Advance Separation Technique Review on papers:

Pervaporation Process
-Krunal J.S M.Tech in Chemical process & plant design

Content:

Where we stand

Reference: Suzlon, at GSFC seminar

Pervaporation
It is one of the most complex membrane separation process where there is liquid on one side of the membrane and a vapor on the other side. The liquid diffuses through membrane and vaporizes.

The partial pressure in the vapor phase is usually reduced

by pulling a vacuum or using a sweep gas. On the liquid side concentration polarization may be important particularly for the removal of trace organics from water.

Pervaporation(PV) Mechanism
The membrane is operated by the solution diffusion mechanism. PV involves partial vaporization of a liquid mixture through a dense membrane whose downstream is usually kept under vacuum.

Mechanism:
1) Upstream partitioning of feed component between flowing liquid mixture and the swollen upstream surface layer of membrane. 2) Diffusion of components from the surface layer through the

membrane.
3) Desorption of these component as the downstream surface of the membrane.

Separation of organic-organic mixture by Pervaporation using different membrane material

Selectivity: The generally accepted measure of the separation capability of a Pervaporation membrane for a specific binary mixture is the

separation factor, , defined as:

where xp,i and xp,j are the mole fractions of the preferential and secondary permeants, respectively, in the permeate, and xf,i and xf,j are the corresponding mole fractions in the feed.

The separation factor can vary from unity to infinity, where larger -values indicates increased selectivity.

Polar/Non-polar mixtures

Aromatic/Ali cyclic mixtures

Aromatic/ Aliphatic mixtures

Isomer mixtures

Pervaporation of ceramicsupported poly(vinyl alcohol) Chitosan composite membrane

and their applications in

Pervaporation dehydration of organic/water mixtures.

poly(vinyl alcohol) - PVA

Hydrophilic polymeric material Superior hydrophilic property

Good film-forming ability and Chemical stability

By cross-linking and blending the water insolubility of PVA membranes is improved dramatically and the swelling of the membranes is reduced.

Chitosan - CS
CS is an inexpensive and non-toxic polycationic polymer obtained commercially by alkaline deacetylation of chitin (a N-acetyl-

glucosamine polymer), the hydroxyl and amino groups in the repeat units
make it a strong hydrophilic material.

PVACS blending membranes possess the intrinsic properties of both

PVA and CS. PVA has semi crystalline structure while CS has less compact structure

and the free volume of CS is relatively larger.

Blending of PVA with CS can reduce the crystallinity, and as a result, flux can be improved.

Why Ceramic membrane support:

ceramic membranes have unique stable structure, and thereby

they can withstand various kinds of organic solvents and higher

temperatures. To improve chemical, mechanical, thermal stability.

Membrane Preparation
2 wt% CS solution and 7 wt% PVA solution were prepared first After this, both solutions were filtered to remove undissolved particles and impurities, Then they were mixed in certain proportions to form completely homogeneous solutions with different PVACS ratios.

Maleic anhydride and sulfuric acid were used as cross-linking

agent and catalyst, respectively. The resulting solutions were then coated onto the tubular ZrO2/Al2O3 supports, by dip-coating method. The membranes were firstly dried under ambient conditions, and then annealed at 120 C for 3 h.

Experiment: The feed solution was continuously circulated from a feed tank through the tube side of the membrane module using a variable speed feed pump. Vacuum on the permeate side was maintained at about 200 Pa and was monitored by a digital vacuum gauge. The permeated vapor was collected by turns in liquid nitrogen traps. Before Pervaporation, the membranes were immersed in the feed solution for 12h, so that the time for the membrane to come to the steady state permeation in the Pervaporation process was minimized . About 2 h after starting the PV process, the mass transfer equilibrium was established and PV performance was considered to be stable.

Schematic diagram of Pervaporation experiment

At steady state, the weight of permeate collected in the cold trap was measured to obtain the total flux, J J = M/ A*T
where M is the total mass permeated during the experiment time interval, t and A is the effective membrane area.

The experiment results were observed using various equipments:

SEM: The surface and cross-section morphologies of the tubulartype membranes and the thicknesses of organic separation layers were characterized. FTIR spectra: Cross-linking is an effective method to reduce membrane swelling. The water content of feed and permeated samples were analyzed by gas chromatography.

Conclusions
The pore size of ceramic support affects the Pervaporation performance of the composite membrane. The introducing of CS into PVA increased the amorphous region of the membrane whereas reduced the membrane hydrophilicity.

With increasing the CS content, the permeation flux increased

remarkably without a significant drop in separation factor. In the dehydration of alcohol/water mixtures, with increasing of both temperature and feed water concentration, the flux increased without a decrease in separation factor.

The membrane exhibited excellent Pervaporation performance, especially in the dehydration of ethyl acetate/water mixture at 3.5 wt% water in feed with a flux of 1250gm2 h1 and a separation factor larger than 10,000.

In addition, the ceramic support is non-deformable, so the deformation of the organic top layer can be restrained and the membrane performance can be improved.

Our results demonstrate that the ceramic-supported PVACS

composite membranes are suitable candidates for Pervaporation dehydration of organic/water mixtures. When the Chitosan content is 60 wt%, the composite membrane exhibited high performance.

References:
Rate controlled separation, part III, chapter12, page 703 Phillip C. Wankat Journal of membrane science, Jan2010 Yuixin Zhu, Shanshan Xia Separation of organic-organic mixture B.Smith, D Suhanya

Thank you