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On the basis of the transformation of concentration coordinates, the concept of reactive distillation
lines is developed. It is applied to study the feasibility of a reactive distillation with an
equilibrium reaction on all trays of a distillation column. The singular points in the distillation
line diagrams are characterized in terms of nodes and saddles. Depending on the characterization
of the reactive distillation line diagrams, it can be decided whether a column with two feed
stages is required. On the basis of the reaction space concept, a procedure for the identification
of reactive distillation processes is developed, in which the reactive distillation column has to
be divided into reactive and nonreactive sections. This can be necessary to overcome the
limitations in separation which result from the chemical equilibrium. The concentration profile
of this combined reactive/nonreactive distillation column is estimated using combined reactive/
nonreactive distillation lines.
1. Introduction
In recent years many processes for basic and intermediate products were improved by a combination of
reaction and distillation in a reactive distillation column. The conventional process has to be compared with
the reactive distillation process to understand the
possible improvements; see Figures 1 and 2. The
conventional process consists of a reaction and a separation section. Two unitssusually connected by a recycle
streamsare necessary to produce and to separate the
products. In a reactive distillation column, it is possible
to combine two operations in one unit, so that synergistic effects between distillation and reaction occur; see
Figure 2.
Examples are as follows: (a) shift of the chemical
equilibrium by separation of the products and (b)
utilization of the reaction heat for the separation of
educts and products.
These synergistic effects cause benefits of a reactive
distillation process when compared to the conventional
design: (a) lower capital investment, (b) lower energy
consumption, and (c) higher product yields.
Because of these benefits it is necessary to check
during the development of a new process or during the
reengineering of an existing process whether the process
can be improved by reactive distillation. The obstacle
to the synthesis of a reactive distillation process is to
understand the interaction of reaction and distillation.
Consider, for example, that a first simple reactive
distillation process for methyl acetate was developed in
1921 by Backhaus (1921), but it took 60 years to reach
the level of the Eastman Kodak Process patented by
Agreda and Partin (1984).
To fill this gap, the interaction of reaction and
distillation has been a topic of intensive studies, for
example, by Barbosa and Doherty (1988a) and Ung and
Doherty (1995). This research, which is the basis for
the work presented here, focuses on the basic principles
of the interaction of reaction and distillation. Neverthe* To whom correspondence should be addressed. E-mail,
bernd.bessling@ze.basf-ag.de; telephone number, 0049/621/60/
55446; Fax, 0049/621/60/52411.
Dedicated to Prof. Gilbert Froment on the occasion of his
65th birthday.
BASF Ludwigshafen.
University of Dortmund.
S0888-5885(96)00727-0 CCC: $14.00
FG ) 2 + n - - r
(1)
reaction
AaB
AaB
AaB
A+BaC
A+BaC
A+BaC+D
A+BaC+D
A+AaE
A+BaC
A+BaC+D
inerts
type of
phase
equilibrium
no. of
components
C
C,D
D
degrees of
freedom F
(P or T
constant)
2
3
4
3
4
4
5
VLE
VLE
VLE
VLE
VLE
VLE
VLE
0
1
2
1
2
2
2
3
4
VLLE
VLLE
0
1
K)
xi
i)1
(2)
AA + BB + ... a PP + QQ + ...
The transformed liquid and vapor coordinates for an
arbitrary component i are given by Espinosa et al.
(1995b):
(3)
iyP
P
Yi )
TyP
1P
(4)
yi -
nc
(5)
T )
i)1
I ) 0
ixP
P
Xi )
TxP
1P
xi -
X i ) Yi ) 1
i)1
i)1
(6)
(7)
N
h )N 1-
TxP
P
(8)
G)D+L+R
(9)
(10)
Gn-1 ) Ln + D
h
(17)
Gn-1Yn-1 ) LnXn + D
h XD
(18)
(
(
)
)
TxnP
P
Ln
v)
)
D
h
TxDP
D 1P
Ln 1 -
(19)
Yn-1 )
v
1
X +
X
v+1 n v+1 D
(20)
G 1-
G yGi -
) (
) (
) (
) (
)
)
TyGP
TxDP
TxLP
)D 1+L 1P
P
P
(11)
iyGP
ixDP
ixLP
) D xDi + L xLi (12)
P
P
P
L/D )
( )
XDi - YGi
YGi - XLi
1-
(13)
)
)
TxmP
P
Lm
)
v* )
B
h
TxBP
B 1P
Ym-1 )
TxDP
P
TxLP
1P
(
(
Lm 1 -
v*
1
X X
v* - 1 m v* - 1 B
(21)
(22)
(
(
)
)
TxLP
L
h )L 1P
(14)
TxDP
P
(15)
D
h )D 1-
L
h /D
h )
XDi - YGi
YGi - XLi
(16)
Yn-1 ) Xn
(23)
Yn ) f(Xn,P)
(24)
F
h XFi ) D
h XDi + B
h XBi
(25)
Xi ) Yi
(26)
FA + MeOH a MF +H2O
Kx ) 5
2FA a FADim
The dimerization equilibrium is described by the chemical theory (Gmehling et al., 1979). In the systems there
are five components and two equilibrium reactions.
Therefore the system has 2 degrees of freedom at a given
pressure or temperature.
yn-1 ) xn
(27)
yn ) f(xn,P)
(28)
Figure 28. Reaction space and concentration profile for the reactive distillation of A, B, and D with D as inert component. A and B are
converted to C. The equilibrium constant is K ) 10. The relative volatilities of the components A/B/C/D are 4/2/1/8. The pressure is P )
1.013 bar.
Table 2. Guideline for the Combination of Reactive and
Nonreactive Distillation in One Reactive Distillation
Column
reaction
inerts
AaB
AaB
AaB
C,D
A+BaC
A+BaC
A+BaC+D
desired products
section
only with
distillation
required
A or B
B/C
A/C
BC/D; BD/C; B/CD
AC/D; AD/C; A/CD
C
A/B
C/D
AD/B; A/BD
A/B
C/D
+
+
+
+
+
+
+
-
Table 3
Antoine parameters
volatility
b[C]
c[C]
8
4
2
1
14.044
13.351
12.658
11.965
3984.923
3984.923
3984.923
3984.923
233.426
233.426
233.426
233.426
Table 4
Antoine parameters
liquid molar
volume
component
b [C]
c [C]
vL (cm3/mol)
water (H2O)
methyl formate (MF)
methanol (MeOH)
formic acid (FA)
11.9647
10.2965
11.9869
9.3703
3984.9228
2801.0487
3643.3136
2982.4463
233.426
240.37
239.726
218
18.07
61.54
40.73
37.91
Appendix
Physical Properties. For the calculations of the
vapor-liquid equilibrium the parameters listed in
Tables 3 (Figures 15-23 and 28) and 4 (Figures 24 and
25) were used. The Antoine equation is defined as
follows:
ln(P) ) a -
b
; P [bar]
T+c
a21 ) 80.1
a31 ) 74.5
a41 ) 758.5
42 ) 1
a32 ) 907.572
43 ) 1
chemical theory (Gmehling et al., 1979). The parameters are A ) -18.12 and B ) 7099 K.
Literature Cited
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production of methyl acetate. U.S. Patent 4,435,595, 1984.
Backhaus, A. A. Continuous process for the manufacture of esters.
U.S. Patent 1,400,849, 1921.
Barbosa, D.; Doherty, M. F. The simple distillation of homogeneous
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Barbosa, D.; Doherty, M. F. Design of Minimum Reflux Calculations for Single-Feed Multicomponent Reactive Distillation
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Block, U. Carrying Out Continuous Reactions with Superposed
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Espinosa, J.; Aguirre, P. A.; Perez G. A. Some Aspects in the design
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Espinosa, J.; Aguirre, P. A.; Perez, G. A. Product Composition
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93-810612, 1993.
Gmehling, J.; Onken, U.; Arlt, W. Vapor-Liquid Equilibrium Data
Collection. Chemistry Data Series; DECHEMA: Frankfurt,
FRG, 1979.
Jakobs, R.; Krishna, R. Multiple Solutions in Reactive Distillation
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Jones E. M. Catalytic distillation reactor. EP 91305245.2, 1991.
Nijhuis, S. A.; Kerkhof, F. P. J. M.; Mak, A. N. S. Multiple Steady
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