Organosolv Fractionation of Lignocellulosic Biomass for an Integrated Biorefinery

February 2015 ECN-V--14-010

D U U RZA M E TEC H N O LO G IE

ORGANOSOLV FRACTIONATION OF LIG N O C ELLU LO SIC BIO M A SS FO R AN INTEG RATED BIOREFINERY

he econom ics of lignocellulosic biorefineries w ould substantially im prove w ith Tvalue-added applications for lignin. Organosolv fractionation processes for lignocellulosic biom ass can be a way tow ards this end. Two organosolv fra c tio n a tio n p ro c e sse s w e re c o m p a re d a s p a rt o f th e E U F P 7 B IO C O R E p ro je c t: th e C IMV acetic acid / formic acid process and the ethanol organosolv process. It was found that both processes have a clear potential within the field of biorefining. The C IM V process seem s more suitable to produce sugars from the hem icellulose fraction, whereas the ethanol organosolv process yields lignin with a higher purity. P.J. d e W ild , W .J.J. H u ijg e n , R . v a n d e r Lin d e n , H . d e n U il, E n e rg y R e se a rc h C e n tre of the N etherlands (EC N , Biom ass & Energy Efficiency J. S n e ld e rs, K U Le u v e n , La b a ra to ry o f F o o d C h e m istry a n d B io c h e m istry B. Benjelloun-M layah, Com pagnie Industrielle de la M atière Végétale (CIM V)

IN T R O D U C T IO N B IO R E F IN E R Y �� G lobally, a limited num ber of biorefineries that �� u se lig n o c e llulo sic b io m a ss a s fe e d sto c k a re c u rre n tly in o p e ra tio n o r u n d e r c o n stru c tio n �� (T a b le ).1 Mo s t lig n o c e llu lo s ic b io re fin e rie s �� primarily aim at utilization of sustainable �� carbohydrates from (hem i)cellulose. How ever, �� there currently exist few com m ercial applica-�� tions for lignin other than com bustion. Value- � �� added applications for lignin would substanti-�� a lly im p ro v e th e e c o n o m ic s o f a lig n o c e�� llu lo s ic �� b io re fin e ry . A re c e n t a rtic le in th is jo u rn a l g a v e a g e n e ra l in tro d u c tio n o n [3lig ]. n inIn n a �� earlier paper on organosolv in NPT Proces- te c h n o lo g ie , th e a p p lic a tio n s o f lig n in w e re�� discussed and it was stated that sulphur-free � ��!�� lignins are preferred, in particular organosolv lig n in s [4 ]. B e c a u se o f its re la tive ly h ig h e r �� "�� #� h o m o g e n e ity , p u rity , a n d re a c tiv ity , o rg a n o - �� solv lignins are prom ising and probably 'first �� choice' candidates for direct applications as �! �� $�$�� %&�� w e ll a s fo r fu rth e r p ro c[1 e ssin ]. g �� ORGANOSOLV FRACTIONATION �� ' �� O rg a n o so lv is b a se d o n th e tre a tm e n t o f �� biom ass with an (aqueous) organic solvent at�(� �� ' elevated temperatures[5-8] . Cmmonly o used �� solvents are ethanol, methanol, acetone and o rg a n ic a c id s lik e a c e tic a c id a n d fo rm ic a c id or com binations thereof. O rganosolv processes delignify lignocellulose, with the tio n s u ita b le fo r fu rth e r p ro c e s s in g w ith o uof t cellulose for paper or second generation organic solvent functioning as lignin extrac-re c o v e ry o f a p u rifie d lig n in fra c tio n . b io e th a n o l. T h e la tte r a re a c o m p le x m ixture o f tant, while the hem icellulose is depolym erized unconverted carbohydrates, lignin, minerals through acid-catalysed hydrolysis. In general, O rg a n o s o lv lig n in h a s a h ig h p u rity (lima ite n d d p ro c e ss c h e m ic a ls o r m ic ro b ia l re sid u e s. organosolv processes aim to fractionate the am ounts of residual carbohydrates and mine-H ardly any applications for such com plex by- lignocellulosic biom ass as much as possible ra ls) d u e to its iso la tio n p ro c e ss. C o n se qproducts u e n tly, have been identified other than in to its in d iv id u a l m a jo r fra c tio n s in c o nits tra sapplication t to spectrum is broader com paredc o m b u stio n fo r c o m b in e d h e a t a n d p o w e r other pre-treatment technologies such as steamto th e m o re im p u re lig n in -c o n ta in in g re s id(C u e H s P ). O rg a n o so lv lig n in s a lso h a ve a re la ti- e x p lo sio n a n d d ilute a c id h y d ro lysis. T h e sederived from conventional pre-treatments whichve ly lo w m o le c u la r w e ig h t w ith a n a rro w d istri- technologies merely make the cellulose frac-are targeted primarily tow ards the productionb u tio n a n d a ve ry lo w su lp h u r c o n te n t.

1 0 N P T P ro ce ste ch n o lo g ie 1 • F e b ru a ri 2 0 1 5 npt.pmg.nl References �� D U U RZA M E TEC H N O LO G IE �� !" 1 P .J. d e W ild , W .J.J. H u ijg e n & R .J.A G o sse lin k (2 0 1 4 ) Lig n in p y ro lysis fo r p ro fita b le lig n o c e llu lo s ic b io re fin e rie s , B io fu e ls , B io p ro d u c ts & B io re fin in g (b io F P R ), 8 (5 ), 6 4 5 -6 5 7 2 D . B a c o vsky , N . N iko la u s, M . O g n issa n to , M . W ö rg e tte r (2 0 1 3 ) S ta tus o f A d va n c e d B io fu e ls D e m o n stra tio n Fa c ilitie s in 2 0 1 2 , A R E P O R T T O IE A B IO E N E R G Y T A S K 3 9 . T 3 9 -P1 b 3 F. V a n H e sse n (2 0 1 3 ) Lig n in e - ‘V e rg e te n ’ g ro n d sto f o f sp rin g p la n k naar bio-aromaten?, NPT Procestechnologie 2013-4, 16-17 4 J.H . R e ith , H . d e n U il, R. va n d e r Lin d e n , W .J.J. H u ijg e n & J. W ild - sc h u t (2 0 1 1 ) A ste p to w a rd s the d e ve lo p m e n t o f a b io re fin e ry , N P T Procestechnologie, 2011-1, 26-28 5 X .B . Z h a o , K .K . C h e n g , D .H . Liu (2 0 0 9 ) O rg a n o so lv p re tre a tm e n t o f lig n o c e llu lo s ic b io m a s s fo r e n z y m a tic h y d ro ly s is . A p p l. M ic ro b io l. F ig 1 Biotechnol. 82(5), 815 6 B . B e n je llo u n -M la y a h , M . D e lm a s(2 0 1 1 ) P ro c e ss fo r the se p a ra tio n o f �� lig n in s a n d su g a rs fro m a n e x tra c tio n liq u o r. P a te n t �� W O 2011/154293 7 J. S n e ld e rs, E . D o rn e z , B . B e n je llo u n -M la y a h , W .J.J. H u ijg e n , P .J. d e �� W ild , R .J.A . G o sse lin k, J. G e rritsm a & C .M . C o u rtin (2 0 1 4 ) B io re fi- �� ning of wheat straw using an acetic and formic acid based organosolv fractionation process, Bioresource Technology 156, 275-282 �� )*�#�+�� ,�&�#��-*�� 8 J. W ild sc h u t, A .T . S m it, J.H . R e ith & W .J.J. H u ijg e n (2 0 1 3 ) E th a n o l- �� based organosolv fractionation of wheat straw for the production of lig n in a n d e n z y m a tic a lly d ig e s tib le c e llu lo s e , B io re s o u rc e T e c h n o lo g y 135, 58-66 ��#�� $�$�� 9w w w .biocore-europe.org �� 1 0 M . O ’D o n o h u e (2 0 1 4 ), B IO C O R E Fin a l Pu b lish a b le S u m m a ry ��' �� $� Report. FP7-241566. Downloadable fromw w w .biocore-europe.org � �� .� �� 1 1 J. S n e ld e rs, E . D o rn e z , B . B e n je llo u n -M la y a h , W . H u ijg e n , P . d e W ild and C. (2014) Com parison CIMV and EC N organosolv �� 20&1��'� �� $� �� ' processes, Poster presentation at Conference Tom orrow 's biorefineries .� ��/0,1 �� in E u ro p e , F e b ru a ry 1 1 -1 2 , 2 0 1 4 , B ru sse ls, B e lg iu m �� 3�� '� �� 3�� '� ��'�� '�� m a n c e p ro d u c t p o rtfo lio s. In su m m a ry , th e ��4� % 563�� 4� % 563�� BIOC O RE project addressed the efficient �� p ro d u c tio n a n d u tilis a tio n o f fra c tio n s produced from lignocellulosic biomass by the �� 3�� 3�� C IM V acetic acid/ formic acid process[6 ,7 ]. �� F o r c o m p a riso n p u rp o se s, th e E C N ��4� % 563�� 4� % 563�� ethanol/w ater organosolv technology[8 ] w a s �� ' used as a benchm ark. M ultiproduct manufac- � �� turing value-chains were developed in ��' �� 3�� 3��'��' BIOC O RE and sustainability and benefits for � �� '��'�� the whole of society were dem onstrated. �� 4� % 563�� 4� % 563�� C O M P A R IS O N C IM V A N D E C N �� T h e C IM V a c e tic a c id / fo rm ic a c id a n d th e EC N ethanol/w ater organosolv processes w e re stud ie d in th e B IO C O R E p ro je c t a s tw o A PPLICATION S FO R ORG A N O SO LV sfully dem onstrated the application of lignin representativeas exam ples of organosolv fractio- LIG N IN ; T H E B IO C O R E P R O JE C T a liq u id c o -p o lyo l fo r rig id P U[10] fo. a mIn s nation. F ig 1 p re se n ts a sc h e m a tic o ve rvie w o f O rg a n o so lv lig n in s c a n b e u se d a s a b o th c a se s P U ’s c o n ta in in g u p to 3 0 wboth t% oprocesses f as executed on pilot/lab- fu n c tio n a l h ig h -q u a lity a d d itiv e in in k s , lig n in c o u ld b e p re p a re d . In g e n e ra l, PUscale. 's a re Both organosolv processes were varnishes and paints. Other examples are theam ong the most versatile plastic materials thoroughly com pared based on experimental use in blends with polyethylene oxide, as kn o w n a n d fo rm th e b a sis o f m a n y c o na su n dm e r A s p e n P lu s m o d e llin g [1re 0 ]s. u T lts a b le 2 radical scavenger (anti-oxidant) and as matrixp ro d ucts, insulating p a ne ls, sho e s (soles), p re se n ts a q u a lita tive c o m p a riso n o f th e tw o m aterial in biobased com posites. Organosolvm a ttre sse s, to y s, kitc h e n sp o n g e s ... D e p eo n rg- a n o so lv p ro c e sse s. It is c le a r th a t th e lignin is also a candidate for high-value d in g o n th e n a ture o f th e c o m p o n e n ts uoverall se d , performance of both organosolv fracti- applications such as carbon fibres and th e P U c a n ta ke th e fo rm o f rig id o r ofle na x tion ib le p ro ce sses is ro ug hly sim ilar d e sp ite a ro m a tic (sp e c ia lty) c h e m ic a ls. F o r th e la ttefoam r , or that of elastom er-type plastic. th e d iffe re n c e s su c h a s th e in c o rp o ra tio n o f a p p lic a tio n th e lig n in sh o u ld in g e n e ra l b e p u lp p u rific a tio n in th e C IM V p ro c e ss w h ic h depolym erized by appropriate technology A lso in B IO C O R E , C H IM A R (G re e c e ) h a sw a s n o t in c lud e d in th e E C N p ro c e ss. A lso in such as chem ocatalytic depolym erization, sh o w n th a t o rg a n o so lv lig n in c a n b e u seth d e toc u rre n t o p e ra tio n th e C IM V p ro c e ss is partial oxidation or pyrolysis. Finally, the high-d ire c tly s u b s titu te u p to 5 0 w t% o f p hc e o n no tin l u oin u s, w h ile th e E C N p ro c e ss is b a tc h - quality organosolv lignin is a preferable th e p re p a ra tio n o f P F re sin s fo r th e m a nw u isefa c - at bench-scale. candidate for phenolic resins and poly- ture of plyw ood panels[10] . In g e n e ra l, re sin s u re th a n e (P U ) fo a m s. In th e E u ro p e a n 7 thm ade from phenol and formaldehyde (PF- W h ile th e C IM V o rg a n ic a c id p ro c e ss is m o re fram ew ork project 'BIOC O RE' (Biocom odity re sin s) a re th e m a jo r a d h e sive s u se d to sub ita in db le to p ro d u c e su g a rs fro m th e h e m ic e llu - refinery, 2010-2014[9 ]) lig n in w a s c o n s i- w ood, creating products such as moulded lo se fra c tio n a n d y ie ld s a m o re p u re c e llulo se d e re d a s a p o te n tia l so u rc e o f h ig h e r leproducts, ve l lum ber, timber products and panelspulp (due to additional delignification step revenues (com pared to cellulose). O rganosolvsuch as plyw ood, particleboard, medium u s in g 2HO2), th e e th a n o l o rg a n o so lv p ro c e ss lignin was successfully applied by BIOC O REd e n sity fib e rb o a rd s e tc., w h ic h in so m e yc iea se ld s lig n in w ith a h ig h e r p u rity . B o th partner SYN PO (Czech Republic) as a solidw ill b e sp e c ific a lly d e sig n e d to re sist o u tdprocesses o o r clearly show a good potential for co-polyol for the solvent-free production of use conditions. These three BIOC O RE u s e in lig n o c e llu lo s ic b io re fin e� rie s . castor oil-based polyurethane (PU) elastom ers examples show that products that valorize [10]. B IO C O R E p a rtn e r IW C (La tvia ) su c c elignin s- are valuable features of higher perfor-dew ild@ ecn.nl

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