Вы находитесь на странице: 1из 119

MASS TRANSFER CH313

1
INTRODUCTION
Fraz Saeed Butt
Masters in Chemical and Energy Engineering (August 2014),
Otto Von Guericke University, Germany.
E-mail: fraz@giki.edu.pk
Office: M06, FMCE
Phone Extension: 2427

2
COURSE
CONTENT
3
4
5
REFERENCE BOOKS
Text Book:
1. Ernest J. Henley, J. D. Seader, D. Keith Roper, “Separation Process Principles”
3rd Edition, 2011, John Wiley and Sons Inc. ISBN: 978047064611
2. McCabe & Smith, “Unit Operations of Chemical Engineering”, 7th Edition.
Reference Books:
3. Coulson J.M., Richardson J.F. “Coulson & Richardson’s Chemical Engineering
Series” Volume I, 6th Revised edition, 1999. Butterworth-Heinemann Ltd; ISBN:
9780750644440
4. Coulson J. M, Richardson J. F., “Coulson & Richardson’s Chemical
Engineering Series”, (Particle Technology and Seperation Processes) Volume II,
2002, 5th revised edition, Butterworth-Heinemann Ltd; ISBN: 9780750644457 6
MARKS DIVISION
Mid-Term 30 %
Final Term 45 %
Quizes, Assignments, Group Projects, Presentations 25 %
Note:
A part of the Mid-term syllabus will also be included in the Final exam.
Book Reading is highly recommended, a part of the exam will taken from Text book as well.

7
8
QUIZES
4 Quizzes in total (Best 3 will be considered).
No Retake of missed Quizzes until and unless:
Health Reasons, Family Issues or any other Random Reason.
In either case, leave form should be submitted after being signed by the Dean of the
department.
Quiz retake will only be in a form of “Oral Exam”.
Checking of any Quiz and relevant discussion in only liable within 24 hours of result display.
(after that any request regarding checking and discussion will not be entertained).

Dates for Semester Quizzes


Quiz. 1 28 Sep, 2017, Thursday, 5:30 p.m Quiz. 3 30th Nov, 2017, Thursday, 5:30 p.m
Quiz. 2 17th Oct, 2017, Tuesday, 5:30 p.m Quiz. 4 14th Dec, 2017, Thursday, 5:30 p.m
Mid-Term 3rd Nov, 2017 - 6th Nov, 2017 Final Term 1st Jan, 2018 – 7th Jan, 2018
Quiz. 5 Surprise Quiz

9
ATTENDENCE AND DISCIPLINE
45 lectures in total, more than 80%
attendance is required to sit in the
final exam.
Any student having attendance less
than 80% will not be allowed to
attend the remaining classes.
Discipline….!!!!!!!!!
No one will be allowed to enter into
the class after 5 minutes.
10
CLASS TIMINGS
TIMING DAY Lecture Hall
09:00-09:50 a.m Tuesday LH1
02:30-03:20 p.m Wednesday LH1
10:30-11:20 p.m Thursday LH1

11
TRANSFER
PROCESSES
12
TRANSFER PROCESSES

13
TRANSFER PROCESSES

14
TRANSFER PROCESSES

15
TRANSFER PROCESSES

16
OPERATION TYPES
A chemical or biological plant is operated in a Batch-wise, semi-continuous or continuous manner.
The operations may be divided into two major types,
Key Operations:
Operations that are unique to Chemical Engineering and involves changes in Chemical
Composition.
Key operations may include,
1. Chemical Reactions,
2. Separation of Chemical Mixture.

Auxiliary Operations:
Heat addition or removal (Heat Exchangers), Shaft work (Pumps or Compressors), Mixing or
dividing of streams, Solid Agglomeration, Size Reduction of solids, and separation of solids by
size.
17
MODES OF OPERATIONS
Separations processes can be run in various modes of operation:
 Batchwise: no flows,
 Continuous: continuous flows in and out of separators,
 Semicontinuous: pauses in flows.
BASIC DESCRIPTION OF OPERATIONS
Block Flow Diagrams :
Indicate,
Key Operations by rectangles while Flows and Streams by lines.

Process Flow Diagrams:


Indicates processes by:
Realistic symbols of process equipment including auxiliary operations
18
19
BASIC SEPARATION TECHNIQUES
(SEPARATION BY PHASE CREATION)
The most common separation technique is the creation of a second
phase immiscible with the feed phase by the application of
energy or by pressure reduction.
Common example of this type are,
 Distillation which involves the transfer of species between liquid
and vapor species, exploiting difference in volatility (e.g: vapor
pressure or boiling point) among the species,
 Crystallization, that exploits the difference in melting points.

20
BASIC SEPARATION TECHNIQUE
(SEPARATION BY PHASE ADDITION)
This technique includes the addition of another fluid phase which selectively
absorbs, extracts or strips certain species from the feed.
The most common operations of this type are,
 Liquid-liquid extraction where the feed is liquid and a second immiscible
liquid phase is added,
 Absorption, where the feed is vapor and liquid of low volatility is added.
In both cases, species solubilities are significantly different in the added
phase.

21
BASIC SEPARATION TECHNIQUES
(SEPARATION BY SOLID AGENT)
 Another technique of growing importance is contacting a vapor
or liquid feed with solid reagent.
 The solid reagents are mostly porous to achieve high surface
area and differences in species adsorbability is exploited.

22
BASIC SEPARATION TECHNIQUES
(SEPARATION BY BARRIER)
 Less common, but of growing importance is the use of barrier.
 Usually a polymeric membrane, which involves a gas or liquid
feed and exploits differences in species permeabilities through
the barrier.

23
BASIC SEPARATION TECHNIQUES
(SEPARATION BY FORCE FIELD OR GRADIENT)
 Finally, external fields (centrifugal, thermal, electrical, flow etc)
are applied in special cases to liquid or gas feeds.
 For example, in electrophoresis being especially useful for
separating proteins by exploiting differences in electric charge
and diffusivity.

Electrophoresis is the method for separation and analysis of


macromolecules (DNA, RNA and proteins) and their fragments
based upon their size and charge.
24
NOTE
 Size of separation equipment depends upon the rate of mass
transfer of species from one phase or location to another,
relative to the mass transfer of all species.
 The extent of separation depends on the exploitation of
differences in molecular, thermodynamic and transport
properties of the species.

25
26
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
1. Extraction of Metals from Ores,

27
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
2. Extraction of Perfume from Flowers,

28
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
3. Extraction of Potash from the Ashes of burnt Plants,

29
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
4. Evaporation of Sea Water to obtain Salt,

30
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
5. Refining of Rock Asphalt,

31
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation Processes developed by early civilizations include,
6. Distilling of Liquors,

32
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation process in context to human body,
7. Kidney functionality in Separating water and waste products of metabolism from blood,

33
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
8. Chromatography (an example of lab scale separation of hydrocarbons),

Separation is based upon the differential


Chromatographic Technique helps, portioning between mobile and stationary phase.

To determine the composition of complex mixtures, Various constituents of mixture travels at
different speed based upon their affinities with
stationary phase.
As Preparative Separation technique to recover chemicals.
34
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
9. Distillation Column (an example of Industrial Scale separation of hydrocarbons),

Component separation based upon their difference in boiling point. 35


MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
10. Liquid-Liquid Extraction,

Transfer of Solute from less soluble to more soluble phase.


After extraction, the phase that is enriched in solute is called Extract and
other is called as Raffinate.
36
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)

11. Drying,

37
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
12. Absorption and Desorption Column,

38
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
13. Crystallization,

39
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
14. Membrane Separation,

40
MASS TRANSFER PROCESSES
(SEPARATION PROCESSES)
Separation process in context to human body,
15. Function of lungs,

41
(A) SEPARATION BY PHASE ADDITION
OR CREATION 42
(A) SEPARATION BY PHASE ADDITION OR CREATION
 If the feed is a single phase solution, a second separable phase
must be developed before separation of species can be
achieved.
 The second phase can be developed by an Energy-Separating
Agent (ESA) and/or added as a Mass-Separating Agent (MSA).
 An ESA involves heat transfer or transfer of shaft work (energy
transfer) to or from the mixture (an example of shaft work is the
creation of vapor from liquid phase by reducing the pressure).
 MSA may be miscible with the liquid feed mixture, but may
selectively alter the partitioning of species between liquid and
vapor phase…Alternatively an MSA may be partially immiscible
with one or more mixture components.
 MSA facilitates a separation process when used in conjunction with
ESA, as in Extractive Distillation. 43
EXTRACTIVE DISTILLATION
(EXAMPLE REGARDING MSA & ESA IN CONJUNCTION)

44
DISADVANTAGES OF
USING MSA
 Need for an
additional separator
to recover the MSA
for recycle.
 Need for MSA
makeup.
 Possible MSA product
contamination.
 More difficult design
procedure.
45
46
47
48
WHEN THE FEED MIXTURE INCLUDES SPECIES THAT DIFFER WIDELY IN VOLATILITY

Operation: Partial condensation or Operation: Flash vaporization


partial vaporization operation
E.g. Recovery of H2 and N2 from E.g. Recovery of water from sea
Ammonia. water

In both cases the resulting vapor – liquid phases are then


separated by gravity.
WHEN THE VOLATILITY DIFFERENCES AMONG SPECIES ARE
NOT SUFFICIENTLY LARGE
The degree of separation achieved
by a single contact of two phases is
inadequate.
Then the multiple contacts between
counter-currently flowing liquid and
vapor phases is considered.
Each contact is called a stage.
The contacts are often made on
horizontal trays arranged in a column.

Operation: Distillation
E.g. Separation of crude oil
into its constituents
WHEN THE VOLATILITY DIFFERENCE BETWEEN TWO SPECIES TO BE SEPARATED IS
SO SMALL AS TO NECESSITATE MORE THAN ABOUT 100 TRAYS
A miscible mass separating agent (MSA)
is added, acting as a solvent.
Which increases the volatility difference
among species in the feed.
Thereby reducing the number of trays.
Generally, the MSA is the least volatile
species and is introduced near the top of
the column.
A subsequent operation, usually
distillation, is used to recover the MSA for
recycling. Operation: Extractive distillation
E.g. Separation of acetone and
methanol
If it is difficult to condense the If the feed is vapor and the
vapor leaving the top of a stripping section of the column
distillation column, a liquid MSA is not needed, the operation is
called an absorbent may be referred to as absorption.
fed to the top tray in place of
reflux. The resulting operation E.g. Separation of carbon
is called reboiled absorption. dioxide from combustion
products.
E.g. Removal of ethane and
lower molecular weight
hydrocarbons for LPG
production.

Absorbers generally do not require an ESA and are frequently


conducted at ambient temperature and elevated pressure.
The inverse of absorption is stripping, where liquid mixtures are
separated, at elevated temperature and ambient pressure, by
contacting the feed with a vapor stripping agent.
The MSA eliminates the need to re-boil the liquid at the bottom
of the column, which may be important if the liquid is not
thermally stable.
If trays are needed above the feed tray to achieve the
separation, a refluxed stripper, may be employed.
If the bottoms product from a stripper is thermally stable, it may
be re-boiled without using an MSA. In that case, the column is a
re-boiled stripper.
FORMATION OF MINIMUM-BOILING AZEOTROPES MAKES AZEOTROPIC
DISTILLATION POSSIBLE
E.g. Separation of acetic acid from water
using n-butyl acetate as an entrainer to form
an azeotrope with water.
The MSA, n-butyl acetate, which forms a
two-liquid, minimum-boiling azeotrope with
water, is used as an entrainer in the
separation of acetic acid from water.
The azeotrope is taken overhead,
condensed, and separated into acetate and
water layers.
The MSA is recirculated, and the distillate
water layer and bottoms acetic acid are the
products.
55
WHEN DISTILLATION IS IMPRACTICAL, ESPECIALLY WHEN THE MIXTURE
TO BE SEPARATED IS TEMPERATURE SENSITIVE
A solvent is added sometimes
two which selectively dissolves
only one or a fraction of the
components in the feed.
The operation is then called
liquid-liquid extraction.
E.g. E.g. Recovery of penicillin
from aqueous fermentation
medium by methyl isobutyl
ketone. As with extractive distillation, additional
operations are required to recover solvent
E.g. Use of propane and from the streams leaving the extraction
cresylic acid as solvents to operation.
separate paraffins from
aromatics and naphthenes
WHEN THE CHEMICAL PROCESS IS WET BUT THE PRODUCT
HAS TO BE SOLD DRY
Then the operation is called drying.
The vapor pressure of the liquid to be
evaporated from the solid be higher
than its partial pressure in the gas
stream.
In addition temperature, humidity, air E.g. Removal of water from
flow, and degree of solid subdivision on polyvinylchloride with hot
drying rate, the effects of internal air in a fluid-bed dryer
diffusion conditions, capillary flow,
equilibrium moisture content, and heat
sensitivity must be considered.
WHEN TRANSFER OF LIQUID INTO GAS IS REQUIRED.

The operation is said to be


evaporation.
Defined as the transfer of volatile
components of a liquid into a gas by
heat transfer.
Applications include humidification,
air conditioning, and concentration of
aqueous solutions.

E.g. Evaporation of water


from a solution of urea and
water
WHEN THE DESIRE PRODUCT IS FINELY DIVIDED SOLID
The feasible operation is
crystallization.
It is carried out in some organic, and
in almost all inorganic, chemical
plants.
This is a purification step, so the
conditions must be such that impurities
do not precipitate with the product.
Crystallization of p-xylene
from a mixture with m-xylene
WHEN CONVERSION OF SPECIES FROM GASEOUS TO
SOLID PHASE IS INVOLVED
Sublimation is the transfer of a species from the solid to the gaseous
state without formation of an intermediate liquid phase.
Examples are separation of sulfur from impurities, purification of
benzoic acid, and freeze-drying of foods.
The reverse process, desublimation, is practiced in the recovery of
phthalic anhydride from gaseous reactor effluent.

A common application of sublimation is the use


of dry ice as a refrigerant for storing ice cream,
vegetables, and other perishables.
WHEN THE EXTRACTION FROM SOLID IS REQUIRED
Liquid–solid extraction,
leaching, is used in the
metallurgical, natural product,
and food industries.
To promote rapid solute
diffusion out of the solid and
into the liquid solvent, particle
size of the solid is usually
reduced.
E.g. Extraction of sucrose from
sugar beets with hot water
62
(B) SEPARATION BY BARRIERS
63
(B) SEPARATION BY BARRIERS
 For Micro-Porous membranes, separation is affected by the rate of species
diffusion through the pores; for Non-Porous membranes, separation is
controlled by the differences in solubility in the membrane and rate of
species diffusion.

64
65
It make use of microporous and nonporous membranes as semipermeable
barriers for selective separations.
Fabricated mainly from natural fibers and synthetic polymers.
Membranes are fabricated into flat sheets, tubes, hollow fibers, or spiral-
wound sheets.
For microporous membranes, separation is effected by rate of species
diffusion through the pores.
For nonporous membranes, separation is controlled by differences in
solubility in the membrane and rate of species diffusion.
The most complex and selective membranes are found in the trillions of
cells in the human body.
Osmosis: involves transfer, by a concentration gradient of a solvent
through a membrane into a mixture of solute and solvent. The membrane is
almost impermeable to the solute.
67
68
PROTON EXCHANGE MEMBRANE
IN FUEL CELLS (PEMFC)

69
PROTON EXCHANGE MEMBRANE
IN FUEL CELLS (PEMFC)

70
Reverse osmosis: In this operation transport of solvent in the opposite direction is
effected by imposing a pressure higher than the osmotic pressure on the feed side.
Using a nonporous membrane, reverse osmosis desalts brackish water commercially.
Dialysis: is the transport by a concentration gradient of small solute molecules
through a porous membrane. Microporous membranes selectively allow small solute
molecules and/or solvents to pass through the membrane, while preventing large
dissolved molecules and suspended solids from passing through.
Microfiltration: refers to the retention of molecules from 0.02 to 10 mm.
Ultrafiltration: refers to the retention of molecules that range from 1 to 20nm.
Pervaporation: Same as reverse osmosis but the species transported through the
nonporous membrane is evaporated as a result lesser pressure is needed.
Gas permeation: Separation of gases by selective membrane using pressure as a
driving force.
Liquid membranes: which is only a few molecules thick can be formed from
surfactant-containing mixtures at the interface between two fluid phases.
72
73
74
(C) SEPARATION BY SOLID AGENTS
75
(C) SEPARATION BY SOLID AGENTS
 The solid, in the form of Granular material or packing, is the adsorbent itself,
or it acts as an inert support for a thin layer of adsorbent by selective
adsorption or chemical reaction with species in the feed.
 Adsorption is confined to the surface of solid adsorbent, unlike absorption,
that occurs throughout the absorbent.

76
ADSORPTION VS ABSORPTION

77
78
79
ADSORPTION
Adsorption is used to remove species in low
concentrations and is followed by desorption to
regenerate the adsorbents.
These include activated carbon, aluminum
oxide, silica gel, and synthetic sodium or
calcium, aluminosilicate, zeolites (molecular
sieves).
Equipment consists of a cylindrical vessel
packed with a bed of solid adsorbent particles
through which the gas or liquid flows.
Because regeneration is conducted
periodically, two or more vessels are used, one
desorbing while the other adsorb.
CHROMATOGRAPHY
Separate gas or liquid mixtures by passing them through a packed bed.
The bed may be solid particles (gas–solid chromatography or a solid–inert support
coated with a viscous liquid (gas–liquid chromatography).
Components move through the bed at different rates, thus effecting the separation.
Because of selective adsorption on the solid surface, or absorption into liquid
absorbents followed by desorption.
ION EXCHANGE
Resembles adsorption in that solid particles are used and regenerated.
However, a chemical reaction is involved.
In water softening, an organic or inorganic polymer in its sodium form removes
calcium ions by a calcium–sodium exchange. After prolonged use, the (spent) polymer,
saturated with calcium, is regenerated by contact with a concentrated salt solution.
(D) SEPARATION BY EXTERNAL FIELD
OR GRADIENT 84
(D) SEPARATION BY EXTERNAL FIELD OR GRADIENT
 External Fields can take advantage of differing degrees of response of
molecules and ions to force fields.

85
86
87
(D) SEPARATION BY EXTERNAL FIELD OR GRADIENT
 Centrifugation operation, establishes a pressure field that separates fluid mixtures
according to molecular weight. It is used to separate uranium isotopes and large
polymer molecules according to molecular weight.
 Thermal diffusion, uses temperature gradient to enhance diffusion rate.
 In electrodialysis, cation- and anion-permeable membranes carry a fixed charge,
thus preventing migration of species of like charge.
 In electrophoresis, the different migration velocities of charged colloidal or
suspended species in a electric field is exploited. Positively charged species, such
as dyes, hydroxide sols ad colloids migrate to cathode while most small,
suspended, negatively charged particles go to the anode.
 Another separation technique for biochemical and heterogeneous mixtures of
micromolecular and colloidal materials is field-flow fractionation. An electrical or
magnetic field or thermal gradient is established perpendicular to a laminar-flow
field that will cause separation.

88
COMPONENT RECOVERIES AND
PRODUCT PURITIES 89
COMPONENT RECOVERIES AND PRODUCT PURITY

90
COMPONENT RECOVERIES AND PRODUCT PURITY

91
COMPONENT RECOVERIES AND PRODUCT PURITY

92
COMPONENT RECOVERIES AND PRODUCT PURITY

93
COMPONENT RECOVERIES AND PRODUCT PURITY

94
COMPONENT RECOVERIES AND PRODUCT PURITY

95
COMPONENT RECOVERIES AND PRODUCT PURITY

96
COMPONENT RECOVERIES AND PRODUCT PURITY

97
COMPONENT RECOVERIES AND PRODUCT PURITY

98
COMPONENT RECOVERIES AND PRODUCT PURITY

99
COMPONENT RECOVERIES AND PRODUCT PURITY

100
COMPONENT RECOVERIES AND PRODUCT PURITY

101
SEPARATION SEQUENCE
102
SEPARATION SEQUENCE

103
SEPARATION SEQUENCE

104
SEPARATION SEQUENCE

105
106
SEPARATION FACTOR
107
SEPARATION FACTOR
 If the feed enters near the middle of the column as in distillation, it has both
Enriching and Stripping sections, and is often possible to achieve a sharp
separation between two key components.
 The Stripping section purifies the heaving key and enriching section purifies the
light key.
 A measure of relative degree of separation between two key components, ‘i’ and
‘j’, is the Separation Factor or Power (SP), defined in term of component splits as
measured by the compositions of the two products, (1) and (2):

 Where ‘C’ is some measure of composition. ‘SP’ is readily converted to following


forms in terms of ‘Split Fractions’ or ‘Split Ratios’:

108
SEPARATION FACTOR
 Achievable values of SP depend on the number of stages and the properties of
components ‘i’ and ‘j’.
 In general, components ‘i’ and ‘j’ and products ‘1’ and ‘2’ are selected so that
𝑆𝑃𝐼,𝐽 > 1.
 Then the large value corresponds to high degree of separation and low value
corresponds to low degree of separation.

109
110
111
112
113
SELECTION OF FEASIBLE SEPARATION
PROCESSES 114
SELECTION OF FEASIBLE SEPARATION PROCESSES

115
SELECTION OF FEASIBLE
SEPARATION PROCESSES
Keller’s Correlation
Technological and Use Maturities
Ease of Scale-Up

116
KELLER’S CORRELATION

117
TECHNOLOGICAL AND USE MATURITIES OF SEPARATION PROCESS

118
EASE OF SCALE-UP

119