Ref. : 56 SIMULATION OF LIGNIN SOLUBILITY IN IONIC LIQUIDS USING COSMO-RS.

Ana Casas1, Jose Palomar2, Mercedes Oliet1, M Virginia Alonso1, rancisco Rodrig!e"1 #e$artment of C%emical &ngineering, Com$l!tense 'ni(ersit) of Madrid. A(da. Com$l!tense *+,, 2-./. Madrid, *$ain. 0el.: 123/45135/-5.5. a6: 123/45135//2/3. &7mail: moliet89!im.!cm.es 2 #e$artment of A$$lied P%)sical C%emistr) 1C%emical &ngineering *ection4, A!tonoma 'ni(ersit) of Madrid. C+ rancisco 0om:s ) Valiente, ;, 2-./5 Madrid, *$ain
<ignin, a readil) a(aila=le form of =iomass, is one of t%e most a=!ndant =iorene>a=le $ol)mers in &art% and a $otential so!rce of rene>a=le aromatic c%emicals t%ro!g% catal)tic con(ersion. Acco!nting for 15?3.@ of >ood) =iomass, it is $rod!ced toda) in large 9!antities as a =)$rod!ct of >ood $!l$ing and mainl) em$lo)ed as f!el in t%e Araft $rocess. #e(elo$ing of green tec%nologies for lignin se$aration from >ood >o!ld =e e6tremel) interesting in t%e conte6t of =iorefiner). Recent >orBs %a(e demonstrated t%at ionic li9!ids 1C<s4 are e6cellent sol(ents for $rocessing >ood) =iomass and lignin 11,24. C<s re$resent a ne> t)$e of green sol(ent >it% attracti(e $ro$erties, s!c% as lo> melting $oint, negligi=le (a$o!r $ress!re, and %ig% t%ermal sta=ilit) 134. One of t%e most remarBa=le feat!res associated >it% t%e !se of C<s is t%at t%e) can =e designed for a s$ecific a$$lication t!ning t%e str!ct!re of t%e ions. 0aBing into acco!nt t%e enormo!s (ariet) of e6isting C<s, $redicti(e tools for selecting t%e most $romising C<s to dissol(e and+or reco(er lignin contained in >ood attending to t%e c%emical affinit) lignin7C< >o!ld =e reall) !sef!l. Cn t%is regard, DCond!ctor7liBe *creening Model for Real *ol(entsE 1CO*MO7R*4 is a f!nctional met%od for $redicting t%e t%ermod)namic $ro$erties of mi6t!res on t%e =asis of !nimolec!lar 9!ant!m c%emical calc!lations for t%e indi(id!al molec!les 1/4. Cn t%is >orB, t%e com$!tational tool CO*MO7R* %as =een em$lo)ed to sim!late t%e sol!=ilit) of lignin in 53 different C<s !sing t%e FC2AG molec!lar model of inde$endent co!nterions and t%e acti(it) coefficient and t%e e6cess ent%al$) as reference $ro$erties. Cn t%is FC2AG molec!lar model, C<s are considered as e9!imolar mi6t!re of cation and anion. H!aiac)lgl)cerol727conifer)let%er %as =een em$lo)ed in t%e CO*MO7R* as lignin model com$o!nd to de(elo$ t%e sim!lations. 0%!s, according to t%e CO*MO7R* res!lts, t%e most $romising anions for t%e se$aration of lignin from >ood are acetate, formate and c%loride, >%ereas, in t%e case of t%e cations, t%e =est res!lts %a(e =een o=tained >it% ammoni!m7, $%os$%oni!m7 and imida"oli!m7=ased C<s. Cn addition, t%e st!d) of t%e intermolec!lar interactions 1electrostatic, %)drogen =onding and Van der Iaals4 =et>een t%e com$o!nds of t%e mi6t!re lignin+C<s s%o>ed t%at t%e main forces in(ol(ing t%e lignin dissol!tion $rocess are t%e %)drogen =onding. 0%erefore, com=ining t%e cations and anions c%osen =) CO*MO7R*, different C<s can =e o=tained, >%ic% co!ld =e f!rt%er tested in t%e la=orator) to (alidate t%e model. Cn concl!sion, CO*MO7R* is a !sef!l com$!tational tool, >%ic% $ro(ides t%e =ase for c%oosing C<s for a s$ecific $oint, in t%is case t%e se$aration of lignin from >ood =) sim!lation, decreasing t%e e6$erimental >orB. Acknowledgement 0%e a!t%ors are gratef!l to t%e JMinisterio de Ciencia e Cnno(aciKnL of *$ain 1MCCC,,4 and t%e JCom!nidad de MadridL for financial s!$$ort of ProMects C0N2.1.715;/2 and *2..5+PPN715/5, res$ecti(el).
1

1. Oa(rel, M.P Qross, #.P !nBe, M.P Q!c%s, J.P *$iess, A. C. Rig%7t%ro!g%$!t screening for ionic li9!ids
2. 3. /. dissol(ing 1ligno74cell!lose. Bioresource Technol., !!"# 1.. 154, 25-.725-;. MSBi7Ar(ela, P.P An!g>om, C.P Virtanen, P.P *MT%olm, R.P MiBBola, J.P. #issol!tion of lignocell!losic materials and its constit!ents !sing ionic li9!ids7A re(ie>. Ind. Crops Prod., !$!, doi:1..1.16+M.indcro$.2.1.../...5 ort, #.A.P Rogers, R.#.P Remsing, R.C.P *>atlosBi, R.P.P Mo)na, P.P Mo)na, H. Can ionic li9!ids dissol(e >oodU Processing and anal)sis of lignocell!losic materials >it% 17n7=!t)l737 met%)limida"oli!m c%loride. Green Chem., !!%, 9, 63765. Alamt, A. CO*MO7R*: rom N!ant!m C%emistr) to l!id P%ase 0%ermod)namics and #r!g #esign. Elsevier: Amsterdam, !!&.