Membranes

Introduction:

Membrane permeation is a separation process involving the selective transport of gas

molecules through a permeable polymeric film. Unlike most chemical engineering separation

processes which are governed by phase equilibrium relations, membrane separation is based

primarily on the relative rates of mass transfer.

The use of membranes was first commercialized by Monsanto in the mid-1970's with

their development of the hollow-fiber Prism system. Today there are many manufacturers as this

form of fluid separation continues to emerge as a simple cost effective separation process. It has

several industrial applications, including enhanced oil recovery, inert gas generation, and

ammonia production. Another important application is for waste gas treatment. To conform to

government regulations, membranes can be installed to filter out the harmful emissions.

In industry, membranes are used extensively

for several tasks. Shown here is a large industrial

membrane in use at a Japanese refinery. In the

petrochemical industry, membranes are used to

recycle, recover and purify hydrogen. They can

achieve permeate purities of up to 99.9 % (by

1: MEDAL Membrane unit for Japan:
41,500 Nm3/h for residual desulfurizer purge
volume) and 98 % hydrogen recovery. gas (courtesy of Air Liquide [1])
 Figure 2 (also courtesy of

Air Liquide [1]) shows the flow

patterns of a conventional

membrane. In this case, nitrogen

gas is separated from an air

mixture, allowing the N2 free air to Figure 3: Conventional Membrane Flow Patters.
escape out the side while the nitrogen

gas leaves through the end. Therefore, the membrane used is selectively permeable to allow O2,

CO2, and H2O through but not N2.

A significant benefit of gas membrane permeation rather than conventional unit

operations is the reduction in energy requirements. Realized worth, however, is dependent upon

the application since capital costs are high for special operations, requiring expensive membrane

materials.
Objectives:

♦ To familiarize the student with process material balance calculations

♦ To study the use of a simple stage model for the interpretation of mass-transfer data.

♦ To study the affects of feed flow rate, pressure, temperature, and stage cut on the separation

process.

♦ To determine the best configuration to separate oxygen from the air feed based on recovery

and oxygen purity of the product gas.

♦ To develop a good understanding of the properties of membrane permeability and what

factors control it.

Theory:

Membrane processes can be thought of as simple separation techniques which employ the

membrane as partitioning phase. In the process, a driving force, usually pressure or

concentration, is applied to one side of the membrane and the selective component(s)

preferentially pass to the other side as the permeate. The permeation can be described by Fick’s

Law:

 dC 
N a = − Da  a  (1)
 dx 

where: N / flux of permeating molecules of “a” (flow of molecules/area)

D / diffusivity of component “a” in the membrane

Ca / concentration of component “a”

x / distance through the membrane

Using Henry’s Law for equilibrium of molecules, this equation can be modified to the familiar
form:

N a = Pa
p1 − p2
= Pa
(
Pf ⋅ ( ya , f + ya ,r ) 2 − Patm ⋅ ya , p ) (2)
z z

where Pa / permeability of a component in the membrane

Pf, Patm / pressure of feed and atmosphere, respectively

p1, p2 / partial pressures of non-permeate (retentate) and permeate sides

ya,f, ya,r, ya,p / concentrations of feed, retentate, and permeate gas

z / membrane thickness

The separation factor is frequently used to quantify the degree of separation in a binary system.

Typically, it takes the form of the following ratios of concentration:

Pa
α = (3)
Pb

One of the main controlled variables in the experiment is the stage cut, θ. It is the ratio of

permeate flow to feed. It is controlled by manipulating the valve on the reject stream to change

the permeate/feed ratio. Since the permeate flow is a function of the feed pressure, adjusting the

rejects stream valve will not affect it.

Apparatus:

Two separators are available, each consisting of a bundle of asymmetric hollow fibres of

polysulphone in a shell and tube arrangement. The “asymmetry” of the fibers is in their tubular

design: the polysulphone is supported by a stron “porous” layer.

Separator Specifications:

Model: PPA-22A
Membrane: Polysulfone hollow fiber
Fiber outside diameter: 450 :m (nominal)
Surface Area: 2.2 m2 (24 ft2)
Packing Factor: 47% (nominal)
Maximum Operating Pressure: 790 kPa (100 psig)
Maximum Operating Temperature: 45 oC (120 oF)
Shell Length: 51 cm
Shell Outside Diameter: 3.65 cm

Pressure Feed Capacity @ 5% Oxygen

psig SLPM SLPM of Non-permeate
50 2.4 1.0
80 4.3 2.0
100 5.6 2.7
References:

[1] Air Liquide. http://www.airliquide.com/

[2] McCabe W. L. et al., Unit Operation of Chemical Engineering. McGraw-Hill, 5th Ed.,

New York, NY. 1993

[3] Slater, C. S., et. al., International Journal of Applied Engineering and Education. 8 (1),

pp. 1-7, 1992

[4] Blackhouse, I. W. Membranes in Gas Separation and Enrichment, Royal Society of

Chemistry, London. 1986