3

Clifton E. Meloan Chemical separations

A Wiley-Interscience Publication,1999

Contents

Introduction
Distillation
Solvent Extraction
Solid Phase Extraction
Solid Phase micro Extraction
Supercritical Fluid Extraction
Supercritical Fluid Chromatography
Field Flow Fractionation
Electrophoresis
Membrane separations

Introduction

Introduction
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)

Introduction
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.)

1.Principle of separation
used, separation gradient
applied (temperature,
concentration, chemical
potential, magnetic field
etc.)

Distillation theory
and practice

Clausius- Clapeyron equation

This relationship can be used to determine the
Hvap from the p0 of a liquid at two temperatures.

Clausius- Clapeyron equation

An estimate of P0 can be made of any
temperature provided the Hvap and the boiling
point at atmospheric pressure is known.

Field Flow
Fractionation

Flow FFF
Two crossed flow streams are superimposed on
the same channel.

Channel walls are permeable and the pore size

determines the lower size limit for separation.

Field flow fractionation

The driving force is the viscous force
exerted on the particle by the cross stream
based on sample diameter.

Solid Phase
Extraction

Solid Phase
Micro Extraction

< TARGET="display">

Supercritical Fluids

Supercritical Fluid
Extraction

Supercritical Fluid
Chromatography

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Electrophoresis

Capillary Electrochromatography

Membrane
Separations

 Definition: A membrane is a thin

barrier which allows selective
passage of different species
through it.
This selectivity is utilized for
separation.

 The selectivity is due to:

1.Size
2.Shape
3.Electrostatic charge
4.Diffusivity
5.Physicochemical interactions
6.Volatility
7.Polarity/solubility

Membrane separation
processes: Applications
Product concentration, i.e. removal of
solvent from solute/s
Clarification, i.e. removal of particles
from fluids, a special case being
sterilization which refers to removal of
microorganisms from fluids

 Removal of solute from solvent, e.g.

desalting, desalination,
demineralization, dialysis

Fractionation, i.e. separation of one

solute from another

 Gas separation, i.e. separation of

one gas from another

Pervaporation, i.e. removal of

volatiles from non volatiles (usually
solvents)

Membrane material
Organic polymers
Polysulfone (PS)
Polyethersulfone (PES)
Cellulose acetate (CA)
Regenerated cellulose
Polyamides (PA)
Polyvinylidedefluoride (PVDF)
Polyacrylonitrile (PAN)

Membrane material

Inorganics

-alumina
-alumina
Borosilicate glass
Pyrolyzed carbon
Zirconia/stainless steel
Zirconia carbon

Membrane preparation

Polymer casting
Precipitation from vapour
phase
Precipitation by evaporation
Immersion precipitation
Thermal precipitation

Membrane preparation

Other methods
Stretching
Sintering
Slip casting
Leaching
Track etching

Driving force in membrane

processes

Transmembrane pressure (TMP)

Concentration gradient
Chemical potential
Osmotic pressure
Electric field
Magnetic field
Partial pressure
pH gradient

Membrane processes primarily based

on species size
Microfiltration (MF)
Micron sized pores
Mainly used for particle-fluid separation
TMP: 1 to 50 psig

Membrane processes primarily based on

species size
Ultra filtration (UF)
Pores: 10 1000 angstroms
Used for: Concentration, desalting,
clarification and fractionation
TMP: 10 100 psig

Membrane processes primarily based on

species size

Nanofiltration (NF)

TMP: 40 200 psig

Reverse osmosis (RO)

TMP: 200 300 psig

Dialysis
Concentration gradient driven
Selectivity based indirectly on
size

Membrane processes based

on principles other than
species size
Pervaporation (PV)
Driven by partial pressure
Selectivity depends on volatility
and solubility of species in
membrane

 Gas separation
Driven by partial pressure
Selectivity depends on solubility of
species in membrane

Electrodialysis (ED)
Driven by electric field
Selectivity depends of charge
exclusion

Membrane Separations
In membrane separations a
mixture is separated by using a
semi permeable membrane

Membrane Separations
which allows one component to
move through faster than others
resulting in differential transport

Membrane Separations

The mixture is separated into a

retentate, enriched in the less
mobile species and a permeate,
enriched in the components
which move through the
membrane fastest.

Membrane Separations

Feed mixture

Retentate
Membrane

Purge
(

optional)

Permeate

Transport Mechanisms Through

Membranes
Transport Through Membranes:
Bulk flow through pores (membrane is
microporous with pores larger than the
mean free path).
Diffusion through pores (pores are large
enough for diffusion, but small relative to the
MFP).

Transport Mechanisms Through

Membranes
Restricted diffusion through pores (if
pores are large enough for some
species, but not others).
Solution-diffusion (Diffusion through
dense membranes with diffusant
dissolved in polymer matrix).

Transport Mechanisms Through

Membranes
Bulk flow through pores

Restricted diffusion

Diffusion through pores

Solution-diffusion

Microfiltration and Ultrafiltration

Microfiltration is based on the
restricted diffusion of species
through pores: Larger species
or particles are restricted from
entering pores of 0.1 to 1 micron in
size.

Microfiltration and Ultrafiltration

Restricted diffusion

 Ultrafiltration is similar, except the

pore size is even smaller (on the order
of
the molecule size) and the number of
pores small. This allows for separation

 of smaller components, for example

separating a small molecule from
solvent.

Bulk Flow Through Membranes

Bulk flow through pores

D
L

Bulk flow through pores (if membrane is microporous with

pores larger than the mean free path).

If flow is in the laminar regime then the Reynolds

Number NRe (which is related to the pore and fluid

properties) is less than 2,100:
N Re

D

32 L

2 , 100

P0

D
4

Similar to
Darcys Law

Bulk Flow Through Membranes

Combining:

D

P0 P
32 L

Velocity

D
4

Porosity

N
Density
Flux (molar or mass)

Note that the the porosity gives the total cross-sectional area
of the flow perpendicular to the flow direction:
A

N (nA) V

 If the pores are not straight or cylindrical

then we must modify this equation by
factors that describe
the tortuosity and specific surface area.

D
nD
N
P0 P
P0 P
32 L
128 L
2

Electrodialysis
Feed solution

Electrode rinse solution

Electrode rinse solution

+

Cathode

+
+

Cation
selective
membranes

Concentrate
(brine)
Diluate
(less salts)

Anion
selective
membranes

Anode

Osmosis and Reverse Osmosis

Membrane
(only permeable
to solvent)

A, B, C
P1

C
P2

Initial
Condition
(equal pressures)

A, B, C
P1

P2

Equilibrium
Condition
(pressure difference
maintained by
osmotic pressure)

A, B, C
P1

P2

Reverse
Osmosis
(Transport against
concentration gradient
if pressure above
osmotic pressure)