US 2016004655441 cu») United States cz) Patent Application Publication — co) Pub. No.: US 2016/0046554 A1 oy oy my) an @ (86) G0) LANGE PROCESS FOR PRODUCING STYR NE Applicant: w Inveator: Jean Paul Andre Marle Joseph Gishlain LANGE, Amsterdam (NL) O11, COMPANY, Howson, TX Assignee: SHELL OIL COMPANY, Houston, TX ws) Appl.No: 1477834120 PCT Filed: Apr. 9,2014 PCT Nos PCT/EP2014/087208 $371 CX), (2)Date "Oct. 8, 2015 Foreign Application Priority Data Apr 12,2013 (EP) 131634867 (43) Pub, Date Feb. 18, 2016 ication Classification (1) Ince Core 4548 200601) core 29145 (2005.01) core 450 (2005.01), eV (2006.01) 2) US.C CUTE 45455 (2013.01), COPE 124 (2013.01), €07C 204145 (2013.01); C07C “45/00 2013.01) on ABSTRACT Te invention relates to @ process for producing styrene comprising renting benzene and acetic aed nto methyl phe fy Ketone and converting the methyl phenyl ketone into styrene, Preferably, the methyl pheay! Ketone is converted into styrene by converting the methyl phenyl ketone into snetyl phenyl carbinol and converting The methyl pheny] carbinol into styrene,Patent Application Publication Feb. 18, 2016 US 2016/0046554 AI 42 =U Fig.1US 2016/0046554 AI PROCESS FOR PRODUCING STYRENE FIELD OF THE INVENTION 10001] The present invention relates to a process for pro- “ducing styrene BACKGROUND OF THE INVENTION 10002] _Itis knownto produce styrene by alkylation of ben- zene with ethylene resulting in ethylbenzene, followed by “dehydrogenation of ethylbenzene into styrene, 3s follows O--Or- 10003}, The reguired ethylene feedstocks alo produced by Aadehydogenation reaction, that isto say by dehydrogenation ‘fae. Therefore, on two occasions inthe above syrene production process, hiahly oxidized components a pro- {ced by expensive debydrogention steps, sume in the ‘dehy dogenation of ethane to ethylene and in the debiydroge- nation of ethytbenzene to styrene. These dehydrogenation steps require high eaital expenditure {0004} known atematve for the above-deserbe dicot styrene production process isa process wherein the above- tmentional second dehydrogenation step whersia eilben- ‘aes dretly convert styrene is replaced by aseauence ‘ofthe steps including the co-produetiono propylene oxide ‘These thre steps comprise: () reacting ethylbenzene with ‘oxygen otto form es benzene hydroperbde, i) eoct- ing the ethylbenzene hydroperoxide with propylene inthe presence of an epoxidation catalyst to yield propylene oxide dn methyl phen earbinl, and Gi) converting the meth phenyl carbino into styrene by dehydration using a dehyde tion catalyst. This altemative styrene production process is also commonly fee s the SM/PO proces fb prod ing styrene monomer (SM) and propstene oxide (PO)- As ‘compared (o the above-described iret styrene production proces, by adding twoadtional step inthe SMI/PO process fn increase in capt expenditur is disadvantazeusly tfc 10005], Thus, in said SM/PO proces, styrene is produced Via ethylbenzene hydroperoxide Which s used t0 convert propylee into propylene oxide tnereby also forming mil Phenyl cacbinol sTllows Feb. 18, 2016 10006] In a next sep, ssid methyl phenyl earbinol is con: verted into styrene by dehydration, a follows: oe [0007] further disadvantage of the production of styrene via the above-mentioned SMPO process is that ssid ethyl- benzene hydroperoxide is produced fom ethylbenzene. As siscussed above in connection with the direct production of styrene from ethylbenzene, production of ethylbenzene requires dehydrogenation of ethane © etlylene followed by alkylation of benzene with ethylene resulting in ethylben- ‘ene, Therefor, inthis ease, a highly oxidized component is produced by an expensive dehydrogenation step, namely in the dehydrogenation of ethane to ethylene. This dehylroge- ation step requires «high capital expenditure. [0008] A still further disadvantage of the production of ‘styrene via the above-mentioned SM/PO process is that sty~ reneund propylene oxide are produced in fixed SM:PO rio ‘of quantities. That isto say, ina ease where the demand for styrene would increase as compared to the demand for pro- pylene oxide, it may be that this increase in demand for yreaecantot be met incase where total production capac- ity is maintained, ot may be that this inerease in demand for styrene can be met ina ease where total production capacity js increased but only atthe cost of a remaining quantity of propylene oxide for which there is ao demand. Both said Situations are undesirable from both technical and « com mercial perspective [0009] "Terefore itis desired to provide a process for pro- ‘ducing styrene which does not comprise any dehydrogen- tion step such as the above-diseussed deiydrogenation steps from the known styrene production processes. Additionallit is desired to provide a process for producing styrene which ‘may compensate for any higher demand for styrene in the shove-mentioned SMIPO process SUMMARY OP THE INVENTION [0010] Surprisingly itwas found that the above-mentioned problems are solved by a process wherein benzene and acetic ‘acid are reacted into methyl phenyl ketone, and the methy] phenyl ketone is converted into styrene. Advantageously, the present invention does not contain any dehydrogenation step Torpmelocinga highly oxidized component. One ofthe start- ‘ng materials forthe present invention i in Tact acetic acid ‘which in selfs already a highly oxidized component. Addi- sionally, the present inveation adds more flexibility for the hove-mentioned SM/PO process i relation to any increase inthe demand for styrene [011] Accordingly, the present invention relates toa pro~ cess for producing styrene, comprising reacting benzene and acetic acid into methyl phenyl Ketone and converting the ‘methyl pheny! ketone into styrene [0012] Apart fom solving the above-mentioned problems relating to the known styrene produetion processes, the resent invention also provides a process wherein acetic acid ‘blained as sice-proct in biomass conversion processes can advantageously be used as valuable feedstock to pro-US 2016/0046554 AI ‘duce styrene. Thus, in the present process there is no nee for first producing a highly exidized component, such 3s acetic ‘acid, by means ofan expensive dehydrogenation step sinee in the present inveation the acetic acid may simply originate froma biomass conversion process. BRIEF DESCRIPTION OF THE DRAWING 10013] FIG. 1 isa diagram showing an embodiment ofthe present styrene prodiction process wherein there isan inte- triton with the sbove-nientioned SM/PO process DETAILED DESCRIPTION OF THE INVENTION 10014) Ina first step of the present process for producing styrene, benzene and deetc acid are acted into methyl phe- yl ketone, 10015] In the present invention, the aeete acid which is nosed in the first step may originate from a biomass cover sion process, that isto siy a process wherein a renewable ‘material (the biomass) is converted. In such biomass eonver- sion process, the biomass is converted to mainly provide @ fuel (eg ethanol) or other valuable chemicals. However, in suel biomass conversion process, acetic acid may also be recovered or generated asa side-product for which an advan- tageous use is also desired, Thus, apart from solving the bowe-mentioned problems relating tothe known styrene pro- ‘duetion processes, the preset invention advantageously also provides a process wherein acctic acid oblained as a side- product in biomass conversion processes can be used as & Yaluable feedstock to produce styrene. 10016) Specifically inthe present invention, the acetic acid may originate from biomass, preferably from a cellulosic rmaleral, such asa lignocellulosic material. Acetic acid is a ment ofTignocellulosie mate- ‘accounts for 2-3 Wt, % oF grasies and 3-6 Wt, 96 oF [0017] Various methods exis for obtaining acetic acid rom biomass, preferably a cellulosic material, such asa lignocel- Iufosie material. 10018] _ first method isto rocover acetic acid by’ treat- ‘ment of the biomass at a relatively low temperature, prefer ably inthe rang of ftom 50 to 250° C., more preferably 100 to 200° C., in either liquid phase (also referred to as “pre- treatment”) or gas phase (aso referred to as “torrefsction”) {allowed by extraction ofthe desired acetic acid. Tbe remain- Jing biomass can be used for other purposes, such as paper pulp, heaupower, biofuel or chemical manufacture. Such treatment i preferably caried out nan ier atmosphere and, ‘optionally, inthe presence of an acid or base. Torrefaction of ‘willow wood releases about 3 wt. % of acetic acid 10019] A second method iso recover acetic acid by @ Treatment of the biomass at a relatively high temperature, preferably in therange a fom 250 t0 600° C.,ineither liquid phase (also refered to as “hydrolysis” or “liquefaction”) or 2 phase (also refered to as “pyrolysis") followed by extrac- tion o the desired acetic acid, The emaining biomass can be used forother pupases, such asheat/pawer, biofuel or chemi ‘al manufacture, Sued treatment is preferably carried fn inert atmosphere and, optionally. nthe presence of an acid ‘or base. Hydrolysis of birch wood releases about 6 wt. % of soctc acid [0020] A third method is to convert sugars contained ia biomans into acetic seid by fermentation Feb. 18, 2016 [021] Thus, on a large scale, for example in a pla ‘wherein ethanol is produced as main product by converting cellulosic materials, such plant having production capacity fof 600 ka (kilo per annum), its expected that about 30 va (5 wt. %) of eeatie acid is produced, 0022} Atleast fortwo reasons, tomefacton isa particularly interesting method for obtaining acetie acid from biomass, preferably a cellulosic material, such as a lignocelivosic ‘material, and for providing the seete acid thus obtained as 4 feedstock in the present process for producing styrene. [0023] Firstly, by means of torefiction acetic acid can be ‘delivered in siream having s reasonably hig concentration ofaceticacid, that isto say about 20 wt % ofueetic acid, upon recycling the gas eluent to the reactor buildup pred, as Torexumple disclosed in a publication on the world wide web ‘whieh isentiled "Torrelsetion forentrained flow gasification ‘of iomass” (report ECN-C-05-067), by P.C. A. Bergman ct al, Energy research Cente ofthe Netherlands (ECN), ECN Biomass, web) Ingp/imwwcen.ndoes/ibraryepor’2005/e0S067 pdt). On the other hand, in a wet lignocelhslose conversion process ‘wherein the ignocelfulose is converted ina iguid (water), a stream containing only about | wt. % of acctic acid may be ‘oblained. Such higher acetic acid concentration by tonetie- tion greatly facilitates covery of the acetic acid and subse- {quent valorization thereo in the present process for produe- ing styrene. [0024] Secondly; torefaction may become major process Since itis seen as serious candidate for making cellulosic ‘materials. commodity for power generation plants or for BAL plans. “BL” refers tothe "Bio-o-L iguide” process that pro- ‘coeds va gasification and Fischer-Tropsch synthesis. Replac- ing only $%ofcoal consumption, which coals globally used ‘nan amount of about 5 Gla (gigaton per anim) to generate power, by cellulosic material consumption could already eo- produce about 12.5 Mva (million ton per annum) of acetic acid (at 5 wt % content in lignocellulose). On the other band, the curent global demand for soetic acid is about 11 Mu ‘which is Tess than the above-expected production of about 12SMilaoFcetic acid. Currently, the major outlets foracetic acid are in producing vinyl acetate (33%), terephthalie acid (TPA) solvent (22%), acetate ester solvents (15%) and acetic ankydride (14°). However, by commercial application ofthe resent process lor producing styrene, a furher advantageous ‘outlet for acetic acid would be created by which a good portion ofthe ahove-expected production of about 12.5 MUa Df acetic acid ean effectively be absorbed [02S] In the present inveation, the benzene which is ‘needed inthe fist step may also originate from a biomass, ‘mor’ in particular from a biomass conversion proces, just like the deste ail as discussed above, In such way, avan- ‘ageously i the present invention, fully bio-based styrene is produced. For example, benzene may be obtained from ague- ‘us phase reforming of sugar, as for example disclosed in 'W0201 1143391 and US2012019870. Furher, benzene may be obtained from catalytic pyrolysis of lignocellulose, as for example disclosed by'T. Carlson tal. in "Groen Gasoline by Catalytic Fast Pyrolysis of Solid Biomsss Derived Com- pounds", ChemSusChem, 2008. Sil further, benzene may be ‘obiained from hydrleoxyzenation of pyrolysis ol or lignin, fs forexample disclosed by B. Valle in Selective Production ‘of Aromatics by Caide Bio-il Valorization with a Nickel- Modified HZSM-S Zeolite Catalyst”. Energy Fuels, 2010, 24 pages 2060-2070, All these routes give a stream of mixedUS 2016/0046554 AI -aromaties including benzene, which can further be treated to make further benzene, lor example va hydrodealkylation or ‘wansalkylation 10026) In the present process for producing styrene fist benzene and acetic acid are reacted into methyl phenyl ketone, In this eylation resetion, water is co-produced as follows Ou 10027) ‘The sbove benzene seylation step, wherein benzene ‘and acetic acid are reacted into methyl phenyl ketone, is known as such, For example, tis reaction is disclosed by A. Singh eal. in J. Molec, Catal. A= Chem., 1997, 123, pates 141-147, Suitable conditions for effecting suid reaction ae disclosed in said publication, the entre disclosure of whichis, herein incorporated by reference, 10028] In particular, in sid publication in J. Molec, Catal. A: Chem, 1997, 123, pages 141-147, a 90% selectivity (based on aeetic acid) is reported for a ease where in the reaction of benzene with aetic acid a HZSMS zeolite was used as a catalyst and further the following conditions were pplied: sas phase, 250° C., atmosphere. benzene-aetic ‘molar ratio 1:2, and LTISV=1/h. Reported by-products are di- and tr-acylated prosacs, 10029] Generally, the above benzene acylation step, ‘wherein benzene and acetic aed ar reacted into methyl phe= nyl ketone, can be caried ata temperature in the range of from 150 to 350° C., preferably 200 to 300° C., and at 2 pressure ringing from stmospheric pressure to lower tha 10 bar. Tho catalyst to he used isnot essential and may bea solid d.etalyst, such asa zeolite. Said step may be cared aut in the gas phase or in the liquid phase, preferably inthe gas phase. Before performing the nent step in the present process, preferably water is removed, Further, preferably, any wneon- Verted starting material andor any d-and i-aeyluted prod Uucis are removed before performing the next step. [0030] Ina next step of the present process for producing styrene, the meth! pheny! Ketone thus obtained is converted into styrene 10031] Preferably, in the present process for producing sty- rene, the methyl phenyl ketone is converted into styrene vis the following two reactions, In a fist reaction, the methy pheay] ketone is converted into methyl phenyl earbinol by hydrogenation, as follows oof Feb. 18, 2016 [0032] In. second reaction, said methyl phenyl caebinol is converted into styrene by dehydration, as follows -CO« [0033] ‘Ths. in the present process it is preferred tha the ‘methyl phenyl Ketone fs converted ino styrene by converting ihe melt pleny Ketone into methyl poerylearbnol and ‘converting the methyl phenyl carbino! into styrene. [0034] Both the conversion of methyl pheny! Ketone into ‘methyl phenyl earbino as such and the conversion of methy phenyl carbinol into styrene as such are known, Fr example, In theabove-mentioned SM/PO process ethylbenzene hydro- peroxide is reacted with propylene to yield propylene oxide ‘and methyl phenyl cariool In next step the meth] pheny] ‘arbinol is converted ino styrene. In tis proces, part ofthe eflbenzanehydroperoxie earangs into meth phen ot [0035] ‘This hs the result chat the reaetion mixture obtained by reacting ety benzene iydroperoxide with propylene not ‘only contains propylene oxide and methyl phenyl earbinol ‘but also methyl phenyl ketone. Said methyl pheay! ketone cannot be deliydrated in the next step wherein styrene is pradced from melhiyl phenyl carbinol. After the later sep the methyl phenyl Ketone has to be separated and then is hydrogenated resulting in methyl phenyl carbinal whieh is thea subjected to dehy tration resulting in styrene as yt [0036] An advantage of the present styrene prodtion pro- ‘cess is that the final step of converting the methyl phenyl Ketone into styrene can he integrated with the sbove-men- tioned SM/PO process whereia methyl phens| ketone isso converted into styrene. Therefore, preferably, the preset sty- rene production process additionally comprises [037] converting mixture comprising ethylbenzene hydroperoxide and propylene into mixture comprising pro= pulene oxide, methyl pony carbo and mets! phen [038] scparating propylene oxide from the mixture com- prising propylene oxide, methyl phenyl earbinol and methyl phenyl ketone resulting ina mixture comprising methyl phe- yl earbino! and methyl phenyl Ketone, [0039] converting the mixture comprising methyl phenyl ‘arbinol and methyl phen ketone nto a mixture comprising styrene and methyl phenyl ketone, [040 » separating methyl phenyl ketone from the mixture ‘comprising styrene and methyl phenyl ketone, [0041] converting the separated methyl pheny! ketone into ‘methyl phenyl carbinol and combining siid methyl phenyl carbinol with the mixture comprising methyl phenyl carbinol ‘and methyl phenyl Ketone resulting fom separating prop Tene oxide from the mixture comprising propylene oxide, vethsl phenyl carbinol and methyl phenyl Ketone,US 2016/0046554 AI 10042] wherein the methyl phenylketone resulting fom the reaction of benzene with acetic acid is combined with the methyl phenyl ketone separated from the mixture comprising styrene and methyl phenylketone, [0043] | Thesbove embodiment wherein the present styrene production process is inteyeated with the above-mentioned SMIPO process is exemplified in FIG. 1, In FIG. 1, ethylben- ‘zane hydroperoxide and propylene are seut via lines 1 and 2, respectively to reaction unit3 Wherein hey are converted into ‘2 mixture comprising. propylene oxide, methyl phenyl ‘carbinol and methyl phenyl Ketone. Said mixture comprising propylene oxide, methyl phenyl earbinol and! methy! phenyl Ketone may also comprise unconverted propylene which may be separated from said mixture and yeeyeledto reaction unit 3 (oot shown in FIG. 1). Said mixture comprising propylene ‘oxide, methyl phen carbinol and methyl phen! Ketone is ‘ent via line 4 separation unit § wherein propylene oxide is separated via ine 6 from the mixture comprising propylene ‘oxide, methyl phenyl carbinol and methyl phenyl Ketone resulting ina minture comprising methyl phenyl earbinol and ‘methyl pheay! ketone, Said mixtre comprising methyl phe- ny carbinol and methyl phenyl Ketone is sent via line 7 reaction uait 8 wherein iis converted into mixture co rising styrene and methyl phenyl ketone. Suid mixture com prising styrene and mediy] phenyl ketone may also comprise ‘water which may be separated from said mixture (no shown Jn FIG. 1), Said mixture comprising styrene and methyl phe- yl Ketone is sent via line 9 to separation unit 10 wherein styrene and methyl phenyl Ketone are separated from the mixture comprising styrene and methyl phenyl ketone via Tines 11 and 12, respectively. The separated methyl phenyl ketone is sent via line 12 to reaction unit 13 wherein itis ‘converted into methyl phenyl earbinol by means of hydrogen, provided to reaction unit 13 via line 1. Said methyl phenyl ‘carbinol is sent va ine 1Sto line 17 where itiscombined with the mixture comprising methyl phenyl earhinol and methy] pheay! Ketone resulting from separating propylene oxide fiom the mixture comprising propylene oxide, mthy phenyl ‘carbinol and methyl phenyl Ketone in separation unit 5. Fur ther, in FIG. 1, benzene and acetic acid are sent via lines 16 ‘and 17, respectively 1 reaction unit 18 wherein they are ‘converted into methyl phenyl Ketone. Said methyl phenyl Ketone is sent via ine 1910 line 12 where itis combined with the methy] phenyl Ketone separated from the mixture com- prising styrene and methyl phenyl ketone in separation unit 10. 10044} In the present invention, the methyl phenyl Ketone may be converted ino styrene in any knowa way. More spe- ‘ilically, in an embodiment of the present inveation as “described above, methyl phenyl ketonemay beconverted into meth phenyl carbine! and said methyl phenyl earbinol may then be converted into styrene in any known ways. Likewise, jn an embodiment of the present invention as described above, ethylbenzene hydroperoxide and propylene may be ‘converted into propylene oxide, methyl phenyl carbinol and methyl phenyl ketone in any known way. More particulary, the reaction conditions that are known in relation to the ‘above-mentioned SM/PO process for elfecting said reactions may equally be applied in the present styrene production process 10045] |The reaction conditions under which sad eonver sions may be caried out, such as catalyst, temperature, pres- sure, e.,are not essential for obtaining the advantages ofthe Feb. 18, 2016 present invention, For illustration purposes only, some reae- tion conditions are exemplified hereinbelow. {0046} For example, said conversion of methyl phen! ketone (MPX) into methyl pheny! earbinol may becarried out by treatment with an excess of hydrogen (H,), wherein the molar ratio of FH, to MPK is higher than 1:1, at a pressure of from to 10Obar preferably 10t0 90 bar. The catalyst may be a catalyst containing at least one transition metal, such as copper (Cu), chromium (Cr) andor zine (Za), preferably Cu Preferably, the catalyst isa supported catalyst, Suitable eta. Iysts are a copper chromite (CuCr,0,) catalyst, a catalyst containing copper supported on silica o alumina, anda cata Iystcomprising CuZan, The temperstire may be of frm 500 200° C., preferably 700 150° C, [0047 " Further, for example, said conversion of methyl phe- yl carbinol into styrene may be carried out inthe gas phase faa temperature of from 150 to 450° C,, preferably 250 10 350° C.and ata pressure of from 0.1 to 3 bar, preferably 0.$ ‘o 1 bar by using a titania, alumina or zeolite catalyst Said lumina catalyst may be moderated by an alkali metal. When ng a zeolite catalyst, said conversion may’ iteratively be carried out inthe liquid phase, forexampleat a temperature of from 100 f0 200° C. Suitable conditions for effecting said conversion are disclosed by J. KF. Buijink tal in Section 33 (Catalytic dehydration”) from Chapter 13 (Propylene [Epoxidaion via Shells SMPO Process: 30Years of Research and Operation”) from “Mechanisms in Homogeneous and tem gencous Epoxidation Catalysi", edited by T. Oyama, Elsevier, 2008, pies 367-369, the entire disclosure of which is herein incorporated by reference. [0048] Sui! further, for example, said conversion of ethyl- benzene hydroperoxide (FBHP) and propylene into propy- Tene oxide, meh] phenyl earbinol und methy] phenyl ketone ‘maybe carried out inthe liquid phase ata temperature of rom 30 to 200° C,, preferably 500 150°C. and ata pressure of ‘rom 10 to 100 bar, preferably 30 to 70 bar Propylene may be sedi excess. The molar ratio of propylene to EBHP may be of from 210 10, typically 3 10 8. Further, preferably, the catalyst is titanium containing catalyst, which is preferably supported on silica. The later catalyst may’ be prepared in rullistep gax-phase process by treatment of a silica carrer ‘with titanium tetrachloride, heating the obtained material, followed by steaming and silylation. Suitable conditions for effecting said conversion are disclosed by J. K.F. Buijink et al. in Section 2 ("Catalytic Epoxidation”) from Chapter 13 (Propylene Epoxidation va Shell's SMPO Process: 30 Years ff Research and Operation”) from "Mechan ‘geneous and Heterogencous Epoxidation Catalysis”, by T. Oyama, Elsevier, 2008, papes 358362, the entire di closine of which is herein incorporated by reference 1. A process lor producing styrene, comprising reacting ‘benzene and acesie acid into methyl phenyl Ketone and eon- vertng the meth phen! ketone into styrene. 2..A process acconling to claim 1, wherein the methyl heny| Ketone is converted into styrene by convening the pethsl phenyl ketone into methyl phenyl carbinol and con- vertng the methyl phen carbinol into styrene. 3.Aprocessacconding to claim additionally comprising: ‘converting a mixture comprising ethylbenzene hydroper ‘oxide and propylene into @ mixture comprising propy~ lene exide, methyl phenyl carbinol and methyl pheayl ketone, separating propylene oxide from the mixture comprising Propylene oxide, methyl phenyl carbinol and) methylUS 2016/0046554 AI phenyl carbinol and methyl phenyl ketone, converting the mixture comprising methyl phenyl eaebinol and methyl pheay! ketone into a mixture comprising styrene nd methyl phenyl Ketone, separating methyl phenyl Ketone from the mixture com- ‘prising styrene and methyl phenyl ketone, cotvertng the separated methy phenyl Ketancinto methyl ‘phenyl carbinol and combining said methy! phenyl Carbinol with the mixture comprising mets] phenyl cearbinol snd methy/ phen! ketone resulting fom sepa rating propylene oxide from the mixture comprising propylene oxide, methyl phenyl eatbinol and methy phenyl ketone, ‘wherein the met] pheny1 ketone resulting from the rae> tion of heazene With acetic acid is combined with the ‘methyl phenyl! ketone separate from the mixture com ‘rising Styrene and methyl phenyl Ketone 4. process sevording to els 1, wherein the aetie seid ‘and/or benzene originates from a biomass conversion pro- 5. A process aooording to claim 1, wherein the aetie acid “originates from acelfulosie material such asa lignocellulosic material Feb. 18, 2016