LEC 4

MEMBRANE GAS SEPARATION

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MAIN DEFINITIONS
Permeation rate or flux is the rate at which a gaseous component can diffuse through
the membrane medium to the low-pressure side.
Permeability : the ease of gas to dissolve and diffuse through the membrane
Selectivity refers to the ratio of permeation rates of a fast gas (carbon dioxide) and
a slow gas (methane or other hydrocarbon). The selectivity of carbon dioxide to
methane determines the efficiency of the separation, and thus the hydrocarbon
recovery

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MAIN DEFINITIONS
For better understanding for the term “selectivity” we need to understand the
Mechanism of membrane separation.

The main phenomenon are solution and diffusion

Gas molecules dissolves in the membrane material due to high pressure

The solute molecules diffuses in the membrane material due to difference in

concentration on both sides of the membrane

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MECHANISM OF OPERATION

The different components of the mixture have different solubility in the polymer of the
membrane and each gas has a different permeability in the porous medium of the
membrane.
Using these characteristics one component can permeate faster than the other
component .
First, molecules of the gas dissolve in the non-porous layer.
Then, it diffuses through the porous medium of the membrane because of the pressure
difference between the sides of the membrane..

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MECHANISM OF OPERATION

Both components dissolve and go through the membrane but with different rates
Components with higher solubility and higher diffusivity called fast components and
they form the higher concentration in the permeate stream.
Due to the differences in the ability of the components of the mixture to dissolve and
diffuse in the polymer, separation happens.
The penetrating stream is called the permeate and the rejected component is called
the residual.

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CONSTRUCTION OF MEMBRANE ELEMENT
The single element consists of several layers of membrane sheets , each membrane
layer is separated by 2 other layers called feed spacer and permeate spacer.

Gas is feed to the feed spacer , the membrane layer does the separation , and the
permeate spacer carries permeate gas to permeate side

These layers are wrapped in a spiral form and connected to a perforated tube that
collects all permeate gas.

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CONSTRUCTION OF MEMBRANE ELEMENT

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DEVELOPMENT OF (TECHNICAL) MEMBRANE PROCESSES
Membrane Process Country Year Application

Microfiltration Germany 1902 Laboratory use(bacteria filter)

Ultrafiltration Germany 1930 Laboratory use

Hemodialysis Netherland 1950 Artificial kidney

Electrodialysis USA 1955 Desalination

Reverse Osmosis USA 1960 Sea water desalination

Ultrafiltration USA 1960 Conc of macromolecules

Gas separation USA 1979 Hydrogen recovery

Membrane distillation Germany 1981 Conc of aqueous solutions

Pervaporation Germany/Netherland 1982 Dehydration of organic solvents

POLYMERIC MEMBRANES, THE PRODUCERS AND THEIR APPLICATIONS
Principal membrane material
Company Principal Markets Module type
used
Permea(Air Products) Polysulfone Hollow fiber

Medal(Air Liquide) Nitrogen/air, Polyimide/polaramide Hollow fiber

IMS(Praxair) Hydrogen separation Polyimide Hollow fiber

Generon(UOP) Tetrabromo polycarbonate Hollow fiber

GMS(Kvaerner) Spiral-wound

Separex(UOP) Mostly natural gas separations Cellulose acetate Sprial-wound

Cynara(Natco) Hollow fiber

Polyphenylene oxide
Aquilo Hollow fiber

Parker-Hannifin Hollow fiber

Polyimide
Ube Vapor/gas separation, air Hollow fiber

GKKS Licensees Dehydration, other Plate and frame

MTR Spiral wound

Silicon rubber

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COMPARISON OF DIFFERENT MEMBRANE MATERIALS

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Fundamentals of gas Transport in Membrane
PERMEABILITY OF RUBBERY AND GLASSY POLYMERS

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DIFFUSION IN RUBBERY AND GLASSY POLYMER

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DIFFUSIVITY SOLUBILITY AND PERMEABILITY OF NATURAL RUBBER

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CRITICAL TEMPERATURE AND SOLUBILITY COEFFICIENT OF GASES IN RUBBER

Gas Tc (K) S (cm3 cm-3 cmHg-1)

H2 33.3 0.0005

N2 126.1 0.0010

O2 154.4 0.0015

CH4 190.7 0.0035

CO2 304.2 0.0120

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GAS SORPTION IN RUBBERY AND GLASSY POLYMERS

Sorption isotherms for ideal and non- Polymer specific volume as a function
ideal systems of temperature

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 MEMBRANE UNIT CONFIGURATION
Pressure = 62 bar
Compressor is used to raise
Temperature = 57 C
the pressure of the stream to Residual gas to
the required value which sales
ensures the required value of
flux
P=0.89 bar
T=0.42 C Permeate to
Turbo flare
PTU Permeate gas
Expander
to 2nd stage 5.91 MMSCFD
Pre-treatment Unit.
The purpose of this unit is to remove any liquids or HX PTU
condensates before the membrane.
The presence of liquids or condensates will damage
membrane elements. Residual gas
recycled

11.51 MMSCFD
PRE-TREATMENT UNIT
Coalescence Filter Catalyst guard bed Particle filter
COLLESANCE FILTER
To remove Bulk CATALYST GUARD BED

Liquids and
Using activated
Condensates. To trap any fine
carbon powder to particles that
Presence of liquids
absorb heavy
will damage the may have
hydrocarbon escaped from the
membrane polymer
vapors
catalyst
FACTORS AFFECTING THE SEPARATION PERFORMANCE
OF POLYMERIC MEMBRANES
 Penetrant size and shape:
Generally the permeability of ideal gases i.e. H2, N2 and O2 decreases as the size of
the penetrant is increasing due to decrease of diffusion coefficient[35, 36]. For non
ideal gases i.e. CH4, CO2 etc, permeability increases as the size of penetrant increases
due to increase of solubility.
 Penetrant Condensability:
The solubility of gases increases with the increase of condensability. Gas condensability
can well be represented by the critical temperature Tc. Hence the solubility is directly
proportional to the critical temperature of the gas.
 Temperature: Temperature dependence of the permeability of non interactive gases
in polyethylene
 Pressure:Generally the effect of pressure on gas permeability of polymers may have
two opposing effects i.e. (a) the concentration of the penetrant dissolved in the polymer
is increased, thereby increasing the free volume and (b) the hydrostatic pressure on the
membrane is increased, which causes a decrease in the free volume. If the overall
effect is an increase in the free volume of the polymeric membrane, the permeability
will increase and vice versa.

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THE PRESSURE DEPENDENCE OF PERMEABILITY AT 35 °C FOR: (A) PERMANENT GASES IN GLASSES OR RUBBERS; (B)
SOLUBLE GASES IN GLASSES; (C) VAPORS IN RUBBERS AND (D) VAPORS OR PLASTICIZING PENETRANTS IN GLASSES

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 Free Volume: Both the diffusivity and solubility depends strongly on the polymer
fractional free volume, however diffusivity is more a strong function of fractional
free volume than the solubility.
 Structure of the polymer:The composition of the main chain and side group
attached to a polymer has significant effect on the thermal, mechanical and
separation properties.

At 35 oC

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PERMEABILITIES OF NITROGEN AND OXYGEN IN VARIOUS POLYMERS
Polymer PO2(Barrer) PN2 αideal (PO2/PN2)

Polytrimethylsilylpropyne 10040.0 6745.0 1.5

Polydimethylsiloxane 600.0 280.0 2.2

Poly-(t-butyl acetylene) 200.0 118.0 1.7

Polymethylpentene 37.2 8.9 4.2

Polyvinyltrimethylsilane 36.0 8.0 4.5

Polyisoprene 23.7 8.7 2.7

Poly(phenylene oxide) 16.8 3.8 4.4

Ethyl cellulose 11.2 3.3 3.4

Polystyrene 7.5 2.5 2.9

Polyethylene 6.6 2.1 3.2

Polypropylene 1.6 0.30 5.4

Polycarbonate 1.4 0.30 4.7

Butyl ruber 1.3 0.30 4.3

Polytriazole 1.1 0.13 8.4

Cellulose acetate 0.7 0.25 3.0

Poly(vinylidene fluoride) 0.24 0.055 4.4

Polyamide(nylon 6) 0.093 0.025 2.8

Poly(vinyl alcohol) 0.0019 0.00057 3.2

Polyimide(Kapton) 0.001 0.00012 8.0

1 Barrer = 10-10 cm3(STP).cm.cm-2.s-1.cmHg-1 = 127.4 m3(STP).m.m-2.h-1.bar-1 24

Polymer Tg (°C)
Polydimethylsiloxane -123
Polyethylene -120
Poly-(cis-1,4-butadiene) -90
Poly-(cis-1,4-methylbutadiene) -73
Natural rubber -72
Butyl rubber -65
polychloroprene -50
Poly(vinylidene fluoride) -40
Poly-(cis-1,4-propylene) -15
Poly(methylacrylate) 10
Poly(vinylacetate) 29
GLASSTRANSITION TEMPERATURE OF
VARIOUS POLYMERS
Polymethylpentene 30
Ethylcellulose 43
Nylon-6(alif.polyamide) 50
Cellulose nitrate 53
Polyethyleneterephtalate 69
Cellulose diacetate 80
Poly(vinyl alcohol) 85
Polyphenylene sulfide) 85
Poly(vinyl chloride) 87
Polystyrene 100
Polymethylmethacrylate 110
Polyacrylonitrile 120
Polytetrafluoroethylene 126
Polyetherketone 143
Polycarbonate 150
Polyvinytrimethylsilane 170
Polysulfone 190
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Polytrimethylsilylpropyne 200
Poly(ether imide) 210
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