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‡ 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

1
    

Comparing
÷

"

#  :
"   pervaporation with
distillation.

‡ Actually there are 120 PV installations in ‡ Significant energy savings of up to 55%

used world wide. could be achieved by replacing all the
thermal separation processes in the EU and
‡ Le Carbone-Lorraine is a very important
Norway by pervaporation.
French company that has built many of
them. ‡ Because pervaporation systems make use
of more advanced technologies than
‡ Pervaporation still have to compete
conventional separation methods,
against other membrane separation
investment costs are considered
techniques.
comparable.

# !


 ‡ Simple pay back times of less than 1 year
have been reported for pervaporation
installations.
‡ Lack of information.
‡ Operation and maintenance costs (O&M)
‡ Poor availability of investment capital. are expected to be higher than the
‡ Perceived risks associated with the conventional separation process.
reliability of the process.

2
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Vacuum
‡ Is the only membrane process where Pervaporation
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 Gas carrier
Pervaporation
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 Temperature
than the saturation pressure of the difference
permeant to achieve the separation. Pervaporation

3 Figure 2. Schematic draws of pervaporation processes.

    



Pervaporation involve a sequence of Because of its characteristics, pervaporation

three steps: is often mistakenly considered as a kind of
extractive distillation but VLE † Solution-
‡ Selective sorption
Diffution mechanism.
‡ Selective diffusion through the
membrane.
‡ Desorption into a vapor phase on the
permeate side.

Figure 3. Comparison between

VLE and pervaporation

4
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There are two ways to rationalize the observed separation effects in pervaporation:

Solution-Diffusion Model Thermodynamic accounting approach

‡ Membrane permeability is a function of
solubility and diffusivity:
  Ë
ü
 >  Ë
ü

‡ Diffusivity and solubility are strongly
dependent of feed composition.
‡ The liquids have more affinity towards
polymeric membranes than gases (Flory²
Huggins theory instead Raoult·s law).
‡ Equation of transport:
‡ 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).




Ë

È |= ƒ ||

5
Figure 4. Thompson diagram
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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,
equilibrium). membrane ² permeant
interaction
‡ The concentration of the liquid on the feed side of the membrane is maximum whilst on
the permeate side is almost zero. Concentration dependance diffusion coef.
=ü  =ü >
|Ë > 
‡ Flux equation (pure liquid): 

Ë
|Ë >  a
ƒ(

‡ 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.

6
 
 

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

7
Figures 6. Mixture of liquids
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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:


|
Flory-Huggins Isotherm
    | 
  
   
 (Glassy: liquid sorption)
‡ Separation factor, O





     
 :
 :

Henry Isotherm
 (Rubbery: liquid and
‡ Enrichment factor, 

: gas sorption)

2. Sorption selectivity: Permeability is

function of solubility and diffusivity
Langmuir Isotherm
and both may be selective. (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.

8 O  O  >O  Figure 7. Sorption isotherms

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3. Evaporation selectivity: The separation factor is considered to be a product of

evaporation separation and membrane separation yields:

|
|

 |   | 
  :   |
O  O  > O  

|

    | 
  :   :

Membrane selectivity depends on permeate pressure, while evaporation invariably

enriches the more volatile solution compound.

Ô ( 
Ô ‘(

Pervaporation favors the Pervaporation favors the less

more volatile compound volatile 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.

9
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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:
|:
È |=  |=

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

Positive deviation È (  È ‘( Negative deviation

from Raoul·s law from Raoult·s 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.

10
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  !

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
11 is 1 atm.
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 "!

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
  
  
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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
restricted to molecular
vibrations (no rotation or
move in the space of the
chains)

2. Elastomeric: Polymers interact preferentially

with the organic solution component, the sorption
isotherm is of the Henry type. Figure 8. Amorphous polymer

Polymers
soft and
flexible.
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‡ 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.

Log E

glassy rubbery
O
 O


Tg T

Figure 9. Tensile module vs T. Figure 10. Diffusivity vs degree

of swelling (non porous polymers)
14
  
 #
 

 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 Mechanical resistance and swelling

 Not pose technical resistance to withdrawal.

 Have dimensional stability under swelling conditions.

The Requirements for the substructure are: To minimize transport resistance

and avoid capillary condensation
 Open substructure.
 A high surface porosity with a narrow pore size distribution.

15
Figure11. Non porous composite Figure 12. Non porous asymmetric
membrane membrane
  

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:
Polar/Non polar
Volatile organic
Dehydration
compounds from water Aqueous mixtures Non-aqueous mixtures
‡ Removal of water from organic solvents.

}
‡ Alcohols/aromatics (methanol/toluene)

{
‡ Alcohols from fermentation broths ‡ Alcohols/aliphatics (ethanol/hexane)
(ethanol, butanol, etc..)
‡ Alcohols/ethers (Methanol/MTBE)
‡ Volatile organic contaminants from waste
water (aromatics, chlorinated hydrocarbons) ‡ Cyclohexane/benzene

‡ Removal of flavor and aroma compounds. ‡ Hexane/toluene. } Aromatics/Aliphatics

‡ Removal of phenolic compounds. ‡ Butane/butene. Saturated/Unsaturated

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

styrene).
16 Isomers
 
  !
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 14. Hybrid process
17 distillation and pervaporation.
Figure 13. Pervaporation of 50-50
azeotropic mixture.
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.
  

The more suitable modules types are:

Hollow fiber module: This module is

used with an inside²out configuration to
avoid increase in permeate pressure
within the fibers, but the outside²in
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.

18
Figure 16. Plate and frame module.
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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
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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

  |


   
_  |(
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:

 

| ü  Ë    |
 |

22
 #


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‡ Low energy consumption. ‡ Scarce membrane market.

‡ Low investment cost.
‡ Better selectivity without thermodynamic
limitations.
‡ Clean and close operation.
‡ No process wastes.
‡ Compact and scalable units.
‡ 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.

23
 #
  !

Membranes: Composite membranes with an

elastomeric or glassy polymeric top layer.
Thickness: ù 0.1 to few m (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: m m Dehydration of organic solvents.

m m Removal of organic compounds from

water.
m m Polar/non-polar.

m m Saturated/unsaturated.

m m Separation of isomers.

24