Membrane Separation

Processes
Bernan, Shariff Molzir
Calma, Joseph
Maat, Daren
Quiño, Rasti
Membrane Separation Processes

• Membrane separations represent a new type of unit operation. The

membrane acts as a semipermeable barrier and separation occurs by
the membrane controlling the rate of movement of various molecules
between two liquid phases, two gas phases, or a liquid and a gas
phase. The two fluid phases are usually miscible and the membrane
barrier prevents actual, ordinary hydrodynamic flow.
1. Classification of membrane processes
• Porous membrane
1. Gas diffusion - The rates of gas diffusion depend on the pore sizes and the
molecular weights. We may have molecular, transition, and Knudsen diffusion
regions depending on the relative sizes of pore and gas molecule.
2. Microfiltration (MF) -This refers to membranes that have pore diameters from
0.1 to 10 m. It is used to filter suspended particulates, bacteria or large
colloids from solution.
3. Ultrafiltration (UF): - This refers to membranes having pore diameters in the
range 20-1000 . It can be used to filter dissolved macromolecules, such as
proteins and polymers, from solution.
4. Reverse osmosis (RO): - The membrane pores are in the range of 5-20 in
diameter, which are within the range of the thermal motion of the polymer
chains.
5. Dialysis
• Tight (nonporous, or dense) membrane - Here the permeants are
sorbed into the membrane material under the influence of their
thermodynamic potential and pass it as a result of a driving force
exerted:
1. Gradient of vapor pressure - pervaporation (feed is liquid) , vapor
permeation (feed is vapor)
2. Pressure gradient - gas permeation (feed & permeant are gases),
reverse osmosis (feed & permeant are liquids)
3. Temperature gradient - thermoosmosis
4. Concentration gradient - dialysis (osmosis, liquid permeation),
pertraction
5. Gradient in electric potential - electrodialysis (ion-selective
membrane)
Membrane Classification
Types of membrane structures
• Dialysis (liquid permeation)
• In this case the small solutes in one liquid phase diffuse through a
porous membrane to the second liquid phase where the permeants
are diluted by means of a so-called sweeping solvent. The driving
force is a concentration gradient so the flux rates are low. If the
boiling point of the permeants is much lower than that of the
sweeping liquid, the permeants can be separated by flashing from the
sweeping liquid, the dialysis process is called pertraction.
• In practice dialysis is used to separate species that differ appreciably
in size, which have a large difference in diffusion rates. Applications
include recovery of sodium hydroxide in cellulose processing,
recovery of acids from metallurgical liquors, removal of products from
a culture solution in fermentation, and reduction of alcohol content
of beer.
2. Series Resistances in Membrane Processes
• In dialysis, the solute molecules must first be transported or diffuse
through the liquid film of the first liquid phase on one side of the solid
membrane, through the membrane itself, and then through the film
of the second liquid phase. This is shown in Figure 2, where c1 is the
bulk liquid phase concentration of the diffusing solute A in kg mol
A/m3, c1i is the concentration of A in the fluid just adjacent to the
solid, and c1iS is the concentration of A in the solid at the surface and
is in equilibrium with c1i. The mass transfer coefficients are kc1 and
kc2 in m/s. The equilibrium distribution coefficient
K’ is defined as:
• The flux equations through each phase are all equal to each other at
steady state:
where pM is the permeability in the solid in m/s, L is the thickness in m,
and DAB is the diffusivity of A in the solid in m2/s. Instead of
determining DAB and K’ in two separate experiments, it is more
convenient to determine pM in one experiment. The concentration
differences can be obtained from Eq. (3):

By adding three equations, the internal concentrations drop out, the

final equation is
• The denominator can be considered as the inverse of overall mass transfer
coefficient. In some cases, the resistances in the two liquid films are quite small
compared to that of the membrane resistance, which controls the permeation
rate.

Example 1: Membrane diffusion and liquid film resistances

A liquid containing dilute solute A at a concentration c1=0.030 kg mol/m3 is
flowing rapidly by a membrane of thickness L=3.0x10-5 m. The distribution
coefficient K’=1.5 and DAB=7.0x10-11 m2/s in the membrane. The solute diffuses
through the membrane and its concentration on the other side is c2=0.0050 kg
mol/m3. The mass transfer coefficient kc1 is large and can be considered as
infinite and kc2 =2.02x10-5 m/s.
• (a) Derive the equation to calculate the steady-state flux NA and make a sketch.
• (b) Calculate the flux and the concentrations at the membrane interfaces.
3. Gas Permeation
3.1 Series resistances in membrane processes
• Similar equations to dialysis can be written for gas permeation. The
equilibrium relation between the solid and gas phases is given by

• where S is the solubility of A in 𝑚3 (STP)/atm 𝑚3 3 solid, and H is the

equilibrium relation in kg mol/ 𝑚3 atm. This is similar to Henry’s law.
The flux equations in each phase are as follows:
 3.2 Types of membranes and permeabilities
for gas separation
• The permeation flux is inversely proportional to the thickness of the
membrane. So if the membrane is thick (100 µm), as used in the early
stage to prevent any tiny holes which reduced the separation, the flux is
low. Some newer asymmetric membranes include a very thin but dense
skin on one side of the membrane supported by a porous substructure.
• The dense skin has a thickness of about 1000 Å and the porous support
thickness is about 25-100 µm. The flux is thousands of times higher
than the 100-µm-thick original membranes. Some typical materials of
present membranes are a composite of polysulfone coated with silicon
rubber, cellulose acetate and modified cellulose acetate, aromatic
polyamides or aromatic polyimides, and silicon-polycarbonate
copolymer on a porous support.
• Experiments are necessary to determine the permeabilities of gases
in membranes. Some typical data are listed in Table 1. In a given
membrane the permeabilities of various gases may differ significantly.
• For the effect of temperature T in K, the ln PA’ increases with T
following approximately a linear function of 1/T. However, operation
at high temperatures can often degrade the membranes. When a
mixture of gases is present, the permeability of an individual
component may be reduced by up to 10%. Hence, when using a
mixture of gases, experimental data should be obtained to determine
if there is any interaction between the gases. The presence of water
vapor can also have similar effects.
3.3 Types of equipment for gas permeation
• 3.3.1 Flat membranes. These are mainly used to experimentally
characterize the permeability of the membrane. The modules are
easy to fabricate and use and the areas of the membranes are well
defined. In some cases modules are stacked together like a multilayer
sandwich or plate-and-frame filter press. The major drawback of this
type is the very small membrane area per unit separator volume.
• 3.3.2 Spiral-wound membranes. This configuration increases
markedly the membrane area per unit separator volume up to 328
m2/ m3 and decreases the pressure drop. The assembly consists of a
sandwich of four sheets wrapped around a central core of a
perforated collecting tube.
3.3.2 spiral membrane
• The four sheets consists of a top sheet of an open separator grid for the
feed channel, a membrane, a porous felt backing for the permeate channel,
and another membrane as shown in Fig. 4. The spiral-wound element is
100 to 200 mm in diameter and is about 1 to 1.5 m long in the axial
direction. The flat sheets before rolling are about 1 to 1.5 m by 2 to 2.5 m.
The space between the membranes (open grid for feed) is about 1 mm and
the thickness of the porous backing (for permeate) is about 0.2 mm.
• The whole spiral-wound element is located inside a metal shell. The feed
gas enters at the left end of the shell, enters the feed channel, and flows
through this channel in the axial direction of the spiral to the right end
where the exit residue gas leaves. The feed stream permeates
perpendicularly through the membrane. This permeate then flows through
the permeate channel toward the perforated collecting tube, where it
leaves the apparatus at one end.
• 3.3.3 Hollow-fibre membranes. The membranes are in the shape of
very small diameter hollow fibres. The inside diameter of the fibres is
in the range of 100 to 500 m and the outside 200 to 1000 m with
the length up to 3 to 5 m. The module resembles a shell-and-tube
heat exchanger. Thousands of fine tubes are bound together at each
end into a tube sheet that is surrounded by a metal shell having a
diameter of 0.1 to 0.2 m, so that the membrane area per unit volume
is up to 10000 m2/ m3.
• The high pressure feed enters into the shell side at one end and
leaves at the other end. The hollow fibres are closed at one end of
the tube bundles. The permeate gas inside the fibres flow
countercurrently to the shell-side flow and is collected in a chamber
where the open ends of the fibres terminate.
3.4 Types of flow in gas permeation
• Because of the very high diffusion coefficient in gases, concentration
gradients in the gas phase in the direction normal to the surface of
the membrane are quite small. Hence, gas film resistance compared
to the membrane resistance can be ignored.
• If the gas stream is flowing parallel to the membrane in plug flow, a
concentration gradient occurs in this direction. Hence, several cases
can occur in the operation of a membrane module. Both permeate
and feed sides can be operated completely mixed or in plug flow.
Countercurrent or cocurrent flow can be used when both sides are in
plug flow. This is summarized in Figure 7.
4. Complete-mixing model for gas separation
• 4.1 Basic equations used
• A detailed diagram is shown in Fig. 8 for complete mixing. The overall
material balance is

• where qf is the total feed flow rate in 𝑐𝑚3 (STP)/s; q0 is outlet reject
flow rate in the same unit; and qp is outlet permeate flow rate, 𝑐𝑚3
(STP)/s. The cut or fraction of feed permeated, Ɵ,
• The rate of diffusion or permeation of species A (in a binary of A and
B) is given below
• where PA’ is the permeability of A in the membrane, 𝑐𝑚3 (STP) cm/(s
𝑐𝑚2 cm Hg); qA is the flow rate of a in permeate, 𝑐𝑚3 (STP)/s; Am is
membrane area, 𝑐𝑚2 ; t is membrane thickness, cm; Ph is the total
pressure in the high pressure (feed) side, cm Hg; pl is the total
pressure in the low pressure or permeate side, cm Hg; x0 is the mole
fraction of A in the reject side; and yp is the mole fraction of A in the
permeate. Note that phx0 is the partial pressure of A in the reject gas
phase.
• A similar equation can be written for component B:
• This equation relates yp, the permeate composition, to x0, the reject
composition, and the ideal separation factor α* is defined as
4.2 Solution of equations for the design of
complete-mixing case
• For the design of a complete-mixing model, there are seven variables,
xf, x0, yp, Ɵ, α*, pl/ph, and Am, four of which are independent
variables. Let us consider two common cases.
• Case 1. xf, x0, α *, and pl/ph are given and yp, Ɵ , and Am are to be
determined by solution of the equations. Eq. (16) can be rearranged
as
4.3 Minimum concentration of reject stream
• If all of the feed is permeated, then Ɵ = 1 and the feed composition xf
= yp. For all values of Ɵ< 1, the permeate concentration yp > xf.
Rearranging Eq. (16) to give
• which means that x0 is a monotonic increasing function with yp. When
yp is at its minimum value of xf, the reject composition have its
minimum as

• Hence, a feed of xf concentration cannot be stripped lower than a

value of x0M even with an infinitely large membrane area for a
complete mixed system. To strip beyond this limiting value a cascade-
type system or a single unit of plug flow should be used
5. Cross-flow model for gas separation
• A detailed flow diagram is shown in Figure 9. The flow in the high-
pressure or reject stream is considered to be of plug flow. On the low-
pressure side the permeate stream is pulled into vacuum, so the flow
is perpendicular to the membrane. No mixing in both sides is
assumed. This cross-flow pattern is an approximation to the actual
spiral-wound membrane separator with a high-flux asymmetric
membrane resting on a porous support.
• The local permeation rate over a differential membrane area dAm at
any point in the stage is

• where dq is the total flow rate permeating through the area dAm.
Dividing Eq. (26) by (27) gives
• This relates the permeate composition y to the reject composition x
at a point along the path. It is similar to Eq. (16) for complete-mixing.
• Case 1. The values of xf, x0, α*, and Pl/Ph are given and yp, Ɵ,
and Am, are to be determined. Ɵ * or Ɵ can be calculated
from directly from Eq. (29). Since all other variables are
known, yp can be calculated from Eq. (19). The membrane
area Am is calculated from Eq. (30) numerically.
• Case 2. xf, Ɵ, α*, and Pl/Ph are given and yp, x0, and Am, are
to be determined. This is trial and error. An initial value of x0
is assumed and substituted into Eq. (19) to calculate yp.
Reference

• C.J. Geankoplis, “Transport Processes and Unit Operations”, 3rd ed.,

Prentice Hall, Englewood Cliffs, New Jersey, 1993. (Chapter 13)
• W.L. McCabe, J.C. Smith, P. Harriott, "Unit Operations of Chemical
Engineering", 5th ed., McGraw-Hill, New York, 1993. (Chapter 26)