Introduction to Membrane

Separation Processes
Jairo Rubiano
Separation process and NT
Universidad de La Sabana

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Dates for this third
Final exam: Thursday, November 12th, 2020

Classes:
Oct 20: Gas permeation
Oct 22: Reverse Osmosis and Ultrafiltration
Oct 26: Pervaporation
Oct 29: Class Exercise
Nov 3: HW3 activity
Nov 5: Exam preparation

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Non-equilibrium Thermodynamics
Electroneutrality Condition (Pauling’s principle):

All aqueous ionic solution are electrically neutral:

The number of positive elementary charges is equal to the

number of negative elementary charges.

Aqueous solution of sodium chloride:

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Non-equilibrium Thermodynamics
 Electroneutrality Condition:

"There is, of course, always a threat to

academic freedom – as there is to the
other aspects of the freedom and rights
of the individual, in the continued
attacks which are made on this
freedom, these rights, by the selfish, the
overly ambitious, the misguided, the
unscrupulous, who seek to oppress the
great body of mankind in order that
they themselves may profit – and we
must always be on the alert against this
threat, and must fight it with vigor
when it becomes dangerous.”

Linus Pauling 4
Non-equilibrium Thermodynamics
Fundamental Gibbs Equation

Electrochemical potential

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Non-equilibrium Thermodynamics
Gibbs-Duhem relation for isotermic and isobaric
conditions

Nerst Equation
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Non-equilibrium Thermodynamics

Van’t Hoff equation

Non-equilibrium Thermodynamics

Condición de electroneutraulidad
Phase B
Na+ Cl- P-  
1 -1 -10z
128,077641 78,0776406 5[ion] mmol/l
128,077641 -78,0776406 -50 0
Phase A
Na+ Cl- P-  
1 -1 -10z
100 100 0[ion] mmol/l
100 -100 0 0

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Membranes

https://www.youtube.com/wa
tch?v=5iRUYpIoN50
https://www.youtube.com/wa
tch?v=c0A56QlrYNs

Desireble features of membranes

Most commun materials.
Application of gas permeation and its materials.
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PSD membrane processes

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Gas permeation
Hollow-fiber or spiral-wound membranes

The feed gas is forced into the membrane

module under pressure.

Retentate, which does not go through the

membrane, will become concentrated in
the less permeable gas.

Retentate exits at a pressure that will be

close to the input pressure.

Cost: compression.
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 Permeation
 For gas permeation the steady-state general flux for gas A becomes:

 where JA is the volumetric flux of gas A, is the molar transfer rate of gas which permeates
through the membrane
 yt,A is the mole frac A in the gas that transfers (or permeates) through the membrane
 ρA is the molar density of the solute in the gas transferring through the membrane
 A is the membrane area available for mass transfer
 PA is the permeability of species A in the membrane
 ΔpA, the driving force for the separation, is the difference in the partial pressure of A across
the portion of the membrane which does the separation
 tms is the thickness of the membrane skin which actually does the separation.
 The ratio PA/tms is known as the permanence, and is often the variable that is measured
experimentally.
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Permeation

 Since partial pressure = (mole frac)(total pressure) or pA = yA p:

 where pr is the total pressure on the retentate (high pressure)

side
 yr,w,A is the mole frac A on the retentate side at the membrane
wall
 pp and yp,w,A are the pressure and mole frac at the wall on the
permeate (low pressure) side. 14
Gas Permeation of Binary Mixtures
In binary mixtures: y=yA=1-yB
A: the faster permeating species
The flux of the slower moving component B becomes:

Usually:
 There is no concentration gradient on the permeate side
perpendicular to the membrane; thus, we replaced yp,w,A with yp,A
 Mass transfer rates in gas systems are high enough that the mole
frac at the membrane surface is almost equal to the mole frac in the
bulk gas.

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 Permeation mechanism
 Solution-diffusion:
Feed (high P)

Membrane
Low P
A
dissolves

A diffuses

 Here, the permeability is:

 Where HA the gas solubility in the membrane and Dm is the diffusivity in
the membrane

https://www.youtube.com/watch?v=08ZH7vwzzEg
https://www.sciencedirect.com/topics/engineering/lennard-jones-parameter 16
Research conducted in GEMA*

H2 production from biomass: biological and catalytic combined process

*Néstor Sánchez, Bernay Cifuentes, Ruth Ruiz and Martha Cobo 17

Permeation of gases in polymer membranes
 Small molecules such as helium
have high diffusivities but low
solubilities
 While large gas molecules such as
carbon dioxide have high
solubilities but low diffusivities.
 The resulting product, the
permeability P is relatively large
for both small and large
molecules, but has a minimum
for molecules around the size of
nitrogen.

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Permeabilities
of gases in
various
membranes

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Selectivity
 If the driving forces are equal, gases with higher permeabilities transfer
through the membrane at higher rates:

 Calculate the selectivity of 2 systems according to the table data.

 αAB values of 20 and higher are preferred instead of the much more
modest values commonly employed in distillation.

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Binary Permeation in Perfectly Mixed
Systems
 The simplest.
 The mole fracs and pressures on each side of the membrane are
constant.: yp=yt
 We will also assume that the module has a high rate of mass transfer
from the bulk fluid to the membrane surface. This assumption makes
yr=yr,w

 And for B:

 Make them iqual in Fp:

Rate transfer (RT) curve
 Solving for yr:

 RT curve: relates the mole fracs on both sides of the membrane based
on the RT parameters and the driving force.
 It can take the place of an equilibrium expression for binary systems.
 This equation is applicable to other flow configurations if written in
terms of yt and applied point-by-point on the membrane.
 For a perfectly mixed separator values are constant: yr,sal=yr,prom=yr;
yp,sal=yp y Fr=Fsal

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Completely mixed membrane module

 A single feed goes into a well-mixed chamber and two products are withdrawn.
 The more permeable species concentrates in the permeate product which is
analogous to the more volatile component concentrating in the vapor.
 However, the two products are not in equilibrium but are related by the RT
expression.
 Because of the geometric similarity, we can use an analysis procedure
analogous to that used for binary flash distillation.

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Completely mixed membrane module

 The overall mole balance and the mole balance on the more permeable
component?

 Combining and solving:

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The operating equation

 For the well-mixed gas permeator.

 θ=Fp/Fent known as the “cut,” is an important operating parameter.

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Another method…

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Minimum retentate composition
If the cut=1 and Yin=Yp
for all cut<1 Yp>Yin

We make Yin=Yp and solve

obtaining:

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Exercises
Work during class on:
17-D1
17-D2

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