«2 United States Patent Burket et al 'US008524924B2 (10) Patent No.: US 8,524,924 B2 (45) Date of Patent: Sep. 3, 2013 (54) PROCESS FOR FURFURAL PRODUCTION FROM BIOMASS (75) Inventors: Christopher Burket, Wilmington, DE (US); Subramaniam Sabesan, Wilmington, DE (US) Edu Pont de Nemours and ‘Company, Wilmington, DE (US) (73) Assignee: (4) Notice: Subject to any diselaimer, the tem of this patent is extended or adjusted under 35 USC. 154(b) by 269 days. (21) Appl. Nos 12973,980 (22) Filed: Dee. 21,2010 ws) Prior Publication Data US 201210157697 Aun. 21,2012 6) Inc. coz 307/80 corD 307742 (2006.01) (2006.01) (2) 549/489, 549/488 (58) Field of Clasifcation Search usPC’ 549/489 ‘Se application file for complete rearc history. 66) References Cited US. PATENT DOCUMENTS 2750304 A 61956 Peniston Aasirad A $1999 Hamada al SSHNTES A RIDSS. Medeiros 941202 BL $2002 Cipher Ssmons 2 £2009 aoovoanisig AL 22003 2oosoos3iss AL 22008, dooney AL $2000 dovooo0usa7 AL 1/2010. Binderet a FOREIGN PATENT DOCUMENTS Wo WO200TI46636 AL 122007 (OTHER PUBLICATIONS Croker ot lla. Eng. Chem, Fundamentals, vol. 23, (oss) ‘Moreau ct al Industial Crops Products, vl. 7. p. 98-9 (1998) Amitiet a, Brodtionol rane from ie srawby single-phase and bypsie stems, Carbohyrae Research, 200, 2133-2138, 90 aus ‘Weingarten et, Kinetics of furfural production by dchydationof| slse ina biphsie reactor with microwave heating. Green Che Iaty, The Royal Socey of Chemistry, 2010, 1423-149, vo. 12 ‘Zhao ta, Metal Chlorides in oie Liquid Solvonts Comer Sugars ‘o SHiyoxymethylfurful,Sience, 207, 1597-1600, vol. 316 Dias et aly Dehydation of xylose into furfural over micro- mesoporous sulfonic acid catalyst, Journal of Catalysis, 2008, 414. '23. ol 229, CChhedaeial, Prodstion of ShyoxsmethytrTral and eral by ‘eho af biomasederived mono- and poly-saccrides, Green ‘Chemistry. The Royal Society of Chemistry. 207, 42-38, v0.9. ‘Maniman etal, Furuta: Henicelllose ose derived biochen- al: Biofuels Biopuoducts & Hinefiing, 208, 438-454, vol 2. Vane tl Hytroyss of sorghum saw wing phosphoric act: Evaltion of furfural production, Bioresource Technelogy. 2007 3053-3060, vo. 98, International Search Report, PCT later PCT US201 1065332, Mail Nov. 30, 2013. 4 ional Application No. * cited by examiner Primary Examiner — Berard Dente 6 ABSTRACT Furfual is produced from 9 lignocelfulosie feedstock com- prising glucen and xylan, The feadstack is contacted with ‘water inthe presence of an acid eatalyst, The resulting mix- ture is contacted with a least one water immiscible organic solvent to form a mixture comprising an aqueous phase and ‘anorganic phase, Under suitable reaction conditions, fariral is produced and prefereatially paritions into the organic phase fom whieh it may’ be recovered. 14 Claims, No DrawingsUS 8,524,924 B2 1 PROCESS FOR FURFURAL PRODUCTION FROM BIOMASS FIELD OF THE INVENTION ‘Methods for the procuction of furfural from biomass are provided. Specifically, methods for obtaining furfural selec- tively in good purity from fignoeeulosie biomass under biphasic conditions ae provided BACKGROUND Purfurlis a indus useflchemicul Conventionally furfural can be produced fom C, sugars which have been ‘obiained from hydrolysis of the hemicellulose contained in biomass. Typically, the hydrolysis of biomass is performed with aqueous ais at relatively high temperatures o olan Cand, sugars derived fom xlan.and gean respectively. ‘Ay Trfrl generated, when ein the monopse agueos reaction mixture of sugars can undergo degradation via cone ‘densation initiated by reactive sugar intermedistes, Besides resulting in lower yield of the dosired furlural product, costly separation steps 1 isolate the furfural from other intermedi- ates is nooed. Such separation stp(s) can increase process ‘complexity as well, ‘USS. Pat No. 4,154,744 rolates to an improved process for producing furan derivative having te formula shown below AM “Ho wherein Ris hydrogen, methyl, or chloromethyl, whieh com- privs reacting a monosaccharide or a disaechaide with hydrochloric acid in a mixture containing water, an organic solvent and a catalytic amount ofa surface active agent. US. Pat. No. 4,533,743 discloses that furfural yield and selectivity are maximized by reaeting | to 10 percent pen- tose 0.05 t0 0.2 normal mincral acid aqueous soliton in & plug low reactor operated ata temperature between 227 C. tnd 300° C, Two preferred armingements are disclosed: & single phase, pentose reeyele operation in whieh te furfural is pecovered by solvent exirction and distillation, and a Wo phase, solvent recycle operation in which solvent i added t0 the reactor and furfural is recovered from the solvent by sisillation, ‘United States Patent Application Publication No. 2008! (0033188 relates to a process to make furan derivative come pounds, The process comprises deiydrating a earboliydrate Teedstock solution, optionally in the presence ofan acid eata- lyst, in a reaction vessel containing a biphasic reaction medium comprising an agusois reaction soliton anda sub- stantially immiseible oganic extraction solution. The ague- ‘ous reaction solution, the organic extraction solution, or both the aqueons reaction solution and the organic extraction solu- tion, contain at least one modifier to improve selectivity ofthe process to yield fra derivative compounds in general, and Sshydroxymethyl-2-furfural (HMF) in particular Processes lor obtaining furfural in high purity and selee~ tivity from biomass continue to be sought. In particular, pro- ‘esses are desired in which lignocellulosic biomass compris= jing both glucan and xylan can be used as feedstock to provide ‘rural selectively and in good purity, relatively ree of IMP. Also desired are processes in which the separation of furfural trom HMF is simplified 0 o 2 SUMMARY, Described herein awe processes for the production and separation of furfural from lignocellulosic biomass. The described processes involve vontating the biomass, in the presence of an acid catalyst and under suitable conditions, ‘with water and atleast one water-immiseible organic solvent as described herein. The reaction conditions are selected 10 favor conversion of the xylan component of the biomass eedstock to furfural, and the atleast one watersinamiseible ‘onganie solvent i chosen to preferentially partition the fur {url int the organi phase Tnone embodiment. a provess forthe production of furfural is described, the process comprising the steps of 8) providinga lignocellulosic feedstock comprising ghican and xylan; ‘contacting the feedstock with waterin he presence ofan ‘acid catalyst to form a mixture «©)contacting the mixture formed in step b) witht eastone ‘water-immiseible organic solvent comprising at least ‘one aliphatic hydrocarbon, cycloalkane, aromat hydrocarbon, polyether contsining ester of ether end ‘ous plant-derived oil. or mixtures thereof under sui ableresetion conditions to forma mixture comprising an ‘aqueous phase anda furfursl-containing organic phase: and 4) optionally, recovering furfural from the organic phase DETAILED DESCRIPTION OF THE INVENTION Delinitons ‘The methods described herein are described with reference to the following terms. As usod hecein, where the indefinite article “a” or “an is ‘sed with respect to astatement or deseription ofthe presence ‘ofa step ina process ofthis invention, itis o be understood, ‘unless the statement or description explicitly provides to the contrary, that the use of such indefinite artiele doesnot limit the presence ofthe step in the process to one in number “As used herein, when an amount, concentration of other value or parameters given as cither a range. preferred range, ‘ora list of upper preferable values ad lower preferable val- tes, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lover range limit or prefered value ‘eganlless of whether ranges are separately disclosed, Where range of numerical values recited herein, unless otherwise Stated, the range i intended to include the endpoints thereof, fad all integers and fractions within the range, It is not intended that the seope of the invention be limited to the “comprises.” “comprising.” ving," “contains” or“con- ‘ray other variation thereof, are intended t cover nonexclusive inclusion, For example, a composition, a ‘mixture, process, method, article, or apparatus thateomprises alist of elements is not necessarily imited to only those elements but may inelude other elements not expressly listed or inlerent to such composition, mixture, process, method, aniele, or apparatus. Further, unless expressly stated to the ‘contrary, “or” refers to an inclusive or and not oan exclusive or For example. condition Aor Bis saisfid by any one of the following: A is true (or present) and Bis false (or not present) Ais false (or not present) and Bis trac (or present) ‘and both A aad B ate true (or preset)US 8,524,924 B2 3 Asused herein, the tenn “shout” modifying the quantity of sn ingredient or reactant of the invention employed refers to variation in the numerical quantity that can oceur, for ‘example, through typical measuring and liquid handling pro- cedures sed for making concentrates or use solutions in the real world: through inadvertent error in these procedures through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry ‘out the methods: athe like. The teem “about” also encom= passes amounts that differ due to different equilibrium com ‘ivions for @ composition esuling feom a particular initial mixture. Whether or not modified by the tem “about” the ‘lsims include equivalents tothe quantities, The term “about” ‘may mean within 10% of the reported numerical value, pref- ‘erably within 5% ofthe reported numerical valve “As used herein, the term “biomass” refers to auy hemicel= Iulosic oF Hianocelivlosie material and includes materials ‘comprising hemicellulose, and optionally further comprising cellulose, lignin, starch, oligosiccharides and/or monosac~ charides. ‘As used herein, the tom “lignocellulosic” refers to acom- position comprising both lignin and hemicellulose. Lignocel- fulosie material may also comprise cellulose ‘As used herein, the term “Wwater-immiseible” refers (0 2 solvent o¢ solvent mixture which sineapable of mixing with Water or an aqueous solution to form one lguid pase As used herein the term “partition coefficient”, abbreviated herein as K,. means the ratio of the eoneengation of eom- pound in the two figuid phases of a mixture of to imimiseible Solventsat equilibrium. A partition coeficent isa measure of the differential solubility ofa compound between two immise ible solvents. As used herein, the term “partition coefficient {or furfural” refers to the ratio of concentrations of furfural between the onzanie phase comprising the organic solvent or solvent mixture and the water or aqueous phase. Putition ‘covtlicient, as used herein, s synonymous with the erm “diss tribution ebeficent.” As used herein, the term “fity acid” refers to a monocare boxylicacid with an unbranched aliphatic tail, or chain. Fatty ‘eid are derived from, oF contained in esterified Form in, animal or vegetable fat, ol, or wax. Natural fatty acids com- ‘monly havea chain of 4 to 28 carbon atoms, Fatty acids can be bound to other molecules suchas in triglycerides. ‘As used herein, the term “free fat acid” refers to fay ‘cids which arenot bound other molecules. fre fay acid js obianed, for example, when a teigyeeride is broken down ino its components ity acids and glycer). Asused herein, the tem “triglyceride” refers oa glyeeride formed by esterification of a glycerol molecule with three fatty acids. The three faty acids can be al differen, all the same, or only two the same. Triglycerides are the main con- stituent of vegetable oil and animal fats. In the processes described herein, a lignocellulosic fee stock comprising gncan and xylan is contacted with water in the presence of an acid catalyst, then with at least one water- ‘immiscible organic salvent as described herein under suitable reaction conditions to forma mixtre comprising an aqueous phase and a furfural-contsning organic phase. Optionally, the processes fieer comprise recovering ffural fom the ‘organic phase. One of the economical advantages ofthe pro- ‘cesses is that no modifiers are used in the aqueous or ompanic phases, and thus no modifiers need 4 be separated from the rural or any process steams. “The soutee ofthe lignocellulosic feedstock isnot determi native of the invention, and the biomass may be from any source. Biomass may be derived from a single source, of biomans can comprise a mixture derived fom more than one 0 o 4 source: for example, biomass could comprise @ mixture of om eobs and com stover, ora mixture of grass and leaves. Biomass includes, but is not limited to, bioenergy erops, agricultural residues, municipal solid waste, industrial solid ‘waste, sige from paper manulacture, yard waste, Wood and {orestry waste ora combination thereof. Examples of biomass include, but are not limited to, com grain, com cabs, crop residues such as com husks, corn stover. grasses, wheat ‘wheat sta, barley barley’str; ay, rice straw, switchers, ‘waste paper, sugar cane bagasse, sorghum, soy, components obiained from milling of grains, tees, branches, roots, leaves, ‘wood chips, sawdust, shrubs and bushes. vegetables, fruits Flowers, and animal manuee or a combination thereof. Biom: ass that s usefil forthe invention may inclode biomass that has a relatively igh carbohydrate value is elatvely dense, andor is relatively easy to colleet, transport, store andor Fhandle. In one embodinient of the invention, biomass that is useful inclodes com cobs, wat straw, sawdust, and sugar cane bagasse. ‘The lignocellulosic feedstock may be used directly as jobiained from the soures, or energy may be applied to the biomass to rxduce the size, increase the exposed sae area, andr increase the availablity of lignin, celislose, hemice- Inlose, andor oligosaccharides present inthe Biomass to the acid catalyst, 10 the water, and to the water-immiscible ‘onzanie solvent used ia the contacting steps). Energy’ usefl for reducing the size, increasing the exposed surface area, andor increasing the availabilty of lignin, cellulose, hemicellulose, andor oligossecharides present in the ligno- calilosie feedstock elude, but aze not Fimited to, milling, cnishing, grinding, shredding, chopping. cise refining, ltr sound, and mierowave. This application of energy may ooeur before andor during contacting with the water andor ims cible runic solvent, The Fgnocellulosie feedstock may be ‘used directly as obtained from the source or may be dried to reduce the amount of moisture comained therein. "The lignocelilosic fesdstock iscontacted with water inthe presence of an acid catalyst. In one embodiment, an amount ff water is used which is atleast quivalent to that of the lignocelilosie feedstock on a weight basis, Typical, the use ‘of more water provides « mare dite soliton af xylose (Irom hydrolysis ofthe xylan contained in the lignocelulosicbio- sats), which enables a higher overall yield of furfural to be realized. However, minimizing the amount of water used zenenlly improves process economics by reducing process volumes. In practical tes, theamount of water used relative to the lignocellulosic feedstock will depend on the moistire content of the feedstock and on the desied yield of frfural, aswell a the ability to provide sufficient mixing, or intimate contact, for the biomass hydrolysis and furfural production ‘actions to oocur at a practical oe ‘The acid catalyst comprises @ mineral ac, a heteropoly- acid, an omganie acid, or a combination thereat. In one embodiment, the acid catalyst is a mineral acid comprising sulfuric acid, phosphoric acid, hydrochloric acid, or a com- bination of these. In one embodiment, the acid catalyst is a hheteropolyacid comprising, phosphotungstic acid, molyb- sdophosphorie acid, or combination ofthese. In one embed fica, the ack caalyst is a organic acid comprising oxal acid, formie acid, aetie ac, an alkyl sulfone acid, an aryl sulfone aid, a halogenated acetic acid, a halogenated alkyl- sulfone acd, a halogenated aryl sulfonic acid, or acombina- ‘ion ofthese” An example ofa suitable allyl sulfonic acid is ‘ethane sulfonic acid. An example ofa suitable aryl sulfonic acid is toluenesulfoni acid. An example ofa suitable halo- ‘enated acetic acid is triflooracetic acid. An example of a stitable halogenated alkylsulfonie acid is teiluoromethaneUS 8,524,924 B2 5 sulfonic acid, An example of a suitable halogenated aryl sulfone acid is Huorobenzenesulfonic acd. “The acid catalyst catalyzes hydrolysis of the xylan and ‘alucan contained in the biomass to monomeric sugars, and also the conversion of xylose to furfural and glucose t0 hhydroxymethylfurfurl. The concentration ofthe acd e Iystin the aqueons solution is selected to provide acceptable rales of xylanconversion to furfural through the combination ‘of xylan hydrolysis and xylose dehydration) while minimize ing unwanted side reactions. In one embodiment, the acid ‘ealalyst may be combined with a least portion of the water ‘and contacted with the lignocellulosie Feedstock as an aque ‘ous solution, The acid catalyst may be obtained from com- mercial sources or prepared according to known methods ‘Oryanie solvents vseful in the methods described herein ‘are waterimmiscible. A suitable organi solvent or solvent mixture should meet the ertria for an deal solvent for two liguid phase production or recovery of furfural. Specially, the organic solvent composition should i) be substantially immiscible with water or the aqueous phase Gi) have w high parition coefficient (K,,) forthe extraction of furfural have a low partition coeicent for the extraction of S-hy- ‘droxymethylfurural, and (iv) have a low tendency to form ‘emulsions with water or the aqueous phase. In addition, for improved process operability and economics, the organic sl- point suitable for dow: separation of the solvent and the furfural. The boiling point ‘can affect the eost and method of furfural recovery: For ‘example, inthe ease where the Furfural is recovered fom the ‘organic phase by dsilation, the boiling point of the organic solvent should be suiciently higher or ower than the boiling point of furfural so as to enable facile distillation of the furfural from the solvent or distillation of the solvent from sueura ‘Witer-imniscible oganic solvents useful inthe methods “described herein comprise least onealiphatie hydrocarbon, ‘eloalkane, aromatic hydrocarbon, polyether containing fester or ether end groups, plant-derived cil, or mixtures thereo. As sed herein, the term “mixtures thereof” encom- passes oth mixtures withinand mixtures between the solvent ‘lasses, for example mixtures within aliphatic hydrocarbons, and also mixtures between aliphatic hydrocarbons and aro- matic hydrocarbons, for example. “The a east one water-immiscible organi solvent may be ‘one or more aliphatic hydrocarbons, for example an aliphatic hydrocarbon having from 3 to about carbon atoms, o rom 3 to about 8 carbon atoms, for example. The aliphatic hydro- ‘carbon may’ be linear or branched. Optionally, the aliphatic hydrocarbon may be substituted, forexample with atleastone halogen atom. In one embodiment, the organic solvent is an aliphatic hydrocarbon comprising CFCHCH,CHP., (CE,CFCFHICFHCF,, CP CF.CHCI,, or mixtures thereot “The at least one water immiscible organic solvent may be ‘one or more eycloalkanes, for example a cyeloalkane having from 6 to about 8 carbon atoms, The eyeloalkane may be unsubstituted or substituted, for exampie with atleast one halogen atom, In one embodiment, the onganie solvent is a ‘ycloakane comprising cyclohexane, methyleyelohexane, oF mixtures ther ‘The at least one water-immiscible organic solvent may be ‘one or note aromatic hydrocarbons, for example an aromatic hydrocarbon having from 6 to about 8 carbon atoms. The aromatic hydrocarbon may be substituted, for example with alkyl, halogenated alkyl, or halogen suibstitments. In one ‘embodiment, the organic Solvents an aromatic hydrocarbon. ‘comprising heavens, toluene, a xylene, triurotolene, oF mixtuzes there 0 o 6 The a least one waterimmniseible ongatc solvent may be polyether af eulicent molecular weight to be immiscible in Water and containing ester or eer end groups of one (0 six carbon atoms, Polyethers containing ester end groupsmay’be oblained commercially or by reacting polyethers containing ayo end groups with carboxylic acids under appropriate reaction conditions, for example by reseting polyethylene alyenl with acetic anhydride ad pyridine, a reaetion method ‘well knovsn in the at. The ester end groups may be linea or branched and may include, for example, acetate, propionate, or butyrate groups. Polyethers containing ether end groups ‘may be obtained commercially or by reacting polyethers eon- ‘aining hydroxyl end groups with alcohols under appropriate reaction conditions, for example by reacting polyethyleneg- |yool with benzyl iodide and sedium hydride, a methodology Well knowin inthe art (see for example, Theodara W. Greene, Peter G. M. Wuts, Protective Groups i Organic Synthesis Second Edition, John Wiley & Sons lnc, New York 1991). The ether end groups may be linear or brancied and may include, for example, methoxy, ethoxy, propoxy, or Butoxy groups. The polyether may include polyethylene glyeol or polypropylene glycol, forexample.Inone embodiment theat Teast oe walerimmiscible omganic solvent is a polyether ‘comprising polyethylene glycol containing ester or ether end aroups, polypropylene glyco! containing ester or ether end soups, or mixtures thereof ‘The at least one wate-immiseible organic solvent may be at least one plant-derived oil. In one embodiment, the plan Serived oil may comprise one or more fee fatty acids. For example, the plantderived oi may comprise laurie acid, ‘myristie acid, palmitic acid ora combination ofthese. Inone ‘embodiment, the plant-derived oil may comprise one oe more triglycerides, whercin the triglycerides are derived from a fatty acid In one embodiment, the plant-derived oil may comprise \wilyeerides derived from a plant selected from the group consisting of com, pine, rape seod, canola, sunflower ath- ropa, seashore mallow, and combinations of two oF more thereof. Oil frm genetically modified plant varieties may also be used, for example genetically modified high stearic fcidor high laurie acid canola varieties. In one embodiment, the plantlerived oil may be a vegetable ol selected from the aroup consisting of corn cil, coeonst oil, pal kere ol palm oil soybean oil, and cottonseed ol, or mixtures thereof. “Table | shows the fatty acid chain lengths of several rig Iyeeride and fatty aid sourees by weight percent The fatty eid chain lengths in Table | are given using lipid nomencla- tre ofthe form C:D, whore Cis the mamber of earbon atoms in the fatty acid and D isthe numberof double bonds in the fay acid. For example, C18:1 refers to an 18 earbon chain with 1 unsatursted bond, C18:2 refers to an 18 carbon chia ‘with 2 unsaturated bonds, and C18:3 refers to an 18 earboo chain with 3 unsaturated bonds. ln Table 1,C,, refers to fay ‘acids containing greater than 8 carbons. The values in Table {are representativeof the tiglyeeride content of the indicated oils, which ean vary from sample to samp. TABLE L ory Ac Chain La of Tighe ad Tassos waht acamh CosomeOil_PalmKemel Oil Pain Oil_SepteaUS 8,524,924 B2 1 ‘TABLE continued ty Act Chan Leng oF Teenie and som Oi! Pak Ker OH Pan Oil Soph Oi cis 33 ‘ ical a cist cis 2a 3 09 32 cuss a5 Frode - Refined com ol is typically 99% riglyerie, with propor- tions of approximately 65% polyunsaturated fay acid, 33% monounsaturated fatty acid, and 15% saturated fity acid. OF the saturated fatty acids, 80% are palmitic acid (lipid number ‘of C16:0), 149% stearic avid (C180), and 3% arachiic acid (C2020), Over 99% of the monounsaturated fatty acids are ‘oleic seid (C181 €). 98% of the polyunssturated fatty acids fare the omega-6 linoleic acid (CI8:2 n-6 cc) with the 2% remainder being the omegs-3alpat-linlenic cid (C18:3 3 ce). In one embodiment, the at feast one water-immiseible ‘orgie solvent comprises toluene triftuoratoluene, com oil, ‘or mixtures thereof, The at least one watersimumiscible organic solvent is tpi= cally available commercially from various sourees, such as Sigma-Aldrich (St Louis, Mo.) in various grades, many of swhich may be suitable for use in the processes disclosed herein. Technical prides of a solvent can contain a mixture of ‘compourals, including the desired component and higher and Jower molecular weight eomponents of isomers, “The at last one water-immiseible organe solvent can be added with the water of afer addition of the water to the Tignocelfulosie feedstock. In one embodiment, the step of ‘contacting the feedstock with water inthe presence ofan acid catalyst [step (b) of the processes disclosed herein} is per- qormed prio to the step of contacting the mixture formed ia step (b) with at Teast one Waterimmiseible organic solvent 0 orm a mixture comprising an aqueous phase and a furlal- ‘containing organic phase [step (€) ofthe processes disclosed hein ones er () (6) apres ‘The relative amounts of the water (or aqueous acide solu tion) and the organic solvent can vary within suitable range. In one embodiment, the volume mito of water t onganic solvent used to form a mixture comprising an aqueous pase ‘ad furfurl-contsiing organi pase is fom about 95:5 10 about $295. In one embodiment, the volume ratio of water 10 ‘organic solvent is from about 10:1 to about 1:10. In one ‘embodiment, the volume ratio of water to organic solvent is from about 5:1 to about I:S. In one embodiment, the volume ratio of water organic solventis from about 2:1 to about 1:2 The optimal range reflects maximization of the extraction process, for example balancing a relatively high partition ‘coefficient for furlural with an acceptable solvent cost or an scceptable boiling point. For the processes deseribed herein forthe production or recovery of furfural from a Hignocellu- Josic feedstock, the temperature, contacting time, xylan con- teat ofthe lignocelulosie feedstock, furfural concentrations jn the agueous and organic phases, relative amounts of ‘organic solvent and water (or aqueous acidic solution), spe 8 Cie solven() used, presence of ember organic solutes, and presence of agucous solutes are related Uns these varisbles tay be adjusted as necessary within appropriate limits ‘optimize the proces as deseribed hers, Ta the methods descrbod herein, the rato of solid biomass to the sum of the aqueous seid soliton and the organic solvent may’ be from about TI to about 1:250 on a weight basis. When expressed as 8 percentage, the solids loading ‘may peal be from about S040 about 0.4%, for example {rom about 25% to about $e, Useful ranges of solids loading ar dependent on the viseosity ofthe lignocelulosic fee Stock combiaaton with he aid cat water, nd water Jnmiscbie oranie solvent, and may be afte by the type orbiemass used and the parce size, for example. The Bit- ‘mass concentration may be maximized tothe extent possible torminimize the volume ofthe contacting vessel and io make th process more economical. From 2 practical Viewpoint, bh ratios ofthe weight of biomans to the weight of waters ‘waterimmiscible solvent may be limited by the ability t0 provide sllcent mixing, or itimate conte, for eotacting fo occa practical rat Sitable rection conditions wo forma mixture comps an aguonss phase and a firfral-containing organic phase Jnl temperstre of about IMP C. to abo 220° C, for example from about 120° €-10 about 160" C The contacting ofthe Hpocellulsie feedstock with water and at Teast one waterinmiseible orn sovent may be aed out for pri fine ranging Irom about 10 seonds to about 30 hours for example fon $ minutes to about 1S hours. Typically, te contacting may be fom hour to about Shows The contacting ofthe Higocellulosie feedstock with water and at lest one wslernuiscible organic solvent may Be performed ata relatively high temperature fora relatively $host period of time, for example al about 140° Ct aboxt 220°C. for out 180 minutes to bout 10 minutes, For contacting ofthe lignocelilosc feedstock with water an at least one water immiscible organic solvent, the em: Pale contacting tine, ai, acid concentration, mous of ‘ate, ao of water to organic solvent, the biomass concen- tention, the biomass type, the amount of lignin present ad the biomass particle size are related ths, these varables may be adjusted as necesary to produce a two-phase mixture comprising an aqueous phase unl a furual-contiing ‘rune phase at sullen rte and in proctieal maar. “The contacting af the ignoceluosie feedstock with water an atleast one Watereumisible organic solvent may Be performed in any suitable vessel, such a a bath reactor 9 Continous reactor The stable vessel may be equipped with {1 means, such as impellers, for agitating the biomassacid toixture Realor design i discus in Lin, KH and Van Ness, N.C. ia ery, K.H-and Chilton, CH. (eas), Chemical Engineer's Handbook $® Edition’ (1973) Chapter 4 -MeGraw-Hil,N1¥) The contacting stp may be carried out ava ateh proces, as continvous proces In one embod ‘ment, contacting the lanocelllosi Fostock with at least ‘ne water immiseible organic solvent may be performed in the same vesiel ay the contacting wih water and an acid catalyst In one embodiment, contacting the linocello feedstock with water inthe presence ofan aid eatalyst may be performed in one vessel, and the resultant mixture wans- ferredto another vessel for contacting withat least one water immiscible organi solvent. Contacting the ignocelistose feedstock with water and a vwaterimnsible orgnic solvent under suitable reation onions as described herein ahoweprovidesamixtre com prising an aqueous pse and an organic phase. ResidualUS 8,524,924 B2 9 biomass can be present a an adltionl, solid phase. Purfural (FF) preferentially partitions into the orzane phase, deereas- Jing the concentration of furfural inthe aqueous phase. Appro- priate choices of organic solvent and contacting conditions ‘enable compounds such as hydroxymethylfurural to pari tion preferentially into the aqueous phase, which provides furfural in good purity, relatively fre of HME, in the organic phase. In one embodiment, the organic phase further com prises HIME, and the ratio of FF:HMF in the organic phase is atleast 10:1 on a weight basis. In one embodiment, the ratio ‘of FE-HIMF in the organie phase is at least 12:1 on a weight, basis. Such mits of FF to HMF in the onzanie phase, oF higher, are desirable asthe furfural can be recovered from the ‘organic phase selectively and in good purity The furfural-containing organic phase can be separated fom the aqueous phase using methods known in the at, including but not limited to, siphoning, docantation, eontrifi- ‘gation, usinga gravity settler, membrane-asisted phase spit- ting, and the lke: Recovery ofthe furfural from the furfural ‘containing organic phase can be done using methods known, ‘nthe ar, inchuding but not limited to, distillation, adsorption by resins, separation by molecular sieves, pervaporation, and the like. In one embodiment, distillaion may be used to recover the furfral from the furTural-containing organic phase. The organic solvent may he recycled to contact addic Fiona lignoseulosie Feedstock, EXAMPLES “The methods described herein are illustrated inthe follow ing examples, Fromthe abovediscussion and these examples, ‘onestilled in thear can ascertain the essential characte ‘of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications oF the invention Yo adapt ito various uses and conditions ‘The following materials were used in the examples. All ‘commercial reagents were used as received. Sulfuric ack, ‘eyclohexane,teiflorotolvene, and methyl isobutyl Ketone (MIBK) were obtained from Sipma-Aldtich (St.Louis, Mo). ‘Toluene was supplied by EMD (Darmstadt, Germany), Corn cil was purchased from a Toeal grocery. Calum carbonate was obtained from Fisher Scieaifie Fair Lawn, N.1). Dis- tilled water was uilized inal examples. Com cob particles (410/-14 mesh) were purchased from Independence Com Byproducts Co, (Independence, wa). ‘Wheat str and sugarcane bagasse were obtained frm the National Institute of Standards & Technology (Gaithersburg, Mé.). Both were ~201+74 mesh. Poplar sawdust was eol- lected froma local sawmill. Allbiomas feedstocks were used 8 received. ‘The carbolydrate composition of the biomasses was deter- mined accordingto the NREL method NREL/TP-510-42618, “The moisture content ofthe com cob and poplar sawdust was dermined by weighing the biomass before and after drying Jina vacuum oven ovemight at 120° C. The moisture content ‘of the bagasse and wheat straw was measured according (0 NREL/TP-S10-42621. The initial carbohydrate compositions ‘ofthe feedstocks are reported in Table 2, The xylan contents reported as the sum ofthe xylan andl arabinan components. Xylose concentrations ate reported as the sum of xylose and arabinose. 0 o 10 TARL 2 Wheat Sia 1» = 316 Bags & Bi an PoporSewaue a int nr ex(s)," WL ismicro~ Tien(), “mi” is milliliters), “min” is minutes), “a” is grams), “wt” is weight, “wt 9” means weight percent, “RPM is revolutions per minute, “GC” is gs chromerogr- phy "HPLC" s high pressure liquid chromatography, “FF” is {urfural, “HMP" is hydroxymethylfurfural, “Comp.” is Com- patative Example, General Procedure for Examples 1-10 Preparation of furfural from biomass in biphasic (ign! liquid) conditions was conducted in batch mode using the procedure described here. Batch reactions were performs in {4300 mil. mini bench top autoclave reactor emodel 4561, Part Instrument Co., Moline, Ii) with all intemal wetted parts constructed from ZR705. Extemal fitings were constricted ‘with 316 stainless steel. Heat was supplied by an extemal electrical mantle. The reaction mixture was stitred at 300) RPM. Ina typical experiment an aqueous solution containing the mineral seid (3.75 wt % sulfuric seid) was added to the biomass in 100m. beaker. The resulting mixture was thor: ‘oughly mixed with a spatula and transferred to the reactor ‘The specified amount of organic solvent was added and the reactor was scaled and purged with nitrogen prior to beating, Atthe conelusion ofthe reaction the vessel was submerged in ‘an ce bath to rapidly quench the mixture to room temperate (25°C), The contents ofthe reactor were transferred to a lass botle and he organic and aqueous phases were allowed to separate, ‘Samples ofthe aqueous and organic phases were collected and passed through a 0.2 um syringe filter prior analysis “The aqueous phase wos neutralized with calcium carbone and refltered before it was analyzed by high pressure liquid chromatography (HPLC), The HPLC instrument employed was a HP 1100 Series equipped with Agilent 1200 Series refractive index (RD detector and an auto injector (Santa Clara, Calif). The analyteal method was adapted from an NREL procedure (NREL/TP-510-42623). Separation and {quantitation of monomerie sugars (glusose, xylose, andar Dinose), furfural (FP), and hydroxymethylfurfural (HME) in the aqueous layer was performed! by injecting the agueots sample (10 ji.) on to & Bio-Rad HPX.87P (Bio-Rad, Her cules, Cali) column maintained at 85° C, Water was used as ‘he chnant, with a flowrate oF 0.6 ml/min. The restion prod vets in the eluant were identified with the RI detector operat ng at $5° C. Products inthe onzanic layer were analyzed by sas chromatography (GC) using a HP $890 GC instrument (Santa Clara, Calif), The GC eolumn was 30 M DB-17 capillary with 0.320 mm LD. and a 0.25 um film thickness. “Typically, | UL of omganie solution was injected into the GC instrament. The injector and the detector temperature were sot at 280° C. An intemal standard of phenol in eli! acetate ‘was add tothe samples in order to quantity the amounts of FFF and HMF in the sample,US 8,524,924 B2 ul Purfural and hydroxymethylfurfural yields are based on the respective glucan and xylan plusarabinan compositions in the unreacted lignocellulosi biomass. "For the Comparative Examples and Examples 1-8 and 10 the mass of biomass added 1o the reactor was selected to. $ ‘maintain @ maximum xylose concentration in the aqueous phase of less than 6 wt %. ‘Table 3 summarizes the reaction conditions and product _ylelds foe the Comparative Examples and Examples 1-10. ‘Comparative Example A ‘Com Cob Contacted Only with Aqueous Acid A suspension of comm cob ($2.9) in aqueous sulfuric acid (200.0 g 3.75 wi %) was heated in the reactor to 150°C. for 78min. The weaction mixmre was processed and analyzed as described above but with no addition of onganie solvent and no formation of a mixture comprising an aqueous phase and ‘an organi phase, The yield of Furfiral Was 23% and that of HME was 1%, Comparative Example 2 Corn Cob Contacted with Agucous Acidanda 2 ‘Non-Selective Solent A suspension of com cob (3.5 g) in aqueous sulfuric acid (203g, 2.75 we %) and MIBK (141.4 2) was heated in the reactor to 150° C. for 75 min. The reaction mixture was processed and analyzed as deseribed above. The yield of FP ‘a8 61% and that of HIME was 23%. The ratio ot FF to HME in the ganic phase was 2:1 by weight Example 1 s Com Cob Contacted with Aqueous Acid and Toluene (Short Contact Time) A suspension of eom cob (3.3 g) in aqueous sulfuric acid (20.0 g, 3.75 w1 96) and toluene (167.1 g) was heated in the reactor to 150° C. for 79 min. The reaction mixture was processed and analyzed as described above. The yield of FF ‘vas 72%%and that of HMF was 6, The aio of FE to HME ia the organie phase was 24:1 by weight. 6 Example 2 Com Cob Contacted with Aqueous Acid and Toluene (Long Contact Time) % A suspension of com cob (3.1 g) in aqueous sulfuric acid (20.1 g, 3.75 wt %) and toluene (174.2 g) was heated in the Feactor to TS0P C. for 180 min, The reaction mixture was processed and analyzed as deseribed above. The yield of FP ‘was 67% and that of HMF was 3%, The ratio of FF to HME the oman phase was 42:1 by weight Example 3 o Comm Cob Contacted with Aqueous Acid and “Triftorotoluene [A suspension of eom cob (3.3) in aqueous sulfuric acid (19.9 g, 3.75 w1%) and wifluorotoluene (2349 g) ws heated 150°C. for 74 min, Theresction mixture as ‘analyze as described above, The yield of FF 12 was 69% and that of HME was 7%, The ratio of FF to HME the onze phase was 25:1 by weight. Example 4 ‘Com Cob Contacted with Aqueous Acid and Cyclohexane A suspension of eon cob (2.9 g) in aqueous sulfrie acid (20.1 g, 3.75 wt %) and cyclohexane (150.4 g) was heated in the reactor to 150° C. for 79 mi, The reaction mixture was processed and analyzed as deseribed above. The yield of FE ‘Was 62% and that of HMP was 2%, HIME was not detected ia the organi phase. Example 5 ‘Wheat Straw Contated with Aqueous Acid and “Toluene A suspension of wheat stanv (5.0 g) in aqueous sulfuric acid (20.2, 3.75 wi %) and toluene (150.4 g) was heated in the reactor to 150° C. for 79 min. The reaction mixture was processed and analyzed as deseribed above. The yield of FE ‘Was 66% and that of HIME was 2%, The iio of FE vo HME ia ‘the organi phase was 27:1 by weight. Example 6 agnsse Contacted with Aqueous Acid and Toluene A suspension of bagasse (4.9 g) in aqueous sulfuric acid (20.1 g, 3.75 wt %) and toluene (177.0 g) was heated in the reactor (© 150° C, for 75 min, The reaction mixture was processed and analyzed as deseribed above. The yield of FF ‘was 72% nd tha of IMF was 5%, The ratio of FF to HME in the organi phase was 29:1 by weight. Example 7 Poplar Sawdust Comtacted with Aqueous Acid and Toluene A saspension of poplar sawdust (9.8g) in aqueous sulfuric acid (20.0 , 3.75 WY) and lolwene (163.6 g) was heated in the reactor to 150° C. for 75 min. The reaction mixture was processed and analyzed as described above. The yield of FF ‘was 57% and that of IMP was 2%, HIME was not detects in the organi phase, Example 8 Corn Cob Contacted with Aqueous Acid and Toluene {Low Xylose Concentration) In this Example, the mass of biomass ade tothe reactor was selected to maintain a maximum xylose concentration ia the aqueois phase of ess than 0.5. %.A suspension of com cob (0.3 g) in aqueous sulfuric acid (22.3 g, 3.75 wt %) and toluene (165.52) was heated in the reactor 150° C. for 100 The reaction mixture was processed and analyzed asUS 8,524,924 B2 13 described above, The yield of FF was 91% and that of HMF was 2% FIMF was not deteeted inthe organic phase, xamples 9A, 9B, and 9C Com Cob Contacted with Aqueous Acid and Toluene (igh Xylose Concentration) A series of three experiments were perfomied to vary the reaction time at 150° C. The mass of biomass added to the reactor was selected to maintain a maximum xylose eoncen- tration inthe agucous phase of less than 46 wt Toluene was used as the organic phase. Results are presented in Table 3. ‘9A: A suspension of com cab (6.0 g) ia aquocts sulfuric acid (6.2g, 3.75 wt) and toluene (170.6 g) was heated inthe reactor 10 150° C. for 48 min. The reaction mixture was processed and analyzed as deeribod above. The yield of FP ‘a8 68% an that of HME was 8%, The ratio of FF to HMF in the organi phase was 16:1 by Weight, ‘9B: A suspension of com eob (6.0 ) in aqueous sulfuric ‘acid (5.9 g, 3.75 WI) and toluene (169.4 g) Was heated inthe rangle Bim Organi Soak comp Comces—NBK S$ WhewStaw abene $e Bate & Cameat Take 5B Cameos Take Bale bs 5 t 7 ° ° 14 reactor to 150° C, for 76 min, The reaction mixture was processed and analyzed as deseribed above. The yield of FF ‘Was 69% and that of IMF was 13%, The ratio of FF to HME Jn the organic phase was 12:1 by weight 9C: A suspension of com cab (5.3 g) in aqueous sulfuric acid (54g, 3.75 w1%) and toluene (167 0g) washeated inthe reactor to 150° C. for 144 min, The reaction mixture was processed and analyzed as deseribed above. The yield of FE ‘Was 69% and that of IMF was 13%, The ratio of PF to HIME inthe organic phase was 15:1 by weight Example 10 Com Cob Contacted with Aqueous Acid and Com, Oil A suspension of com cob (3.5 g) in aqueous sulfuric acid (202g. 3.75 w1%) and com ol (1703 g) was heated inthe reactor to 150° C, for 75 min, The reaetion mixture was processed and analyzed as described above. The yield of FE ‘was 56% and that of IMF was 2%. The ratio of FF to HME in the organic phase was 43:1 by weight. TABLE 3 Comet Sule Acid lomast Omasic FFORG FFAQ Time(oun)—Sohien fs) isle) PS) 8 30S tw) 100 23. 03 163 2 %6 ee Yet MASS RATIO RG HMEAQ EMETOTAL FF MF INORGANIC Pal Bal AQORG AQOKG PHASE 3 oa 2 fas ‘Sage ong panto pat pe wa Ain el ton ae pF TOTAL Fragons rotor orc hn hi HM AD th fi eld lone ge psn OE TOTAL he HO A086 a oD re es nr en "AIIM wnt tbr FORME incom ied et eaeUS 8,524,924 B2 15, The data in Table 3 demonstrate that by starting from 3 lignocellulosic feedstock comprising both glucan and xylan ‘and using a water-immiseible organic solvent of the Examples under the indicated reaction conditions, farfiral ‘can be obtained relatively fee of HMF inthe organic phase, ‘despite the formation of FIMP from the biomass, Purfiral to HMF ratios ona weight basi reat least 12:1,or higher, inthe Examples. In contrast, use of # non-selective organic solvent such ak MIBK does no provide furfural in high selectivity in the onzanic phase as shown by the FF:HMF mass ratio of 2-1 Jor Comparative Example B. ‘What is claimed is 1. A process for the selective production of furiral, the process comprising the steps of 8) providinga lignocellulosic feedstock comprising gean ‘and xylan: ‘contacting the feedstock with water in the presence ofan acid catalyst to foom a mixture; «© contacting the mixture fomed in stepb)withat Ieastone ‘Water immiscible onzanie solvent in a reactor ad heal- ‘ng toa temperature fom about 100° Co about 220°C. to form a mixture comprising an aqueous phase and & furfural-containing onganie phase, ‘wherein the organic solvent and water are present in a ‘weight ratio in the mage of 77:1 to 32.1:1, Wherein the onzanie phase further comprises S-hy- slroxymethyl-2-furfural, and the weight ratio of R= furl to S-hydroxymethy1-2-furfural ia the omganic hase isa least 10:1 or higher, and wherein the waterimmiseible onganie solvent com prises least one aliphatic hydrocarbon, eyeoalkane, Aromatic hydrocarbon, polyether containing ester oF ccther ead groups, plantalerived il, or mixtures thereof: and «) recovering furfural frm the organic phase. 2. The process of claim 1, wherein step b) is performed prior o step e) ‘3. The process of claim 1, wheeoin steps b) and e) are performed concurrently. 16 4. The process of claim 1, wherein the acid catalyst com= prises a mineral acid, heteropolyacid, an organie acid ora ‘combination thereof. '. The process of claim 4, wherein the acid catalyst is a ‘mineral seid comprising, slfric acid, phosphoric ai hydrochloric acid, ora combination of these ‘6. The process of claim 4, wherein the acid catalyst is 3 heteropolyacid comprising. phosphotungstic acid, motyb- \dophosphorie aed, oF combination ofthese, 71 Te process of claim 4, wherein the acid catalyst is an ‘organic acd comprising oxaie seid, formic seid, acetic aid an alkyl sulfonic acid, an aryl sulfonic acid, a halogenated acetic acd, a halogenated alkylsulfonic acid, a halogenated ary sulfonic acid, or combination of these '8, The process of claim 1, wherein the a least one water- immiscible organic solvent san aliphati hydrocarbon com prising CF,CH.CH.CHF,, CF,CF,CFHCFHCE,, CE{CE,CHCI, or mixtures theteof. 9. The proogss of claim 1, wherein the a least one water- immiscible organic solvent #8 a cycloalkane comprising cyclohexane, methyleyelohexane, or mixtures threo 10, The process of claim 1, wherein the atleast one water- ‘mmseible organic solvent sn aromatic hydrocarbon com- Prkng benzene, theme,» xylene tools oF mix res thereof 11, The process of claim 1, wherein the at least one water immiscible organic solvent isa polyether comprising poly~ ethylene glycol containing esteror ether end groups, polypro- pylene glycol containing ester or ether end groups, oF ‘tures thereo. 12, The process of claim 1, wherein thea least one water mmiscible onyanie solvent is a plant-derived oil selected rom the group consisting feornoil coconut oil palmkemel cil, palm oil, soybean oil, and cottonseed oil, or mixtures thereo 13, The process of claim 1, wherein the at least one water- immiscible oganic solvent comprises toluene triflurotoh- ene, com ol, or mixtnes there 14. The process of claim 1, wherein the step of recovering furfural is by distiation,