Pervaporation

Overview
Pervaporation
Overview
Camilo Mancera Arias
Ph. D. Student
Graduate Program of Chemical
and Process Engineering - URV.
Tarragona - 2004.
Membrane Separations
Discussion Topics
Discussion Topics
Pervaporation Principles
Model Description
Performance parameters
Influence Parameters
Membranes for Pervaporation
Applications
Modules
Process Design
Process energy requirements
A Little of History
A Little of History
1
• Was discovered in 1917 by Kober.
• The first full scale plant was installed in
Brazil in 1982 for the production of
ethanol.
• Appears as a promising and commercially
competitive process for separation (more
cost effective for some specific problems).
Figure 1. Membrane market
2
Current position market

• Actually there are 120 PV installations in
used world wide.
• Le Carbone-Lorraine is a very important
French company that has built many of
them.
• Pervaporation still have to compete
against other membrane separation
techniques.
A Little of History
Future potential

• Significant energy savings of up to 55%
could be achieved by replacing all the
thermal separation processes in the EU and
Norway by pervaporation.
• Because pervaporation systems make use
of more advanced technologies than
conventional separation methods,
investment costs are considered
comparable.
• Simple pay back times of less than 1 year
have been reported for pervaporation
installations.
• Operation and maintenance costs (O&M)
are expected to be higher than the
conventional separation process.
Market barriers

• Lack of information.
• Poor availability of investment capital.
• Perceived risks associated with the
reliability of the process.
Comparing
pervaporation with
distillation.
Pervaporation Principles
• Is the only membrane process where
phase transition occurs.
• At least the heat of vaporization have to
be supply.
• The mass transport is achieved lowering
the activity of the permeating component
on the permeate side by: gas carrier,
vacuum or temperature difference.
• The driving force is the partial pressure
difference of the permeate between the
feed and permeate streams.
• The permeate pressure has to be lower
than the saturation pressure of the
permeant to achieve the separation.
Figure 2. Schematic draws of pervaporation processes. 3
Vacuum
Pervaporation
Gas carrier
Pervaporation
Temperature
difference
Pervaporation
Mechanism of Transport
Pervaporation involve a sequence of
three steps:
• Selective sorption
• Selective diffusion through the
membrane.
• Desorption into a vapor phase on the
permeate side.
Because of its characteristics, pervaporation
is often mistakenly considered as a kind of
extractive distillation but VLE = Solution-
Diffution mechanism.
Figure 3. Comparison between
VLE and pervaporation
4
Model Description
Solution-Diffusion Model
• Membrane permeability is a function of
solubility and diffusivity:

• Diffusivity and solubility are strongly
dependent of feed composition.
• The liquids have more affinity towards
polymeric membranes than gases (Flory–
Huggins theory instead Raoult’s law).
• Equation of transport:
( ) ( )
j i i j i i i
C C S C C D P , , · =
( )
p i i i i
i
i
p y p x
l
P
J ÷ =
0
¸
Thermodynamic accounting approach
• It’s distinguished two steps:
• Equilibrium evaporation.
• Membrane permeation of the
hypothetic vapor.
• Membrane selectivity contribution to
overall separation is showed as a change of
composition for the vapor phase lowering the
total pressure below equilibrium vapor
pressure (Thompson diagram).
There are two ways to rationalize the observed separation effects in pervaporation:
Figure 4. Thompson diagram
5
Activity Profile
Figure 5. Activity profile
• The liquid swells the membrane in pervaporation (anisotropic swelling).
•The activity of the liquid is equal to the activity on the membrane (Thermodynamic
equilibrium).
• The concentration of the liquid on the feed side of the membrane is maximum whilst on
the permeate side is almost zero.
• Flux equation (pure liquid):
• The concentration inside the membrane (c
i
m
) is the main parameter, implying that
permeation rate is mainly determine for the interaction membrane-penetrant.
• When concentration inside the membrane increase the permeation rate also increase.
( ) ( ) 1
, 0
÷ · =
m
i i
i
i
c k Exp
l
D
J
Concentration dependance diffusion coef.

( )
i i i i
c k Exp D D · · =
, 0
k
i
Plasticizing constant,
membrane – permeant
interaction
6
Mixture of Liquids
For the transport of liquid mixtures through a polymeric membrane the flux can also
be described in terms of solubility and diffusivity, then two phenomena must be
distinguished:
• Flow coupling: Is described in terms of the non-equilibrium thermodynamics and
accounts for that the transport of a component is affected due to the gradient of
the other component.

• Thermodynamic interaction: Is a much more important phenomenon. It accounts for
the interaction of one component over the membrane, it becomes more accessible to
the other component(s) because the membrane becomes more swollen (the diffusion
resistance decrease).
Figures 6. Mixture of liquids
7
Overall
sorption
Overall
Flux
Sorption
selectivity
Pervaporation
selectivity
Performance Parameters
Some of the most important parameters used to assess the pervaporation process are:

1. Pervaporation selectivity: This parameter compare the analytical compositions of
permeate and feed. There are two forms:


• Separation factor, o:

• Enrichment factor, |:
Feed
Permeate
Feed
Permeate
ij
cj
ci
pj
pi
cj
ci
cj
ci
|
.
|

\
|
|
.
|

\
|
=
|
.
|

\
|
|
.
|

\
|
= o
iF
iP
i
c
c
= |
2. Sorption selectivity: Permeability is
function of solubility and diffusivity
and both may be selective.
Sorption selectivity may or may not be
equal to pervaporation selectivity. Due
to contribution of selective diffusivity
to the overall separation effect.
S D PV
o o o · =
Figure 7. Sorption isotherms
8
Flory-Huggins Isotherm
(Glassy: liquid sorption)
Langmuir Isotherm
(Glassy: gas sorption)
Henry Isotherm
(Rubbery: liquid and
gas sorption)
Performance Parameters (2)
3. Evaporation selectivity: The separation factor is considered to be a product of
evaporation separation and membrane separation yields:




Membrane selectivity depends on permeate pressure, while evaporation invariably
enriches the more volatile solution compound.





4. Flux: Denote the amount of permeate per unit membrane area and unit time at given
membrane thickness. It’s a realy important parameter for the operation of the process.
F
j
i
p
j
i
F
j
i
F
j
i
M EV PV
p
p
p
p
c
c
p
p
|
.
|

\
|
|
.
|

\
|
×
|
.
|

\
|
|
.
|

\
|
= · = o o o
1 1 s >
M M
or o o
Pervaporation favors the
more volatile compound
Pervaporation favors the less
volatile compound
9
Influence Parameters
1. Feed concentration: Refers to the concentration of the preferentially permeating
(usually minor) solution component, being depleted in the process. There are two
aspects to be considered:the activity of the target component in the feed and the
solubility of the target component in the membrane.

• Activity coefficient: The activity of a liquid solution component is given by its partial
vapor pressure:

The behavior of the liquid solution is determined for the activity coefficient:


• Azeotropic mixture: Positive solution non-ideality is asociated with positive
azeotropes, and negative solution non-ideality is asociated with negative azeotropoes.
Pervaporation can separate only positive azeotropes.
• Concentration polarization: In pervaporation, a depletion of the preferentially
permeating species near the membrane boundary is to be expected, limiting its polymer
sorption. But depends of the concentration dependance and sign of the activity
coefficient of the penetrant species.
0 0
i i i i i F
p a p x p = = ¸
1 1 s >
i i
or ¸ ¸
Positive deviation
from Raoul’s law
Negative deviation
from Raoult’s law
10
Influence Parameters (2)
2. Membrane thickness:
• Refers to dry thickness.
• Because flux is inversely proportional to membrane thickness, thin membranes favors
the overall flux but decrease selectivity.
• Thin membranes are used for low swelling glassy membranes and thick membranes are
used for high swelling elastomeric membranes to maintain the selectivity.

3. Pemeate pressure:
• Permeate pressure provides the driving force in pervaporation.
• The permeation rate of any feed component increases as its partial permeate
pressure is lowered. The highest conceivable permeate pressure is the vapor pressure
of the penetrant in the liquid feed.
• The effect of this parameter on pervaporation performance is dictated by the
magnitude of the vapor pressures encountered, and by the difference in vapor
pressures between them.
The highest
vacuum feasible
is 1 atm.
11
Influence Parameters (3)
4. Temperature
• Refers to feed temperature or any other representative between feed and retentate
streems.
• The feed liquid provided the heat of vaporization of the permeate, and in consequence
there is a temperature loss between the feed and retentate stream where the
membrane act as a heat exchanger barrier.
• Temperature affects solubility and diffusivity of all permeants, as well as the extent
of mutual interaction between them. Favoring the flux and having minor effect on
selectivity.
Pervaporation
at elevated
feed
temperatures.
12
Membranes for Pervaporation
Membrane Polymers:
The choice of the membrane material has direct bearing on the separation effect to
be achieved. Two main kinds of polymers for pervaporation may be identified:
13
Figure 8. Amorphous polymer
1. Glassy (Amorphous polymers): Preferentially
permeates water and follows a Flory-Huggins
type sorption isotherm.
2. Elastomeric: Polymers interact preferentially
with the organic solution component, the sorption
isotherm is of the Henry type.
Molecular motion is
restricted to molecular
vibrations (no rotation or
move in the space of the
chains)
Polymers
soft and
flexible.
Membranes for Pervaporation (2)
Important remarks for polymer choice:
• Glassy polymers may behave as an elastomer when Toperation > Tg (Swelling takes
down Tg).
• It’s important that membranes don’t swells too much because the selectivity will
decrease drastically.
• In other hand low sorption or swelling will result in a very low flux.
• Crosslinking should be used only when the membrane swells excessively (p.e. High
concentrated solutions). Because crosslinking has a negative influence on the
permeation rate.
Figure 9. Tensile module vs T.
Figure 10. Diffusivity vs degree
of swelling (non porous polymers)
14
glassy
state
rubbery
state
Log E
Tg T
Membrane Structure
* Non-porous membranes.
* Anisotropic morphology.
* Asymmetric or composite membranes (porous top layer and open porous sublayer)

Pervaporation membranes should meet:
* Have a proportional thickness with performance
* Not pose technical resistance to withdrawal.
* Have dimensional stability under swelling conditions.

The Requirements for the substructure are:
* Open substructure.
* A high surface porosity with a narrow pore size distribution.
To minimize transport resistance
and avoid capillary condensation
Mechanical resistance and swelling
Figure 12. Non porous asymmetric
membrane
15
Figure11. Non porous composite
membrane
Applications
Aqueous mixtures
• Removal of water from organic solvents.
• Alcohols from fermentation broths
(ethanol, butanol, etc..)
• Volatile organic contaminants from waste
water (aromatics, chlorinated hydrocarbons)
• Removal of flavor and aroma compounds.
• Removal of phenolic compounds.
Non-aqueous mixtures
• Alcohols/aromatics (methanol/toluene)
• Alcohols/aliphatics (ethanol/hexane)
• Alcohols/ethers (Methanol/MTBE)
• Cyclohexane/benzene
• Hexane/toluene.
• Butane/butene.
• C-8 isomers (o-xylene, m-xylene, p-xylene,
styrene).
Are found usually on the chemical process industry but there are other areas for is
application as:
* Food.
* Farmaceutical industries.
* Enviromental problems.
* Analytical aplications.
Since there are a lot of applications there is a classification that can be useful:
Dehydration
Volatile organic
compounds from water
{
Polar/Non polar
}
}
Aromatics/Aliphatics
Saturated/Unsaturated
Isomers
16
Applications (2)
Pervaporation is used mainly to remove a small
amount of liquid from a azeotropic liquid mixture
where simple distillation can’t make the
separation.
Figure 13. Pervaporation of 50-50
azeotropic mixture.
Figure 14. Hybrid process
distillation and pervaporation.
Other common application is when a
binary mixture as located the
azeotrope somewhere in the middle of
the composition range, in this case
pervaporation don’t made the
complete separation but break the
azeotrope.
17
Modules
The more suitable modules types are:
Hollow fiber module: This module is
used with an inside–out configuration to
avoid increase in permeate pressure
within the fibers, but the outside–in
configuration can be used with short
fibers. Another advantage of the
inside-out configuration is that the thin
top layer is better protected but
higher membrane area can be achieved
with the outside-in configuration
Plate and Frame: This module is mainly
used for dehydration of organic
compounds.
Figure 15. Hollow fiber module.
Figure 16. Plate and frame module.
18
Modules (2)
Spiral wound module: This module is
very similar to the plate and frame
system but has a greater packing
density. This type of module is used
with organophilic membranes to
achieved organic–organic separations.
Tubular modules: Inorganic (ceramic)
membranes are produced mainly as
tubes, then the obvious module is the
tube bundle for applications that used
this kind of membranes. On the other
hand, for sweep gas pervaporation,
tubular membranes conducting the gas-
permeate mixture are the only option.
Figure 17. Spiral wound module
Figure18. Tubular module
19
Process Design
Pervaporation stage: Pervaporation is a cross flow operation at ambient feed
pressure. The enthalpy of evaporation produces a temperature loss of the feed
stream, suggesting developing the process into individual separation units
interspersed with heat exchangers.
Figure 19. Ethanol dehydration
20
The size of the separation
units (membrane area) will
depend on the allowable
temperature drop!
Process Design
In membrane separation cascades, the permeate of one stage constitutes the feed to
a subsequent stage. The characteristics of pervaporation allow the design of
pervaporation cascades for the recovery of the dilute feed components. p.e. Using an
appropiate membrane, the target component is enrich in the permeate in the initial
pervaporation stage and employing a different type of membrane the remaining
solvent is removed from the first stage permeate, recovering the target component
on the retentate of the second stage.
Figure 20. Cascade configuration
21
Process Energy Requirements
As partial pressure is the driven force for pervaporation and when a
vacuum pump is used to adjust the partial pressure at the permeate side,
then the power required is give by:
There is another need of energy related to the evaporation of the
permeate, here the feed stream is heat up before entering the process
to supply this heat:
|
|
.
|

\
|
÷ =
1
2
ln
p
p nRT
E
n
( )
vap
p
r f f p
f
H m T T C m A = ÷
- -
,
Molar flow rate
Isothermal efficiency
22
Summary
23
Advantages

• Low energy consumption.
• Low investment cost.
• Better selectivity without thermodynamic
limitations.
• Clean and close operation.
• No process wastes.
• Compact and scalable units.
Drawbacks

• Scarce membrane market.
• Lack of information.
• Low permeate flows.
• Better selectivity without thermodynamic
limitations.
• Limited applications:
• Organic substances dehydration.
• Recovery of volatile compounds at low
concentrations.
• Separation of azeotropic mixtures.

Membranes: Composite membranes with an
elastomeric or glassy polymeric top layer.
Thickness: ~ 0.1 to few um (for top layer)
Pore size: Non-porous
Driven force: Partial vapor pressure or activity
difference.
Separation principle: Solution/Diffusion
Membrane material: Elastomeric and glassy.
Applications:  Dehydration of organic solvents.
 Removal of organic compounds from
water.
 Polar/non-polar.
 Saturated/unsaturated.
 Separation of isomers.
24
Summary (2)

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