifted syngas com-
positions from some literature sources are given in Table 1.
Table 1 e Shifted syngas composition given in mol% from
different feedstocks and reforming/gasification. The
syngas is normally saturated with water, but all
compositions are converted to dry basis. Where not
specified in the source, % is assumed to be mol%.
SMR þ WGS Air-blown Coal
[5,15] ATR gasification
þ WGS [16,17] þ WGS [18e22]
H2 70e80 44e49 54e57
CO2 15e25 17 38e44
CO 0.5e3 0.52e0.58 0.6e1.7
N2 trace 33e38 1.0e4.8
Ar 0.39e0.45 0.47e0.90
CH4 3e6 0.07e0.09 %1.33
H2S %0.06
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
Fig. 4 e The concept of pressure swing adsorption e
adsorption and desorption of impurities.
Separation technologies
After the production of shifted syngas, hydrogen and CO2 have
to be separated from the other components and purified. The
relevant separation technologies for hydrogen production
with CO2 capture are adsorption, absorption, membranes and
cryogenic/low temperature processes.
Adsorption
Adsorption is a physical process where molecules fix them-
selves on the surface of adsorbents (usually solid materials).
Molecules have different affinities for various types of adsor-
bents, and this phenomenon can be used to purify gases. For
the purpose of hydrogen purification multiple types of ad-
sorbents can be selected so that all types of impurities are
adsorbed and hydrogen passes through with very limited
adsorption. For the purpose of CO2 capture, adsorbents that
selectively adsorb CO2 from a gas mixture can be used.
Several types of adsorption processes exist, such as pres-
sure swing adsorption (PSA), temperature swing adsorption
(TSA) or electric swing adsorption (ESA). For the purpose of
hydrogen and CO2 separation from syngas PSA is most
Fig. 5 e Flow diagram for a multiple column PSA process.
4975
relevant, because the syngas is at elevated pressure allowing
for pressure swing with limited energy penalty.
PSA for hydrogen purification
PSA is the currently most used technology for hydrogen pu-
rification with the possibility to obtain very pure hydrogen
(sometimes exceeding 99.9999 mol% [15]). The technology has
been used in hydrogen plants since the early 1980s [5]. Thor-
ough overviews of the topic are given by Ritter and Ebner [5]
and Sircar and Golden [15].
When PSA is applied to purify hydrogen from syngas, the
syngas is sent through an adsorbent column at high pressure,
where impurities are adsorbed while hydrogen passes
through with very limited adsorption. When the adsorbent is
saturated, it is regenerated by lowering the pressure and
purging with hydrogen. The adsorption and desorption steps
are illustrated in Fig. 4.
Several columns are typically operated simultaneously
(Fig. 5), with adsorption, depressurisation, purge and pres-
surisation steps shifted in time. The hydrogen used in a purge
step is supplied from another column that is in a depressur-
isation step [15]. The resulting process is semi-continuous,
and produces a high-purity hydrogen stream, and an off-gas
containing the CO2, other impurities and some hydrogen.
For hydrogen purification, columns with multiple adsor-
bents (layered beds) are normally used. Typical adsorbents
include silica gel, alumina, activated carbon, and zeolite, and
they have different relative strength of adsorption to different
components [5,23]. Although the method is well established,
there is still room for optimisation of adsorbent material. New
types of adsorbent are under development, such as metal-
organic frameworks (MOFs) [24,25].
PSA units are typically operated at ambient temperature
(adsorption is promoted at low temperature) and feed pres-
sure of 20e60 atm [5]. The hydrogen product is produced at
slightly lower pressure than the feed (typically with a pressure
drop of less than 1 bar) and the PSA off-gas is delivered at low
pressure, typically 1.1e1.7 atm [15]. A variation of PSA is
vacuum swing adsorption (VSA), where pressure is reduced
below atmospheric pressure with vacuum pumps.
4976 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
PSA technology can produce 98e99.9999þ mol% hydrogen
with a hydrogen recovery of 60e95%, depending on feed gas
composition [5,15]. PSA units can be adjusted to provide very
low levels of CO, CO2 and CH4 in the hydrogen while they will
have more difficulty retaining argon, oxygen and nitrogen.
Furthermore, higher purity levels require higher adsorbent
volumes and result in lower hydrogen yield [23]. In standard
plants without CO2 capture, the CO2-rich off-gas is often used
as fuel due to the content of combustible components. It can
be observed that for transport and storage of the CO2, the PSA
unit is not sufficient, and another separation unit has to be
added to the process.
PSA for CO2 capture
Adsorption can be used to capture and purify CO2 from other
gases with a CO2 selective adsorbent. Air Products and
Chemicals patented already in 1979 a PSA process for pro-
duction of high-purity hydrogen and CO2 [26]. This process
consists in principle of two steps: first six parallel adsorbent
beds with activated carbon selectively removes wet CO2,
before three parallel adsorbent beds with zeolites removes
CH4, CO, N2, and the remaining CO2 from the hydrogen [15,27].
They have since 2013 run a demonstration plant where they
have retrofitted an existing hydrogen production facility by
adding a VSA unit that captures wet CO2, between the already
existing SMR and PSA units. More than 90% of the CO2 is
captured with purity greater than 97% (after compression and
drying) from a syngas containing >15% CO2 [28e31].
Alternative process set-ups have been patented but not
realized in large-scale. Krishnamurthy et al. [32] suggest a
process where a CO2 PSA step is performed after the hydrogen
purification PSA step, thus eliminating the impact of any
ingress of air in the CO2 PSA step on the hydrogen purity.
Couche [33] suggests a process where a single PSA step con-
sisting of a set of parallel adsorption columns produces one
stream with purified hydrogen, one stream with wet CO2 and
one stream with off-gas with a mixture of hydrogen, CO2 and
other components. The two latter streams are produced dur-
ing regeneration of the columns at different pressure levels.
This concept is a rare example on hydrogen- and CO2 purifi-
cation combined in one process unit.
Absorption
Gas separation by absorption is carried out industrially by
bringing the gas in contact with a liquid solvent in a scrubber
column, where certain impurities are absorbed. The rich sol-
vent is then heated and/or depressurised and sent to a
regeneration column which produces one stream with the
absorbed components, and one with lean solvent that is sent
back to the scrubber column. The principle is shown for CO2
absorption from syngas in Fig. 6.
CO2 absorption is a commercially mature technology,
frequently used in natural gas sweetening (first done in the
1930s with TEA [34]). It was commonly used for purification in
hydrogen plants prior to 1980 when PSA which could produce
high-purity hydrogen for the same costs became commer-
cially available [5,35]. The technology is still commonly used
for purification of hydrogen in ammonia plants with a sub-
sequent methanator [5].
Fig. 6 e Principle of CO2 absorption from syngas.
Liquid solvents can be divided into chemical and physical
solvents. Chemical solvents react with CO2 and require a
considerable amount of heat for regeneration [36]. They offer
fast reaction rates, meaning small plant sizes [37]. Typical
chemical solvents are aqueous solutions of amines such as
MEA, TEA and MDEA, or aqueous solution of hot potassium
carbonate (eg. the Benfield process) [37,38]. Physical solvents
dissolve CO2, and are regenerated with reduced pressure and/
or increased temperature, requiring less heat than chemical
solvents [34,36]. They commonly allow combined CO2/H2S
removal [39]. Typical technologies utilising physical solvents
are the Rectisol®, Selexol™, and Purisol® technologies [34].
The absorption capacity of chemical solvents is relatively
high at low CO2 partial pressures. It increases with the CO2
partial pressure, but at a certain point it begins to saturate.
The absorption capacity of physical solvents is lower than for
chemical solvents at low CO2 partial pressures, but increases
linearly with CO2 partial pressure according to Henry's law.
Chemical solvents are therefore preferred at low CO2 partial
pressures while physical solvents are preferred at high CO2
partial pressures [40].
For CO2 capture from syngas various solvents may be
optimal depending on the syngas conditions and the targeted
purity of the product. In CO2 capture from syngas in IGCC
processes, there have been several studies comparing sol-
vents with different conclusions (process simulation studies
such as [40,41], or pilot testing such as the Eagle project [42]).
In the Puertollano demonstration project activated MDEA was
used [43], while the Selexol process is selected in the Kemper
County project [44]. The conclusions may be different when
hydrogen of high purity is targeted. For instance, Rectisol is
the technology that can give the deepest purification. It has
the ability to purify coal gasification syngas to 0.1 ppm total
sulfur and CO2 in ppm range [8], [45].
The purity of the produced CO2 stream also depends on the
syngas and on the selected technology. For instance, MDEA is
shown to be able to capture CO2 at >99% purity with 95% re-
covery rate from ATR syngas [16]. Rectisol can capture CO2 at
95% (standard) or >98.5% (advanced) purity. Very high recov-
ery rates can be achieved, while for IGCC applications CO2
recovery rates of typically 90e97% are reported. Selexol can
capture CO2 at 98e99.7% purity. All these solvents capture
sulfur components together with CO2, but it is possible to
modify some of the processes to produce CO2 and sulfur as
separate streams [46]. On overall it can be observed that
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
absorption technology can produce CO2 at high purity. CO2
recovery rates can be very high, but impurities such as CO and
CH4 are not removed. The hydrogen is therefore produced at
lower purity.
Membrane separation
Membranes are selective barriers that are ideal for separation
purposes because they let certain components pass through
more easily than others. The part of the feed that passes
through the membrane is denoted permeate while the part that
does not pass through is denoted retentate. Characteristics
essential for membranes are (i) high selectivity, (ii) high flux,
(iii) low cost, (iv) high mechanical stability and (v) high
chemical stability. The transport of molecules through the
membrane is driven by difference in partial pressures over the
membrane, and depending on the process there may be a
demand for compression power.
For hydrogen production with CO2 capture, both hydrogen
and CO2 selective membranes are relevant. Hydrogen selec-
tive membranes produce a permeate consisting of high-purity
hydrogen (although the purity depends on membrane type) at
low pressure, and a retentate with impure CO2 at higher
pressure. CO2 selective membranes typically produce a CO2
enriched permeate at low pressure, and a CO2 depleted
retentate at high pressure.
Hydrogen selective membranes
The most mature type of hydrogen selective membranes is
polymeric membranes. They have operating temperatures below
100 ! C, and have been used for hydrogen recovery from low-
temperature process streams for many years [5,47,48]. They
can withstand high pressure drops and they are relatively
cheap [49]. However, such membranes have relatively low
hydrogen selectivity and hydrogen flux, limited mechanical
strength, high sensitivity to swelling and compaction and they
are vulnerable for poisoning from components such as HCl,
SOx and CO [49,50]. Their poor selectivity of hydrogen against
CO2 is a large drawback for use in CO2 capture [51]. This is also
a drawback for production of high-purity hydrogen.
High-temperature hydrogen selective membranes are under
development and subject to extensive research. Such mem-
branes have high operating temperatures, and can be divided
into metallic membranes (300e700 ! C), microporous ceramic
membranes (200e600 ! C), porous carbon membranes (500e900 ! C)
and dense ceramic membranes (600e900 ! C) [50]. These mem-
branes have the potential to offer higher hydrogen flux and
selectivity compared to polymeric membranes [47]. However,
they are currently too expensive for industrial use. For bulk
separation of hydrogen after WGS, the membranes with
operating temperatures in the range 200e400 ! C are of highest
interest. The membranes with higher operating temperatures
are more relevant for separation after SMR, or in a SMR-MR.
Many reviews on hydrogen membranes are available, such
as [5,47e50,52].
The most widely studied membranes for hydrogen sepa-
ration are metallic membranes, most often made from palla-
dium or palladium alloys. Their theoretical selectivity is
infinite, and membranes giving hydrogen purities of
99e99.995% have been developed. One major challenge is the
4977
mechanical stability: very thin membrane materials are
developed to increase the hydrogen flux, but these materials
must withstand the pressure differential over the membrane.
Another major challenge is the chemical stability: the mate-
rials are sensitive to poisoning by components such as CO and
H2S. Furthermore, the production costs are high due to the use
of precious metals [50]. Palladium-based membranes are
available on the market, but these are relatively thick, and
therefore expensive and with low hydrogen permeance
[47,50]. Dense ceramic membranes have also very high
selectivity, but they have generally lower flux than the
metallic membranes, and they are also sensitive to poisoning
[50]. Microporous membranes have lower selectivities, but
they are cheaper and have greater chemical stability (although
water vapour can affect performance) [53]. So far, there is no
clear winner among the high-temperature membranes and
none are commercial on large scale [53].
In overall, high-temperature hydrogen membranes are
available, and they are continuously improved. The main
challenges for large-scale industrial application are fabrica-
tion reproducibility, material costs, and the chemical and
mechanical stability [47,49,50]. However, the technology is
under transition to pilot stage. Kinetics Technologies have
tested three types of commercial membranes in a 20 Nm3/h
hydrogen production plant for over 1300 h, and demonstrated
that all three membranes showed operational stability for
operation with SMR syngas [54]. Reinertsen and SINTEF are
presently in the beginning of a project where they aim for up-
scaling hydrogen purification with a Pd-based membrane in a
pilot producing 25e100 Nm3/h hydrogen [55].
CO2 selective membranes
It is challenging to separate CO2 selectively from mixtures
with hydrogen, since the CO2 molecule is much larger than the
hydrogen molecule. However, several membrane types exist:
polymeric CO2 selective membranes based on either solution-
diffusion mechanism (the solution effect must dominate
over diffusion), or facilitated transport mechanism [53]; mixed
matrix membranes, which consist of inorganic particles
dispersed uniformly in a polymer matrix [56]; and porous
inorganic membranes that are CO2 selective either by surface
diffusion or capillary condensation. One interesting mem-
brane type under development is dual-phase membranes con-
sisting of a molten carbonate phase and metal or ceramic
phase, that show great potential for high temperature opera-
tion [57], [58].
There are currently commercial membranes on the market
that can separate CO2 from hydrogen, albeit with low selec-
tivity and with low operating temperature [53]. As stated by
Scholes et al. [53] (in the context of CO2 capture from IGCC),
CO2 selective membranes are significantly less advanced than
hydrogen selective membranes, and considerable more
research is required before they can be applied. At the current
state, such membranes can be used for CO2 enrichment, but
CO2 at transport quality is not achieved directly.
Cryogenic/low-temperature separation
In cryogenic or low-temperature separation gas is cooled, and
differences in boiling point is used in order to separate
4978 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
different chemical components. For separation of hydrogen,
the gas mixture is cooled to cryogenic temperatures
(<$150 ! C). Contaminant gases are condensed at different
temperature levels, while the hydrogen remains in gas phase.
For separation of CO2, the gas mixture is cooled below the
boiling point of CO2 at the given pressure (above the CO2 triple
point at 5.2 bar and $56.6 ! C), and the CO2 is condensed from
lighter gaseous species.
Cryogenic separation of hydrogen
Cryogenic separation processes can be used to produce
moderately pure hydrogen from syngas, and are in some
existing syngas plants used to adjust the composition of
syngas for a chemical feedstock unit [5]. In ammonia pro-
ductioncryogenic separation is often integrated in the purge
gas recovery loop from the back to the front end of the
ammonia unit [59]. It is also used in refineries to recover
hydrogen from gas streams vented from hydrocracking or
hydrotreating operations [60]. One of the earliest processes for
cryogenic separation of hydrogen from syngas is the Linde-
Bronn process [59,61]. Cryogenic separation is generally not
used as the main separation system in hydrogen and
ammonia plants, as can be seen in the plant overviews pre-
sented by Ritter and Ebner [5]. This is probably due to a high
refrigeration demand.
Low-temperature separation of CO2
CO2 can be separated from gases with higher boiling temper-
atures by cooling and physical phase separation. Coal and
natural gas derived syngases have generally CO2 partial
pressures above the CO2 triple point pressure, and are there-
fore suitable for vapoureliquid separation [20].
There are many process design options for low-
temperature separation. One possible process sheet for low-
temperature capture from coal gasification syngas is pre-
sented by Berstad et al. [62] (Fig. 7). First drying (eg. with mo-
lecular sieves) is necessary in order to avoid solid formation.
The syngas is then compressed with intercooling to
Fig. 7 e Exemplified process flow diagram for low-temperature syngas separation.
90e115 bar, before it is cooled to around $55 ! C with a multi-
stream process-to-process heat exchanger, and a cascade
propane and ethane refrigeration cycle. CO2 is then
condensed out from the syngas in a separator. In order to
obtain a high CO2 purity and avoid loss of hydrogen, the ob-
tained CO2 is purified with a flash separator at lower pressure
and higher temperature. In the process described, expanders
are used to recover power from the hydrogen-rich process
stream. Process simulations have shown that CO2 purities in
the range of 99.7e99.9 mol% can be obtained.
Berstad et al. [63] provide a review on the applications and
potential of low-temperature separation, showing that the
process shows promising potential and competitive energy
figures for capture from syngas (in particular coal-derived).
The CO2 separation and compression work decreases with
increasing CO2 concentration in the feed. CO2 recovery of
85e90% may be obtained. Alternative low-temperature sepa-
ration principles are capture by condensed rotational sepa-
ration [64] and distillation [20].
An advantage with low-temperature separation is that the
captured CO2 is in liquid state and can be pressurized for
transport by pumping at low energy cost [20]. The option is
particularly practical for transport with ship, where CO2 most
likely will be transported in liquid form.
Tokyo Gas (Japan) used low-temperature separation to
capture CO2 from the off-gas (or retentate) of a reformer
membrane reactor (see Section 7.4). The gas had a high CO2
concentration (70e90%), and the CO2 was liquefied through
compression and cooling. Over 90% of the CO2 in the off-gas
was captured. The overall efficiency (HHV) of their process
was 81.4% for production of hydrogen without CO2 capture,
and was only reduced to 78.6% when the low-temperature CO2
capture was introduced [65].
The low-temperature separation process consists of well-
known process components only, and there should be no
technical constraints to hinder large-scale low-temperature
CO2 separation from syngas.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2 4979

Table 2 e Summary of performance for different options for hydrogen and CO2 separation from syngas. For the high-purity
product, literature values are given for purity and recovery. Where not specified in the source, % is assumed to be mol%. For
the low-purity product values in brackets are approximate values calculated based on syngas compositions from Table 1.
Values are given on dry basis.
Adsorption Adsorption Absorption Absorption Membrane Low -temperature
e H2 PSA e CO2 VSA e MDEA e Physical e Pd-based CO2 capture
H2 purity, mol% 98e99.9999þ Low (<91) Low (58a) Low (83e86) 99e99.995 Low (81e83)
H2 recovery, % 70e95 High High High n/a High
CO2 purity, mol% Low (39e57) >97 99.9 95e99.7 Low 99.7e99.9
CO2 recovery, % High >90 95 90e97 High 85e90
Source [5,27] [31,66] [16] [46] [50] [62,63]
Syngas in source SMR SMR Air-blown ATR Gasified coal SMR Gasified coal
a
Note that this value is for air-blown ATR for power generation. The hydrogen contains 40% nitrogen.

Technology performance summary separation in sorption-enhanced WGS, and that the

A summary of separation performance for the most relevant
technologies presented above are given in Table 2. Note that
the selected figures come from various sources, and the pro-
cesses are not always optimised for hydrogen production.
Purity and recovery values are dependent on the use of re-
sources such as adsorbent, steam, membrane area, refriger-
ation etc.
Advanced hydrogen production with CO2 capture
Integrated syngas production and gas separation
The hydrogen producing reactions are equilibrium-limited,
which implies that if hydrogen or CO2 is continuously
removed, the reactions will be shifted in favour of increased
conversion. This can be obtained in practice by combining
the reaction and separation steps, which can lead to advan-
tages such as increased energy efficiency, reduced reactor
or catalyst volume etc. The concept of such advantageous
combinations of process steps is known as process
intensification.
There are several technologies for hydrogen production
where the reaction and separation steps are integrated:
reforming/gasification step, the WGS step and CO2 separa-
tion can be combined in sorption-enhanced reforming. Most
of the technologies that produce high-purity hydrogen will
produce impure CO2, while most of the technologies that
produce CO2 of transport quality will produce impure
hydrogen.
Membrane reactors
In membrane reactors for hydrogen production, the chemical
reactions take place in membrane reactors where hydrogen or
CO2 is selectively removed. This shifts the equilibrium-limited
reaction towards the product side, giving increased conver-
sion, and/or allowing to carry the reactions out at milder
thermal conditions.
This field has been subject to substantial research. The
amount of papers on membrane reactors for hydrogen pro-
duction has escalated since 1996, and more than 100 papers
have been published each year since 2008, as shown by Gal-
lucci et al. [50]. Although CO2 selective reactors have been
studied [53,67,68], research and development of hydrogen
selective reactors for hydrogen production are far more
advanced, and focused on in this paper. This might be
explained by looking at the reaction stoichiometrics: the
motivation for hydrogen removal is higher, because it will
have a higher effect on conversion (for the overall reaction)
compared to CO2 removal.

& Wateregas shift membrane reactors (WGS-MR)

& Steamemethane reforming membrane reactors (SMR-MR)
& Sorption-enhanced wateregas shift (SE-WGS)
& Sorption-enhanced steamemethane reforming (SE-SMR)

The technologies are shown schematically in Fig. 8. The

figure shows the conventional process route in the center,
where fuel is transformed into syngas by reforming or
gasification and further to hydrogen and CO2 (shifted syn-
gas) by the WGS reaction. The hydrogen is thereafter puri-
fied and/or CO2 is captured using different technologies. On
the left-hand side it can be seen that the WGS step can be
combined with hydrogen separation in a WGS membrane
reactor, and that the reforming/gasification step, the WGS
step and the hydrogen separation step can be combined in a
reformer membrane reactor. On the right-hand side it can Fig. 8 e Overview on integrated syngas production and gas
be seen that the WGS step can be combined with CO2 separation technologies.
4980 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
Membrane property requirements. The membrane in a mem-
brane reactor has to be able to operate under the thermal
conditions where the reaction takes place, and this has been a
big motivator for research on high-temperature membranes.
Under normal operation (no equilibrium shift), relatively mild
thermal requirements (200e400 ! C) are present under the
WGS reaction, higher temperatures are required for the
reforming of natural gas (500e900 ! C), and gasification of coal
often requires temperatures exceeding 1000 ! C. It is also
important that the membrane can withstand high pressure,
and has a high durability. Furthermore, the hydrogen
permeability must be high e it is critical that the hydrogen flux
is comparable to the rate of the catalytic reaction [47].
It is also critical to develop membranes that are not
poisoned by the components that are inevitably present in
the syngas. Presently many high-temperature membranes
are vulnerable for certain chemical compounds. For
instance, for palladium based membranes the presence of
components such as H2S, HCl, CO2 and CO can decrease the
performance. The presence of H2S can cause a significant
loss of hydrogen flux [69]. Sulfur components can be
removed prior to the membrane reactor in the process, but
CO2 and CO will be present in the syngas. Most critical is the
CO adsorption, but it is more evident at temperatures below
250 ! C [14].
WGS membrane reactors. In a WGS-MR, the WGS reaction is
combined with hydrogen membrane purification (Fig. 9). The
WGS reaction is exothermic, and conversion is therefore fav-
oured at low temperatures. However, when hydrogen is
continuously removed, the equilibrium is shifted, and it is
possible with a higher conversion at higher temperatures [14].
This reduces the cooling demand. Operating temperatures of
300e500 ! C are suitable for the WGS-MR, and various micro-
porous, dense metallic and dense ceramic membranes can be
operated at these temperatures [50].
As for normal WGS increased S/C ratio increases conver-
sion. However, a too large amount of steam can negatively
affect the membrane structure. Increased pressure increases
the hydrogen transport over the membrane and therefore also
the conversion. However, for microporous membranes, that
are not perfectly hydrogen selective, it has been observed that
an increased pressure on the reactor side has given an
increased permeation of the reactants. Furthermore, mass
transport can also be increased by sweep gas on the permeate
side that decreases the partial pressure of hydrogen. Sweeping
is most effective for membranes with high hydrogen selec-
tivity [14]. In the case of high-purity hydrogen production,
sweeping with steam is most relevant, since it can be removed
by condensation.
Fig. 9 e Principle of a WGS-MR.
Conventional Cu- and Fe-based catalysts are not well
suited for WGS-MRs due to a retardation effect of the reaction
products that is more intense in membrane reactors. There is
therefore focus on the development of alternative catalysts,
such as Cu-ceria and precious metals [14].
The research on WGS-MRs is presently on lab scale, but it is
ready for transition to pilot scale [70].
SMR membrane reactors. In an SMR-MR, the SMR, WGS and
hydrogen purification process steps are combined (Fig. 10).
Normally, the chemical reactions have to be carried out at
different operating conditions in order to obtain sufficient
conversion and reaction rates. However, when hydrogen is
continuously removed, the resulting equilibrium shift makes
it possible to carry out both these reactions simultaneously.
The SMR reaction is strongly endothermic, and the WGS
reaction mildly exothermic. In total, heat has to be added to
the reaction system, and conversion is favoured at high
temperatures (modern plants operated at >900 ! C). Among
the hydrogen membranes, ceramic membranes have the
closest operating temperatures (600e900 ! C). Some of them
are promising for integration with SMR [71]. Also membranes
with slightly lower operating temperatures can be used,
because the SMR can due to the equilibrium shift be carried
out at lower temperatures [50]. Like for WGS-MRs, conver-
sion can be increased by using sweep gas and by increasing
pressure [72].
Tokyo Gas has in cooperation with Mitsubishi Heavy In-
dustries demonstrated small-scale (40 Nm3/h) membrane
reformer systems with hydrogen production. They first
developed a system with hydrogen production efficiency of
70e76% (HHV) and product hydrogen purity higher than
99.999% [73]. The reformer was a packed bed membrane
reactor with a <20 mm Pd-alloy membrane, and it was tested
for more than 3000 h. Towards the end of the testing period,
impurity concentrations in the permeate started to increase.
However, the purity of hydrogen was still higher than 99.99%
at the end of the durability test. Later they developed an
improved system with a hydrogen production efficiency of
81%. They found that key issues for commercialization of their
reformer system is long-term durability and cost [74]. This
pilot is the largest membrane reactor that has been demon-
strated for hydrogen production so far.
Reactor configuration. Traditional SMR and WGS reactors are
packed bed reactors, and the simplest and most studied
membrane reactor type is the packed bed membrane reactor
configuration. However, with such reactors the hydrogen
Fig. 10 e Principle of an SMR-MR.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
transport between the catalyst bed and the membrane wall
can be rate limiting. If this transport is slower than the
hydrogen transport through the membrane, a concentration
gradient between the catalyst bed and the membrane will
emerge. This effect is known as concentration polarization
[75,76]. Furthermore, temperature control is quite difficult in
packed bed membrane reactors, and a decreased temperature
on the membrane surface can lead to a lower hydrogen flux
while an increased temperature can lead to cracks in the
membrane surface. Finally, to limit pressure drop along the
reactor, large catalyst particles have to be used, and this gives
intra-particle mass transfer limitations [50].
There is an increasing interest in novel reactor configura-
tions such as fluidized bed membrane reactors and micro-
membrane reactors. Gallucci et al. [50] argues that industrial
types of membrane reactors for production of pure hydrogen
most likely will be based on such reactor configurations, and
that the success of membrane reactors for hydrogen produc-
tion are highly dependent on design of innovative reactor
concepts.
It should be noted that increased conversion due to equi-
librium shift also can be obtained by operating membrane
modules in sequence with reactors, as demonstrated in a pilot
for SMR [54] and by simulation for WGS [77].
Sorption-enhanced hydrogen production
The concept of sorption-enhanced hydrogen production is to
use adsorbents to selectively remove one or more of the
products formed in the equilibrium-limited reactions used in
hydrogen production, shifting the equilibrium and obtaining
higher conversion at milder thermal conditions. It is in prin-
ciple a combination of the hydrogen producing reaction steps
and PSA/TSA. In sorption-enhanced WGS (SE-WGS) the WGS
reaction is carried out while CO2 is continuously removed by a
solid sorbent, while in sorption-enhanced SMR (SE-SMR) the
SMR and WGS are carried out simultaneously while CO2 is
continuously removed. There exist several review papers on
the concept [5,78,79].
Sorbent properties. Common adsorbents developed for PSA
have low sorption capacities at the elevated temperatures
required for SE-WGS or SE-SMR [5]. The high-temperature CO2
adsorbents that have received most attention are calcium-
based sorbents and hydrotalcite sorbents, although alterna-
tives such as mixed metal oxides are also being studied [78].
Calcium oxide is a temperature reversible adsorbent, which
has high adsorption capacity at around 500 ! C and high
regeneration rates at 700e900 ! C [5]. It is inexpensive but has a
high heat demand for regeneration [79]. The adsorption ca-
pacity can be increased while the regeneration temperature
can be decreased by addition of NaOH [80]. K-promoted
hydrotalcite is a pressure (and temperature) reversible
adsorbent with adsorption and regeneration temperatures
around 400 ! C, relatively fast kinetics, but relatively low
adsorption capacity [78,79]. This sorbent has shown to
reversibly adsorb H2S when present [81].
In general, sorbents for SE-WGS and SE-SMR require a
trade-off between high mechanical stability, high adsorption
capacity, fast reaction kinetics and low regeneration heat
demand. The mechanical stability is particularly important if
4981
the sorbent is to be mixed with metallic catalyst in entrained
flow reactors.
Sorption-enhanced WGS. The principle of SE-WGS is shown in
Fig. 11. In the reaction step, adsorption of CO2 shifts the re-
action towards increased hydrogen yield. This is followed by a
decrease in pressure and/or increase in temperature, and
purging with steam, giving desorbed CO2 and regenerated
sorbent. A semi-continuous process can be performed with
fixed bed reactor columns packed with WGS catalyst pellets
and CO2 sorbent pellets. Several columns are then run in
parallel, but at different stages in the process cycle with multi-
level depressurisation and repressurisation steps, similar to
the concept used for PSA. Alternatively, a continuous process
can be performed with circulating fluidized bed reactors: one
reactor where the sorption-enhanced reaction takes place and
one reactor for regeneration of the sorbent.
Due to the equilibrium shift, the exothermic WGS reaction
can take place at higher temperatures than normal, which
improves reaction kinetics and reduces the need for large
cooling and reheating systems. The shift also allows lower S/C
ratios, reducing the steam demand [80]. Laboratory tests have
shown a significant improvement in CO conversion for SE-
WGS both using hydrotalcites [82,83], and calcium oxide
[80,84], and simulation studies have shown promising per-
formance for optimized SE-WGS processes [85].
Experiments have shown both that typical WGS catalysts
are robust towards periodic atypical conditions encountered
within a SE-WGS cycle [86], and that a complete CO conver-
sion can be obtained by SE-WGS without any catalyst [87].
For process configurations based on promoted hydro-
talcite, pressure swing and purging with steam, the produced
hydrogen is typically around 400 ! C, 30 bar and 90e95% purity,
while the CO2 is around 400 ! C and ambient pressure [87].
Alternative processes are also suggested, for instance a pro-
cess where CO2 is produced at higher pressure [88]. Depending
on the sorbent used, H2S can be captured simultaneous with
the CO2 if present. Then an additional unit for removal of H2S
from the CO2 is required. CO2 purity of 99% is realistic, and the
optimum CO2 capture ratio is around 90e95% [89].
The SE-WGS technology is on lab scale, but under transi-
tion to pilot scale. ECN in the Netherlands with collaborators
established proof of principle in a lab scale facility using
Fig. 11 e Principle of SE-WGS with fixed bed reactor
columns. The symbol ∑ represents the solid sorbent.
4982 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
pressure swing and potassium-promoted hydrotalcite-based
materials under realistic conditions [90]. As a continuation of
their work SE-WGS will be demonstrated on pilot scale adja-
cent to the SSAB steel plant in Sweden in the Horizon 2020
project STEPWISE, which started on May 1st 2015.
Sorption-enhanced SMR. In SE-SMR, the SMR and WGS re-
actions take place simultaneously with CO2 separation over a
reforming catalyst mixed with a CO2 sorbent. The equilibrium
shift allows both the reforming and water gas shift reactions
to approach completion [78,91]. The principle is similar to SE-
WGS, but the reactions take place at higher temperatures.
Circulating fluidized bed reactors are ideal for SE-SMR.
Fixed-bed reactors systems have also been suggested, but
might not be optimal due to the high reaction temperature.
For instance, the operation of large valves at high tempera-
tures might be problematic [78]. The principle of SE-SMR in
circulating fluidized bed reactors is shown in Fig. 12. Heat for
regeneration of the sorbent can be supplied either by burning
fuel in the regenerator or by indirect heating from an external
source [92].
The equilibrium shift enables higher conversion at lower
temperatures than for normal SMR e typically around 600 ! C.
High system pressure reduces the vessel sizes, however
increasing pressure of the regeneration step will require
higher regeneration temperature [93].
The SE-SMR technology is also under transition to pilot
scale. It has been tested at laboratory scale by various groups
[92,94]. For instance, a hydrogen concentration of 98e99 vol%
was obtained in an experimental bubbling fluidized bed
reactor after four reforming/regeneration cycles [92]. IFE
(Norway) is currently in the test phase of a 30 kW SE-SMR
prototype with a dual bubbling fluidized bed reactor system.
The reformer is run at 600 ! C and the regenerator at 850 ! C
with calcined dolomite as CO2-sorbent and a commercial Ni-
based reforming catalyst [93]. Initial batch test runs with
biogas have given a product with ~94 vol% hydrogen and
<0.1 vol% CO2 [93]. ZEG Power (Norway) has developed a
concept for thermal integration of SE-SMR producing
hydrogen and a solid oxide fuel cell producing electric power.
They are currently testing a 20 kW fuel cell system, and the
Fig. 12 e Principle of SE-SMR in a circulating fluidized bed
reactor. The symbol ∑ represents the solid sorbent.
aim is to integrate it with an SE-SMR process. Exhaust gas
from the fuel cell afterburner will provide the heat required in
the regeneration step of the SE-SMR. They are aiming to
demonstrate 70% overall efficiency for cogeneration of
hydrogen and power [95].
Chemical looping hydrogen production
Different concepts for hydrogen production using chemical
looping have developed from the concept of chemical looping
combustion (CLC). In CLC an oxygen carrier (typically a metal
oxide) is used to provide the oxygen required for fuel oxidation
in a fuel reactor. Since pure oxygen is provided, the produced
flue gas contains mainly CO2 and H2O. The reduced oxygen
carrier is then oxidized back to its initial state by air in an air
reactor and reused. Reviews on this technology are given by
Hossain et al. [96] and Adanez et al. [97].
The concepts developed for hydrogen production can be
divided into two main classes. In the first class the oxygen
carrier is merely used to provide pure oxygen. The air required
in ATR can be provided by the oxygen carrier, or the heat
required in SMR can be provided by integration with CLC. The
hydrogen production process is not significantly changed in
these concepts. They are described by eg. Adanez et al. [97],
but not discussed further here. In the second class the oxygen
carrier is used to reduce steam in a dedicated steam reactor.
These concepts are described in a review by Fan et al. [98], and
are also the focus in this section.
In general the success of chemical looping processes re-
quires development of oxygen carriers that are chemically
and physically stable throughout many cycles with reduction
and oxidation, and high velocity circulating transport
operation.
Syngas chemical looping process
In the syngas chemical looping process a system with three
reactors is proposed. The concept is illustrated in Fig. 13 with
iron oxide as oxygen carrier. In a fuel reactor the oxygen
carrier is reduced by syngas, producing a flue gas with mainly
CO2 and H2O. The reduced oxygen carrier is sent to a steam
reactor where steam is reduced producing hydrogen, and the
oxygen carrier is partly oxidised. The oxygen carrier is then
sent to an air reactor where it is fully oxidised with air, before
it is recycled to the fuel reactor [98]. This concept can in theory
produce both high-purity hydrogen and CO2 at transport
quality. Possible impurities present in the CO2 will depend on
the syngas composition (which depends on the raw material
and potential syngas purification).
The following reactions (unbalanced) are carried out in the
three reactors:
Fuel reactor : Fe2 O3 þ CO þ H2 /Fe=FeO þ CO2 þ H2 O (9)
Steam reactor : Fe=FeO þ H2 O/Fe3 O4 þ H2 (10)
Air reactor : Fe3 O4 þ O2 /Fe2 O3 (11)
The fuel reactor is typically operated at 750e900 ! C, while
the steam reactor is operated at 500e750 ! C. In the air reactor
heat is generated and a portion of this heat is transported to
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
Fig. 13 e Principle of the syngas chemical looping process.
the fuel reactor through the oxygen carrier particles, while
the rest will be contained in the exhaust air which can be
utilised for power production or for heating purposes. A sub-
stoichiometric amount of steam can be introduced in the
steam reactor if more heat or power and less hydrogen is
desired [98].
This process has been tested in a 25 kWth sub-pilot unit
operated at isothermal conditions maintained with heating
from heating elements. Steady profiles of 99.99% hydrogen
production and nearly 100% syngas conversion were ach-
ieved. The setup was also tested using methane as fuel. An
average CH4 conversion and CO2 purity of 99.67% was then
achieved in the fuel reactor [99].
Direct chemical looping gasification
In direct chemical looping gasification the same setup is used
(Fig. 13), but coal or other solid fuel is gasified directly in the
fuel reactor.
Utilisation of solid fuels in chemical looping is chal-
lenging due to operational aspects such as increased oxygen
carrier deactivation, slow gasification requiring long resi-
dence time in the fuel reactor, and requirement of good
contact between oxygen carriers and released volatiles
[100]. In a proposed design the fuel reactor is divided into
one region for solid fuel injection and devolatilization, one
region for reduction of oxygen carrier by gaseous volatiles,
and one region for fuel gasification and oxygen carrier
reduction [101].
Tests of several coal direct chemical looping combustion
units with sizes of 0.5e100 kWth and different types of coal
and oxygen carriers have been reported. Gas conversions of
77e100% were achieved, with lower conversions of the solids
[100]. In one of these units also biomass was tested as fuel
Table 3 e Separation performance of technologies for integrated hydrogen production and gas separation. Values are given
on dry basis.
WGS-MR SMR-MR
(Pd-based) (Pd-based)
H2 purity, % 99.99a 99.99
CO2 purity, % Low Low
Source [73,74]
a
Assumed similar to SMR-MR.
4983
[102]. Heavy fraction of bio-oil have been tested at laboratory
scale [103].
Technology performance summary
A summary of separation performance for the technologies
presented above are given in Table 3. Only product purities are
given. Recovery cannot be defined similarly for all technolo-
gies, and limited information is available in the literature.
Hydrogen membrane reactors are hydrogen removal
focused, while sorption-enhanced reactors are CO2 removal
focused. It can be observed in Table 3 that for the hydrogen
membrane reactors, the purity of the produced hydrogen is
high while the purity of the CO2 is low. For the sorption-
enhanced reactors, the opposite can be observed. This in-
dicates that additional CO2 separation technologies are
needed downstream hydrogen membrane reactors, while
hydrogen separation technologies are needed downstream
sorption-enhanced reactors. Syngas chemical looping has the
potential to produce both CO2 at transport quality and high-
purity hydrogen. However, the types and amounts of impu-
rities present in the CO2 depends on the purity of the syngas
that is used as fuel.
Not much work has been published on benchmarking such
processes for hydrogen production. This is in contrast to the
topic pre-combustion CO2 capture where several
benchmarking/techno-economic evaluations are performed.
CO2 and hydrogen product purity requirements
When selecting a process route for production of hydrogen
with CO2 capture, attention must be given to the requirements
on both CO2 and hydrogen purities. Complexity lies in that
these requirements are not always fully known. Concerning
the requirements for CO2 purity, most research has been done
on the requirements for CO2 pipeline transport, while it is
scarce for ship transport. At the time of writing this paper, ISO
standards for CO2 pipeline transport, are being elaborated
(ISO/TC 265). Hydrogen purity requirements will vary
depending on the application. For some applications there are
ISO standards available [104e106].
CO2 purity requirements
The CO2 purity specifications are dependent on transportation
method (pipeline or ship transport) as well as the final desti-
nation (eg. storage in saline aquifers, EOR, or use in industrial
products).
SE-WGS SE-SMR Syngas chemical looping
(hydrotalcite) (dolomite) process
90e95 94e98 99.99
~99 n/a '99.67
[87] [78,93] [99]
4984 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
When transported in pipelines, the CO2 is usually at su-
percritical pressure and subcritical temperature. Recom-
mendations on CO2 purity for transport in pipeline and
storage in saline reservoirs or use for EOR have been given by
several groups such as the Dynamis project [107] and The
European Benchmarking Task Force [108]. NETL provided in
2012 an overview of estimated permissible CO2 impurity
levels from studies, pipeline design guides, pipe trans-
portation specifications and sequestration plant experience,
and based on this they set recommended CO2 purity speci-
fications for pipeline transport, EOR and saline reservoir
sequestration [109]. They recommended CO2 concentration of
>95 vol% for all cases, with <300 ppmwt H2O, <35 ppmv CO
and <0.01 vol% H2S. The concentration should be <4 vol% for
all non-condensable gases for pipeline transport and saline
reservoir sequestration, and for EOR the concentration
should be <0.01 vol% for O2 (potential unwanted exothermic
reactions with hydrocarbons) and <1 vol% for other non-
condensable gases (potential reduced miscibility). The limits
are set based on considerations such as toxicity, compression
work, and risk for hydrate formation, running ductile frac-
tures and corrosion.
In the case of CO2 captured from hydrogen production, the
effect of loosing hydrogen with the CO2 should be considered.
Since hydrogen is a valuable product, the amount of hydrogen
in the CO2 should be limited, where the optimal limit depends
on economic considerations. This will most likely motivate
CO2 purities higher than 95 vol%.
For ship transport of CO2 less work has been done on CO2
purity recommendations. CO2 can be transported with ship in
compressed or liquefied form. Ship transport of compressed
CO2 will require expensive pressure vessels, so it is here
assumed that the CO2 will be transported in liquid form. A
tentative value for water content is then 50 ppm H2O, to avoid
operational problems in the liquefaction process. The exact
specification will depend on the liquefaction process and
equipment [110]. Volatile gases will be separated from the
captured CO2 as part of the liquefaction process, whereas
heavier compounds have to be removed prior to liquefaction.
The optimum extent of CO2 purification performed prior to the
liquefaction process compared to the extent of purification
performed as a part of the liquefaction is not settled yet.
Table 4 e Hydrogen purity requirements for various hydrogen users in the energy and transport sectors.
H2 purity (min) [%]
Refining ~95
Ammonia 23e25 (N2:74e77)
PEM fuel cells for automotive 99.97
purposes
PEM fuel cells for stationary Cat. 1 50
purposesa Cat. 2 50
Cat. 3 99.9
Gas turbines Low
Industrial fuel (eg. power 99.90b
generation or heat
energy source)
NC ¼ not to be condensed, HC ¼ Hydrocarbons on methane basis, S ¼ Sulfur compounds.
a
The categories are defined to meet the needs of different stationary applications.
b
This value is from an ISO standard and should not be taken as a definite limit.
Hydrogen purity requirements
The purity requirements of hydrogen vary largely depending
on the application of the hydrogen. The largest present and
potential future uses of hydrogen are (cf. Fig. 2):
& Refining/hydrocarbon upgrading
& Ammonia production
& Methanol production
& Fuel cells (transport, power generation)
& Combustion (eg. atmospheric boilers, gas turbines, internal
combustion engines)
Out of these users methanol production is not relevant in a
CO2 capture context, since CO and CO2 is used in the methanol
synthesis, and no excess CO2 is produced [111]. Current
hydrogen purity requirements for the other major users are
discussed below and summarised in Table 4.
Hydrogen is needed in refineries mainly in hydrotreating
and hydrocracking units. Hydrogen can either be imported or
produced by SMR or POX at the plant. In these cases, hydrogen
purities around 95% are usually aimed at. The content of
sulfur components should be limited, in order to prevent
degradation of catalysts [60,112].
In production of ammonia, hydrogen is reacted with ni-
trogen, which usually is introduced as air in the reforming
process. The H2/N2 mixture must have very low levels of CO,
CO2, water and sulfur components, as these components
poison the ammonia synthesis catalyst [38].
Hydrogen for use in fuel cells need to have very low levels
of CO and sulfur components in order to avoid catalyst
poisoning, and very low level of NH3 to protect the membrane
from degradation. The amount of CO2 and hydrocarbons must
also be kept relatively low in order to limit performance
degradation. ISO standards have been developed for PEM fuel
cells for automotive and stationary purposes [105,106].
Besancon et al. [23] have studied the impact of impurities in
hydrogen produced by SMR, ATR and coal gasification on fuel
cell performance, and have suggested to relax the restrictions
for some components.
For combustion of hydrogen in gas turbines, inert compo-
nents in the fuel is not an issue. With today's technology, the
Impurity limits (max) [ppm] Source
S: low levels [60,112]
CO2, CO, H2O and S: low levels [5,38]
H2O:5, HC:2, O2:5, He:300, N2 þ Ar:100, CO2:2, CO:0.2, S:0.004, NH3:0.1 [105]
H2O:5, HC:100, O2:5, He þ N2 þ Ar:500, CO2:2, CO:0.5, S:0.01, NH3:0.1 [23]
H2O:NC, HC:10, O2:200, N2 þ Ar þ He:50%, CO:10, S:0.004 [106]
H2O:NC, HC:2, O2:200, N2 þ Ar þ He:50%, CO:10, S:0.004 [106]
H2O:NC, HC:2, O2:50, N2 þ Ar þ He:0.1%, CO:2, S:0.004 [106]
Limited amount of Na, K, V and S [115]
H2O:NC, HC:NC, O2:100, N2:400, S:10 [104]
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
hydrogen will in any case be diluted with large amounts of
nitrogen or steam to reduce the combustion temperature, and
thus limit NOx emissions [113]. Combustible components such
as CH4 and CO can be present in the hydrogen, but it has to be
taken into consideration that they influence the combustion
characteristics of the fuel [114]. The content of components
that can cause high-temperature corrosion such as Na, K, V
and S has to be limited. However, the limit depends on
whether coatings are applied to the gas turbine blades, or
whether corrosion inhibitors are added to the fuel [115].
An ISO standard for industrial fuel (eg. power generation or
heat energy source) has been developed [104], with a purity
limit of 99.9% hydrogen and eg. maximum 400 ppm nitrogen.
This seems strict in light of the low purity requirement due to
technical limitations discussed for gas turbines.
It may in some cases prove to be costly to produce
hydrogen with as high quality as specified in the ISO stan-
dards. Use of hydrogen for fuel cells and combustion are
emerging technologies and it can therefore be expected that
as more experience is gained about the production and use of
hydrogen for these purposes, both ISO standards will be
revised.
The hydrogen purity requirements discussed above are
relevant in cases with on-site hydrogen production and use.
For other cases it may be that transport and/or intermediate
storage will put the highest restrictions on hydrogen purity. If
hydrogen is to be transported over long distances, liquefaction
and transportation by ship is the preferable option. Also, for
road transport to hydrogen fuelling stations, liquid hydrogen
by truck may be preferable compared to compressed gas, if
feasible from a safety point of view [116]. Hydrogen is liquefied
at $253 ! C, and although current PSA technology can deliver
hydrogen with 10 ppm impurities or less, additional purifica-
tion to <1 ppm through adsorption is required, and is effec-
tuated inside the cold box at $193 ! C [117]. Altogether,
hydrogen that is transported in the liquid state will require a
purity that is significantly higher than the requirements listed
in Table 4.
Large-scale plants
There exist several large-scale plants that combine the
hydrogen production and purification and CO2 capture tech-
nologies various ways.
Ammonia synthesis with CO2 capture by absorption
At fertiliser plants, ammonia is produced with hydrogen as an
intermediate product. As mentioned in Section 5.2, hydrogen
used in ammonia synthesis need to have low levels of CO2, CO,
H2O and sulfur. CO2 and sulfur removal is often done by ab-
sorption (eg. Benfield and Selexol processes). Some of the CO2
can be used at the plant while the rest is usually emitted. Such
plants are relatively easy to retrofit with CO2 capture, by
installing compression and TEG dehydration systems. So far
two fertiliser plants have been retrofitted this way: the Enid
(USA) and Coffeyville (USA) plants ([37,118e120]). The Agrium
plant (Canada) is being retrofitted with anticipated start of
operation in 2015 [42].
4985
Hydrogen production for refineries with CO2 capture by
absorption
In the Quest project (Alberta, Canada), a hydrogen production
plant for heavy oil upgrading is being retrofitted. CO2 will be
captured after SMR using activated MDEA. Around 1 Mtonne/
year of CO2 will be captured and stored in a saline formation.
The purity of the CO2 prior to transport is expected to be 99.2%
[120].
In the ACTL Sturgeon project (Alberta, Canada), a new re-
finery complex is under construction where CO2 capture will
be integrated. Generated asphaltene residue will be gasified,
followed by WGS and a Rectisol® unit that will remove 95% of
the CO2 at a purity of 99.6% and produce a separate stream
with sulfur components. The CO2 recovered by the Rectisol®
unit is expected not to need drying. The resulting hydrogen
contain <0.1 ppmv sulfur components. The CO2 will be used
for EOR [120,121].
Hydrogen production for refineries with CO2 capture by VSA
Air Products and Chemicals is running a large-scale demon-
stration plant at the Valero refinery in Port Arthur (Texas,
USA). They have retrofitted a hydrogen production facility by
adding a vacuum swing adsorption (VSA) unit, that captures
wet CO2 between the already existing SMR and PSA units. The
wet CO2 is compressed and dried, and transported with
pipeline for onshore EOR. The produced hydrogen is trans-
ported by pipeline for use in refineries. It captures 1 Mtonne/
year of CO2, and has been in operation since 2013. More than
90% of the CO2 with purity greater than 97% is captured from
syngas that consists of more than 15% CO2 [28e30,66].
Selection of process route
As reviewed in this paper, there are many possible process
routes for hydrogen production with CO2 capture.
Retrofit versus new plants
The existing large-scale plants for hydrogen production with
CO2 capture have been developed by retrofitting existing
plants. The ease of retrofit depends on the hydrogen purifi-
cation facilities present at the plant. Some plants (in particular
ammonia/fertiliser plants) remove CO2 with absorption units,
which produce CO2 at high concentration (that they partly
need in their process). Two such fertiliser plants have been
retrofitted simply by compressing and dehydrating CO2 from
the existing absorption units. Hydrogen purification using PSA
gives hydrogen at higher purity, but results in a waste stream
with lower CO2 concentration and a significant amount of
valuable hydrogen. The Port Arthur plant that produce
hydrogen for refineries purified the hydrogen using PSA, and
has been retrofitted by addition of VSA units (with compres-
sion and dehydration of captured CO2) upstream the existing
PSA units.
When designing new plants, we are free to select the route
between the feedstock and the products. The feedstock can
vary between biomass, coal, oil or natural gas. The required
4986 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
CO2 quality depends on whether it will be transported by
pipeline (>95% CO2) or by ship (liquefied CO2). The required
purity of the hydrogen is low if it is to be used as fuel, while the
purity must be very high for certain other applications e in
particular for automotive PEM fuel cells. When the constraints
are set for (i) feedstock, (ii) CO2 transport option, and (iii)
hydrogen application, the most suitable syngas production
and separation technologies should be chosen.
Process intensification
As reviewed in Section 4 there are several possible options for
process intensification. As summarised by Mayorga et al.
[122], sorption-enhanced hydrogen production can simplify
hydrogen purification, allow less expensive materials in re-
actors due to decreased temperatures, reduce or possibly
eliminate carbon deposition in the reforming reactor, elimi-
nate shift reactors (for SE-SMR) and decrease the size of heat
exchanger equipment. Also, the WGS catalyst may be elimi-
nated [87], and there is no need for a separate CO2 capture
step. Membrane reactors can give reduced capital costs due to
reduced reactor size, reduced downstream separation costs
and operation in milder thermal conditions (resulting in less
heating/cooling) [14,50]. Also the concept of coal/biomass
direct chemical looping gasification processes implies process
intensification: the solid fuel is gasified directly in the fuel
reactor, eliminating a preliminary process that supplies syn-
gas to the fuel reactor. This drastically simplifies the fuel
conversion scheme [98].
Drawbacks with these technologies are low maturity e
they are currently on maximum pilot scale. Even though the
number of process units are decreased, the process they are
replaced with entail several technical challenges due to
increased complexity.
Process integration
The requirement for heating and cooling in the processes, and
the production of waste streams containing combustible
components, indicates that there are potentially great benefits
from integration with other processes.
Several configurations for co-production of hydrogen and
electricity with CO2 capture have been investigated in simu-
lation studies. Examples are studies on systems with coal
gasification or natural gas reforming, solvent absorption and
PSA that are closely integrated with combined cycles or con-
ventional steam cycles [123,124], studies on ATR with WGS-
MRs integrated with combined cycle [125], and studies on an
IGCC-based concept where the produced hydrogen-rich syn-
gas is either purified in a PSA and exported, or used in a
combined cycle for power generation, with close integration
between the subsystems [126]. Chemical looping hydrogen
production appears to be ideal for co-production of hydrogen
and electricity given successful scale-up of the technology,
and such processes with coal and biomass direct chemical
looping have been simulated and optimised [127e129]. Also, a
self-sustained system where a coal gasification hydrogen
production plant combining membranes and low-
temperature separation has been studied. The off-gas from
the low-temperature separation system was used as fuel in a
combined cycle, generating the power needed by the system,
plus a surplus of electricity that potentially could be employed
for hydrogen liquefaction [130].
For the case of sorption-enhanced WGS or SMR using
calcium-based sorbents, high-temperature heat is needed for
the regeneration step taking place at 700e900 ! C. This case is
particularly benefited by integration with a high-temperature
heat source. For instance, the heat can be provided by utilising
waste heat from a SOFC as suggested by ZEG Power [95].
Furthermore, both hydrogen and CO2 are generated at high
temperatures, and heat could be recovered from these
streams.
Combination of technologies
Most of the reviewed technologies can not produce high-
purity hydrogen and CO2 at transport quality simultaneously
(cf. Tables 2 and 3).
Hydrogen can be produced at very high purity using PSA or
hydrogen membrane technologies, and such technologies are
preferred for production of hydrogen eg. for PEM fuel cells or
for transport in liquid form. However, the waste stream will be
a mix of CO2, hydrogen and other impurities, and an addi-
tional separation unit dedicated for CO2 capture has to be
added to the process. This is the case in the configuration
shown in Fig. 3 showing the presently most mature route: a
CO2 absorption unit is added upstream a PSA unit. Although
CO2 absorption is considered most mature for CO2 capture in
general, it is not necessarily the best option in the context of
hydrogen production. At the Port Arthur refinery, a VSA unit
was installed for CO2 capture upstream the existing PSA units.
Furthermore, as shown by Berstad et al. [63] low-temperature
CO2 separation is competitive to absorption from gases with
high CO2 partial pressures (in this context syngas from coal
gasification or off-gas from a hydrogen purification unit). For
instance, Tokyo Gas [65] chose to purify the SMR-MR off-gas by
liquefaction, and this reduced the overall efficiency of the
process with less than 3%-points compared to the same pro-
cess with no CO2 capture. The option of low-temperature
separation is particularly interesting in cases where the CO2
will be transported by ship, since it provides CO2 in liquid
form.
In the case of absorption, low-temperature CO2 capture,
and sorption enhanced WGS and SMR, transport grade CO2 (in
gas or liquid form) can be achieved, but the hydrogen-
containing off-gas normally needs further purification. For
instance, Barelli et al. [79] mention that although SE-SMR can
directly produce higher purity hydrogen than a conventional
reactor, it is not enough to satisfy high-purity customers, and
an additional unit is required to purify the effluent gas.
One exception is PSA technology, that potentially can
produce both high-purity hydrogen and CO2 [33]. The same
concept can also be applied to sorption enhanced processes
that are based on fixed beds and pressure-swing. However, the
production of an off-gas containing both these components
and impurities can hardly be avoided. Another exception is
chemical looping hydrogen production that potentially can
produce streams with high-purity hydrogen and CO2 at
transport quality.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
Proper considerations have to be taken when technologies
are combined, making sure that each technology as far as
possible operate in its optimal operating windows.
Trade-off
In general we can say that the purer product, the more
resource use and valuable products lost in the off-gas, and as
discussed in the previous section, high-purity products
require more complex process routes. Hence, there is a trade-
off situation between the advantages with high-purity prod-
ucts, and the resources used to purify them, and it is worth-
while to further investigate the optimum limits for CO2 and
hydrogen purity.
Furthermore, the CO2 capture rate will be subject to trade-
off with the resource use. As long as the cost of CO2 emissions
is low, there will be additional costs associated with CO2
capture. The specific cost per amount of CO2 avoided is a
parameter that should be kept optimum when selecting pro-
cess route.
Outlook on production and use of hydrogen in a
CCS context
The global CO2 emissions from fuel combustion were
32.2 Gtonne in 2013. The different shares of main CO2 emitters
were: electricity and heat production (42%), transport (23%)
and industry (24%) [131]. Increased use of hydrogen as energy
carrier can help reducing these emissions, provided that the
hydrogen production, compression/liquefaction and trans-
port in itself do not contribute to considerable CO2 emissions.
Globally, the use of hydrogen is around 7.2 EJ/year, with a
distribution among end-users as shown in Fig. 2. This corre-
sponds to CO2 emissions of around 0.5 Gtonne/year [3]. The
amount of future hydrogen production will depend on tech-
nology development, economic factors such as cost of
renewable energy versus the cost of fossil fuels, and on po-
litical decisions. In the IEA high hydrogen 2DS (also shown in
Fig. 2), a significant increase in the global use of hydrogen is
anticipated by 2050. In this scenario the two main causes of
increased hydrogen use are transport (~10 EJ/year) and in-
dustrial use (~15 EJ/year).
In the rest of this section we briefly discuss the possible
impact of hydrogen production with CCS for the transport
sector, the potential for use of hydrogen with CCS in industry
and power production, and the potential CO2 emissions from
liquefaction of hydrogen.
Emission reductions in the transport sector
In the hydrogen production pathway in the high-hydrogen
2DS for the US, the shares of hydrogen production for trans-
port in 2050 are: 4% reforming of natural gas without CCS, 36%
reforming of natural gas with CCS, 29% gasification of coal
with CCS and the rest is biomass gasification and low cost
renewable electricity [3]. To make a simple estimate on CO2
emissions from transport in 2050, we calculate from the
chemical reactions involved that natural gas reforming pro-
duces 7.7 kg CO2 per kg hydrogen, while coal gasification
4987
produces 16.5 kg CO2 per kg hydrogen. Furthermore, we as-
sume that net CO2 emissions from renewables and biomass
are negligible, that CCS technologies have 90% CO2 capture
rate, and that the global hydrogen production scenario will be
similar to the US scenario. An annual production of ~10 EJ
hydrogen (~83 Mtonne) then corresponds to ~0.1 Gtonne CO2
emitted to the atmosphere.
Road transport accounted for 5.5 Gtonne CO2 emissions in
2013 [131]. Around 2/3 of the emissions from road transport
come from LDVs while around 1/3 come from HDVs [1]. 10 EJ/
year of hydrogen could be used to fuel FCEVs that replace 25%
of the LDV fleet and 10% of freight road transport fleet [3].
Referring back to the previous paragraph, this means that
vehicles that now account for ~1.1 Gtonne of CO2 emissions/
year could be replaced by vehicles that altogether account for
~0.1 Gtonne CO2 emissions/year.
The picture presented here is simplified, and merely
intended to provide an order of magnitudes. Growth in the
global car fleet is not taken into account, and fuel and power
consumption along the CCS and hydrogen transport chains
will increase the CO2 emissions (refer to Section 8.3 below for
CO2 emissions from hydrogen liquefaction). However, it is
evident that introduction of hydrogen as fuel in the transport
sector, with the hydrogen produced mainly by a mix of re-
newables and fossil fuels with CCS has the potential to dras-
tically reduce CO2 emissions in the transport sector.
Use of hydrogen in industry and power generation
For the anticipated second largest user of hydrogen in the
future, industry, the picture is more heterogeneous since the
usefulness of hydrogen will vary from one industrial appli-
cation to another. Industry must reduce its direct CO2 emis-
sions by 17% by 2025 to meet 2DS targets [132]. IEA [2] mention
that hydrogen can be used to substitute coal and coke in ore
reduction (although the technology currently is far from the
demonstration phase [133]), and that hydrogen could be used
to replace fossil fuel-based feedstocks and energy use in
various ways in the chemical sector.
From the perspective of power generation, extensive
research has been undertaken for more than 20 years in order
to understand and realize safe and stable low-emission
hydrogen combustion, and this research will need to
continue. The main problem with hydrogen combustion is the
formation of NOx due to high combustion temperatures. Dilu-
tion with steam or nitrogen gives an efficiency penalty, since
the nitrogen and the steam have to be produced. An alternative
approach subject to research is a system with premixing of
hydrogen with air. For this possible solution the high flam-
mability and low ignition temperature of hydrogen causes
safety and stability issues, such as the possibility for flashback
[113,134]. However, much effort has been put into modelling of
hydrogen combustion, which has increased the understanding
of eg. hydrogen flammability [135]. If these challenges were
resolved, both power generation with pre-combustion capture
of CO2 and hydrogen-fuelled combined cycles for power gen-
eration would be attractive options for efficient low-carbon
power generation with good load-following capacity. Such
power plants are expected to be able to balance the natural
variations in power generation from renewable energy
4988 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
sources, by producing hydrogen by electrolysis in periods with
excess power production, and utilising it in periods when the
power production is low. Another alternative is to mix in a
fraction of hydrogen in the fuel of gas turbines run on natural
gas. This is a way of utilising for instance low-grade hydrogen
or PSA off-gas. Furthermore, stationary fuel cells could play a
role in future hydrogen-fuelled power generation, eg. for do-
mestic purposes [136] or in combination with gas turbine
combined cycles [133].
When evaluating fuel substitution in the industry, as well
as stationary power generation with hydrogen, it should be
highly relevant to investigate in detail both the total carbon
footprint and the total efficiency from hydrogen production,
via compression/liquefaction, transport and storage to the
end user. As an example, IEA mention for the case of com-
bined cycle utilizing hydrogen from electrolysis that the effi-
ciency for the power generation is high (60%), but the total
efficiency is below 32% due to the electrolyser and hydrogen
storage [133].
CO2 emissions between hydrogen production and end user
Production of hydrogen with CO2 capture may take place
onsite industrial plants or fuelling stations, or it may take
place on large dedicated hydrogen production plants and be
transported to the users. The challenges associated with
storing and transporting hydrogen have generally lead to
onsite production for large industrial users, such as for
ammonia plants [37]. Also, there are studies concerning onsite
hydrogen production with CO2 capture on fuelling stations
(eg. the ZEG-project [95] and the membrane reformer project
by Tokyo Gas [65,73]). However, hydrogen would most likely
have to be transported to small end users, and for some in-
dustrial sites it would not be possible with hydrogen produc-
tion with CO2 capture for practical reasons (eg. no CO2 storage
site or transport system available). If onsite production is
found infeasible, the power demand and associated CO2
emissions for hydrogen compression or liquefaction prior to
transport, as well as the transport itself must be taken into
account when considering the CO2 emission reduction po-
tential from hydrogen energy.
It is beyond the scope of the present paper to provide
complete chain analyses of hydrogen production compres-
sion/liquefaction and transport. However, estimates are pro-
vided for hydrogen liquefaction in order to exemplify the
order of magnitude of potential additional CO2 emissions: Our
calculations show that with present liquefaction and power
generation technology without CO2 capture, hydrogen lique-
faction generates an additional 55% of CO2, while future
hydrogen liquefaction and power generation technology is
estimated to enable a reduction of additional CO2 emissions to
26% (see Supplementary Information for calculations).
Hydrogen liquefaction is envisaged as a means of enabling
long-distance transport of hydrogen by ship but also to enable
more efficient road transport of hydrogen [116].
The essential insight gained from this is that hydrogen
production from fossil fuels will not only generate CO2 due to
its production, but if hydrogen has to be transported to the
users, the handling of hydrogen (liquefaction and/or
compression) will require substantial amounts of power.
Again several aspects are subject to trade-off: the benefits of
onsite hydrogen production versus the benefits of dedicated
plants, transport of hydrogen versus transport of CO2, and use
of limited renewable power on electrolysis versus hydrogen
liquefaction/compression.
Conclusions
Methods for production and purification of hydrogen from
fossil fuels with CO2 capture are reviewed. Hydrogen pro-
duction with CO2 capture implies the production of two
product streams: hydrogen at the desired purity and CO2 at
transport and storage quality. An additional waste stream
with some combustable components will also be produced in
most cases. Producing hydrogen from fossil fuels, while
capturing the CO2 for transport and storage is a matter of
matching hydrogen and CO2 separation technologies in a best
possible manner, taking into account the planned transport
option for the CO2 and the planned use of the hydrogen.
Hydrogen production with CO2 capture could be a key tran-
sition technology for moving in the direction of a sustainable
hydrogen-using society, with the potential for large emission
reductions in the transport and industry sectors.
Acknowledgements
This work was conducted with support from the BIGCCS
Centre, performed under the Norwegian research program
Centers for Environment-friendly Energy Research (FME). The
authors acknowledge the following partners for their contri-
butions: Gassco, Shell, Statoil, TOTAL, Engie and the Research
Council of Norway (193816/S60). Thanks are due to David
Berstad, SINTEF Energy Research for sharing his knowledge
about hydrogen liquefaction.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2016.01.009.
references
[1] International Energy Agency (IEA). Energy technology
perspectives 2015. 2015. Paris.
[2] International Energy Agency (IEA). Energy technology
perspectives 2012. 2012. Paris.
[3] International Energy Agency (IEA). Technology roadmap:
hydrogen and fuel cells. 2015. Paris.
[4] Damen K, Van Troost M, Faaij A, Turkenburg W. A
comparison of electricity and hydrogen production systems
with CO2 capture and storage. Part A: review and selection
of promising conversion and capture technologies. Prog
Energy Combust Sci 2006;32(2):215e46.
[5] Ritter JA, Ebner AD. State-of-the-Art adsorption and
membrane separation processes for hydrogen production in
the chemical and petrochemical industries. Sep Sci Technol
2007;42(6):1123e93.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
[6] Song C. Introduction to hydrogen and syngas production
and purification technologies. In: Liu K, Song C,
Subramani V, editors. Hydrogen and syngas production
and purification technologies. John Wiley & Sons; 2010.
p. 1e13.
[7] Kenarsari SD, Yang D, Jiang G, Zhang S, Wang J, Russell AG,
et al. Review of recent advances in carbon dioxide
separation and capture. RSC Adv 2013;3(45):22739e78.
[8] Jansen D, Gazzani M, Manzolini G, van Dijk E, Carbo M. Pre-
combustion CO2 capture. Int J Greenh Gas Control
2015;40:167e87.
[9] Subramani V, Sharma P, Zhang L, Liu K. Catalytic steam
reforming technology for the production of hydrogen and
syngas. In: Liu K, Song C, Subramani V, editors. Hydrogen
and syngas production and purification technologies; 2010.
p. 14e126.
[10] Rostrup-Nielsen T. Manufacture of hydrogen. Catal Today
Oct. 2005;106(1e4):293e6.
[11] Liu K, Deluga GD, Bitsch-Larsen A, Schmidt LD, Zhang L.
Catalytic partial oxidation and autothermal reforming. In:
Liu K, Song C, Subramani V, editors. Hydrogen and syngas
production and purification technologies. Hoboken, New
Jersey: John Wiley & Sons; 2010. p. 127e55.
[12] Liu K, Cui Z, Fletcher TH. Coal gasification. In: Hydrogen and
syngas production and purification technologies. John
Wiley and Sons, Inc; 2010. p. 156e218.
[13] Platon A, Wang Y. Water-Gas shift technologies. In: Liu K,
Song C, Subramani V, editors. Hydrogen and syngas
production and purification technologies; 2010. p. 311e28.
[14] Mendes D, Mendes A, Madeira LM, Iulianelli A, Sousa JM,
Basile A. The water-gas shift reaction: from conventional
catalytic systems to Pd-based membrane reactors e a
review. Asia-Pacific J Chem Eng 2010;5:111e37.
[15] Sircar S, Golden TC. Pressure swing adsorption technology
for hydrogen production. In: Liu K, Song C, Subramani V,
editors. Hydrogen and syngas production and purification
technologies; 2010. p. 414e50.
[16] Romano MC, Chiesa P, Lozza G. Pre-combustion CO2 capture
from natural gas power plants, with ATR and MDEA
processes. Int J Greenh Gas Control 2010;4(5):785e97.
[17] Nord LO, Anantharaman R, Bolland O. Design and off-
design analyses of a pre-combustion CO2 capture process in
a combined cycle power plant. Int J Greenh Gas Control
2009;3(4):385e92.
[18] Franco F, Anantharaman R, Bolland O, Booth N, van Dorst E,
Ekstrom C, et al. European best practice guidelines for
assessment of CO2 capture technologies. 2011.
[19] Abu-Zahra M, Feron M, Jansens P, Goetheer E. New process
concepts for CO2 post-combustion capture process
integrated with co-production of hydrogen. Int J Hydrogen
Energy 2009;34(9):3992e4004.
[20] Berstad D, Nekså P, Gjøvåg GA. Low-temperature syngas
separation and CO2 capture for enhanced efficiency of IGCC
power plants. Energy Proced 2011;4:1260e7.
[21] Chaney R. Beluga coal gasification feasibility study. 2006.
Report number: DOE/NETL-2006/1248.
[22] Cormos C-C. Evaluation of power generation schemes
based on hydrogen-fuelled combined cycle with carbon
capture and storage (CCS). Int J Hydrogen Energy
2011;36(5):3726e38.
[23] Besancon BM, Hasanov V, Imbault-Lastapis R, Benesch R,
Barrio M, Mølnvik MJ. Hydrogen quality from decarbonized
fossil fuels to fuel cells. Int J Hydrogen Energy
2009;34(5):2350e60.
[24] Li J-R, Ma Y, McCarthy MC, Sculley J, Yu J, Jeong H-K, et al.
Carbon dioxide capture-related gas adsorption and
separation in metal-organic frameworks. Coord Chem Rev
2011;255(15e16):1791e823.
4989
[25] Agueda VI, Delgado JA, Uguina MA, Brea P, Spjelkavik AI,
Blom R, et al. Adsorption and diffusion of H2, N2, CO, CH4
and CO2 in UTSA-16 metal-organic framework extrudates.
Chem Eng Sci 2014;124:1e11.
[26] S. Sircar, “Separation of multicomponent gas mixtures,”
US4171206 A, 1979.
[27] Sircar S, Golden TC. Purification of hydrogen by pressure
swing adsorption. Sep Sci Technol 2000;35(5):667e87.
[28] Baade W, Farnand S, Hutchison R, Welch K. CO2 capture
from SMRs: a demonstration project. Hydrocarb Process
2012;(September):63e8.
[29] Collins J. Air products celebrates texas carbon capture
demonstration project achievement. 2013 [Online].
Available: http://www.airproducts.com/Company/news-
center/2013/05/0510-air-products-celebrates-texas-carbon-
capture-demonstration-project-achievement.aspx.
[accessed 01.10.15].
[30] U.S Department of Energy, Breakthrough large-scale
industrial project begins carbon capture and utilization.
[Online]. Available: http://energy.gov/fe/articles/
breakthrough-large-scale-industrial-project-begins-carbon.
[accessed: 01.10.15]
[31] ENERGY.GOV Office of Fossil Energy, “APCI Port Arthur ICCS
Project”. [Online]. Available: http://energy.gov/fe/air-
products-chemicals-inc. [accessed 01.10.15].
[32] R. Krishnamurthy, V. A. Malik, and A. G. Stokley, “Hydrogen
and carbon dioxide coproduction,” US Patent 4,963,339, 1990.
[33] M. R. Couche, “Hydrogen generation process,” US5669960 A,
1995.
[34] Kohl AL, Nielsen RB. Gas purification. 5th ed. Houston: Gulf
Publishing Company; 1997.
[35] Hochgesand G. Efficient acid gas removal. Eur Jpn Chem Ind
Symp 1970;62(7):37e43.
[36] Global CCS Institute. CO2 capture technologies: pre
combustion capture. 2012. Canberra, Australia.
[37] Zakkour P, Cook G. CCS roadmap for industry: high-purity
CO2 sources. 2010.
[38] Appl M. Ammonia: principles and industrial practice.
Weinheim: Wiley-VCH; 1999.
[39] Li B, Duan Y, Luebke D, Morreale B. Advances in CO2
capture technology: a patent review. Appl Energy
2013;102:1439e47.
[40] Kanniche M, Gros-Bonnivard R, Jaud P, Valle-Marcos J,
Amann J-M, Bouallou C. Pre-combustion, post-combustion
and oxy-combustion in thermal power plant for CO2
capture. Appl Therm Eng 2010;30(1):53e62.
[41] Padurean A, Cormos C-C, Agachi P-S. Pre-combustion
carbon dioxide capture by gaseliquid absorption for
integrated gasification combined cycle power plants. Int J
Greenh Gas Control 2012;7:1e11.
[42] Global CCS Institute. The global status of CCS: 2014. 2014.
Melbourne, Australia.
[43] Davidson R. Pre-combustion capture of CO2 in IGCC plants.
2011 [Online]. Available: http://www.iea-coal.org.uk/
documents/82847/8346/Pre-combustion-capture-of-CO2-in-
IGCC-plants-CCC/191 [accessed 27.10.15].
[44] Koneru P, Siddiqui A, Rush R. Kemper County: constructing
the world's first IGCC with CCS. Mod Power Syst
2012;32(6):10e2.
[45] Linde Engineering, “Rectisol(R) Wash,” Rectisol(R) Wash.
[Online]. Available: http://www.linde-engineering.com/en/
process_plants/hydrogen_and_synthesis_gas_plants/gas_
processing/rectisol_wash/index.html. [accessed 23.10.15].
[46] Walspurger S, van Dijk HAJ. EDGAR CO2 purity: type and
quantities of impurities related to CO2 point source and
capture technology: a literature study. 2012 [Online].
Available: http://www.ecn.nl/docs/library/report/2012/
e12054.pdf [accessed 23.10.15].
4990 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
[47] Lu GQ, Diniz JC, Duke M, Giessler S, Socolow R, Williams RH,
et al. “Inorganic membranes for hydrogen production and
purification: a critical review and perspective. J Colloid
Interface Sci 2007;314:589e603.
[48] Adhikari S, Fernando S. Hydrogen membrane separation
techniques. Ind Eng Chem Res 2006;45:875e81.
[49] Ockwig NW, Nenoff TM. Membranes for hydrogen
separation. Chem Rev Oct. 2007;107(10):4078e110.
[50] Gallucci F, Fernandez E, Corengia P, van Sint Annaland M.
Recent advances on membranes and membrane reactors
for hydrogen production. Chem Eng Sci Apr. 2013;92:40e66.
[51] Atsonios K, Panopoulos KD, Doukelis A, Koumanakos AK,
Kakaras E, Peters TA, et al. Introduction to palladium
membrane technology. In: Doukelis A, Panopoulos K,
Koumanakos A, Kakaras E, editors. Palladium membrane
technology for hydrogen production, carbon capture and
other applications. Woodhead Publishing; 2015.
[52] Bredesen R, Jordal K, Bolland O. High-temperature
membranes in power generation with CO2 capture. Chem
Eng Process 2004;43:1129e58.
[53] Scholes CA, Smith KH, Kentish SE, Stevens GW. CO2
capture from pre-combustion processes e strategies for
membrane gas separation. Int J Greenh Gas Control
2010;4(5):739e55.
[54] Iaquaniello G, Palo E, Salladini A, Cucchiella B. Using
palladium membrane reformers for hydrogen production.
In: Doukelis A, Panopoulos K, Koumanakos A, Kakaras E,
editors. Palladium membrane technology for hydrogen
production, carbon capture and other applications.
Woodhead Publishing; 2015.
[55] The CLIMIT programme. Reinertsen AS blazes new trails in
CO2 removal. News letter; 2015 [Online]. Available: http://
www.climit.no/en/Pages/Reinertsen-AS-blazes-new-trails-
in-CO2-removal.aspx [accessed 14.08.15].
[56] Ramasubramanian K, Zhao Y. CO2 capture and H2
purification e prospects for CO2-selective membrane
processes. AIChE J 2013;59(4):1033e45.
[57] Fontaine ML, Peters TA, McCann MTP, Kumakiri I,
Bredesen R. CO2 removal at high temperature from multi-
component gas stream using porous ceramic membranes
infiltrated with molten carbonates. Energy Proced
2013;37(1876):941e51.
[58] Anderson M, Lin YS. Carbonate-ceramic dual-phase
membrane for carbon dioxide separation. J Memb Sci
2010;357(1e2):122e9.
[59] Mukhopadhyay M. Fundamentals of cryogenic engineering.
New Delhi: PHI Learning Private Limited; 2010.
[60] Gary JH, Handwerk GE. Petroleum refining. 4th ed. New
York: Marcel Dekker; 2001.
[61] Brownlie D. Bulk production of hydrogen. Ind Eng Chem
1938;30(10):1139e46.
[62] Berstad D, Anantharaman R, Nekså P. Low-temperature
CCS from an IGCC power plant and comparison with
physical solvents. Energy Proced 2013;37(1876):2204e11.
[63] Berstad D, Anantharaman R, Nekså P. Low-temperature CO2
capture technologies e applications and potential. Int J
Refrig Apr. 2013;36(55):1403e16.
[64] Brouwers B, van Kemenade E. Condensed rotational
separation for CO2 capture in coal gasification processes. In:
4th International Freiberg Conference on IGCC & XtL
Technologies; May, 2010.
[65] Kurokawa H, Shirasaki Y, Yasuda I. Energy-efficient
distributed carbon capture in hydrogen production from
natural gas. Energy Proced 2011;4:674e80.
[66] National Energy Technology Laboratory. Demonstration of
CO2 capture and sequestration of steam methane reforming
process gas used for large-scale hydrogen production. Air
Products and Chemicals, Inc; 2014.
[67] Zou J, Huang J, Ho W. CO2-Selective water gas shift
membrane reactor for fuel cell hydrogen processing. Ind
Eng Chem Res 2007;46(4):2272e9.
[68] Huang J, Zou J, Ho WSW. CO2-selective membranes for
hydrogen fuel processing. In: Liu K, Song C, Subramani V,
editors. Hydrogen and syngas production and purification
technologies; 2010. p. 385e413.
[69] Peters TA, Kaleta T, Stange M, Bredesen R. Hydrogen
transport through a selection of thin Pd-alloy membranes:
membrane stability, H2S inhibition, and flux recovery in
hydrogen and simulated WGS mixtures. Catal Today
2012;193(1):8e19.
[70] Størset SØ, Brunsvold A, Jordal K, Langørgen Ø,
Anantharaman R, Berstad D, Ditaranto M, et al. Technology
survey and assessment for piloting of CO2 capture
technologies. 2013 [Online]. Available: http://www.tcmda.
com/PageFiles/1544/SINTEF report.pdf [accessed 22.12.15].
[71] Polfus JM, Xing W, Fontaine M-L, Denonville C,
Henriksen PP, Bredesen R. Hydrogen separation membranes
based on dense ceramic composites in the La27W5O55.5-
LaCrO3 system. J Memb Sci 2015;479:39e45.
[72] Hacarlioglu P, Gu Y, Oyama ST. Studies of the methane
steam reforming reaction at high pressure in a ceramic
membrane reactor. J Nat Gas Chem 2006;15(2):73e81.
[73] Shirasaki Y, Tsuneki T, Ota Y, Yasuda I, Tachibana S,
Nakajima H, et al. Development of membrane reformer
system for highly efficient hydrogen production from
natural gas. Int J Hydrogen Energy 2009;34(10):4482e7.
[74] Yakabe H, Kurokawa H, Shirasaki Y, Yasuda I. Operation of
a palladium membrane reformer system for hydrogen
production: the case of Tokyo Gas. In: Doukelis A,
Panopoloulos K, Koumanakos A, Kakaras E, editors.
Palladium membrane technology for hydrogen production,
carbon capture and other applications. Woodhead
Publishing; 2015. p. 303e18.
[75] Tiemersma TP, Patil CS, Van Sint Annaland M, Kuipers JAM.
Modelling of packed bed membrane reactors for
autothermal production of ultrapure hydrogen. Chem Eng
Sci 2006;61(5):1602e16.
[76] Peters TA, Stange M, Klette H, Bredesen R. High pressure
performance of thin Pde23%Ag/stainless steel composite
membranes in water gas shift gas mixtures; influence of
dilution, mass transfer and surface effects on the hydrogen
flux. J Memb Sci 2008;316(1e2):119e27.
[77] Atsonios K, Koumanakos AK, Panopoulos KD, Doukelis A,
Kakaras E. Using palladium membranes for carbon capture
in natural gas combined cycle (NGCC) power plants: process
integration and techno-economics. In: Doukelis A,
Panopoulos K, Koumanakos A, Kakaras E, editors. Palladium
membrane technology for hydrogen production, carbon
capture and other applications; 2015. p. 247e85.
[78] Harrison DP. Sorption-enhanced hydrogen production: a
review. Ind Eng Chem Res 2008;47:6486e501.
[79] Barelli L, Bidini G, Gallorini F, Servili S. Hydrogen production
through sorption-enhanced steam methane reforming and
membrane technology: a review. Energy Apr.
2008;33(4):554e70.
[80] Stevens RW, Shamsi A, Carpenter S, Siriwardane R.
Sorption-enhanced water gas shift reaction by sodium-
promoted calcium oxides. Fuel 2010;89(6):1280e6.
[81] van Dijk HAJ, Walspurger S, Cobden PD, van den Brink RW,
de Vos FG. Testing of hydrotalcite-based sorbents for CO2
and H2S capture for use in sorption enhanced water gas
shift. Int J Greenh Gas Control 2011;5(3):505e11.
[82] Allam RJ, Chiang R, Hufton JR, Middleton P, Weist EL,
White V. Development of the sorption enhanced water gas
shift process. In: Carbon dioxide capture for storage in deep
geologic formations; 2005. p. 227e71.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
[83] Van Selow ER, Cobden PD, Verbraeken PA, Hufton JR, Van
Den Brink RW. Carbon capture by sorption-enhanced water
e gas shift reaction process using hydrotalcite-based
material. Ind Eng Chem Res 2009;48:4184e93.
[84] Symonds RT, Lu DY, Hughes RW, Anthony EJ, Macchi A. CO2
capture from simulated syngas via cyclic Carbonation/
Calcination for a naturally occurring limestone: pilot-plant
testing. Ind Eng Chem Res 2009;48(18):8431e40.
[85] Boon J, Cobden PD, van Dijk HAJ, van Sint Annaland M.
High-temperature pressure swing adsorption cycle design
for sorption-enhanced wateregas shift. Chem Eng Sci
2015;122:219e31.
[86] van Dijk HAJ, Walspurger S, Cobden PD, Jansen D, van den
Brink RW, de Vos FG. Performance of wateregas shift
catalysts under sorption-enhanced wateregas shift
conditions. Energy Proced 2009;1(1):639e46.
[87] Jansen D, van Selow E, Cobden P, Manzolini G, Macchi E,
Gazzani M, et al. SEWGS technology is now ready for scale-
up! Energy Proced 2013;37:2265e73.
[88] Lee KB, Beaver MG, Caram HS, Sircar S. Reversible
chemisorption of carbon dioxide: simultaneous production
of fuel-cell grade H2 and compressed CO2 from synthesis
gas. Adsorption Sep. 2007;13(3e4):385e97.
[89] Gazzani M, Macchi E, Manzolini G. CO2 capture in integrated
gasification combined cycle with SEWGS e Part A:
thermodynamic performances. Fuel 2013;105:206e19.
[90] van Selow ER, Cobden PD, van den Brink RW, Hufton JR,
Wright A. Performance of sorption-enhanced water-gas
shift as a pre-combustion CO2 capture technology. Energy
Proced 2009;1(1):689e96.
[91] Balasubramanian B, Lopez Ortiz A, Kaytakoglu S,
Harrison DP. Hydrogen from methane in a single-step
process. Chem Eng Sci 1999;54(15e16):3543e52.
[92] Johnsen K, Ryu HJ, Grace JR, Lim CJ. Sorption-enhanced
steam reforming of methane in a fluidized bed reactor with
dolomite as CO2-acceptor. Chem Eng Sci
2006;61(4):1195e202.
[93] Meyer J, Mastin J, Pinilla CS. Sustainable hydrogen
production from biogas using sorption-enhanced
reforming. Energy Proced 2014;63(1876):6800e14.
[94] Lopez Ortiz A, Harrison DP. Hydrogen production using
sorption-enhanced reaction. Ind Eng Chem Res
2001;40(23):5102e9.
[95] Andresen B, Norheim A, Strand J, Ulleberg Ø, Vik A,
Wærnhus I. BioZEG e pilot plant demonstration of high
efficiency carbon negative energy production. Energy
Proced 2014;63:279e85.
[96] Hossain MM, de Lasa HI. Chemical-looping combustion
(CLC) for inherent separationsda review. Chem Eng Sci
2008;63(18):4433e51.
[97] Adanez J, Abad A, Garcia-Labiano F, Gayan P, de Diego LF.
Progress in chemical-looping combustion and reforming
technologies. Prog Energy Combust Sci 2012;38(2):215e82.
[98] Fan LS, Li F. Chemical looping technology and its fossil
energy conversion applications. Ind Eng Chem Res
2010;49(21):10200e11.
[99] Tong A, Sridhar D, Sun Z, Kim HR, Zeng L, Wang F, et al.
Continuous high purity hydrogen generation from a syngas
chemical looping 25 kWth sub-pilot unit with 100% carbon
capture. Fuel 2013;103:495e505.
[100] Lyngfelt A. Chemical-looping combustion of solid fuels e
status of development. Appl Energy 2014;113:1869e73.
[101] Kim HR, Wang D, Zeng L, Bayham S, Tong A, Chung E, et al.
Coal direct chemical looping combustion process: design
and operation of a 25-kWth sub-pilot unit. Fuel
2013;108:370e84.
[102] Tong A, Bayham S, Kathe MV, Zeng L, Luo S, Fan LS. Iron-
based syngas chemical looping process and coal-direct
4991
chemical looping process development at Ohio State
University. Appl Energy 2014;113:1836e45.
[103] Xiao R, Shang S, Peng S, Shen D, Liu K. Use of heavy fraction
bio-oil as fuel for hydrogen production in iron-based
chemical looping processes. Int J Hydrogen Energy
2014;39(35):19955e69.
[104] The International Organization for Standardisation. ISO
14687 hydrogen fuel e product specification. The
International Organization for Standardisation; 1999.
[105] The International Organization for Standardisation. ISO
14687-2 hydrogen fuel e product specification e part 2:
proton exchange membrane (PEM) fuel cell applications for
road vehicles. The International Organization for
Standardisation; 2012.
[106] The International Organization for Standardisation. ISO
14687-3 hydrogen fuel e product specification e part 3:
proton exchange membrane (PEM) fuel cell applications for
stationary appliances. Geneva: The International
Organization for Standardisation; 2014.
[107] de Visser E, Hendriks C, Barrio M, Mølnvik MJ, de Koeijer G,
Liljemark S, et al. Dynamis CO2 quality recommendations.
Int J Greenh Gas Control 2008;2(4):478e84.
[108] Franco F, Bolland O, Booth N, Macchi E, Manzolini G,
Naqvi R, et al. Common framework definition document.
2009.
[109] National Energy Technology Laboratory (NETL). Quality
guidelines for energy system studies e CO2 impurity
design parameters. 2012. Report number: DOE/NETL-341/
011212.
[110] Aspelund A, Jordal K. Gas conditioningdThe interface
between CO2 capture and transport. Int J Greenh Gas
Control Jul. 2007;1(3):343e54.
[111] Lee S. Methanol synthesis technology. Boca Raton, Florida:
CRC Press; 1990.
[112] Alves JJ, Towler GP. Analysis of refinery hydrogen
distribution systems. Ind Eng Chem Res
2002;41(23):5759e69.
[113] Chiesa P, Lozza G, Mazzocchi L. Using hydrogen as gas
turbine fuel. J Eng Gas Turbines Power 2005;127(1):73.
[114] Choudhuri AR, Gollahalli SR. Combustion characteristics of
hydrogen e hydrocarbon hybrid fuels. Int J Hydrogen
Energy 2000;25:451e62.
[115] Eliaz N, Shemesh G, Latanision RM. Hot corrosion in gas
turbine components. Eng Fail Anal 2002;9(1):31e43.
[116] Lowesmith BJ, Hankinson G, Chynoweth S. Safety issues of
the liquefaction, storage and transportation of liquid
hydrogen: an analysis of incidents and HAZIDS. Int J
Hydrogen Energy 2014;39(35):20516e21.
[117] Bracha M, Lorenz G, Patzelt A, Wanner M. Large-scale
hydrogen liquefaction in Germany. Int J Hydrogen Energy
1994;19(1):53e9.
[118] Chaparral Energy. A ‘CO2 Midstream’ overview e EOR
carbon management workshop. 2013 [Online]. Available:
http://www.co2conference.net/wp-content/uploads/2014/
01/13-Chaparral-CO2-Midstream-Overview-2013.12.09new.
pdf [accessed 02.06.15].
[119] UOP. UOP selexol technology for acid gas removal. 2009
[Online]. Available: http://www.uop.com/?document¼uop-
selexol-technology-for-acid-gas-removal&download¼1
[accessed 02.06.15].
[120] Global CCS Institute. Status of CCS project database.
2015 [Online]. Available: http://www.globalccsinstitute.
com/projects/status-ccs-project-database [accessed
02.06.15].
[121] Heal K, Kemp T. North West Sturgeon refinery project
overview e carbon capture through innovative commercial
structuring in the Canadian oil sands. Energy Proced
2013;37:7046e55.
4992 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 4 9 6 9 e4 9 9 2
[122] Mayorga SG, Hufton JR, Sircar S, Gaffney TR. Sorption
enhanced reaction process for production of hydrogen,
phase I final report. 1997.
[123] Chiesa P, Consonni S, Kreutz T. Co-production of hydrogen,
electricity and CO from coal with commercially ready
technology. Part A: performance and emissions. Int J
Hydrogen Energy 2005;30(7):747e67.
[124] Consonni S, Vigano ! F. Decarbonized hydrogen and
electricity from natural gas. Int J Hydrogen Energy
2005;30:701e18.
[125] Manzolini G, Vigano ! F. Co-production of hydrogen and
electricity from autothermal reforming of natural gas by
means of Pd-Ag membranes. Energy Proced
2009;1(1):319e26.
[126] Cormos C-C. Evaluation of energy integration aspects for
IGCC-based hydrogen and electricity co-production with
carbon capture and storage. Int J Hydrogen Energy
2010;35(14):7485e97.
[127] Xiang W, Chen S, Xue Z, Sun X. Investigation of coal
gasification hydrogen and electricity co-production plant
with three-reactors chemical looping process. Int J
Hydrogen Energy 2010;35(16):8580e91.
[128] Cormos AM, Cormos CC. Investigation of hydrogen and
power co-generation based on direct coal chemical looping
systems. Int J Hydrogen Energy 2014;39(5):2067e77.
[129] Cormos C-C. Biomass direct chemical looping for
hydrogen and power co-production: process
configuration, simulation, thermal integration and
techno-economic assessment. Fuel Process Technol
2015;137:16e23.
[130] Jordal K, Anantharaman R, Peters TA, Berstad D, Morud J,
Nekså P, et al. High-purity H2 production with CO2 capture
based on coal gasification. Energy 2015;88:9e17.
[131] International Energy Agency (IEA). CO2 emissions from fuel
combustion: highlights. 2015. Paris.
[132] International Energy Agency (IEA). Tracking clean energy
progress 2014. 2014. Paris.
[133] International Energy Agency (IEA). Energy technology
perspectives 2014. 2014. Paris.
[134] Jordal K, Anantharaman R, Gruber A, Peters T,
Henriksen PP, Berstad D, et al. Performance of the IGCC with
distributed feeding of H2 in the gas turbine burner. Energy
Proced 2014;63(1876):2037e44.
[135] Sa" nchez AL, Williams FA. Recent advances in
understanding of flammability characteristics of hydrogen.
Prog Energy Combust Sci Apr. 2014;41:1e55.
[136] Wang Y, Chen KS, Meshler J, Cho SC, Adroher XC. A review
of polymer electrolyte membrane fuel cells: technology,
applications, and needs on fundamental research. Appl
Energy 2011;88(4):981e1007.