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Pervaporation
Overview
Overview
Membrane Separations
Camilo Mancera Arias
Ph. D. Student
Graduate Program of Chemical
and Process Engineering - URV.
Tarragona - 2004.
A Little of History
Pervaporation Principles
Model Description
Performance parameters
Discussion Topics
Influence Parameters
Membranes for Pervaporation
Applications
Modules
Process Design
Process energy requirements
A Little of History
A Little of History
Comparing
Comparing
pervaporation with
pervaporation with
distillation.
distillation.
Future potential
Lack of information.
Poor availability of investment capital.
Perceived risks associated with the
reliability of the process.
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Pervaporation Principles
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.
Model Description
There are two ways to rationalize the observed separation effects in pervaporation:
Solution-Diffusion Model
Membrane permeability is a function of
solubility and diffusivity:
Pi Di Ci , C j S i Ci , C j
Ji
Pi
xi i pi0 yi p p
l
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Figure 4. Thompson diagram
Activity Profile
interaction
side of the membrane is maximum whilst on
The concentration of the liquid on the feed
the permeate side is almost zero.
Concentration dependance diffusion coef.
D0,i
Exp ki cim 1
Flux equation (pure liquid): J i
l
Di D0,i Exp ki ci
The concentration inside the membrane (cim) 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.
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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).
Overall
Overall
Sorption
Pervaporation
sorption
Flux
selectivity
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:
ci
cj
Separation factor, ij ci
cj
Permeate
Feed
ciP
i
Enrichment factor,
ciF
pi
pj
ci
cj
Permeate
Feed
Flory-Huggins Isotherm
(Glassy: liquid sorption)
Henry Isotherm
(Rubbery: liquid and
gas sorption)
Langmuir Isotherm
(Glassy: gas sorption)
PV D S
PV EV M
ci
pi
p j
c j
pi
p j
p j
4. Flux: Denote the amount of permeate per unit membrane area and unit time at given
membrane thickness. Its a realy important parameter for the operation of the
process.
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:
0
0
pF xi i pi ai pi
The behavior of the liquid solution is determined for the activity coefficient:
Positive deviation
Positive deviation
from Raouls law
from Raouls law
i 1 or i 1
Negative deviation
Negative deviation
from Raoults law
from Raoults law
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.
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The highest
The highest
vacuum feasible
vacuum feasible
is 1 atm.
is 1 atm.
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
Pervaporation
at elevated
at elevated
feed
feed
temperatures.
temperatures.
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Polymers
Polymers
soft and
soft and
flexible.
flexible.
Log E
glassy
rubbery
state
state
Tg
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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.
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Applications
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:
Volatile organic
Volatile organic
compounds from water
compounds from water
{
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Aqueous mixtures
Dehydration
Dehydration
Non-aqueous mixtures
Polar/Non polar
Polar/Non polar
Alcohols/aromatics (methanol/toluene)
Alcohols/aliphatics (ethanol/hexane)
Cyclohexane/benzene
Alcohols/ethers (Methanol/MTBE)
Hexane/toluene.
Butane/butene.
Aromatics/Aliphatics
Aromatics/Aliphatics
Saturated/Unsaturated
Saturated/Unsaturated
Applications (2)
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Modules
The more suitable modules types are:
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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 organicorganic separations.
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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.
The size of the separation
The size of the separation
units (membrane area) will
units (membrane area) will
depend on the allowable
depend on the allowable
temperature drop!
temperature drop!
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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.
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nRT p2
ln
p
1
Isothermal efficiency
Isothermal efficiency
m f C p , f T f Tr m p H vap
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Summary
Advantages
Drawbacks
Lack of information.
No process wastes.
Limited applications:
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Summary (2)
Membranes:
Thickness:
Pore size:
Driven force:
Separation principle:
Membrane material:
Applications:
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