Isopropanol dehydration by Pervaporation by using various

composite membranes of polyvinyl alcohol and chitosan.

Ashwani Mehta, Rahul Kumar, Prince Sourabh, Rahul Kumar verma P.K. Mishra

Email- ashwani.mehta.che14@itbhu.ac.in

Department of Chemical Engineering & Technology IIT-BHU, Varanasi, Uttar

Pradesh, 220115, India.

ABSTRACT

Pervaporation, a membrane process for separation of liquid mixtures, is becoming recognized as an

energy efficient alternative of distillation and other separation methods. The performance of a
pervaporation membrane can be characterized in terms of permeation flux and separation factor.
Dehydration of isopropanol by Pervaporation was done, by using different water perm-selective
membranes. Membranes were prepared from a) polyvinyl alcohol (PVA) and b) chitosan.
Furthermore the membranes were crosslinked using various cross linkers and fillers at different
proportions. These membranes were characterized and further evaluated for separation of
azeotropic isopropyl alcohol (IPA)/water mixtures by Pervaporation. Indigenous setup for
Pervaporation was designed and also fabricated. Various proportions of isopropyl alcohol ranging
from 30%-5% IPA was tested and nearly 99.1% pure IPA was obtained. The change in permeation
rate and the selectivity by using various cross linkers and fillers was also observed. Also the
comparison of the separation behaviour of the membranes is being done on various PVA and
Chitosan membranes.

INTRODUCTION

Separation of various mixtures, especially liquid mixtures, is a very necessary industrial requirement.
A large number of such techniques are available, such as distillation, adsorption, liquid– liquid
extraction, and fractional crystallization.

Membrane technologies are gaining increasing interest from both the scientific and applied points of
view , and membrane separation is one of the most studied membrane technologies Gas separation
, ultra-filtration , nano-filtration , reverse osmosis , membrane distillation , and pervaporation
constitute the main scope of membrane separations.

The pervaporation principle was postulated in 1950. However, its commercial application as an
energy efficient alternative to conventional techniques has gained importance only recently. This
technique has been applied extensively for the separation of the ethanol/water mixture obtained
during fermentation. One of the most attractive features of pervaporation is that no high-pressure
system is necessary to circulate the liquid through the pervaporation unit. The unit can operate at
low temperature, so that degradation-sensitive constituents can be handled more safely.
Membrane materials are of crucial importance for successful membrane separation technologies. .
Poly(vinyl alcohol) (PVA) is one of the most studied membrane materials due to its outstanding
membrane forming ability, easy processing and abundant availability.Cross-linking or curing is a vital
tool for the modification of existing polymers to achieve new and improved material. Being a
biodegradable synthetic polymer, poly(vinyl alcohol) (PVA) acquires special attention because of its
good transparency, lusture, antielectrostatic properties, chemical resistance and toughness. PVA is
largely used as fiber (vinylon), film, in the paper industry, in textile sizing, as a modifier of
thermosetting resins, in plywood manufacture,aspressure-sensitiveadhesives,emulsifier,etc.
Dehydration of isopropanol by Pervaporation was done, by using different water perm-selective
membranes. Membranes were prepared from a) polyvinyl alcohol (PVA) and b) chitosan.
Furthermore the membranes were crosslinked using glutaraldehyde(GLU) and fillers at different
proportions.

EXPERIMENTAL SECTION

1. MATERIAL USED

Polyvinyl Alcohol (PVA), Mw =125,000 and Chitosan flakes (Flonac -N) with MW of 100,000
(99% Ndeacetylation degree) were purchased . High purity, HPLC grade 1,4-dioxane was
purchased to form glutaradehyde by mixing of 1,4 dioxane and PVA glutaraldehyde.
inorganic hydrophilic filler, i.e. sodium aluminosilicate . Water was deionized and distilled
before use.

2. MEMBRANE PREPARATION

Membranes were prepared by solution casting method. The preparation of both the
homogeneous and composite membranes involved dissolution of the polymer in a solvent to
form the casting solution, casting of the polymer solution onto a plate to form a membrane
film, treatment.

A 5wt.% PVA solution was prepared in a boiling water under vigorous stirring condition on a
hot plate with a magnetic or mechanical stirrer. Then this homogenous solution was mixed
with chitosan and aqueous dispersion of fine sodium aluminosilicate (inorganic filler) and
stirred continuously about 8 hours get a filler incorporated stable polymer dispersion. It was
then mixed with aqueous solution of crosslinker i.e glutraldehyde. This filler incorporated
polymer solution was then poured uniformly on a clean glass plate leveled perfectly. Water
was evaporated by keeping the glass plate at ambient condition for 24h. Dried membrane
was further heated in an air oven at 120◦C for 2h for the crosslinking reaction. The cured
membrane was then peeled off from the glass plate and the membrane of desired thickness
is obtained. Now the membrane is taken for subsequent testing.

3. Membrane characterization

 Studies of FTIR spectroscopy

 Morphology of the PVOH membranes by scanning electron microscopy (SEM)
 Differential scanning calorimetry (DSC)
  Thermogravimetric analysis (TGA)
 X ray diffraction
 Swelling experiments
 Particle size measurement

4. Pervaporation experiment

The procedure used in PV experiments described by figure. Weight of the feed mixture taken in the
PV cell . Temperature of the feed mixture was maintained constant by a thermostatic water jacket.
Downstream pressure was maintained below 10Torr using a vacuum pump . Before the actual
experiment, the test membrane was equilibrated for about 2h with the feed mixture. After
establishment of a steady state, permeate vapors were collected in traps immersed in liquid
nitrogen. PV experiments were performed with the feed mixture of water–isopropanol taken in
different compositions. The weight of permeate collected in the trap was noted and permeate
composition was determined by measuring the refractive index and by comparing it with the
previously established graph of refractive index versus mixture composition.

Membrane performance was studied by calculating permeation flux, J and selectivity, α using the
equations:

J = W/AT
And
α= (PA/(1-PA)) * ((1-FA)/FA)

Here:-
FA = mass% of water in the feed
PA = mass% of water in permeate
W= weight (kg) of liquids permeated
A = effective membrane area ,(m2)
T= measurement time, (h)
 These three independent measurements of flux and selectivity were taken under the same
conditions of temperature and feed composition to confirm the steady-state permeation.