A Theoritical Study On Removal And Recovery Of

Volatile Organic Compounds From Aqueous

Solutions By Pervaporation

ABSTRACT

Strategies for dealing with industrial liquid wastes involve both reducing the quantity
produced and their environmental impact. So there is a considerable amount of research
work going on throughout the world for better and better technologies for reduction, recovery
and recycling of hazardous liquid wastes. Adsorption methods using activated charcoal and
biological treatment are the presently practicing methods industrially for the treatment of
liquid discharges. However these are not very energy efficient methods. Pervaporation proves
to be a good alternative to the currently practicing methods of recovering organic solvents
from process effluents since it has the advantages – improved selectivity, reduced energy
consumption and separation of azeotropic mixtures and mixture of components with close
boiling points.
Pervaporation is an energy efficient (low temperatures and pressures) combination of
membrane permeation and evaporation. It is often an attractive alternative to other
separation methods. Pervaporation is a membrane process in which a liquid is maintained at
atmospheric pressure on the feed or upstream side of the membrane and where permeate is
removed as a vapor because of a low vapor pressure existing on permeate or downstream
side. This low (partial) vapor pressure can be achieved by employing a carrier gas or using a
vacuum pump.
Membranes like poly dimethylsiloxane (PDMS), polyamide, copolymers and ceramic-
filled membranes have shown high selectivity for removal of VOCs such as chloroform,
benzene and toluene from water by pervaporation due to their hydrophobic nature. In this
present study the factors affecting the membrane performance such as molecular flux, perm
selectivity, permeability coefficient are described. The status of the research work carried out
on preparation of various suitable membranes for the removal of VOCs has also been
explained.

Key words: Pervaporation, Volatile organic compounds, membrane materials

INTRODUCTION

Pervaporation is a membrane technology utilizing a dense non-porous polymeric film

to separate the contaminated water from a vacuum source. In the last three decades
considerable interest has been evinced in membrane based separation processes. Kober(1)
observed, that water evaporated out of a tightly closed colloidion bag, which was suspended
1
 in the air. He named this phenomenon as pervaporation (PV).In 1956, Heisler(2), for the
first time reported quantitative work on PV of ethanol-water mixtures using a cellulose
membrane. In the sixties Binning(3), and his coworkers applied for several patents, among
these, a process for removal of water from organic chemicals using a cross-linked PVA
membrane gained commercial interest. Till 1980, the low permeation flux of membrane
remained a barrier to the development of the PV process on industrial scale. In 1983,
Mulder(4) reported results on the dehydration of ethanol by asymmetric membranes with a
thin dense top layer in order to increase the permeability. In the following year
Brueschke(5), Gesellschaft Fiir Trenntechnik mbH, (GFT), a German company, came up with a
composite membrane, the first commercial membrane for the dehydration of ethanol. GFT
has since installed more than 100 such plants. In their process the ethanol feed to the
membrane generally contains about 10% water. The PV process removes the water as
permeate, producing pure ethanol with <1% water concentration. All the problems of
azeotropic distillation are avoided. Spurred on by this success, a great deal of effort is being
made to apply PV to other difficult separations. PV offers the possibility of separating
solutions, mixtures of components with close boiling points, or azeotropes that are difficult to
separate by distillation or other means.

The major applications of the pervaporation process are;

1) Dehydration of liquid mixtures
Azeotropic mixtures: Ethanol – water, Hydrazine - water
Close boiling mixtures: acetic acid – water
2) Removal of organics from water
Pollution control: toluene-water
Aroma recovery: Apple juice
3) Separation of organic –organic mixtures
Azeotropic mixtures: Benzene – cyclohexane, MTBE – methanol
Wine and beer dealcoholisation
Aromatics removal from gasoline
4) Reactive pervaporation
Esterification reactions

Volatile Organic Compounds are Organic compounds that have a boiling point less
0
than or equal to 100 C and/or a vapor pressure grater than 1mmHg are generally considered to
0 0
be VOC. Example Vinyl chloride BP = -13.9 C; VP= 2548 mmHg at 20 C

2
Treatment of VOC s is of great concern because
1) Vapor state more mobile and more likely released to the environment
2) Pose a significant public health risk
3) Increase in reactive hydrocarbons, leads to formation of photochemical oxidants.

Water contaminated with volatile organic compounds is encountered throughout

industry and in many groundwater and site remediation applications. Volatile organic
compounds (VOCs) are common contaminants in wastewater, leachate and contaminated
groundwater. About half of the priority pollutants are VOCs and are known to be toxic and/or
carcinogenic. VOCs are emitted in large quantities from waste treatment, storage and disposal
facilities. VOCs are also present at abandoned industrial sites. So there is a considerable
amount of research work going on throughout the world for better and better technologies for
reduction, recovery and recycling of hazardous liquid wastes. Adsorption methods using
activated charcoal and biological treatment are the presently practicing methods industrially
for the treatment of liquid discharges.

The Pervaporation process has proven to be an alternative to conventional technology

because it removes the amount of VOC's without requiring any pre/post treatments. The
process is most applicable to recovery of VOCs that are more hydrophobic than acetone in
streams that contain VOC levels between 200 and 50,000 ppm and have a volumetric flow of
10 to 100 gal per minute. In this range, pervaporation offers significant economic
and technical advantages over alternative processes.

Fig.1 Comparision of the separation methods for VOC removal

3
Pervaporation is the separation of liquid mixtures by partial vaporization through a non-
porous selectively permeable membrane. A phase change occurs when the permeate
changes from liquid to vapor during its transport through the membrane. A gradient in the
chemical potential of the substance on the feed side and the permeate side is the driving force
for the process. This force is kept maximum by applying low pressure to the permeate side of
the membrane. A concentrate and vapor pressure gradient is used to allow one component to
preferentially permeate across the membrane. Pervaporation is typically suited to separating a
minor component of a liquid mixture, thus high selectivity through the membrane is essential.
Fig.2 shows an overview of the pervaporation process.

P2
Recycle

P1
Feed Membrane Retentate

Feed pump T

P – Pressure gauge
P3 T – Temperature ga
Permeate

Fig.2 Schematic representation of membrane

separation process
Membrane is a selective barrier that permits the
separation of some certain species of fluid by a
combination of sieving and sorption diffusion
mechanism. It can selectively separate components over
a wide range of particle sizes and weights. A membrane
unit splits the feed into 2 streams: the permeate stream
consisting of components small enough to pass through
the pores and the retentate stream consisting of large
molecules retained by the membrane.

4
MECHANISM OF PERVAPORATION PROCESS

The pervaporation of dilute organic-water mixtures has been relatively well described
by a resistance-in-series model. The mass transfer process of a single component across the
membrane occurs in 4 consecutive steps:
1- Mass transfer from the bulk of feed to the membrane interface.
2- Selective absorption into the membrane at the feed side.
3- Selective diffusion through the membrane.
4- Desorption into the vapor phase at the permeate side.

The second and third steps are primarily responsible for the permselectivity. As
material passes through the membrane a "swelling" effect makes the membrane more
permeable, but less selective, until a point of unacceptable selectivity is reached and the
membrane must be regenerated.

SIMPLIFIED PERVAPORATION PROCESS

The feed is allowed to flow along one side of the membrane and a fraction of the feed
(permeate) passes through the membrane and leaves in the vapor phase on the opposite side
of the membrane. The "vapor phase" side of the membrane is either kept under a vacuum or it
is purged with a stream of inert carrier gas. The permeate is finally collected in the liquid
state after condensation. The liquid product is rich in the more rapidly permeating component
of feed mixture. The retentate is made up of the feed materials that cannot pass through the
membrane. This process can be operated batchwise or continuously depending on
requirements.
Batch pervaporation is a simple system with great flexibility, however a buffer tank is
required for batch operation. Continuous pervaporation consumes very little energy, operates
best with low impurities in the feed, and is best for larger capacities. Vapor phase permeation
is preferred for direct feeds from distillation columns or for streams with dissolved solids.

FACTORS AFFECTING THE PROCESS:

Although membrane materials govern the pervaporation process and determine the
separation factor, operational conditions do effect the permeation flux and selectivity:
Temperature
This parameter effects the process in all steps. It can be modeled by an Arrhenius expression:
(-Ea/RT)
J =Je . Generally, flux increases with temperature due to kinematics viscosity. Too
o
high a temperature may result in increasing hydraulic resistance.
Pressure
As mentioned above, vapor difference is the driving force for pervaporation. The larger the
transmembrane pressure difference is, the larger is the permeate flux. However, a large
pressure difference can result in no effect or in fouling of the membrane.
Crossflow velocity
Within small Reynolds number range, flux can be enhanced by reducing hydraulic diameter
or by increasing flow velocity. A critical velocity is necessary to achieve the maximum
separation potential. However, in turbulent flow regimes, very small flow effect is observed.
Feed concentration
Since overall permeability of a component depends on its solubility and diffusion rate
through the membrane, the permeate flux is significantly influenced by feed concentration.

PERVAPORATION CHARACTERISTICS
Molecular Flux
Molecular flux is the amount of a component permeated per unit area per unit time
for a given membrane.
Ji=Qi/(A.t) ------------- (1)
2
Where, Ji = Flux of component "i" (moles/h cm )
Q = Moles of component "i" permeated in time "t"
i
2
A = Effective membrane surface area (cm )

Permselectivity
The performance of a given membrane can be expressed in terms of a parameter called
Permselectivity
P P f f
α = (Xi /Xj )/ (Xi /Xj )---------------(2)
P P P P f f f f
α = (Vi . ρi /Vj . ρj )/ (Vi . ρi /Vj . ρj )------------- (3)
Assuming the density of the components in the feed is the same, then:
P P f f
α = (Vi /Vj )/ (Vi /Vj )------------------ (4)
Where, X = Weight fraction, V = Volume fraction, ρ = Density
Superscripts "p" and "f" denote "permeate" and "feed" respectively while "i" and "j"
represent individual components.

Permeability Coefficient
The molecular flux for pervaporation across a membrane can be related to the
Permeability coefficient by
Ji=-Pi.ΔP/L----------(5) or Ji=-KΔP--------(6)
0
Here, ΔP=P1-P2, P1=Pi Xr,i γi and P2=P.YP,i
therefore
0
ΔP=( Pi Xr,i γi -P.YP,i)----------- (7)
Equation 5 becomes,
0
Ji=-Pi. (Pi Xr,i γi -P.YP,i)/L-------------
0
(8) Pi=-Ji.L/( Pi Xr,i γi - P.YP,i
)-------------(9)

MEMBRANES AND THEIR SELECTIVITY

Membranes are available in different configurations: plate and frame, tubular,

hollow fiber and spiral wound. They are made of various materials such as polymer and
ceramic. Membranes that are used in pervaporation are normally manufactured as
composites. This is for mechanical reasons and the desire for high mass flux. The membranes
used in pervaporation processes are classified according to the nature of the separation being
performed. Hydrophilic membranes are used to remove water from organic solutions. These
types of membranes are typical made of polymers with glass transition temperatures above
room temperatures. Polyvinyl alcohol is an example of a hydrophilic membrane material.
Organophilic membranes are used to recover organics from solutions. These membranes are
typically made up of elastomer materials (polymers with glass transition temperatures below
room temperature). The flexible nature of these polymers make them ideal for allowing
organic to pass through. Examples include nitrile, butadiene rubber, and styrene butadiene
rubber.
In selecting membranes, three issues must be emphasized: membrane productivity,
selectivity and stability. Membrane productivity is a measure of the quantity of a component
that permeates through a specific area of membrane surface in a given unit of time. It is
characterized by permeation flux, which relates the product rate to the membrane required to
achieve separation. Flux is modeled by Fick’s law. Permeation flux depends on both the
intrinsic permeability and the effective thickness of a membrane. Another important
parameter is the selectivity factor α that describes the ability of the process to separate two
ij
substances i and j. When the selectivity factor is unity, no separation occurs. When it
approaches infinity, the membrane becomes perfectly semi-permeable. It is the membrane
selectivity that forms the basis for separating a mixture. There usually is a trade off between
membrane permeability and selectivity. The enrichment factor is used as an indication of the
separation selectivity for a component.

Membrane stability is affected by the chemical, mechanical and thermal properties

of the membrane. Indeed, due to the nonporosity of membrane used in pervaporation, there is
almost no limitation of the transmembrane transport induced by a fouling of the membrane.
Also, the feed operating conditions of low temperature and low pressure are generally
compatible with membrane stability. Factors Affecting Membrane Performance according to
the solution-diffusion model, higher fluxes can be obtained with an increased thermal motion
of the polymer chains and the diffusing species. Properties of the polymers that affect
diffusion include the "backbone" material, degree of cross-linking, and porosity. Molecular-
level interactions between membranes and diffusing species is expressed via a permeability
constant used in the Arrhenius relationship:
(-E /RT)
P=P0.e P -------------------(10)
Where, E = Activation energy, P = Permeability constant,
p o
R = Gas constant, T = Temperature

Table.1 Selective and transport properties of different types of pervaporation

membranes

.
Membranes for removal of VOCs from aqueous solutions
Membranes in these applications are rubbery polymers such as silicone rubber,
polybutadiene, polyether copolymers, polydimethylsiloxane (Tab.1). The separation achieved
is determined by the individual rates of permeation through the membrane and the relative
volatility of the components of the feed mixture. Usually the VOCs permeate through
hydrophobic membrane orders of magnitude faster than water, as a result of which the VOCs
are highly concentrated.

Table2. Pervaporation separation factors for VOC s removal from water

Separation factor for VOC over water Volatile organic compound(VOC)
200-1000 Benzene, toluene, ethyl benzene, xylenes,
Chloroform, Vinyl chloride, ethylene
dichloride, methylene chloride, perflouro
carbons,hexane
20-200 Ethyl acetate, propanols, butanols, MEK,
acetone, aniline, amyl alcohol, methyl t-butyl
ether
5-20 Methanol, ethanol, phenol,acetaldehyde
1-5 Acetic acid, ethylene glycol,DMF, DMAC

Now a days, pervaporation with organophilic membranes can be used for solvent
recovery, pollution abatement, concentration of organics (for disposal or incineration),
recovery of aroma compounds and production of beverages with low content of alcohol.
Methyl acetate (MeAc) and MTBE are the examples of VOCs which can be found in the
effluents from many chemical, pharmaceutical or petrochemical factories in Poland. MTBE,
widely used as an octane enhancer, has relatively high water solubility and vapor pressure
MTBE is very toxic and is also suspected for its carcinogenic properties [12, 13]. Recently,
MTBE has been detected in lakes, reservoirs, and groundwater used as potable water supplies
in concentrations exceeding, in some cases, allowed levels for taste, odor and human
health[12].

Figs.4 and 5 present the efficiency of two commercially available hydrophobic

membranes (Sulzer Chemtech) in the removal of MTBE/MeOH and MeAc/MeOH mixtures
from water [13]. PERVAP-1070 is a composite membrane with a selective top layer made of
PDMS filled with hydrophobic zeolite. The toplayer of PERVAP-1060 membrane is made of
PDMS. Both membranes shows very high efficiency toward less polar components of the
ternary mixture at moderate temperatures. Pervaporation with organophilic membranes can
also be applied in the treatment of wash waters used to remove organics from solvent-laden
airstreams. The dilute aqueous solution is treated by pervaporation to remove the solvent into
the permeate and to produce water, with a minor amount of solvent, to recycle to the air
scrubbing unit.
Fig.4. Batch mode pervaporation. Removal of MTBE and MeOH from water using PERVAP-
3 2
1070 membrane. Feed volume to membrane area ratio 120 dm /dm . Initial
organics concentration: MeOH: 2%, MTBE:1%.

Fig. 5. Batch mode pervaporation. Removal of MeAc and MeOH from water using PERVAP-
3 2
1060 membrane. Feed volume to membrane area ratio 120 dm /m . Initial
organics concentration: MeOH: 6.4%, MeAc: 1.6%.
Three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three
aromatic dianhydrides of 4,4 -(hexa fluoro isopropylidene) diphthalic anhydride (6FDA),
3,3 ,4,4 -benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride
(PMDA) with a siloxane-containing diamine shows high pervaporation selectivity and
permeation flux towards hydrophobic compounds. These PSI membranes with 150- m
thickness exhibit a high pervaporation selectivity of 6000-9000 and a high permeation flux of
2
0.031-0.047 kg/m h for 0.05 wt % of the toluene/water mixture(14).

CONCLUSIONS
Pervaporation continues to evolve as a feasible separation technology for many
different applications. One of the major economical advantages of pervaporation is its low
energy consumption. Compactness, flexibility, simplicity and versatility are some of the
strong points of pervaporation. As in the distillation and extraction, there is no need of
entrainer and functions independent of vapor liquid equilibrium. This makes pervaporation
the most used separation technique next only to distillation and extraction. This method has
become a more cost-effective unit process for many food manufacturers. It is applied mostly
for the dehydration of solvent in azeotropes, the separation of organic mixtures and the
removal of organics from water. Recently, the separation of VOCs from aqueous waste
streams, the removal of small amounts of water from organic solutions and the drying of
organic liquids by removing small volumes of water appear to be having promising
applications.

REFERENCES

1. Kober, P. A. Pervaporation, Perstillation and Percrystallization, J. Amer. Chem. Soc.,

39:944-50 (1917).

2. Heisler, E. G., A. S. Hunter, J. Sicilino, and R. H. Treadway, Science, 124:77 (1956).

3. Binning, R. C., R. J. Lee, J. F. Jennings and E. C. Mar, Separation of liquid mixtures by

permeation, Ind. Eng. Chem., 53:45 (1961).

4. Mulder, M. H. V., J. E. O. Hendrkman and C. A. Smoloers, Ethanol-Water separation by

pervaporation, J. Membrane Science, 16:269-284 (1983).

5. Bruschke, H. E. K and N. P. Wynn, Pervaporation, in Encyclopedia of Separation

Science, edited by Ian D. Wilson, published by Academic Press, A Harcourt Science and
Technology Company, Harcourt Place, 32 James Town Road, London, 2000b, pp. 1777-
1786.

6. Shinsuke, T., Y. Hideki and T. Shoji, Dehydration of Water/Ethanol Mixtures by

Pervaporation Using Modified Poly (Vinyl Alcohol) Membrane, Polymer. J., 24:1239-50
(1992).
7. Marcel Mulder, Basic Principles of Membrane Technology, published by Kluwer
Academic Publishers, 1991, pp. 283-285.

8. Munir Cheryan, Basic Principles of Membrane Separations, in Practical Short Course in

Membrane Separation in Food Processing Applications, edited by S. S. Koseoglu, C. J.
Vavra and K. C. Rhee, Food Protein Research and Development Center, Texas
Engineering Experiment Station, The Texas A&M University System, College Station,
Texas, 1991.

9. Wijmans, J. G., R. W. Baker, The Solution-Diffusion Mode l- A Review, Journal of

Membrane Science, 107 (1995) 1-21.

10. Kujawski, W., Membrane Selectivity in Pervaporation, Separation Science and

Technology, 31:1555-1571 (1996).

11. Kujawaski, W., Application of pervaporation and vapor permeation in environmental

protection, polish journal of environmental studies,9(1) 2000 13-26

• Unit operations of chemical engineering, McCabe & Smith

• Hand book of Chemical engineering, Perry
www.cheresources.com
• www.membrane.nl
• www.scej.org

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