CO2 Capture and Usage: Harnessing

the CO2 Content in Natural Gas for

Environmental and Economic Gains
Emmanuel O. Agiaye and Mohammed Othman, Nigerian Agip Oil Company

Summary power generation, as capable of contributing up to 19% in CO2 re-

Carbon dioxide (CO2) capture and usage (CCU) is currently a global ductions (IEA 2008, page 69). These are not withstanding the as-
topical issue, and is viewed as one possible route to reduction of CO2 sessment performed by IEA (2012) with respect to “high potential
concentrations in the atmosphere. The core issues facing the world CO2 emissions” found with global “carbon reserves,” and thereby
in current times—development, economy, and environment—are outlining the deployment of CCS as the major technology required
identified as being dependent on the provision of clean, efficient, af- for sustaining the projected demand on fossils. “The assessment has
fordable, and reliable energy services. Currently, the world is highly attributed almost 63% to coal, 22% to oil and 15% to gas in CO2
dependent on fossil fuels for provision of energy services, and the emissions potential locked in these reserves.” The case of CO2 in
amount of which renewable energies can sufficiently replace is min- natural gas represents a typical scenario for a number of oil and gas
imal. The deployment of appropriate CO2-separation technologies companies faced with the enormous challenge of reduced energy
for the processing of natural gas is viewed as an abatement measure level of sales gas making it subquality or when disposal by flaring
toward global CO2-emissions reduction. Selection of the optimum increases the source of CO2 emissions to the atmosphere. However,
technology among the several separation technologies for a partic- the amount of natural gas flared globally has been shown to con-
ular separation need requires special attention to harness the eco- tribute approximately 1.2% of the global CO2 emissions, which is
nomic and environmental benefits. The captured CO2 would also given to be more than one-half of the certified emissions reductions
require appropriate disposal or usage so as to sequester or “delay” under the Kyoto Protocol (ICF International 2006).
its re-entry into the atmosphere. These challenges of CCU— There are several technologies and techniques now available for
involving natural gas particularly during processing, which has be- separation of CO2 (or acid gases) from gas mixture, either as flue
come an area of intense research—shall be discussed in the paper gas from power plants or from natural gas. In addition to deploy-
with respect to the selected technique for CO2 capture. A typical nat- ment of these technologies, the captured or separated CO2 must be
ural-gas-production scenario in Nigeria shall be analyzed for poten- disposed of in such a manner as to prevent it from seeping back into
tial CO2 capture. Further discussion shall be on the identification of the atmosphere. This is required to achieve the aims of the CDM
the recovered CO2 gas-usage framework, such as CO2 flooding [in from the use of fossil fuels. Among the fossil fuels, natural gas has
enhanced oil recovery (EOR)], for additional revenue generation, been shown to contain the least amount of CO2 emitted per tonnage
assessment of the CO2 savings, and the contribution to the clean de- of fuel burnt as compared with coal and oil. In addition to the CO2
velopment mechanism (CDM). emitted during combustion, natural gas on production also contains
a certain amount of impurities, including CO2 gas. The maximum
Introduction level of CO2 permitted in natural-gas fuel is typically less than 3%.
The separation of CO2 from the gas stream is currently a global Hence, all natural gas is treated to remove the solids and free liq-
issue. The increasing amounts of greenhouse gases (GHGs) in the uids and to reduce water-vapor content to acceptable levels and,
atmosphere in recent years, considered to be partly responsible for especially, to meet pipeline specifications. Hence, natural gas must
climate change, have been a serious global concern, and CO2 gas be purified through the removal of CO2 and other acid gases and
has been identified to as a major contributor of GHGs. Several pos- impurities (where present) because these impurities can form acids
tulations have proposed a long-term global stabilization of CO2 con- in the presence of water to corrode pipelines and other equipment.
centrations in the atmosphere to be a possible panacea for curtailing In addition, higher concentrations of CO2 in natural gas reduce the
climate change and global warming. The use of fossil fuels inclusive heating value or energy level, which is below pipeline specifica-
of natural gas currently dominate the source of global energy supply, tions, necessitating its removal before distribution to the end con-
which are considered capable of meeting the world’s increasing en- sumer. Natural gas has been a main source in meeting the world’s
ergy needs up to 84% by 2030 (IEA 2008, page 47) from the current energy demand, contributing an estimated 23.81% in 2010 to the
demand of approximately 81% (IEA 2012, page 10). CO2 emission world energy supply mix (Rufford et al. 2012, page 123). This con-
to the atmosphere from combustion of fossil fuels (coal, oil, and nat- tribution is projected to increase because natural gas is considered
ural gas) and during production/processing of natural gas is consid- the cleaner fossil fuel compared with coal and oil. The deploy-
ered to be the major cause of high CO2 volumes in the atmosphere. ment of appropriate CO2-capture technology in processing natural
It has been outlined that energy scenarios involving the use of clean- gas stands to improve its value as the cleaner fossil fuel. In this
energy technologies can result in a more than 50% reduction in paper, a brief review of related acid-gas separation processes will
global CO2 emissions up to 2050 (IEA 2010) with the deployment be reviewed and recommendations will be presented. Economic
of carbon capture and sequestration (CCS), inclusive of industry and opportunities by use of the captured CO2 for additional revenue
generation through EOR by CO2 flooding, as well as appropriate
transportation and storage infrastructure, will be reviewed.
Copyright © 2016 Society of Petroleum Engineers

This paper (SPE 178316) was accepted for presentation at the SPE Nigeria Annual CO2-Capture Technologies
International Conference and Exhibition, Lagos, 4–6 August 2015, and revised for
publication. Original manuscript received for review 7 September 2015. Revised manuscript
There are different techniques or technologies available today that
received for review 15 February 2016. Paper peer approved 22 February 2016. are used for the separation of CO2 from natural gas or from flue

June 2016  •   Oil and Gas Facilities 1

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Property CH4 CO2 N2
Kinetic diameter (Å) 3.80 3.30 3.64
Normal boiling point [K (oC)] 111.7 (–161.45) – 77.3 (–195.85)
Critical temperature [K (oC)] 3.80 (–269.35) 304.1 (30.95) 126.2 (–46.95)
Critical pressure [psi (bar)] 667.2 (46) 1,070.4 (73.8) 493.1 (34)
∆Hvap at NBP (KJ/mol) 8.17 26.1 5.58
Polarizability (Å3) 2.448 2.507 1.710
Quadrupole moment (DÅ) 0.02 4.3 1.54
Table 1—Physical properties of CH4, CO2, and N2 (Rufford et al. 2012; Scholes et al. 2008, page 54).

gas (from power plants). The type of separation process required •  Adsorption on a solid—involves the gas component to be sep-
in any particular case is often affected by the specifications of the arated, binding to the surface of a solid adsorbent such as acti-
product gas and the amount and composition of the gas mixture. As vated carbon, silica gel, zeolites, and finely divided platinum.
simple as it may seem, the selection of the optimum technology suit- A typical example of an adsorption mechanism is the molec-
able for the separation process may become an issue as a result of a ular-sieves-separation process for natural-gas purification.
number of factors. This is because no one technology can perfectly •  Permeation mechanism—involves separating components by
suit all the conditions required for separation. Hence, each is associ- use of the principle of solubility diffusion to permeate through
ated with its advantages and disadvantages. Typical factors that may a membrane.
be considered for the separation of CO2 from natural gas include •  Chemical conversion to another compound—for instance, the
•  The CO2 content in the product gas, which is typically re- steam-reformation process of natural gas to produce H2 and
quired at less than 2% CO2, otherwise known as hydrogen economy.
•  The presence and concentration of other impurities in the feed •  Phase creation by heat transfer—to (or from) the gas mixture,
gas, such as H2S and water content which involves use of phenomena such as condensation, de-
•  The presence and concentration of heavy hydrocarbon (HC) sublimation, or distillation.
ends, contaminants, and water vapor The separation mechanisms as outlined in the preceding are
•  The conditions available for processing the gas, such as the each characterized by a major property known as selectivity with
pressure, temperature, and volume of the feed gas respect to the components to be separated. In particular, the equi-
However, the choice of a CO2-capture technology could be sim- librium selectivity of the feed stream is usually a very important
plified by “exploiting the differences in the molecular properties property for the evaluation of absorption and adsorption separa-
or the thermodynamic and transport properties of the components tion processes. In membrane-permeation mechanisms, selectivity,
in the mixture” (Rufford et al. 2012, page 125). Table 1 shows the for instance, is applied in the analysis of the process-separation ca-
physical properties of a gas mixture [methane (CH4), CO2, and ni- pability, depending on the concentrations of the permeate (CO2-
trogen (N2)] that can be exploited by use of the molecular-proper- rich gas) and feed stream. The performance of a separation process
ties approach to achieve separation of these gases. can therefore be viewed as governed by the selectivity behavior
Thermodynamic and transport properties can also be used to of the separation mechanism and engineering decisions leading to
achieve separation by use of properties such as solubility, adsorp- the selection and implementation of the separation process. Typical
tion capacity, diffusivity, vapor pressure, and boiling points. engineering decisions include aspects that will enhance or maxi-
On the basis of the molecular or thermodynamic and transport mize the process efficiency, such as mitigation decisions of CO2
properties of the gas components to be separated (Rufford et al. plasticization of membranes. The separation-process performance,
2012, page 125), approximately five separation mechanisms are which is dependent on selectivity behavior, could therefore be re-
usually applied, with which a suitable separation process could be lated to the SP that is used to quantify the performance of the entire
selected. Generally, selection of the appropriate separation process separation process in terms of the feed-gas compositions (Seader
depends more on its characteristic separation power (SP) to achieve and Henley 2006). In Table 2, typical inherent selectivity values
the desired gas specifications in addition to its economic viability are shown as applicable to the separation mechanisms of the most
in terms of the separated-products value. common separation technologies, especially for natural-gas-sweet-
The following five separation mechanisms are commonly ap- ening applications. The SP of each of the technologies is also given.
plied in any of the separation processes: The values show estimation of the inherent selectivity and SP re-
•  Absorption—involves absorption in a liquid or solid sorbent quired to produce typical pipeline-quality gas to less than 2% CO2
through diffusion into the liquid or solid absorbing medium from a natural-gas feed mixture of 5% CO2 (Rufford et al. 2012,
(for instance, amine absorption of CO2 in a scrubber process). page 126). From the table, one can easily notice the higher inherent

Typical Inherent Typical Process

Separating Equilibrium SP
Process Agent Selectivity ( aCO2 -CH4 ) (SPCO2 -CH4)
Membrane permeation – CO2 Membrane 15–20 20–40
selective
Adsorption—CO2 selective Solid adsorbent 2.0–8.5 6.0–22
Amine absorption (MDEA) Liquid absorbent 860 3,300
Physical solvent (Chilled CH4) Liquid absorbent 318 1,900
MDEA = methylenedioxyethylamphetamine.

Table 2—The inherent equilibrium selectivity and SP for the separation of CO2 from CH4 (Rufford
et al. 2012).

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selectivity values with respect to CO2-component separation in stream, usually at high pressure and low temperature, to form
the process mechanisms of absorption by use of chemical-amine a carbamate-ion nitrogen/carbon bond, thereby capturing the
absorption and physical-solvent absorption as compared with the CO2 from the gas stream. The carbamate-ion bond is then
membrane-permeation and -adsorption processes. The higher SP broken down at a higher temperature and low pressure to en-
values are also an indication that the absorption mechanisms are dothermically strip the CO2 in a regeneration process, while
possibly better in separation of CO2 gas from natural gas. the lean amine solution is recycled back for another round of
Given that considerations for inherent selectivity or SP alone capture. The aqueous amine-based absorption can be achieved
are not enough to determine the appropriate separation technology by use of primary, secondary, or tertiary amine solvents. De-
for gas separation, other design steps are usually to be taken by the pending on the key requirement for CO2 capture, tertiary
design engineer through good-engineering practice toward the se- amines have an advantage over secondary and primary amines
lection of the optimum and most-economical separation process. In by regeneration-energy and loading-capacity requirements,
the case of natural-gas purification involving the removal of CO2, whereas the primary and secondary amines are preferred in
other factors worthy of consideration include terms of faster reaction rates with the acid gas (CO2) (Rackley
•  The assessment of the level of contaminants and impurities 2010, page 105).
in the feed composition and requirement for removal level to •  Hot-carbonate (alkali salt) systems: Use of hot solutions of
meet end-use specifications. potassium carbonate (K2CO3) or sodium carbonate (NaCO3)
•  The feed-gas conditions, such as temperature, pressure, water to remove CO2 from high-pressure gas streams (Rufford et al.
content, and flow rate. 2012, page 130):
•  The method of removal of other acid gases other than CO2,
such as H2S present in the feed gas. This requires the engineer
to decide on the choice of either the selective- or the simulta- CO 2 ( g ) + K 2 CO3 + H 2 O(1) 2KHCO3−( s )
neous-removal method or the appropriate separation mecha-
nism to achieve an optimum process. Similar to the amine-based process, the simplified reaction
•  The method of disposal or market usage of the separated in the preceding gives the absorption of CO2 in a lean hot-
component(s). Typical instances could include finding a potassium-carbonate stream, usually occurring in a counter-
market for the captured CO2 for additional revenue genera- flow arrangement between the hot alkali (sorbent) and the nat-
tion, reinjection of the CO2 for EOR, and venting of N2 to at- ural-gas stream. The rich alkali solution containing captured
mosphere or N2 generation. CO2 is then regenerated and recycled back, with the entire
A detailed cost and performance analysis, which can ultimately process occurring at high temperatures.
lead to the determination of the best separation process under given •  Aqueous ammonia-based absorption: Similar to the amine-
conditions, can thereby be performed by use of the preceding se- based absorption, ammonia-based absorption involves the
lection factors. chemical reaction of ammonia and its derivatives with CO2
to form a weak bond where CO2 is removed on application
Absorption in a Liquid (or Solid) Sorbent of heat. Compared with the amine-based process, the aqueous
Absorption is referred to as “the transfer of a component of gas ammonia process is shown to have lower energy requirements
phase (CO2, H2S) into a liquid (or solid) phase in which it is soluble” (Rufford et al. 2012, page 130), thereby lending it to possible
(Kohl and Nielsen 1997, page 1). The process involves passing a significant energy efficiency improvement and lower costs
gas mixture through a liquid (or solid) such that one or more com- (Rackley 2010, page 105).
ponents of the gas mixture are dissolved selectively to provide a Physical absorption involves the selective absorption or sepa-
solution with the liquid (or solid). The gas component (the solute), ration of CO2 from the natural-gas stream, where the rate of ab-
forming solution with the liquid or solid (the sorbent), is said to be sorption increases with increasing pressure and at low temperature.
absorbed by the sorbent. This absorption mechanism has been used The physical-absorption process uses the principle of gas (solute)
in many commercial gas-separation processes worldwide, espe- solubility in the sorbent such that the dissolved volume is propor-
cially in oil and gas operations, and is generally carried out in con- tional to the partial pressure at a given temperature without reacting
ventional industrial pressure vessels known as contactors, where a chemically with the sorbent (Rackley 2010, page 109). Physical-
mass transfer by direct contact and dispersion of one phase within absorption processes are generally favored at acid-gas (CO2) par-
another takes place (Dindore 2003, page 4). Depending on whether tial pressures greater than 200 psia (14 bara) (Rufford et al. 2012,
there is a chemical or physical reaction between the solute and the page 128). Other factors considered favorable include low concen-
sorbent, absorption processes are basically available as chemical tration of HCs (C6+) and requirement for selective and bulk capture
absorption and physical absorption, respectively. of CO2 in the gas mixture. The most common physical-absorption
The basic process in chemical absorption in CO2 capture from processes used in the industry include Selexol® (using the union
natural gas involves the reaction of the CO2 with the sorbent to carbide sorbent made of dimethyl ether of polyethylene glycol),
form weakly bonded intermediate compounds. On application of Rectisol® (using chilled methanol sorbent), and fluor (based on
heat, the CO2 is released from the compound, thereby regenerating propylene carbonate sorbent) processes.
the sorbent. The chemical solvents are somewhat favored at lower In both the physical- and chemical-absorption processes, the
partial pressures (60 to 100 psia) above which physical solvents are amount of CO2 gas to be captured, as well as the CO2 loading ca-
preferable (Freireich and Tennyson 1977). pacity of the sorbent, determines the rate of circulation of the re-
Some of the common chemical-absorption processes for acid-gas quired sorbent; in addition to the energy required to regenerate the
treating (particularly CO2 capture from natural gas) in the industry sorbent, these form the major cost factors in the absorption pro-
are as follows: cesses (Rufford et al. 2012, page 128). Despite the preceding con-
•  Aqueous amine processes derived from ammonia (NH3): For straints, the chemical-absorption processes with amine solutions,
instance, a tertiary amine process, such as MDEA (Rufford for instance, have been commonly used absorption processes for
et al. 2012, page 128) CO2 capture and gas sweetening within the natural-gas industry.
In comparison with the physical-absorption solvents, the chemical
RR ′R ′′N + CO 2 + H 2 O RR ′R ′′NH + + HCO3− . solvents generally have higher energy requirements for regenera-
tion (because the heat of absorption is much higher) and higher
In the preceding simplified reaction, the tertiary amine (sor- acid-gas loading capacity at low/moderate CO2 partial pressures
bent) reacts exothermically with the CO2 in the ­natural-gas (Olajire 2010, page 2610). Both physical- and chemical-absorption

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processes are suitable process techniques for treating high-volume water (which is strongly attracted) are adsorbed by the solid desic-
gas streams containing CO2 and/or H2S. However, when the acid- cants (a pack of aluminum silicates or zeolites), while the nonpolar
gas partial pressure is low (less than 200 psi), the physical-absorp- components (CH4+) pass on. The dehydrator vessels are then re-
tion processes are known to become economically uncompetitive generated by increasing the temperature and reducing the total and
(Kohl and Nielsen 1997, page 4). partial pressure of the system with a hot fuel gas that displaces the
The physical- and chemical-absorption processes are further water and CO2, thereby removing them from the system.
characterized as follows: The most-common adsorption processes are based on the use
•  Physical solvents are particularly useful in capturing a higher of solid desiccants as the sorbents (or adsorbents), such as the mo-
percentage of CO2 gas from the total gas stream with a very lecular-sieve (zeolite), activated-bauxite, activated-alumina, and
low heat input compared with the chemical-absorption pro- silica-gel processes. These commonly use any one or more basic
cess (amine or potassium carbonate sorbents), during which cycles, such as the temperature-swing adsorption, which regener-
substantial heat input, which forms a major cost factor, is re- ates by use of temperature for regeneration, and pressure-swing ad-
quired for regeneration of the sorbent. The physical-absorption sorption, which regenerates by lowering the partial pressure of the
sorbents, which are nonreactive organic solvents, physically adsorbate (Kohl and Nielsen 1997, pages 1025–1035). Among the
dissolve the acid gas (CO2 or H2S) and then strip through re- solid-dessicants-based-adsorption processes, only the molecular-
ducing the pressure without the application of heat (Kohl and sieve (zeolite) process finds a wider application in the removal of
Nielsen 1997, page 1188). The leading physical-absorption other gas impurities (acid gas such as CO2 and H2S), other than the
technologies used mostly to treat feed gas with very high CO2 popular use of gas dehydration (water removal) (Kohl and Nielsen
concentrations include Selexol and Rectisol processes (Burr 1997, page 1071; Ebenezer 2005, page 18). However, the molec-
and Lyddon 2008, page 12). ular-sieve process is characterized by higher regeneration temper-
•  Commercially available physical solvents have relatively low atures (Kohl and Nielsen 1997, page 1030) and is suitable for the
acid-gas-absorption (loading) capacities, requiring high circu- removal of small concentrations of acid gas from feeds usually
lation rates. These usually create room for massive absorption containing no more than 2% acid gas, such as CO2, “because the
and solvent-regeneration vessels, thereby making physical- quantity of adsorbent required to capture greater volumes of CO2 is
absorption technologies unsuitable for use in areas where large” (Rufford et al. 2012, page 137).
space constraints exist, such as offshore locations (Rufford et In summary, adsorption processes that use solid desiccant and
al. 2012, page 130). that are regeneration based for gas purification can be argued to be
•  Physical sorbents are known to have affinity for HCs in ad- characterized by requirement for high regeneration temperatures,
dition to higher concentrations of acid gas. Hence, their addi- high pressure drop through the unit, and high initial-investment
tional absorption capacity for HCs, which is higher than that capital cost. They, however, have inherent advantages for suit-
of chemical sorbents (Shimekit and Mukhtar 2012, page 242), ability for gas dehydration and acid-gas removal at the same time,
can impact their consideration for application in cases where have wider capabilities to accommodate fluctuations in feed-gas-
the feed gas contains HC ends. flow properties, and are basically free from problems of mechan-
•  Absorption-based processes, as argued by Shimekit and ical degradation and corrosion of units.
Mukhtar (2012, page 246), are further limited by corrosion is-
sues in the “units” associated with the solvents, such as amines Membrane Permeation
capable of causing erosion of the units when reacted with cor- The membrane-permeation mechanism for gas-separation processes
rosion inhibitors. This is in addition to “environmental haz- is new in comparison to some other similar processes, such as amine
ards” caused by the losses associated with the sorbent that absorption, adsorption, and cryogenic distillation. Membrane-per-
occur during regeneration. meation technologies have been applied to remove acid gases such
as CO2 and H2S from natural gas and in commercial quantities since
Adsorption the 1980s (Rufford et al. 2012, page 141; Scholes et al. 2012, page
According to Kohl and Nielsen (1997, page 2), adsorption, as ap- 16; Baker and Lokhandwala 2008, page 2). However, the membrane
plied to natural-gas separation, involves the retention of selective processes to remove CO2 from natural gas (as compared with their
components of the feed gas when in contact with a solid adsorbent use for removal of other gas components such as NGL, N2, and H2S)
that has the ability to retain (adsorb) the feed-gas component(s), have been among the most commonly applied processes in industry
called the adsorbate. The adsorbate (for instance, CO2) is then re- since commercialization and are considered currently to be the only
leased from the solid adsorbent by either reducing the partial pres- natural-gas-separation process (CO2 capture) for which membrane
sure of the gas component or increasing the temperature. The processes are competitive with the conventional technologies, such
adsorption mechanism for acid-gas removal is an established pro- as amine adsorption (Rufford et al. 2012, page 141). Membrane-per-
cess technology used in the natural-gas industry to remove the meation technology is a process that involves the use of a membrane
undesirable components from natural gas, such as CO2, water, mer- (polymeric in nature) to separate gases passing through it by selec-
cury, and HCs. tive permeation of gas components through the polymer. Through
The mechanism of separation in adsorption, which is principally the principle of solubility and diffusion, rather than operating as a
based on physical adsorption, is achieved because the forces (Van filter, selective components of the feed gas, such as CO2, H2O, and/
der Waal and electrostatic forces) (Shimekit and Mukhtar 2012, or H2S, dissolve into the membrane material, thereby diffusing (or
page 247) holding the adsorbate on the adsorbent are weaker than permeating) through it, and are collected from another side of the
the forces of chemical reaction between the adsorbate and adsor- membrane (as the permeate) at a lower partial pressure, whereas
bent surface (Kohl and Nielsen 1997, page 2). The basic concepts the remaining gas from the feed (known as the residue) does not
involved in adsorption-process designs as applied to the removal of permeate through the membrane and leaves the membrane unit at
gas impurities in a feed stream are mainly the same. In some oil- a pressure nearly close to that of the feed gas. “Membranes can be
and-gas-production companies, for instance, the adsorption mecha- fabricated either in a hollow-fiber or spiral-wound format” with
nism that uses the molecular-sieves process (using solid dessicants) three main types of membrane materials available commercially for
is used for the final removal of water (down to 0.1 ppmv) and CO2 CO2 removal, including cellulose acetate, polyimides, and perfluo-
(down to 25 ppmv) from natural gas before its usage for natural- ropolymers (Scholes et al. 2012, page 16).
gas-liquid (NGL) production. When feed gas containing CH4 (non- Industry experience available for the application of membrane
polar), water (polar), and CO2 (nonpolar, but linear) is passed technologies as gas-separation techniques have shown them to be
through the molecular sieves, the CO2 (because it is linear) and particularly advantageous in several ways other than the estab-

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Flow Rate
Vendor/Licensor Membrane Material Module Type Natural-Gas Separation (MMscf/D)
SeparexTM/UOP Polymeric (cellulose acetate) Spiral wound CO2 (e.g., 6.5 to 2%)/CH4 Up to 680

LPG-SepTM /MTR Polymeric Spiral wound LPG, NGL / CH 4 2–50

Z-Top/MTR Polymeric (perfluoro) Spiral wound CO2(< 2%)/CH4 1–300

nitroSepTM/MTR Polymeric Spiral wound N2(≤ 4%)/CH4 0.4–100

PRISM /APCI
®
Polymeric (polysulfone) Hollow fiber CO2 (e.g., 4.5 to 2%)/CH4 <8

CO2 membrane/UBE Polymeric (polyimide) Hollow fiber CO2 (e.g., 9.6% to < 2%) / CH4 14–100
LPG = liquid petroleum gas.

Table 3—Membrane-separation technologies for natural-gas treatment (Rufford et al. 2012, page 141).

lished processes already enumerated. Such advantages as lower separated from the other side as low-pressure permeate, leaving the
capital and operating costs over the investment span of the plant are nonpermeable (CH4+) at high pressure as residue gas. The solubility
considered. They are mostly modular in design, and are suitable for diffusion assumptions are summed up in the following equation,
skid mounting as compared with the popular amine absorption or according to Fick’s law (Baker and Lokhandwala 2007, page 3;
molecular-sieves adsorption, where the plants are larger, leading to Kohl and Nielsen 1997, page 1242):
lower capital investment. Minimal energy for operation, absence of
moving parts, and no requirement for solvent replacement all equal
lower operating costs. The only major operating cost is that associ- Di ki ∆Pi , ..........................................................................(1)
ji =
ated with membrane-material replacement, which is performed at l
approximately 3 to 5 years (Baker and Lokhandwala 2007, page 6),
depending on the contaminant level and plasticization effect on the where ΔPi = Pio – Pii and is the partial pressure differential through
membrane material. Their modularity offers additional advantages the membrane; DiKi is the membrane permeability measured in
of reduced weight and space-efficiency management, which make barrers, which is a measure of the membrane’s ability to permeate
them particularly suitable for deployment in remote and offshore gas; ji is the volume (molar) flux (cm3-STP) of component i; Di is
applications. They also offer design and operational flexibility such the diffusion coefficient; Ki is the gas sorption coefficient (cm3-
that a number of operations can be integrated into one system for STP of component i per cm3 of polymer per unit pressure), which
gas-purification processes. This means that one system can be de- is an indication of the number of molecules dissolved in the mem-
signed to remove multiple unwanted components such as water brane material; l is the membrane thickness; Pio is the partial pres-
(dehydration), H2S, CO2, mercury, and HC ends from the feed gas sure of component i on the feed side; Pii is the partial pressure of
by integration of operations such as the pretreatment packages. component i on the permeate side; and 1 barrer = 10–10 [cm3(STP)]
Some of the major disadvantages known to be associated with (cm)/(cm2)(sec)(mmHg).
the membrane-permeation mechanism include For a hollow-fiber-type membrane (hollow tubular), the molar
•  CO2 plasticization phenomena, which necessitate the require- volume of gas permeation, ji , is given by (Kohl and Nielsen 1997,
ment for a clean feed, usually requiring the addition of pre- page 1242)
treatment packages, thereby increasing complexity and cost
•  Requirement to compress the low-pressure permeate (CO2-
rich gas) for usage leading to additional energy requirement Di ki ( 2L ∆Pi ) , ................................................................(2)
•  Little economies of scale associated with large installations, ji =
R 
which increases the average cost per unit module (Kohl and ln  o 
Nielsen 1997, page 1239)  Ri 
Considering that the widest application of membrane-permeation
mechanisms as gas-separation membranes is during the removal of where L is the length of the tube, Ro is the effective outer radius of
CO2 (and H2S) from natural gas, some emphasis shall be placed in the tube, and Ri is the effective inner radius of the tube.
explaining the process technology in detail. Surveys of membrane- The typical permeation rates by specific components of a feed
separation technologies that have been used in the natural-gas in- gas through commercial membrane materials are given in Table 4.
dustry are presented in Table 3, showing the leading manufacturers According to Kohl and Nielsen (1997), these rates vary with the gas
and licensors of membrane technologies and their capabilities for properties and composition.
separating CO2 from natural gas (Rufford et al. 2012, page 141). The membrane selectivity, aij , as given by the following equa-
Current installations have been shown to be capable of processing tion (Baker and Lokhandwala 2007, page 3), gives a measure of the
up to 680 MMscf/D for CO2 inlet concentration ranging from 5 to membrane’s ability to separate two gases i and j on the basis of the
70%, while projects of up to 1,200 MMscf/D are currently being ratio of their permeabilities.
developed (Scholes et al. 2012, page 16).

aij =
Pi Di K i
= =
Di D j ( )
, ...................................................(3)
Membrane-Separation Mechanism Pj D j K j K j Ki ( )
Permeation theory, as applied to the membrane-separation mecha-
nism, describes the transport of permeable gases through a mem- where aij is the selectivity or separation factor (SF) between com-
brane material by a solubility diffusion mechanism. By use of ponents i and j; Di /Dj is the ratio of the diffusion (selectivity)
differences in permeability and inherent selectivity between the coefficients of the two gases, indicating the relative motion of indi-
permeable and nonpermeable gases, the permeable gases (CO2, vidual molecules of the two components; and Ki /Kj is the ratio of
H2S, and/or H2O) dissolving selectively into the surface of the the sorption (selectivity) coefficients, indicating the relative con-
membrane material and diffusing through the membrane layer are centration of components i and j in the membrane material.

June 2016  •   Oil and Gas Facilities 5

SPE_OGF_178316_160002.indd 5 26/03/16 3:10 PM

Permeation Rate (GPU)
Membrane CO2 CH4 O2 N2 H2 H2O H2S CO C2H6 He
Cellulose acetate 93 3.10 15.5 2.71 202 1550 155 4.65 1.55 232
Polysulfone 93 3.41 15.5 3.10 186 – – – – –
Polyamide – 0.78 7.75 0.78 140 – – – – –
Dow product 1442 – 496 124 2108 – – – – –
PDMS – – 9362 4356 10060 – – – – –
Permea product 140 6.20 3565 6.2 341 – – – – –
GPU = gas-permeation unit.
PDMS = Poly(dimethylSiloxane).
Permeation rates (permeance) measured at room temperature and 7 bar.

Table 4—Permeation rates of gases through selected membrane materials (Kohl and Nielsen 1997, page 1243).

From Eqs. 1 through 3, it can be seen that the success of the Design Considerations for Membranes
solubility diffusion mechanism is dependent on the type of mem- Development work has been carried out on a number of mem-
DK brane-based gas-separation technologies with emphasis on mate-
brane material defined by the i i coefficient and the process
l rials, techniques of formation, and module designs of membranes,
properties of the feed gas defined by the ∆Pi coefficient. Higher but the most-popular configurations that have been commercial-
selectivity or SF of component i (such as CO2) over component j ized are the hollow-fiber and spiral-wound designs because of
(such as CH4) translates to higher membrane performance. For in- their high packing density (Rufford et al. 2012, page 141). Figs.
stance, typical SF for CO2/CH4 ranges from 10 to 50 and is approx- 2 and 3 show hollow-fiber and spiral-wound configurations of
imately 25 for cellulose acetate material (Kohl and Nielsen 1997, membranes. Both configurations have been used to develop nu-
page 1244), which means that CO2 will permeate selectively 25 merous membrane-module designs, and all are aimed at opti-
times faster than CH4 in a cellulose acetate material. Apart from the mizing the features of gas-flow distribution, pressure drop, and
permeability and selectivity considered for the performance of the membrane area per unit volume (of gas) (Kohl and Nielsen 1997,
membrane-permeation process, other factors usually considered in- page 1249).
clude “chemical, thermal and mechanical stability, fouling tenden- In selecting an optimum membrane system for gas purification,
cies, working lifetime, production costs and modularity” (Rufford some of the key design factors usually considered by the engineer,
et al. 2012, page 142). Depending on the component to be separated in addition to higher permeability and selectivity of the component
from the natural-gas mixture, two categories of membrane polymer to be separated to ensure higher membrane performance as outlined
materials are preferred. The “glassy” polymer materials (such as in the preceding membrane-separation mechanism, include
cellulose acetate, polyimide, perfluoro-polymer) generally separate •  Thermal and chemical resistance of the membrane material
components by use of differences in size and are a preferred option capable of withstanding the required operating conditions of
for CO2 separation from natural gas. The “rubbery” polymer mate- the feed gas
rial (such as ether-amide block copolymer) separates by use of dif- •  Ability of the membrane material to withstand plasticiza-
ferences in condensability. These materials are depicted in Fig. 1. tion effects

Glassy polymers separate by use of differences in size.

C3H8 CH4 N2 H2S CO2 H2O

Relative 4.30 3.80 3.64 3.60 3.30 2.65

Size, A
Low Permeability High Permeability
(a) Glassy Polymers

Rubbery polymers separate by difference in condensability.

N2 CH4 CO2 H2S C3H4 H2O

Relative 77 112 216 213 245 373

Condensability (˚K)
Low Permeability High Permeability
(b) Rubbery Polymers

Fig. 1—Separation mechanisms of polymeric materials.

6 Oil and Gas Facilities  •   June 2016

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Feed Residual
Nonpermeate
Permeate (slow gas)
outlet
Feed Residual Fiber
bundle
Feed spacer Permeation plug
Membrane Path
Permeate spacer
Membrane Hollow-
Feed spacer fiber
membrane
(a) Spiral-wound membrane permeation element
(Koch et al. 2011, page 4).
2, 4 or 8-in.
diameter
by 10 ft

Feed
stream
ASME
of mixed
coded
gases
carbon
steel
shell

Permeate
(fast gas)
outlet

(b) Cellulose acetate membrane plant, which uses (c) Hollow-fiber membrane-permeation
the spiral-woundconfiguration for the removal of element (Kohl and Nielsen 1997, page 1249).
CO2 from natural gas (Baker and Lokhandwala 2008, page 5).

Fig. 2—Membrane configurations that use the hollow-fiber and spiral-wound designs.

•  Cost-effectiveness of the entire process technology, with spe- The presence of the varying levels of condensable vapors and im-
cial consideration given to ease of manufacture of the mem- purities in the feed gas is shown to be capable of inducing plastici-
brane modules (Brunetti et al. 2010, page 116) zation on the membrane material (Ismail and Lorna 2003, page 38).
The proper choice of design factors will enhance the durability However, in the case of CO2/CH4 separation, the major cause
of the membrane material and the performance, which otherwise of membrane plasticization, in addition to those causes mentioned
could be affected by varying levels of condensable vapors and im- in the preceding, is CO2-induced plasticization, which may occur
purities present in the feed gas. Hence, the life of the membrane as a result of permeability increase of CO2 because of increasing
material, which according to Kohl and Nielsen (2007, page 1246) feed pressure above the plasticization pressure. Bos et al. (1999,
is typically between 3 and 7 years, forms a major design consid- page 67) defines the plasticization pressure as “the minimum pres-
eration in the design of the membrane system, especially with gas sure necessary to induce the permeability-increase” of CO2 through
separation involving CO2/CH4. the membrane. Plasticization of the membrane material reduces its
selectivity and allows the permeation of CH4 gas, thereby making
the process less economical. However, studies reveal that rubbery
polymers are less affected by membrane plasticization compared
with glassy polymers (Baker and Lokhandwala 2007, page 6).
One key consideration is the incorporation of a pretreatment-pro-
cess package into the membrane-permeation process to necessitate
the removal of the varying levels of impurities and condensable va-
pors such as water, oil mist, HCs, and entrained liquids. Other con-
siderations, as suggested by Baker and Lokhandwala (2007, page 6),
include crosslinking the membrane material or using polymeric ma-
terials, such as nonstick-type perfluoro polymers known to be highly
resistant to plasticization, as the selective layer of the membrane.

Phase Creation by Heat Transfer

The phase-creation process involves the condensation or cooling
of the feed gas at a certain pressure range to allow phase change of
the main separable components of the gas mixture. When applied
for the separation of CO2 from natural gas, it involves cooling the
dry feed gas to temperatures sufficiently below 0°C to obtain CO2
liquid and CH4 gas, as desired. This is possible considering that,
Fig. 3—Cellulose acetate membrane plant that uses the spiral- for a typical natural-gas mixture, main components with freezing
wound configuration. points include CH4 (–182°C), CO2 (–78°C), H2O (0°C), and N2

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Molar flow (MMscf/D) 180 process gas. Given the gas compositional analysis performed for a
typical gas-production facility, the major constituents of the gas mix-
Feed pressure (barg) 95 ture from a production separator are estimated as shown in Table 5.
Temperature ( C)o
37.8 From Table 5, one can see a relatively high flow rate of more
Hydrocarbon dewpoint (oC) 28
than 170 MMscf/D of gas, a high pressure of 95 barg (1,378 psig),
and a low concentration of HC ends (typically above C6+). In com-
Water dewpoint ( C) o
25.5 paring the suitability of the separation processes reviewed given
Molecular weight (g/g mol) 19.77 these process conditions, the importance of inherent selectivity or
SP as a major governing factor in the performance of the separating
Constituents (%)
mechanism has been highlighted. It is noticed from Table 2 that ab-
N2 0.32 sorption processes typically have higher inherent selectivities and
CO2 6.5 SPs for CO2 separation from natural gas as compared with others
(such as membrane permeation and adsorption), which could pos-
CH4 84.7
sibly explain why amine absorption (for instance) has been a most
C2H6 4.5 commonly applied technique for acid-gas removal from process
C3H8 1.94 gas. However, absorption processes have major cost implications
in the energy requirement for regeneration of the sorbent with re-
i-C4H10 0.48
spect to the amount of CO2 to be removed and the CO2 loading
n-C4H10 0.69 capacity of the sorbent (amine) in determining the rate of circula-
i-C5H12 0.35 tion of the sorbent. The adsorption processes, especially those that
use solid dessicants and that are regeneration-based processes (for
n-C5H12 0.3
instance, the molecular sieves), are given to be characterized by
C6H14 0.15 higher regeneration temperatures and may be suitable for removal
C7H16+ 0.07 of a small concentration of acid gas of not more than 2% because
the quantity of adsorbent (such as zeolites and activated carbon) re-
Total (%) 100.0
quired to remove greater volumes of acid gas is large (Rufford et
Molecular weight C7+ 97.57 al. 2012, page 137). However, in addition to their suitability to re-
move water (dehydration) and CO2 (acid gas) simultaneously from
Table 5—Feed-gas conditions and composition from a production
separator unit.
process gas, they have also been shown to have the potential for en-
ergy and capital-investment savings when compared with the con-
ventional absorption (amine) processes. With the foregoing, it can
(–196°C), which makes CO2 to condense out as liquid and CH4- be inferred that for the adsorption-based separation process to be
rich vapor at a pressure and temperature of approximately 870 psig the preferred option for the separation of CO2 from natural gas,
(60 barg) and 212K (–61°C). Rufford et al. (2012, page 125) re- there would be the need for a high partial pressure and low concen-
ports the application of cryogenic distillation as a most commonly tration (typically 2%) of CO2. The membrane-permeation process
used phase-change method for the removal of N2 from natural gas has been reviewed and shown to have been an accepted natural-
capable of recovering high-purity CH4 and N2. However, the pro- gas-treatment technology, especially for the removal of CO2 from
cess is particularly useful for cases of high CO2 or N2 concentra- natural gas, with significant advantages compared with the other
tions in natural gas, and may be a key consideration for applications processes reviewed. It is given to be both economic for gas streams
in remote and offshore locations because refrigerants or solvents with high feed CO2 concentration and high pressure as well as low
will not be required, as is the case of absorption (amine) and ad- concentrations of other acid gases, such as H2S. This phenomenon
sorption processes that are capable of reducing plant size. A key correlates with studies by Scholes et al. (2012, page 21) and Baker
disadvantage, however, is the considerable energy requirement for and Lokhandwala (2007, page 5), as depicted in Fig. 4, indicating
achieving cryogenic temperatures at the recommended pressures, the relative comparison of membrane and amine (absorption) in
which increases cost. There is also the possibility of equipment- their application suitability. It shows that the membrane process
channels blockage because of frozen or solid components. as more competitive in application at very low gas-flow rates (less
than 50 MMscf/D).
Steam-Reformation Process of Natural Gas Because of operational flexibility and ease of incorporation of
The steam-reformation process of natural gas is one of the chem- new membrane developments, membrane systems now in place are
ical-conversion processes of gas separation used to produce other capable of processing upwards of 250 MMscf/D of gas. Typical ex-
products from natural gas such as methanol, ammonia, and CO2. amples are the CO2-removal systems in Qadirpur and Kadawari,
It is also a well-established technology used for the production of both in Pakistan, which use membrane-permeation technology
hydrogen from natural gas. The process is summarized by the fol- (Löwenstein 2012, page 10; UNFCCC/CCNUCC 2012).
lowing (Gaudernack and Lynum 1998, page 1087): The Kadawari system is a two-stage unit capable of treating 210
MMscf/D of feed gas at 90 barg with CO2 content reduced from
CH4 + H2O → CO + 3H2 ∆H = +Ve (endothermic reaction), 12% to less than 3%. The Qadirpur, Pakistan, membrane system
is designed to process up to 500 MMscf/D of natural gas at 59
CO + H2O → CO2 + H2 ∆H = +Ve (endothermic reaction), barg from an initial 235 MMscf/D, with CO2 content reduced from
6.5% to less than 2%. The permeate (CO2-rich) gas is sold to Engro
CH4 + 2H2O → CO2 + 4H2 ∆H = +Ve (endothermic reaction). Power, operating a 220-MW gas-fired plant that uses the permeate
gas for power production.
CO2-Capture Recommendations for a Typical Given the characteristics of the gas-processing facility depicted
Gas-Production Plant in Table 5, the following can be affirmed:
Some of the process technologies for CO2 removal from process gas •  High flow rate of gas of approximately 200 MMscf/D of
have been reviewed in the preceding, and a suitable technique for feed gas.
CO2 capture from natural gas has been determined to be one that •  Low concentration of CO2 content, typically 6.5 mol%.
will exploit the differences in molecular properties or the thermo- •  High feed pressure of up to 103 barg (1,514 psig).
dynamic and transport properties of CO2 with respect to CH4 in the •  Hydrocarbon dewpoint of approximately 35°C (95°F).

8 Oil and Gas Facilities  •   June 2016

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Low concentration, mechanism by use of cryogenic temperatures as previously out-
high flow, lined, would not be suitable considering the high energy require-
favors amine
500
ment for achieving cryogenic temperatures. Phase creation is also
High concentration, shown to be a more-suitable method for removal of N2 from natural
high flow, favors gas (Rufford et al. 2012, page 125) compared with CO2, as depicted
Amine combination process in Fig. 1b, which shows the relative condensability temperatures
of some natural-gas components. Though each of the acid-gas-re-
100
Gas-Flow Rate (MMscf/D)

Combination process moval processes has its own advantages (as already highlighted),
50 membrane plus amine the membrane-permeation process had, in recent years, enjoyed
the popularity of being increasingly selected for newer projects
involving removal of CO2, especially for applications that had
Membrane
and amine large flows in remote locations. Shown in Table 6 is a summary of
10 compete characteristics for the main commercial CO2-removal techniques,
which further show the membrane-permeation process as a better-
5 Membrane suited method for the removal of CO2 for the particular case being
analyzed. The membrane technique also offers an advantage for
High concentration, wide application in EOR, in which the captured CO2 is reinjected
low flow, favors into the oil well (CO2 flooding) to enhance oil production for addi-
membrane process
tional revenue generation. This principle (discussed briefly later in
0 10 20 30 40 the paper) makes the membrane process well-suited for the usage
CO2 Concentration (mol%) of permeate (CO2-rich) gas.
<2% CO2
no treatment
The reviewed membrane-permeation process indicated CO2
needed plasticization of the membrane material as one of the major fac-
tors affecting performance, thereby requiring the addition of a pre-
Fig. 4—Comparison of membrane and amine (absorption) pro- treatment unit to facilitate the production of a clean gas feed. The
cesses for CO2 removal from natural gas (Scholes et al. 2012). gas-composition scenario discussed previously, for instance, has
minimal amounts of HCs (C6+) and little variation in the feed-gas
content compared with well-data compositions and analysis, as
shown in Table 7. The presence and concentration of HC ends and
•  Use of the permeate (CO2-rich) gas for additional generation contaminants in the feed stream affect the performance and reli-
of revenue and contribution to the CDM. ability of the membrane system and are instrumental in increasing
•  The flow station is assumed to be located in a relatively re- the hydrocarbon dewpoint temperature of the feed-gas stream,
mote location with respect to other gas-production facilities, which leads to a possible shift in the feed-gas envelope. The pre-
where existing conventional techniques (amine absorption treatment of the feed gas for the membrane system shall therefore
plant and molecular sieves) may have already been used for be considered a prerequisite to control of membrane plasticization
acid-gas treatment. and condensation of HC ends. The pretreatment configurations for
From the preceding characteristics, the use of the membrane- the feed streams into the membrane system vary from minimum (or
permeation process would be considered a more-economical op- traditional) to enhanced (or regenerative) systems, with the amount
tion suitable for the processing of natural gas. Given the need to of pretreatment dependent on the type of membrane used and the
use permeate (CO2-rich) gas and increase the profitability index gas composition to be processed. For instance, a membrane system
of the investment, an absorption mechanism (commonly the amine that uses cellulose acetate material has high sensitivity to water be-
process) would not be appropriate for the reasons already enumer- cause of higher permeability (approximatley 2.65 Armstrong com-
ated. Phase creation by heat transfer, especially the condensation pared with 3.30 Armstrong for CO2, as depicted in Fig. 1a) and

Membranes
Chemical Absorption Physical Absorption Adsorption Permeation
Process technology Amines Solvents PSA on solid Permeation
Commercial examples aMDEA, econamine Selexol, Rectisol Molecular gate Separex, Z-Top
Xebec PSA
CO2 inlet concentration ≤ 70% – ≤ 40% ≤ 90%
CO2 outlet concentration ≤ 2% 50 ppm possible 50 ppm possible ≤ 2% down to 1%
Simultaneous H2S removal Yes (depends on solvent) Yes (most solvents) Possible Possible
Typical flow rate (MMscf/D) Low to >350 100 to 400 ≤2 Low to >350
Typical operating pressure (barg) Absorber: 50 to 70 Absorber: 65 to80 10 to 35 20 to 100
Typical operating temperature (°C) Regenerator: 150 –73 to ambient 25 < 60 (materials limit)
Absorber: 30 to 60
H2O saturation in outlet residue gas H2O saturated Gas dehydrated Gas dehydrated Gas dehydrated
CO2 outlet pressure (barg) ≈ 0.13 <5 <5 <5
Footprint (plant size) High High Medium Low
Energy requirements
Comparative process costs High/medium Medium/low Medium/low Medium/low (1-stage)
(capital/operating) Medium (2+ stages)
PSA = pressure-swing adsorption.

Table 6—Summary of characteristics for the main commercial CO2-removal techniques (Rufford et al. 2012).

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Separator Sour-Gas Off-Gas Gas to
Sampling Point Well 1 Well 2 Well 3 Well 4 Well 5 Gas Outlet KO Drum Stream Pipeline
Sampling temperature (°C) 47.2 38.6 48.8 51.7 56.2 39.6 37.8 16 60.1
Sampling pressure (barg) 103 107 98 99 99.0 97 95 0.2 93
Flow rate (MMscf/D) 86.4 25.3 33.1 15.9 31.0 104.4 174.7 38 174.4

Parameters Values (mol%)

N2 0.24 0.37 0.45 0.21 0.29 0.29 0.32 0.36 0.28
CO2 7.01 4.12 10.16 5.85 4.98 6.07 6.5 28.65 1.055
H2O 0.115 0.082 0.13 0.075 0.101 – – 0.1671 0.002
C1 86.54 82.01 83.82 84.17 88.86 85.21 84.7 68.63 89.783
C2 3.98 7.8 3.51 6.14 3.71 4.53 4.5 1.843 5.58
C3 1.24 3.54 1.12 2.14 1.19 2.04 1.94 0.282 1.95
i-C4 0.28 0.61 0.24 0.49 0.25 0.46 0.48 0.028 0.39
n-C4 0.3 0.9 0.29 0.5 0.31 0.66 0.69 0.029 0.52
i-C5 0.163 0.27 0.12 0.22 0.13 0.29 0.35 0.0025 0.19
n-C5 0.09 0.21 0.09 0.13 0.1 0.25 0.3 0.0014 0.17
C6 0.01 0.06 0.04 0.05 0.04 0.13 0.15 0.002 0.05
C7+ 0.03 0.03 0.03 0.03 0.04 0.07 0.07 0.005 0.03
Molecular weight (g/g mol) 19.37 20.3 20.14 19.84 18.75 19.9 19.77 18.65 19.29
Specific gravity (air = 1) 0.669 0.701 0.695 0.685 0.647 0.687 0.682 0.684 0.666
C7 (mol%) 0.03 0.03 0.03 0.03 0.04 0.07 0.07 – 0.03
Molecular weight C7 96.67 99.67 99.67 99.67 101.5 97.57 97.57 – 96.67
Water dewpoint (°F) 78.6 75.3 82.5 78.9 82.8 77.5 77.9 – 83.4
Hydrocarbon dewpoint (°F) 84.2 80.6 85.1 84.2 85.1 83.3 82.4 – 86

Table 7—Compositional analysis of the scenario case.

may require the introduction of dehydration and gas-drying pre- •  Particle filters for dust removal
treatment equipment. •  Preheaters to provide sufficient super heat to the gas
The choice of a membrane system with similar characteristics is The preceding scheme is foreseen to be very adequate for light,
considered suitable in application to the CO2-capture requirements stable-composition gases, but its main limitations are the nonregen-
of the scenario identified. The criteria for the suitability of the mem- erable nature of the adsorbent guard bed, which presents a risk when
brane-system type and configuration shall be based on the character- there is a sudden surge in HC content (C7+) in the feed-gas stream than
istics of the membrane material, module type, and flow arrangement. that initially estimated, which is capable of saturating the carbon bed in
A simplified process-flow configuration for a CO2-removal a lesser operating period, rendering it inefficient in performance, such
system by use of the membrane-permeation technique is depicted that it can become functional only after replacement of the adsorbent.
in Figs. 5 and 6. Also, the gas preheater is the only equipment providing heating
•  Feed-gas coolers to cool the feed gas or maintain the inlet for effective control of the hydrocarbon dewpoint so as to provide
temperature at approximately 45°C to allow liquid condensate protection for the membrane unit against hydrate formation and hy-
formation for efficient separation in the sour knock-out (KO) drocarbon-liquid dropout. Hence, malfunction of the heater system
drum and coalescing filters may require the entire membrane system to be taken offline, which
•  Coalescing filters for removal of mist and liquid can be avoided by sparing the heater system.
•  Nonregenerable adsorbent guard (carbon) bed filters for trace In the situation in which higher (or fluctuating) HC levels (C7+) are
contaminants removal expected, the enhanced pretreatment system can be used. The enhanced

Superheated
fuel gas

optional
Adsorbent
Feed Sour guard Gas
Cooler Coalescing Particle
KO (carbon) bed Preheaters
Gas filter (A/B) filters (A/B)
drum (A/B) package
(01/02)

Fuel gas

Membrane
optional unit
To users (EOR,
Compression Permeate
power generation, Residue to
industrial users) facilities (CO2-rich)
Pipeline

Fig. 5—Process-flow scheme of a CO2-removal system that uses the membrane-permeation technique.

10 Oil and Gas Facilities  •   June 2016

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Superheated
Adsorbent Particle fuel gas
Filter guard (carbon) filters
coalescers bed (A /B) (A /B)
Sour gas Gas Preheaters
KO drum Package (01/02)

Feed
Gas

Fuel gas

CD Permeate
(CO2-rich)

Bypass to CO2 membrane unit

export line

Sales Gas to Residue

Pipeline
(CO2-depleted)

CO2-rich Gas
to Users

Fig. 6—Process-flow configuration of a CO2-removal system by use of the membrane-permeation technique.

pretreatment by use of a regenerative system can be used to replace the the gas of any water remaining in the feed alongside HCs and mer-
nonregenerative adsorbent guard bed (although at a higher cost). The cury that would normally be achieved by separate pieces of equip-
pretreatment system modification will be as illustrated in Fig. 7. ment, as well as being able to create room for heat recovery within
Cooling of the gas stream is first achieved in a feed-gas cooler the system.
(or a heat-recovery exchanger), and then passed through the KO Several studies have been conducted on membrane materials
drum and filter coalescers, which remove any condensates that may with respect to performances and suitability for separation of dif-
have formed. The regenerable adsorbent package receives the gas ferent gases. Among these, polymeric materials (which include rub-
(free of liquid), where the HC ends and other contaminants are sep- bery or glassy polymers) have dominated industrial usage mostly
arated. The resultant gas passes through the particle filters and is because of the advantages they offer in terms of versatility and
heated in the preheaters package before being passed to the CO2- lower cost (Adewole et al. 2013, page 48; Zhang et al. 2013, page
removal membrane units. The regenerable adsorbent guard system 84). A review of some of the polymeric materials and their perfor-
is shown to have the additional benefit of being able to dehydrate mances is given in Table 8. From the table, the polyimide materials

Parti-
KO Coalescer MemGuardTM
Feed cle
drum filter system
Gas filter
Heat
recovery
exchanger
(or feed-gas Superheated Permeate (CO2-rich) gas
fuel gas Compression
cooler)
facilities to users
Membrane
unit
Preheater

Product (Residue)
Fuel gas
gas to pipeline

Fig. 7—Process-flow scheme of membrane-permeation system by use of the enhanced pretreatment system.

June 2016  •   Oil and Gas Facilities 11

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Membrane material Cellulose Ethyl Permasep Polyetherimide PDMS Matrimid- Polystyrene Polysolfone
acetate cellulose (polyester) (fluorinated) (silicone 5218 (PSF) (PSF)
rubber)
Membrane network AN AN AN DN DN DN AN AN
CO2/CH4 selectivity(ref) 20(4) – – 33.5(3) 3.17(4) 34(6) 47.5(7) 33(5)
Reference (3) (1) (2) (3) (1) (6) (1) (5)

Permeation Rates of Gases Through the Polymer

Barrers GPU
CO2 2.3 47.5 0.31 45.8 2700 6.5 23.3 13.9
CH4 0.43 7.47 0.04 1.25 800 0.19 2.72 0.42
O2 – 11.2 – 11.5 500 – 7.47 –
N2 72.6 3.29 0.03 1.88 250 – 2.55 –
H2 20.1 49.2 1.65 – 550 – 56.0 –
H2S – – – – – – – –
C2H6 3.4 – – – – – – –
CO – – 0.03 – – – – –
He – 35.7 – – 300 – 40.8 –
PDMS = poly(dimethylsiloxane). (1) Abdel-Aal et al. (2003)
AN = asymmetric network. (2) Hwang and Kammermeyer (1975)
DN = dense network. (3) Luis et al. (2012)
GPU = gas-permeation units. (4) Zhang et al. (2013)
1 barrer = 1GPU·cm. (5) Ismail and Lorna (2003)
1 GPU = 10–6 cm3 (STP)·(cm–2)·(sec–1)·(cmHg–1). (6) Scholes et al. (2012)
1 barrer = 10–6 cm3 (STP)·cm·(cm–2)·(sec–1)·(cmHg–1). (7) Xu et al. (2001)

Table 8—Performance characteristics of some glassy-polymer materials in membrane systems for CO2/CH4 separation.

[for instance, polyetherimide (fluorinated) and Matrimid-5218], The capture (or removal) of CO2 from natural gas, however, pres-
which are mostly used in the dense membrane network (such as ents a more unique challenge compared with its capture from flare
hollow fiber), are shown to have better performance characteristics gas or other sources. While an operator of a power plant or an emitter
with respect to selectivity and permeability for CO2/CH4 separa- of flare gas can choose to ignore the harmful effects of CO2 when
tion compared with cellulose acetate. However, commercial appli- emitted to the atmosphere and adopt a do-nothing approach to its
cation of polyimide in hollow-fiber CO2-membrane systems (UBE capture, especially if (for instance) the cost of capture is more than
Industries 2016; Ruffold et al. 2012, page 141) shows to have a lim- the environmental penalty (where it exists), the producer of natural
itation of feed-gas processing of not more than 100 MMscf/D. This gas may not easily do the same. This is because the presence of CO2
is in contrast to commercial applications involving cellulose ace- (or H2S) in the natural gas reduces the economic value of the product
tate in spiral-wound CO2-membrane systems, as indicated in Table and is a potential threat to pipeline and other equipment conveying
3. The glassy polymers reviewed previously exhibit higher selec- the natural gas with CO2 content typically more than 2%. Therefore,
tivities, but mostly lower permeabilities than the rubbery polymers for the producer of natural gas (with varying contents of CO2 more
(Adewole et al. 2013, page 48). than 2%), purification of the natural gas through removal of CO2 and
The versatility of the glassy polymers, especially polyimides other impurities is seen as mandatory to meet pipeline specifications.
and cellulose acetate, allows permeability and selectivity balance This selection process has significant capital and operating
by management of plasticization effects, temperature control, and costs, which requires technical and commercial-feasibility studies
physical aging. Hence, commercial applications in natural-gas pro- to establish a selection process of the most appropriate treatment
cessing have had cellulose acetate and polyimide materials more technique to implement. This is further influenced by the avail-
widely selected for CO2/CH4 separation. There is, however, a com- ability of disposal or usage routes for the removed contaminants,
petitive edge in membrane-application selection between cellulose including reinjection of CO2 for EOR.
acetate material and the polyimides (particularly those that are flu- In this study, three criteria shall be proposed. The aim is to en-
orinated) (Scholes et al. 2012, pages 16–19). sure that an appropriate market route is developed for the captured
CO2 from a natural-gas production plant such that the gains/ben-
The Market Route to Captured CO2 efits of capture are further maximized instead of the captured CO2
The use of CCS technologies dates back to the 1970s, when the at- being flared, thereby contributing to emission of GHGs. The three
tention and popularity paid to them was mainly for economic rea- criteria are accessibility, availability, and acceptability.
sons, especially for EOR operations by oil and gas companies and
not for concerns about the GHG effects and climate change. Accessibility
One of the major concerns over the years about CCS (whether The aim of the accessibility criterion is to explore the opportunities
captured from the power plants flue gas or directly from oil and gas within an oil-and-gas-producing company framework that will be
production) has been that the cost of capture is expensive and not required to make CO2 accessible to the end user such that the cost
economically feasible, but these concerns have gradually received is both affordable and sustainable. The sustainability index will
abatements as other various concerns, such as the environment be such that the eventual price of supplying (or making CO2 ac-
(GHG emissions and global warming) and gainful uses of CO2 cessible) is reflective of the full marginal costs of production and
(EOR), come into play. These have been accelerated by intense re- distribution. Such opportunities that can be explored include trans-
search and development of CCS techniques and applications. portation and storage facilities.

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Natural gas

Biomass
Electricity generation
+ CO2 capture Coal
Cement/steel/ & petrochemical
refineries etc. plants
+ CO2 capture
CO2

Future
Mineral carbonation H2 use

Gas to
domestic
Industrial uses
supply
Geological
storage options

Natural gas
+ CO2 capture

Ocean storage
CO2 geological (Ship or pipeline)
storage

Fig. 8—CCU system (IPCC 2005).

CO2 gas in its pure state has no color or odor and is nonflam- tified, the major users include the use of high-pressure CO2 for EOR
mable. Transportation of CO2 can be achieved in a dense, solid, (which will be of significant value to oil and gas producers), pow-
gas, or liquid phase with the dense-phase being the most-efficient ering gas-fired power plants for electricity and energy generation,
state for transport. According to Doctor et al. (2005, page 184), and storage in geological formations (as a direct climate-change-
pipeline transportation of CO2 in a compressed dense phase is more mitigation method of usage). Other industrial uses for captured CO2
cost-effective compared with low-pressure gas. Pipelines have include its use as a valuable industrial gas for chemical production
been used effectively to transport large volumes of CO2 for injec- (such as urea for fertilizer production, welding equipment, fire ex-
tion. In the USA, millions of tonnes of CO2 are transported through tinguishers, and several small-scale applications).
more than 6000 km of pipeline network primarily for CO2 injec- Captured CO2 can also be used as a raw material in the produc-
tion into depleted reservoirs for EOR (Global CCS Institute 2012, tion of some fuels such as gasoline, methanol, and carbon-based
page 5; Cook 2012). Norway’s Statoil has been transporting CO2 liquid. However, this method of usage does not provide the re-
(extracted from natural gas) through a 160-km pipeline for CO2 in- quired CO2 net emissions because fossil carbon still forms the root
jection into deep geological formations (Parliamentary Office of source of energy. For instance, hydrogen and CO2 can be used as
Science and Technology 2009, page 2). feedstocks for the production of methanol or gasoline fuel, which
Existing idle oil and gas pipeline networks may be used to trans- eventually results in CO2 as a byproduct of emission.
port CO2. This is under consideration in the Niger Delta, requiring Some of the major users shall be discussed briefly to access the
the addition of CO2-compression facilities. Other alternative means availability index required to meet their needs.
of creating accessibility include the use of trucks to transport CO2 The needs of most of the industrial processes are met through
to light users such as fertilizer-producing industries. commercial production of CO2 from other sources (such as anthro-
CO2 captured from natural-gas feed by use of cellulose acetate pogenic sources). Other production sources, such as the fermen-
membrane material is expected to be relatively pure compared with tation of sugar, limekilns, and direct extraction from natural CO2
CO2 captured from power-plant emissions, reducing compression wells, were discussed extensively in Mazzoti et al. (2005).
and pipeline risks. All the preceding are in addition to CO2, which is also produced
The accessibility criterion is therefore relevant in maximizing from the treatment of natural gas, as is widely discussed in this
the economic gains through establishment of a transport frame- study. Fig. 8 illustrates some of the CO2-capture sources and the
work, such as the construction of a (or use of an existing) pipeline major uses.
network and/or storage facilities (such as CO2-storage vessels) to The ready availability of captured CO2 combined with supply in
service the localized CO2 applications around the gas-production an affordable and sustainable manner can ensure deliverability of
facility for which CO2 is to be captured. CO2 to potential users (such as industrial users) in comparison to
deployment of separate CO2-production equipment that could trans-
Availability late to more capital and operating costs for industrial consumers.
The availability criterion will seek to ensure that the produced CO2 CO2-storage (sequestration) in geological formations is one of
is made open and easily available to potential users. As already iden- the major users of captured CO2, which can be greatly exploited

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Size of CO2
Location/Operator CO2 Source Injected/Stored Type of Storage
In-Salah, Algeria (operating Gas processing (natural gas of • 1.2 Mt/a • A depleted gas reservoir located near the
since 2004)/BP approximately 5.5% CO2 • Injection cost is gas-processing plant (1.8 km depth)
approximately • No leakage has been reported so far
USD 6/t CO2
Barrow Island, Natural-gas processing (14% 3.3 Mt/a (start date Reinjection of the extracted CO2 from the
Australia/Chevron- CO2) of 2014) CO2-rich gas field into a sandstone
Exxonmobil-Shell-etc J.V. reservoir (2.5 km) below Barrow Island
Abu Dhabi/Masdar and BP Precombustion CO2 capture 0.8 Mt/a* For EOR; CO2 feed stream from the steel
technology from a 400-MW plant to be compressed, dehydrated and
power plant pumped though 50 km of pipeline and
injected in an onshore field for EOR
Alberta, Canada, near Gas processing (5–8% CO2, 3– 0.067 Mt/a For EOR in Zama Keg River oil field at 5 km
Zama City/PCOR, 13% H2S). Permeate output is depth
Apache Canada Ltd. 70% CO2 and 30% H2S
Mt/a = million tonnes per year.
*Start date of 2011 delayed because of issues with negotiating prices for the CO 2 and electricity produced at the H2 plant

Table 9—CO2-injection/-storage projects (MIT 2013).

as an economic and CO2-mitigation option. This requires that cap- forms approximately 0.5% of the total CO2 emissions (put at 24
tured CO2 be readily available. Storage options for CO2 use well- Gt/a of CO2). Globally, use of captured CO2 in industrial processes
developed technologies that have been applied in the oil and gas could only have a minimal effect on reduction of net CO2 emis-
industry and that have bright prospects for the future. A number of sions. There exist urea-production industries in Nigeria that use
studies have discussed in depth the storage opportunities for cap- great amounts of CO2, such as Notore Chemical Industries Limited
tured CO2, such as the Intergovernmental Panel on Climate Change (formerly National Fertilizers Company of Nigeria, NAFCON), lo-
(IPCC) special reports on CO2. It has been proved to a larger extent cated at Onne near Port Harcourt Rivers State. Notore’s production
that injection of CO2 into deep geological formations at selected capacity has been estimated at 1000 t/d of ammonia and 1500 t/d of
sites or wells is a long-term storage technique in which almost 99% urea, with an estimated capability of producing up to 300 000 t/a of
or more of the injected CO2 is retained for up to 1,000 years or ammonia (NPK) and 500 000 t/a of urea (Notore 2012). According
more (Benson et al. 2005, page 197). Among the oil-recovery tech- to the International Fertilizer Industry Association (IFA 2009), for
niques used most by oil and gas companies, CO2 miscible flooding every 1.0 tonne of urea produced, approximately 1.0 tonne of CO2
is shown to be the fastest growing EOR technique, especially in the is required for the production process. Urea is produced by the syn-
USA. With an average recovery factor estimated at 35% from CO2 thesis of ammonia through reaction of low-cost natural gas and
EOR (Jikich 2012, page 28), approximately 310,000 BOPD oil pro- CO2 recovered from the off-gas of the ammonia-synthesizing pro-
duction, representing up to 5% of total USA oil, has been reported cess. For instance, in the scenario analyzed, feed gas of approxi-
(Koottungal 2012, page 46). mately 200 MMscf/D is capable of producing approximately 160
Capture of CO2 from natural gas for EOR is viewed as having MMscf/D of residue gas and 38 MMscf/D of permeate (CO2-rich
the benefit of sequestering CO2 in the oil-and-gas-producing for- gas). This is an equivalent of approximately 29 800 t/d of CO2 (ap-
mations, as well as being seen as a critical component of future proximately 10.8 Mt/a of CO2). Other fertilizer-production plants
GHG-management programs. In earnest, some of the major oil- being planned in Nigeria include Dangote Petrochemical and Fer-
and-gas-producing companies in Nigeria have applied oil-recovery tilizer Plant Olokola, Indorama Fertilizer Plant Eleme, Brass Fer-
techniques successfully for their wells, such as direct natural-gas tilizer Company Brass, and Nagarjuna Fertilizer Plant Ogidigben
reinjection and water reinjection. However, the availability of the (Eboh 2013). The existence of all these plants creates a potential
captured CO2 is expected to offer a better alternative to EOR in sink for the captured CO2 for which the technique is expected to
these companies, first as an economic resource and second as a produce the desired effect on climate change.
contribution to climate-change-mitigation measures. A well-known
example of a CO2 EOR operation is found in the Sleipner field op- Acceptability
erated by Statoil in Norway, which captures CO2 from natural gas The aim of the acceptability criterion is to present the captured CO2
(of approximatley 9.5% CO2) and injects approximately 1.0 mil- as a clean, efficient, affordable, and reliable form of energy among
lion t of CO2 annually through a 3-km-long well and stores it in a the users and to place it in a comparative range with other clean-
porous and permeable reservoir rock called the Utsira sand (British energy services, such as renewable-energy technologies. It will seek
Geological Survey 2015). A survey of some other CO2-injection/- to promote its transfer to users. While it should be acknowledged
storage projects, as published in the MIT map of projects (MIT that the technological process leading to capture of CO2 from its
2013), is given in Table 9. source will always be more expensive than just emitting or venting
The recovered CO2 is injected into the desired depleted reser- to the atmosphere, its attractiveness among producers has increased
voir, which pushes and displaces the water by introducing kinetic considering the cost per tonne of CO2 to be paid as a penalty in
energy to the waterdrive, which in turn increases the bottomhole emission and the awareness of economic gains. However, current
pressure thereby increasing the productivity index and mobility in environmental regulations in Nigeria do not include a penalty cost
oil or gas around the reservoir, with an increase in vertical sweep for CO2 emissions, but for gas flaring. While venting the captured
efficiency for the well flow. The final result is an increase in oil or CO2 from natural-gas purification to the flare can be regarded as
gas production from the resultant well that has stopped flowing be- less expensive than additional investment in compression, storage,
cause of high water cut. This phenomenon is illustrated in Fig. 9. and/or transport to the end user, the CO2-separation process is man-
For the industrial users of CO2, it has been estimated that ap- datory to achieve pipeline-gas specifications in which substantial
proximately 115 Mt/a of CO2 is used in industries, with urea pro- investment has already been made. Therefore, the deployment of
duction (for fertilizers) accounting for more than 60% of that total additional compression, transportation, and storage facilities could
(Mazzoti et al. 2005, page 33). This total industrial use, however, make it even more economical at a commercial level. Among the

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SPE_OGF_178316_160002.indd 14 26/03/16 3:11 PM

Viscosity of oil is reduced, providing more-efficient miscible displacement.
Produced Fluids (Oil, Gas and Water)
Separation and Storage Facilities
CO2

Injection Well Water- Production Well

Injection
Pump

Drive Additional
CO2 Water CO2 Miscible Oil Oil
Water Zone Bank Recovery

Fig. 9—CO2-injection cycle for EOR (Ekmann 2011).

different CO2-capture processes, capture from natural-gas pro- f­avorable combination of circumstances to achieve successful
cessing has been shown to be the least expensive—from USD 5 implementation; the weaknesses to spotlight the flaws or weak
and 25/t of CO2 compared with USD 15 to 75/t of CO2 captured points; and the threats to look into the menaces or sources of dan-
from power plant or USD 25 to 115/t of CO2 captured from other ger to implementation.
industrial sources (Thambimuthu et al. 2005). Estimated costs are Strengths. The following are considered as strengths, but are
shown in Table 10. not all-inclusive of the implementation of CO2 capture, especially
The acceptability criterion in the context of oil- and gas-produc- within Nigeria’s framework of emission mitigation and the gains
tion operations will therefore seek to make the comparative cost of within the confines of oil-and-gas-producing companies:
captured CO2 acceptable and affordable to its end usage. For in- •  Ability to produce natural gas to pipeline specifications.
stance, the use of captured CO2 for EOR activities, as already dis- •  Commercializing the captured CO2, instead of flaring directly,
cussed, is viewed as a very profitable business option of oil recovery will result in a net reduction of carbon emissions, thereby in-
compared with others, such as water or gas reinjection, or as a more- creasing the sustainability index of the oil-and-gas-producing
profitable option for a fertilizer company to purchase than to produce companies. This shall fulfill the investment by oil companies
within its own industrial sources, as clearly depicted in Table 10. in strategic innovation in the enhancement of renewable en-
ergy and the development of innovative methods for envi-
Strengths, Weaknesses, Opportunities, and Threats (SWOT) ronmental protection as part of the distinctive elements to a
Analysis. SWOT is a criterion used to structure and analyze the sustainable approach.
strengths, weaknesses, opportunities, and threats of a system. It •  Successful application of CO2 capture in “CO2 contented”
shall be used in this study as a qualitative tool in the valuation natural-gas-production plants is capable of creating a compet-
of the CO2 capture for environmental and economic gains ob- itive edge for oil and gas companies toward innovative solu-
jective. The strengths shall look into the durability and viability tions to CO2-capture applications, which is fast becoming a
of implementation, the opportunities to unveil the chances and global phenomenon on climate-change issues.

CCS Process Cost Range

Capture from gas processing (or ammonia production) USD 5–25/t of CO2 net captured
Capture from a power plant USD 15–75/t of CO2 net captured
Capture from other industrial sources USD 25–115/t of CO2 net captured
Transportation USD 1–8/t of CO2 transported
Geological storage USD 0.5–8/t of CO2 injected
Geological monitoring USD 0.1–0.3/t of CO2 injected
Ocean storage USD 50–30/t of CO2 injected
Mineral carbonation USD 50–100/t of CO2 net
mineralization
Table 10—CCS costs (IPCC 2005).

June 2016  •   Oil and Gas Facilities 15

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Natural-gas production (feed gas) 200 MMscf/D
Sales (residue) gas production 160 MMscf/D
Fraction of CO2 (6.5%) in feed gas at inlet of sour-gas 13.0 MMscf/D (33 150 t/d of CO2)
KO drum (before capture)
Fraction of CO2 in residue gas (after capture) 1.688 MMscf/D (3344 t/d of CO2)
Captured CO2 (29% of off-gas) 11.3 MMscf/D (29 810 t/d of CO2)
CO2 savings (prevented from entry into atmosphere) 29 800 t/d of CO2 (10.8 Mt/a of CO2)
Table 11—CO2 savings.

•  The use of the existing legal framework/permit procedure in •  Placement of CO2-capture plants and storage sites (EOR)
Nigeria for the transport of captured CO2 to its users shall close to each other will positively affect the reduction in cost
serve as a major strength. and environmental impact.
•  The transport of CO2 gas is an established technology. This •  Experience from similar CO2-capture projects, such as in Eni
implies lesser considerations for fresh research in the field of Pakistan, Sleipner, and EOR operations, provides huge oppor-
CO2 transport and leads to faster application. tunities for faster implementation and deployment.
•  Efficient transport of large volumes of CO2 in pipeline, ship, •  New and growing market opportunities are available, espe-
or truck, as well as storage of large volumes in a vessel as a cially in the areas of fertilizer production, agriculture (bio-
result of high compressibility ratio and low density compared mass), and automobiles (hydrogen economy).
with similar gases such as natural gas. •  It will offer the Nigerian oil and gas industry flexibility in
•  The use of CO2 for EOR has the additional and added eco- the way flare down targets are met, thereby contributing to
nomic benefit of incremental oil production, which is capable meeting the climate-change targets of the CDM of which Ni-
of offsetting the costs of CO2 capture, transport, and injection. geria is part.
Oil recovery is argued to be capable of being increased by as •  Presents a large opportunity for companies to play a direct
much as 10 to 15% through injection of captured CO2 in EOR role in reducing emissions by applying industry-specific
(IEA Greenhouse Gas R&D Programme 2001, page 14), as is knowledge and tools.
already being implemented on a commercial scale in the USA, •  CO2 injection can replace the much-needed natural gas that
Canada, Turkey, and Trinidad and Tobago. is being injected for oil recovery in many of the Nigerian on-
•  The usage of existing data available from similar capture tech- shore reservoirs.
niques, hydrocarbon surveys, and operation of field for CO2 Threats.
use in enhanced oil and gas recovery and abandoned hydro- •  There exists currently a very low public awareness, which re-
carbon reservoirs. quires education and outreach to all stakeholders.
•  EOR is a well-known and established technology. •  There is an absence of a regulatory framework (legal, permit-
•  CO2 is not a poisonous or harmful gas. ting, licensing) for certain aspects of CO2 capture, storage,
Weaknesses. Some of the weaknesses of the CO2 objective include and transportation.
•  High energy demand associated with the separation of CO2
from natural gas through the tendency to achieve a higher pu-
CO2 Savings and Contribution to CDM. As demostrated in
rity of the CO2 gas, usually leading to additional equipment,
the subsection Acceptability, the use of the membrane process at
thereby increasing overall energy demand.
the scenario presented is capable of producing approximately 38
•  Captured CO2 can have other contaminant gases or impurities
MMscf/D of off-gas (CO2-rich gas) on the basis of 160 MMscf/D
that are capable of affecting the CO2 compressibility into vol-
of residue natural gas to be exported as sales gas. The composi-
umes required for storage or transportation, thereby reducing
tional analysis of the scenario case is given in Table 7. Hence, the
capacities in which it can be stored or moved.
anticipated CO2 savings and contribution to CDM through use of
•  Additional compression facilities are required to transport
the membrane process is given in Table 11. By use of the AGA8-
captured CO2 through the pipeline to the intended destina-
92DC detailed characterization equation for determining the mass
tions, which requires energy.
density of natural gas, the mass density of the feed gas at the inlet of
•  Public acceptance and/or knowledge of CO2 gas as a viable
the sour-gas KO drum at an inlet temperature of 37.8°C and pres-
gas for alternative uses, such as fuel for power supply and
sure of 95 barg is estimated to be 90.111 kg/m3.
even as an injection gas, is still very low.
•  CO2 gas is toxic to the cardiovascular system and upper respi-
ratory tract at concentrations greater than 3%. Conclusion
Opportunities. The following are some opportunities available From this case study, it can be inferred that the implementation of
to the CO2-capture and -commercialization implementation: CCU is worth embarking on by oil- and gas-production companies
•  Use of existing transport infrastructure, such as flowlines to in Nigeria. Given the high regard to sustainability issues, the im-
wells and pipelines that are no longer used optimally for trans- plementation of CO2-capture projects is viewed as having several
port and/or injection, capable of dramatically reducing the costs gains and economic benefits. Some of these gains have been high-
to a larger percentage and maximizing the economic gains. lighted in the SWOT analysis and include company image, CO2
•  Use of existing pipeline routes and rights of way to make the EOR, industrial supply of CO2, and emission control. If there is
permit procedure easier and faster. any topic in modern times that is much discussed and of concern
•  Improve the global industry image by creating opportunities to governments, analysts, professionals, and corporate planners, it
for oil and gas companies to be seen and projected as “green.” is the issue of global warming, climate change, emission of GHGs,
•  No serious health and safety risks are associated with CO2 and the depletion of the ozone layer. This has led to evolving
processing—capture, storage, or transport. For instance, pipe- methods of transformation of the world economy from a hydro-
line leakage of CO2 and its products of degradation are not le- carbon (fossil) based economy to one based on energy forms that
gally classified as toxic substances. CO2 is nonhazardous on are sustainable, such as the deployment of renewable-energy tech-
inhalation, is a nonirritant, and does not permeate the skin. nologies and use of advanced clean technologies on conventional

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ments in Membrane-Based Technologies for CO2 Capture. Progress Emmanuel O. Agiaye is a mechanical/piping engineer at NAOC. He has
in Energy and Combustion Science 38 (3): 419–448. http://dx.doi. been with the company for more than 8 years, having previously worked
org/10.1016/j.pecs.2012.01.004. for engineering companies in electric-power generation and in building
Mazzoti, M., Abanades, J. C., Allam, R. et al. 2005. Mineral Carbonation construction for more than 3 years, with experience in upstream-facil-
and Industrial Uses of Carbon Dioxide. In IPCC Special Report on ities engineering, projects management, and project controls. Agiaye’s
Carbon Dioxide Capture and Storage, prepared by Working Group current interests include facilities optimization, design strategy, asset
III of the Intergovernmental Panel on Climate Change, eds. B. Eli- evaluation, project execution, renewable-energy technologies, and
asson and R. T. M. Sutamihardja, Chapter 7, 319–337. New York CO2-emissions reduction. He holds a BEng degree in mechanical en-
City: Cambridge University Press. gineering from the University of Benin, Nigeria, and an MSc degree in
MIT. 2013. Carbon Dioxide Capture and Storage Projects. http://sequestra- energy from Heriot-Watt University. Agiaye is a member of SPE, the Ni-
tion.mit.edu/tools/projects/map_projects.html (22 December 2015). gerian Society of Engineers, the Nigerian Institution of Mechanical En-
Notore. 2012. Notore Set To Increase Fertiliser Production Through Joint gineers, and the UK Institute of Mechanical Engineers. He is also a
Development With Mitsubishi Corporation. Editorial, Notore Chem- registered professional engineer of the Council for the Regulation of En-
icals Industries, Lagos, Nigeria (24 April 2012). http://www.notore. gineering in Nigeria and an incorporated engineer in the UK.
com/index.php/article/read/42.
Olajire, A. A. 2010. CO2 Capture and Separation Technologies for End-
of-Pipe Applications—A Review. Energy 35 (6): 2610–2628. http:// Mohammed Othman is a senior completion, workover, and well-services
dx.doi.org/10.1016/j.energy.2010.02.030. supervisor with NAOC, where he has worked for more than 18 years.
Parliamentary Office of Science and Technology. 2009. CO2 Capture, His research interest is in converting unwanted natural resources into
Transport and Storage. Postnote Number 335, Parliamentary Office proper usage for economic gain. Othman holds a BTech degree in in-
of Science and Technology, London (June 2009) www.parliament.uk/ dustrial chemistry from the Abubakar  Tafawa  Balewa  University,  Ni-
documents/post/postpn335.pdf. geria. He is an SPE member, having served in different capacities as a
Rackley, S. 2010. Carbon Capture and Storage. Burlington, Massachusetts: board member and conference-committee chair, and having received
Butterworth-Heineman. numerous service awards from the SPE Nigerian Council. Othman
Rufford, T. E., Smart, S., Watson, G. C. Y. et al. 2012. The Removal of CO2 is currently an adviser for the planning of the upcoming 2016 SPE Ni-
and N2 From Natural Gas: A Review of Conventional and Emerging geria Annual International Conference and Exhibition in Lagos.

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