LABORATORY MANUAL

SUBJECT: ADVANCE SEPARATION PROCESS

(3160507)

Prepared By:

Prof. Hitesh R. Ramchandani

Approved By:

Prof. Pushpajitsinh K. Barad

CHEMICAL ENGINEERING DEPARTMENT

PACIFIC SCHOOL OF ENGINEERING

Kadodara, Surat
 PRACTICAL / TUTORIAL Date: 25/01/2024

Department: Chemical Engineering Page : 01 of 01

PSE, Surat
Term: Summer - 2024 Class &Semester: Ch-21 / 6th
Subject: ASP (3160507) Faculty Department: Chemical Engg.
Name of Faculty: Mr. Hitesh R. Ramchandani

SR.
TITLE OF PRACTICAL / TUTORIAL
NO.
1. Practical 1: To study different types of membrane materials used in membrane processes.
2. Practical 2: To study different types of membrane modules used in membrane processes.
Practical 3: To prepare an acetate membrane using solution casting method and evaluate its
3.
thickness.
4. Practical 4: To study the principle and working of short path distillation unit.
5. Practical 5: To study principle and working of Supercritical Fluid Extraction
6. Practical 6: To study reactive and catalytic distillation process.
7. Practical 7: To study pervaporation method.
8. Practical 8: To study reverse osmosis for treatment of brackish water.

9. Practical 9: To study column chromatography and Ion exchange chromatography

Notes:

Prepared By: Approved By:

Mr. Hitesh R. Ramchandani Mr. Pushpajitsinh K. Barad

Assistant Professor Head,
Dept. of Chemical Engineering Dept. of Chemical Engineering
 EXPERIMENT NO: Date:
AIM:
To study different types of membrane materials used in membrane processes.
THEORY:
Membrane separation:

Membrane separations represent a new type of unit operation. The membrane acts as a semi
permeable barrier and separation occurs by the membrane controlling the rate of movement
of various molecules between two liquid phases, two gas phases, or a liquid and a gas phase.
The two fluid phases are usually miscible and the membrane barrier prevents actual, ordinary
hydrodynamic flow.

Classification of membrane processes

1. Gas diffusion: The rates of gas diffusion depend on the pore sizes and the molecular
weights. We may have molecular, transition, and Knudsen diffusion regions
depending on the relative sizes of pore and gas molecule.
2. Microfiltration (MF): This refers to membranes that have pore m. It is diameters
from 0.1 to 10 filter suspended particulates, bacteria orused to large colloids from
solution.
3. Ultra filtration (UF): This refers to membranes having pore diameters in the range 2-
100 nm . It can be used to filter dissolved macromolecules, such as proteins and
polymers, from solution. Reverse osmosis (RO): The membrane pores are in the range
of 0.5-2 nm in diameter, which are within the range of the thermal motion of the
polymer chains.

Membrane Materials:

1. Mircoporous membranes: A microporous membrane is very similar in structure and

function to a conventional filter. It has a rigid, highly voided structure with randomly
distributed, interconnected pores. However, these pores differ from those in a
conventional filter by being extremely small, on the order of 0.01–10 μm in diameter.
Thus, separation of solutes by microporous membranes is mainly a function of
molecular size and pore size distribution. In general, only molecules that differ
considerably in size can be separated effectively by microporous membranes, for
example, in ultrafiltration and microfiltration.
2. Nonporous dense membranes: Nonporous, dense membranes consist of a dense film
through which permeants are transported by diffusion under the driving force of a

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 pressure, concentration, or electrical potential gradient. The separation of various
components of a mixture is related directly to their relative transport rate within the
membrane, which is determined by their diffusivity and solubility in the membrane
material. Thus, nonporous, dense membranes can separate permeants of similar size if
the permeant concentrations in the membrane material (that is, their solubilities) differ
significantly. Most gas separation, pervaporation, and reverse osmosis membranes use
dense membranes to perform the separation. Usually these membranes have an
anisotropic structure to improve the flux.
3. Electrically charged membrane: Electrically charged membranes can be dense or
microporous, but are most commonly very finely microporous, with the pore walls
carrying fixed positively or negatively charged ions. A membrane with fixed
positively charged ions is referred to as an anion exchange membrane because it binds
anions in the surrounding fluid. Similarly, a membrane containing fixed negatively
charged ions is called a cation exchange membrane. Separation with charged
membranes is achieved mainly by exclusion of ions of the same charge as the fixed
ions of the membrane structure, and to a much lesser extent by the pore size. The
separation is affected by the charge and concentration of the ions in solution
4. Ceramic, Metals and Liquid membranes: The discussion so far implies that
membrane materials are organic polymers and, in fact, the vast majority of
membranes used commercially are polymer based. However, in recent years, interest
in membranes formed from less conventional materials has increased. Ceramic
membranes, a special class of microporous membranes, are being used in
ultrafiltration and microfiltration applications for which solvent resistance and
thermal stability are required. Dense metal membranes, particularly palladium
membranes, are being considered for the separation of hydrogen from gas mixtures,
and supported liquid films are being developed for carrier facilitated transport
processes.
5. Zeolite membranes: Zeolites are silicalite or aluminosilicate materials formed from a
three-dimensional network of SiO4 and AlO4 tetrahedra. The tetrahedra are linked by
shared oxygen atoms to form cages. In a zeolite structure, these individual cages are
linked together in various geometric forms that create pore openings with defined
regular shapes and sizes. Figure 1 shows how one type of building block, the sodalite
β-cage, can form several structures with pores ranging from 3 to 8 A˚ . There are
ove140 known zeolites structure. Aluminosilicate structures carry a negative charge
which is usually balanced by Na+, K+, or Ca2+ counter ions. Fine tuning of the pore
openings of the zeolite structure is possible by exchanging K+ and Ca2+ for Na+
counter ions.

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 Fig 1: Zeolite structure

6. Mixed – Matrix membrane: The ceramic and zeolite membranes described above
have been shown to have exceptional selectivities for a number of important
separations. However, the membranes are difficult to make, and are usually more than
10 μm thick so permeances are low. As a consequence, the membranes are
prohibitively expensive for most separations. One solution that has been suggested is
to prepare membranes consisting of zeolite particles dispersed in a polymer matrix.
Makers of these membranes hope to combine the selectivity of zeolite membranes
with the low cost and ease of manufacture of polymer membranes. Such membranes
are called mixed-matrix membranes.

Fig 2: Mixed Matrix membrane

SIGNATURE:_______________

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 EXPERIMENT NO: Date:
AIM:
To study different types of membrane modules used in membrane processes.
THEORY:
Industrial membrane plants often require a membrane area in the range of hundreds to
thousands square meters to perform the separation on a commercial scale. Therefore, methods
for packaging large membrane areas economically and efficiently are required. Different
types of modules, depending on the different applications are used. Below, a list of the
principal modules is presented.
1. Plate and Frame Membrane Modules. They were one of the earliest types of
membrane system. A schematic of a plate and frame membrane module for reverse
osmosis is illustrated in figure 1. Membrane, feed spacers and product spacers are
layered together between two end plates. The feed mixture is forced across the surface
of the membrane, enters the permeate channel, and exit from a central permeate
collection manifold. Plate and frame units have been developed for some small-scale
applications. However, they are expensive compared to alternative membrane
modules, and still affected by leakages. Currently, plate and frame modules are used
in electrodialysis, pervaporation and, in a limited number, in reverse osmosis and
ultrafiltartion applications with highly fouling feeds. Such modules can be operated
both in co- and countercurrent flow.

Fig 1: Plate and Frame Membrane Module

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2. Tubular Membrane Modules: This type of modules is characterized by a high
resistance to membrane fouling, due to the good fluid hydrodynamics, i.e. turbulent
flow. On the other hand, the cost is elevated due to the low surface to volume ratio.
For this reason, tubular modules are nowadays limited to ultrafiltration applications,
where the benefit connected to the the high resistance to fouling outweights their high
cost. Typically, the tubes consist of a porous paper of fiberglass, which serves as a
support, with the membrane on the inside of the tubes, as shown in figure 2. In a
typical tubular membrane system, many tubes are manifolded in series. The permeate
is removed from each tube and sent to a permeate collection header.

Fig 2: Tubular Membrane Module

3. Spiral-Wound Membrane Modules: Spiral-wound membrane modules were used in

a number of early artificial kidney designs, and were originally developed for
industrial reverse osmosis applications. Nowadays, the are used for reverse osmosis,
ultra-filtration and gas separation. The design shown in figure 3 consists of a
membrane envelope of spacers and membrane wound around a perforated central
collection tube. The feed passes axially down the module across the membrane
envelope. The permeate spirals toward the center and exits through the collection
tube. The module is then operated in cross-current flow. Four to six spiral-wound
membrane modules are normally connected in series inside a tubular pressure vessel,
illustrated in figure 4.5. A typical 0.2 m diameter tube containing six modules has a
150 - 250 m2 membrane area. In general, spiral-wound modules are characterized by a
fairly low manufacturing cost and a high surface to volume ratio.

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 Fig 3: Spiral Wound Membrane

4. Hollow-Fiber Membrane Modules. Hollow fiber membrane modules are widely used
for different membrane applications. They are found in two basic geometries: – The
shell-side feed design is illustrated in figure 4. This geometry is used, for example, by
Monsanto in their hydrogen separation systems and by Du Pont (until about 2000) in
their reverse osmosis systems. A loop or a closed bundle of fibers is contained in a
pressure vessel. The system is pressurized from the shell side; the permeate passes
through the fiber wall and exits through the open fiber ends. This design is fairly easy
to make, and allows very large membrane area to be contained in an economical
system. Because the fiber wall must support considerable hydrostatic pressure, the
fibers usually have small diameters and thick walls, typically 50 µm internal diameter
and 100 - 200 µm external diameter. This configuration is mostly used in high-
pressure applications, particularly gas separation and reverse osmosis. It can be
operated both in co-current and counter-current flow, with the second having a

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 favorable partial pressure build-up. The second type of hollow-fiber module is the
bore-side feed type, depicted in figure 4(bottom). In this type of unit, the fibers are
open at both ends; the feed fluid is circulated through the bore of the fibers. In order
to minimize pressure drop inside the fibers, the diameters are larger than those of the
fine fibers used in the shell-side feed system. This geometry is mostly used in ultra-
filtration and pervaporation, mainly in co-current flow. Generally, they are operated at
pressure lower than 10 bar. In bore-side feed modules, it is important to ensure that all
of the fibers have identical fiber diameters and permeances, since this can
significantly influence the removal achieved by the module.

Fig 4: Hollow Fiber Membrane (a) Shell Feed (b) Bore feed

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 EXPERIMENT NO: Date:
AIM:
To prepare an acetate membrane using solution casting method and evaluate its thickness.

APPARATUS AND CHEMICALS:

Sodium acetate / Cellulose Acetate, acetic acid(glacial), deionized water, beaker, measuring
cylinder, stirrer, petri dish, spatula, drying oven.
OPERATING PROCEDURE:
1. Prepare the casting solution: Dissolve 5-15 gm of sodium acetate in 20 ml of
deionized water in beaker. Heat the solution at 40-500C with continuous stirring
until sodium acetate completely dissolves. Slowly add 5-15 ml of glacial acetic
acid to solution while stirring continuously for 30-50 minutes. Filter the solution
through fine filter paper to remove solid impurities.
2. Casting the membrane: Pour the filtered solution into a clean petri dish and
swirl to form even layer. Place the petri dish in dust free environment to cool at
room temperature for 24-48 hours. Once the solvent is evaporated, solid
membrane is formed, using spatula remove membrane and note its thickness.
3. Repeat the procedure for different time for drying and concentration.
OBSERVATION:
1. Room Temperature: _______
2. Drying Temperature: _________
OBERSERVATION TABLE:
Sr. No. Conc. of Acetate : Drying time Membrane
Conc. of Acetic Acid Thickness
1. 5:5
2. 5:10
3. 10:15

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RESULT AND CONCLUSION:

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 EXPERIMENT NO: Date:
AIM:
To study the principle and working of short path distillation unit.

THEORY:
Operating principle of short path distillation unit (SPDU) is similar to thin evaporator except
internal condenser. Here internal condenser is installed inside rotor cage assembly. lm on the
insideThe feed enters the unit at top and get distributed into a thin surface of shell. Heating
medium passing through the jacket evaporates volatile component in feed. The vapor
generated condenses on internal condenser. This short path of vapor eliminate pressure drop.
Hence evaporation can be done at high vacuum as 0.001 mbar (a). The distilled product and
balance bottoms are taken out through separate outlets.

Advantages of SPDU:

1. Operating pressure as low as 0.001 mbar(a). Hence product can be distilled at lower
temperature to avoid degradation.
2. With high vacuum and high heating temperature, very high boiling components can
be distilled easily.

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 3. Residence time of few seconds..
4. Single pass evaporation.
5. Good turn down capability.
6. Low product hold up
7. Use of metal blades at high temperature gives more conventional roller design.

Applications for the Short Path Distillation are:

1. Oil and Fat Industry:

 Separation of free fatty acids from vegetable oil
 Fractionation of tall oil Concentration of glycerol Isolation of Monoglyceride
 Purification and deodorization of fish oil
2. Petrochemical Industry:
 Separation of my crocristalline wax out of crude oil high vacuum pump
residue
 Fractionation of synthetic and petrochemical waxes to soft-and hard waxes
3. Environmental care:
 Purification of spent lubricants, brake fluids, glycerol and transformer oils
 Recycling of dimethylsulfoxid (DMSO) mother liquors Processing of mother
liquors in pharmaceutical industry and the production of advanced organic
intermediates
 Waste water concentration
 Solvent recover
4. Chemical Industry:
 Purification of polyphenol compounds
 Separation of aromatic amines from oxidized components and by products
 Separation of long chain acid chlorides from impurities and free acids
 Solvent separation from silicon oils
 Concentration and purification of esters
 Purification of organic esters
 Concentration of herbicides and insecticides
 Purification of candelilla wax and other natural waxes
5. Food Industry:
 Purification Elimination of terpens and concentration of ethereal oils

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  Separation of solvents from flavors
 Concentration of juices or extracts
 Concentration of tocopheroles
 Concentration and isolation of lactic acid
 Concentration of capsicum
6. Pharmaceutical and Food Industry:
 Separation and purification of the valuable product from solvent and by
products
 Separation of extracting solvent from plant and herbs extracts
 Volume reducing of fermentation broth
 Concentration of sugar / Glycose solutions and fruit pulps.

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 EXPERIMENT NO: Date:

AIM:
To study principle and working of Supercritical Fluid Extraction

THEORY
Supercritical fluids have been investigated since last century, with the strongest
commercial interest initially focusing on the use of supercritical toluene in petroleum and
shale oil refining during the 1970s. Supercritical water is also being investigated as a
means of destroying toxic wastes, and as an unusual synthesis medium. The biggest
interest for the last decade has been the applications of supercritical carbon dioxide,
because it has a near ambient critical temperature (310C), thus biological materials can be
processed at temperatures around 350C. The density of the supercritical CO2 at around 200
bar pressure is close to that of hexane, and the solvation characteristics are also similar to
hexane; thus, it acts as a non-polar solvent. Around the supercritical region, CO2 can
dissolve triglycerides at concentrations up to 1% mass. The major advantage is that a small
reduction in temperature, or a slightly larger reduction in pressure, will result in almost the
entire solute precipitating out as the supercritical conditions are changed or made sub
critical. Supercritical fluids can produce a product with no solvent residues. Examples of
pilot and production scale products include decaffeinated coffee, cholesterol-free butter,
low-fat meat, evening primrose oil, squalene from shark liver oil, etc. The solvation
characteristics of supercritical CO2 can be modified by the addition of an entrainer, such as
ethanol, however some entrainer remains as a solvent residue in the product, negating
some of the advantages of the "residue-free” extraction.

Supercritical fluid A supercritical fluid is any substance at a temperature and pressure

above its critical point. It can diffuse through solids like a gas, and dissolve materials like a
liquid. Additionally, close to the critical point, small changes in pressure or temperature
result in large changes in density, allowing many properties of a supercritical fluid to be
"fine-tuned". Supercritical fluids are suitable as a substitute for organic solvents in a range
of industrial and laboratory processes. Carbon dioxide and water are the most commonly
used supercritical fluids, being used for decaffeination and power generation, respectively.
CO2 is the kind of extraction solvents for botanicals. It leaves no toxic residue behind. Its
extraction properties can be widely and precisely manipulated with subtle changes in
pressure and temperature. There are 2 types of CO2 extraction –

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1. Low pressure cold extraction Ii involves chilling CO2 at 35-550F and pumping it
through the plant material at between 800-1500 psi.
2. Supercritical extraction It involves heating the CO2 to above 870 F and pumping it
above 1100 psi. Usually, this is between 6000-10000 psi. Supercritical fluid CO2 can
best be described as a dense fog when CO2 is used in a dense liquid state. Low-pressure
CO2 is often the best method for producing high quality botanical extracts. CO2
loading rate in this state means that you have to pump many volumes of CO2 through
botanical. The loading rate is typically 10-40 volumes. For this reason, it is important
to have pumped CO2, which has a much faster loading rate 2-10 volumes and a wide
range of uses.

Supercritical fluid extraction process:

The system must contain a pump for the CO2, a pressure cell to contain the sample, a
means of maintaining pressure in the system and a collecting vessel. The liquid is pumped
to a heating zone, where it is heated to supercritical conditions. It then passes into the
extraction vessel, where it rapidly diffuses into the solid matrix and dissolves the material
to be extracted. The dissolved material is swept from the extraction cell into a separator at
lower pressure, and the extracted material settles out. The CO2 can then be cooled,
recompressed and recycled, or discharged to atmosphere.
Pumps: Carbon dioxide is usually pumped as a liquid, usually below 5°C and a pressure
of about 50 bars. The solvent is pumped as a liquid as it is then almost incompressible. As
a supercritical fluid, much of the pump stroke will be "used up" in compressing the fluid,
rather than pumping it. For small-scale extractions (up to a few grams/minute),
reciprocating CO2 pumps or syringe pumps are often used. For larger scale extractions,
diaphragm pumps are most common. The pump heads will usually require cooling, and
the CO2 will also be cooled before entering the pump.
Pressure vessels: Pressure vessels can range from simple tubing to more sophisticated
purpose built vessels with quick release fittings. The pressure requirement is at least 74
bars, and most extractions are conducted at less than 350 bar. However, sometimes,
higher pressures will be needed, such as extraction of vegetable oils, where pressures of
800 bars are sometimes required for complete miscibility of the two phases. The vessel
must be equipped with a means of heating. It can be placed inside an oven for small
vessels, or oil or electrically heated jacket for larger vessels. Care must be taken if rubber

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 seals are used on the vessel, as the CO2 may dissolve in the rubber, causing swelling, and
the rubber will rupture on depressurization.

Collection: The supercritical solvent is passed into a vessel at lower pressure than the
extraction vessel. The density, and thus, dissolving power, of supercritical fluids varies
sharply with pressure, and hence, the solubility in the lower density CO2 is much lower,
and the material precipitates for collection. It is possible to fractionate the dissolved
material using a series of vessels at reducing pressure. The CO2 can be recycled or
depressurized to atmospheric pressure and vented. For analytical SFE, the pressure is
usually dropped to atmospheric, and now the gaseous carbon dioxide is bubbled through
the solvent to trap the precipitated components.

Heating and cooling: This is an important aspect. The fluid is cooled before pumping to
maintain liquid conditions, and then heated after pressurization. As the fluid is expanded
into the separator, heat must be provided to prevent excessive cooling. For small-scale
extractions, such as for analytical purposes, it is usually sufficient to pre-heat the fluid in a
length of tubing inside the oven containing the extraction cell. The restrictor can be
electrically heated, or even heated with a hair dryer. For larger systems, the energy
required during each stage of the process can be calculated using the thermodynamic
properties of the supercritical fluid.

Advantages:

1. Environmental improvement and reduced product contamination: SFE is an alternative

to liquid extraction using solvents such as hexane or dichloromethane. There will

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 always be some residual solvent left in the extract and matrix, and there is always some
level of environmental contamination from their use. In contrast, carbon dioxide is easy
to remove simply by reducing the pressure, leaving almost no trace, and it is also
environmentally benign. The use of SFE with CO2 is approved by the Soil Association
for organic products. The CO2 used is largely a by-product of industrial processes or
brewing, and its use in SFE does not cause any extra emissions.
2. Selectivity: The solvent strength of a supercritical fluid can be varied by change in the
pressure and a lesser extent in the temperature. For example, volatile oils can be
extracted from a plant with low pressures (100 bar), whereas liquid extraction would
also remove lipids. Lipids can be removed using pure CO2 at higher pressures, and then
phospholipids can be removed by adding ethanol to the solvent.
3. Speed: It is a fast process and completed in 10 to 60 minutes. It is a diffusion-based
process, with the solvent required to diffuse into the matrix, and the extracted material
to diffuse out of the matrix into the solvent. Diffusivities are much faster in
supercritical fluids than in liquids, and therefore extraction can occur faster. Also, there
is no surface tension and viscosities are much lower than in liquids, so the solvent can
penetrate into small pores within the matrix inaccessible to liquids.
4. Purity: A supercritical fluid can be separated from analyte by simply releasing
pressure. Supercritical fluids are cheap, inert and nontoxic. Thus, they are readily
disposed off after an extraction is completed by allowing them to evaporate into the
atmosphere.

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 EXPERIMENT NO: Date:
AIM:
To study reactive and catalytic distillation process.

THEORY:
In most of the chemical plants one can find the reaction followed by separation. Usually
reaction and separation are performed one by one. First reactants are allowed to react in the
reactor, then in a separate equipment product mixture is separated from unconverted reactants
and/or from byproducts and inerts. It is rarely seen that both reaction and separation
combined and carried out simultaneously in one equipment. However, by combining reaction
and separation of product in one equipment one can get two advantages.
1. Removal of the product from the reaction mass at the reaction conditions increases
equilibrium conversion of reactant or increases the extent of reaction. As per LeChatelier's
law, for the reaction in equilibrium, if any change in any process variable like pressure,
temperature or composition of reaction mass is made, reaction or process is moved in such a
direction which will nullify the effect of the change in the variable. In reactive distillation,
change in the composition of reaction mass is made by continuously removing the product
from the reacting mass. Hence, to nullify the effect of this change, reaction proceeds in the
forward direction and produces more and more products and so equilibrium conversion is
improved.
2. Separate equipment for the separation is not required. Also separate piping, instruments,
etc. are not required. There are four commonly used techniques to combine reaction and
separation.
(i) Reactive distillation (Reaction + Distillation )
(ii) Membrane reaction (Reaction + Membrane separation )
(iii) Extractive reaction (Reaction + Extraction )
(iv) Reaction with absorption ( Reaction + Absorption)
In reactive distillation, reaction and distillation both are carried out simultaneously in one
equipment. If reactive distillation is carried out in presence of heterogeneous solid catalyst,
then it is called catalytic distillation.
Manufacturing of Ethyl Tertiary Butyl Ether (ETBE):
Ethyl tertiary butyl ether is used as octane number improver, like MTBE. ETBE has higher
octane rating and lower volatility compared to MTBE. However, oxygen content of ETBE is

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less compared to MTBE, hence larger volumes of ETBE is required. Also, cost of ETBE is
higher than the same of MTBE.
REACTION:
60−90 𝐶
(𝐶𝐻3 )2 𝐶 = 𝐶𝐻2 + 𝐶2 𝐻5 𝑂𝐻 ↔ (𝐶𝐻3 )3 𝐶𝑂𝐶2 𝐻5
SIDE REACTION:
(𝐶𝐻3 )2 𝐶 = 𝐶𝐻2 + (𝐶𝐻3 )2 𝐶 = 𝐶𝐻2 ↔ ((𝐶𝐻3 )2 𝐶 = 𝐶𝐻2 ))2

(𝐶𝐻3 )2 𝐶 = 𝐶𝐻2 + 𝐻2 𝑂 ↔ (𝐶𝐻3 )3 𝐶𝑂𝐻

In reactive (catalytic) distillation technology only equilibrium conversion is increased
in reactive distillation unit. Up to almost 80% conversion of isobutylene is achieved in a
(conventional) separate isothermal shell and tube heat exchanger type plug flow reactor.
Hence, feed to reactive distillation column is rich in ETBE but still contains ethanol and
isobutylene. Instead of rectified spirit, absolute alcohol is used as raw material with
isobutylene. Overhead product from reactive distillation column is non-reactive hydrocarbons
(n-butane, n-butylene, etc.), isobutylene and ethanol, respectively. Reactive Distillation
column has total ten packing sections. First and second packing sections use simple
structured packing, act as rectification or enriching section. Third, fourth and fifth packing
sections use ordered packing and act as reactive distillation zones. Sixth to tenth packing
sections used simple structural packing which act as stripping section.
Typical data of this process are as follows.
(a) Feed composition: 29.1% ETBE, 9.1% ethanol,
73% isobutylene, 54.5% n-butylene (by mole)
(Feed to reactive distillation unit)
(b) Isobutylene conversion: 97.4%
(c) Operating pressure = 900 kPa a
(d) Reflux ratio = 5.0
(e) Bottom composition = 96.5% ETBE, 2.8% ethanol, 0.7% butylene, 0.04% diisobutylene
(by mole)

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 EXPERIMENT NO: Date:
AIM:
To study pervaporation method.

THEORY:
Azeotrope, heat sensitive mixtures, nonvolatile mixture and mixtures with relative volatility
nearly equal to one are difficult to separate. Different unit operation techniques like
adsorption, extractive distillation, distillation of azeotropic mixtures and liquid-liquid
extraction are in exercise in chemical engineering practices for the separation of such
mixtures. But all of these conventional separation techniques demand extensive amount of
energy, external entrainer and downstream processing to recover key hese techniques often
cause product contamination and environmental pollution . In order to enhance the efficiency
of separation process an advanced separation technique pervaporation (PV) has been
introduced. It is an economical, energy saving and safe membrane separation technique. It
provides efficient separation at normal operating conditions without using any external
chemical separating agent or any other downstream processing.

Pervaporation is a membrane separation process conducted by partial vaporization using a

nonporous membrane. The driving forces which cause the transport through the selective
membrane are chemical potential difference, partial pressure difference and membrane
transport rate. Membrane serves as a selective transport barrier during the separation of solute
from the bulk solvent. Membranes used for the pervaporation process are nonporous made up
with synthetic polymeric composite material having high functional selectivity. Name of this
membrane-based process is a contraction of permeation and evaporation, representing two
basic steps of the process i.e. the permeation through the membrane and then its evaporation
into the vapor phase. The feed constituent which passes through the membrane is termed as
permeate and the remainder of the feed stream which retains on the membrane is termed as
retentate. Membrane Modules used for the pervaporation process are available with various
fabrication designs e.g. tubular, plate and frame, spiral-wound, hollow fibrous, capillary fiber
etc. In pervaporation Module liquid feed mixture associates the upstream side of the
membrane. One component of feed (solute) is transported through the membrane
preferentially and is removed as a vapor from the downstream side. Basic schematic diagram
for pervaporation process is shown in Fig 1. The selective transport through the membrane is

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followed by a three step mechanism termed as Solution-Diffusion Model which involves
sorption, diffusion and desorption

Fig 1: Schematic diagram of Pervaporation low pressure process

Applications:

Pervaporation has a large list of industrial applications for the separation of liquid mixtures.
Although it is a developing industrial membrane separation process but still its leading
perspectives have compelled the industrialist to fabricate pervaporation plants which are
effectively playing their role in production. Typical separations being conducted by
pervaporation technique are separation of azeotropic mixtures in chemical process industries,
organic-organic separation, separation of dissolved organics from water, separations in
petroleum and petrochemical industries, increasing distillation column efficiency by hybrid
pervaporation unit, increasing reaction yield by Perstillation and water and waste water
treatment etc.

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Comparision of other separation process with Pervaporation

Characteristic Azeotropic / Liquid-Liquid Drying agents Pervaporation

parameter Extractive Extraction technique
Distillation
Separating Heat Immiscible Solid solvent Membrane
medium Liquid interface
Driving Force Relative Density phases Water absorbing Concentration
volatility tendency and partial
pressure
difference
Operational High Medium Medium Low
pressure
Operational High Medium Medium Medium
temperature
Energy High High High Low
consumption
Operation High Medium Medium Low
Hazard
Space High High Medium Low
Requirement
Maintenance High Medium Medium Low
cost
Operation cost High Medium Medium Low
Product purity Fine Fine Fine Ultrafine
Capital cost High Medium Medium Low

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 EXPERIMENT NO: Date:
AIM:
To study reverse osmosis for treatment of brackish water.

THEORY:
The salinity of brackish water is usually between 2000 and 10 000 mg/l. The World Health
Organization (WHO) recommendation for potable water is 500 mg/l, so only 90% of the salt
must be removed from these feeds in many cases. Early cellulose acetate membranes could
achieve this removal easily, so treatment of brackish water was one of the first successful
applications of reverse osmosis. Plants were installed as early as the 1960s. The osmotic
pressure of brackish water is approximately 0.8 bar per 1000 ppm salt, so osmotic pressure
effects do not generally limit water recovery significantly. Limitations are generally due to
scaling. Typical water recoveries are in the 85–90% range, which means calcium, sulfate, and
silica ions present in the feed are concentrated up to 10-fold in the brine stream leaving the
system. If scaling occurs, the last modules in the system are affected most and must be
replaced first. Disposal of the 10–15% of the brackish water that remains as concentrated
brine represents a significant problem.

A two tage membrane process was proposed to eliminate this problem. In the first stage, 85–
90% of the water would be permeated in the normal way. Calcium, silica, and other potential
scalants in the brine would then be precipitated by addition of sodium hydroxide. The treated
brine would then be reacidified, antiscalants added, and a further fraction of the water
removed, thus achieving an overall water recovery of up to 98%. The final small concentrate
stream can then be sent to an evaporation pond. A simplified flow scheme for a brackish
water reverse osmosis plant is shown in Figure 1. In this example, it is assumed that the
brackish water is contaminated with suspended solids, so flocculation followed by a sand
filter and a cartridge filter are used to remove particulates. The pH of the feed solution might
be adjusted, followed by chlorination to sterilize the water to prevent bacterial growth on the
membranes and addition of an antiscalant to inhibit precipitation of multivalent salts on the
membrane.

Finally, if chlorine-sensitive interfacial composite membranes are used, sodium sulfite is

added to remove excess chlorine before the water contacts the membrane. Generally, more

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pretreatment is required in plants using hollow fiber modules than in plants using spiral-
wound modules. This is one reason why hollow fiber modules have been displaced by spiral-
wound systems in brackish water installations. A feature of the system design shown in
Figure 5.25 is the staggered arrangement of the module pressure vessels. The volume of the
feed water is reduced as water is removed in the permeate, and the number of modules
arranged in parallel is reduced accordingly.

Fig 1: Flow diagram of Brackish water treatment using RO Process

In the example shown, the feed water passes initially through four modules in parallel, then
through two, and finally through a single module in series. This is called a “Christmas tree”
or “tapered module” design and provides a high average feed solution velocity through the
modules. The operating pressure of brackish water reverse osmosis systems has gradually
fallen over the past 20 years as the permeability and rejection rates of membranes have
steadily improved. The first plants operated at pressures of 50 bar, but typical brackish water
plants now operate at pressures in the 10–20-bar range.

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 EXPERIMENT NO: Date:
AIM:
To study column chromatography and Ion exchange chromatography

THEORY:
Column chromatography is a technique which is used to separate a single chemical
compound from a mixture dissolved in a fluid. It separates substances based on differential
adsorption of compounds to the adsorbent as the compounds move through the column at
different rates which allow them to get separated in fractions. This technique can be used on
small scale as well as large scale to purify materials that can be used in future experiments.
This method is a type of adsorption chromatography technique.
Principle: When the mobile phase along with the mixture that needs to be separated is
introduced from the top of the column, the movement of the individual components of he
mixture is at different rates. The components with lower adsorption and affinity to stationary
phase travel faster when compared to the greater adsorption and affinity with the stationary
phase. The components that move fast are removed first whereas the components that move
slow are eluted out last. The adsorption of solute molecules to the column occurs in a
reversible manner. The rate of the movement of the components is expressed as:
Rf = the distance travelled by solute/ the distance travelled by solvent
Rf is the retardation factor.

Fig 1: Column Chromatography

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Ion Exchange Chromatography: The principle of separation is thus by reversible exchange
of ions between the target ions present in the sample solution to the ions present on ion
exchangers. In this process two types of exchangers i.e., cationic and anionic exchangers can
be used.

1. Cationic Exchangers: These possess negatively charged group, and these will attract
positively charged cations. These exchangers are also called “Acidic ion exchange”
materials, because their negative charges result from the ionization of acidic group
2. Anionic Exchangers : These have positively charged groups that will attract
negatively charged anions. These are also called “Basic ion exchange” materials. Ion
exchange chromatography is most often performed in the form of column
chromatography. However, there are also thin-layer chromatographic methods that
work basically based on the principle of ion exchange.

Working: Consider a column having E-Y+ cation exchanger in which E– is negative charged
exchanger and Y+ is the mobile counter ion. Let X+ be the cation in the sample having charge greater
than Y+. The X+ ion can exchange sites with the counter ion Y+ with satisfying the following
relationship;

𝐸−𝑌+𝑋+ → 𝐸 −𝑋+𝑌+

Desired bounded cation (X+) can now be eluted by either of the two ways;
1. By adding a component M+ having magnitude of charge more than that of X+ so that M+
will replace X+ and X+ will be eluting out.
2. By changing pH of the solvent (mobile phase so that X+ have no charge and is then
unbounded from the matrix and can be eluted out

Fig 1: Ion Exchange Process

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Factors Affecting Ion Exchange Separation:

1. Ion Exchange Resins: The swelling factor and cross linking is important for the
effective separation. The cross linking should be controlled as its affects the
exchanger’s capacity. Swelling helps in proper exposure of charged functional groups
for exchange of ions.
swells less → separation of ions of different sizes is difficult.

2. Nature of Exchange Ions: Valency of ions, Size of ions, Polarizability,

Concentration of solutions and concentration of charged ions.
3. pH of the mobile phase
4. Ionic strength
5. Mobile phase modifiers
6. Temperature
7. Buffer: The pH of the buffer should impart the same charge to the sample ions as
present in the Column. Anionic Exchange Chromatography should be carried out with
cationic buffers and vice versa because buffer ion will indulge in ion exchange, which
will be of no use.

Application of Ion Exchange separation:

1. An important use of ion-exchange chromatography is in the routine analysis of amino
acid mixtures. The 20 principal amino acids from blood serum or from the hydrolysis
of proteins are separated and used in clinical diagnosis.
2. This is most effective method for water purification. Complete deionization of water
(or) a non-electrolyte solution is performed by exchanging solute cations for hydrogen
ions and solute anions for hydroxyl ions. This is usually achieved by method is used
for softening of drinking water.
3. In the analysis of products of hydrolysis of nucleic acids. In this way, information is
gained about the structure of these molecules and how it relates to their biological
function as carriers of hereditary information.
4. Chelating resins are used to collect trace metals from seawater.

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Advantages of Process:

1. It is one of the most efficient methods for the separation of charged particles.
2. It can be used for almost any kind of charged molecule including large proteins, small
nucleotides and amino acids.
3. Ion exchange is used for both analytical and preparative purposes in the laboratory, the
analytical uses being the more common.
4. Inorganic ions also can be separated by ion-exchange chromatography.

Limitations of Process:

1. Only charged molecules are separated

2. Buffer

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