Introduction to Membrane Separation

Processes (Chapter 19)

Instructor: Dr. Shaowei Yang
Office: FH 462, Email: [email protected]

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Summary of Objective
Membranes are common

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Membrane Overview

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19.1 Membrane Fabrication and Separation Equipment

Fabric woven
Spiral wound module

Hollow fiber spinning

Hollow fiber membrane module

Supported membranes Tubular membrane module

Huang T. et al. ACS Appl. Mater. Interfaces, 2018, 10, 30732-30740; Park S. R. et al. J. Membr. Sci. Sep. 2015, 4, 8-14;
Luque S. et al. Membr. Sci. Technol. 2008, 13, 177-216.
 Membrane materials
Polymer/Organic: polytetrafluoroethylene (PTFE), cellulose acetate, polystyrene.
Inorganic: ceramic, metal, carbon, zeolite, metal-organic framework (MOF), Graphene oxide
Hybrid: zeolite/polymer and MOF/polymer mixed matrix membranes
Others: liquid membranes, bipolar membranes
Robeson Plot

𝑄
Permeance: 𝑃𝑚,𝑖 = 𝐴
𝑚 ∙𝑡∙𝛥𝑃𝑖
Membrane
𝑦𝑖 Τ𝑦𝑗
Selectivity: 𝛼𝑖Τ𝑗 =
𝑥𝑖 Τ𝑥𝑗

Materials Permeability: 𝑃𝑏,𝑖 = 𝑃𝑚,𝑖 ∙ δ

Generally, polymer membranes have lower permeability but better processability while
inorganic membranes have better permeability but higher cost

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Polymer and polymer membranes
Polyamide-imides (Torlon)

Polymer with Intrinsic Microporosity-1 (PIM-1)

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http://dx.doi.org/10.1039/D0PY01226B
Polymer membrane fabrication-casting

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Polymer membrane fabrication-woven

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Polymer membrane fabrication-hollow fiber spinning

Hollow fiber spinning apparatus

Polymer hollow fiber

Carbon hollow fiber Ceramic hollow fiber

Dense membrane
Sorbent or catalyst fiber
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Polymer membrane fabrication-hollow fiber spinning

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 Crystalline Microporous Materials-Zeolite, MOFs, COFs
Zeolite Molecular Sieves Metal Organic Frameworks (MOFs)
➢ Zeolites are microporous crystalline aluminosilicates,
composed of TO4 tetrahedra (T=Si, Al etc.)

➢ Key characteristics of zeolites: ordered pores,

uniform pore size, high thermal and chemical stability

Pore size ~0.4 nm

Covalent Organic Frameworks (COFs)

International Zeolite Associate structure database; Lee Y.-R. et al., Chem. Eng. J. 271, 2015, 276-280; 12
Luo Z. et al. Angew. Chem. Int. 57, 2018, 9443-9446.
Crystalline Microporous Membrane-Zeolite

Crystal growth

Precursor solution Nucleation Crystal growth

Example: SiO2 : TPAOH : H2O : Na2O = 100 : 30 : 1330 : 5.2

Zeolite crystals

Membrane growth

Precursor solution Nucleation Crystal growth

Zeolite membrane on alumina substrate

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Crystalline Microporous Membrane-Zeolite

One-step 20-fiber synthesis SEM pictures

Hollow fiber module

Single gas permeation results CO2/CH4 separation

A novel “pseudo in-situ” method was successfully developed for hollow fiber membrane fabrication.
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19.1 Membrane Equipment

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 19.2 Membrane Concepts
The driving force depends on the type of membrane separation.
For GP, the driving force is the difference in partial pressure of
the transferring species across the membrane. For RO, the
𝑄
driving force is the pressure difference minus the osmotic
Permeance: 𝑃𝑚,𝑖 = 𝐴 pressure difference across the membrane. For UF, the driving
𝑚 ∙𝑡∙𝛥𝑃𝑖
Membrane force is the same as for RO but usually simplifies to pressure
𝑦𝑖 Τ𝑦𝑗 difference across the membrane since osmotic pressures are
Selectivity: 𝛼 𝑖 Τ𝑗 = small. Because osmotic pressure differences are tiny for MF, the
𝑥𝑖 Τ𝑥𝑗 driving force is the pressure difference across the membrane.
These driving force effects are specific to each membrane
separation and are discussed in more detail in later sections.
Materials Permeability: 𝑃𝑏,𝑖 = 𝑃𝑚,𝑖 ∙ δ

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 19.3 Gas Permeation

where JA is volumetric flux of gas A, Fm,p is molar transfer rate of permeate

(gas that permeates through the membrane), yp,A is mole fraction A in the
permeate, ρm,p,A is molar density of solute A in permeate, A is membrane
area available for mass transfer, PA is permeability of species A, driving
force for separation ΔpA is difference in partial pressure of A across
membrane, and tms is thickness of membrane skin that actually does the
separation. Because partial pressure=(total pressure)(mole fraction) or
pA=pyA, Eq. (19-2a) can be expanded to

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Example 1
A membrane system is used to separate a gas mixture of 50/50 mol.
CO2/CH4 at 298 K, the permeate side is purged with 100 mL/min He, the
composition of CO2 and CH4 is analyzed with gas chromatography to
determine the composition of the permeate. Membrane area is 5 cm2.
Membrane thickness is 2 μm. Feed is at 2 bar pressure and permeate is
at 1 bar pressure. CO2 and CH4 composition in the permeate is 4 mol.%
and 0.02 mol.%, respectively. Calculate the permeance and permeability
of the membrane. Steady state gas permeation test system
(a) Assume feed flow rate is high enough that feed composition can be
considered as unchanged.
(b) Feed has flow rate of 100 mL/min (at 1 bar).
𝑄
Permeance: 𝑃𝑚,𝑖 =
𝐴𝑚 ∙𝑡∙𝛥𝑃𝑖
Membrane
𝑦𝑖 Τ𝑦𝑗
Selectivity: 𝛼𝑖Τ𝑗 =
𝑥𝑖 Τ𝑥𝑗

Materials Permeability: 𝑃𝑏,𝑖 = 𝑃𝑚,𝑖 ∙ δ

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Example 1

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Example 1

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Example 1

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Example 1

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 Example 2
A membrane system is used to separate a gas mixture of 50/50 mol.
CO2/CH4 at 50 bars, the permeate side is at 1 bar without purging. Given
the membrane have permeance of 10-6 mol/m2∙Pa∙s and CO2/CH4
permselectivity of 200. Calculate the composition of the retentate, r
permeate and/or molar fraction of gas coming out as permeate. For:
(a) Retentate has composition of 10/90 mol. CO2/CH4.
(b) 40% molar fraction of gas coming out in the permeate stream.
Steady state gas permeation test system
(c) For case (a), given 100 tons/hr of gas needs to be handled through
the process, what will be the required membrane area?
𝑄
Permeance: 𝑃𝑚,𝑖 = 𝐴
𝑚 ∙𝑡∙𝛥𝑃𝑖
Membrane
𝑦𝑖 Τ𝑦𝑗
Selectivity: 𝛼𝑖Τ𝑗 =
𝑥𝑖 Τ𝑥𝑗

Materials Permeability: 𝑃𝑏,𝑖 = 𝑃𝑚,𝑖 ∙ δ

Logarithmic mean pressure is typically more accurate. To simplify

our cases, we will just use normal average in tests and examples 23
Example 2

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Example 2

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 19.4 Osmosis and Reverse Osmosis (RO)
In RO, liquid water is forced under pressure through a nonporous semipermeable membrane in the opposite direction of
osmosis (osmosis is defined shortly). A typical seawater desalination system recovers between 50% and 55% of feed water as
potable water. Inlet pressure should be at least twice the inlet osmotic pressure and operational temperature <45°C (Woods,
2007).

In practice, large-scale systems may have hundreds of membrane modules arranged both in series and in parallel (Figure 19-
2C) in what is often called a Christmas-tree pattern (Baker, 2004). Large-scale systems have pressure exchangers on high-
pressure retentate waste lines that recover more than 90% of the energy used to pressurize fluid that has not passed through
the membrane.

In these equations, Ksolv′ is solvent (usually water) permeability through the membrane with an effective membrane skin thickness
of tms. Pressure drop across the membrane, Δp=pr−pp. Δπ is the difference in osmotic pressure across the membrane. Typical
units for terms in Eq. (19-13) are pressure p and osmotic pressure π in atm, solvent permeance (Ksolv′/tms) in g/(atm·s·m2),
solvent flux Jsolv′ in g/(m2s). 26
 19.4 Osmosis and Reverse Osmosis (RO)
In RO, liquid water is forced under pressure through a nonporous semipermeable membrane in the opposite direction of
osmosis (osmosis is defined shortly). A typical seawater desalination system recovers between 50% and 55% of feed water as
potable water. Inlet pressure should be at least twice the inlet osmotic pressure and operational temperature <45°C (Woods,
2007).

Osmotic pressure π is additional pressure required on the concentrated side to stop osmotic flow, assuming the permeate
side is pure water that contains no solute. Osmotic pressure is a thermodynamic property of the solution. Thus, π is a state
variable that depends on temperature, pressure, and concentration but does not depend on the membrane as long as the
membrane is semipermeable.
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 19.4 Osmosis and Reverse Osmosis (RO)
For dilute systems osmotic pressure is often a linear function of concentration:

Osmotic pressure, in Pa, for natural waters containing salts can be determined from the following empirical correlations with T in
°C and salt concentration Cs in kg/m3 (Geraldes et al., 2005):

If we convert Eq. (19-14h) to π in atm with a′ in atm/weight fraction, the resulting equation is very close to linear in the range
of validity.

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 19.4 Osmosis and Reverse Osmosis (RO)
Concentration polarization causes xw>xr, osmotic pressure becomes higher on the retentate side and, following Eq. (19-
13), flux declines.

Define the concentration polarization modulus, M, in terms of weight fractions:

The mass solute flux across the membrane, J′A, can be written as

where K′A is solute permeability, and xw and xp are mass fractions of solute at the membrane wall on the retentate side and in
the permeate, respectively. For a membrane with perfect solute retention, K′A=0. Typical units for terms in Eq. (19-17a) are
salt permeance (K′A/tms) in g/(m2s·mass fraction), and salt flux J′A in g/(m2s).
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 19.4 Osmosis and Reverse Osmosis (RO)

Define membrane selectivity α′ as

For RO of aqueous salts, we usually have α′a′>>1, and Eq. (19-19a) simplifies to

Because RO often operates with high retention of solute and thus very low values of xp, it is useful to simplify RT Eq. (19-
19a) for small xp. As xp→0[xp<<1.0 and (xpα′a′)<<1.0], Eq. (19-20a) becomes

If α′(pr−pp)>>1, which is usually true for aqueous salt solutions, Eq. (19-20a) is

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 19.4 Osmosis and Reverse Osmosis (RO)
External mass balances (in mass units) are

RO data are often reported as the rejection coefficient R:

The rejection coefficient measured with no concentration polarization (M=1.0) is called the inherent rejection coefficient,
Ro, since xout=xr=xw when M=1.0. The inherent rejection coefficient can be used with concentration polarization if we know
the wall concentration or M:

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19.4 Osmosis and Reverse Osmosis (RO)

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19.4 Osmosis and Reverse Osmosis (RO)

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