Membrane separation techniques

1. Dialysis and electrodialysis

2. Reverse osmosis
3. Gas permeation
4. pervaporation
Dialysis

(wash)
 Dialysis
Feed: Liquid at P1, containing solvent, solutes of type A, solutes of type B,
and/or insoluble colloids.
Wash: solvent at P2 .
Product: liquid diffusate (permeate) containing solvent, solute A, small
amounts of solute B
Retentate: dialysate solvent containing remaining A,B and retained colloidal
matter.
Membrane: thin, microporous. Size of pores allowing solutes of type A to
pass, for larger solutes of type B reduced or no passage.

Example: Recovery of H2SO4 from an aqueous stream containing sulfates.

streams in streams out

feed wash dialysate diffusate
Flow rate, gph 400 400 420 380
H2SO4, g/L 350 0 125 235
CuSO4, g/L as Cu 30 0 26 2
 Commercial applications of dialysis
1. Recovery of sodiumhydroxide from waste streams,
2. Recovery of chromic, hydrochloric and hydrofluoric acids from
contaminating metal ions,
3. Recovery of sulfuric acid from aqueous solutions containing NiSO4,
4. Removal of alcohol from beer to produce low-alcohol beer,
5. Recovery of nitric acid and hydrofluoric acid from spent stainless-
steel pickle liquor.
6. Removal of mineral acids from organic compounds,
7. Removal of low-molecular-weight contaminants from polymers,
8. Purification of pharmaceuticals.

Of great importance is hemodialysis: Urea, creatine, uric acid,

phosphates and chlorides are removed from blood without removing
essential higher-molecular-weight compounds and blood cells
(artificial kidney).
 Estimation of membrane area
At a differential location in a dialyzer, the rate of mass transfer of solute
across the dialysis membrane is:

dni = Ki (ciF -ciP ) dAM

Ki : overall mass transfer coefficient.

In terms of individual coefficients Ki is given by:

(1/Ki) = (1/kiF ) + (lM/PMi ) + (1/kiP )

kiF , kiP : mass-transfer coefficients for the feed side and permeate-side
boundary layers.

The necessary membrane area can be found by integrating the above

equation.
 Electrodialysis
• It is an electrolytic process for separating an aqueous
electrolyte feed solution into a concentrate (brine) and a
dilute or desalted water (diluate) by means of an electric
field and ion-selective membranes.
• Ion-selective membranes are of two types, cation
selective and anion selective, arranged in an alternating-
series pattern. Both types do not allow water to pass.
• A direct current voltage is applied across the anode and
cathode which are made of chemically neutral materials.
Electrons are metalically conducted through wiring from
anode to cathode then through the cell by ionic conduction
from the cathode back to the anode.
• The acidic electrode rinse solution that circulates through
compartments 1 and 5 neutrilizes the remaining OH- ions
and prevents precipitation of compounds such as CaCO3 and
Mg(OH)2
Electrodialysis; C, cation transfer membrane; A, anion transfer membrane
Reactions:
At the cathode:
Reduction of water: 2H2O + 2e- → 2OH- + H2(g)

At the anode:
Oxidation of water: H2O → 2e- + ½ O2 (g) + 2H+
If Cl- are present: 2 Cl- → 2e- + Cl2 (g)

• In commercial electrodialysis systems, 100-600 cell pairs are used.

• Typically, 50-90% brackish water is converted to potable water. Main
application is desalination of water for salt conc. of 500-5000ppm.
Below this range, ion exchange, above this range reverse osmosis is
more economical. There are some other commercial applications
similar to applications of dialysis.
 Estimation of the required membrane area
Current density rather than permeability is used.
Applying Faraday’s Law:
AM = zFQ∆ c / iξ
AM = total area of cell pairs, m2
z = electrochemical valance of the ions being transported through the membranes,
F = Faraday’s Constant (96520 amp-s/equivalent)
Q = Volumetric flow rate of the diluate (potable water), m3/s
∆ c = difference between feed and diluate ion concentration in equivalents/m3
i = current density, amps/m2 of a cell pair
ξ = current efficiency <1.00

Power consumption is given by; P = I E , where

P = power, watts
I = electric current flow through the stack, amps
E = voltage across the stack, volt
 Osmosis and reverse osmosis

initial condition at equilibrium after reverse osmosis

osmosis
 Reverse Osmosis
• Separation technique used to partially remove a solvent from a solute-
solvent mixture applying a pressure gradient.
• The feed is a liquid at high pressure P1, containing solvent (water),
solubles (inorganic salts) and colloidal matter. No sweep liquid is used,
permeate side of membrane kept at a much lower pressure, P2.
• A dense membrane is used that is permselective for the solvent. To
withstand large pressure difference, thick, asymmetric, composite
membranes are utilized.
• Products of RO are a permeate of almost pure solvent and a retentate
of solvent-depleted feed.
• Main application of RO is for desalination and purification of
seawater, brackish water and wastewater. Over 750 million
gallons/day drinkable water is is produced using RO.
• In a typical RO for desalination; salt content is 3.5%w, π is 350psi,
feed pressure is 800-1000psi, transmembrane water flux is
0.365m3/m2-day. 45% of feed water with 99.95% purity is obtained.
Reverse osmosis
• A typical cylindirical module is 20cm in diameter by 100cm long,
contains 33.9 m2 of membrane surface.
• Other uses of RO in industry are:
1. Treatment of industrial wastewater to remove heavy metal ions,
nonbiogradable substances and other components of commercial
value,
2. Treatment of rinse water from electroplating processes to obtain a
metal ion concentrate and a permeate that can be used as rinse,
3. Separation of sulfites and bisulfits from effluents in pulp and paper
processes,
4. Treatment of wastewater in dyeing processes,
5. Recovery of constituents having food value from wastewaters in food
processing plants (lactose, lactic acid, sugars, starches, proteins).
6. Treatment of municipal water to remove inorganic salts, low-
molecular-weight organic compounds, viruses and bacteria.
7. Concentration of certain food products, coffee, tea, soups, milk,
fruit juices and tomato juice,
8. Concentration of amino acids, alkaloids, enzymes and like.
 Estimation of solvent flux
When RO takes place with solute on each side of the membrane, at
equilibrium:
( P1 - π 1 ) = ( P2 - π 2 )

The driving force for the transport of solvent through the membrane
is: (∆ P - ∆ π ) and the rate of mass transport is:

NH2O = ( PMH2O / lM ) (∆ P - ∆ π )

∆ P = hydraulic pressure difference across the membrane (PF – PP),

∆ π = osmotic pressure difference across the membrane, (π P - π F),
often π P ≅ 0, since pure solvent,
The flux of solute (salt) through the membrane is given by:

Ni = ( Di / lM ) ( c’io – c’iL )

Di is the diffusivity of solute in the membrane, c’io and c’iL are feed side
and permeate side solute concentrations in the membrane. The flux
of solute is independent on pressure. The higher ∆ P, the purer the
permeate water.
For RO of seawater and of solutions with low salt content, the osmotic
pressure can be estimated by:

π = 1.12 T Σ mi

π = osmotic pressure, psi

T = temperature, K
Σ mi = summation of molalities of all dissolved ions and nonionic
species in the solution, mol/liter
 Concentration polarization
• A phenomenon, called CP is particularly important on the feed side of
the RO-membrane. CP is the buildup or depletion of species in the
boundary layer due to mass-transfer resistance.
• For concentrations for water and salt, cW , cS ; (cSl – cSF) causes mass
transfer of salt by diffusion from the membrane surface back to the
bulk feed. The lower the mass-transfer coefficient, the higher cSl. The
value of cSl fixes the osmotic pressure. A salt balance at the upstream
membrane surface gives:

NH2O cSF = kS (cSl – cSF)

cSl = cSF ( 1 + NH2O / kS )

CP effect is seen to be most significant for high water fluxes and low
mass-transfer coefficients.
 cWP
cWF
cWl

cSl

cSF
cSM
cSP

Concentration polarization effects in reverse osmosis

 PF PC
PC ≅ 85-90% PF

abt. 50% of feed,

purity = 99.95%w

Reverse osmosis process for production of potable water

Gas permeation
• Gaseous feed at high pressure, contains some low-MW species
(MW<50), to be separated from small amounts of higher-MW
species.
• Permeate side of the membrane kept at a much lower pressure.
• Membrane used is often dense, sometimes microporous,
permselective for certain low-MW species in the feed gas.
Permselectivity depends on both membrane absorption and
membrane transport rate.
• Products are a permeate enriched in A-type species and a retentate
enriched in B-type species.
• Transport through the membrane modeled by solution-diffusion
model.
• If membrane microporous, pore size extremely important to block
passage of B-type species.
• Since 1980, applications of GP with dense polymeric membranes have
increased dramatically.
Industrial Applications of GP:
1. Separation of H2 from CH4, (H2 permeation rate through dense
membrane is very high)
2. Adjustment of H2-to-CO ratio in synthesis gas,
3. O2 enrichment of air,
4. Removal of CO2
5. Drying of natural gas and air,
6. Removal of He and organic solvents from air.

• At low temperature processes GP is preferred to absorption and

pressure-swing adsorption separation tecniques due to low capital
investment, ease of installation and operation, absence of rotationg
parts, high flexibility, low weight and less space requirements.
• Available GP membranes for bulk separation of air achieve separation
factors of 3-7 for O2-N2. Product purities are 95-99% N2 retentate,
and 30-45% O2 permeate.
• In GP usually spiral wound or hollow fiber modules are used because of
their higher packing density. Typical feed side pressures are 300-500
psia, may be as high as 1650 psia.
Pervaporation
• The term pervaporation is a combination of terms permselective
and evaporation.
• Different phases on two sides of the membrane. Feed is a liquid
mixture at a pressure high enough to maintain a liquid phase as the
feed is depleted of species A and B to produce vapor phase
permeate.
• A composite membrane is used that is selective for species A,
selectivity for B is a lot less. The retentate is enriched in
species B.
• Permeate pressure is maintained below the dew point of the
permeate to rocover it as a vapor, often under vacuum. The vapor
permeate is enriched in species A.
• Overall permeabilities of species A and B depend upon their
solubilities in and diffusion rates through the membrane.
• Major commercial applications of PV are:
1. Dehydration of ethanol,
2. Dehydration of other organic alcohols, ketones and esters,
3. Removal of organics from water.
Separation of organic mixtures by PV is receiving much
attention

• PV is best applied when the feed solution is dilute in the main

permaent since the latent heat of vaporization of the permaent is
provided by the sensible heat of the feed.
 99,5 %w ethanol
95%w ethanol

60%w ethanol

25%w ethanol

Pervaporation integrated with distillation

for removal of water from ethanol
Ethanol-water separability for polyvinylalcohol membrane
at 60oC and 15 torr (0.02atm.) vacuum.
 Enthalpy balance in PV
A PV module typically operates adiabatically. The enthalpy of
vaporization is supplied by sensible enthalpy of the feed. For PV of a
binary liquid mixture of components A and B; assuming:
1. constant pure component liquid specific heats,
2. neglicible heat of mixing,
an enthalpy balance in terms of mass flow rates m, liquid sensible heats
CP, and heats of vaporization ∆ H gives:

(mAF CpA + mBF CpB ) (TF-TR) = (mAP CpA + mBP CpB ) (TP-TR)

+ (mAP ∆ HA + mBP ∆ HB )

TP = temperature of the permeate = permeate dew point at permeate

vacuum,
 Estimation of flux
• Transport of a permeant through a membrane by PV is different from dialysis or gas permeation
since there is a phase change and there are nonideal solution effects in the liquid feed. The driving
force for permeation is expressed in terms of partial vapor pressure difference.
• Since pressures on both sides of the membrane are low, the gas phase obeys the ideal gas law.

At the upstream membrane surface (1), permeant activity for i is:

ai(1) = pi(1) / PiS(1) PiS(1) = vapor pressure of i at TF

The liquid on the upstream side is generally nonideal:

ai(1) = γ i
(1)
xi(1)

Combining: pi(1) = γ i
(1)
xi(1) PiS(1)
At the downstream vapor side (2), the partial pressure is:

pi(2) = yi(2) PP(2) PP = total permeate pressure

The driving force will be: [γ i

(1)
xi(1)PiS(1) - yi(2) PP(2) ]

The permeant flux: Ni = (PMi/lM) [ γ i

(1)
xi(1)PiS(1) - yi(2) PP(2) ]

In PV, the permeability PMi depends on permeant, on the polymer, on the

temperature but also on the concentrations of permeants in the
polymer, which can be large enough to cause polymer swelling.