MEMBRANE-BASED GAS SEPARATION (MS)

OBJECTIVES
Your company has tasked you with utilizing semi-permeable membrane modules to
create an inert (> 95 mol% N2) gas supply from air. You are to use the two membrane modules
installed in the pilot plant to examine the effects of various parameters on the permeation of gas
through the membranes. You are also to determine whether a simple mathematical model
adequately describes the module behavior. Specific objectives to be completed are:
i. Determine the membrane selectivity to O2 from measurements of the membrane
transmissibility to N2 and O2.
ii. Characterize the membrane to determine how air-separation performance depends on
feed pressure, retentate flow rate, and module configuration (i.e., co-current or
counter-current).
iii. Develop a mathematical model to predict the dependence of permeate flow rate and
purity on the retentate production rate, pressure, and composition, as well as the
membrane transmissibilities. Discuss model limitations.
iv. Based on the experimental and model results, recommend optimal operating
conditions (pressure, flow rate, module configuration) to produce a >95 mol% N2
product stream. Describe tradeoffs in operating conditions.

BACKGROUND & THEORY

Membrane-based gas separations typically employ a non-porous, semi-permeable
membrane to separate mixtures of gases based on different permeation rates through the
membrane. In this way, a gaseous feed stream is fractionated into two streams. Figure 1 shows a
schematic of a single hollow-fiber membrane with a feed-gas mixture flowing through the tube
side of the membrane. The gas permeating through the membrane is called permeate and that
remaining on the feed side is called retentate. Membranes are typically asymmetric with a thin,
non-porous, selective membrane backed by a thicker, porous support layer. The inset in Figure 1
shows such a membrane. Transport through the selective membrane occurs by a solution-
diffusion mechanism, whereby permeating species first dissolve into the membrane and then
diffuse through the membrane. Accordingly, membrane selectivity is based on the relative
permeation rates of the each of the components through the membrane.
Gas-permeation membrane systems were first developed in the 1960-1970s as an
offshoot from liquid-based membrane technologies such as dialysis. They were first introduced
for purification of H2 gas, but they are now found in gas recovery from waste gas streams,
landfill gases, ammonia, and petrochemical products. These systems are also utilized in gas
generation and purification, including the production of nitrogen and enriched oxygen gases.
Gas-permeation membrane systems are capable of producing retentate streams with greater than
99.9 mol% N2 purity. Membrane-based separation units produce inert N2 streams for a number of
applications including food storage and packaging, tire filling, wave soldering, and on-board

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 Figure 1: Schematic diagram of a hollow-fiber gas-separation membrane with labeled feed,
permeate, and retentate streams. The inset includes details on the asymmetric membrane, which
consists of a thin, non-porous selective layer and a thick porous support layer. The lines labeled with
pressures p and concentrations C show a schematic concentration/pressure profile through the
membrane consistent with a solution-diffusion mechanism.

inerting of aircraft fuel-tanks.

As mentioned, the mechanism for transport is based on diffusivity and solubility. The
inset in Figure 1 shows a schematic concentration profile through the asymmetric membrane
assuming no mass-transfer resistances in the porous support layer or in the gas adjacent to either
side of the membrane. Diffusive flux through the membrane follows Ficks Law:
J i Di ( Cimr Cimp ) / Lm (1)
where Ji is the flux of component i [mol/m2-s]; Di is the diffusivity of component i in the
membrane [m2/s]; Cimr and Cimp are the concentrations [mol/m3] of component i inside
membrane wall on the feed (retentate) and permeate sides, respectively; and Lm is the
membrane wall thickness [m]. Equation 1 assumes that the permeating gases are dilute in the
membrane and do not interact with each other.
However, each gas dissolves to a different extent. Dilute gas-species partition coefficient
or solubility in the membrane is expressed by Henrys Law:
Cim Si pi (2)

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where Si is solubility constant or partition coefficient for gas species i in the membrane [mol/m3-
Pa] and pi is the partial pressure of species i in the gas phase [Pa].
If there are no mass-transfer limitations on either the retentate or permeate sides of the
membrane, Equations 1 and 2 combine to read

J i i pir pip (3)
Lm
where i is the permeability of gas species i through the membrane based on a partial-pressure
driving force [mol/m-s-Pa], pir is the partial pressure of gas species i on the retentate side [=] Pa,
and pip is the partial pressure of gas species i on the permeate side [=] Pa. The quantity i /Lm is
defined as the transmissibility, kpi, [mol/m2-s-Pa]. Equation 3 applies locally along the flow axis.
It is the starting point for membrane-separation design. Remember the restrictions are dilute gas
species and no mass-transfer resistances other than diffusion through the selective membrane.
Note the similarity of Equation 3 to that describing mass transfer between phases in other
separation processes.
In most hollow-fiber units, retentate and permeate pressures, although clearly different,
remain essentially constant along the length of the unit. The compositions and flows, however,
do change. Hence, Ji in Equation 3 is not a constant. However, from mass balance, we can
express the exit molar flow rate of the permeate species i, Vie [mol/s], simply in terms of the
average flux over the unit length, J i :
Vie AT J i (4)
where AT is the total membrane area. How to establish J i is covered below and in MSH Ch.
26 [1] and SHR Ch. 14 [2].
Membrane selectivity, ij is based on the different coefficients of permeation of the gas
components, as defined by
ij i j (5)
where, by convention, the ith species is the most permeable of the two. Selectivity is an
important parameter in membrane separation processes as it defines the relative improvement in
recovery compositions.
For a binary mixture of, for example, O2 and N2, recovery is defined by the equations
below. Let L and x denote molar flow rate and oxygen mole fraction on the tube side,
respectively. Also let V and y represent molar flow rate and oxygen mole fraction on the shell
side, respectively. Then we have that
yV
O2 recovery e e (6a)
x f Lf
(1 xe ) Le
N 2 recovery (6b)
(1 x f ) L f

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where the subscripts e and f denote exiting and feed streams. Thus, Ve, Le, and Lf are the
permeate, retentate, and feed molar flow rates. These subscripts are essential as the molar flows
and compositions within the membrane unit are not constant along the flow axis.
Another important design variable used later is the stage cut, s:
s Ve / L f (7)
Stage cut defines the ratio of permeate molar flow rate to total feed molar flow rate. For the case
of recovery of high-purity N2 from air with an oxygen-selective membrane, larger stage cuts are
sought.

EXPERIMENTAL APPARATUS
Membrane-module specifications and design
Each of the two apparatuses (MS1 and MS2) contains two Generon 210 membrane
cartridges. Figure 2 shows a diagram and relevant characteristics of the cartridge. Each
membrane module contains 38,000 asymmetric, polycarbonate hollow fibers, each finer than a
typical human hair. Many fibers are collected into a bundle and inserted into a tubular shell,
similar to the construction of a shell and tube heat exchanger. A cutaway of the inside of the
module to expose the fiber bundle is located near MS1. Air is introduced to the tube side of the
bundle and flows toward the other end of the tube. Ideally, the flow distributes equally among
the hollow fibers. A fraction of the air flowing down the tubes permeates through the fibers and
exits the module via the permeate outlet.
The Generon 210 membrane module is designed for versatility in the study of different
process parameters such as flow rates and pressures. These bench-scale membrane modules can
effectively separate air (21 mol% O2, 79 mol% N2) using normal operating pressures (~90 psig)
and temperatures to produce a purified nitrogen stream and an oxygen-enriched stream. It is
important that the high-pressure stream flows through the tube-side of the membrane. Otherwise,
the membrane may collapse.

Experimental apparatus
There are two nearly identical apparatuses located in S1 Gilman, labeled 1 (MS1) and
2 (MS2). Figures 3a and 3b show process-flow diagrams of MS1 and MS2, respectively.
Although the two are generally mirror images of each other, there are some slight differences.
Both apparatuses consist of two identical Generon 210 modules containing hollow-fiber,
polycarbonate membranes. The two modules are mounted separately in parallel; one module is
configured for co-current flow and the other for counter-current flow. Compressed air, nitrogen,
or oxygen can be fed to the unit at pressures up to a maximum operating pressure of 90 psig. The

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 Figure 2: Schematic diagram and chacteristics of Generon 210 module cartridge. Module is labeled
for counter-current operation; for co-current operation, feed and retentate streams are reversed.

recommended temperature range is 5-50 C, but since there is no temperature control, you are
limited to ambient temperature.
Three toggle valves select the feed-gas source. Two cylinders of compressed gas (one for
N2 and one for O2) provide pure species feedstock at desired pressures up to 90 psig. The high-
pressure house air line provides compressed air up to 100 psig. Take care not to pinch your
finger while closing the toggle valves. Prior to the toggle valves, high-pressure air runs through a
coalescing filter, dryer, carbon filter, a pressure regulator, and a gauge in series. The
pretreatment filters prevent membrane damage or fouling. Dried air then enters the feed port to
the parallel membrane modules.
Downstream of the toggle valves, a pressure gauge indicates the inlet (feed) pressure.
After passing a pressure-relief valve set at 100 psig, a thermocouple measures the inlet
temperature. The temperature console enables measurement of either the inlet or permeate
temperature. Note that the temperature measurements are necessary for determining the molar
flow rate of permeate.
The inlet gas distributes to the two membrane modules depending upon the positions of
the one-way feed valves Vf1 and Vf2 that allow flow to modules 1 and 2, respectively. Module 1
operates in co-current flow and module 2 operates in counter-current flow. For process-flow
diagrams illustrating the flow paths in both of these modes, see Appendix A.

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Figure 3a: Process flow diagram of MS1 showing membrane modules and accompanying pre-filters,
measurement devices, and piping.

Permeate exits each module and flows through a common line which passes through a
rotameter. Valves Vp1 and Vp2 are three-way valves that direct permeate to the atmosphere or to
the downstream rotameter. Permeate flow rate is indicated on a rotameter and is measured by a
dry-test gas meter. The dry-test gas meter is highly accurate and registers total volume in ft3
(note: this is not the volume at STP). To measure permeate flow rate, use a stopwatch to make
timed-volume measurements with the dry-test gas meter. Note that for MS2 permeate meter, the
needle does not always rotate at a constant rate, so care must be taken to measure a full rotation
or average multiple readings. The permeate thermocouple is located just upstream of the dry-test
meter.
Retentate exits modules 1 and 2 through the one-way valves Vr1 and Vr2, respectively,
before passing through a needle valve and rotameter. The needle valve allows for control of the
retentate-stream flow rate. Thus, the retentate needle valve provides indirect control of the feed
flow rate. The rotameter measures the retentate volumetric flow rate. The calibration relating the
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Figure 3b: Process flow diagram of MS2 showing membrane modules and accompanying pre-filters,
measurement devices, and piping. Note that MS1 (Figure 3a) is not the same as MS2 shown here.

rotameter reading (Sho-Rate) to the volumetric flow rate in standard ft3/s (SCFS) appears in
Appendix B (note: standard indicates the reported volume is at STP). A pressure gauge just
prior to the needle valve measures the retentate pressure. Note that valve Vrm enables mixing of
the retentate streams from modules 1 and 2 in the case that both operate simultaneously (mixed
flow configuration).
Finally, both the permeate and retentate flow past O2 sensors that measure their
compositions before venting to the atmosphere. The labeled permeate O2-sensor port is used
exclusively for sample the permeate composition, while the retentate port serves dual purposes.
A selector valve located just upstream of the relief valve directs the feed stream either to the
membrane modules or directly to the retentate O2-sensor port. This enables calibration of the O2
sensors with pure O2 from the compressed cylinder. In the other position, the retentate port
simply measures the retentate composition. The O2 sensors must be calibrated at the beginning of
each lab session; the calibration should be checked periodically. Calibration instructions for the

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sensors are located in Appendix C. The oxygen sensors are not to be removed from their ports in
the flowing streams except for calibration in air. When inserting an O2 sensor probe into its port,
be very careful not to damage the active portion of the sensor.

SAFETY
This experiment involves high-pressure gases that could cause damage in case of over-
pressurization and/or equipment failure. Wear safety glasses and standard lab PPE at all times to
minimize the risk of injury from projectiles. All apparatus equipment is rated above the pressures
utilized and a pressure-relief valve is installed in both apparatuses. Thus, any risks are
significantly mitigated. In case of an emergency, immediately turn off the valve to the high-
pressure-air line.
Read the SOP for pressurized oxygen located on the bCourses website. The pressurized
oxygen (and nitrogen) tanks should be treated with care to prevent any rupture. Oxygen is a
flammability hazard, so take care to avoid sparks and open flames while using this experiment.
In case of an emergency, or fire, close the valve to the oxygen tanks.

PRE-LAB EXERCISES
1. What experiments must you conduct to address all of the stated objectives? Describe in
detail the procedures necessary for each experiment. Be sure to include the following
details:
a. Which parameters are varied and which are held constant. Where possible,
include ranges for varied parameters and values for parameters held constant.
b. What measurements you will make and how you will convert the raw
measurement into the desired units or form.
c. Pre-made tables in your lab notebook or Excel spreadsheets for data collection.
d. Description of the analyses required to extract any parameters.
2. Provide a sample calculation for determination of the molar flow rate of permeate from
the raw measurement. Which flow meter do you use? Are any additional measurements
or conversions necessary? Repeat this procedure for the retentate flow rate (see the Felder
reference in the References section of bCourses if there are questions on converting
SCFS to mol/s).
3. Calculate the effective membrane area for one membrane cartridge.
4. Draw the tube-side and shell-side concentration profiles along the module for co-current
and counter-current operation. Which of the configurations do you expect to be the most
effective at air separation and why?
5. Explain how you would calculate the membrane transmissibility of O2 and N2 from
measured parameters. How do you express selectivity from this? Do you have enough
information to calculate the membrane permeability from its transmissibility?
6. If you are unfamiliar with the operation of regulator valves, ask your GSI to train you at
the beginning of the first lab session.

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PROCEDURE
For this experiment, you must design your own procedure to answer the lab objectives.
There are two sets of experiments to be completed:
(1) Measurement of membrane transmissibility to N2 and O2
(2) Parametric studies on the effect of feed pressure and retentate flow rate on air
separation.
From the stated objectives and information in the lab manual, work as a group to write your own
procedure for these two sets of experiments.
Keep in mind that you may not be able to plan exact flow rates or pressures until you
come into lab and work with the apparatus. However, make sure to identify beforehand how you
will determine which pressures and flow rates to use.
It is important to test a wide range of each parameter to guarantee you will see a
statistically significant trend. If you test too small a range, the changes in each measured variable
may be small relative to the experimental error or relative to the observed trend. The apparatus is
capable of operating at a wide range of pressures and flow rates, so take advantage of this.
Make sure that you choose your fixed parameter in such a way that varying the other
parameters results in >95 mol% N2 in the retentate stream. Since you will utilize your
experimental results in the design task, it is ideal that you conduct experiments near the design
specifications. This avoids, or at least minimizes, the need to extrapolate and increases
confidence in your design.
In your procedure, make sure to leave time in between runs for the system to reach its
new steady state. Failure to do so invalidates most of the analyses. You will have to pay close
attention to the O2 meters to determine when compositions level off to within the measurement
ability.
Lastly, it is advised that you arrive in lab with a pre-made Excel spreadsheet fitted with
columns for data collection and conversion. This enables you to visualize the trends as you take
measurements. You will know right away whether you should repeat a measurement and whether
you need a larger range or if you can stop collecting more points. Ideally, you will arrive in lab
with an idea of what the trends should look like. Thus, when you plot the data points in real time,
you can identify immediately if there is an experimental issue (i.e., a leak). On the other hand, an
unexpected trend may indicate that you must revisit your initial reasoning.
In case of an emergency, immediately close the house high-pressure air valve. Otherwise,
it is important that all groups follow proper shut-down procedure:
1. Open the needle valve on the retentate stream. Do not open too far because this may
disable the valve mechanism.
2. Shut the house pressure valve.
3. Fully open the pressure regulating valve to bleed any of the remaining air out of the
system, then close the valve.
4. Turn off the switches on both O2 meters. Otherwise, the batteries may be dead when
the next group tries to use the equipment.

MS-9
ANALYSIS & DESIGN
1. Determine the transmissibility of pure nitrogen and of pure oxygen by plotting the
permeate flux as a function of the total pressure difference across the membrane, p.
(You expect a straight line through the origin.) Are the transmissibilities constant over the
entire range of pressure? What might cause deviation from the ideal expectation? What is
the ideal selectivity of the membrane?
2. For each data point taken with air as feed, carry out a mass balance on the system. Note
that you have measured enough flow rates and compositions to have redundancy. Check
the feed flow rate calculated from an overall mass balance against that calculated from a
component balance. How different are the quantities?
3. Derive Equation 3 given Equations 1 and 2. How is i related to Di and Si?

4. Analyze your experimental data to describe how feed pressure and retentate flow rate
affect membrane performance. Most importantly, what are the effects on these variables
on retentate nitrogen purity and nitrogen recovery?

Figure 4: Schematic of counter-current membrane-separation unit emphasizing a differential

control volume over which an oxygen mass balance is applied on the shell side. Note that only
the oxygen fluxes are labeled.

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 One of your objectives is to construct a simple model that predicts the permeate flow rate
and composition for a given retentate production rate and composition and retentate
composition. Questions (5)-(10) outline approaches to model the system.

5. As shown in Figure 4, one can draw a control volume on a differential volume on the
shell side of the separator. Write out the mass balance on oxygen for this control volume
and transform it into a differential equation, but do not solve. Can you solve for x(z) and
y(z) analytically?
6. Given the difficulty of solving the full set of governing equations outlined in Question 5,
we will develop a simpler model for approximate analysis. Consider again the control
volume depicted in Figure 4. Define ym as the oxygen mole fraction in the gas entering
the control volume through the membrane at z. What is the difference between ym and y?
Assume that y is constant within the control volume, i.e. perfect radial mixing.
7. The following expression describes ym in terms of the oxygen and nitrogen fluxes through
the membrane:
J O2
ym (8)
J O2 J N 2

Utilize Equations 3 and 8 to express ym in terms of x, y, P, i , and Lm.

8. We wish to extend the equation developed in Question 7 that describes local permeate
composition, ym, to describe the performance of an entire separation unit. Assume a
homogeneous composition along the tube side of the membrane. Also, assume that the
shell-side composition is homogeneous and equivalent to that of the gas crossing the
membrane. In this case, y = ym. Under what conditions or in what region(s) of the
separation unit does this assumption hold?
9. Solve the expression from Question 8 to predict the permeate flow rate and composition.
What values are reasonable to use for x?
10. Compare the values predicted by your simplified model to your experimental data. In
particular, look at the effect of feed pressure on permeate composition. Describe what
assumptions made in developing the model may be responsible for deviations between
model and experiment. Does your model predict a difference between co- and counter-
current operation? Why or why not? How might you improve your model to obtain better
matching between experiment and results?
11. Design a membrane-separation process to achieve a 95% pure nitrogen stream. What
process variables must you set to get the most economical separation? The oxygen-rich
stream has no economic value. Discuss the tradeoffs between purity and recovery in
designing such a process. Quantify the work or power required from the process. How do
different flow rates and pressures affect the energy requirements for the process?

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REFERENCES

1. McCabe W.L., Smith J.C., Harriott P. Unit Operations of Chemical Engineering, 7th ed.;
McGraw-Hill: New York, 2005.
2. Seader J.D., Henley E.J., Roper D.K. Separation Process Principles, 3rd ed.; Wiley: New
York, 2011.

SUGGESTED REFERENCE LITERATURE

1. Koros W.J., Fleming G.K. Membrane-Based Gas Separation. J. Mem. Sci. 1993, 83, 1-
80.
2. Chern R.T., William J.K., Fedkiw P.S. Simulation of a Hollow-Fiber Gas Separator:
The Effects of Process and Design Variables. Ind. Eng. Chem. Process Des. Dev.
1985, 24, 1015-1022.
3. Pan C.Y., Habgood H.W. "An Analysis of the Single-Stage Gaseous Permeation
Process." Ind. Eng. Chem. Fundam. 1974, 13(4), 323-331.
4. Robeson L.M. Correlation of separation factor versus permeability for polymeric
membranes. J. Mem. Sci. 1991

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APPENDICES
Appendix A: Flow-Configuration Diagrams
Each flow configuration requires the correct combination of open and closed valves.
Correct operation requires you to trace the lines and double-check that you have chosen the
correct valve positions from upstream to downstream. Figures A-1 and A-2 show the operational
valves and lines for the co-current and counter-current configurations, respectively. These
diagrams may help you in preparing for operation in each configuration.

Figure A-1: Process-flow diagram indicating the gas flow path for co-current module operation.

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 Figure A-2: Process-flow diagram indicating the gas flow path for counter-current module
operation.

Appendix B: Rotameter Calibration Curves

There are four total rotameters in MS1 and MS2, one for the permeate and retentate in
each setup. Calibration curves are needed only for the retentate rotameters because the permeate
flow rates are measured with more accurate dry-test gas meters. Figure B-1 shows the volumetric
flow rate in SCFS for various rotameter Sho-Rate readings. The points indicate measured
values and the lines correspond to a linear fit. The linear fit labeled Left in Figure B-1
corresponds to the retentate rotameters for MS1 and MS2. Note that these volumetric flow rates
are listed at STP, meaning they can be readily converted to molar flow rates.

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Figure B-1: Calibration curve for the retentate rotameters relating the volumetric flow rate in SCFS to the
rotameter Sho-Rate reading. The equations at the top give the linear best fits to the data for each
rotameter Left corresponds to the retentate rotameters in MS1 and MS2. Ignore Middle and Right.

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Appendix C: Oxygen-Sensor Calibration Procedure
The oxygen sensors must be calibrated at the beginning of each lab session and should be
checked periodically throughout the period. If the calibration drifts significantly or you are
unable to successfully calibrate the sensor, notify your GSI. Follow the steps below to calibrate
the sensors.
1. Turn ON the O2 meter and check the battery.

2. Open the oxygen cylinder. The pressure of the oxygen can be controlled by a pressure
regulator installed on the cylinder. Set the pressure regulator to 5 psig.
3. Open O2 toggle feed valve (black). This allows oxygen to flow into the apparatus. The
feed-pressure gauge should be equal to the pressure set by the regulator.
4. Check that the black knob (the selector valve), located downstream of the feed-pressure
gauge, points in the correct direction to direct pure oxygen directly to the top sample port
(see description of apparatus).
5. Place the oxygen sensor into the top sample port.
6. Press and hold the ON/OFF key down until the LCD starts to count from 3 to 0. Release
the key as soon as the count starts and wait for LCD to read 100 plus or minus a few
percent. Note: Holding ON/OFF key down during the automatic calibration sequence will
shut the unit off when released.
7. Take out the sensor and expose it to air. Let the sensor equilibrate. Repeat step #6,
waiting for the LCD to read 20.9 plus or minus a few percent.
8. Repeat steps 5-7, until the calibration is constant.
9. Close the oxygen feed valve and tank valve unless you plan to do more work with pure
oxygen.

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