This document describes a new extractive distillation process for producing anhydrous ethanol that combines salt effects and traditional extractive distillation methods. Some key advantages of this process are a reduced recycling amount and number of theoretical plates needed compared to common extractive distillation. Experimental results show that adding salt to the solvent increases the relative volatility of ethanol-water systems. Optimal performance was found using ethylene glycol and potassium acetate. Gas-liquid equilibrium data was collected for ethanol-water systems with and without solvent and salt to characterize the process. This novel technique offers improved efficiency and purity over traditional distillation methods for anhydrous ethanol production.
This document describes a new extractive distillation process for producing anhydrous ethanol that combines salt effects and traditional extractive distillation methods. Some key advantages of this process are a reduced recycling amount and number of theoretical plates needed compared to common extractive distillation. Experimental results show that adding salt to the solvent increases the relative volatility of ethanol-water systems. Optimal performance was found using ethylene glycol and potassium acetate. Gas-liquid equilibrium data was collected for ethanol-water systems with and without solvent and salt to characterize the process. This novel technique offers improved efficiency and purity over traditional distillation methods for anhydrous ethanol production.
This document describes a new extractive distillation process for producing anhydrous ethanol that combines salt effects and traditional extractive distillation methods. Some key advantages of this process are a reduced recycling amount and number of theoretical plates needed compared to common extractive distillation. Experimental results show that adding salt to the solvent increases the relative volatility of ethanol-water systems. Optimal performance was found using ethylene glycol and potassium acetate. Gas-liquid equilibrium data was collected for ethanol-water systems with and without solvent and salt to characterize the process. This novel technique offers improved efficiency and purity over traditional distillation methods for anhydrous ethanol production.
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 A