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Chang-Han Yun / Ph.D.
National Chungbuk University
November 4, 2015 (Wed)
Chapter 6. Membrane Process
(Pressure Driving Force)
2 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
Contents
Contents Contents
6.5 Other Driving Force
6.4 Concentration Driving Force
6.3 Pressure Driven Force
6.2 Osmosis
6.1 Introduction
3 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
Cellulose esters(Cellulose diacetate, Cellulose triacetate)
Very suitable for desalination
• High permeability towards water
• Low solubility towards the salt
Stability against chemicals, temperature and bacteria = very poor
Typical operation conditions
• pH : 5 ∼ 7
• Temperature : < 30°C
Biological degradation is a severe problem.
Poor selectivity towards small organic molecules
6.3.4.1 Membrane for RO and NF
4 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
Aromatic polyamide – composite type
High selectivity towards salts
Water flux is somewhat lower
pH : 5 ∼ 9
Main drawback : weak against free chlorine Cl2
Hollow fiber type RO membrane
OD < 100 μm
Membrane thickness ≈ 20 μm ⇨ Permeation rate has decreased dramatically
Extremely high membrane surface area = 30,000 m2/m3
Other materials for RO (the 3rd Class of material)
polybenzimidazoles, polybenzimidazolones, polyamidehydrazide and polyimides
6.3.4.1 Membrane for RO and NF
5 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
Composite membranes
Most of RO and all of NF : composite membranes
Top- & Sub-layer : different polymer ⇨ optimized separately
Porous sub layer
• Criteria of sub-layer : surface porosity and pore size distribution
• Asymmetric UF membranes are often used
Methods for placing a thin dense layer on top of sub layer
• dip coating
• in-situ polymerization
Most composite RO and NF membranes are prepared by interfacial polymerization
6.3.4.1 Membrane for RO and NF
• interfacial polymerization
• plasma polymerization
6 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
※ Interfacial polymerization
Two very reactive bifunctional monomers (e.g. a di-acidchloride and a di-amine) or
trifunctional monomers (e.g. trimesoylchloride) are allowed to react with each other
at a water/organic solvent interface and a typical network structure is obtained.
6.3.4.1 Membrane for RO and NF
[Table 6-6] Example of monomers used for interfacial polymerization
7 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
Application of NF/RO
Application for purification
Salty water purifying
• Brackish water : 1,000 ∼ 5000 ppm
• Seawater : about 35,000 ppm
Production of ultrapure water for the semiconductor industry
Application for concentration
Concentration in the food industry (fruit juice, sugar, coffee)
Galvanic industry (concentration of waste streams)
Dairy industry (concentration of milk prior to cheese manufacture)
6.3.4.2 Applications
Purification(where the permeate is the product) : Major
Solute concentration(where the feed is the product)
8 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
NF
NF : network structure is more open than RO
Retention for monovalent salts(Na+, Cl-) : much low
Retention for bivalent ions(Ca2+, CO22-) : high
Retention for micro-solutes and low MW organics : high
(herbicides, insecticides, pesticides, dyes, sugars etc)
6.3.4.2 Applications
Solute RO NF
Monovalent ions (Na, K, CI, NO3)
Bivalent ions (Ca, Mg, SO4, CO3)
Bacteria and virus
Microsolutes (Mw > 100)
Microsolutes (Mw < 100)
> 98%
> 99%
> 99%
> 90%
0∼99%
< 50%
> 90%
< 99%
> 50%
0∼50%
[Table 6-7] Comparison of retention characteristics between NF and RO
9 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
6.3.4.3 Summary of Nanofiltration(NF)
Items Characteristics
Membranes Composit
Thickness Sub layer ≈ 150 μm, Top layer ≈ 1 μm
Pore sizes < 2 nm
Driving force Pressure(10 ∼ 25 bar)
Separation principle Solution-diffusion
Membrane material polyamide (Interfacial polymerization)
Main applications
Desalination of brackish water
Removal of micropollutents
Water softening
Waste water treatment
Retention of dyes (textile industry)
10 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.4 RO & NF
6.3.4.4 Summary of Revers Osmosis(RO)
Items Characteristics
Membranes Asymmetric or Composite
Thickness Sub layer ≈ 150 μm, Top layer ≈ 1 μm
Pore sizes < 2 nm
Driving force Pressure : Brackish water 15 ∼ 25 bar(Sea water 40 ∼ 80 bar)
Separation principle Solution-diffusion
Membrane material Cellulose triacetate, Aromatic polyamide
Polyamide and Poly(ether urea) (Interfacial polymerization)
Main applications
Desalination of brackish and seawater
Production of ultrapure water (electronic industry)
Concentration of food juice and sugars (food industry)
Concentration of milk (dairy industry)
11 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.5
Pressure Retarded Osmosis
(PRO)
PRO
Salt concentration difference(Osmotic pressure) ⇨ generate energy
Flow through semipermeable membrane(dilute → concentrate) by osmotic pressure
Jv = A (Δπ - ΔP) (6-36)
E = Jv∙AP = A (Δπ - ΔP)∙ΔP (6-37)
where E = power, Watt or J/sec
Maximum power (E = Emax) at dE/d(ΔP) = 0 ⇨ ΔP = 0.5 Δπ
Emax = A / (4 Δπ) (6-38)
Emax = about 1.5 W/m2 on the basis of lab experiments
Principle of pressure retarded osmosis.
12 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.5
Pressure Retarded Osmosis
(PRO)
Practical problems
Osmosis : Concentration of concentrated solution↓ ⇨ π↓
Salt flux : R < 100% ⇨ π↓
Concentration polarization : major problem(See )
Direction of Jv is opposite with Js
cs on concentrate-side membrane surface < in bulk of concentrate
cs on dilute-side membrane surface > in bulk of dilute π↓
Concentration polarization
in pressure retarded osmosis
13 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.5
Pressure Retarded Osmosis
(PRO)
Items Characteristics
Membranes Asymmetric or Composite
Thickness Sub layer ≈ 150 μm, Top layer ≈ 1 μm
Pore sizes < 2 nm
Driving force Concentration difference (Osmotic pressure)
Separation principle Solution-diffusion
Membrane material Cellulose triacetate, Aromatic polyamide
Poly(ether urea) (Interfacial polymerization)
Main applications Production of energy
6.3.5.1 Summary of Retarded Osmosis(PRO)
14 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.6
Piezodialysis
Piezodialysis
Driving force : Pressure
Ionic solutes permeate through membrane rather than solvent
Operated by mosaic membranes
Principle
Pressure applied at one side of the membrane ⇨ generate electromotive force (ΔE)
ΔE = -β ΔP where β = proportionality constant(Electric Osmotic Coefficient) (6-39)
• β < 0 for anion-exchange membranes
• β > 0 for cation-exchange membranes
The transport of ions through a mosaic membrane during piezodialysis
15 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.6
Piezodialysis
Structure of mosaic membranes
Cation-exchange and anion-exchange groups separated by a neutral region
Generation of a current loop
Ion transport > solvent transport ⇨ salt concentration : permeate > feed
Salt enrichment in permeate : about 2
Major factor to increase the flux = ion-exchange capacity of the membrane
※ Although the basic principle has been demonstrated in the laboratory,
it has not been employed on a commercial scale.
Electro-neutralized by simultaneous
passage of both ions through the membrane
Transport of anions through
anion-exchange region
Transport of cations through
cation-exchange region
16 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.3 Pressure Driven Membrane Process 6.3.6
Piezodialysis
6.3.6.1 Summary of Piezodialysis
Items Characteristics
Membranes Mosaic membranes
(cation-exchange regions adjacent to anion-exchange regions)
Thickness ≈ few hundred μm
Pore sizes Non-porous
Driving force Concentration difference (Osmotic pressure)
Separation principle Ion transport (Coulomb attraction and electro-neutrality)
Membrane material Cation/anion-exchange membrane
Main applications Salt enrichment
Chang-Han Yun / Ph.D.
National Chungbuk University
November 4, 2015 (Wed)
Chapter 6. Membrane Process
(Gas Separation)
18 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
Contents
Contents Contents
6.5 Other Driving Force
6.4 Concentration Driving Force
6.3 Pressure Driven Force
6.2 Osmosis
6.1 Introduction
19 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
Substances diffuse spontaneously from a high to a low chemical potential.
Processes using concentration difference as the driving force
6.4.1 Introduction
Gas separation Driving Force
Partial pressure difference
or Activity difference Vapor permeation
Pervaporation
Dialysis
Diffusion dialysis
Concentration difference
Carrier mediated processes
Membrane contactor
6.4 Concentration Driving Force
20 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
Nonporous membrane
No information about the permeability of a certain species
Difference of permeability of gas between elastomeric and glassy > 105
Glassy state
Presence of a large free volume
Presence of crystallites ⇨ mobility↓
Low MW penetrant ⇨ segmental mobility (or chain mobility)↑
Concentrations of penetrant inside the polymeric membrane↑ ⇨ chain mobility↑
⇨ permeability (or diffusivity)↑
Affinity of penetrant with polymer
Activity of penetrant in feed
6.4.1 Introduction
Synthetic solid membrane
(gas separation, dialysis and pervaporation) On the basis of structure
and functionality Liquid (with or without a carrier) as the membrane
Large differences in segmental motion
Determine concentration of penetrant
inside polymeric membrane
6.4 Concentration Driving Force
21 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
In gas separation with inert gases(He, H2, N2, O2)
No interaction between gas molecule ↔ membrane material
Gas concentration in the membrane : very low at low feed pressures
With liquid penetrant
Solubility in the membrane = appreciably high ⇨ enhanced chain mobility
High interaction between liquid ↔ membrane in dialysis ⇨ high swelling of the polymer
⇨ allows relatively large molecules diffuse through open membrane
※ Swelling of membrane = wt. of penetrant inside membrane / wt. of dry polymer
Diffusion coefficient can vary over the range 1019 to 10-9 m2/sec.
Swelling↑ ⇨ Mobility of the polymer chains↑
※ Diffusion coefficient in liquids is 10-9 m2/sec
6.4.1 Introduction 6.4 Concentration Driving Force
22 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
Swelling : very important factor in transport through nonporous membranes
demonstrates
D can change by up to 10 orders of magnitude.
D of benzene in PVA at zero penetrant concentration < 10-19 m2/sec
D of water in hydrogels > 10-9 m2/sec( ≈ self-diffusion coefficient of water)
6.4.1 Introduction
Diffusivity
as f(degree of swelling in nonporous polymer)
6.4 Concentration Driving Force
23 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Viscous flow like MF ⇨ no separation
∵ λ of the gas molecules ≪ Pore diameter
Pore diameter↓ ⇨ Mean free path(λ) of gas > Pore diameter ⇨ Knudsen flow
Knudsen flow, (6-40)
where Dk = Knudsen diffusion coefficient, is given by
T and Mw = temperature and molecular weight, respectively
r = pore radius
Flux ∝ [MW]-0.5 ⇨ Separation factor(J1 / J2) ∝ [MW1 / MW2]-0.5 ⇨ low separation factors
For high separation, cascade connection of many module ⇨ economics↓
Commercial application
Enrichment of uranium hexafluoride(235UF6, a very expensive material)
Separation factor for 235UF6 from 238UF6 < 1.0064 (for ideal case)
Plant using porous ceramic membranes operates in France (at Tricastin).
6.4.2.1 Gas separation in porous membranes Gas separation
Membrane : Porous or Nonporous
Transport mechanism : Completely different
6.4 Concentration Driving Force
24 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Permeability ⇨ determine separation through nonporous membranes
Fick's law : simplest description of gas diffusion through a nonporous structure
(6-41)
where J = flux through the membrane
D = diffusion coefficient
dc/dx = driving force (concentration gradient across the membrane)
By integration of Eq(6-41) under steady-state conditions,
(6-42)
where co,i = ci in membrane on upstream side
cℓ,i = ci in membrane on downstream side
ℓ = thickness of the membrane
6.4.2.2 Gas separation through nonporous membranes
Nonporous membrane separating two gas phases.
6.4 Concentration Driving Force
25 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Henry's law
ci = Si∙pi (6-43)
where ci = concentration inside the membrane
pi = partial pressure of gas outside the membrane
Si = solubility coefficient of component i in membrane (cm3(STP)/cm3∙bar)
※ Henry’s law is mainly applicable to amorphous elastomeric polymers
※ Solubility behavior : very often much more complex below Tg (Glassy state)
By combining Eq(6-42) with Eq(6-43),
(6-44)
Permeability coefficient, P = D∙S (6-45)
(6-46)
J ∝ (Δp across membrane) and (ℓ)-1
Ideal selectivity (αi/j ideal) ∝ ratio of the permeability coefficients ⇨ (6-47)
6.4 Concentration Driving Force
26 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Plasticisation
Occur at high partial pressure of permeating gas having high chemical affinity for polymer
By plasticisation ⇨ Real separation factor ≠ Ideal separation factor
In real, Permeability↑ ⇨ Selectivity↓ by plasticisation
Selectivity dependency on partial pressure ratio across membrane
For high pressure ratio (Pℓ / Po → 0) ⇨ Separation efficiency = maximum
Pressure ratio↑ ⇨ Selectivity↑
Schematic drawing of a gas separation process.
6.4 Concentration Driving Force
27 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Permeability coefficient (P)
Constant : intrinsic parameter of membrane
Unit : Barrer
※ l Barrer=10-10cm3(STP)∙cm/(cm2∙s∙cmHg)=0.76×10-17m3(STP)∙m/(m2∙s∙Pa)
Interactive systems(Henry's law does not apply.)
Permeability coefficient (P) ≠ constant = f(pressure)
2 important parameters relating to the nature of the polymer (chemical structure)
• Glass transition temperature (Tg)
Glass transition temperature (Tg)
Determines whether a polymer is in the glassy or in the rubbery state
Segmental motion
• Limited for an amorphous polymer in the glassy state
• Enough thermal energy to rotate in the main chain in rubbery state
6.4.2.3 Aspects of separation
• Crystallinity
6.4 Concentration Driving Force
28 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
In general([Table 6-8])
Permeability : Rubbery polymer > Glassy polymers
(∵ Higher mobility of the chain segments)
Selectivity : Rubbery polymer < Glassy
Polymer P of CO2(Barrer) P of CO2 / P of CH4
polytrimethylsilylpropyne(PTMSP)
silicone rubber
natural rubber
polystyrene
polyamide (Nylon 6)
poly(vinyl chloride)
polycarbonate (Lexan)
polysulfone
polyethyleneterephthalate (Mylar)
cellulose acetate
poly(ether imide) (Ultem)
poly(ether sulfone) (Victrex)
polyimide (Kapton)
33100
3200
130
11
0.16
0.16
10.0
4.4
0.14
6.0
1.5
3.4
0.2
2.0
3.4
4.6
8.5
11.2
15.1
26.7
30.0
31.6
31.0
45.0
50.0
64.0
[Table 6-8] The permeability of CO2
and CH4 in various polymers
6.4 Concentration Driving Force
29 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Exception([Table 6-9])
Permeability of glassy polymers > those of elastomers
※ Fractional free volume of the polymer↑ ⇨ permeability↑
[ex, polytrimethylsilylpropyne(PTMSP), polyphenyleneoxide(PPO)]
Polymer Tg(℃) PO2(Barrer) PN2(Barrer) αideal(PO2/PN2)
PPO
PTMSP
ethylcellulose
polymethylpentene
polypropylene
polychloroprene
polyethylene LD
polyethylene HD
210
≈200
43
29
-10
-73
-73
-23
16.8
10,040.0
11.2
37.2
1.6
4.0
2.9
0.4
3.8
6,745.0
3.3
8.9
0.3
1.2
1.0
0.14
4.4
1.5
3.4
4.2
5.4
3.3
2.9
2.9
[Table 6-9] The permeability of O2 and N2 for some elastomers and glassy polymers
6.4 Concentration Driving Force
30 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Basic concept of gas separation
Governed by permeability coefficient(P) = solubility(S) × diffusivity(D)
Affinity of gas molecule with polymer↑ ⇨ Solubility↑
Solubility of CO2 : in hydrophilic polymers > in hydrophobic polymers
Affinity for polymer : Liquid ≫ Gas ⇨ Solubility of gas = very low(< 0.2%)
Noble gases
• No polymer interaction
• Ease of condensation ⇨ determine solubility
※ Solubility is determined only by their ease of condensation
• Molecule size(or Tc, Tb)↑ ⇨ condensing↑ ⇨ solubility↑
Solubility of noble gases(Ne < Ar < Kr < Xe)
Ne in silicone rubber = 0.04 cm3(STP)/(cm3∙atm)
Kr in silicone rubber = 1.0 cm3(STP)/(cm3∙atm)
6.4 Concentration Driving Force
31 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Diffusivity : depend on 2 factor(Molecular size of penetrant and membrane)
Size of the gas molecule
Size↓ ⇨ diffusion coefficient↑
MW : O2 > N2
Size : O2 < N2
Thermodynamic diffusion coefficient, (6-48)
where f = frictional coefficient
Relationship between Diffusion coefficient(D) ↔ Molecular size(r)
Stokes' law, f = 6π η∙r (6-49)
Eq(6-48) with Eq(6-49) for ideal systems (DT = D)
⇨ (6-50)
⇨ (Diffusivity) ∝ (Molecular size, r)-1
Small differences in size ⇨ very large effect on D
D of Ne(MW : 20 g/mol) in PMMA = 10-10 m2/sec
D of Kr(MW : 83.8 g/mol) in PMMA ≒ 10-12 m2/sec
Diffusion coefficient : O2 > N2
⇨ Permeability : O2 > N2
Gas Molecule Diameter(Å)
He
Ne
H2
NO
CO2
C2H2
Ar
O2
N2
CO
CH4
C2H4
C3H8
2.6
2.75
2.89
3.17
3.3
3.3
3.4
3.46
3.64
3.76
3.80
3.9
4.3
[Table 6-10] The kinetic diameter
of some gas molecules.
6.4 Concentration Driving Force
32 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Relationship between D ↔ Nature of polymer
∙ D of Kr in polydimethylsiloxane ≒ 10-9 m2/sec
∙ D of Kr in PVA ≒ 10-13 m2/sec
Separation depend on S/D, not S or D
Cellulose acetate or other ester-containing polymers
Solubility and solubility ratio of CO2 = especially high ⇨ high selectivity(P ratio)
Polymer DCO2/DCH4 SCO2/SCH4 PCO2/PCH4
Cellulose acetate
Polyimide(Kapton)
Polycarbonate
Polysulfone
4.2
15.4
6.8
8.9
7.3
4.1
3.6
3.2
30.8
63.6
24.4
28.3
[Table 6-11] Ratios of the diffusivity(D), solubility(S) and permeability(P)
of CO2 and CH4 in various polymers
6.4 Concentration Driving Force
33 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Diffusivity or changes in diffusivity : much stronger effect on the selectivity
Polyimide(Kapton) : glassy polymer with a very rigid structure
Diffusivity ratio ⇨ determines selectivity
Very definite pore structure ⇨ exclude larger molecule
Diffusion effect > Specific interaction effect
⇨ Selective diffusion of O2 to N2
⇨ Selectivity for permanent gas
: glassy polymers > elastomers
Component Permeability
(Barrer)
Nitrogen
Oxygen
Methane
Carbon dioxide
Ethanol
Methylene chloride
Carbon tetrachloride
1,2-Dichloroethane
1,1,1-Trichloroethane
Chloroform
Trichloroethylene
Toluene
280
600
940
3200
53,000
193,000
290,000
248,000
247,000
329,000
740,000
1,106,000
[Table 6-12] Permeability of various gases and vapors
in polydimethylsiloxane at an activity of a = 1 (p = po).
6.4 Concentration Driving Force
34 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Permeability of a gas = f(polymer) strongly
Organic vapors
Difference between Gas ↔ Vapor : Condensable under standard condition(O°C and 1 bar)
Size : Vapor ≫ Permanent gas ⇨ D : Vapor ≪ Permanent gas
But Permeability : Vapor ≫ permanent gas
∵ P = Diffusivity × Solubility ⇨ Solubility : Vapor ≫ permanent gas ⇨ High permeability
∵ Vapor molecules ⇨ plasticising action on the polymer
(make chains more flexible ⇨ free volume↑considerably ⇨ solubility↑)
Exponential relationship from the free volume theory
Empirical relationship : D = Do exp(ϕ∙γ) (6-51)
where Do = diffusion coefficient at zero penetrant concentration
γ = constant related to plasticising effect of penetrant on polymer
ϕ = volume fraction of the penetrant in the membrane
Concentration ↔ diffusion coefficient = not the same for all polymers
6.4 Concentration Driving Force
35 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Penetrant size
Penetrant shape
Membrane
Penetrant size↑ ⇨ Do↓
Do : methanol in PVA > about 3 orders of magnitude for n-propanol
For a given penetrant, chain flexibility↑ ⇨ Do↑ ⇨ Do : glassy polymer ≪ elastomer
Do of benzene : in PVA ×10 < in polydimethylsiloxane (silicone rubber)
※ Exception : poly(dimethylphenylene oxide) & polytrimethylsilylpropyne :
very high diffusivities ⇨ very high permeability
Solubility prediction
For permanent gases : use Henry's law
For vapor : use Flory-Huggins thermodynamics(as for liquids)
Determine Do
6.4 Concentration Driving Force
36 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Joule-Thomson effect
Very peculiar phenomenon in gas separation
Occur if a gas is expanded across a membrane(as in the case of a gas permeation)
Adiabatic expansion of a real gas(not ideal gas) ⇨ T↓ ⇨ P↓ & Selectivity↑
He : Adiabatic expansion ⇨ T↑ (∵ Joule-Thomson coefficient < 0)
Gas expansion from the high pressure side (subscript 1) to the low pressure side (subscript 2)
at adiabatic condition(no heat transfer, q = 0)
Internal energy change, ΔU = U2-U1 =-P2V2 + P1V1 (6-52)
or U1 + P1V1 = U2 + P2V2 (6-53)
or H1 = H2 (isenthalpic) (6-54)
6.4.2.4 Joule-Thomson effect
Schematic representation of
the principle of the Joule-Thompson effect.
6.4 Concentration Driving Force
37 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Joule-Thompson coefficient, μJT = (∂T/∂P)H
H = f(T, P) ⇨ (6-55)
Furthermore
(6-56) and (6-57)
For the enthalpy change of a reversible process,
dH = V dP + T dS (6-58)
differentiation with respect to P at constant temperature
(6-59)
From the Maxwell’s relation,
(6-60)
Eq(6-56), (6-59) and (6-60) → Eq(6-57),
(6-61)
Gas μJT (K/bar)
He
CO
H2
O2
N2
CH4
CO2
-0.06
0.01
0.03
0.30
0.25
0.70
1.11
[Table 6-13] Joule-Thomson coefficient
of various gases at 1 bar and 298 K
6.4 Concentration Driving Force
38 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Variation of Permeability(P) of gas or vapor
[Table 6-8] ⇨ Permeability variation of a given gas by > 106 in various polymer
[Table 6-11] ⇨ Permeability variation of various gases and vapors : > 106 for a given polymer
『Meaning』Many materials can be used as a membrane depending on the application.
Gas separation : based on permeability and selectivity(ratio of the permeability)
Thin dense top-layer : hydrodynamic resistance = large
Permeability ratio : usually large([Table 6-11])
Choose highly permeable material(such as silicone rubber or natural rubber)
Elastomers : low selectivity, Glassy polymers : much lower permeability
Permeation rate = P/ℓ ∝ (membrane thickness)-1
Minimize effective membrane thickness
Two types of membranes for gas separation :
• Asymmetric membranes
6.4.2.5 Membranes for gas separation
• Composite membranes
6.4 Concentration Driving Force
39 Chapter 6. Membrane Process(Pressure Driving Force) Chungbuk University
6.4.2 Gas Separation
Immersion precipitation technique used to manufacture
asymmetric membranes
sub-layer in composite membrane
Top-layer manufacturing technique
dip-coating
interfacial polymerization
plasma polymerization
Requirement for top-layer : absolutely defect-free
Requirement for porous support layer
Provide mechanical support for the top-layer
Open porous network to minimize resistance to mass transfer
No macro-voids (weak spots for high-pressure applications)
Schematic representation of an asymmetric membrane
and the corresponding electrical circuit analogue.
6.4 Concentration Driving Force
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6.4.2 Gas Separation
Defect-free thin top-layer from a glassy polymer : Very difficult
Method to make a defect-free asymmetric membrane
Dual bath method
Evaporation method
Deposit a coating of a highly permeable polymer upon
an asymmetric membrane containing some defects.
⇨ Coating surface pores ⇨ Defects free membrane
Flux of gas i, (6-62)
Overall permeability(P), (6-63)
where Rtot = total membrane resistance
For the uncoated membrane (see [Figure 6-18])
Rtot,un = (R2-1 + R3
-1 ) -1 + R4 -1 (6-64)
For the coated layer (see [Figure 6-19])
Rtot,c = R1 -1 + (R2
-1 + R3 -1 ) -1 + R4 (6-65)
Schematics of a coated
Asymmetric membrane and corresponding
electrical circuit analogue.
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6.4.2 Gas Separation
Resistance of sub-layer (R4) = negligible
Flux of component i across the uncoated (Jun,i)
(6-66)
Flux of component i across the coated membranes (Jc,i)
(6-67)
where ℓ1 = thickness of the coating layer
ℓ2 = thickness of the top-layer in the sub-structure
ε = represents the surface porosity
Selectivity and flux as a function of the surface
porosity for coated and uncoated membranes
on the basis of the resistance model.
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6.4.2 Gas Separation
[Figure 6-20]
J and αCO2/CH4 vs. Surface porosity for the uncoated and coated membranes
Support membrane : polysulfone
Coating layer : silicone rubber (data given in [Table 6-8])
Top layer thickness of 1 μm (ℓ1 = ℓ2 = 1 μm).
⇨ By coating with a very permeable low-selective polymer
• Very effective in obtaining a defect-free layer
Uncoated membrane : high defect ⇨ selectivity↓
Coated membranes :
No decrease in selectivity up to 10-4 of porosity
No change in permeability up to 10-4 of porosity No defect
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6.4.2 Gas Separation
Composite membrane
In general, transport through the thin top-layer : rate-determining step
Plugging of defects with a high permeable polymer
⇨ Special type of composite membrane
∵ Support layer(Sub-layer) determines the separation performance
Top-layer material penetrated into sub-layer(pore penetration)
Overall resistance(effective thickness)↑
Glassy top-layers supported by glassy sub-layer(supports)
Not preferable
Double composite membrane
Highly permeable third layer(e.g., polydimethylsiloxane) is used between the sub-layer
and top-layer ⇨ Intermediate layer or 'gutter'.
Surface of sub-layer = very highly porous
(difficult to deposit a thin selective coating directly)
Top-layer = glassy polymer(difficult to obtain defect-free)
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※ Balance between permeability ↔ selectivity
High permeable materials are used if high selectivity are not required
Production of O2 enriched air
• medical applications
• combustion processes
• sterile air for aerobic fermentation processes
Separation of organic vapors from non-condensable gases
• High selectivity with highly permeable materials
• Hydrophobic elastomeric polymer : Permeability of N2 and CH4 ≪ of any organic vapor
If a moderate selectivity is required
Use Low permeable materials (glassy polymers)
1) CO2/CH4
6.4.2.6 Applications
6.4.2 Gas Separation
• Purification of CH4 from landfill drainage gas
• Purification of CH4 from natural gas
• Recovery of CO2 in enhanced oil recovery
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2) H2 or He from other gases
• H2 or He : relatively small molecular sizes
• High selectivity ratios in glassy polymers
• Recovery of H2 from purge gas in NH3 synthesis, petroleum refineries and methanol synthesis
3) H2S/CH4
• Separate H2S(very toxic, highly corrosive gas) in natural gas below 0.2%
4) O2/N2 : (N2 enriched air, 95 ∼ 99.9%)
• Inert gas in the blanketing of fuel tanks, and in storage of food and agricultural products
5) H2O from gases
• Dehydration of natural gas, air conditioning, and drying of compressed air
6) Acid gas(SO2, CO2 and NOx) from smoke or flue gas
• Relatively low concentrations at atmospheric pressures
• not very suitable for pressure driven operations (low driving force)
• prefer to membrane contactor, carrier mediated processes and membrane reactors
6.4.2 Gas Separation 6.4 Concentration Driving Force
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6.4.2 Gas Separation
6.4.2.7 Summary of gas separation
Items Characteristics
Membranes Asymmetric or Composite membranes with an elastomeric or glassy
polymeric top layer
Thickness ≈ 0.1 to few μm(top layer)
Pore sizes non-porous(or porous < 1 μm)
Driving force Pressure, upstream to 100 bar or vacuum downstream
Separation principle Solution-diffusion(non-porous membrane)
Knudsen flow(porous membrane)
Membrane material Elastomer : polydimethylsiloxane, polymethylpentene
Glassy polymer : polyimide, polysulfone
Applications
• H2 or He recovery
• CH4/CO2
• O2/N2
• Organic vapors from air
• Dehydration (compressed air, natural gas, air conditioning)
• Acid gases from flue gas
6.4 Concentration Driving Force
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