346

Miller, K. J .; Noddings, C. R.; Nattkemper, R. C. Preventing Bed

Fires in Carbon Adsorption Systems. &'roc.-APCA Annu. Meet.
1987, 80th, Vol. 3, 87/50.7, 1-11.
Naujokas, A. A. Preventing Carbon Bed Combustion Problems. Loss
Prev., CEP Man. 1979,12,128-135.
Naujokas, A. A. Spontaneous Combustion of Carbon Beds. Plant/
Oper. h o g . 1985,4 (2), 120-126.
Takeuchi, Y.; Mizutani, M.; Ikeda, H. Prevention of Activated Car-
Ind. Eng. Chem. Res. 1992,31,346-357
bon Bed Ignition and Degradation During the Recovery of Cy
clohexanone. J. Chem. Eng. J pn. 1990,23 (lo), 68-74.
Wildman, J. Practical Problems in Solvent Recovery Using Activated
Carbon. Proc. Znt. Conf. Carbon 1988, 185-187.
Received for review February 4, 1991
Revised manuscript received August 2, 1991
Accepted August 15, 1991
A New Pressure-Swing-Distillation Process for Separating
Homogeneous Azeotropic Mixtures
Jeffrey P. Knapp and Michael F. Doherty*
Department of Chemical Engineering, Goessmann Laboratory, University of Massachusetts, Amherst,
Massachusetts 01003
Mixtures in which the desired products lie in different distillation regions can be separated by a
new pressure-swing process when one end of the distillation boundary isa pressure-sensitive azeotrope.
Thus pressure-insensitive binary azeotropes can be separated using novel entrainers that form
pressure-sensitive distillation boundaries. Because the columns already operate at different preasures,
such sequences are readily thermally integrated. The separations of ethanol from water and acetone
from methanol are used to demonstrate the new pressure-swing technique. These examples exhibit
some interesting behavior such as (1) a region of multiplicity in the number of trays required to
achieve the same separation at fixed reflux ratio, (2) a maximum reflux above which no feasible
column exists, (3) a separation where the unexpected component is the distillate due to a reversal
of the relative volatility as the pressure changes, and (4) a nonazeotropic separation that becomes
easier as the pressure is increased.
Introduction
Azeotropic mixtures are typically separated by either
homogeneous azeotropic distillation (includes extractive
distillation), heterogeneous azeotropic distillation, distil-
lation using salt effects, or pressure-swing distillation. Of
these four methods, pressureswing distillation is the least
studied. However, with a recent National Research
Council report (King et al., 1987) declaring that energy
conservation in nonideal mixture separations is a vital
research area, pressure-swing distillation deserves a second
look, since these sequences are readily thermally inte-
grated.
Although the pressure sensitivity of azeotropes has been
known since the 18609 (Roscoe and Dittmar, 1859; Roscoe,
1860, 1862), Lewis (1928) appears to be the first one to
exploit this property to distill azeotropic mixtures. Since
then pressure-swing distillation has been proposed to
separate the ethanol-water azeotrope (Lewis, 1928; Black,
1980), a number of alcohol-ketone azeotropes including
methanol-acetone, methanol-methyl ethyl ketone (MEK),
ethanol-MEK, ethanol-methyl n-propyl ketone, 1-
propanol-methyl n-propyl ketone, and 2-propanol-MEK
(Britton et al., 1943), and the tetrahydrofuran (THF)-
water azeotrope (Abu-Eishah and Luyben, 1985; Chang
and Shih, 1989). In fact, pressureswing distillation is the
method often used by industry to separate THF and water,
and Chang and Shih (1989) showed that there is no cost
advantage in switching to heterogeneous azeotropic dis-
tillation with n-pentane. Table I lists some other azeo-
tropes that may also be amenable to this technique.
Since the conventional pressure-swing-distillation pro-
cess is restricted to binary mixtures with pressure-sensitive
azeotropes, it is of limited usefulness. In this paper, we
will show how pressure-swing distillation can be extended
to separate the much broader class of pressure-insensitive
azeotropes by using an entirely new class of entrainers, and
how it can be used to separate some multicomponent
mixtures containing distillation boundaries that lie be-
0808-5885192 f 2631-0346$03.00/0
Table I. Selected Examples of Pressure-Sensitive Binary
Azeotropes
components rep
carbon dioxideethylene
hydrochloric acid-water
water-formic acid
water-acetonitrile
water-acrylic acid
water-acetone
water-propylene oxide
water-methyl acetate
water-propionic acid
water-2-methoxyethanol
water-2-butanone (methyl ethyl ketone [MEK])
water-tetrahydrofuran (THF)
carbon tetrachloride-ethanol
carbon tetrachloride-ethyl acetate
carbon tetrachloride-benzene
methanol-acetone
methanol-2-butanone (MEK)
methanol-methyl propyl ketone
methanol-methyl acetate
methanol-ethyl acetate
methanol-benzene
methylamine-trimethylamine
ethanol-dioxane
ethanol-benzene
ethanol-heptane
dimethylamine-trimethylamine
2-propanol-benzene
propanol-benzene
propanol-cyclohexane
2-butanone (MEK)-benzene
2-butanone (MEK)-cyclohexane
isobutyl alcohol-benzene
benzene-cyclohexane
benzene-hexane
phenol-butyl acetate
aniline-octane
' (1) Horsley, 1973. (2) Britton et al., 1947.
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1, 2
1, 2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
tween the desired products without the addition of an
entrainer. A second intent of this paper is to point out
0 1992 American Chemical Society
Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992 347
Entrainer
Material Balance Line
. .. . . . . . . Recycle Balance Line
Distillation Boundary
at cited pressure
---
pressure
I Azeotrope
Pure B F F1 Pure A
Comporltlon
(a)
I
, Pressure , P :, , 1 Pressure pP ,
D2
I
Pure A Pure B
(b)
Figure 1. Conventional pressure-swing distillation. (a) Presswe-
sensitive, minimum-boiling azeotrope. (b) Column sequence.
some of the typical behavior that can occur during the
distillation of azeotropic mixtures. These effects are not
limited to pressure-swing distillation nor are they patho-
logical artifacta of the particular mixtures discussed below.
Conventional Pressure-Swing Distillation
Before explaining the new pressure-swing-distillation
process, it is helpful to recall how the traditional pres-
sure-swing-distillation process works. The conventional
procedure requires two columns that operate at different
pressures. For a binary mixture forming a homogeneous
minimum-boiling azeotrope (Figure l), the fresh feed (F)
is mixed with the recycled stream from the second column
to form the feed stream (F,) to the first column, which
operates at pressure P1. Since F1 lies to the right of the
azeotrope at pressure P,, pure A is removed as the bottom
product (B,) and a mixture near the azeotropic composi-
tion at pressure P1 is the distillate (D,). Stream D, is
changed to pressure P2 and fed to the next column (as
stream F2). Since F2 now lies to the left of the azeotropic
composition at pressure P2 (Figure la), the other pure
component, 8, can berecovered in the bottom stream (B2)
and a near azeotropic mixture becomes the distillate (D2)
for recycling to the fmt column. An analogous procedure
is used for binary homogeneous maximum-boiling mixhues
(see Van Winkle, 1967).
Clearly t hi s process cannot beused when the azeotropic
composition does not change with pressure.
New Pressure-Swing-Distillation Process
If the binary azeotrope to be separated is pressure-in-
sensitive, then an entrainer must beused. If the selected
Pure A Pure B
I
Pressure P1 I Pressurepp
I
Entrainer
Make-up
I D2
I I
Pure A
Figure 2. Pressure-swing distillation with an entrainer. (a) Material
balance lines. (b) Column sequence.
entrainer forms no boundaries dividing the pure compo-
nents into different distillation regions, then the methods
of homogeneous azeotropic distillation can be used
(Foucher et al., 1991; Doherty and Caldarola, 1985).
Naturally, the columns in such sequences may be operated
at different pressures in order to exploit thermal integra-
tion opportunities (see Knapp and Doherty (1990)). If the
entrainer does form a boundary that divides the pure
components into different distillation regions (henceforth
called a feasibility boundary to distinguish it from other
boundariea which may be present in the mixture but which
do not constrain the separation), then it is not normally
possible to find a feasible sequence in which all columns
operate at the same pressure (Caldarola, 1983). [ An ex-
ception to this rule occurs when the boundary is very
curved (see Figures 10-12 in Levy et al. (1985)). Levy
(1985) and Van Dongen (1983) discuss boundary crossing
in detail and they conclude that it is rarely cost compe-
tative and normally not practical.] However, if the fea-
sibility boundary moves with pressure (even though it does
not move at the pressure-insensitive binary azeotrope),
then ternary pressure-swing sequences can be devised.
Thus, it is sometimes possible to overcome the restrictions
imposed by the presence of distillation boundaries.
For illustration, consider the simplest case where the
entrainer forms only one pressure-sensitive azeotrope and
one distillation boundary between the desired products
(Figure 2). As the pressure is changed from PI to P2 the
boundary moves, pivoting around the pressure-insensitive
azeotropic composition (Figure 2a). By operating two
columns at different pressures, with the streams connecting
348 Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992
Entrainer
Material Balance Line
---
I Azeotrope
Pure A Pure 0
(a)
Entrainer
Pure A Pure 0
(b)
Figure 3. Estimating optimal stream compositions. (a) Preferred
stream compositions. (b) Less desirable stream compositions.
the columns lying in the region between the positions of
the boundary at the two pressures, it is possible to separate
the original pressure-insensitive azeotrope into its pure
components A and B. This is shown by the material
balance lines in Figure 2a for the sequence in Figure 2b.
The distillate from column 2 (D2) is recycled and mixed
with the fresh feed (F) to form the feed to the first column
(FJ . In the fiirst column (operating at pressure Pl), pure
A is removed as the bottom product (B,) and a stream
whose composition lies near the boundary at pressure P1
is the distillate (D1). Stream D1then becomes the feed (F,)
to the second column (operating at pressure Pa), where it
is separated into pure B and a distillate (D2) near the
boundary at pressure P2 for recycle. Notice that no ma-
terial balance line crwes the boundary at its own pressure
and that the streams D1 =F2 and D2 interconnecting the
columns lie between the two positions of the boundary, as
stated. The resulting column sequence is the same as that
used in the conventional process to separate binary pres-
sure-sensitive azeotropes (Figure lb).
Optimal stream compositions tend to minimize the en-
trainer recycle rate and maximize the product flow rates.
A quick estimate of the optimal compositions can be made
by applying the lever-arm principle to the material balance
lines superimposed on a skeleton residuecurve map, which
shows only the positions of the distillation boundaries
(Figure 3). The ratio of the recycle stream (DJ to the
original feed (F) is the ratio of the lengths of the line
segments F-F1 to F1-D2. Comparing Figure 3a and Figure
3b, it is clear that the preferred case (Figure 3a) has a
smaller ratio than the less desirable case (Figure 3b) and
--
hence has a smaller recycle ratio and total cost (smaller
flow rates mean smaller columns and lower utilities). The
ratio of the product to nonproduct flow rates is given by
the ratio of Fl-D1 to Fl-Bl in column 1 and Dl-D2 to
D1-B2 in column 2 (recall D1 =F2). Clearly, these ratios
are larger in the more desirable case, Figure 3a, than in
Figure 3b. Thus, the preferred stream compositions in
pressure-swing distillation minimize the recycle-to-fresh-
feed ratio by locating the recycle stream composition in
the residue-curve-map region where the boundaries shift
most with changing pressure, and simultaneously maximize
the product flow rates by positioning the nonproduct
streams close to their respective boundaries.
Many systems contain multiple distillation boundaries.
As long as only one of these boundaries separates the
desired products (i.e., there is only one feasibility bound-
ary), the column configuration remains essentially the same
as shown in Figure 2b. However, when multiple bounda-
ries lie between the pure components, pressure-swing
distillation becomes rather complex, requires more than
two columns, and will only work if all the feasibility
boundaries shift with varying pressure. Therefore, it is
very unlikely that it will ever be advantageous to use
pressureswing distillation when more than one boundary
lies between the desired products.
Suitable pressure-swing entrainers cause distillation
boundaries to move in one of three ways.
(i) The entrainer forms no new azeotropes at atmos-
pheric pressure, but when the pressure is increased (de-
creased), new azeotrope(s) appear which moverapidly with
changing pressure, e.g., the dehydration of ethanol with
acetone.
(ii) The entrainer forms one or more new azeotropes
whose composition(s) change rapidly with pressure.
(iii) The entrainer forms one or more new azeotropes at
atmospheric pressure, but they disappear as the pressure
is increased (decreased), e.g., the separation of acetone and
methanol using methyl ethyl ketone.
This suggests a modification of the entrainer selection
guidelines given by Doherty and Caldarola (1985) which
can lead to the use of novel entrainers. Potential entrainers
can be screened by the following four-step procedure:
(i) First check if the composition of the azeotrope in the
original mixture changes appreciably with pressure. If so,
one option is to separate the mixture without adding an
entrainer by using conventional pressureswing distillation.
(ii) From the b o i i points of the two pure components,
the potential entrainer, and all azeotropes, make a sketch
of the residue-curve map (see Foucher et al. (1991) for
details).
(iii) If the resulting map is one of the seven most at-
tractive for homogeneous azeotropic distillation (see Figure
7 of Foucher et al. (1991)), then the candidate entrainer
deserves further study. This screening process has been
automated by Foucher et al. (1991). Doherty and Calda-
rola (1985) list 28 other maps that are potentially useful
for homogeneous azeotropic distillation.
(iv) If the resi duewe map has one or more boundaries
between the required products, check whether these
boundaries can be shifted by varying the pressure. If they
move sufficiently, then this is a viable entrainer for
pressure-swing distillation.
Once a group of feasible entrainers has been found, an
economic comparison of the resulting sequences can be
used to discriminate between them.
Because the columns necessarily operate at different
pressures, thermal integration of preasure-swing-distillation
sequences is straightforward. However, choosing the best
--
Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992 349
Pure B
Material BalanceLine
. . . . . . . . . Recycle Balance Line
)-I Distillation Boundary
at cited pressure
Azeotrope
---
8 2
Pure A
Pressure Pressure
Pl p2
(a)
Pure C
I I
I I
I I
I I
I I
I I
02 I D3 Dl I
-
column pressure is not trivial for mixtures with distillation
boundaries. Because the boundaries move with pressure,
the feasible distillate and/or bottom compositions also
change with pressure. Therefore, selecting the pressure
for the high-pressure column of the pressure-swing se-
quence requires calculating the position of the boundaries
at each possible pressure, determining the likely near-op-
timum, nonproduct stream compositions, performing
bubble-point and dew-point calculation on the bottoms
and distillate to be matched, checking whether the re-
sulting condenser temperature is high enough to supply
heat to the reboiler of the low-pressure column, and as-
suring that the boundary movement is sufficient for the
pressure-swing process to work. In practice, the column
pressures that optimize the nonintegrated pressure-swing
sequence are usually sufficient for thermal integration.
Since the pressure level of each column is fixed relative
to the other columns in the sequence in order to make the
separation work, only one thermal integration alternative
exists and multiple effects will not be useful.
Pressure-Swing Distillation of Ternary Mixtures
In the previous section, the objective was to separate a
binary azeotropic mixture into ita two pure components.
Another use for this generalized pressure-swing technique
is the separation of ternary mixtures containing distillation
boundaries into the three constituent pure components
without the addition of a fourth component (entrainer).
The presence of a boundary in a ternary mixture means
that the three pure components cannot be separated
without the addition of an entrainer. However, if the
boundary (boundaries) can be shifted by changing the
pressure, a pressure-swing sequence like that shown in
Figure 4 can be used. The precise sequence required de-
pends on the position of the feed as well as the number
and location of the boundaries. As the number of
boundaries increases, this pressure-swing process becomes
increasingly more complex, requires more columns, typi-
cally has higher recycle ratios (by the lever-arm rule), and
thus becomes less attractive.
The minimum number of columns required for a given
separation (but not necessarily the optimum, especially for
dilute feeds-see Knight (1986)) can be calculated from
Nco, =Np +N* - 1 (1)
where N, , is the minimum number of columns required;
Np is the number of pure component products leaving the
distillation sequence; NB is equal to unity for extractive
distillation and equal to the number of boundaries crossed
for pressure-swing distillation. This does not include
boundaries that disappear as the pressure changes.
For nonazeotropic systems, this reduces to the familiar
Nm1 =Nc - 1, where Nc is the number of pure components.
Equation 1 tells us that the minimum number of col-
umns required to separate ternary mixtures with bound-
aries by pressure-swing distillation is greater than or equal
to the minimum number required for extractive distilla-
tion, i.e., three columns (assuming that an entrainer can
be found which forms no boundaries with the original
ternary mixture). The equality holds when only one
boundary needs to be crossed. Consequently, it is unlikely
that the pressure-swing process will be advantageous when
more than one boundary is present.
Design of Pressure-Swing Sequences
To illustrate the design principles for the new pres-
sure-swing process, we have selected two commercially
important mixtures: (1) ethanol-water and (2) acetone-
F t h * , I F3
I I
I I
I I
I I
I I
- 3
(b)
F m 4. Pressureswing distillation for separating ternary mixtures
into the three constituent pure components. (a) Material balance
lines. (b) Corresponding column sequence.
methanol. Although only pressures greater than atmos-
pheric are used in these examples, subatmospheric pres-
sures may also be of interest.
Example 1. First consider the ethanol-water system.
With todays emphasis on waste minimization and envi-
ronmental concerns, there is a growing trend to seek
suitable entrainers among the chemicals already present
in the plant. Taking this approach, wehave chosen ace-
tone, a common industrial solvent, as the entrainer. The
first step is to determine the number and position of all
the azeotropes and distillation boundaries in the system
over a moderate pressure range by calculating residue-
curve maps at several pressures using the methods pro-
posed by Doherty and Perkins (1978). Unfortunately,
there is an extreme shortage of experimental vapor-liquid
equilibrium (VLE) data above ambient pressure. In the
absence of such data, we use vapor-liquid equilibrium
models to extrapolate atmospheric VLE data up to 10-atm
pressure and compare the predicted azeotropic composi-
tions with those available in the literature. In performing
this extrapolation, weassume that the vapor phase remains
a mixture of perfect gases.
Of the four liquid solution models tried (Wilson, Van
Lam, and one- and two-parameter Margules), the Wilson
model is the best. (See the Appendix for the parameter
values used.) The predicted ethanol-water azeotropic
compoeitions closely follow the experimental ones of otsuki
and Williams (1953) and Kleinert (1933). Two additional
binary azeotropes and one ternary azeotrope appear as the
pressure is increased. The acetone-water azeotrope is
350 Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992
Acetone
Acetone
Water
Acetone
Ethanol
Pressure =5.0 ATM
Azeotrope
Water
X l Ethanol
(b)
Pmssum 10.0 ATM
m Azeotrope
Water
Acetone
Ethanol
- 1 ATM
- - - - - 5 ATY
0000 10ATM
Azeotrope
0.4-
0.2-
0.0 0.2 0.4 0.6 0.8 1 .o
Water X l Ethanol
(d)
Figure 5. Residue-curve maps for the ethanol-water-acetone mixture. (a) 1.0 atm. (b) 5.0 atm. (c) 10.0 atm. (d) Summary of the distillation
boundary positions at the three pressures.
predicted to appear at a lower pressure than that cited by
Horsley (1973), but the agreement improves as the pressure
increases. The ethanol-acetone azeotrope is also predicted
to appear at a lower pressure, contains more ethanol, and
is more pressure sensitive than found experimentally by
Campbell et al. (1987). (See Knapp (1991) for a more
detailed comparison.) All the models predict a ternary
azeotrope at elevated pressure. While there are no ex-
perimental data to confirm this, it is in qualitative
agreement with Horsleys (1973) data for the system with
the next higher ketone, ethanol-water-MEK, and is
therefore most likely correct. The predicted azeotropic
compositions and distillation boundaries at 1, 5, and 10
atm are shown in Figure 5. This information can be
summarized conveniently by superimposing the boundaries
at each pressure onto a single diagram (Figure 5d).
For comparison with other designs from the literature,
approximately 40.1 million kg/year of 99.8 mol % ethanol
will be produced from a 4.2 mol % ethanol fermentation
broth. Sizing and costing correlations are taken from
Doherty and Malone (1991) using fourth-quarter 1986
prices. As a starting point, wechose the high-pressure
column to operate at the highest pressure considered (10
atm) where the boundary movement is the greatest. Figure
6 shows the boundary movement between 1 and 10 atm.
Though the movement of the feasibility boundary is not
very great, it is sufficient for pressure-swing distillation
to work.
For dilute feeds it is often economical to add a precon-
centrating column. However, since the entrainer, acetone,
is the lightest component in the mixture, the heavy com-
ponent, water, can be removed fromthe bottom of the first
Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992 361
Acetone
Water XI Ethanol
Figure 6. Position of the distillation boundaries at 1 and 10 atm for
the ethanol-water-acetone mixture. The shaded region is where the
streams interconnecting the columns must lie. The optimal material
balance lines are also shown.
column, eliminating the need for a preconcentrator. In
contrast, an extractive distillation sequence requires a
preconcentrator before the extractive column to remove
most of the water, because extractive entrainers are the
heaviest component in the extractive distillation process;
otherwise all the water would have to be boiled up twice
before leaving in the distillate of the entrainer recovery
column. (See Knight (1986) for an economic comparison
of extractive distillation sequences with and without a
preconcentrator.)
Because the low-pressure column of the pressure-swing
sequence separates two streams of different composition
(the fresh feed and the recycle stream), it seems likely that
a doublefeed column would be preferred over a single-feed
column. However, because the fresh feed flow rate is much
larger than the flow rate of the recycle stream (apply the
lever-arm rule to the material balance line F-F,-D2 on
Figure 6), the overall feed is nearly coincident with the
fresh feed and there is virtually no difference between
single- and double-feed columns. Thus, two single-feed
columns will be used. (In this example either a single- or
double-feed column can be used because the products,
ethanol and water, are both nodes on the residue-curve
map (Figure 5). In contrast, for the extractive distillation
residue-curve map (see example 2 below or the mixtures
discussed in Knapp and Doherty (1990)) the pure com-
ponent products are saddles on the residue-curve map and
the desired separations are only feasible in a double-feed
column.)
The columns are designed and optimized using the
method of Knight and Doherty (1989). The dominant
optimization variables are the stream compositions con-
necting the columns (because they control the recycle-to-
fresh-feed ratio and the product flow rates), and the en-
thalpic state of the feed to the first column. Notice that
the optimal location of the nonproduct streams (D1 and
D2) is near their respective boundaries (see Figure 6) as
di scussed above. The optimized sequence (Figure 6, Figure
7, and Table 11) has a total annualized cost (TAC) of $4.03
million/year and an energy requirement of 15 850 kJ /kg
of ethanol. Of course it is very unlikely that the sequence
would ever be operated without taking advantage of the
Table 11. Optimal Column Pressure for Thermally
Integrated Pressure-Swing Distillation of Ethanol and
Water with Acetone
sp energy
TAC, I O6 consumption,
$/year kJ/kg
high-pressure column at 10 atm 3.47 7500
high-pressure column at 8 atm 3.69 8870
high-pressure column at 9 atm 3.55 8070
2664.3
2492.6
FRACTION Water
.
Acetone
Figure 7. Flowsheet for the optimized, nonthermally integrated,
pressure-swing sequence for the ethanol-water-acetone mixture.
c. w
63.5%
' 0 +
l i m -!? 139.3%
n
Steam
Figure 8. Thermally integrated, pressure-swing sequence for etha-
nol-water-acetone at 10 atm.
energy integration opportunities that arise from having two
adjacent columns at different pressures. Thermal inte-
gration (see Figure 8 and Table 11) reduces the TAC by
14% to $3.47 million/year and cuts the energy consump-
tion by 53% to 7500 kJ /kg. The optimal pressure for the
high-pressure column is between 9 and 10 atm (Table 11).
Comparing our pressure-swing results with the extractive
distillation designs of Knight and Doherty (1989) and
Knapp and Doherty (1990), and the heterogeneous azeo-
352 Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992
120 1
0.0
90
-
u)
b- L o -
.c
0
70 -
s
z
60 -
50 -
40 -
,
mm
0 5 10 15 20
Reflux Ratio
Figure 9. Multiple solutions and maximum reflux. For fixed
product purities and feed composition, two solutions exist for reflux
ratios between 11.467 and 18.977 (r-).
tropic distillation design of Ryan and Doherty (1989), we
see (Table 111) that thermally integrated pressure-swing
distillation of ethanol and water with acetone consumes
less energy than heterogeneous azeotropic distillation with
benzene and consumes about the same amount of energy
as conventional extractive distillation, but costs more to
build and operate on an annualized basis. (Black (1980)
concluded that conventional pressure-swing distillation is
not practical for this mixture.) However, on the basis of
energy alone, none of these alternatives can compete with
thermally integrated extractive distillation. Thus, despite
its higher cost, wehave shown that even the smal l amount
of boundary movement that occurs between 1 and 10 atm
in the ethanol-water-acetone system is sufficient for
pressure-swing distillation to work, though the movement
is not enough to make it economical.
The high-pressure column in the ethanol-wateracetone
pressure-swing process exhibits some interesting behavior.
As the reflux ratio is increased at fixed feed and product
compositions, the column-section profiles move relative to
each other in the composition triangle, and the number
of column profile intersections (solutions) changes from
zero, to one, to two, to one, and then back to zero, all for
finite reflux (Figures 9 and 10). Thus, there is a range
of reflux ratios where multiple solutions to the design
problem exist (Figure 9). In this range, it is possible to
design two columns operating at the same reflux and
yielding the same product compositions, but with different
numbers of trays. (Once a column is built, this multiplicity
is no longer an issue because the number of trays has been
fixed). These multiple solutions are different from those
found by other researchers (e.g., Rovaglio and Doherty
(1990), Venkataraman and Lucia (1988), Chavez et al.
(19861, or Prokopakis and Seider (1983a,b)), who formulate
the problem as a column simulation and not a column
design. They find multiple sets of distillate and bottom
-- -..-
A Distillate
+Feed
o Bottoms
Tray Composition
I ' \ Reflux - Ratio =11.467
Acetone
i
-
-
1 .o
0.8
0.6
*2
0.4
0.2
First solution
I
0.0 0.2 0.4 0.6 0.8 1 .o
Mol eFnc F n d Dlrtlllatr Bot t om
Ethanol 0.5500 0.3231 0.9980
Water 0.0600 0.0894 0.0020
Acetone 0.3900 0.5875 1.0 lo'*
\
First solution
Acetone
1.0
Laand
0.8
0.6
XZ
0.4
0.2
0.0
First solution
I
I 0.2 0.4 0.6 0.8 1 .o
Water
Acetone
1 .o
Ethanol
Xl
(b)
0.8
0.6
x2
0.4
0.2
0.0
Water Xl Ethanol
(C)
nl. I 1 .. - .* n I - L . . , 1 .
r igure iu. cIoiumn prorues snowing me mumpie soiuuons. \a)
Minimum reflux for the first solution. (b) Minimum reflux for the
second solution. (c) Maximum reflux. No feasible column exists
above this reflux ratio.
Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992 363
Acetone
56.1 %
1 .O^
Table 111. Comparison of Pressure-Swing Distillation and
Extiactive Dietillation for Distilling Ethanol and Water
sp energy
TAC, 108 consumption,
$/year k J / k EtOH
pressure-swing distillation 3.47 7500
high pressure =10 atm
thermally integrated
extractive distillation with
ethylene glycol
feed preheatera added
optimized, nonthermally
integrated extractive distillation
with ethylene glycol
distillation with ethylene glycol
azeotropic distillation with
benzene
Knight and Doherty (1989)o 2.51 8920
Knapp and Doherty (1990) 2.01 7670
Knapp and Doherty (1990) 2.36 2700
thermally integrated extractive
Ryan and Doherty (1989)O 2.05 10380
optimized heterogeneous
feed preheater added
"Corrected cost.
(1990) for more details.
See the appendix of Knapp and Doherty
compositions for fixed feed composition, reflux ratio, and
number of trays, while wefind multiple number of trays
for fixed feed, reflux ratio, and product compition. This
new type of multiplicity was also observed by Van Dongen
(1983) and is not limited to pressure-swing distillations.
It is commonly believed that all reflux ratios above the
minimum yield a feasible column, with the number of trays
decreasing as the reflux ratio increases. However, as il-
lustrated in Figures 9 and 10, this is not always true for
nonideal mixtures. For fixed feed and product composi-
tions (i.e., the design problem) a finite maximum reflux
ratio (r-) can exist beyond which no feasible column is
possible. In fact, the existence of a maximum reflux ratio
in the design problem is not uncommon. As described in
a forthcoming article (Knapp and Doherty, 1991), every
extractive distillation exhibits a maximumreflux ratio. For
the ethanol-water-acetone example presented here, r-
These two phenomena can have important implications
for the design and control of distillation columns. If a
column is operated close to the maximum reflux, either
because the true minimum reflux was not found at the
design stage (a difficult task with the commonly used
process simulators) or because the reflux was increased to
achieve a product specification, then it is possible to exceed
rmm, making the desired separation impossible. In the
region of multiple solutions, choosing the wrong solution
needlessly increases the cost of the column.
Example 2. Next consider the separation of acetone
and methanol. The azeotrope in this binary mixture is
sufficiently pressure sensitive that the conventional
pressure-swing technique is one option. Methyl ethyl
ketone (MEK) appears to bean excellent pressure-swing
entrainer for this system. The VLE data for this system
are modeled using the Van Laar equation with the pa-
rameters given in the Appendix. These parameters accu-
rately represent the available experimental VLE and
azeotropic data over the pressure range 1-10 atm. (See
Knapp (1991) for more details.) At 1 atm MEK and
methanol form an azeotrope containing 85 mol % meth-
anol and the ternary mixture has a distillation boundary
running from the methanol-acetone azeotrope to the
methanokMEK azeotrope, putting the desired acetone and
methanol products into different distillation regions
=18.977.
Pressure L 1 .O atm
79.0% 64.2OC 64.5OC
(a)
Acetone
103.4%
0.0 0.2 0.4 0.6 0.8 1 .o
130.3'C 704.4OC
MEK X1 Methanol
(b)
Figure 11. Residue-curve maps for the acetone-methanol-MEK
mixture at (a) 1.0 and (b) 4.0 atm. Notice the disappearance of the
methanol-MEK azeotrope and the distillation boundary.
(Figure lla). Therefore, this mixture cannot beseparated
by homogeneous azeotropic (extractive) distillation at
atmospheric pressure. However, by about 4 atm the
methanol-MEK azeotrope has moved to the methanol
vertex, ceasing to exist and causing the distillation
boundary to disappear. The resulting residue-curve map
(Figure l l b) contains only the acetone-methanol azeotrope
and is the map for extractive distillation. Thus one option
is to distill this mixture by extractive distillation with all
of the columns operating above 4 atm. A better choice is
to use pressure-swing distillation to purify acetone in an
atmospheric column and methanol in a column operating
above 4 atm.
For comparison with existing extractive distillation and
traditional pressure-swing-distillation designs, approxi-
mately 204.4 million kg/year of a saturated-liquid, equi-
molar, binary, acetonemethanol mixture will be separated
into acetone and methanol products of 99.5 mol % purity
354 Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992
MEK
I
Figure 12. Schematic diagram of the methanol-acetone-MEK
pressure-swing-distillation sequence.
Acetone
Legend
Azeotrope
A Distillate
+Feed
o Bottoms
#Tray Composition
Pressure 10.00 atrn
0.60
'..k 0.20 \
0.00 0.20 0.40 0.60 0.80 1 .oo
MEK x, Methanol
Figure 13. Column profile for the first column of the methanol-
acetone-MEK pressure-swing-distillation sequence. Notice the
tangent pinch in the rectifying section.
with fractional recoveries of 99.9%. The columns are re-
stricted to operate between 1 and 10 atm. The sequence
is designed, costed, and optimized as described in the first
example.
This example also contains interesting effects. From
looking at the residue-curve maps (Figure ll), wewould
expect to remove the lowest boiling pure component,
acetone, in the distillate of the first column operating at
1 atm and obtain essentially a binary methanol-MEK
st r eam as the bottom product. Then, in the second column
operating above 4 atm, this mixture would be separated
into the methanol product and the MEK recycle stream.
However, it is impossible to bring acetone out of the top
of the first column at any pressure between 1 and 10 atm.
Instead, the binary methanol-MEK azeotrope comes off
as the distillate in the pressure range 1-4 atm. At higher
pressures, pure methanol comes off the top of the first
column. Methanol changes from being the intermediate-
boiling pure component'to the low-boiling pure component
between 4 and 5 atm due to the different slopes of the
vapor pressure curves for acetone and methanol. (See
Knapp and Doherty (1991) for a method to a priori predict
which component will be the distillate and for examples.)
Consequently, the first column of the pressure-swing se-
quence (Figures 12 and Figure 13) operates above 4 atm
and produces methanol as the distillate. The bottom
1 .o
0.5
0.0
0.0 0.5 1 .o
XI
Mole Fraction of Methanol
Figure 14. Binary vapor-liquid equilibrium curves for methanol-
MEK at 1, 4, and 10 atm showing how the azeotrope becomes a
tangent pinch that is still present at 10 atm.
stream from this first column is essentially a binary ace-
tone-MEK mixture, which is separated into pure acetone
and pure MEK for recycle in the second column which
operates at atmospheric pressure.
Now that weknow where each product will be removed,
the sequence can be designed and optimized. The sepa-
ration of methanol from acetone and MEK turns out to
be a very difficult separation. The optimization procedure
drives the pressure of the high-pressure column above the
maximum pressure considered, so we set the column
pressure at the upper bound, 10 atm. The minimum feed
ratio (upper feed flow rate divided by lower feed flow rate)
for the separation is 0.79. That is over five and a half times
higher than for extractive distillation of the same ace-
tonemethanol mixture with water and indicates that the
double-feed column will be considerably larger, more ex-
pensive, and consume more energy than its counterpart
in the extractive distillation process. The minimum reflux
ratio (rmh) is on the order of 4.2, and the separation re-
quires about 110 theoretical trays at 1.2rmin (95 trays at
l.5rmin) with a feed ratio of 1.7.
The reason for the very difficult separation is a severe
tangen pinch in the rectifying section. The extremely large
number of trays in the rectifying section near the methanol
distillate in Figure 13 indicates that there is a tangent
pinch at 10 atm. Since the rectifying section essentially
lies on the methanol-MEK edge of the composition tri-
angle, wecan visualize its behavior by examining the bi-
nary y-x diagram for methanol and MEK. Figure 14
shows VLE data for methanol and MEK between 1 and
10 atm. At atmospheric pressure there is an azeotrope
containing about 85 mol 9% methanol. As the pressure
increases to 4 atm, the amount of methanol in the azeo-
trope increases until it reaches 100% methanol (i.e., the
azeotrope disappears), and the azeotrope is replaced by
a severe tangent pinch. (The relationship between the
appearance or disappearance of an azeotrope and tangent
pinches is explained in Knapp (1991)J As the pressure
is further increased from 4 to 10 atm, the tangent pinch
becomes leas severe and the VLE curve moves farther away
from the 45O line, indicating that the separation becomes
easier (i.e., lower rmin and fewer trays required). This is
Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992 355
Table IV. Comparison of Conventional and New
Pressure-Swing Distillation with Extractive Distillation
for Separating Acetone and Methanol
sp energy
TAC, lo6 consumption,
$/year kJ/kg EtOH
Extractive Distillation with Water
feed ratio =0.55
sequence
optimized, nonthermally integrated 2.70 3190
thermally integrated sequence 2.72 1950
optimized, nonthermally integrated 2.79 3120
thermally integrated sequence 2.73 1750
feed ratio =1.0
sequence
Pressure-Swing Distillation with MEK
optimized, nonthermally integrated 6.97 7800
sequence
thermally integrated sequence 5.83 3810
optimized, nonthermally integrated 3.54 5140
thermally integrated sequence 3.29 3660
Conventional Pressure-Swing Distillation
sequence
Table V. Antoine Equation Constants
component A B C
methanol 23.4832 -3634.01 -33.768
ethanol 23.5807 -3673.81 -46.681
acetone 21.3099 -2801.53 -42.875
water 23.2256 -3835.18 -45.343
MEK (2-butanone) 21.1480 -2899.47 -51.392
Table VI. Wilson Constants (AiJ for the
Ethanol-Water-Acetone Mixture
component j
component i ethanol water acetone
ethanol 1 0.1782 0.692
water 0.8966 1 0.492
acetone 0.726 0.066 1
in direct contrast to conventional wisdom which says
distillation becomes more difficult as the column pressure
increases. This rule of thumb is correct in most instances,
but whenever an azeotrope disappears with increasing
pressure, the azeotrope will bereplaced by a tangent pinch,
which becomes less pronounced as the pressure continues
to be increased, resulting in an easier separation. (Simi-
larly, distillation becomes continually more difficult and
tangent pinches become more restrictive as the pressure
is increased when azeotropes appear with increasing
pressure (see example 2 of Knapp and Doherty (1990))J
The fact that the separation becomes easier as the pressure
increases accounts for the optimization procedure driving
the pressure of the high-pressure column above 10 atm.
Unfortunately, for the specified methanol product purity,
the tangent pinch remains severe at 10 atm, resulting in
a difficult and expensive separation. The final version of
the sequence costa $6.97 million/year and consumes 7800
kJ fkg of acetone. Thermal integration reduces the cost
by 16% to $5.83 millionfyear and cuts the energy con-
sumption by 51% to 3810 kJ fkg. This is more than twice
the cost and energy consumption of extractive distillation
with water (see Table IV). The new pressure-swing-dis-
tillation process using MEK was also compared with tra-
ditional pressure-swing distillation (Figure 1) of methanol
and acetone. Because of the tangent pinch problem dis-
cussed above, pressureswing distillation with MEK is also
considerably more expensive than the conventional pres-
sure-swing process (Table IV), though the energy con-
sumptions of the thermally integrated versions are com-
Table VII. Van Laar Constants (Aij) for the
Methanol-AcetoneMEK Mixture
component j
component i methanol acetone MEK
methanol 0 196.0 242.20
acetone 182.0 0 15.20
MEK (2-butanone) 237.60 101.20 0
parable. This example demonstrates the need to consider
more than just the amount of boundary movement for
potential pressure-swing-distillation systems. One must
also be aware of the presence of tangent pinches and the
influence of pressure on their severity. Therefore, move-
ment of distillation boundaries is a necessary, but not
sufficient, condition for pressure-swing distillation to be
practical.
Conclusions
A pressure-swing process for separating azeotropic
mixtures has been developed. This new technique uses
varying pressure to move distillation boundaries that lie
between the desired products which otherwise would make
the separation impossible. Both pressure-sensitive and
pressure-insensitive binary azeotropes can thus be sepa-
rated in a two-column, pressureswing sequence using novel
entrainers that form pressure-sensitive distillation
boundaries between the two pure components to be iso-
lated. New entrainer selection guidelines which include
potential pressure-swing entrainers are presented. The
new distillation method was applied to the separation of
ethanol and water, and acetone and methanol.
The new pressure-swing process can also be used to
separate ternary mixtures containing distillation bounda-
ries into the three pure components, without the addition
of an entrainer (fourth component). However, such
schemes are not of practical interest when more than one
distillation boundary must be crossed.
Although only ternary mixtures were discussed, the new
pressure-swing-distillation technique can be extended to
multicomponent mixtures in an obvious way. For ternary
mixtures the distillation boundary that must move with
pressure is a line. For quaternary mixtures the feasibility
boundary which must be pressure-sensitive is a two-di-
mensional surface. In general, for an N-component mix-
ture the feasibility boundary will bean ( N - 1)-dimensional
surface.
Several phenomena were observed in the examples
studied. First, in the high-pressure column of the etha-
nol-water-acetone system, for fixed compositions and
reflux ratio there were two feasible column designs, each
with a different number of trays. Second, in the same
column, there was a maximum reflux ratio above which
no feasible column design was possible. Third, in the
acetone-methanol-MEK system, the relative volatility of
acetone and methanol reverses and methanol becomes the
overhead product. Lastly, this separation becomes easier
as the column pressure is increased. All of these effects
have been observed for other mixtures and other distilla-
tion methods and are discussed more thoroughly in Knapp
(1991) and Knapp and Doherty (1991).
Acknowledgment
We acknowledge G. A. Caldarola, who did some prelim-
inary work on this problem in his Masters Thesis at the
University of Massachusetts (1983). We are also grateful
for the research support provided by the Link Foundation
in the form of an Energy Fellowship for J. P. Knapp.
356 Ind. Eng. Chem. Res., Vol. 31, No. 1, 1992
Nomenclature
B =bottom stream
D =distillate stream
F =feed stream
NB =unity for extractive distillation and equal to the number
Nc =number of pure components to be separated
Ncol =minimumnumber of columns required for a given
Np .=number of pure component products leaving the dis-
P =pressure
r,, =maximumreflux ratio
rmin =minimumreflux ratio
Appendix
Vapor-liquid equilibrium calculations were carried out
using an in-house thermodynamic-property software
package and database. This appendix contains the model
equations and physical property parameters used for the
mixtures discussed in the text.
Vapor pressures are calculated using Antoine's equation:
of boundaries crossed for pressure-swing distillation
separation
tillation sequence
B
In et =A +-
T + C
(A-1)
with the vapor pressure in pascals and the temperature
in kelvin. Antoine constants are given in Table V.
Vapor-liquid phase equilibrium was calculated assumi ng
that the vapor phase is a mixture of perfect gases, Le., by
solving
subject to Cyi =1. Activity coefficients were calculated
using the model which most closely matched the available
experimental data. The ethanol-water-acetone mixture
was modeled using a nonstandard form of the Wilson
equation
yip =xi Yi (x, T) PYT) (A-2)
n n n
j = l i =l j = 1
In Yk =1 - In (XAkjXj) - C(XiAik/CXjA;j) (A-3)
In this model Aii =1 and ideality is implied by Aij =1.
Wilson interaction parameters are given in Table VI. The
methanol-acetone-MEK mixture was modeled by the Van
Laar equation:
(A-4)
where zi is the effective volume fraction
(A-5)
If Aji/Aij =O/O, set Aji/Aij =1. In this model Aii =0 and
ideality is implied by A, =0. The Van Laar interaction
parameters are given in Table VII.
67-64-1; MeOH, 67-56-1.
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GENERAL RESEARCH
An Investigation on the Reaction of Phosphoric Acid with Mica at
Elevated Temperatures
Chandrika Varadachari*
Department of Agricultural Chemistry & Soil Science, University of Calcutta, 35 B.C. Road, Calcutta 700 019,
India
Various aspects of the reaction of phosphoric acid with muscovite mica at 250,300, and 350 "C were
studied with a view to understanding the nature of such reactions, particularly (i) the reaction kinetics,
(ii) the relation between muscovite dissolution and polymerization of phosphoric acid, (iii) the
probable mechanism of reaction, and (iv) the nature of the residue. Solubilization of the K+ ion
from muscovite was observed to be linearly dependent on the degree of dehydration of the system
as well as the average chain length of the poly(phosphoric acid) formed. It is suggested that the
breakdown of the complex muscovite structure is due to attack by OH- ions, which are produced
when phosphoric acid polymerizes; oxide bonds are cleaved forming M-OH and M-O-P bonds, and
the elimination of water from other P-OH groups results in polyphosphates. The reaction product
consists of soluble and insoluble amorphous polyphosphates that form a coating over the core of
unreacted mineral.
1. Introduction
Phosphoric acid at elevated temperatures shows a re-
markable reactivity that is unique among the inorganic
acids. Thus, at high temperatures, phosphoric acids and
phosphates have been observed to react with quartz
(Mellor, 1925), with silicates and glasses (Kingery, 1950;
Ray, 19701, and with a large number of metals and oxides
(Bailar et al., 1973; Thilo, 1962), including gold and
platinum (Van Wazer, 1966). Such reactions of phosphates
find use in the manufacture of phosphate glasses (Ohashi,
1964), phosphate-bonded refractories (Kingery, 1950;
Mamykin et al., 1973), and micronutrient fertilizer glasses
(Roberts, 1975). In spite of the varied application of the
phosphate-silicate/oxide reactions, however, the nature,
mechanism, and products of such reactions have neither
been investigated in detail nor been established with
certainty. Thus, although the nature of polymerization
of phosphoric acid and phosphate melts (Van Wazer, 1966)
is now fairly well understood, its reactions with silicates
and refractory oxides are subject to a great deal of spec-
ulation. There are indeed very few studies pertaining to
the mechanism of such reactions. Reactions of glasses with
phosphoric acid have been studied by Ray (1970) and
Walters (1983). According to Ray (1970), the reactivity
of the glass is a function of acid dehydration, whereas
Walters (1983) attributed the solubilization to attack by
polyphosphates produced during heating. Ohashi (1964)
proposed that the reaction occurs due to the ability of PO4
* Present address: Polymer Science Unit, Indian Association
for the Cultivation of Science, J adavpur, Calcutta 700 032, India.
0SSS-5SS5/92/2631-0357$03.00/0
units to form copolymers with silicates and other elements
having X04 tetrahedra. Workers who have extensively
inveatigated the products of the reaction of phosphoric acid
with phyllosilicates concluded that various crystalline
phosphates of silicon and aluminium are produced by the
replacement of SO4 tetrahedra of the silicate, by the
corresponding tetrahedra of the acid; their nature depends
on the temperature and the relative proportions of the
constituents (Kingery, 1950; Lyon et al., 1966; Mamykin
et al., 1973; Zamyatin et al., 1972). The existing knowledge
is, however, quite inadequate for understanding exactly
how and why stable polymeric structures, such as the
silicates, are broken down so readily to their component
units by hot phosphoric acid. Neither can it explain the
unique reactivity of this acid and the cause of the unusual
change in its properties on heating.
In this paper, the results of a comprehensive study on
the high-temperature reaction of phosphoric acid with a
silicate are presented. It is hoped that this investigation
will provide a better understanding of the reactions of hot
phosphoric acid with silicates and oxides in general and
perhaps also provide a clue to the cause of ita phenomenal
solubilizing power. The study has accordingly been dealt
with in four parts, which may be broadly classified as (1)
the reaction kinetics of muscovite dissolution by phos-
phoric acid, (2) kinetics of polycondensation of phosphoric
acid, (3) deduction of the reaction mechanism, and (4)
identification of the products of reaction.
2. Methodology
2.1. Studies on the Dissolution of Muscovite by
Phosphoric Acid. Large flakes of muscovite (from Gir-
0 1992 American Chemical Society