Professional Documents
Culture Documents
1.technical Traits of Extractive Distillation With Salt in Solvent
1.technical Traits of Extractive Distillation With Salt in Solvent
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(2040%) 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 1/41/5, 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.
Solvent
We have performed experimental research, so as to collect relevant data of saltadded 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
formula
molecular purity
weight
density
(kg/m3)
boiling
point()
ethylene glycol
anhydrous ethanol
95% ethanol
sodium chloride
anhydrous
C2H6O2
C2H5OH
C2H5OH
NaCl
CaCl2
62.07
46.07
46.07
58.44
110.99
A.R.
C.P.
C.P.
A.R.
A.R.
1.11103
0.79103
0.82103
198
78
265.62
133.34
101.11
241.60
357.15
98.14
A.R.
A.R.
A.R.
A.R.
A.R.
C.P.
138.2
C.P.
calcium chloride
strontium chloride SrCl26H2O
aluminum chloride AlCl3
potassium nitrate KNO3
copper nitrate
Cu(NO3)23H2O
aluminum nitrate Al(NO3)39H2O
potassium acetate K CO2CH3
anhydrous
potassium
K2CO3
carbonate
minutes later, the desired phase equilibrium was achieved. Samples were taken and
analyzed. Then the relative volatility was calculated from:
y /x
1 1
y 2 / 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
1.01
ethylene glycol
1.85
calcium chloride 3.13
potassium acetate 4.05
ethylene glycol+NaCl
ethylene glycol+CaCl2
ethylene glycol+SrCl2
ethylene glycol+AlCl3
ethylene glycol+KNO3
ethylene glycol+Cu(NO3)2
ethylene glycol+Al(NO3)3
ethylene glycol+ K CO2 CH3
ethylene glycol+K2CO3
relative volatility
2.31
2.56
2.6
4.15
1.9
2.35
2.87
2.4
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.
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
4
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
0.81
1:1
with ethylene
x 0.08
0.81
0.957
0.979
glycolCaCl2(10%)
y 0.679 0.79
0.882 0.917
0.986
We
get
the
following result from those data: the effect of salt-dissolved solvent is better than that
of the solvent without salt.
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
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.
REFERENCES
[1] . .
19762-39398
Petrochemical Factory of Lanzhou Chemical Industry Corporation,et
al.
First stage renovation of extraction distillation tower for
refining
propenyl cyanide. Petrochemical Technology,1976,2-3: 9398
[2] Furter W F. Salt effect in distillation : a literature review.
Inter. J. Heat Mass Transfer, 1967,10 : 2336
[3] Furter W F. Salt effect in distillation : a literature review.
Canadian J.Chem.Eng., 1977,55:229239
[4] . . 1983.
153162
Huang Ziqing. Introduction of Electrolyte Solution Theory .
Beijing:
Science Press, 1983.153162