18th European Symposium on Computer Aided Process Engineering ESCAPE 18 Bertrand Braunschweig and Xavier Joulia Editors!

! " #$$8 Elsevier B%&%'(td% All rights reserved%

Optimisation of a Bio-ethanol Purification Process Using Conceptual Design and Simulation Tools
Patricia )% *och+a Jos, Espinosa+a

PLAPIQUI-UNS-CONICET, Camino La Carrindanga km 7-8000, Baha Blan a, Arg!n"ina # IN$A%-CONICET-UNL, A&!llan!da '()7, S'00* $+C San"a ,!, Arg!n"ina

Abstract
.n this wor/+ we propose an evolutionary optimisation procedure which intensively uses -oth conceptual and rigorous models 0or the design and simulation o0 unit operations involved in a -io1ethanol puri0ication process% 2hile conceptual models are used to determine initial values 0or design and operating varia-les o0 a given operation unit+ rigorous simulation departing 0rom initial estimates generated at conceptual design level ena-les to remove simpli0ying assumptions+ interconnect e3uipments and calculate operating and investment costs% 4nce an initial design o0 the puri0ication plant is o-tained+ opportunities o0 improvement are easily recogni5ed and then tested -y per0orming the design and simulation steps until a cost1e00ective -io1ethanol puri0ication plant is achieved% Key ords6 Bio1ethanol Puri0ication Plant+ Evolutionary 4ptimisation+ Conceptual 7esign+ 8igorous Simulation%

!" #ntroduction
4ptimisation o0 -oth design and operation varia-les o0 a -io1ethanol puri0ication plant intended to produce 0uel grade ethanol is a challenge to ma/e the -io10uel a realistic alternative in the energy mar/et% 9iven the plant comple:ity and the high non1linearity o0 the corresponding models+ we propose an evolutionary optimisation procedure which uses intensively -oth conceptual and rigorous models 0or the design and simulation o0 unit operations% .t is 3uite di00icult to o-tain an initial estimation o0 the total num-er o0 trays o0 the main distillation column+ placement o0 0eed and side streams+ and steam 0low rate in the simulation environment+ -ut this tas/ is easily accomplished in the conceptual design environment% .n addition+ convergence o0 the rigorous model is enhanced -y using initial estimates o0 internal pro0iles generated at the conceptual design level despite o0 the highly non1ideal -ehaviour o0 the multicomponent a5eotropic mi:ture% Applying the same philosophy to estimate initial values 0or design and operating varia-les o0 the whole process+ optimal values 0or a cost1e00ective -io1ethanol puri0ication plant are reported% ;he methodology is applied to the puri0ication process 0or a 0eed leaving the 0ermentation step o0 a conventional corn dry1grind processing 0acility producing #< million liters'year o0 ethanol and 1= million /g'year distiller>s dry grains with solu-les 779S!% ;he 0eed to the puri0ication plant ##1?$ /g'h! is mainly composed -y ethanol 1$%8$ @ w'w! and water 88%=8 @ w'w! with traces o0 methanol $%$##A @! and 0usel $%#$$= @!% A simpli0ied 0low diagram is shown in Bigure 1%

P- .o h and +- E/0ino/a

Bigure 1% Simpli0ied 0low diagram o0 a -ioethanol puri0ication plant%

$" #nitial Design

*-1- B!!r Col2mn ;he vapour stream leaving the stripping column captures nearly all o0 the ethanol and components in traces produced during the 0ermentation step% ;he minimum energy demand o0 the process i%e%+ minimum re-oil ratio! is calculated through the lever arm rule -y setting the -ottom product as high purity water and the composition o0 the vapour stream as the corresponding to the vapour in e3uili-rium with hot wine% .n other words+ a pinch at the top o0 the stripping column is considered% .n order to o-tain a 0easi-le design the 0ollowing steps are per0ormed6 i! determine the ma:imum 0easi-le separation and minimum energy demand s min! -y applying pinch theory% Bor this tas/+ it is re3uired an e3uili-rium calculation that can -e per0ormed in a conceptual model 0ramewor/ li/e 7.S;.( *yprotech+ 1===!C ii! calculate the re-oil ratio s D 1%$E sminC iii! set a value 0or the num-er o0 stages FC iv! simulate a stripping column with re-oiler 0irst and then replace the re-oiler with steam ta/ing into account the re-oiler duty and the latent heat o0 condensation o0 steam% ;his tas/ can -e done in a simulation 0ramewor/ li/e *ysys *yprotech+ 1===!% Bew simulations were needed to achieve a 3uasi1optimal column design with G8 e3uili-rium stages+ a column diameter o0 $%= m+ a section pressure drop o0 G<%? /Pa and a steam 0low rate o0 GA$$ /g'h% ;he values o-tained 0or the num-er o0 e3uili-rium stages and steam demand+ together with the composition o0 ethanol in the outlet stream E1%E# @ w'w! agree well with results presented in Hwiat/ows/i et al% #$$A!% *-*- .3#rid Col2mn As a multicomponent system 0ormed -y ethanol and water with traces o0 methanol and 0usel is to -e separated into a single column+ a three steps conceptual design and rigorous simulation process is proposed% Birst+ ethanol and methanol are lumped into one pseudo1component in order to o-tain a 0irst estimation o0 steam 0low rate+ num-er o0 stages necessary to separate an ethanol1rich stream 0rom a 0usel1rich stream+ 0eed stage and side stream location 7.S;.(!% A0ter rigorous simulation o0 the 3uaternary mi:ture in *ysys+ separation -etween a methanol1rich stream and an ethanol1rich stream is considered -y ta/ing into account the distillation line departing 0rom the composition o0 the distillate 7.S;.(!% Binally+ -oth columns are integrated into a single one *ysys!%

O0"imi/a"ion o4 a Bio-!"hanol 02ri4i a"ion 0ro !// 2/ing on !0"2al d!/ign and /im2la"ion "ool/ G *-*-1- Sid!-S"r!am Col2mn .n order to o-tain a 0easi-le design the 0ollowing steps are per0ormed6 i! calculate s min t! 0or the separation ethanol'water'11pentanol 7.S;.(!+ ii! estimate the num-er o0 e3uili-rium stages Fstages t!+ 0eed stage F0eed t! and side stream location F Side Stream t! 0or s t! I smin t! 7.S;.(!+ iii! simulate the 3uaternary system *ysys! 0or the design and operating varia-les o-tained in step ii!+ iv! calculate the steam 0low rate & steam 3! through the energy -alance and simulate the column without re-oiler *ysys!+ v! simulate the system side1stream column plus decanter and water1rich phase recycle *ysys!% ;a-le 1 presents the results o0 the conceptual design per0ormed in 7.S;.( steps i! and ii!! 0or the ternary mi:ture ethanol'water'11pentanol+ with the last component used to appro:imate the -ehaviour o0 a 0usel component% Compositions o0 -oth ethanol and 0usel in the -ottom stream were selected ta/ing into account the -ehaviour o0 the residue curve 7.S;.(! corresponding to the li3uid in e3uili-rium with the vapour 0eed in the neigh-ourhood o0 water verte:% As -oth 0or the ternary and 3uaternary mi:ture+ the residue curve approaches the water verte: with compositions o0 ethanol a-ove the mole 0raction o0 0usel+ the selected -ottom composition re0lects this -ehaviour% Bigure # a! shows the corresponding composition pro0ile in the composition simple:% ;he 0igure also shows a distillation -oundary departing 0rom the a5eotrope ethanol1water and ending at the hetero1a5eotrope water10usel% ;he side stream is located inside the li3uid1li3uid gap as this stream will -e separated in a decanter into a 0usel1rich phase 0eed to the 0usel plant! and a water1rich phase recycle to column!%
;a-le 1% 8esults 0or the ternary system ethanol'water'11pentanol 7.S;.(!%

Product Compositions+ r+ s and F Beed vapor! 7istillate Side Stream Bottom 8min t! ' Smin t! 8 t! ' S t! Fstages t! Jincluding condenser and re-oilerK F0eed t!' FSide Stream t!
1.0

J$%#=?=8+ $%A==1G#+ $%$$#888K J$%?<1<<+ $%#E8E$+ A%$ E1$EK J$%$E11E+ $%=1<<#+ $%$G<<GK J=%A E1$A+ $%=====+ <%$ E1$?K #%8G= ' 1%$$ #%8G= ' 1%$$ 1? J$ L 111E L 1AK <'11
1.0

(a)
0.8

(b)

0.8

%ethanol

0.4

%methanol
0.2 0.4 0.6 0.8 1.0

0.6

0.6

0.4

0.2

0.2

%ethanol ater Bigure #% a! .nternal pro0ile in the composition simple: corresponding to the -ase design with phase separator and water1rich phase recycle *ysys!C -! 7istillation lines corresponding to the distillate composition o0 the methanol column% System methanol'ethanol'waterL11pentanol at 1$1%G /Pa 7.S;.(!%

0.0 0.0

0.0 0.0

0.2

0.4

0.6

0.8

1.0

<

P- .o h and +- E/0ino/a

.t is noteworthy that minimum re-oil ratio 0or the given separation does not re3uire an in0inite num-er o0 stages% ;his -ehaviour can -e e:plained in terms o0 -i0urcation o0 adia-atic pro0iles and it will -e su-Mect o0 0urther analysis in a ne:t contri-ution% *-*-*- 5!"hanol Col2mn and .3#rid Col2mn ;he distillate stream o0 the side1stream column contains small amounts o0 methanol that must -e separated 0rom ethanol to agree with stringent 3uality standards $%1 @ &'& methanol in dehydrated ethanol at #$ oC!% At a 0irst glance+ this separation could -e per0ormed in another distillation column% A di00erent alternative would -e to integrate this column with the side1stream column% ;he distillate line 7.S;.(! corresponding to the distillate composition o0 the side1stream column shown in Bigure # -! resem-les the -ehaviour o0 the internal pro0ile at total re0lu: and it can -e considered as a good appro:imation to the actual operation o0 the methanol recti0ying column+ as the distillate 0low rate o0 this column is low enough to produce a high re0lu: ratio% ;here0ore+ it is possi-le to estimate the optimal num-er o0 stages in the recti0ying section o0 the hy-rid column as the num-er o0 trays necessary to separate the methanol in e:cess 0rom the ethanol1rich stream% As shown in Bigure # -!+ the methanol1rich distillate stream will also contain small amounts o0 ethanol and water due to the distillation line running 0rom pure methanol to ethanol1water a5eotrope% Bigure G shows the internal pro0ile in the composition tetrahedron a0ter simulation o0 the hy-rid column in *ysys% A loss o0 a-out $%18 @ w'w o0 ethanol in methanol1rich distillate occurs% ;he side streams are located near the ma:imum in ethanol ethanol1 rich stream+ 88%=8 @ w'w! and 0usel 0usel1rich stream+ 18%E @ w'w!+ respectively% ;he column has GE e3uili-rium stages+ a column diameter o0 1%G?# m+ a section pressure drop o0 11%8 /Pa and a steam 0low rate o0 18$$ /g'h% ;he vapour ethanol1rich stream is diverted to the 0irst e00ect o0 the evaporation sector to provide heating while minimi5ing the steam demand o0 the plant% ;he condensed ethanol1rich stream is then 0ed to the 3D pervaporation sector to remove the e:cess water%
Costs (two dist. col. and pervap.sector)
1.0

MeOH

250 225 200 175 150 125 100 75 50 0.700

initial design 3uasi1optimal design

0.8

Z Axis

0.6 0.4

.nvestment Costs+ NOS'h 4perating Costs+ NOS'h 4verall Costs+ NOS'h

Rot Inc

1-C5ol
0.2

15

EtOH
0.0 0.0

0.2

0.4

0.6 0.6 0.8 1.0 0.4

0.8

1.0

0.725

0.750

0.775
D et!anol

0.800

0.825

0.850

0.2

0.0

Bigure G% .nternal pro0ile in the composition tetrahedron corresponding to the hy-rid column with phase separator+ 0usel plant and pervaporation sector%

Bigure <% 4verall investment an costs 0or the two distillation c pervaporation sector versus et 0raction in the distillate o0 the hy-r

*-*-'- ,2/!l Plan" and P!r&a0ora"ion S! "or ;he 0usel1rich stream leaving the decanter is 0ed to the 0usel sector where the stream is washed with water to recover a-out =A @ o0 the incoming ethanol% ;he resulting water1 rich stream is recycled to the hy-rid column% ;o do this+ an overall amount o0 GAG /g'h

O0"imi/a"ion o4 a Bio-!"hanol 02ri4i a"ion 0ro !// 2/ing on !0"2al d!/ign and /im2la"ion "ool/ E wash1water and seven separation steps are necessary% ;he conceptual design o0 a cross1 0low operation is per0ormed using 7.S;.(+ while process simulation is done in *ysys% A conceptual design o0 pervaporation P&A'PAF )4( 11<$ mem-rane -y 9B;+ 9ermany! 0ollowing the model proposed -y &ier 1==E! and Bausa and )ar3uardt #$$$! was implemented in 7elphi environment Borland+ 1==?! to determine pseudo optimal operating values 0or -oth ma:imum temperature =$ oC! and permeate pressure #%$#A /Pa!% ;he model was also implemented in *ysys as a user operation e:tension+ which calculates the re3uired mem-rane area a re3 as are3 D1%#E amin Bausa and )ar3uardt+ #$$$!% Both heat and re0rigeration duties are calculated in *ysys 0rom the energy -alance% Behaviour o0 trace components is ta/en into account -y using water1alcohol separation 0actors% Appro:imate values were ta/en 0rom 7% &an Baelen et al% #$$E!% *igh purity -ioethanol ==%E @ v'v! is o-tained with an actual mem-rane area o0 =G$ m#+ while the water1rich permeate is recycled to the hy-rid column% *-*-6- 77$S Plan" ;he coproduct plant is 0ormed -y a decanter centri0uge which separates the -ottom stillage 0rom the -eer column in a wet ca/e GE @ solids+ #A8G /g'h water! and a thin stillage 18<<G /g water'h!% Appro:imately <A#A /g water'h is recycled into the second step o0 the li3ue0action process+ while 1G81? /g water'h is 0eed to a three1e00ect evaporator% ;he resulting syrup GE @ solids+ 1#8? /g water'h! is mi:ed with the wet ca/e coming 0rom the centri0uge and sent to a rotary drum dryer% 2hile the multiple e00ect evaporator is simulated in *ysys+ only mass and energy -alances 0or the dryer are incorporated in *ysys% ;he conceptual design o0 the dryer is per0ormed according to the method presented in Nlrich and &asudevan #$$<! and data 0rom Fational Corn1;o Ethanol 8esearch Center #$$E1#$$?!% ;a-le # summari5es the investment and operation costs o0 the 779S sector% ;he operation cost o0 GE%= O'ton 779S agrees well with the value reported -y Batelle )emorial .nstitute #$$E!%
;a-le #% 4peration O'ton 779S! and .nvestment O! Cost corresponding to 779S plant% JPK /g natural gas' /g o0 water evaporated% JPPK 4verall operating costs D G<%EE O'ton 779S .tem 8otary 7ryer Characteristics 7 JmKD 1%AA< ( JmKD 1G%G1 R JminKD 1=%A rpmD #%8A= Sair J/g'hKD G=1E$ TFat% 9as D $%$<8 JPK AreaoverallJm#KD =<$ PressureJ/PaKD 0rom 1$1G$ /Pa Ssteam J/g'hKD #?$$ .nvest%'4p% Cost Nlrich Q &asudevan 1%G= E$A'1=%?< .nvest%'4p% Cost JPPKC Batelle )% .% JPPPK 1%E? E$A

Evaporator

1%E#G E$A'1A%1A

1%<? E$A

7ecanter Centri0uge

1%$?E$AJPPPK'not calculated

1%$? E$A

&" '(olutionary Optimisation

4nce an initial design is o-tained+ the 0ollowing improvement opportunities were tested6 i! design o0 the -eer column in the neigh-ourhood o0 minimum energy demand done 0rom the very -eginning o0 design process!+ ii! heat integration -etween the hy-rid

P- .o h and +- E/0ino/a

column and evaporation 0irst e00ect 1#?$ /g'h o0 steam are saved!+ iii! heat recovery 0rom the hot air leaving the dryer saving $%$1< /g natural gas'/g water evaporated!% Binally+ a change in distillate composition o0 the hy-rid column is proposed in order to capture the trade1o00s -etween distillation and pervaporation costs% 8esorting again to the conceptual design o0 the hy-rid column 0or a set o0 distillate compositions+ results shown in Bigure < are o-tained% ;he decrease o0 investment costs 0or distillate compositions richer in ethanol is related to a decrease in the mem-rane area needed to o-tain dehydrated -ioethanol are3D8<8 m#!% ;a-le G shows -oth investment and operating costs o0 the 3uasi1optimal plant% All cases include improvements i!+ ii! and iii! mentioned a-ove% .nvestment and operation costs are reduced -y A%A< @ with respect to the -ase case and -y 11%<8 @ with respect to the worst case analy5ed% Cost coe00icients used to o-tain the reported values are C steamD#%G=AE1#+ CwaterDE%?GE1G+ Cre0rDG%8#<E1#+ CelectrD$%$8 all in JO'/2hK+ Cnat gasD#8= O'tn+ C mem- repl D <$$ O'm#%
;a-le G% 4verall costs 0or a -ioethanol plant producing #< million liters'year% ;he 0acility considers -oth the ethanol and co1product processing plants% 779S Plant Separation ;otal .nvestment+ O G%=8E EL$A G%?A8 EL$A ?%?EG EL$A 4perating O'h =A%G? 11?%=A #1<%GG .nvestment+ O'h 81%$? ?A%AA 1E?%?G ;otal+ O'h 1??%<< 1=<%A# G?#%$A

)" Conclusions
A cost e00ective design 0or a -io1ethanol separation plant using conceptual design 0ollowed -y rigorous simulation is 0ound% ;he minimum in the operation costs corresponds to a minimum in the steam 0low rate o0 the hy-rid column 1A$$ /g'h!% ;he minimum in steam 0low rate can -e only e:plained -y the presence o0 the 0usel component+ which in0luences -oth the energy demand and 0easi-le products o0 the process% ;here0ore+ designs -ased on the -inary system ethanol1water do not represent the system -ehaviour in an accurate way%

*" Ac+no ledgements

;his wor/ was supported -y NF(+ NFS+ C4F.CE; and AFPCy; 0rom Argentina%

,eferences
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O0"imi/a"ion o4 a Bio-!"hanol 02ri4i a"ion 0ro !// 2/ing on !0"2al d!/ign and /im2la"ion "ool/ ?
&an Baelen+ 7%C &an der Bruggen+ B%C &an den 7ungen+ H%C 7egreve+ J% and C% &andecasteele+ #$$E+ Pervaporation o0 water1alcohol mi:tures and acetic acid1water mi:tures% Chemical Engineering Science+ A$+ 1E8G11E=$% &ier+ J%+1==E+ Pervaporation a5eotroper wUssriger und rein organischer Sto00gemische1 &er0ahrensentwic/lung und integration+ Ph% 7% ;hesis+ .nstitut 0Vr &er0ahrenstechni/+ 82;* Aachen+ Sha/er &erlag+ Aachen+ 9ermany%