Chapter 1.

Separation Processes

2012. 1

Energy Consumption
/
.
/ .

: enantiomerically pure components
Softenon : (R-enantiomer),

mer)
Aspartame : (S, S) , (R, R)
Limonen : (S), (R)

(S-enantio

Separations
Separations
Enrichment
Concentration
Purification
Refining
Isolation
Separations are important to chemist and chemic
al engineers
Chemist : Small scale (Analytical separation methods)
Chemical Engineers : Economical, large scale methods

Industrial Chemical Processes

Feed

Natural raw material

Plant or animal matter
Chemical intermediate
Chemicals of commerce
Waste products

Mode of Operation

Batchwise
Continuous
Semicontinuous

Operation
Key Operation
Reaction
Separation
Auxiliary Operation
Heat / Work
Mixing, Dividing
Size reduction

Hypothetical vs. Industrial Processes

Simple ,hypothetical proces

s is not possible
Impurities in the feed
Side Reactions

Separation processes are im

portant in real industrial ap
plication

Mechanism of Separation

Mixing : Spontaneous, natural process

Separation : Not spontaneous process

Require energy (heat / work)

Question : Why ?

General Separation Technique

Separation by Phase Creation

Energy (heat/work)
,

Separation by Phase Addition

3 (MSA : Mass Separating Agent)

Separation by Barrier

Barrier (membrane )

Separation by Solid Agent

Separation by Force Field or Gradient

, ,
,

Classification of Separation Techniques

Phase 1

Phase 1

Mass Separating
Agent

Feed

Feed
Phase 2

MSA

Phase 2
Phase 1

(i) By Phase Creation

Feed

(ii) By Phase Addition

Barrier

Phase 2
Feed

(iii ) By Barrier
Phase 1

Feed

Phase 1
Force field
or gradient

Phase 2

Phase 2
(iV) By Solid Agent

(Vi) By Force Field or Gradient8

Driving Force of Separation :

Gradient of Concentration

Rate of Separation : how fast ?

Governed by mass transfer

Extent of Separation : how far ?

Limited by thermodynamics

Handbooks
Journals
Electronic Databases
Commercial Process Simulators

Properties of Importance
Molecular Properties

Thermodynamic and Transport Properties

Molecular Weight
Van der Waals Volume
Van der Waals Area
Molecular Shape (Accentric Factor)
Dipole Moment
Polarizability
Dielectric Constant
Electric Charge
Radius of Gyration

Vapor Pressure
Solubility
Adsorptivity
Diffusivity

<i and ii> Separation By Phase Addition or Creation -1

V/L

V/L

ESA
(Energy-Separating Agent)

L
Partial Condensation or Vaporization
(Heat Transfer)

L
Flash Vaporization
(Pressure Reduction)
10

Separation By Phase Addition or Creation - 2

Condenser

Reflux
Rectifying section

V/L
Stripping section
Reboil

When the volatility difference

among species are not sufficiently
large
Most widely used industrial
separation technique
Multiple contact between counter
current flow of V/L in trays
(stages) .

Reboiler

L
Distillation
(Heat transfer (ESA) or sometimes work transfer)

11

Distillation Tower

12

Separation By Phase Addition or Creation - 3

Recovery of acetic acid from water
using n-butyl acetate

Recycle MSA
L
Makeup MSA
V/L

L
Azeotropic Distillation
Liquid entrainer (MSA)
and Heat Transfer (ESA)

13

Separation By Phase Addition or Creation - 4

Recovery of Aromatics

Use of Propane and Cresylic acid as solvents to separate

paraffins from aromatics and naphthenes

L1

MSA (L)

MSA1 (L)
L

L1

MSA2 (L)
L2
Liquid Liquid Extraction

Liquid solvent(MSA)

L
Liquid-Liquid Extraction
(Two Solvent)
14

Separation By Phase Addition or Creation - 5

Drying
V

Evaporation
(V)

L/(S)

Crystallization

Heat transfer (ESA)

L
Removal of water from PVC

(V)

V
L

Evaporation
of water from
Water + Urea
Heat transfer (ESA)

Desublimation

S
Crystallization o
p-Xylene
from m-Xylene

Recovery of
phthalic anhydride

Heat transfer (ESA)

Heat transfer (ESA)

15

Crystallizer

16

Separation By Phase Addition or Creation - 6

Leaching (Liquid-Solid Extraction)

Foam Fractionation
V

L (foam)

MSA (L)

Detergent tend to
rise with gas bubble

MSA (g)
S
Extraction of sugar using hot water
Liquid Solvent

L
Recovery of detergent from water soln.

Gas Bubbles (MSA)

17

<iii> Separation by barrier

Use of microporous / nonporous

membrane as semipermeable barr
iers
Membranes

Natural fibers
Synthetic polymers
Ceramics
Metals
Liquid films

Fabrications
Flat sheets
Hollow fibers
Spiral-wound sheets

18

Separation by barrier - 1
L

L
L
smaller
solute

solvent
solvent

L
Osmosis
Nonporous membrane
Concentration gradient

Reverse Osmosis
Nonporous membrane
Pressure Gradient
Desalination of sea water

L
Dialysis
Porous membrane
Concentration Gradient
Pressure Gradient
Recovery of caustic
from hemicellulose
19

Separation by barrier - 2
L
L

L
solvent

Microporous membrane
Pressure gradient
Removal of bacterial
From drinking water

0.02-10 m

gas (evaporation)

solvent

L
Microfiltration

Ultrafilration

Pervaporation

Microporous membrane

Nonporous membrane

Pressure Gradient

Pressure Gradient

Separation of whey from

cheese

Separation of azeotropic
mixtures

1 20 nm

20

Separation by barrier - 3
V
V

Gas mixture

V/L
V/L
Liquid layer

gas

V
Gas permeation
Nonporous membrane
Pressure Gradient
Hydrogen enrichment

V/L
Liquid Membrane
Liquid membrane
Pressure Gradient
Removal of hydrogen sulfide
21

Liquid Membrane

22

<iv> Separation by solid agent

Solid mass separating agent

Granular material or packing

Saturation Periodical regeneration required

Batchwise or semicontinuous operation

pore
Molecular sieve

Silica gel
23

Separation by solid agent

V/L

V/L

V/L
Adsorption
Solid Adsorbent
Purification of
p-xylene

V/L

V/L
Chromatography
Solid adsorbent or liquid
Adsorbent on solid support

Ion Exchange
Resin with ion-active sites
Demineralization of water

Separation of xylene isomers

and ethylbenzene

24

Separation by solid agent

Adsorption
Adsorbent

Activated carbon
Aluminum oxide
Silica gel
Zeolite adsorbents (Molecular
sieve)

Adsorption / Regeneration
Regeneration methods

Thermal Swing (TSA)

Pressure Swing (PSA)
Inert purge stripping
Displacement desorption
Hydrogen PSA Units
25

<vi> Separation by external field or gradient

Separation operation

Initial or Feed Phase

Force field or gradient

Industrial Example

Centrifugation

Vapor

Centrifugal force

Separation of Uranium
isotope

Thermal diffusion

Vapor or liquid

Thermal gradient

Separation of chlorine
isotope

Electrolysis

Liquid

Electrical force field

Concentration of heavy
water

Electrodialysis

Liquid

Electrical force field

and membrane

Desalinization of sea
water

Electrophoresis

Liquid

Electrical force field

Recovery of
hemicelluose

Field-flow
fractionaltion

Liquid

Laminar flow in force

field
26

Centrifugation

27

Electrodialysis

28

Electrophoresis ( )
Using different migration velocities of charged colloidal or
suspended species in a electrical field
Application : Biochemicals

29

Field Flow Separation

Field Flow Fractionation (FFF)

Micromolecular and
colloidal materials

30

Component Recoveries and Product Purity

Separation process
No reaction
Continuous and steady state
N

ni( F ) ni( p ) ni(1) ni( 2 ) ni( 3) ... ni( N 1) ni( N )

p 1

i : 1 ~ C Number of Components
p : 1~ N Product phases
F : feed

31

Example Hydrocarbon Recovery Plant

Purpose :
Production of polymers
- PP
- PB
.

32

Split Fraction and Split Ratio

Split fraction ( 0 1)
SFi , k

ni(,1k)

i product /feed

ni(,Fk )

Split ratio ( 0 very large value)

SRi ,k
i
k

ni(,1k)
( 2)
i ,k

SFi ,k
(1 SFi ,k )

i top / bottom

: component
: separator

(F) : feed
(1) : first product (ex: top product)
(2) : second product (ex : bottom product)

33

Separation Power
C
SPi , j
C

(1)
i
(1)
j

/C
/C

( 2)
i
( 2)
j

SFi / SF j
SRi

SR j (1 SFi ) /(1 SF j )

Key-component split

Column

SP
Separation Power

nC4H10 / iC5H12

C1

137.1

C3H8/iC4H10

C2

7103

iC4H10/nC4H10

C3

377.6

34

Selection of Feasible Separation

Selection of a best separation processes

Selection among a number of feasible candidates

Two or more operations may be the best
Important Factors that influence the selection
of feasible separation operations
Feed conditions
Product conditions
Property differences
Characteristics of separation
35

Factors that Influence the Selection of Feasible

Separation Operation
Feed condition

Compositions
Flow rate
Temperature
Pressure
Phase state

Product conditions

Required purities of products

Temperatures
Pressures
Phase states

Property differences

Molecular
Thermodynamic
Transport

Characteristics of separation
operation

Ease of scale-up
Ease of staging
T, P, Phase-state requirements
Physical size limiation
Energy requirement

Most important
Can be altered by pump,
Compressor, heat exchangers,

36

Technological and Use Maturity of Separation Process

es

Separation
By Barrier

Expensive

Separation by
Solid agent
Creation of Addition of
Second Phase

Cheap

37

Ease of Scale-up

= 200 %

= 150 %

38