UNIT-I-REVIEW OF CONVENATIONAL SEPARATION PROCESSES

OVERVIEW OF CHEMICAL ENGINEERING SEPARATION PROCESSES:

The traditional concept of unit operations has been a major factor in the phenomenal success
of chemical engineers and chemical engineering in last fifty years or so. Unit operations is
concerned with those separation processes that depend upon the differences in the physical
properties, rather than chemical behavior. Such processes depend either upon a difference in
composition of phases at equilibrium or upon a difference in the rate of mass transfer of
constituents of mixture. A typical process, which a chemical engineer might work with, is
production of gasoline from crude oil.

Process = Sequence of “ unit operations” (physical changes) + Chemical reactors.

In this process chemical engineers realized that the many process involved the same physical
and chemical operations. Examples of this include: filtration, drying, distillation, crystallization,
grinding, sedimentation, combustion, catalysis, heat exchange, extrusion, coating, and so on.
These "Unit Operations" repeatedly find their way into industrial chemical practice, and became
a convenient manner of organizing chemical engineering knowledge.

Unit Operations

• Separations • Distillation
• Mixing • Leaching
• Heating/cooling • Extraction
• Pumps • Absorption/Stripping
• Drying • Membrane Separations
• Humidification • Mechanical Separations
• Crystallization
• Adsorption in fixed-bed separations
Examples for early separation techniques:

 Salt by evaporating seawater,

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 Metals extracted from ores,

 Perfumes extracted from plants,

 Various drinks, medicines extracted from plants,

 Liquors distilled form plants.

Critical separations in human body

 Separation of oxygen from air and of CO2 from blood in the lungs.

 Selective removal of water and waste products of metabolism from blood in the kidneys.

 Selective absorption of nutrients in the intestines.

In chemical industry, separation techniques are mainly used for:

 Isolating and manufacturing valuable chemicals from mixtures,

 Removing impurities from raw materials,

 Purification of products,

 Removal of contaminants and valuable constituents from effluent streams

(Environmental Protection).

MECHANISM OF SEPARATION:

Mixing: spontaneous, natural process accompanied by increase in entropy and

randomness. Second Law of Thermodynamics states that all natural processes take place so as to
increase the entropy or randomness of the universe.

Separation: Reverse of mixing, demixing. Equivalent of thermodynamic work has to

supplied to cause the separation to occur.

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Separation process is the technology of unmixing and isolating the wanted product or
products economically, feasibly and without harming the environment. To accomplish a
separation there are usually several competing techniques available.

Each technique has to be analyzed in terms of:

 Economic conditions

 Customer requirements

 Applicable official regulations

In order to affect a separation, separating agents are needed in the form of either:

 Energy input (heat, pressure, electricity, magnetism, kinetic or potential energy).

 Withdrawal of energy (cooling, freezing).

 Matter (filter, membrane, chemicals).

A separation process is an operation carried out in a special separation device, which

transforms a mixture into at least two product streams, which are different in composition. In the
separation device, separation takes place due to an imposed gradient such as temperature,
concentration, pressure or electrical field.

Two important elements of separation are:

1. Separating agent used (heat, pressure, solvent, matter such as resins, filters, adsorbents
etc.).

2. Principle of separation used, separation gradient applied (temperature, concentration,

chemical potential, magnetic field etc.).

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SELECTION OF SEPARATION PROCESSES:

Basic Principle:

Examine physical properties and exploit differences in physical properties between

components being separated.

General Rules of Thumb for Selection of Separation Processes:

a) Consider processes that exploit vapor-liquid equilibrium first (e.g., distillation) since these
processes tend to be energy efficient and simple to design, build, and operate. Difference in
boiling points between components being separated usually gives a good indication of the
feasibility:

 A boiling point difference (TBoiling) of greater than 100°C usually indicates a single stage
process is feasible.

 A boiling point difference between 10 and 100°C usually indicates that a multistage
distillation process is feasible.

 A boiling point difference less than 10°C usually means distillation is unlikely to work
since a very large number of stages is required.

In general, a boiling point difference of 10°C corresponds to a relative volatility of 1.2

between components. In close cases, estimate the relative volatility and use it as a criterion since
a relative volatility greater than 1.2 is usually needed for multistage distillation to be successful.

b) Don't use distillation if:

 Boiling points are high (e.g., greater than 200°C).

 Components decompose when heated.

 Boiling point difference is less than 10°C (see above).

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c) If vapor-liquid equilibrium processes are not promising, consider liquid-liquid extraction next.
Solubility in various solvents are the key physical property.

 For physically interacting solvents (e.g., no hydrogen bonding) the "cohesive energy
density" (which is also related to the solubility parameter in regular solution theory) is the
key property. Try to select a solvent so that the solubility parameter of the solvent is
within 3 (cal/cm3)2 of the solubility parameter of one of the components to be separated
and more than 3 units from the other component.

 For chemically interacting solvents, try to exploit hydrogen bonding, acid-base

interactions, or other "specific" chemical interactions.

d) Consider membrane processes next. A key consideration is whether an appropriate membrane

material exists.

e) Consider adsorption processes next.

f) Other Considerations:

 Favor processes that remove a minor component from a major component.

 Adsorption processes become favorable as the solute concentration becomes very small
since the fact these processes are batch process becomes less of a disadvantage under
these conditions. This is because an adsorption bed can be left on stream for long time
between regeneration cycles when the solute concentration is dilute.

Selection of Feasible Separation Process:

The selection of a best separation process must be frequently made from among a number
of feasible candidates. When the feed mixture is to be separated into more than two products, or
a combination of two or more operations may be best. Even when only two products are to be
produced, a hybrid process of two or more operations may be most economical. The important
factors in the selection of feasible separation operations are listed in Table. These factors have to
do with feed and product conditions, property differences.

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FACTORS THAT INFLUENCES THE SELECTION OF FEASIBLE SEPARATION

OPERATIONS:

A. Feed Conditions:

1. Composition, particularly concentration of species to be recovered or separated

2. Flow rate
3. Temperature
4. Pressure
5. Phase state (Solid, liquid, and/or gas)
B. Product Conditions:

1. Required purities of products

2. Temperature
3. Pressure
4. Phase States
C. Property differences that may be exploited:

1. Molecular
2. Thermodynamic

3. Transport
D. Characteristics of separation operation:

1. Ease of scale-up
2. Ease of staging
3. Temperature, pressure, and phase-state requirements
4. Physical size requirements
5. Energy requirements

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PROCEDURE FOR SEPARATION PROCESS SELECTION:

1. Lay out the nature of the separation task; listing feed rate and its composition and
different product streams required and their purities.

2. Apply first guides for deciding on alternative separation techniques taking into account
various factors regarding physical, chemical properties of the feed components, and the
production rate of the process.

3. Compare economic analyses for alternative procedures that use the selected separation
techniques.

3. Evaluate possible column/unit sequences and determine the best flow sheet based on the
lowest overall capital plus operating costs.

CLASSIFICATION OF SEPARATION PROCESSES:

Several ways to classify separation processes:

1. Mechanical (heterogeneous-feed) Vs. Diffusional (homogeneous-feed) techniques.

2. Equilibration processes vs. rate-governed techniques.

3. Energy-separating agent vs. mass separating agent techniques.

CLASSES OF SEPARATION OPERATIONS:

1. Equilibration processes: Equilibration of two immiscible phases, which have

different compositions at equilibrium.

2. Rate governed processes: Differences in transport rate through some medium under
the influence of an imposed force, resulting from a gradient in pressure, temperature,
composition, electric potential, or the like.

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3. Mechanical processes: Heterogeneous feed consisting of more than one phase of

matter. These simply serve to separate phases from each other.

SOLVENT SELECTION:

The solvent is the key to a successful separation by liquid-liquid extraction. The several
criteria are:

1. Distribution Coefficient

This is the ratio (at equilibrium) of the concentration of solute in the extract and raffinate
phases. It gives a measure of the affinity of the solute for the two phases.

A distribution coefficient other than unity implies that the solute must have different
affinity in the two phases. If only one solute is involved (such as in the recovery of an impurity
from an effluent stream), only the distribution coefficient need be considered, and it is desirable
for this to be as large as possible.

2. Selectivity (Separation Factor)

If there are more than one solutes (say two solutes A and B), then consideration should be
given to the selectivity of the solvent for solute A as against B. The selectivity between the 2
solutes A and B is defined as the ratio of the distribution coefficient of A to the distribution
coefficient of B. For all useful extraction operation the selectivity must exceed unity. If the
selectivity is unity, no separation is possible.

3. Insolubility of Solvent

The solvent should have low solubility in the feed solution, otherwise the separation is
not "clean". For example, if there is significant solubility of solvent in the raffinate stream, an
additional separation step is required to recover the solvent.

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4. Recoverability

It is always necessary to recover the solvent for re-use, and this must ordinarily be done
by other means, eg. distillation. If distillation is to be used, the solvent should form no azeotrope
with the extracted solute and mixtures should show high relative volatility. The solvent should
also be thermally-stable under the distillation temperature.

5. Density

A large difference in density between extract and raffinate phases permits high capacities
in equipment. This is especially important for extraction devices utilizing gravity for phase
separation.

6. Interfacial Tension

The larger the interfacial tension, the more readily coalescence of emulsions will occur
but the more difficult the dispersion of one liquid in the other will be. The more readily coalesces
the emulsions the easier phase separation will be. Low interfacial tension aids dispersion and
thus improves contacting mass-transfer efficiency. Coalescence is usually of greater importance,
and interfacial tension should therefore be high.

7. Chemical Reactivity

The solvent should be stable chemically and inert toward the other components of the
system and toward the common materials of construction.

8. Viscosity, Vapour Pressure, Freezing Point

These should be low for ease in handling and storage, for example, a high viscosity leads
to difficulties with pumping , dispersion and mass-transfer rate.

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9. Availability and Cost

An excellent solvent may not be commercially available. Or it may represent a large

initial cost for charging the system, and a heavy continuing expense for replacing inevitable
operating losses.

10. Other Criteria

Toxicity and flammability of the solvent are important occupational health and safety
considerations. Stability of the solvent (i.e. resistance to breakdown), particularly in the recovery
steps, is significant, especially if the breakdown products might contaminate the products of the
main separation. Corrosivity of the solvent leads to the usual problems with materials of
construction. Finally, compatibility of the solvent with the mixture to be separated can have
many manifestations, particularly when easily contaminated materials such as food or
pharmaceuticals are being handled.

Note: The solvent may not always be a single chemical species. For example, the most
appropriate liquid may not have suitable physical properties for direct use as solvent. In such
cases it can be used dissolved in another suitable liquid. The active component of the mixture is
then known as the extractant and the liquid in which it is dissolved as the diluent. The solvent
comprises the two together.

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