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Pervaporation

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

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

A Little of History
Comparing
Comparing
pervaporation with
pervaporation with
distillation.
distillation.

Current position market

Future potential

Actually there are 120 PV installations in


used world wide.

Significant energy savings of up to 55%


could be achieved by replacing all the
thermal separation processes in the EU and
Norway by pervaporation.

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.
Market barriers

Lack of information.
Poor availability of investment capital.
Perceived risks associated with the
reliability of the process.
2

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.

Pervaporation Principles

Vacuum
Pervaporation

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.

Gas carrier
Pervaporation

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.

Temperature
difference
Pervaporation

Figure 2. Schematic draws of pervaporation processes.

Mechanism of Transport
Pervaporation involve a sequence of
three steps:
Selective sorption
Selective diffusion through the
membrane.

Because of its characteristics, pervaporation


is often mistakenly considered as a kind of
extractive distillation but VLE SolutionDiffution mechanism.

Desorption into a vapor phase on the


permeate side.

Figure 3. Comparison between


VLE and pervaporation

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

Diffusivity and solubility are strongly


dependent of feed composition.
The liquids have more affinity towards
polymeric membranes than gases (Flory
Huggins theory instead Raoults law).
Equation of transport:

Ji

Pi
xi i pi0 yi p p
l

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Figure 4. Thompson diagram

Thermodynamic accounting approach


Its 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).

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
ki Plasticizing constant,
ki Plasticizing constant,
equilibrium).
membrane permeant
membrane permeant
interaction

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

Concentration dependance diffusion coef.

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

Figures 6. Mixture of liquids

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

2. Sorption selectivity: Permeability is


function of solubility and diffusivity
and both may be selective.

pi

pj

ci
cj

Permeate

Feed

Flory-Huggins Isotherm
(Glassy: liquid sorption)

Henry Isotherm
(Rubbery: liquid and
gas sorption)

Langmuir Isotherm
(Glassy: gas sorption)

Sorption selectivity may or may not be


equal to pervaporation selectivity. Due
to contribution of selective diffusivity
to the overall separation effect.
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PV D S

Figure 7. Sorption isotherms

Performance Parameters (2)


3. Evaporation selectivity: The separation factor is considered to be a product of
evaporation separation and membrane separation yields:
pi

PV EV M

ci

pi

p j

c j

pi

p j

p j

Membrane selectivity depends on permeate pressure, while evaporation invariably


enriches the more volatile solution compound.
M 1 or M 1
Pervaporation favors the
Pervaporation favors the
more volatile compound
more volatile compound

Pervaporation favors the


Pervaporation favors the
less volatile compound
less volatile compound

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

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.
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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.
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The highest
The highest
vacuum feasible
vacuum feasible
is 1 atm.
is 1 atm.

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
Pervaporation
at elevated
at elevated
feed
feed
temperatures.
temperatures.

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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:

1. Glassy (Amorphous polymers): Preferentially


permeates water and follows a Flory-Huggins
type sorption isotherm.
Molecular motion is
Molecular motion is
restricted to molecular
restricted to molecular
vibrations (no rotation or
vibrations (no rotation or
move in the space of the
move in the space of the
chains)
chains)

2. Elastomeric: Polymers interact preferentially


with the organic solution component, the sorption
isotherm is of the Henry type.

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Polymers
Polymers
soft and
soft and
flexible.
flexible.

Figure 8. Amorphous polymer

Membranes for Pervaporation (2)


Important remarks for polymer choice:
Glassy polymers may behave as an elastomer when Toperation > Tg (Swelling takes
down Tg).
Its important that membranes dont 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.

Log E

glassy

rubbery

state

state

Tg

Figure 9. Tensile module vs T.

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Figure 10. Diffusivity vs degree


of swelling (non porous polymers)

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.

Mechanical resistance and swelling


Mechanical resistance and swelling

* Have dimensional stability under swelling conditions.


The Requirements for the substructure are:
* Open substructure.

To minimize transport resistance


To minimize transport resistance
and avoid capillary condensation
and avoid capillary condensation

* A high surface porosity with a narrow pore size distribution.

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Figure11. Non porous composite


membrane

Figure 12. Non porous asymmetric


membrane

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

Removal of water from organic solvents.

Alcohols/aromatics (methanol/toluene)

Alcohols from fermentation broths


(ethanol, butanol, etc..)

Alcohols/aliphatics (ethanol/hexane)

Volatile organic contaminants from waste


water (aromatics, chlorinated hydrocarbons)

Cyclohexane/benzene

Alcohols/ethers (Methanol/MTBE)

Removal of flavor and aroma compounds.

Hexane/toluene.

Removal of phenolic compounds.

Butane/butene.

Aromatics/Aliphatics
Aromatics/Aliphatics

Saturated/Unsaturated
Saturated/Unsaturated

C-8 isomers (o-xylene, m-xylene, p-xylene,


styrene).
Isomers
Isomers

Applications (2)

Pervaporation is used mainly to remove a small


amount of liquid from a azeotropic liquid mixture
where simple distillation cant make the
separation.

Figure 13. Pervaporation of 50-50


azeotropic mixture.

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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 dont made the
complete separation but break the
azeotrope.

Modules
The more suitable modules types are:

Hollow fiber module: This module is


used with an insideout configuration to
avoid increase in permeate pressure
within the fibers, but the outsidein
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

Figure 15. Hollow fiber module.

Plate and Frame: This module is mainly


used for dehydration of organic
compounds.

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Figure 16. Plate and frame module.

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.

Figure 17. Spiral wound module

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 gaspermeate mixture are the only option.
Figure18. Tubular module

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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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Figure 19. Ethanol dehydration

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

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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:
Molar flow rate
Molar flow rate

nRT p2

ln

p
1
Isothermal efficiency
Isothermal efficiency

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:

m f C p , f T f Tr m p H vap

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Summary

Advantages

Drawbacks

Low energy consumption.

Scarce membrane market.

Low investment cost.

Lack of information.

Better selectivity without thermodynamic


limitations.

Low permeate flows.

Clean and close operation.

Better selectivity without thermodynamic


limitations.

No process wastes.

Limited applications:

Compact and scalable units.

Organic substances dehydration.


Recovery of volatile compounds at low
concentrations.
Separation of azeotropic mixtures.

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Summary (2)

Membranes:
Thickness:
Pore size:
Driven force:
Separation principle:
Membrane material:
Applications:

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Composite membranes with an


elastomeric or glassy polymeric top layer.
0.1 to few m (for top layer)
Non-porous
Partial vapor pressure or activity
difference.
Solution/Diffusion
Elastomeric and glassy.
Dehydration of organic solvents.
Removal of organic compounds from
water.
Polar/non-polar.
Saturated/unsaturated.
Separation of isomers.