CO2 Removal

Membranes

for Gas Processing

Matt Henley
KCC ProcessEquipment, Inc.
Houston, Texas

Abstract

CO2 reduction is a significant and growing part of gas processing due to equipment and pipline
corrosion. Membrane basedCO2 removal systemsprovide a cost effective, low maintenanceapproach
for removing CO2 from gas streams. Operational experiencein the gas field combined with thousands
of units in refineries and air processing has shown what parameters are important in design and
operation of units that have both long life and low maintenance.

CO2 Removal Membranes for Gas Processing

Introduction
Natural gas as it flows from a well typically requires a number of treatment stepsbefore it can be put
into a pipeline for sale. The primary treatmentsinclude dehydration and liquids separationto meet the
specification required for the pipeline. Sour components such as Carbon Dioxide and Hydrogen
Sulfide which cause co1Tosionof pipelines and equipment may also require removal. CO2 removal
membranesare one method for meeting thesespecifications.
Amine type systemshave been traditionally used to remove sour componentsand work well for this
purpose. However, these systemstypically have high capital and operational costs. They also can
have high maintenanceand require a close watch by operations.
There are many caseswhere a large amine systemis not required, for example: There are thousandsof
gas plants that have little or no Hydrogen Sulfide but do have enough CO2to cause concern for the
pipline companies. This has become a greater concern as pipeline owners inspect their piplines and
di~over the extent of damagethat CO2has calLc;ed.
Another areais the bulk removal of CO2from a gas streamwhere the amount of CO2would otherwise
require an extremely large amine unit.
In either case,CO2removal membranescan provide a low maintenanceoption for the removal of CO2.
However, from operational experencein air separation,refinery and gas production areas,KCC and
Air Products have identified a number of operational issuesthat must be addressedin order to design
and operatea low maintenanceand long life membranesystem.

Membrane

Theory

Most membrane systems are semipermeablepolymers such as cellulose acetate, poly sulfone and
polyimide and polyamides. Air Products PRISM Membranes are constructed of a proprietary
polyimidc formulation which is tolcrant to liquid water and hydrocarbons and allows opcration at
elevatedtemperaturesto avoid more elaborateand costly pretreatment Membranesallow transport of
different molecules through the membrane based on the rate of solubilization into the membrane
material and diffusion through it [I]. Each molecule dissolves and diffuses through a membrane at
different rates that allow separation of the molecules. Partial pressure of that speciesprovides the
driving force for this transport.
As the gas mixture flows along the surfaceof the membrane,the componentsthat have a faster rate of
permeation pass tlu"ough the membrane leaving belJiIld tIre components with a slower rate of
penneation. This phenomenoncan be expressedas

p
Qi=-

(p i2-Pil)A
Q;
p I
p

(I)

= Molar Penneate Flow of Component i

= Pe11lleability of Component i
= Membrane Thickness
= Partial Pressure of i on Low Pressure Side

Pil

= Partial Pressure of i on High Pressure Side

Pi2
A

= Membrane Area

This equation has to be evaluated along the length of the membrane as the partial pressme of the
component will change along that surface as more is transported through the membrane.
A number of things can be seen when evaluating the above equation. First, since the driving force of
the transport is partial pressures, the greater the difference in partial pressme between the low and high
pressure of the membrane, the greater the permeation rate of that component through the membrane.
Sccond, thc gas flux through thc mcmbranc incrcascs as thc thickncss dccrcascs. Lastly, as thc
required amount of CO2 removal goes up, smface area needs to be increased.
Selectivity of the membrane is another important factor. This is the difference in the permeability rates
of different components in the gas mixtw-es. The larger this difference, the greater the efficiency of the
separation and the lower the loss of salable gases are. Relative permeabilities of a number of
components for Polyimide membranes are shown in Figme I.

Fast

Slow Gases~

Gases

Figure 1 Relative Permeability of Selected Gasesthrough Gas Membranes

In the caseof removal of CO2 from natural gas, one of the important considerationsis the amount of
CO2removed verses the amount of methanerecovered. This is typically an inverse relationship, ie, as
the amount of CO2removed goesup, the amount of methanerecovered goes down as shown in Figure
2. To compensatefor this, many units are broken into two stage systems wherein the permeate is
recompressedand separatedagain to improve the hydrocarbon recovery of the system. The different
systemconfigurations are shown in the next section.
100

90
~
0

~
...
GI
>
O
U
GI

Q:

80

C
0
.c
...
~
U
O
...
j,

70

601
0

10

20

30

40
CO2

-5%

CO2 in Feed --15%

50

60

Removal

70

CO2 in Feed --30%

Figure 2: CO2 Removed verses Methane Recovered

00

00

CO2 in Feed

100

Membrane

System

Design

Design of a practical membrane system begins witil tile membrane unit itself.
should be included:
.High

surface area to membrane volume

.Counter-current
.Resistant

Several design criteria

flow to keep tile greatest partial pressure difference across tile membranes

to harsh conditions of Gas Processing

With a diameter of about 0.5 mm, Hollow fiber membranestypically have a surface area of over 5000
m2 per cubic meter. This is the most compact type membranecurrently in use. An example of hollow
fiber membranesis shown in Figure 3.

Figure 3: Hollow fiber membranes

Air Productsproduceswhat are called asymmetricmembranes. Theseare membranesthat have several

layers that have different purposes. As shov.1lin Figure 4, these membraneshave a porous layer that
serves as a support structure to add strength and resistanceto high pressures. This is the thickest
portion of the membrane. However, the pores are relatively large and therefore it does not hinder the
mass flux of the gas. The second layer of the membrane is the actual membrane skin that does the
separationof the components.This layer is kept as thin as possible. The outside layer of the membrane
is a defect repairing layer.This layer prevents gas bypassof any gas through defects in the membrane
skin and allows the skin to be fabricatedthinner.

Figure 4 Cross Section of Hollow Fiber Membrane

The membranesare packagedinto modules in a variety of sizeschosento fit the application. As shown
in Figure 5, eachmodule is designedto allow for counter current flow of the gases. This allows for the
maximum relative partial pressuresof the gassesto be removed which improves flow through the
membrane. The gas is evenly distributed through the membrane fibers by a gas distributor which is
built into the membranemodule.

Non-Permeate
Product

c-:;

Membrane Filter Bundle

Feed
Gas

~I

:Feed
,

,Gas
,
,
I
I

i.,J

Permeate
Product

Figure 5 Hollow Fiber Separator Module

Figure 6 shows a typical flow schemefor a singe stagemembranesystemwhere the gas is coalescedto
remove any liquid droplets and then heated to keep the gas away from its hydrocarbon dewpont. It
then goes through the membranesto remove the CO2. The high CO2 offgas typically still has enough
calorific value to be used as fuel for the gas heateror other service in the plant. The advantageof this
flow schemeis its simplicity and low maintenancerequirements.

Non-Permeate
Product

Permeate
Product

Entrained
Liquids
Figure 6 Single Stage Membrane

System Scheme

A two stage membrane system can be used to achieve high hydrocarbon recovery rates while still
removing large amountsof CO2. The off gas from the secondstageis typically up to 60% CO2but will
boost hydrocarbonrecovery rates close to 99%.

Figure 7 Two Stage Membrane

System Scheme

Operational

Experience

The use of membranes in the gas industry has been around for ahnost 20 years. However, there is a
growing amount of operational experience that shows which issues are unique to this technology that
should be taken into consideration when considering about their use.

Contamination

and Pretreatment

Requirements

The largest area of concern in designing a reliable membrane system is the area of contamination.
Contamination is the causeof most membranefailures and lack of performance Becauseof this, it is
very important to carefully considerthe required pretreatmentrequirementsof each system.
There are two distinct types of results from membranecontamination. If the membraneis coatedwith
a depositedlayer of hydrocarbon or oil that stayson its surface,the efficiency of the membranewill be
reduced. This is becausethe hydrocarbon forms a layer on top of the membranethat the gas has to
traverse before it can start the processof moving through the membrane. Very heavy contamination
can effectively block off a portion of the active surfaceareaof the membrane.
Liquid hydrocarbon contamination can be effectively eliminated with a combination of a high
performancecoalescerand a heater. The coalescerremoves entrained liquid in the gas and the heater
vaporizes any that might be left. In addition, the heater servesanother purpose. The gas entering a
membrane stagewould otherwise be close to saturation. As the COz is removed, the composition of
the gas changes. In cases such as the second stage of a two stage system or bulk COz removal, the
composition change may be enough to causehydrocarbonsto condenseon the membraneitself. The
heatermovesthe gas away from its saturationpoint and keeps theseliquids from forming.

A tubesheet separatesthe high pressure side of the membrane from the low pressure side. The
tubesheetis cast on one end of the fiber bundle using a specialized epoxy formulation. The tubesheet
is very strong and can withstand differential pressureswell in excess of the maximum differential
pressure across the membrane. However, certain contaminants can adsorb into the membrane and
epoxy materials causing them to swell. Methanol is one such swelling agent that is sometimes
encounteredin natural gas streams due to upstream injection for prevention of hydrate formation.
Liquid methanol can causeswelling to an extent that tubesheetfailure can occur.

Another issue in the use of membranesand the pretreatmentrequired is the membrane'scompatability

with water and water vapor. Different membranesmaterials have varying abilities to tolerate water in
different forms. Before committing to a particular type of membrane, determine what the effects of
water are on the membranesparticular material and what pretreatment that may entail. Air Products
mcmbranc matcrial was in part choscn for its cxccllcnt watcr handling abilitics. Whilc cfficicncy of
any wetted portions of the membrane will be temporarily reduced, the membranewill return to full
capacity as it dries. Water vapor travels through the membrane at a rate faster than that of even CO2
allowing the membranesto also be used in gas dehydration applications. This provides the added
benefit of dehydrating the gas while removing CO2. In addition, membranescan be provided for the
purposeof dehydration.
In two stageunits where compressionbetween stagesis used, particular care should be taken with the
choice of cylinder lublicant. A low vapor pressuresynthetic lubricant should be chosenand engine oils
that contain additive packagesthat may causeemulsions should be avoided. An oil with a high vapor
pressuremay cany over into the membranevia the vapor phaseand be depositedonto the membrane.
We have seencaseswhere the additives in compressoroil have formed stable emulsions that clogged
the coalescerand causedfrequent changoutof filter elements. This issue can be resolved by changing
the lubricant used for the compressor.

Conclusions
Gas Membranes provide a cost effective way to reduce CO2 in natural gas. They can do this while
having low maintenancerequirementsthat are suitable for unmanned facilities and remote fields. As
long as attention is paid up front to pretreatmentrequirements,theseunits have both a long life and low
maintenance.

Acknowledgments
Bill Pope, Air Products for help with the technical details of membranes
John Branch for producing the diagrams

References Cited
1

MacLean D.L., Stookey D.l., and Metzger T.R., "Fundamentals of Gas Pemleation",
Hydrocarbon Processing,August 1983.