ChE 382: Unit Operations Laboratory

MEMBRANE AIR SEPARATION rev: Fall 2005

Introduction
Processes based on synthetic or modied natural polymeric membranes membranes are widespread and impact many commercial technologies. Several dierent types of membrane separation processes are used in chemical industries that include desalination and component gas separation. Treatment of gas streams with nonporous membranes enables the recovery of component gases without the need to use more costly approaches such as evaporation or liquefaction. Membrane permeation is a separation process involving the selective transport of gas molecules through a permeable polymeric lm. Unlike most chemical engineering separation processes which are governed by phase equilibrium relations, membrane separation is based primarily upon the relative rates of mass transfer. Transport will occur by a solution-diusion mechanism comprised of: adsorption of the gas molecule onto the interface of the high-pressure side of the membrane dissolution of the gas into the membrane at the interface and diusion of the gas through the membrane elution of the gas from the membrane at the interface desorption of the gas molecule from the low pressure side of the membrane

Theory
Gas permeation is the term used to describe a membrane separation process using a nonporous semi-permeable membrane. In this, a gaseous feed stream is fractionated into permeate and non-permeate streams. Transport occurs by a solution-diusion mechanism and membrane selectivity is based upon the relative permeation rates of the components through the membrane. Each gaseous component transporting through the membrane has a characteristic permeation rate that is a function of the ability to dissolve and diuse. The two relationships upon which the equations are based are Ficks Law (diusion) and Henrys Law (solubility).

Diusive ux through the membrane can be expressed by Ficks Law related to the membrane system by: Ji = Di (Cin1 Cin2 ) L (1)

where: mol Ji = ux of component i in m2 s 2 Di = diusivity of component i in m s L = thickness of membrane in meters Cin1 = concentration of component i inside membrane wall on feed side in mol m3 Cin2 = concentration of component i outside membrane wall on permeate side in

mol m3

The total ux of component i, Ji , can be calculated from the following expression. Ji = Qip nA
m3 s

(2)

where: Qip = volmetric ow rate of species i in the permeate in = density of permeate in mol m3 A = area of membrane, in this case 2.7m2 per module n = number of modules used. From Henrys Law: Cim = Si pi

(3)

where: Cim = concentration of component i inside membrane wall in mol m3 mol Si = solubility constant for component i in the membrane in m3 P a pi = partial pressure of component i in the gas phase in Pa Permeation through the membrane is a function of solubility as well as diusivity: P i = Di S i where: 2 Di = diusivity of component i in m s Si = solubility constant for component i in the membrane in Pi = component i membrane permeability in mmol a 3 sP (4)

mol m3 P a

Separation eciency is based on the dierent rates of permeation of the gas components. Data are not commonly available. ij = where: Pi as dened before. An experimental separation factor is frequently used to quantify the separation of a binary system of components can be dened in terms of mole fractions which is convenient as the oxygen sensors measure concentrations in mole percent.
xip
x xjr

Pi Pj

(5)

and

aij = xjp ir
xip
x xjf

(6)

where: aij = separation factor based on non-permeate composition a = separation factor based on feed composition ij Recovery is dened by the following equations: Qp CO2 p Qf CO2 f Qr CN2 r Qf CN2 f

a = xjp ij if

(7)

O2 Recovery = N2 Recovery =

(8) (9)

where: 3 Qp = volumetric ow rate of permeate in m s Qf = volumetric ow rate of feed CO2 f = molar concentration of oxygen in feed in mol m3 CO2 p = molar concentration of oxygen in permeate in CN2 f = molar concentration of nitrogen in feed in mol m3 mol CN2 r = molar concentration of oxygen in feed in m3

mol m3

Stage cut is dened as the fractional amount of the total feed entering a membrane module that passes through a membrane as a permeate. Qp Qp + Qr

ST AGECUT = Where: Qp = volumetric ow rate of permeate in 3 Qf = volumetric ow rate of feed in m s

(10)

m3 s

The design of the experimental system is such that the concentrations and ow rates are measured at atmospheric pressure for both the permeate and non-permeate streams.

Apparatus
The experimental apparatus consists of two PrismTM separator modules (columns) that can be operated in series or parallel. Each module contains thousands of non-porous, semipermeable membranes in the form of hollow bers. The bers are held within a cylindrical shell, similar to a shell and tube heat exchanger. Oxygen and nitrogen permaet the ber walls into the cylindrical shell at dierent rates and are collected in a manifold at the bottom of the separator as the permeate stream. The less permeable nitrogen and residual oxygen pass through the ber lumens and exit from the end of the separator as the non-permeate stream. The two modules are mounted together ona common manifold. Each has approximately 2.7m2 of membrane area. The modules have a 1 inch diamter and three feet of length. The polysulfone post-treated with silicone hollow bers that comprise the the membranes have diameters of approximately 450 micrometers. Flow through them can be directed in series or parallel fashion to study the dierences between congurations. The process diagram on the following page.

In parallel conguration the valves should be as follows: Valve Valve Valve Valve A: LEFT B: Up to sample module 2 shell, Down to vent C: DOWN D: Up to sample module 1 shell, Down to vent

Series conguration is the following: Valve Valve Valve Valve A: RIGHT B: Up to sample module 2 shell, Down to vent C: UP D: Up to sample module 1 shell, Down to vent

Since all piping and valves are visible, these congurations can easily be veried. DO NOT ALLOW THE 3-WAY VALVES TO BE PLACED IN THE MIDDLE POSITION. Safety is of overriding importance so it is imperative that you: Wear eye protection at all times Make sure all electrical components and metal parts are well grounded Check tank cylinder supports Close air ow into experiment when completed

Experimental Procedure
Open the valve on the high-pressure air cylinder and set the outlet pressure to 140 psig using the cylinder regulator. This will allow operation up to 100 psig at the outlet of the second pressure regulator. Turn on the battery-powered (9V) oxygen analyzers and allow them several minutes to reach a steady reading. If desired, they can be calibrated by gently removing the gray transducer cell from the aluminum holder and waving it slowly in the air. If the percentage by volume of oxygen indicated is not near 20.9%, use the calibrate knob on the front of the the meter panel (a jewellers screwdriver is best; ask if you need assistance). The o-ring is placed around the transducer near the active end and the transducer is inserted gently into the holder. The oring should be near the middle of the annular space provided. If necessary, a small rod can be used to push the o-ring further into the annulus. Make sure there is a good seal and proceed. The mass ow meters are driven by a power supply plugged into a power strip. Locate and power on this strip. If necessary, reset the GFCI if there has been a ground fault. Allow a few minutes between experimental runs for the system to reach a new steady state. Cover a range of operating pressures and tube side ow rates.

Data Analysis
The essential idea is to derive from the data estimates of the overall mass transport coefcients KO2 and KN2 through the ber wall. Relate the oxygen and nitrogen ow rates and pressures to these coecients. Carry out any necessary balances on each species, recall calculations for partial pressures for each species at the various junctions, and relate the respective permeation rates to the transport coecients. Plot these as functions of operating pressure with tube side gas ow rate as a parameter. Discuss the constancy of your results. Use calculated transport coecients based on on the parallel conguration data to calculate the euent oxygen levels for the series conguration runs and discuss the extent of agreement. Include in your report calculations and discussions for the terms discussed in the Theory section.

References
[1] R. H. Perry and D. W. Green, Eds., Perrys Chemical Engineers Handbook, 7th ed. McGraw-Hill, 1997.