Extractive Distillation with Salt in Solvent

Zhou Rongqi( ) Duan Zhanting()

1
Department of Chemical Engineering, Tsinghua University, ei!ing 1"""#$
ABSTRACT
E%tractive &istillation 'ith salt in solvent is a ne' process for pro&ucing
anhy&rous ethanol (y com(ining the principle of )salt effect* an& some tra&itional
e%tractive &istillation metho&s+ Compare& 'ith the common e%tractive &istillation the
performance of solvent is improve&, the recycling amount of solvent is re&uce& to 1,$
-1,., an& the num(er of theoretical plates is re&uce& to 1,/+ Energy consumption an&
cost of equipment are also re&uce& an& continuous pro&uction is reali0e&+ 1igh
efficiency an& lo' solvent 'astage ma2e this technique feasi(le+
Key words e%tractive &istillation, salt, solvent, anhy&rous ethanol
1.Technical Traits of Extractive Distillation with Salt in Solvent
3nhy&rous ethanol is not only use& as chemical reagent an& organic solvent, (ut
also use& as the ra' material of many important chemical pro&ucts an& interme&iates+
4t has foun& &iverse applications in many fiel&s such as pharmaceutical, electronic an&
military in&ustries+
The metho& of manufacturing anhy&rous ethanol has (een ameliorate& incessantly
&ue to the increasingly strict requirements for quantity an& quality of this pro&uct+ 3s
one of the most primitive 'ays, the &ehy&rating process 'as notorious for large
intensity of la(or an& poor pro&uct quality+ Dehy&ration (y utili0ing molecular sieve or
ion e%change resin may provi&e high5quality pro&ucts, (ut this operation can only (e
applie& to some small5scale (atch apparatus+ 4t also has other &ra'(ac2s such as
&ifficulty in refreshing, tremen&ous po'er consumption an& lo' yiel&+ 3lthough
a0eotropic &istillation 'ith (en0ene 'as use& in large5scale manufacture, the
unaccepta(le num(er of to'er plates an& resi&ual (en0ene in final pro&uct ma&e it
unsuita(le for me&ical or chemical uses+ esi&es, poisoning of (en0ene happens
occasionally in practical process+
4n recent years, pentane5com(ine& a0eotropic &istillation has (een reporte& 'ith
o(vious a&vantages such as simple process, small num(er of plates an& suita(ility for
large5scale pro&uction+ ecause of the lo' (oiling point of pentane an& the a0eotropic
agent, it shoul& (e operate& un&er artificial high pressure+ esi&es this su(stance is
easy to evaporate in normal room temperature, an& the consumption of a0eotropic
1
6anuscript receive&7 188#5"$51"
1
agent is un(eara(le+
3nother alternative metho& is e%tractive &istillation 'ith ethylene glycol as
solvent+ 4t has features of high quality of pro&ucts an& suita(ility for large5scale
pro&uction, relatively less volatili0ation amount an& lo'er consumption of solvent+
1o'ever, the solvent ratio (the ratio of solvent to fee&) is too large, normally .71+
ecause of the great amount of recycling solvent, the a&&itional consumption of
energy is high+ 3t the same time, the high liqui&5phase loa& an& lo' plate
Efficiency(9"-$":) increase the num(er of plates an& offset the effects of raising
relative volatility an& re&ucing the num(er of plates (y intro&ucing solvent to a great
e%tent
;1<
+
=ith salt &issolve& in ethanol5'ater system, its relative volatility can (e
improve&
;1<
+ >alt a&&e& e%tractive &istillation !ust ma2es use of this property
;9,/<
+
This application can lea& to satisfactory effect of &ehy&ration, smaller num(er of
theoretical plates an& simplifie& process+ 4n in&ustrial operation, 'hen a soli& salt is
use& in place of a liqui& separating agent, it is normally fe& to the column (y filling the
&issolu(le into the refle% stream imme&iately (efore the entry of the refle% at the top of
the column+ ecause the salt is nonvolatile, it 'ill remain entirely 'ithin the liqui&
phase an& hence flo' only &o'n'ar&+ >o it can elu&e the conventional stripping
section+ ?ure pro&uct is achieve& from the column top+ 1o'ever, &issolution, reuse
an& transport of salt is quite a pro(lem+ The concurrent tu(5!am an& erosion limit the
in&ustrial value of this technique+
3fter comparing all 2in&s of techniques availa(le at present, 'e put for'ar& the
novel e%tractive &istillation 'ith salt in solvent+
This invention com(ines the principle of )salt effect* an& the e%tractive &istillation
an& it is calle& as e%tractive &istillation 'ith &issolve& salt+
The ne' technique avoi&s the &efects of tra&itional processes, an& is an i&eal
process for anhy&rous ethanol pro&uction+ >ome characteristics are liste& as follo's7
(1)+ 3meliorate the performance of solvent+ Compare& 'ith common e%tractive
&istillation, the recycling amount of solvent is re&uce& to 1,$-1,., num(er of
theoretical plates is re&uce& to 1,/, energy consumption an& equipment cost are also
re&uce&+
(9)+ Continuous pro&uction is reali0e&+ 1igh efficiency an& lo' solvent 'astage
ma2e this technique feasi(le+
(/)+ @o pollution+ ?ro&uct sho's e%traor&inary purity+

2. Experiental Research on Extractive Distillation with Salt in
9
Solvent
=e have performe& e%perimental research, so as to collect relevant &ata of salt5
a&&e& e%tractive &istillation critical for in&ustrial application+
?roperties of salts an& solvents involve& are liste& in Ta(le 1+
Ta(le 1 ?roperties of salts an& solvents
&efinition molecular
formula
molecular
'eight
purity &ensity
(2g,m
/
)
(oiling
point()
ethylene glycol C
9
1
A
B
9
A9+"C 3+R+ 1+11 1"
/
18#
anhy&rous ethanol C
9
1
.
B1 $A+"C C+?+ "+C8 1"
/
C#
8.: ethanol C
9
1
.
B1 $A+"C C+?+ "+#9 1"
/
so&ium chlori&e @aCl .#+$$ 3+R+
anhy&rous
calcium chlori&e
CaCl
9
11"+88 3+R+
strontium chlori&e >rCl
9
DA1
9
B 9A.+A9 3+R+
aluminum chlori&e 3lCl
/
1//+/$ 3+R+
potassium nitrate E@B
/
1"1+11 3+R+
copper nitrate Cu(@B
/
)
9
D/1
9
B 9$1+A" 3+R+
aluminum nitrate 3l(@B
/
)
/
D81
9
B /.C+1. 3+R+
potassium acetate E CB
9
C1
/
8#+1$ C+?+
anhy&rous
potassium
car(onate
E
9
CB
/
1/#+9 C+?+
9+1 ?reparation of 3nhy&rous >alt
6ost salts availa(le contain crystal 'ater or a(sor( am(ient moisture easily+ 3n&
the &ehy&ration &egree of salts has &irect effect on the relative volatility+ For
non&ecomposa(le species, 'e use& high5temperature san& to e%pel moisture+ =hile
&ecomposa(le species 'ere &issolve&, they 'ere &ehy&rate& (y &istillation un&er
vacuum until 'ater5content is re&uce& to (elo' "+9:+
9+9 3nalytic 3pparatus
The compositions of (oth liqui& an& gas phases 'ere analy0e& (y local 9/". GC
an& the type of chromatographical column 'as ?orpa2a H+
9+/ >election of >olvent an& >alt
Typical recycling liqui&5gas equili(rium systems 'ere utili0e& in the e%periment+
First, the a0eotropic ethanol5'ater solution 'as fe& into the equili(rium system+ >alt
an& solvent 'ere at the ratio(volume ratio) of 171, an& the concentration of salt 'as
"+9g(salt),ml(solvent)+ 3fter >hoo2 'ell, the mi%ture 'as heate& to (oil+ T'enty
/
minutes later, the &esire& phase equili(rium 'as achieve&+ >amples 'ere ta2en an&
analy0e&+ Then the relative volatility 'as calculate& from7
=
y x
y x
1 1
9 9
,
,
'here
y
1
,
y
9
stan& for the molecular fractions of ethanol an& 'ater in the gas phase
respectivelyI
x
1
,
x
9
stan& for those in the liqui& phase+
For a0eotropic ethanol5'ater system, the effects of solvent, salt an& solvent5salt
on the relative volatility are sho'n in Ta(le 9+
Ta(le 9 Effects of solvent, salt an& solvent5salt on relative volatility
salt or solvent relative volatility

solvent5salt relative volatility

1+"1 ethylene glycolJ@aCl 9+/1

ethylene glycol 1+#. ethylene glycolJCaCl
9
9+.A
calcium chlori&e /+1/ ethylene glycolJ>rCl
9
9+A
potassium acetate $+". ethylene glycolJ3lCl
/
$+1.
ethylene glycolJE@B
/
1+8
ethylene glycolJCu(@B
/
)
9
9+/.
ethylene glycolJ3l(@B
/
)
/
9+#C
ethylene glycolJ E CB
9
C1
/
9+$
ethylene glycolJE
9
CB
/
9+A
The relative volatility of the system 'ithout salt or solvent 'as measure&+ The
goal of this 'or2 is to verify the correctness of the e%perimental metho& an& stu&y the
selection of salt an& solvent+ The result is the inten&e& value equal to 1+"1+
=hen solvent is intro&uce& 'ith small amount of salt, the relative volatility is
increase& (y /":+ >o the conclusion that salt in solvent (enefits separation can (e
&ra'n+ The relative effect of specific 2in&s of salt o(eys the Dy(el static5electric theory
a(out salt effect
;$<
7 the higher the valence of metal ion is, the more o(vious the effect is+
The salt effect gra&ually &ecreases in the or&er of 3lCl
/
,CaCl
9
an& @aCl+ The
tren& is the same in the or&er of 3l(@B
/
)
/
,Cu(@B
/
)
9
an& E@B
/
+ esi&es, the salt
effect gra&ually &ecreases in the or&er of 3c
5
,Cl
5
an& @B
5
/
+
The in&ustrial requirements for salt selection are lo' cost, chemical sta(ility, high
&issolva(ility, minor apparatus corrosion, less poisoning, (esi&es the possi(ly highest
volatility+ Therefore, the optimal system is ethylene glycol5potassium acetate+
9+$ Gas5Kiqui& Equili(rium Data
=e measure& the equili(rium &ata of the ethanol5'ater system 'hich accor&e&
'ith the pu(lishe& &ata appro%imately+ Then, 'e &etermine& the &ata 'ith solvent
$
ethylene glycol (solvent ratio is 171) an& salt5&issolve& separating agent(solvent ratio
'as 171 an& concentration of salt 'as "+1 g,ml (solvent)) in the 'hole range of
concentrations+ The e%perimental results are sho'n in Ta(le / an& Fig+1+
Ta(le / Equili(rium &ata of ethanol5'ater system
with ethylene !lycol x "."# ".1$2 ".$$% ".& ".#1 ".%"1% ".%"#2 ".%'"&
1(1 y ".$1% ".&1' ".#1) ".#&2$ ".%"#$ ".%*% ".%$& ".%&%
with ethylene
!lycol+
x "."# ".1$2 ".$$% ".& ".#1 ".%"1% ".%"#2 ".%'"&
CaCl2,1"-. y ".'&% ".&% ".##2 ".%1& ".%**% ".%'&2 ".%'% ".%#'
=e get the follo'ing result from those &ata7 the effect of salt5&issolve& solvent is
(etter than that of the solvent 'ithout salt+
). /ractical Experient on Salt+Added Extractive Distillation
The practical e%periment on salt5a&&e& e%tractive &istillation 'as carrie& out in a
small glass &istillation column 'ith a &iameter of /"mm+ The canon pac2ing, 'hich
'as containe& in the column an& amounte& to 1. theoretical plates, ha& a height of
#""mm+ Lapor fee& 'as ##: ethanol 'ith a0eotropic composition+ The follo'ing
solvents 'ere use&7 ethylene glycol an& ethylene glycol 'ith salt+ The process 'ithout
salt o(taine& 88+.: ethanol 'hen solvent ratio 'as up to $ or .+ The process 'ith salt
(.:ECl) o(taine& M88+.: ethanol 'hen solvent ratio 'as only 171+ >olvents 'ere
refreshe& in the pac2e& &istillation column at A#"mm1g vacuum &egree+ =ater
evaporates from the top of the column an& refreshe& solvent containing N"+9: 'ater
came out from the (ottom 'hen (ottom temperature 'as 1$.+ The refreshe&
.
solvent ha& satisfactory performance 'hen use& in su(sequent e%tractive &istillation+
*. S0ary
3 novel e%tractive &istillation process 'ith salt in solvent has (een for'ar&e& on
the (asis of e%amining various 2in&s of metho&s+
1+ This ne' technique has the a&vantages of (oth e%tractive &istillation an&
&istillation 'ith &issolve& salt an& overcomes their &ra'(ac2s+ There has (een no
report on this approach (oth at home an& a(roa&+
9+ 4t is more a&vance& than the 'i&ely use& e%tractive &istillation employing
ethylene glycol+ The ne' technique improve efficiency, re&uces solvent ratio an&
num(er of necessary plates, an& saves operation cost an& equipment investment+
/+ The ne' technique has replace& out5&ate& apparatus in many factories+
Technical maturity has ena(le& it to create great economic profit+ y no', more than
thirty factories have utili0e& this metho&+
$+ @ecessary (asic research an& engineering scale5up e%ploration have (een
un&erta2en (ase& on the in&ustrial e%perience an& technical &ata, an& &esign
calculating metho& is for'ar&e&+
.+ This approach can (e transplante& to other chemical systems, so it has (roa&
in&ustrial prospect+
REFERE@CE>
[1] . . 19762!"9!#9$
%&'()*+&,-*./ 1.*')(2 )3 4.56+)7 8+&,-*./ 95:7;'(2
8)(<)(.'-)5=&'./.
1-(;';'.>&(&5)?.'-)5)3&@'(.*'-)5:-;'-//.'-)5')A&(3)((&3-5-5>
<()<&52/ *2.5-:&. %&'()*+&,-*./ B&*+5)/)>2=1976=2!C9!#9$
[2]17('&(D1.E./'&33&*'-5 :-;'-//.'-)5 C./-'&(.'7(&(&?-&A. 95'&(.F.
G&.'H.;;B(.5;3&(=1967=1IC2!#!6
[!]17('&(D1.E./'&33&*'-5:-;'-//.'-)5C./-'&(.'7(&(&?-&AJ.
8.5.:-.5 F.8+&,.K5>.= 1977=LLC229#2!9
[M] NO . P QRS TU VW .XY"Z [V\ 19$!. 1L!#162
G7.5> ]-^-5>. 95'():7*'-)5)3K/&*'()/2'&E)/7'-)5B+&)(2._&-`-5>C
>cience ?ress, 18#/+1./#1A9
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