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 FIGURE 1 -- Feed 0000100 102 104 106 BTX - > 100 Raw feedstock processing 102 Conversion 104 Conditioning 106 Condensation U . S . Patent Jan . 23, 2018 Sheet 2 of 11 US 9 ,873 ,836 B2 FIGURE 2 100 102 104 x 106 108 00000100 Processing 102 Conversion 104 Conditioning 106 Condensation 108 Aromatics Plant Ueno . S . Patent .Jan .. 23, 2018 -Sheet -3 of 11 US 9 ,-873 ,836 B2 FIGURE 3 DIEFeed - > 100 102 104 106 BTX - > 100 Processing 102 Conversion 104 Conditioning 106 Condensation Uen . S . Patent Jan . 23, 2018- -Sheet 4 - of 11 . US 9 ,873 ,836 B2. FIGURE 4 --Feed - >0000 100 102 104 106 BTX - > 100 Processing 102 Conversion 104 Conditioning 106 Condensation U . S . Patent Jan . 23, 2018 Sheet 5 of 11 US 9 ,873 , 836 B2 FIGURE 5 -Feed 0000100 102 104 106 BTX 100 Processing 102 Conversion 104 Conditioning 106 Condensation U . S . Patent Jan . 23, 2018 Sheet 6 of 11 US 9 ,873 ,836 B2 FIGURE 6 104 INI 104A 104B > 105A105A 105B U . S . Patent Jan . 23 , 2018 Sheet 7 of 11 ? US 9, 873 , 836 B2 ? FIGURE 7 ? ? ? 3 ?? ? ! …… ?? ? ???? *? 333 283 … ? ? ?????????? ????*** ??? ?1 33288??? U . S . Patent Jan . 23, 2018 Sheet 8 of 11 US 9 ,873 , 836 B2 FIGURE 8 Uy Kects to Ho . seminaripomienky . setaldehyde . HC brother n HO . a eittsiste HICA atent Jan . 23 , 2018 Sheet 9 of ll US 9 , 873 ,836 B2 FIGURE 9 ** * * * * * * * . } - - a {{ { ?? - , * {{ x } ? ? ? % , } } , * * * . } { { {{ { ? } }} U . S . Patent Jan . 23, 2018 Sheet 10 of 11 US 9 ,873 ,836 B2 FIGURE 10 Aromatics ¥ % . parapintados p AromaticsYield(CarbonBasis) aracriandets . 1 . 6 22 *Feed HotHints U . S . Patent Jan. 23, 2018 Sheet 11 of 11 US 9 ,873 , 836 B2 Figure Il Normalized Aromatics Yield ????? NormalizedYield(%ofcarbonfeed] ° • - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - .. … . - - - - - - - - - - - - - - - - - 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.