6.1.

Distillation
Ethanol is recovered as an azeotrope from ethanol water mixtures by means of distillation [313], [314] !he boilin" point dia"ram for this system is shown in #i"ure 3$% the pure water azeotrope at the azeotropic point &a' contains ($ $) wt * &() 3 vol *' ethanol and has a boilin" point of )+ 1$ ,-

#i"ure 3$ .oilin" point dia"ram of ethanol water mixtures a' /zeotropic point

!o obtain anhydrous ethanol, the pure ethanol water azeotrope must be dehydrated !his is "enerally accomplished by azeotropic distillation with an entrainin" a"ent, usually benzene !he water is thus removed in the form of an overhead ternary benzene ethanol water azeotrope

6.1.1. Distillation of Azeotropic Ethanol

!he crude ethanol synthesized by the direct or indirect hydration of ethylene contains ca $0 vol * ethanol, whereas the crude product obtained after fermentation contains no more than 10 vol * ethanol -onse1uently, the distillation of synthetic ethanol re1uires less ener"y and is less expensive than that of fermentation ethanol !he distillation of synthetic azeotropic ethanol obtained by the direct and indirect hydration of ethylene is described in 2ections 3roduction 3rocess and 3roduction 3rocess, respectively !he principles on which it is based are the same as those used in the distillation of fermentation ethanol described in this section !he low4ener"y distillation of ethanol from a fermentation feedstoc5 is shown schematically in #i"ure 36 [3144316] #ermented mash containin" ca 10 wt * ethanol and ca 10 wt * total solids is preheated to near saturation temperature, de"assed to remove -78, and fed to the strippin" column !he overhead product leavin" the strippin" column contains )$ +$ vol * ethanol !he bottom li1uid &stilla"e' contains less than 0 08 wt * ethanol and is sent either for disposal or for animal feed production / vapor recompression system may be used to heat the reboiler of the strippin" column for steam economy #i"ure 36 9istillation of ($ vol * ethanol from a fermentation feedstoc5 a' 9e"asser% b' 2trippin" column% c' Extractive distillation column% d' :ectifyin" column% e' #usel oil washer% f' -oncentratin" column% "' -harcoal filtration% h' 2tora"e tan5

!he overhead distillate from the strippin" column is mixed with recycled ethanol from the concentratin" column and fed into the extractive distillation column, which operates at a pressure of 0 6 0 ) ;3a !his column removes essentially all fermentation byproducts, mainly aldehydes, ethers, methanol, and hi"her alcohols, from the ethanol !he aldehydes, ethers, and methanol are more volatile than ethanol and leave the top of the column <owever, the hi"her alcohol byproducts, 5nown collectively as fusel oil, are normally less volatile than ethanol !he avera"e composition of fusel oil from fermentation ethanol derived from different raw materials is shown in !able 81 [31)] !he techni1ue used to extract fusel oil from ethanol exploits the fact that hi"her alcohols are more volatile than ethanol in solutions containin" a hi"h concentration of water !hey can, therefore, also be steam distilled and removed in the overhead steam to leave a virtually pure ethanol water mixture !able 81 /vera"e composition of fusel oils &in wt *' Fusel oil 11- utanol 2-%eth#l-1- 2-%eth#lPropanol !n-"ut#l propanol 1-"utanol [71-23-8] alcohol$ !iso"ut#l !acti&e [71-36-8] alcohol$ a'#l [78-83-1] alcohol$ [137-32-6] ;olasses 13 8 0 8 0 ) 1$ + 8+ 4 =heat c ( 1 0 8 0 ) 1( 0 80 0 ereals 3otatoes 14 0 0$ 1$ $ 1$ 0 2ulfite )0 88 0 13 0 waste li1uor #ruit +0 80 1( 0 14 0 3-%eth#l1-"utanol !isoa'#l alcohol$ [123-(1-3] 3) 4 $1 8 $$ 0 $$ 0 $) 0

9ilute ethanol is then sent from the bottom of the strippin" column to the rectifyin" column where it is brou"ht up to stren"th !he rectifyin" column is heated by overhead vapors from the extractive distillation column and the concentratin" column !he ethanol &($ vol *' is withdrawn as a side stream from one of the upper trays% it is then filtered throu"h charcoal and stored !he water that collects at the bottom of the rectifyin" column contains traces of ethanol and is recycled to the extractive distillation column #usel oil is withdrawn as a side stream from one of the lower trays of the rectifyin" column and fed to the fusel oil washer >n the concentratin" column, overhead vapor from the extractive distillation column, which contains aldehyde, ether, and alcohol impurities, is separated into low4boilin" and hi"h4boilin" fractions Ethanol is also recovered and recycled to the extractive distillation column / small stream is ta5en from the overhead condensate &low4boilin" fraction', which contains acetaldehyde and a small amount of ethanol >t may be sold as a byproduct or burned as a fuel / side stream containin" a hi"h concentration of fusel oil is sent throu"h a cooler to the fusel oil washer >n the washer, ethanol is extracted from the fusel oil with water, and the washin"s are recycled to the concentratin"

column <i"h4boilin" fusel oil is also run off from the bottom of the concentratin" column !he combined fusel oil &hi"h4boilin"' fractions may be sold as a byproduct

6.1.2. Deh#)ration "# Azeotropic Distillation

/zeotropic distillation systems are desi"ned for the production of pure, anhydrous ethanol &(( (+ vol *', which contains ?800 m"@5" of water and ?80 m"@5" of total impurities &for other specifications, see !able 80' [3144316] / flow scheme for the two4column azeotropic distillation of anhydrous ethanol is shown in #i"ure 3) !he dehydratin" column and the hydrocarbon strippin" column operate at atmospheric pressure !herefore, they may be heated with low4pressure steam, hot condensate, or hot waste streams from other parts of the ethanol processin" plant, thus minimizin" steam consumption #i"ure 3) 3roduction of anhydrous ethanol by azeotropic distillation a' 9ehydratin" column% b' 9ecanter% c' -ondenser% d' -ooler% e' <ydrocarbon strippin" column% f' Entrainer tan5 =ater is removed from the ethanol water azeotrope in the form of a ternary azeotrope which is produced by addin" an entrainin" a"ent such as benzene, heptane &-6 -+ cut', or cyclohexane !he ($ vol * ethanol feed enters the dehydratin" column near the midpoint !he anhydrous ethanol product collects at the bottom of the tower and is sent throu"h a cooler prior to stora"e !he ternary azeotrope leaves the column as an overhead product which is condensed and then separated into an or"anic and an a1ueous phase in the decanter !he upper or"anic layer containin" the entrainer is returned to the top of the dehydratin" column !he lower a1ueous layer is pumped to the hydrocarbon stripper, where the hydrocarbon entrainer, the ethanol, and some water vapor are recovered overhead and sent to the condenser decanter system =ater from the stripper is pumped off as waste% if it contains a substantial amount of ethanol, it may be recycled to the ethanol distillation unit !he overall efficiency and reliability of the anhydrous ethanol system are the result of the followin" special featuresA 1 8 3 4 $ !he use of a common condenser and decanter for the two columns reduces capital costs !he use of very efficient column trays which can operate at a low throu"hput !he .79 of the wastewater is low -onsumption of the entrainin" a"ent is low 2team consumption is lowA 1 1 $ 5" is re1uired per liter of anhydrous ethanol dependin" on the 1uality of the end product

>n some plants that produce motor fuel ethanol, "asoline is substituted for benzene as the entrainer 2ince "asoline is re1uired in the end product, the hydrocarbon strippin" step is eliminated <owever, "asoline dehydratin" a"ents "ive products of varyin" composition because the "asoline contains a number of different components

6.1.3. %otor Fuel Ethanol

!wo types of ethanol for motor fuel are produced industrially [3144316], namely, anhydrous and hydrous motor fuel ethanol & /utomotive #uels' /nhydrous ;otor #uel Ethanol !he distillation and dehydration of motor fuel ethanol from a fermentation feedstoc5 are shown schematically in #i"ure 3+ #i"ure 3+ 3roduction of anhydrous motor fuel ethanol a' 9e"asser% b' 2trippin" rectifyin" column% c' #usel oil washer% d' #ilter% e' 9ehydratin" column% f' 9ecanter% "' Entrainer tan5% h' Entrainer strippin" column% i' -ooler% B' -ondenser 2trippin" :ectifyin" Ethanol is distilled in a sin"le strippin" rectifyin" column where the fermented mash is separated into an overhead, ca ($4vol * ethanol fraction and a bottom li1uid fraction &stilla"e' containin" ?0 08 wt * ethanol !he mash is preheated at its saturation temperature and de"assed to remove residual -78 before it enters the strippin" rectifyin" column !he column operates at a pressure of ca 0 3 ;3a and is heated with steam by a forced circulation reboiler !his is the only part of the system that uses steam !he stilla"e leavin" the bottom of the column is cooled to its boilin" point at atmospheric pressure by heat exchan"e, the extracted heat bein" used to preheat the mash feed !he temperature of the resultin" stilla"e is such that it can be subBected to vaporrecompression evaporation without preheatin" or flashin" in an evaporator !he pressurized overhead vapors from the strippin" rectifyin" column are used to preheat the mash feed and to heat the reboilers of the dehydration column and of the entrainin" strippin" column !he condensed vapors are returned to the top of the strippin" rectifyin" column / small overhead stream is drawn off to remove volatile acetaldehyde from the system% it contains ?1 * of the product ethanol and is either added to the purified anhydrous ethanol product or burned as a fuel in the plant boiler / side stream containin" fusel oil is also ta5en from the rectifyin" section of the column and sent to a fusel oil washer !he a1ueous washin"s are returned to the strippin" section of the column% the decanted, washed oil is combined with the ethanol product stream and fed to the dehydration column #usel oil has a hi"her ener"y value than ethanol and acts as an a"ent for blendin" ethanol with "asoline 9ehydration /fter leavin" the stripper rectifier, the ($ vol * ethanol and fusel oil are filtered and fed to a dehydratin" column, which operates at atmospheric pressure <ere, water is removed from the feed by use of benzene, heptane &-6 -( cut', cyclohexane, or some other entrainin" a"ent !he bottom stream from the dehydratin" column consists of anhydrous, (( $ vol * ethanol and is cooled prior to stora"e !he overhead fraction from the dehydratin" column is a ternary azeotrope, which is combined with overhead vapors from the entrainer strippin" column !he combined vapors are condensed and cooled, formin" two phases that are separated in a decanter !he upper entrainer layer from the decanter is pumped to the top of the dehydratin"

tower, while the lower a1ueous layer is fed to the entrainer strippin" column for recovery of the entrainer and ethanol 2team consumption in this system is 1 + 8 $ 5" per liter of ethanol produced, dependin" on the alcohol concentration of the mash

6.2. *on)istillati&e %etho)s

!he ener"y re1uired to remove water from ethanol can be reduced si"nificantly by usin" methods that do not rely on distillation

6.2.1. +ol&ent E,traction

Ethanol dissolves in some li1uids that are virtually immiscible with water !hese solubility differences can be exploited to recover ethanol from an a1ueous solution by means of solvent extraction [388] >n the Cnited 2tates, the Ener"ol -orporation employs li1uid li1uid extraction with a proprietary solvent to separate ethanol from water !he solvent is then removed by distillation !his method does not re1uire ener"y4intensive azeotropic distillation and thus has a low ener"y consumption !he ener"y bud"et for the entire plant is 3$00 3)00 5D per 5ilo"ram of ethanol produced >n 1(+), Ener"olEs techni1ue was used in four 40 000 to 4$ 0004F@d plants which came into operation in the mid 1(+0s !he Cniversity of 3ennsylvania and General Electric have developed a process that uses dibutyl phthalate [+44)448] as a water4immiscible solvent for purifyin" ethanol !his solvent has a much hi"her boilin" point than ethanol, and ethanol can therefore be separated in a sin"le distillation step% solvent losses are low

6.2.2. -ar"on Dio,i)e E,traction

/nother type of solvent extraction ma5es use of a critical fluid, i e , a "as compressed to the point at which the distinction between "as and li1uid disappears Ethanol is selectively extracted from "rain mash with carbon dioxide close to its critical point of ) 3 ;3a and 31 ,- [381] !he ethanol4rich stream is flashed at ca 4 + ;3a to remove the carbon dioxide, leavin" ethanol separated in the li1uid phase !his route re1uires a third to a half of the ener"y needed for conventional ethanol distillation, but the capital cost is 80 * hi"her / further advanta"e of this method is that the carbon dioxide used as solvent is obtained as a low4cost byproduct of fermentation !his is

important because some solvent inevitably escapes durin" ethanol recovery and has to be replaced

6.2.3. A)sorpti&e Deh#)ration

;olecular 2ieves Ethanol azeotropes are dehydrated industrially by adsorption with molecular sieves whose pores are permeable to water but not to ethanol [383438$] !he molecular sieve may be a synthetic or naturally occurrin" zeolite &e " , clinoptilolite' or a proprietary resin !he ($ vol * ethanol is dehydrated in molecular sieve columns% )$ * of the adsorbed material is water and 8$ * ethanol =hen the column is saturated, the stream is directed to a fresh column and the saturated column is re"enerated !he re"eneration stream containin" 8$ vol * ethanol is fed bac5 to the ethanol distillation system 2olid /"ents Ethanol can also be dehydrated by adsorption with solid a"ents [386] .ess ener/# is re0uire) to &aporize 1ater fro' cellulose or corn-starch than fro' calcium hydroxide, because of their low heats of adsorption !herefore, "round cornmeal is used as a dehydratin" a"ent for removin" water from an +$ * ethanol feed stream !he cornmeal adsorbent can be recycled ca 80 times before bein" used as animal feed

6.2.2. %e'"rane 3echnolo/#

3ervaporation / new method of ethanol purification based on pervaporation has been developed [38)], [38+] and is shown schematically in #i"ure 40 !he pervaporator consists of a number of semipermeable membrane modules made of poly&vinyl alcohol' resins #i"ure 40 3roduction of anhydrous ethanol by pervaporation a' 3ump% b' <eater% c' 3ervaporator% d' -ondenser% e' Hacuum pump !he (4 vol * ethanol feed is preheated to 60 ,- and pumped to the semipermeable membrane modules of the pervaporator =ater permeates the membrane down its concentration "radient% a phase chan"e occurs from the li1uid phase at the membrane inlet to the vapor phase in the permeate =ater is thus separated without azeotrope formation !he drivin" force for permeate flow is provided by a vacuum of less than 1 53a at the permeate condenser inlet !he total ener"y consumption is the sum of the evaporation and the condensation enthalpies !he condensed permeate contains a small amount of ethanol and can be recycled to a rectifyin" or distillation tower for recovery of ethanol 3ervaporation of 10(6 F of a (1 wt * &(4 vol *' ethanol feed yields 1000 F of anhydrous ethanol &(( +$ wt *,

(( ( vol *' and 10) $ F of permeate byproduct containin" 83 wt * ethanol !he production of 1000 F of anhydrous ethanol re1uires 13$ 5" of steam &800 53a', 10 m3 of coolin" water &80 ,-', and 1$ 5= I h of electricity :everse 7smosis 3urification of ethanol by reverse osmosis employs membranes that are relatively impermeable to ethanol but permeable to water [38(] / pressure of 4 ) ;3a is usually applied to remove the water by forcin" it across the membrane !he ethanol retention of new noncellulosic membranes is much hi"her than that of the cellulose acetate membranes used earlier &+0 * compared to $0 *' :everse osmosis may prove useful for savin"s in ener"y costs by concentratin" ethanol to about 10 * prior to distillation

6.2.(. 4arn-Fille) -olu'n

!extile yarns, such as rayon, retard the movement of water vapor but allow ethanol vapor to pass !his phenomenon has been exploited to develop a techni1ue for separatin" ethanol water mixtures [330] =ater containin" 18 wt * ethanol is vaporized by inBectin" it into a stream of air% the ethanol water air mixture is then sent throu"h a yarn4filled column e1uipped with heatin" elements / zone of water builds up at the be"innin" of the column% air and ethanol pass throu"h and are cooled to condense the ethanol .efore the water zone moves too far into the column, the direction of flow is reversed and the water is flushed out with air !he cycle ta5es about 8$ s% flow occurs for 10 s in the forward direction and 1$ s in the reverse direction / continuous version of the process is bein" developed in which the yarn is made into a continuous belt by tyin" the ends to"ether !he belt moves slowly throu"h the column, in the opposite direction to the flow of the ethanol water air vapor Ethanol is then produced continuously at one end of the column !he yarn leaves the other end of the column and passes throu"h a heatin" zone where water is driven off