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cn

Computers and Chemical Engineering 26 (2002) 1213 – 1221

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Solvent improvement for separating C4 with ACN

Zhigang Lei a,*, Hongyou Wang b, Rongqi Zhou b, Zhanting Duan b
a
The Key Laboratory of Science and Technology of Controllable Chemical Reactions, Ministry of Education,
Beijing Uni6ersity of Chemical Technology, P.O. Box 35, Beijing 100029, People’s Republic of China
b
Department of Chemical Engineering, Tsinghua Uni6ersity, Beijing 100084, People’s Republic of China

Received 20 November 2000; received in revised form 9 October 2001; accepted 4 March 2002

Abstract

This paper reports the work to find the best additives added to acetonitrile (ACN) for improving the separation of C4 mixtures
with the help of computer-aided molecular design (CAMD). CAMD is programmed to provide necessary information for our
search of the additives. The two types of additives we seek, liquid solvents and salts, are designed by CAMD. The selected
additives are then tested by experiments. It is found that the addition of salt is more efficient than the addition of liquid solvents
(including water) for improving the separation ability of ACN. After taking implicit properties into consideration, salts NaSCN
and KSCN, are the best candidates to improve ACN. As a strong tool, CAMD greatly reduces experimental working in
separating C4 by extractive distillation with ACN. © 2002 Elsevier Science Ireland Ltd. All rights reserved.

Keywords: CAMD; C4; ACN; Salts; Extractive distillation

1. Introduction grounds in this aspect by largely reducing experiments

We are well aware that a suitable solvent plays an
important role in the economical design of extractive
distillation. Among C4 mixtures (n-butadiene, 1-butyl-
ene, trans-butylene-2, cis-butylene-2, 1,3-butadiene
etc.), 1,3-butadiene is a basic organic raw material. In
industry, 1,3-butadiene is usually separated from C4
mixtures by extractive distillation with solvent acetoni-
trile (ACN) (Coogler, 1967; Bannister & Buck, 1969).
However, a relative large amount of recycled ACN and
high solvent and feed mass ratio up to 8 in the current
commercial process lead to much consumption of en-
ergy. To solve the problem, it seems inconvenient to
substitute ACN with other solvents. Therefore, a better
way is to add some substances to ACN to make into a
mixture solvent. As an alternative, we adopt the strat-
egy to add some substances to ACN.
It is tiresome to choose the best additive from thou-
sands of different substances for a system through
experiments. The computer-aided molecular design
(CAMD) developed in the 1980s may break new
* Corresponding author. Tel.: + 86-10-6443-3695; fax: + 86-10-
6442-9057.
E-mail address: leizhg@sina.com (Z. Lei).
(Venkatasubramanian, Chan & Caruthers, 1995;
Joback & Stephanopoulos, 1995; Churi & Achenie,
1996; Marcoulaki & Kokossis, 1998; Mavrovouniotis,
1998; Meniai, Newsham & Khalfaoui, 1998; Ourique &
Telles, 1998; Pistikopoulos & Stefanis, 1998; Raman &
Maranas, 1998; Sinha, Achenie & Ostrovsky, 1999;
Harper, Gani, Ishikawa & Kolar, 1999; Hostrup,
Harper & Gani, 1999). The application of CAMD in
chemical engineering is mostly based on the UNIFAC
group contribution. Incalculable feasible molecules will
be formulated by UNIFAC groups in accordance with
certain rules, but in terms of given target properties, the
desired molecules are screened by computers. The
groups of UNIFAC provide building blocks for assem-
bling molecules. CAMD is essentially the inverse of
property prediction by group contribution. Given a set
of desirable properties, it is proposed to find a combi-
nation of structural groups, satisfying the property
specifications. In most cases, more than one solution is
produced. Thus, a screening is needed since only one of
the alternatives must be chosen for the specified prob-
lem. At this point, factors such as corrosion, prices,
source, etc. should be taken into consideration. Of
course, it is a procedure after CAMD.

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1214 Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221

Many studies in this field have been made, yet most for the synthesis of liquid solvents. CAMD for liquid
are limited to unit operations, such as gas absorption, solvents is conducted in the following four steps.
liquid–liquid extraction, etc. The application of
CAMD in extractive distillation has seldom been sys-
tematically reported in references (Pretel, Lopez, Bot-
tini & Brignole, 1994). Moreover, in general, CAMD
2.1.1. Group sorting and pre-selection
focuses on the design of organic molecules instead of
Molecular design makes full use of the group con-
salts. In recent years, extractive distillation with salt
cept raised by Franklin (1949), which is built on the
addition has been applied more and more widely in
UNIFAC groups (Jorgensen, Kolbe, Gmehling &
the industry (Duan, Lei & Zhou, 1980; Lei, Duan &
Xu, 1982; Zhang, Qian & Jiang, 1984) and it is very Rasmussen, 1979; Gmehling, Rasmussen & Fre-
important to extend the range of CAMD to the addi- denslund, 1982; Macedo, Weidlich, Gmehling & Ras-
tives including salts. In this work, liquid solvents and mussen, 1983). The groups must be systematically
salts are both designed by CAMD and then tested by ordered to facilitate their use.
experiments. On this basis, the best additives for C4 There are different approaches to sorting the
separation by extractive distillation with ACN are se- groups (Gani & Brignole, 1983; Gani, Nielsen & Fre-
lected. denslund, 1991; Gani & Fredenslund, 1993; Pretel et
al., 1994). The approach we adopt is that a certain
group is determined by the number of attachments
2. Selection of liquid solvents present in a given group (or the valence number of
the group) and the degree of difficulty that the group
2.1. Procedure of CAMD for the liquid sol6ents combines other groups (or the type of attachment).
The UNIFAC groups are sorted and listed in Table 1.
The UNIFAC groups are used as building blocks If a group belongs to several different classes, it
means that this group takes on different types of
Table 1 characterization in different molecules.
Attachment type characterization of UNIFAC groups
Since the groups in Table 1 are based on the UNI-
Type of Groups FAC definition of functional group, they can be used
attachment to obtain the values of some properties related to
UNIFAC-based methods. For the computation of
(N,0) CH3OH CH3NO2 H2O CH3NH2
other properties based on certain group contributions,
CF3 CH3SH CH3CN Furfural
HCOOH DMSO (CH2OH)2 CH2Cl2 but not related to UNIFAC-based methods, new
CHCl3 ACRY DMF NMP parameter tables for the groups in Table 1 have been
CH3NH2 CS2 CCl3F CHCl2F developed using information on the group contribu-
CHClF2 CClF3 CCl2F2 C4H4S
tions and their corresponding parameter tables
Morph AmHCH3 Am (CH3)2
(Joback & Reid, 1987; Reid, Prausnitz & Poling,
(M,1) (CH3)
1987).
(J,2) (CH2)
(L,1) (CH2Cl) The attachment types are indicated as ordered pairs
(L,2) (CHCl) (i, j ), where i is the type of attachment and j, the
(K,1) (CH2 =CH) (OH) (CH3CO) (CHO) number of i attachment. Five types of attachments
(CH3COO) (HCOO) (CH3O) (CH2NH2) are put forward for non-aromatic groups:
(CH3NH) (C5H4N) (CH2CN) (COOH)
(CHCl2) (CCl3) (CH2NO2) (CH2SH)
N= Single molecules as a group having no at-
(I) (BR) (CH =C) Cl(C= C)
(SiH3) tachment with other groups, such as H2O
K= Severely restricted attachment, such as OH
(K,2) (CH= CH) (CH2 = C) (CH3N) (C5H3N)
(CCl2) (CHNO2) (C= C) (DMF-2)
L= partially restricted attachment, such as
(COO) (SiH2) (SiH2O) CH2Cl
(K,1) (L,1) (CH2CO) (CH2COO) (CH2O) (CHNH2) M= unrestricted carbon attachment in linear dual
(CH2NH) (FCH2O) valence or single valence groups, such as
(I,1) (ACH) (ACF) CH3
(H,1) (ACCH3) (ACOH) (ACNH2) (ACCl)
J= unrestricted carbon attachment in radial dual
(ACNO2) valence groups, such as CH2
(H,1) (M,1) (ACCH2)
(H,1) (J,2) (ACCH) For aromatic molecules, two new attachments are
introduced:
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flZ. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221
I= aromatic carbon ring attachment, such as
ACH
H= substituted aromatic carbon ring attachment,
such as ACCl
Types M and J attachments are extended to aromatic
groups.
M= unrestricted attachment in a carbon linked to
an aromatic carbon, such as ACCH2
J= unrestricted attachment in a radial carbon
linked to an aromatic carbon, such as ACCH
The chemically feasible molecules will be generated
from the above characterized UNIFAC groups in terms
of the rules that must be met in the formation of a
molecule and are to be mentioned afterwards. Not all
of the groups in Table 1 need to be used in CAMD for
a specific application. The groups may be screened in
advance. The pre-selection of groups is conducted on
two criteria:
1. Availability of interaction parameters. The predic-
tion of solvent properties requires the availability of
UNIFAC binary parameters. Therefore, the first
criterion of the selection is the availability of binary
parameters for the synthesis groups.
2. Elimination of unsteady compounds and corrosive,
toxic materials. Sometimes for a specialized separa-
tion process, we need to bear in mind that a lot of
groups could be excluded in advance. For instance,
some groups that may cause corrosion to the equip-
ment are avoided for distillation processes.
By sticking to these criteria, the number of partici-
pating groups is reduced and the time the computer
takes to fulfil the combination of groups is saved.
2.1.2. Combination of groups
The most difficult part in molecular design is assem-
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1215
1991; Gmehling, Li & Schilleer, 1993) and most of
the UNIFAC binary parameters and group parame-
ters are known to us. Many properties can be
calculated from these parameters.
4. In general, a molecule is composed of not more than
eight groups and the polar groups cannot be over
three. The groups in a molecule must accord with
the following attachment criterion: K= M+ J/2+2
for aliphatic compounds; I+ H= 6, H5 2 or H53
for aromatic compounds; for aliphatic–aromatic
compounds, these restriction must be satisfied simul-
taneously. Otherwise, this molecule is unsteady un-
der normal condition.
The number of the molecules combined by groups at
random is often too large to be processed by a com-
puter in a short time, which is the so-called combina-
tion explosion. In the molecular design, we should be
cautious to avoid its occurrence.
Assuming that there are n kinds of different groups
and the molecule combined by them has only m groups,
then the number of ways to combine the molecules
without other restrictions is:
(n+ m− 1)!
(n− 1)!m!
When the number of groups is in the range of 2–m,
the number of such molecules is:
m
(n+m− 1)!
%
m = 2 (n− 1)!m!
If n= 12 and m= 6, the number of combination
ways is very high with 18,551. Therefore, the assembled
rules must be considered to effectively decrease the
combination ways.
2.1.3. Prediction of target properties
Different problems have different sets of properties
as constraints. For CAMD for extractive distillation,
bling groups into one molecule. The assembly must fit such properties as relative volatility (h  ij ), selectivity
to the following rules:
1. The chemical valence of a molecule must be zero.
2. The neighborhood effect of groups must be avoided.
Fortunately, many researchers (Gani et al., 1991;
Gani & Fredenslund, 1993; Pretel et al., 1994) have
discussed the assembly rules from different stand-
points and given different restrictive conditions.
Their work is helpful for us to program CAMD.
3. The group parameters and group interaction
parameters must be known ahead of time. We have
collected 109 groups (Jorgensen et al., 1979; Gmeh-
ling et al., 1982; Macedo et al., 1983; Tiegs, Gmeh-
ling, Rasmussen & Fredenslund, 1987; Hansen,
Rasmussen, Fredenslund, Schiller & Gmehling,
(S 
ij ), solubility capacity (SP), molecular weight (MW)
and boiling point (Tb) are important. Specification of
the problem type identifies the corresponding target
properties. As not all the target properties are com-
putable, it is convenient to classify them as explicit
target properties and implicit target properties. Predic-
tion methods for explicit target properties are available
and can be realized automatically by computer. Predic-
tion methods for implicit properties are not presently
available and thus a combination of experience, infor-
mation from the open references and experiments is
needed to determine them. As a result, implicit proper-
ties are generally obtained manually. The prediction
methods for explicit properties are given in Table 2.
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1216 Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221

Table 2 2-Butylene and 1,3-butadiene are key components

Properties estimation for liquid solvents
(Asatani & Hayduk, 1983) in C4 separation because
Property Method their separation is difficult. So, it is reasonable to
only consider 2-butylene and 1,3-butadience as the
Relative volatility k 0
i pi representatives of C4 mixtures for solvent evaluation.
h
ij =  0
kj pj In this work, CAMD has been programmed with Vi-
sual Basic for Windows. This program can provide
Selectivity k
i
S
ij = much information necessary for the extractive distilla-
k
j
tion. CAMD is an easy-to-use software with user
Solubility 1 MWi friendly interface. One with a little knowledge of ex-
SPi =
capacity k
i MWj
Molecular weight Pure component data bank or by adding
group parameters (Reid et al., 1987)
Normal boiling Pure component data bank or by adding
point group parameters (Joback & Reid, 1987; Reid
et al., 1987)
Vapor pressure Pure component data bank or by Antoine
equation (Reid et al., 1987)
Azeotropic By drawing the curves of x–y to judge
judgement
2.1.4. Selection of additi6es
Although explicit properties can be computed ac-
cording to the methods of Table 2, relative relativity
is the key to the extractive distillation process. For
this reason, compounds are ordered by the values of
their relative volatility. But we know that evaluation
of implicit properties is also required for the selection
of additives. For CAMD for extractive distillation,
implicit properties such as toxicity, cost, stability and
material source are important. The compounds that
do not satisfy the implicit properties are crossed out
from the order. The remaining compounds ranked in
front of the order are the object of the best possible
additives we seek. As a result, by CAMD, the work
to search for the best additives is reduced. The final
additives will be tested with only a minimum number
of experiments.
tractive distillation can become familiar with it in a
few hours.
Fig. 1 shows a block diagram of CAMD for liquid
solvents.
2.2.2. Results of CAMD
CAMD is herein used for the separation of C4 by
extractive distillation with ACN. The restrictions of
additives for the ACN/C4 system are listed in the
following order.
1. Pre-selected group type number: 10 (CH3OH, H2O,
CH3, CH2, CH3COO, CH3CO, COOH, OH,
CH2CN, CH2NH2). The groups are selected on the
basis of the criteria listed in Section 2.1.1.
2. Expected group number: 2–6
3. Maximum molecular weight: 150
4. Minimum boiling point: 323.15 K
5. Maximum boiling point: 503.15 K
The conditions of additives for the ACN/C4 system
are given below:
1. Temperature: 303.15
2. Minimum infinite dilute relative volatility: 1.35
3. Concentration of additive in ACN: 10 wt%
4. Key components: 2-butylene and 1,3-butadiene,
which are at infinite dilution
CAMD has been performed on a PC (Pentium 2
286 MHz). The calculation in this case needs :10
min. The design results of liquid solvents are obtained
by means of CAMD and given in Table 3, where
2.2. CAMD for separating C4
2.2.1. Program of CAMD
Extractive distillation is widely used in purification
of 1,3-butadience from C4 mixtures. ACN is a fre-
quently used basic solvent and is inconvenient to be
completely replaced by other solvents to enhance the
relative volatility of C4. Therefore, water is usually
added to ACN as a cosolvent (Coogler, 1967; Bannis-
ter & Buck, 1969). But the mixed ACN is a disadvan-
tage as it tends to give rise to hydrolysis, which
contributes to the loss of ACN and corrosion of
equipment during production. So, a more efficient ad-
ditive is required to substitute water.
superscript  stands for the condition at infinite dilu-
tion.
Table 3 shows the sorted list of possible molecules
according to the values of relative volatility. Some
have been found in the literatures, such as H2O, No.
1. It indicates that the designed results are reliable to
some degree. After considering such implicit proper-
ties as toxic, boiling point, chemical stability and hy-
drolysis, the molecules, No. 1, 4, 5, 6 and 9 are
regarded as the possible additives.
However, we find from Chen (1997) that C4/
methanol and C4/ethanol can form azeotrope, which
does not correspond with the CAMD results. It mani-
fests that the acceptance of CAMD depends on the
accuracy of the computation methods used for the
中国科技论文在线 http://www.paper.edu.cn
Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221 1217

Fig. 1. Block diagram of CAMD for liquid solvents.

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1218 Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221

Table 3
Results of CAMD for liquid solvent

No. Molecular structure MW Tb/K h

12 S
12 SP Azeotropic judgement

1 and solvent 2 and solvent

1 H2O 18.0 373.2 1.66 2.16 0.38 No No

2 2CH2CN 80.0 495.3 1.51 1.97 0.37 No No
3 CH2 CH2CN OH 71.0 462.5 1.46 1.91 0.36 No No
4 CH3 3CH2 CH3COO 116.0 399.2 1.46 1.90 0.40 No No
5 CH3 CH2 CH3CO 72.0 352.8 1.45 1.89 0.40 No No
6 2CH2NH2 60.0 390.4 1.44 1.88 0.38 No No
7 CH2 OH CH2NH2 61.0 443.5 1.42 1.85 0.36 No No
8 CH3OH 32.0 337.8 1.42 1.86 0.38 No No
9 CH3 CH2 OH 46.0 351.5 1.39 1.81 0.39 No No

properties. Even though the prediction methods have 3. Selection of the salt
been extensively used, they should be considered only
as an approximation for the estimation of solvent prop-
erties. This is where the limitations of CAMD lie. 3.1. CAMD for the salts

The work of CAMD for salts is rarely reported in

2.3. Experimental measurement of the additi6es for liquid
sol6ents
A set of inert gas stripping and gas chromatography
equipment is built to measure the relative volatility of
C4 at infinite dilution (Leroi, Masson & Renon, 1977;
Duhem & Vidal, 1978). In this case, either trans-2-bu-
tylene and 1,3-butadiene or cis-2-butylene and 1,3-bu-
tadiene are regarded as the key components. We
measured the relative volatility of C4 mixtures at infi-
nite dilution at 20 °C in the solvent ACN and at 50 °C
in the solvent N,N-dimethylformamide (DMF). The
experimental values are compared with the reference
values (Chemical Engineering Department of Zhejiang
University, 1973) obtained by gas chromatography
method and are in good agreement except for an error
of 12%, which may be due to the different methods to
measure the relative volatility. The results are listed in
Table 4, where we use the subscript (1 – 5) for n-butane,
1-butylene, trans-2-butylene, cis-2-butylene and 1,3-bu-
tadiene, respectively. On this basis, ACN blended with
additives produced by CAMD is used and the relative
volatility of C4 mixtures are measured. The results at
different additive concentrations are given in Table 5.
From the above it can be seen that water and
ethylenediamine are good potential additives of ACN
of all liquid solvents. If we consider the hydrolysis
influence of ACN, ethylenediamine is the best substance
as liquid solvent that is added to ACN.
Thus, by means of the tool, CAMD, we can find the
best additive, ethylenediamine from a great number of
references despite the frequent use of salts as separating
agents in chemical engineering. With the development
of extractive distillation, the extractive distillation with
salt is becoming more and more applied in industry, as
pointed out in Section 1. Therefore, it is interesting to
consider the salting effect in regard to CAMD.
In this work as a simplified presumption, a salt is
thought to be composed of one positive ion and one
negative ion which are regarded as the groups of salts.
It is consequently easy to assemble the ions into
molecules in the same way as liquid solvents. These ions
are collected and listed in Table 6. In the procedure of
CAMD, the combination rule is simply that the chemi-
cal valence of a salt must be zero, which is impossible
to lead to combination explosion because most
molecules are composed of just two groups, one posi-
tive ion and the other negative ion. Therefore, both
liquid solvents and salts can be designed in our pro-
grammed CAMD, and this goes a further step in the
application of CAMD.
The key of CAMD for salts is the selection of an
appropriate thermodynamic method to obtain the
target properties that are only attained by data bank
search. The prediction methods for explicit properties
Table 4
The comparison results of experimental and reference values
ACN (20 °C) DMF (50 °C)
Ref. Exp. Error % Ref. Exp. Error %
liquid solvents with only a few experiments. It is shown h
15 3.41 3.82 12.02 3.43 3.32 3.21
h
25 2.16 2.11 2.31 2.17 2.12 2.30
that CAMD can effectively decrease the amounts of h 1.70 1.81 6.47 1.76 1.79 1.73
35
experiments and help researchers explore the useful h
45 1.56 1.63 4.49 1.56 1.61 3.21
substances in a short time.
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Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221 1219

Table 5
Experimental values of relative volatility of C4 mixtures at different additives concentration

Additives Concentration/wt% T/°C h

15 h
25 h
35 h
45

– 0 28 3.61 2.08 1.77 1.58

n-Butanone 10 28 3.55 2.08 1.75 1.57
n-Butanone 20 29 3.37 2.06 1.71 1.56
n-Butyl acetate 10 30 3.52 2.04 1.71 1.55
n-Butyl acetate 20 30 3.30 2.01 1.69 1.53
Ethyl alcohol 10 30 3.58 2.09 1.77 1.57
Ethyl alcohol 20 30 3.54 2.11 1.77 1.59
Water 10 29 4.06 2.16 1.84 1.62
Ethylenediamine 10 30 3.77 2.11 1.79 1.62
Ethylenediamine 20 30 3.81 2.15 1.83 1.60
Ethylenediamine 100 30 3.62 2.13 1.89 1.58

are listed in Table 7, in which the values of relative KI. On this basis, some experiments, just as we carried
volatility and selectivity are closely related with salting out for liquid solvents, were performed to investigate
coefficients. Salting coefficients are calculated by the the effect of salts. Table 9 shows the experimental
scaled particle theory (Masterton & Lee, 1970; Pierotti, values at 30 °C with salt concentration 10 wt%. The
1976). The scaled particle theory, deduced from ther- subscripts 1–5 represent n-butane, 1-butene, trans-2-
modynamics and statistical physics, has a defined phys- butene, cis-2-butene and 1,3-butadiene, respectively.
ical meaning and the required molecular parameters are
readily available. In particular, in recent years the study
of scaled particle theory has been further developed.
Table 6
Therefore, it is reasonable to deal with salting effect of Ions of CAMD for salts
extractive distillation with this theory, which is a great
theory and application prospect and should be given Ions Groups
more attention.
Cation Li+ Na+ K+ Rb+
Cs+ Ag+ NH+ 4 Cu+
Mg2+ Ca2+ Sr2+ Ba2+
3.2. Results of CAMD Be2+ Fe2+ Zn 2+
Cu2+
Al3+ Fe3+
The additive constraints for the system of ACN/C4 Anion OH− F− Cl− Br−
are listed in the following order. I− SCN− NO−3 NO−2
1. Pre-selected group type number: 8 (Li+, Na+, K+, CH3COO− ClO−
4 BF−
4

Br−, Cl−, I−, SCN−, NO− 3 ). The groups are se-

lected because the salts formed by them are often
met and easily obtained in the industry. Table 7
Properties estimation for salts
2. Expected group number: 2
The conditions of additives for the system of ACN/ Property Method
C4 are given below:
1. Temperature: 303.15 Salting coefficients Calculated by Scaled Particle Theory
2. Minimum infinite dilute relative volatility: 1.40 ks
Activity Calculated by UNIFAC method
3. Concentration of additive in ACN: 10 wt% coefficient
4. Key components: 2-butylene and 1,3-butadiene that Relative volatility k 0
i pi
h
ij =  0
are at infinite dilution without salt kj pj
CAMD has been performed on a PC (Pentium 2 286 Selectivity without k
i
MHz). The calculation in this case needs a few minutes S
ij = 
salt kj
and the results of CAMD are printed under the condi- Relative volatility h 
s =h exp(kscs )
tion of these constraints. But it is known that the salts with salt
must meet the requirement of implicit properties, e.g. Selectivity with S 
s =S exp(kscs )

chemical stability, oxidation, material source and solu- salt

bility in CAN, etc. These factors taken in, the results of Molecular weight Pure component data bank or by adding
group parameters (Millero, 1971)
the selected salts are listed in Table 8. Vapor pressure Pure component data bank or by Antoine
If the price factor is further considered, the salts equation (Reid et al., 1987)
NaSCN and KSCN are more attractive than NaI and
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1220 Z. Lei et al. / Computers and Chemical Engineering 26 (2002) 1213–1221

Table 8 effective than liquid solvents in increasing the relative

Results of CAMD for salts
volatility of C4 at infinite dilution. Therefore, it is
No. Molecular MW Relative Selectivity S  advisable to add a little salt to ACN as a mixture
12
structure volatility h 
45
solvent for separating C4 by extractive distillation. Af-
ter some factors (implicit properties) are considered, the
1 Na+SCN−1 81.0 1.57 2.00 best salts are NaSCN and KSCN.
2 Na+I−1 150.0 1.56 1.98 It is evident that by CAMD, the experiment working
3 K+SCN−1 97.0 1.55 1.98
4 K+I−1 166.0 1.55 1.97
is greatly decreased in a search for the best additives.
CAMD as a useful tool plays an important role in
finding the additives and shortening the search time. It
Table 9 is believed that with the development of CAMD, it
Experimental values of relative volatility of C4 at infinite dilution would be possible to be applied in many more fields.
Salt h
15 h
25 h
35
NaSCN 4.03 2.19 1.85
KSCN 4.00 2.18 1.85
A comparison of the results of Table 5 and Table 9
demonstrates that the addition of salt is more efficient
than the addition of liquid solvents (including water)
for improving the separation ability of ACN. Because
NaSCN and KSCN are more economic than NaI and
KI, they are the desired additives. Simulation of extrac-
tive distillation process for ACN and ACN/NaSCN
with a 10 wt% salt concentration is carried out. The
results show that the required solvent rate decreases
11.8% and much energy is saved in the extractive
distillation column when salt is added. Therefore, the
mixture of ACN and salt performs more satisfactorily
than a single ACN solvent. Apart from this, the mix-
ture has no problem with dissolution, reuse and trans-
port of salt, which is often brought on by salt.
4. Conclusion
This investigation is concerned with the improvement
of ACN for separating C4 by extractive distillation.
ACN, as a basic solvent, is easy to hydrolyze and needs
to be improved by adding some additives. In this work,
the additives are divided into two types, liquid solvents
and salts. But we know if liquid solvents are selected at
random, they are too large to be measured one by one
by experiments. CAMD has been programmed to
screen the liquid solvents and to reduce the amount of
experiments.
Moreover, it is novel that CAMD has been extended
to the design of salts. In the procedure of CAMD, the
UNIFAC groups are regarded as cations and anions
and the program similar to those for liquid solvents is
used. Most important of all is that the group concept is
extended to include ions and promotes the development
of CAMD.
On the basis of the results of CAMD, the experi-
ments are made and it is shown that salts are more
h
45
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