CHAPTER THIRTEEN

Gas–Gas Separation
by Membranes
Thomas Harlacher and Matthias Wessling
Aachener Verfahrenstechnik, Chemical Process Engineering, RWTH Aachen University, Aachen, Germany

Contents
Nomenclature 558
Indices 558
1. Introduction 559
2. Membrane Modules for Gas Separation 560
2.1 Module Construction 560
2.1.1 Hollow Fibre Modules 560
2.1.2 Spiral Wound Modules 561
2.1.3 Plate and Frame Modules 562
2.2 Membrane Material 563
2.3 Mass Transfer through Polymer Membranes 564
2.3.1 Influence of Gas Phase Pressure 566
2.3.2 Influence of Gas Phase Temperature 566
2.3.3 Concentration Polarization Effects 567
2.4 Concepts of Flow Control 567
3. Process Design 568
3.1 Pressure Ratio and Stage Cut 568
3.2 Driving Force Generation 569
3.3 Feed Pretreatment 570
3.4 Module Interconnection 571
3.5 Economic Parameters for Process Design 573
4. Applications of Gas Permeation Processes 574
4.1 Oxygen/Nitrogen Separation 574
4.1.1 Nitrogen Enrichment 574
4.1.2 Oxygen Enrichment 578
4.2 Biogas Treatment 580
References 584

Ó 2015 Elsevier Ltd.

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Progress in Filtration and Separation
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558 Thomas Harlacher and Matthias Wessling

GLOSSARY
Selectivity Characteristics of a membrane to differentiate among various components.
Stage cut Parameter which defines the fraction of the feed stream which permeates through
the membrane.
Pressure ratio Dimensionless parameter which describes the ratio of the total feed pressure
to the total permeate pressure.
Retentate The part of the feed stream, which is rejected by the membrane, and leaves the
module without passing the membrane on the high pressure side.
Permeate The part of the feed stream, which passes the membrane and leaves the module
on the low pressure side.
Recovery The ratio of the amount of a product, enriched in a useful product stream, to the
total amount of this component in the feed stream.
Permeability Parameter for the trans-membrane flux per unit driving force per unit mem-
brane thickness.
Permeance The trans-membrane flux per unit driving force.

NOMENCLATURE

D Diffusivity m2/s
Ea Activation energy J/kmol
n_ 00 Specific mole flow kmol/m2/s
P Permeability Barrer
S Solubility kmol/m3/bar
T Temperature K
x Mole fraction e
y Mole fraction e
d Membrane thickness mm
DHL Heat of solution J/kmol
P Permeance GPU
F Pressure ratio e
Q Stage cut e

INDICES

i, j, k Component i, j, k
0 Standard conditions
F Feed
P Permeate
Gas–Gas Separation by Membranes 559

1. INTRODUCTION
In recent decades, next to conventional technologies, such as physical
adsorption, chemical or physical absorption and cryogenic fractioning, and
membrane processes have become an industrial alternative for gas separation.
For separation tasks with moderate flow rates and moderate purities, gas
permeation is the state-of-the-art technology in many cases. Compared to
conventional techniques, gas permeation processes are characterized by a
simple, flexible, and compact design. Table 1 shows a detailed collection
of advantages and drawbacks of gas permeation processes.
This chapter gives a condensed overview of the basics of gas permeation
processes. Both the design and operation of membrane modules as well as
approaches for process design are described. Examples of industrial mem-
brane gas separation processes illustrate the application. Detailed information

Table 1 Advantages and drawbacks of membrane gas separation processes in

comparison to conventional techniques (Favre 2011)
Advantages Drawbacks

D Operating flexibility causing - No economies of scale due to

membranes to tolerate modular design, penalty for
fluctuating feed conditions large-scale applications
without losing quality - Pretreatment can be heavy, and,
D Low energy requirement and/ in some cases, as expensive as the
or high energy efficiency costs of the modules
leading to low operating costs - Sensitivity to chemical
D Absence of chemicals, make-up compounds
and solvent emissions - Requires a high-quality energy
D Easy start-up and shut-down source (electrical energy for
D No moving parts and minimal compression), whereas
maintenance and operator absorption processes can use
attention low-quality energy such as heat
D Modular design, easy to scale (often heat excess in chemical
up when increased capacity is processes)
required
D Small footprint and compact
system (advantage for offshore
applications)
D Minimal utilities required, easy
to control, simple sensors
required (pressure,
temperature, and flow rate)
560 Thomas Harlacher and Matthias Wessling

about gas separation processes can be found in Baker (2004), Drioli (2010,
2011), Favre (2011), Melin 2007), Merkel 2010), Mulder (1996), Nunes
(2006), Ohlrogge (2006), and Yampolskii (2010). Yampolskii reports partic-
ularly on membrane materials for gas permeation Yampolskii (2006).

2. MEMBRANE MODULES FOR GAS SEPARATION

2.1 Module Construction
To use membranes in technical processes, the membrane material has
to be assembled into a manageable, custom-designed membrane configura-
tion. This membrane configuration is called the membrane module which is
the main building block of a membrane plant. In a membrane module, the
feed stream is separated into a concentrate stream (retentate) rejected by the
membrane and a filtrate stream (permeate) passing through the membrane.
Membrane modules for gas separation applications are generally designed
as 3-end modules with one inlet-stream and two outlet streams; 4-end
modules are used for applications with an additional sweep stream in the
permeate.
For gas separation module development, the following requirements
have to be taken into account:
• uniform fluid flow without dead zones
• mechanical, chemical, and thermal stability
• high packing density (ratio of membrane area and module volume)
• cost-efficient production
• low pressure losses.
Based on these requirements and on the availability of the membranes in
terms of flat sheet and hollow fibre membranes, three types of membrane
modules are used for gas separation processes. Hollow fibre membranes
are attached to hollow fibre modules and flat sheet membranes to spiral
wound or envelope type modules. Table 2 compares the module properties
of these three module types. Table 3 gives information about industrial gas
separation membrane suppliers.

2.1.1 Hollow Fibre Modules

Hollow fibres with an outer diameter between 80 and 500 mm are usually
arranged in parallel in a pressure pipe. Some module suppliers apply a
chaotic fibre arrangement to introduce turbulent flow on the shell side
of the module. Hence, the boundary layers on the shell side are reduced.
Gas–Gas Separation by Membranes 561

Table 2 Key characteristics of the three major types of modules used for industrial
applications of gas separation processes (Drioli 2010)
Hollow fibre Spiral wound Envelope
2 3
Packing density (m /m ) 500e10,000 200e1000 30e500
Approximate are per module (m2) 300e600 20e40 5e20
Pretreatment requirement High Fair Minimal
Resistance to fouling Poor Fair Good
Pressure drop High Fair Low
Flow distribution Good Moderate Fair
Manufacturing costs Low Medium High

Table 3 Membrane suppliers and their membrane module characteristics for gas
permeation processes (Scholz 2013)
Supplier Module type Polymer

Air liquide medal Hollow fibre Polyimide, polyaramide

Air products Hollow fibre Polysulfone
Borsig Envelope Polyethylene oxide
Evonik Hollow fibre Polyimide
IGS generon membrane Hollow fibre Tetrabromide
technology polycarbonate
Kvaerner membrane Spiral wound Cellulose acetate
systems
MTR Inc. Spiral wound Perfluoro polymer,
silicone rubber
Parker Hollow fibre Polyphenylene oxide
Praxair Hollow fibre Polyimide
UBE membranes Hollow fibre Polyimide
UOP Spiral wound Cellulose acetate

The capillaries are bedded in resin for sealing against the inlet and outlet
sides (Figure 1).
The most important advantage of hollow fibre modules is their high pack-
ing density which is up to 10,000 m2/m. However, the modules are prone to
impurities and pressure losses, due to the small fibre diameter. Feed pressures
up to 15 bar lumen-sided and 70 bar shell-sided can be applied.

2.1.2 Spiral Wound Modules

For a spiral wound module, one or several membrane envelopes combined
with a spacer are spirally wrapped around a permeate collecting pipe. The
membrane envelope is built up of two membrane sheets with a permeate
562 Thomas Harlacher and Matthias Wessling

Pressure pipe Hollow fibre Sealing (resin)

Feed Retentate

Permeate

Figure 1 Hollow fibre module.

spacer in-between. The envelope is sealed on three sides and the fourth,
open side is connected to the collecting pipe. The module is placed inside
a tubular pressure vessel. The feed gas enters the module at the end wall
and passes axially through the module. Meanwhile, the permeate streams
spirally through the spacer to the collecting pipe (Figure 2).
The permeate flow path to the collecting pipe might be very long which
causes significant pressure losses. These pressure losses can be reduced by
using multiple short envelopes.

2.1.3 Plate and Frame Modules

For gas separation applications, the envelope type module, as a further
development of a classical plate and frame module, is used. Two circular
membrane sheets are glued onto the brink with a spacer in-between to
form the envelopes. A centered bore hole is inserted for a permeate collec-
tion from the inner envelope area. In alternation with seals, the membrane

Collec ng pipe Retentate

Permeate
Feed
Spacer
Permeate
Membrane
Retentate flow Spacer

Permeate flow Membrane

Figure 2 Spiral wound module.

Gas–Gas Separation by Membranes 563

Top view on a
membrane envelope
Permeate Feed
Retentate
collec ng pipe

Permeate Permeate
Permeate
Feed

Sealing Membrane Deflec on

envelope sheave
Feed

Retentate

Permeate

Figure 3 Plate and frame module (Helmholtz–Zentrum Geesthacht) (Melin 2007).

envelopes are pushed onto a collecting pipe. For flow conduction, deflec-
tion sheaves are added, whereby the feed flow velocity can be kept in a
defined range by the selection of various envelope numbers per compart-
ment (Figure 3). The modular placing of the single membrane envelopes en-
ables the exchange of individual envelopes, but in contrast to the hollow
fibre and spiral wound modules, the envelope modules have lower packing
densities and more complex sealing is required.

2.2 Membrane Material

Several materials have been developed for membranes in gas permeation
processes. Actually, polymeric membranes are mostly used for industrial ap-
plications. Metal and inorganic membranes show advantages, especially in
high temperature applications, but these membranes are still under investi-
gation and have not yet reached the industrial scale. Therefore, this work
just outlines polymeric membranes.
A variety of polymers and polymer blends are available for the manufac-
ture of membranes. The selection of the polymers determines the chemical,
mechanical and thermal stability, but also the mass transfer of gases through
the membrane. These properties can be adjusted to the gas separation task.
However, the number of potential membranes for industrial applications is
restricted, because only a few polymer gas permeation membranes are
564 Thomas Harlacher and Matthias Wessling

Table 4 Permeabilities of common gas separation polymers in Barrer (Nunes 2006)

Permeability at 30  C (Barrer)
Polymer H2 N2 O2 CH4 CO2

Cellulose acetate (CA) 2.63 0.21 0.59 0.21 6.3

Ethyl cellulose 87 3.2 11 19 26.5
Polycarbonate, 0.18 1.36 0.13 4.23
brominated (PC)
Polydimethylsiloxane 550 250 500 800 2700
(PDMS)
Polyimide 28.1 0.32 2.13 0.25 10.7
(Matrimid) (PI)
Polymethylpentene 125 6.7 27 14.9 84.6
(PMP)
Polyphenylenoxide 113 3.81 16.8 11 75.8
(PPO)
Polysulfone (PSF) 14 0.25 1.4 0.25 5.6
Polyetherimide (PEI) 7.8 0.047 0.4 0.035 1.32
1 Barrer ¼ 1010 cm3 cm/cm2 s cmHg.

commercially available. An overview of the used polymers and their pure gas
permeabilities is given in Table 4.
Membranes for gas separation generally feature an asymmetric structure.
The active layer, responsible for the separation of gas mixtures, is manufac-
tured as thinly as possible to minimize the mass transfer resistance. To ensure
mechanical stability, the active layer is combined with a porous structure.
The thickness generally is around 0.05–0.5 mm for the active layer and
30–200 mm for the porous layer, respectively.
Asymmetric membranes can be differentiated as integrally asymmetric
and composite asymmetric. Integrally asymmetric membranes are produced
by phase inversion and consist of one material, so that the active layer and
the porous support structure only differ by the pore size. During the
manufacturing of composite membranes, a thin polymer layer is applied
on a porous structure, where different polymers for the active layer and
the porous layer can be selected, although a separate optimization of the
two layers with regard to stability and separation performance is possible.

2.3 Mass Transfer through Polymer Membranes

The separation of gases through membranes is a partial pressure driven sep-
aration process. The partial pressure difference between the feed and the
permeate generates the driving force for the respective gas components.
Gas–Gas Separation by Membranes 565

During the permeation process, the gas molecules absorb into the mem-
brane polymer on the feed side, diffuse through the membrane, and desorb
on the permeate side. According to this solution-diffusion model, the gas
transfer through the membrane can be calculated:


n_00k ¼ Pk $ xk pF  yk pP (1)
The flux of a component k through the membrane is proportional to the
partial pressure difference. The permeance Pk is the permeability Pk related
to the membrane thickness d. The permeance is a gas specific and module
specific parameter and has to be determined experimentally. The permeance
is often indicated in GPUs (gas permeation units) whereby one GPU is equal
to 2:7$103 m3N ðm2 h barÞ1 .
The permeance for component k is proportional to the diffusivity Dk and
the solubility Sk of component k in the membrane and inversely propor-
tional to the membrane thickness d:
Dk $Sk
Pk w (2)
d
This correlation illustrates the importance of a preferably thin active
layer. Diffusivity and solubility depend on the respective gas but also on
the polymer.
The diffusion coefficients of gas molecules characterize their mobility in
the polymer and diffusion coefficients generally increase as gas molecule sizes
decrease.
The solubility describes the number of gas molecules sorbed in a polymer
and solubility depends on the boiling point of the respective gas. The solu-
bility rises with a rising boiling point, so that condensable gases generally
have higher solubility than permanent gases.
In view of the influence of the polymer on diffusivity and solubility, the
polymers can be divided into two groups characterized by their glass transi-
tion temperature: Polymers with a glass transition temperature lower than
the operating temperature are in a rubbery state, ones with a glass transition
temperature higher than the operating temperature are glassy. Diffusion ef-
fects dominate mass transfer through glassy polymers. Therefore, smaller
molecules preferentially pass the membrane even if their solubility is rela-
tively low. By contrast, for rubbery polymer membranes the mass transfer
mainly depends on solubility.
Membranes in a glassy state generally have high permeabilities for water va-
por, helium and hydrogen, but are less permeable for nitrogen, methane and
566 Thomas Harlacher and Matthias Wessling

higher hydrocarbons. In contrast, membranes of rubbery polymers have high

permeabilities for organic solvents/vapors compared to the permeabilities of
permanent gases and are suited for the separation of solvents from exhaust gases.
Rubbery membranes also show high permeabilities for water vapor.
Selectivity is the characteristic of a membrane to differentiate among
various components. The ideal selectivity, the maximum achievable selec-
tivity of a membrane, for any two gases (i and j) is given by the pure gas per-
meance coefficient:
Pi
aij ¼ (3)
Pj
Where i is the faster permeating gas so that aij > 1. Statistically the selectivity
of a polymer rises with decreasing permeances. This effect was introduced by
Robeson (1991) and theoretically described by Freeman (1999).

2.3.1 Influence of Gas Phase Pressure

The permeances are often assumed to be pressure independent for the first
calculations with the solution-diffusion model. This assumption applies for
ideal permanent gases in both glassy and rubbery polymers. In contrast,
for gases which show real gas behavior, a considerable influence of the pres-
sure on the permeances is visible.
Influenced by pressure-dependent solubility, the permeances increase
progressively in rubbery membranes with increasing pressures, while the
permeances in glassy membranes are reduced. This effect can be superposed
by a second effect in glassy membranes. Plasticization increases the chain
spacing in the polymer and increases the chain mobility so that the perme-
ances increase. The changed permeances can also result in changed selectiv-
ities, which influence not only the required membrane area but also the
separation performance (Yampolskii 2006).

2.3.2 Influence of Gas Phase Temperature

Since solubility and diffusivity depend on the temperature, the permeabil-
ities of gases through polymers also depend on the temperature. The tem-
perature dependency can be described by an Arrhenius type approach:
  
E 1 1
Pk ðT Þ ¼ Pk0 exp  $  ; E ¼ Ea þ DHL (4)
R T T0
with Ea as the activation energy for diffusion and DHL as the heat of the
solution. Therewith, the permeabilities increase exponentially with rising
Gas–Gas Separation by Membranes 567

Table 5 Joule-Thomson coefficients at 30  C

and 10 bar (Scholz 2013)
J-T coefficient (K/bar)

N2 0.20
O2 0.26
CH4 0.42
CO2 1.05
C3H6 1.95
C3H8 2.03

temperatures. For both glassy and rubbery membranes, selectivity decreases

with increasing temperature.
For high pressure applications, the Joule-Thomson effect, influencing
the operating temperature, has to be attended. Components, passing the
membrane at high pressure difference and with a high Joule-Thomson co-
efficient, cause temperature reduction, which results in lower permeances
and a changed module separation performance. Example for the pressure-
and temperature-dependent Joule-Thomson coefficients of different gases
is given in Table 5.

2.3.3 Concentration Polarization Effects

The membrane preferentially retains certain components on the feed side,
which have to be transported back to the bulk stream. This diffusive trans-
port results from a concentration gradient between the membrane surface
and the bulk stream. Therefore, the concentration of the retained compo-
nents at the membrane surface is higher than the concentration in the
bulk stream and accordingly, the concentrations of the components prefer-
entially passing through the membrane are lower at the membrane surface
than in the bulk stream. This effect results in a reduced driving force for
the favored permeating components and enhances the mass transfer of the
retained gas components. Concentration polarization arises with higher
fluxes through the membrane and higher selectivities. The effects of concen-
tration polarization significantly influence the separation performance, when
the permeability exceeds 1000 GPU with a selectivity higher than 100
(Mourgues 2005).

2.4 Concepts of Flow Control

The form of module structure allows different flow control for certain tech-
nical membrane modules. The feed stream can pass the module inside the
568 Thomas Harlacher and Matthias Wessling

hollow fibres or on the shell side in hollow fibre modules. Furthermore, the
feed and permeate can flow in co-current, counter-current, cross flow, and
ideal-mixed compartments.
For pressures higher than 15 bar, the feed has to flow on the shell side
because of the pressure stability of the hollow fibres. Otherwise, the feed
flow through the hollow fibre lumen is advantageous. In the lumen a defined
flow is realized, whereas channeling often occurs on the shell side, which re-
duces the module separation performance. Furthermore, the influence of
pressure losses is generally lower for applications with a lumen-side feed.
Counter-current flow is to predominate flow conduction in hollow
fibre modules. Since not only the concentrations but also the pressure influ-
ences the driving force, counter current is not generally the superior flow
conduction. If the influence of pressure losses on the driving force is higher
than the influence of concentration changes, the parallel flow leads to a
favorable driving force along the membrane.
In spiral wound modules the feed and permeate stream are led in cross
flow whereupon the channels for feed and permeate are constructional pre-
determined. In envelope modules (plate and frame modules) the flow con-
struction is a combination of co-current and counter-current flows.

3. PROCESS DESIGN
3.1 Pressure Ratio and Stage Cut
Next to selectivity as a membrane property, two operating parameters
determine the separation performance of a gas separation system: the partial
pressure ratio and the stage cut.
According to the mass transfer equation, a flux of a component i through
the membrane only occurs if the partial pressure of component i on the feed
side is higher than its partial pressure on the permeate side:
x i pF > yi pP : (5)
Hence, the maximum separation which can be achieved by the mem-
brane is:
yi pF
< ¼4 (6)
xi pP
The enrichment in the permeate relative to the feed is always smaller
than the feed-to-permeate pressure ratio, even at high membrane
Gas–Gas Separation by Membranes 569

selectivities. Even though the permeate purity rises with increasing pressure
ratios, maximum industrial applied pressure ratios are limited and depend on
the individual process. Since large pressure ratios require expensive compres-
sors or vacuum equipment and significant energy demands are required, the
applied pressure ratio is usually between five and 20.
The stage cut is the fraction of the feed stream which permeates through
the membrane:
permeate flow rate
q¼ (7)
feed flow rate
The stage cut has an influence on the trade-off between a high purified
retentate stream and a high concentrated permeate stream. With a rela-
tively low membrane area for a defined feed stream, low stage cuts are real-
ized and the permeate stream is highly concentrated. However, only a
small fraction of the feed stream is separated and the resulting retentate
stream resembles the feed stream in flow rate and composition. In contrast,
high retentate purity is achieved at high stage cuts. In this case, a high frac-
tion of the feed stream permeates through a relatively high membrane area
and the enrichment of fast permeating components in the permeate is
insignificant.
These parameters illustrate the limit of a single module separation perfor-
mance. A retentate-sided product can be concentrated to any purity by a sin-
gle membrane module with any pressure ratio higher than one and
selectivity. Yet, the achievable product recovery declines with increasing
product purity. In contrast, the achievable purity of a permeate product in
a single membrane module is limited by the membrane selectivity and the
pressure ratio.

3.2 Driving Force Generation

The driving force for the mass transfer in gas permeation processes results
from the partial pressure difference between the feed and permeate of the
respective components. The partial pressure difference can be achieved by
increasing the feed pressure by compression or decreasing the partial pressure
on the permeate side by applying subambient pressure or by using a sweep
gas (Figure 4).
A high pressure difference is adjustable by feed compression, whereby
the required membrane area is reduced, while the energy demand increases.
By expansion of the retentate stream, mechanical energy can be recovered.
Furthermore, the capital cost for compression equipment is two-thirds to
570 Thomas Harlacher and Matthias Wessling

Feed compression Permeate suc on Sweep gas opera on

Retentate Retentate Retentate

Compressor

Feed Feed Feed Sweep gas

Vacuum
pump

Permeate Permeate Permeate + Sweep gas

Figure 4 Different concepts of driving force generation (Follmann 2010).

half of the cost of vacuum equipment of the same power requirement

(Merkel 2010).
For subambient pressure, not the whole feed stream but just the
permeate stream has to be treated. Therefore, suction becomes more and
more advantageous to compression with decreasing stage cut. Furthermore,
the pressure ratio for a certain pressure difference and therewith the
maximum separation applying suction is higher than using compression,
but the maximum pressure difference is limited. Actually, for a vacuum in
industrial gas separation applications a minimum permeate pressure of
200 mbar is realizable. Because of the limited pressure difference, higher
membrane areas are required. Furthermore the efficiency of vacuum pumps
is much lower than for compressors.
To generate the driving force by sweeping, the permeate partial pressure
for the membrane passing component is reduced by diluting the permeate
by an inert gas stream. Because membranes do not separate ideally, the
intended sweep should be present in the feed mixture, too. If not, the sweep
gas diffuses from the permeate side through the membrane to the feed and
contaminates the retentate stream. The sweep potentially has to be separated
from the permeate easily, which has to be taken into account for sweep se-
lection. Condensable vapors are potential sweep streams.
Especially for sweeping, the achievable partial pressure difference does
not provide sufficient driving force. Therefore, a combination of sweeping
with feed gas compression, suction, or a combination of both is applied. The
combination of feed compression and permeate suction can also be advan-
tageous to profit from the benefits of both concepts (Follmann 2010).

3.3 Feed Pretreatment

The chemical, mechanical, and thermal membrane stabilities have to be
ensured for long-term applications of industrial membrane processes.
Gas–Gas Separation by Membranes 571

Acidic sulfur-containing gases (H2S, SO2) easily react with the mem-
brane components and cause destruction of the membrane. Water vapor
can destroy the selective active layer as well. Moreover, water vapor can
induce plasticization which significantly reduces the membrane selectivity.
Contamination of the membrane surface and support layer with liquids,
such as water or condensed hydrocarbons, reduces the mass transfer rate
through the membrane by inducing additional resistance. Particles can phys-
ically damage the active layer or block the feed or permeate channels, in
particular the thin hollow fibres have to be protected from particles. The
operating temperature significantly influences the module separation perfor-
mance and high temperatures even cause a thermal degradation of the mem-
brane material.
To reduce the impact of the treated gas on the membrane module, a feed
pretreatment has to be implemented. Applicable units in a pretreatment pro-
cess are as follows:
• a coalescing filter, knockout drum or mist eliminator vessel for liquid
elimination;
• an adsorbent guard bed for the removal of trace contaminants, such as
hydrocarbons, H2S, and SO2;
• a particle filter for dust removal after the adsorbent bed; and
• a heat exchanger to set the desired feed temperature.

3.4 Module Interconnection

The membrane selectivity and the industrially applicable pressure ratio are
limited. Therefore, a one-stage system may not provide the desired separa-
tion performance in view of purity and recovery so that several intercon-
nected modules are applied. For module interconnection two different
general concepts are used: In multistep processes the retentate is further
treated in an additional module, while the permeate is further purified in
multistage processes (Figure 5).
In a two-step process, the retentate is led into a second module. The
permeate of this module is recycled in front of the compressor. The
permeate of the first module and the retentate of the second module are
the outlet streams of the process. A higher product recovery for a desired pu-
rity can be achieved, though the energy consumption for compression and
the required membrane area increase.
In two-stage processes the permeate of the first module is recompressed
which is fed into a second module. The permeate stream of the second stage
module has a high quality as it is enriched in the first and in the second
572 Thomas Harlacher and Matthias Wessling

Two-step process Two-stage process

Retentate
Retentate

Compressor

Feed Feed

Compressor

Compressor
Permeate
Permeate

Figure 5 Membrane process design concepts.

modules. The retentate of the second stage is recycled to the first module
inlet. A higher permeate purity compared to the one-stage process is realized,
but an additional compressor and higher membrane area are required. Even
several membrane stages can be realized theoretically, economically the num-
ber of stages is limited to two, exceptionally to three in industrial applications.
Combinations of a multistep and multistage design are possible, but they
are only rarely used due to the higher complexity of the process and higher
costs. Generally, several processes with module interconnection can be
designed. The optimum process design and economically acceptable process
complexity depend on the separation task.
Within a certain module interconnection, there are several parameters
which influence the module separation performance and have to be taken
into account. Next to specifying pressures and temperatures, the membrane
material and membrane area of each module have to be determined. The use
of various membrane materials in the different steps or stages might improve
process separation performance. The partition of the membrane area in
several identical constructed parallel lines potentially allows a dynamic
adapting of the membrane area to a change of the feed flow by switching
on and off the parallel lines.
Combining a membrane process with a conventional separation technol-
ogy in a hybrid process may be attractive in using the advantages of the
different technologies. The membrane process may outperform conven-
tional technologies for bulk removal and enrichment, but for further sepa-
ration to high purities (parts per million range) the conventional
technologies may perform better.
Gas–Gas Separation by Membranes 573

3.5 Economic Parameters for Process Design

For the cost calculation of membrane processes, several full cost models are
described in the literature, but the data collection is quite extensive. Since
the main costs are caused by only a few components, a first rough appraisal
gives a significant predication about the economics of the process. In the
detailed engineering of the respective processes, the cost calculation can
be further refined.
The main process costs for a gas separation process result from the driving
force generation and from the membranes. For driving force generation
both the investment costs for the compressor or the vacuum pump and
also the operating costs for the required energy have to be included. For
the calculation of the depreciation of the investment costs, the limited life
of the membranes compared to that of the driving force equipment, has
to be taken into account. While a maximum compressor life of up to
25 years can be assumed, membranes usually have to be replaced after 5 years
at the latest (Calabr
o 2011).
Generally, the costs for driving force generation increase with increasing
pressure ratios, while membrane areas decrease. Calculating the total process
costs, a minimum for one particular pressure ratio can be determined
(Figure 6). Depending on the product value, it might be necessary to include
the costs for product losses because of the incomplete recovery in deter-
mining the most economic operating point.

3
Process costs [€ m ]

2
-3

Total

1 Driving force

Membrane
0
5 10 15 20 25
Pressure ra o [-]
Figure 6 Example of the main costs for gas permeation processes as a function of the
pressure difference.
574 Thomas Harlacher and Matthias Wessling

4. APPLICATIONS OF GAS PERMEATION PROCESSES

Gas permeation processes with polymeric membranes are state-
of-the-art processes for the separation of several gas mixtures. An overview
of the industrial areas, where membrane processes are applied, is given in
Table 6. Next to the challenge of further improving these membrane
processes, membrane processes for H2/CO2 separation during hydrogen
production and CO2 removal from power plant flue gas are major research
areas in which gas permeation processes are applied.
By means of nitrogen/oxygen separation and the treatment of biogas, the
applications of membrane gas permeation processes are discussed in detail
with regard to different membrane materials and process designs. The
further applications, listed in the table, are described in the literature referred
to in the introduction.

4.1 Oxygen/Nitrogen Separation

4.1.1 Nitrogen Enrichment
Meanwhile, gas permeation processes are industrially applied for inert gas
production from air next to cryogenic processes and pressure swing adsorp-
tion (PSA). Membrane processes are the most economic process for nitrogen
purification with low to medium flow rates up to 5000 m3/h and nitrogen
purities up to 99.5 Mol-%.
Since the product N2 accumulates on the retentate side of the mem-
brane, the desired purity can always be adjusted even with a single mem-
brane module. However, with increasing N2 purity, the achievable
product recovery in a single-stage process is reduced. In N2 production,
N2 recovery is less important as the raw material is air. The important param-
eters for process design and optimization are the required membrane area
and the energy demand; though energy demand strongly depends on recov-
ery, because a high fraction of the compressed feed stream permeates is use-
less to the permeate for lower recoveries.
In this chapter, the exemplary process design is discussed for three different
membrane materials. PI is a membrane material with a high O2/N2
selectivity but low permeances, whereas PDMS is a high flux membrane
with lower selectivities. Both the permeances and selectivities of PPO for
O2 and N2 are in-between the values of PDMS and PI (Table 7). Since a
high fraction of the feed stream has to permeate through the membrane to
achieve the required purities, driving force generation by compression is
favored. Sometimes, the compression is supplemented by a sweep stream
Gas–Gas Separation by Membranes 575

Table 6 Industrial application areas for gas permeation processes (Melin 2007)
Gas
components Field of application Remarks and technical challenges

H2/N2 H2-recovery during Industrially applied, but condensable

ammonia synthesis vapor has to be removed
H2/CH4 H2-recovery during Industrially applied, but VOC vapors
refinement disturb (fouling, plasticization)
H2/CO Methanol synthesis gas Industrially applied, but methanol
adjustment has to be removed if necessary
O2/N2 Inert gas production Industrially applied, for moderate
amounts and purities
(up to 5000 m3/h and 99% N2)
O2/N2 O2-enriched air for Up to 60% O2 with polymer
oxidation processes or membranes achievable,
medical attendance (issue of economics)
CO2/CH4 Natural gas/bio gas Industrially applied, but precleaning
treatment, heat value necessary, higher separation
adjustment factors for higher CH4
recovery preferable
CO2/CH4 CH4-recovery for Industrially applied, but precleaning
enhanced necessary, higher separation
oil recovery factors for higher CH4
recovery preferable
H2O/CH4 Natural gas drying and/ Applicable, but CH4 losses are
VOC/CH4 or separation of VOC mostly too high
H2O/air Compressed air drying Industrially applied, air losses caused
by the internal sweep stream
reduce economic efficiency
VOC/air VOC/petrol vapor Industrially applied, concentration
recovery polarization and explosion control
in permeate are problems
CH4/N2 Natural gas treatment at Current available membranes do
low gas qualities not show sufficient selectivity for
acceptable CH4 losses
He/VOC He-recovery from Applicable, but low feed
natural gas concentrations require multistage
processes
He/N2 He-recovery from Applicable, but only a small market
diving air mixtures
576 Thomas Harlacher and Matthias Wessling

Table 7 Membrane properties (Melin 2007)

Permeance Permeance Ideal selectivity
Membrane material O2 (GPU) N2 (GPU) (e)

Poyimide (Matrimid) (PI) 20 3 6.7

Polyphenylenoxide (PPO) 110 25 4.4
Polydimethylsiloxane 1185 590 2.0
(PDMS)

by using a partial stream of the retentate to increase the driving force for
oxygen. In this example, only compression as the driving force generator
is investigated.

4.1.1.1 Single-step Process

First, the separation performance for the single-stage processes is discussed.
The recoveries depend on the membrane selectivity. Low selective mem-
branes, such as PDMS, achieve only very low recoveries, especially when
high purities are required. Generally, the recovery decreases with increasing
purities (Figure 7 left) and increases with an increasing pressure ratio
between the feed and the permeate (Figure 7 right). The achievable product
recovery is only depending on the membrane selectivity and the pressure
ratio for single-stage processes.
Figure 8 shows the influence of the membrane material and the pressure
ratio on the required membrane area as well as the energy demand.
The required membrane area depends on the respective permeances.
Implementing the high flux membranes, the lowest membrane areas are

1.0 0.5
Φ = 11 99 % N2 PI
0.8 PI 0.4
N2 recovery [-]
N2 recovery [-]

0.6 PPO 0.3 PPO

0.4 0.2
PDMS

0.2 0.1
PDMS
0.0 0.0
0.90 0.95 1.00 5 10 15
N2 purity [-] Pressure ra o [-]

Figure 7 Recoveries with different polymer membranes for nitrogen enrichment.

Gas–Gas Separation by Membranes 577

100
10 PDMS

Energy demand [kWh mN ]

Membrane area [m mN h]

-3
-3
2

PI
10 1 PPO

PPO PI

PDMS
1 0.1
5 10 15 5 10 15
Pressure ra o [-] Pressure ra o [-]
Figure 8 Specific energy demand and required membrane area for a fixed product pu-
rity of 99% N2.

required, whereas low permeances demand greater membrane areas

(Figure 8 left). With increasing pressure ratios, the required membrane is
reduced. In contrast, the energy demand increases for higher pressure ra-
tios. Thereby, the highest energy demand occurs for the material with
the highest fluxes.

4.1.1.2 Multistep Processes

Since the achievable recovery for a defined retentate purity is limited in a one-
step process, multistep processes may significantly improve the process perfor-
mance in terms of energy demand and required membrane area. For the
N2-enrichment of air, two- and three-step processes were developed as given
in Figure 9. The data represents the operating point of 11 bar in the feed. The
same membrane area was implemented in all the process steps. The nitrogen
fraction of the permeate streams is higher than that of the feed air for the mod-
ules in the second and third steps. By recycling these streams back to the feed,
the oxygen fraction of the feed streams is reduced. This process modification
results in a reduced membrane area and reduced energy demand. Compared
to single-step processes, the membrane area and energy demand can be
reduced by about 5% for the investigated PI membrane. This process
improvement can be realized without additional costs because only a piping
change is necessary. In contrast, for a further improvement of 2% by imple-
menting a three-step process, a second compressor is necessary. Therefore,
three-step processes are generally implemented economically in large systems,
where the energy and membrane savings compensate for the higher process
complexity and the costs of the second compressor (Baker 2004). Figure 10
578 Thomas Harlacher and Matthias Wessling

Nitrogen product
99 % N2

92.9 % N2

Air 81.9 % N2
79 % N2
88.0 % N2

Nitrogen product
99 % N2

95.9 % N2

90.5 % N2

Air 79.2 % N2 91.9 % N2

79 % N2

Design Rela ve membrane area Rela ve compression energy

One-Step 1 1
Two-Step 0.95 0.95
Three-Step 0.93 0.93
Figure 9 Multistep processes for N2 enrichment (values for PI membrane with
pFeed ¼ 11 bar). (Based on Baker (2004)).

shows the product recovery for the different process designs as a function of
the product purity and the pressure ratio. For multistep processes, the product
recovery is significantly increased compared to the one-step process. This ef-
fect is particularly important, when the feed is a valuable product and is not
gratis, as the air in this example. Next to the membrane material and pressure
ratio selection, the membrane area ratio between the respective process steps
can be adapted for economic process optimization.

4.1.2 Oxygen Enrichment

In contrast to N2 enrichment, with the application of membrane processes
for the production of an O2-enriched gas stream only limited O2 purities
can be achieved. Here, the permeate stream is the product stream. Since
the O2 fraction in the feed is only 21 Mol-%, the partial pressure difference
as the driving force is always higher for N2 than for O2. In combination
Gas–Gas Separation by Membranes 579

1.0 0.7
Φ = 11 99 % N2
0.6 Three-Step
0.8 Three-Step
0.5
Two-Step

N2 recovery [-]
N2 recovery [-]

0.6 0.4
Two-Step
0.4 0.3 One-Step
One-Step 0.2
0.2
0.1

0.0 0.0
0.90 0.95 1.00 5 10 15
N2 purity [-] Pressure ra o [-]

Figure 10 Product recovery of multistep processes compared to the single-step

process.

Oxygen depleted air

10 - 15 % O2

Air
21% O2

Oxygen enriched air

30 - 60 % O2
Vacuum
pump

Oxygen depleted air

10 - 15 % O2

Air
21% O2

Second stage Pure oxygen

separa on unit Nitrogen vent
Vacuum
pump
Figure 11 Membrane processes for the production of oxygen enriched air and pure
oxygen. (Baker 2002).

with limited membrane selectivities, significant quantities of N2 per-

meate through the membrane. Therefore, only O2-enrichment and
no O2-purification is economically feasible in applying membrane processes
(Figure 11).
For O2-enrichment, a vacuum on the permeate side of the membrane is
more favorable than compression of the feed, since only a small fraction of
580 Thomas Harlacher and Matthias Wessling

0.7

0.6 PI

O2 purity [-]
0.5
PPO

0.4

0 2 4 6 8
3
Feed flow [m /h]
Figure 12 O2 purity in a one-step membrane process.

the feed permeates through the membrane. The maximum pressure differ-
ence is limited, so that the required membrane area is comparatively high
(Baker 2002).
The separation performance of a single-stage membrane process using PI
and PPO membranes is shown in Figure 12. By increasing the feed flow, the
O2-depletion in the feed stream of the membrane module is reduced. Thus,
the driving force for O2 is kept higher resulting in higher O2 purity in the
permeate. For a minimum O2 depletion a maximum O2 purity is achieved.
For the PPO membrane with a N2/O2 selectivity of 4.4, the maximum O2
purity is around 50%, for the PI membrane with a N2/O2 selectivity of 6.3
the maximum purity is around 60%.
For higher O2 purities, a hybrid process combining a membrane step
with an additional purification step can be applied. For small units in which
flow rates of up to 200 tons a day are treated, vacuum swing adsorption is
used; cryogenic processes are the most economic processes for product
flow rates of more than 200 tons a day. By air pretreatment using mem-
brane units, the second stage unit is smaller and cheaper compared to the
adsorption or cryogenic stand-alone units fed with air (Baker 2002).

4.2 Biogas Treatment

Raw biogas is mostly polluted with carbon dioxide and hydrogen sulfide.
In order to use these energy sources, the gas has to be delivered to the
central gas grid. Here, defined gas specifications in terms of accepted
carbon dioxide and hydrogen sulfide as well as gas humidity have to be
maintained.
Gas–Gas Separation by Membranes 581

Predominantly, the established processes, such as amine scrubbing, water

scrubbing or PSA, are used for CO2 removal. Nevertheless, the conven-
tional process equipment shows following drawbacks:
• he processes are energy intensive.
• he CH4 rich product gas is at low pressure.
• omplex systems involving several process steps are required to remove
CO2, H2S as well as H2O, hence, reducing the robustness of the system.
• Large equipment sizes.
• Associated materials such as water, amines, or activated carbon are
required.
Next to the afore mentioned advantages of membrane processes in
contrast to the conventional technologies, treatment additional significant
advantages occur in the case of biogas. First, the product gas is already at nat-
ural gas grid pressure. Therefore, no additional compression unit is necessary
for gas supply into the gas grid. Furthermore, not only can the CO2 be sepa-
rated by the membrane, but, since the trace components in the raw biogas,
like hydrogen sulfide or water vapor, permeate faster through the membrane
than CO2, the membrane unit can separate CO2, hydrogen sulfide and
water in one step. Instead of three conventional units, only one membrane
unit could be required which depends on the driving force for the trace
components. However, the membrane stability for H2S has to be ensured
(Figure 13).
Especially for small to intermediate systems, the membrane process is
economically superior to the conventional technologies. Therefore, the
application of membrane gas separation is very promising for local biogas
treatment. Instead of an extensive transport of biomass to a central biogas
plant, the biomass can be used at source, for example at a farm. The resulting
biogas can be purified on-site and directly delivered to the gas grid. The

Figure 13 Process simplification by membrane unit implementation (Scholz 2013).

582 Thomas Harlacher and Matthias Wessling

(a) CH4
(b) CH4

Raw gas
Raw gas

CO2 CO2

(c) CH4 (d) CH4

Raw gas
Raw gas

CO2
CO2

Figure 14 Membrane processes for biogas upgrading (Scholz 2013).

minimal maintenance and operator attention allows the operating of the unit
without detailed technical know-how.
Several process designs are discussed in the literature for membrane sup-
ported biogas treatment. The selection of the most suitable process strongly
depends on the feed composition and the required methane purities.
Figure 14 shows a selection of the discussed process designs.
Since single-stage gas permeation processes are inefficient due to signif-
icant CH4 losses, multistage gas permeation processes are applied to obtain
high product purity and simultaneously increase the CH4 recovery of the
upgrading system.
Figure 14 shows different membrane stand-alone processes. In process
(a), the first module is in charge of the CO2 bulk removal. A relatively
high CO2 fraction is received in the permeate, but the product stream leav-
ing this module does not comply with the gas grid requirements. In order to
purify the CH4 stream, a second membrane module is applied which con-
trols the product purity. In this module, the CH4 losses into the permeate are
quite high. By recycling this stream in front of the compressor, the CH4
recovery of the process is increased.
In process (b) the required product composition is obtained in one step.
Next to the CO2 and the trace components, a huge amount of CH4 perme-
ates through the membrane. Here, a second stage is added to reduce the
CH4 losses. The driving force for this module is generated by a second
Gas–Gas Separation by Membranes 583

compressor. The CH4-enriched retentate stream is recycled in front of the

first compressor, the CO2-rich permeate stream is led out of the process.
Process (c) is similar to process (b), but the retentate of the second stage is
not recycled. Instead, the stream is also purified up to gas grid conditions and
mixed with the retentate of the first module.
Process (d) has the same module connection as process (a). In addition to
the driving force generated by the compressor, the raw biogas is used as a
sweep stream in the second module. This sweep stream can be applied to
increase the driving force for CO2, when the CO2 fraction in the permeate
of the second module is higher than the CO2 fraction in the raw gas.
Since the highest CH4 losses occur in a membrane process when high
product purity is required, hybrid processes can also be economic for biogas
treatment. In general, two different arrangements for a hybrid process are
possible: the retentate configuration and the permeate configuration.
In the retentate configuration (Figure 15(a)), the membrane unit is used
for bulk removal. In the following absorption or adsorption unit, the
required product purity is obtained. In contrast, the gas grid specification
is obtained in the membrane module of the permeate configuration
(Figure 15(b)). In a second unit, using a conventional separation technique,
the permeate stream of the membrane unit is treated. A huge fraction of the
CH4 is recovered and mixed with the CH4 rich retentate stream of the
membrane unit (Scholz 2013).
The selection of a suitable process design should be carried out based on
the given boundary conditions with regard to feed composition, feed
volume and product specification.

(a) CH4 (b) CH4

CH4

Raw gas
Adsorp on
Absorp on

Adsorp on
Absorp on

Raw gas

CO 2
CO 2 CO 2

Figure 15 Hybrid process for biogas upgrading (Scholz 2013).

584 Thomas Harlacher and Matthias Wessling

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