The Removal of CO2 and N2 From Natural Gas Review (Rufford Et Al 2012)

Journal of Petroleum Science and Engineering 9495 (2012) 123154
Contents lists available at SciVerse ScienceDirect
Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol
The removal of CO2 and N2 from natural gas: A review of conventional and
emerging process technologies
T.E. Rufford a, S. Smart b, G.C.Y. Watson a, B.F. Graham a, J. Boxall a, J.C. Diniz da Costa b, E.F. May a,n
a
b
The University of Western Australia, Centre for Energy, 35 Stirling Highway, Crawley, WA 6009, Australia
The University of Queensland, FIMLabFilms and Inorganic Membrane Laboratory, School of Chemical Engineering, College Road, St Lucia, Qld. 4072, Australia
a r t i c l e i n f o
abstract
Article history:
Received 5 September 2011
Accepted 2 June 2012
Available online 19 June 2012
This article provides an overview of conventional and developing gas processing technologies for CO2
and N2 removal from natural gas. We consider process technologies based on absorption, distillation,
adsorption, membrane separation and hydrates. For each technology, we describe the fundamental
separation mechanisms involved and the commonly applied process ow schemes designed to produce
pipeline quality gas (typically 2% CO2, o3% N2) and gas to feed a cryogenic gas plant (typically 50 ppmv
CO2, 1% N2). Amine absorption technologies for CO2 and H2S removal (acid gas treating) are wellestablished in the natural gas industry. The advantages and disadvantages of the conventional amineand physical-solvent-based processes for acid gas treating are discussed. The use of CO2 selective
membrane technologies for bulk separation of CO2 is increasing in the natural gas industry. Novel lowtemperature CO2 removal technologies such as ExxonMobils Controlled Freeze ZoneTM process and
rapid cycle pressure swing adsorption processes are also emerging as alternatives to amine scrubbers in
certain applications such as for processing high CO2 concentration gases and for developing remote gas
elds. Cryogenic distillation remains the leading N2 rejection technology for large scale (feed rates
greater than 15 MMscfd) natural gas and liqueed natural gas plants. However, technologies based on
CH4 selective absorption and adsorption, as well as N2 selective pressure swing adsorption technologies, are commercially available for smaller scale gas processing facilities. The review discusses the
scope for the development of better performing CO2 selective membranes, N2 selective solvents and N2
selective adsorbents to both improve separation power and the durability of the materials used in novel
gas processing technologies.
& 2012 Elsevier B.V. All rights reserved.
Keywords:
CO2 capture
nitrogen rejection
contaminated gas
membrane
absorption
pressure swing adsorption
hydrates for gas separation
1. Introduction
In 2010 natural gas (NG) supplied 23.81% of the worlds energy
demand and the volume of natural gas consumed increased by 7.4%
over 2009 levels driven by economic recovery the USA and the
continuing economic development of China, India and Russia (BP
Statistical Review of World Energy June 2011, 2011). The growth in
the global demand for natural gas has led to a re-evaluation of the
development potential of unconventional, stranded and contaminated gas reserves that were previously considered economically
unviable. Furthermore, many of the signicant natural gas reserves
are located far from the large established gas markets in Western
Europe, Japan and South Korea. Therefore, signicant volumes of
natural gas must be transported long distances from exporting
countries either by pipeline or by tanker as liqueed natural gas
(LNG); the economics of this choice have been discussed by many
Corresponding author.
E-mail address: eric.may@uwa.edu.au (E.F. May).
0920-4105/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.petrol.2012.06.016
authors such as Rojey et al. (1997). Table 1 contains a list of the

major natural gas importing and exporting countries in 2010
including a breakdown of the amounts transported by pipeline
and LNG. The production of LNG is clearly already essential to the
international trade of natural gas and its importance is set to
increase further over the next two decades, particularly in the
Asia-Pacic region.
The estimated world volumes of sub-quality natural gas
reserves, including sour natural gas reserves, are signicant.
Sub-quality natural gas reserves are dened as gas elds containing more than 2% CO2, 4% N2 and 4 parts per million (ppm)
hydrogen sulphide (H2S) (Kidnay and Parrish, 2006). Burgers et al.
(2011), for example, estimate that 50% of the volume of known
gas resources contain more than 2% CO2. The development of
sub-quality, unconventional and remote natural gas reserves,
including development via LNG production, can present new
challenges to gas processing that require more efcient
approaches to the conventional absorption and cryogenic condensation technologies that are most commonly used for the
removal of carbon dioxide and nitrogen, respectively, from
124
T.E. Rufford et al. / Journal of Petroleum Science and Engineering 9495 (2012) 123154
Table 1
Volumes of natural gas traded as pipeline and LNG (billions of cubic metres) by top
natural gas exporting and importing countries in 2010 (BP Statistical Review of
World Energy June 2011, 2011).
Top natural gas exporters
1
2
3
4
5
6
7
8
9
10
Russian Federation
Norway
Qatar
Canada
Algeria
Netherlands
Indonesia
Malaysia
U.S.
Australia
Pipeline
LNG
Total
186.5
95.9
19.2
92.4
36.5
53.3
9.9
1.5
30.3
0.00
13.4
4.7
75.8
0.0
19.3
0.0
31.4
30.5
1.6
25.4
199.9
100.6
94.9
92.4
55.8
53.3
41.3
32.0
32.0
25.4
Pipeline
LNG
Total
93.3
92.8
66.3
35.0
35.0
28.8
8.9
33.0
12.2
93.5
9.1
18.7
13.9
44.4
7.9
27.5
105.5
93.5
92.8
75.3
53.6
48.9
44.4
36.7
36.4
33.0
Top natural gas importers
1
2
3
4
5
6
7
8
9
10
United States
Japan
Germany
Italy
United Kingdom
France
South Korea
Turkey
Spain
Ukraine
natural gas. Additional gas processing challenges arise from new

environmental regulations that may call for capture and sequestration of CO2 from gas elds and stricter regulation of CH4
emissions in N2 vent streams from natural gas production
facilities.
Carbon dioxide, as well as H2S and other acid gases, must be
removed from natural gas because in the presence of water these
impurities can form acids that corrode pipelines and other
equipment. Although this paper is not focussed on the removal
of H2S, it should be noted that health and safety is a key driver for
removal of this highly toxic gas from sour natural gas streams.
Several of the CO2 capture technologies described are more
selective for H2S than CO2. Furthermore, CO2 provides no heating
value and must be removed to meet gas quality specications
before distribution to gas users. The maximum level of CO2
permitted in natural gas transmitted to customers by pipeline is
typically less than 3% (Hubbard, 2010) although local contracts
may stipulate quality specications different to these values. The
specications of CO2 removal from natural gas to be processed in
a cryogenic plant to produce LNG, recover liqueed petroleum gas
(LPG) or natural gas liquids (NGL) are more stringent than those
for typical gas pipelines. For example, in addition to more
extensive dehydration, the CO2 concentration of the natural gas
should be less than 50 ppmv (Hubbard, 2010) before it enters the
cryogenic processes within the plant to avoid the formation of
dry ice.
A typical gas pipeline specication for N2 is 3% (Kidnay and
Parrish, 2006); because N2 is inert the main driver for its removal
from pipeline sales gas is to increase the heating value of the gas.
Nitrogen will not freeze or lead to corrosion in a cryogenic gas
plant, but a maximum concentration of 1% N2 is often specied for
LNG, for example to avoid stratication and rollover of the liquid
product during shipping. To ensure this specication is met in
plants liquefying NG with a high N2 content, cryogenic distillation
columns known as nitrogen rejection units (NRU) are integrated
into the process; these columns are both expensive and energy
intensive. In addition, high N2 concentrations in natural gas
processed by an LNG plant are energetically parasitic because a
signicant amount of energy is wasted cooling the N2 from
ambient temperatures to those of LNG (about 161 1C at atmospheric pressure). Furthermore, even if the NG does not have a
high N2 concentration, an NRU may be necessary because the
liquefaction process produces two product streams: the LNG and
an end-ash gas which is a mixture of N2 and CH4 vapour. This
end-ash gas can be used as fuel gas for the plant and/or blended
into sales gas destined from a conveniently located pipeline.
However, if production of end-ash gas exceeds the fuel gas
requirements and if no pipeline is available for its disposal an
NRU may be necessary to produce a stream pure enough that it
can be vented to atmosphere. Given the increasing regulation of,
and costs associated with mitigation of, greenhouse gas emissions
this relatively expensive NRU option could become increasingly
common.
This review provides an overview of conventional, developing
and novel gas processing technologies for CO2 and N2 removal
from natural gas, with particular attention paid to large scale LNG
production. The introduction sections provide an overview of a
typical process ow sheet and the fundamental unit operations
involved in natural gas processing. The subsequent sections of
this review describe the core concepts and industrial application
of absorption, distillation, adsorption, membrane and hydrate gas
separation technologies.
Many of the process technologies we describe for CO2 capture
from CH4 can also be applied to CO2 capture from combustion ue
gases, for example in coal-red power stations. The recent
advances and future trends in technologies for capturing CO2 at
the power plant are reviewed elsewhere by many other authors,
including Figueroa et al. (2008), MacDowell et al. (2010) and
Ebner and Ritter (2009). However, the process conditions available in the natural gas processing facility can be very different to
those conditions available for post-combustion ue gas (predominantly a mixture of CO2, N2 and H2O) treatment. The two most
signicant differences between these applications are the CO2
partial pressure, and the level of CO2 removal required. In the rst
case, the natural gas feed to the CO2 removal unit is typically
available at high pressures (more than 3000 kPa) while ue gases
are typically at close to atmospheric pressure, so the driving force
for CO2 capture from ue gas (partial pressure CO2 typically less
than 15 kPa) is much lower than from natural gas. In the second
case the level of CO2 removal required for natural gas production
is greater, especially for LNG production plants, than bulk separation of CO2 from ue gas. Thus, some promising strategies for
CO2 capture in thermal power plants such as oxy-combustion
(a modied combustion process that can produce a high CO2
concentration ue gas, Plasynski et al., 2009) are not relevant to
CO2 removal from natural gas.
1.1. Overview of conventional gas processing ow schemes
The major operations that can be used in natural gas processing and LNG production are shown in Fig. 1. Common process
operations include inlet gas compression, acid gas removal,
dehydration, LPG/NGL recovery and hydrocarbon dewpoint control, nitrogen rejection, outlet compression and liquefaction.
Depending on the available markets, feed gas properties, product
specications and the gas ow rate, the units identied in Fig. 1
may not all be required. For example a nitrogen rejection unit
(NRU) may not be required for the production of pipeline gas from
a feed gas containing only low N2 concentrations, or if a high N2
content gas can be blended with richer natural gas streams to
meet pipeline gas specications.
125
Fig. 1. Conventional gas processing operations in a typical natural gas plant with a cryogenic process for liqueed natural gas production. The required operations and
process ow arrangements vary depending on the local feed gas properties, size of the plant, and product specications; and may not all be required (MCHE main
cryogenic heat exchanger).
Table 2
Physical properties of methane, carbon dioxide and nitrogen.
CO2
N2
Property
CH4
(Tagliabue et al., 2009)

Kinetic diameter (A)
Normal boiling point (NBP) (K) (Lemmon et al., 2010)
Critical temperature (K) (Lemmon et al., 2010)
Critical pressure (kPa) (Lemmon et al., 2010)
DHvap at NBP (kJ/mol) (Linstrom and Mallard, 2011)
Polarisability (A 3) (Tagliabue et al., 2009)
3.80
3.30
3.64
111.7
3.80
4600
8.17
2.448
304.1
7380
26.1
2.507
77.3
126.2
3400
5.58
1.710
(Tagliabue et al., 2009)

Quadrapole moment (DA)
0.02
4.3
1.54
In conventional gas processing H2S and CO2 are removed in an

acid gas removal unit (AGRU) using aqueous amine absorption
processes. The sweetened gas leaving the amine process is saturated
with water, so typically the AGRU is located upstream of the
dehydration facilities. The nal sections of the gas liquefaction plant
(main cryogenic heat exchange (MCHE) in Fig. 1) can operate at
temperatures as low as 161 1C, and therefore, it is essential that
components that could freeze, and cause blockages in the cryogenic
equipment, at low temperatures are removed from feed to the
cryogenic plant. In addition to CO2, components that could freeze in
the cryogenic plant include water (typically removed to less than
0.1 ppmv), heavier parafnic hydrocarbons and aromatics such as
benzene. To protect the aluminium plate-n heat exchangers used
in the NRU the feed gas to the cryogenic plant must be free of
mercury (below 0.01 mg/Nm3) (Kidnay and Parrish, 2006). The gas
feed entering the (Pre-Cool section of the) liquefaction plant is
typically delivered, or compressed to, a pressure of more than
3400 kPa and at a temperature close or slightly above ambient.
The conventional method of removing N2 from natural gas is by
cryogenic distillation; hence NRUs are usually closely integrated
within the liquefaction process. There are several variations of
cryogenic liquefaction processes including, for example, Air Products
and Chemicals (APCI) C3MR process and the ConocoPhillips Optimised Cascade process. Commonly a propane refrigeration loop is
used to pre-cool the gas before it enters a main cryogenic heat
exchanger (MCHE) which might use a mixed refrigerant or a cascade
of several pure uid refrigeration cycles. If an NRU is incorporated
with the liquefaction process then it would commonly be located
downstream of the MCHE and before the nal depressurisation
stage of the LNG production process.
1.2. Overview of gas separation mechanisms

Separation processes can be designed to exploit differences in
the molecular properties or the thermodynamic and transport
properties of the components in the mixture. Molecular properties that could be exploited to achieve a separation of CO2, N2 and
CH4 include the differences in kinetic diameter, polarizability,
quadrupole and dipole moments of the molecules (Table 2).
Thermodynamic and (interphase) transport properties that could
be exploited include vapour pressure and boiling points, solubility, adsorption capacity and diffusivity. Based on these properties
of the components to be separated, the primary operations for the
separation and purication of gases apply one of the following
inherent separation mechanisms: (1) phase creation by heat transfer and/or shaft work to or from the mixture, (2) absorption in a
liquid or solid sorbent, (3) adsorption on a solid, (4) permeation
through a membrane and (5) chemical conversion to another
compound (Kohl and Nielsen, 1997; Seader and Henley, 2006).
The rst four of these operations are discussed in this review;
direct chemical conversion of CO2 from natural gas to a useful
product is beyond the current scope. An example of such direct
conversion, which is attracting signicant current research interest, is the dry reforming process where CO2 reacts with CH4 to
produce syngas (a mixture of H2 and CO2) which can then be used
for the production of liquid fuels via FischerTropsch reactions.
Recent reviews on the conversion of CO2 include articles by
Havran et al. (2011), Song (2006) and Zangeneh et al. (2011).
Separations involving the creation of a phase include the partial
condensation or partial vaporisation of species with very different
volatility from a feed mixture; and this category can also include
126
desublimation of CO2. If the volatility differences among species

to be separated are not sufciently large, as is the case for
N2CH4, to achieve the desired separation in a single partial vaporisation or partial condensation contact stage, then a distillation
process involving multiple vapour-liquid contact stages may be
required.
One of the most fundamental properties of an inherent separation mechanism is its selectivity with respect to the components i
and j being separated. As will be discussed, some separation
mechanisms have more than one type of selectivity; however, the
most common and applicable type is the equilibrium selectivity, aij,
which is dened in terms of phase compositions:

yj
x
aij i
1
xj
yi
Here xi and xj are the mole fractions (or convenient concentration units) of components in one equilibrium phase, and yi and yj
are the mole fraction of components in a second equilibrium
phase. This denition of equilibrium selectivity derives from its
central role in distillation theory, where it is also known as the
relative volatility (McCabe et al., 2005). However, the equilibrium
selectivity can be applied more broadly than to vapourliquid
equilibrium in distillation; it is useful in the analysis of adsorption- and absorption-based processes. The equilibrium selectivity
can also be applied, through the use of appropriate analogies and
use of concentrations of the permeate (x) and feed (y) streams, to
the analysis of membrane processes which are not strictly
equilibrium-based. It is important to note that selectivity is often
linked to the characteristic energy of the separation mechanism,
and therefore the regeneration energy needed if the mechanism is
to be used in a cyclical process.
The performance of a separation process is governed by two
factors: the inherent selectivity of the separation mechanism being
utilised and the degree to which that mechanism can be exploited
through appropriate engineering design. This gives rise to another
metric, known as the separation power, SPij (Seader and Henley,
2006), which can be used to quantify the performance of an entire
separation process in terms of the product stream compositions. For
a single stage equilibrium operation aij SP ij ; however, for a process
utilizing multiple separation stages SPij values much larger than the
single stage equilibrium selectivity can be achieved.
0
1
!
C 2
C 1
j
i A
@
SP ij
2
C 1
C 2
j
i
2
Here C 1
i and C i are the concentrations of component i in each of
the product streams, and C 1
, C 2
the concentrations of component j
j
j
in each of the product streams. The symbol C for concentration has
been used here to distinguish Eq. (2) as the separation power of the
process from the equilibrium selectivity of the mechanism, although
in many cases the composition of the product streams used in the
calculation of SPij may be in units of mole fraction. In principle any
selective mechanism with aij 41 could be engineered to achieve a
given separation power if no constraints exist on capital, operational
and energy costs. In practice a separation process will be selected if it
can achieve the separation power necessary to meet the desired
product specications at a cost that is (i) lower than other processing
alternatives, and (ii) economically viable in terms of the
products value.
In Table 3, indicative values of aij and SPij are given for the most
common industrial processes used to separate CO2 or N2 from natural
gas for the purpose of evaluating the prospects of new and emerging
technologies. To generalise this measure for any of the four primary
separation operations the product streams must be dened. For CO2
removal from natural gas, a convenient approach may be to compare
the aCO2 ,CH4 values of the various separation technologies by dening
the equilibrium phases to be used with Eq. (1) as the CO2 selective
phase: that is the amine solution or physical solvent for absorption,
the high-purity liquid CO2 product for distillation, the adsorbed phase
(xi or qi) for gassolid adsorption systems, and the permeate stream
from a CO2 selective membrane stage. Using available data for CO2
removal processes, such as the amine absorption data included in
Kohl and Nielsen (1997), the typical separation power of processes to
produce pipeline quality gas (2% CO2) from a feed mixture containing
5% CO2 can be estimated with Eq. (2) as shown in Table 3. The
inherent equilibrium selectivity can be exploited for each separation
mechanism to achieve SP ij b aij through the arrangement of multiple
separation stages into an engineering process system, for example:
trayed absorption and distillation columns, multiple adsorption beds
operating in adsorptiondesorption cycles, and membrane stages
with interstage recompression and recycle loops. This simplied
analysis shows clearly that the typical inherent process separation
powers for chemical absorption technologies are much larger than
the best alternatives currently available to treat large gas ows; hence
amine absorption is the most commonly applied type of AGRU
despite the energy required for regeneration and corrosive nature of
the amine solutions.
For N2 rejection technologies the conventional cryogenic distillation technology has a separation power more than 8 times that of N2
selective adsorption and membrane processes. However, the
Table 3
Inherent equilibrium selectivity, ai,j, for the separation of CO2 from CH4 and N2 from CH4 by different operations, with the typical process separation power (SPi,j) achieved
in example technologies implementing these separation operations. The separation powers are calculated for typical processes to (a) remove CO2 from a feed gas
containing 5% CO2 to produce pipeline quality gas with 2% CO2, and (b) to reject N2 from a gas containing 4% N2 to produce a stream with 1% N2 for LNG production.
Process
(a) CO2/CH4 separation

Amine absorption (MDEA)
Physical solvent (chilled methanol)
AdsorptionCO2 selective
MembraneCO2 selective
(b) N2/CH4 separation
Cryogenic distillation
AdsorptionN2 selective
AdsorptionCH4 selective
MembraneN2 selective
MembraneCH4 selective
Separating agent
Typical inherent
equilibrium selectivity
Typical process
separation power
aCO2 ,CH4
Liquid absorbent
Liquid absorbent
Solid adsorbent
Membrane
860
318
28.5
1520
Heat transfer
Solid adsorbent
Solid adsorbent
Membrane
Membrane
58
1.32a
0.250.5
23
0.250.3
SPCO2 ,CH4
3300
1900
622
2040
SPN2 ,CH4
320
840a
1.052
210
210
aN2 ,CH4
a
Inherent kinetic selectivities of narrow pore adsorbents are reported from 2 to 10, which could allow a N2 selective process with much higher separation power to be
engineered.
separation of N2 from CH4 in adsorption-based processes is

enhanced by the differences in rates of diffusion of N2 and CH4 that
have been reported for small pore titanosilicate ETS-4 materials
(Marathe et al., 2004a). Guild Associates Molecular GateTM pressure
swing adsorption (PSA) process (Guild Associates, 2007) is a
commercial example of a N2 rejection process that relies on the
kinetic selectivity of N2 over CH4.
In practice, the achievable separation power may be much
lower than the ideal separation powers estimated in Table 3.
Furthermore, there are many other factors beside a separation
power or inherent selectivity that a process engineer designing or
selecting a gas separation process will need to consider. Other
factors that inuence the selection of process technology for CO2/
CH4 and N2/CH4 separations include the level of contaminants in
the feed gas, the required level of contaminant removal or
product purity, the ow rate and condition of the feed gas
(temperature, pressure, water content), and for AGRUs the need
for simultaneous or selective removal of H2S. Process selection is
also inuenced by the available disposal routes for the removed
contaminants, which may include reinjection of CO2 for enhanced
oil recovery (EOR) or enhanced gas recovery (EGR), and venting of
N2 to atmosphere. The process plant layout and available plant
space for the separation process must be considered. If the
separation process is to be installed on an offshore platform, a
oating LNG (FLNG) plant or as a retrot in an existing production
plant, then the process footprint the plan area and/or height
occupied by the process equipment may inuence the choice of
process technology. Each of these process selection criteria may
have material impacts on the feasibility, energy requirements and
costs of CO2 and N2 removal processes.
There are many factors that inuence the cost of a separation
process including the extent to which it has been used
successfully in the past. Consequently, a process engineer designing or selecting a gas separation process is likely to be more
interested in the ratio of its separation power to its cost rather
than in the inherent selectivity upon which the process is based.
However, once a separation process is sufciently mature, its
separation power to cost ratio will generally only improve
asymptotically, unless a signicant improvement in its inherent
selectivity can be achieved. Thus, the starting point for scientists
and engineers aiming to develop a new separation technology
should be an analysis of the inherent selectivities of both the
127
new technology and the conventional one with which it will

compete.
2. Absorption
This section focuses primarily on CO2 absorption processes,
but also introduces technologies for N2 rejection by the selective
absorption of CH4 in hydrocarbon solvents (Mehra and Gaskin,
1997) and the potential for the development of N2 selective
solvents. Although this review is concerned primarily with CO2
removal, the selection of the AGRU process is more often
determined by the H2S removal requirements. Thus, most of the
technical literature concerning acid gas treating focuses on the
absorption of H2S. Commonly, the capacity of a sorbent is
reported as an acid gas loading capacity which includes the
capacity for CO2 and H2S. We have noted in Tables 5 and 10
which of the process technologies are suitable for the simultaneous or the selective absorption of H2S.
A large number of commercial processes are available for CO2
absorption in chemical and physical solvents, including the
technologies listed in Table 4. Chemical absorption processes
with amine solutions are the most commonly used acid gas
removal technologies in the natural gas industry (GPSA
Engineering Data Book, 2004). The chemical absorption processes
rely on reactions of the CO2 with the sorbent to form weakly
bonded intermediate compounds, and these reactions can be
reversed by the application of heat to release the CO2 and
regenerate the sorbent (Olajire, 2010). Physical solvents, such as
the mixture of polyethylene glycoldimethyl ethers used in the
Selexols process, selectively absorb CO2 from the natural gas feed
according to Henrys law so that absorption capacity increases at
high pressure and low temperature.
The two major cost factors in gasliquid absorption processes
are (1) the required sorbent circulation rate, which is determined
by the amount of CO2 that must be removed from the feed gas
and the CO2 loading capacity of the sorbent, and (2) the energy
required to regenerate the sorbent (Kidnay and Parrish, 2006).
The acid gas loading capacity of physical solvents at low to
moderate CO2 partial pressures is generally lower than that of
chemical absorbents. However, physical solvent processes have
lower energy requirements for regeneration because the heat of
Table 4
Examples of commercial absorption technologies for CO2 capture and gas sweetening.
Chemical absorption
EconamineSM
ADIP-X
aMDEAs
GAS/SPEC
UCARSOL
KM CDR
Beneld
Catacarb
Flexsorb HP
Physical absorption
Fluor SolventSM
Selexol
Purisol
Rectisol
Ifpexol
Mixed-solvent processes
Sulnol-D
Amisol
Vendor/licensor
Sorbent
Reference
Fluor
Shell
BASF
Ineos
DOW
Mitsubishi Heavy Industries
UOP
Digylcolamine, mono-ethanolamine
MDEA accelerator
MDEA
MDEA
MDEA
KS-1 hindered amine
Potassium carbonate
Eickmeter and Associates

Exxon Mobil
Potassium carbonate ( organic additive)

Potassium carbonate ( steric amine)
http://www.uor.com
www.shell.com
www.basf.de
www.gasspec.com
http://www.oilandgas.dow.com
Mimura et al., (1995)
UOP Overview of Gas Processing
Technologies and Applications, (2010)
www.catacarb.com
www.exxonmobil.com
Fluor
UOP/DOW
Lurgi
Lurgi
IFP
Dry propylene carbonate

Mixed polyethylene glycol dimethyl ethers
n-Methyl-2-pyrrrolidone
Chilled methanol
Chilled methanol
www.uor.com
www.uop.com
www.lurgi.com
www.lurgi.com
Larue and Lebas, (1996)
Shell
Lurgi
Sulfolane DIPA water

Methanol secondary amine water
www.shell.com (Rajani, 2004)

Kohl and Nielsen, (1997)
128
Fig. 2. Process ow diagram of a typical amine-solvent (MDEA)-based chemical adsorption system for the separation of CO2 and other acid gases from natural gas
(Hubbard, 2010; Kohl and Nielsen, 1997).
absorption for physical solvents is much lower than the heat of

absorption for chemical solvents.
2.1. Chemical absorption processes for acid gas treating
2.1.1. Aqueous amine processes
Amines are organic compounds derived from ammonia (NH3)
where one or more hydrogen atoms have been substituted with
an alkyl or aromatic group. It is the (NH2) functional group of the
amine molecule that provides a weak base that can react with the
acid gases. The absorption of CO2 occurs via a two-step mechanism: (1) the dissolution of the gas in the aqueous solution,
followed by (2) the reaction of the weak acid solution with the
weakly basic amine. The rst physical absorption step is governed
by the partial pressure of the CO2 in the gas feed. The reactions
involved in the second step of CO2 absorption in aqueous amines
have been widely studied, with a large number of reference
materials on the reaction mechanisms (Bindwal et al., 2011;
Kohl and Nielsen, 1997; Penny and Ritter, 1983; Vaidya and
Kenig, 2007; Versteeg et al., 1996) and guidelines for process
operation (GPSA Engineering Data Book, 2004) available in the
literature. The fundamental reactions involved in CO2 absorption
in amine treating are (Kohl and Nielsen, 1997):
Dissociation of water:
H2O"H OH
(3)
Hydrolysis and dissociation of dissolved CO2:

CO2 H2O"HCO3 H
(4)
Protonation of the amine:

RNH2 H "RNH3
(5)
Carbamate formation:
RNH2 CO2"RNHCOO H
(6)
The dissociation reactions are shown here to highlight that the

pH of the amine solution is an important process parameter
because the concentrations of the ionic species H , OH- and HCO-3
in the amine solution affect the other reactions involving
the amine.
Amines can be classied according to the number of hydrogen

atoms that have been substituted, as primary (RNH2, where R is
a hydrocarbon chain), secondary (RNHR0 ) or ternary (R0 NR
R00 ). For primary and secondary amines, such as monoethanolamine (MEA) and diethanolamine (DEA), the carbamate formation
reaction (Eq. (6)) predominates; this reaction is much faster than
the CO2 hydrolysis reaction (Eq. (4)). The stoichiometry of the
carbamate reaction suggests that the capacity of primary and
secondary amines is limited to approximately 0.5 mol of CO2 per
mole of amine. However, DEA-based amine processes can achieve
loadings of more than 0.5 mol of CO2 per mole of amine through
the partial hydrolysis of carbamate (RNHCOO-) to bicarbonate
(HCO3 ), which regenerates some free amine (Kidnay and Parrish,
2006).
Tertiary amines such as MDEA, which do not have a free
hydrogen atom around the central nitrogen, do not react directly
with CO2 to form carbamate. Instead, CO2 reactions with tertiary
amines proceed via equivalent reactions to those shown in Eqs.
(4) and (5), which are much slower than the reaction in Eq. (6), to
give the overall reaction:
RR0 R00 N CO2 H2O"RR0 R00 NH HCO3
(7)
The stoichiometry in Eq. (7) shows that theoretically tertiary

amines can achieve a loading of 1 mol of CO2 per mole of amine,
which is double the CO2 loading capacity of primary amines. Also
the required heat of regeneration is lower for tertiary amines. A
disadvantage of tertiary amines is that the absorption kinetics are
slower than for primary and secondary amines. For some natural
gas treating processes the slow kinetics of CO2 absorption in
tertiary amines can be utilised to achieve selective H2S removal
by optimisation of the contact time in the absorber to minimise
CO2 uptake (GPSA Engineering Data Book, 2004). Alternatively, to
enhance CO2 the absorption kinetics of tertiary amines an
activator (usually a primary or secondary amine) may be added
to increase the rate of hydrolysis of carbamate and dissolved CO2
(GPSA Engineering Data Book, 2004).
Since the rst application of tertiary amines in the mid-1970s,
signicant research has been directed into the further development of novel amine solvents. To accelerate the reaction rate of
tertiary amines with CO2, a primary or secondary amine can
be included as an activator (GPSA Engineering Data Book, 2004).
For example, the cyclic diamine piperazine has been studied as a

promoter to improve the CO2 mass transfer rates of MDEA and
MEA (Bishnoi and Rochelle, 2002); a commercial example of this
technology is the aMDEA solvent from BASF. The piperazine
reacts rapidly with CO2 in the vapour phase, which accelerates
the dissolution of CO2 into carbonic acid, which can then react
quickly with MDEA. Sterically hindered amines are either primary
or secondary amines with large bulky alkyl or alkanol groups
attached to the nitrogen (Seagraves and Weiland, 2011), which
reduces the carbamate stability. The molecular conguration
dictates the amount of CO2 removal: severely hindered amines,
such as ExxonMobils Flexsorb SE, have very low rates of CO2
absorption and allows selective H2S removal. In contrast, moderately hindered amines, such as 2-amino, 2-methyl, 1-propanol
(AMP), are characterised by high rates of CO2 absorption and high
capacities for CO2. Weiland et al. (2010) evaluated the use of AMP
with MEA for CO2 capture from ue gases and found it had several
advantages including at least a 15% reduction in the required
regeneration energy.
A typical process ow diagram for the removal of acid gas from
a sour gas feed using methyldiethanolamine (MDEA) is shown in
Fig. 2. Properties and typical operating conditions for commonly
used aqueous amine solutions are shown in Table 5. The basic
process ow for other amine absorption systems is similar to that
shown for MDEA, although some commercial process designs
often feature multiple column feeds and contactor sections. Any
liquids or solids in the sour feed gas are removed in an inlet
separator before the gas enters at the bottom of amine contactor.
Typical operating pressures for amine contactors are in the range
of 5070 bar (Kidnay and Parrish, 2006). The lean amine solution,
typically an aqueous solution containing 1065%wt amine, is fed
at the top of the column. As the amine solution falls down the
contactor and mixes with the gas, the acid gases dissolve and
react with the amine to form soluble carbonate salts. The
sweetened natural gas leaves the top of the contactor saturated
with water and so dehydration is normally required before the
gas is sold or fed to a cryogenic gas plant. Process temperatures
inside the contactor rise above ambient temperature due to the
exothermic heat of absorption and reaction, with a maximum
temperature observed near the bottom of the column.
The rich amine leaves the bottom of the contactor at a temperature of approximately 60 1C and containing 0.200.81 mol of acid
129
gas per mole of amine (GPSA Engineering Data Book, 2004). The
pressure of the rich amine stream is reduced to around 6 bar in a
ash tank, to separate any dissolved hydrocarbons from the rich
amine, and preheated to 80105 1C before entering the stripping or
regenerator column. In the stripping column, heat supplied by a
steam reboiler generates vapour, which removes the CO2 from the
rich amine as the vapour travels up the column. A stream of lean
amine is removed from the bottom of the stripper, cooled to
approximately 40 1C and recycled to the amine contactor. The
vapour stream from the top of the stripping column is cooled to
condense and recover water vapour, and the acid gas may be vented,
incinerated, sent to a sulphur recovery plant (for H2S rich feed gas)
or compressed for reinjection into a suitable reservoir for enhanced
oil/gas recovery (Hughes et al., 2012).
The process disadvantages with conventional amine treating
processes include: (1) the large amounts of energy required for
regeneration of the amine, (2) the relatively low CO2 loading
capacity of amines requires high solvent circulation rates and
large diameter, high-pressure absorber columns, (3) the corrosive
amine solutions induce high equipment corrosion rates, (4) degradation of amines to organic acids, and (5) co-absorption of
hydrocarbon compounds such as benzene, toluene, ethylbenzene
and xylene (BTEX) which subsequently are emitted with the acid
gas stream (Collie et al., 1998; Morrow and Lunsford, 1997).
Operational issues also include solution foaming, emulsions,
excessive solution losses, heat stable salts and high-lter change
out frequency (Seagraves and Weiland, 2011). Aqueous ammonia
and hot carbonate systems are among the alternative chemical
absorption processes to amines. However, many of the disadvantages of amine treating are also associated with aqueous ammonia and hot carbonate processes.
Future innovations in conventional absorption column technology (e.g., tray and packing designs) could be expected to
achieve only incremental improvements in process efciencies
(MacDowell et al., 2010). However, one promising strategy to
intensify the CO2 absorption process is the use of a hollow bre
membrane as a gasliquid contactor device (Cai et al., 2012;
Ebner and Ritter, 2009; Favre and Svendsen, 2012; Zhou et al.,
2010). In this concept, the membrane does not show any
selectivity for CO2 over CH4; instead the membrane provides a
physical barrier between the gas and liquid phases, and a large
interfacial surface area for mass transfer of CO2. The selective
Table 5
Properties of common aqueous amine solvents for acid gas treating.
Solvent
Monoethanolamine
Diethanolamine
Digylcolamine
Methyldiethanolamine
Acronym
Normally capable of meeting H2S specication
(Kidnay and Parrish, 2006)
Removes COS, CS2, mercaptans (Kidnay and Parrish,
2006)
50 ppm CO2 for cryogenic plant feed (Kidnay and
Parrish, 2006)
Solvent degradation concerns (components) (Kidnay
and Parrish, 2006)
Solution concentrations, normal range wt% (GPSA
Engineering Data Book, 2004)
Acid gas pickup, mole acid gas / mole amine (GPSA
Rich solution acid gas loading, mol/mol amine
normal range (GPSA Engineering Data Book, 2004)
Lean solution acid gas loading, mol/mol normal
range (GPSA Engineering Data Book, 2004)
Stripper reboiler normal range, 1C (GPSA Engineering
Data Book, 2004)
Approximate integral heats of absorption of CO2, kJ/
mol Kohl and Nielsen, 1997
MEA
yes
DEA
yes
DGA
yes
MDEA
yes
partial
partial
partial
partial
no, 100 ppm possible

yes - COS, CO2, CS2, SO2,
SO3, mercaptans
15-25
yes, 50 ppmv in
SNEA-DEA
some - COS, CO2,
CS2, HCN, mercaptans
30-40
no, 100 ppm

possible
yes - COS, CO2,CS2
no, pipeline
quality only
no
50-60
40-50
0.33-0.40
0.20-0.80
0.25-0.38
0.20-0.80
0.45-0.52
0.21-0.81
0.35-0.44
0.20-0.81
0.12
0.01
0.06
0.005-0.01
107-127
110-127
121-132
110-132
84.4
71.6
83.9
58.8
130
absorption of CO2 in the liquid solvent occurs at the liquid

interface of the membrane. For the hollow bre membrane to
operate effectively as a gasliquid contact device the pores must
remain gas lled and preventing liquid penetration into the
membrane pores is one of the practical challenges hindering the
commercialisation of this technology (Favre and Svendsen, 2012).
A gasliquid membrane contactor pilot plant is reported to have
been tested in Scotland to remove CO2 from a 5000 Nm3/h natural
gas feed (Mansourizadeh and Ismail, 2009). Other improvements
in the performance of CO2 absorption processes are likely to come
through the development of new solvent materials. Some acid gas
treating process licensors are also working to develop chemical
additives to inhibit corrosion and solvent degradation, so that
amine-based solvents can be operated at higher amine concentrations and regenerated at higher temperatures (Normand et al.,
2012). Improved understanding of the thermodynamics and
kinetics of CO2-amine systems, including the development of
mass transfer rate-based modelling approaches, is also allowing
optimised design of absorption processes.
2.1.2. Hot carbonate (alkali salt) systems
Technologies using hot solutions of potassium carbonate
(K2CO3) or sodium carbonate (NaCO3) have been employed since
the 1950s to remove CO2 from high pressure gas streams (Kohl
and Nielsen, 1997). The overall reactions for CO2 with potassium
carbonate can be represented by (GPSA Engineering Data Book,
2004):
CO2(g) K2CO3 H2O(l)"2KHCO3(s)
(8)
The basic potassium carbonate process was developed by the

US Bureau of Mines and commercialised as the Beneld Process in
1954, and now licensed by UOP with over 700 units constructed
(UOP Overview of Gas Processing Technologies and Applications,
2010). Other commercial potassium carbonate technologies competing with the Beneld Process include the Catacarb Process
(Eickmeter and Associates), which is mainly used in the ammonia
industry, and the Flexsorb HP Process (Exxon Research and
Engineering).
The process ow diagram for a potassium carbonate absorption system shares many features with the general amine process
ow diagram shown in Fig. 2. In a typical hot carbonate process
design the absorber and stripping columns operate in a temperature range of 100116 1C (GPSA Engineering Data Book, 2004). If
H2S removal is required or if low CO2 concentrations are required
in the product gas, then alternative designs with a two-stage
contactor and a lean-solution pumped to the middle of the
absorber may be used. For gas treatment requiring CO2 removal
to low levels for cryogenic gas processing, or GTL plant feed, the
UOP process design can be modied to a Hi-Pure design that
combines the potassium carbonate process and an amine process
(UOP Overview of Gas Processing Technologies and Applications,
2010; Miller et al., 1999). Amines such as DEA and MEA are also
used as activators to increase the rate of absorption of CO2 in the
potassium carbonate solution (Kohl and Nielsen, 1997). The
Catacarb Process is characterised by the use of a proprietary
organic additives to improve mass transfer rates (Kohl and
Nielsen, 1997). The distinguishing feature of the Flexsorb HP
Process is the use of a sterically hindered amine as the activator
(Kohl and Nielsen, 1997) which is claimed to improve CO2 loading
capacity and mass transfer rates.
2.1.3. Aqueous ammonia solvents
Similar to the acid gas absorption processes using aqueous
amine solutions, processes based on the reaction of CO2 with
ammonia (NH3) in solution have been developed for the capture
of CO2 from natural gas, coal seam gas, and post combustion ue
gases (Darde et al., 2010; Gonzalez-Garza et al., 2009). There are
two variants of the aqueous ammonia process (AAP) reported:
(i) chilled AAP designs operating with absorber temperatures in
the range 020 1C and (ii) processes operating with absorber at
ambient temperatures (2540 1C). Both variants are based on the
same reactions of CO2 and ammonia (NH3) described by Bai and
Yeh (1997), but at low temperatures the chilled AAP allows the
precipitation of ammonium bicarbonate shown in Eq. (9):
CO2(g) NH3(l) H2O(l)"NH4HCO3(s)
(9)
A further advantage of the chilled AAP design is that absorber

operation at low temperatures reduces ammonia slip into the
sweetened gas.
The process ow scheme of an AAP plant is very similar to the
ow scheme for amine absorption cycles (Fig. 2) with an absorption column and a solvent regeneration system. The absorption
column in the AAP operates at low pressures, usually close to
ambient, and the CO2-rich slurry leaving the bottom of the
absorber column must be pumped to a high-pressure, high
temperature regeneration column (Gal, 2006). In the regeneration
column the ammonium bicarbonate solid can be decomposed to
NH3 and CO2 at temperatures greater than about 50 1C (Darde
et al., 2010; Olajire, 2010), although temperatures of 100150 1C
are preferred in some designs (Gal, 2006). Typical AAP solvent
concentrations are in the range 1330% wt NH3 (Kim et al., 2008;
Olajire, 2010).
Although the aqueous ammonia process has potentially lower
energy requirements than amine absorption processes (one study
on AAP for postcombustion CO2 capture suggests 21003100 kJ/
kg CO2 compared to 3700 kJ/kg for CO2 capture by MEA, Darde
et al., 2010), the energy savings are not sufciently large to offset
the additional costs associated with complexity of the ammonia
process (Kohl and Nielsen, 1997) and the need to recompress the
sweetened gas in AAPs. Also, the removal efciency of chilled
AAPs is only 90% (Gal, 2006), hence ammonia processes may not
be capable of achieving very low CO2 concentrations in product
gas required for cryogenic gas processing.
2.2. Physical solvent and hybrid solvent processes
Physical solvent processes may be competitive with amine
absorption when the feed gas is available at high pressure
(generally greater than about 20 bar) or when the acid gas partial
pressure is 10 bar or greater (Nichols et al., 2009). For onshore
natural gas processing facilities all the commercial physical
solvents listed in Table 4 could be used for bulk removal of CO2.
Due to their large plant footprints, physical solvent technologies
are generally not suitable for AGRUs on offshore facilities (Nichols
et al., 2009). To treat feed gas with very high CO2 concentrations,
the leading physical absorption technologies include the Selexols
and Rectisols processes (Burr and Lyddon, 2008).
The regeneration of physical solvents can be achieved by
reducing the pressure of the rich solvent stream in a series of
multi-stage ash vessels, as shown in Fig. 3, or by stripping the
absorbed gas species in a regeneration column. Importantly, the
heat inputs required for regeneration of a physical solvent are
generally much lower than the heat required for the regeneration
of amine or potassium carbonate sorbents. A potential shortcoming of low pressure regeneration cycles is the cost of recompressing the acid gas if it is to be further processed for CO2
sequestration, EOR or sulphur recovery.
The Selexols process, based on a mixture of polyethylene
glycol-dimethyl ethers, is able to remove CO2 simultaneously
with H2S and water (GPSA Engineering Data Book, 2004). In fact,
131
Fig. 3. Process ow diagram of a typical physical solvent process for absorption of CO2 and other acid gases from natural gas.
H2S has a greater solubility in most organic solvents than CO2, a

property that can be used to design H2S selective processes (Kohl
and Nielsen, 1997). As many physical solvents also absorb water,
in contrast to the aqueous amine, AAP and potassium carbonate
technologies which saturate the sweet gas with water, the
required capacity of any dehydration units downstream of the
AGRU may be smaller if a physical absorption process is used.
To produce a sweet gas containing less than 50 ppmv CO2 for
feed to a LNG plant, the Rectisols process using a methanol
solvent operating at temperatures as low as 35 to 75 1C has
been applied successfully (GPSA Engineering Data Book, 2004). A
reported example of a chilled methanol plant is at Riley Ridge,
Wyoming, where 200 MMscfd of ultra-rich CO2 gas (70%) is
treated (CO2 Extraction & Sequestration Project Riley Ridge, WY,
2011).
The main weakness of physical solvent technologies relative to
amine AGRUs remains the issue of relatively low acid gas
adsorption capacities of the commercially available physical
solvents. Consequently physical solvent circulation rates are high;
thus large diameter absorption columns and solvent circulation
equipment are required in physical solvent processes. For onshore
gas processing facilities, the capital costs associated with the high
solvent circulation rates may be at least partially offset by the
lower costs of the carbon steel materials required when using
non-corrosive physical solvents compared to the more expensive
materials required to handle the highly corrosive aqueous amine
solutions (GPSA Engineering Data Book, 2004).
Several mixed-solvent (also known as hybrid solvent) gas
treating processes combine the effects of physical and chemical
absorption processes in a single operation. The most well-known
mixed-solvent processes for CO2 absorption are the Sulnol-Ds
process licensed by Shell Global Solutions (Rajani, 2004) and the
Amisol process licensed by Lurgi (Kohl and Nielsen, 1997). The
Sulnol-Ds process based on a mixture of Sulfolane (tetrahydrothiophene dioxide), DIPA (diisopropanolamine) and water is
capable of deep removal of CO2 to less than 50 ppm from feed gas
containing very high concentrations of CO2 (Kohl and Nielsen,
1997). Another variation of the Shell Global Solutions technology
is the Sulnol-Ms process, which is also based on Sulfolane but
uses MDEA instead of DIPA, used mainly for selective removal of
H2S. The process ow scheme of the Sulnol-Ds process is
essentially the same as that for an amine absorption process
(Fig. 2) with the addition of a ash tank to remove the bulk of the
acid gas from the rich solvent upstream of the stripper column.
The Amisol process is based on a mixture of methanol, water and

either diethylamine (DETA) or diisopropylamine (DIPAM). This
process has most commonly been used for purication of synthesis gas derived from coal, peat, or heavy oils (Kohl and Nielsen,
1997). The advantages of the hybrid solvent technologies over
conventional amine absorption technologies include low energy
consumption for regeneration of the solvent, high acid gas loading
capacities, low foaming tendency, and reduced corrosion. Hybrid
solvent processes are usually only suited for treatment of natural
gas with an acid gas partial pressure of more than 100 kPa. The
main drawback of the mixed-solvent processes is that hydrocarbon losses (to the solvent) are slightly higher than the typical
losses in conventional amine processes.
2.3. Ionic liquids and switchable solvents
Among the materials investigated as new solvents for CO2
absorption processes, ionic liquids (ILs) are one of the solvents
that may in the future offer an alternative to amines and the low
capacity physical solvents. Ionic liquids are commonly dened as
organic salts with melting temperatures of less than 373 K. They
have a range of properties that may make them useful replacements for volatile organic solvents such as extremely low vapour
pressure, nonammability, and in many cases low toxicity (Zhao,
2006). Furthermore, ILs are often considered to be designer
solvents because of the many different possible combinations of
cations and anions which can be used to tune their chemical and
physical properties (Brennecke and Gurkan, 2010). These properties of ILs have generated great scientic interest in their development and investigation into their use in chemical engineering
applications, including gas separations. Reviews by Zhao (2006),
Plechkova and Seddon (2008) and Werner et al. (2010) describe
the present industrial processes which use ionic liquids and
discuss many other possible industrial applications of ionic
liquids. The application of ILs to CO2 capture and natural gas
sweetening has been discussed by many authors, including Bara
et al. (2010b), Karadas et al. (2010), Brennecke and Gurkan (2010)
and MacDowell et al. (2010).
The development of ILs for CO2 capture and natural gas sweetening has been driven by the desire to develop a solvent with a CO2
capacity comparable to that of amine-based solvents but with
greatly reduced energy requirements for regeneration. Initially,
much of the research focussed on the potential of imidazoliumbased ILs as alternative physical solvents. Early studies focussed on
132
the most convenient ILs to synthesise, such as 1-n-alkyl-3-methylimidazolium [Cnmim] cations paired with various anions including
bis(triuoromethylsulfonyl)amide [Tf2N] (Bara et al., 2010b; Hughes
et al., 2011). However, the alkyl chains (in the imidazolium cation)
are not the ideal functional group for separating CO2 from CH4 or N2
and, thus, these alkyl chains were substituted with various groups
containing either ethylene glycol or nitrile units to form
[Rmim][Tf2N] (Bara et al., 2010b). Karadas et al. (2010) summarised
the results of using anions other than [Tf2N] on the solubility of CO2
in various ILs, with anions containing uorinated derivatives showing a modest increase.
Despite these efforts to optimise the molecule, the solubilities
achieved with ILs on a volumetric basis (dissolved moles of CO2 per
liquid volume) have remained comparable with most common
organic solvents (Bara et al., 2010b; Karadas et al., 2010). Much
research has thus focussed on the development of task specic ionic
liquids (TSIL) which incorporate an amine functional group into the
IL, enabling it to serve as a reactive, chemical solvent for CO2. Bates
et al. (2002) reported an imidazolium-based TSIL containing an amine
functional group attached to one of the alkyl chains. The stoichiometry of the absorption reaction achieved was 0.5 mol of CO2 per
mole of TSIL; regeneration of the IL solvent was also achieved by
heating the carbamate product to 80100 1C under vacuum. Gurkan
et al. (2010) and Zhang et al. (2009) used TSILs with amino-acid
functional groups that improve the stoichiometry to nearly 1 mol of
CO2 per mole of IL, which is important if the IL solvent is to be
competitive with the volumetric capacities of aqueous amine solutions (Brennecke and Gurkan, 2010). However, TSILs can be difcult
to synthesise and have large viscosities at ambient temperature,
which increase further upon complexation with CO2 (Brennecke and
Gurkan, 2010; Karadas et al., 2010). Brennecke and co-workers
suggest that the viscosity increase of TSILs upon complexation with
CO2 can be eliminated through the use of aprotic heterocyclic anions
and have led a provisional patent (Brennecke and Gurkan, 2010).
Nevertheless, the synthesis and viscosity challenges associated with
TSILs currently limit their commercial viability.
Currently, the most viable method of applying ILs to CO2 capture
or natural gas sweetening is the use of ILamine mixtures, in which
MEA or DEA is dissolved in an [Rmim][Tf2N] solvent; such solutions
can have up to 116 times the CO2 solubility on a volumetric basis
than the IL alone (Bara et al., 2010a). Camper et al. (2008) found that
MEA-IL and DEA-IL solutions could rapidly and reversibly capture
1 mol of CO2 per mole of amine and thereby reduce feed gas CO2
concentrations to the ppm level, even at CO2 partial pressures below
0.133 kPa. Such ILamine solvents offer signicantly reduced
energy requirements relative to conventional aqueous amine solvents: Bara et al. (2010a) compared a IL-amine process with ash
regeneration (similar to the process ow scheme shown in Fig. 3),
against a conventional amine-based gas sweetening plant (similar to
that shown in Fig. 2). They considered the sweetening of 100
MMSCFD to a sales gas specication of 2% CO2 for an NG feed
containing either 15% or 5% CO2 and concluded that over a 20 yr
plant life cycle, the amineIL process had combined CAPEX and
OPEX savings of about 25%. This was due primarily to the removal of
a regeneration column, the higher amine loadings and lower solvent
circulation rates of the amineIL solvent, and the reduced duties
required to cool, heat and regenerate the amineIL solvent. The
difference in the caloric properties of water and the IL, and in
particular the duty reduction associated with not vaporizing any
solvent during regeneration, is probably the most signicant advantage of the amineIL solvent approach to gas sweetening. A pilot
scale unit is under construction for planned NG sweetening eld
tests in 20112012 (Bara et al., 2010a).
Brennecke and Gurkan (2010) point out that all ILs are
hygroscopic (that is, a material that can adsorb or absorb water
molecules), even those that are usually designated hydrophobic
because they are insoluble in water. This fact represents a serious

challenge for the application of ILs to CCS but it also has
implications for NG sweetening. If the NG contains some water,
then the absorption of that water by the IL could decrease the
solvents capacity, and will also degrade the reduction in regeneration duty associated with an amineIL solution. Thus in
contrast with conventional gas processing practice, a sweetening
process utilising an amineIL solvent should probably be situated downstream of the dehydration process.
Jessop and co-workers reported the development of switchable solvents (Jessop et al., 2005; Phan et al., 2008) where a basic,
non-polar liquid mixture converts into a polar IL upon the
addition of CO2. Several groups are researching the optimisation
of these switchable solvents for improved CO2 capture or NG
sweetening. For example, Heldebrant et al. (2011) reported the
development of 2nd generation switchable solvents that could
capture of nearly 1.3 mol of CO2 per mole of solvent. In these
cases, the viscosity of resulting IL is appreciable and its reduction
is the focus of ongoing research.
2.4. Absorption processes for N2 rejection
Nitrogen rejection using absorption-based technologies is not
a common practice in the natural gas industry. There are several
commercial N2 rejection processes that operate by the physical
absorption of CH4 in a hydrocarbon oil which have been built to
process gas feed rates of 230 MMscfd (AET-Technology, 2007;
TGPE, 2009). The costs of large solvent rates and CH4 recompression are prohibitively high for the use of CH4 selective absorption
NRUs in large scale LNG production plants; thus there is a
growing need for the development of a N2 selective absorbent.
An example of a CH4 selective NRU process is that designed
and constructed by Advanced Extraction Technologies, Inc. (AET,
Houston USA). The ow scheme of the AET process is similar to
the physical solvent process shown in Fig. 3. In a typical CH4
selective absorption process the feed gas is cooled before entering
the absorption column where CH4 is dissolved into a lean oil
solvent (TGPE, 2009). The CH4 is then recovered from the rich
solvent through a series of ash vessels to produce sales gas
containing less than 4% N2. The N2 from the feed gas ows
through the top of the column and is used for precooling the unit
feed, and is then vented. The AET process operates at approximately 32 1C to optimise the CH4 absorption in the solvent.
However, the capacity of most solvents for CH4 is relatively low
and large solvent circulation rates are required to achieve economic recovery of the CH4. Furthermore, because the CH4 is
recovered from the solvent by ashing at low pressure the gas
must be recompressed for pipeline or cryogenic gas plant feed.
Although most solvents have a greater solubility for CH4 than
N2, some organo-metallic complexes (OMCs) have been reported
to preferentially bind N2 from natural gas mixtures. Reversible
transition metal complexes forming with N2 were rst reported in
the scientic literature by Allen and Senoff (1965) who described
the reversible reaction of hydrazine (a N2 source) with ruthenium
chloride. Several scholarly articles describing the preparation and
N2 absorption capacity of these types of transition metals forming
complexes were also published in the 1970s (Allen et al., 1973;
Chatt et al., 1978; Sellmann, 1974). However, there have been few
studies reported on the application of these N2 binding complexes
to natural gas processing. The most extensive applied studies of
N2 selective solvents are reported by Stanford Research Institute
International (SRI), on contract for the US Department of Energy
(Alvarado et al., 1996), and Bend Research Inc. (Friesen et al.,
2000; Friesen et al., 1993). Both the SRI process and the Bend
process exploit the reversible chemical complexing abilities of
multi-dentate transition metal complexes as shown in Fig. 4.
133
Fig. 4. General chemical scheme for the reversible binding of nitrogen with an organo-metallic complex adsorption (Miller et al., 2002). R generic organic functionality.
The absorption of N2 in OMCs is achieved through using metal

ions with six coordination sites, the four equatorial sites complexed
with bi, tri, or tetra dentate ligands; with an electron withdrawing
ion on one axial site leaves the other axial site ready to complex
with a gaseous N2 molecule in an end-on conguration. The strength
and therefore reversibility of the complex formation is dictated
through the use of different ligands and transition metals. The most
promising OMC reported by SRI was a (bis)tricyclohexylphosphine
molybdenum tricarbonyl, in a toluene solution, which formed a
yellow precipitate when bound with a N2 molecule (Bomberger
et al., 1999). This phosphine complex absorbed up to 0.12 mmol of
N2/mL of solution at 1979 kPa (Alvarado et al., 1996) in equilibrium
measurements. However, during absorptionregeneration cycles
measured on a 0.02 MMscfd bench-scale apparatus the SRI researchers encountered issues with the degradation of the phosphine
complex and regeneration of the complex to release the N2. The
problems with the regeneration of the phosphine complex included
difculties in controlling the size of the N2-bound precipitates,
which would bypass the regeneration system if the size was less
than that of the phosphine solids (412 mm) (Bomberger et al.,
1999). Although SRIs economic analysis suggests that this OMC
process could become cost competitive with cryogenic NRUs, the
challenges to reduce the cost of OMC synthesis, improve the stability
of the phosphine complex in the presence of water and oxygen, and
to overcome the problems encountered with solids handling in the
regeneration process are all signicant.
The patents held by Bend Research Inc. (Friesen et al., 2000,
1993) describe OMCs based on several transition metalligand
combinations including complexes with iron, as well as the performance of these complexes in N2 absorptionregeneration cycles. The
patents report N2 uptakes of 0.5 mol N2/mol OMC at a N2 partial
pressure of approximately 1130 kPa and a selectivity for N2 over CH4
close to 6. These complexes are reported to exhibit a high degree of
stability, showing no decrease in capacity through repeated use over
100 days, and exposure to an atmosphere of 3% CO2 and 100 ppm
O2. Although the publically available information on the Bend
process indicates the concept of N2 absorption in these OMCs may
be sound, no commercial process has been developed for this
technology. The main barriers to the use of OMCs in large scale
gas processing operations remain the high cost of synthesis of the
OMCs and improving the chemical resistance of the complexes to
common gas contaminants such as water and H2S. Furthermore, the
Bend Research Inc. iron-based OMCs may present safety and
materials handling issues because these are pyrophoric compounds,
which can ignite spontaneously on contact with air.
3. Condensation, desublimation and distillation

3.1. N2 rejection by cryogenic distillation
The normal boiling point (NBP) of CH4 is 161.5 1C and at a
typical pressure of 3150 kPa in the intermediate stages of the
Fig. 5. Illustration of the binary CH4N2 vapourliquid equilibrium relationship

and the construction of a McCabeThiele diagram to calculate the number of ideal
equilibrium stages for separation by distillation. The vapourliquid equilibrium
data shown here represents a relative volatility, aN2 CH4 , of 7 (calculated using
REFPROP (Lemmon et al., 2010) for an operating pressure of 2757 kPa. In this
hypothetical example, the feed contains 50% N2 with product specications of 5%
N2 in the CH4-rich bottom product and 5% CH4 in the N2-rich overheads product.
These compositions were selected as an example which could be shown clearly on
this gure and do not represent a typical set of operating conditions. To meet more
realistic processing objectives, such as a higher purity CH4-rich bottom product
and 98% recovery of the methane from the feed gas, a much larger number of
equilibrium stages would be required.
cryogenic LNG plant the boiling point (BP) of CH4 is 94.7 1C

(Lemmon et al., 2010), which provides a sufcient difference in
relative volatility with N2 (NBP 195.8 1C, BP of 148.7 1C at
3150 kPa) for separation of CH4 N2 mixtures by cryogenic
distillation. Relevant to such separations are vapourliquid equilibrium curves, such as the one shown in Fig. 5 for N2CH4 at
conditions accessible in a cryogenic LNG plant. The equilibrium
curve in Fig. 5 represents a typical relative volatility aN2 ,CH4 value
of 58. To illustrate the separation of N2 and CH4 in the cryogenic
distillation column, we have applied the McCabeThiele method
(McCabe and Thiele, 1925) to estimate the number of ideal
equilibrium stages required to produce a liquid CH4 bottoms
product of 95% from a feed containing 50% N2 and 50% CH4. These
feed and production compositions were selected here to allow
illustration of the separation process; in a real process to produce
a CH4 containing less than 1% N2 and with a high rate of CH4
recovery, the number of actual equilibrium stages required in the
134
distillation column would be higher than the eight ideal trays

shown in the McCabeThiele construction on Fig. 5. (The corresponding graph would be more difcult to read.) In practice,
modern cryogenic NRUs (with SP N2 ,CH4 320) can produce very
high purity CH4 at high recovery rates, which also reduces the CH4
content in the N2 overheads vapour to less than 3%. This is
achieved through the use of columns with large numbers of
stages and the design of systems with multiple columns.
Currently, cryogenic distillation is the only N2 rejection method
that has been demonstrated at gas ows above 25 MMscfd to
achieve very high methane recovery (typically above 98%) and high
purity N2 (approximately 1% CH4). The selection, and optimised
design, of a cryogenic NRU is principally determined by the
concentration of N2 in the feed gas (Wilkinson and Johnson, 2010).
The feed gas pressure, feed gas ow rate, concentration of contaminants and product specications (sales gas or LNG) also
inuence process selections. The optimum design of cryogenic
NRUs, like for most cryogenic processes, is an exercise in balancing
the energy efciency and process ow sheet integration to reduce
the power consumption required for compression of the CH4
refrigerant loops, which are used to provide the reboiler and
condenser duties (Finn, 2007; Wilkinson and Johnson, 2010). The
compression requirements of this distillation-based separation are
the largest contributor to capital and operating costs of the NRU
process. Cryogenic NRU processes have been constructed by most of
the major process designers such as Linde, Costain, Praxair, ConocoPhillips and APCI. The main variants of cryogenic NRU designs
are (1) the single-column heat-pumped process, (2) the doublecolumn process (Agrawal et al., 2003) and (3) three or two column
designs featuring a prefractionation column (MacKenzie et al., 2002;
Wilkinson and Johnson, 2010).
A typical single-column heat-pumped NRU process is illustrated in Fig. 6. Upstream of the cryogenic NRU, contaminants
that could freeze at cryogenic temperature such as water, CO2 and
heavy hydrocarbons have been removed from the gas. The feed
gas to the NRU is cooled, throttled and fed to an intermediate
stage of the distillation column operating at pressures from 1300
2800 kPa (Agrawal et al., 2003). Rejected N2 vapour (typically
o1% CH4) is drawn from the column overheads and the CH4-rich
liquid product is drawn from the bottom of the column. The
bottoms product then can be reheated against the NRU feed gas.
A closed-loop CH4 heat-pump cycle driven by an external compressor provides the reboiler and condenser duties, with the
closed-loop CH4 condensed at a high pressure in the reboiler
and revaporised at low pressure in the condenser.
As the N2 content in the feed gas increases, the CH4 in the upper
stages of the column becomes more difcult to condense. The
operating exibility of a single-column NRU process is limited by
(1) the critical pressures of nitrogenmethane mixtures, which
limits the maximum pressure of the distillation column to approximately 2800 kPa, and (2) the minimum practical temperature of CH4
after the throttling valve of the heat-pump cycle (MacKenzie et al.,
2002). These limitations mean that the single-column NRU process
is, generally, used for feed gases containing less than 20% N2.
A double-column NRU can provide additional process exibility
compared to the single-column process to allow the separation of
gases containing higher N2 concentrations or gases in which the feed
gas quality varies. In the double-column N2 rejection process the
NRU feed gas is cooled, throttled and fed to a high pressure (HP)
column operating typically at 10002500 kPa (Agrawal et al., 2003).
Having had some of the N2 removed, the crude natural gas liquid
stream from the bottoms of the high pressure column is sub-cooled,
throttled and fed to the low pressure (LP) column (operating at
approximately 150 kPa). In practice both the HP and LP columns are
usually integrated into a single tower to improve process heat
integration and minimise heat transfer to the atmosphere. The
Fig. 6. A process ow schematic of a typical single-column N2 rejection unit

(schematic adapted from GPSA Engineering Data Book, 2004; Agrawal et al., 2003;
MacKenzie et al., 2002).
N2-rich vapour from the HP column is condensed to provide reux

for both the high pressure column and the low pressure column. The
low pressure column produces a high purity N2 stream (o1% CH4);
which is used to cool N2 reux fed to the LP column in the LP
condenser, sub-cool the bottoms of the HP column and to pre-cool
the feed gas. The CH4-rich bottom product of the LP column is
pumped through the crude sub-cooler, which provides the LP
columns reboiler duty by condensing the overheads of the HP
column, vaporised and reheated against the feed gas. Alternatively,
for LNG production the CH4-rich bottoms product of the LP column
may remain liquid.
The three-column NRU process consists of the double-column
process described and a prefractionation column. The prefractionation column recovers some of the hydrocarbons at a higher
temperature than the double-column system and increases the N2
concentration of the feed gas. Importantly, the prefractionation
column reduces the volume of N2-rich gas that must be processed
at low temperatures in the main NRU column(s) and this reduction in gas volume can signicantly reduce the power requirements of the NRU (MacKenzie et al., 2002; Wilkinson and
Johnson, 2010). A further variant of an NRU with a prefractionator
described by MacKenzie et al. (2002) is a two column process
with a high pressure prefractionation column, an intermediate
liquidvapour separator and a low pressure column.
3.2. Low-temperature CO2 removal processes
The separation of CO2 from natural gas by low-temperature
processes (operating at temperatures below 0 1C) can be
categorised as: (1) gasliquid phase separations operating at

temperatures above the CO2 triple point temperature of
56.6 1C (Lemmon et al., 2010) and (2) gassolid phase separations where desublimation of CO2 occurs at temperatures below
the triple point. Although the term cryogenic is often used by
the vendors and in the literature to describe these types of CO2
capture technologies, most of the processes operate at temperatures above the scientic denition of cryogenic as 153 1C
(Agrawal et al., 2003; Radebaugh, 2007). To overcome the
problems associated with the formation of CO2 solids during
cryogenic distillation two technological approaches have been
pursued: (1) extractive distillation by the addition of a heavier
hydrocarbon to alter the solubility of components in the column
(Ryan/Holmes process) and (2) controlled freezing and re-melting
of the solids (Controlled Freeze ZoneTM and CryoCells processes).
Other low-temperature CO2 removal technologies under development include systems in which mechanical methods are used
to separate the CO2 rich phase from the natural gas. For example,
Willems et al. (2010) report the C3sep (condensed contaminant
centrifugal separation) process in which condensed CO2 droplets
are separated from the natural gas using rotational separators,
and Clodic et al. (2005) describe the ALSTOM process which
features a multi-stage thermal swing process that freezes then
melts CO2 on mechanical ns. We focus our discussions in this
review on the commercialised Ryan/Homes process and the pilotplant demonstrated Controlled Freeze ZoneTM (along with the
similar CryoCells process).
The extractive distillation approach to solving the problem of
CO2 freezing in CH4CO2 distillation is most well known through
the Ryan/Holmes process described in the 1982 US Patent
4,318,723 (Holmes and Ryan, 1982). The Ryan/Holmes process
is representative of several similar technologies patented by
various other inventors. The addition of a heavier hydrocarbon
stream (typically a C2C5 alkane) to the condenser of the distillation column shifts the operation away from conditions that favour
solids formation, because the solubility of CO2 in the liquid phase
can be increased, the overheads temperature can be raised, and
the column can be operated at a higher pressure since the
mixtures critical pressure increases. A typical four column
Ryan/Holmes process conguration incorporates a de-ethaniser
column, a CO2 recovery column, a demethaniser column, and a
column for recovery of the hydrocarbon additive. Further details
on Ryan/Holmes congurations and operating issues for separations of methaneCO2, ethaneCO2, and CO2H2S are discussed in
the GPA Engineering Data Book.
The Controlled Freeze ZoneTM (CFZTM) process was rst patented
by ExxonMobil in 1985 (Valencia and Denton, 1983) and tested in a
Texas pilot plant during 19861987 (Nichols et al., 2009). More
recently a commercial demonstration project designed to treat a
feed gas of 14 MMscfd has been constructed in LaBarge, Wyoming
(Controlled Freeze ZoneTMincreasing the supply of clean burning
natural gas, 2010). The separation tower of the CFZTM process is split
into three sections with an upper rectication section and a lower
stripping section (both conventional distillation sections) separated
by the CFZTM section, as shown in Fig. 7 (Fieler et al., 2008). In the
CFZTM section, the liquid falling from the rectication section is
contacted with a cold methane stream ( 90 to 85 1C), which
causes the CO2 to freeze out of the methane mixture. The CO2 solids
( 62 to 45 1C) drop to a liquid layer on a melt tray in the lower
stripping section; the solids melt before falling as liquid through the
downcomers of the melt tray. The standard CFZTM process can
produce pipeline quality gas, and when implemented with a
modied rectication section is claimed to be capable of producing
a sweet gas of less than 50 ppm CO2 (Nichols et al., 2009).
Cool Energys CryoCells was developed by researchers at
Curtin University in Western Australia with industrial partners
135
Fig. 7. General schematic of the Controlled Freeze ZoneTM process with spray
nozzles in the CFZ section (schematic adapted from Fieler et al., 2008).
Woodside Petroleum and Shell Global Solutions (Hart and

Gnanendran, 2009). Like the CFZTM process, the CryoCells process
operates by the controlled freezing and subsequent remelting of
CO2. The basic thermodynamic path for the CryoCells operation
involves cooling a dry, feed gas (at 56006600 kPa) to just above
the CO2 freezing point (for example to 60 1C) to condense some
or all of the vapour, followed by an isenthalpic ash to further
cool the mixture to obtain solids, liquid CO2 and a CH4-rich
vapour. Pilot plant trials of the CryoCells process demonstrated
the production of pipeline quality gas from 2 MMscfd of feed
gases containing 3.560% CO2 (Hart and Gnanendran, 2009). The
cryogenic separation of CO2 has potential as a highly selective
process to treat CO2-rich natural gas, although research efforts to
overcome the operational issues associated with control of the
CO2 freezing and solids handling were underway in 2009.
The key advantages of phase creation processes for CO2
separation from CH4 over amine-based absorption systems for
separation of CO2 from CH4 include the recovery of a high purity,
liquid CO2 product at a reasonable pressure, which facilitates the
subsequent transport or injection for use in EOR; the avoidance of
highly corrosive aqueous amine solvents, and possibly, reduced
process footprint and reduced hydrocarbon inventories, which
may be important considerations for offshore or oating production facilities (Kelley et al., 2011).
4. Adsorption
The separation and purication of gas mixtures by the selective adsorption of components from the gas mixture onto porous
solid adsorbents is an established process technology used in
the production of hydrogen, the separation of O2 and N2 from air,
and the capture of odorous pollutants from various industrial
processes. In the natural gas industry adsorption-based separations are used to remove water, sulphur, mercury and heavy
136
hydrocarbons (for dew point control) from the natural gas

(Tagliabue et al., 2009). Adsorption-based processes for the
separation of mixtures of CH4, N2 and CO2 are also used for
post-combustion CO2 capture (Ebner and Ritter, 2009), the purication of coal mine methane (Richter et al., 1985; Tonkovich,
2004; US Environmental Protection Agency, 2008; US EPA, 1997)
and coal mine ventilation air (VAM) (Warmuzinski, 2008), and for
the purication of biogas (Alonso-Vicario et al., 2010; Esteves
et al., 2008). Central to the development and implementation of
adsorption-based processes are the various selectivity mechanisms that give rise to the separation of components within the gas
mixture.
4.1. Adsorbent selectivity
The preferential adsorption of components from a gas mixture
can be achieved by one, or a combination, of the following
mechanisms: (1) differences in the adsorbatesurface interactions
and/or adsorbate packing interactions when the system reaches
equilibrium (thermodynamic equilibrium mechanism), (2) differences
in the size and/or shape of gas molecules leading to exclusion of
molecules with a critical diameter too large to enter the adsorbent
pores (steric mechanism) and (3) differences in the diffusion rates of
molecules through the adsorbent pores (kinetic mechanism) (Li et al.,
2009; Ruthven, 2011). The kinetic mechanism can include the
quantum sieving effect of different diffusion rates observed for
some light molecules in narrow micropores (Xiao-Zhong et al.,
2009). Most industrial adsorption processes such as NG dehydration
using silica desiccants or molecular sieves (Kohl and Nielsen, 1997)
rely on the thermodynamic equilibrium effect. The separation of N2
from CH4 in the Molecular GateTM PSA process using ETS-4 and the
separation of O2 and N2 from air using carbon molecular sieves and
small pore zeolites (Kerry, 2007) are industrial examples based on
the kinetic mechanism. True steric or size exclusion-based processes
are unlikely to be viable technologies for CO2/CH4 or N2/CH4
separations because the differences in the critical diameters of
CO2, N2 and CH4 are not sufciently large for total exclusion of
one component from the adsorbent pores. Based on these adsorptive
gas separation mechanisms there are two types of adsorbate
selectivitythe equilibrium selectivity achieved in the limit of long
time periods and the kinetic selectivity (or time dependent selectivity). The equilibrium selectivity aij of the adsorption mechanism
dened in Eq. (1) can be written for an equilibrium selective
adsorption process as:
aij
qi =yi
K
i
qj =yj
Kj
as
yi ,yj -0
10
where qi and qj are the equilibrium adsorption capacities determined from pure gas component isotherms, and yi and yj are the
mole fractions of the components in the gas mixture. In many cases,
including at low partial pressures of the component species, the
separation factor can be estimated as the ratio of the Henrys
constants (Ki/Kj) (Tagliabue et al., 2009). This denition of aij serves
as a useful tool to screen potential adsorbents for CO2 and N2
removal from natural gas. However, to adequately design an
adsorption-based separation process the selectivity of the adsorbent
for components from a real gas mixture must be conrmed and the
working capacity of the adsorbent needs to be evaluated (Ackley
et al., 2003). The working capacity is the difference between the
amounts of a component adsorbed and desorbed at the conditions of
the adsorption and desorption steps, and this capacity is inuenced
strongly by temperature and pressure.
The equilibrium capacity for a gas species is inuenced by the
strength of the gassolid interaction and the number of available
adsorption sites. The strength of the gassolid interaction is
determined by the characteristics of the adsorbents surface
Fig. 8. Equilibrium adsorption capacity of CO2, CH4 and N2 at 298 K on zeolite 13X.
Figure constructed from data reported in Cavenati et al. (2004).
chemistry and pore structure; and by the adsorbates properties

including molecule size, polarizability and quadrupole moments.
Typical heats of adsorption for CH4 and N2 on commercial
adsorbents are in the range of 1522 kJ/mol (Cavenati et al.,
2004; Watson et al., 2009; Xu et al., 2008). Carbon dioxide
exhibits a large quadrupole moment, thus adsorbents with polar
surfaces that have a high electric-eld gradient, such as zeolites,
have a stronger interaction with CO2 than with the non-polar CH4
and N2 molecules (Li et al., 2009). For example, Cavenati et al.
(2004) report the isosteric heat of adsorption of CO2 on zeolite
13X is 37.2 kJ/mol, Xu et al. (2008) report 49.9 kJ/mol on Na bzeolite, and Watson et al. (2012) report 44.9 kJ/mol on a natural
chabazite. Fig. 8 illustrates the differences in equilibrium adsorption capacity at 298 K for CO2, N2 and CH4 on zeolite 13X. For
selective adsorption of a non-polar molecule like CH4, an adsorbent with a high surface area (such as microporous carbons)
possessing a large number of adsorption sites is likely to be a good
candidate.
For gas separations based on differences in sorption rates a
kinetic selectivity factor bij which incorporates the effects of each
components sorption mass transfer coefcient ki can be dened
as follows:
!s
s
ki
qi
ki
- b
11
bij aij
kj yj yi ij
qj
kj
As discussed recently by Ruthven (2011) the kinetic selectivity
depends on both the diffusivity ratio (assuming kipDc,i, where
Dc,i is the diffusivity coefcient of component i in adsorbent
pores) and the equilibrium selectivity, which if being inferred
from pure uid measurements can be estimated from the second
equality in Eq. (11). Materials that exhibit a kinetic selectivity for
CO2 or N2 from CH4 include carbon molecular sieves (Bae and Lee,
2005; Cavenati et al., 2005), CuMOF (Bao et al., 2011a) and
small-pore zeolites such as clinoptilolite (Ackley and Yang, 1991;
Hernandez-Huesca et al., 1999).
4.2. Adsorption-based separation processes
Similar to the solvent absorption processes, adsorption-based
processes for gas separation require both adsorption and
137
Fig. 9. Schematic representation of a two-bed cyclic adsorption process with pressure-swing adsorption (PSA) and thermal-swing adsorption (TSA) cycles shown on
isotherms for CO2 adsorption on a carbon molecular sieve Takeda MSC 3K-171 (Watson et al., 2009).
regeneration stages. Adsorbent regeneration, or desorption, can

be achieved by utilizing the differences in adsorption capacities at
different temperatures (thermal-swing adsorption, TSA) and at
different pressures (pressure-swing adsorption, PSA), as illustrated in Fig. 9. Continuous TSA and PSA processes operate with
multiple beds containing a stationary adsorbent and use a manifold of valves to switch gas ow to the beds corresponding to
adsorption and desorption cycles. Less commonly used technologies for continuous adsorption processes are uidised and
moving bed operations (Seader and Henley, 2006), and xedbed electrothermal-swing adsorption (ESA) (An et al., 2011;
Grande and Rodrigues, 2008).
In the TSA method, the adsorbent is regenerated by desorption
at a higher temperature than that used during the adsorption
phase of the cycle. In the natural gas industry TSA processes with
silica gel or zeolite molecular sieve lled adsorbent beds have
been used widely for gas dehydration. The temperature of the bed
can be increased by purging the bed with a hot, inert and nonadsorbing gas, or less commonly by heat transfer from heating
coils located within the bed. After desorption the bed temperature
is reduced with a cool purge gas, and the adsorption cycle starts
again. In gas dehydration TSA units, heating and cooling the bed
can take several hours (or even days). The adsorbents used for
dehydration have a large capacity and high selectivity for water
compared to other natural gas components. However, if the
selectivity of the adsorbent for the contaminant is not so strong
the bed will become saturated quickly. To treat a large volumetric
gas ow with a long cycle TSA process will then require a bed
with a large total adsorption capacity, and thus a large amount of
adsorbent. In the PSA method, adsorption occurs at elevated
pressure (typically in the range 4002000 kPa) and desorption
occurs at near-ambient pressure (Seader and Henley, 2006). Using
the PSA method adsorbent beds can be depressurised and repressurised rapidly, allowing cycle times of several minutes or
even several seconds to be utilised. Accordingly, the amount of
adsorbent required for PSA processes can be much smaller than
for an equivalent TSA processes.
Examples of commercially available PSA-based systems for
CO2 and N2 separation from natural gas are listed in Table 6. Most
adsorption-based CO2 capture technologies are limited to
processing natural gas feeds containing no more than 2% CO2

because the quantity of adsorbent required to capture greater
volumes of CO2 is large. Recent advances in small-footprint PSA
systems for CO2 removal from NG on offshore platforms include a
1 MMscfd Molecular Gate system operated by the Tidelands Oil
Company (Wills and Mitariten, 2009) and the 2.5 MMscfd Xebec
rapid cycle PSA system at a Veneco Inc eld (Toreja et al., 2011),
both in California.
Commercial PSA N2 rejection processes shown in Table 6
include UOPs NitrexTM process (UOP, 2010), the Nitrotec process
(Richter et al., 1985), and a micro-scale NRU designed by
American Energies Pipeline (AEP) (2009) (Nhattacharya et al.,
2009). The NitrexTM process developed by UOP uses the proprietary PolybedTM PSA platform and, in the 1990s, small scale NG
treating units based on this process were commissioned in Texas
(Tagliabue et al., 2009) to process about 2.3 MMscfd. At least two
Nitrotec plants were built in Texas during the 1990s to treat
natural gas ows of 15 MMscfd each (Tagliabue et al., 2009). The
micro-scale AEP system for processing 0.0750.5 MMscfd of low
BTU gas in Kansas includes two adsorbent towers (40 80 up to
60 200 ) lled with activated carbon granules (an off-the-shelf
commercial adsorbent) (American Energies Pipeline, 2009;
Nhattacharya et al., 2009). These processes operate by the
selective adsorption of CH4 on activated carbons or zeolites such
as 13X or 5A, and each of these systems requires a compressor to
return the CH4 rich stream to pipeline delivery pressure. The one
commercial N2 rejection technology that operates by the selective
adsorption of N2 is Guild Associates Molecular GateTM PSA
process (Guild Associates, 2007), which relies on the kinetic
selectivity of N2 over CH4 on proprietary adsorbents based on
synthetic titanosilicate ETS-4 and contracted titanosilicate 1 (CTS-1)
(Butwell et al., 2002a; Kuznicki, 1990; Kuznicki et al., 1999; Kuznicki
et al., 2000).
Adsorption-based processes have potential for energy and
capital investment savings over the conventional CO2 amine
scrubbing and cryogenic distillation NRU technologies, but to
date adsorption-based technologies have been limited to processing natural gas feed rates of only about 15 MMscfd. However,
other industries operate much larger scale modern commercial
cyclic adsorption processes: for example, 200 MMscfd PSA plants
138
Table 6
Survey of pressure-swing adsorption processes for CO2 and N2 separations from CH4 in operation or in patent claims.
Vendor/licensor
Adsorbent
More adsorbed
component
Less adsorbed
component
Flow rate
(MMscfd)
Refs.
M3100 Xebec Rotary-valve

CO2 Sponge
Molecular Gate
UOP MOLSIV
Polybed PSA/Nitrex
Micro-scale N2 rejection unit
Xebec
IACX Energy
Guild Associates
UOP
UOP
American Energies Corporation
Metal-based
Activated carbon
Titanosilicates
Zeolite
Zeolite
Activated carbon
CO2
CO2
CO2
CO2
CH4
CH4
CH4
CH4
CH4
CH4
N2
N2
o 2.5
0.25
0.550
Nitrogen rejection unit

Nitrogen Sponge
Nitrotec
TGPE
IACX Energy
CMS Energy
Activated carbon
Activated carbon
Activated carbon
CH4
CH4
CH4
N2
N2
N2
0.000315
0.35
15
Molecular Gate
Guild Associates/BASF
Titanosilicates
N2
CH4
0.510
Toreja et al. (2011)

CO2 Sponge (2011)
Guild Associates (2007)
UOP (2010)
UOP (2010)
(American Energies Pipeline, 2009;
Nhattacharya et al. (2009)
TGPE (2009)
Reinhold (2010)
Richter et al. (1985) and
Tagliabue et al. (2009)
Guild Associates (2007),
Mitariten (2009)
are used in the production of high purity H2 from steam methane

reformers (Ritter and Ebner, 2007). The two key conceptual
strategies that may help develop adsorption-based processes for
CO2 and N2 removal from natural gas at LNG scales or for gas
elds with very high contaminant concentrations are (i) modications to PSA and TSA process congurations and (ii) improved
performance, cost and reliability of adsorbents.
4.2.1. Adsorption cycle process renements

Modern PSA and TSA processes have expanded on the twobed, four-step conguration of early Skarstrom (1960) cycles
(pressurisation, feed gas adsorption, depressurisation, purge) to
include additional process steps to maximise productivity and
energy savings. Advanced PSA designs include the use of three or
more beds, multi-layered adsorbent beds to remove different
impurities (Cavenati et al., 2006), pre-treatment or guard beds to
remove strongly adsorbed species, and tanks for storing intermediate process streams between cycle steps to use as purge and
repressurisation gases. Novel PSA cycle designs may feature more
than 10 process steps including multiple pressurisation steps, cocurrent and counter-current depressurisation steps, and several
purge steps; the optimum design of such complex cycles requires
new mathematical approaches (Mehrotra et al., 2011) and experimental validation in pilot-scale PSA plants (Zhang and Webley,
2008).
The bed adsorption and desorption cycle times have a strong
inuence on the product purity and ow. The short cycle duration
advantages of PSA processes over TSA processes can be further
enhanced by new hardware technologies that allow rapid cycle
changes. The two areas of development that can allow operation
of rapid cycle PSA systems are structured adsorbents and new
valve technologies. Operation with rapid swings in pressure can
result in the uidisation of small adsorbent pellet or granular
particles. This in turn causes mechanical attrition of the adsorbent
reducing performance, which reduces performance, increases bed
pressure drops, and the solid nes produced can damage valves
and downstream equipment. Structured adsorbents featuring
nanoparticles or nanocrystals of the microporous adsorbent
material (pore widths o2 nm), such as zeolites or active carbon,
on a support material like a honeycomb monolith or cloth sheet
izcontaining macroporous channels (widths 450 nm) (Alcan
Monge et al., 2010; Ribeiro et al., 2008; Thiruvenkatachari et al.,
2009; Vargas et al., 2011) can overcome uidisation and pressure
drop problems in rapid swing operations. Furthermore, structured
adsorbent packings can facilitate improved mass and heat transfer within the solid bed, reduce bed pressure drop and allow for a
greater volumetric density of the adsorbent than can be achieved
2.3
0.0750.5
with pellets (Rezaei and Webley, 2010). Fast gas transport

through the adsorption bed is critical when the duration of the
adsorption process step duration approaches the time scale for
mass transfer within a single adsorbent pellet (Todd, 2003). In
practice, however, valve operation and maintenance issues can
limit the number and frequency of cycle steps.
The development of new valve technologies such as the rotaryvalves used in the Xebec M-3100 Rotary-valve fast cycle PSA
system (Toreja et al., 2011) can help to overcome limitations with
the rate at which conventional gas manifold valves can switch.
Xebec reports that their PSA system can operate at up to 50 cycles
per minute. The increased cycle rates allow more compact PSA
modules, and the rotary-valve design reduces the size of the
switching valve manifolds as well as providing operational exibility through control of the rotation speed, so this technology is
particularly useful for offshore CO2 capture processes. Xebecs
rotary-valve, rapid cycle PSA technology has been applied in
biogas purication, H2 purication and more recently in an
offshore plant for removal of CO2 from natural gas. In 2010 a
Xebec M-3100 Rotary-cycle rapid cycle PSA system was commissioned at the Platform Gail in the Santa Barbara Channel to
process a 2.5 MMscfd gas feed containing 13% CO2 to a sales gas
containing 1.42% CO2 (Toreja et al., 2011). The platform receives
gas containing 4000 ppm H2S, which is removed in a SulFerox
process upstream of the PSA unit. The PSA unit consists of six
adsorbent beds lled with an undisclosed non-silica, metal-based
adsorbent. The size of this rapid cycle PSA unit (18 ft(L)
8 ft(W) 9 ft(H)) is considerably smaller than the alternative of
a conventional amine-based CO2 scrubber.
The process conditions available within a LNG plant provide
opportunities for new PSA processes to be designed to operate in
a completely different region of thermodynamic space than most
of the current commercial PSA process used in industry, which
typically operate at temperatures close to, or slightly above,
ambient. A key process advantage in an LNG plant is the availability of the feed gas at relatively high pressures and the
availability of low temperature streams which could be used for
PSA refrigeration. In particular, a refrigerant loop within the LNG
plant could conveniently be used for cooling of the PSA feed gas
approximately 243 K, and there is reason to expect that PSA
techniques for N2 and CO2 separation from CH4 will be more
effective at low temperatures than at conventional temperatures
(Habgood, 1958). At low temperatures adsorption capacities are
greater and the differences between rates of adsorption of gas
components in narrow adsorbent pores could potentially be
greater at a cooler temperature (Hernandez-Huesca et al., 1999).
Furthermore, at low temperatures for some materials the differences in rates of sorption for gas components may be exaggerated
by changes in the crystalline structure of the adsorbent which

could cause changes in pore aperture size as described by Breck
(1964, 1974). Optimum design of PSA processes to operate at
novel (PSA) conditions for an LNG application require the collection and validation of experimental data for adsorbent performance at low temperature, high pressures and measured with gas
mixtures representative of the industrial application (Jensen et al.,
2012; Watson et al., 2012).
4.3. Adsorbent state-of-the art
The desirable characteristics for an adsorbent to separate CO2
or N2 from natural gas include (i) a high selectivity and good
adsorption capacity for the target gas component, (ii) fast adsorption and desorption kinetics, (iii) good physical and chemical
stability through adsorption/desorption cycles and (iv) be regenerable by modest pressure or temperature swings to minimize
operational energy costs. The selected adsorbent must also show
robust performance in the presence of moisture and other contaminants that may be in the natural gas feed to the adsorption
treating unit. The cost of the adsorbent and the bed packing
density (which inuences the adsorbent bed size) are further
considerations.
4.3.1. Adsorbents for CO2 capture
Commercial adsorbents being used to remove CO2 from
industrial gas streams include zeolites, activated carbons and
titanosilicate molecular sieves (Table 6 lists examples of adsorbents used in commercial PSA systems.) Table 7 provides a survey
of the equilibrium CO2 and CH4 capacities, and CO2/CH4
139
selectivities, of various commercial and novel adsorbents.

Novel-structured materials developed over the past 20 yr that
show potential for higher CO2 capacities include adsorbents based
on metal-organic frameworks (MOFs), zeolitic imidazolate frameworks (ZIFs), surface functionalised silicas and porous carbons
(Hao et al., 2011). Metal oxides (CaO, activated alumina, lithium
zirconate), layered hydroxides and hydrotalcites have been studied extensively as sorbents for CO2 capture from high temperature ue gases (300700 1C) (Abanades et al., 2004; Liu et al.,
2009); these high temperature sorbents are not discussed further
in this review because these temperatures are beyond the
expected range of operating conditions for CO2 removal units in
a natural gas or LNG production plant.
Metal-organic frameworks are crystalline materials with high
internal surface areas (for example, MOF-5 has an apparent
surface area of 2900 m2 g 1, Eddaoudi et al., 2000) and large
pore volumes, capable of achieving high CO2 adsorption capacities. At pressures from 1040 bar CO2 capacities of more than
10 mmol g 1 have been reported for MOF-5 (Saha et al., 2010)
and MOFs with coordinatively unsaturated metal sites (Dietzel
et al., 2009). The porous structures of MOFs can be systematically
tuned through considered selection of the metal-ions and organic
linkers that form their coordination networks (Li et al., 2009) to
improve the selectivity for target gas molecules. Carbon dioxide
selective narrow pore MOFs have been prepared using, for
example, Li (Bae et al., 2011), Mg (Mallick et al., 2010) or Cu
(Bao et al., 2011a) ions. A copperMOF prepared by Bao and coworkers (2011a), with narrow pore apertures of approximately
0.35 0.35 nm, showed a CO2/CH4 kinetic selectivity of 9.7 (or a
value of 25 if calculated using Henry law constants), which is one
Table 7
Equilibrium capacity, equilibrium selectivity and kinetic selectivity of adsorbents for CO2 and CH4 at 100 and 1000 kPa and ambient temperature.
Adsorbent name
Type
Mg-MOF-74
5A (Sinopec)
13X (Sinopec)
Natural chabazite
Na-Beta
TRI-PE-MCM-41
MOF
Zeolite
Zeolite
Zeolite
Zeolite
Aminesilica
AC
AC
CMS
AC/CMS
AC
AC/CMS
Zeolite
Zeolite
MOF
CMS
ZIF
MOF
MOF
AC
AC
AC
AC
Zeolite
MOF
MOF
CMS
Zeolite
CMS
Zeolite
Zeolite
Zeolite
MOF
PCB, Calgon Corp.

Norit RB1 extra
MSC-3K-161
PET-DC-0
Sutcliffe Speakman carbon
CORK-DC-0
H-Beta
Beta
MOF-177
MSC-3K-162
ZIF-100
MOF-5
Cu-MOF
Maxsorb
Sutcliffe Speakman carbon
Norit RB1 extra
PCB, Calgon Corp.
13X
1C0 -Li
2L0 -Li
MSC-3K-161
Natural chabazite
MSC-3K-162
H-Mordenite
Beta
Na-Mordenite
1M0 -Li
CO2 capacity
(mol kg 1)
CH4 capacity
(mol kg 1)
CO2/CH4
equilibrium
selectivity
8.50
4.55
3.30
3.30
2.70
2.50
1.00
0.88
0.37
0.89
0.60
0.10
8.50
5.19
8.92
3.71
4.50
25.00
2.41
2.20
2.15
2.08
1.83
1.81
1.70
1.67
1.59
1.30
1.05
0.91
0.65
13
8.01
7.60
7.20
6.40
5.30
4.60
4.03
3.95
3.20
3.10
3.05
3.00
2.30
0.73
1.10
1.01
0.02
0.71
0.38
0.40
0.32
0.63
0.70
0.30
0.13
0.35
6
3.69
4.00
3.90
2.90
2.40
2.50
2.73
1.69
2.10
1.70
1.44
1.70
0.80
3.29
2.00
2.13
100.00
2.58
4.76
4.25
5.18
2.55
1.86
3.50
7.27
1.86
2.17
2.17
1.90
1.85
2.21
2.21
1.84
1.48
2.34
1.52
1.82
2.12
1.76
2.88
CO2/CH4
kinetic
selectivity
T (K)
P (kPa)
3.8
3.6
4.5
2.5
298
298
298
303
303
298
100
100
100
100
100
100
Bao et al. (2011b)

Saha et al. (2010)
Bao et al. (2011b)
Jensen et al. (2011)
Xu et al. (2008)
Belmabkhout et al. (2009)
296
298
298
298
298
298
303
308
298
303
298
298
298
298
298
298
296
298
298
298
298
303
303
293
308
293
298
100
100
100
100
100
100
100
100
100
100
100
100
100
Ritter and Yang (1987)

Dreisbach et al. (1999)
Watson et al. (2009)
Cansado et al. (2010)
Esteves et al. (2008)
Xu et al. (2008)
Huang et al. (2009)
Saha et al. (2010)
Bae and Lee (2005)
Wang et al. (2008)
Saha et al. (2010)
Bao et al. (2011a)
Himeno et al. (2005)
Ritter and Yang (1987)
Cavenati et al. (2004)
Bae et al. (2011)
Bae et al. (2011)
Bae and Lee (2005)
Delgado et al. (2006)
Huang et al. (2009)
Bae et al. (2011)
100.0
8.9
3.2
5.8
9.7
48.2
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
1000
Refs.
140
of the highest selectivities reported for CO2/CH4 separations.

Although a variety of MOFs show good CO2 adsorption capacity
and excellent selectivity, at present their industrial application
may be limited by their powder form, high cost and small
available quantities, and poor chemical and thermal stability.
In addition to the widely available synthetic zeolites such as
13X and 4A, a new class of zeolitic materials known as zeolitic
imidazolate frameworks (ZIFs) are emerging as potential high
capacity CO2 adsorbents. The framework of ZIFs is formed from
tetrahedral metal ions (for example, Zn, Co) and imidazolate
organic bridges. This structure allows ZIFs to be prepared with
tailored pore structures, similar to the preparation of MOFs, but
the chemistry also provides good chemical and thermal stability
like traditional zeolites. Wang and co-workers report a CO2/CH4
selectivity for ZIF-100 of 5.9 (with 1.05 mmol/g CO2 adsorbed at
800 Torr, 298 K) (Wang et al., 2008).
Mesoporous silica materials such as MCM-41 (Beck et al.,
1992) have been widely used for industrial gas separation, as
well as for catalyst supports for gas phase reactions. The channels
in these mesoporous silica materials such as MCM-41 and SBA-15
(Zhao et al., 1998) facilitate rapid gas diffusion, but the afnity of
CO2 with silica surfaces is not as strong compared to the interaction of CO2 with cationic sites of zeolites and MOFs. The CO2
capacity of mesoporous silicas can be enhanced by grafting amine
groups to the hydroxyl sites on the silica surface (Belmabkhout
et al., 2009; Gray et al., 2005; Xu et al., 2002). Likewise, the CO2
capture capacity of carbonaceous adsorbents can also be
enhanced by (i) grafting amine functional groups onto activated
carbon surfaces, or (ii) nitrogen enrichment via ammoxiation of
activated carbons (Plaza et al., 2010) or the utilisation of nitrogen

rich carbon precursors including melamine resins (Drage et al.,
2007), polypyrrole (Sevilla et al., 2011) or agricultural by-products such as soybean waste (Thote et al., 2010).
4.3.2. Adsorbents for N2 rejection

A survey of reported CH4 and N2 adsorption capacities of a
range of commercial and novel adsorbents at 100 kPa and
ambient temperatures is shown in Table 8. This pure gas equilibrium adsorption data is widely available for many materials, but
it should be noted that such experimental data allows an initial
ranking of adsorbents only; kinetic data for both pure uids and
gas mixtures are required for a full assessment of the adsorbents
potential for a real pressure swing adsorption process. Most
adsorbent materials show equilibrium selectivity for CH4 over
N2. The methane selective activated carbons used in the PSAbased N2 rejection technologies described by American Energies
Corporation, TGPE, IACX Energy, and CMS Energy (in the Bergwerksverband patent, Richter et al., 1985) are standard commercial activated carbon grades, such as steam activated carbons.
Typical commercial activated carbons that are used for CH4
selective N2 rejection systems have (BET) surface areas of 800
1200 m2 g 1.
As well as the adsorbents specic surface area, the size of the
pores is also important. Several experimental and theoretical
studies identied that CH4 adsorption capacity correlates with
iz-Monge et al., 2009; Contreras et al.,
micropore volume (Alcan
2009; Kluson et al., 2000): for example, Kluson et al. (2000)
Table 8
Capacities and selectivities of adsorbents for CH4 and N2 at 100 kPa and 1000 kPa.
Adsorbent name
Type
CH4 capacity
(mol kg 1)
N2 capacity
(mol kg 1)
CH4/N2
equilibrium
selectivity
CH4/N2
kinetic
selectivity
T (K)
P (kPa)
Refs.
Sr-ETS-4, activated 543 K

G2X7/12 (Takeda)
Norit RB1 extra
AX21 (MAST)
PET-DC-9-CVD
WS42 (Chemviron)
MSC 3K-161
BPL (Calgon)
Columbia Grade L
Natural chabazite
Maxsorb
5A (Sinopec)
Mg-clinoptilolite
Na-Mordenite
Sutcliffe Speakman Carbon
MOF-177
NaX (Linde)
Na-Beta
13X (CECA)
5A (WR Grace & Davison)
Ca-ETS-4, activated 543 K
MOF-5
PET-DC-0
Norit RB1 extra
Sutcliffe Speakman Carbon
Columbia Grade L
13X (CECA)
MSC 3K-161
MSC-3K-162
Na-Mordenite
Natural chabazite
Titanosilicate
AC
AC
AC
AC/CMS
AC
CMS
AC
AC
Zeolite
AC
Zeolite
Zeolite
Zeolite
AC
MOF
Zeolite
Zeolite
Zeolite
Zeolite
Titanosilicate
Titanosilicate
MOF
Titanosilicate
Titanosilicate
AC/CMS
AC
AC
AC
Zeolite
CMS
CMS
Zeolite
Zeolite
Titanosilicate
1.30
1.18
1.10
1.09
1.06
1.02
1.01
1.01
0.94
0.89
0.88
0.84
0.80
0.75
0.71
0.67
0.65
0.63
0.59
0.58
0.22
0.20
0.13
0.10
0.02
0.02
4.00
3.69
3.47
3.06
2.73
2.10
1.70
1.69
0.90
2.00
0.38
0.39
0.31
0.25
0.39
0.36
0.34
0.34
0.45
0.32
0.56
0.45
0.44
0.27
0.17
0.41
0.41
0.28
0.20
0.20
0.22
0.11
1.46
0.24
0.08
2.02
1.82
1.78
1.83
1.33
1.40
1.50
1.46
3.80
0.65
3.11
2.77
3.52
4.24
2.62
4.25
2.97
2.81
1.96
2.76
1.50
1.78
1.70
3.41
3.94
1.59
1.54
2.11
2.90
1.09
0.83
1.18
0.07
0.08
0.26
1.98
2.03
1.95
1.67
2.05
1.50
1.13
1.16
0.24
0.17
273
298
298
293
298
303
298
298
303
303
300
298
295
303
298
298
305
303
298
303
323
323
298
298
295
298
298
298
303
298
298
303
303
303
298
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
1000
1000
1000
1000
1000
1000
1000
1000
1000
Marathe et al. (2004b)

Olajossy et al. (2003)
Scaife et al. (2000)
Watson et al. (2009), Cavenati et al. (2005)
Valenzuela and Myers, (1989)
Jensen et al. (2011)
Sheikh et al. (1996)
Saha et al. (2010)
(Jayaraman et al., 2004)
Saha et al. (2010)
Dunne et al. (1996)
Xu et al. (2008)
Nam et al. (2005)
Saha et al. (2010)
Kuznicki et al. (2001)
Jayaraman et al. (2004)
Valenzuela and Myers (1989)
Watson et al. (2009), Cavenati et al. (2005)
Bae and Lee (2005)
Kuznicki et al. (2001)
4.63
0.37
1.86
0.10
0.14
0.05
0.02
0.18
0.17
reported that the optimum pore width for CH4 selective adsorption over N2 on carbon adsorbents is 871 A (based on Density
Functional Theory and Ideal Adsorbed Solution Theory models).
The optimum pore size of 871 A allows the adsorption of a single
layer of methane within the pore. From the available data on CH4
and N2 adsorption capacities surveyed in Table 8, the best
materials exhibit (pure gas) CH4/N2 selectivities above 4, which
is consistent with the predictions of Kluson et al. (2000) for a
typical commercial activated carbon (AX21).
Although most commercial adsorbents show equilibrium
selectivity for CH4 over N2, there are adsorbents that show kinetic
selectivity for N2. There are even adsorbents reported such as
certain Sr-exchanged ETS-4 that exhibit equilibrium selectivity
for N2. Restricted diffusion of CH4, relative to the rate of N2
diffusion, has been observed in materials with pores narrower
than 6 A including small pore zeolites, carbon molecular sieves
and titanosilicates. The difference in the kinetic diameters of N2
and CH4 (3.8 A)
molecules is small, so a separation
(3.64 A)
process based on the differences in the diffusion rates of N2 and
CH4 in an adsorbents pores requires a well-controlled, narrow
pore size distribution. The most industrially signicant examples
for N2 rejection from natural gas are the synthetic titanosilicates
ETS-4 and CTS-1 (Butwell et al., 2002b; Kuznicki et al., 2001;
Kuznicki et al., 1999, 2000) used in the Molecular GateTM PSA
technologies. The structure of ETS-4 is an interconnected
octahedraltetrahedral (with TiO6, SiO4 and TiO5 units) framework with narrow 8 member ring pore openings (Kuznicki et al.,
2001). The size of the 8 member ring openings can be controlled
by exchanging the framework sodium cations for other atoms. For
example barium- (Kuznicki et al., 1999) and calcium-exchanged
ETS-4s (Cavenati et al., 2009) were reported to have enhanced
N2/CH4 selectivities over the Na-ETS-4 form. Likewise, controlled
dehydration of the ETS-4 at temperatures from 373573 K can
affect the selectivity of the adsorbent as shown by the differences
in selectivity for the ETS-4 materials listed in Table 8.
Small pore zeolites have crystalline structures that may also
favour kinetic selectivity for N2 from natural gas and the most
widely studied small pore zeolite specically for this purpose is
clinoptilolite (Ackley and Yang, 1991; Faghihian and Pirouzi,
2009; Hernandez-Huesca et al., 1999; Jayaraman et al., 2004).
Although volumetric experiments to measure equilibrium
adsorption capacities of pure gases CH4 and N2 show that MSC
3K-161 has a selectivity for CH4 at very long adsorption times
(Watson et al., 2009), the kinetic selectivity of MSC 3K-161 for N2
over CH4 has been observed in volumetric adsorption experiments by Bae and Lee (2005) and Cavenati et al. (2005).
5. Membranes
Membrane technologies potentially offer signicant advantages over traditional gas separation operations like gasliquid
absorption and cryogenic distillation. The features that make
141
membrane technologies highly attractive for process separation

units include the ability to separate chemical species without a
phase change, low thermal energy requirements, simple process
ow schemes with few pieces of rotating equipment, compact
plant footprints and convenient start up and shutdown procedures. These features of membranes systems are potentially
attractive for remote, unmanned and footprint conscious sites.
The most successful industrial applications of membrane technologies have been conned to liquid separations such as the
purication and desalination of water. Membrane separation
technologies have been applied since the 1980s in the natural
gas industry to remove CO2, N2, H2S and NGLs (examples are
given in Table 9); however, membrane separation technologies
still account for less than 5% of the market for new natural gas
processing equipment installed (Baker and Lokhandwala, 2008;
Laverty and OHair, 1990). At least one plant uses a membrane
operation for helium extraction from natural gas (Laverty and
OHair, 1990).
Of the membrane technologies deployed in the natural gas
industry, processes to capture CO2 have been the most widely
used and, currently, CO2 capture is the only natural gas separation
process for which membrane processes are competitive with the
conventional technology (in this case amine absorption) (Baker
and Lokhandwala, 2008). This section explores the recent developments in membrane technologies that seek to overcome the
key materials performance and process challenges contributing to
the limited deployment of membrane technologies for natural gas
processing.
5.1. Membrane classications and permeation theory

Membranes for gas separation typically fall into three categories dened by their materials of manufacture: polymeric,
inorganic and mixed matrix membranes. Membrane technologies
may also be categorised by the mechanism of gas transport
through the membrane, for example, sorptiondiffusion, solution
diffusion and molecular sieving (Koros and Mahajan, 2000). The
commercial membrane technologies employed in the natural gas
industry are predominantly nonporous polymeric membranes
that separate components by the solution-diffusion mechanism
(Membrane Technology & Research, 2010). Transport of gas
molecules through the membrane by the solution-diffusion
mechanism occurs rst by absorption of the gas molecule into
the membrane and then by diffusion, or permeation, of the
molecule through the membrane material. Separation of gas
components is therefore achieved by the differences in the
solubility and mobility behaviours of the components of the
natural gas feed.
Polymeric membranes can be further classied as rubbery
polymers and glassy polymers based on whether the membrane
process operates above or below the polymers glass transition
temperature. Glassy polymers operate below the glass transition
Table 9
Survey of membrane separation technologies used in the natural gas industry.
Vendor/
licensor
Membrane material
Membrane module type Natural gas separation
Z-Top
LPG-SepTM
SeparexTM
MTR
MTR
UOP
Polymeric (Peruoro)
Spiral-wound
Polymeric
Spiral-wound
Polymeric (cellulose acetate) Spiral-wound
Medal
PRISMs
CO2 membrane
NitroSepTM
Air Liquide
APCI
UBE
MTR
Polymeric (polyimide)
Polymeric (polysulfone)
Polymeric (polyimide)
Polymeric
Hollow bre
Hollow bre
Hollow bre
Spiral wound
CO2 from CH4 to o 2%

LPG, NGLs from gas
CO2 from CH4, examples CO2 in feed
reduced from 6.5% to 2%
CO2 reduced from 4.5% to, 2%

CO2 reduced from 9.6% to o 2%
N2 from CH4 to 4% N2 in product gas
Flow rate
(MMscfd)
Refs.
1300
www.mtrinc.com
250
www.mtrinc.com
Up to 680 www.uop.com
o8
14100
0.4100
www.medal.airliquide.com
www.airproducts.com
www.ube.com
www.mtrinc.com
142
temperature where the polymeric chains are rigid and separation

ability is primarily a function of the difference in kinetic diameter
of the gaseous species. Rubbery polymers by contrast operate
above the glass transition temperature where the polymer chains
are elastic and mobile. In this case diffusion is no longer hindered
by molecular size; rather it is the differences in the solubility of
the gases in the polymer that determines performance.
Membrane performance is chiey characterised by two parameters (1) permeability, which is a measure of the volume of gas
the membrane can process and (2) selectivity, which is a measure
of the membranes ability to separate components. Other factors
such as chemical, thermal and mechanical stability, fouling
tendencies, working lifetime, production costs and modularity
are also important to the success or otherwise of a membrane
unit operation. Permeability, or the permeability coefcient Pe, is
dened as the transport ux per unit of cross membrane driving
force (pressure difference) (mol m m 2 s 1 Pa 1). The total gas
ux, J, through the membrane can be calculated using Eq. (12),
which shows that the volume of gas the membrane can process
can be increased with a larger permeability coefcient, a larger
membrane area A, a decrease in membrane thickness l, and/or an
increase in the pressure gradient between the feed and permeate
streams Dp pf pp :

P e A pf pp
Q A pf pp
J
12
l
The second equality in Eq. (12) introduces a new coefcient
also used to compare membrane performance known as permeance Q, which is dened as the permeability per unit membrane thickness (mol m 2 s 1 Pa 1). While the permeability is an
inherent property of the material and is commonly used in the
membrane literature to compare membrane performance for
different materials it is, however, calculated by rearranging Eq.
(12), which requires a knowledge or measurement of the membrane thickness. For ultrathin membranes this is not always
possible and so to avoid confusion, the remainder of this article
will only discuss permeance data.1
Gas transport of component i through the dense polymer
membranes utilised in natural gas processing can be further
described by (Baker and Lokhandwala, 2008)

Di K i A pi,f pi,p
13
Ji
l
where Ji is the volume (molar) ux (std cm3 of component
i/(cm2 s)) and l the membrane thickness. The diffusion coefcient
Di describes the motion of the gas molecule within the membrane
material, and this parameter is largely dependent on the size of
the gas molecule. The gas sorption coefcient Ki is an indicator of
the solubility of the gas molecules in the membrane material.
The selectivity of a membrane is often represented in the
scientic literature as the permselectivity, or ideal selectivity,
determined by the permeance ratio of two components as given
by Eq. (14):

Kj
Q
Di
Sij i
14
Qj
Dj
Ki
Here Qi and Qj are the permeances of component i and j,
respectively, obtained from single component permeation
1
A barrer is a common unit of measure for permeability of a membrane
(10-10 std cm3 cm cm 2 s 1 cmHg 1) whilst a GPU gas permeation unit is a unit
for permeance introduced in an attempt to simplify the units so that
1 GPU 10 6 std cm3 cm 2 s 1 cmHg 1. To convert between the two units, one
needs to know the membrane thickness. As an example a membrane with a
permeability of 10 barrer and a thickness of 0.1 mm would have a permeance of
100 GPU.
measurements. However, for real gas mixtures, such as natural

gas streams, the transport of gas molecules through the membrane will be affected by the interactions between gas components, as well as the interaction between the components and
membrane material. Hence, the true ability of a membrane to
separate components from a mixture deviates from the ideal
selectivity, and separation performance for mixtures should

ij
instead

be described by a separation coefcient Sc xi =xj =
yi =yj (Koros et al., 1996), which is analogous to the aij dened
in Eq. (1). In this case, xi,j and yi,j are the mole fraction of
the components i and j in the permeate and feed streams,
respectively.
From these relationships it can be seen that the selectivity of
polymeric membranes is a function of the materials chemistry
and not the process parameters. In particular, the selectivity is a
function of the ratio of the diffusion coefcients (Di/Dj) which is
proportional to the ratio of molecular diameters of the two
permeants, and the ratio of the solubility coefcients (Ki/Kj) of
the components in the membrane material. Furthermore, a tradeoff exists between a membranes permeance and selectivity
which is encapsulated by the empirical Robeson upper bounds
for gas pairs (Robeson, 1991, 2008). The Robeson upper bounds
highlight the maximum expected performance of rubbery and
glassy polymer membranes for gas separation applications. These
limits also provide a reference standard to which new membrane
materials can be compared. Many research groups have sought to
develop new materials that can push membrane performance for
gas separations beyond the current Robeson limits. Strategies for
improving membrane performance include the incorporation of
inorganic materials with high sorption capacities or molecular
sieving capabilities into a polymer matrix to create mixed matrix
membranes (Merkel et al., 2002) and synthesis of facilitated
transport membranes (FTMs). These novel membrane technologies will be further discussed relative to their specic applications
in natural gas processing.
Inorganic membranes including membranes prepared from
silica, zeolites and carbon molecular sieves have potential applications in natural gas processing. These porous inorganic membranes function by a molecular sieving or activated transport
mechanism, in contrast to the sorption-diffusion mechanism
discussed above for polymeric membranes. Inorganic membranes
that can operate at high temperatures (500 1C and above), where
polymeric membranes are not stable, are the focus of signicant
research efforts aimed at developing technologies for post-combustion CO2 capture from ue gases (Duke et al., 2010), syngas
processing and H2 purication (Lu et al., 2007; Smart et al., 2010;
Smith Scheinder et al., 2007). However, the removal of CO2 and N2
from natural gas does not require such high temperature processes, and could in fact benet from sub-ambient process
temperatures, and so the use of porous inorganic membranes in
natural gas processing has not been widely reported, although the
separation of NGLs from CH4 with zeolitic membranes has been
reported (Arruebo et al., 2001).
5.2. Membrane separation processes
Membranes operate as a semi-permeable barrier wherein a
component of the gas mixture will pass through the membrane
given a sufcient driving force or chemical potential gradient
between the feed and the permeate stream (Fig. 10). In the case of
natural gas processing the driving force takes the form of a partial
pressure gradient (Dpi pf ,i pp,i , for component i with partial
pressures pf,i and pp,i at the feed and permeate sides of the
membrane, respectively). The process and energy requirements
of a membrane system are limited to pre-treatment and compression of the feed stream to generate the desired driving force.
Fig. 10. Block ow diagram for a single-stage membrane separation of CO2 from
natural gas.
Fig. 11. Asymmetrical membrane morphology with dense selective layer on

porous support.
In the case of natural gas processing, the feed stream is often

already at sufcient pressure, although additional compression
may be required.
The separation ability of the membrane will determine whether
recycling and/or reprocessing of the permeate or retentate streams
in multiple stages is required to achieve the process objectives
(Fig. 10). Poor selectivity will dictate multiple membrane stages and
excessive recycling to attain the product purities required, increasing the complexity of the process, energy usage, overall footprint of
the membrane unit operation and its capital cost.
The principal parameters in Eqs. (12) and (13) demonstrate
that the engineering design of a membrane system for CO2 or N2
removal from natural gas is determined by the volume of gas to
be processed, the feed gas pressure, concentration of the contaminants in the feed gas, and the required purity of the product
from the membrane unit. The membrane material has a large
effect on the capital cost of the membrane unit as the performance of the membrane material determines both the membrane
area and the number of stages required. A signicant amount of
research has focussed on reducing the cost of membrane units
through the production of asymmetric composite membranes
which utilise an ultra-thin layer of high performance polymer
on a porous support as shown in Fig. 11. This serves the dual
purpose of reducing the quantity of the high performance polymer and, as illustrated in Eq. (13), the ux increases because the
membrane is thinner. This strategy has been applied to both at
sheet and hollow bre geometries (Al-Juaied and Koros, 2006;
Omole et al., 2011; Strathmann, 2001).
The operational cost of a membrane unit is principally determined by the compression requirements; compression of the feed
gas and inter-stage streams is required to meet the partial
pressure gradients necessary to achieve sufcient component ux
across each membrane stage. The number of membrane stages
required is determined by the membrane selectivity for CO2/CH4
or N2/CH4 gas pairs and the desired level of contaminant removal
per stage. Most process simulation studies on membrane separation units for the removal of CO2 from natural gas or CO2/CH4
binary gas mixtures, report that a conguration of 2 or 3 membrane stages is required to be most efcient and cost-effective
143
(Bhide and Stern, 1993a,b; Datta and Sen, 2006; Hao et al., 2002,
2008; Makaruk et al., 2010; Qi and Henson, 1998). Only once a
partial pressure gradient between the feed and the permeate has
been established can the membrane unit operate at all. Thus, if
the concentration of the component in the feed to be removed is
low, then the pressure of the feed stream must be increased
sufciently to establish the required driving force for sufcient
gas component ux through the membrane. For example, a
natural gas stream with 4% CO2 would need to be compressed
to a pressure greater than 10,000 kPa to generate a permeate
stream of 80% CO2 at 500 kPa. In addition, this partial pressure
gradient sets the product purity in the retentate stream; as once
the retentate and permeate streams reach equilibrium the net
ux through the membrane ceases. In the previous example, to
reduce the CO2 content in the feed to below the required 50 ppm
for cryogenic gas processing, the membrane system would
require 10 stages with the highest pressure membrane unit
operating in excess of 9,830,000 kPa, assuming a 50% CO2 stage
cut each time. Clearly, this simple analysis shows that membrane
separation technologies are more suited to bulk separation of CO2
or N2 from gas streams to meet pipeline specications than they
are to gas purication for cryogenic processing. To overcome
these limitations, hybrid membrane-amine absorption processes
have been designed, for example by UOP (UOP Overview of Gas
Processing Technologies and Applications, 2010), in which a
membrane separation unit rst provides a bulk removal of CO2
from the sour gas and then a conventional amine absorption unit
is used to reduce the CO2 content of the gas to less than 50 ppmv.
There are several other issues which must also be taken into
consideration when using membrane systems for the processing
of natural gas. Chief among these issues is the loss of selectivity
and separation performance that results from plasticisation and
degradation of polymer membranes during operation. Plasticisation can be caused by the common impurities found in natural gas
including CO2, water and aromatic hydrocarbons. When the
polymer matrix swells from plasticisation the increase in free
volume ultimately leads to a reduction in the relative differences
of the diffusion coefcients of the components to be separated,
and thus a deterioration in membrane selectivity is observed
(Koros and Mahajan, 2000; Visser et al., 2005; Xiao et al., 2009).
Glassy polymers suffer more severe performance degradation
than rubbery polymers and mixed matrix membranes. Although
sometimes plasticisation can be reversed, in many industrial
applications the regeneration of membranes is not feasible and
several membrane materials are known to undergo a swelling
induced conditioning history effect (Al-Juaied and Koros, 2006).
Membrane plasticisation can be managed by incorporating pretreatment operations to remove the contaminant plasticizers.
However, for membrane systems being used to remove CO2, the
plasticizing effect of the CO2 cannot be mitigated by pre-treatment (Ismail and Lorna, 2002, 2003; Visser et al., 2007). Pretreatment is also required to alleviate fouling from oil mists,
particulates and to prevent condensation of the heavier hydrocarbons and water on the surface of the membranes as the phase
envelope for the natural gas often changes during operation
(Baker and Lokhandwala, 2008). Other strategies for minimising
plasticisation of polymer membranes include cross-linking of the
polymer network and/or the addition of llers to resist swelling
which have the added benet of increasing membrane selectivity
(Ismail and Lorna, 2002, 2003; Omole et al., 2011; Visser et al.,
2005; Visser et al., 2007; Xiao et al., 2009).
5.3. Application of membrane technology to CO2 removal
Cellulose acetate (CA) is the earliest and the most commonly
applied polymeric membrane for CO2 removal from natural gas.
144
Cellulose acetate is a glassy polymer that can be easily produced

as at sheets for spiral-wound membrane modules or as hollow
bres. Typically, CA displays permeance values of 60 GPU
(Zimmerman and Koros, 1999) and in laboratory tests has an
ideal CO2/CH4 selectivity of 40. In eld trials the performance of
CA membranes is reduced to a selectivity of approximately 20
(Baker and Lokhandwala, 2008). Like all glassy polymers, CA
membranes are susceptible to plasticisation, especially from CO2
and aromatic hydrocarbons. This is particularly problematic in
CO2 removal applications given that membrane systems are most
suited to natural gas feeds containing high concentrations of CO2
and yet these very same conditions can result in substantial
declines in selectivity (Donohue et al., 1989). By contrast, aromatic hydrocarbons need only be present in concentrations of
2001000 ppm to degrade the selectivity by 3050% (Vu et al.,
2002). However, CA membrane modules have also demonstrated
long term stability when exposed to high H2S concentrations (1
4% mol). For example, at the Kinder Morgan Yates gas plant the
CA membrane units have been reported to achieve normal working lifetimes of 3.5 yr despite increasing concentrations of CO2
and H2S in the plant feed during this period (Kumar et al., 2011).
Despite the myriad of new polymers that have been developed
since the introduction of CA, few new materials have challenged
the widespread industrial application of CA membranes. Polyimides (PI) are temperature resistant polymers with a high glass
transition temperature and high ideal CO2/CH4 selectivities of
between 3060 (Ayala et al., 2003; Stern, 1994). However PI
membranes, especially the uorinated PI polymers, are highly
susceptible to plasticisation in natural gas applications (StaudtBickel and Koros, 1999). The other polymers of interest include
the polysulfones which demonstrate permeance values of 2040
barrer and CO2/CH4 selectivities of 1535 (Gabelman et al., 2005)
and peruoro-type polymers which demonstrate increased resistance to plasticisation in natural gas applications (Merkel et al.,
2006).
Permeation and selectivity data for a range of polymeric,
inorganic and mixed matrix membranes is presented in a modied Robeson plot shown in Fig. 12. This modied Robeson plot
takes account of the thickness of the membrane used in the

experiments, which allows direct comparison between polymeric
and inorganic membrane types of different thicknesses. Fig. 12
demonstrates that the industrial dominance of polymeric membranes over their inorganic counterparts has less to do with
superior performance and more to do with the ease and economics of manufacturing membranes on a large scale.
Many of the synthesis and processing technologies for the
development of polymeric membranes for gas separation
undoubtedly grew from the earlier advances in membrane technology for water treatment (Reid and Breton, 1959). For example,
the successful methods for producing low cost polymeric membranes in sufcient quantities to satisfy demand in the water
treatment industry has ensured that polymeric membranes have
been the main focus of membrane manufacturers for the last
three decades. Problems with plasticisation and low selectivities
have been, for the most part, overcome with clever process
engineering solutions. As a result, the drive for new materials
solutions has not been strong enough to warrant widespread
industrial investigation of inorganic membranes. Furthermore,
research groups specialising in inorganic membranes have
focussed specically on high temperature applications where
polymeric membranes are not feasible and have left the natural
gas processing space alone. Indeed, silica membranes are able to
achieve more than an order of magnitude higher permeance
compared to polymeric membranes with comparable selectivities.
However most of the results for silica membranes presented in
Fig. 12 are from studies where H2 separation is the main focus and
the authors have investigated the behaviour of larger gas species
simply to probe the pore size distribution of the silica. Whether
industrial application of silica membranes for H2 production is
feasible is still under investigation, and the effect of transfer of
any future developments in inorganic membrane technology from
H2 purication to the natural gas industry remains difcult to
assess.
One solution that is gaining signicant attention in the
scientic literature is the incorporation of inorganic and polymer
materials into mixed matrix membranes (Merkel et al., 2002).
Fig. 12. Performance of various membranes for CO2/CH4 separation. Polymer() Membranes refer to mixed matrix membranes. Robeson limit shown corresponds to 1 mm
membrane thickness. (Araki et al., 2007; Asaeda and Yamasaki, 2001; Battersby et al., 2006; Boffa et al., 2009; Boffa et al., 2008; de Lange et al., 1995a, b; de Vos et al., 1999; de
Vos and Verweij, 1998; Diniz da Costa et al., 2002; Diniz da Costa et al., 1999; Gopalakrishnan et al., 2006; Gu et al., 2008; Gu and Oyama, 2007; Gu and Oyama, 2009; Ikuhara
et al., 2007; Iwamoto et al., 2005; Jiang et al., 2004; Kim et al., 2001; Kim et al., 2003; Kusakabe et al., 1999; Kusakabe et al., 2003; Lee and Oyama, 2002; Lee et al., 2004; Li
et al., 2010a; Li et al., 2008; Li and Chung, 2008; Lokhandwala et al., 2010; Saimani et al., 2010; Syrtsova et al., 2004; Visser et al., 2005; Visser et al., 2007; Vu et al., 2002).
These combine the cheap, simple manufacturing techniques used

to produce polymeric membranes with the enhanced separation
characteristics of inorganic materials (Hu et al., 1997). In practice,
however, the synthesis of mixed matrix membranes is not a
simple task, with the compatibility of both phases crucial for
eliminating membrane defects and achieving good separation
performance (Mahajan and Koros, 2000; Zimmerman et al.,
1997). This is especially true for the glassy polymers employed
in natural gas processing, where poor interfacial interactions
between the polymer and the inorganic llers, for example
zeolites, degrade both membrane performance and mechanical
stability (Jiang et al., 2006). As a result, very few mixed matrix
membranes have displayed the performance enhancements initially promised, although some have broken Robesons upper
bound (Hillock et al., 2008).
Finally, and continuing the theme of selective enhancement,
some of the most exciting advances in membrane technology in
recent years have appeared in the form of facilitated transport
membranes (FTMs). These are membranes that incorporate mobile
carriers that selectively interact with CO2 molecules to expedite the
ux of CO2 through the membrane (Ebner and Ritter, 2009). The
selective interaction in FTMs can produce vastly superior membrane
performance compared to traditional polymeric membranes (Bara
et al., 2008; Moore et al., 2004). The four types of FTMs include thin
liquid lm membranes, ion-exchange membranes, polymer/metal
ion dispersions and modied polymer membranes. Thin liquid lm
membranes can be realised by depositing the liquid into a porous
support (immobilised liquid membrane), around bres (supported
liquid membrane) or between surfaces (contained liquid membrane)
(Bao and Trachtenberg, 2006). Chemicals used as the liquid membrane include amine solutions, alkaline solutions such as potassium
carbonate, or an enzyme such as carbonic anhydrase which is
employed in the novel Carbozyme process (www.carbozyme.us).
The main obstacle to the successful deployment of FTMs in natural
gas processing applications are the well-publicised stability problems, in particular the evaporation of the carrier medium for
immobilised liquid membranes or water which acts as a swelling
medium in many ion-exchange membranes (Bara et al., 2010b;
Eriksen et al., 1993a, b; Noble et al., 1988). The evaporation of water
is less of a concern for natural gas feeds which, upstream of
145
dehydration units, may contain sufcient moisture to maintain

membrane performance (Ebner and Ritter, 2009).
The most common approach to overcome evaporation in
immobilised liquid membranes is to employ non-volatile solvents
such as polyelectrolytes and room temperature ionic liquids
(RTILs). These materials can also be considered to essentially
operate as high surface area liquid scrubbing units (Park et al.,
2009). Indeed, one particularly novel approach to the evaporation
problem is the so-called bulk-ow liquid membrane, where the
carrier medium is permeated and recycled through the support
pores in a manner resembling an ultra-high surface area scrubbing unit or membrane contactor (Duke et al., 2010). The most
promising FTMs are those with the carrier bonded to the polymer
backbone, which eliminates many of the stability concerns discussed above (Zhang et al., 2002). Ultimately, however, the
successful adoption of FTMs into natural gas processing will hinge
on the economics of producing large-scale membrane modules for
long-term operation, although the proposed trials of a FTM for
CO2 separation in several large European power plants is highly
encouraging (Kim et al., 2004).
5.4. Application of membrane technology to N2 rejection
In comparison to the extensive research and industrial work
undertaken using membranes for CO2 removal from natural gas,
the use of membranes for N2 removal is sparse. This is primarily
due to the competing and counterproductive separation coefcients of diffusion and solubility that render virtually all polymeric membranes unable to effectively remove either component.
The similar kinetic diameter of N2 and CH4 limits the effectiveness
of separation by diffusion and typical ideal N2/CH4 selectivities for
glassy polymers are less than 3 and whilst CH4 has a higher
solubility, ideal CH4/N2 selectivities for rubbery polymers are less
than 5 (Lokhandwala et al., 2010). These values can be enhanced
slightly through the addition of inorganic llers to create mixed
matrix membranes. However, the separation behaviour of polymeric membranes for N2/CH4 mixtures is so mediocre that no
Robeson upper bound currently exists. A comparison of N2/CH4
membrane performance for polymeric and inorganic membranes
is shown in Fig. 13.
Fig. 13. Performance of various membranes for N2/CH4 separation. Polymer( ) Membranes refer to mixed matrix membranes. Robeson limit shown corresponds to 1 mm
membrane thickness. (Araki et al., 2007; Asaeda and Yamasaki, 2001; Battersby et al., 2006; Boffa et al., 2009; Boffa et al., 2008; de Lange et al., 1995b; de Vos et al., 1999;
de Vos and Verweij, 1998; Gopalakrishnan et al., 2006; Ikuhara et al., 2007; Iwamoto et al., 2005; Kim et al., 2001; Kim et al., 2003; Kusakabe et al., 1999; Kusakabe et al.,
2003; Li et al., 2008; Li and Chung, 2008; Lokhandwala et al., 2010; Saimani et al., 2010; Syrtsova et al., 2004; Visser et al., 2005; Visser et al., 2007; Vu et al., 2002).
146
Fig. 13 indicates, however, the potential of inorganic membranes

for this natural gas processing application with silica achieving
selectivities of N2/CH4 greater than 10, with permeances of more
than 2 orders of magnitude higher than comparable polymeric
membranes. Indeed, silica membranes can reach a performance
level that could only be afforded by theoretical polymer membranes
with a membrane thickness less than a single atom. However,
despite this potential, the difculties of N2 removal from natural
gas streams are clearly illustrated in Fig. 13 in the slope of the
Robeson upper bounds. For every order of magnitude increase in
selectivity, permeance drops 4.5 orders of magnitude for N2 permeation in Fig. 13, by comparison CO2 permeation only drops
2.6 orders of magnitude. Despite this poor performance, membrane
systems for N2 removal from natural gas have been realised
industrially through clever process engineering solutions. In particular they employ multi-stage or multi-step process designs to
theoretically treat a variety of feed streams with N2 concentrations
varying from 4% to 30%. Engineering and economic analysis shows
that the cost of treatment rises sharply with increasing N2 feed
concentrations and desired product purity. As a result most commercial systems, of which NitroSepTM from Membrane Technology
and Research, Inc. are the most prominent, are for natural gas feeds
with less than 16% N2 and reduce the N2 concentration by roughly
half (Lokhandwala et al., 2010).
6. Separation by hydrates
6.1. Fundamentals of gas separation using hydrate phenomena
Clathrate hydrates are ice-like crystalline inclusion compounds that consist of hydrogen-bonded water molecule cages,
within their cages. Although
which trap small molecules ( o10 A)
discovered in 1810 by Sir Humphrey Davy, it was not until
Hamerschmidt attributed problems in gas transport pipelines in
1934 to the formation of hydrates that signicant engineering
interest and research in these peculiar compounds took off.
Natural gas hydrates are now an important consideration for
most oil and gas production and processing activities due to their
tendency to agglomerate and cause a blockage in the pipeline or
process equipment (Sloan and Koh, 2008). Natural gas hydrates
also represent a potentially signicant energy resource with
current global estimates of (23) 103 gigatonnes of hydratebound methane (Milkov, 2004).
There are three main structures for hydrates as illustrated in

Fig. 14a (Walsh, 2011). They consist of different congurations of
small (512cages with 12 pentagonal faces) and large (51262,
51264, etc.) cages: for example structure I (sI) hydrate has two
small (512) and six large (51262) cages. The equilibrium hydrate
structure (for simple hydrates) depends on the guest molecule as
illustrated in Fig. 14b. The structure is important for gas separation as certain molecules will only go into certain cages. For
example, propane can only enter the large cages of structure II
(sII) hydrate, whereas CH4 and CO2 can enter either cage.
Research on the intentional formation of gas hydrates has
mainly focussed on the use of hydrates as a medium for
transporting stranded gas in the form of natural gas hydrate
pellets (e.g., as an alternative to LNG). This concept was analysed
by Gudmundsson et al. (2004), who demonstrated the potentially
favourable economics of using gas hydrates over LNG for short to
medium transportation distances and smaller volumes of gas.
Hydrates have also been studied as a mechanism to store cool
energy for air-conditioning applications (Herri et al., 2005) and as
a method for desalination of seawater (Barduhn et al., 1962).
Using clathrate hydrates for gas separation has been explored
since the 1930s, where Nikitin used SO2 hydrates to separate rare
gases (Sloan and Koh, 2008). Happel et al. (1994) show that
hydrates can be used to produce a gas stream leaner in the
hydrate forming gas. Upon dissociation of the hydrate, another
stream that is richer in the hydrate former is produced. They used
the rejection of N2 from a gas mixture with CH4 to demonstrate
this process. Lee and Kang (2003) showed that hydrates can be
used to separate CO2 from ue gas. These studies lead the way for
various studies on the removal of CO2 from ue gas (typically CO2
and N2 mixtures) using hydrates (Englezos et al., 2007b; Herri
et al., 2007; Kumar et al., 2006a; Lee et al., 2009) and also for the
pre-combustion removal of CO2 from H2 using hydrates (Englezos
et al., 2007a; Englezos et al., 2007b). The removal of CO2 from
natural gas mixtures has received somewhat less attention (e.g.,
Golombok et al., 2009) as is the case for separating N2 from a
natural gas mixtures (Happel et al., 1994; Hnatow and Happel,
1995; Johnson et al., 2009). However, at the recent triennial
international gas hydrate conference (ICGH7, July 1721 2011,
Edinburgh, UK) there were at least 28 papers submitted that
studied the separation of gases using hydrates.
The different afnity of certain gases to form hydrates (for
mixtures this results in a different composition of the gas in the
hydrate to the gas composition) allows the separation of mixture
Fig. 14. (a) Basic hydrate cage structures that combine to form the unit cells for the most common hydrate structures (Walsh, 2011), (b) hydrate structure versus size of
hydrate former (redrawn from Ripmeester, 2000).
147
components using hydrate formation. For CO2N2CH4 gas mixtures, CO2 is the more stable molecule in the hydrate phase,
whereas N2 is the least stable. This results in the preferential
occupation of CO2 over CH4 in the hydrate cage, or in the absence
of CO2, the preferential occupation of CH4 over N2. Seo et al.
(2001) showed that at lower pressures CO2 also preferentially
occupies the hydrate cages from measurements of the composition of the gas phase and hydrate phase in equilibrium with a
CO2CH4 gas mixture.
One of the limitations for the use of hydrates to separate gas
mixtures is the typically high pressure that is required to form gas
hydrates, which can represent a signicant cost to the process
(Tajima et al., 2004). A typical natural gas hydrate forms at high
pressure ( 430 bar) and low temperature ( o20 1C). A common
method for overcoming this high pressure requirement is to use a
hydrate formation promoter molecule, which can signicantly
reduce the hydrate formation pressure for a given temperature. In
their patent, Lee and Kang (2003) in their patent proposed a
process for separating a multi-component gaseous mixture using
a hydrate promoter. The two most common examples of promoter molecules that have been studied for hydrate separation
technologies include tetra-n-butylammonium bromide (TBAB)
(Clarke et al., 2011; Guo et al., 2011; Kamata et al., 2004; Li
et al., 2011; Li et al., 2010b; Shimada et al., 2003) and tetrahydrofuran (THF) (Lee and Kang, 2000; Lee et al., 2008; Sun et al.,
2010). Other promoters include cyclopentane (Fan et al., 2010)
and propane (Kumar et al., 2006b). It is important to note that the
addition of a promoter molecule can affect the selectivity of
certain gas molecules in the hydrate (Sun et al., 2011a) For
example, THF which occupies the large cage of sII hydrates has
been shown to selectively inhibit the enclathration of ethane,
which does not occupy the small cage at moderate pressures,
from a binary mixture with methane (Sun et al., 2011b).
enclatherated gas in the hydrate phase is often not very different

from that of the original gas mixture. For CO2/CH4 separations,
van Denderen et al. (2009) reported values of aij 1.42.6 for
selectivity of the CO2 in the hydrate phase. A typical apparatus
used to study the separation of a mixed gas using hydrates is
shown in Fig. 15 and described by Happel et al. (1994). The
apparatus produces a methane lean stream out of the hydrate
forming reactor (from a mixture of CH4N2) and methane rich
stream exiting the hydrate settler vessel. The apparatus would
likely represent a single stage in any separation process. The gas
stream exiting the hydrate forming reactor is lean in methane due
to the preferential occupancy of CH4 in the hydrate cages over N2.
If the same apparatus were applied to treat a CO2CH4 feed gas
mixture, the efuent from the top of the reactor would then be a
methane rich stream (lean in CO2) and the exit stream from the
settler vessel would be lean in methane (CO2 rich).
Hydrate formation is an exothermic reaction and thus the
removal of heat from the process is an important consideration. A
novel approach of achieving this is the use of a uidised-bed heat
exchanger for hydrate formation (Waycuilis and York, 2002).
Marathon oil company has developed this method into a pilotscale continuous ow gas hydrate reactor capable of generating a
410 wt% hydrate slurry at 4750 kg/day production rate. Beads
of solid media are uidised inside the heat exchanger tubes by the
upward ow of the liquid which acts to continuously but gently
scour the inside tube surface. This helps to both (a) prevent solid
deposition from the hydrates, and (b) improve the internal heat
transfer coefcients. Preliminary engineering work has been
conducted to scale this process to a 3000 tonne/day slurry
generation (Waycuilis et al., 2011).
6.2. Applications and demonstrations of hydrate gas separation for

CO2 and N2 capture.
The characteristics of the primary gas separation operations

applied to CO2 and N2 removal from natural gas covered in this
review are summarised in Tables 10 and 11, respectively. For CO2
removal, amine absorption technologies for acid gas treating are
well-established in the natural gas industry. The current industry
dominance of chemical absorption processes for acid gas treating
is likely to remain in the near future for the largest scale gas
processing applications because these processes have high
separation powers for CO2 (and H2S) and the technology has been
proven. The use of CO2 selective membrane technologies for bulk
separation of CO2 is increasing in the natural gas industry and in
the capture of CO2 from combustion ue gases (Olajire, 2010).
Novel low-temperature process technologies such as ExxonMobils Controlled Freeze ZoneTM (CFZTM) process (Fieler et al., 2008)
There are a several patented processes proposed for gas

separation using hydrate formation although there is currently
no commercial-scale process in operation. Most of the processes
involve the use of a stirred tank reactor and include the use of
promoter molecules to reduce the operating pressure. An alternative approach is the use of a bubble-column to promote the
contact of gas and water (Chen et al., 2007), which is often a
limiting factor in the formation of gas hydrates.
The separation of CO2 from a gas mixture using hydrates
typically requires the process to contain multiple steps to achieve
an adequate separation power because the composition of
7. Summary and outlook
Fig. 15. General schematic of an apparatus for producing a methane rich and a methane lean stream using hydrate formation and dissociation (redrawn from Happel et al.,
1994).
148
Table 10
Summary of characteristics for the main CO2 removal (and gas sweetening) technologies.
Process technology
Amines
Physical solvents
Hot potassium carbonate Condensation, distillation

or desublimation
Adsorption (PSA)
Membranes
Mechanism/phase change
Chemical absorption
Absorption in liquid
Chemical absorption
Phase creation
Permeation
Stage of deployment of
technology
Commercial examples
Mature
Mature
Mature
Commercial demo
Selexol, purisol, rectisol
CO2 inlet concentration
ADIP-X, EconamineSM,
aMDEA, GAS/SPEC
Up to 70%
Beneld, catacarb,
exsorb HP
550%
Ryan/Holmes, CFZTM,
Cryocells
3.565%
Selective CO2
adsorption on solid
Commercial up to
2 MMscfd
Xebec PSA, Molecular
GateTM
Up to 40%
Up to 90%
CO2 outlet concentration
2%, down to 50 ppmv
23%;
50 ppmv possible
Down to 12%
Simultaneous H2S removal
Yes (depends on solvent) Yes (most solvents)
Z 1.5% (single-stage)
50 ppmv in modied
CFZTM
(Nichols et al., 2009)
Z 0.1% (two-stage)
(30 ppmv with hybrid)
(GPSA Engineering
Data Book, 2004)
With two-stage scheme
Possible
Possible
Low to 4350
Absorber: 50007000
100400
Absorber: 65008000
Low to 4260
Absorber: 50007000
Yes, but limits on H2S in

CO2 product
CDPs: 214
20004000
CDPs: Up to 2
10003500
Low to 4350
200010,000
Regenerator: 150
Absorber: 3060
73 to ambient
Regenerator: 150
100116
142 to 45
25
o60 (materials limit)
50007000
65008000
50007000
20004000
10003500
200010000
Outlet gas H2O saturated Gas dehydrated

Very low
Very low
Gas dehydrated
Co-adsorption of
heavy hydrocarbons
Pressure
(kPa)
Temperature
(1C)
Sweetened gas outlet pressure

(kPa)
Sweetened gas H2O saturation
Hydrocarbon recovery/losses
(Bergel and Tierno, 2009)
Acid gas outlet pressure (kPa)
Footprint/layout considerations
(Bergel and Tierno, 2009)
Main equipment items (Bergel
and Tierno, 2009)
Energy requirements (main use)

Comparative process costs (Bergel Capital
and Tierno, 2009)
Operating
Outlet gas H2O saturated Gas dehydrated

o 1% losses
Absorbs heavy hydrocarbons
and aromatics
SeparexTM, Z-Top, Medal
130
High
o 500
High
High
Liquid CO2
High; CFZ/CryocellLow
o 500
Medium
Gas dehydrated
1 stage: 815% (Bergel and
Tierno, 2009)
2 stages: o2%
o500
Low
Contactor
Contactor
Contactor
Cryogenic tower(s)
Adsorbent vessels
Membrane modules
Regenerator column
Multiple ash drums
Regeneration system
Refrigeration system
Flash tank
Heat exchangers
Gas/gas exchangers
Gas/gas exchangers
Waste/regen gas
Pretreatment modules
compressors
Valve and piping skids Compressors (2 stage
processes)
Lean/rich amine heat

exchanger
Lean amine cooler
Solvent circulation
pumps
CO2 ash drum
Lean solution cooler
Liquid CO2 pump
Recycle compressors
Chiller
Circulation pumps
High (solvent
regeneration)
High
Solvent circulation pumps

Medium (solvent circulation)
Medium (regeneration)
Medium
Medium
Low
High
Medium (refrigeration
system)
Medium
Low (purge gas/

recompression)
Medium
Lowmedium (feed gas and

interstage compression)
Medium
Low
Medium
Low
1 stage: low
2 stages: medium
Typical ow rate (MMscfd)

Typical operating conditions
P CO2 4 3.5 bar (GPSA

50 ppmv possible
Commercial
Table 11
Summary of characteristics for nitrogen rejection technologies.
Distillation
Physical solvents
Adsorption (PSA)N2 selective
Adsorption (PSA)CH4
selective
Membranes
Mechanism/phase change
Condensation
Absorption in liquid
(typically CH4 absorbs)
AET; TGPE
Selective N2 adsorption on solid
Permeation
Molecular Gate
Selective CH4 adsorption on

solid
Nitrotec; IAXC
NitroSepTM
Mature
Commercial up to 10 MMscfd
855%
15630
Up to 40%
230
Up to 40%
0.510 (Mitariten, 2009)
Up to 40%
0.515
N2 in CH4-rich product gas
o1%
o4%
Typically 4%
Typically 4%
Hydrocarbon losses
o2%
Absorbs heavy
hydrocarbons
and aromatics
Propane and heavier adsorb on

binder of molecular sieve
(Mitariten, 2009)
Up to 90%
0.525 (Hale and Lokhandwala,
2004)
1 stage bulk separation only
2 stages o 4%
1 stage: High
Typical operating conditions Pressure (kPa)

Temperature (1C)
Sales gas outlet pressure
(kPa)
Footprint/ layout
comparative
Main equipment items
13002800
161 to 110 1C
2040
2003000
32 to ambient
o5
4002000
25
4002000
4002000
25
o400
2 stages: low losses (o2%)

200010,000
2560
200010000
High
High
Medium
Medium
Low
Cryogenic tower(s)
Refrigeration system
Gas/gas exchangers
Contactor
Multiple ash drums
Recycle compressors
Solvent circulation pumps
Adsorbent vessels
Adsorbent vessels
Membrane modules
Waste/regen gas compressors
Compressors
(2 stage processes)
Pretreatment modules
Commercial examples
Linde, Praxair, Costain,

ConocoPhillips, APCI
Mature
Technology development
stage
N2 inlet concentration
Typical ow rate (MMscfd)
Energy requirements
(overall)
High (refrigeration
system)
Comparative process costs
Capital
Operating
Chiller
Medium (solvent
circulation,
recompression)
Medium (with LNG)
Medium
TM
Low
Valve and piping skids

Medium (CH4-rich gas
recompression)
Lowmedium (feed gas and

interstage compression)
Medium
Medium
Medium
Low
Medium
Low
Medium
Medium
Item
149
150
and adsorption-based systems such as Xebecs rapid cycle pressure-swing adsorption (PSA) process (Toreja et al., 2011) are
emerging as alternatives to amine scrubbers for CO2 removal in
certain applications such as for processing high CO2 concentration
gases and for developing remote gas elds. Although the application of hydrate formation to capture CO2 is gathering signicant
research attention, with a large increase in the number of papers
on this topic observed at the recent 7th International Conference
on Gas Hydrates, the separation performance of hydrates is limited
by the relatively small differences between the free energies for
CO2 and CH4 in the hydrate cage. Thus, hydrates are unlikely to be
applied widely for treating sour natural gas elds.
From the technologies for N2 rejection listed in Table 11,
cryogenic distillation is the leading NRU technology for large
scale (feed rates greater than 15 MMscfd) natural gas and LNG
plants, but technologies based on CH4 selective absorption (AETTechnology, 2007) and adsorption (Reinhold, 2010; Richter et al.,
1985) are commercially available for smaller scale gas processing
facilities. In the future there is potential for more efcient N2
rejection technologies based on N2 selective solvents and N2
selective rapid cycle PSA systems. There remains signicant scope
for the development of better performing CO2 selective membranes, N2 selective solvents and N2 selective adsorbents to both
improve the separation power of, and the stability of materials, in
these emerging gas processing technologies.
Acknowledgements
We thank David Uhlmann (UQ), Hatim Essajee (UWA),
Mohamed El-Zaemey (UWA) and Thomas Saleman (UWA) for
their assistance with data collection during preparation of this
manuscript. The support of the Chevron Energy Technology
Company through the Chevron-UWA University Partnership Program, the Western Australian Energy Research Alliance (WA:ERA)
and the Australian Research Council for UWAs gas process
engineering research program is also acknowledged.
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Journal of Petroleum Science and Engineering 9495 (2012) 123154

Contents lists available at SciVerse ScienceDirect

Journal of Petroleum Science and Engineering

authors such as Rojey et al. (1997). Table 1 contains a list of the

Top natural gas importers

natural gas. Additional gas processing challenges arise from new

(Tagliabue et al., 2009)

(Tagliabue et al., 2009)

In conventional gas processing H2S and CO2 are removed in an

1.2. Overview of gas separation mechanisms

desublimation of CO2. If the volatility differences among species

(a) CO2/CH4 separation

separation of N2 from CH4 in adsorption-based processes is

new technology and the conventional one with which it will

Eickmeter and Associates

Potassium carbonate ( organic additive)

Dry propylene carbonate

Sulfolane DIPA water

www.shell.com (Rajani, 2004)

absorption for physical solvents is much lower than the heat of

Hydrolysis and dissociation of dissolved CO2:

Protonation of the amine:

The dissociation reactions are shown here to highlight that the

Amines can be classied according to the number of hydrogen

The stoichiometry in Eq. (7) shows that theoretically tertiary

For example, the cyclic diamine piperazine has been studied as a

no, 100 ppm possible

no, 100 ppm

absorption of CO2 in the liquid solvent occurs at the liquid

The basic potassium carbonate process was developed by the

A further advantage of the chilled AAP design is that absorber

H2S has a greater solubility in most organic solvents than CO2, a

The Amisol process is based on a mixture of methanol, water and

because they are insoluble in water. This fact represents a serious

The absorption of N2 in OMCs is achieved through using metal

3. Condensation, desublimation and distillation

Fig. 5. Illustration of the binary CH4N2 vapourliquid equilibrium relationship

cryogenic LNG plant the boiling point (BP) of CH4 is 94.7 1C

distillation column would be higher than the eight ideal trays

Fig. 6. A process ow schematic of a typical single-column N2 rejection unit

N2-rich vapour from the HP column is condensed to provide reux

categorised as: (1) gasliquid phase separations operating at

Woodside Petroleum and Shell Global Solutions (Hart and

hydrocarbons (for dew point control) from the natural gas

chemistry and pore structure; and by the adsorbates properties

regeneration stages. Adsorbent regeneration, or desorption, can

processing natural gas feeds containing no more than 2% CO2

M3100 Xebec Rotary-valve

Nitrogen rejection unit

Toreja et al. (2011)

are used in the production of high purity H2 from steam methane

4.2.1. Adsorption cycle process renements

with pellets (Rezaei and Webley, 2010). Fast gas transport

by changes in the crystalline structure of the adsorbent which

selectivities, of various commercial and novel adsorbents.

PCB, Calgon Corp.

Bao et al. (2011b)

Ritter and Yang (1987)

of the highest selectivities reported for CO2/CH4 separations.

activated carbons (Plaza et al., 2010) or the utilisation of nitrogen

4.3.2. Adsorbents for N2 rejection

Sr-ETS-4, activated 543 K

Marathe et al. (2004b)

membrane technologies highly attractive for process separation