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
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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. Experi ental 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 ethylene glycol anhy&rous ethanol 8.: ethanol so&ium chlori&e anhy&rous molecular formula C91AB9 C91.B1 C91.B1 @aCl CaCl9 molecular purity 'eight A9+"C $A+"C $A+"C .#+$$ 11"+88 9A.+A9 1//+/$ 1"1+11 9$1+A" /.C+1. 8#+1$ 1/#+9 3+R+ C+?+ C+?+ 3+R+ 3+R+ 3+R+ 3+R+ 3+R+ 3+R+ 3+R+ C+?+ C+?+ &ensity (2g,m/) 1+11 1"/ "+C8 1"/ "+#9 1"/ (oiling point( ) 18# C#

calcium chlori&e strontium chlori&e >rCl9DA19B aluminum chlori&e 3lCl/ potassium nitrate E@B/ copper nitrate Cu(@B/)9D/19B aluminum nitrate 3l(@B/)/D819B potassium acetate E CB9C1/ anhy&rous potassium E9CB/ car(onate

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 = 1 1 y9 , x9 'here y1 , y 9 stan& for the molecular fractions of ethanol an& 'ater in the gas phase respectivelyI x1 , 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 ethylene glycolJ@aCl ethylene glycolJCaCl9 ethylene glycolJ>rCl9 ethylene glycolJ3lCl/ ethylene glycolJE@B/ ethylene glycolJCu(@B/)9 ethylene glycolJ3l(@B/)/ ethylene glycolJ E CB9 C1/ ethylene glycolJE9CB/ relative volatility 9+/1 9+.A 9+A $+1. 1+8 9+/. 9+#C 9+$ 9+A

1+"1 ethylene glycol 1+#. calcium chlori&e /+1/ potassium acetate $+".

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;$<7 the higher the valence of metal ion is, the more o(vious the effect is+ The salt effect gra&ually &ecreases in the or&er of 3lCl/ ,CaCl9 an& @aCl+ The tren& is the same in the or&er of 3l(@B/)/,Cu(@B/)9 an& E@B/+ esi&es, the salt 5 5 5 effect gra&ually &ecreases in the or&er of 3c ,Cl an& @B /+ The in&ustrial requirements for salt selection are lo' cost, chemical sta(ility, high &issolva(ility, minor apparatus corrosion, less poisoning, (esi&es the possi(ly highest volatility+ Therefore, the optimal system is ethylene glycol5potassium acetate+ 9+$ 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
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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(1 ".1$2 ".$$% ".& ".#1 ".%"1% ".%"#2 ".%'"& ".%$& ".%&%

y ".$1% ".&1' ".#1) ".#&2$ ".%"#$ ".%*%

with ethylene !lycol+ CaCl2,1"-.

x "."#

".1$2 ".$$% ".& ".##2 ".%1&

".#1

".%"1% ".%"#2 ".%'"& ".%#'

y ".'&% ".&%

".%**% ".%'&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 Experi ent 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+

*. S0

ary

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&+ $+ @ecessary (asic research an& engineering scale5up e%ploration have (een un&erta2en (ase& on the in&ustrial e%perience an& technical &ata, an& &esign calculating metho& is for'ar&e&+ .+ This approach can (e transplante& to other chemical systems, so it has (roa& in&ustrial prospect+ REFERE@CE> [1] . .1976 2 !" 9! #9$ %&'()*+&,-*./ 0 1.*')(2 0 )3 0 4.56+)7 0 8+&,-*./ 0 95:7;'(20 8)(<)(.'-)5=&'0./. 0001-(;'0;'.>&0(&5)?.'-)5 0)30&@'(.*'-)50:-;'-//.'-)5 0')A&(03)(0(&3-5-5> 0 000<()<&52/ 0*2.5-:&. 0%&'()*+&,-*./ 0B&*+5)/)>2=1976=2 !C09! #9$
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