EKC 316 SEPARATION PROCESS

LECTURE SERIES

AZEOTROPIC DISTILLATION
OPTIONS PART 1

30.10.2024
 REVIEW FROM LAST LECTURE

2 main criteria: Bottom, Feed & Top must lie on the straight line
Bottom & Top must lie on the same Residue curve
REVIEW FROM LAST LECTURE
F F
 F

F
F F
 FUG
+ DETAIL DESIGN SIMULATOR
RESIDUE CURVE
Pressure Swing Distillation ➢ A binary azeotrope that changed composition by > 5 mol% over a moderate range of
pressure
➢ 2 ordinary distillation columns operating in series at different pressure
➢ A pump/compressor is needed to increase the pressure
Extractive Distillation ➢ Adding solvent to alter the volatility of 1 component in azeotrope mixture
➢ Solvent Restriction: Highest boiling point & does not form azeotrope
➢ Minimum-boiling azeotrope - solvent (with a lower volatility than the key
components of the feed mixture) is added to a tray just a few trays below the top of
the column
➢ Maximum boiling azeotrope- solvent enters the column with the feed
➢ Recycle pure entrainer
➢ Start with A Pre-Concentrator. Max 3 columns

Homogeneous Azeotrope ➢ Solvent Restriction: Use of any entrainer that form azeotrope of entrainer + one of
Distillation components. At least 1 maximum boiling point must form (Quite rare).
(modified Extractive Distillation) ➢ Instead of recycling pure entrainer, an azeotrope of entrainer with one of
component is recycled. Thus, require to find solvent that can form azeotropic
mixture.
➢ Only 2 columns
Heterogeneous Azeotrope ➢ Solvent that can form binary/ternary azeotrope. No restrictions
Distillation ➢ Overhead vapour from the column is set close to the composition of the
(based on liquid-liquid heterogenous azeotrope
extraction) ➢ When condensed 2 liquid phases are formed in a decanter. The 2 liquid usually lie in
different regions of Residue Curve. Thus, HAD can cross the distillation boundary.
➢ Only 2 columns
Reactive Distillation ➢ Simultaneous reaction and distillation. Reaction normally in liquid phase or at
surface solid catalyst in contact with liquid.
➢ Separation of azeotrope A and B if chemically reacting with entrainer E
PRESSURE SWING DISTILLATION
➢A binary azeotrope that changed composition by > 5 mol% over a
moderate range of pressure
➢2 ordinary distillation columns operating in series at different
pressure
➢A pump/compressor is needed to increase the pressure
Distillation sequence for minimum-boiling azeotrope
Distillation sequence
for maximum-boiling
azeotrope.
EXTRACTION DISTILLATION
➢Adding solvent to alter the volatility of component in azeotrope mixture
➢Solvent Restriction: Highest boiling point & does not form azeotrope
➢Minimum-boiling azeotrope - a solvent, with a lower volatility than the key
components of the feed mixture, is added to a tray just a few trays below
the top of the column
➢Maximum boiling azeotrope- the solvent enters the column with the feed
➢Recycle pure entrainer
➢Start with A Pre-Concentrator. Max 3 columns
➢Extractive distillation is used to separate azeotropes and close-boiling
mixtures
➢minimum-boiling azeotrope - a solvent, with a lower volatility than
the key components of the feed mixture, is added to a tray just a few
trays below the top of the column so that (1) the solvent is present in
the down-flowing liquid, and (2) little solvent is stripped and lost to
the overhead vapor
➢maximum boiling azeotrope- the solvent enters the column with the
feed. The components in the feed must have different solvent
affinities so that the solvent causes an increase in a of the key
components, to the extent that separation becomes feasible and
economical.
➢ The solvent should not form an azeotrope with any components in
the feed. Usually, a molar ratio of solvent to feed on the order of 1
is required. The bottoms are processed to recover the solvent for
recycle and complete the feed separation. Can be calculated using
Level Arm Rule
 DESIGN STAGES
As in azeotropic distillation, design of extractive distillation system will
also require significant preliminary work including:
➢Choosing the solvent
➢Developing or finding necessary data, such as azeotropic condition or
residue curve
➢Preliminary screening, distillation sequence, compositions, etc
➢Computer simulation
➢Small scale testing
LET US DESIGN THE DISTILLATION SEQUENCE FOR THE SYSTEM BELOW

F1
REVIEW: BASIC LEVER ARM RULE
IN CLASS EXAMPLE ADO(1)
 Chloroform, 61.10C Residue curve

Benzene
What is the compositions of F1?
80.24C Acetone
56.16C
 61.10C

64.43C

80.24C
A ratio of 3.1667 moles of
56.16C benzene per mole of (acetone +
chloroform) in the combined
feed to the first column
 F F1 D1 B2=F2 D2 B2
Acetone 12.00 12
Chloroform 9.8857 12
Benzene 76
TOTAL 21.89 100 12.24 87.76

Data:
If the fresh feed is 21.89 mol/s of 54.83 mol% acetone, with the balance chloroform
99% of acetone in D1, 99% Chloroform in D2
A ratio of 3.1667 moles of benzene per mole of (acetone + chloroform) in the
combined feed to the first column
 PART 2

HOMOGENEOUS DISTILLATION
➢Solvent Restriction: Use of any entrainer that form of azeotrope of
entrainer + one of components. At least 1 maximum boiling point
must be formed (Quite rare).
➢Instead of recycling pure entrainer, an azeotrope of entrainer with
one of component is recycled. Thus, require to find solvent that can
form azeotropic mixture.
➢Only 2 columns
The conditions that a potential entrainer must satisfy have been
studied by Doherty and Caldarola [16]; Stichlmair, Fair, and Bravo [1];
Foucher, Doherty, and Malone [14]; Stichlmair and Herguijuela [18];
Fidkowski, Malone, and Doherty [13]; Wahnschafft and Westerberg
[38]; and Laroche, Bekiaris, Andersen, and Morari [39]. If it is
assumed that a distillation boundary, if any, of a residue curve map is
straight or cannot be crossed, the conditions of Doherty and
Caldarola apply. These are based on the rule that for entrainer E, the
two components, A and B, to be separated, or any product azeotrope,
must lie in the same distillation region of the residue-curve map.
Thus, a distillation boundary cannot be connected to the A–B
azeotrope. Furthermore, A or B, but not both, must be a saddle.
Seader, page 432, Section 11.5
B
HETEROGENEOUS DISTILLATION
➢Solvent that can form binary/ternary azeotrope
➢Overhead vapour from the column is set close to the composition of
the heterogenous azeotrope
➢When condensed 2 liquid phases are formed in a decanter. The 2
liquid usually lie in different regions of Residue Curve. Thus, HAD can
cross the distillation boundary.
➢Only 2 columns. (Can be 3 columns if include preconcentrator)
If it has two, the overall, two-liquid-phase composition is equal to that
of the vapor phase. Thus, all three phases have different compositions.
The overhead vapor from the column is close to the composition of the
heterogeneous azeotrope. When condensed, two liquid phases form in
a decanter. After separation, most or all of the entrainer-rich liquid
phase is returned to the column as reflux, while most or all of the other
liquid phase is sent to the next column for further processing. Because
these two liquid phases usually lie in different distillation regions of the
residue-curve map, the restriction that dooms homogeneous
azeotropic distillation is overcome. Thus, in heterogeneous azeotropic
distillation, the components to be separated need not lie in the same
distillation region
Seader, page 436
In thermodynamics, the binodal, also
known as the coexistence
curve or binodal curve, denotes the
condition at which two
distinct phases may coexist.

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ALTERNATIVELY, REARRANGE THE COLUMNS. MAKE FULL USE OF TERNARY AZEOTROPE
F
D1

F1
D2
F2

L2
 TO CHANGE TO NON TERNARY AZ

F
D1

F1
D2
F2

L2
IN CLASS EXAMPLE ADO(2)
REACTIVE DISTILLATION
➢ This technique embodies
simultaneous reaction and
separation. Catalysts are enclosed
in special packing inside a
distillation column. This method
uses distillation to remove products
as they are formed in order to shift
the chemical equilibrium of a
reaction toward 100% conversion.
➢ In reactive distillation, one or more
feeds can be used, and the reactive
zone can be anywhere in the
column, and depending on the
product, it may exit from either the
overhead or bottom.
➢ Today, reactive distillation is used mainly for etherification and esterification
reactions, but it has also been successfully applied to alkylation and nitration
reactions. Most early applications involved liquid-phase reactions; and if a
catalyst was utilised, it was in solution. In more recent applications, solid
catalysts had been used. An example is the production of methyl-tertbutyl-
ether (MTBE), an octane booster for gasoline.
➢ The pre-reactor provides a reaction equilibrium of over 90% MTBE, with the
reactive distillation pushing the reaction another 5-10% to almost total
conversion of the reactants. In the reactive zone, bales containing beads of
catalyst resins are stacked on top each other.
➢ The advantage of reactive distillation is the elimination of complicated product
recovery and, separation and recycling of unconverted reactants, all of which
lead to savings in equipment and energy costs.
Commercial application of reactive
distillation
➢Simultaneous reaction and distillation. Reaction normally in liquid
phase or at surface solid catalyst in contact with liquid.
➢Separation of azeotrope A and B if chemically reacting with entrainer E