SCHOOL OF SCIENCE AND HUMANITIES

DEPARTMENT OF CHEMISTRY

UNIT – I – PROCESS AND SEPARATION

IN CHEMICAL INDUSTRY – SCH 1314
Chemical processes usually have three interrelated elementary processes
 Transfer of reactants to the reaction zone

 Chemical reactions involving various unit processes

 Separation of the products from the reaction zone using various unit operations
Processes may involve homogeneous system or heterogeneous systems. In homogeneous system,
reactants are in same phase-liquid, gases or solids while heterogeneous system include two or
more phases; gas liquid, gas–solid, gas-gas, liquid–liquid, liquid solid etc. Various type reactions
involve maybe reversible or irreversible, endothermic or exothermic, catalytic or non-catalytic.
Various variables affecting chemical reactions are temperature pressure, composition, catalyst
activity, catalyst selectivity, catalyst stability, catalyst life, the rate of heat and mass transfer. The
reaction may be carried out in batch, semi batch or continuous. Reactors may be batch, plug flow,
CSTR. It may be isothermal or adiabatic. Catalytic reactors may be packed bed, moving bed or
fluidised bed
Along with knowledge of various unit processes and unit operation following information are
very important for the development of a process and its commercialization [Austin,1984] Basic
Chemical data: Yield conversion, kinetics
 Material and energy balance, raw material and energy consumption per tone of product,
energy changes
 Batch vs Continuous, process flow diagram

 Chemical process selection: design and operation, pilot plant data, Equipment required,
material of construction
 Chemical Process Control and Instrumentation

 Chemical Process Economics: Competing processes, Material and, Energy cost, Labour,
Overall Cost of production
 Market evaluation: Purity of product and uniformity of product for further processing

Plant Location

 Environment, Health, Safety and Hazard

 Construction, Erection and Commissioning

 Management for Productivity and creativity: Training of plant personals and motivation at all
levels
 Research, Development and patent

 Process Intensification
In order to improve productivity and make the process cost effective and for improving overall
economy, compact , safe, energy efficient and environmentally sustainable plant, process
intensification has become very important and industry is looking beyond the traditional
chemical engineering.

UNIT PROCESSES AND UNIT OPERATIONS IN CHEMICAL PROCESS INDUSTRIES

Chemical process is combination of unit processes and Unit operation. Unit process involves
principle chemical conversions leading to synthesis of various useful product and provide basic
information regarding the reaction temperature and pressure, extent of chemical conversions and
yield of product of reaction nature of reaction whether endothermic or exothermic, type of
catalyst used. Unit operations involve the physical separation of the products obtained during
various unit processes. Various unit processes in chemical industries are given in Table
 UNIT OPERATIONS IN CHEMICAL INDUSTRIES
Unit operations are very important in chemical industries for separation of various products
formed during the reaction.

DISTILLATION
Distillation has been the king of all the separation processes and most widely used separation
technology and will continue as an important process for the foreseeable future . Distillation is
used in petroleum refining and petrochemical manufacture Distillation is the heart of petroleum
refining and all processes require distillation at various stages of operations.

MEMBRANE PROCESSES
Membrane processes have emerged one of the major separation processes during the recent years
and finding increasing application in desalination, wastewater treatment and gas separation and
product purification. Membrane technology is vital to the process intensification strategy and has
continued to advance rapidly with the development of membrane reactors, catalytic membrane
reactor, membrane distillation, membrane bioreactors for wide and varied application .

ABSORPTION
Absorption is the one of the most commonly used separation techniques for the gas cleaning
purpose for removal of various gases like H2S, CO2, SO2 and ammonia. Cleaning of solute gases
is achieved by transferring into a liquid solvent by contacting the gas stream with liquids that
offers specific or selectivity for the gases to be recovered. Unit operation and is mass transfer
phenomena where the solute of a gas is removed from being placed in contact with a nonvolatile
liquid solvent that removes the components from the gas. Solvent: Liquid applied to remove the
solute from a gas stream. Solute: Components to be removed from entering streams.

CRYSTALLIZATION PROCESS
Crystallization processes are used in the petroleum industry for separation of wax. The process
involves nucleation, growth, and agglomeration and gelling. Some of the applications of
crystallization is in the separation of wax, separation of p-xylene from xylenes stream. Typical
process of separation of p-xylene involves cooling the mixed xylene feed stock to a slightly
higher than that of eutectic followed by separation of crystal by centrifugation or filtration.

LIQUID –LIQUID EXTRACTION

Liquid –liquid extraction has been commonly used in petroleum and petrochemical industry for
separation of close boiling hydrocarbons. Some of the major applications are:
 Removal of sulphur compound from liquid hydrocarbons

 Recovery of aromatics from liquid hydrocarbon

 Separation of butadiene from C4 hydrocarbons

 Extraction of caprolactam

 Separation of homogenous aqueous azeotropes

 Extraction of acetic acid

 Removal of phenolic compounds from waste water

 Manufacture of rare earths

 Separation of asphaltic compounds from oil

 Recovery of copper from leach liquor

 Extraction of glycerides from vegetable oil Some of the important property of a good solvent

 High solvent power/capacity

 High selectivity for desired component

 Sufficient difference in boiling points of the solvent and the feed for effective separation

 Low latent heat of evaporation an specific heat to reduce utility requirement

 high thermal an chemical stability

 Low melting point

 Relatively inexpensive
Raw Materials

Human insulin is grown in the lab inside common bacteria. Escherichia coli is by far the most
widely used type of bacterium, but yeast is also used.

Researchers need the human protein that produces insulin. Manufacturers get this through an
amino-acid sequencing machine that synthesizes the DNA. Manufacturers know the exact order
of insulin's amino acids (the nitrogen-based molecules that line up to make up proteins). There
are 20 common amino acids. Manufacturers input insulin's amino acids, and the sequencing
machine connects the amino acids together. Also necessary to synthesize insulin are large tanks
to grow the bacteria, and nutrients are needed for the bacteria to grow. Several instruments are
necessary to separate and purify the DNA such as a centrifuge, along with various
chromatography and x-ray crystallography instruments.

The Manufacturing Process

Synthesizing human insulin is a multi-step biochemical process that depends on basic

recombinant DNA techniques and an understanding of the insulin gene. DNA carries the
instructions for how the body works and one small segment of the DNA, the insulin gene, codes
for the protein insulin. Manufacturers manipulate the biological precursor to insulin so that it
grows inside simple bacteria. While manufacturers each have their own variations, there are two
basic methods to manufacture human insulin.

Working with human insulin

 1 The insulin gene is a protein consisting of two separate chains of amino acids, an A
above a B chain, that are held together with bonds. Amino acids are the basic units that
build all proteins. The insulin A chain consists of 21 amino acids and the B chain has 30.
 2 Before becoming an active insulin protein, insulin is first produced as preproinsulin.
This is one single long protein chain with the A and B chains not yet separated, a section
in the middle linking the chains together and a signal sequence at one end telling the
protein when to start secreting outside the cell. After preproinsulin, the chain evolves into
proinsulin, still a single chain but without the signaling sequence. Then comes the active
protein insulin, the protein without the section linking the A and B chains. At each step,
the protein needs specific enzymes (proteins that carry out chemical reactions) to produce
the next form of insulin.
STARTING WITH A AND B

 3 One method of manufacturing insulin is to grow the two insulin chains separately. This
will avoid manufacturing each of the specific enzymes needed. Manufacturers need the
two mini-genes: one that produces the A chain and one for the B chain. Since the exact
DNA sequence of each chain is known, they synthesize each mini-gene's DNA in an
amino acid sequencing machine.
 4 These two DNA molecules are then inserted into plasmids, small circular pieces of
DNA that are more readily taken up by the host's DNA.
 5 Manufacturers first insert the plasmids into a non-harmful type of the bacterium E.
coli. They insert it next to the lacZ gene. LacZ encodes for 8-galactosidase, a gene widely
used in recombinant DNA procedures because it is easy to find and cut, allowing the
insulin to be readily removed so that it does not get lost in the bacterium's DNA. Next to
this gene is the amino acid methionine, which starts the protein formation.
 6 The recombinant, newly formed, plasmids are mixed up with the bacterial cells.
Plasmids enter the bacteria in a process called transfection. Manufacturers can add to the
cell’s DNA ligase, an enzyme that acts like glue to help the plasmid stick to the
bacterium's DNA.
 7 The bacteria synthesizing the insulin then undergo a fermentation process. They are
grown at optimal temperatures in large tanks in manufacturing plants. The millions of
bacteria replicate roughly every 20 minutes through cell mitosis, and each expresses the
insulin gene.
 8 After multiplying, the cells are taken out of the tanks and broken open to extract the
DNA. One common way this is done is by first adding a mixture of lysozome that digest
the outer layer of the cell wall, then adding a detergent mixture that separates the fatty
cell wall membrane. The bacterium's DNA is then treated with cyanogen bromide, a
reagent that splits protein chains at the methionine residues. This separates the insulin
chains from the rest of the DNA.
 9 The two chains are then mixed together and joined by disulfide bonds through the
reduction-reoxidation reaction. An oxidizing agent (a material that causes oxidization or
the transfer of an electron) is added. The batch is then placed in a centrifuge, a
mechanical device that spins quickly to separate cell components by size and density.
  10 The DNA mixture is then purified so that only the insulin chains remain.
Manufacturers can purify the mixture through several chromatography, or separation,
techniques that exploit differences in the molecule's charge, size, and affinity to water.
Procedures used include an ion-exchange column, reverse-phase high performance liquid
chromatography, and a gel filtration chromatography column. Manufacturers can test
insulin batches to ensure none of the bacteria's E. coli proteins are mixed in with the
insulin. They use a marker protein that lets them detect E. coli DNA. They can then
determine that the purification process removes the E. coli bacteria.

PROINSULIN PROCESS

 11 Starting in 1986, manufacturers began to use another method to synthesize human

insulin. They started with the direct precursor to the insulin gene, proinsulin. Many of the
steps are the same as when producing insulin with the A and B chains, except in this
method the amino acid machine synthesizes the proinsulin gene.
 12 The sequence that codes for proinsulin is inserted into the non-pathogenic E.
coli bacteria. The bacteria go through the fermentation process where it reproduces and
produces proinsulin. Then the connecting sequence between the A and B chains is spliced
away with an enzyme and the resulting insulin is purified.
 13 At the end of the manufacturing process ingredients are added to insulin to prevent
bacteria and help maintain a neutral balance between acids and bases. Ingredients are also
added to intermediate and long-acting insulin to produce the desired duration type of
insulin. This is the traditional method of producing longer-acting insulin. Manufacturers
add ingredients to the purified insulin that prolong their actions, such as zinc oxide. These
additives delay absorption in the body. Additives vary among different brands of the
same type of insulin.

Analog insulin

In the mid 1990s, researchers began to improve the way human insulin works in the body by
changing its amino acid sequence and creating an analog, a chemical substance that mimics
another substance well enough that it fools the cell. Analog insulin clumps less and disperses
more readily into the blood, allowing the insulin to start working in the body minutes after an
injection. There are several different analog insulin. Humulin insulin does not have strong bonds
with other insulin and thus, is absorbed quickly. Another insulin analog, called Glargine, changes
the chemical structure of the protein to make it have a relatively constant release over 24 hours
with no pronounced peaks.
Instead of synthesizing the exact DNA sequence for insulin, manufacturers synthesize an insulin
gene where the sequence is slightly altered. The change causes the resulting proteins to repel
each other, which causes less clumping. Using this changed DNA sequence, the manufacturing
process is similar to the recombinant DNA process described.

Manufacturing steps for insulin.

Quality Control

After synthesizing the human insulin, the structure and purity of the insulin batches are tested
through several different methods. High performance liquid chromatography is used to determine
if there are any impurities in the insulin. Other separation techniques, such as X-ray
crystallography, gel filtration, and amino acid sequencing, are also performed. Manufacturers
also test the vial's packaging to ensure it is sealed properly. Manufacturing for human insulin
must comply with National Institutes of Health procedures for large-scale operations. The United
States Food and Drug Administration must approve all manufactured insulin.

Purification. Processes for purification are highly selective and separate the product from
impurities with similar properties. Typical unit operations are chromatography, ultrafiltration and
fractional precipitation.

Final isolation. The final purity required depends on the product application. Crystallisation,
followed by centrifugation or filtration and drying, are typical operations used for high-quality
products such as pharmaceuticals.

Process Flow Diagrams

Because of the complexity of large-scale manufacturing processes, communicating information
about these systems requires special methods. Flow diagrams or flow sheets are simplified
pictorial representations of processes and are used to present relevant process information and
data. Flow sheets vary in complexity from simple block diagrams to highly complex schematic
drawings showing main and auxiliary process equipment such as pipes, valves, pumps and
bypass loops.
ETHANOL
India is amongst two largest sugar producing countries in the world and converts the molasses
from sugar plant to alcohol. India is fourth largest producer of ethanol in the world and second
largest in Asia. India produces about 2.75 billion liters alcohol annually. The demand for potable
alcohol has been ever increasing. Today 95 percent of ethanol is produced by fermentation and
only 5percent is produced from petroleum feed stock by ethylene route

Ethanol has become one of the important products as alternative feedstock for large number of
organic chemicals and fuel. Ethanol is an oxygenated fuel that contains 35percent oxygen, which
reduces particulate and NOx emissions from combustion. Alcohol is now being used for potable
liquor, as chemical feed stock, as solvent and as oxygenates. Process manufacturing of alcohol is
shown in fig Various routes for manufacture of ethanol are:
 Alcohol from Fermentation of molasses
 Alcohol from Lignocelluloses biomass
 Alcohol from starchy feed stocks
 Petrochemical route via Catalytic hydration of ethylene and Ethylene etherification and
hydrolysis
Fermentation of Molasses
Molasses is the residue left after extraction of crystallized sugar and is one of the major
byproducts of the sugar industry. Ethyl alcohol is made from molasses by fermentation process
utilizing yeast enzymes. A typical distillery consist of
 Molasses handling
 Fermentation feeding system
 Preparation of yeast inculam, propagation of yeast
 Fermentation
 Distillation of dilute alcohol for removal of impurities
 Concentration of the dilute alcohol to rectified spirit and absolute alcohol
Molasses handling involves weighing of the molasses and pumping of molasses to the molasses
tank from which the measured quantity of molasses is transferred to the fermenter. Preparation of
yeast inculam, propagation of yeast: Yeast material is prepared in water cooled yeast vessels by
inoculating molasses with yeast and then transferred to aerated yeast activation vessel to allow
time for yeast cell multiplication Fermentation involves fermentation of fermentable sugars by
microorganism and formation of alcohol and other by-products. Yeast (Saccharomyces
cerevisiae) is commonly used for the fermentation of glucose to ethanol. After the fermentation
alcohol of 7-8percent strength is obtained. Fermentation is exothermic process and heat is
generated. Removal of heat is necessary to maintain the temperature in fermenter. High
temperature lowers the alcohol productivity. Nutrients are added to the fermented intermittently
depending upon the requirement. Sulphuric acid is added to adjust the pH of fermenter liquid.
Excess foaming in the fermenter is controlled by antifoam solution. During the normal operation
treated yeast cells
recovered from the fermented wash are recycled from the yeast treatment system to activation
vessel and after that transfer to the fermenter

After fermentation is completed, the dil. liquor ((8-10percent alcohol) is preheated and
pumped to the beer still where the alcohol 50-60percent) and other volatiles like aldehydes are
distilled off from the top and send to the aldehyde column for separation of aldehydes and other
low boiling impurities. The residue from the bottom of the beer column is known as slops or
tillage are discharged and treated for recovery of energy or concentrated and used. Alcohol
drawn from side stream of the aldehyde column is sent to rectifying column. The azeotrop
alcohol containing alcohol about 95-96percent alcohol is taken as top side stream from the
rectifying column.

Process of Manufacturing of Ethanol

Alcohol recovery: this section involves the recovery of alcohol from the fermentation section to
minimize the possible losses of alcohol along with generated CO2 and sludge from fermented.
Typical reactions involved are

CITRIC ACID
Urea
 1

SCHOOL OF SCIENCE AND HUMANITIES

DEPARTMENT OF CHEMISTRY

UNIT – II – PROCESS AND SEPARATION

IN CHEMICAL INDUSTRY – SCH 1314

MAGESH.N SCH1101
SCH1314 Unit
II

MATERIAL BALANCES
Material balances are important first step when designing a new process or analyzing an existing one.
They are almost always prerequisite to all other calculations in the solution of process engineering
problems.
Material balances are nothing more than the application of the law of conservation of mass, which
states that mass can neither be created nor destroyed. Thus, you cannot, for example, specify an input
to a reactor of one ton of naphtha and an output of two tons of gasoline or gases or anything else. One
ton of total material input will only give one ton of total output, i.e. total mass of input = total mass of
output.
A material balance is an accounting for material. Thus, material balances are often compared to the
balancing of current accounts. They are used in industry to calculate mass flow rates of different
streams entering or leaving chemical or physical processes.

General Material Balance Equation

A balance (or inventory) on a material in a system (a single process unit, a collection of units, or an
entire process) may be written in the following general way:

Input + Generation – Output – Consumption = Accumulation

(enters (produced (leaves (consumed (buildup within
Through within through within system) system)
System system system
boundaries) boundaries) boundaries)

This general balance equation may be written for any material that enters or leaves any process system;
it can be applied to the total mass of this material or to any molecular or atomic species involved in the
process.

Steady -state operation: Under steady-state, the values of all variables associated with the process do not
change with time. That is, at any given location in the process, the values of temperature, pressure,
composition, flow rates, etc. are independent of time. The general balance equation may be simplified
according to the process at hand. For example, by definition, the accumulation term for steady-state
continuous process is zero. Thus the above equation becomes:

Input + Generation = Output + Consumption

For physical process, since there is no chemical reaction, the generation and consumption terms will
become zero, and the balance equation for steady-state physical process will be simply reduced to:

Input = Output

Differential balances: The terms in a differential material balance are expressed as rates; that is, rate of
input (e.g. moles/s, kg/s), rate of generation, rate of output, and rate of accumulation. Differential
balances are applied to continuous processes.

Integral balances: These usually apply to batch processes. The terms in a batch material balance are
expressed as amounts (molar or mass). Input is the amount placed into the system initially at the start of
the process. The process is then sealed while the

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SCH1314 Unit
II

reaction/transformation of the input materials takes place. At the end, the process is opened and the
contents are removed: output is the amount removed at this stage, including products and any
unconverted reactants. Generation/consumption are the amounts produced/consumed during the time
between the start and the end of the process. Accumulation is the amount left behind in the process
(this is zero if all materials are removed).

Degree of Freedom Analysis

Recall: If you have N unknown variables (such as flowrates, compositions) whose value you need to
solve for, you will need exactly N independent equations relating these variables (“number of
independent equations = number of unknowns”).

Independent equations: equations are independent if none of them can be derived from the others. For
example, not one of the set of equations can be obtained by adding or subtracting multiples of the
others.

Degrees of freedom, ndf = nunknowns – nindep eqns

If, for a given problem,
ndf = 0: A numerical value for each unknown can be obtained. The problem is solvable.
ndf > 0: The problem is underspecified (underdetermined). There is not enough
information (i.e. not enough independent equations) to provide a solution.
ndf < 0: The problem is overspecified (overdetermined). The problem is
mathematically and possibly physically inconsistent.

Procedure for Material Balance Calculations

In material balance problems, you will usually be given a description of a process, the values of several
process variables, and a list of quantities to be determined. In order to be trained on using a systematic
procedure to solve material balance problems, you are advised to follow the steps summarized below:
1. Read and understand the problem statement.
2. Draw a sketch of the process and specify the system boundary
3. Place labels (symbols, numbers, and units) on the diagram for all of the known flows, materials,
and compositions.
4. Obtain any data you know are needed to solve the problem but are missing.
5. Choose a basis.
6. Determine the number of variables whose values are unknown (the unknowns), the number of
independent equations and carry out a degree-of-freedom analysis.
7. Write down the equations to be solved in terms of the knowns and unknowns.
8. Solve the equations and calculate the quantities asked for in the problem.
9. Check your answer(s).

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SCH1314 Unit
II

Material Balance around distillation column

Consider a steady-state distillation process,

Since the process is at steady-state condition and no chemical reaction is involved, the material balance
equation becomes
Input = Output
This balance equation can be applied to:
1. The total mass entering and leaving the process – Overall Balance
2. Mass of individual component entering and leaving the process – Component Balance.
Total Mass (Overall Material Balance)
F=D+B
Component A Balance
mA1 = mA2 + mA3 FxAF =
DxAD + BxAB
Component B Balance
mB1 = mB2 + mB3 FxBF =
DxBD + BxBB

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SCH1314 Unit
II

Material Balance for Mixing Process

Material Balances (Steady-State, Non-Reactive Process): Total

Balance:
m1 + m2 = m3
Methanol-Balance:
m1xM1 + m2xM2 = m3xM3
Water-Balance:
m1xW1 + m2xW2 = m3xW3

Physical Constraint (applied to mixture 3):

xM3 + xW3 = 1.00

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SCH1314 Unit
II

Material Balance for Evaporation Process

Material Balances (Steady-State, Non-Reactive Process): Total

Balance:
F=V+L
Solute Balance:
FxsF = VysV + LxsL
Since ysV = 0, the above equation becomes
FxsF = LxsL
Solvent (Water) Balance:
FxwF = VywV + LxwL

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SCH1314 Unit
II

Multiple Unit Processes

When an interconnected network of process units is involved in a material balance calculation, one
typically has to make balances on individual process units, combinations of several units, as well as the
overall, multiple unit system in order to arrive at the solution. Balances that are taken on the overall
system, which do not involve any internal process streams, are referred to as overall balances. For each
subsystem (e.g. a single unit, a combination of units), as well as the total process, a degree of freedom
analysis will apply. You may need to solve the balances on one subsystem first in order to determine
values of variables needed to solve balances on another.

Bypass, Recycle & Purge

When a part of a process stream is fed forward into a later stage of the process, the stream is being
“bypassed.” Bypass is useful, for example, for decreasing the extent
of conversion of input materials or for providing improved control over stream temperatures.

Recycle stream is a term denoting a process stream that returns material from downstream of a process
unit back to the process unit. When a part of a process stream is fed back into an earlier stage of the
process, the stream is said to be “recycled.” Recycle is often used to increase the rates of conversion of a
reactant. By passing a reactant molecule through the process several times, its chances to react and
convert to product are increased. Other reasons to recycle part of a stream include recovery of valuable
materials, such as catalysts, improved temperature control over a process, and decreased waste of
working (carrier) fluid.

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SCH1314 Unit
II

Purge stream is a stream bled off to remove an accumulation of inerts or unwanted material that might
otherwise build up in the recycle stream.

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SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – III – PROCESS AND SEPARATION

IN CHEMICAL INDUSTRY – SCH 1314
SCH 1314 UNIT III

Fundamentals of Separation Processes

In most of the chemical engineering systems, separation processes are integral part of the entire process
flowsheet. If we consider a reactive system, where, certain products are of primary interest, separation
units are either put in the upstream or downstream. In such a system, the reactor is the heart of the
system. It may happen that the reactants are gaseous and should be devoid of moisture. In such cases,
a separation unit must be present as an upstream unit. On the other hand, if a particular product is kept
in mind, a separation unit must be placed at the downstream of the flowsheet. There may be processes,
where, the separation is the only objective. For example, if we consider a treatment process of an
industrial effluent, separation is the only process that is involved. There may be a number of separation
processes involved in a system. In an effluent treatment process, there are three steps, namely, primary,
secondary and tertiary treatment processes. All these processes are primarily separation processes.
Primary treatment processes include coagulation, flocculation, etc. Secondary treatment processes are
mainly oxidation ponds, etc. Tertiary treatment processes involve adsorption, membrane separation,
etc. In food and juice processing industries, separations are primary stages of operation. Most of the
pharmaceutical industries have separation units as integral parts in the downstream or they are the main
units. In milk processing separation processes are primary.
Most of the separation processes involve, either separation of solutes from the solvent or, separation
of a mixture of solutes. It may be noted that the components those need to be separated are in a mixture
naturally. In order to effect separation, one has to put either energy or an extra material from outside
to disturb stability. This is equivalent to the concept of exceeding the activation energy of separation
by an external agent (agent may be energy or matter). This point can be elaborated by some examples.
Consider a case of separation of salt from sea water. In this system, thermal energy is added to the
system and water is evaporated leaving behind the salts. Consider another case of separation of charged
colloidal particles which are stable in a solution. In such systems, a coagulant, like potassium alum or
ferric chloride or calcium oxide (selection depends upon the operating pH) is added. These coagulants
are generally of opposite charges of the colloids. These colloids get themselves attached to the
coagulants by electrostatic attractive forces and the whole assembly becomes heavier and settles down.
In this case, we add an external agent (a matter i.e., coagulant) to effect separation. This can be
schematically presented in Fig.1.1.

Fig.1.1: Schematic of a separation process

Various Separation processes and Identification of novel separation processes

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SCH 1314 UNIT III

As discussed in the earlier chapter, the separation processes are divided in equilibrium and rate
governed separation process. In equilibrium governed separation processes, the product phases are in
equilibrium with the inlet phases. In rate governed separation processes, difference of rate of physical
transport of species brings the separation. Some of the specific separation processes under these two
categories are elaborated below.

Equilibrium governed processes

Four popular and quite common equilibrium governed separation processes are
described.

Distillation
Distillation is based on the differences in boiling points of the constituents in a mixture. The component
having the lower boiling point will go to the vapor phase earlier, leaving behind the other component
in the residual mixture. In this process, external heating is required to heat up the system. Therefore,
the top vapor phase is condensed and is rich in one component and the residual liquid phase is rich in
other component. This is known as flash distillation. In another process, a part of the condensed stream
from the top is recycled down the column. This is known as reflux. In this case, there is intimate mixing
of the liquid stream coming down and vapor going up. This operation is carried out in counter current
fashion and this enhances the efficiency of the process. This is generally used for separation of aqueous
mixture of various organic solvents, like, toluene, benzene, acetone, ethyl benzene, etc.

Absorption
In this process, a vapor in an inert gas is absorbed in a liquid stream. The vapor is soluble in the liquid.
The liquid stream rich in solubilized vapor components is separated by distillation or some other
suitable techniques. The liquid can be recovered and reused in the process itself. An example is removal
of ammonia from ammonia – water mixture using water as solvent. Removal of carbon di oxide from
a mixture of air and carbon dioxide using a solvent like primary or secondary or tertiary amines is
another example. Typically this operation is carried out in counter current manner to enhance the
efficiency of this process. Sometimes, the packed beds or staged beds like trays are used to have better
mixing during the transfer process. It may be mentioned that absorption is a bulk phenomena, i.e., the
gaseous solutes are transported to the bulk of the liquid stream. It may be noted that to effect separation,
a matter is introduced in the system.

Adsorption
Separation of solutes by transporting it from gaseous or liquid streams on a solid surface is known as
adsorption. As opposed to absorption it is a surface phenomenon. The solute is fixed on the solid
surface only. Typically, the solid surface is specific for a particular component present in the feed
stream. For example, in a liquid stream having organic as well as inorganic components, the organics
are preferentially adsorbed on the surface of activated carbon. Typically, in a bed, the adsorbent
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SCH 1314 UNIT III

particles are kept and the fluid is pumped through the system for intimate mixing. In the process, the
solute is transferred to the solid phase. After sometime, the solid phase is completely saturated and the
transfer of species becomes extremely slow due to lack of driving force. In such case, the bed has to
be replaced by new adsorbents or the bed has to be regenerated by a suitable washing protocol. It may
be noted, that a reasonably lower particle size of adsorbents provides sufficient surface area for
separation. Removal of organics from an aqueous mixture using activated carbon is an example of
adsorption. It may be noted that to effect separation, a matter is introduced in the system.

Drying
In drying, water vapours from a solid material are removed by using a vapor stream to an acceptable
small limit. Generally, it is carried out by applying thermal energy as compared to introduction of a
matter in case of absorption or adsorption. The process efficiency depends on the temperature, relative
humidity and other thermo physical properties of the drying vapor as well as the temperature and other
thermo-physical properties of the solid.

APPLICATIONS OF MATERIAL BALANCE

Material Balance around distillation column

Consider a steady-state distillation process,

Since the process is at steady-state condition and no chemical reaction is involved, the material
balance equation becomes
Input = Output
This balance equation can be applied to:
1. The total mass entering and leaving the process – Overall Balance
4
SCH 1314 UNIT III

2. Mass of individual component entering and leaving the process – Component Balance.
Total Mass (Overall Material Balance)
F=D+B
Component A Balance
mA1 = mA2 + mA3 FxAF =
DxAD + BxAB
Component B Balance
mB1 = mB2 + mB3 FxBF =
DxBD + BxBB

5
SCH 1314 UNIT III

Material Balance for Mixing Process

Material Balances (Steady-State, Non-Reactive Process): Total

Balance:
m1 + m 2 = m 3
Methanol-Balance:
m1xM1 + m2xM2 = m3xM3
Water-Balance:
m1xW1 + m2xW2 = m3xW3

Physical Constraint (applied to mixture 3):

xM3 + xW3 = 1.00

6
 7

Material Balance for Evaporation Process

Material Balances (Steady-State, Non-Reactive

Process): Total Balance:
F=V+L
Solute Balance:
FxsF = VysV + LxsL
Since ysV = 0, the above equation becomes
FxsF
= LxsL Solvent
(Water) Balance:
FxwF = VywV + LxwL

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SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – IV – PROCESS AND SEPARATION

IN CHEMICAL INDUSTRY – SCH 1314
 2

Unit 4

Heat capacity (C)

Heat capacity or thermal capacity is the measurable physical quantity that characterizes the amount

of heat required to change a body's temperature by a given amount. In the International System of

Units (SI), heat capacity is expressed in units of joules per kelvin.

Derived quantities that specify heat capacity as an intensive property, independent of the size of a

sample, are the molar heat capacity, which is the heat capacity per mole of a pure substance, and the

specific heat capacity, often simply called specific heat, which is the heat capacity per unit mass of

a material.

The units for the specific heat capacity are [C]= J/kg.K.

The units for molar heat capacity, [Cmol]= J/mol.K

Heat capacity per unit volume and has SI units

Heat of Reaction

The Heat of Reaction (also known and Enthalpy of Reaction) is the change in the enthalpy of a

chemical reaction that occurs at a constant pressure. It is a thermodynamic unit of measurement

useful for calculating the amount of energy per mole either released or produced in a reaction. Since

enthalpy is derived from pressure, volume, and internal energy, all of which are state functions,

enthalpy is also a state function.

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Introduction

ΔH, or the change in enthalpy arose as a unit of measurement meant to calculate the change in energy

of a system when it became too difficult to find the ΔU, or change in the internal energy of a system,

by simultaneously measure the amount of heat and work exchanged. Given a constant pressure, the

change in enthalpy can be measured as

ΔH=q

See section on enthalpy for a more detailed explanation.

The notation ΔHº or ΔHºrxn then arises to explain the precise temperature and pressure of the heat of

reaction ΔH. The standard enthalpy of reaction is symbolized by ΔHº or ΔHºrxn and can take on both

positive and negative values. The units for ΔHº are kilo Joules per mole, or kj/mol.

ΔH and ΔHºrxn

• Δ = represents the change in the enthalpy; (ΔH products -ΔH reactants)

o a positive value indicates the products have greater enthalpy, or that it is an endothermic

reaction (heat is required)

o a negative value indicates the reactants have greater enthalpy, or that it is an exothermic

reaction (heat is produced)

• º = signifies that the reaction is a standard enthalpy change, and occurs at a preset

pressure/temperature

• rxn = denotes that this change is the enthalpy of reaction

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The Standard State: The standard state of a solid or liquid is the pure substance at a pressure of 1 bar (

105 Pa) and at a relevant temperature.

The ΔHºrxn is the standard heat of reaction or standard enthalpy of a reaction, and like ΔH also

measures the enthalpy of a reaction. However, ΔHºrxn takes place under "standard" conditions,

meaning that the reaction takes place at 25º C and 1 atm. The benefit of a measuring ΔH under standard

conditions lies in the ability to relate one value of ΔHº to another, since they occur under the same

conditions.

• vp= stoichiometric coefficient of the product from the balanced reaction

• vr= stoichiometric coefficient of the reactants from the balanced reaction

• ΔHºf= standard enthalpy of formation for the reactants or the products

To calculate the standard enthalpy of reaction the standard enthalpy of formation must be utilized.

Another, more detailed, form of the standard enthalpy of reaction includes the use of the standard

enthalpy of formation ΔHºf:

ΔH⊖=∑ΔvpΔH⊖f(products)−∑ΔvrΔH⊖f(reactants)

with

• vp= stoichiometric coefficient of the product from the balanced reaction

• vr= stoichiometric coefficient of the reactants from the balanced reaction

• ΔHºf= standard enthalpy of formation for the reactants or the products

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Since enthalpy is a state function, the heat of reaction depends only on the final and initial states, not

on the path that the reaction takes. For example, the reaction A→BA→B goes through intermediate

steps (i.e. C→DC→D), but A and B remain intact.

Therefore, one can measure the enthalpy of reaction as the sum of the ΔH of the three reactions by

applying Hess' Law.

Heat Formation

One way to report the heat absorbed or released by chemical reactions would be to compile a massive

set of reference tables that list the enthalpy changes for all possible chemical reactions, which would

require an incredible amount of effort. Fortunately, Hess’s law allows us to calculate the enthalpy

change for virtually any conceivable chemical reaction using a relatively small set of tabulated data,

starting from the elemental forms of each atom at 25 oC and 1 atm pressure.

Enthalpy of formation (ΔHf) is the enthalpy change for the formation of 1 mol of a compound from its

component elements, such as the formation of carbon dioxide from carbon and oxygen. The

corresponding relationship is

elements→compound ΔHrxn=ΔHf

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For example, consider the combustion of carbon:

C(s)+O2(g)⟶CO2(g)

then

ΔHrxn=ΔHf[CO2(g)]

The sign convention for ΔHf is the same as for any enthalpy change: ΔHf<0ΔHf<0 if heat is released

when elements combine to form a compound and ΔHf>0ΔHf>0 if heat is absorbed.

Heat of Combustion

In efforts to reduce gas consumption from oil, ethanol is often added to regular gasoline. It has a high-

octane rating and burns more slowly than regular gas. This "gasohol" is widely used in many countries.

It produces somewhat lower carbon monoxide and carbon dioxide emissions, but does increase air

pollution from other materials.

Heat of Combustion

Many chemical reactions are combustion reactions. It is often important to know the energy produced

in such a reaction so we can determine which fuel might be the most efficient for a given purpose.

The molar heat of combustion (He) is the heat released when one mole of a substance is completely

burned.

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Typical combustion reactions involve the reaction of a carbon-containing material with oxygen to form

carbon dioxide and water as products. If methanol is burned in air, we have:

CH3OH+O2→CO2+2H2OHe=890kJ/mol

In this case, one mole of oxygen reacts with one mole of methanol to form one mole of carbon dioxide

and two moles of water.

It should be noted that inorganic substances can also undergo a form of combustion reaction:

2Mg+O2→2MgO

In this case there is no water and no carbon dioxide formed. These reactions are generally not what we

would be talking about when we discuss combustion reactions.

Heat of Mixing.

The enthalpy of mixing (or heat of mixing or excess enthalpy) is the enthalpy liberated or absorbed

from a substance upon mixing. When a substance or compound is combined with any other substance

or compound the enthalpy of mixing is the consequence of the new interactions between the two

substances or compounds. This enthalpy if released exothermically can in an extreme case cause an

explosion.

Enthalpy of mixing can often be ignored in calculations for mixtures where other heat terms exist, or

in cases where the mixture is ideal. The sign convention is the same as for enthalpy of reaction: when

the enthalpy of mixing is positive, mixing is endothermic while negative enthalpy of mixing

signifies exothermic mixing. In ideal mixtures the enthalpy of mixing is null. In non-ideal mixtures

the thermodynamic activity of each component is different from its concentration by multiplying with
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the activity coefficient.

Heat Exchangers

In any process industry, we need to transfer heat for different operations (like cooling, heating,
vaporizing, or condensing) to or from various fluid streams in various equipment like condensers,
water heaters, re-boilers, air heating or cooling devices etc., where heat exchanges between the two
fluids. In a chemical process industry, the heat exchanger is frequently used for such applications. A
heat exchanger is a device where two fluids streams come into thermal contact in order to transfer the
heat from hot fluid to cold fluid stream.

In this chapter, we will discuss about the technical analysis of the heat exchangers along with the
method for predicting heat exchanger performance and operational parameters. Moreover the
discussion on heat exchanger size will also be discussed. However, we will not discuss the economics
(though discuss the heat exchanger size) of the heat exchanger. We will consider that the heat transfer
will primarily be taken by conduction and convection only. We will describe the commonly used heat
exchangers and their important characteristics.

In general heat exchangers may be categorized into two general classes depending on the relative
orientation of the flow direction of the two fluid streams. If the two streams cross one another in space,
usually at right angles, the heat exchangers are known as cross flow heat exchanger as shown in the
fig.1(a).

In the second class of heat exchanger the two streams move in parallel direction in space. The usual
shell and tube heat exchanger or concentric pipe exchanger or double tube exchanger is the most
frequently used exchanger in the class. Two situations may arise when the fluid flow in the parallel
direction, one in which the fluids flow in same direction and the other in which the fluids flow in
opposites direction. “Parallel –flow” or “Co-current flow” is used when the flow is in same direction
and counter current is used when the fluid flow is in the opposite direction.

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Before understanding the principle of heat exchanger we would first understand it from the point of
construction.

Elements of shell and tube heat exchanger

We will discuss shell and tube heat exchanger as they or the most commonly used heat exchangers in
the chemical process industries. Schematic of a typical shell and tube heat exchanger is shown in
fig.2.

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Fig.1: Orientation of fluid stream in heat exchanger (a) cross flow (b) counter current flow (c)
parallel flow

The heat exchanger as shown in fig.2 consists of a bundle of tubes properly secured at either ends in
tube sheets. The tube sheets are drilled plates into which the tubes are fixed up using different technique
to have leak proof joints. The entire tube bundles shown in the fig.3 is placed inside a closed shell,
which seals around the tube sheet periphery to form the two immiscible zones for hot and cold fluids
are shown in fig.4.

Fig.2: A schematic of (a) one-shell pass, one tube pass heat exchanger; (b) parallel flow; and
(c) counter flow
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Fig.4: Tube bundle inside a shell

One fluid flows through the tubes while the other fluid flows around the outside of the tubes, it is the
space between the tube sheets and enclosed by the outer shell.

For a thorough distribution of the shell side fluid, baffles are placed normal to the tube bundle. This
baffle creates turbulence in the shell side fluid and enhances the transfer coefficients for the shell side
flow.

Fig.2 shows the simplified diagram of a shell and tube heat exchanger, showing a few of the important
components. Infact, the present heat exchanger used in the process industry are quite complex and
have improved design such as factors for thermal expansion stresses, tube fouling due to contaminated
fluids, ease of assembly and disassembly, size, weight, etc.

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The heat exchanger shows in fig.2 is having one shell and one tube pass since both the shell and tube
side fluid make a single traverse through the heat exchanger. Thus, this type of shell-and-tube heat
exchangers is designated as 1-1 exchanger. If we desire to pass the tube fluid twice, then it is designated
as 1-2 exchangers. Similarly, if there are 2 shell pass and 4 tube pass, the designation will be 2-4
exchanger. The number of pass in tube side is done by the pass partition plate. A pass particular plate
or pass divider as shown in fig.5. The shell side pass can be creator by a flat plate as shown in fig.6.

The three most common types of shell-and-tube exchangers are (1) fixed tubesheet design, (2) U-tube
design, and (3) floating-head type. In all three types, the front-end head is stationary while the rear-
end head can be either stationary or floating depending on the thermal stresses in the shell, tube, or
tubesheet, due to temperature differences as a result of heat transfer. The exchangers are built in
accordance with three mechanical standards that specify design, fabrication, and materials of unfired
shell-and-tube heat exchangers. Class R is for the generally severe requirements of petroleum and
related processing applications. Class C is for generally moderate requirements for commercial and
general process applications. Class B is for chemical process service. The exchangers are built to
comply with the applicable ASME Boiler and Pressure Vessel Code, Section VIII (1998), and other
pertinent codes and/or standards. The TEMA standards supplement and define the ASME code for
heat exchanger applications. In addition, state and local codes applicable to the plant location must
also be met. The TEMA standards specify the manufacturing tolerances for various mechanical classes,
the range of tube sizes and pitches, baffling and support plates, pressure classification, tubesheet
thickness formulas, and so on, and must be consulted for all these details. In this book, we consider
only the TEMA standards where appropriate, but there are other standards, such as DIN 28 008.
Tubular exchangers are widely used in industry for the following reasons. They are custom designed
for virtually any capacity and operating conditions, such as from high

CLASSIFICATION OF HEAT EXCHANGERS FIGURE

(a) Shell-and-tube exchanger (BEM) with one shell pass and one tube pass; (b) shell and-tube
exchanger (BEU) with one shell pass and two tube passes. vacuum to ultrahigh pressure [over 100
MPa (15,000 psig)], from cryogenics to high temperatures [about 11008C (20008F)] and any
temperature and pressure differences between the fluids, limited only by the materials of construction.
They can be designed for special operating conditions: vibration, heavy fouling, highly viscous fluids,

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erosion, corrosion, toxicity, radioactivity, multi-component mixtures, and so on. They are the most
versatile exchangers, made from a variety of metal and nonmetal materials (such as graphite, glass,
and Teflon) and range in size from small [0.1 m2 (1 ft2) to supergiant [over 105 m2 (106 ft2 )] surface
area. They are used extensively as process heat exchangers. in the petroleum-refining and chemical
industries; as steam generators, condensers, boiler feed water heaters, and oil coolers in power plants;
as condensers and evaporators in some air-conditioning and refrigeration applications; in waste heat

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recovery applications with heat recovery from liquids and condensing fluids; and in environmental

control

Fig 6: 2-4 exchanger showing shell and tube passes

It can be understood that for a given number of tubes; the area available for flow of the tube side fluid
is inversely proportional to the number of passes. Thus, on increasing the pass the area reduces and as
a result the velocity of fluid in the tube increases and henceforth the Reynolds number increases. It

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would result in increased heat transfer coefficient but at the expense of high pressure drop. Generally,
even numbers of tube passes are used for the multi-pass heat exchangers.

Figure 2 shows some baffles. These baffles (or shell-side baffles) are a metal plate usually in the form
of the segment of a circular disc having holes to accommodate tubes. Shell-side baffles have two
functions. The first is to create turbulence in the shell side fluid by changing the flow pattern parallel
or cross flow to the tube bundles and thus increases the shell side heat transfer coefficient. The second
major function of these baffles is to support the tube all along its length otherwise the tube may bend.
Moreover, these baffles may have horizontal or vertical cuts (segmental baffle) as shown in fig.7.

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Fig.7: Baffles; (a) horizontal cut baffles; (b) Vertical cut baffles; (c, d and e)the shaded region
show the baffle area

The cut portion of the baffle, which is called baffle window, provides the area for flow of the shell
fluid. The baffle window area ranges from 15% to 50%. At 25% cut segmental baffle means that the
area of the cut-out portion is 25% of the area of the baffle. The spacing between the baffles is an
important aspect. A larger baffles spacing reduces the shell side pressure drop but at the same time
decreases the turbulence and heat transfer coefficient. Smaller baffle spacing increases the turbulence
and heat transfer coefficient. However, the pressure drop may increase significantly, thus the advantage
attained due to the higher heat transfer coefficient may be nullified. Therefore baffle spacing is selected
considering the allowable shell side pressure drop and the heat transfer coefficient desired. A rule of
thumb is that the minimum spacing of segmental baffles is one by fifth of the shell diameter or 5 cm,
whichever is larger.

Evaporation

Evaporation is the vaporization of a liquid. Chemical process industries, in general, use evaporator for
the vaporization of a solvent from a solution. We have already discussed the heat transfer for boiling
liquids in early chapter. However, the evaporation is so important operation in chemical process
industry that it is considered an individual operation. In this chapter we will focus on the evaporation
with an objective to concentrate a solution consisting of a non-volatile solute and a volatile solvent. If

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we continue the evaporation process, the residual mater will be solid, which is known as drying.
However, our aim is not to dry but to concentrate the solution, moreover, we will also not deal with
the crystallization, in which the evaporation leads to formation of crystal in the solution. It is suggested
that reader should learn the difference between evaporator, drying and crystallization.

Types of evaporator
Natural circulation evaporator
In this category the main evaporators are,

1. Calandria type or short tube evaporator

2. Long tube vertical evaporator

As the name indicates, the circulation of the solution is natural and the density difference derives it.
The solution gets heat up and partially vaporized as it flows up the tubes. The heated liquid flows up
because of the density difference. Vapor-liquid disengagement occurs above the tube. Thick liquor
comes down from this down comer and withdrawn from the bottom. The natural-circulation
evaporators may be used if the solution is quite dilute. In the dilute solution the natural circulation will
be at sufficient speed. It may also be used when the solution does not have suspended solid particles.
As the solution stays in the tube for larger time, the solution should not be heat sensitive.

The Calandria type or short-tube evaporators have short tubes as compared to the long tube
evaporators. The short-tube evaporation uses circulation and solution flows many times in the
evaporators. However, in case of the long tube evaporator the flow is once through.

Forced circulation evaporator

Natural circulation evaporators have many limitations (as mentioned earlier) through they are
economical as compared to forced circulation evaporator. A forced circulation evaporator has a
tubular exchanger for heating the solution without boiling. The superheated solution flashes in the
chamber, where the solution gets concentrated. In forced circulation evaporator horizontal or vertical
both type of design is in- practice. The forced circulation evaporators are used for handling viscous
or heat sensitive solution.
Falling film evaporator
Highly heat sensitive materials are processed in falling film evaporators. They are generally once-
through evaporator, in which the liquid enters at the top, flows downstream inside the heater tubes as
a film and leaves from the bottom. The tubes are heated by condensing steam over the tube. As the
liquid flows down, the water evaporates and the liquid gets concentrated. To have a film inside of the
tube, the tube diameter is kept high whereas the height low to keep the residence time low for the
flowing liquid. Therefore, these evaporators, with non-circulation and short resistance time, handle
heat sensitive material, which are very difficult to process by other method. The main problem in
falling film evaporator is the distribution of the liquid uniformly as a thin film inside the tube.

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MAGESH.N SCH1314
 SCHOOL OF SCIENCE AND HUMANITIES
DEPARTMENT OF CHEMISTRY

UNIT – V – PROCESS AND SEPARATION

IN CHEMICAL INDUSTRY – SCH 1314

MAGESH.N SCH 1314

 2

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

• 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.

• Microfiltration (MF): This refers to membranes that have pore m. It is used

to diameters from 0.1 to 10 filter suspended particulates, bacteria or large colloids
from solution.

• Ultrafiltration (UF): This refers to membranes having pore diameters in the range
20-1000 A o . 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 5-20 A o in diameter, which are within the range of the thermal motion of
the polymer chains.

• Dialysis

Membrane modules:

The practical equipment where the actual membrane-based separation occurs is known as
membrane modules. The basic aim of development of these modules is to provide
maximum membrane area in relatively smaller volume, so that the permeate flux i.e., the
productivity of the system is maximum.
These membrane modules are of four types,
(i) plate and frame module,
(ii) hollow fiber module,
(iii) spiral wound and
(iv) tubular modules.

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Plate and frame modules

The heart of plate-frame module is the support plate that is sandwiched between two flat
sheet membranes. The membranes are sealed to the plate, either gaskets with locking
devices, glue or directly bonded. The plate is internally porous and provides a flow channel
for the permeate which is collected from a tube on the side of the plate. Ribs or grooves on
the face of the plate provide a feed side flow channel. The feed chanel can be a clear path
with chanel heights from 0.3 to 0.75 mm. The higher channel heights are necessary for high
viscosity feeds; reduction in power consumption of 20 to 40% can be achieved by using a
0.6 mm chanel compared to a 0.3 mm chanel. Alternatively, retentate separator screens (20
or 50 mesh polypropelyne) can be used. Commercial plate-frame units are usually
horizontal with the membrane plates mounted vertically. They can be run with each plate
in parallel plates in two or three series.

Tubular modules
In such modules, the membrane is cast on the inside surface of a porous tube. Tubular
membranes operate in tangential, or cross-flow, design where process fluid is pumped
along the membrane surface in a sweeping type action. The feed solution is pumped
through the center of the tube at velocities as high as 6 m/s. These cross-flow velocities
minimize the formation of a concentration polarization layer on the membrane surface,
promoting high and stable flux and easy cleaning, especially when the objective is to
achieve high suspended solids in the MF, UF or NF concentrate. Permeate is driven through
the membrane to be directed out of the system or back into the process depending on the
application. There are many advantages in tubular membrane configurations. Besides their
rugged construction, they have a distinct advantage of being able to process high suspended
solids, and concentrate product successfully and repeatedly to relatively high end point
concentration levels without plugging. A common objective of an end-of-pipe waste
treatment UF system is to reduce waste volume as much as possible to reduce concentrate
hauling costs. For juice clarification applications, tubular membrane systems produce the
greatest yields and the highest final suspended solids concentration levels. Tubular MF, UF
and NF systems do not require significant prefiltration. Some tubular products have the
ability to be mechanically cleaned with spongeballs. Spongeballs can be used in process,
and are also used to enhance chemical cleaning by reducing time and cleaning chemicals.
Tubular membranes are ideally suited to treatment of metalworking oily waste, wastewater
minimization and recovery from industrial processes, juice clarification, treatment of pulp
and paper industry waste, etc. Tubular membranes typically have life upto 2 to 10 years.

Hollow fiber module

In hollow fiber module, lots of hollow fibers (each fiber is a tubular module) are kept in a
large pipe. Geometry allows a high membrane surface area to be contained in a compact
module. This means large volumes can be filtered, while utilizing minimal space, with low
power consumption. Hollow fiber membranes can be designed for circulation, dead end
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and single pass operation. Some of the many hollow fiber membrane filtration applications
include, potable water treatment, juice clarification, wine filtration, dairy processing, etc.
The advantages of such modules include reduction in space requirement, lowering in labor
cost, lowering in chemical cost, delivery of high quality product water, etc. Hollow fiber
membranes offer the unique benefits of high membrane packing densities, sanitary designs
and, due to their structural integrity and construction, can withstand permeate back pressure
thus allowing flexibility in system design and operation. Most hollow fiber products are
available in (i) 1" diameter laboratory test cartridges ranging up to 10" diameter for
commercial products, (ii) Standard commercial cartridge lengths of 25", 43", 48", 60" and
72", (iii) Nominal separation ranges from 0.2 micron down to 1,000 MWCO, (iv) Fiber
inside diameters from 0.02"(.5mm) up to 0.106"(2.7mm), (v) Various materials of
construction including polysulfone and polyacrylonitrile. The following figure (Fig. 3.5c)
shows some hollow fiber cartridges of 5, 8 and 10” diameter with endcaps. Benefits of
hollow fiber membranes include (i) controlled flow hydraulics, (ii) tangential flow along
the membrane surface limits membrane fouling, (iii) membranes can be backflushed to
remove solids from the membrane inside surface, thus extending the time between two
chemical cleaning cycles, (iv) high membrane packing density resulting in high
throughput, (v) modular in structure so that future extension of the plant becomes easier.

Spiral wound module

In spiral wound membrane, membrane is cast as a film onto flat sheet. Membranes are
sandwiched together with feed spacers (typical thickness 0.03 to 0.1 inch) and permeate
carrier. They are sealed at each edge and wound up around a perforated tube. The module
diameter ranges from 2.5 to 18 inch and length varies from 30 to 60 inch.

Driving forces in membrane separation processes:

Separation in membrane is the result of differences in the transport rates of chemical
species through it. Transport rate is determined by the driving force acting on individual
components, their mobility, concentration of solute in membrane phase, etc.. Mobility :
Depending on solute size and structure of membrane. Concentration : Chemical
compatibility of solute & interface material.

Fouling of membrane:
Fouling of membrane is of two types reversible and irreversible.
Reversible fouling: It can be washed away by adopting an appropriate cleaning protocol,
like membrane washing. After cleaning, membrane permeability is restored. Concentration
polarization is reversible fouling.

Irreversible fouling: In this case, membrane pores are blocked permanently and they
cannot be removed, even after proper washing. Permeability is lost permanently.

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Fouling results in a continuous decline in membrane permeation rate, an increased rejection

of low molecular weight solutes and eventually blocking of flow channels. On start-up of
a process, a reduction in membrane permeation rate to 30–10 per cent of the pure water
permeation rate after a few minutes of operation is common for ultrafiltration. Such a rapid
decrease may be even more extreme for microfiltration. This is often followed by a more
gradual decrease throughout processing. Fouling is partly due to blocking or reduction in
effective diameter of membrane pores, and partly due to the formation of a slowly
thickening layer on the membrane surface.

The extent of membrane fouling depends on the nature of the membrane used and on the
properties of the process feed. The first means of control is therefore careful choice of
membrane type. Secondly, a module design which provides suitable hydrodynamic
conditions for the particular application should be chosen. Process feed pretreatment is also
important. The type of pretreatment used in reverse osmosis for desalination applications .
In biotechnological applications pretreatment might include prefiltration, pasteurisation to
destroy bacteria, or adjustment of pH or ionic strength to prevent protein precipitation.
When membrane fouling has occurred, backflushing of the membrane may substantially
restore the permeation rate. This is seldom totally effective however, so that chemical
cleaning is eventually required. This involves interruption of the separation process, and
consequently time losses due to the extensive nature of cleaning required. Thus, a typical
cleaning procedure might involve: flushing with filtered water at 35–50 .C to displace
residual retentate; recirculation or back-flushing with a cleaning agent, possibly at elevated
temperature; rinsing with water to remove the cleaning agent; sterilisation by recirculation
of a solution of 50–100 ppm of chlorine for 10–30 minutes (600–1800s) at (293–303 K)
(20–30 .C); and flushing with water to remove sterilising solution. More recent approaches
to the control of membrane fouling include the use of more sophisticated hydrodynamic
control effected by pulsated feed flows or non-planar membrane surfaces, and the
application of further perturbations at the membrane surface, such as continuous or
pulsated electric fields.

What is membrane?
A membrane may be defined as “an interphase separating two phases and
selectively controlling the transport of materials between those phases”. A membrane is an
interphase rather than an interface because it occupies a finite, though normally small,
element of space.
What is mean by membrane separation?
The use of thin barriers (membranes) between miscible fluids for separating a
mixture; a suitable driving force across the membrane, for example concentration or
pressure differential, leads to preferential transport of one or more feed components.

Separations of liquids and gases are commonly accomplished using membrane

separation methods which include dialysis, reverse osmosis, and ultrafiltration Hybrid and

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more exotic membrane methods that have also proven effective are electrodialysis,
helium separation through glass, hydrogen separation through Palladium and alloy
membranes, immobilized solvent and liquid-surfactant membranes.

Permeation of liquids and gases through polymeric membranes occurs where a

constituent passes through the membrane by diffusion and sorption by the fluid on the other
side of the membrane. The driving force is achieve either by pressure or concentration
difference across the membrane.
Membranes modules can be configured in three ways

1. single stage feed and bleed

2. multistage feed and bleed

3. continuous single pass as shown in figures

Principle of Operation
When a solution and water are separated by a semi-permeable membrane, the water
will move into the solution to equilibrate the system. This is known as osmotic pressure If
a mechanical force is applied to exceed the osmotic pressure (up to 700 psi), the water is
forced to move down the concentration gradient i.e. from low to high concentration.
Permeate designates the liquid passing through the membrane, and retentate (concentrate)
designates the fraction not passing through the membrane.

Advantage of membrane over other process

• A higher overall liquid removal rate is achieved by prevention of the

formation of an extensive filter cake.
• The process feed remains in the form of mobile slurry suitable
for further processing.
• The solids content of the product slurry may be varied over a wide range.
• It may be possible to fractionate particles of different sizes.
Limitation of membrane processes
The specification and the characteristics of the feed is important in membrane
process, cleaning of membranes at regular interval is necessary, concentration polarization,
membrane fouling are the two usual phenomena in membranes

Example for membrane separation process

Some of the membrane processes are dialysis, reverse osmosis, ultrafiltration, and
electrodialysis.

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Membrane materials for various application

Initially most of the membranes were cellulosic in nature. These are now being
replaced by polyamide, polysulphone, polycarbonate and a number of other advanced
polymers. These synthetic polymers have improved chemical stability and better resistance
to microbial degradation. Membranes have most commonly been produced by a form of
phase inversion known as immersion precipitation.
Uses of membrane separation
In general, membrane separation techniques are especially useful in separating:

• Mixtures of similar chemical compounds,

• Mixtures of thermally unstable components (since no heating is needed), and In
conjunction with conventional separation methods (such as using membranes to
break azeotropic mixtures before feeding them)
• proteins can be separated in whey for the production of whey protein concentrate
(WPC)
• milk can be concentrated prior to cheese making at the farm level apple juice and
wine can be clarified.

• waste treatment and product recovery is possible in edible oil, fat, potato, and fish
processing

• fermentation broths can be clarified and separated

• whole egg and egg white ultrafiltration as a pre concentration prior to spray

Distinguish between osmosis & reverse osmosis

When two solutions of differing concentrations of dissolved materials are separated
by a semi-permeable membrane, the liquid component will tend to flow from the lower to
the more highly concentrated side. In a sense, the concentration difference will tend to
equilibrate across the membrane. This process is called osmosis.

If the liquid on the more concentrated side is maintained at a higher pressure,

however, this process can be reversed: the solvent will flow from the concentrated side to
the less concentrated side. Since the membrane blocks the passage of the dissolved waste
constituents, the concentrated solution becomes even more concentrated. This process is
called reverse osmosis.
What is ultra-filtration?

Ultrafiltration (UF) is a membrane separation process, driven by a pressure

gradient, in which the membrane fractionates components of a liquid as a function of their
solvated size and structure.

MAGESH.N SCH1314
Electro dialysis
A ionic mobility under the influence of an electric field through the anionic
and cationic membranes is known as electrodialysis. Charged ions can be removed from a
solution by synthetic polymer membranes containing ion exchange groups. Anion
exchange membranes carry cationic groups which repel cations and are permeable to
anions, and cation exchange membranes contain anionic groups and are permeable only to
cations. Electrodialysis membranes are comprised of polymer chains - styrene-divinyl
benzene made anionic with quaternary ammonium groups and made cationic with
sulphonic groups. 1-2V is then applied across each pair of membranes. Some applications
are

• Cheese whey demineralization

• Brackish water desalination

• Nitrate removal for drinking water

• Food/sugar products desalting

• Tartaric wine stabilization

• NaCl removal from amino acid salts

• Acid removal from organic product

• Conversion of organic salts into acid and base

• Desalting of amines.

• De-acidification of fruit juices

• Metals removal from ethylene glycol

Ion exchange.
The ion exchange is the exchange of equivalent numbers of similarly charged ions,
between an immobile phase, which may be a crystal lattice or a gel, and a liquid
surrounding the immobile phase. If the exchanging ions are positively charged, the ion
exchanger is termed cationic,and anionic if they are negatively charged. The rate at which
ions diffuse between an exchanger and the liquid is determined, not only by the
concentration differences in the two phases, but also by the necessity to maintain
electroneutrality in both phases.
 Ion exchange is not a membrane process but it is used for product of protein isolates
of higher concentration than obtainable by membrane concentration. Fractionation may
also be accomplished using ion exchange processing. It relies on inert resins (cellulose or
silica based) that can adsorb charged particles at either end of the pH scale. The design can
be a batch type, stirred tank or continuous column. The column is more suitable for
selective fractionation. Whey protein isolate (WPI), with a 95% protein content, can be
produced by this method. Following adsorption and draining of the deproteined whey, the
pH or charge properties are altered and proteins are eluted. Protein is recovered from the
dilute stream through UF and drying. Selective resins may be used for fractionated protein
products or enriched in fraction allow tailoring of ingredients.

Application examples of ion exchange membrane

* Production of High Purity Chemicals

* Production of Ultra Pure Water

* Battery Diaphragm

* Recovered developing solution.

* Food and pharmaceutical

* Demineralization of Cheese Whey

* Demineralization of Organic Acids and Amino Acids

* Desalination of Soy-Sauce

* Stabilization of Wine

* Demineralization, Deacidification of Fruit Juice

* Demineralization of Natural Extract

Environmental conservation
* Desalination of Leachate

* Removal of Nitrate from Under-Ground Water

 Others
* Production of Salt from Sea water

* Production of Drinking Water from Brackish Water

* Desalination of Deep Sea Water

* Acid Recovery from Waste Acid

* Recovery of Valuable Metals

* Recovery of Acid from Pickling Waste

Principles of ion exchange

The ion-exchange solids first used were porous, natural or synthetic minerals
containing silica, the zeolites, such as the mineral Na20.AI20s.4Si02.2H20, for example.
Positively charged ions (cations) of a solution which are capable of diffusing through 'the
pores will exchange with the Na+ ions of such a mineral, and the latter is therefore called
a cation exchanger. For example,

Ca++ + Na2R → CaR + 2Na+

where R represents the residual material of the zeolite. In this manner "hard" water
containing Ca++ may be softened by contact with the zeolite, the less objectionable Na+
replacing the C++ in solution and the latter becoming immobilized in the solid. The reaction
is reversible, and after saturation with Ca++ the zeolite may be regenerated by contact with
a solution of salt,
CaR + 2NaCl → Na2R + CaCl2

Later certain carbonaceous cation exchangers were manufactured by treating substances

such as coal with reagents such as fuming sulfuric acid, and the like. The resulting
exchangers can be regenerated to a hydrogen form, HR, by treatment with acid rather than
salt. Thus, hard water containing Ca(HCO3)2 would contain H2COs after removal ofthe Ca++
by exchange, and since the carbonic acid is readily removed by degasification procedures,
the total solids content of the water may be reduced in this manner. Early applications of
ion exchangers using these principles were largely limited to water- softening problems.

synthetic, insoluble polymeric resins containing sulfonic, carboxylic, .or phenolic groups
can be considered as consisting of an exceedingly large anion and a replaceable or
exchangeable cation. These make exchanges of the following type possible,

Na+ + HR ↔NaR + H+
and different cations will exchange with the resin with different relative ease. The Na+
immobilized in the resin may be exchanged with other cations or with H+, for example,
much as one solute may replace another adsorbed upon a conventional adsorbent. Similarly
synthetic, insoluble polymeric resins containing amine groups and anions may be used to
exchange anions in solution. The mechanism of this action is evidently not so simple as in
the case of the cation exchangers, but for present purposes it may be considered simply as
an ion exchange. For example,

RNH3OH + Cl- ↔ RNH3CI + OH-

H+ + OH- → H20

where RNH3 represents the immobile cationic portion of the resin. Such resins may be
regenerated by contact with solutions of sodium carbonate or hydroxide. The synthetic
ion-exchange resins are available in a variety of formulations of different exchange
abilities, usually in the form of fine, granular solids or beads, ]6 to 325 mesh. The
individual beads are frequently nearly perfect spheres.
Ion exchange resins
Ion-exchange operations are essentially chemical reactions between an electrolyte
in solution and an insoluble electrolyte with which the solution is contacted. The
mechanisms of these reactions and the techniques used to bring them about resemble those
of adsorption so closely that for most engineering purposes ion exchange may be simply
considered as a special case of adsorption.

There are two general types of ion exchange resins: those that exchange positive
ions, called cation resins, and those that exchange negative ions, called anion resins. A
cation is an ion with a positive charge. Common cations include Ca , Mg , Fe, and H . A
cation resin is one that exchanges positive ions. An anion is an ion with a negative charge.
Common anions include Cl , SO , and OH . An anion resin is one that exchanges negative
ions. Chemically, both types are similar and belong to a group of compounds called
polymers, which are extremely large molecules that are formed by the combination of many
molecules of one or two compounds in a repeating structure that produces long chains. A
mixed-bed demineralizer is a vessel, usually with a volume of several cubic feet, that
contains the resin. Physically, ion exchange resins are formed in the shape of very small
beads, called resin beads, with an average diameter of about 0.005 millimeters. Wet resin
has the appearance of damp, transparent, amber sand and is insoluble in water, acids, and
bases. Retention elements or other suitable devices in the top and bottom have openings
smaller than the diameter of the resin beads. The resin itself is a uniform mixture of cation
and anion resins in a specific volume ratio depending on their specific gravities. The ratio
is normally 2 parts cation resin to 3 parts anion resin. In some cases, there may be chemical
bonds formed between individual chain molecules at various points along the chain.

Such polymers are said to be cross-linked. This type of polymer constitutes the
basic structure of ion exchange resins. In particular, cross-linked polystyrene is the polymer
commonly used in ion exchange resins. However, chemical treatment of polystyrene is
required to give it ion exchange capability, and this treatment varies depending on whether
the final product is to be an anion resin or a cation resin. All of the resin, except the
exchangeable ion, is inert in the exchange process.

Osmosis And Reverse Osmosis

When two solutions of differing concentrations of dissolved materials are
separated by a semi-permeable membrane, the liquid component will tend to flow from
the lower to the more highly concentrated side. In a sense, the concentration difference
will tend to equilibrate across the membrane. This process is called osmosis.

If the liquid on the more concentrated side is maintained at a higher pressure,

however, this process can be reversed: the solvent will flow from the concentrated side to
the less concentrated side. Since the membrane blocks the passage of the dissolved waste
constituents, the concentrated solution becomes even more concentrated. This process is
called reverse osmosis.
 Reverse osmosis (RO) designates a membrane separation process, driven by a
pressure gradient, in which the membrane separates the solvent (generally water) from
other components of a solution. The membrane configuration is usually cross-flow. With
reverse osmosis, the membrane pore size is very small allowing only small amounts of
very low molecular weight solutes to pass through the membranes. It is a concentration
process using a 100 MW cutoff, 700 psig, temperatures less than 40°C with cellulose
acetate membranes and 70-80°C with composite membranes.

Reverse osmosis is often used to remove dissolved organics and metals where
concentrations are less than 300 parts per million. However, special care and testing must
be performed to assure that the wastes don't dissolve or clog the membrane. Low solubility
salts are also prone to precipitate on the membrane surface.
Electrodialysis
Ions in aqueous solution can be separated using a direct current electrical driving
force on an ion-selective membrane. Electrodialysis usually uses many thin compartments
of solution separated by membranes that permit passage of either positive ions (cations) or
negative ions (anions) and block passage of the oppositely charged ion.

Cation-exchange membranes are alternatively stacked with anion-exchange

membranes placed between two electrodes. The solution to be treated is circulated through
the compartments and a direct current power source is applied. All cations gravitate toward
the cathode (negatively terminal) and transfer through one membrane,

while anions move in the opposite direction, thereby concentrating in alternative

compartments.

Electrodialysis is commonly used to recover spent acid and metal salts from plating
rinse. It obviously is not effective for non-polar solutions. Electrodialysis is used for
demineralization of milk products and whey for infant formula and special dietary
products. Also used for desalination of water.

Principles of operation:
Under the influence of an electric field, ions move in an aqueous solution. The
ionic mobility is directly proportioned to specific conductivity and inversely proportioned
to number of molecules in solution. ~3-6 x 102 mm/sec.Charged ions can be removed from
a solution by synthetic polymer membranes containing ion exchange groups. Anion
exchange membranes carry cationic groups which repel cations and are permeable to
anions, and cation exchange membranes contain anionic groups and are permeable only to
cations.Electrodialysis membranes are comprised of polymer chains - styrene-divinyl
benzene made anionic with quaternary ammonium groups and made cationic with
sulphonic groups. 1-2V is then applied across each pair of membranes.
Electrodialysis process:
Anion and cation exchange membranes are arranged alternately in parallel between
an anode and a cathode (see schematic diagram). The distance between the membranes is
1mm or less.
APPLICATIONS OF ELECTRODIALYSIS:

• Cheese whey demineralization

• Brackish water desalination
• Nitrate removal for drinking water
• Food/sugar products desalting
• Tartaric wine stabilization
• NaCl removal from amino acid salts
• Acid removal from organic product
• Conversion of organic salts into acid and base (bipolar membrane ED)
• Desalting of amines.
• De-acidification of fruit juices
• Metals removal from ethylene glycol
Categories of membrane separation
Membrane separation processes are classified under different categories depending on the materials
to be separated and the driving force applied:

(1) In ultrafiltration, liquids and low-molecular-weight dissolved species pass through porous
membranes while colloidal particles and macromolecules are rejected. The driving force is a pressure
difference.

(2) In dialysis, low-molecular-weight solutes and ions pass through while colloidal particles and
solutes with molecular weights greater than 1000 are rejected under the conditions of a concentration
difference across the membrane.

(3) In electrodialysis, ions pass through the membrane in preference to all other species, due to
a voltage difference.

(4) In reverse osmosis, virtually all dissolved and suspended materials are rejected and the
permeate is a liquid, typically water.

(5) For gas and liquid separations, unequal rates of transport can be obtained through nonporous
membranes by means of a solution and diffusion mechanism. Pervaporation is a special case of this
separation where the feed is in the liquid phase while the permeate, typically drawn under
subatmospheric conditions, is in the vapor phase.

(6) In facilitated transport, separation is achieved by reversible chemical reaction in the

membrane. High selectivity and permeation rate may be obtained because of the reaction scheme.
Liquid membranes are used for this type of separation.

Ultrafiltration
Suspended materials and macromolecules can be separated from a waste stream using a
membrane and pressure differential, called Ultrafiltration. This method uses a lower pressure
differential than reverse osmosis and doesn't rely on overcoming osmotic effects. It is useful for
dilute solutions of large polymerized macromolecules where the separation is roughly proportional
to the pore size in the membrane selected. Ultrafiltration membranes are commercially fabricated in
sheet, capillary and tubular forms. The liquid to be filtered is forced into the assemblage and dilute
permeate passes perpendicularly
through the membrane while concentrate passes out the end of the media. This may prove useful
for the recovery and recycle of suspended solids and macromolecules.

Ultrafiltration (UF) designates a membrane separation process, driven by a pressure gradient, in

which the membrane fractionates components of a liquid as a function of their solvated size and
structure. The membrane configuration is usually cross-flow. In UF, the membrane pore size is larger
allowing some components to pass through the pores with the water. It is a separation/ fractionation

MAGESH.N SCH 1314

 16

process using a 10,000 MW cutoff, 40 psig, and temperatures of 50-60°C with polysulfone
membranes. In UF milk, lactose and minerals pass in a 50% separation ratio; for example, in the
retentate would be 100% of fat, 100% of protein, 50% of lactose, and 50% of free minerals.

Excellent results have been achieved in textile finishing applications and other situations where
neither entrained solids that could clog the filter nor dissolved ions that would pass through are
present. Membrane life can also be affected by temperature, pH, and fouling.

Microfiltration (MF) designates a membrane separation process similar to UF but with even larger
membrane pore size allowing particles in the range of 0.2 to 2 micrometers to pass through. The
pressure used is generally lower than that of UF process. The membrane configuration is usually
cross-flow. MF is used in the dairy industry for making low-heat sterile milk as proteins may pass
through but bacteria do not. Please click above link for a schematic diagram of these membrane
processes.
Uses of membrane separation
The use of thin barriers (membranes) between miscible fluids for separating a mixture; a
suitable driving force across the membrane, for example concentration or pressure differential, leads
to preferential transport of one or more feed components.

Separations of liquids and gases are commonly accomplished using membrane separation
methods which include dialysis, reverse osmosis, and ultrafiltration Hybrid and more exotic
membrane methods that have also proven effective are electrodialysis, helium separation through
glass, hydrogen separation through Palladium and alloy membranes, immobilized solvent and liquid-
surfactant membranes. Permeation of liquids and gases through polymeric membranes occurs
where a constituent passes through the membrane by diffusion and sorption by the fluid on the
other side of the membrane. The driving force is achieve either by pressure or concentration
difference across the membrane.

In general, membrane separation techniques are especially useful in separating:

• Mixtures of similar chemical compounds,

• Mixtures of thermally unstable components (since no heating is needed), and In conjunction
with conventional separation methods (such as using membranes to break azeotropic
mixtures before feeding them)
• proteins can be separated in whey for the production of whey protein concentrate (WPC)
• milk can be concentrated prior to cheese making at the farm

• waste treatment and product recovery is possible in edible oil, fat, potato.

MAGESH.N SCH1314
 17

MAGESH.N SCH1314