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Selecting Entrainers For: Reactions and Separations
Selecting Entrainers For: Reactions and Separations
In all other cases, the only way to separate homogeneous azeotropic mixtures via distillation is by adding an
extraneous component, referred to as an entrainer or massseparating agent, to facilitate the separation. Entrainers are
also used to enable the separation of non-azeotropic mixtures where the direct separation is either not feasible due
to process constraints (e.g., maximum operating temperature) or highly uneconomical (e.g., due to the presence of
a severe tangent pinch, as in the case of acetic acid and
water).
An entrainer facilitates the separation of an azeotropic
mixture by selectively altering the relative volatilities of the
components in question, thereby effectively breaking the
azeotrope. The entrainer is specific to the mixture in question e.g., benzene is a feasible entrainer for separating
ethanol and water, but not for separating ethanol and methyl
ethyl ketone so there are no universal entrainers.
Because the choice of an entrainer determines the separation sequence (the number and order of distillation
columns and decanters, and how they are interconnected),
and hence the overall economics of the process, entrainer
selection is a critical step in the synthesis and conceptual
design of azeotropic distillation processes.
Entrainers are commonly selected based on prior experience with the same or a similar process. This approach
rarely identifies novel entrainers that could have a dramatic
impact on the economics of the entire process.
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Distillation Region 1
0.3
0.2
0.1
Acetone
(56.1C)
64C
Binary Azeotrope
Distillation
Region 2
55.2C
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Methanol
(64.5C)
Distillation Boundary
Methyl Ethyl Ketone
(79.3C)
b.
0.9
Residue Curve
0.8
0.7
0.6
0.5
Distillation
Region 1
Distillation
Boundary
0.4
Binary Azeotrope
0.3
64C
0.2
0.1
Acetone
(56.1C)
Distillation
Region 2
55.2C
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Methanol
(64.5C)
Binary Azeotrope
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Types of experiments
After identifying the key properties or missing data
that need to be verified, determine which experiments are
appropriate to confirm the characteristics desired in an
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Acetone
(56.1C)
Entrainer
0.9
0.9
Distillation Boundary
0.8
0.8
Isovolatility Curve
0.7
Binary Azeotrope
0.7
0.6
0.6
0.3
0.3
Distillation
Region 2
Binary Azeotrope
0.1
Isopropanol
(82.3C)
80.4C
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
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0.2
Isovolatility Curve
0.1
Binary Azeotrope
Water
(100C)
50
0.9
0.4
Distillation
Region 1
0.4
0.2
0.8
0.5
0.5
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Figure 3. In the RCM corresponding to classic extractive distillation for a given A-B-E system such that the isovolatility curve intersects the B-E edge of the composition space, B will be the distillate
from the extractive column. An industrial separation corresponding
to this RCM is water (A), ethanol (B), and ethylene glycol (E).
Extractive Column
A+B
1
0.95
0.9
Azeotrope
(1.5% Ethylene Glycol)
Azeotrope
(no Ethylene Glycol)
tillate. In addition,
the closer the intersection is to the
0.6
0.8
pure component A
0.8
0.85
0.9
0.95
1
or B, the better the
0.4
Liquid Mole Fraction (Ethanol)
No Ethylene Glycol
entrainer for this
10 mol% Ethylene Glycol
25 mol% Ethylene Glycol
0.2
separation (i.e., the smaller the entrainer-to-feed ratio).
50 mol% Ethylene Glycol
1.5 mol% Ethylene Glycol
Therefore, the isovolatility curve can be used to quickly
0
and efficiently rank candidate entrainers for extractive
0
0.2
0.4
0.6
0.8
1
distillation.
Liquid Mole Fraction (Ethanol)
The component recovered as the extractive-column
Figure 5. A pseudo-binary VLE diagram for ethanol/water at fixed
distillate
can also be determined using a pseudo-binary
ethylene glycol compositions shows that as the ethylene glycol
phase diagram, in which VLE data are plotted on an
composition is increased, the ethanol/water pseudo-azeotrope
entrainer-free basis (Figure 5). As the amount of
moves toward ethanol and eventually disappears. At this point,
ethanol is more volatile, so it will be the distillate from the extractive
entrainer is increased, the composition of the pseudocolumn in Figure 4.
azeotrope (i.e., the point at which the pseudo-binary VLE
curve crosses the 45-deg. line) changes until it completely
Example 2. Extractive distillation
disappears. The more volatile of the two components at
In extractive distillation, a heavy (high-boiling, lowthis point will be the distillate from the extractive column.
volatility) entrainer is used to separate a mixture exhibitThe smaller the composition of the entrainer at which the
ing a minimum boiling azeotrope. The typical extractivepseudo-binary azeotrope disappears, the better the
distillation entrainer has a higher boiling point than the
entrainer is (smaller entrainer-to-feed ratio). Consepure components, and it does not form any azeotropes
quently, pseudo-binary phase diagrams can also be used
with either of the pure components.
to rank candidate extractive-distillation entrainers. In
A common industrial example of extractive distillaaddition, these diagrams are very useful for understanding
tion is the use of ethylene glycol to separate ethanol and
the effect of mixed extractive-distillation entrainers.
water. The residue curve map corresponding to a similar
Example 3. Using water to separate
extractive distillation is shown in Figure 3. Since this
n-butanol and n-butyl acetate
RCM does not exhibit any distillation boundary, the
components to be separated (A and B) lie in the same
Since butanol and water form a minimum-boiling homodistillation region, and hence the candidate entrainer (E)
geneous azeotrope, they cannot be separated without the use
is feasible. Analysis of the extractive distillation RCM
of an entrainer. One possible candidate entrainer is water.
reveals that A and B (at all feed compositions) can be
The residue curve map for butanol/butyl-acetate/water
separated using the sequence shown in Figure 4. Note
(Figure 6) shows that this system exhibits three binary
that the first column, the extractive column, must be a
azeotropes (butanol/butyl-acetate [homogeneous],
double-feed column, with two separate feed locations
butanol/water [heterogeneous], butyl-acetate/water [heteroand stages, both above and below each feed. The
geneous]) and a heterogeneous ternary azeotrope, and three
entrainer is introduced at the upper feed location and the
distillation boundaries divide the composition space into
feed to be separated is introduced at the lower location.
three distinct distillation regions. Note that butanol and butyl
One of the components is recovered as the distillate
acetate lie in different distillation regions. However, since
from the extractive column and the other as the distillate
this mixture also exhibits a multiple-liquid-phase region,
from the second column, the entrainer recovery column.
with tie-lines that cross the boundary separating butanol and
The isovolatility curve (the locus of points at which
butyl acetate into different distillation regions, water is a feathe relative volatility of A and B is equal to 1) can be
sible entrainer for separating butanol and butyl acetate.
used to determine which of the two components, A or
The RCM in Figure 6a is similar but not identical to
B, is the distillate from the extractive column. This
the classical ethanol/water/benzene example. The flowcurve (Figure 3) starts at the binary azeotrope and ends
sheet sequence in Figure 6b also resembles one of the
at one of the other edges of the composition triangle. If
feasible sequences for separating ethanol/water using a
it intersects the B-E edge, then B will be the distillate
heterogeneous entrainer. The difference in the RCMs is
from the extractive column; alternatively, if it intersects
in the nature of the multiple-liquid-phase region. The
ethanol/water/benzene system has a Type I phase envethe A-E edge, then A will be the extractive-column dis0.8
0.85
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Butanol
(117.7C)
c
0.9
0.8 116.9C
0.7
Multiple-Liquid-Phase Region
0.6
a
Tie-Line
0.5
0.4
d
L2
0.3
Binary Azeotrope
b
92.6C
0.2
Ternary
Azeotrope
90.7C
0.1
91.2C
Butyl Acetate
(126C) e
0.1
0.2
0.3
0.4
0.5
0.6
Water
0.7
0.9 L1 (100C)
0.8
b
d
L1
Feed
L2
Butanol
Butyl Acetate
lope, i.e., only a single binary pair (namely benzene/water) exhibits a liquid-liquid behavior, whereas
the butanol/butyl-acetate/water system has a Type II
envelope, where two binary pairs (butanol/water and
butyl-acetate/water, show heterogeneous behavior.
Table 1 lists all the thermodynamic conditions that water
must satisfy to be a feasible entrainer for separating butanol
and butyl acetate using either of the two separation sequences.
This list can be used to determine what experiments are necessary to validate entrainer feasibility (e.g., a simple LLE
experiment could be used to verify that one end of the liquidliquid equilibrium tie-line does indeed lie in the distillation
region that contains butyl acetate). Feasibility conditions are
unique to each particular RCM and describe the thermodynamic conditions necessary to make an entrainer feasible
based on either of the previously discussed rules of feasibility
(that is, the entrainer does not divide the components to be
separated into different distillation regions, or it induces a
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Example 4. Diethoxymethane/ethanol
separation using water
A key advantage of using a residue curve map for
entrainer selection is that it can be used to find novel
entrainers and/or separation sequences.
Consider water as a potential entrainer for separating a
binary mixture containing 50 mol% diethoxymethane
(DEM) and 50 mol% ethanol. This binary mixture forms a
minimum-boiling homogeneous azeotrope (2). The residue
Ethanol
(78.3C)
Feed
Binary Azeotrope
0.9
78.1C
0.8
0.7
76.7C
Ternary Azeotrope
0.6
Binary
Azeotrope
76C
0.4
Diethoxymethane
Tie-Line
0.3
0.1
80C
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Water
(100C)
Binary Azeotrope
Literature Cited
1.
2.
3.
4.
5.
6.
Water
0.2
Diethoxymethane
(87.6C)
Ethanol
Multiple-Liquid-Phase Region
0.5
Final thoughts
Although the RCM-based methodology is very powerful and can be used to find innovative new separation
sequences and identify novel entrainers, several limitations have hindered its widespread use in industry. While
there are now good commercially available tools for computing and sketching residue curve maps, they still
require either a good physical-property model or an
extensive azeotrope database. A bigger limitation is that
interpreting the structure of the RCM and synthesizing
feasible separating sequences requires significant knowledge and expertise in RCM technology. However, new
software programs have recently become available that
significantly reduce this hurdle and make the technology
accessible to process engineers and chemists.
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VIVEK JULKA, PhD, is a principal engineer at ClearWaterBay Technology,
Inc. (E-mail: vjulka@cwbtech.com) and is the product manager for the
AzeoDESK software for azeotropic distillation. He is an expert in the
synthesis and conceptual design of separation processes. He
previously worked for AspenTech, and Union Carbide Corp. He holds a
PhD in chemical engineering from the Univ. of Massachusetts Amherst.
MADHURA CHIPLUNKAR, is an advanced engineer at ClearWaterBay
Technology, Inc (E-mail:mchiplunkar@cwbtech.com). Her interests lie
in the synthesis of distillation-based processes, with special emphasis
on azeotropic and reactive systems. She has also been involved in the
development of the AzeoDESK software for azeotropic distillation. She
holds an MS in chemical engineering from the Univ. of Massachusetts
Amherst.
LIONEL OYOUNG, PhD, is president and co-founder of ClearWaterBay
Technology, Inc. (4000 Valley Blvd., Suite 100, Walnut, CA 91789;
Phone: (909) 595-8928; Fax: (909) 595-6899; E-mail:
lionel@cwbtech.com). He has more than 15 years of experience in
process synthesis and development and owns several process
patents. Before ClearWaterBay Technology, he worked for Mitsubishi
Chemical Corp., Union Carbide Corp., and Linnhoff March, in a variety
of engineering and management positions. He holds BS and PhD
degrees in chemical engineering from the Univ. of Manchester
(formerly UMIST), Manchester, UK. He is a member of AIChE and
recipient of AIChEs 2007 Computing Practice Award.
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