MAIMOTOMONTANT US009873836B2 HIU MIU MIU MIUI (12 ) United States Patent (10 ) Patent No. : US 9 ,873 , 836 B2 Blommel et al. (45 ) Date of Patent: * Jan . 23, 2018 ( 54 ) PROCESS FOR CONVERTING BIOMASS TO ( 2013 .01 ) ; C12P 7 /02 (2013 . 01 ) ; C12P 7/ 10 AROMATIC HYDROCARBONS (2013 .01 ) ; C12P 7/ 40 (2013 . 01 ) ; CIOG 2300 / 1011 ( 2013 .01 ); CIOG 2300 / 1025 (71 ) Applicant: Virent , Inc. , Madison , WI (US ) ( 2013 .01 ); C10G 2400 / 30 (2013 .01 ); YO2E (72 ) Inventors : Paul Blommel, Oregon , WI (US ) ; 50 / 16 (2013 . 01 ) ; YO2P 30 /20 (2015 . 11 ) Andrew Held , Madison , WI (US ) ; ( 58 ) Field of Classification Search Ralph Goodwin , Madison , WI (US ) ; None Randy Cortright, Madison , WI (US ) See application file for complete search history. (73 ) Assignee : Virent , Inc. , Madison , WI (US ) (56 ) References Cited ( * ) Notice : Subject to any disclaimer, the term of this U .S . PATENT DOCUMENTS patent is extended or adjusted under 35 3 ,702 ,886 A 11 / 1972 Argauer et al . U . S . C . 154 ( b ) by 0 days . 3 ,709 , 979 A 1 / 1973 Chu This patent is subject to a terminal dis (Continued ) claimer . FOREIGN PATENT DOCUMENTS (21 ) Appl. No. : 14 /285 , 158 GB 1446522 8 / 1976 (22 ) Filed: May 22, 2014 GB 1526461 9 /1978 (Continued ) (65 ) Prior Publication Data US 2014 /0349361 A1 Nov. 27 , 2014 OTHER PUBLICATIONS Related U .S . Application Data International Search Report and Written Opinion for PCT/ US2014 / (60 ) Provisional application No .61 /826 , 358 , filed on May 039154 dated Aug. 27 , 2014 . 22 , 2013 (Continued ) (51 ) Int . Cl. Primary Examiner — Philip Louie CO7C 1/ 20 ( 2006 .01 ) ( 74 ) Attorney, Agent, or Firm — Quarles & Brady LLP C10G 3 / 00 ( 2006 .01 ) C10G 1 / 00 ( 2006 .01 ) (57 ) ABSTRACT C12P 5700 ( 2006 .01 ) The present invention provides methods, reactor systems , C12F 3 /02 ( 2006 . 01 ) and catalysts for increasing the yield of aromatic hydrocar C12P 7 /02 ( 2006 .01 ) bons produced while converting biomass to hydrocarbons . (Continued ) The invention includes methods of using catalysts to (52 ) U . S . CI. increase the yield of benzene, toluene , and mixed xylenes in ??? CI0G 1 / 002 (2013 .01 ) ; C10G 1 /00 the hydrocarbon product. (2013 . 01 ) ; C10G 3 /42 (2013 .01 ); CIOG 3 /49 (2013 .01 ) ; C12F 3 /02 (2013 . 01 ); C12P 5 /005 20 Claims, 11 Drawing Sheets

-- -Feed 100 HONE102 104 106 BTX 100 Raw feedstock processing 102 Conversion 104 Conditioning 106 Condensation US 9, 873 ,836 B2 Page 2

(51 ) Int. Ci. 2010 / 0077655 A1 * 4 / 2010 Bauldreay ...... CIOL 1 /04 C12P 7 / 10 ( 2006 .01 ) 44 /437 2010 /0197959 A1 * 8 / 2010 Johnston ...... C07C 67/ 00 C12P 7 / 40 ( 2006 . 01 ) 560 / 265 2011/ 0294163 Al* 12/ 2011 Li ...... C12P 7 / 10 (56 ) References Cited 435 / 72 2012 / 0035390 A1 * 2 / 2012 Gadewar ...... B01D 3 /001 U . S . PATENT DOCUMENTS 560 / 239 3 , 832 ,449 A 8 / 1974 Rosinski et al. 3 , 894 , 103 A 7 / 1975 Chang FOREIGN PATENT DOCUMENTS 3 . 894 . 104 A 7 / 1975 Chang 3 , 894 , 105 A 7 / 1975 Chang 50 -076027 6 / 1975 3 , 894 , 106 A 7 / 1975 Chang JP 52 - 008005 1 / 1977 3 , 907 ,915 A 9 / 1975 Chang JP 57 - 102835 6 / 1982 3 , 998, 898 A 12/ 1976 Chang WO 2010065643 A2 6 /2010 4 ,016 ,245 A 4 / 1977 Plank et al. WO 2012162403 Al 11 /2012 4 ,039 ,600 A 8 / 1977 Chang 4 ,076 , 761 A 2 / 1978 Chang 4 ,076 , 842 A 2 / 1978 Plank et al. OTHER PUBLICATIONS 4 , 107, 195 A 8 / 1978 Rollmann 4 , 139 ,600 A 2 / 1979 Rollmann et al. Chen , N . Y . et al . “ Liquid fuel from carbohydrates .” Chemtech 16 . 8 4 , 359 , 587 A 11 / 1982 Abdurakhmanov ( 1986 ) : 506 -511 . 4 , 375 ,573 A 3 / 1983 Young Zhang , Huiyan , et al. “ Catalytic conversion of biomass -derived 5 ,019 ,663 A 5 / 1991 Chou et al. feedstocks into olefins and aromatics with ZSM - 5 : the hydrogen to 7 , 022 , 888 B2 4 / 2006 Choudhary et al. 7 ,767 , 867 B2 8/ 2010 Cortright carbon effective ratio .” Energy & Environmental Science 4 . 6 7 , 898, 664 B2 3 / 2011 Cortright ( 2011 ) : 2297 - 2307 . 7 , 977 , 517 B2 7 / 2011 Cortright et al . Fuhse , Jürgen et al . “ Conversion of organic oxygen compounds and 8 ,053 ,615 B2 11 / 2011 Cortright et al. their mixtures on H - ZSM - 5 .” Chemical engineering & technology 8 , 153 , 850 B2 4 /2012 Hall et al . 10 . 1 ( 1987 ) : 323 - 329 . 2007 /0244208 A1 * 10 / 2007 Shulenberger ...... C01B 3 / 34 Chen , N . Y ., et al . “ Fluidized -bed upgrading of wood pyrolysis 518 /726 liquids and related compounds .” 1988 . 277 - 289 . 2009/ 0287019 Al* 11/ 2009 Hazin ...... B01J 23 /002 562 /598 * cited by examiner U . S . Patent Jan . 23, 2018 Sheet 1 of 11 US 9 ,873 ,836 B2

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° • ------.. . . … ...... ------0. 5 1152. H : caff ratio US 9 ,873 ,836 B2 2 PROCESS FOR CONVERTING BIOMASS TO AROMATIC HYDROCARBONS H - 20 ( equation 1) H : Ceff = - CROSS -REFERENCE TO RELATED APPLICATIONS 5 where H represents the number of hydrogen atoms, O represents the number of oxygen atoms, and C represents the This application claims benefit of U . S . Provisional Appli number of carbon atoms. The H :Ce ratio applies both to cation Ser. No . 61/ 826 , 358 filed on May 22 , 2013 , which is individual components and to mixtures of components , but incorporated by reference herein in its entirety . 10 is not valid for components which contain atoms other than TECHNICAL FIELD carbon , hydrogen , and oxygen . For mixtures , the C , H , and O are summed over all components exclusive of water and The present invention is directed to processes and systems molecular hydrogen . The term “ hydrogen ” refers to any for producing aromatic hydrocarbons at increased yields, hydrogen atom while the term “ molecular hydrogen ” is including benzene, toluene , xylenes (dimethylbenzenes ), 15 limited to diatomic hydrogen , Hz. ethylbenzene , paraxylene , metaxylene, orthoxylene and Zhang et al. studied the impact of the H : Ceff ratio on the other C , aromatics . conversion of various biomass -derived oxygenated hydro carbons to coke , olefins and aromatics using a ZSM - 5 BACKGROUND OF THE INVENTION catalyst ( Zhang et al. , Catalytic conversion of biomass 20 derived feedstocks into olefins and aromatics with ZSM - 5 : Aromatic hydrocarbons , notably benzene , toluene, and the hydrogen to carbon effective ratio , Energy Environ . Sci. , xylenes are important industrial commodities used to pro - 2011, 4 , 2297) . Zhang reported that biomass -derived feed duce numerous chemicals , fibers , plastics , and polymers , stocks having H : Ceff ratios of between 0 and 0 . 3 produced including styrene , phenol, aniline , polyester, and nylon . high levels of coke , making it non - economical to convert Typically , such aromatic hydrocarbons are produced from 25 such feedstocks to aromatics and chemicals . However, by petroleum feedstocks using well - established refining or hydroprocessing the feedstock to add hydrogen , Zhang was chemical processes. More recently , there is a growing inter- able to produce aromatics and olefins using a ZSM - 5 cata est in providing aromatic hydrocarbons from alternative lyst at yields 2 to 3 times higher than a process without resources , such as biomass, synthesis gases and natural gas . hydrogenation . Specifically , Zhang reported that the aro One type of alternative resource is plant biomass . Plant 30 matic and olefin yields increased from 12 % to 24 % and 15 % biomass is the most abundant source of carbohydrate in the to 56 % , respectively , with increasing H : Ce ratio . The ratio world due to the lignocellulosic materials composing the cell of olefins to aromatics also increased with increasing H :Cell walls in higher plants . Plant cell walls are divided into two ratio , with the olefin yield higher than the yield of aromatics sections , primary cell walls and secondary cell walls . The for all feedstocks . It was also reported that there is an primary cell wall provides structure for expanding cells and 35 inflection point at a H : Ceff ratio of 1 . 2 , where the aromatic is composed of three major polysaccharides ( cellulose , pec - and olefin yield does not increase further , indicating that at tin , and hemicellulose ) and one group of glycoproteins. The most the yield of high value aromatic chemicals , such as secondary cell wall, which is produced after the cell has benzene , toluene , and xylenes (BTX ) , may be limited to finished growing , also contains polysaccharides and is 24 % when using zeolite catalysts according to the Zhang strengthened through polymeric lignin covalently cross- 40 process. linked to hemicellulose. In another study by Fuhse and Bandermann , the research The resulting composition of the biomass provides ers studied the conversion of a number of different types of roughly 40 - 50 % cellulose , 20 - 25 % hemicellulose , and oxygenates over a ZSM - 5 catalyst to aromatic hydrocarbons 25 -35 % lignin , by weightpercent . Cellulose is typically the (Fuhse and Bandermann , Conversion of Organic Oxygen primary sugar source for bioconversion processes and 45 Compounds and their Mixtures on H - ZSM - 5 , Chem . Eng. includes high molecular weight polymers formed of tightly Technol. , 1987 , 10 , 323 - 329 ) . The researchers reported linked glucose monomers . Hemicellulose is generally con oxygenates having H : Ceff ratios less than 1 . 6 cause the sidered a secondary sugar source and includes shorter poly - problem of coking , decreasing the catalyst' s lifetime, but mers formed of various sugars . Lignin includes phenylpro - also that conversion of carboxylic acids and esters cannot be panoic acid moieties polymerized in a complex three - 50 explained solely by the H :Ceff ratio because these types of dimensional structure and is often viewed as a waste reactants undergo the side reactions of decarbonylation , material or byproduct useful for other processes. Collec - decarboxylation , and ester pyrolysis . For example , the tively, the components of cellulose , hemicellulose , and researchers reported that the reaction of acetic acid yields lignin are often referred to as oxygenated hydrocarbons. only acetone and CO2 . Moreover, when the researchers Heterogeneous catalysts have shown great promise for 55 investigated mixtures , the researchers stated that the con converting oxygenated hydrocarbons into fuels and chemi version of mixtures to products depends on the individual cals. The main challenge is how to obtain high yields of components . select hydrocarbons while minimizing coke formation and As a result , there exists a need for methods and systems catalyst deactivation . to effectively and efficiently convert biomass - derived feed Chen et al. developed the hydrogen to carbon effective 60 stocks to aromatic hydrocarbons . ( “ H : C ) ratio as a tool to assist in determining the suit ability of oxygenated hydrocarbon feedstocks for catalytic SUMMARY OF THE INVENTION conversion to hydrocarbons using zeolite catalysts ( N . Y . Chen , J. T. F. Degnan and L . R . Koeing, Chem . Tech . 1986 , The invention is generally directed to making aromatic 16 , 506 ). The H :Ceff ratio is based on the amount of carbon , 65 hydrocarbons by conditioning a feedstock to provide an oxygen and hydrogen in the feed , and is calculated as oxygenate mixture having a H :Cofratio between 0 .8 and 1 . 8 . follows: One aspect of the invention is a method for producing US 9 ,873 ,836 B2 aromatic hydrocarbons, the method comprising : ( a ) process . The hydrogenation catalyst may further comprise a member ing a raw feedstock to form an intermediate feedstock ; (b ) selected from the group consisting of Ag, Au , Cr, Zn , Mn , converting the intermediate feedstock to a feedstock stream Mg, Ca, Cr, Sn , Bi, Mo, W , B , P , alloys thereof , and a comprising an alcohol, a carboxylic acid , or combinations combination thereof . In certain embodiments , the condition thereof; ( C ) conditioning the feedstock stream to provide an 5 ing catalyst is a dehydrogenation catalyst and ( i ) the condi oxygenate mixture having a H :Ce ratio of between 0 . 8 and tioning temperature is between about 80° C . and 500° C .; ( ii ) 1 . 8 ; and ( d ) exposing the oxygenate mixture to a conden - the conditioning pressure ranges from atmospheric pressure sation catalyst to produce aromatic hydrocarbons . to about 1000 psig ; or both ( i ) and ( ii ) . In other embodi In certain embodiments , the intermediate feedstock com - ments , the conditioning catalyst is a hydrogenation catalyst prises oxygenated hydrocarbons, alkanes, alkenes , CO , mol- 10 and (i ) the conditioning temperature is in the range of about ecules, hydrogen , or combinations thereof. In certain 80° C . to 350° C .; ( ii ) the conditioning pressure is in the embodiments, the converting step ( b ) comprises fermenta range of about 50 psig to 5000 psig ; or both ( i) and ( ii ). tion , hydrogenolysis , hydrolysis , pyrolysis , aqueous phase In certain embodiments , the condensation catalyst is a reforming, alcohol synthesis, Fisher - Tropsch synthesis , zeolite . In particular embodiments , the condensation catalyst steam reforming , partial oxidation , hydroformylation , car- 15 is ( i ) a ZSM - 5 catalyst; ( ii ) modified by a material selected bonylation , or combinations thereof. In a particular embodi from the group consisting of phosphorous, gallium , zinc , ment, step (b ) comprises the steps of: fermenting the inter - nickel , tungsten , and mixtures thereof ; ( iii ) contained within mediate feedstock with one or more species of a binder selected from the group consisting of clay, alumina , microorganism to form a fermentation broth comprising silica, silica -alumina , titania , zirconia , aluminum phosphate , alcohols or carboxylic acids ; removing the alcohols or 20 and mixtures thereof; or any combination of ( i ) , ( ii ) , and carboxylic acids from the fermentation broth to provide the ( iii ) . In certain embodiments ( i ) the condensation tempera feedstock stream , and purifying the feedstock stream prior to ture is between about 250° C . and 550° C . ; ( ii ) the conden exposing the oxygenate mixture to the conditioning catalyst . sation pressure ranges from less than atmospheric pressure In certain embodiments , the raw feedstock is biomass , to about 1000 psig ; or both (i ) and ( ii ) . natural gas , coal, or petroleum . In certain embodiments , the 25 In certain embodiments , greater than 40 % , or greater than processing step ( a ) comprises sugar processing , biomass 45 % , or greater than 50 % , or greater than 60 % , of the carbon deconstruction , gasification , pyrolysis , combustion , lique in the feedstock stream is contained in the aromatic hydro faction , steam reforming , cracking , partial oxidation , or carbons. In particular embodiments , the aromatic hydrocar combinations thereof. bons are selected from the group consisting of benzene , In certain embodiments , the alcohol is selected from the 30 toluene, orthoxylene, metaxylene , paraxylene, ethylbenzen , group consisting of a primary alcohol, a secondary alcohol, C , aromatics , and combinations thereof . a polyhydric alcohol, and combinations thereof. In particular One aspect of the invention is that a portion of the embodiments , the alcohol may be selected from the group feedstock stream is less than 100 years old as calculated consisting of methanol, ethanol, n - propanol, iso - propanol, from the carbon 14 concentration of the feedstock stream . n - butanol, 2 -butanol , isobutanol, n - pentanol, n -hexanol , eth - 35 In certain embodiments , the oxygenate mixture comprises ylene glycol, propylene glycol, glycerol, erythritol , threitol, two or more members selected from the group consisting of sugar alcohols , and combinations thereof. an alcohol, a carboxylic acid , an ester , a ketone , and an In certain embodiments , the carboxylic acid is selected aldehyde . from the group consisting of mono - carboxylic acid , di- In certain embodiments , hydrogen is produced by step ( a ) , carboxylic acid , hydroxycarboxylic acid , and combinations 40 step ( b ), step ( c ), step ( d ) , or combinations thereof . In thereof. In particular embodiments , the carboxylic acid is particular embodiments , hydrogen is produced by exposing selected from the group consisting of formic acid , acetic the feedstock stream to the conditioning catalyst at the acid , propionic acid , butyric acid , isobutyric acid , valeric conditioning temperature and the conditioning pressure . The acid , isovaleric acid , caproic acid , oxalic acid , malonic acid , method may also further comprise the step of recovering the succinic acid , glutaric acid , adipic acid , glycolic acid , acrylic 45 hydrogen and processing the hydrogen to provide a hydro acid , lactic acid , pyruvic acid , maleic acid , fumaric acid , gen stream having a hydrogen concentration of greater than glutaconic acid ,muconic acid , citric acid , and combinations 90 mol % . The method may also further comprise the step thereof. of recovering the hydrogen and processing the hydrogen to In certain embodiments , the conditioning step ( c ) com provide a hydrogen stream having a hydrogen concentration prises exposing the feedstock stream to a conditioning 50 of greater than 90 mol % . catalyst at a conditioning temperature and a conditioning In certain embodiments , CO , molecules are produced by pressure to produce the oxygenate mixture . In particular s tep ( a ) , step ( b ) , step ( c ) , step ( d ) , or combinations thereof. embodiments , the conditioning catalyst is ( i ) a dehydroge - In particular embodiments , the fermenting of the interme nation catalyst comprising a support and a metal selected diate feedstock produces CO , and the CO , is recovered to from the group consisting of Cu , Ru , Ag , CuCr, CuZn , Co , 55 provide a CO2 stream having a CO2 concentration of greater alloys thereof , and combinations thereof; or ( ii ) a hydroge than 50 % . In other embodiments , a hydrogen stream is nation catalyst comprising a support and a member selected combined with COx molecules to produce hydrocarbons , from the group consisting of Fe , Ru , Co , Pt, Pd , Ni, Re, Cu , alcohols , carboxylic acids, or combinations thereof. In par alloys thereof, and a combination thereof. The dehydroge - ticular embodiments , a hydrogen stream is combined with nation catalyst support may also comprise a material 60 CO , molecules to produce methane , methanol, ethanol, or selected from the group consisting of alumina , silica , silica - combinations thereof . In other embodiments , a hydrogen alumina , titania , carbon , zirconia , zinc aluminate , and mix - stream is combined with the CO2 stream produced by the tures thereof. The hydrogenation catalyst supportmay also fermenting of the intermediate feedstock to produce hydro comprise a member selected from group consisting of a carbons, alcohols , carboxylic acids, or combinations thereof. carbon , silica , alumina , zirconia , titania , vanadia , ceria , 65 In other embodiments , a hydrogen stream is combined with silica - aluminate , zeolite , kieselguhr , hydroxyapatite , zinc the CO , stream produced by the fermenting of the interme oxide , magnesium oxide , chromia , and mixtures thereof. diate feedstock to produce methane , methanol, ethanol, or US 9 ,873 ,836 B2 6 combinations thereof. In other embodiments , a hydrogen lyst at a condensation pressure ranging from less than stream is combined with the CO , molecules to produce atmospheric pressure to about 1000 psig and a condensation methane and wherein a portion of the conditioning heat temperature of between about 250° C . and 550° C . to requirement is provided by the methane -producing reaction produce aromatic hydrocarbons . In other embodiments , a hydrogen stream is combined with 5 Another aspect of the invention is a method for producing the CO , stream produced by the fermenting of the biomass derived feedstock to produce methane and wherein a portion biomass - derived aromatic hydrocarbons, the method com of the conditioning heat requirement is provided by the prising : ( a ) processing a first biomass to form a first bio methane - producing reaction . mass -derived feedstock , and fermenting the first biomass In certain embodiments , hydrocarbons are produced by 10 derived feedstock with one or more species of step ( a ), step ( b ) , step ( c ) , step ( d ) , or combinations thereof. microorganism to form a fermentation broth comprising In certain embodiments , an oxygen stream is combined with carboxylic acids ; and removing the carboxylic acids from the hydrocarbons to produce alcohols , carboxylic acids , or the fermentation broth to provide a first feedstock stream combinations thereof . In particular embodiments , an oxygen comprising one or more of a mono - carboxylic acid , a stream is combined with the hydrocarbons to produce 15 di - carboxylic acid , formic acid , acetic acid , propionic acid , methanol, ethanol, or combinations thereof. butyric acid , isobutyric acid , valeric acid , isovaleric acid , In certain embodiments , a portion of the conditioning heat caproic acid , oxalic acid , malonic acid , succinic acid , glu requirement is provided by heat generated in step ( d ) . taric acid , adipic acid , glycolic acid , acrylic acid , lactic acid , Another aspect of the invention is a method for producing pyruvic acid , maleic acid , fumaric acid , glutaconic acid , biomass- derived aromatic hydrocarbons, the method com - 20 muconic acid , itaconic acid , or citric acid ; (b ) processing a prising : (a ) processing biomass to form a biomass -derived second biomass to form a second biomass -derived feed feedstock ; ( b ) converting the biomass -derived feedstock to a stock , and fermenting the second biomass- derived feedstock feedstock stream comprising an alcohol or carboxylic acid ; with one or more species of microorganism to form a ( c ) conditioning the feedstock stream to provide an oxygen - fermentation broth comprising alcohols ; and removing the ate mixture having an H : Ceff ratio of between 0 . 8 and 1 . 8 ; 25 alcohols from the fermentation broth to provide a second and ( d ) exposing the oxygenate mixture to a condensation feedstock stream comprising one or more of a primary catalyst at a condensation pressure and a condensation alcohol, methanol, ethanol, n -propanol , iso -propanol , n -bu temperature to produce aromatic hydrocarbons . tanol, 2 -butanol , isobutanol, n - pentanol, n -hexanol , ethylene Another aspect of the invention is a method for producing glycol, propylene glycol, glycerol, erythritol, threitol and biomass -derived aromatic hydrocarbons, the method com - 30 sugar alcohols ; ( c ) combining a portion of the first feedstock prising : ( a ) processing biomass to form a biomass -derived stream with a portion of the second feedstock stream to feedstock ; ( b ) fermenting the biomass - derived feedstock provide an oxygenate mixture having an H :Ce ratio of with one or more species of microorganism to form a between 0 . 8 and 1 . 8 ; and ( d ) exposing the oxygenate mix fermentation broth comprising alcohols ; ( c ) removing the ture to a condensation catalyst at a condensation pressure alcohols from the fermentation broth to provide a feedstock 35 ranging from less than atmospheric pressure to about 1000 stream comprising one or more of a primary alcohol, metha - psig and a condensation temperature of between about 250° nol, ethanol, n - propanol, iso -propanol , n -butanol , 2 -butanol , C . and 550° C . to produce aromatic hydrocarbons . isobutanol, n - pentanol, n -hexanol , ethylene glycol , propyl ene glycol, glycerol, erythritol, threitol and sugar alcohols ; DESCRIPTION OF THE DRAWINGS ( d ) exposing the feedstock stream to a dehydrogenation 40 catalyst at a dehydrogenation temperature and a dehydro - FIG . 1 is a schematic diagram of one embodiment of the genation pressure to produce diatomic hydrogen and an present invention . oxygenate mixture having an H : C ratio of between 0 . 8 and FIG . 2 is a schematic diagram of one embodiment of the 1 .8 ; and (e ) exposing the oxygenate mixture to a condensa present invention including an integrated aromatics com tion catalyst at a condensation pressure ranging from less 45 plex . than atmospheric pressure to about 1000 psig and a conden - FIG . 3 is a schematic diagram of one embodiment of the sation temperature of between about 250° C . and 550° C . to present invention including a CO , recovery andmethanation produce aromatic hydrocarbons . system for providing process heat to offset temperature Another aspect of the invention is a method for producing reduction in the conditioning step . biomass - derived aromatic hydrocarbons, the method com - 50 FIG . 4 is a schematic diagram of one embodiment of the prising : (a ) processing biomass to form a biomass - derived present invention wherein heat from the condensation step is feedstock ; (b ) fermenting the biomass -derived feedstock captured and used to provide process heat to offset tempera with one or more species of microorganism to form a ture reduction in the conditioning step . fermentation broth comprising carboxylic acids ; ( c ) remov - FIG . 5 is a schematic diagram of one embodiment of the ing the carboxylic acids from the fermentation broth to 55 present invention including a H , recovery system . provide a feedstock stream comprising one or more of a FIG . 6 is an alternative embodiment illustrating a con mono -carboxylic acid , a di- carboxylic acid , formic acid , figuration employing hydrogen capture and multiple reac acetic acid , propionic acid , butyric acid , isobutyric acid , tors for the conditioning step of the present invention . valeric acid , isovaleric acid , caproic acid , oxalic acid , FIG . 7 is an illustration of the chemistry involved in one malonic acid , succinic acid , glutaric acid , adipic acid , gly - 60 aspect of the present invention involving lactic acid as one colic acid , acrylic acid , lactic acid , pyruvic acid , maleic acid , component of the feedstock stream . fumaric acid , glutaconic acid , muconic acid , itaconic acid , or FIG . 8 is an illustration of the chemistry involved in one citric acid ; ( d ) exposing the feedstock stream to hydrogen aspect of the present invention using acetic acid as one and a hydrogenation catalyst at a hydrogenation temperature component of the feedstock stream . and a hydrogenation pressure to produce an oxygenate 65 FIG . 9 is an illustration of the chemistry involved in one mixture having an H :Coff ratio of between 0 . 8 and 1 .8 ; and aspect of the present invention using ethanol as one com ( e ) exposing the oxygenate mixture to a condensation cata ponent of the feedstock stream . US 9 ,873 ,836 B2 FIG . 10 is a chart illustrating expected aromatics yield The term “ carboxylic acids ” refers to , without limitation , based on the H : Ceff ratio of the oxygenated mixture in organic acids characterized by the presence of at least one accordance with the present invention . carboxyl group . The general formula of the carboxylic acid FIG . 11 is a chart illustrating the yield of aromatic is R - COOH , where R is a functional group containing hydrocarbons for mixture of acetic acid and ethanol in 5 hydrogen ; carbon and hydrogen ; or carbon , hydrogen , and comparison to acetic acid only and ethanol only . oxygen . In one embodiment, the carboxylic acid has the formula C H2n + 1 CEO )OH , but may also include mol DETAILED DESCRIPTION OF THE ecules having two or more carboxyl moieties. Carboxylic INVENTION acids may also include other moieties containing oxygen , 10 such as carbonyl and / or hydroxyl moieties . A person of The present invention relates to continuous processes and ordinary skill in the art will be able to determine the formula systems for producing aromatic hydrocarbons at high yields. for carboxylic acids having two or more moieties containing The invention also includes methods and catalysts to pro oxygen . Carboxylic acids suitable for use as feedstocks in duce aromatic hydrocarbons, including benzene, toluene , accord with the invention include C , to Comono - carboxylic , xylene (dimethylbenzene ), ethyl benzene , para xylene , meta 15 di- carboxylic acids, and tri- carboxylic acids. Carboxylic xylene , ortho xylene and other Co aromatics , at high yields . acids may also include , without limitation , oxocarboxylic An aspect of the invention is that the aromatic hydrocarbons acids or hydroxycarboxylic acids. Examples include, with may be derived from a raw feedstock derived from alterna out limitation , one or more of formic acid , acetic acid , tive resources , such as biomass , synthesis gases and natural propionic acid , butyric acid , isobutyric acid , valeric acid , gas . 20 isovaleric acid , caproic acid , oxalic acid , malonic acid , As illustrated in FIG . 1 , the method generally involves : succinic acid , glutaric acid , adipic acid , glycolic acid , acrylic ( 1 ) a raw feedstock processing step for the preparation of an acid , lactic acid , pyruvic acid , maleic acid , fumaric acid , intermediate feedstock ; ( 2 ) a conversion step for converting glutaconic acid , itaconic acid , muconic acid , and citric acid . the intermediate feedstock to a feedstock stream containing The term " ester ” refers to , without limitation , an organic one or more alcohols , carboxylic acids, or combinations 25 compound with the structure RC ( O )OR ', where R and R ' thereof; ( 3 ) a conditioning step for converting the feedstock can be a variety of hydrocarbon substituents . Esters feature stream to an oxygenate mixture having an H : Ceff ratio of a carboxyl group CCOO bonded to two carbon atoms. In between 0 . 8 and 1 . 8 ; and ( 4 ) exposing the oxygenate mix - one embodiment, the ester has a formula C „ H2n + 1CEO ) ture to a condensation catalyst at a condensation temperature OC ,, H . Esters may also include other moieties contain and a condensation pressure to produce an aromatic hydro - 30 ing oxygen , such as carbonyl and/ or hydroxyl moieties . A carbons. By performing the conditioning step , aromatic person of ordinary skill in the art will be able to determine hydrocarbons may be produced with yields greater than the formula for esters having two or more moieties contain those achieved in processes converting oxygenate mixtures ing oxygen . Esters suitable for use as feedstocks in accord having an H :Ce ratio outside of the range of between 0 . 8 with the invention include esters having C , to Co R and /or and 1 . 8 . In one embodiment, the raw feedstock is biomass , 35 C to CG R ' substituents , hydroxyesters and oxoesters . and the intermediate feedstock is a biomass - derived feed Examples of esters include, without limitation , one or more stock . Alternatively , as illustrated in FIG . 2 , the method may of methyl formate , methyl acetate , methyl propanoate , further include the processing of a stream of aromatic methyl butanoate , methyl pentanoate, methyl hexanoate , hydrocarbons to provide one or more product streams con ethyl formate , ethyl acetate , ethyl propanoate , ethyl butano taining relatively pure benzene , toluene , mixed xylenes 40 ate , ethyl pentanoate , ethyl hexanoate , propyl formate , pro ( dimethylbenzenes ) , ethylbenzene , paraxylene, metaxylene pyl acetate , propyl propanoate , propyl butanoate , propyl or orthoxylene . pentanoate , propyl hexanoate , butyl formate , butyl acetate , As used herein , the term “ oxygenates” refers to , without butyl propanoate , butyl butanoate , butyl pentanoate , butyl limitation ,molecules of the general formula C Hmon where hexanoate , pentyl formate, pentyl acetate , pentyl propano L , M , and N are greater than or equal to one . In certain 45 ate , pentyl butanoate , pentyl pentanoate , pentyl hexanoate , embodiments L is between 1 and 6 , including L equal to 1 , hexyl formate , hexyl acetate , hexyl propanoate , hexyl 2 , 3 , 4 , 5 , or 6 ; M is between 1 and 2L + 2 , including M equal butanoate , hexyl pentanoate , hexyl hexanoate , hydroxy to 1, 2, 3, 4 , 5 , 6 , 7, 8, 9 , 10 , 11 , 12 , 13 , or 14 ; and N is esters thereof, and oxoesters thereof . between 1 and 6 , including N equal to 1 , 2 , 3 , 4 , 5 , or 6 . The The term “ aldehyde” refers to , without limitation , an oxygenates may also include , without limitation , alcohols, 50 organic compound with the structure RC ( OH , where R carboxylic acids, esters , aldehydes, or ketones. can be a variety of hydrocarbon substituents . Aldehydes As used herein , the term " alcohols ” refers to , without feature a carbonyl group (C = 0 ) bonded to one other carbon limitation , aliphatic alcohols . In certain embodiments, the atom and a hydrogen atom . In one embodiment, the alde alcohols have the general formula C H2n + 201, but may also hyde has a formula C H2n + 1C ( O ) H , but may also include include molecules having two or more hydroxyl moieties, 55 molecules having two or more carbonyl moieties , or other such as glycols , glycerols , polyhydric alcohols , and / or sugar moieties containing oxygen , such a hydroxyl moiety. A alcohols. A person of ordinary skill in the art will be able to person of ordinary skill in the art will be able to determine determine the formula for alcohols having two or more the formula for aldehydes having two or more moieties hydroxyl moieties . Alcohols suitable for use in feedstocks in containing oxygen . Aldehydes suitable for use as feedstocks accord with the invention include C , to Coalcohols , includ - 60 in accord with the invention include C , to Co aldehydes , ing primary , secondary , tertiary , or polyhydric alcohols . dialdehydes , hydroxyaldehydes, or ketoaldehydes. Examples include , without limitation , one or more ofmetha - Examples of ketones include , without limitation , one or nol , ethanol, n - propanol, iso -propanol , n -butanol , 2 -butanol , more of formaldehyde , acetaldehyde , propanal , butanal, isobutanol, n -pentanol , n -hexanol , ethylene glycol , propyl - pentanal, hexanal, 1 , 2 - ethandial , 1 , 3 - propandial, 1 , 4 -butan ene glycol, glycerol, erythritol, threitol and sugar alcohols . 65 dial, 1 ,5 -pentandial , 1, 6 -hexandial , 2 - oxopropanal, If tertiary alcohols are used , they should be combined with 2 -oxobutanal , 3 -oxopropanal , 2 - oxopentanal, 3 - oxopenta primary or secondary alcohols . nal, 4 - oxopentanal , 2 -oxohexanal , 3 - oxohexanal, 4 -oxo US 9 ,873 ,836 B2 10 hexanal, 5 -oxohexanal , 2 -hydroxylethanal , 2 -hydroxypro ethylbenzenes ), ethyl benzene , para xylene , meta xylene, panal, 3 -hydroxypropanal , 2 -hydroxybutanal , ortho xylene, and C , aromatics . 3 -hydroxybutanal , 4 -hydroxybutanal , 2 - hydroxypentanal, 3 - hydroxypentanal, 4 -hydroxypentanal , 5 -hydroxypentanal , Biomass Conversion 2 -hydroxyhexanal , 3 -hydroxyhexanal , 4 - hydroxyhexanal , 5 5 -hydroxyhexanal , or 6 - hydroxyhexanal. The components of the feedstock stream ( e . g ., alcohols , aldehydes, ketones, esters, and carboxylic acids ) may origi The term “ ketone” refers to , without limitation , an organic nate from any source , but in one embodiment are derived compound with the structure RCTOR' , where R and R ' from a raw feedstock of biomass . As used herein , the term can be a variety of hydrocarbon substituents . Ketones fea 10 “ biomass ” refers to , without limitation , organic materials ture a carbonyl group ( C = O ) bonded to two other carbon produced by plants ( such as leaves, roots , seeds and stalks) , atoms. In one embodiment, the ketone has a formula C , H , and microbial and animal metabolic wastes . Common IC ( = O ) C ,H it , but may also include molecules having sources of biomass include : ( 1 ) agricultural wastes, such as two or more carbonyl moieties or other moieties containing corn stalks, straw , seed hulls, sugarcane leavings, bagasse , oxygenoxygen ,, such a nyaroxy?hydroxyl motely moiety . A person of ordinary skill 15 nutshells , and manure from cattle , poultry , and hogs ; ( 2 ) in the art will be able to determine the formula for ketones wood materials , such as wood or bark , sawdust , timber having two or more moieties containing oxygen . Ketones slash , and mill scrap ; ( 3 ) municipal waste , such as waste suitable for use as feedstocks in accord with the invention paper and yard clippings; and ( 4 ) energy crops, such as include Cz to Co ketones , whether symmetric or asymmetric . poplars, willows, pine, switch grass, alfalfa , prairie blues Examples ofketones suitable for use in accordance with this 20 tream , corn , soybean , and the like . The term also refers to the invention include , without limitation , hydroxyketones, dike - primary building blocks of the above , namely, saccharides , tones, and one or more of acetone , butanone , pentanone , lignin , cellulosics, hemicellulose and starches , among oth hexanone, hydroxyacetone, hydroxybutanone , hydroxypen ers . anone , hydroxyhexanone, butandione, pentandione , hexan Referring to FIGS. 1 - 6 , the biomass is processed into a dion , and isomers thereof . 25 biomass -derived intermediate feedstock containing sugars The term “ alkane” refers to , without limitation , an organic and other soluble oxygenates in biomass processing step compound C Hy where L and M are greater than or equal 1 00 . For raw feedstocks ( e . g ., sugar cane , grain starch , to one . In certain embodiments , L is between 1 and 6 , sugarbeets , etc . ) , various sugar processing methods are well including L equal to 1 , 2 , 3 , 4 , 5 , or 6 ; and M is between 1 known in the art and commercially practiced at large scale . and 2L + 2 , including M equal to 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 30 For example , in processes using sugar cane , the sugar cane 11 , 12 , 13 , or 14 . Examples of alkanes in accord with the is generally washed , crushed or diffused , and lime clarified invention include C , to Co alkanes , whether linear or to isolate and provide an aqueous biomass - derived interme branched . Examples, include , without limitation , methane , diate feedstock stream rich in sucrose , fructose , and glucose . ethane , propane, butane , 2 -methylpropane , pentane, 2 ,2 In processes using sugar beets , the sugar beets are likewise dimethylpropane , 2 -methylbutane , hexane, 2 -methylpen - 35 washed , sliced , extracted , and clarified to isolate and provide tane , 3 -methylpentane , 2 , 2 - dimethylbutane , and 2 , 2 -meth - an aqueous biomass -derived intermediate feedstock stream ylbutane . in sucrose , fructose , and glucose . For processes involving The term “ alkene ” refers to , without limitation , an organic cereal grains, the cereal grain is cleaned and then processed compound C?Hy where L and M are greater than or equal to provide wet milled starches ( corn ) or dry milled / ground to one. In certain embodiments , L is between 2 and 6 , 40 starches ( corn , wheat, barley , sorghum grain ) . including L equal to 2 , 3 , 4 , 5 , or 6 ; and M is between 1 and For a raw feedstock of lignocellulosic biomass , the bio 2L , including M equal to 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11, 12 , mass processing step 100 deconstructs complex biopoly 13 , or 14 . Examples of alkanes in accord with the invention mers into sugars and soluble oxygenates . In one embodi include C2 to Co alkenes , whether linear or branched or ment, the raw lignocellulosic feedstock ( such as corn stover ) whether the alkene has one or more double bonds. Examples 45 undergoes deconstruction by dilute acid thermochemical include , without limitation , ethene , propene, 1 - butene , pretreatment, pH adjustment by base such as ammonium 2 -butene , 1 ,3 -butadiene , 2 -methyl - 1 -propene , 1 - pentene , hydroxide , lime, sodium hydroxide or potassium hydroxide 2 -pentene , 1 , 3 -pentadiene , 1 , 4 - pentadiene , 2 -methyl - 1 - and enzymatic hydrolysis to form soluble sugars. Optional butene , 2 -methyl - 1 , 3 -butadiene , 2 -methyl - 2 -butene , hex - preconversion methods include fractionation in the harvest enes, hexadienes , methylpentenes , methylpentadienes , and 50 ing of the feedstock , fractionation by sieving, chemical dimethylbutenes . preprocessing to leach out undesired components , fermen The term " aromatic hydrocarbons” refers to , without tative preprocessing such as treatment by white rot fungi, limitation , aromatic hydrocarbons in either an unsubstituted mechanical methods such as steam explosion , torrefaction , (phenyl ) , mono - substituted or multi - substituted form . In the or pelleting . Alternate means of deconstruction include case of mono - substituted and multi- substituted compounds , 55 thermochemical pretreatment by autohydrolysis ( hot water the substituted group may include a branched Cz alkyl, a only ), alkali ( for example , ammonia , sodium hydroxide , straight chain C1 + alkyl, a branched C3 + alkylene , a straight potassium hydroxide ), oxidation ( for example , peroxide , chain C2 + alkylene, a phenyl, or a combination thereof. In oxygen , air ), organosolv ( for example , ethanol, acetic acid , one embodiment, at least one of the substituted groups catalytically - derived solvents ) , and ionic liquids . The pro include a branched C3. 12 alkyl, a straight chain C1- 19 alkyl, 60 cessing step 100 may also include additional processing to a branched C3- 12 alkylene , a straight chain C2- 12 alkylene, a provide biomass that has been chopped , shredded , pressed , phenyl or a combination thereof. In yet another embodiment, ground or processed to a size amenable for conversion . at least one of the substituted groups include a branched C3- 4 Once prepared , the biomass -derived intermediate feed alkyl, a straight chain C1- 4 alkyl, a branched C3- 4 alkylene , stock is converted in conversion step 102 to a feedstock straight chain C2- 4 alkylene, a phenyl or a combination 65 stream containing one or more alcohols , ketones , aldehydes, thereof. Examples of various aromatic hydrocarbons esters , or carboxylic acids . The conversion may be per include, without limitation , benzene, toluene, xylenes (dim - formed using any one or more methods known in the art . US 9 ,873 ,836 B2 1 Such methods include, without limitation , fermentation , as a plant- based source of sugars , such as sugar cane or a hydrogenolyis of sugars , hydrolysis of triglycerides, gasifi grain starch ( such as corn starch ) . Integration of the instant cation followed by mixed alcohol synthesis reactions to conditioning /condensation process with any of these large produce C2- 10 alpha alcohols , pyrolysis technologies which scale production methods is contemplated herein . produce alcohol or carboxylic acid streams, aqueous phase 5 In some embodiments, the biomass conversion step 102 reforming or other catalytic conversion processes . In one can be combined with part of the biomass treatment step embodiment, the components of the feedstock stream are 100 , such as simultaneous saccharification and fermentation produced using catalytic reforming technologies, such as the (SSF ) in which hydrolytic enzymes are combined with the BioForming® technology developed by Virent , Inc . (Madi - fermentation . Key benefits are fewer process steps , reduced son , Wis . ) , and described in U . S . Pat . No. 7 ,767 , 867 ( Cor - 10 inhibition by the fermentation intermediates ( cellobiose tright ) , U . S . Pat. No. 7 , 898 ,664 (Cortright ), U . S . Pat . No. inhibits cellulases ) , and better controls for contamination 8 ,053 , 615 (Cortright et al. ) , U . S . Pat. No . 8 ,017 ,818 (Cor - through the conversion of monomeric sugars as soon as tright et al. ) , and U . S . Pat. No . 7 ,977 ,517 ( Cortright et al. ) , produced , rather than additional steps requiring the transfer all of which are incorporated herein by reference . Beyond of the sugars to another processing step where contamina thermochemical pretreatment, alternative deconstruction 15 tion may occur. methods include gasification , pyrolysis , hydrothermal liq - The components of the feedstock stream produced by the uefaction , solvolysis , and catalytic deconstruction . These biomass conversion step 102may also be recovered , purified methods are able to produce a mixture of water soluble and /or concentrated prior to further processing in condition oxygenates from the lignin , cellulose and hemicellulose ing step 104. The nature of the recovery and purification will components of biomass , and generally produce oxygenates 20 be depend on the specific feedstock components and the with a lower hydrogen to carbon effective ratio . required specifications for conditioning step 104 . Volatile In another embodiment, the components of the feedstock feedstock components , such as alcohols , aldehydes and stream are produced using a fermentation process. Fermen ketones ( or their low -boiling azeotropes ), may also be tation processes to produce alcohols , aldehydes, ketones , stripped from fermentation broths using heat and then recov esters , and /or carboxylic acids from biomass are well known 25 ered through the subsequent condensing of component in the art , and generally include ( 1 ) pretreating the biomass vapors . Optionally, less volatile feedstock components , such under well -known conditions to loosen lignin and hemicel - as polyols and lower organic acids , may be recovered by lulosic material from cellulosic material , ( 2 ) breaking down using vacuum distillation , or made volatile by the addition the cellulosic material into fermentable saccharide material of an entrainer . Less volatile components may also be by the action of a cellulase enzyme, and ( 3 ) fermentation of 30 converted into volatile derivative products using reactive the saccharide material, typically by the action of a ferment- separation . For example, organic acids can be reacted with ing organism , such as yeast or one of various bacterium , alcohols to form volatile esters which can be recovered and algae or fungi capable of producing the desired alcohols , purified by distillation . ketones or carboxylic acids. Microorganisms known to Feedstock purification may also optionally include solid produce such compounds from sugars include gram positive 35 resin -based purification systems, such as ion exchange or and gram negative enteric bacteria ( e. g . Bacillus sp ., Lac - chromatography practiced in a fixed bed or simulated mov tobacillus sp . , Clostridia sp . , Escherichia sp . ) , yeasts ( e . g . ing bed , liquid ion exchangers , chemical precipitation , elec Saccharomyces sp ., Pichia sp . ), fungi, and algae. trodialysis , carbonation , chemical adsorbants such as acti In one embodiment, the conditioning and condensation vated carbon , hydrodemetalization , reactive extraction , process of the present invention is integrated with a fermen - 40 liquid - liquid extraction ,microfiltration , ultrafiltration , nano tation process , wherein the fermentation process produces filtration , and reverse osmosis . one or more of the components of the feedstock stream used For lignocellulosic feedstocks , the biomass treatment step for later conditioning . The term “ integrated ” is intended to 100 may also include deconstruction by gasification to mean that the feedstock component is produced at a fer - produce a synthesis gas ( syngas ) containing mainly H , and mentation facility or within a fermentation process that is 45 CO , followed by fermentation of the syngas directly to linked to a facility which performs the conditioning and produce ethanol with byproduct organic acids. The syngas condensation process described herein . To minimize pro may also be catalytically converted to a mixture of alcohols . duction costs in some embodiments , the fermentation pro cess is in close enough proximity to the conditioning Alternative Feedstocks condensation facility , or includes appropriate conduits for 50 transferring the feedstock stream to the facility , thereby not Although one aspect of the present invention includes the requiring the feedstock to be shipped . In particular embodi production of aromatic hydrocarbons from biomass- derived ments , the fermentation stream produced in the fermentation feedstocks , other embodiments may be practiced with feed facility is directly transferred to the conditioning / condensa - stocks derived from alternative sources, including raw feed tion facility , generally with removal of solids from the raw 55 stocks of petroleum , coal, natural gas, or any other sources . stream ( generally by filtration or settling ) before contact of Methods for processing raw feedstocks from petroleum , the stream with the catalyst . coal , natural gas , or other sources include , without limita In some embodiments , the fermentation process is per - tion , sugar processing , biomass deconstruction , gasification , formed in an autonomous fermentation facility , i. e ., where pyrolysis , combustion , liquefaction , steam reforming , crack saccharides , produced elsewhere , are loaded into the fer - 60 ing , partial oxidation , or any method described herein ( e . g . , menting system to produce the feedstock components. In processing , conversion , conditioning or condensation ), or other embodiments , the fermentation process is part of a combinations thereof. The raw feedstocks may be processed larger biomass conversion facility , i . e . , where biomass is to produce an intermediate feedstock comprising oxygen decomposed into fermentable saccharides , which are then ated hydrocarbon , alkanes , alkenes , CO molecules , hydro processed in a fermentation zone . 65 gen , synthesis gas ( syngas ) , or combinations thereof. Pro In other embodiments, the components of the feedstock cesses for converting an intermediate feedstock to stream are produced from a more direct sugar source , such oxygenates ( such as alcohols and carboxylic acids ) include, US 9 ,873 ,836 B2 13 14 without limitation , fermentation , hydrogenolysis , hydroly - the hydrogen released by the formation of aromatics is sis , pyrolysis , aqueous phase reforming , alcohol synthesis , transferred to unsaturated oxygenates such as esters , Fisher - Tropsch synthesis, steam reforming , partial oxida ketones , aldehydes , and carboxylic acids. tion , hydroformylation , carbonylation , or combinations As used herein , oxygenates capable of reacting with thereof . 5 hydrogen in themanner described above are termed “ hydro In certain embodiments , an intermediate feedstock com gen acceptors ”. It is believed that carbonyls , carboxylic prising oxygenated hydrocarbons, alkanes , alkenes, CO acids, esters , cyclic ethers , diols , polyols , furans and other molecules , hydrogen , synthesis gas ( syngas ) , or combina oxygenates characterized by having a H :Ce ratio less than tions thereof, may be produced as a byproduct of any of the 2 are capable ofbeing hydrogen acceptors , either directly or processes described herein , including , without limitation , 10 following other reactions ( such as dehydration ), which have the processing of the raw feedstock to produce an interme converted the components to hydrogen acceptors. After diate feedstock , converting the intermediate feedstock to an accepting hydrogen , the hydrogen acceptors may be con oxygenate , conditioning the oxygenate to produce the con verted into species that readily dehydrate to form olefins or ditioned mixture, or by exposing the conditioned mixture to are capable of accepting further hydrogen . The net impact of the condensation catalyst. The intermediate feedstock pro - 15 transferring hydrogen to unsaturated oxygenates is to pro duced may be used as a reactant in any of the other methods duce fewer paraffins and increase the aromatic hydrocarbon described herein , including converting the intermediate yield . feedstock to an oxygenate such as an alcohol or a carboxylic It is notable that carboxylic acids , in isolation , exhibit low acid . By capturing and using byproducts of the process , the reactivity across the condensation catalyst and evolve sig overall efficiency and / or carbon utilization may be maxi - 20 nificant amounts of carbon dioxide for those reactions that mized . do occur (N . Y . Chen , D . E . Walsh and L . R . Koeing , Chapter 24 : Fluidized -Bed Upgrading of Wood Pyrolysis Liquids Feedstock Conditioning and Related Compounds, ACS Symposium Series ; Amer. Chem . Soc . , Washington D . C . 1988 ) . In contrast, when Surprisingly, the aromatic hydrocarbon yield can be 25 reacted in the presence of other oxygenates such as alcohols . increased by conditioning the feedstock stream to provide an carboxylic acids readily react to form aromatics. This illus oxygenate mixture having an H : Cefratio of between 0 . 8 and trates that only a portion of a carboxylic acid feed needs to 1 . 8 . In one embodiment, the oxygenate mixture has a be converted to more hydrogen rich oxygenates to facilitate hydrogen to carbon effective ratio of less than 1 . 8 , 1 . 75 , 1 . 7 , the overall conversion of the carboxylic acid feedstock . 1 .65 , 1 . 6 , 1 .55 , 1 . 5 , 1 .45 , or 1 . 4 . In another embodiment, the 30 oxygenate mixture has a hydrogen to carbon effective ratio Conditioning by Hydrogenation of greater than 0 . 8 , 0 . 85, 0 . 9 , 0 . 95 , 1 . 0 , 1. 05 , 1 . 1 , 1 . 15 , 1 . 2 , 1 . 25 , 1 . 3 , 1 .35 , 1 . 4 , 1 .45 , or 1 . 5 . In yet another embodiment, In one embodiment, the feedstock stream includes one or the oxygenate mixture has a hydrogen to carbon effective more carboxylic acids , such as acetic acid or lactic acid . As ratio between 1 . 0 and 1 . 8 , 1. 05 and 1 . 75 , 1 . 1 and 1 . 7 , 1 . 15 35 illustrated in FIG . 7 , the oxygenates produced from acetic and 1 .65 , or 1 . 2 and 1 . 6 . Water and molecular hydrogen acid generally include acetaldehyde , ethanol and ethyl ( diatomic hydrogen , H , ) are excluded from the calculation . acetate . Upon reaction , other primary carboxylic acids will The H :Ceff ratio applies both to individual components and produce equivalent products corresponding to the carbon to mixtures of components , but is not valid for components number of the carboxylic acid . The specific products depend which contain atoms other than carbon , hydrogen , and 40 on various factors including the composition of the carbox oxygen . For mixtures, the carbon , hydrogen , and oxygen ylic acid feedstock , reaction temperature , reaction pressure, atoms are summed over all components exclusive of water carboxylic acid concentration , the reactivity of the catalyst, and molecular hydrogen . and the flow rate of the carboxylic acid feedstock as it affects Without being bound to any particular theory, the inven - the space velocity ( the mass/ volume of reactant per unit of tors believe that hydrogen atoms made available through the 45 catalyst per unit of time ). conversion of relatively hydrogen - rich alcohols to aromatics For illustration purposes, the H :Cox ratio of various car can be transferredred to unsaturated components . IfIf the hydro - boxylic acids is shown in Table 1 below . gen is transferred to an olefin , a paraffin is generated . Because olefins are precursors to aromatics , the conversion TABLE 1 of an olefin to a paraffin reduces the available pool of 50 – material that is able to be converted to aromatics . If the H : C . Ratio of Select Carboxylic Acids hydrogen is transferred to a ketone or aldehyde , an alcohol is formed . In this manner , the carbonyl group of the ketone Carboxylic Acid H :Ceff or aldehyde acts as a hydrogen sink , removing reactive Formic Acid - 2 . 00 hydrogen and preventing the conversion of olefins to par - 55 Acetic Acid 0 . 00 Propionic Acid 0 .67 affins , thereby reducing the amount of paraffins and increas Butyric Acid 1 .00 ing the overall aromatics yield . Isobutyric Acid 1. 00 In the case of carboxylic acid feedstocks, it is believed Valeric Acid 1 . 20 Isovaleric acid 1 . 20 that hydrogen atoms, made available through the conversion Caproic acid 1 . 33 of relatively hydrogen -deficient carboxylic acids to alcohols, 60 Oxalic Acid - 3 . 00 esters , ketones and aldehydes, allows reaction pathways to Malonic Acid - 1 . 33 be exploited across the condensation catalyst that are not Succinic Acid - 0 . 50 Glutaric Acid 0 .00 feasible for an isolated carboxylic acid feedstock . These Adipic Acid 0 . 33 reaction pathways include reactions ( such as dehydration ) Glycolic Acid - 1 . 00 that can directly lead to olefin intermediates . Additional 65 Acrylic Acid 0 .00 olefin intermediates may be indirectly generated through the Lactic acid 0 . 00 release and transfer ofhydrogen as aromatics are formed and US 9, 873 ,836 B2 15 16 TABLE 1 -continued TABLE 5 H :Cf Ratio of Select Carboxylic Acids Ratio of Aldehydes and Ketones Aldehydes or Carboxylic Acid H :Ceff 5 Ketone carbon number H : Cet

Pyruvic Acid - 0 .67 o Maleic Acid - 1 .00 1 . 0 Fumaric Acid - 1 .00 1 . 33 10 1 . 5 Glutaconic Acid - 0 . 40 1 . 6 Muconic Acid - 0 . 33 1 .67 Citric Acid - 1 .00 1 .71 1. 75 JOJOJO09?08 1 .78 Paraffins generally have a H :Ce ratio greater than 2, while 2 alkyl mono -aromatic compounds generally have a H :Cell ratio between 1 and 2 , as shown in Tables 2 and 3 below . The H :Ceff ratio of ethanol (and of all alcohols ) is 2, as shown in Table 6 below . TABLE 2 20 Ratio of Paraffins TABLE 6 Paraffins H :CofCelf H :Ceff Ratio of Alcohols

- Alcohol (by number of 25 8 tm carbon atoms) H :CeffCold C - 2 . 67

5 2 .5

P 2 . 4

O 2 . 33 OOOO 2 . 29 ?? 2 . 25 30 ?'?????”- 0 2 . 22

TABLE 3 NNNNNNNNNN Other species include carbon dioxide (CO2 ) with a H :Cell Car Ratio of Alkyl Substituted Mono - Aromatics ratio of - 4 , carbon monoxide (CO ) with a H : Ce ratio of - 2 , Aromatic H : Cell and carbon with a H :Ceff ratio of 0 . Carbonaceous residue , Benzene 1 . 0 or coke, that may accumulate on catalyst or other surfaces Toluene 1 . 14 exhibits a range of H :Ceftratios , depending on the amount of Xylene 1. 25 residual hydrogen and oxygen within the coke . Co 1 . 33 In accordance with the invention , the process for convert ing carboxylic acids to aromatic hydrocarbons can be a 2 45 two - step process ( in which the hydrogenation catalyst and the condensation catalyst are separate catalysts ) or a one When the hydrogen acceptors are passed as reactants over step process in which the hydrogenation catalyst and the condensation catalyst are one multi - functional catalyst ) . a condensation catalyst , an improved aromatic hydrocarbon When separate catalysts are provided , they may be present yield is realized , relative to the yield realized when the 50 in separate vessels, in separate beds within a single vessel, reactants are carboxylic acids alone . The H :Ceff ratio of the in alternating layers in a single bed of catalyst , or physically esters , aldehydes and ketones that may be formed by hydro mixed within the same bed . genation of carboxylic acids is between zero and 2 as shown The general conditioning process 104 for carboxylic acids in Tables 4 and 5 below . in accordance with the present invention is as follows. A 55 carboxylic acid feedstock is first passed into contact with TABLE 4 hydrogen and a hydrogenation catalyst in a reactor at a H :Coff Ratio of Select Esters hydrogenation temperature and a hydrogenation pressure , thereby producing a mixture of oxygenates . The carboxylic Esters H :Cell acid feedstock may be an essentially pure carboxylic acid Methyl Formate 0 . 00 60 stream or , alternatively , the carboxylic acid feedstock may Methyl Acetate 0 .67 be mixed with water and / or an alcohol to create a solution Ethyl Formate 0 .67 wherein the carboxylic acid concentration is greater than Ethyl Acetate 1 .00 1 % , or greater than 5 % , or greater than 10 % , or greater than Propyl Propanoate 1 . 33 Ethyl Lactate 0 . 80 20 % , or greater than 30 % , or greater than 40 % , or greater Propyl Lactate 1 . 00 65 than 50 % . Various processes are known for hydrogenating carbox ylic acids. The hydrogenation catalyst generally includes Fe , US 9 ,873 ,836 B2 17 18 Ru , Co , Pt, Pd , Ni, Re, Cu, and alloys or combinations Conditioning by Dehydrogenation thereof, either alone or with promoters such as Ag, Au, Cr, In one embodiment, the feedstock stream includes one or Zn , Mn, Mg, Ca , Cr, Sn , Bi, Mo, W , B , P , and alloys or more alcohols , such as ethanol. As illustrated in FIG . 9 , the combinations thereof. The hydrogenation catalyst may also oxygenates produced from ethanol generally include acet include any one of several supports , depending on the 5 aldehyde , acetic acid , and ethyl acetate . Primary alcohols desired functionality of the catalyst . Such supports may produce the equivalent products corresponding to the carbon include carbon , silica , alumina, zirconia , titania , vanadia , number of the starting alcohol . Secondary alcohols are ceria , silica - aluminate , zeolite , kieselguhr , hydroxyapatite , unable to proceed to acids or esters and will produce zinc oxide , magnesium oxide , chromia , and mixtures primarily ketones, unless used in a mixture with other thereof. 10 alcohols . The specific products depend on various factors In general, the hydrogenation reaction is carried out at including the composition of the alcohol feedstock , reaction hydrogenation temperatures of between about 80° C . to 350° temperature , reaction pressure , alcohol concentration , the C ., and hydrogenation pressures in the range of about 50 reactivity of the catalyst , and the flow rate of the alcohol psig to 5000 psig . The hydrogen used in the reaction may feedstock as it affects the space velocity ( themass /volume of include in situ hydrogen generated from other reactions 15 reactant per unit of catalyst per unit of time) . occurring in series or parallel within the reactor , external H2, Ethers may also be produced from alcohols . For instance , recycled H2, or a combination thereof. the conversion of methanol to dimethyl ether can be used to The extent to which the carboxylic acid feedstock stream reduce the exotherm of the condensation reaction . Dialkyl is hydrogenated can be measured by the amount of molecu - ethers may also be present in the oxygenate mixture as a lar hydrogen consumed during hydrogenation and may 20 product of the dehydrogenation catalyst or as a separately range from 0 . 05 to 2 . 0 moles of molecular hydrogen con - fed component. Dialkyl ethers , such as diethylether , dim sumed per mole of carboxylic acid groups in the feed . In ethylether, etc . , have a H : Ceff ratio of 2 . 0 and can impact the general, the reaction should be conducted under conditions aromatic to paraffin ratio of the product the same as an where the residence time of the carboxylic acid feedstock alcohol. over the catalyst is appropriate to generate the desired 25 As indicated previously , the H :Ceff ratio of the reactants oxygenates. For example , the residence time may be estab - impacts the H :Ceff ratio of the reaction products . When the lished at a weight hourly space velocity (WHSV ) of between hydrogen acceptors are passed as reactants over a conden 0 .01 and 30 , or between 0 .05 and 10 , or between 0 .1 and 5 . sation catalyst, an improved aromatic hydrocarbon yield is Desirable levels of hydrogenation depend on the compo - realized , relative to the yield realized when the reactants are sition of the carboxylic acid feedstock stream . To enhance 30 alcohols alone. the production of aromatics during condensation step 106 , In accordance with the invention , the process for convert longer chain carboxylic acids must be hydrogenated to a ing alcohols to hydrocarbons can be a two - step process ( in lesser extent than short chain carboxylic acids . For an acetic which the dehydrogenation catalyst and the condensation acid feedstock , greater than 0 . 8 moles of molecular hydro - catalyst can be separate catalysts ) or a one - step process in gen should be consumed per mole carboxylic acid feedstock 35 which the dehydrogenation catalyst and the condensation to the system during hydrogenation , and greater than 1 mole catalyst can be one multi - functional catalyst ) . When sepa of molecular hydrogen per mole of carboxylic acid is rate catalysts are provided , they may be present in separate preferred to prevent an excessive coking rate . Lower extent vessels , in separate beds within a single vessel, in alternating of hydrogenation is required as carbon chain length of the layers in a single bed of catalyst, or physically mixed within carboxylic acid increases in the absence of other functional 40 the same bed . groups, such as hydroxyls ) . For a propionic acid feedstock , The general conditioning process step 104 for alcohol for example , greater than 0 . 2 moles of molecular hydrogen feedstock streams is as follows. An alcohol feedstock is first should be consumed per mole carboxylic acid feedstock passed into contact with a dehydrogenation catalyst in a during hydrogenation . Greater than 0 . 5 mole of molecular reactor at a dehydrogenation temperature and a dehydroge hydrogen per mole of carboxylic acid is preferred to prevent 45 nation pressure , thereby releasing molecular hydrogen and an excessive coking rate . For mixed carboxylic acid feed producing the oxygenates illustrated in FIG . 9 . The alcohol stocks, the overall extent of hydrogenation should be such feedstock may be an essentially pure alcohol stream or, that the overall H : Ceff ratio of the resulting oxygenate stream alternatively, the alcohol feedstock may contain water to is less than 1 . 8 , 1 .75 , 1 . 7 , 1 .65 , 1 .6 , 1 . 55 , 1 . 5 , 1 . 45 , or 1 . 4 , create an aqueous solution wherein the alcohol concentra and greater than 0 . 8 , 0 . 85 , 0 . 9 , 0 .95 , 1 . 0 , 1 . 05 , 1 . 1 , 1 . 15 , 1 . 2 , 50 tion is greater than 1 % , or greater than 5 % , or greater than 1 . 25 , 1 . 3 , 1 . 35 , 1 . 4 , 1 . 45 , or 1 . 5 . For example , the overall 10 % , or greater than 20 wt % , or greater than 30 wt % , or extent of hydrogenation should be such that the carbon greater than 40 wt % , or greater than 50 wt % , or greater than effective ratio is between 0 . 8 and 1 . 8 , or between 1 . 0 and 72 wt % , or greater than 80 wt % , or greater than 90 wt % , 1 . 8 , or between 1 .05 and 1 .75 , or between 1 . 1 and 1 . 7 , or or greater than 95 wt % . The alcohol feedstock stream may between 1 . 15 and 1 .65 , or between 1 . 2 and 1 . 6 . Hydroge - 55 be also combined with other components to assist in arriving nation extent may be controlled by varying the catalyst and at the desired H : Ceff ratio . operating conditions . Higher temperatures generally lead to The dehydrogenation catalyst includes one or more mate lower equilibrium levels of hydrogenation but higher cata - rials of metal and / or basic functionality capable of catalyz lyst activity . Higher hydrogen partial pressure generally ing the conversion of hydroxyl elements to carbonyls . Suit leads to greater levels of hydrogenation . Other components , 60 able metallic components include , without limitation , Cu , such as additional oxygenates , like alcohols , may be added Ru , Ag, CuCr, CuZn , Co , Sn , Mo, and combinations thereof. to the hydrogenation products to ensure that the overall Suitable base -catalyzed dehydrogenation catalysts include H : Ceff ratio of the resulting oxygenate stream is achieved . Li, Na, K , Cs, Mg, Ca , Ba , Zn , Ce, La, Y , Zr, hydrotalcite , In addition to the hydrogenation reactions , additional reac - base - treated aluminosilicate zeolite . The base catalyst may tions may be supported during the hydrogenation step , 65 also include an oxide of Ti, Zr, V, Mo, Cr, Mn , Al, Ga , Co , including esterification , dehydration , and aldol condensa - Ni, Si, Cu , Zn, Sn , Mg, P , Fe , and combinations thereof. tion . Preferred Group IA materials include Li, Na, K , and Cs. US 9 ,873 ,836 B2 19 20 Preferred Group IIA materials include Mg, Ca , and Ba . A and 1 . 8 , 1 . 1 and 1 . 7 , or 1 . 2 and 1 . 7 . For alcohols containing preferred Group JIB material is Zn . Preferred Group 111B three or more carbons , any level up to complete dehydro materials include Y and La. Basic resins include resins that genation may be desirable . Dehydrogenation extent may be exhibit basic functionality , such as Amberlyst A26 and controlled by varying the catalyst and operating conditions . Amberlyst A21 . The base catalyst may be self -supporting or 5 Higher temperatures generally lead to greater levels of adhered to any one of the supports further described below , dehydrogenation . Hydrogen may be added to the reaction to including supports containing carbon , silica , alumina , zir - limit the extent of dehydrogenation and to prevent deacti conia , titania , vanadia , ceria , alloys and mixtures thereof. vation of the dehydrogenation catalyst. The base catalyst may also include zeolites and other microporous supports that contain Group IA compounds , 10 Conditioning by Mixture such as Li, Na, K , and Cs . Preferably , the Group IA material is present in an amount greater than that required to neu In another embodiment, the conditioning process step 104 tralize the acidic nature of the support. These materials may includes combining a feedstock stream containing carbox be used in any combination , and also in combination with ylic acids with a feedstock stream containing alcohols to alumina or silica . A metal function may also be provided by 15 arrive at a oxygenate mixture having an H : Ceff ratio of the addition of group VIIIB metals , or Cu , Ga, In , Zn , Cr, or between 0 . 8 and 1 . 8 . Sn . Other components, such as additional oxygenates and The dehydrogenation catalyst is either self -supporting or, hydrogen , may be added to the oxygenate mixture. If preferably , includes a supporting material. The support for additional components are added , it may be preferable to the metallic component may contain any one or more of 20 dehydrogenate smaller chain alcohols such as methanol and alumina , silica , silica -alumina , titania , carbon , zirconia , and ethanol to a greater extent so that the overall H : Ce ratio is mixtures thereof. Copper on a silica support, Raney copper , between 1 . 0 and 1 . 8 , 1 . 1 and 1 . 7 , or 1 . 2 and 1 . 6 . and copper -zinc - aluminate are particularly preferred dehy drogenation catalysts. For the copper catalyst on a silica Production of Aromatics support , the copper contentmay generally range from 0 . 05 % 25 to 40 % , preferably from 0 . 1 % to 20 % , and most preferably The oxygenate mixture , including unreacted feedstock from 0 . 2 % to 10 % . components , is then passed in whole or in part into contact In some embodiments , the dehydrogenation temperature with a condensation catalyst in a condensation reactor under is between about 80° C . and 500° C . , preferably between conditions of temperature and pressure effective to convert about 100° C . and 450° C . , and most preferably between 30 a portion of the oxygenate mixture to aromatic hydrocar about 150° C . and 400° C . The dehydrogenation pressure bons . In general, the condensation catalyst has one or more ranges from below atmospheric pressure up to about 1000 acidic materials capable of catalyzing the conversion of the psig , preferably from about atmospheric pressure to about oxygenate mixture components to the desired aromatic 700 psig , and most preferably from about 10 psig to about hydrocarbons. The condensation catalyst may include, with 500 psig . 35 out limitation , aluminosilicates (zeolites ) , silica - alumina The extent to which the alcohol feedstock stream is phosphates (SAPO ) , aluminum phosphates (ALPO ) , amor dehydrogenated can be measured by the amount ofmolecu - phous silica alumina , zirconia , sulfated zirconia , tungstated lar hydrogen released during dehydrogenation and may zirconia , titania , acidic alumina , phosphated alumina , phos range from 0 .05 to 2 . 0 moles of molecular hydrogen phated silica , sulfated carbons , phosphated carbons, het released per mole of alcohol feed . Values greater than 1 mole 40 eropolyacids, and combinations thereof. In one embodiment, of molecular hydrogen released per mole of feed are pos - the catalyst may also include a modifier, such as Ce , Y , Sc , sible when carbonyls are further converted to acids, with an La, P , B , Bi, Li, Na, K , Cs , Mg, Ca , Ba , and combinations associated consumption of water and release of molecular thereof. The catalyst may also be modified by the addition of hydrogen . In general, the reaction should be conducted a metal, such as Cu , Ag, Au , Pt, Ni, Fe , Co , Ru , Zn , Cd, Ga, under conditions where the residence time of the alcohol 45 In , Rh , Pd , Ir, Re , Mn, Mg, Cr, Mo, W , Sn , Os, alloys and feedstock over the catalyst is appropriate to generate the combinations thereof, to provide metal functionality , and /or desired dehydrogenation products. For example , the resi- oxides of Ti, Zr, V , Nb , Ta , Mo, Cr, W , Mn , Re, Al, Ga, In , dence time may be established at a weight hourly space Fe, Co , Mg, Ni, Si, Cu , Zn , Sn , P, and combinations thereof . velocity (WHSV ) of between 0 .01 and 30 , or between 0 .05 The condensation catalyst may be self- supporting or adhered and 10 , or between 0 . 1 and 5 , or between 1 . 0 and 4 . 50 to any one of the supports further described below , including Desirable levels of dehydrogenation depend on the com supports containing carbon , silica , alumina , zirconia , titania , position of the alcohol feedstock stream . To produce a shift zinc oxide , magnesium oxide , aluminum phosphate , zinc in the aromatic - to -paraffin ratio during the oxygenate con - aluminate , vanadia , ceria , heteropolyacids, alloys and mix version , longer chain alcohols must be dehydrogenated to a tures thereof. greater extent than short chain alcohols . For a methanol 55 Ga, In , Zn , Fe, Mo, Ag, Au , Ni, P , Sc , Y , Ta, and feedstock , less than 50 % dehydrogenation is desirable ( 0 . 5 lanthanides may also be exchanged onto zeolites to provide moles of molecular hydrogen released per mole of total a zeolite catalyst. The term “ zeolite ” as used herein refers feedstock to the system ) , and less than 37 % is preferred to not only to microporous crystalline aluminosilicate but also prevent an excessive coking rate . For an ethanol feedstock , to microporous crystalline metal - containing aluminosilicate less than 85 % dehydrogenation is desirable ( 0 . 85 moles of 60 structures, such as galloaluminosilicates and gallosilicates . molecular hydrogen released per mole of total feedstock to Metal functionality may be provided by metals such as Cu , the system ) , and less than 75 % is preferred . For mixed Ag, Au , Pt, Ni, Fe , Co , Ru , Zn , Cd , Ga, In , Rh , Pd , Ir , Re, alcohol feedstocks, the overall extent of dehydrogenation Mn, Cr, Mo, W , Sn , Os, alloys and combinations thereof. should be such that the overall H : Ceff ratio is less than 2 . 0 , Examples of suitable zeolite catalysts include ZSM - 5 . 1 . 9 , 1 . 8 , 1 . 7 or 1 . 6 , and greater than 1 . 0 , 1 . 1 , 1 . 2 , 1 . 3 , 1 . 4 or 65 ZSM - 11, ZSM -12 , ZSM - 22 , ZSM - 23 , ZSM - 35 and ZSM 1 . 5 . For example , the overall extent of dehydrogenation 48 . Zeolite ZSM - 5 , and the conventional preparation should be such that the carbon effective ratio is between 1 . 0 thereof, is described in U . S . Pat. Nos. 3 , 702 , 886 ; Re. 29 , 948 US 9 ,873 ,836 B2 (highly siliceous ZSM -5 ); U . S . Pat. Nos. 4 ,100 , 262 and ing and condensation catalysts discussed above . One par 4 , 139 ,600 , all incorporated herein by reference . Zeolite ticularly useful catalyst is copper loaded onto silica - bound ZSM - 11, and the conventional preparation thereof, is ZSM - 5 . In this single - step embodiment , the conditioning described in U . S . Pat . No. 3 ,709 ,979 , which is also incor reaction and the condensation reactions occur in the same porated herein by reference. Zeolite ZSM - 12 , and the con - 5 reaction vessel under conditions of temperature and pressure ventional preparation thereof, is described in U . S . Pat . No. as described above and which are suitable for both the 3 ,832 , 449 , incorporated herein by reference . Zeolite ZSM conditioning and condensation reactions to proceed . 23 , and the conventional preparation thereof, is described in U . S . Pat. No. 4 ,076 ,842 , incorporated herein by reference . Aromatics Processing Zeolite ZSM - 35 , and the conventional preparation thereof, is 10 described in U . S . Pat. No . 4 ,016 ,245 , incorporated herein by In one embodiment , the present invention further includes reference . Another preparation of ZSM - 35 is described in an aromatics complex 108 for processing the aromatic U . S . Pat. No. 4 , 107, 195 , the disclosure of which is incor - hydrocarbons to provide one or more product streams con porated herein by reference . ZSM - 48 , and the conventional taining relatively pure concentrations of benzene , toluene , preparation thereof, is taught by U . S . Pat. No . 4 ,375 , 573, 15 xylenes (dimethylbenzenes ), ethylbenzene , paraxylene , incorporated herein by reference . Other examples of zeolite metaxylene or orthoxylene . In one embodiment, the method catalysts are described in U . S . Pat . No . 5 , 019 , 663 and U . S . of the present invention is integrated with an aromatics Pat. No. 7 ,022 , 888 , also incorporated herein by reference . complex , wherein the aromatics complex produces the final As described in U . S . Pat. No. 7 , 022 ,888 , the condensation products distributed to the market . In some embodiments , catalyst may be a bifunctional pentasil zeolite catalyst 20 the aromatics processing is performed in an autonomous including at least one metallic element from the group of Cu , aromatics complex , i. e . , where reformate , produced else Ag , Au , Pt, Ni, Fe, Co , Ru , Zn , Cd , Ga, In , Rh, Pd , Ir, Re, where, is loaded into the aromatics complex to provide the Mn, Cr, Mo , W , Sn , Os, alloys and combinations thereof, or final product streams. The term “ integrated ” is intended to a modifier from the group of Ga, In , Zn , Fe, Mo, Au , Ag, Y , mean that the reformate is produced at the conversion Sc , Ni, P , Ta , lanthanides, and combinations thereof. The 25 facility or within a conversion process that is linked to the zeolite may be used with reactant streams containing an aromatics complex . Preferably, to minimize production oxygenated hydrocarbon at a temperature of below 600° C . costs , the reformate is produced in close enough proximity The zeolite may have ZSM - 5 , ZSM -8 or ZSM - 11 type to the aromatics complex , or includes appropriate conduits crystal structure consisting of a large number of 5 -mem - for transferring the produced reformate to the aromatics bered oxygen - rings , i. e . , pentasil rings . The zeolite with 30 complex , thereby not requiring the reformate to be shipped . ZSM -5 type structure is a particularly preferred catalyst. In particular embodiments , the reformate stream produced in The catalyst may optionally contain any binder such as the conversion facility is directly transferred to the aromatics alumina , silica or clay material. The catalyst can be used in complex , generally following distillation and further sepa the form of pellets , extrudates and particles of different ration to remove product streams appropriate for other shapes and sizes . In one aspect, the condensation catalyst is 35 processes . ZSM - 5 or beta zeolite . An aromatics complex is generally a combination of In general, the condensation temperature is between about process units typically used to convert reformate into the 250° C . and 550° C ., preferably between about 300° C . and basic chemical intermediates — benzene , toluene and 500° C . , and most preferably between about 320° C . and xylenes (BTX ) . The xylene product , also known as mixed 480° C . The condensation pressure ranges from below 40 xylenes, contains four different Cg aromatic isomers : parax atmospheric pressure up to about 1000 psig , preferably from ylene , orthoxylene , metaxylene and ethylbenzene . Aromat about atmospheric pressure to about 700 psig, and more ics complexes are well known in the art and can have many preferably from about 10 psig to about 500 psig . In general, different configurations depending on the available refor the reaction should be conducted under conditions where the mate and the desired products . The simplest complexes residence time of the oxygenate mixture over the conden - 45 produce only BTX and , for purposes of the present inven sation catalyst is appropriate to generate the desired aro - tion , would include one ormore catalytic reforming units for matic hydrocarbons. For example , the residence time may be producing aromatics from naptha, and one ormore aromat established at a weight hourly space velocity (WHSV ) of ics extraction units for the extraction of BTX . between 0 . 01 and 30 , or between 0 . 05 and 10 , or between 0 . 1 Alternatively, the aromatics complex may be designed to and 5 , or between 1 . 0 and 4 . 50 maximize the yield of para - xylene and / or benzene . Such Excluding molecular hydrogen ( H ) , the overall H :Ceff designs typically include additional units for the isomeriza ratio of the oxygenate mixture is generally greater than 0 . 8 tion of xylenes sand the conversion of ethylbenzene , and and less than 1 . 8 , resulting in an increased yield of aromat- units for the conversion of toluene and heavy aromatics to ics, and an improvement over traditional methods of con xylenes and benzene by toluene disproportionation and verting oxygenates to aromatic hydrocarbons . When the 55 transalkylation of toluene plus C , aromatics. The principal conditioning and condensation are complete , more than products from this configuration are benzene , para - xylene , 40 % , or 45 % , or 50 % , or 60 % , or 70 % , or 75 % , of the (optionally ) metaxylene , and ( optionally ) ortho -xylene . If carbon in the carboxylic acid feedstock is contained within desired , a fraction of the toluene and C , aromatics can be the aromatic hydrocarbon product . taken as products , or some of the reformate may be used as The present invention may also be practiced as a one - step 60 a high -octane gasoline blending component. process in which the conditioning catalyst and the conden sation catalyst is a multi - functional catalyst . In this Process Configurations approach , oxygenates are converted to hydrocarbons employing a multi - functional catalyst having one or more In some embodiments , the oxygenate mixture is separated materials capable of catalyzing both the conditioning and 65 to provide one or more streams which are directed to the condensation reactions. The multi -functional catalyst may condensation step 106 and one or more streams which are include any of the elements suitable for separate condition - not directly fed into the condensation step . The streams US 9 ,873 ,836 B2 23 24 which are not directly fed into the condensation step 106 gen may also be used for provide process heat as described may be removed from the system or recycled to the condi- above or simply recovered and sold as a valuable co tioning step 104 for further conversion . Means of separation product. include, without limitation , separation based on volatility The conditioning step 104 may be equilibrium limited . differences between components , extraction , membranes, 5 Accordingly , the rate of reaction slows as reaction products and ion exchange . In one preferred embodiment, the prod are formed . This can limit the extent to which reactor feed ucts of the conditioning step 104 are cooled and a portion of is converted into products . To overcome this limitation , for the molecular hydrogen unused in the reaction is removed as conditioning steps that release hydrogen , some of the hydro a gas phase product prior to sending the remaining compo - gen produced by the conditioning reaction can be removed nents to the condensation reactor, as illustrated in FIG . 5 . In before the remaining reaction mixture after the feed to another preferred embodiment, the oxygenate mixture is conditioning step 104 is partially converted and then fed to separated by distillation to provide an aldehyde enriched a subsequent stage of reaction to force formation of more stream which is recycled to the conditioning reactor to effect desirable reaction products ( see FIG . 6 ) . This process of conversion of the aldehydes to alcohols and esters . In yet 15 removing some of hydrogen after further conversion can be another preferred embodiment, unreacted carboxylic acids repeated though multiple stages . All hydrogen , including are separated from the product stream and recycled to the hydrogen collected from 105B , may be usefully recovered conditioning reactor to increase the overall carboxylic acid for other uses . conversion . In other embodiments , oxygenates other than carboxylic acids or alcohols (e . g. , ketones ) may be used in 20 EXAMPLES addition to and as a supplement to the feedstock stream . If the carboxylic acids , ketones , aldehydes, esters , or To demonstrate the advantage of using a mixture of alcohols are derived from biomass , the age of the com - oxygenates , experiments using comprising ethanol, acetic pounds, or fractions containing the compounds, are less than acid , and both ethanol and acetic acid were performed . 100 years old , preferably less than 40 years old , more 25 In the experiment, two Inconel reactors aligned in series preferably less than 20 years old , as calculated from the were loaded with the catalyst prepared in the following carbon 14 concentration of the component. manner: nickel nitrate (Sigma Aldrich , St Louis , Mo . ) was Because the reaction of the conditioning step is endother added to a commercially available A1 ,0z - bound ZSM - 5 mic for alcohol based intermediates , the temperature will support (116 " extrudates , 20 % Al2O3 Binder , ZSM - 5 SAR decrease and the rate of reaction will diminish as the reaction 30 30 . Zeolyst) using excess water and evaporating the water proceeds. To make effective use of the conditioning catalyst while heating at 60° C . under vacuum and rotating in a round and to minimize the size of the reactors , a minimum tem bottom flask until dry to achieve a target Ni loading of 1 wt perature should be maintained in the conditioning reactors . Ordinarily this might be done by reheating the reaction % . Each reactor had an internal diameter of 0 .87 inches with mixture in the conditioning reactor through heat exchange 35 an Inconel thermowell with an OD of 0 .1875 inches running equipment supplied by a heat transfer fluid such as steam or through the center of the reactor. The catalyst was loaded to hot oil. Referring to FIG . 3 , in one embodiment, the CO , a depth of 11 . 5 inches , accounting for 72 g of catalyst per formed in 102 can be reacted with the hydrogen produced in reactor. The catalysts were heated up at atmospheric pres 104 to form methane . The heat generated by the exothermic sure flowing approximately 200 ml/min N2 across the cata methane- forming reaction will aid in maintaining the desir - 40 lyst while ramping the temperatures from 25° C . to 375° C . able reaction temperaturenperature forfor the endothermic precondition in 2 hours . Once at temperature , the reactors were pressur ing reaction and reduce or eliminate utility load of the ized with N2 to 200 psig . A compressor was turned on to conditioning reactor. The heat generation rate, and therefore provide a gas recirculation stream across these two reactors the temperature of the conditioning reactor 104 , can be at a rate of approximately 1300 sccm . At this point, a feed controlled by metering the CO2 fed to the conditioning 45 mixture consisting of 80 % ethanol and 20 % water (by mass ) reaction 104 . Because the conditioning reaction 104 is was fed downflow into the first reactor at a rate of 0 .63 equilibrium limited , an additional benefit of consuming the g /min . Once steady state conditions were achieved , an hydrogen is that it overcomes the conversion limitations analysis of reaction products was completed . The gas prod imposed by equilibrium and therefore allows conversion of ucts were analyzed by means of a gas chromatograph more feed to products . 50 equipped with a flame ionization detector , the aqueous phase In another embodiment illustrated by FIG . 4 , a portion of products were analyzed for total carbon and with a gas the heat required to provide the conditioning temperature is chromatograph equipped with a mass spectrometry detector, provided by heat generated in the condensation step 106 . In and the organic phase components were analyzed using a gas this embodiment, the reaction mixture is reheated through chromatograph equipped with both flame ionization and direct process to process heat exchange or by a heat transfer 55 mass spectrometry detectors . Four separate data points were fluid , such as steam or hot oil. The heat required may be obtained , and the results are presented in Table 7 and FIG . provided directly through process to process heat exchange 4 below . or indirectly to form the steam or heat the hot oil and is at The experiment was repeated with a feed of acetic acid . least partially obtained by cooling the reaction products In other words, the catalyst, reactors , and procedures were from the condensation step 106 . Use of this source of heat 60 the same, but the 2nd feed mixture consisted of 80 % acetic will improve the process efficiency by reducing the utility acid and 20 % water ( by mass ) . Two separate data points duty of the plant. were obtained , and the results are presented in Table 7 and In most applications , the conditioning step 104 will pro - FIG . 4 below . duce hydrogen or result in unreacted hydrogen . As illus - The experiment was repeated with a feed comprising trated in FIG . 6 , this hydrogen can be recovered for use 65 ethanol and acetic acid having a H :Ce ratio of 1 . 5 . In other elsewhere in the process , such as in catalyst reduction or for words, the catalyst, reactors , and procedures were the same, aromatics processing in an aromatics complex . The hydro - but the 3rd feed mixture consisted of 56 % ethanol, 24 % US 9 ,873 ,836 B2 25 26 acetic acid , and 20 % water (by mass ). Two separate data fermenting the intermediate feedstock with one or more points were obtained , and the results are presented in Table species of microorganism to form a fermentation broth 7 and FIG . 4 below . comprising alcohols or carboxylic acids; The experiment was repeated again with a different feed removing the alcohols or carboxylic acids from the fer comprising acetic acid and ethanol having a H :Ce ratio of 5 mentation broth to provide the feedstock stream ; and 1. 0 . In other words , the catalyst , reactors, and procedures purifying the feedstock stream prior to exposing the were the same, but the 4th feed mixture consisted of 34 . 7 % oxygenate mixture to the conditioning catalyst . ethanol, 45 . 3 % acetic acid , and 20 % water (by mass ) . Two 5 . The method of claim 1, wherein the raw feedstock is separate data points were obtained , and the results are biomass , natural gas, coal, or petroleum . presented in Table 7 and FIG . 4 below . 6 . The method of claim 1 , wherein the processing step ( a ) The experiment illustrates the advantage of using a mix - comprises sugar processing , biomass deconstruction , gasifi ture of oxygenates . A straight line connects the acetic acid cation , pyrolysis , combustion , liquefaction , steam reform only and the ethanol only cases , which illustrates the ing , cracking, or combinations thereof. expected yield from a linear combination of the individual 15 7 . The method of claim 1, wherein the alcohol is selected oxygenate yields . The results illustrate the advantage of from the group consisting of a primary alcohol, a secondary converting a mixture of oxygenates to aromatic hydrocar- alcohol, a polyhydric alcohol, and combinations thereof. bons as the yield of aromatic hydrocarbons is substantially 8 . The method of claim 1 , wherein the carboxylic acid is higher than would be predicted from a linear combination of selected from the group consisting of mono - carboxylic acid , the oxygenate components . 20 di- carboxylic acid , hydroxycarboxylic acid , and combina tions thereof. TABLE 7 9 . The method of claim 1 , wherein the conditioning step ( C ) comprises exposing the feedstock stream to a condition Aromatic chemical yield as a function of a mixture of ing catalyst at a conditioning temperature and a conditioning ethanol and acetic acid 25 pressure to produce the oxygenate mixture or combining a H :Cell Aromatics Yield Normalized Yield portion of the feedstock stream with a portion of a second Feed Ratio ( % of feed Carbon ) ( % of feed Carbon ) feedstock stream to produce the oxygenate mixture . Ethanol 2 .0 39 . 9 % 1 . 00 10 . The method of claim 1 , wherein the aromatic hydro Ethanol 2 . 0 40 . 0 % 1 . 00 carbons are selected from the group consisting of benzene , Ethanol 2 .0 40 . 9 % 1 . 02 30 toluene , orthoxylene, metaxylene, paraxylene , ethylben Ethanol 2 . 0 39 . 2 % 0 . 98 Acetic Acid 0 . 0 26 . 7 % 0 .67 zene , C , aromatics , and combinations thereof. Acetic Acid 0 . 0 27 . 1 % 0 . 70 11 . Themethod of claim 1 , wherein the oxygenate mixture Ethanol/ Acetic Acid 1 . 5 70 . 7 % 1 . 77 comprises two or more members selected from the group Ethanol/ Acetic Acid 1 .5 65 . 1 % 1 . 63 consisting of an alcohol, a carboxylic acid , an ester , a ketone , Ethanol/ Acetic Acid 1 . 0 58 . 6 % 1 . 47 35 and an aldehyde . Ethanol/ Acetic Acid 1 . 0 53 . 2 % 1 . 33 12 . The method of claim 1 , wherein hydrogen is produced by step ( a ), step ( b ) , step ( c ) , step ( d ) , or combinations thereof. The invention claimed is : 13 . The method of claim 1 , wherein CO molecules are 1 . A method for producing aromatic hydrocarbons, the 40 produced by step ( a ) , step (b ) , step ( c ), step (d ), or combi method comprising: nations thereof. ( a ) processing a raw feedstock to form an intermediate 14 . The method of claim 13 , wherein a hydrogen stream feedstock ; is combined with the CO , molecules to produce hydrocar ( b ) converting the intermediate feedstock to a feedstock bons, alcohols , carboxylic acids , or combinations thereof. stream comprising an alcohol, a carboxylic acid , or 45 15 . The method of claim 1 , wherein hydrocarbons are combinations thereof; produced by step ( a ), step (b ), step (c ), step ( d ), or combi ( c ) conditioning the feedstock stream to provide an oxy - nations thereof. genate mixture having a total H : C # ratio of between 16 . The method of claim 15 , wherein an oxygen stream is 1 . 2 and 1 . 6 ; and combined with the hydrocarbons to produce alcohols , car ( d ) exposing the oxygenate mixture to a condensation 50 boxylic acids , or combinations thereof. catalyst comprising a member selected from the group 17 . The method of claim 1 , wherein a portion of a consisting of aluminosilicates , silica - alumina phos conditioning temperature is provided by heat generated in phates , and aluminum phosphates to produce aromatic step ( d ) . hydrocarbons , wherein greater than 40 % of carbon in 18 . A method for producing biomass - derived aromatic the intermediate feedstock is contained within the aro - 55 hydrocarbons, the method comprising : matic hydrocarbons. ( a ) processing biomass to form a biomass -derived feed 2 . The method of claim 1 , wherein the intermediate stock ; feedstock comprises oxygenated hydrocarbons, alkanes, alk ( b ) converting the biomass -derived feedstock to a feed enes , CO , molecules, hydrogen , synthesis gas , or combina stock stream comprising an alcohol or carboxylic acid ; tions thereof. 60 (c ) conditioning the feedstock stream to provide an oxy 3 . The method of claim 1 , wherein the converting step ( b ) genate mixture having a total H :Cor ratio of between comprises fermentation , hydrogenolysis , hydrolysis , pyroly 1. 2 and 1 .6 ; and sis , aqueous phase reforming , alcohol synthesis , Fisher ( d ) exposing the oxygenate mixture to a condensation Tropsch synthesis , steam reforming, partial oxygenation , or catalyst comprising a member selected from the group combinations thereof. 65 consisting of aluminosilicates , silica - alumina phos 4 . The method of claim 1 , wherein step ( b ) comprises the phates , and aluminum phosphates at a condensation steps of: pressure and a condensation temperature to produce US 9 ,873 ,836 B2 27 28 aromatic hydrocarbons, wherein greater than 40 % of psig and a condensation temperature of between about carbon in the feedstock stream is contained within the 250° C . and 550° C . to produce the aromatic hydro aromatic hydrocarbons . carbons . 19 . The method of claim 18 , wherein 20 . The method of claim 18 , wherein step (b ) comprises fermenting the biomass -derived feed - 5 step ( b ) comprises fermenting the biomass -derived feed stock with one or more species of microorganism to stock with one or more species of microorganism to form a fermentation broth comprising alcohols or car form a fermentation broth comprising alcohols or car boxylic acids and removing the alcohols or carboxylic boxylic acids ; and removing the alcohols or carboxylic acids from the fermentation broth to provide a feed stock stream comprising ( i ) one or more of a primary 10 acids from the fermentation broth to provide a feed alcohol, methanol, ethanol, n - propanol , iso -propanol , stock stream comprising ( i ) one or more of a primary n -butanol , 2 - butanol, isobutanol, n - pentanol, n -hexa alcohol, methanol, ethanol, n -propanol , iso - propanol, nol, ethylene glycol, propylene glycol, glycerol, eryth n -butanol , 2 -butanol , isobutanol, n -pentanol , n -hexa ritol, threitol or sugar alcohols or ( ii ) one or more of a nol, ethylene glycol, propylene glycol, glycerol, eryth mono - carboxylic acid , a di -carboxylic acid , formic 15 ritol, threitol and sugar alcohols or ( ii ) one or more of acid , acetic acid , propionic acid , butyric acid , isobu a mono - carboxylic acid , a di- carboxylic acid , formic tyric acid , valeric acid , isovaleric acid , caproic acid , acid , acetic acid , propionic acid , butyric acid , isobu oxalic acid , malonic acid , succinic acid , glutaric acid , tyric acid , valeric acid , isovaleric acid , caproic acid , adipic acid , glycolic acid , acrylic acid , lactic acid , oxalic acid , malonic acid , succinic acid , glutaric acid , pyruvic acid , maleic acid , fumaric acid , glutaconic 20 adipic acid , glycolic acid , acrylic acid , lactic acid , acid , muconic acid , itaconic acid , or citric acid ; pyruvic acid , maleic acid , fumaric acid , glutaconic step ( c ) comprises exposing the feedstock stream to a acid , muconic acid , itaconic acid , or citric acid ; dehydrogenation catalyst at a dehydrogenation tem step ( c ) comprises combining a portion of the feedstock perature and a dehydrogenation pressure to produce stream with a portion of a second feedstock stream to diatomic hydrogen and an oxygenate mixture having a 25 provide an oxygenate mixture having a total H :Ce ratio total H : Ceff ratio of between 1 . 2 and 1 . 6 or exposing the of between 1 . 2 and 1 . 6 ; and feedstock stream to hydrogen and a hydrogenation step ( d ) comprises exposing the oxygenate mixture to the catalyst at a hydrogenation temperature and a hydro condensation catalyst at a condensation pressure rang genation pressure to produce an oxygenate mixture ing from less than atmospheric pressure to about 1000 having a total H :Ceff ratio of between 1 . 2 and 1 . 6 ; and 30 psig and a condensation temperature of between about step ( d ) comprises exposing the oxygenate mixture to the 250° C . and 550° C . to produce the aromatic hydro condensation catalyst at a condensation pressure rang carbons. ing from less than atmospheric pressure to about 1000 * * * *