CEN 314 Separation Processes

2021-2022 Summer
Assoc.Prof.Dr. Suna ERTUNÇ

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Instructor: Doç.Dr. Suna ERTUNÇ Course Layout
Date & Time Monday 09.00-13.45 (AOD), Wednesday 13.30-18.15 (AOD)
Teaching Assistant: - Week Subject
Credit: (4 0) 4 Introduction to Separation Processes
ECTS: 5
Distillation: Phase balance and vapor-liquid equilibrium
Type : Compulsory 1
Enthalpy-concentration diagrams, Equilibrium plate operations
Prerequisites: --- (CEN2205, CEN2202, CEN3311 and CEN3313 must have
Simple batch distillation (differential), Single-stage continuous distillation (flash)
been taken)
Multi-stage continuous distillation: McCabe-Thiele method
Sources/Required Textbooks
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Multi-stage continuous distillation: McCabe-Thiele method-cont.
1. Geankoplis, C.J., 2009.Transport Processes and Separation Process Principles, 4th ed., Prentice- Midterm Exam (1-7 August 2022)
Hall.
2. Treybal, R.E., 1980. Mass-Transfer Operations, 3rd ed., Mc Graw-Hill Kogakusha Ltd., Tokyo. 3 Multi-stage continuous distillation: Ponchon-Savarit method
3. Coulson, J.M., Richardson, J.F., Backhurst J.R., 1996. Chemical Engineering: Particle Technology Multi-stage continuous distillation: Ponchon-Savarit method-cont.
and Separation, Vol 4, Butterworth & Heinemann. Liquid-liquid extraction: Liquid-liquid equilibrium, batch and continuous contact
4. Hines, A.L., Maddox, R.N., 1995. Mass Transfer, Fundamentals and Applications, Prentice-Hall Inc.,
4 devices
New Jersey.
Batch/continuous, single/multi-stage counter current extraction
5. Cussler, E.L., 1997. Diffusion: Mass Transfer in Fluid Systems, 2nd ed., Cambridge University Press.
6. Uysal, B.Z., 2003. Kütle Transferi Esasları ve Uygulamaları, 2. Baskı, Gazi Üniversitesi, Ankara. Solid-liquid extraction: Solid-liquid equilibrium, Intermittent and continuous
7. Alpay E., 2011. Mass Transfer and Mass Transfer Operations, Ege Üniversitesi Yayınları No:50, 5 contact solid-liquid extraction
İzmir. Batch/continuous, single/multi-stage counter current solid-liquid extraction
8. Foust, A. S., Wenzel, L. A., Clump, C. W., Maus, L., Andersen, L. B., 1980. Principles of Unit
Operations, 2nd ed., John WileyδSons.
Final Exam (22-28 August 2022)

Grading
Assessment Type Number Weighting
Midterm Exam 1 20%
Homework 3 10%
Final Exam 1 80%
TOTAL 110
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 1. Introduction to Separation Processes
▪ Separation of mixtures constitues a major class of operations in the chemical process
industry and allied industries.
▪ Some mixtures are amenable to separation by purely mechanical techniques. Typical
examples comprise separation of suspended solids from a liquid by filtration, settling
or centrifugation; separation of a mixture of solid particles of different
sizes/densities by elutriation; sepration of small particles from a gas by a cyclone or a
bag filter; or separation of two immisible liquids by phase separation followed by
decantation (lab scale example is separation funnel).
▪ But there are many other mixtures, like gas and liquid mixtures (or solutions) in
general, which cannot be separated by any of the above techniques. The strategy of
separation of such a mixture is based on the use of either an externally supply agent.
▪ This separation processes of this kind are based on the principles of mass transfer
and have traditionally been called mass transfer operations.
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▪ The principles of mass transfer, both diffusional and convective, form the basis of most of the separation
processes used in the chemical industries.
▪ Here we define a separation process as a technique that transforms a mixture of substances into two or
more products differing in composition.
▪ In this course we shall deal with concentration-driven separation processes only and not with the
mechanical separation processes.

❑ Separations including enrichment, concentration, purification, refining, and isolation, are

important to Chemists and Chemical Engineers.

Chemists Chemical Engineers

• use analytical separation methods, such as • more concerned with the manufacture of chemicals using
chromatography, to determine compositions of complex economical, large-scale separation methods, which may
mixtures quantitatively differ considerably from laboratory techniques
• also use small-scale preparative separation techniques,
often similar to analytical separation methods, to recover
and purify chemicals

❑ For example, in a laboratory, chemists separate and analyze light-hydrocarbon mixtures by gas-liquid
chromatography, while in a large manufacturing plant a chemical engineer uses distillation columns
which are the height of tens of meters to separate the same hydrocarbon mixtures.
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▪ A separation process needs some kind of a separating agent to split a mixture into more than two streams of different
compositions.
▪ For example, a gas mixture gets separated when it is contact with a solvent that selectively or preferentially absorb one
or more components. Here the solvent is the separating agent. The separating agent is left out after a job is completed.
▪ Thermal energy is the separating agent in distillation. It is supplied for vaporization of a liquid mixture and is removed
from the top vapour when it is condensed.
▪ In the liquid-liquid extraction, the externally added solvent is the separating agent. It is removed from the extract to
recover the product.
▪ A hot gas is the common separating agent in drying and an adsorbent is the agent for separation by adsorption.
▪ Table 1.1 shows a list of the separating agents for the common separation processes.

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▪ The separation of chemical mixtures into their constituents has been practiced, as an
art, for milenia.
▪ Early civilizations developed various techniques in order to
(1) extract metals from ores, perfumes from flowers, dyes from plants, and potash
from the ashes of burnt plants,
(2) evaporate sea water to obtain salt,
(3) refine rock asphalt, and
(4) distill liquors

• We have a very important separation unit in our body for healthy life.

• The human body could not function for long if it had no kidney, a
membrane that selectively removes water and waste products of
metabolism from blood. What is the separation
principle for kidney ???
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▪ This course includes the principles of large-scale component separation operations, with emphasis on methods
applied by chemical engineers to produce useful chemical products economically.
▪ Distillation
▪ Liquid-liquid extraction CEN314
▪ Leaching (solid-liquid extraction)
▪ Drying
▪ Absorption
▪ Crystallization
▪ Newer methods: are also important but we’ll not examine in CEN314
▪ Super-critical extraction
▪ Adsorption
▪ Membrane separation.

▪ Using the principles of separation operations, chemical engineers can successfully develop, design, and
operate industrial processes
▪ Furthermore in recent years increasingly, chemical engineers are being called upoun to deal with industrial
separation problems on a smaller scale, e.g. manufacture of speciality chemicals by batch processing,
recovery of biologial solutes, crystal growth of semiconductors, recovery of valuable chemicals from
wastes.
▪ In addition investigation on the membrane materials that it is used for the efficient separation give an
attraction in the field of chemical engineering.

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✓ During the last few decades spectacular developments have taken place in several new areas such as materials,
biotechnology, pharmaceuticals, and alternative fuels.
✓ These developments accompanied by challenging separation problems often beyond the scope of the
traditional mass transfer operations .
✓ Improving selectivity of separation by using better separating agents (for example, better solvents),
concentration of high-value products from dilute solutions, improving efficiency and reducing equipment size,
reducing energy requirements are a few of these challenges.
✓ In addition, growing concern for environment and rising energy costs are the two major factors having
significant influence on reshaping separation processes.
✓ On a broader perspective, the two important present-day criteria of evaluation of a process, new or
conventional, are whether it is «sustainable» and «green».
✓ Alongside development and adoption of green technologies has come up the idea of «green separation
processes».
✓ So far as the chemical process industries are concerned, green technologies and green separation processes are
complementary.
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❑ Why does chemical engineer require the study of separation techniques?
Because separations are crucial in chemical engineering.

Raw materials are prepurified in separation devices and fed to the chemical reactor; unreacted feed is
separated from the reaction products and recycled back to the reactor. Products must be further
separated and purified before they can be sold.
Some chemical plants such as sugar factories and vegatable oil production from peanuts, soybeans,
sunflower seeds, cotton seeds consist of only separation units.
Chemical plants commonly have from 40% to 70% of both capital and operating costs in separations. So
chemical engineers try to improve the reaction conversion and yield in order to decrease the total cost of
the process (What does it do ?).
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 ▪ The reactor effluent is neccessarily a mixture of
chemical compounds: the desired product, side
products, unconverted reactants, and possibly
reaction catalyst. Typically, the desired product
must be separated from this mix in relatively pure
form, and the unconverted reactants and any
catalyst should be recovered for recycle. All the
reactants may have to be prepurified.
▪ Often separation itself can be the main function or
entire process. Such is the case for sugar refining,
recovery of metals from various mineral resources
etc.

▪ Some kind of separation process is necessary in every stage from purification of raw materials to
product separation and treatment of effluent streams.
▪ This is schematically shown in Fig.1.1.
▪ The core separation processes in the chemical industry are; Gas absorption and stripping,
Distillation, Liquid-liquid extraction, Solid-liquid extraction, Drying of wet solids, Adsorption and
Crystallization.
▪ All these separation processes involve mass transfer from one phase to another. Such two-phase
systems may be categorized as gas (or vapour)-liquid, liquid-liquid, gas-solid, and liquid-solid.
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▪ Petroleum (or oil) refineries are also most common plants Light products
including separation processes mainly distillation columns.

▪ They include ;
• distillation to separate crude oil into various boiling-
point fractions or cuts,
• alkylation to combine small hydrocarbon molecules into
larger molecules,
• catalytic reforming to change the structure of medium-
size hydrocarbon molecules,
• fluid catalytic cracking to break apart large hydrocarbon
molecules,
• hydrocracking to break apart even larger molecules,
• and other processes to convert the crude-oil residue to
coke and lighter fractions.
Heavy products
bbl: Blue Barrels of Oil 11

https://youtu.be/OPXudQ0_q8g
1. Introduction to Separation Processes- cont.
▪ Summary of Industrial Chemical Processes

▪ The operations may be classified as;

Key operations Auxiliary operations

• unique to chemical engineering • necessary to the success of the key operations
but may be designed by mechanical engineers
because they involve changes in as well because the auxiliary operations do not
chemical composition involve changes in chemical composition.
• (1) chemical reactions and (2) • include phase separation, heat addition or
removal (to change temperature or phase
separation of chemical mixtures. condition), shaft-work addition or removal (to
change pressure), mixing or dividing of streams
or batches of material, solids agglomeration,
size reduction of solids, and separation of solids
by size.
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▪ The key operations for the separation of chemical mixtures into new mixtures and/or
essentially pure components are of central importance.

▪ Block-flow diagrams are used to represent

chemical processes. They indicate by square or
rectangular blocks, chemical reaction and
separation steps and, by connecting lines, the
major process streams that flow from one
processing step to another.
▪ Considerably more detail is shown in process-
flow diagrams which also include auxiliary
operations and utilize symbols that depict more
realistically the type of equipment employed.
▪ Process and Intrumentation Diagram (P&ID) Block-flow diagram of synthetic process for
anhydrous HCl production
shows the measurement and control equipments
or instrumentation details of the process.
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▪ Mechanism of Separation
Mixing of chemicals is a spontaneous, natural process that accompanied by an increase in
entropy or randomness, inverse process, the separation of that mixture into its constituent
chemical species, is not a spontaneous process; it requires an expenditure of energy.

• A mixture to be separated usually originates

as a single, homogeneous phase (solid,
liquid, or gas).
• If it exists as two or more immiscible
phases, it is often best to first use a
mechanical separations based on gravity,
centrifugal force, pressure reduction, or an
electric and/or magnetic field to separate
the phases.
• Then, appropriate separation techniques are General separation process
applied to each phase.
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The separation is accomplished by forcing the different chemical species in the feed into different
spatial locations by any of five general separation techniques, or combinations thereof, as shown in
Figures below.

(a) Separation by phase creation

The most common industrial technique involves the creation

of a second phase (vapor, liquid, or solid) that is immiscible
with the feed phase. The creation is accomplished by energy
(heat and/or shaft-work) transfer to or from the process or
by pressure reduction. (distillation, crystallization, drying)

(b) Separation by phase addition

In the second technique is to introduce the second phase

into the system in the form of a solvent that selectively
dissolves some of the species in the feed. (liquid-liquid
extraction, solid-liquid extraction-leaching, absorption)

MSA: mass separating agent (e.g. solvent ) 16

(c) Separation by barrier
Less common, but of growing importance, is the use of a
barrier, which restricts and/or enhances the movement of
certain chemical species with respect to other species.
(membrane separation)

(d) Separation by solid agent

Also of growing importance are techniques that involve the
addition of solid particles which act directly or separation.
(adsorption)

(e) Separation by force field or graient

Finally, external fields of various types are sometimes
applied for specialized separations. (centrifuging)
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• For all techniques of separations are achieved by enhancing the rate of
the mass transfer by diffusion of certain species relative to mass transfer
of all species by bulk movement within a particular phase.

• The driving force and direction of mass transfer by diffusion is governed

by thermodynamics, with the usual limitations of equilibrium.

• Thus, both transport and thermodynamic considerations are

crucial in separation operations.

• The rate of separation is governed by mass transfer, while the extend of

separation is limited by thermodynamic equilibrium.
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• All separation processes involve mass transfer from one phase to
another.

• Such two-phase contact systems may be categorized as ;

a) Gas – Gas Contact
b) Gas (or vapour) – Liquid Contact
c) Liquid1 – Liquid2 Contact
d) Gas – Solid Contact
e) Liquid – Solid Contact

a. Gas – Gas Contact

Since with very few expections all gases are completely soluble in each
other, this contact type is not parctically.
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b. Gas (or vapour) – Liquid Contact

In this contact type of the phases we can include gas absorption, distillation, desorption,
humidification and dehumidification, stripping

i. Separation of a soluble species from a gas mixture by using a solvent is called « gas absorption»
which is a gas-liquid contact operation. (removal of ammonia from a mixture af ammonia-air by
means of liquid water. Amonia is transferred from gas to liquid phase)
ii. The absorbed gas is recovered by «stripping» when the solvent also gets regenerated and fit for
reuse.
iii. The most common technique of separation of a liquid mixture is fractional distillation. This
technique relies upon the difference in volatility of a component over another in the mixture.
Heat is supplied to vaporize a part of the liquid which flows up through a properly designed column
and gets into intimate contact with a down-flowing liquid when the Exchange of the component
occurs. The more volatile components migrate into the vapour phase and the less volatile ones get
transferred into the liquid phase. The concentration of the more volatiles increases up the column
and that of the less volatiles increses down the column. The top product, which comes up as a
vapour, is condensed. The less volatile part is taken out as the bottom product.
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c. Liquid1 – Liquid2 Contact

If some or all of the components have low volatility and are thermally
unstable in a liquid mixture or solution, it becomes convenient to introduce
a suitable liquid, into the separation device to extract the target
compounds. This is liquid-liquid extraction. The desired species is recovered
from the extract by using another separation technique, say distillation or
crystallization. (penicillin is extracted from the fermentation broth by using
an ester like butyl acetate and the final product recovery is done by
crystallization)

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d. Gas – Solid Contact

i. Separation of a solute from a gas mixture can sometimes be done by adsorption in

a solid material. (separation of organic vapours present in low concentration in a
gaseous emmisions by using a bed of active carbon).The adsorbed solute is
recovered frequently by thermal stripping.

ii. Another important application of gas-solid contacting is for drying of a moist solid
using a drying gas. The hot gas is brought in intimate contact with the solid when
the moisture leaves the solid and migrates into the gas as a vapour.

iii. Gas-solid contact also occurs in a less common separation like gas chromatography.

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e. Solid – Liquid Contact

i. One type of solid-liquid contact operation aims at solubilizing or extracting a target

substance from a solid matrix. This is solid-liquid extraction or leaching. (acid-
leaching of ores or extraction of oil from flaked oil seeds or fragnance from flowers.)

ii. Another type of solid-liquid contact involves simultaneous separation and

purification of a substance from a supersaturated solution by crystallization.

iii. A dissolved solute, particularly at a low concentration, can be conveniently

separated by using a solid «agent» that adsorbs the target substance, called as
adsorption. The solid adsorbent loaded with the solute is now further treated to
recover the product. Here the adsorbent plays the same role as a solvent does in gas
absorption.

iv. Another important case of solid-liquid contact is the separation of ionic species from
a solution by a solid ion exchange resign. 23
As a result, separation operations in industrial chemical processes are employed not only
to separate a feed mixture into other mixtures and relatively pure components, to
recover solvents for recycle, and to remove wastes, but also when used in conjunction
with chemical reactors, to purify reactor feeds, recover reactants from reactor effluents
for recycle, recover by-products, and purify products General separation process

• If the feed mixture is a homogenous, single phase solution (gas, liquid, or solid), a second immisible phase
must often be developed or added before separation of chemical speciec can be achieved.
• This second phase is created by an Energy Separating Agent (ESA) and/or added a Mass Separating Agent
(MSA)
• Application of ESA involves heat transfer and/or transfer of sahft work to or from the mixture to be seperated.
• Alternatively, vapour may be created from a liquid phase by reducing the pressure.
• An MSA may be partially immisible with one or more of the species in the mixture. In this case, the MSA
frequently remains the constituent of highest concentartion in the added phase.
• Alternatively, the MSA may be completely miscible with a liquid mixture to be separated, but may selectively
alter the partitioning of species between liquid and vapour phases. This facilitates a more complete separation
when used in conjuction with an ESA, as in extractive diatillation.

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 ESA; energy-separating agent
Table 1. Separation Operations Based on Phase Creation or Addition [1] MSA; mass-separating agent

ESA

MSA

Other

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[1] J. D. Seader, Ernest J. Henley-Separation Process Principles 2nd Edition-Wiley (2005)
Table 1. Separation Operations Based on Phase Creation or Addition- cont. [1]

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 Table 1. Separation Operations Based on Phase Creation or Addition- cont. [1]

* Fairly routine or well known separation operation 27

Selection of Feasible Separation Processes
• Separation processes comprise 40%-70% of both capital and operating cost of the
chemical plant.
• Important factors for the selection of feasible separation operations are;

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