Lecture 1:

Introduction to
Separation Process Principles

Chapters 1, 2 & 4 covered in lectures 1 & 2.

Chapter 3 will be covered later, together
with parts of Ch. 6, 7 and 12 (see course
schedule)

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 Examples of Industrial Chemical Processes
Refinery for converting crude oil into a variety of
marketable products
Production of chemicals (HCl, Ethanol, …..)

Crude Oil Oil products

Crude
separation …
processes

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Examples of Industrial Chemical Processes
Separation of alcohols (methanol, ethanol, propanol, …)
from water by reverse extraction
1 1 1 1

2 2 2 S14
2 3 4
4 3
3 5 4 6
4 6 5 8
7 10
5 8 6
9 12
7 14
6 10 8
11 S5 16
7 12 9 18
13 10 20
8 14
15 11 22
9 S2 16 12 24
10 17 13 26
18
11 19 14 28
20 15 30
12 21 16 32
22 34
13 23 17
24 18 36
14 25 19 38
15 26 S16 40
S17 27 20
16 28 21 42
29 22 44
17 30 46
31 23
18 32 48
24 S10 50
19 33 25
34 52
20 35 26 54
36 27
21 37 56
38 28 58
22 39 29 59
S1 S7
C1 23 C2 40 C3 30 C4 60
M2 E1 S15

S3

S9

S6

S8

4
S11
5

8
S13
9

10

11
E2 M1
SC1
12
S4
13

C5 14
S12

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 Mechanism of Separation

Phase 1 Phase 1 Phase 1

Feed Phase Feed Feed Barrier

Creation
(b)
(a) MSA (c)
Phase 2 (Solvent) Phase 2 Phase 2
Feed Phase 1

Phase 1
Feed Force field
or gradient

(d) Phase 2 (e)

Phase 2

Phase Creation & addition; Barrier; Solid agent; Force field

or Gradient

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 Some Definitions - 1
Component Recoveries & product Purity
ni(F) = P ni (P) = ni (1) + ni (1) + ni (1) + ni (1) + … NP
Product recovery in stream k: ni (k) / ni (F)
Product Purity in stream k: ni(k)/ i ni (k)
Split Fractions, SFi: same as product recovery in stream k
Split Ratio (only for 2 product streams), SRi:
ni(1)/ni(2) = SFi/(1-SFi)

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 Some Definitions - 2
Separation Power or Separation Factor: SP
SPi,j = [Ci(1)/Ci(2)]/[Cj(1)/Cj(2)] for split between components i & j
= SRi/SRj
= [SFi/SFj]/[(1-SFi)/(1-SFi)]
Note: SPi,j only indicates the desired separation and not whether
it is achievable. In order to verify if the desired separation is
achievable, the design of the operation, thermodynamic
relations, transport properties, etc., needs to be evaluated.

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Selection of Feasible Separation Techniques

Important Factors
• Feed Conditions (composition, flow rates, T, P, state, …)
• Product conditions (purity/recovery, T, P, state)
• Property Differences (molecular, thermodynamic,
transport)
• Characteristics of Separation Operation (scale-up; stages;
T, P, state requirements; size limitation; energy
requirements; …)

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 Thermodynamic Insights: Levels I & II
1. Analyse process - divide into blocks of reaction,
separation, ...
2. List separation techniques to be considered.
3. External mediums? Eliminate if none found.
4. Screen out infeasible separation techniques.
5. Binary mixture analysis: Azeotropes, miscibility, …
6. Generate solvent alternatives.
7. Multicomponent mixture analysis: Separation
boundaries, etc.
8. Check separation stream for reactants. Recycle?
9. Formulate optimization problem in terms of
superstructure, objective function, constraints, etc.

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 Identify Unit Operations (Separation)
For each binary pair of components,
1. Compute for property k, Bij = pik / pjk
2. If Bij > , separation technique k is
feasible
Repeat steps 1 & 2 for properties k=1,NS

If Bij for pure component boiling points >> 1,

separation by distillation, flash are feasible; if Bij for
melting points >> 1, crystallization is feasible; if Bij
for Van der Waals volume >> 1, membrane based
separation is feasible, ...
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 Binary Mixture Analysis
For each binary pair of components,
1. Check for binary azeotropes, eutectic points
for a range of pressure
2. Check for miscibility
3. Determine driving force diagram with
respect to separation technique k
….

Identifies the need for solvents/external agents;

eliminates alternatives; determines feasible and
near optimal separation schemes
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Selection of Feasible Separation Techniques
Consider the separation of a binary mixture of
acetone-chloroform into two pure products
How many ways can we separate them?
Important Factors: Property Differences

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Generate Binary Ratio Matrix

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List of Feasible Separation Techniques

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 Alternatives Binary Azeotrope Separation
Separation technique Class Phases involved
Absorption Solvent-based Gas-Liquid
External material-based Gas-Gas
Adsorption External material-based Gas-Liquid
Pervaporation External material-based Vapour-Liquid
Filtration External material-based Solid-Liquid
Crystallisation Property difference Solid-Liquid
Distillation Property difference Vapour-Liquid
Distillation plus decanter Property difference Vapour-Liquid plus Liquid-Liquid
Extractive distillation Solvent-based Vapour-Liquid
Azeotropic distillation Solvent-based Vapour-Liquid-Liquid
Liquid-Liquid extraction Solvent-based Liquid-Liquid
Super-critical extraction Solvent-based Fluid-Vapour-Liquid

• Need for (appropriate) thermodynamic models.

Thermodynamic Model Selection
• Need for Properties (Database/Property prediction)

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 Representation of all alternatives
Separation of a binary mixture Y18
DEC Y19

Y20 Y13

Y21 Y14

Y22 Y15

Y23 P1

Y6
Y8

Y1 Y9
D2
Y2 Y7
Feed
D1

Y3
Y10
Y11

Y12 Y16
Y4
Y17
EX

Y5 P2

Y24

Solvent1 Y25+1 Y25

Solvent make up Solvent2 Y25+2

.
.
.
Y25+N
SolventN

Use of thermodynamic insights makes the problem easy to solve

15
 Acetone-Chloroform Separation
Separation
Problem:techniques considered:
A process Nomole%
stream of 50 external medium
Acetone known
and 50
Adsorption
mole% (liquid, gas) at 300K, isBinary
Chloroform ratios of properties
to be separated.
Crystallization identify the following
Desublimation alternatives
Distillation – simple
Distillation – extractive Separation techniques:
Distillation with decanter Distillation – simple
Liquid-liquid extraction Distillation – extractive
Flash/evaporation Distillation – azeotropic
Membrane (gas, liquid) Liquid extraction
Microfiltration Pressure swing
Partial condensation

Note: Acetone-chloroform forms a high boiling azeotrope

that is pressure sensitive

16
Phase diagram: Pressure dependence

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 Problem formulation & Solution
Objective function:
Maximize
Profit = Earnings
– Solvent cost
– Energy costs
Constraints:
Acetone purity > 0.99
Chloroform purity > 0.98
Results:
Solvent Solvent Reflux Reflux Objective
flow rate Reb. 1 Reb. 2 function
1-hexanal 0.082 kmol/hr 0.45 0.65 2860.51 $/hr
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