Extractive Distillation with Salt in Solvent

Zhou Rongqi(周荣琪) Duan Zhanting(段占庭)1

Department of Chemical Engineering, Tsinghua University, Beijing 100084

ABSTRACT
Extractive distillation with salt in solvent is a new process for producing
anhydrous ethanol by combining the principle of “salt effect” and some traditional
extractive distillation methods. Compared with the common extractive distillation the
performance of solvent is improved, the recycling amount of solvent is reduced to 1/4
—1/5, and the number of theoretical plates is reduced to 1/3. Energy consumption
and cost of equipment are also reduced and continuous production is realized. High
efficiency and low solvent wastage make this technique feasible.
Key words extractive distillation, salt, solvent, anhydrous ethanol

1.Technical Traits of Extractive Distillation with Salt in Solvent

Anhydrous ethanol is not only used as chemical reagent and organic solvent, but
also used as the raw material of many important chemical products and intermediates.
It has found diverse applications in many fields such as pharmaceutical, electronic
and military industries.
The method of manufacturing anhydrous ethanol has been ameliorated
incessantly due to the increasingly strict requirements for quantity and quality of this
product. As one of the most primitive ways, the dehydrating process was notorious
for large intensity of labor and poor product quality. Dehydration by utilizing
molecular sieve or ion exchange resin may provide high-quality products, but this
operation can only be applied to some small-scale batch apparatus. It also has other
drawbacks such as difficulty in refreshing, tremendous power consumption and low
yield. Although azeotropic distillation with benzene was used in large-scale
manufacture, the unacceptable number of tower plates and residual benzene in final
product made it unsuitable for medical or chemical uses. Besides, poisoning of
benzene happens occasionally in practical process.
In recent years, pentane-combined azeotropic distillation has been reported with
obvious advantages such as simple process, small number of plates and suitability for
large-scale production. Because of the low boiling point of pentane and the azeotropic
agent, it should be operated under artificial high pressure. Besides this substance is
easy to evaporate in normal room temperature, and the consumption of azeotropic

1
Manuscript received: 1998-04-10

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agent is unbearable.
Another alternative method is extractive distillation with ethylene glycol as
solvent. It has features of high quality of products and suitability for large-scale
production, relatively less volatilization amount and lower consumption of solvent.
However, the solvent ratio (the ratio of solvent to feed) is too large, normally 5:1.
Because of the great amount of recycling solvent, the additional consumption of
energy is high. At the same time, the high liquid-phase load and low plate
Efficiency(20—40%) increase the number of plates and offset the effects of raising
relative volatility and reducing the number of plates by introducing solvent to a great
extent[1].
With salt dissolved in ethanol-water system, its relative volatility can be
improved[1]. Salt added extractive distillation just makes use of this property[2,3].
This application can lead to satisfactory effect of dehydration, smaller number of
theoretical plates and simplified process. In industrial operation, when a solid salt is
used in place of a liquid separating agent, it is normally fed to the column by filling
the dissoluble into the reflex stream immediately before the entry of the reflex at the
top of the column. Because the salt is nonvolatile, it will remain entirely within the
liquid phase and hence flow only downward. So it can elude the conventional
stripping section. Pure product is achieved from the column top. However,
dissolution, reuse and transport of salt is quite a problem. The concurrent tub-jam and
erosion limit the industrial value of this technique.
After comparing all kinds of techniques available at present, we put forward the
novel extractive distillation with salt in solvent.
This invention combines the principle of “salt effect” and the extractive
distillation and it is called as extractive distillation with dissolved salt.
The new technique avoids the defects of traditional processes, and is an ideal
process for anhydrous ethanol production. Some characteristics are listed as follows:
(1). Ameliorate the performance of solvent. Compared with common extractive
distillation, the recycling amount of solvent is reduced to 1/4—1/5, number of
theoretical plates is reduced to 1/3, energy consumption and equipment cost are also
reduced.
(2). Continuous production is realized. High efficiency and low solvent wastage
make this technique feasible.
(3). No pollution. Product shows extraordinary purity.

2. Experimental Research on Extractive Distillation with Salt in

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 Solvent
We have performed experimental research, so as to collect relevant data of salt-
added extractive distillation critical for industrial application.
Properties of salts and solvents involved are listed in Table 1.
Table 1 Properties of salts and solvents

definition molecular molecular purity density boiling

formula weight (kg/m3) point(℃)
ethylene glycol C2H6O2 62.07 A.R. 1.11╳103 198
anhydrous ethanol C2H5OH 46.07 C.P. 0.79╳103 78
95% ethanol C2H5OH 46.07 C.P. 0.82╳103
sodium chloride NaCl 58.44 A.R.
anhydrous CaCl2 110.99 A.R.
calcium chloride
strontium chloride SrCl2·6H2O 265.62 A.R.
aluminum AlCl3 133.34 A.R.
chloride
potassium nitrate KNO3 101.11 A.R.
copper nitrate Cu(NO3)2·3H2O 241.60 A.R.
aluminum nitrate Al(NO3)3·9H2O 357.15 A.R.
potassium acetate K CO2CH3 98.14 C.P.
anhydrous
potassium K2CO3 138.2 C.P.
carbonate
2.1 Preparation of Anhydrous Salt
Most salts available contain crystal water or absorb ambient moisture easily. And
the dehydration degree of salts has direct effect on the relative volatility. For
nondecomposable species, we used high-temperature sand to expel moisture. While
decomposable species were dissolved, they were dehydrated by distillation under
vacuum until water-content is reduced to below 0.2%.
2.2 Analytic Apparatus
The compositions of both liquid and gas phases were analyzed by local 2305 GC
and the type of chromatographical column was Porpaka Q.
2.3 Selection of Solvent and Salt
Typical recycling liquid-gas equilibrium systems were utilized in the experiment.
First, the azeotropic ethanol-water solution was fed into the equilibrium system. Salt
and solvent were at the ratio(volume ratio) of 1:1, and the concentration of salt was

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0.2g(salt)/ml(solvent). After Shook well, the mixture was heated to boil. Twenty
minutes later, the desired phase equilibrium was achieved. Samples were taken and
analyzed. Then the relative volatility was calculated from:
y /x
α= 1 1
y2 / x2
where y1 , y 2 stand for the molecular fractions of ethanol and water in the gas phase
respectively; x1 , x 2 stand for those in the liquid phase.
For azeotropic ethanol-water system, the effects of solvent, salt and solvent-salt
on the relative volatility are shown in Table 2.
Table 2 Effects of solvent, salt and solvent-salt on relative volatility

salt or solvent relative volatility solvent-salt relative

α volatility
α
1.01 ethylene glycol+NaCl 2.31
ethylene glycol 1.85 ethylene glycol+CaCl2 2.56
calcium chloride 3.13 ethylene glycol+SrCl2 2.6
potassium acetate 4.05 ethylene glycol+AlCl3 4.15
ethylene glycol+KNO3 1.9
ethylene glycol+Cu(NO3)2 2.35
ethylene glycol+Al(NO3)3 2.87
ethylene glycol+ K CO2 CH3 2.4
ethylene glycol+K2CO3 2.6
The relative volatility of the system without salt or solvent was measured. The
goal of this work is to verify the correctness of the experimental method and study the
selection of salt and solvent. The result is the intended value equal to 1.01.
When solvent is introduced with small amount of salt, the relative volatility is
increased by 30%. So the conclusion that salt in solvent benefits separation can be
drawn. The relative effect of specific kinds of salt obeys the Dybel static-electric
theory about salt effect[4]: the higher the valence of metal ion is, the more obvious the
effect is.
The salt effect gradually decreases in the order of AlCl3 ,CaCl2 and NaCl. The
trend is the same in the order of Al(NO3)3,Cu(NO3)2 and KNO3. Besides, the salt
effect gradually decreases in the order of Ac-,Cl- and NO-3.
The industrial requirements for salt selection are low cost, chemical stability,
high dissolvability, minor apparatus corrosion, less poisoning, besides the possibly
highest volatility. Therefore, the optimal system is ethylene glycol-potassium acetate.

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 2.4 Gas-Liquid Equilibrium Data
We measured the equilibrium data of the ethanol-water system which accorded
with the published data approximately. Then, we determined the data with solvent
ethylene glycol (solvent ratio is 1:1) and salt-dissolved separating agent(solvent ratio
was 1:1 and concentration of salt was 0.1 g/ml (solvent)) in the whole range of
concentrations. The experimental results are shown in Table 3 and Fig.1.
Table 3 Equilibrium data of ethanol-water system

with ethylene glycol x 0.08 0.152 0.559 0.7 0.81 0.9019 0.9082 0.9607
1:1 y 0.519 0.716 0.813 0.8725 0.9085 0.949 0.957 0.979

with ethylene x 0.08 0.152 0.559 0.7 0.81 0.9019 0.9082 0.9607
glycol-
CaCl2(10%) y 0.679 0.79 0.882 0.917 0.9449 0.9672 0.969 0.986

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 We get the following result from those data: the effect of salt-dissolved solvent is
better than that of the solvent without salt.

3. Practical Experiment on Salt-Added Extractive Distillation

The practical experiment on salt-added extractive distillation was carried out in a
small glass distillation column with a diameter of 30mm. The canon packing, which
was contained in the column and amounted to 15 theoretical plates, had a height of
800mm. Vapor feed was 88% ethanol with azeotropic composition. The following
solvents were used: ethylene glycol and ethylene glycol with salt. The process
without salt obtained 99.5% ethanol when solvent ratio was up to 4 or 5. The process
with salt (5%KCl) obtained >99.5% ethanol when solvent ratio was only 1:1.
Solvents were refreshed in the packed distillation column at 680mmHg vacuum
degree. Water evaporates from the top of the column and refreshed solvent containing
<0.2% water came out from the bottom when bottom temperature was 145℃. The
refreshed solvent had satisfactory performance when used in subsequent extractive
distillation.

4. Summary
A novel extractive distillation process with salt in solvent has been forwarded on
the basis of examining various kinds of methods.
1. This new technique has the advantages of both extractive distillation and
distillation with dissolved salt and overcomes their drawbacks. There has been no
report on this approach both at home and abroad.
2. It is more advanced than the widely used extractive distillation employing
ethylene glycol. The new technique improve efficiency, reduces solvent ratio and

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number of necessary plates, and saves operation cost and equipment investment.
3. The new technique has replaced out-dated apparatus in many factories.
Technical maturity has enabled it to create great economic profit. By now, more than
thirty factories have utilized this method.
4. Necessary basic research and engineering scale-up exploration have been
undertaken based on the industrial experience and technical data, and design
calculating method is forwarded.
5. This approach can be transplanted to other chemical systems, so it has broad
industrial prospect.

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