REPORT

Separation of Binary Mixture By Using Pervaporation
Chapter 1
INTRODUCTION TO PERVAPORATION
1.1 BACKGROUND:
Most industrial scale separation processes are based on energy intensive methods
such as distillation, evaporation, and freeze crystallization. Membrane separations offer
significant advantages over existing separation processes. Current membrane separation
technologies can offer energy savings, low-cost modular construction, high selectivity of
separated materials, and processing of temperature- sensitive products [1-5]. Membranes
separate mixtures by discriminating the components on the basis of physical or chemical
attributes, such as molecular size, charge, or solubility [6]. By passing water and
retaining salts, membranes are used to produce over half of the world's desalinized
potable water. Membranes can also separate oxygen and nitrogen from air as well as
hazardous organics from contaminated water in applications such as groundwater
remediation. The need for membrane separation technology increases as environmental
requirements tighten, water circuits close, the recycling of wastes increases and the purity
requirements for foodstuff and pharmaceuticals increase Six major membrane processes
(microfiltration, ultrafiltration, reverse osmosis, electrodialysis, gas separation and
pervaporation) have found use in such application areas as water purification, chemical
and food processing, drug delivery, bioseparations, and medical treatment [1-6].
Compared with traditional separation processes, such as distillation, extraction and
filtration, membrane technology is a relatively new method that has been developed in
the past few decades, but it has been widely adopted in many industries. The membrane
processes have the following distinguishing characteristics [Mulder 1991]:
1) Continuity and simplicity of the processes,
2) Adjustability of the separation properties,
3) Feasibility of incorporation into hybrid processes,
4) Low energy consumption and moderate operating conditions.
Developments in membrane formation techniques and materials
science accelerate the research and applications of membrane
technology. Now commercial membrane applications have successfully
1
displaced some conventional processes, and membrane technology

has become an indispensable component in many industrial fields and
our daily life.
Figure 1.1 Schematic membrane separation processes
Figure 1.1 shows a schematic membrane process [Mulder 1991;

Baker 2004]. Separation membranes are located between the feed
side and the permeate side. In most membrane processes, such as gas
separation, reverse osmosis and ultra filtration, both the feed and the
permeate sides are in the same phases, gas or liquid, while in
pervaporation, the liquid feed is separated into vaporous permeates
with the aid of vacuum or a purge gas in the downstream side.
Pervaporation has become a very important technique to separate azeotropes, close-
boiling mixtures, and recover volatile organic chemicals from liquid mixtures, and now it
has emerged as a good choice for separating heat sensitive products. The phenomenon of
pervaporation was first discovered in 1917 by Kober [1995], but no extensive research
was carried out until in the 1950s by Binning et al. [1961].
In pervaporation processes with functional polymer membranes,
the non-porous dense membranes are essential. By choosing proper
membranes, pervaporation has great advantages as an alternative
separation method in the following separation tasks:
1) Dehydration of organic solvents,
2) Removal of organics from water,
3) Separation of organic liquids.
2
Non-porous dense membranes can also be applied in other separation

processes such as gas separation. Furthermore, both gas separation
and pervaporation can be interpreted with the solution diffusion
mechanism for mass transport in membranes. Membrane-based
pervaporation or vapor permeation is a promising alternative to
distillation since it is an energy-saving one-step separation process. If
the proper membrane material is selected, pervaporation can separate
azeotropic mixtures and close boiling mixtures that traditional
distillation has difficulties in processing [3].
Membrane Feed phase / Driving Force Membrane Main application

Process Permeate phase
Pervaporation Liquid / vapor Chemical dense,liophilic Separation of liquid
potential gradient mixture
Vapor Vapor / vapor Chemical potential dense,liophilic Separation of liquid
permeation gradient mixtures or vapors from
gases
Pertraction Liquid / liquid Concentration dense,liophilic Separation of organic
gradient solutions
Gas separation Gas/gas Hydrostatic pressure Porous or dense Separation of gaseous
gradient mixture
Membrane Liquid/vapor Vapor pressure Porous,liophilic Ultrapure water,
Distillation gradient concentration of
solutions
Table 1.1.Overview of chosen membrane separation processes
1.2 MEMBRANE BASED PERVAPORATION SEPARATION:

1.2.1 Pervaporation Process
Pervaporation is recognized as a separation process in which a binary or

multicomponent liquid mixture is separated by partial vaporization through a dense non-
porous membrane. During pervaporation, the feed mixture is in direct contact with one
side of the liophilic membrane whereas the permeate is removed in a vapor state from the
opposite side into a vacuum or sweeping gas and then condense. Pervaporation is unique
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among membrane separations, involving the liquid-vapor phase change to achieve the
separation [7, 8].
In Pervaporation (PV), components of a volatile liquid feed will permeate through a
nonporous permselective membrane and evaporate into the permeate space (Figure
1.2.1). The feed components undergo a phase change, making PV a unique membrane
processes (Néel, 1991; Villaluenga and Tabe-Mohammadi, 2000).
Figure 1.2.1 The pervaporation process (Schleiffelder and

Claudia, 2001).
Liquid feed flows along one side of the membrane and various feed components
selectively permeate into and through the membrane. In laboratory-scale batch-PV, liquid
retentate is returned to the feed tank, depleted in preferentially permeating components.
The enriched permeate vapour is swept from the membranes downstream surface under
vacuum conditions or by an inert sweep gas, and is collected in a condenser (Feng and
Huang, 1997; Schleiffelder and Claudia, 2001).
Pervaporation, in its simplest form, is an energy efficient combination of
membrane permeation and evaporation. Liquid mixtures can be separated by partial
vaporization through a non-porus permselective membrane. This technique, which was
originally called “Liquid permeation” has subsequently been termed “pervaporation” in
order to emphasized the fact that permeate undergoes a phase change, from liquid to
vapor, during the transport through the barrier.
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It's considered an attractive alternative to other separation methods for a variety of

processes. For example, with the low temperatures and pressures involved in
pervaporation, it often has cost and performance advantages for the separation of
constant-boiling azeotropes. Pervaporation is also used for the dehydration of organic
solvents and the removal of organics from aqueous streams. Additionally, pervaporation
has emerged as a good choice for separation heat sensitive products. Pervaporation
involves the separation of two or more components across a membrane by differing rates
of diffusion through a thin polymer and an evaporative phase change comparable to a
simple flash step. A concentrate and vapor pressure gradient is used to allow one
component to preferentially permeate across the membrane. A vacuum applied to the
permeate side is coupled with the immediate condensation of the permeated vapors.
Pervaporation is typically suited to separating a minor component of a liquid mixture,
thus high selectivity through the membrane is essential.
In addition, a pervaporation unit can be integrated into a bioreactor to improve
bioconversion rate and reduce downstream processing costs, if membranes can
selectively remove volatile inhibitory substances from fermentation broths [7]. Compared
to the relatively easy separation of non-aggressive chemicals from water in industry, very
few commercial systems have been developed to separate aggressive organics-water
systems [8-11]. The most significant opportunity to use pervaporation is in splitting an
azeotrope or a close boiling-temperature mixture, where distillation is less efficient due to
the huge amount of energy consumption. Theoretically, if a liquid feed contacts a
nonporous membrane with vacuum downstream, the vaporization rate of each component
in the liquid is limited by the membrane permeability. In other words, the concentration
distribution of each component in the liquid and vapor is not only controlled by the
thermodynamic equilibrium [12], but also is governed by the membrane permeability. In
this case, the membrane is sometimes referred to as a “mass separating agent”.
Nevertheless, the membrane-mediated evaporation is generally regarded as
pervaporation. In order to maximize the driving force, i.e. an activity difference between
a feed liquid and permeate vapor, heating the feed liquid at the boiling temperature on
one side of the membrane and pulling a vacuum or cooling the permeate vapor to
condense on the other side are generally applied in the pervaporation process [3].
5
Figure 1.2.2: Membrane-based pervaporation separation processes Vacuum

Operation
Pervaporation can used for breaking azeotropes, dehydration of solvents and other
volatile organics, organic/organic separations such as ethanol or methanol removal, and
wastewater purification.
1.2.2 Possible modes of Pervaporation
Pervaporation units can operate either in the straight-forward or batch mode (Fig.
1.2.3). The straightforward mode is best applied to continuous feed streams, a relatively
small amount of the component to be removed and systems for which concentration
polarization is not a major problem (Fig. 1.2.3(A)). For small streams with large amounts
of one component to separate, or with many different operating conditions, it may be
advantageous to design a batch plant (Fig. 1.2.3(B)) with one or several modules, and a
large feed circulation rate. The product is recycled to the feed tank until the required
concentration is reached. This process simplifies plant design and offers maximum
flexibility, however, with increased utility requirements.
Fig.1.2.3 (A) Continuous Pervaporation
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Fig.1.2.3 (B) Batch Pervaporation

Fig.1.2.3 Possible modes of Pervaporation
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.
Characteristics of the Pervaporation process include:
1. Low energy consumption
2. No entrainer required, no contamination
3. Permeate must be volatile at operating conditions
4. Functions independent of vapor/liquid equilibrium
1.2.3 Pervaporation for Separation
Liquid transport in pervaporation is described by various solution-diffusion

models1. The steps included are the sorption of the permeate at the interface of the
solution feed and the membrane, diffusion across the membrane due to concentration
gradients (rate determining steps), and finally desorption into a vapor phase at the
permeate side of the membrane. The first two steps are primarily responsible for the
permselectivity1. 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. The other driving force for separation is
7
the difference in partial pressures across the membrane. By reducing the pressure on the
permeate side of the membrane, a driving force is created. Another method of inducing a
partial pressure gradient is to sweep an inert gas over the permeate side of the membrane.
1.2.4 Pervaporation applications

There are three common applications of pervaporation (Koops and Smolders, 1991; Feng
and Huang, 1997):
• Dehydrating organic solvents using hydrophilic membranes (i.e., water-alcohol,
-ethers, -ketones, -carboxylic acids),
• Removing organic compounds from aqueous solutions using hydrophobic
Membranes (i.e., water-chlorinated hydrocarbons, -phenol), and
• Separating anhydrous organic mixtures using organo-selective membranes (i.e.,
MTBE/methanol).
1.2.5Alternative techniques
The requirements for technological or economic operation of the most common
processing techniques for separating organic-organic mixtures are given in Table 2:01.
Separating close boiling organic-organic solvent mixtures by distillation or liquid-liquid
extraction is difficult, as the components have very similar physical and chemical
properties (Young, 1973).
Process Requirements for basic or economical operation
Azeotropic distillation Requires high aromatic content (>90%)
Extractive distillation Requires medium aromatic content (65–90%)
Liquid-liquid extraction Requires low aromatic content (20–65%)
Crystallization Distillative pre-separation (e.g., o-xylene and ethylbenzene

separated from C8 aromatic fractions)
Adsorption on solids Continuous, reversible and selective adsorption
Table 1.2.5 Processes for aromatic recovery (Villaluenga and Tabe-Mohammadi,

2000; Porter, 2001).
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Because PV is based on sorption and diffusion properties of the feed components

and membrane permselectivity rather than relative volatility, this process is especially
attractive for azeotropes and close boiling point mixtures, if close boiling point mixture
is challenging process in the chemical industry. Conventional distillation produces a low
purity product (85–98%), so azeotropic distillation and extractive distillation are
commonly used. However, these processes require addition of a third component, which
increases the process complexity and cost (Villaluenga and Tabe- Mohammadi, 2000).
Adsorption is primarily used for aqueous-organic separations. However, PV is a
better process when the organic components concentration is relatively high. The organic
can be removed continuously so the process is not limited by adsorber capacity (Shao,
2003).
Systems combining PV membranes with traditional techniques (e.g.,
PV/distillation) have been used (Ishida and Nakagawa, 1985; Hömmerich and
Rautenbach, 1998; Ferreira et al., 2002). However, membrane performance is still the
key factor limiting PV efficiency (Smitha et al., 2004).
1.3 MEMBRANE STRUCTURE
Work on membrane separations began in the early 1960s, using membrane materials
such as dense metals, zeolites, polymers, ceramics and biological materials. Of these,
polymers are the most widely used material (Smitha et al., 2004). Several different
polymer membrane structures are commonly used today, including porous, dense and
asymmetric membranes. Selecting a good membrane requires a sound knowledge of
membrane structures. Much of the following discussion is based on the excellent review
by Smitha et al. (2004).
1.3.1 Membrane
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
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recover organics from solutions. These membranes are typically made up of elastomeric
materials (polymers with glass transition temperatures below room temperature). The
flexible nature of these polymers makes them ideal for allowing organic to pass through.
Examples include nitrile, butadiene rubber, and styrene butadiene rubber.
Synthetic membranes are thin, solid-phase barriers that allow preferential passage
of certain substances under the influence of a driving force. Both the chemical and the
physical nature of the membrane material control membrane separation. Membrane
separation occurs because of differences in size, shape, chemical properties, or electrical
charge of the substances to be separated. Microporous membranes control separation by
size, shape and charge discrimination, whereas nonporous membranes depend on sorption
and diffusion. The performance of the membrane is determined by the degree of
separation of fluid mixtures and permeation rate (flux). (3, 33) Three general categories of
inorganic membranes are ceramics, metals and glass. Because they are so rigid, ceramic
microfilters accommodate fluxes five to ten times greater than those of asymmetric
polymeric membranes. They can be backwashed frequently without damaging the
membrane skin layer. Ceramic membranes are highly resistant to cleaning chemicals and
can be sterilized repeatedly by high pressurized steam. Their life span is up to ten years
compared to the typical life spans for polymer membranes, which are about one year for
hydrophobic membranes and up to four years for fluoropolymers. Ceramic membranes
are brittle and are more expensive than polymeric membranes. (3,34) Pervaporation
membranes are typically composites. The first layer is a porous, polymeric support coated
with a second polymer, the "active" or "permselective" layer, which is engineered to
preferentially absorb the chemical species of interest. The membranes’ separation
characteristics can be further refined by varying the thickness of the permselective layer.
(4,88)
For example, asymmetric composite hydrophilic membranes such as composite PVA-
PS (Poly(vinyl alcohol)-Polysulfone) are used for pervaporation. Pervaporation
separation plants contain between ten and one hundred m2 of membrane area, which must
be packaged efficiently and economically into units called membrane modules. Flat-sheet
and spiral-wound modules are commonly used.(3,41) Silicon rubber membranes are also
used in pervaporation. Spiral wound configuration offers a high membrane surface area
per module and allows for relatively high feed flow rates which are common for
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pervaporation. Silicone rubber pervaporation modules are remarkably effective at

separating organic solutes from dilute aqueous solutions.(2,35) Spiral wound modules are
available in 2, 4 and 8 inch diameters to accommodate a variety of feed flow
requirements and to allow for economical system design.(4,89) The choice membrane
depends on the feed solution. The most efficient application of any membrane is to
permeate the minor component of a mixture.(2,35)
1.3.2 Membrane morphology

Membranes used for laboratory scale organic mixture separation are generally
homogeneous and symmetric (Figure 1.4.1a). These are easy to cast and will directly give
the intrinsic separation properties of the polymer. However, to attain commercial
viability, membranes need to be prepared in asymmetric or composite form. These two
morphologies give a thin effective separation layer, enabling high flux while maintaining
the desired mechanical strength of the membrane. Asymmetric membranes have a thin
dense layer on top of a porous support layer of the same material (Figure 1.4.1b). They
are generally prepared by a phase inversion technique – a homogeneous polymer solution
is cast as a thin film or spun as a hollow fibre and immersed in a non-solvent bath after a
brief evaporation time in air. The membrane is formed by precipitating polymer when the
solvent is replaced by a non-solvent.
Figure 1.4.1. Morphology of the pervaporation composite membrane
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Composite membranes consist of a porous support layer with a thin dense skin
layer on top (Figure 1.4.1 c). The skin is usually a different polymer material from the
support layer. Composite membrane structures minimize membrane cost by reducing the
quantity of expensive high-performance material used. In principle, composite
membranes allow the properties of the dense separating layer and the porous support
layer to be optimized individually, and to a greater extent, than in the phase inversion
process.
1.3.3 Membrane module
When a highly selective material is selected, membrane performance can be
optimized further by reducing the effective membrane thickness. It is best to use a thin
film of the discriminating layer deposited on a highly porous support structure. This
means that either asymmetric or composite membranes have to be developed with a
dense toplayer and an open porous sublayer. The requirements for the sublayer are such
that the resistance for permeate transport must be neglectable compared to the resistance
of the toplayer. Therefore, optimization of the sublayer is very important [12]. It might
even be worthwhile to develop a three layer membrane consisting of a very porous
sublayer, than a nonselective intermediate layer and dense toplayer (Fig. 1.4.3) [12].
The composite membranes can be produced either in a flat configuration or in a
tubular configuration. Membranes have to be incorporated into modules in order to be
used in the process. The main module designs are the plate-and-frame system and the
spiral-wound system that are based on the flat membranes and the tubular, capillary and
hollow fiber modules that are based on the tubular membrane configuration [39]. Fig.
1.4.2 shows a schema of the plate-and-frame module. Plates made of stainless steel form
the feed channels and compartments, which are sealed to the membranes by gaskets. The
membranes are supported by stainless steel perforated plates and spacers, which form the
permeate channels. The latter ones are open to all sides, allowing for a fast and easy
removal of the permeate. The arrangement assures a uniform, parallel flow of the feed
mixture over all membranes in a module.
12
Figure 1.4.2. Schema of a plate-and-frame module
The spiral wound modules (Fig. 1.4.3) are flat sheets arranged in parallel to form
a narrow slit for fluid flow. In a typical construction two flat membrane sheets are placed
together with active sides facing the feed spacer.
Figure 1.4.3. Schema of a spiral-wound module
Membranes are separated by the permeate spacer and glued together on 3 sides.
The fourth side is open and fixed around a perforated centre tube. The feed spacer is
placed outside the membrane and forms the feed channel. The whole assembly is roled
around the centre tube in a spiral and fitted inside the appropriate housing. Such
configuration is compact and relatively inexpensive. Spiral wound modules are used
mainly for organic extraction, with low organic concentration and lower temperatures.
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1.4 AIM OF REPORT

Pervaporation continues to evolve as a feasible separation technology for many
different applications. As a proven method of separation at low temperatures and
pressure. Pervaporation have number of application ranging from wastewater treatment to
food processing.
The objective of present work is to study the separation of binary systems which
could be difficult or uneconomical to separate by conventional methods for that a
ethanol-water systems was studied by using poly (vinyl alcohol) membrane material
and different temperature conditions. Also effect of variation of one component
concentration on a flux and selectivity of that component will be studied.
Chapter 2
LITERATURE SURVEY
2.1 SEPARATION PRINCIPALS

In separation technologies, membranes are defined as the semi-permeable inter-
phase media between two bulk phases [Paul and Yampol'skii 2000]. A membrane process
allows selective and controlled transfer of species from one bulk phase to the other. The
permeability and selectivity define the characteristics of separation membranes.
Generally speaking, components in a mixture are separated by membranes based on the
principles as follows [Huang 1990]:
1) Separation occurs because of size/steric effects that are related with
macroscopic pores in porous membranes or molecular level interspace between
macromolecules in non-porous membranes. The size difference of the two components
results in the difference in flow rates, components with large sizes diffusing with more
resistance than those with smaller steric factors. A good selectivity can be achieved for
mixtures of components with dissimilar steric factors.
2) Separation properties are related with the interactions between the membrane
materials and the components to be separated. In non-porous membranes, these factors
are often dominant in controlling the separation performances. Mass transport in a
membrane occurs when there exists a driving force or a potential difference across the
membrane [Timashev and Kemp 1991]. Table 2.1 shows the driving forces and
14
separation mechanisms for different membrane processes [Moon 2000; Matsuura 1994;
Mulder 1991]. Mass transport in non-porous membranes is complicated, but gas
separation and pervaporation share many characteristics.
2.2 PERVAPORATION THEORY

Polymer films used in PV have a nonporous selective layer, and do not function
by a molecular sieving action or convective flow. Binning et al. (1961) were the first to
use the “solution-diffusion” model to describe PV through a homogenous polymeric
membrane. Overall mass transport through the membrane can be represented by three
steps:
• Solution of liquid in the membrane surface in contact with the liquid charge
Mixture;
• Migration (diffusion) through the body of the membrane;
• Vaporization of the permeating material at the downstream interface where
permeate is immediately swept away.
Different from other membrane processes, pervaporation occurs between two different
phases in the feed and permeate sides. Some mass transport models have been developed
to describe pervaporation processes [Feng and Huang 1997; Shao 2003]. There is not a
fully accepted theory for pervaporation, but the following models give some explanation
of specific properties. Table 2.1 shows comparison of various membrane separation
processes.
Membrane processes Phases of Driving forces Separation mechanism
feed / permeate
Microfiltration Liquid / Liquid Hydrostatic pressure Sieving
Ultra filtration Hydrostatic pressure Sieving

Liquid / Liquid
Preferential sorption and
Hyper filtration Effective pressure
Liquid / Liquid capillary flow
Sieving and hindered

Dialysis Liquid / Liquid Concentration gradient
diffusion
Electrical potential
Electro dialysis Liquid / Liquid Counter-ion transport
gradient
15
Preferential sorption and

Reverse osmosis Liquid / Liquid Hydrostatic pressure
capillary flow
Pervaporation Liquid / Vapor Chemical potential

Solution
gradient
Vapor permeation Vapor / Vapor Chemical potential
Solution
gradient
Partial pressure Solution-diffusion and
Gas separation Gas / Gas
difference sieving
Table 2.1 Comparison of various membrane separation processes
2.2.1 Solution-Diffusion Model
The solution-diffusion model is a semi-empirical or phenomenological model

originally developed by Graham in 1866 to describe gas permeation through rubber septa.
This model is also used for reverse osmosis, gas separation and PV (Lipnizki et al.,
1999).
A component’s sorption rate is related to the total energy required to dissolve it in
the polymer. The component with the lowest energy requirement is preferentially sorbed
into the membrane polymer. Migration through the membrane depends on feed
components, 17 membrane polymer and process parameters. Typical chemical potential
(μ), pressure (p), and activity gradient (a) profiles through a membrane (Figure 2.1) show
that pressure change from feed to permeate has a negligible effect on mass transfer
(Lipnizki et al., 1999).
16
Figure 2:1 Schematic diagram of the solution-diffusion model (Lipnizki et al., 1999).
Transport parameters will depend on whether the retentate is liquid or gaseous. In

liquid permeation, the permeating liquid can dissolve in the polymer membrane to give a
swollen "solution" of polymer and permeating organic compounds. However, a "dry"
membrane exists in gas permeation. Permeation rate in liquid permeation is independent
of the pressure differential across the membrane because of the large concentration
gradient. However, liquid and gas permeation both follow Fick's first law of diffusion,
where the steady-state rate is inversely proportional to membrane thickness

(Binning et al., 1961).
q = D (C2 − C1)
L ------------------ (2.1)
where q is the amount of liquid permeating a unit area of membrane in unit time, L is
membrane thickness, D is diffusion coefficient and C2 – C1 is concentration differential
across the membrane.
The solution-diffusion model is the most widely accepted transport mechanism
for many membrane processes, such as reverse osmosis, gas separation and pervaporation
[Wijmans and Baker 1995; Baker 2004]. The earliest application of the solution-diffusion
model in pervaporation was proposed by Binning et al. [1961], and he suggested that the
selectivity took place in a boundary layer between the liquid zone and the gas zone in the
membrane. Later, many researchers tried to interpret pervaporation processes based on
the solution-diffusion model, and this model is now widely accepted. According to this
model, the mass transport can be divided into three steps, as shown in Figure 2.2:
1) Sorption of liquids into the membrane at the feed side,
2) Diffusion of the sorbed components through the membrane,
3) Desorption/evaporation of the sorbed components at the permeate side.
Mass transport in solution-diffusion model
17
Figure 2.2 Polymer membrane under liquid permeation conditions with a solution phase
zone and vapour phase zone (Binning et al., 1961).
Vaporization at the permeate side of the membrane is generally considered to be a

fast and nonselective step if the partial pressure is kept low, i.e. far less than the saturated
vapor pressure of the permeates [Ho and Sirkar 1992]. The selectivity and permeability of
a pervaporation membrane mainly depend on the first two steps, that is, the solubility and
diffusivity of the components in the membrane.
Binning et al. (1961) theorized that liquid moves rapidly within the solution
phase, and between the liquid feed phase and the solution phase; with most of the
selectivity occurring at the interface between the solution phase and the vapour phase.
The permeating species slowly diffuses through the vapour phase and is the rate-
controlling step in the process. Because selectivity is not a function of membrane
thickness, some researchers suggest that the unswollen fraction of the skin layer (vapour
phase) controls permselectivity (Binning et al. 1961, 1974; Néel, 1991).
2.2.1(A) Driving force
A difference in chemical potential (due to partial pressure or activity) between

feed and permeate side of the membrane is the driving force in PV (Lipnizki et al., 1999).
Feed components have different sorption and diffusion rates through the membrane,
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which govern selectivity and permeation rate (Qariouh et al., 1999; Villaluenga and
Tabe-Mohammadi, 2000).
2.2.1(B) Selectivity
Selectivity (or separation factor, α) can be used to express the separation

capability of a PV membrane for a binary mixture of components i and j (Smitha et al.,
2004). Overall selectivity is the product of sorption selectivity, αS, and diffusion
selectivity, αD (Villaluenga and Tabe-Mohammadi, 2000):
αij = xp, i / xp,j = αD* αS

xf, i / xf, j ---- (2.2)
where xp,i and xp,j are 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. Selectivity can vary from unity (no selective permeation) to infinity, and is affected
by membrane/component solubility, feed hydrodynamic conditions, permeate resistance
due to elevated partial pressures, and changes in diffusion rate due to membrane swelling
(Smitha et al., 2004). Membrane selectivity (especially in organic/organic separations
with components of comparable size) is mainly governed by αS due to the chemical
interaction between permeant molecules and the membrane. Therefore, choosing a
membrane with appropriate affinity is a crucial factor in PV (Villaluenga and Tabe-
Mohammadi, 2000).
2.2.1(C) Membrane affinity

A polymer with higher affinity for one feed component gives greater selectivity.
However, if the affinity is too high, the membrane is excessively swollen by the
component, loses its integrity and therefore its selectivity. Consequently, it is important
to suppress or control the degree of swelling by crosslinking or other methods
(Villaluenga and Tabe-Mohammadi, 2000).
2.2.1(D) Flux rate
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Component permeate fluxes are commonly obtained using the mass transfer
resistance-inseries model (Karlsson and Trägårdh, 1993a; Feng and Huang, 1997).
Overall permeate flux (Jk) for component k, where k = i or k = j for a binary feed is
defined by:
Jk = Cf, k −Hk Cp, k
Rov, k ---------------------- (2.3)
where Cf,k and Cp,k are component feed and permeate concentrations, Hk is a
dimensionless equilibrium partition coefficient (i.e. Ck liq/Ck vap) and Rov,k is the
overall component mass transfer resistance (Smitha et al., 2004)
2.2.2 Pore-Flow Model
The pore-flow model for pervaporation was first proposed by Sourirajan et al.
[Matsuura 1994], and Okada et al. [1991] used this model to interpret experimental
observations in pervaporation. In the pore-flow model, it is assumed that there are a
bundle of straight cylindrical pores of specific lengths penetrating across the active
surface layer of the membrane, and all pores are in an isothermal condition [Matsuura
1994]. The mass transport involves
1) Liquid transport from the pore inlet to the liquid-vapor phase boundary,
2) Evaporation at the phase boundary,
3) Vapor transport from the phase boundary to the pore outlet.
The main difference between the solution-diffusion model and the pore-flow
model is the phase change location in the membrane. In the pore-flow model, as shown in
Figure 2.2, the phase change occurs at a certain distance from the membrane surface
contacting with the liquid feed, and accordingly the transport mechanism changes from
liquid permeation to vapor permeation at the liquid-vapor boundary [Matsuura 1994].
Pore-flow model
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Figure 2.2 Schematic description of pore-flow model
The pore-flow model is on the basis of the presence of pores in the membranes, so
whether the pores really exist or how small the pore size is remains hard to answer.
Nonetheless, the theoretical calculations based on the pore flow model have been shown
to be able to reproduce semi-empirical features of the experimental results [Matsuura
1994].
2.2.3 Carrier Transport Mechanism
The basic idea of the carrier transport mechanism for pervaporation comes from
biological membranes consisting of polypeptides, and is based on the similarity of the
molecular interactions between the peptides and the functional groups in synthetic
polymers [Moon 2000]. Membranes with carriers are classified into two categories
[Shimidzu and Yoshikawa 1991]: Non-fixed carrier membrane (Liquid membrane) and
fixed carrier membrane. Figure 2.3 shows the mass transport in non-fixed carrier
membranes and fixed carrier membranes. The transport energy in the fixed carrier
membranes is much higher than that in the non-fixed carrier membranes, since adsorption
and desorption are repeated continuously when a permeating component forms a complex
with a carrier in the membrane. On the other hand, once a component forms a complex
with a carrier in a non-fixed carrier membrane, the other component can move only after
21
one carrier is released from the former complex formed previously, for which high
selectivity is achieved.
Non-fixed carrier membrane
Fixed carrier membrane
C: Carrier, S: Permeating component
Figure 2.3 Schematic description of mass transport by the carrier transport

mechanism
2.3 ORGANIC-ORGANIC SEPARATIONS
Organic-organic liquid separations are commonly classified by the

categories polar/non-polar, aromatic/alicyclic, aromatic/aliphatic, and isomeric
mixtures.
2.3.1 Polar/non-polar solvent mixtures

Smitha et al. (2004) summarised performance of various membranes for
separating polar/nonpolar solvents such as alcohols/alkanes and alcohol/ether
mixtures. The first demonstrations of polar/non-polar PV separations using
cellulose membranes were done in the 1950s (Heisler et al., 1956), but laboratory
scale applications for removing organics from diluted organic liquid streams were
studied in the 1960’s (Binning et al., 1961) using hydrophobic membranes made
from polyethylene (PE) and polypropylene (PP). However, these membranes had
22
low selectivities for polar/non-polar organic mixtures, primarily because they did
not have any functional groups to create differential interactions between the
components being separated (Smitha et al., 2004).
2.3.2 Aromatic/alicyclic mixtures

Potential applications of PV for separating aromatics/alicyclic separations
include removing cyclohexane from benzene/cyclohexane mixtures formed in
benzene, toluene and xylene production plants, and removing aromatics from the
feedstock of ethylene plants to enhance their production capacities (Smitha et al.,
2004). Benzene/cyclohexane (Bz/cHx), one of the most common aromatic/alicyclic
mixtures, is also the most difficult to separate. Many researchers have assessed PV
properties of membrane materials for this separation (Cabasso et al., 1974b;
Rautenbach and Albrecht, 1980; Suzuki and Onozato, 1982; Terada et al., 1982;
Sun and Ruckenstein, 1995; Inui et al., 1997b; Uragami et al., 1998). Smitha et al.
(2004) summarised some of the membranes for PV of aromatic/alicyclic mixtures.
2.3.3 Aromatic/aliphatic hydrocarbons

Separating aromatic-aliphatic hydrocarbon mixtures was first investigated in
a European project (Rautenbach & Albrecht, 1980). Little further research was
reported until the mid 1980s when Brun et al. (1985) investigated separating
benzene/n-heptane mixtures using elastomers. This research stimulated interest in
elastomeric membranes and their blends (Smitha et al., 2004).
2.3.4 Isomers
Mulder et al. (1982) used thin membranes of cellulose esters treated with an
organic solvent to separate isomeric xylenes. Relatively good fluxes but low
selectivities were achieved Since the 1980s a variety of membranes have been used
to extract isomeric components such as xylene isomers, and 1º, 2º or 3º alkanes and
alcohols (Funke et al., 1997; Gump et al., 1999; Wegner et al., 1999; Chen et al.,
23
2000; Gump et al., 2000; Nair et al., 2001; Schleiffelder and Claudia, 2001). The
use of PVA membranes for purifying mixed xylenes on an industrial scale has been
limited by the very small separation factors (Smitha et al., 2004).
2.3.5 Miscellaneous separations

Smitha et al. (2004) summarised a number of miscellaneous organic/organic
separations including organic/chlorinated hydrocarbon, alkane/alkene, and
alcohol/ketone mixtures etc. Dutta and Sikdar (1991) used a composite
PGSA/Teflon membrane to separate methanol and carbon tetrachloride with good
flux rates (60 kg.μm.m-2.h-1) and selectivity (α = 14.6).
2.3 MEMBRANE CHARACTERISTICS
2.3.1Factors affecting membrane performance
Specific characteristics of the feed components, the membrane, and process

operating parameters influence overall PV performance. These factors include
trans-membrane pressure, process temperature, feed composition and concentration,
concentration polarization, feed turbulence, membrane thickness and the materials
the membranes are made from (Binning et al., 1961; Cabasso, 1983; Néel, 1991;
Mathys et al., 1997; Miranda and Campos, 1999; Villaluenga and Tabe-
Mohammadi, 2000; Miranda and Campos, 2001a; Matsui and Paul, 2002; Yoshida
and Cohen, 2003; Smitha et al., 2004).
Factor Condition that induces:
Major Influence Minor Influence
Feed pressure - ---- • 20 atm
Permeate pressure • Pp > 0.3 Po permeant • Pp < 0.3 Po permeant

• Pp ≈ > 10 kPa • Pp ≈ < 10 kPa
Process temperature • Close to polymer melting • Close to normal working

Point temp for polymer
• Termolabile product
Feed composition and • One component very • Components less
24
concentration attracted to polymer attracted to polymer
Concentration • Presence of particulates • ‘Clean’ organic liquid

polarization or mixtures
or fouling cells
Feed turbulence ----- • Sub-turbulent flow rates
Membrane thickness • All thicknesses -----
Membrane materials • All membrane materials -----
Table 2.3.1 Factors influencing pervaporation separation

characteristics.
2.3.2 Pressure differential

Pressure differential between the feed and permeate side of the membrane is
directly related the activity of the components at the permeate side. At pressure
differentials close to the vapour pressure of the liquid, permeate pressure strongly
influences the pervaporation characteristics (Dutta and Sikdar, 1991; Smitha et al.,
2004).
Permeate and feed pressure
Increasing downstream permeate pressure decreases both selectivity and
flux of a polar/nonpolar PV separation.
2.3.3 Effect of temperature on flux
Many researchers show that increasing the temperature increases membrane
permeability and decreases selectivity (Kucharski and Stelmaszek, 1967; Cabasso
et al., 1974a; McCandless et al., 1974; Acharya et al., 1988; Inui et al., 1999;
Villaluenga and Tabe-Mohammadi, 2000). Binning et al. (1961) found that flux rate
approximately doubled with a 20ºC increase in temperature. Several researchers
showed that temperature has an Arrhenius type effect on PV membrane
permeability (Huang and Lin, 1968; Cabasso et al., 1974a; Acharya et al., 1988;
Inui et al., 1999; Villaluenga and Tabe-Mohammadi, 2000; Smitha et al., 2004):
Qi = Q0i exp {− Ep/ RT} or J = J0 exp {Ep / RT} -------------

(2.4)
25
where Qi0 is a constant, Ep is activation energy for permeation, R is the universal

gas constant, and T is absolute temperature.
Sun and Ruckenstein (1995) explained that temperature had two effects on the
membrane
(Villaluenga and Tabe-Mohammadi, 2000):
• Increasing polymer chain mobility, which facilitated diffusion of both
components.
• Weakening the interaction between the preferentially attracted molecule
and the
membrane, which lowered its sorption.
Huang and Lin (1968) also described how increasing the temperature increased
agitational energy or motion of the polymer chains. At lower temperatures,
permeation based on diffusional cross section (size) of the permeating molecules is
restricted. As agitational energy of the polymer chains increases, there are larger
gaps in the amorphous regions of the membrane, so larger molecules that had
previously been restricted can permeate. This increases flux and decreases
selectivity (Huang and Lin, 1968).
2.3.4 Feed concentration and composition

In theory, PV can be used to separate any liquid mixture in all concentration
ranges (Johnson and Thomas, 1999). However, it is primarily used for removing or
recovering the minor component in organic/organic azeotropic, close-boiling point,
or isomeric mixtures (Mulder et al., 1982; Blume et al., 1990; Böddeker et al.,
1990). Permselective properties of PV membranes are determined by sorption and
diffusivity of the permeating components in the membrane. Because both sorption
and diffusion phenomena depend on composition of the liquid mixture, membrane
permeation characteristics are usually strongly influenced by feed composition
(Johnson and Thomas, 1999).
2.3.5 Feed concentration and composition
26
In theory, PV can be used to separate any liquid mixture in all concentration

ranges (Johnson and Thomas, 1999). However, it is primarily used for removing or
recovering the minor component in organic/organic azeotropic, close-boiling point,
or isomeric mixtures (Mulder et al., 1982; Blume et al., 1990; Böddeker et al.,
1990). Permselective properties of PV membranes are determined by sorption and
diffusivity of the permeating components in the membrane. Because both sorption
and diffusion phenomena depend on composition of the liquid mixture, membrane
permeation characteristics are usually strongly influenced by feed composition
(Johnson and Thomas, 1999).
2.3.6 Membrane material

The chemical nature of the polymer used in the membrane, and the presence
of plasticizers and solvents, influences permeation rate and separation (Binning et
al., 1961). Membranes containing polar groups tend to preferentially permeate polar
feed components (and vice versa for non-polar membranes) (Sweeny and Rose,
1965; Huang and Lin, 1968). Chemical and thermal stability of the films in the
presence of the feed under operating conditions are also important characteristics.
Some thin polymer films are much more stable and selective under permeation
conditions than others, depending on their solubility in the feed components
(Binning et al., 1961).
2.3.7 Membrane thickness

Permeation rate is inversely proportional to membrane thickness but
selectivity is said to be independent of thickness in the range considered practical
for commercial use. Binning et al. (1961) established a linear inverse relationship
between flux and film thickness (0.8- 1.9 mm), yet selectivity of the n-heptane / iso-
octane mixture (50 Vol%) was essentially the same at all four membrane
thicknesses. For film thicknesses that could be produced in 1961, Binning et al.
(1961) felt that PV could still retain selectivity and rapid permeation rates even
when operating with very thin films (800 μm). Modern polymer membranes can be
27
as thin as 10-35 μm (Smitha et al., 2004), and modern literature makes little
mention of membrane thickness affecting selectivity.
2.3.8 Membrane swelling

If sorption dominates over diffusion in a PV separation, membrane swelling
can occur (Sun and Ruckenstein, 1995). Swelling will change both flux and
selectivity (Smitha et al., 2004), and the degree of membrane swelling must be
suppress or controlled (Villaluenga and Tabe40 Mohammadi, 2000), because
swelling decreases membrane performance, and causes loss of membrane integrity
(Feng and Huang, 1997).
A trade-off between sorption and swelling is needed. For preferential
permeation to occur, there must be a high degree of chemical affinity between one
component and the membrane. However, if affinity is too great, the membrane will
swell and lose integrity. Thus, a membrane suitable for an organic-organic
separation such as Bz/cHx, must possess both polar groups to facilitate benzene
sorption, and a rigid molecular structure resistant to swelling to maintain membrane
integrity (Villaluenga and Tabe-Mohammadi, 2000).
Baddour et al. (1964) found that osmotic stresses during swelling
fragmented and disoriented the crystalline structure of their PE membranes.
Crystallization and or stress relaxation caused steady-state flux to decrease after the
rearrangement of chain segments in the swollen state. Cross-linking the polymer
membrane strands is the primary method to overcome rearrangement of polymer
chain segments due to swelling (Smitha et al., 2004).
2.3.9 Membrane fouling

Deposition of impermeable substances in the feed, on the membrane surface
is called fouling. Fouling is less a problem in PV than in other membrane separation
processes like reverse osmosis, electrodialysis and nanofiltration; and as such is
usually caused by scale formation rather than clogging or blocking of pores.
Membrane fouling reduces flux and ultimately makes the membrane ineffective. It
can be minimised by using a highly turbulent flow regime, ceaning the membrane
semi-continuously, or by filtering the feed before PV (Smitha et al., 2004):
28
2.3.10 Performance Parameters of Membranes
The performance of a given membrane in pervaporation or vapor

permeation is estimated in terms of its selectivity and the permeate flux. The
assessment is based on the mass transfer of the preferentially permeating species,
regardless of whether the permeate or the retentate is the target product of the
pervaporation process [11]. The selectivity of a given membrane can be estimated
by using the following two dimensionless parameters [11]:
YA YA
α => α=
YB
=
(1 − YA)
Separation factor -------------------------------
YA XA
XB (1 − XA)
(01)
YA
Enrichment factor => β β= ---------------------------------------------------
XA
(02)
Where:
XA - weight fraction of preferentially permeating species in the feed phase,
YA - weight fraction of preferentially permeating species in the permeate phase,
with XA + XΒ = 1 and YΑ + YΒ = 1.
Figure 1.3.1 McCabe-Thiele separation diagram. Comparison of pervaporation

selectivity with distillation selectivity. System: water-ethanol. Membrane: PVA
composite hydrophilic membrane
29
Fig. 1.3.1 compares the distillation and pervaporation through hydrophilic

polyvinyl alcohol membrane of water-ethanol binary mixture. It is seen that
pervaporation with highly hydrophilic membrane favors the transport of the higher
boiling water. The high efficiency of pervaporation also occurs near the azeotropic
composition of the water-ethanol system. The diagonal line in Fig. 2 represents
azeotropic compositions, for which separation does not take place (compositions of
the product and the feed mixture are the same, i.e. a = 1).
2.4 MEMBRANES MATERIAL SELECTION AND MEMBRANE

MODULES
Selecting membrane materials for PV is often done by trial and error. This is
time consuming and the best membrane may not be found due to the limited
number of membranes tested. A more rational method would match the physico-
chemical properties of the membrane material with the components of the liquid to
be separated. This is done simplistically for common PV applications such as
organic liquid dehydration or waste-water treatment by choosing hydrophilic or
hydrophobic membranes. However, hydrophobicity is not a major distinguishing
factor for components in an organic/organic mixtures so a more comprehensive
approach is required.
2.4.1 Membrane selection procedures

`Three aspects are important when selecting polymers for a separation: the
polymer should have high chemical resistance (compatibility), sorption capacity,
and good mechanical strength in the solution. It should also interact preferentially
with one of the components being separated (Sridhar et al., 2000). Generally it is
more economical to preferentially transport the component with the smallest weight
fraction across the membrane. Koops and Smolders (1991) recommend that
potential membrane materials be identified by: (1) literature search, (2) properties
of the mixture, and (3) chemical and thermal stability of polymer.
Literature search
30
A literature search will identify prior research for PV separation of the

mixture under study. Problems occur if the exact mixture has not been previously
studied or if very few membranes have been identified. Most membranes reported
in the literature were selected by trial and error, so the number of polymers tested
may have been limited, which may have lead to the use of less than optimal
membrane materials.
Feed mixture properties
Membrane selection for aqueous/organic separations has been dominated by
choices between ‘organophilic' or ‘hydrophilic’ membranes. However, choosing
between these two membranes does not always work and very few investigations
have dealt with the criteria for an ideal membrane. Selecting membranes for PV of
compounds with widely differing polarity is relatively easy. Thus, silicone rubber
membranes are often chosen for removing non-polar organics from water; and
polyvinyl alcohol or similar hydrophilic membranes are commonly used for
dehydrating organics. Hydrophilic membranes are also effective for separating
relatively polar organics such as methanol from non-polar organics such as pentane.
Finding a suitable polymeric membrane with good selectivity and flux for
compounds of similar polarity is difficult, and the selection criteria may include
complex thermodynamic considerations (Ray et al., 1999a).
Membrane stability
Membranes need to be stable in terms of permeability and selectivity under
standard operating conditions for extended periods. Membrane stability is vital in
organic/organic separations, and is primarily affected by the chemical, mechanical,
and thermal properties of the membrane (Feng and Huang, 1997).
The composition and morphology of the membranes are a key to effective use
of membrane technology. The choice of the membrane strongly depends on the type
of application [12]. It is important which of the component should be separated
from the mixture and whether this component is water or an organic liquid.
Generally, the component with the smallest weight fraction in the mixture should
preferentially be transported across the membrane. Looking at the mixtures to be
31
separated and their compositions, the following different kinds of pervaporation and
vapor permeation processes can be distinguished [12-23]
2.4.2 Dehydration of organic liquids
For the removal of water from water/organic liquid or vapor mixtures

hydrophilic polymers have to be chosen. The hydrophilicity is caused by groups
present in the polymer chain that are able to interact with water molecules.
Examples of hydrophilic polymers are: ionic polymers, polyvinyl alcohol (PVA),
polyacrylonitryle (PAN), polyvinylpyrrolidone (PVPD).
2.4.3 Removal of organics from water or air streams
Removal of organics from water or air streams. For the removal of an

organic liquid from water/organic or organic/air mixture hydrophobic polymers are
the most suitable polymers as membrane materials. These polymers possess no
groups that show affinity for water. Examples of such polymers are:
polydimethylsiloxane (PDMS), polyethylene (PE), polypropylene (PP),
polyvinylidenefluoride (PVFD), polytetrafluoroethylene (PTFE).
2.4.4 Separation of two organic solvents.
For the mixture of two organic liquids or vapors, again three kinds of
mixtures can be distinguished: polar/apolar, polar/polar and polar/apolar mixture.
For the removal of the polar component from polar/ apolar mixture polymers with
polar groups should be chosen and for the removal of the apolar component
completely apolar polymers are favorable. The polar/polar and apolar/apolar
mixtures are very difficult to separate, especially when the two components have
similar molecular sizes. In principle all kinds of polymers can be used for these
systems, the separation has to take place on the basis of differences in molecular
size and shape, since no specific interaction of one of the two components can take
place. Recently, ceramic membranes and membranes pre pared from conducting
polymers have also been used as the selective barriers in pervaporation [24-27].
Ceramic membranes combine high thermal and chemical stability with very high
32
performance. Ceramic membranes can be used in a wide range of applications,

including separation of mixtures at acid and alkaline conditions [25].
2.4.5 Membrane materials for Pervaporation:-
Potentially plastics and rubbers, including homopolymers, copolymers and

polymer blends, can be used as membrane materials in pervaporation processes
[Huang 1990]. Besides the mechanical properties, chemical and thermal stabilities,
high permeability and high selectivity are the important factors that should be
considered when choosing polymer materials for membranes. Among these factors,
the selectivity should be emphasized over the others, because low separation factors
cannot be compensated by other properties [Huang 1990]. A high permeation flux
and a high separation factor are always desired for industrial applications.
The properties of a pervaporation membrane are determined by the chemical
structure and physical properties of the membrane, and the interactions between the
membrane material and the permeant. Several methods have been developed for the
selection of pervaporation membrane materials [Feng and Huang 1997]:
1) Solubility parameter approach [Matsuura 1994; Mulder 1991],
2) Surface thermodynamics approach [Van Oss et al. 1983; Lee et al. 1989],
3) Polarity approach [Shimidzu and Yoshikawa 1991],
4) Chromatographic approach [Matsuura 1994; Pawlish et al. 1987, 1988],
5) Contact angle approach [Lukas et al. 1997; Nabe et al. 1997].
For pervaporation dehydration of organic liquids, hydrophilic polymers are
the most suitable membrane materials. The hydrophilicity of a polymer is caused by
the functional groups that are able to interact with water molecules by H-bonding or
dipole-dipole interactions. Water normally permeates through hydrophilic
membranes preferentially. Poly (vinyl alcohol), poly (acrylic acid), poly (vinyl
pyrrolidone), chitosan and polyelectrolytes are the hydrophilic polymers commonly
used. For the removal of organics from water, rubbery polymers are favorable.
Organic components can preferentially penetrate rubbery polymers, and the
membranes show relatively high permeation flux.
33
However, for separation of organic liquids, the criteria for selecting proper
polymer materials are not very clear yet. Both rubbery polymers and glassy
polymers have been used in research.
2.4.6 Poly (vinyl alcohol) Pervaporation Membranes

Poly (vinyl alcohol) (PVA) is one of the most important water-soluble vinyl
polymers, prepared by partial or complete hydrolysis of poly (vinyl acetate)
[Chiellini 2003]. The hydroxyl groups in PVA can form strong hydrogen bonds
between intra- and intermolecular hydroxyl groups, which causes PVA to show a
high affinity to water [Finch 1973]. The solubility parameters of PVA and the
affinity to solvents are shown in Appendix A. Therefore, in pervaporation, PVA is
mainly used for dehydration of organic solvents. To be used as membranes, PVA is
usually modified before use to attain long-term stability [Finch 1973].
The first commercial composite membrane, crosslinked poly(vinyl alcohol)
on a microporous polyacrylonitrile (PAN) support, was developed by GFT in 1982
to dehydrate ethanol/water mixtures [Huang 1990; Volkov 1994]. Though
continuous efforts are made to develop new membranes and to explore new
separation applications, PVA is still attracting significant interest from researchers
because of its excellent film forming property and hydrophilicity.
Lee and Hong [1997] investigated the relationship between the degree of
hydrolysis of PVA membranes and the pervaporation performance for separation of
isopropanol/water mixtures. Upadhyay and Bhat [2005] modified PVA membranes
with lithium chloride to investigate the effect of addition of alkali salt on
dehydration of isopropanol, and it was shown that the PVA membrane became
amorphous by addition of lithium chloride, and the separation performance was also
affected.
Rhim et al. [1998] crosslinked PVA membranes with sulfosuccinic acid
(containing –SO3H), and investigated the effect of the crosslinking density on the
pervaporation properties in dehydration of water-alcohol mixtures. The
performance for water/methanol separation is not good due to the existence of
sulfonic acid groups, but the membranes containing 7 wt. % sulf-succinic acid
34
showed good selectivity for water-ethanol mixtures. Extensive research was

conducted on the pervaporation properties of the metal-ion-exchanged
PVA/sulfosuccinic acid membranes [Rhim et al. 2002]. Peters et al. [2006] dip-
coated PVA on ceramic hollow fiber supports, and crosslinked the ultra-thin layer
of PVA with maleic anhydride for dehydration of alcohols.
2.5 SUMMARY OF THE INVENTION

The primary factors influencing selectivity and flux of permeants through a
PV membrane include: feed component size, shape and chemical nature; membrane
materials, thickness, and degree of swelling; process temperature and pressure; feed
composition and concentration. Permeation through a PV membrane involves three
primary steps: solution of the liquid feed mixture in the film surface; migration of
feed components through the body of the film; and vaporization of the permeating
material at the downstream interface where permeate is immediately removed
(Binning et al., 1961). The primary influence on this process ismolecular affinity
between the polymer membrane and permeating molecules. If permeants cannot
adsorb onto the membrane surface (e.g., one repelled by the membrane), they
cannot begin to diffuse through the membrane to the permeate. The scope of PV
process variables that can be studied include the influence of feed composition and
concentration, upstream and downstream pressures, feed and permeate
temperatures, membrane thicknesses and swelling (Binning et al., 1961), feed
streams turbulence over membrane surfaces (Miranda and Campos, 1999),
membrane concentration polarization or fouling (Miranda and Campos, 2001a), and
performances of membrane materials (Cabasso, 1983; Néel, 1991; Mathys et al.,
1997; Matsui and Paul, 2002; Yoshida and Cohen, 2003).
Of the three major pervaporation separations; dehydrating organic liquids,
removing trace organics from aqueous streams, and organic-organic mixture
separations; the latter has been the least developed industrially. Despite being a
promising alternative to conventional separation techniques, which are energy
intensive and far less eco-friendly than pervaporation, this process has not become
widespread for organic-organic separations, primarily due to the lack of
35
commercially-available high-performance membranes. Literature indicates that

pervaporation is suitable for separating a wide variety of organic liquid mixtures
including polar/non-polar, aromatic/alicyclic, aromatic/aliphatic, and even isomeric
components. Solution-diffusion is believed to be the primary model for transport
through a pervaporation membrane.
In accordance with the present invention, it has been found that the
pervaporation for separation of binary mixture is good and cost effective by other
method in accordance with the present invention ethanol water mixture is selected
as binary organic mixture and polyvinyl(alcohol) material membrane for the
process.
36
Chapter 3
ETHANOL - WATER SEPARATION BY PERVAPORATION
3.1 EHANOL ASPECTS:-
Ethanol, also called ethyl alcohol, pure alcohol, grain alcohol, or drinking
alcohol, is a volatile, flammable, colorless liquid. It is a psychoactive drug, best
known as the type of alcohol found in alcoholic beverages and in modern
thermometers. Ethanol is one of the oldest recreational drugs known to man. In
common usage, it is often referred to simply as alcohol or spirits.
Ethanol is a straight-chain alcohol, and its molecular formula is C2H5OH. Its

empirical formula is C2H6O. An alternative notation is CH3-CH2-OH, which
indicates that the carbon of a methyl group (CH3-) is attached to the carbon of a
methylene group (-CH2-), which is attached to the oxygen of a hydroxyl group (-
OH). It is a constitutional isomer of dimethyl ether.
The fermentation of sugar into ethanol is one of the earliest organic

reactions employed by humanity. The intoxicating effects of ethanol consumption
have been known since ancient times. In modern times, ethanol intended for
industrial use is also produced from by-products of petroleum refining.[1]
Ethanol has widespread use as a solvent of substances intended for human

contact or consumption, including scents, flavorings, colorings, and medicines. In
chemistry, it is both an essential solvent and a feedstock for the synthesis of other
products. It has a long history as a fuel for heat and light and also as a fuel for
internal combustion engines.
Ethanol, C2H5OH, (also called Ethyl Alcohol) is the second member of the
aliphatic alcohol series. It is a clear colorless liquid with a pleasant smell. Except
for alcoholic beverages, nearly all the ethanol used industrially is a mixture of 95%
ethanol and 5% water, which is known simply as 95% alcohol. Although pure ethyl
37
alcohol (known as absolute alcohol) is available, it is much more expensive and is

used only when definitely required.
Fig 3.1 Structure of ethanol
Other names: Ethyl alcohol; grain alcohol; pure alcohol; hydroxyethane; drinking
alcohol; ethyl hydrate.
3.1.1 Physical properties of ethanol
Ethanol is a volatile, colorless liquid that has a strong characteristic odor. It

burns with a smokeless blue flame that is not always visible in normal light. It is
also used in finger nail polish remover.The physical properties of ethanol stem
primarily from the presence of its hydroxyl group and the shortness of its carbon
chain. Ethanol’s hydroxyl group is able to participate in hydrogen bonding,
rendering it more viscous and less volatile than less polar organic compounds of
similar molecular weight.
Ethanol is a versatile solvent, miscible with water and with many organic
solvents, including acetic acid, acetone, benzene, carbon tetrachloride, chloroform,
diethyl ether, ethylene glycol, glycerol, nitromethane, pyridine, and toluene.[9][10] It
is also miscible with light aliphatic hydrocarbons, such as pentane and hexane, and
with aliphatic chlorides such as trichloroethane and tetrachloroethylene.[10]
Ethanol’s miscibility with water contrasts with that of longer-chain alcohols

(five or more carbon atoms), whose water miscibility decreases sharply as the
number of carbons increases.[11] The miscisbility of ethanol with alkanes is limited
to alkanes up to undecane, mixtures with dodecane and higher alkanes show a
miscibility gap below a certain temperature (approx. 13 °C for dodecane[12]). The
38
miscibility gap tends to get wider with higher alkanes and the temperature for
complete miscibility increases.
Physical Properties of ethanol
Molecular formula C2H6O
Molar mass 46.07 g mol−1
Appearance colorless clear liquid
Density 0.789 g/cm3
Melting point −114.3 °C, 159 K, -174 °F
Boiling point 78.4 °C, 352 K, 173 °F

Solubility in water Fully miscible
Acidity (pKa) 15.9
Viscosity 1.200 m Pa·s (cP) at 20.0 °C
Dipole moment 5.64 fC·fm (1.69 D) (gas)
Specific Gravity 0.79
Flash point 286.15 K (13 °C or 55.4 °F)
Ethanol-water mixtures have less volume than the sum of their individual
components at the given fractions. Mixing equal volumes of ethanol and water
results in only 1.92 volumes of mixture.[9][13] Mixing ethanol and water is
exothermic. At 298 K up to approx. 777 J/mol[14] are set free.
Mixtures of ethanol and water form an azeotrope at approx. 89 mole-% ethanol and
11 mole-% water[15] or a mixture of about 96 volume percent ethanol and 4 % water
39
at normal pressure and T=351 K. This azeotropic composition is strongly

temperature- and pressure-dependent and vanishes at temperatures below 303 K[16].
3.1.2 Source of ethanol
Ethanol is an important industrial ingredient and has widespread use as a

base chemical for other organic compounds, manufacturing of ethanol the feedstock
used as corn, sorghum, cane sugar, cellulose.
3.2 CHEMICAL AND PHYSICAL PROPERTIES OF WATER
Water is the chemical substance with chemical formula H2O: one molecule of water
has two hydrogen atoms covalently bonded to a single oxygen atom.
• Water is a tasteless, odorless liquid at standard temperature and pressure.

The color of water and ice is, intrinsically, a very light blue hue, although
water appears colorless in small quantities. Ice also appears colorless, and
water vapor is essentially invisible as a gas.[7]
• The boiling point of water (and all other liquids) is directly related to the
barometric pressure. For example, on the top of Mt. Everest water boils at
about 68 °C (154 °F), compared to 100 °C (212 °F) at sea level. Conversely,
water deep in the ocean near geothermal vents can reach temperatures of
hundreds of degrees and remain liquid.
• Water has a high surface tension caused by the weak interactions, (Van Der
Waals Force) between water molecules because it is polar. The apparent
elasticity caused by surface tension drives the capillary waves.
• Water also has high adhesion properties because of its polar nature.
• The maximum density of water is at 3.98 °C (39.16 °F).[9] Water becomes

even less dense upon freezing, expanding 9%. This causes an unusual
phenomenon: ice floats upon water, and so water organisms can live inside a
40
partly frozen pond because the water on the bottom has a temperature of
around 4 °C (39 °F).
Physical Properties of Water
Property Value
Molar mass 18.015
Molar Volume 55.5 moles/liter
Boiling Point (BP) 100°C at 1 atm
Freezing point (FP) 0°C at 1 atm
Triple point 273.16 K at 4.6 torr
Surface Tension 73 dynes/cm at 20°C
Vapor pressure 0.0212 atm at 20°C
Heat of vaporization 40.63 kJ/mol
Heat of Fusion 6.013 kJ/mol
Heat Capacity (cp) 4.22 kJ/kg.K
Dielectric Constant 78.54 at 25°C
Viscosity 1.002 centipoise at 20°C
Density 1 g/cc
Density maxima 4°C
Specific heat 4180 J kg-1 K-1 ( T=293…373 K)
Heat conductivity 0.60 W m-1 K-1 (T=293 K)
Melting heat 3.34 x 105 J/kg
Evaporation heat 22.6 x 105 J/kg
Critical Temperature 647 K
Critical pressure 22.1 x 106 Pa
Speed of sound 1480 m/s (T=293 K)
Relative permittivity 80 (T=298 K)
• Water is miscible with many liquids, for example ethanol, in all proportions,
forming a single homogeneous liquid. On the other hand, water and most
oils are immiscible usually forming layers according to increasing density
from the top. As a gas, water vapor is completely miscible with air.
• Water forms an azeotrope with many other solvents.
41
3.3 PROCESS DESCRIPTION:-

3.3.1 System Studied
Experiments were conducted with ethanol-water system and effect of
variation of ethanol concentration on a flux and selectivity of ethanol was
investigated
3.3.2 Experimental Procedure
Pervaporation experiments were carried out in a batch-stirred cell operated
under vacuum. The downstream pressure was maintained at 10 mm Hg. The cell
had two flanged compartments. The upper one is for feed.
Ethanol- water mixture of different concentration100 ml is introduced in the
upper compartment of Pervaporation cell. The PVA (Polyvinyl alcohol) membrane
was supported on a porous stainless steel sintered disc and sealed with rubber o-
ring. Effective membrane separation area was 19.62 cm2 the temperature was
maintained at 60 0C and speed of agitation was maintained at 250 rpm and the
experiment was carried out for 1 Hr. The permeate was collected in the condenser
cooled by salt and ice mixture.
42
Chapter 4
EXPERIMENTAL SET-UP & PROCESS
4.1 PERVAPORATION SYETEM

Figure shows a typical Pervaporation system. 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.
Figure 4.1 Simplified Pervaporation Process
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.
43
4.2 Experimental Setup:
The Pervaporation experiment is carried out in a batch stirred cell operated

under vacuum. The Pervaporation cell was made of SS-304. It consisted of two
flange compartment was provided with a jacket through which hot water from a
constant temperature bath was circulated. The Pervaporation cell was provided with
two opening at the top.
A propeller type impeller was introduced through the central opening to

agitate the feed liquid whereas the other opening was used to feed and remove the
solution continuously. Feed compartment by a tube just above the impeller and the
solution continuously overflowed from an outer tube concentrating to the feed tube.
A porous stainless steel sintered disc used as support for the membranes was
fixed in a rubber o-ring. This rubber o-ring was places in the groove in the permeate
compartment. The PVA membrane is placed on porous stainless steel sintered disk
and sealed with rubber o-ring. Vacuum on the downstream face of the membrane
was generated using a vacuum pump. A condenser was used to trap ethanol and
water vapours from the permeate compartment.
Fig. Experimental Setup
44
Niacin was first described by Weidel in 1873 in his studies of nicotine. The
original preparation remains useful: the oxidation of nicotine using nitric acid.
Niacin was extracted from livers by Conrad Elvehjem who later identified the
active ingredient, then referred to as the "pellagra-preventing factor" and the "anti-
blacktongue factor." When the biological significance of nicotinic acid was
realized, it was thought appropriate to choose a name to dissociate it from nicotine,
in order to avoid the perception that vitamins or niacin-rich food contains nicotine.
The resulting name 'niacin' was derived from nicotinic acid + vitamin. Niacin is
referred to as Vitamin B3 because it was the third of the B vitamins to be
discovered. It has historically been referred to as "vitamin PP."
4.2 DIETARY NEEDS
Severe deficiency of niacin in the diet causes the disease pellagra, where as
mild deficiency slows the metabolism, causing decreased tolerance to cold. Dietary
niacin deficiency tends to occur only in areas where people eat corn (maize), the
only grain low in niacin, as a staple food, and that do not use lime during meal/flour
production. Alkali lime releases the tryptophan from the corn in a process called
nixtamalization so that it can be absorbed in the intestine, and converted to niacin.
The recommended daily allowance of niacin is 2-12 mg/day for children, 14 mg/day
for women, 16 mg/day for men and 18 mg/day for pregnant or breast-feeding
women.
4.3 PROPERTIES:
1. Anti pellagra vitamin.
2. Colorless or white crystalline powder.
3. Soluble in water and boiling alcohol.
4. Insoluble in most lipid solvent.
5. No hygroscopic and stable in air.
6. It is resistant to heat, oxidation and alkalis.
7. It is in fact, one of the most stable vitamins.
4.3 PHARMACOLOGICAL USES:-
45
Niacin, when taken in large doses, blocks the breakdown of fats in adipose
tissue, thus altering blood lipid levels. Niacin is used in the treatment of
hyperlipidemia because it reduces very-low-density lipoprotein (VLDL), a
precursor of low-density lipoprotein (LDL) or "bad" cholesterol. Because niacin
blocks breakdown of fats, it causes a decrease in free fatty acids in the blood and, as
a consequence, decreased secretion of VLDL and cholesterol by the liver. By
lowering VLDL levels, niacin also increases the level of high-density lipoprotein
(HDL) or "good" cholesterol in blood, and therefore it is sometimes prescribed for
patients with low HDL, who are also at high risk of a heart attack. Niacin is
sometimes consumed in large quantities by people who wish to fool drug screening
tests, particularly for lipid soluble drugs such as marijuana. It is believed to
"promote metabolism" of the drug and cause it to be "flushed out." Scientific
studies have shown it does not affect drug screenings, but can pose a risk of
overdose, causing arrhythmias, metabolic acidosis, hyperglycemia, and other
serious problems.
4.4 TOXICITY
People taking pharmacological doses of niacin (1.5 - 6 g per day) often
experience a syndrome of side-effects that can include one or more of the
following:
 Dermatological complaints.
 Facial flushing and itching.
 Dry skin.
 Skin rashes including acanthosis nigricans .
 Gastrointestinal complaints.
 Dyspepsia (indigestion).
 Liver toxicity.
 Fulminant hepatic failure.
 Hyperglycemia.
 Cardiac arrhythmias.
 Birth defects.
46
Facial flushing is the most commonly-reported side-effect. It lasts for about

15 to 30 minutes, and is sometimes accompanied by a prickly or itching sensation,
particularly in areas covered by clothing. This effect is mediated by prostaglandin
and can be blocked by taking 300 mg of aspirin half an hour before taking niacin, or
by taking one tablet of ibuprofen per day. Taking the niacin with meals also helps
reduce this side-effect. After 1 to 2 weeks of a stable dose, most patients no longer
flush. Slow or "sustained"-release forms of niacin have been developed to lessen
these side-effects .One study showed the incidence of flushing was significantly
lower with a sustained release formulation though doses above 2 g per day have
been associated with liver damage, particularly with slow-release formulations.
High-dose niacin may also elevate blood sugar, thereby worsening diabetes
mellitus. Hyperuricemia is another side-effect of taking high-dose niacin, and may
exacerbate gout. Niacin at doses used in lowering cholesterol has been associated
with birth defects in laboratory animals, with possible consequences for infant
development in pregnant women. Niacin at extremely high doses can have life-
threatening acute toxic reactions. Extremely high doses of niacin can also cause
niacin maculopathy, a thickening of the macula and retina which leads to blurred
vision and blindness.
4.5 BIOSYNTHESIS
Biosynthesis: Tryptophan → Kynurenine → Niacin
The liver can synthesize niacin from the essential amino acid tryptophan,
requiring 60 mg of tryptophan to make one mg of niacin. The 5-membered aromatic
heterocycle of tryptophan is cleaved and rearranged with the alpha amino group of
tryptophan into the 6-membered aromatic heterocycle of niacin.
Vitamin B3 is made up of niacin (nicotinic acid) and its amide, niacinamide,

and can be found in many foods, including yeast, meat, fish, milk, eggs, green
47
vegetables, and cereal grains. Dietary tryptophan is also converted to niacin in the
body. Vitamin B3 is often found in combination with other B vitamins including
thiamine, riboflavin, pantothenic acid, pyridoxine, cyanocobalamin, and folic acid.
4.6 PHYSICAL PROPERTIES OF NICOTINIC ACID (11)

Property Value
Molecular weight 123.11
Melting point 2360 C
Sublimation range >1500 C
Density of Crystals 1.473 gm/cm3
True dissociation constants in water at 250C
Ka 1.5X10-5
Kb 1.04X10-12
pH of saturated aqueous solution 2.7
Solubility of Niacin in Water
At 00 C 8.6 gm/lit.
At 380 C 24.7 gm/lit.
At 1000C 97.6 gm/lit.
Solubility of Niacin in Ethanol,96 %
At 00 C 5.7 gm/lit.
At 780 C 76.0 gm/lit.
Solubility of Niacin in Methanol
At 00 C 63.0 gm/lit.
At 620C 345.0 gm/lit.
Basically, the coenzymes of niacin help break down and utilize proteins,
fats, and carbohydrates. Vitamin B3 also stimulates circulation, reduces cholesterol
levels in the blood of some people, and is important to healthy activity of the
nervous system and normal brain function. Niacin supports the health of skin,
tongue, and digestive tract tissues. Also, this important vitamin is needed for the
synthesis of the sex hormones, such as estrogen, progesterone, and testosterone, as
well as other corticosteroids.
Niacin, taken orally as nicotinic acid, can produce redness, warmth, and
itching over areas of the skin; this "niacin flush" usually occurs when doses of 50
mg. or more are taken and is a result of the release of histamine by the cells, which
causes vasodilation. This reaction is harmless; it may even be helpful by enhancing
blood flow to the "Flushed" areas, and it lasts only 10-20 minutes. When these
larger doses of niacin are taken regularly, this reaction no longer occurs because
48
stores of histamine are reduced. Many people feel benefit from this "flush," but if it
is not enjoyable, supplements that contain vitamin B3 in the form of niacinamide or
nicotinamide can be used, as they will not produce this reaction. (Note: When
vitamin B3 is used to lower cholesterol levels, the nicotinic acid form must be used;
the niacinamide form does not work for this purpose.)
Niacin is used to support a variety of metabolic functions and to treat a

number of conditions. Many niacin deficiency symptoms can be treated by
adjusting the diet and by supplementing B3 tablets along with other B complex
vitamins. Many uses of niacin are based primarily on positive clinical experience
and are not as well supported by medical research, although more studies are being
done. Niacin helps increase energy through improving food utilization and has been
used beneficially for treating fatigue, irritability, and digestive disorders, such as
diarrhea, constipation, and indigestion. It may also stimulate extra hydrochloric acid
production. Niacin, mainly as nicotinic acid, helps in the regulation of blood sugar
(as part of glucose tolerance factor) in people with hypoglycemia problems and
gives all of us a greater ability to handle stress. It is helpful in treating anxiety and
possibly depression. B3 has been used for various skin reactions and acne, as well as
for problems of the teeth and gums. Niacin has many other common uses. It is
sometimes helpful in the treatment of migraine-type headaches or arthritis, probably
in both cases through stimulation of blood flow in the capillaries. This vitamin has
also been used to stimulate the sex drive and enhance sexual experience, to help
detoxify the body, and to protect it from certain toxins and pollutants. For most of
these problems and the cardiovascular-related ones mentioned below, the
preference is to take the "flushing" form of niacin, or nicotinic acid, not
niacinamide.
49
4.7 FUNCTIONS OF VITAMIN B3 NIACIN:-
Niacin is important for proper blood circulation and the healthy functioning of the
nervous system.
It maintains the normal functions of the gastro-intestinal tract and is essential for the
proper metabolism of proteins and carbohydrates.
It helps to maintain a healthy skin.
Niacin dilates the blood vessels and increases the flow of blood to the peripheral
capillary system.
This vitamin is also essential for synthesis of the sex hormones, namely, oestrogen,
progesterone, and testosterone, as well as cortisone, thyroxin, and insulin.
4.8 CHEMICAL STRUCTURE (25)
Nicotinic Acid is water soluble. This is quite important because it may be

lost when we cook our food by boiling it in water! It is also important because it
cannot be stored in the body and must therefore be present in our diet to replace that
which is lost in urine. It is more important for us to understand why a deficiency of
this chemical causes pellagra.
Nicotinamide
can be used instead
of nicotinic acid. As we can see from these two structural formulae they are almost
the same.
4.9 BIOLOGICAL SYNTHESIS
50
Humans do not have the ability to synthesise sufficient nicotinic acid, this
means that it is an essential component of a balanced diet. Some mammals are able
to synthesise this chemical so it is not an essential component of their diets. For
example, dogs can synthesise nicotinic acid from the amino-acid tryptophan. This
might be an essential amino-acid, but for dogs, nicotinic acid is definitely NOT a
vitamin. Bacteria in our large intestines, the colon, may convert tryptophan into
nicotinic acid; this means that we could survive if sufficient bacterial activity took
place. Our intestinal bacteria would require 60 mg of tryptophan to synthesise 1 mg
of nicotinic acid so don't count on them.
4.10 SOURCES
Nicotinic Acid is found in milk, yeast, eggs, etc. Here is a table of average
values for the Nicotinic Acid content of a variety of foods.
Food Content mg/100gg/10gm
Meat Extract 60.0
Marmite 58.5
Roast Beef 5.0
Sardines in Oil 5.0
Kippers 4.2
Whole meal Bread 3.5
Beer 0.7
Boiled Cabbage 0.15
Milk 0.08
Pellagra is associated with a low standard of living. It is particularly

prevalent; in areas where maize forms the staple diet. Maize has a very low content
of nicotinic acid; furthermore, the proteins in maize are deficient in tryptophan.
51
4.11 SOURCE CATEGORIES:

 Richest Sources: Yeast, Rice polishing, & Tobacco.
 Good sources: Meat, Liver & Poultry.
 Fair sources: Milk, Eggs, Tomatoes, Leafy green vegetables.
 Poor sources: Most Fruits & Vegetables.
4.12 DEFICIENCY DISEASE:
The main deficiency disease caused by lack of nicotinic acid is “pellagra”.

This disease affects epithelia & nervous system. It is accused by the accumulation
of the intermediate products of respiration; this is because nicotinic acid is required
for the synthesis of co-enzymes used by dehydrogenises. Nervousness, headaches,
fatigue, mental depression, skin, disorders, muscular weakness, & indigestion are
the symptoms of deficiency of niacin.
4.13 IDENTIFICATION TESTS FOR NIACIN (2)
1. Mix about 100 mg with 1 ml of dil NaOH solution & boil, no ammonia is
evolved (distinction from nicotinamide).
2. Mix about 100 mg with 10mg of citric acid & 3 drops of acetic anhydride
& heat on a water bath, a red – violet colour is produced.
Synonyms: - Acid Nicotinique (French), Acidum Nicotinicum, Akotin, Anti-

pellagra Vitamin, Apelagrin, Nico, etc.
4.14 PRECAUTIONS:
 The use of large doses of niacin for long periods causes release of
histamine. This in turn can cause severe flushing, severe itching of the
skin and gastro intestinal disturbances.
 If taken in does of 3gm per day, niacin has been reported to cause
elevation of uric acid in the blood and glucose.
52
4.14 NIACIN ANALOGUES:-
Tobacco products are considered to be predisposing factors in several forms

of cancer. Accordingly there are 43 carcinogenic substances in tobacco smoke, and
nicotine makes the use of tobacco products addictive. Smokeless tobacco (plug or
leaf chewable tobacco or snuff) is considered to be a predisposing factor in oral
cancers (US Surgeon General, 1986). Cadmium and nickel also have been
implicated in the carcinogenicity of tobacco products. Since removal of tar by filters
and the use of smokeless tobacco do not eliminate the risk of cancer associated with
tobacco, the question remains "What are the components of tobacco most
responsible for the increased risks of cancer?" One obvious possibility from our
perspective is nicotine, itself, for its potential to interfere with monooxygenase-
catalyzed reactions in about five ways.
1. Nicotine is a known substrate of this monooxygenase, so this non-

nutritive compound can interfere directly with oxidations of regulatory
substrates catalyzed by this enzyme.
2. Nicotine is also a close structural analogue of nicotinamide and has

the potential for depleting NADPH by competitively inhibiting the
absorption and incorporation of the vitamin.
3. Theoretically, nicotine can also interfere with the production and

redox recycling of NADPH from NADP+, NAD+, and NADH.
4. In addition to the possibility of causing metabolic losses of NADPH,

nicotine may compete directly with NADPH for the monooxygenase and
other critical regulatory enzymic activities Consistent with this inhibitory
potential is the observation that porcine liver monooxygenase catalyzes
the oxidation of nicotine at a saturated maximum rate that is only 60 to
67% of that reported for good substrates for this monooxygenase.
5. Finally, any depletion of NADPH by nicotine described, can result in

an additional irreversible inactivation of the monooxygenase by normal
53
body temperatures. The monooxygenase is highly vulnerable to thermal

inactivation under two very interesting circumstances:
1) When deprived of NADP+ and especially NADPH, or
2) When deprived of oxygen in the presence of NADPH. The latter

condition may exist in the center of rapidly growing tumors.
An interesting general feature about the regulation of biological systems is

that minor inhibition at any one step in a regulatory cascade (10% here, 10% there)
can be amplified by multiple affected sites along the entire pathway to produce
dramatic inhibition at the end point. The potential for cascade-amplified inhibition
of the monooxygenase with nicotine clearly exists. If nicotine proves to be a
predisposing factor through this proposed mechanism, nicotine patches will solve a
tobacco consumer's risk for cancer only if used to completely end the addiction.
4.15 VITAMIN B3 USES
Nicotinic acid, niacinamide, and inositol hexaniacinate (the three forms of

Vitamin B3) have all proved very successful in various clinical applications.
However, the forms of nicotinic acid and niacinamide consumed in access may
prove to be toxic.Conversely, inositol hexaniacinate has been supplemented in
excess in scientific studies and proved tolerable. Inositol hexaniacinate has been
shown to lower elevated LDL (bad cholesterol) and triglyceride (fat) levels in the
blood, while concurrently raising the HDL (good cholesterol) levels. Inositol
hexaniacinate has also been used for the prevention and treatment of peripheral
vascular disease, especially intermittent claudication (or the atherosclerosis of the
blood vessels in the legs that can cause pain with walking).Vitamin B3 may also be
helpful in preventing the development of atherosclerosis, and may aid in the
reduction of complications arising from those who suffer from specific heart
conditions. As well, vitamin B3 may prove to be as effective as prescription
medications for treatment of atherosclerosis and problems associated with the heart.
Niacin, specifically the form of niacinamide, has also been shown to provide
relief with complications resulting from diabetes. In a recent clinical study
54
consisting of 343 individuals without diabetes and 125 with the disease, roughly
3000 milligrams per day were administered. Hemoglobin A1C (a particular
measure of blood sugar over a period of time) actually decreased in the diabetic
group over a 60-week follow-up period. Further research is needed on niacinamide,
but intial studies indicate its potentiality in the treatment of arthritis. In addition,
Vitamin B3 may reduce inflammation, increase joint mobility, and may also aid in
cartilage repair.
Eye health is another area of interest regarding the dietary supplementation

of niacin. In a recent study that included participants from the U.S. and Australia,
participants whose diets were supplemented with the highest amount of protein,
Vitamin A, B1, B2, and B3 (niacin) were considerably less likely to develop
cataracts. Studies have also shown riboflavin and niacin alone, to be effective in the
prevention of cataract formation. Ongoing applications of this B-vitamin compound
include; vitamin replacement in burn victims, topical solutions for acne, and as an
anti-cancer agent.
Taking niacin with food may reduce stomach upset and the risk of stomach
ulcer. Doses are usually started low and gradually increased to minimize the
common side effect of skin flushing. Taking aspirin or non-steroidal anti-
inflammatory drugs (NSAIDs) at the same time during the first one to two weeks
may reduce this flushing. Use of an antihistamine 15 minutes prior to a niacin dose
may also be helpful. The flushing response may decrease on its own after one to
two weeks of therapy. Extended release niacin products may cause less flushing
than immediate release (crystalline) formulations, but may have a higher risk of
stomach upset or liver irritation. In general, not all niacin products are equivalent.
Patients switching from one product to another may have an increase or decrease in
side effects.
Other Members of the Vitamin B Complex
Thiamine (B1), Riboflavin (B2), Pyridoxine (B6), Pantothenic Acid, Biotin,

Cyanocobalamin (B12). (23)
55
Chapter 5
IMPORTANTS OF NIACIN
Niacin deficiency symptoms can be seen in diets with niacin intake below
7.5 mg. per day, but often this is not the only deficiency; vitamin B1, vitamin B2,
and other B vitamins, as well as protein and iron may be low. To treat pellagra and
niacin deficiency disorders, vitamin B3 supplements should be taken along with
good protein intake to obtain adequate levels of the amino acid tryptophan. As
described earlier, about 50 % of daily niacin comes from the conversion in our liver
of tryptophan to niacin with the help of pyridoxine (vitamin B6).
5.1 REQUIREMENTS:
Many food charts list only sources that actually contain niacin and do not
take into account tryptophan conversion into niacin. Approximately 60 mg. of
tryptophan can generate 1 mg. of niacin. But tryptophan is available for conversion
only when there are more than sufficient quantities in the diet to synthesize the
necessary proteins as tryptophan are used in our body with the other essential amino
acids to produce protein.
Niacin needs are based on caloric intake. We need about 6.6 mg. per
1,000 calories, and no less than 13 mg. per day. Women need at least 13 mg. and
men at least 18 mg. per day and for children ranges from 9-16 mg.
Niacin needs are increased during pregnancy, lactation, and growth

periods, as well as after physical exercise. Athletes require more B3 than less active
people. Stress, illness, and tissue injury also increase the body's need for niacin.
People who eat much sugar or refined processed foods require more niacin as well.
Realistically, 25-50 mg. per day is adequate intake of niacin if minimum

protein requirements are met. On the average, many supplements provide at least
50-100 mg. per day of niacin or niacinamide, which is a good insurance level. For
treatment of the variety of conditions described previously, higher amounts of
niacin may be needed to really be helpful, and levels up to 2-3 grams per day are
56
not uncommon as a therapeutic dose. The other B vitamins should also be supplied
so as to not create an imbalanced metabolic condition.
Excellent sources of vitamin B3 (niacin) include crimini mushrooms and

tuna. Very good sources include salmon, chicken breast, asparagus, halibut, and
venison.
Vitamin B3, also commonly called niacin, is a member of the B-complex

vitamin family whose discovery was related to work by the U.S. Public Health
Service in the early 1900's. At that time, a disease called pellagra, characterized by
cracked, scaly, discolored skin, digestive problems, and overall bodily weakness
was increasingly prevalent in the southern region of the country. The Public Health
Service established a connection between the prevalence of the disease and
cornmeal-based diets, and addition of protein to these diets was found to cure many
cases of pellagra.
Several years later, vitamin B3 was formally identified as the missing

nutrient in the cornmeal-based diets that had led to the symptoms of pellagra. We
now know that corn as a whole food contains significant amounts of vitamin B 3, but
that vitamin B3 cannot readily be absorbed from corn unless corn products (like
cornmeal) are prepared in a way that releases this vitamin for absorption.
For example, the use of lime (as in limestone, the mineral, not lime juice in
the fruit) can help release vitamin B3 from corn and make it available for
absorption. Native American food practices that involve the addition of ash from
cooking fires ("pot ash" or "potash") to corn-based recipes are one type of cooking
technique that helps make vitamin B3 available for absorption.
The term "niacin" used interchangeably with vitamin B3 is actually a non-

technical term that refers to several different chemical forms of the vitamin. These
forms include nicotinic acid and nicotinamide. (Nicotinamide is also sometimes
called niacinamide.) The names "niacin," "nicotinic acid," and "nicotinamide" are
all derived from research studies on tobacco in the early 1930's. At that time, the
first laboratory isolation of vitamin B3 occurred following work on the chemical
nicotine that had been obtained from tobacco leaves.
57
5.2 FUNCTION OF VITAMIN B3
Like its fellow B-complex vitamins, niacin is important in energy

production. Two unique forms of vitamin B3 (called nicotinamide adenine
dinucleotide, or NAD, and nicotinamide adenine dinucleotide phosphate, or NADP)
are essential for conversion of the body's proteins, fats, and carbohydrates into
usable energy. Niacin is also used to synthesize starch that can be stored in the
body's muscles and liver for eventual use as an energy source.
5.3 METABOLISM OF FATS
Vitamin B3 plays a critical role in the chemical processing of fats in the

body. The fatty acid building blocks for fat-containing structures in the body (like
cell membranes) typically require the presence of vitamin B3 for their synthesis, as
do many fat-based hormones (called steroid hormones).
Interestingly, although niacin is required for production of cholesterol by the

liver, the vitamin has repeatedly been used to successfully lower total blood
cholesterol in individuals with elevated cholesterol levels. This cholesterol-lowering
effect of vitamin B3 only occurs at high doses that must be obtained through
nutrient supplementation, and most likely involves a chemical feature of vitamin B3
that is not directly related to fat or fat processing.
5.4 SUPPORT OF GENETIC PROCESSES
Components of the primary genetic material in our cells, called deoxyribose

nucleic acid (DNA) require vitamin B3 for their production, and deficiency of
vitamin B3 (like deficiency of other B-complex vitamins) has been directly linked to
genetic (DNA) damage. The relationship between vitamin B3 and DNA damage
appears to be particularly important in relationship to cancer and its prevention.
58
5.5 DEFICIENCY SYMPTOMS
Because of its unique relationship with energy production, vitamin B3

deficiency is often associated with general weakness, muscular weakness, and lack
of appetite. Skin infections and digestive problems can also be associated with
niacin deficiency.
5.6 TOXICITY SYMPTOMS
Use of high-dose, supplemental niacin to lower serum cholesterol levels has

given nutritional researchers a unique opportunity to examine possible toxicity
symptoms associated with this vitamin. In the amounts provided by food, no
symptoms of toxicity have been reported in the scientific literature. In 1998, the
Institute of Medicine at the National Academy of Sciences set a tolerable upper
limit (UL) for niacin of 35 milligrams. This UL applies to men and women 19 years
or older, and is limited to niacin that is obtained from supplements and/or fortified
foods.
5.7 FACTORS THAT AFFECT FUNCTION
Intestinal problems, including chronic diarrhea, inflammatory bowel

disease, and irritable bowel disease can all trigger vitamin B3 deficiency. Because
part of the body's B3 supply comes from conversion of the amino acid tryptophan,
deficiency of tryptophan can also increase risk of vitamin B3 deficiency.
(Tryptophan deficiency is likely to occur in individuals with poor overall protein
intake.) Physical trauma, all types of stress, long-term fever, and excessive
consumption of alcohol have also been associated with increased risk of niacin
deficiency.
5.8 NIACIN PROTECTS AGAINST ALZHEIMER'S DISEASE AND AGE-

RELATED COGNITIVE DECLINE
Niacin (vitamin B3) is already known to lower cholesterol. Now, research

published in the August 2004 issue of the Journal of Neurology, Neurosurgery and
Psychiatry indicates regular consumption of niacin-rich foods also provides
protection against Alzheimer's disease and age-related cognitive decline.
59
Researchers from the Chicago Health and Aging Project interviewed 3,718
Chicago residents aged 65 or older about their diet, then tested their cognitive
abilities over the following six years. Those getting the most niacin from foods (22
mg per day) were 70% less likely to have developed Alzheimer's disease than those
consuming the least (about 13 mg daily), and their rate of age-related cognitive
decline was significantly less. In addition to eating the niacin-rich foods, another
way to boost our body's niacin levels is to eat more foods rich in the amino acid
tryptophan. Our body can convert tryptophan to niacin, with a little help from other
B vitamins, iron and vitamin C. Foods high in tryptophan include shrimp, crimini
mushrooms, yellow fin, tuna, halibut, chicken breast, scallops, salmon, turkey and
tofu. As we can see, several foods rich in tryptophan provide two ways to increase
niacin levels as they are also rich in the B vitamin. (August 23, 2004)
5.9 FORMS IN DIETARY SUPPLEMENTS
The term "niacin," often used interchangeably with the term "vitamin B3," is
a non-chemical term that can actually refer to several different forms of the vitamin.
Most often, "niacin" is used to refer to "nicotinic acid," the form of vitamin B 3 with
documented cholesterol-lowering potential. This form of the vitamin also carries
with it the greatest risk of side effects. Supplements focused on cholesterol
reduction and alteration of fat metabolism typically include vitamin B3 in the form
of nicotinic acid. The nicotinamide form of vitamin B3 is also widely available in
supplement form. This chemical form of vitamin B3 carries a much lower risk of
side effects and is commonly used in supplement formulas designed to support
health in conditions not involving cholesterol excess or altered fat metabolism.
Particularly in formulas for pregnancy or in children's formulas, the nicotinamide
version is often preferred. Many formulas include both forms of vitamin B3, with
small amounts of nicotinic acid and larger amounts of nicotinamide.
5.10 INTRODUCTION TO NUTRIENT RATING SYSTEM CHART
In order to better help we identify foods that feature a high concentration of

nutrients for the calories they contain, we created a Food Rating System. This
system allows us to highlight the foods that are especially rich in particular
60
nutrients. The following chart shows the World's Healthiest Foods that are either an
excellent, very good, or good source of vitamin B3 (niacin). Next to each food
name, we shall find the serving size we used to calculate the food's nutrient
composition, the calories contained in the serving, the amount of vitamin B3
(niacin) contained in one serving size of the food, the percent Daily Value (DV%)
that this amount represents, the nutrient density that we calculated for this food and
nutrient, and the rating we established in our rating system. For most of our nutrient
ratings, we adopted the government standards for food labeling that are found in the
U.S. Food and Drug Administration's "Reference Values for Nutrition Labeling."(25)
World's Healthiest Foods ranked as quality sources of:vitamin B3 (niacin)
World's
Nutrien
Serving Amount DV Healthiest
Food Cals t
Size (mg) (%) Foods
Density
Rating
Crimini mushrooms, 26.
5 oz-wt 31.2 5.39 15.6 Excellent
raw 9
Tuna, yellowfin, 157. 67.
4 oz-wt 13.54 7.7 Excellent
baked/broiled 6 7
Tamari (Soy Sauce) 1 tbs 10.8 0.72 3.6 6.0 Good
Chicken breast, 223. 72.
4 oz-wt 14.41 5.8 very good
roasted 4 0
187. 48.
Calf's liver, braised 4 oz-wt 9.61 4.6 very good
1 0
Halibut, 158. 40.
baked/broiled 8 4
Asparagus, boiled 1 cup 43.2 1.95 9.8 4.1 very good
Salmon, chinook, 261. 56.
baked/broiled 9 7
179. 38.
Venison 4 oz-wt 7.61 3.8 very good
2 0
Romaine lettuce 2 cup 15.7 0.56 2.8 3.2 Good
229. 38.
Lamb loin, roasted 4 oz-wt 7.75 3.0 Good
1 8
214. 36.
Turkey breast, roasted 4 oz-wt 7.22 3.0 Good
3 1
61
Tomato, ripe 1 cup 37.8 1.13 5.6 2.7 Good

Mustard greens,
1 cup 21.0 0.61 3.0 2.6 Good
boiled
Shrimp, 112. 14.
4 oz-wt 2.94 2.4 Good
steamed/boiled 3 7
Summer squash,
1 cup 36.0 0.92 4.6 2.3 Good
cooked, slices
134. 16.
Green peas, boiled 1 cup 3.23 2.2 Good
4 1
119. 14.
Cod, baked/broiled 4 oz-wt 2.82 2.1 Good
1 1
Collard greens, boiled 1 cup 49.4 1.09 5.5 2.0 Good
Carrots, raw 1 cup 52.5 1.13 5.6 1.9 Good
Broccoli, steamed 1 cup 43.7 0.94 4.7 1.9 Good
Eggplant, cooked,
1 cup 27.7 0.59 3.0 1.9 Good
cubes
0.25 207. 22.
Peanuts, raw 4.40 1.9 Good
cup 0 0
Spinach, boiled 1 cup 41.4 0.88 4.4 1.9 Good
Fennel, raw, sliced 1 cup 27.0 0.56 2.8 1.9 Good
Turnip greens,
1 cup 28.8 0.59 3.0 1.8 Good
cooked
144. 14.
Spelt grains, cooked 4 oz-wt 2.91 1.8 Good
0 6
Beef tenderloin, lean, 240. 22.
4 oz-wt 4.44 1.7 Good
broiled 4 2
Raspberries 1 cup 60.3 1.10 5.5 1.6 Good
Winter squash, baked,
1 cup 80.0 1.44 7.2 1.6 Good
cubes
Swiss chard, boiled 1 cup 35.0 0.63 3.1 1.6 Good
Cauliflower, boiled 1 cup 28.5 0.51 2.5 1.6 Good
Kale, boiled 1 cup 36.4 0.65 3.3 1.6 Good
Green beans, boiled 1 cup 43.8 0.77 3.9 1.6 Good
Mustard seeds 2 tsp 35.0 0.60 3.0 1.5 Good
Cantaloupe, cubes 1 cup 56.0 0.92 4.6 1.5 Good
World's Healthiest Rule
Foods Rating
excellent DV>=75% OR Density>=7.6 AND DV>=10%
very good DV>=50% OR Density>=3.4 AND DV>=5%
62
good DV>=25% OR Density>=1.5 AND DV>=2.5%
63
Chapter 6
MATERIAL BALANCE
6.1 BASIS: 1 KG OF TOBACCO PER BATCH (18)
6.1.1 Mixing tank:-
5lit of H2O Mixer Wet slurry (6 Kg.)
1 Kg of Raw tobacco
Overall material balance over mixer
Water added + Raw tobacco = Wet slurry
5 lit of water + 1Kg of tobacco = Wet slurry
∴ Wet slurry = 6 Kg
As tobacco contains 5% nicotine
Material balance of nicotine
Let “X” be the quantity of nicotine in wet slurry
Nicotine in tobacco = Nicotine in wet slurry
0.05 X 1000 = X
∴ X = 50 gm
∴ Nicotine in wet slurry = 50 gm
64
6.1.2 Filtration:-
Wet Tobacco
Wet slurry [i.e.4Kg wet tobacco]
Filtration
(6 Kg)
Filtrate
(1400 ml)
Overall material balance
Wet Slurry in = Wet Tobacco + Filtrate + Loss
6000 = 4000 + 1400 + Loss
Loss = 600 ml
The wet tobacco after filtration can be dried and send to the cigarette
manufacturing unit to get non addictive cigarette.
6.1.3 Steam Distillation:-
Nicotine Solution
1400 ml of Steam 1040 ml
Distillation
Filtrate
Waste
360 ml

Filtrate = Nicotine Solution + Waste
1400 = 1040 + Waste
Waste = 360 ml
65
6.1.4 Separation:-
Nicotine layer
Nicotine solution Separator

(1040 ml)
Other constituents
Overall material balance over separator
Nicotine solution = Nicotine layer + other constituents
After measurement we get 1007 ml of other constituents from bottom of separator
1040 = Nicotine layer + 1007
Nicotine layer = 33 ml.
6.1.5 Oxidation Reaction:-
33ml of HNO3
Reaction
33ml of Reactor Product
110-115 0 C
Nicotine 30 min Niacin,
Methylamine;
Oxalic acid &
CO2
Overall material balance:

33 ml of HNO3 + 33 ml of Nicotine = Reaction Product
∴ Reaction Product = 45 gm.
The product from oxidation reaction in the form of precipitate was kept in
the accumulator for near about half hour. In the accumulator there was formation of
two layers due to density difference, the lower layer of Oxalic acid and upper layer
of Nicotinic acid, which was send to dryer.
66
Top Nicotinic
acid
(45 gm) layer (36 gm)
Accumulator
Reaction
Product
Bottom Oxalic
acid
layer (9 gm)
Reaction product = Top Nicotinic acid layer + Bottom Oxalic acid layer
45 = Top Nicotinic acid layer + 9
∴ Top Nicotinic acid layer = 36 gm
6.1.6 Drying:-
Moisture removed
Top Niacin layer Tray Dry Product
80 % Solid Dryer 95 % Solid

20 % Moisture 5 % Moisture
Let X and Y are the gm of water removed and product Niacin obtained.
Top Nicotinic acid layer = Dried product + Moisture removed
36 = X+Y
67
Solid balance
0.8 X 36 = 0.95 Y
Y = 30 gm
Nicotinic acid = 30 gm
X = 6 gm
Moisture removed = 6 gm
(18)
6.2 ENERGY BALANCE
6.2.1 Mixing Tank:
T = 250C Wet Slurry (6 Kg.)

0
Mixer at 60 C
5 lit H2O
1Kg of (T = 580C)
Tobacco
(T = 300C)
Amount of heat required to raise the temperature of tobacco mixture in mixing tank
from room temp. (i.e. 300C) to 600C
Q = m Cp ∆ T
Q = 6 X Cp X (60-30)
Approximate Specific heat capacity (Cp) values can be calculated for solids
and liquids by using a modified form of Kopp’s law, which is given by Werner
(1941). (19)
Molecular formula of Nicotine is C1OH14 N2
Element Mol. Mass Heat capacity
C 120 120 X 7.5 = 900.0
H 14 14 X 9.6 = 134.4
68
N 28 28 X 26.0 = 728.0
162 1762.4
1762.4
∴ Specific heat = ------------ - = 10.88 J / g oc [ KJ / Kg 0C ]
Capacity 162
(Of Nicotine extract)
∴ Q = 6 X 10.88 X 30 = 1958.4 KJ
6.2.2 Steam Distillation:
Steam in
Feed Steam (110 0C)

1400 ml Product
Distillation
of filtrate
(280C)
Condensate
Amount of heat required in steam distillation section.
Q = m Cp ∆ T
= 1.4 X 10.88 X (110-28)
Q = 1249.024 KJ/hr
Amount of steam required is
Q = mCp ∆ T
1249.024 = m X 1 X (110-28)
∴ m = 15.232 kg/hr
∴ Amount of steam required was = 15.232 Kg/hr.
69
6.2.3 Oxidation Reactor:
Feed (30 0 C) Reactor 45 gm
33mlof Nicotine 1100C Product
33mlofHNO3
Amount of heat required in reactor is
Q = mCp ∆ T
Q = 0.066X10.88 X (110-30)
Q = 57.4464 KJ /hr
70
Chapter 7
REACTOR DESIGN
For 33 lit. of total reaction mixture.
V = 33 lit.
1m3 = 1000 lit.
= 33 lit.
For design purpose 10 % extra,
∴ V = 33 X 10-3 + 10 % Excess
∴ V = 36.3 X 10-3 m3
Diameter of reactor can be found out from volume of reactor; as we know.(16)
Volume = Area X Length --------------- (1)
Let, Diameter of reactor = D
Length of the reactor = L
Volume of the reactor =V
∴ Area of = π D2
Reactor 4
For plate thickness up to 50 mm (16)
L = 6
D
∴ Length of reactor = L = 6 D
Substituting area & length in equation (1)
∴ Volume = π D 2 X 6 D
4
∴ V = 1.5π D3
71
36.3X10-3 = 4.712 D 3
∴ D 3 = 7.7X 10-3
∴ D = 0.19 m
Di = 20 cm ≈ 200mm
Since L = 6
D
∴ L = 6 D = 6 X 20 = 120 cm
L = 1.2 m
P = 1atm
=101.325 X103 N/m2
Thickness is t = PD +C
D= 0.2 m
2fJ F = For Steel plate
The steel plate IS : 2041- 1962 allowable stress
3 3 = 3.5 X 106N/m2
= 101.325 X 10 X 0.2 + 1 X 10
J = 80%
2 X 3.5X106X 0.80
t = 4.62 mm ≈ 5mm
The Volume of metal used for constructing the vessel
v = t [π DL + π D 2 ]
2
-3
v = 5X 10 [0.754 +0.063]
v= 40.8 X 10-3 m3
72
Stoichiometric proportion of Nicotine & HNO3 for oxidation reaction (18)
According to the oxidation reaction
C10H14N2 + 9[O] --HNO3--- C6H5NO2 + C2H2O4.H2O + CH3NH2 + CO2
Nicotine Nascent Oxygen Nicotinic acid Oxalic Acid

Ethylamine
1 mole of Nicotine ≡ 3 mole of HNO3
1X162 kg of Nicotine ≡ 3 X 63 kg HNO3
162 kg of Nicotine ≡ 189 kg HNO3
Specific gravity of Nicotine = 1.009
1.009 = Density of Nicotine

Density of H2O
1.009 = Nicotine
1 gm/cm3
∴ Density of Nicotine = 1.009 gm/cm3 = 1009 kg/m3
But Density = M i.e V = M = 162kg = 0.1605m3
V Density 1009 kg/m3
∴ Volume of Nicotine = 0.1605 m3 = 160.5 lit.
Volume of Nicotine = 160 lit.
Again specific gravity of HNO3 = 1.502
Density of HNO3
∴ 1.502 = ------------------
Density of H2O
73
∴ Density of HNO3 = 1.502 gm/cm3 = 1502 kg / m3
m 189 Kg
Volume of HNO3 = -------- = --------- = --------- = 0.1258 m3
1502 Kg/m3
∴ Volume of HNO3 = 0.1258 m3 = 125.8 lit
Volume HNO3 = 125 lit.
So for carrying oxidation reaction, take 1.6 ml of Nicotine & 1.25 ml HNO3
to get the desired product i.e. Nicotinic acid (Niacin). (18)
74
Chapter 8
COST ESTIMATION
8.1 COST OF EQUIPMENT:-
Sr.No Item Uni Cost / Total
. t Unit Cost(Rs.)
1 Pulverizer 1 200000 200000
2 Mixing Tank 1 3200000 320000
3 Filter press 1 480000 480000
4 Storage Tank 4 4000 16000
5 Steam Distillation 1 500000 500000
Setup
6 Condensor 1 100000 100000
7 Reactor 1 25000 25000
8 Dryer 1 150000 150000
Total ( E ) 1791000
8.2 FIXED CAPITAL INVESTMENT:-
8.2.1 Direct Cost:-

Sr.No Item % Cost
. E (Rs.)
1 Purchase Equipment Cost E 1791000
2 Equipment Installation 30 537300
3 Instrumentation & Control 15 268650
4 Piping Cost 15 268650
5 Electrical Fitting Cost 5 89550
6 Building Construction & Other 40 716400
Services
7 Yard Investment 3 53730
8 Land 30 537300
Total Direct Plant Cost (D) 4262580
75
8.2.2 Indirect Cost:-

Sr.No Item % Cost
. E (Rs.)
1 Engineering & Supervision 17 304470
Cost
2 Construction Expenses 32 573120
Total Indirect Cost ( I ) 877590
Total direct & indirect cost (I + D) = Rs. 5140170
Contractor Fees 5 % (I+D) = Rs.257000
Fixed Capital Investment (FCI) = Rs.5397170
Working Capital (WC) 20 % (I+D) = Rs.1028034
Total Capital Investment = FCI + WC
= 5397170 + 1028034
= Rs. 6425204
8.3 TOTAL PRODUCTION COST:-
8.3.1 Direct Production Cost:-
1) Raw Material Cost:-

Sr.No Raw Material Quantity/Batc Cost/ Kg Cost
. h (Rs.)
1 Waste Tobacco 500 Kg. Rs. 30 / Kg 15000
2 NaoH 5 Kg. Rs.180 / Kg 900
3 50 % HNO3 16.5 lit. Rs. 225 / 3713
lit.
Raw Material 19613
Cost
For one day three batches
Therefore raw material cost per day = 19613 X 3
76
= Rs. 58839
Raw material cost per month = 58839 X 30
= Rs. 1765170
8.3.2 Utilities:-
a) Water:-
Water requirement per batch = 25000 lit.
Cost of Water = Rs. 1 / lit.
Cost of Water per batch = Rs.2500
b) Steam:-
Requirement of Steam per batch = 900 Kg.
Cost of Steam = Rs. 5.33 / Kg.
Cost of Steam per batch = Rs. 4800
Cost of steam per day = 3 X 4800 = Rs. 14400
c) Electricity:-
Requirement of Electricity per batch = 800 Kwh
Cost of Electricity = Rs. 6 /Kwh
Cost of Electricity per batch = 800 X 6 = Rs. 4800
Cost of Electricity per Day = 3 X 4800 = Rs. 14400
B) Total cost of Utilities = 7500 + 14400 + 14400
= Rs. 36300 /day
Total cost of Utilities per month = 30 X 36300
= Rs. 1089000
77
8.4 OPERATING LABOUR COST:-

Post Number Salary / Total
month salary
General Manager 1 Rs. 15000 Rs. 15000
Engineer 2 Rs. 10000 Rs.20000
Skilled Worker 4 Rs. 5000 Rs.20000
Unskilled Worker 4 Rs. 3000 Rs.12000
Clerk 1 Rs. 3000 Rs.3000
Administrative 2 Rs.3500 Rs.7000
staff
Total Labour Rs.77000
Cost
Bonus = 0.3 X Total labour cost
= 0.3 X 77000
= Rs.23100
Operating labour cost per month = 77000 + 1925
O.L.C. = Rs. 78925 /month
Lab Charges = 10 % OLC
= 0.1 X78925
= Rs.7893 /month
Maintenance & repair = 0.5 % FCI
= 0.005 X 5397170
= Rs. 26986 / month
A) Direct production cost = Raw material cost + Cost of Utilities + Operating Cost
+ Lab
Charges + Main. &

repair.
D.P.C. = 1765170 + 1089000 + 78925 + 78925 + 26986
78
= Rs. 2967974 / month
B) Depreciation & Taxes = 2 % FCI
= 0.02 X 5397170
= Rs. 107943
C) Insurance = 1 % FCI
= 0.01 X 5397170
= Rs. 53972
D) Distribution & Marketing = 20 % OLC
= 0.2 X 78925
= Rs.15785
E) Other Cost (R & D ) = 1 % FCI
= 0.01 X 5397170
= Rs. 53972
Total production cost per month = A + B + C + D + E
= 2967974 +107943 + 53972 + 15785 + 53972
= Rs.3199646
Now, 15 Kg Niacin, 15 Kg of Oxalic acid and 450 Kg of nonaddictive tobacco were

obtained from one batch process. Therefore for one month,
Niacin produced = 15 X 3 = 45 Kg / day
= 45 X 30 = 1350 Kg / month
Similarly Oxalic acid = 1350 Kg / month
And Nonaddictive tobacco = 450 X 3 X 30
= 40500 Kg / month
79
Sale:- (14)
Selling price of Niacin = Rs. 2100 / Kg
Selling price of Oxalic acid = Rs. 280 /Kg
Selling price of Tobacco = Rs. 15 / Kg
Monthly Sale:-
Niacin = 1350 X 2100 = Rs. 2835000
Oxalic acid = 1350 X 280 = Rs. 378000
Tobacco = 40500 X 15 = Rs. 607500
Total monthly sale = 2835000 + 378000 +607500
= Rs. 3820500
Gross profit = Total monthly sale - Total monthly production cost
= 3820500 – 3199646
= Rs. 620854
Income tax = 40 % Gross profit
= 0.4 X 620854
= Rs. 248342
Net profit = Gross profit – Income tax
= 620854 – 248342
= Rs. 372512 /month = 372512 X 12 = Rs. 4470144 /year
Rate of return on investment = Net profit per year
Fixed Capital Investment
= 4470144
5397170
= 0.83
Rate of return = 0.83
This evaluation is based on laboratory readings & previous literature on Niacin, so
before going for large scale production a test on pilot plant is necessary. (14)
80
Chapter 9
PLANT LAYOUT
After the process flow diagram was completed and before detailed piping
design and layout can begin, the layout of process unit must be planned and
equipment within these process unit must be planned. This layout can play an
important role in determining constructing and manufacturing cost; and thus must
be planned carefully. Good plant layout keeps safety, appearance, convenience,
overall cost, erecting cost, operating and maintenance cost to the minimum. Safety
and optimum utilization of available area should be given prime importance in plant
layout. The key to economical construction and efficient operation is a carefully
planned functional agreement of equipment, piping and building. An accessible and
aesthetically pleasing plot plan can make major contribution to safety, employee
satisfaction and sound community relation.
The handling of the material is kept to minimum by provision of gravity

transportation wherever possible. Provision should be also made for necessary
service area; the administration or office building, canteen, workshops, laboratories,
etc. The main process plant should be isolated from administration building,
canteen, workshops, laboratories, etc, the storage tanks area, security room should
be also isolated from main plant. The canteen should also be neat to office building,
laboratories; workshops etc. process plant should be located on one side of a tank
farm while shipping, transport, and loading/unloading facilities on another side.
Intermediate tanks should be located close to the process unit. Administration and
service facilities should be located near the process plant entrance. Warehouses,
salvage yard should be close together. Cooling towers should be located where
water drift from the tower will not cause excessive corrosion of process equipment.
They should be oriented cross way to the wind direction in order to minimize
recycling of air from the discharge of one tower to an adjacent tower. All hazardous
tank of larger size should be located at least 65m away from the building, process
plant, fired heaters. Pumping arrangement of liquid from the tank should be
decentralized. In process plant there should be sufficient space between the process
81
equipment. It avoids congestion after piping, valves, instrumentation is done on

equipment.
Storage Layout:-
Raw material storage tank should be located such that the transportation to
the process area is done easily loaded and unloaded.
Equipment Layout:-
Equipment should be installed in the process direction, maintaining

reasonable space between them. To consume space economically they should be
arranged so that the final product and initial reactants are near to storage tanks. The
equipment should be installed in the process direction in such a manner that
handling of the material is kept to minimum by provision of gravity transportation
wherever it is possible; without disturbing the main process.
Safety: -
Fire station should be located nearer to process area. In every unit hose
pipes, fire extinguisher should be placed.
Plant Expansion: -
Some space should be allocated for future expansion of the plant.
Utilities: -
Placing them nearer to the process area should effectively do distribution of

steam, power, water etc.
Administrative building: -
This should be located at the entrance of the main gate of the factory and
there must be provision made for communicating with every plant.
Laboratory and Quality Control: -
These should be located near the process plant. Due to which the evaluation
results and hence correction can be easily done within no time.
Commodities: -
82
Parking and canteen should be located near to the unit but not too close to
the unit. They should be separated from actual plant by the road.
Security Office: -
The security office and time office (checkers gate) should be located near to
the entrance of the factory.
In short the plant should fill the following points:
 More efficient use of land space.
 Lower cost of construction per square feet floor space.
 The upper stores building (e.g. administrative building etc) should be

free from street noise, dust, odor, etc).
 Use of gravity flow of materials, which is cheaper method of

transportation.
 More compact layout because of vertical arrangement of production

area.
Market Area: -
Nicotinic acid is used by wider range of pharmaceutical industries. Major

part of nicotinic acid is exported and there were large transportation facilities in
Ankalashawar . Previously Amsal Chemical and their group is the only major
manufacturer of nicotinic acid. This provides opportunity to capture nearby market
easily.
Raw Material Supply: -
Raw material required for production of Nicotinic Acid i.e. Waste Tobacco
was collected from tobacco farming nearby area and also from tobacco processing
industries.(13)
83
Chapter 10
CONCLUSION
Nicotinic acid is an antipellagra factor is a group of vitamin B3 . Majority
sources of it are Yeast, Rice polishing, Meatextract & Tobacco. By oxidation of
tobacco with the help of HNO3, nicotine is converted to nicotinic acid (Niacin).
With this treatment to tobacco the addictive nature of man towards tobacco
becomes non-addictive & also provide an improved tobacco product, so that blood
plasma nicotine level resulting about 0 to 5 nanograms /ml. The main aim is to go
for experimental work in lab-scale for conversion of Nicotine to Nicotinic acid from
Tobacco.It is a two step process,firstly Extraction of nicotine from tobacco and
secondly conversion of nicotine to nicotinic acid. The reactor was to be designed
for this oxidation process and the analysis of product & by- products was to be
carried out.
The objective of the process is to get non addictive tobacco product, the
poisonous Nicotine is converted to Vitamin B3, and to reduce the Carcinogenic
effect of tobacco on human health i.e. to get alternate use of tobacco for Nicotine
Sulphate (as pesticide), Niacin (Vitamin B3) pharmaceutical product, etc.
This invention relates in general to certain new and useful improvement in

processing of tobacco to eliminate or convert nicotine in the tobacco in to nicotinic
acid as a harmless or beneficial product such that the nicotine level which can be
achieved by use of the tobacco product result in a blood plasma level consonant
with non-addiction. The primary objects of the present invention is to provide a
tobacco product adapted for human use and which eliminates an addictive response
to the user there of the another object of the present invention to provide an
improved tobacco product of the type which utilized an oxidized tobacco in which
nicotine has been converted to nicotinic acid or extraction to a level resulting in the
user is about 0 to about 5 nanograms per milliliter.
The another object of the present invention to provide an improved tobacco

product of the type stated in which a tobacco product is converted chemically or by
84
physical means to obviate any effects on the acetykholine brain receptors in an

individual smoking or otherwise ingesting such tobacco product.
In accordance with the present invention it has been found that by

converting the nicotine of a tobacco product in to a harmless and actually beneficial
substance, such as nicotinic acid, addiction to the tobacco product can be avoided.
Thus the conversion of the nicotine in accordance with the present invention not
only elements the addiction but also reduces some of the harmful effects of the
identified as being generally recognized as safe or approved. Nicotinic acid is also
known as Niacin, Nicotineamide and anti pellagra factor is a group of vitamin B3.
Its compound was known before its vitamin activity observed. It is widely used in
the food, pharmaceutical & biochemical industries. An odorless, white, crystalline
substance, readily soluble in water. It is resistant to heat, oxidation, and alkalis. It is,
in fact, one of the most stable vitamins. Cooking causes little actual destruction of
niacin, but a considerable amount may be lost in the cooking water and drippings
from cooked meat if these are discarded. In a mixed diet, 15 to 25 percent of niacin
of the cooked food stuff may be lost in this way. It is excreted in the urine, mostly
as its salts, and to a smaller extent, as free niacin. The main deficiency disease
caused by lack of nicotinic acid is “pellagra”. This disease affects epithelia &
nervous system. It is accused by the accumulation of the intermediate products of
respiration, this is because nicotinic acid is required for the synthesis of co-enzymes
used by dehydrogenises. Nervousness, headaches, fatigue, mental depression, skin,
disorders, muscular weakness, & indigestion are the symptoms of deficiency of
niacin.
Exposure to nicotine and combustible products from cigarette smoking is

toxic to renal function. In particular, nicotine has an adverse effect on behavior as it
results in people becoming addicted. Patients are predisposed to urinary tract
cancers. Further kidney damage can result from accumulation of heavy metals from
tobacco. Associated with altered renal function is a direct effect on nervous
innervations, blood pressure and blood vessels. Antismoking campaigns should be
focused on achieving more success. For instance, banning smoking in public venues
and at workplaces will decrease the deleterious effects of long-term exposure to
85
nicotine. From 2nd Oct. 2008 it was banned to smoke at public places and also at
work places by the Government. Nicotine could also be removed from combustion
tobacco products. Alternatively nicotine-replacement therapies may be used. One
should avoid smoking by inhalation either actively or passively
FUTURE PROSPECTS
1. With the help of this treatment to the tobacco the addictive nature of tobacco
due to Nicotine becomes non-addictive.
2. The harmful nicotine can be converted to Niacin.
3. The carcinogenic effect of tobacco due to nicotine can be reduced.
4. We can convert the harmful nicotine to the niacin which was pharmaceutical
product.
5. For the waste coming from the tobacco industries & also from tobacco farming,
this was the important technique to get the valuable product.
6. The treated tobacco can also be used as a fertilizer for the farming purpose.
7. The main aim is to get alternative use of tobacco for Farmers due to the ban of
tobacco for beedi, hooka, chewing etc. by the Government.
8. To treat one cancer patient approximately Rs. 3.5 lacks required and near about
7.5 lacks people die due to cancer from tobacco, this can be avoided.
9. Due to commercialization of this process, the addictive tobacco becomes

nonaddictive and the pharmaceutical product Niacin can be produced.
10. By this method we can convert waste tobacco to the valuable pharmaceutical
product
11. By optimizing the process the yield of Niacin from tobacco can be increased.
86
REFERENCES
1. Agarwal O.P. “Chemistry of Organic Natural Product”(2004) Volume I,
Himalaya Publishing House, (p.280,281).
2. Dr.Deb A. C. “Fundamentals of Biochemistry”(1990) A.Sen New

Central Book Agency, Calcutta,(p.191,192).
3. Kirk- Othmer “Encyclopedia of Chemical Technology”III rd ed.(1984)

Volume 24 A Wiley- Interscience Publication John Wiley & Sons (p.80-
87).
4. Gurdeep Chatural “Organic Chemistry of Natural Products”(2004)

Volume I Himalaya Publishing House(p.571,573).
th
5. “The Pharmaceutical Codex” XI ed.(1979) The Pharmaceutical Press
London (p.593,594).
6. Harold Varley “Practical Clinical Biochemistry” IVth ed.(1969), CBS

Publisher & Distributors, Daryaganj New Delhi (p.622).
7. Richard J.Lewis Sr, Van Nostraud Reinhold “Hazardous Chemicals

Desk Reference” IInd ed. (2002),McGraw Hill Publication New York
(p.844).
8. David L. Nelson & Michael M. Cox “Lehningers Principles of

Biochemistry” IVth ed (2005) W.H. Freeman & company New York
(p.514, 515).
9. Finar I .L. “Organic Chemistry”(1994) Vth ed. Longman Singapore

Publishers Ltd. Singapore (p.717)
10. Douglas M. Considine “Chemical and Process Technology

Encyclopedia” (2004) Mc Graw Hill Book Company (page 71, 946).
87
11. Robert H. Perry, Don W. Green, “Perry,s Chemical Engineering Hand

Book” VIIth ed.(1997) Mc Graw Hill Publications,New York (p 2-
41,42,43).
12. Larry Ricci & The Staff of Chemical Engineering “Seperation

Techniques in Liquid-Liquid System”.(2001) McGraw Hill Publications
Co, New York (p.552)
13. Khana O.P. “Industrial Engineering & Management” (1999), Dhanpat
Rai Publications (P.) Ltd.(p.4.1-4.35).
14. Peter Timmerhaus, West “Plant Design & Economics for Chemical
Engineers” Vth ed. (2004) Mc Graw Hill Publication, New York (p.323)
15. Warren L. McCabe, J.C. Smith, Peter Harriott, “Unit Operations of Chemical
Engineering V th ed. (1993) McGraw Hill Book Co. Singapore (p.614, 615).
st
16. Dr. S.D. Dawande “ Process Design of Equipments” I ed. (1999),
Central Techno Publications,Nagpur-12 (p.19,20).
rd
17. Robert E. Treybal “Mass– Transfer Operations”III ed. (1981)
McGraw-Hill Book Co. Singapore (p.717, 718,719).
18. Bhatt B.I. & Vora S.M. “Stoichiometry” III rd ed. (1998) Tata Mc Graw
Hill Publishing Company Ltd. (p.66, 67,187).
19. Richardson and Colusion. “Chemical Engineering Volume IV th ed.

“Chemical Engineering Design” (2008), Elsevier India Private Ltd.
(p.322,323).
20. http://icmr.nic.in/ijmr/2006/september/0905.pdf cited on 1/11/2006.
21. http://www.Properties of Tobacco.htm cited on 30/5/2008.
22. http://en.wikipedia.org/wiki/Nicotinicacid, cited on 25/10/2008.
23. http://www.Vitamin B3 Niacin Healthy Body,Healthy Mind, Holistic

Healing,Home Remedi, cited on 18/4/2008
88
24. http://Non-addictive tobacco products – Patents 5713376.htm cited on

22/9/2007.
25. http://www.purchon.com/biology/nicotinic acid cited on 3/3/2007.
26. http://www.Nicotine & its Derivatives from Tobacco Waste.htm, cited

on 30/5/2008.
89
INDEX
Introduction to pervaporation 1
1.2MEMBRANE BASED PERVAPORATION SEPARATION:.........................3
.................................................................................................................................6
Literature survey 14
2.1 SEPARATION PRINCIPALS........................................................................14
2.2 PERVAPORATION THEORY..................................................................15
...........................................................................................................................21
...........................................................................................................................22
2.5 SUMMARY OF THE INVENTION .............................................................35
ETHANOl - WATER SEPARATION BY PERVAPORATION 37
3.1 EHANOL ASPECTS:-...................................................................................37
3.3 Process Description:- .....................................................................................42
experimental set-up & process 43
4.1 PERVAPORATION SYETEM......................................................................43
...............................................................................................................................43
4.2 Dietary needs..................................................................................................45
4.3 Properties: .....................................................................................................45
4.3 Pharmacological uses:-...................................................................................45
4.4 Toxicity...........................................................................................................46
4.5 Biosynthesis....................................................................................................47
4.6 Physical Properties of Nicotinic Acid (11).....................................................48
4.7 Functions of Vitamin B3 Niacin:-...................................................................50
4.8 Chemical Structure (25)..................................................................................50
4.9 Biological Synthesis .......................................................................................50
4.10 Sources..........................................................................................................51
4.11 Source Categories:........................................................................................52
4.12 Deficiency Disease:......................................................................................52
4.13 Identification Tests for NIACIN (2).............................................................52
4.14 Precautions:...................................................................................................52
4.14 Niacin Analogues:-.......................................................................................53
4.15 Vitamin B3 Uses...........................................................................................54
IMPORTANTS OF NIACIN 56
5.1 Requirements: ...............................................................................................56
5.2 Function of vitamin B3...................................................................................58
5.3 Metabolism of Fats .......................................................................................58
5.4 Support of genetic processes...........................................................................58
5.5 Deficiency Symptoms.....................................................................................59
5.6 Toxicity Symptoms.........................................................................................59
5.7 Factors that Affect Function...........................................................................59
5.8 Niacin Protects against Alzheimer's disease and Age-related Cognitive
Decline..................................................................................................................59
5.9 FORMS in Dietary Supplements....................................................................60
90
5.10 Introduction to Nutrient Rating System Chart..............................................60

MATERIAL BALANCE 64
6.1 Basis: 1 Kg of tobacco per BATCH (18)........................................................64
6.1.1 Mixing tank:-...........................................................................................64
6.1.2 Filtration:-................................................................................................65
6.1.3 Steam Distillation:-..................................................................................65
..........................................................................................................................65
6.1.4 Separation:-..............................................................................................66
6.1.5 Oxidation Reaction:-..............................................................................66
6.1.6Drying:- ....................................................................................................67
6.2 Energy Balance (18) ...............................................68
6.2.1 Mixing Tank: ..........................................................................................68
6.2.2 Steam Distillation:...................................................................................69
6.2.3 Oxidation Reactor:...................................................................................70
Reactor Design 71
Cost Estimation 75
8.1 Cost of Equipment:-........................................................................................75
8.2 Fixed Capital Investment:-..............................................................................75
8.2.1 Direct Cost:-.............................................................................................75
8.2.2 Indirect Cost:-..........................................................................................76
8.3 Total Production Cost:-...................................................................................76
8.3.1 Direct Production Cost:-..........................................................................76
8.3.2 Utilities:-..................................................................................................77
8.4 Operating Labour Cost:-.................................................................................78
PLANT LAYOUT 81
CONCLUSION 84
Future Prospects....................................................................................................86
REFERENCES 87
Index 90
91
LIST OF TABLE
SR. DESCRIPTION PAGE

NO. NO.
1 Liquid phase o`xidation reaction yields 10
2 Sources 22
3 Physical properties 24
4 Physical properties of Niacin 30
5 Food Sources 33
6 Worlds healthiest foods ranked as quality sources 43, 44
of Niacin
92

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Separation of Binary Mixture By Using Pervaporation

displaced some conventional processes, and membrane technology

Figure 1.1 Schematic membrane separation processes

Figure 1.1 shows a schematic membrane process [Mulder 1991;

Non-porous dense membranes can also be applied in other separation

Membrane Feed phase / Driving Force Membrane Main application

Table 1.1.Overview of chosen membrane separation processes

1.2 MEMBRANE BASED PERVAPORATION SEPARATION:

Pervaporation is recognized as a separation process in which a binary or

Figure 1.2.1 The pervaporation process (Schleiffelder and

It's considered an attractive alternative to other separation methods for a variety of

Figure 1.2.2: Membrane-based pervaporation separation processes Vacuum

Fig.1.2.3 (A) Continuous Pervaporation

Fig.1.2.3 (B) Batch Pervaporation

1.2.3 Pervaporation for Separation

Liquid transport in pervaporation is described by various solution-diffusion

1.2.4 Pervaporation applications

Process Requirements for basic or economical operation

Azeotropic distillation Requires high aromatic content (>90%)

Extractive distillation Requires medium aromatic content (65–90%)

Liquid-liquid extraction Requires low aromatic content (20–65%)

Crystallization Distillative pre-separation (e.g., o-xylene and ethylbenzene

Adsorption on solids Continuous, reversible and selective adsorption

Table 1.2.5 Processes for aromatic recovery (Villaluenga and Tabe-Mohammadi,

Because PV is based on sorption and diffusion properties of the feed components

1.3 MEMBRANE STRUCTURE

The membranes used in pervaporation processes are classified according to the

pervaporation. Silicone rubber pervaporation modules are remarkably effective at

1.3.2 Membrane morphology

Figure 1.4.1. Morphology of the pervaporation composite membrane

Figure 1.4.2. Schema of a plate-and-frame module

Figure 1.4.3. Schema of a spiral-wound module

1.4 AIM OF REPORT

2.1 SEPARATION PRINCIPALS

2.2 PERVAPORATION THEORY

Ultra filtration Hydrostatic pressure Sieving

Sieving and hindered

Preferential sorption and

Pervaporation Liquid / Vapor Chemical potential

Table 2.1 Comparison of various membrane separation processes

2.2.1 Solution-Diffusion Model

The solution-diffusion model is a semi-empirical or phenomenological model

Transport parameters will depend on whether the retentate is liquid or gaseous. In

where the steady-state rate is inversely proportional to membrane thickness

Vaporization at the permeate side of the membrane is generally considered to be a

2.2.1(A) Driving force

A difference in chemical potential (due to partial pressure or activity) between

Selectivity (or separation factor, α) can be used to express the separation

αij = xp, i / xp,j = αD* αS

2.2.1(C) Membrane affinity

2.2.1(D) Flux rate

2.2.2 Pore-Flow Model

Figure 2.2 Schematic description of pore-flow model

2.2.3 Carrier Transport Mechanism

Non-fixed carrier membrane

Fixed carrier membrane

C: Carrier, S: Permeating component

Figure 2.3 Schematic description of mass transport by the carrier transport

2.3 ORGANIC-ORGANIC SEPARATIONS

Organic-organic liquid separations are commonly classified by the

2.3.1 Polar/non-polar solvent mixtures

2.3.2 Aromatic/alicyclic mixtures

2.3.3 Aromatic/aliphatic hydrocarbons