Simultaneous Heat and Mass Transfer

Ch.E - 402

Muhammad Rashed Javed

2 Enhanced Distillation Techniques
 In the systems considered previously, the vapor becomes steadily
richer in the more volatile component on successive plates.
 There are two types of mixture where this steady increase in the
concentration of the more volatile component, either does not take
place, or it takes place so slowly that an uneconomic number of
plates is required.
 If, for example, a mixture of ethanol and water is distilled, the
concentration of the alcohol steadily increases until it reaches 96
per cent by mass, when the composition of the vapor equals that of
the liquid, and no further enrichment occurs. This mixture is called
an azeotrope, and it cannot be separated by straightforward
distillation.

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3 Enhanced Distillation Techniques
 Such a condition is shown in the y − x curves of Fig. 11.4 where it is
seen that the equilibrium curve crosses the diagonal, indicating the
existence of an azeotrope. A large number of azeotropic mixtures
have been found, some of which are of great industrial importance,
such as water-nitric acid, water-hydrochloric acid, and water-
alcohols.

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4 Enhanced Distillation Techniques
 The second type of problem occurs where the relative volatility of a
binary mixture is very low, in which case continuous distillation of the
mixture to give nearly pure products will require high reflux ratios
with correspondingly high heat requirements.
 In addition, it will necessitate a tower of large cross-section
containing many trays.
 An example of the second type of problem is the separation of n-
heptane from methyl cyclohexane in which the relative volatility (a)
is only 1.08 and a large number of plates is required to achieve
separation.
 When Relative Volatility (a) < 1.10, separation by ordinary distillation
may be uneconomical, and even impossible if an azeotrope forms.
In that event, enhanced distillation techniques must be explored.

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5 Raoult’s Law and Activity Coefficients
 For an ideal mixture, the partial pressure is related to the
concentration in the liquid phase by Raoult’s law which may be
written as:

 Where yAP = PA is partial pressure of component A in the mixture,

PA0 is the vapour pressure of pure A at the same temperature, P is
the total pressure and yA and xA are mole fractions of component A
is vapor and liquid phase respectively.
 For a non-ideal system the term γ, the activity coefficient, is
introduced to give:

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6 Raoult’s Law and Activity Coefficients
 The activity coefficient (γi) is a measure of the liquid-phase non-
ideality of a mixture and its value varies with both temperature and
composition.
 When γi =1 the liquid phase is said to form an ideal solution
governed by Raoult’s law. Nonideal mixtures (γi ≠1) can exhibit
either positive (γi >1) or negative (γi <1) deviations from Raoult’s law.
 Positive deviations are more common and occur when the
molecules of the different compounds in the solution are dissimilar
and have no preferential interactions between them.
 Negative deviations occur when there are preferential
attractive forces (hydrogen bonds, etc.) between the molecules of
the different species that do not occur in the absence of the other
species.

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 7 Activity Coefficients
Activity
Behavior Type
Coefficient
1 Ideal Solution Behavior γi =1
2 Positive Deviations from Ideal Solution Behavior γi >1
3 Negative Deviations from Ideal Solution Behavior γi <1
4 Two-Liquid Phase-Heteroazeotropes

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8 Activity Coefficients and Azeotropes
 In many highly nonideal mixtures deviations from ideality (γi =1)
become so large that the pressure-composition (P-x,y) and
temperature-composition (T-x,y) phase diagrams exhibit a
minimum or maximum azeotrope point.
 In the context of the T-x,y phase diagram, these points are
called the minimum boiling azeotrope (where the boiling
temperature of the azeotrope is less than that of the pure
component) or
 maximum boiling azeotrope (the boiling temperature of the
azeotrope is higher than that of the pure components).
 About 90% of the known azeotropes are of the minimum
variety. At these minimum and maximum boiling azeotrope,
the liquid phase and its equilibrium vapor phase have the
same composition.

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 Minimum Boiling or Positive Azeotrope
9 (γi >1)

Positive azeotrope – mixture of

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chloroform and methanol
 Maximum Boiling or Negative Azeotrope
10 (γi <1)

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Negative azeotrope – mixture of formic
acid and water
 Heterogenous & Homogeneous
11 Azeotropic Mixtures
 Two main types of minimum boiling azeotropes exist, i.e. the
homogeneous azeotrope, where a single liquid phase is in the
equilibrium with a vapor phase; and the heterogeneous
azeotropes, where the overall liquid composition which form two
liquid phases, is identical to the vapor composition.

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T-xy diagrams for a homogeneous (left) and
heterogeneous azeotrope (right).
12 Separation of Azeotropic Mixtures
 For the separation of azeotropic mixtures different approaches can
be used, see for example:
A. Methods without external components (entrainers)
 Two-pressure rectification (in some mixtures the azeotrope can be
broken by changing system pressure);
 Pressure-swing distillation where a series of column operating at
different pressures are used to separate binary azeotropes which
change appreciably in composition over a moderate pressure range.

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13 Separation of Azeotropic Mixtures
B. Methods with external components (entrainers)
 Extractive distillation and homogeneous azeotropic distillation where
the liquid separating agent is completely miscible.
 Heterogeneous azeotropic distillation, or more commonly, azeotropic
distillation where the liquid separating agent, called the entrainer, forms
one or more azeotropes with the other components in the mixture and
causes two liquid phases to exist over a wide range of compositions. This
immiscibility is the key to making the distillation sequence work.
 Distillation using ionic salts: The salts dissociates in the liquid mixture and
alters the relative volatilities sufficiently that the separation become
possible.
 Reactive distillation, where the separating agent reacts preferentially
and reversibly with one of the azeotropic constituents. The reaction
product is then distilled from the nonreacting components and the
reaction is reversed to recover the initial component.
 Pressure-swing distillation where a separating agent which forms a
pressure-sensitive azeotrope is added to separate a pressure-insensitive
azeotrope.
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 Methods without external components
14 (entrainers)-Pressure-swing distillation
 If a binary azeotrope disappears at some pressure, or changes
composition by 5 mol% or more over a moderate range of pressure,
consideration should be given to using two ordinary distillation
columns operating in series at different pressures. The effect of
pressure on temperature and composition of two minimum-boiling
azeotropes is shown in Figure 11.22.
 The mole fraction of ethanol in the ethanol–water azeotrope
increases from 0.8943 at 760 torr to more than 0.9835 at 90 torr. Not
shown in Figure 11.22b is that the azeotrope disappears at below 70
torr.

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 Methods with external components
15 (entrainers)
 When an entrainer is added to a binary mixture, a ternary
mixture results, and it is then necessary to consider the phase
equilibria for this new mixture as well as to predict the ranges of
possible overhead and bottoms compositions.
 Triangular diagrams are often used to describe the equilibrium
relationships for ternary mixture. Especially important are the
residue curves on the diagrams.

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 Extractive distillation
16
 Extractive distillation is used to separate azeotropes and
close-boiling mixtures.
 Extractive distillations can be divided into three categories,
each correspond to the different residue curve maps,
 the minimum boiling azeotropes,
 maximum boiling azeotropes and
.
 the non-azeotrope mixtures.
 If the feed is a 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.
 If the feed is a maximum boiling azeotrope, the solvent enters
the column with the feed.
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17 Extractive distillation
 The components in the feed must have different solvent
affinities so that the solvent causes an increase in relative
volatility 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.

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 Extractive distillation-Industrial
18 Applications

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 Solvent Selection for Extractive
19 Distillation
 One of the most important steps in developing a successful
(economical) extractive distillation sequence is selecting a good
solvent. In general, selection criteria include the following:
 Should enhance significantly the natural relative volatility of the key
component.
 Should not require an excessive ratio of solvent to nonsolvent
.
(because of cost of handling in the column and auxiliary equipment.
 Should remain soluble in the feed components and should not lead to
the formation of two phase.
 Should be easily separable from the bottom product.
 Should be inexpensive and readily available.
 Should be stable at the temperature of the distillation and solvent
separation.
 Should be nonreactive with the components in the feed mixture.
 Should have a low latent heat.
 Should be noncorrosive and nontoxic.
 Naturally no single solvent or solvent mixture satisfy all the criteria,
and compromises must be reached.
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 Solvent Selection for Extractive
20 Distillation
 Perry's handbook serve as a good reference for the solvent
selection procedure:
 Homologous series: Select candidate solvent from the high
boiling homologous series of both light and heavy key
components.
 Robbins
. Chart: Select candidate solvents from groups in the
Robbins Chart that tend to give positive (or no) deviations
from Raoult's law for the key component desire in the distillate
and negative (or no) deviations for the other key.
 Hydrogen-bonding characteristic: are likely to cause the
formation of hydrogen bonds with the key component to be
removed in the bottoms, or disruption of hydrogen bonds with
the key to be removed in the distillate. Formation and
disruption of hydrogen bonds are often associated with strong
negative and positive deviations, respectively from Raoult's
Law.
 Polarity characteristic: Select candidate solvents from
chemical groups that tend to show higher polarity than one
key component or lower polarity than the other key.
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 Solvent Selection for Extractive
21 Distillation
 Boiling point characteristic: Select only candidate solvents
that boil at least 30-40 0C above the key components to
ensure that the solvent is relatively nonvolatile and remains
largely in the liquid phase. With this boiling point difference,
the solvent should also not form azeotropes with the other
components.
.
 Selectivity at the infinite dilution: Rank the candidate solvents
according to their selectivity at infinite dilution.
 Experimental measurement of relative volatility: Rank the
candidate solvents by the increase in relative volatility caused
by the addition of the solvent. Residue curve maps are of
limited usefulness at the preliminary screening stage because
there is usually insufficient information available to sketch the
them, but they are valuable and should be sketched or
calculated as part of the second stage of the solvent
selection.

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 Distillation using ionic salts
22  Using ionic salts as entrainers in extractive distillation. The salts
dissociates in the liquid mixture and alters the relative
volatilities sufficiently that the separation become possible.
 Water, as a solvent in the extractive distillation of acetone
and methanol, has the disadvantages that a large amount is
required to adequately alter a and, even though the solvent
is introduced into the column several trays below the top,
.
enough water is stripped into the distillate to reduce the
acetone purity to 95.6 mol%.
 The water vapor pressure can be lowered, and thus the purity
of acetone distillate increased, by using an aqueous
inorganic-salt solution as the solvent.

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23 Distillation using ionic salts
 A 1927 patent by Othmer [23] describes use of a
concentrated, calcium chloride brine. Not only does calcium
chloride, which is highly soluble in water, reduce the volatility
of water, but it also has a strong affinity for methanol. Thus, a
of acetone with respect to methanol is enhanced. The
separation of brine solution from methanol is easily
.
accommodated in the subsequent distillation, with the brine
solution recycled to the extractive distillation column. The
vapor pressure of the dissolved salt is so small that it never
enters the vapor, provided entrainment is avoided.
 An even earlier patent by Van Raymbeke [24] describes the
extractive distillation of ethanol from water using solutions of
calcium chloride, zinc chloride, or potassium carbonate in
glycerol.
 Salt can be added as a solid or melt into the column by
dissolving it in the reflux before it enters the column.

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24 Distillation using ionic salts
Salt distillation is accompanied by several problems:
 First and foremost is corrosion, particularly with aqueous
chloride-salt solutions, which may require stainless steel or a
more expensive corrosion-resistant material.
 Feeding and dissolving a salt into the reflux poses problems
since. the solubility of salt will be low in the reflux because it is
rich in the more-volatile component, the salt being most
soluble in the less-volatile component.

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 Homogeneous azeotropic distillation
25
 An azeotrope can be separated by extractive distillation,
using a solvent that is higher boiling than the feed
components and does not form any azeotropes.
 Alternatively, the separation can be made by homogeneous
azeotropic distillation, using an entrainer not subject to such
restrictions.
 The conditions that a potential entrainer must satisfy have
been studied. 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.

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 Heterogeneous azeotropic distillation
26
 Required for homogeneous azeotropic distillation is that A and
B lie in the same distillation region of the residue-curve map as
entrainer E. This is so restrictive that it is difficult, if not
impossible, to find a feasible entrainer.
 A better, alternative technique that finds wide use is
heterogeneous azeotropic distillation to separate close-
.
boiling binaries and minimum-boiling binary azeotropes by
employing an entrainer that forms a binary and/or ternary
heterogeneous (two-phase) azeotrope.

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 Reactive distillation
27
 Reactive distillation denotes simultaneous chemical reaction
and distillation. The reaction usually takes place in the liquid
phase or at the surface of a solid catalyst in contact with the
liquid.
 One application of reactive distillation, described by Terrill,
Sylvestre, and Doherty [57], is the separation of a close-boiling
or azeotropic
. mixture of components A and B, where a
chemically reacting entrainer E is introduced into the column.
 If A is the lower-boiling component, it is preferable that E be
higher boiling than B and that it react selectively and
reversibly with B to produce reaction product C, which also
has a higher boiling point than component A and does not
form an azeotrope with A, B, or E.
 Component A is removed as distillate, and components B and
C, together with any excess E, are removed as bottoms.
Components B and E are recovered from C in a separate
distillation, where the reaction is reversed C B+E; B is taken
off as distillate, and E is taken off as bottoms and recycled to
the first column.

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 Reactive distillation
28
Reactive distillation should be considered whenever the
following hold:
 The chemical reaction occurs in the liquid phase, in the
presence or absence of a homogeneous catalyst, or at the
interface of a liquid and a solid catalyst.
 Feasible
. temperature and pressure for the reaction and
distillation are the same. That is, reaction rates and distillation
rates are of the same order of magnitude.
 The reaction is equilibrium-limited so that if one or more of the
products can be removed by distillation, the reaction can be
driven to completion; thus, a large reactant excess is not
necessary for a high conversion.

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 References
29
 Seader, J. D., and Ernest J. Henley. Separation Process
Principles. New York, NY: Wiley, 1998.

Simultaneous Heat & Mass Transfer