OA16507A - Processing biomass. - Google Patents
Processing biomass. Download PDFInfo
- Publication number
- OA16507A OA16507A OA1201300323 OA16507A OA 16507 A OA16507 A OA 16507A OA 1201300323 OA1201300323 OA 1201300323 OA 16507 A OA16507 A OA 16507A
- Authority
- OA
- OAPI
- Prior art keywords
- feedstock
- plant
- materials
- modified
- percent
- Prior art date
Links
- 239000002028 Biomass Substances 0.000 title description 22
- 239000000463 material Substances 0.000 claims abstract description 262
- 241000196324 Embryophyta Species 0.000 claims description 116
- -1 vitamîns Substances 0.000 claims description 75
- 229920002678 cellulose Polymers 0.000 claims description 37
- 239000001913 cellulose Substances 0.000 claims description 37
- 229920005610 lignin Polymers 0.000 claims description 33
- 244000005700 microbiome Species 0.000 claims description 31
- 102000004190 Enzymes Human genes 0.000 claims description 28
- 108090000790 Enzymes Proteins 0.000 claims description 28
- 235000000346 sugar Nutrition 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 235000015097 nutrients Nutrition 0.000 claims description 17
- 230000002829 reduced Effects 0.000 claims description 17
- 230000001965 increased Effects 0.000 claims description 16
- 150000001720 carbohydrates Chemical class 0.000 claims description 15
- 235000014633 carbohydrates Nutrition 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 15
- 150000008163 sugars Chemical class 0.000 claims description 14
- 150000001298 alcohols Chemical class 0.000 claims description 13
- 102000004169 proteins and genes Human genes 0.000 claims description 11
- 108090000623 proteins and genes Proteins 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000002363 herbicidal Effects 0.000 claims description 8
- 239000004009 herbicide Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000006011 modification reaction Methods 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 7
- 240000006962 Gossypium hirsutum Species 0.000 claims description 7
- 240000008529 Triticum aestivum Species 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- 235000021307 wheat Nutrition 0.000 claims description 7
- 240000007842 Glycine max Species 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 6
- 240000001016 Solanum tuberosum Species 0.000 claims description 6
- 241000607479 Yersinia pestis Species 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 201000010099 disease Diseases 0.000 claims description 6
- 235000013399 edible fruits Nutrition 0.000 claims description 6
- 239000010907 stover Substances 0.000 claims description 6
- 240000002791 Brassica napus Species 0.000 claims description 5
- 235000004977 Brassica sinapistrum Nutrition 0.000 claims description 5
- 241000238631 Hexapoda Species 0.000 claims description 5
- 235000017585 alfalfa Nutrition 0.000 claims description 5
- 235000017587 alfalfa Nutrition 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 235000005824 corn Nutrition 0.000 claims description 5
- 230000002538 fungal Effects 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 235000016068 Berberis vulgaris Nutrition 0.000 claims description 4
- 241000335053 Beta vulgaris Species 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 4
- 239000004368 Modified starch Substances 0.000 claims description 4
- 230000035784 germination Effects 0.000 claims description 4
- 235000019426 modified starch Nutrition 0.000 claims description 4
- 239000010908 plant waste Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Diphosphoinositol tetrakisphosphate Chemical compound OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 230000036740 Metabolism Effects 0.000 claims description 3
- 108020004511 Recombinant DNA Proteins 0.000 claims description 3
- 240000000111 Saccharum officinarum Species 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 239000003925 fat Substances 0.000 claims description 3
- 230000004060 metabolic process Effects 0.000 claims description 3
- 230000035786 metabolism Effects 0.000 claims description 3
- 239000002417 nutraceutical Substances 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 240000004658 Medicago sativa Species 0.000 claims 1
- 102000007312 Recombinant Proteins Human genes 0.000 claims 1
- 108010033725 Recombinant Proteins Proteins 0.000 claims 1
- 238000000855 fermentation Methods 0.000 abstract description 30
- 230000004151 fermentation Effects 0.000 abstract description 30
- 239000000543 intermediate Substances 0.000 abstract description 18
- 239000000446 fuel Substances 0.000 abstract description 12
- 235000013305 food Nutrition 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 47
- 150000002500 ions Chemical class 0.000 description 37
- 230000003647 oxidation Effects 0.000 description 34
- 238000007254 oxidation reaction Methods 0.000 description 34
- 239000002245 particle Substances 0.000 description 29
- 229910052760 oxygen Inorganic materials 0.000 description 26
- 239000001301 oxygen Substances 0.000 description 26
- 238000000197 pyrolysis Methods 0.000 description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000000527 sonication Methods 0.000 description 17
- 229940088598 Enzyme Drugs 0.000 description 16
- 230000001678 irradiating Effects 0.000 description 14
- 238000010791 quenching Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 238000003801 milling Methods 0.000 description 13
- 230000001590 oxidative Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 230000000171 quenching Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000010504 bond cleavage reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 241001019659 Acremonium <Plectosphaerellaceae> Species 0.000 description 9
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 229920001732 Lignosulfonate Polymers 0.000 description 8
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 8
- 108010047754 beta-Glucosidase Proteins 0.000 description 8
- 102000006995 beta-Glucosidase Human genes 0.000 description 8
- 230000005670 electromagnetic radiation Effects 0.000 description 8
- 239000002657 fibrous material Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 125000004429 atoms Chemical group 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 238000002309 gasification Methods 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 239000011782 vitamin Substances 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 101700071133 BCAM Proteins 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 5
- 108010059892 Cellulase Proteins 0.000 description 5
- 241000195493 Cryptophyta Species 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 229920002488 Hemicellulose Polymers 0.000 description 5
- 241000219823 Medicago Species 0.000 description 5
- 229920000903 Polyhydroxyalkanoate Polymers 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 230000000813 microbial Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butanoic acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- BJHIKXHVCXFQLS-UYFOZJQFSA-N Fructose Natural products OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 description 4
- 229940088597 Hormone Drugs 0.000 description 4
- JTEDVYBZBROSJT-UHFFFAOYSA-N Indole-3-butyric acid Natural products C1=CC=C2C(CCCC(=O)O)=CNC2=C1 JTEDVYBZBROSJT-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N Isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 241001520808 Panicum virgatum Species 0.000 description 4
- SRBFZHDQGSBBOR-SQOUGZDYSA-N Xylose Natural products O[C@@H]1CO[C@@H](O)[C@@H](O)[C@@H]1O SRBFZHDQGSBBOR-SQOUGZDYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000002708 enhancing Effects 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000005556 hormone Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003431 steroids Chemical class 0.000 description 4
- 241000609240 Ambelania acida Species 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 240000003917 Bambusa tulda Species 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001474374 Blennius Species 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 108010084185 Cellulases Proteins 0.000 description 3
- 102000005575 Cellulases Human genes 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 240000007170 Cocos nucifera Species 0.000 description 3
- 240000002275 Cucumis melo Species 0.000 description 3
- 240000001980 Cucurbita pepo Species 0.000 description 3
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000285963 Kluyveromyces fragilis Species 0.000 description 3
- 235000014663 Kluyveromyces fragilis Nutrition 0.000 description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 description 3
- 240000006240 Linum usitatissimum Species 0.000 description 3
- 240000005561 Musa balbisiana Species 0.000 description 3
- 210000004940 Nucleus Anatomy 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 241000209504 Poaceae Species 0.000 description 3
- 240000006394 Sorghum bicolor Species 0.000 description 3
- 229940088594 Vitamin Drugs 0.000 description 3
- 230000003078 antioxidant Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000010905 bagasse Substances 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001488 breeding Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 210000004027 cells Anatomy 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000001461 cytolytic Effects 0.000 description 3
- 235000004879 dioscorea Nutrition 0.000 description 3
- 230000002255 enzymatic Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing Effects 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- 229930003231 vitamins Natural products 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-Butanol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- YJISHJVIRFPGGN-UHFFFAOYSA-N 5-[5-[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxy-6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 YJISHJVIRFPGGN-UHFFFAOYSA-N 0.000 description 2
- 241001438635 Acremonium brachypenium Species 0.000 description 2
- 241001438625 Acremonium dichromosporum Species 0.000 description 2
- 241000228209 Acremonium persicinum Species 0.000 description 2
- 241001019292 Acremonium pinkertoniae Species 0.000 description 2
- 240000005337 Agave sisalana Species 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N Arabitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 2
- 244000075850 Avena orientalis Species 0.000 description 2
- 235000007319 Avena orientalis Nutrition 0.000 description 2
- 235000007558 Avena sp Nutrition 0.000 description 2
- 239000004788 BTU Substances 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 2
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- 240000000218 Cannabis sativa Species 0.000 description 2
- 241000135254 Cephalosporium sp. Species 0.000 description 2
- 241000123346 Chrysosporium Species 0.000 description 2
- 240000006740 Cichorium endivia Species 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 241000193403 Clostridium Species 0.000 description 2
- 240000007154 Coffea arabica Species 0.000 description 2
- 240000000491 Corchorus aestuans Species 0.000 description 2
- 235000011777 Corchorus aestuans Nutrition 0.000 description 2
- 235000010862 Corchorus capsularis Nutrition 0.000 description 2
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 description 2
- 235000009854 Cucurbita moschata Nutrition 0.000 description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 description 2
- GZCGUPFRVQAUEE-KCDKBNATSA-N D-(+)-Galactose Natural products OC[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-KCDKBNATSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241000223218 Fusarium Species 0.000 description 2
- 241000223221 Fusarium oxysporum Species 0.000 description 2
- 241001019284 Gliomastix roseogrisea Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 241000223198 Humicola Species 0.000 description 2
- 241001480714 Humicola insolens Species 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 206010061217 Infestation Diseases 0.000 description 2
- VQHSOMBJVWLPSR-WUJBLJFYSA-N Maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N MeOtBu Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 240000005158 Phaseolus vulgaris Species 0.000 description 2
- 241000235648 Pichia Species 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- 102100002032 RAPGEF3 Human genes 0.000 description 2
- 101710009870 RAPGEF3 Proteins 0.000 description 2
- 241000235070 Saccharomyces Species 0.000 description 2
- 241000190542 Sarocladium kiliense Species 0.000 description 2
- 241000906075 Simplicillium obclavatum Species 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241001313536 Thermothelomyces thermophila Species 0.000 description 2
- 241001494489 Thielavia Species 0.000 description 2
- 235000015450 Tilia cordata Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 240000006909 Tilia x europaea Species 0.000 description 2
- 241000223259 Trichoderma Species 0.000 description 2
- 240000008536 Vaccinium myrtillus Species 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N Xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 Xylitol Drugs 0.000 description 2
- 229960003487 Xylose Drugs 0.000 description 2
- 241000588901 Zymomonas Species 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000001580 bacterial Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 235000003733 chicria Nutrition 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000016213 coffee Nutrition 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000593 degrading Effects 0.000 description 2
- 229920003013 deoxyribonucleic acid Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000010685 fatty oil Substances 0.000 description 2
- 230000002068 genetic Effects 0.000 description 2
- 230000005017 genetic modification Effects 0.000 description 2
- 235000013617 genetically modified food Nutrition 0.000 description 2
- 150000004676 glycans Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 235000012765 hemp Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 235000012766 marijuana Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Polymers 0.000 description 2
- 230000036961 partial Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 239000010817 post-consumer waste Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002285 radioactive Effects 0.000 description 2
- 230000000284 resting Effects 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N α-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-Cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- GLJCPHKWYYCHCQ-UHFFFAOYSA-N 2,5-dimethoxybenzene-1,4-diol Chemical compound COC1=CC(O)=C(OC)C=C1O GLJCPHKWYYCHCQ-UHFFFAOYSA-N 0.000 description 1
- OLBNOBQOQZRLMP-UHFFFAOYSA-N 2,6-Dimethoxy-p-benzoquinone Chemical compound COC1=CC(=O)C=C(OC)C1=O OLBNOBQOQZRLMP-UHFFFAOYSA-N 0.000 description 1
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N 2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-Hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- 229940100198 ALKYLATING AGENTS Drugs 0.000 description 1
- 240000004507 Abelmoschus esculentus Species 0.000 description 1
- 235000009436 Actinidia deliciosa Nutrition 0.000 description 1
- 240000001101 Actinidia deliciosa Species 0.000 description 1
- 235000005254 Allium ampeloprasum Nutrition 0.000 description 1
- 240000006108 Allium ampeloprasum Species 0.000 description 1
- 240000002840 Allium cepa Species 0.000 description 1
- 240000000116 Alocasia Species 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 241000219194 Arabidopsis Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 240000005781 Arachis hypogaea Species 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000233788 Arecaceae Species 0.000 description 1
- 241000082175 Arracacia xanthorrhiza Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 240000001498 Asparagus officinalis Species 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000879125 Aureobasidium sp. Species 0.000 description 1
- 235000000832 Ayote Nutrition 0.000 description 1
- 101710041002 BCAN Proteins 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 244000060924 Brassica campestris Species 0.000 description 1
- 235000005637 Brassica campestris Nutrition 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000011297 Brassica napobrassica Nutrition 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 240000000385 Brassica napus var. napus Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000004221 Brassica oleracea var gemmifera Nutrition 0.000 description 1
- 235000017647 Brassica oleracea var italica Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 240000004448 Brassica oleracea var. gemmifera Species 0.000 description 1
- 235000006618 Brassica rapa subsp oleifera Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 235000004936 Bromus mango Nutrition 0.000 description 1
- 240000001358 Bromus mango Species 0.000 description 1
- 101700010451 CELB Proteins 0.000 description 1
- 229940106157 CELLULASE Drugs 0.000 description 1
- 229910052686 Californium Inorganic materials 0.000 description 1
- 235000002566 Capsicum Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000009467 Carica papaya Nutrition 0.000 description 1
- 240000006432 Carica papaya Species 0.000 description 1
- 241001619326 Cephalosporium Species 0.000 description 1
- 241001147674 Chlorarachniophyceae Species 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 240000007646 Chrysanthemum x morifolium Species 0.000 description 1
- 235000005986 Chrysanthemum x morifolium Nutrition 0.000 description 1
- 241001674013 Chrysosporium lucknowense Species 0.000 description 1
- 240000008051 Cichorium intybus Species 0.000 description 1
- DERZBLKQOCDDDZ-JLHYYAGUSA-N Cinnarizine Chemical compound C1CN(C(C=2C=CC=CC=2)C=2C=CC=CC=2)CCN1C\C=C\C1=CC=CC=C1 DERZBLKQOCDDDZ-JLHYYAGUSA-N 0.000 description 1
- 240000000613 Citrullus lanatus Species 0.000 description 1
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 240000002268 Citrus limon Species 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 241001508811 Clavispora Species 0.000 description 1
- 241001508813 Clavispora lusitaniae Species 0.000 description 1
- 241001508812 Clavispora opuntiae Species 0.000 description 1
- 241000193401 Clostridium acetobutylicum Species 0.000 description 1
- 241001147704 Clostridium puniceum Species 0.000 description 1
- 241000429427 Clostridium saccharobutylicum Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 241000222511 Coprinus Species 0.000 description 1
- 244000251987 Coprinus macrorhizus Species 0.000 description 1
- 235000001673 Coprinus macrorhizus Nutrition 0.000 description 1
- 240000006773 Coriandrum sativum Species 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000007582 Corylus avellana Species 0.000 description 1
- 235000003901 Crambe Nutrition 0.000 description 1
- 241000220246 Crambe <angiosperm> Species 0.000 description 1
- 235000011309 Crambe hispanica subsp abyssinica Nutrition 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 244000302526 Cucurbita pepo subsp pepo Species 0.000 description 1
- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- 235000003954 Cucurbita pepo var melopepo Nutrition 0.000 description 1
- 229910052685 Curium Inorganic materials 0.000 description 1
- 235000017788 Cydonia oblonga Nutrition 0.000 description 1
- 240000000590 Cydonia oblonga Species 0.000 description 1
- 240000008966 Cynara cardunculus Species 0.000 description 1
- 235000019106 Cynara scolymus Nutrition 0.000 description 1
- FBPFZTCFMRRESA-KAZBKCHUSA-N D-Mannitol Natural products OC[C@@H](O)[C@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KAZBKCHUSA-N 0.000 description 1
- 240000002860 Daucus carota Species 0.000 description 1
- 235000002243 Daucus carota subsp sativus Nutrition 0.000 description 1
- 241000235035 Debaryomyces Species 0.000 description 1
- 241001523681 Dendrobium Species 0.000 description 1
- 235000005903 Dioscorea Nutrition 0.000 description 1
- 240000005760 Dioscorea villosa Species 0.000 description 1
- 235000000504 Dioscorea villosa Nutrition 0.000 description 1
- 240000000019 Diospyros kaki Species 0.000 description 1
- 235000011508 Diospyros virginiana Nutrition 0.000 description 1
- 235000014466 Douglas bleu Nutrition 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- 240000000437 Eucalyptus leucoxylon Species 0.000 description 1
- 235000004694 Eucalyptus leucoxylon Nutrition 0.000 description 1
- 235000010705 Eucalyptus maculata Nutrition 0.000 description 1
- 235000009683 Eucalyptus polybractea Nutrition 0.000 description 1
- 235000009687 Eucalyptus sargentii Nutrition 0.000 description 1
- 235000009419 Fagopyrum esculentum Nutrition 0.000 description 1
- 240000008620 Fagopyrum esculentum Species 0.000 description 1
- 241000234642 Festuca Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- SKCKOFZKJLZSFA-FSIIMWSLSA-N Fucitol Chemical compound C[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO SKCKOFZKJLZSFA-FSIIMWSLSA-N 0.000 description 1
- 101700041462 GUX2 Proteins 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N Galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000245654 Gladiolus Species 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N Glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 241000206759 Haptophyceae Species 0.000 description 1
- 240000006669 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 241000271915 Hydrophis Species 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-ZXXMMSQZSA-N Iditol Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-ZXXMMSQZSA-N 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 240000003613 Ipomoea batatas Species 0.000 description 1
- SERLAGPUMNYUCK-DCUALPFSSA-N Isomalt Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O SERLAGPUMNYUCK-DCUALPFSSA-N 0.000 description 1
- 241000235649 Kluyveromyces Species 0.000 description 1
- 229940031154 Kluyveromyces marxianus Drugs 0.000 description 1
- 235000003228 Lactuca sativa Nutrition 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 240000004322 Lens culinaris Species 0.000 description 1
- 235000014647 Lens culinaris subsp culinaris Nutrition 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000208682 Liquidambar Species 0.000 description 1
- 235000006552 Liquidambar styraciflua Nutrition 0.000 description 1
- 241000209082 Lolium Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 229920002521 Macromolecule Polymers 0.000 description 1
- 240000007119 Malus pumila Species 0.000 description 1
- 235000011430 Malus pumila Nutrition 0.000 description 1
- 235000015103 Malus silvestris Nutrition 0.000 description 1
- 235000014826 Mangifera indica Nutrition 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 241000123318 Meripilus giganteus Species 0.000 description 1
- 240000003433 Miscanthus floridulus Species 0.000 description 1
- 241001675980 Moniliella acetoabutens Species 0.000 description 1
- 241000723128 Moniliella pollinis Species 0.000 description 1
- 235000003805 Musa ABB Group Nutrition 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 241000226677 Myceliophthora Species 0.000 description 1
- 241001674208 Mycothermus thermophilus Species 0.000 description 1
- 229910052781 Neptunium Inorganic materials 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 240000008962 Nicotiana tabacum Species 0.000 description 1
- 235000008469 Oxalis tuberosa Nutrition 0.000 description 1
- 240000000645 Oxalis tuberosa Species 0.000 description 1
- 241000235652 Pachysolen Species 0.000 description 1
- 241000235647 Pachysolen tannophilus Species 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical class [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 240000008426 Persea americana Species 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 235000008577 Pinus radiata Nutrition 0.000 description 1
- 241000218621 Pinus radiata Species 0.000 description 1
- 235000008566 Pinus taeda Nutrition 0.000 description 1
- 241000218679 Pinus taeda Species 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 240000000129 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 235000015266 Plantago major Nutrition 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000005204 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 240000002799 Prunus avium Species 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 240000001416 Pseudotsuga menziesii Species 0.000 description 1
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 1
- 241000222180 Pseudozyma tsukubaensis Species 0.000 description 1
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 244000046146 Pueraria lobata Species 0.000 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 240000006764 Punica granatum Species 0.000 description 1
- 229940100486 RICE STARCH Drugs 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 240000007742 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 241000206572 Rhodophyta Species 0.000 description 1
- HEBKCHPVOIAQTA-ZXFHETKHSA-N Ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 235000017848 Rubus fruticosus Nutrition 0.000 description 1
- 240000007651 Rubus glaucus Species 0.000 description 1
- 235000011034 Rubus glaucus Nutrition 0.000 description 1
- 235000009122 Rubus idaeus Nutrition 0.000 description 1
- 241000193448 Ruminiclostridium thermocellum Species 0.000 description 1
- 235000018368 Saccharomyces fragilis Nutrition 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000192263 Scheffersomyces shehatae Species 0.000 description 1
- 241000235060 Scheffersomyces stipitis Species 0.000 description 1
- 241000223255 Scytalidium Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 240000002057 Secale cereale Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 240000003670 Sesamum indicum Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M Sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 240000002686 Solanum melongena Species 0.000 description 1
- 241000746413 Spartina Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- 240000003453 Spinacia oleracea Species 0.000 description 1
- 235000009184 Spondias indica Nutrition 0.000 description 1
- 241001466451 Stramenopiles Species 0.000 description 1
- 241000187747 Streptomyces Species 0.000 description 1
- 241001495429 Thielavia terrestris Species 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 241000006364 Torula Species 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H Tricalcium phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 241000378866 Trichoderma koningii Species 0.000 description 1
- 241000499912 Trichoderma reesei Species 0.000 description 1
- 241000223261 Trichoderma viride Species 0.000 description 1
- 241001079965 Trichosporon sp. Species 0.000 description 1
- 241000908249 Trichosporonoides Species 0.000 description 1
- 241001480015 Trigonopsis variabilis Species 0.000 description 1
- 241000918129 Typhula variabilis Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 241000221533 Ustilaginomycetes Species 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 240000001717 Vaccinium macrocarpon Species 0.000 description 1
- 235000012545 Vaccinium macrocarpon Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 235000002118 Vaccinium oxycoccus Nutrition 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- 229940046009 Vitamin E Drugs 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 229940100445 WHEAT STARCH Drugs 0.000 description 1
- 241000235015 Yarrowia lipolytica Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000005042 Zier Kohl Nutrition 0.000 description 1
- 241000235017 Zygosaccharomyces Species 0.000 description 1
- 241000588902 Zymomonas mobilis Species 0.000 description 1
- 241000222292 [Candida] magnoliae Species 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 description 1
- 229910052767 actinium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229930013930 alkaloids Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005262 alpha decay Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001479 arabinose derivatives Chemical class 0.000 description 1
- 235000016520 artichoke thistle Nutrition 0.000 description 1
- 235000000183 arugula Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine(.) Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 description 1
- 238000004774 atomic orbital Methods 0.000 description 1
- 244000052616 bacterial pathogens Species 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000005255 beta decay Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 235000021029 blackberry Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 210000000081 body of the sternum Anatomy 0.000 description 1
- 235000008984 brauner Senf Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- HGLDOAKPQXAFKI-UHFFFAOYSA-N californium Chemical compound [Cf] HGLDOAKPQXAFKI-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000002354 carica papaya Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 101700046922 cex Proteins 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 235000004634 cranberry Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 230000002939 deleterious Effects 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004520 electroporation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000001612 eucalyptus Nutrition 0.000 description 1
- 235000001617 eucalyptus Nutrition 0.000 description 1
- 235000001621 eucalyptus Nutrition 0.000 description 1
- 235000006356 eucalyptus Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 238000009645 freezer milling Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 244000053095 fungal pathogens Species 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 235000009754 grape Nutrition 0.000 description 1
- 235000012333 grape Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000003621 hammer milling Methods 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000905 isomalt Substances 0.000 description 1
- 235000010439 isomalt Nutrition 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003622 knife milling Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton(0) Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000832 lactitol Substances 0.000 description 1
- 235000010448 lactitol Nutrition 0.000 description 1
- 229960003451 lactitol Drugs 0.000 description 1
- 150000007527 lewis bases Chemical group 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000001638 lipofection Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 230000003505 mutagenic Effects 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- LFNLGNPSGWYGGD-UHFFFAOYSA-N neptunium Chemical compound [Np] LFNLGNPSGWYGGD-UHFFFAOYSA-N 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atoms Chemical group N* 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 235000002732 oignon Nutrition 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 244000045947 parasites Species 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000000149 penetrating Effects 0.000 description 1
- 235000005426 persea americana Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 125000004437 phosphorous atoms Chemical group 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 230000000243 photosynthetic Effects 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon(0) Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000005227 red mallee Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 108010027322 single cell proteins Proteins 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000003583 soil stabilizing agent Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- ZSLUVFAKFWKJRC-UHFFFAOYSA-N thorium Chemical compound [Th] ZSLUVFAKFWKJRC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000003612 virological Effects 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 150000003712 vitamin E derivatives Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000003313 weakening Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 235000005765 wild carrot Nutrition 0.000 description 1
- 241000960357 x Tritordeum Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Feedstocks, obtained at least in part from a plant material that has been modified with respect to its wild type, are processed to produce useful intermediates and products, such as energy, fuels, foods or materials. For example, systems are described that can treat such feedstock materials, e.g., to reduce the recalcitrance of the feedstock, and use the treated feedstock materials to produce an intermediate or product, e.g., by saccharification and/or fermentation.
Description
PROCESSING BIOMASS
RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application Serial No. 61/442,781, filed February 14, 2011. The complété disclosure of this provisional application is hereby incorporated by reference herein.
BACKGROUND
Cellulosic and lignocellulosic materials are produced, processed, and used in large quantifies in a number of applications. Often such materials are used once, and then discarded as waste, or are simply considcred to bc waste materials, e.g., bagasse, sawdust, and stover. In some cases, cellulosic and lignocellulosic materials are obtained by growing and harvesting plants.
SUMMARY
Generally, this invention relates to using and/or processing feedstock materials e.g., cellulosic and/or lignocellulosic feedstock materials, including plants that have been modified with respect to their wild types, e.g., genetically modified plants, and to intermedtates and products made therefrom. Many of the methods described herein provide materials that can be more readily utilized by a variety of microorganisms to produce useful intermediates and products, e.g., energy, a fuel, a food or a material. In one aspect, the invention features methods for making products that include physically treating a cellulosic, lignocellulosic and/or starchy feedstock obtained at least in part from a plant that has been modified with respect to a wild type variety of the plant e.g., the plant has been genetically modified. In some embodiments the entire plant can bc used. In certain embodiments, a portion of the plant is utilized.
Some implémentations include one or more of the following features. The feedstock may include a plant that has recombinant DNA and/or recombinant genes. The 25 modified plant may express one or more recombinant materials, for cxamplc, a protein, a polymer and/or a macromolecule. The method may further include obtaining from the feedstock materials such as pharmaceuticals, nutriceuticals, proteins, fats, vitamine, oils,
fiber, minerais, sugars, carbohydrates and alcohols. The feedstock can include a crop residue e.g., com cobs and/or corn stover, wheat straw, or the feedstock can be a genetically modified com, wheat or soybean plant. The method may further include treating the feedstock with an organism and/or enzyme, in some cases producing a sugar e.g., in the form of a solution or suspension. Optionally the sugar can be fermented. The physical treatment can include irradiation of the feedstock. In some implémentations, the irradiated feedstock may be utilized as an edible material, e.g., as an animal feed. If desired, an enzyme such as a cellulase can be added to the edible material, e.g., to increase the nutrient value release.
Irradiating may in some cases be performed using one or more électron beam devices. In some cases, irradiating comprises applying a total dose of from about 5 Mrad to about 50 Mrad of radiation to the feedstock. Irradiation can sterilize the material prior to further processing and or storage prior to use. In preferred implémentations, irradiating reduces the recalcitrance of the feedstock.
The plant may hâve been modified, for example, with a modification including enhancement of résistance to insects, fungal diseases, and other pests and diseasc-causing agents; increased tolérance to herbicides; increased drought résistance; extended température range; enhaneed tolérance to poor soil; enhaneed stability or shclf-lifc; greater yield; Iarger fruit size; stronger stalks; enhaneed shatter résistance; reduced time to crop maturity; more uniform germination fîmes; higher or modified starch production; enhaneed nutrient production, such as enhaneed, steroid, sterol, hormone, fatty acid, glycerol, polyhydroxyalkanoate, amino acid, vitamin and/or protein production; modified lignin content; enhaneed cellulose, hemicellulose and/or lignin dégradation; including of a phenotype marker to allow qualitative détection; reduced recalcitrance and enhaneed phytate metabolism. The plant may be, for example, a genetically modified alfalfa, potato, beet, com, wheat, cotton, rapeseed, rice, or sugarcane plant. The feedstock may include a crop residue from a modified plant, for example the feedstock may include com cobs and/or com stover. The plant may be, for examplc, a genetically modified com or soybean plant, or any of the many genetically modified plants that are grown.
κ V » ·
In another aspect, the invention features a product comprising sugar derived from a feedstock obtained at least in part from a plant that has been modifîed with respect to a wild type variety of the plant, for example the plant has been genetically modifîed.
In a further aspect, the invention features a product comprising an irradiated cellulosic or lignocellulosic feedstock obtained at least in part from a plant that has been modifîed with respect to a wild type variety of the plant. The product may further include a microorganism and/or an enzyme, and in some cases a liquid medium.
Without being bound by any theory, it is believed that the use of modifîed plants can be advantageous over the non-modified wild type. For example, an enhancement of résistance to insects, fungal diseases, and other pests and disease-causing agents; an increased tolérance to herbicides; increased drought résistance; an extended température range; enhaneed tolérance to poor soil; a larger fruit size; stronger stalks; enhanced shatter résistance; reduced time to crop maturity; more uniform germination times; can provide higher yields and a more varied feedstock source, both of which can lower the biomass feedstock cost. In another example, enhanced stability or shelf-lîfe can be advantageous to biomass inventory quality. As another example, enhanced nutrient production, such as enhanced steroid, stcrol, hormone, fatty acid, glycerol, polyhydroxyalkanoatc, amino acid, vitamin and/or protein production can providc products or intermediates with higher nutrient quality that may improve a process e.g., a fermentation, or a product, e.g., an animal feed. Furthermore, for example, higher or modifîed starch production, modifîed lignin content; and/or enhanced cellulose, hemicellulose and/or lignin dégradation can reduce the recalcitrance of the feedstock making it easier to process.
The term “plant,” as used herein, refers to any of various photosynthetic, cukaryotîc, multicellular organisms of the kingdom Plantae, including but not limited to agricultural crops, trees, grasses, and algae.
“Structurally modifying” a feedstock, as that phrase is used herein, means changing the molecular structure of the feedstock in any way, including the chemical bonding arrangement, crystalline structure, or conformation of the feedstock. The change may be, for example, a change in the integrity of the crystalline structure, e.g., by microfracturing within the structure, which may not be reflected by diffractivc
i measurements of the crystallinity of the material. Such changes in the structural integrity of the material can be measured indirectly by measuring the yield of a product at different levels of structure-modifying treatment. In addition, or alternatively, the change in the molecular structure can include changing the supramolecular structure of the material, oxidation of the material, changing an average molecular weight, changing an average crystallinity, changing a surface area, changing a degree of polymerization, changing a porosity, changing a degree of branching, grafting on other materials, changing a crystalline domain size, or changing an ovcrall domain size.
Unless otherwise defined, ail technical and scientific terms used herein hâve the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or équivalent to those described herein can be used in the practice or testing of the présent invention, suitable methods and materials are described below. Ail publications, patents applications, patents and other référencés mentioned herein are incorporated by reference in their entirety. The materials, methods, and exemples are illustrative only and not intended to be limiting.
Other features and advantages will be apparent from the following detailcd description, and from the claims.
DESCRIPTION OF DRAWINGS
FIG. I is a block diagram illustrating conversion of a feedstock into products and co-products.
FIG. 2 is a block diagram illustrating treatment of the feedstock and the use of the treated feedstock in a fermentation process.
DETAILED DESCRIPTION
Feedstocks that are obtained from plants that hâve been modified with respect to a wild type variety, e.g., by genetic modification or other types of modification, can be proccssed to producc useful intermediates and products such as those described herein. Systems and processes are described herein that can use as feedstock materials e.g., cellulosic and/or lignocellulosic materials that are readily available, but can be difïïcult to process by processes such as fermentation. Many ofthe processes described herein can
> · *
effectively lower the recalcitrance level of the feedstock, making it easier to process, such as by bioprocessing (e.g., with any microorganism described herein, such as a homoacetogen or a heteroacetogcn, and/or any enzyme described herein), thermal processing (e.g., gasification or pyrolysis) or chemîcal methods (e.g., acid hydrolysis or oxidation). The feedstock can be treated or processed using one or more of any of the methods described herein, such as mechanical treatment, chemîcal treatment, radiation, sonication, oxidation, pyrolysis or steam explosion. The various treatment Systems and methods can be used in combinations of two, three, or even four or more of these technologies or others described herein and elsewhere.
In addition to reducing the recalcitrance, the methods outlined above can also sterilize lignocellulosic or cellulosic feedstocks. This can be advantageous because feedstocks can be infected with, for example, a bacteria, a yeast, an insect and/or a fungus, that may hâve a deleterious effect on further processes and/or prematurely dégradé the materials.
Feedstock materials, such as cellulosic and lignocellulosic feedstock materials, can be obtained from plants that hâve been modified with respect to a wild type variety. Such modifications may be for example, by any of the methods described in any patent or patent application rcfcrcnccd herein. As another example, plants may bc modified through the itérative steps of sélection and breeding to obtain desired traits in a plant. Furthermore, the plants can hâve had gcnetic material removed, modified, silenced and/or added with respect to the wild type variety. For example, genetically modified plants can be produced by recombinant DNA methods, where genetic modifications include introducing or modifying spécifie genes from parental varieties, or, for example, by using transgenic breeding wherein a spécifie gene or genes are introduced to a plant from a different species of plant and/or bacteria. Another way to create genetic variation is through mutation breeding wherein new alleles are artifïcially created from endogeneous genes. The artificial genes can bc crcatcd by a variety of ways including treating the plant or seeds with, for example, chemîcal mutagens (e.g., using alkylating agents, epoxides, alkaloids, peroxides, formaldéhyde), irradiation (e.g., X-rays, gamma rays, neutrons, beta particles, alpha particles, protons, deuterons, UV radiation) and température shocking or other external stressing and subséquent sélection techniques. Other methods of providing
modified genes is through errer prone PCR and DNA shuffling followed by insertion of the desired modified DNA into the desired plant or seed, Methods of introducing the desired genetic variation in the seed or plant include, for example, the use of a bacterial carrier, biolistics, calcium phosphate précipitation, electroporation, gene splicing, gene 5 silcncing, lipofection, microinjection and viral carriers.
Feedstock can be derived from a plant including, but not limited to canola, crambe, coconut, maize, mustard, castor bcan, sesame, cottonseed, linsecd, soybean, Arabidopsis phascolus, peanut, alfalfa, wheat, ricc, oat, sorghum, rapeseed, ryc, tritordeum, millet, fescue, rye grass, sugarcane, cranberry, papaya, banana, safïlower, oil 10 palms, flax, muskmelon, apple, cucumbcr, dendrobium, gladiolus, chrysanthemum, liliaccae, cotton, eucalyptus, sunflower, Brassica campestris, Brassica napus, turfgrass, switch grass, cord grass, sugarbeet, coffee, dioscorea, acacia, apricot, artichoke, arugula, asparagus, avocado, barley, beans, beet, blackberry, blueberry, broccoli, brussels sprouts, cabbage, cantaloupe, carrot, cassava, cauliflower, celery, cherry, cilantro, clémentine, 15 com, cotton, Douglas fir, bamboo, seaweed, algac, eggplant, endive, escarole, fennel, fîgs, forest tree, gourd, grape, grapefruit, honcy dew, jîcama, kiwifruit, lettuce, leeks, lemon, lime, loblolly pine, mango, melon, mushroom, nut, oat, okra, onion, orange, parslcy, pea, pcach, pcar, pepper, persimmon, pine, pincapplc, plantain, plum, pomegranate, poplar, potato, oryza sativa, pumpkin, quince, radiata pine, radicchio, radish, raspberry, rye, southem pine, soybean, spinach, squash, strawberry, sweet potato, sweetgum, tangerine, tca, tobacco, tomato, watermelon, wheat, yams, zucchini or mixtures of these. Preferably the feedstock material is derived from plant material not suitable for human consumption such as wood, agricultural waste, grasses such as switchgrass or miscanthus, rice hulls, bagasse, cotton, jute, hemp, flax, bamboo, sisal, 25 abaeâ, straw, com cobs, com stover, hay, coconut hair, seaweed, algae or mixtures of these.
The advantages of plant modification include, for cxamplc, an cnhanccmcnt of résistance to insects, fungal diseases, and other pests and discasc-causing agents; an increased tolérance to herbicides; increased drought résistance; an extended température 30 range; enhanced tolérance to poor soil; enhanced stability or shelf-life; a greater yield; larger fruit size; stronger staiks; enhanced shatter résistance; reduced time to crop maturity; more uniform germination times; higher or modified starch production; cnhanccd nutrient production, such as cnhanced steroid, stcrol, hormone, fatty acid, glycerol, polyhydroxyalkanoate, amino acid, vitamin and/or protein production; modified lignin content; enhanced cellulose, hemiccllulose and/or lignin dégradation; inclusion of a phenotype markcr to allow qualitative détection (e.g., seed coat color); and modified phytatc content. Any feedstock materials derived from these modified plants can also benefit from these many advantages. For examplc, a fccdstock material such as a lignoccllulosic material can have better shelf life, bc casier to process, have a better landto-energy conversion ratio, and/or have a better nutritional value to any microbes that are used in processing of the lignocellulosic material. In addition, any feedstock material derived from such plants can be less expensive and/or more plcntiful. In some cases, modified plants can be grown in a greater variety of climates and/or soil types, for cxample in marginal or deplctcd soils.
Feedstock materials can be obtained from modified plants having an increased résistance to disease. For example, potatoes which have reduced symptoms from the infestation of fungal pathogen Phytophthora infestans arc discussed in U.S. Patent No. 7,122,719. A possible advantage of such résistance is that the yield, quality and shelf life of the fccdstock materials may bc improved.
Feedstock materials can be obtained from modified plants with increased résistance to parasites, for cxample, by cncoding genes for the production of δ-cndotoxins as exemplified in U.S. Patent No. 6,023,013. A possible advantage of such résistance is that the yield, quality and shelf life of the feedstock materials may be improved.
Feedstock materials can be obtained from modified plants having an increased résistance to herbicides. For cxample, the alfalfa plant J-101, as described in U.S. Patent No. 7,566,817, has an increased résistance to glyphosphate herbicides. As a further example, modified plants described in U.S. Patent No. 6,107,549 have an increased résistance to pyridine family herbicides. Furthcrmorc, modified plants described in U.S. Patent No. 7,498,429 have increased résistance to imidazolinoncs. A possible advantage of such résistance is that the yield and quality of the fccdstock materials may be improved.
« < ’
Feedstock materials can be obtained from modified plants having an increased stress résistance (for example, water déficit, cold, heat, sait, pest, disease, or nutrient stress). For example, such plants hâve been described in U.S. Patent No. 7,674,952, A possible advantage of such résistance is that the yield and quality of the feedstock materials may be improved. Moreover, such plants may be grown in adverse conditions, e.g., marginal or depleted soil or in a harsh climate.
Feedstock materials can be obtained from modified plants with improved charactcristics such as larger fruits. Such plants have been described in U.S. Patent No. 7,335,812. A possible advantage of such résistance is that the yield and quality of the feedstock materials may be improved.
Feedstock materials can be obtained from modified plants with improved charactcristics such reduced pod shatter. Such plants have been described in U.S. Patent No. 7,659,448. A possible advantage of such résistance is that the yield and quality of the feedstock materials may be improved.
Feedstock materials can be obtained from modified plants having enhaneed or modified starch content. Such plants have been described in U.S. Patent No. 6,538,178. A possible advantage of such modification is that the quality of the feedstock is improved.
Feedstock materials can be obtained from modified plants with a modified oil, fatty acid or glycol production. Such plants have been described in U.S. Patent No. 7,405,344. Fatty acids and oils are excellent substrates for mîcrobial energy-yielding metabolism and may provide an advantage to downstream processing of the feedstock for, for ex ample, fuel production. Fatty acids and oil variation may also be advantageous in changing the viscosity and solubility of various components during downstream processing of the feedstock. The spent feedstock may have a better nutrient mix for use as animal feed or have higher calorie content useful as a direct fuel for buming.
Feedstock materials can be obtained from modified plants with a modified steroid, stcrol and hormone content. Such plants have been described in U.S. Patent No. 6,822,142. A possible advantage is that this may provide a better nutrient mix for microorganisms used in processing of the feedstock. After processing, the spent feedstock may have a better nutrient mix for use as animal feed.
Feedstock materials can be obtained from modified plants with polyhydroxyalkanoate producing ability. Such plants hâve been described in U.S, Patent
No. 6,175,061. Polyhydroxyalkanoates are a useful energy and carbon reserve for various microorganisms and may be bénéficiai to the microorganisms used in downstream feedstock processing. Also, since polyhydroxyalkanoate is biodégradable, it may impart advantages by possibly reducing rccalcitrance in plant material after an aging period of the stored feedstock. Further downstream, the spent feedstock may hâve a better nutrient mix for use as animal feed or hâve higher calorie content useful as a direct fuel for buming.
Feedstock materials can be obtained from modified plants with enhaneed amino acid production. Such plants hâve been described in U.S. Patent No. 7,615,621. A possible advantage is that this may provide a better nutrient mix for microorganisms used in processing of the feedstock. After processing, the spent feedstock may hâve a better nutrient mix for use as animal feed.
Feedstock materials can be obtained from modified plants with elevated synthesis of vitamine. Such plants hâve been described in U.S. Patent No. 6,841,717. A possible advantage is that this may provide a better nutrient mix for microorganisms used in processing of the feedstock. After processing, the spent feedstock may hâve a better nutrient mix for use as animal feed.
Feedstock materials can be obtained from modified plants that dégradé lignin and cellulose in the plant after harvest. Such plants hâve been described in U.S. Patent No. 7,049,485. Feedstock materials can also be obtained from modified plants with modified lignin content. Such plants hâve been described in U.S. Patent No. 7,799,906. A possible advantage of such plants is reduced recalcitrance relative to the wild types of the same plants.
Feedstock materials can be obtained from modified plants with a modified phenotype for easy qualitative détection. Such plants have been described in U.S. Patent No. 7,402,731. A possible advantage is case of managing crops and seeds for different product streams such as biofuels, building materials and animal feed.
Feedstock materials can be obtained from modified plants with a reduced amount of phytate. Such plants have been described in U.S. Patent No, 7,714,187. A possible
A advantage is that this may provide a better nutrient mix for microorganisms used in processing of the feedstock. After processing, the spent feedstock may hâve a better nutrient mix for use as animal feed.
Modified plants and/or plant materiais and methods for making such modifications hâve been described in lhe U.S. Patents and U.S. Published applications listed at the end of this document (immcdiately before the daims), the entire disclosure of each of which is hereby incorporated by reference herein in its entircty.
SYSTEMS FOR TREATING A FEEDSTOCK
FIG. 1 shows one particular process for converting a feedstock, particularly a feedstock obtained at least in part from a modified plant material, into useful intermediates and products. Process 10 includes initially mechamcaily treating the feedstock (12), e.g., to reduce the size of the feedstock 110. The mechanically treated feedstock is then treated with a physical treatment (14) to modify its structure, for example by weakening or microfracturing bonds in the crystalline structure of the material. Next, the structurally modified material may in some cases be subjected to further mechanical treatment (16). This mechanical treatment can bc the same as or different from the initial mechanical treatment. For example, the initial treatment can be a size réduction (e.g., cutting) step followed by a shearing step, while the further treatment can be a grinding or milling step.
The material can then be subjected to further structure-modifying treatment and mechanical treatment, if further structural change (e.g., réduction in recalcitrance) is desired prior to further processing.
Next, the treated material can be processed with a primary processing step 18, e.g., saccharification and/or fermentation, to produce intermediates and products (e.g., energy, fuel, foods and materiais). In some cases, the output of the primary processing step is dircctly useful but, in other cases, requires further processing provided by a post-proccssing step (20). For example, in the case of an alcohol, post-processing may involve distillation and, in some cases, dénaturation.
As described herein, many variations of process 10 can be utilized.
L
FIG. 2 shows one particular system that utilizes the steps described above for treating a feedstock and then using the treated feedstock in a fermentation process to produce an alcohol. System 100 includes a module 102 in which a feedstock is initially mechanically treated (step 12, above), a module 104 in which the mechanically treated feedstock is structurally modified (step 14, above), e.g., by irradiation, and a module 106 in which the structurally modified feedstock is subjected to further mechanical treatment (step 16, above). As discussed above, the module 106 may be of the same type as the module 102, or a different type. In some implémentations the structurally modified feedstock can bc retumed to module 102 for further mechanical treatment rather than being further mechanically treated in a separate module 106.
As described herein, many variations of system 100 can be utilized.
After these treatments, which may be repeated as many times as required to obtain desired feedstock properties, the treated feedstock is delivered to a fermentation system 108. Mixing may be performed during fermentation, in which case the mixing is preferably relatively gentle (low shear) so as to minimize damage to shear sensitive ingrédients such as enzymes and other microorganisms. In some embodiments, jet mixing is used, as described in U.S. Serial No. 12/782,694, 13/293,977 and 13/293,985, the complété disclosurcs of which arc incorporated herein by reference.
Referring again to FIG. 2, fermentation produces a crude éthanol mixture, which flows into a holding tank 110. Water or other solvent, and other non-ethanol components, arc stripped from the crude éthanol mixture using a stripping column 112, and the éthanol is then distilled using a distillation unit 114, e.g., a rectifier. Distillation may be by vacuum distillation. Finally, the éthanol can be dried using a molecular sieve 116 and/or denatured, if necessary, and output to a desired shipping method.
In some cases, the Systems described herein, or components thereof, may be portable, so that the System can bc transported (e.g., by rail, truck, or marine vessel) from one location to another. The method steps described herein can bc performed at onc or more locations, and in some cases onc or more of the steps can bc performed in transit. Such mobile processing is described in U.S. Serial No. 12/374,549 and International Application No. WO 2008/011598, the fiill disclosurcs of which arc incorporated herein by reference.
Any or ail of the method steps described herein can be performed at ambient température. If desired, cooling and/or heating may be employed during certain steps. For example, the feedstock may be cooled during mechanical treatment to increase its brittlcness. In some embodiments, cooling is employed before, during or after the initial mechanical treatment and/or the subséquent mechanical treatment. Cooling may be performed as described in U.S. Serial No. 12/502,629, now U.S. Patent No. 7,900,857 the iull disclosure of which is incorporatcd herein by reference. Morcover, the température in the fermentation system 108 may be controlled to enhance saccharification and/or fermentation.
The individual steps of the methods described above, as well as the materials used, will now be described in further detail.
PHYSICAL TREATMENT
Physical treatment processes can include one or more of any of those described herein, such as mechanical treatment, chemical treatment, irradiation, sonication, oxidation, pyrolysis or steam explosion. Treatment methods can be used in combinations of two, three, four, or even ail of these technologies (in any order), When more than one treatment method is used, the methods can be applied at the same time or at different fîmes. Other processes that change a molecular structure of a feedstock may also be used, alone or in combination with the proccsscs disclosed herein.
Mechanical Treatments
In some cases, methods can include mechanically treating the feedstock. Mechanical treatments include, for example, cutting, milling, pressing, grinding, shearing and chopping. Milling may include, for example, bail milling, hammer milling, rotor/stator dry or wet milling, freezer milling, blade milling, knife milling, disk milling, relier milling or other types of milling. Other mechanical treatments include, e.g., stonc grinding, cracking, mechanical ripping or tearing, pin grinding or air attrition milling.
Mechanical treatment can be advantageous for opening up,” stressing,” breaking and shattering cellulosic or lignocellulosic materials in the feedstock, making the cellulose of the materials more susceptible to chain scission and/or réduction of
crystallinity. The open materials can also be more susceptible to oxidation when irradiatcd.
In some cases, the mechanical treatment may include an initial préparation of the feedstock as received, e.g., size réduction of materials, such as by cutting, grinding, shearing, pulverizing or chopping. For example, in some cases, loose feedstock (e.g., recycled paper, starchy materials, or switchgrass) is prepared by shearing or shredding.
Alternatively, or in addition, the feedstock material can first be physically treated by onc or more of the other physical treatment methods, e.g., chemical treatment, radiation, sonication, oxidation, pyrolysis or steam explosion, and then mechanically treated. This sequence can be advantageous since materials treated by one or more of the other treatments, e.g., irradiation or pyrolysis, tend to be more brittle and, therefore, it may be easier to further change the molecular structure of the material by mechanical treatment.
In some embodiments, the feedstock is in the form of a fibrous material, and mechanical treatment includes shearing to expose fîbers of the fibrous material. Shearing can be performed, for example, using a rotary knife cutter. Other methods of mechanically treating the feedstock include, for exemple, milling or grinding. Milling may bc performed using, for example, a hammer mill, bail mill, colloid mill, conical or cône mill, disk mill, edge mill, Wiley mill or grist mill. Grinding may be performed using, for example, a stonc grinder, pin grinder, coffee grinder, or burr grinder. Grinding may be provided, for example, by a reciprocating pin or other element, as is the case in a pin mill. Other mechanical treatment methods include mechanical ripping or tearing, other methods that apply pressure to the material, and air attrition milling. Suitable mechanical treatments further include any other technique that changes the molecular structure of the feedstock.
If desired, the mechanically treated material can be passed through a screen, e.g., having an average opening size of 1.59 mm or less (1/16 inch, 0.0625 inch). In some embodiments, shearing, or other mechanical treatment, and screening arc performed concurrently. For example, a rotary knife cutter can be used to concurrently shear and screen the feedstock. The feedstock is sheared between stationary bladcs and rotating bladcs to provide a sheared material that passes through a screen, and is captured in a bin.
The feedstock can be mechanically treated in a dry state (e.g., having little or no free water on its surface), a hydrated state (e.g,, having up to ten percent by weight absorbed water), or in a wet state, e.g., having between about 10 percent and about 75 percent by weight water. The fiber source can even be mechanically treated while partially or fully submerged under a liquid, such as water, éthanol or isopropanol.
The feedstock can also be mechanically treated under a gas (such as a stream or atmosphère of gas other than air), e.g., oxygen or nitrogen, or steam.
If desired, lignin can bc removed from any of the fibrous materials that include lignin. Also, to aid in the breakdown of the materials that include cellulose, the material can be treated prior to or during mechanical treatment or irradiation with heat, a chemical (e.g., minerai acid, base or a strong oxidizer such as sodium hypochlorite) and/or an enzyme. For example, grinding can be performed in the presence of an acid.
Mechanical treatment système can be confîgured to produce streams with spécifie morphology characteristics such as, for example, surface area, porosity, bulk density, and, in the case of fibrous feedstocks, fiber characteristics such as length-to-width ratio.
In some embodiments, a BET surface area of the mechanically treated material is greater than 0.1 m2/g, e.g., greater than 0.25 mz/g, greater than 0.5 m2/g, greater than 1.0 m2/g, greater than 1.5 m2/g, greater than 1.75 m2/g, greater than 5.0 m2/g, greater than 10 m2/g, greater than 25 m2/g, greater than 35 m2/g, greater than 50m2/g, greater than 60 m2/g, greater than 75 m2/g, greater than 100 m2/g, greater than 150 m2/g, greater than 200 m2/g, or even greater than 250 m2/g.
A porosity of the mechanically treated material can be, e.g., greater than 20 percent, greater than 25 percent, greater than 35 percent, greater than 50 percent, greater than 60 percent, greater than 70 percent, greater than 80 percent, greater than 85 percent, greater than 90 percent, greater than 92 percent, greater than 94 percent, greater than 95 percent, greater than 97.5 percent, greater than 99 percent, or even greater than 99.5 percent.
In some embodiments, after mechanical treatment the material has a bulk density of less than 0.75 g/cm3, e.g., less than about 0.7, 0.65, 0.60, 0.50, 0.35, 0.25, 0.20,0.15, 0.10, 0.05, or less, e.g., less than 0.025 g/cm3. Bulk density is determined using ASTM D1895B. Briefly, the method involves filling a measuring cylinder of known volume
with a sample and obtaining a weight of the sample. The bulk density is calculated by dividing the weight of the sample in grams by the known volume of the cylinder in cubic centimeters.
If the feedstock is a fibrous material the fibers of the mechanically treated material can have a relatively large average lcngth-to-diameter ratio (e.g., greater than 20-to»l), even if they have been shearcd more than once. In addition, the fibers of the fibrous materials described herein may have a relatively narrow length and/or length-todiameter ratio distribution.
As used herein, average fiber widths (e.g,, diameters) are those determined optically by randomly selecting approximately 5,000 fibers. Average fiber lengths are corrected length-weighted lengths. BET (Brunaucr, Emmct and Tellcr) surface areas are multi-point surface areas, and porosities arc those determined by mercury porosimetry.
If the feedstock is a fibrous material the average length-to-diameter ratio of fibers of the mechanically treated material can be, e.g., greater than 8/1, e.g., greater than 10/1, greater than 15/1, greater than 20/1, greater than 25/1, or greater than 50/1. An average fiber length of the mechanically treated material can be, e.g., between about 0.5 mm and
2.5 mm, e.g., between about 0.75 mm and 1.0 mm, and an average width (e.g., diameter) of the second fibrous material 14 can be, e.g., between about 5 gm and 50 gm, e.g., between about 10 gm and 30 gm.
In some embodiments, if the feedstock is a fibrous material the standard déviation of the fiber length of the mechanically treated material can be less than 60 percent of an average fiber length of the mechanically treated material, e.g., less than 50 percent of the average length, less than 40 percent of the average length, less than 25 percent of the average length, less than 10 percent of the average length, less than 5 percent of the average length, or even less than 1 percent of the average length.
In some situations, it can be désirable to prépare a low bulk density material, densify the material (e.g., to makc it casier and less costly to transport to another site), and then revert the material to a lower bulk density state. Dcnsificd materials can be processcd by any of the methods described herein, or any material proccssed by any of the methods described herein can be subsequcntly dcnsificd, e.g., as disclosed in U.S.
Serial No. 12/429,045 now U.S. Patent No. 7,932,065 and WO 2008/073186, the full disclosures of which are incorporated herein by reference.
Radiation Treatment
One or more radiation processing sequences can be used to process the feedstock, and to provide a structurally modified material which functions as input to further processing steps and/or sequences. Irradiation can, for example, rcduce the molecular weight and/or crystallinity of feedstock. Radiation can also sterilize the materials, or any media needed to bioprocess the material.
In some embodiments, energy deposited in a material that releases an électron from its atomic orbital is used to irradiaie the materials. The radiation may be provided by (1) heavy charged particles, such as alpha particles or protons, (2) électrons, produced, for example, in beta decay or électron beam accelerators, or (3) electromagnetic radiation, for example, gamma rays, x rays, or ultraviolet rays. In one approach, radiation produced by radioactive substances can be used to irradiate the feedstock. In another approach, electromagnetic radiation (e.g., produced using électron beam emitters) can be used to irradiate the feedstock. In some embodiments, any combination in any order or concurrcntly of (1) through (3) may be utilized. The doses applied dépend on the desired effect and the particular feedstock.
In some instances when chain scission is désirable and/or polymer chain functionalization is désirable, particles heavicr than électrons, such as protons, hélium nuclei, argon ions, silicon ions, néon ions, carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be utilized. When ring-opening chain scission is desired, positively charged particles can be utilized for their Lewis acid properties for enhanced ringopening chain scission. For example, when maximum oxidation is desired, oxygen ions can be utilized, and when maximum nitration is desired, nitrogen ions can be utilized. The use of heavy particles and positively charged particles is described in U.S. Serial No. 12/417,699, now U.S. Patent No. 7,931,784, the full disclosure of which is incorporated herein by reference.
In one method, a first material that is or includes cellulose having a first number average molecular weight (Mni) is irradiated, e.g., by treatment with ionizing radiation
(e.g., in the form of gamma radiation, X-ray radiation, 100 nm to 280 nm ultraviolet (UV) light, a beam of électrons or other charged particles) to provide a second material that includes cellulose having a second number average molecular weight (MN2) lower than the first number average molecular weight. The second material (or the first and second material) can bc combined with a mîcroorganism (with or without enzyme treatment) that can utilize the second and/or first material or its constituent sugars or lignin to produce an intermediate or product, such as those described herein.
Since the second matériel includes cellulose having a reduced molecular weight relative to the first material, and in some instances, a reduced crystallinity as well, the second material is generally more dispersible, swellable and/or soluble, e.g., in a solution containing a mîcroorganism and/or an enzyme. These properties make the second material casier to process and more susceptible to chemical, enzymatic and/or biological attack relative to the first material, which can greatly improve the production rate and/or production level of a desired product, e.g., éthanol.
In some embodiments, the second number average molecular weight (Mn2) is lower than the first number average molecular weight (Mnj) by more than about 10 percent, e.g., more than about 15, 20, 25, 30, 35, 40, 50 percent, 60 percent, or even more than about 75 percent.
ln some instances, the second material includes cellulose that has a crystallinity (C2) that is lower than the crystallinity (Ci) of the cellulose of the first material. For cxample, (C2) can be lower than (Ci) by more than about 10 percent, e.g., more than about 15, 20, 25, 30, 35,40, or even more than about 50 percent.
In some embodiments, the starting crystallinity index (prior to irradiation) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after irradiation is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent. However, in some embodiments, e.g., after extensive irradiation, it is possible to have a crystallinity index of lower than 5 percent. In some embodiments, the material after irradiation is substantially amorphous.
In some embodiments, the starting number average molecular weight (prior to irradiation) is from about 200,000 to about 3,200,000, e.g., from about 250,000 to about
.V
1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after irradiation is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments, e.g., after extensive irradiation, it is possible to hâve a number average molecular weight 5 of less than about 10,000 or even less than about 5,000.
In some embodiments, the second material can hâve a level of oxidation (O2) that is higher than the level of oxidation (Oi) of the first material. A higher level of oxidation of the material can aid in its dispcrsabilîty, swcllability and/or solubility, further enhancing the material’s susccptibility to chemîcal, enzymatic or biological attack. In some embodiments, to increase the level of the oxidation of the second material relative to the first material, the irradiation is performed under an oxidizing environment, e.g., under a blankct of air or oxygen, producîng a second material that is more oxidized than the first material. For example, the second material can hâve more hydroxyl groups, aldéhyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.
Ionizine Radiation
Each form of radiation ionizes the carbon-containing material via particular interactions, as determined by the energy of the radiation. Heavy charged particles primarily ionize matter via Coulomb scattering; furthermore, these interactions produce 20 energetic électrons that may further ionize matter. Alpha particles are identical to the nucléus of a hélium atom and are produced by the alpha decay of various radioactive nucleî, such as isotopes of bismuth, polonium, astatine, radon, francium, radium, several actinides, such as actinium, thorium, uranium, neptunium, curium, californium, américium, and plutonium.
When particles arc utilized, they can bc ncutral (uneharged), positively charged or ncgativcly charged. When charged, the charged particles can bcar a single positive or négative charge, or multiple charges, e.g., one, two, three or even four or more charges. In instances in which chain scission is desired, positively charged particles may be désirable, in part due to their acidic nature. When particles are utilized, the particles can hâve the mass of a resting électron, or greater, e.g., 500,1000, 1500, 2000, 10,000 or even 100,000 times the mass of a resting électron. For example, the particles can hâve a mass of from about 1 atomic unit to about 150 atomic units, e.g., from about 1 atomic unit to about 50 atomic units, or from about 1 to about 25, e.g., 1, 2, 3,4, 5, 10, 12 or 15 amu. Accéléra tors used to accelerate the particles can be electrostatic DC, electrodynamic DC, RF linear, magnetic induction linear or continuons wave. For example, cyclotron type accelerators are available from IBA, Belgium, such as the Rhodotron® systern, while DC type accelerators arc available from RDI, now IBA Industrial, such as the Dynamitron®. Ions and ion accelerators are discussed in Introductory Nuclcar Physics, Kenneth S, Krane, John Wiley & Sons, Inc. (1988), Krsto Prclcc, F1Z1KA B 6 (1997) 4, 177-206, Chu, William T., “Ovcrvicw of Light-lon Bcam Therapy” Columbus-Ohio, 1CRU-IAEA Meeting, 18-20 March 2006, Iwata, Y. et al., “Altemating-Phase-Focuscd IH-DTL for Hcavy-Ion Medical Accelerators” Procecdings of EPAC 2006, Edinburgh, Scotland and Leaner, C.M. et al, “Status of the Superconducting ECR Ion Source Venus” Procecdings of EPAC 2000, Vienna, Austria.
Gamma radiation has the advantage of a significant pénétration depth into a variety of materials. Sources of gamma rays include radioactive nuclei, such as isotopes of cobalt, calcium, technicium, chromium, gallium, indium, iodine, iron, krypton, samarium, sélénium, sodium, thalium, and xénon.
Sources of x rays include électron beam collision with métal targets, such as tungsten or molybdcnum or alloys, or compact light sources, such as those produced commercially by Lyncean.
Sources for ultraviolet radiation include deuterium or cadmium lamps.
Sources for infrared radiation include sapphire, zinc, or selenide window ceramic lamps.
Sources for microwaves include klystrons, Slevin type RF sources, or atom bcam sources that employ hydrogen, oxygen, or nitrogen gases.
In some embodiments, a beam of électrons is used as the radiation source. A beam of électrons has the advantages of high dose rates (e.g., 1, 5, or even 10 Mrad per second), high throughput, less containment, and less confinement equipment. Electrons can also be more efficient at causing chain scission. In addition, électrons having
( energies of 4-10 MeV can hâve a pénétration depth of 5 to 30 mm or more, such as 40 mm.
Electron beams can be generatcd, e.g,, by electrostatic generators, cascade generators, transformer generators, low energy accelerators with a scanning system, low energy accelerators with a linear cathode, linear accelerators, and pulsed accelerators. Electrons as an ionizing radiation source can be useful, e.g., for relatively thin sections of material, e.g., less than 0.5 înch, e.g., less than 0.4 inch, 0.3 inch, 0.2 inch, or less than 0.1 inch. In some embodiments, the energy of each électron of the électron bcam is from about 0.3 MeV to about 2.0 MeV (million électron volts), e.g., from about 0.5 MeV to about 1.5 MeV, or from about 0.7 MeV to about 1.25 MeV.
Electron beam irradiation devices may be procured commercially from Ion Bcam Applications, Louvain-la-Ncuve, Belgium or the Titan Corporation, San Diego, CA. Typical électron energies can be 1 MeV, 2 MeV, 4.5 MeV, 7.5 MeV, or 10 MeV. Typical électron beam irradiation device power can be 1 kW, 5 kW, 10 kW, 20 kW, 50 kW, 100 kW, 250 kW, or 500 kW. The level of depolymerization of the feedstock dépends on the électron energy used and the dose applied, while exposure time dépends on the power and dose. Typical doses may take values of 1 kGy, 5 kGy, 10 kGy, 20 kGy, 50 kGy, 100 kGy, or 200 kGy. In a some embodiments énergies between 0.25-10 MeV (e.g., 0.5-0.8 MeV, 0.5-5 MeV, 0.8-4 MeV, 0.8-3 MeV, 0.8-2 MeV or 0.8-1.5 MeV) can be used. In some embodiments doses between 1-100 Mrad (e.g., 2-80 Mrad, 5-50 Mrad,
5-40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used. In some preferred embodiments, an energy between 0.8-3 MeV (e.g., 0.8-2 MeV or 0.8-1.5 MeV) combined with doses between 5-50 Mrad (e.g., 5-40 Mrad, 5-30 Mrad or 5-20 Mrad) can be used.
Ion Particle Beams
Particles heavicr than électrons can be utîlized to irradiate materials, such as carbohydrates or materials that include carbohydrates, e.g., ccllulosic materials, lignocellulosic materials, starchy materials, or mixtures of any of these and others described herein. For example, protons, hélium nuclei, argon ions, silicon ions, néon ions carbon ions, phosphorus ions, oxygen ions or nitrogen ions can be utilized. In some embodiments, particles heavicr than électrons can induce higher amounts of chain
scission (relative to lighter particles). In some instances, positively charged particles can induce higher amounts of chain scission than negatively charged particles due to their acidity.
Heavîer particle beams can be generated, e.g., using linear accelerators or cyclotrons. In some embodiments, the energy of each particle of the beam is from about l .0 MeV/atomic unit (MeV/amu) to about 6,000 MeV/atomic unit, e.g., from about 3 MeV/ atomic unit to about 4,800 MeV/atomic unit, or from about 10 MeV/atomic unit to about 1,000 MeV/atomic unit.
In certain embodiments, ion beams used to irradiate carbon-containing matériels, e.g., materiais obtained from plants, can include more than one type of ion. For example, ion beams can include mixtures of two or more (e.g., three, four or more) different types of ions. Exemplary mixtures can include carbon ions and protons, carbon ions and oxygen ions, nitrogen ions and protons, and iron ions and protons. More generally, mixtures of any of the ions discussed above (or any other ions) can be used to form irradlating ion beams. In particular, mixtures of relatively light and relatively heavier ions can be used in a single ion beam.
In some embodiments, ion beams for irradiating materiais include positivelychargcd ions. The positively charged ions can include, for exemple, positively charged hydrogen ions (e.g., protons), noble gas ions (e.g., hélium, néon, argon), carbon ions, nitrogen ions, oxygen ions, silicon atoms, phosphorus ions, and métal ions such as sodium ions, calcium ions, and/or iron ions. Without wishing to be bound by any theory, it is belicved that such positively-charged ions behave chemically as Lewis acid moieties when exposed to materiais, initiating and sustaining cationic ring-opening chain scission reactions in an oxidative environment.
In certain embodiments, ion beams for irradiating materiais include negativelycharged ions. Negatively charged ions can include, for example, negatively charged hydrogen ions (e.g., hydridc ions), and negatively charged ions of various relatively clcctroncgativc nuclci (e.g., oxygen ions, nitrogen ions, carbon ions, silicon ions, and phosphorus ions). Without wishing to be bound by any theory, it is believed that such negatively-charged ions behave chemically as Lewis base moieties when exposed to
materials, causing anionie ring-opening chain scission reactions in a reducing environment.
In some embodiments, beams for irradiating materials can include neutral atoms. For example, any one or more of hydrogen atoms, hélium atoms, carbon atoms, nitrogen atoms, oxygen atoms, néon atoms, silicon atoms, phosphorus atoms, argon atoms, and iron atoms can be included in beams that are used for irradiation. In general, mixtures of any two or more of the above types of atoms (e.g., three or more, four or more, or even more) can bc présent in the beams.
In certain embodiments, ion beams used to irradiate materials include singlycharged ions such as one or more of H+, H, He+, Ne*, Ar*, C*, C', O*, O', N*, N’, Si*, Si', P+, P’, Na+, Ca+, and Fe*. In some embodiments, ion beams can include multiply-charged ions such as onc or more of C2*, C3*, C4+, N3*, N5*, N3, Ο2*, Ο2’, Oj2’, Si2*, Si4*, Si2', and Si4'. In general, the ion beams can also include more complex polynuclear ions that bear multiple positive or négative charges. In certain embodiments, by virtue of the structure of the polynuclear ion, the positive or négative charges can be effectively distributed over substantially the entire structure of the ions. In some embodiments, the positive or négative charges can be somewhat localizcd over portions of the structure of the ions.
Electromagnetic Radiation
In embodiments in which the irradiating is performed with electromagnetic radiation, the electromagnetic radiation can hâve, e.g., energy per photon (in électron volts) of greater than lO2 eV, e.g., greater than ΙΟ3, ΙΟ4,105, ÎO6, or even greater than ÎO7 eV. In some embodiments, the electromagnetic radiation has energy per photon of between ÎO4 and 107, e.g., between 105 and 10û eV, The electromagnetic radiation can hâve a frequency of, e.g., greater than 1016 hz, greater than 1017 hz, ΙΟ18, 1019, 1020, or even greater than 1021 hz. Typical doses may takc values of greater than 1 Mrad (e.g., greater than 1 Mrad, greater than 2 Mrad). In some embodiments, the electromagnetic radiation has a frequency of between 1018 and 1022 hz, e.g., between 1019 to 1021 hz. In some embodiment doses between 1-100 Mrad (e.g., 2-80 Mrad, 5-50 Mrad, 5-40 Mrad,
5-30 Mrad or 5-20 Mrad) can be used.
t
I
Quenching and Controlled Functionalization
After treatment with ionizing radiation, any of the materials or mixtures described herein may become ionized; that is, the treated material may include radicals at levels that are détectable with an électron spin résonance spectrometer. If an ionized feedstock rcmains in the atmosphère, it will be oxidized, such as to an extent that carboxylic acid groups are generated by reacting with the atmospheric oxygen. In some instances with some materials, such oxidation is desired becausc it can aid in the further breakdown in molecular weight of the carbohydratc-containing biomass, and the oxidation groups, e.g., carboxylic acid groups can bc hclpful for solubility and microorganism utilization in some instances. Howcver, since the radicals can “live” for some time after irradiation, e.g., longer than 1 day, 5 days, 30 days, 3 months, 6 months or even longer than 1 year, material properties can continue to change over time, which in some instances, can be undesirable. Thus, it may be désirable to quench the ionized material.
After ionization, any ionized material can be quenched to reduce the level of radicals in the ionized material, e.g., such that the radicals are no longer détectable with the électron spin résonance spectrometer. For example, the radicals can be quenched by the application of a sufficient pressure to the material and/or by utilizing a fluid in contact with the ionized material, such as a gas or liquid, that rcacts with (qucnchcs) the radicals. Using a gas or liquid to at least aid in the quenching of the radicals can be used to functîonalizc the ionized material with a desired amount and kind of functîonal groups, such as carboxylic acid groups, enol groups, aldéhyde groups, nitro groups, nitrile groups, amino groups, alkyl amino groups, alkyl groups, chloroalkyl groups or chlorofluoroalkyl groups.
In some instances, such quenching can improve the stability of some of the ionized materials. For example, quenching can improve the résistance of the material to oxidation. Functionalization by quenching can also improve the solubility of any material described herein, can improve its thermal stability, and can improve material utilization by various microorganisms. For cxamplc, the functîonal groups imparted to the material by the quenching can act as receptor sites for attachment by microorganisms, e.g., to enhance cellulose hydrolysis by various microorganisms.
t
In some embodiments, quenching includes an application of pressure to the ionized material, such as by mcchanically deforming the material, e.g., directly mechanically compressing the material in one, two, or three dimensions, or applying pressure to a fluid in which the material is immersed, e.g., isostatic pressing. In such instances, the deformation of the malerial itself brings radicale, which are often trapped in crystalline domains, in close enough proximity so that the radicale can recombine, or react with another group. In some instances, the pressure is applied together with the application of heat, such as a sufficicnt quantity of heat to elevate the température of the material to above a melting point or softening point of a component of the material, such as lignin, cellulose or hemicellulose. Heat can improve molecular mobility in the material, which can aid in the quenching of the radicals. When pressure is utilized to quench, the pressure can be greater than about 1000 psi, such as greater than about 1250 psi, 1450 psi, 3625 psi, 5075 psi, 7250 psi, 10000 psi or even greater than 15000 psi.
In some embodiments, quenching includes contacting the ionized material with a fluid, such as a liquid or gas, e.g., a gas capable of reacting with the radicals, such as acetylene or a mixture of acetylene in nitrogen, ethylene, chlorinated ethylenes or chlorofluorocthylcnes, propylenc or mixtures of these gases. In other particular embodiments, quenching includes contacting the ionized material with a liquid, e.g., a liquid soluble in, or at least capable of penetrating into the material and reacting with the radicals, such as a diene, such as 1,5-cyclooctadiene. In some spécifie embodiments, quenching includes contacting the material with an antioxidant, such as Vitamin E. If desired, the feedstock can include an antioxidant dispersed thercin, and the quenching can corne from contacting the antioxidant dispersed in the feedstock with the radicals.
Functionalization can be enhanced by utilizing heavy charged ions, such as any of the heavier ions described herein. For example, if it is desired to cnhance oxidation, charged oxygen ions can be utilized for the irradiation. If nitrogen functional groups are desired, nitrogen ions or anions that include nitrogen can bc utilized. Likcwisc, if sulfur or phosphorus groups arc desired, sulfur or phosphorus ions can bc used in the irradiation.
I
Doses
In some instances, the irradiation is performed at a dosage rate of greater than about 0.25 Mrad per second, e.g., greater than about 0.5,0,75,1.0,1.5, 2.0, or even greater than about 2.5 Mrad per second. In some embodiments, the irradiating is performed at a dose rate of between 5.0 and 1500.0 kilorads/hour, e.g., between 10.0 and 750.0 kilorads/hour or between 50.0 and 350.0 kilorads/hour. In some embodiments, irradiation is performed at a dose rate of greater than about 0.25 Mrad per second, e.g., greater than about 0.5,0.75, 1,1.5, 2, 5, 7, 10,12,15, or even greater than about 20 Mrad per second, e.g., about 0.25 to 2 Mrad per second.
In some embodiments, the irradiating (with any radiation source or a combination of sources) is performed until the material receives a dose of 0.25 Mrad, e.g., at least 1.0, 2.5, 5.0, 8.0, 10, 15, 20, 25, 30, 35, 40, 50, or even at least 100 Mrad. In some embodiments, the irradiating is performed until the material receives a dose of between 1.0 Mrad and 6.0 Mrad, e.g., between 1.5 Mrad and 4.0 Mrad, 2 Mrad and 10 Mrad, 5 Mrad and 20 Mrad, 10 Mrad and 30 Mrad, 10 Mrad and 40 Mrad, or 20 Mrad and 50 Mrad. In some embodiments, the irradiating is performed until the material receives a dose of from about 0.1 Mrad to about 500 Mrad, from about 0.5 Mrad to about 200 Mrad, from about 1 Mrad to about 100 Mrad, or from about 5 Mrad to about 60 Mrad. In some embodiments, a relatively low dose of radiation is applied, e.g., less than 60 Mrad.
Sonicatlon
Sonication can reduce the molecular weight and/or crystallinity of materials, such as one or more of any of the materials described herein, e.g., one or more carbohydrate sources, such as cellulosic or lignocellulosic materials, or starchy materials. Sonication can also be used to sterilize the materials. As discussed above with regard to radiation, the process parameters used for sonication can be varied depending on various factors, e.g., depending on the lignin content of the feedstock. For exemple, feedstocks with higher lignin levels generally require a higher résidence time and/or energy level, resulting in a higher total energy delivered to the feedstock.
In one method, a first material that includes cellulose having a first number average molecular weight (Mm) is dispersed in a medium, such as water, and sonicated
and/or otherwise cavitated, to provide a second material that includes cellulose having a second number average molecular weight (Mnï) lower than the first number average molecular weight. The second material (or the first and second material in certain embodiments) can be combined with a microorganism (with or without enzyme treatment) that can utîlize the second and/or first material to produce an intermediate or product.
Sînce the second material includes cellulose having a reduced molecular weight relative to the first material, and in some instances, a rcduccd crystallinity as well, the second material is generally more dispersible, swellable, and/or soluble, e.g., in a solution containing a microorganism.
In some embodiments, the second number average molecular weight (Mn2) is lower than the first number average molecular weight (Μχι) by more than about 10 percent, e.g., more than about 15,20, 25,30, 35, 40, 50 percent, 60 percent, or even more than about 75 percent.
In some instances, the second material includes cellulose that has a crystallinity (C2) that is lower than the crystallinity (Cj) of the cellulose of the first material. For cxample, (C2) can be lower than (Ci) by more than about 10 percent, e.g., more than about 15, 20,25, 30, 35, 40, or even more than about 50 percent.
In some embodiments, the starting crystallinity index (prior to sonication) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after sonication is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent. However, in certain embodiments, e.g., after extensive sonication, it is possible to hâve a crystallinity index of lower than 5 percent. In some embodiments, the material after sonication is substantially amorphous.
In some embodiments, the starting number average molecular weight (prior to sonication) is from about 200,000 to about 3,200,000, e.g., from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after sonication is from about 50,000 to about 200,000, e.g., from about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments,
, 1
e.g., after extensive sonication, it is possible to have a number average molecular weight of less than about 10,000 or even less than about 5,000.
In some embodiments, the second material can have a level of oxidation (O2) that is higher than the level of oxidation (Oj) of the first material. A higher level of oxidation of the material can aid in its dispersabilîty, swellability and/or solubility, further cnhancing the material’s susceptibility to chemical, cnzymatic or mîcrobial attack. In some embodiments, to increase the level of the oxidation of the second material relative to the first material, the sonication is performed in an oxidizing medium, producing a second material that is more oxidized than the first material. For example, the second material can have more hydroxyl groups, aldéhyde groups, ketone groups, ester groups or carboxylic acid groups, which can increase its hydrophilicity.
In some embodiments, the sonication medium is an aqueous medium. If desired, the medium can include an oxidant, such as a peroxide (e.g., hydrogen peroxide), a dispersing agent and/or a buffer. Examples of dispersing agents include ionic dispersing agents, e.g., sodium lauryl sulfate, and non-ionic dispersing agents, e.g., poly(ethylene glycol).
In other embodiments, the sonication medium is non-aqucous. For example, the sonication can be performed in a hydrocarbon, e.g., toluene or heptane, an ether, c.g„ diethyl ether or tetrahydrofuran, or even in a liquefied gas such as argon, xénon, or nitrogen.
Pvrolysls
One or more pyrolysis processing sequences can be used to process carboncontaining materials from a wide variety of different sources to extract useful substances from the materials, and to provide partially degraded materials which fonction as input to forther processing steps and/or sequences. Pyrolysis can also be used to sterilize the materials. Pyrolysis conditions can bc varied depending on the charactcristics of the feedstock and/or other factors. For example, fccdstocks with higher lignin levels may requirc a higher température, longer résidence time, and/or introduction of higher levels of oxygen during pyrolysis.
ln one example, a first material that includes cellulose having a first number average molecular weight (Mni) is pyrolyzed, e.g., by heating the first material in a tube fumace (in the presence or absence of oxygen), to provide a second material that includes cellulose having a second number average molecular weight (MN2) lower than the first 5 number average molecular weight.
Since the second material includes cellulose having a reduced molecular weight relative to the first material, and in some instances, a reduced ciystallinity as well, the second material is generally more dispcrsiblc, swellable and/or soluble, e.g., in a solution containing a microorganism.
In some embodiments, the second number average molecular weight (Mnî) is lower than the first number average molecular weight (Μχι) by more than about 10 percent, e.g., more than about 15, 20,25, 30, 35,40, 50 percent, 60 percent, or even more than about 75 percent.
In some instances, the second material includes cellulose that has a crystallinity (C2) that is lower than the crystallinity (Ci) of the cellulose of the first material. For example, (C2) can be lower than (Ci) by more than about 10 percent, e.g., more than about 15, 20, 25, 30, 35,40, or even more than about 50 percent.
In some embodiments, the starting crystallinity (prior to pyrolysis) is from about 40 to about 87.5 percent, e.g., from about 50 to about 75 percent or from about 60 to about 70 percent, and the crystallinity index after pyrolysis is from about 10 to about 50 percent, e.g., from about 15 to about 45 percent or from about 20 to about 40 percent. However, in certain embodiments, e.g., after extensive pyrolysis, it is possible to have a crystallinity index of lower than 5 percent. In some embodiments, the material after pyrolysis is substantially amorphous.
In some embodiments, the starting number average molecular weight (prior to pyrolysis) îs from about 200,000 to about 3,200,000, e.g., from about 250,000 to about 1,000,000 or from about 250,000 to about 700,000, and the number average molecular weight after pyrolysis is from about 50,000 to about 200,000, e.g., fforn about 60,000 to about 150,000 or from about 70,000 to about 125,000. However, in some embodiments,
e.g., after extensive pyrolysis, it is possible to have a number average molecular weight of less than about 10,000 or even less than about 5,000.
In some embodiments, the second material can have a level of oxidation (O2) that is higher than the level of oxidation (Oj) of the first material. A higher level of oxidation of the material can aid in its dispersability, swellability and/or solubility, further enhancing the susceptibility of the material to chemical, enzymatic or microbial attack,
In some embodiments, to increase the level of the oxidation of (he second material relative to the first material, the pyrolysis is performed in an oxidizing environment, producing a second material that is more oxidized than the first material. For example, the second material can have more hydroxyl groups, aldéhyde groups, kctonc groups, ester groups or carboxylic acid groups, than the first material, thereby increasing the o hydrophi licity of the materi al.
In some embodiments, the pyrolysis of the materials is continuous. In other embodiments, the material is pyrolyzed for a pre-determined time, and then allowed to cool for a second pre-determined time before pyrolyzing again,
Oxidation
One or more oxidative processing sequences can be used to process carboncontaining materials from a wide variety of different sources to extract useful substances from the materials, and to providc partially degraded and/or altcrcd material which functions as input to further processing steps and/or sequences. The oxidation conditions 20 can be varied, e.g., depending on the lignin content of the feedstock, with a higher degree of oxidation generally being desired for higher lignin content feedstocks.
In one method, a first material that includes cellulose having a first number average molecular weight (Mni) and having a first oxygen content (O|) is oxidized, e.g., by heating the first material in a stream of air or oxygen-cnriched air, to provide a second 25 material that includes cellulose having a second number average molecular weight (Μχ2) and having a second oxygen content (O2) higher than the first oxygen content (Oj).
The second number average molecular weight of the second material is generally lower than the first number average molecular weight of the first material. For examplc, the molecular weight may be reduced to the same extent as discussed above with respect 30 to the other physicaï treatments. The crystallinity of the second material may also be
reduced to the same extent as discussed above with respect to the other physical treatmcnts.
In some embodiments, the second oxygen content is at least about five percent higher than the first oxygen content, e.g., 7.5 percent higher, 10.0 percent higher, 12.5 percent higher, 15.0 percent higher or 17.5 percent higher. In some preferred embodiments, the second oxygen content is at least about 20.0 percent higher than the first oxygen content of the first material. Oxygen content is measured by elemental analysis by pyrolyzing a sample in a furnace operating at 1300 °C or higher. A suitable elemental analyzer is the LECO CHNS-932 analyzer with a VTF-900 high température pyrolysis furnace.
Generally, oxidation of a material occurs in an oxidizing environment. For example, the oxidation can bc effected or aided by pyrolysis in an oxidizing environment, such as in air or argon enriched in air. To aid in the oxidation, various chemîcal agents, such as oxidants, acids or bases can be added to the material prior to or during oxidation. For example, a peroxide (e.g., benzoyl peroxide) can be added prior to oxidation.
Some oxidative methods of reducing recalcitrance in a biomass feedstock employ Fcnton-type chemistry. Such methods are disclosed, for example, in U.S. Serial No. 12/639,289, the complète disclosure of which is incorporated herein by référence.
Exemplary oxidants include peroxides, such as hydrogen peroxide and benzoyl peroxide, persulfates, such as ammonium persulfate, activated forms of oxygen, such as ozone, permanganates, such as potassium permanganate, perchlorates, such as sodium perchlorate, and hypochlorites, such as sodium hypochlorite (household bleach).
In some situations, pH is maintained at or below about 5.5 during contact, such as between 1 and 5, between 2 and 5, between 2.5 and 5 or between about 3 and 5. Oxidation conditions can also include a contact period of between 2 and 12 hours, e.g., between 4 and 10 hours or between 5 and 8 hours. In some instances, température is maintained at or below 300 °C, e.g., at or below 250,200, 150,100 or 50 °C. In some instances, the température romains substantially ambient, e.g., at or about 20-25 °C.
In some embodiments, the one or more oxidants are applied as a gas, such as by generating ozone in-situ by irradiating the material through air with a bcam of particles, such as électrons.
In some embodiments, the mixture further includes one or more hydroquinones, such as 2,5-dimethoxyhydroquinone (DMHQ) and/or one or more benzoquinones, such as 2,5-dimethoxy-l,4-benzoquinone (DMBQ), which can aid in électron transfer réactions.
In some embodiments, the one or more oxidants are electrochemically-generated in-situ. For example, hydrogen peroxide and/or ozone can be electro-chemically produced within a contact or réaction vcssel.
Other Processes To Solubilize, Red u ce Recalcitrance Or To Functionalîze
Any of the processes of this paragraph can be used alone without any of the processes described herein, or in combination with any of the processes described herein (in any order): steam explosion, chemical treatment (e.g., acid treatment (including concentrated and dilute acid treatment with minerai acids, such as sulfuric acid, hydrochloric acid and organic acids, such as trifluoroacetic acid) and/or base treatment (e.g., treatment with lime or sodium hydroxide)), UV treatment, screw extrusion treatment (see, e.g., U.S. Serial No. 13/099,151, solvent treatment (e.g., treatment with ionic liquids) and freeze milling (see, e.g., U.S. Serial No. 12/502,629 now U.S. Patent No. 7,900,857).
PRODUCTION OF FUELS. ACIDS, ESTERS AND/OR OTHER PRODUCTS
AND USES
A typical feedstock obtained at least in part from plants contains cellulose, hemiccllulose, and lignin plus lesser amounts of proteins, cxtractables and minerais. After onc or more of the processing steps discusscd above hâve been performed on the feedstock, the complex carbohydrates containcd in the cellulose and hemicellulose fractions can in some cases bc proccsscd into fcrmcntablc sugars, optionally, along with acid or enzymatic hydrolysis. The sugars liberated can be converted into a variety of products, such as alcohols or organic acids. The product obtained dépends upon the microorganism utilized and the conditions under which the bioproccssing occurs. In other embodiments, the treated feedstock can be subjected to thermochemical conversion, 30 or other processing.
»
Examples of methods of further processing the treated feedstock are discussed in the following sections.
Saccharification
In order to convert the treated feedstock to a form that can be readily fermented, in some implémentations the cellulose in the feedstock is first hydrolyzcd to low molecular weight carbohydrates, such as sugars, by a saccharifying agent, e.g., an enzyme, a process referred to as saccharification. In some implémentations, the saccharifying agent comprises an acid, e.g., a minerai acid. When an acid is used, coproducts may be generated that are toxic to microorganisms, in which case the process can further include removing such co-products. Removal may be performed using an activated carbon, e.g., activated charcoal, or other suitable techniques.
The treated feedstock can be hydrolyzcd using an enzyme, e.g., by combining the material and the enzyme in a solvent, e.g., in an aqueous solution.
Enzymes and biomass-destroying organisme that break down biomass, such as the cellulose and/or the lignin portions of the feedstock, contain or manufacture various ccllulolytic enzymes (ccllulascs), lîgninases or various small molécule biomassdestroying métabolites. These enzymes may be a complex of enzymes that act synergistically to dégrade crystalline cellulose or the lignin portions of biomass. Examples of cellulolytic enzymes include: endoglucanases, ccllobiohydrolases, and cellobiases (β-glucosidases). A cellulosic substratc is initially hydrolyzed by endoglucanases at random locations producing oligomeric intermediates. These intermediates are then substrates for cxo-splitting glucanases such as ccllobiohydrolase to produce cellobiose from the ends of the cellulose polymer. Cellobiose is a water-soluble l ,4-linked dimer of glucose. Finally cellobiase cleaves cellobiose to yield glucose.
Fermentation
Microorganisms can produce a number of useful intermediates and products by fermenting a low molecular weight sugar produced by saccharifying the treated feedstock. For example, fermentation or other bioprocesses can produce alcohols, organic acids, hydrocarbons, hydrogen, proteins or mixtures of any of these materials.
«
Yeast and Zymomonas bacteria, for example, can be used for fermentation or conversion. Other microorganisms are discussed in the Materials section, below. The optimum pH for fermentations is about pH 4 to 7. The optimum pH for yeast is from about pH 4 to 5, while the optimum pH for Zymomonas is from about pH 5 to 6. Typical fermentation times are about 24 to 168 (e.g., 24-96 hrs) hours with températures in the range of 20 °C to 40 °C (e.g., 26 °C to 40 °C), however thcrmophilic microorganisms prefer higher températures.
In some embodiments e.g., when anaérobie organisme arc used, at least a portion of the fermentation is conductcd in the absence of oxygen e.g., under a blanket of an inert gas such as N2, Ar, He, CO2 or mixtures thereof. Additionally, the mixture may have a constant purge of an inert gas flowing through the tank during part of or ail of the fermentation. In some cases, anaérobie condition can be achieved or maintained by carbon dioxide production during the fermentation and no additional inert gas is needed.
In some embodiments, ail or a portion of the fermentation process can be interrupted before the low molecular weight sugar is completely converted to a product (e.g. éthanol). The intermediate fermentation products include high concentrations of sugar and carbohydrates. The sugars and carbohydrates can be isolated as discussed below. These intermediate fermentation products can bc used in préparation of food for human or animal consumption. Additionally or aiternatively, the intermediate fermentation products can be ground to a fine particle size in a stainless-steel laboratory mill to producc a flour-like substance.
The fermentations include the methods and products that are disclosed in U.S. Provisional Application Serial No. 61/579,559, filed Dcccmber, 2011 and U.S. Provisional Application Serial No. 61/579,576, filed Dccember, 2011 incorporated herein by reference.
Mobile fermentons can be utilized, as described in U.S. Provisional Patent Application Serial No. 60/832,735, now Publishcd International Application No. WO 2008/011598. Similarly, the saccharification equipment can bc mobile. Further, saccharification and/or fermentation may bc performed in part or entirely during transit.
Fuel Cells
Where the methods described herein produce a sugar solution or suspension, this solution or suspension can subsequently be used in a fuel cell. For example, fuel cells utilizing sugars derived from cellulosic or lignocellulosic materiais are disclosed in U.S. Provisional Application Serial No. 61/579,568, filed December 22,2011, the complété disclosure of which is incorporated herein by reference.
Thermochemical Conversion
Thcrmochemical conversion can be performed on the treated feedstock to produce one or more desired intermediates and/or products. A thermochemical conversion o process includes changing molecular structures of carbon-containing material at elevated températures. Spécifie examples include gasificatîon, pyrolysis, reformation, partial oxidation and mixtures of these (in any order).
Gasification couverts carbon-containing materiais into a synthesis gas (syngas), which can include methanol, carbon monoxide, carbon dioxide and hydrogen. Many 15 microorganisms, such as acetogcns or homoacctogens are capable of utilizing a syngas from the thermochemical conversion of biomass, to produce a product that includes an alcohol, a carboxylic acid, a sait of a carboxylic acid, a carboxylic acid ester or a mixture of any of these, Gasification of biomass (e.g., cellulosic or lignocellulosic materiais), can be accomplishcd by a variety of techniques. For example, gasification can be accomplished utilizing staged steam reformation with a fluidized-bed reactor in which the carbonaceous material is first pyrolyzed in the absence of oxygen and then the pyrolysis vapors are reformed to synthesis gas with steam providing added hydrogen and oxygen. In such a technique, process heat cornes from burning char. Another technique utilizes a screw auger reactor in which moisture and oxygen are introduced at the pyrolysis stage and the process heat is generated from burning some of the gas produced in the latter stage. Another technique utilizes entrained flow reformation in which both cxtcmal steam and air are introduced in a single-stage gasification reactor. In partial oxidation gasification, pure oxygen is utilized with no steam,
POST-PROCESSING
Distillation
After fermentation, the resulting fluids can be distilled using, for example, a “beer column” to separate éthanol and other alcohols from the majority of water and residual solids. The vapor exiting the beer column can be, e.g., 35% by weight éthanol and can be fed to a rectification column. A mixture of nearly azcotropic (92.5%) cthanol and water from the rectification column can bc purified to pure (99.5%) cthanol using vapor-phasc molecular sieves. The beer column bottoms can bc sent to the first effect of a thrce-effect evaporator. The rectification column reflux condenser can provide heat for this first effect. After the first effect, solids can be separated using a centrifuge and dried in a rotary dryer. A portion (25%) of the centrifuge effluent can be recycled to fermentation and the rest sent to the second and third evaporator effects. Most of the evaporator condensate can be retumed to the process as fairly clcan condensate with a small portion split off to waste water treatment to prevent build-up of low-boiling compounds.
Other Possible Processine of Sugars
Proccssing during or after saccharification can include isolation and/or concentration of sugars by chromatography e.g., simulated moving bed chromatography, précipitation, centrifugation, crystal lization, solvent évaporation and combinations thereof. In addition, or optionally, processing can include isomerization of one or more of the sugars in the sugar solution or suspension. Additionally, or optionally, the sugar solution or suspension can be chemically processed e.g., glucose and xylose can be hydrogenated to sorbitol and xylitol respectively. Hydrogénation can bc accomplished by use of a catalyst e.g., Pt/y-AhCh, Ru/C, Raney Nickel in combination with H2 under high pressure e.g., 10 to 12000 psi.
Some possible proccssing steps arc disclosed in in U.S. Provisional Application Serial No. 61/579,552, filed December 22, 2011, and in U.S. Provisional Application Serial No. 61/579,576 , filed December 22, 2011, incorporated by référencé above.
( 4
INTERMEDIATES AND PRODUCTS
Using, e.g., such primary processes and/or post-processing, the treated biomass can be converted to one or more products, such as energy, fuels, foods and materials. Spécifie examples of products include, but are not limited to, hydrogen, sugars (e.g., glucose, xylose, arabinose, mannose, galactose, fructose, disaccharides, oligosaccharides and polysaccharides), alcohols (e.g., monohydric alcohols or dihydric alcohols, such as cthanol, n-propanol, isobutanol, .vec-butanol, tert-butanol or n-butanol), hydrated or hydrous alcohols, e.g., containing greater than 10%, 20%, 30% or even greater than 40% water, sugars, biodiescl, organic acids (e.g., acetic acid and/or lactic acid), hydrocarbons, co-products (e.g., proteins, such as cellulolytic proteins (enzymes) or single cell proteins), and mixtures of any of these in any combination or relative concentration, and optionally in combination with any additives, e.g., fuel additives. Other examples include carboxylic acids, such as acetic acid or butyric acid, salts of a carboxylic acid, a mixture of carboxylic acids and salts of carboxylic acids and esters of carboxylic acids (e.g., methyl, ethyl and n-propyl esters), ketones, aldéhydes, alpha, beta unsaturated acids, such as acrylic acid, olefins, such as ethylene, and mixtures of any of these. Other alcohols and alcohol dérivatives include propanol, propylene glycol, 1,4-butanediol, 1,3propancdiol, sugar alcohols (e.g., crythritol, glycol, glyccrol, sorbitol thrcitol, arabitol, ribitol, mannitol, dulcitol, fucitol, iditol, isomalt, maltitol, lactitol, xylitol and other polyols), methyl or ethyl esters of any of these alcohols, Other products include methyl acrylate, methylmethacrylate, lactic acid, propionic acid, butyric acid, succinic acid, 3hydroxypropionic acid, a sait of any of the acids and a mixture of any of the acids and respective salts.
In some embodiments using, e.g., such primary processes and/or post-processing, the treated biomass can be converted to a platform chemical. For exemple, as stated above, the treated biomass can bc converted to butanols (e.g., isobutanol, sec-butanol, tcrt-butanol or n-butanoi) which arc important platform chcmicals. For exemple, déhydration of butanols can producc butcncs such as 1-butcnc, cw-2-butcnc, trans-2butene and isobutene, which are highly valuable starting materials for synthetic fuels, lubricants and other valuable chemicals. Specifically, 1-butene can be used in the créations of polymers, e.g., linear low density polyethylene, 2-butene isomers are » · · valuable starting materials for lubricants and agricultural chemicals, and Isobutene can be polymerized to butyl rubber, methyl tert-butyl ether and isooctane. In addition, synthetic petroleum kerosene can be synthesized by oligomérization of butenes. Other intermediates and products, including food and pharmaceutical products, for example edible materials selected from the group consisting of pharmaceuticals, nutriceuticals, proteins, fats, vitamine, oils, fiber, minerais, sugars, carbohydrates and alcohols, are described in U.S. Serial No. 12/417,900, the full disclosure of which is hcrcby incorporatcd by reference herein.
MATERIALS
Modifîed Plant Materials
The plant feedstock is obtained at least in part from one or more types of modifîed plants, as dîscussed herein. In some cases, the feedstock includes more than one type of plant, and/or more than one portion of the plant, e.g., the stalk, fruit, and cob of a com plant. The plant may be, for example, a com, soybean, beet, cotton, rapeseed, potato, rice, alfalfa, or sugarcanc plant. The plant may also be any of the many types of genetically modifîed plants that are grown. The feedstock may contain a mixture of different types of plants, different parts of a particular plant, and/or mixtures of plant materials with other materials e.g., biomass materials.
In some cases the entire plant can be used. For cxample, in cases where a crop is ruined by adverse growing conditions (e.g., drought, frost, flooding, pest infestation) the ruined crop can be useful in the methods and processcs described herein.
Other Feedstock Materials
In addition or as an alternative to the modifîed plant materials dîscussed above, the feedstock can include other materials e.g., bïomass materials, that may or may not be genetically modifîed. The biomass can bc, e.g., a cellulosic or lignocellulosic material. Such materials include paper and paper products (e.g., polycoated paper and Kraft paper), wood, wood-related materials, e.g., particle board, grasses, rice hulls, bagasse, jute, hemp, flax, bamboo, sisal, abaca, straw, switchgrass, alfalfa, hay, com cobs, corn stover,
coconut haïr; and materials high in α-cellulose content, e.g., cotton. Feedstocks can be obtained from virgin scrap textile materials, e.g., rcmnants, post consumer waste, e.g., rags. When paper products are used they can be virgin materials, e.g., scrap virgin materials, or they can be post-consumer waste. Aside from virgin raw materials, post5 consumer, industrial (e.g., offal), and processing waste (e.g., effluent from paper processing) can also be used as fiber sources. Biomass feedstocks can also be obtained or derived from human (e.g., sewage), animal or plant wastes. Additional cellulosic and lignocellulosic materials hâve been described in U.S. Patent Nos. 6,448,307; 6,258,876; 6,207,729; 5,973,035 and 5,952,105.
In some embodiments, the biomass material includes a carbohydrate that is or includes a material having one or more p-l,4-linkagcs and having a number average molecular weight between about 3,000 and 50,000. Such a carbohydrate is or includes cellulose (I), which is derived from (β-glucose 1) through condensation of β(1,4)~ glycosidic bonds. This linkage contrasts itself with that for a(l,4)-glycosîdic bonds présent in starch and other carbohydrates.
fl
I «
I
Starchy materials include starch itself, e.g., corn starch, wheat starch, potato starch or rice starch, a dérivative of starch, or a material that includes starch, such as an edible food product or a crop. For example, the starchy material can be arracacha, buckwheat, banana, barley, cassava, kudzu, oca, sago, sorghum, regular household potatocs, swcet potato, taro, yams, or one or more beans, such as favas, lentils or peas. Blends of any two or more starchy materials are also starchy materials.
In some instances the biomass is a microbial material. Microbial sources include, but arc not limited to, any naturally occurring or gcnctîcally modified microorganism or organism that contains or is capable of providing a source of carbohydrates (e.g., cellulose), for exemple, protists, e.g., animal protists (e.g., protozoa such as flagellâtes, amoeboids, ciliatcs, and sporozoa) and plant protists (e.g., algae such alveolates, chlorarachniophytes, cryptomonads, cuglenids, glaucophytes, haptophytes, red algae, stramenopiles, and viridaeplantae). Other examples include seaweed, plankton (e.g., macroplankton, mesoplankton, microplankton, nanoplankton, picoplankton, and femptoplankton), phytoplankton, bactcria (e.g., gram positive bacteria, gram négative bacteria, and extrcmophiles), yeast and/or mixtures of these. In some instances, microbial biomass can be obtained from natural sources, e.g., the océan, lakes, bodies of water, e.g., sait water or fresh water, or on land. Alternatively or in addition, microbial biomass can be obtained from culture Systems, e.g., large scale dry and wet culture Systems.
Saccharifving Agents
a
Suitable enzymes include cellobiases and cellulases capable of degrading biomass.
Suitable cellobiases include a cellobiase from Aspergillus niger sold under the tradename NOVOZYME 188™.
Cellulases are capable of degrading biomass, and may be of fungal or bacterial origin. Suitable enzymes include cellulases from the généra Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, Chrysosporium and Trichoderma, and include species of Humicola, Coprinus, Thielavia, Fusarium, Myceliophthora, Acremonium, Cephalosporium, Scytalidium, Pénicillium or Aspergillus (see, e.g., EP 458162), especially those produced by a strain selected from the species Humicola insolens (reclassified as Scytalidium thermophilum, see, e.g., U.S. Patent No. 4,435,307), Coprinus cinereus, Fusarium oxysporum, Myceliophthora thermophila, Meripilus giganteus, Thielavia terrestris, Acremonium sp., Acremonium persicinum, Acremonium acremonium, Acremonium brachypenium, Acremonium dichromosporum, Acremonium obclavatum, Acremonium pinkertoniae, Acremonium roseogriseum, Acremonium incoloratum, and Acremonium furatum', preferably from the species Humicola insolens DSM 1800, Fusarium oxysporum DSM 2672, Myceliophthora thermophila CBS 117.65, Cephalosporium sp. RYM-202, Acremonium sp. CBS 478.94, Acremonium sp. CBS 265.95, Acremonium persicinum CBS 169.65, Acremonium acremonium AHU 9519, Cephalosporium sp. CBS 535.71, Acremonium brachypenium CBS 866.73, Acremonium dichromosporum CBS 683.73, Acremonium obclavatum CBS 311.74, Acremonium pinkertoniae CBS 157.70, Acremonium roseogriseum CBS 134.56, Acremonium incoloratum CBS 146.62, and Acremonium furatum CBS 299.70H. Ccllulolytic enzymes may also be obtained from Chrysosporium, preferably a strain of Chrysosporium lucknowense. Additionally, Trichoderma (particularly Trichoderma viride, Trichoderma reesei, and Trichoderma koningii), alkalophilîc Bacillus (sce, for exampic, U.S. Patent No. 3,844,890 and EP 458162), and Streptomyces (scc, e.g., EP 458162) may bc used.
Enzyme complexes may bc utilized, such as those available from Gcncncorc under the tradename ACCELLERASE®, for example, Accellerase® 1500 enzyme complex. Accellerase 1500 enzyme complex contains multiple enzyme activities, mainly exoglucanase, endoglucanase (2200-2800 CMC U/g), hemi-cellulase, and beta-
glucosidasc (525-775 pNPG U/g), and has a pH of 4.6 to 5.0. The endoglucanase activity of the enzyme complex is exprcssed in carboxymethylcellulose activity units (CMC U), while the beta-glucosidase activity is reported in pNP-glucoside activity units (pNPG U).
In one embodiment, a blend of Accelierase® 1500 enzyme complex and NOVOZYME™ 5 188 cellobiase îs used.
Fermentation Agents
The microorganism(s) used in fermentation can bc naturel microorganisms and/or engineered microorganisms. For example, the microorganîsm can be a bacterium, e.g., a cellulolytic bacterium, a fungus, e.g., a yeast, a plant or a protist, e.g., an algae, a protozoa or a fungus-like protist, e.g., a slime mold. When the organisme are compatible, mixtures of organisms can be utilized.
Suitable fermenting microorganisms have the ability to convert carbohydrates, such as glucose, fructose, xylosc, arabînose, mannose, galactose, oligosaccharides or 15 polysaccharides into fermentation products. Fermenting microorganisms include strains of the genus Sacchromyces spp. e.g., Sacchromyces cerevisiae (baker’s yeast), Saccharomyces distaticus, Saccharomyces uvarunv, the genus Kluyveromyces, e.g., spccics Kluyveromyces marxianus, Kluyveromyces fragilis', the genus Candida, e.g., Candidapseudotropicalis, and Candida brassicae, Pichia stipitis (a relative of Candida shehatae, the genus Clavispora, e.g., species Clavispora lusitaniae and Clavispora opuntiae, the genus Pachysolen, e.g., species Pachysolen tannophilus, the genus Bretannomyces, e.g., species Bretannomyces ciausenii (Philippidis, G. P., 1996, Cellulose bioconversion technology, in Handbook on Biocthanol: Production and Utilization, Wyman, C.E., ed., Taylor & Francis, Washington, DC, 179-212). Other suitable microorganisms include, for example, Zymomonas mobilis, Clostridium thermocellum (Philippidis, 1996, supra), Clostridium saccharobutylacetonicum, Clostridium saccharobutylicum, Clostridium Puniceum, Clostridium beijernckii, Clostridium acetobutylicum, Moniliella pollinis, Yarrowia lipolytica, Aureobasidium sp., Trichosporonoides sp., Trigonopsis variabilis, Trichosporon sp., Moniliellaacetoabutans,
Typhula variabilis, Candida magnoliae, Ustilaginomycetes, Pseudozyma tsukubaensis, yeast species of généra Zygosaccharomyces, Debaryomyces, Hansenula and Pichia, and fiingi of the dematioid genus Torula.
Commercially available yeasts include, for example, Red Star®/Lesaffre Ethanol Red (available from Red Star/Lesaffre, USA), FALI® (available from Fleischmann’s 5 Yeast, a division of Bums Philip Food Inc., USA), SUPERSTART® (available from Alltech, now Lalemand), GERT STRAND® (available from Gert Strand AB, Sweden) and FERMOL® (available from DSM Specialtics).
OTHER EMBODIMENTS
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention.
For example, the process parameters of any of the processing steps discussed herein can be adjusted based on the lignin content of the feedstock, for example as 15 disclosed in U.S. Serial No. 12/704,519, the full disclosure of which is incorporated herein by reference.
The process may include any of the features described in U.S. Application Serial No. 13/276,192, the full disclosure of which is incorporated herein by reference, including treating a ccllulosic or lignoccllulosic material to altcr the structure of the material by irradiating the material with relativeiy low voltage, high power électron beam radiation, boiling or steeping the feedstock prior to saccharification, and irradiating a ccllulosic or lignocellulosic material with an électron beam at a dose rate of at least 0.5 Mrad/sec.
While it is possible to perform ail the processes described herein at one physicaï location, in some embodiments, the processes arc completed at multiple sites, and/or may be performed during transport.
Lignin lîbcratcd in any process described herein can bc capturcd and utilizcd. For cxample, the lignin can bc used as capturcd as a plastic, or it can be synthetically upgradcd to other plastics, ln some instances, it can bc utilizcd as an energy source, e.g., 30 bumed to provide heat. In some instances, it can also be converted to lignosulfonates, which can be utilized as bïnders, dispersants, emulsifiers or as séquestrants.
. 1
Measurement of the lignin content of the starting feedstock can be used in process control in such lignin-capturing processes.
When used as a binder, the lignin or a lignosulfonate can, e.g., be utilized in coal briquettes, in ceramics, for binding carbon black, for binding fertilizers and herbicides, as a dust suppressant, in the making of plywood and particle board, for binding animal feeds, as a binder for fibergiass, as a binder in linoléum paste and as a soil stabilizer.
As a dispersant, the lignin or lignosulfonates can bc used, e.g., concrète mixes, clay and ceramics, dycs and pigments, Icathcr tanning and in gypsum board.
As an emulsifier, the lignin or lignosulfonates can be used, e.g., in asphalt, pigments and dyes, pesticides and wax émulsions.
As a séquestrant, the lignin or lignosulfonates can be used, e.g., in micro-nutrient Systems, cleaning compounds and water treatment Systems, e.g., for boiler and cooling Systems.
As a heating source, lignin generally has a higher energy content than holocelhilose (cellulose and hemicellulose) since it contains more carbon than homocellulosc. For example, dry lignin can hâve an energy content of between about 11,000 and 12,500 BTU per pound, compared to 7,000 an 8,000 BTU per pound of holoccllulosc. As such, lignin can bc dcnsificd and convcrtcd into briquettes and pellets for buming. For example, the lignin can be converted into pellets by any method described herein. For a slower buming pellet or briquette, the lignin can be crosslinked, such as applying a radiation dose of between about 0.5 Mrad and 5 Mrad. Crosslinking can make a slower buming form factor, The form factor, such as a pellet or briquette, can be converted to a “synthetic coal” or charcoal by pyrolyzing in the absence of air, e.g., at between 400 and 950 °C. Prior to pyrolyzing, it can be désirable to crosslînk the lignin to maintain structural integrity.
Accordingly, other embodiments are within the scope of the foliowing daims.
EXAMPLES OF GENETICALLY MODIFIED PLANTS
The foliowing US Patents and US Patent applications disclose, by example, genetically modified material (e.g., plants, parts of plants) for the proccsscs described herein or together with any materials described herein.
7566817 | 7763783 | 7714209 | 7659459 | 7615694 | 7534943 |
7652202 | 7763782 | 7714208 | 7659458 | 7615693 | 7531724 |
7569747 | 7763780 | 7709712 | 7659457 | 7615692 | 7528305 |
7405344 | 7759563 | 7709711 | 7659456 | 7612268 | 7528304 |
7683237 | 7759562 | 7709710 | 7659455 | 7612267 | 7525029 |
7615621 | 7759561 | 7709709 | 7655849 | 7612266 | 7525027 |
7816591 | 7759560 | 7709708 | 7655847 | 7612260 | 7525026 |
7816590 | 7759559 | 7705221 | 7655846 | 7608765 | 7521614 |
7816589 | 7750215 | 7705220 | 7655845 | 7608763 | 7521613 |
7816587 | 7745707 | 7705216 | 7655844 | 7608762 | 7521612 |
7807904 | 7741547 | 7700859 | 7655841 | 7605316 | 7521609 |
7807903 | 7741546 | 7700858 | 7642433 | 7605315 | 7521607 |
7807902 | 7737348 | 7700857 | 7642432 | 7605314 | 7518044 |
7807901 | 7737347 | 7692077 | 7642431 | 7605313 | 7518043 |
7807900 | 7737346 | 7682076 | 7642430 | 7605312 | 7518042 |
7807899 | 7737345 | 7687689 | 7642429 | 7605311 | 7518041 |
7807898 | 7737344 | 7683243 | 7642428 | 7605309 | 7514612 |
7807897 | 7737343 | 7683242 | 7638694 | 7601900 | 7514611 |
7807896 | 7732685 | 7683241 | 7638693 | 7601899 | 7514610 |
7807895 | 7732684 | 7683239 | 7638692 | 7598441 | 7514609 |
7807894 | 7728208 | 7678978 | 7638691 | 7598440 | 7511204 |
7807893 | 7723589 | 7678975 | 7638690 | 7595440 | 7511203 |
7807892 | 7723588 | 7678974 | 7638689 | 7595439 | 7511202 |
7807891 | 7723587 | 7678973 | 7632995 | 7595438 | 7511201 |
7807890 | 7723588 | 7678972 | 7632994 | 7595437 | 7511200 |
7807889 | 7723585 | 7678971 | 7632990 | 7592527 | 7507880 |
7807880 | 7718870 | 7678970 | 7629519 | 7592526 | 7507879 |
7807887 | 7718869 | 7678969 | 7629518 | 7592525 | 7504569 |
7804011 | 7718868 | 7678968 | 7629517 | 7592521 | 7504567 |
7804010 | 7718867 | 7678967 | 7629516 | 7592520 | 7504566 |
7804009 | 7718866 | 7678966 | 7629515 | 7582434 | 7501565 |
7804008 | 7718865 | 7674961 | 7626101 | 7576265 | 7501564 |
7804007 | 7718864 | 7671256 | 7626100 | 7566822 | 7498494 |
7804006 | 7718863 | 7667113 | 7626099 | 7563966 | 7495157 |
7804005 | 7718862 | 7667112 | 7626098 | 7563965 | 7495156 |
7804004 | 7718861 | 7667111 | 7622680 | 7560625 | 7495155 |
7804003 | 7718860 | 7667110 | 7622659 | 7557279 | 7488874 |
7804002 | 7718859 | 7667109 | 7619153 | 7650655 | 7488873 |
7804001 | 7714216 | 7663037 | 7619152 | 7547827 | 7488872 |
7804000 | 7714215 | 7663036 | 7619151 | 7547826 | 7485783 |
7803999 | 7714214 | 7663035 | 7619150 | 7547824 | 7479589 |
7786359 | 7714213 | 7663034 | 7619147 | 7544868 | 7479586 |
7781651 | 7714212 | 7659462 | 7615697 | 7544867 | 7479585 |
7781650 | 7714211 | 7659461 | 7615696 | 7541527 | 7476785 |
7772469 | 7714210 | 7659460 | 7615695 | 7541523 | 7476784 |
7476703 | 7301070 | 7262348 | 7179972 | 7737332 | 7544863 |
7473Θ30 | 7301009 | 7259303 | 7179969 | 7732879 | 7544862 |
7473Θ29 | 7301860 | 7256335 | 7176365 | 7728206 | 7534939 |
7473826 | 7375266 | 7256334 | 7173172 | 7718854 | 7531718 |
7470639 | 7375265 | 7256333 | 7169983 | 7714202 | 7528246 |
7470036 | 7371946 | 7250564 | 7166778 | 7714201 | 7521594 |
7460477 | 7371947 | 7247777 | 7166777 | 7709706 | 7511130 |
7462765 | 7371946 | 7241944 | 7166776 | 7709705 | 7465849 |
7462764 | 7371945 | 7235728 | 7164068 | 7388135 | 7423203 |
7462763 | 7368643 | 7235725 | 7164065 | 7388134 | 7417177 |
7459613 | 7360640 | 7235724 | 7161070 | 7381861 | 7417176 |
7459612 | 7365252 | 7235722 | 7161069 | 7253345 | 7408096 |
7459611 | 7365251 | 7235720 | 7157630 | 7250583 | 7405343 |
7456345 | 7365250 | 7232945 | 7157626 | 7247774 | 7385107 |
7456344 | 7365249 | 7232944 | 7157625 | 7223907 | 7365241 |
7456343 | 7361020 | 7232943 | 7157624 | 7189514 | 7335812 |
7456342 | 7361819 | 7230173 | 7157281 | RE39.580 | 7329799 |
7453031 | 7361810 | 7227062 | 7154031 | 7816581 | 7304206 |
7453030 | 7361817 | 7227061 | 7151208 | 7812219 | 7294711 |
7449622 | 7361015 | 7223908 | 7148410 | 7807874 | 7288408 |
7449621 | 7361814 | 7220900 | 6906250 | 7807873 | 7268276 |
7449620 | 7350427 | 7217074 | 6864409 | 7807812 | 7262339 |
7449619 | 7355107 | 7217873 | 6855877 | 7007811 | 7250501 |
7439424 | 7351890 | 7217872 | 6825400 | 7803928 | 7244877 |
7432427 | 7351Θ8Θ | 7217871 | 6114610 | 7799970 | 7230165 |
7432426 | 7342156 | 7211717 | 6103959 | 7790953 | 7227056 |
7429696 | 7342155 | 7211716 | 6103958 | 7706353 | 7217867 |
7423207 | 7342152 | 7208663 | 6084161 | 7788350 | 7217865 |
7423206 | 7339101 | 7208662 | 6054640 | 7750207 | 7205457 |
7423204 | 7339100 | 7208661 | 7112725 | 7745694 | 7195917 |
7417103 | 7339099 | 7208660 | 7825304 | 7728190 | 7186893 |
74171Θ2 | 7339098 | 7205466 | 7825303 | 7714189 | 7157619 |
7414101 | 7335827 | 7205465 | 7825302 | 7705201 | 7151204 |
7408099 | 7335826 | 7205464 | 7025301 | 7700838 | 7148398 |
7399915 | 7335022 | 7199291 | 7025300 | 7692067 | 7141722 |
7399912 | 7329803 | 7199290 | 7025300 | 7874952 | 7138278 |
7399911 | 7321088 | 7193146 | 7820888 | 7674894 | 7122719 |
7394003 | 7321087 | 7193143 | 7820887 | 7662940 | 7112717 |
7390946 | 7321086 | 7109906 | 7803997 | 7655838 | 7078592 |
7390945 | 7321085 | 7109904 | 7799972 | 7635764 | 7067722 |
7388140 | 7321084 | 7189903 | 7750213 | 7625738 | 7064249 |
7388139 | 7319182 | 7186906 | 7750212 | 7615680 | 7022897 |
7385122 | 7317155 | 7186904 | 7745704 | 7805244 | 6943281 |
7305121 | 7297848 | 7186903 | 7741543 | 7601890 | 8916970 |
7305120 | 7294772 | 7186901 | 7737335 | 7595382 | 6841717 |
7381874 | 7208704 | 7186899 | 7737334 | 7589188 | 6822142 |
7301873 | 7268279 | 7183471 | 7737333 | 7553952 | 8803501 |
6620988 | 7728196 | 7626089 | 7557277 | 7491870 | 7301867 |
6538179 | 7723583 | 7626088 | 7557276 | 7488069 | 7381866 |
6538178 | 7714198 | 7626087 | 7557275 | 7488868 | 7378570 |
6501009 | 7709703 | 7626086 | 7557274 | 7488867 | 7370577 |
6476295 | 7705211 | 7622646 | 7557273 | 7485701 | 7375262 |
6448476 | 7705208 | 7622645 | 7557272 | 7485780 | 7371938 |
6448473 | 7705207 | 7622644 | 7557271 | 7482516 | 7368637 |
6264949 | 7700849 | 7622643 | 7557270 | 7479583 | 7368635 |
6281016 | 7700847 | 7622642 | 7554016 | 7479582 | 7350420 |
6177615 | 7700846 | 7619143 | 7554015 | 7468474 | 7355103 |
6175061 | 7700844 | 7619142 | 7554014 | 7459609 | 7355102 |
6156573 | 7700843 | 7619141 | 7554013 | 7453029 | 7351886 |
6107549 | 7692070 | 7619140 | 7550653 | 7453028 | 7351885 |
6023013 | 7687686 | 7619139 | 7531722 | 7446244 | 7345228 |
5463175 | 7667685 | 7615688 | 7531721 | 7442864 | 7345227 |
7531725 | 7687684 | 7615687 | 7531720 | 7442863 | 7345226 |
7468476 | 7678965 | 7612259 | 7531719 | 7442862 | 7345225 |
7253346 | 7678964 | 7608761 | 7528306 | 7442860 | 7345224 |
7214863 | 7678963 | 7605306 | 7528301 | 7439422 | 7342151 |
7186900 | 7676962 | 7598434 | 7525020 | 7423200 | 7342150 |
7166780 | 7659454 | 7595435 | 7525025 | 7423199 | 7332656 |
7166779 | 7659453 | 7592517 | 7525019 | 7414177 | 7332655 |
7157628 | 7659452 | 7592516 | 7525018 | 7414176 | 7329001 |
7157627 | 7655839 | 7592514 | 7525017 | 7408097 | 7326832 |
7563949 | 7652199 | 7592513 | 7521608 | 7405349 | 7321082 |
7807684 | 7652198 | 7592512 | 7521605 | 7405348 | 7321079 |
7799973 | 7652197 | 7592511 | 7518036 | 7399909 | 7314983 |
7790964 | 7649129 | 7562810 | 7514607 | 7399907 | 7314982 |
7786357 | 7649128 | 7579525 | 7514606 | 7396983 | 7314981 |
7781649 | 7649127 | 7579524 | 7514605 | 7394000 | 7314980 |
7777104 | 7649126 | 7579523 | 7514604 | 7390942 | 7312382 |
7777103 | 7642413 | 7572960 | 7514603 | 7390941 | 7312380 |
7767887 | 7642412 | 7572958 | 7514602 | 7390940 | 7309818 |
7759556 | 7642411 | 7572957 | 7507878 | 7390939 | 7307201 |
7759553 | 7642410 | 7572956 | 7507877 | 739093Θ | 7304218 |
7759551 | 7642409 | 7569752 | 7504565 | 7388132 | 7304214 |
7732677 | 7642408 | 7569751 | 7504564 | 7388131 | 7304213 |
7732676 | 7642407 | 7569750 | 7501563 | 7388130 | 7301076 |
7732675 | 7632987 | 7566821 | 7501562 | 7385117 | 7297843 |
7732674 | 7632985 | 7566820 | 7501560 | 7385116 | 7294770 |
7732673 | 7629510 | 7563955 | 7490491 | 7385115 | 7294768 |
7732672 | 7629509 | 7563954 | 7498490 | 7385113 | 7294765 |
7728204 | 7629508 | 7563953 | 7498489 | 7385112 | 7294764 |
7728203 | 7629507 | 7560619 | 7498486 | 7385111 | 7294763 |
7728202 | 7629506 | 7560618 | 7498485 | 7385110 | 7291771 |
7728201 | 7626091 | 7560617 | 7498484 | 7385109 | 7291769 |
7728199 | 7628090 | 7580616 | 7491871 | 7385108 | 7285704 |
7279621 | 7132591 | 7045687 | 6900373 | 6080916 | 5902923 |
7278648 | 7129399 | 7045886 | 6900372 | 6063990 | 5898100 |
7271324 | 7126046 | 7041881 | 6894207 | 6063989 | 5880346 |
7265277 | 7119260 | 7041880 | 6888049 | 6051761 | 5880345 |
7265276 | 7119259 | 7041879 | 6888048 | 6043414 | 5880344 |
7265275 | 7119258 | 7038114 | 6884927 | 6040499 | 5872304 |
7265274 | 7115801 | 7034210 | 6884926 | 6037529 | 5872303 |
7265273 | 7109399 | 7034209 | 6884925 | 6034303 | 5866774 |
7265272 | 7105728 | 7030301 | 6884924 | 6034302 | 5866773 |
7265271 | 7105727 | 7030300 | 6884923 | 6034301 | 5866772 |
7265270 | 7105726 | 7019199 | 6881879 | 6034300 | 5866771 |
7259299 | 7102062 | 7012174 | 6875908 | 6034299 | 5859352 |
7259298 | 7102081 | 7005583 | 6870079 | 6031159 | 5723745 |
7256330 | 7098385 | 7002062 | 6861579 | 6020542 | 7268274 |
7247772 | 7098384 | 7002058 | 6858784 | 6020541 | 7402731 |
7247771 | 7091403 | 6982367 | 6858783 | 6018108 | 6865556 |
7244881 | 7087815 | 6982366 | 6852912 | 6018107 | 5424412 |
7241941 | 7084328 | 6979761 | 6849786 | 6005171 | 5463175 |
7241939 | 7084326 | 6979760 | 6849785 | 6005170 | 5484956 |
7235718 | 7084325 | 6972355 | 6846973 | 6002073 | 5554798 |
7217870 | 7084324 | 6972354 | 6835873 | 5998709 | 559387 |
7217869 | 7081572 | 6972353 | 6828409 | 5998708 | 5641876 |
7217868 | 7078600 | 6969787 | 6815589 | 5998707 | 5659122 |
7196253 | 7078598 | 6967263 | 68155ΘΘ | 5998706 | 571084 |
7196252 | 7078597 | 6960707 | 6815587 | 5998705 | 5728925 |
7196251 | 7078595 | 6958436 | 6815586 | 5998704 | 5750871 |
7193140 | 7074989 | 6953876 | 6809237 | 5998703 | 5804425 |
7193139 | 7074988 | 6951973 | 6781040 | 5990391 | 5859347 |
7193137 | 7071390 | 6936754 | 6653534 | 5986179 | 6020190 |
7189900 | 7071389 | 6936753 | 6198027 | 5986178 | 6025545 |
7189898 | 7071388 | 6933423 | 6177618 | 5981851 | 6040497 |
7183467 | 7071387 | 6924418 | 6169227 | 5981850 | 6051753 |
7183465 | 7067723 | 6919498 | 6137034 | 5981849 | 6180774 |
7183464 | 7064253 | 6914174 | 6133510 | 5981848 | 6218188 |
7183463 | 7060878 | 6914173 | 6124527 | 5981845 | 6340593 |
7183462 | 7060877 | 6914172 | 6121518 | 5977449 | 6489542 |
7183461 | 7057096 | 6911585 | 6121517 | 5977448 | 6501009 |
7176359 | 7057095 | 6911581 | 6121516 | 5977447 | 6548291 |
7176358 | 7057094 | 6911580 | 6121515 | 5977444 | 6573240 |
7176357 | 7057093 | 6911579 | 6114604 | 5973235 | 6645497 |
7173168 | 7057092 | 6911578 | 6103957 | 5969218 | 6660911 |
7169976 | 7053280 | 6906248 | 6100454 | 5969217 | 6737273 |
7169975 | 7053279 | 6906247 | 6096949 | 5945588 | 6753463 |
7169974 | 7053272 | 6906246 | 6091005 | 5942666 | 6825400 |
7166774 | 7049494 | 6903253 | 6087562 | 5932786 | 6893872 |
7148408 | 7049493 | 6903251 | 6084159 | 5929310 | 6900371 |
7138570 | 7045691 | 6900376 | 6080918 | 5907088 | 6943282 |
6949696 | 7462510 | 7834247 | 7772465 | 7663031 | 7601894 |
6962705 | 7473819 | 7834246 | 7772370 | 7663029 | 7598443 |
7064249 | 7465850 | 7834245 | 7767889 | 7655848 | 7598442 |
7112665 | 7456337 | 7834240 | 7767888 | 7655843 | 7598439 |
7112725 | 7456335 | 7829764 | 7763778 | 7655842 | 7598438 |
7141722 | 7442853 | 7829760 | 7763465 | 7652201 | 7598437 |
7157281 | 7439417 | 7825310 | 7759564 | 7652200 | 7598435 |
7223907 | 7435875 | 7825309 | 7759555 | 7652195 | 7595436 |
7227056 | 7427698 | 7825308 | 7759554 | 7645923 | 7592524 |
7250501 | 7427696 | 7825307 | 7759544 | 7645922 | 7592523 |
7288643 | 7425666 | 7825299 | 7759543 | 7645921 | 7592522 |
7381861 | 7425665 | 7825294 | 7754949 | 7642421 | 7592519 |
7435807 | 7423196 | 7825234 | 7754948 | 7642420 | 7592505 |
7449564 | 7399904 | 7820895 | 7750216 | 7642419 | 7589264 |
7514544 | 7399903 | 7820894 | 7745706 | 7642418 | 7589263 |
RE38825 | 7375209 | 7820893 | 7745705 | 7642417 | 7589261 |
RE39247 | 7317140 | 7820892 | 7745702 | 7638695 | 7589260 |
7829761 | 7303919 | 7820891 | 7745701 | 7638688 | 7589259 |
7807882 | 7271316 | 7820886 | 7741545 | 7632993 | 7589258 |
7803987 | 7259294 | 7820885 | 7737342 | 7832992 | 7589257 |
7799971 | 7238856 | 7816586 | 7737341 | 7632989 | 7589178 |
7795500 | 7235713 | 7816585 | 7737340 | 7632988 | 7586028 |
7795414 | 7220585 | 7812231 | 7737336 | 7629514 | 7586027 |
7790873 | 7189893 | 7812230 | 7737330 | 7629513 | 7586026 |
7763777 | 7186561 | 7812226 | 7736897 | 7629512 | 7586025 |
7763776 | 7179962 | 7812225 | 7732683 | 7629511 | 7582816 |
7718858 | 7176026 | 7812223 | 7732668 | 7629505 | 7582815 |
7718857 | 7166767 | 7812216 | 7728207 | 7629504 | 7582614 |
7714190 | 7164057 | 7807883 | 7718856 | 7624533 | 7582813 |
7709698 | 7161063 | 7807876 | 7714205 | 7622647 | 7582812 |
7652203 | 7135618 | 7803998 | 7714187 | 7622637 | 7582811 |
7622570 | 7125719 | 7803996 | 7714184 | 7619149 | 7582808 |
7619137 | 7105723 | 7803993 | 7709702 | 7619148 | 7579530 |
7608750 | 7067261 | 7603990 | 7705219 | 7615690 | 7579520 |
7608757 | 7034208 | 7803989 | 7705218 | 7612265 | 7579522 |
7598431 | 6867351 | 7799977 | 7700856 | 7612264 | 7576271 |
7579517 | 6825399 | 7799975 | 7700855 | 7612263 | 7576270 |
7563948 | 6818805 | 7799974 | 7700854 | 7612262 | 7576269 |
7521598 | 6784338 | 7799566 | 7700836 | 7612256 | 7576268 |
7521597 | 6774288 | 7795508 | 7700832 | 7612254 | 7576267 |
7514599 | 6720477 | 7795506 | 7692061 | 7612251 | 7576266 |
7504559 | 6710229 | 7790969 | 7687687 | 7608764 | 7572963 |
7498482 | 6669939 | 7790874 | 7683240 | 7608755 | 7572982 |
7498429 | 6677504 | 7777107 | 7667115 | 7608752 | 7572961 |
7495151 | 6320518 | 7777106 | 7667107 | 7605307 | 7572955 |
7485775 | 6225526 | 7772468 | 7663033 | 7601898 | 7569757 |
7402511 | 7834257 | 7772467 | 7863032 | 7601897 | 7569756 |
7569755 | 7525023 | 7456339 | 7371936 | 7317149 | 7276650 |
7569754 | 7525022 | 7442881 | 7365253 | 7317148 | 7276849 |
7569753 | 7525021 | 7439425 | 7361812 | 7317147 | 7276647 |
7569749 | 7525020 | 7439421 | 7361807 | 7317146 | 7276596 |
7566619 | 7521611 | 7439348 | 7358425 | 7317145 | 7273975 |
7563964 | 7521610 | 7435885 | 7358424 | 7317143 | 7273973 |
7563963 | 7521604 | 7435883 | 7358423 | 7317137 | 7273972 |
7563962 | 7521603 | 7435881 | 7355108 | 7314990 | 7273971 |
7563961 | 7521602 | 7435880 | 7355106 | 7314989 | 7273965 |
7563960 | 7521601 | 7435879 | 7355105 | 7314988 | 7271327 |
7563959 | 7518037 | 7432424 | 7355104 | 7314987 | 7271326 |
756395Θ | 7514601 | 7432423 | 7351882 | 7312385 | 7271323 |
7563957 | 7511205 | 7432422 | 7351878 | 7312384 | 7271319 |
7560624 | 7511196 | 7432421 | 7348469 | 7312377 | 7270380 |
7560623 | 7511195 | 7432418 | 7348468 | 7312375 | 7268278 |
7560612 | 7511194 | 7429695 | 7345230 | 7309816 | 7268277 |
7557266 | 7511193 | 7427702 | 7342157 | 7306948 | 7268270 |
7557263 | 7511192 | 7427701 | 7342154 | 7304222 | 7268226 |
7554020 | 7511188 | 7427700 | 7339097 | 7304221 | 7265279 |
7553951 | 7504568 | 7423202 | 7339096 | 7304212 | 7265265 |
7550657 | 7504558 | 7423197 | 7339092 | 7304211 | 7262350 |
7550656 | 7501561 | 7420103 | 7335828 | 7301082 | 7262349 |
7550575 | 7498488 | 7414180 | 7335825 | 7301080 | 7262347 |
7547832 | 7498487 | 7414179 | 7335824 | 7301079 | 7262346 |
7547831 | 7498413 | 7414174 | 7335823 | 7301075 | 7262345 |
7547830 | 7495154 | 7411118 | 7335817 | 7301069 | 7262342 |
7547829 | 7495150 | 7411113 | 7332660 | 7297850 | 7259305 |
7547825 | 7491869 | 7411112 | 7332659 | 7297849 | 7259304 |
7547822 | 7485779 | 7399914 | 7332658 | 7297841 | 7259302 |
7544869 | 7485778 | 7399910 | 7332650 | 7294774 | 7259301 |
7544866 | 7482515 | 7399908 | 7329806 | 7294769 | 7256332 |
7544865 | 7482513 | 7399908 | 7329805 | 7294767 | 7256331 |
7544864 | 7479588 | 7396980 | 7329804 | 7294766 | 7256322 |
7544857 | 7479581 | 7393999 | 7326836 | 7291774 | 7256280 |
7541526 | 7476781 | 7388141 | 7326835 | 7291773 | 7253000 |
7541525 | 7473828 | 7388137 | 7326833 | 7288703 | 7250552 |
7541524 | 7473827 | 7388133 | 7326830 | 7288701 | 7241943 |
7541521 | 7473821 | 7388128 | 7323623 | 7288700 | 7241942 |
7541520 | 7470838 | 7388125 | 7321089 | 7288699 | 7241940 |
7541517 | 7470834 | 7381872 | 7321083 | 7285707 | 7241934 |
7538261 | 7470833 | 7381871 | 7321031 | 7285706 | 7238859 |
7528308 | 7468278 | 7381865 | 7319183 | 7285702 | 7235723 |
7528307 | 7465858 | 7381863 | 7317154 | 7282629 | 7232946 |
7528300 | 7465852 | 7378574 | 7317153 | 7282627 | 7230172 |
7528299 | 7462766 | 7375264 | 7317152 | 7282626 | 7230171 |
7528293 | 7462760 | 7375263 | 7317151 | 7279615 | 7230169 |
7525024 | 7459610 | 7371944 | 7317150 | 7276652 | 7230158 |
V
7227065 | 7179971 | 7151207 | 7064255 | 7005565 | 6951974 |
7227064 | 7179970 | 7151205 | 7064252 | 7002061 | 8949699 |
7227063 | 7179968 | 7148406 | 7064251 | 7002056 | 6946589 |
7227060 | 7179967 | 7148401 | 7064250 | 6998518 | 6943279 |
7227059 | 7179963 | 7141721 | 7064247 | 6995305 | 6936756 |
7227056 | 7179955 | 7129402 | 7060879 | 6995304 | 6936755 |
7220902 | 7179599 | 7129401 | 7060813 | 6995303 | 6936752 |
7220901 | 7176364 | 7129395 | 7053286 | 6992240 | 6936751 |
7214Θ65 | 7176363 | 7122725 | 7053285 | 6992239 | 6933427 |
7214864 | 7176362 | 7115802 | 7053284 | 6992238 | 6933425 |
7214860 | 7176360 | 7112731 | 7053283 | 6992237 | 6930230 |
7214857 | 7176356 | 7112729 | 7053282 | 69Θ94Θ1 | 6930229 |
7214855 | 7176349 | 7112728 | 7053275 | 6989480 | 6930225 |
7214054 | 7176027 | 7109403 | 7049499 | 6989479 | 6927327 |
7214852 | 7173174 | 7109391 | 7049495 | 6989478 | 6927326 |
7211716 | 7173173 | 7109390 | 7045692 | 6989475 | 8924421 |
7211714 | 7169908 | 71020Θ4 | 7045682 | 8989474 | 6921852 |
7211712 | 7169987 | 7102063 | 7041887 | 6987217 | 6921850 |
7205455 | 7169906 | 7098390 | 7041886 | 6987212 | 6921847 |
7205453 | 7169905 | 7098301 | 7041874 | 6984778 | 6919500 |
RE39.562 | 7169984 | 7094957 | 7038109 | 6982371 | 6919499 |
7202403 | 7169980 | 7094956 | 7038108 | 6979764 | 6916975 |
7202402 | 7169979 | 7091407 | 7034214 | 6979763 | 6914178 |
7199294 | 7169978 | 7091406 | 7034213 | 6979759 | 6914177 |
7199293 | 7169977 | 7091398 | 7034211 | 6977327 | 6914171 |
7199292 | 7169973 | 7087823 | 7030303 | 6974900 | 6914170 |
7199289 | 7166764 | 7087822 | 7030302 | 6974899 | 6911587 |
7196256 | 7166782 | 7087821 | 7030290 | 6972357 | 6911577 |
7196255 | 7166781 | 7087820 | 7026533 | 6972356 | 6909039 |
7196254 | 7166769 | 7084335 | 7022904 | 6972352 | 6909038 |
7193145 | 7166765 | 7004332 | 7022902 | 6969790 | 6906251 |
7193144 | 7164070 | 7084327 | 7022099 | 6969789 | 6906243 |
7193141 | 7164069 | 7001566 | 7019200 | 6969780 | 6905857 |
7193136 | 7164067 | 7078603 | 7019198 | 6969706 | 6903254 |
7193135 | 7164066 | 7078602 | 7015386 | 6967269 | 6903205 |
7193130 | 7164063 | 7078601 | 7015385 | 6987268 | 6900370 |
7189905 | 7164062 | 7078596 | 7015381 | 6967267 | 6900377 |
7189Θ02 | 7164061 | 7078589 | 7015380 | 6967264 | 6097365 |
7189901 | 7164056 | 7074991 | 7015379 | 6965063 | 6897364 |
7189899 | 7161074 | 7071397 | 7015376 | 6960708 | 6097363 |
7169089 | 7161073 | 7071396 | 7015375 | 6958438 | 6897362 |
7106905 | 7161072 | 7071395 | 7012177 | 6958437 | 6897361 |
7186902 | 7161071 | 7071394 | 7012176 | 6956153 | 6897360 |
7186096 | 7161068 | 7071393 | 7009094 | 6956150 | 6891090 |
7183472 | 7161065 | 7067727 | 7009093 | 6953878 | 6891085 |
7183469 | 7157632 | 7067720 | 7009087 | 6953877 | 6888051 |
7103460 | 7154030 | 7064258 | 7005566 | 6951975 | 6887708 |
6681881 | 6815585 | 6759578 | 6706949 | 6555732 | 6333452 |
8881880 | 6815584 | 8759577 | 6700041 | 6555673 | 6333451 |
687ΘΘ65 | 6815583 | 6756530 | 6693231 | 6541684 | 6331661 |
6878864 | 6815578 | 6756529 | 6677503 | 6538177 | 6329579 |
6878863 | 6812304 | 6756528 | 6677502 | 6538176 | 6326530 |
6875907 | 6812383 | 8753464 | 6667427 | 6528704 | 6328529 |
6872874 ' | 6812380 | 6750384 | 6660907 | 6518487 | 6323402 |
6872873 | 6009242 | 6750380 | 6657107 | 6510483 | 6323401 |
6864411 | 6Θ09241 | 0747196 | 6646182 | 6515202 | 6323400 |
6864408 | 6009236 | 6747193 | 6639131 | 6504084 | 6323399 |
6864407 | 6006408 | 6743970 | 6639126 | 6504083 | 6323398 |
6861577 | 6806407 | 6740798 | 6635807 | 6504082 | 6323015 |
6858785 | 6806406 | 6740798 | 6630615 | 6479730 | 6320106 |
6858782 | 6806405 | 6740795 | 6630614 | 6476292 | 6320105 |
6858781 | 6806404 | 6737566 | 6627797 | 6472105 | 6316704 |
6858778 | 6806401 | 6737565 | 6617499 | 6444074 | 6316703 |
6855878 | 6803508 | 6737562 | 6617498 | 6441151 | 6316702 |
6855876 | 6803498 | 6737560 | 6613967 | 6433259 | 6316700 |
6855875 | 6800796 | 6734348 | 6613966 | 6429362 | 6313384 |
6855874 | 6800795 | 6734347 | 6613965 | 6426452 | 6313383 |
6855871 | 6797868 | 6734345 | 6613964 | 6423008 | 6313382 |
6852913 | 6797867 | 6734341 | 6613963 | 6423806 | 6313381 |
6849791 | 6797866 | 6730837 | 6610911 | 6410829 | 6313376 |
6849789 | 6797865 | 6730836 | 6610910 | 6407315 | 0313375 |
6849708 | 6797864 | 6730035 | 6608243 | 6403862 | 6310274 |
6849767 | 6797863 | 6730834 | 6608240 | 6403060 | 6307132 |
6846976 | 6797859 | 6730829 | 6605762 | 6399056 | 6307131 |
6846975 | 6794563 | 6727413 | 6605761 | 6392127 | 6303051 |
6846974 | 6791016 | 6727412 | 6605760 | 6392126 | 6297433 |
6844480 | 6784350 | 6727410 | 6605759 | 6388179 | 6297432 |
6838593 | 6784349 | 6723903 | 6605758 | 63Θ8171 | 6297426 |
6835877 | 6784347 | 6723902 | 6605757 | 6380169 | 6291745 |
6835875 | 6784341 | 6720487 | 6605756 | 6384302 | 6288310 |
6833498 | 6781043 | 6720486 | 6605755 | 6372961 | 6287843 |
6831215 | 6781042 | 6720481 | 6600095 | 6369301 | 6284953 |
6828493 | 6781041 | 6720478 | 6586659 | 6369300 | 6284950 |
6828490 | 6777599 | 6720475 | 6586657 | 6362400 | 6284948 |
6825405 | 6777598 | 6717040 | 6583343 | 6359201 | 6271439 |
6825404 | 6777597 | 6717039 | 6583342 | 6346657 | 6271437 |
6825397 | 6777596 | 6717038 | 6583341 | 6344603 | 6268553 |
6822144 | 6777590 | 6717037 | 6580018 | 6342659 | 6265646 |
6822140 | 6774290 | 6717036 | 6576819 | 6339186 | 6265636 |
6818813 | 6774209 | 6717033 | 6576814 | 6339144 | 6259005 |
6810811 | 6774202 | 6713666 | 6573433 | 6337100 | 6259004 |
6818809 | 6770802 | 6713665 | 6566589 | 6335476 | 6255090 |
681Θ80Θ | 6765132 | 6706954 | 6566584 | 6335197 | 6248935 |
6815592 | 6759580 | 6706951 | 6563020 | 6333453 | 6242673 |
6242672 | 6156958 | 6111167 | 5990392 | 5902921 | 5792909 |
6235976 | 6153817 | 6107551 | 5990389 | 5900526 | 5792908 |
6235972 | 6153816 | 6107550 | 5986185 | 5900524 | 5792907 |
6232529 | 6147285 | 6107545 | 5986184 | 5895835 | 5783100 |
6232527 | 6147284 | 6100030 | 5986183 | 5889188 | 5773697 |
6229079 | 6147283 | 6096953 | 5981854 | 5866768 | 5773684 |
6229078 | 6143962 | 6096951 | 5977457 | 5866767 | 5773682 |
6229077 | 6143956 | 6096947 | 5977456 | 5866766 | 5770790 |
6229074 | 6143955 | 6093875 | 5977451 | 5866765 | 5767347 |
6229073 | 6143954 | 6091007 | 5977445 | 5861541 | 5767344 |
6225537 | 6140562 | 6091006 | 5973237 | 5859354 | 5767343 |
6225529 | 6140557 | 6087567 | 5973234 | 5859341 | 5767340 |
6222103 | 6137037 | 6087566 | 5982772 | 5859320 | 5763757 |
6222102 | 6137036 | 6087565 | 5962771 | 5859319 | 5763747 |
6222101 | 6133514 | 6087564 | 5959185 | 5859318 | 5763746 |
6215049 | 6133513 | 6087559 | 5955361 | 5859317 | 5763744 |
6211445 | 6133508 | 6084164 | 5952550 | 5859316 | 5763743 |
6211440 | 6130370 | 6084160 | 5952549 | 5859313 | 5763243 |
6211437 | 6127610 | 6080919 | 5948957 | 5852226 | 5750868 |
6211435 | 6127609 | 6080913 | 5945587 | 5852225 | 5750849 |
6211434 | 6127603 | 6077998 | 5945586 | 5850024 | 5750847 |
6211433 | 6127602 | 6077997 | 5942671 | 5850016 | 5750843 |
6198026 | 6127600 | 6077993 | 5942670 | 5850013 | 5750842 |
6197561 | 6124535 | 6075186 | 5942669 | 5850012 | 5750841 |
6194638 | 6124534 | 6075182 | 5942668 | 5850011 | 5750839 |
6194637 | 6124533 | 6072104 | 5942667 | 5850010 | 5750838 |
6191343 | 6124532 | 6069304 | 5939608 | 5850009 | 5750835 |
6166001 | 6124531 | 6057491 | 5939607 | 5850007 | 5750834 |
6188000 | 6124530 | 6054639 | 5936148 | 5844118 | 5750832 |
6184448 | 6124529 | 6040505 | 5936147 | 5844117 | 5750831 |
6184445 | 6124526 | 6037530 | 5936142 | 5844116 | 5750829 |
6184439 | 6121524 | 6037523 | 5936141 | 5841015 | 5741684 |
6180857 | 6121523 | 6028254 | 5936140 | 5827940 | 5736627 |
6180856 | 6121522 | 6028252 | 5929313 | 5824844 | 5731499 |
6180850 | 6121520 | 6025547 | 5929311 | 5824524 | 5731497 |
6177613 | 6121514 | 6020543 | 5929301 | 5817918 | 5731496 |
6177611 | 6118056 | 6018113 | 5920002 | 5811651 | 5731494 |
6175065 | 6118055 | 6018112 | 5917134 | 5811650 | 5731493 |
6175058 | 6118054 | 6018111 | 5917130 | 5811639 | 5731492 |
6169234 | 6118053 | 6018110 | 5917129 | 5811638 | 5731491 |
6166305 | 6118052 | 6018109 | 5917125 | 5811637 | 5728926 |
6166303 | 6118051 | 6015941 | 5912417 | 5804692 | 5728921 |
6166296 | 6114614 | 6013859 | 5910634 | 5804691 | 5728920 |
6162968 | 6114613 | 6005172 | 5910633 | 5792915 | 5728919 |
6162964 | 6114612 | 6005168 | 5908976 | 5792912 | 5728558 |
6160211 | 6114607 | 5998711 | 5907086 | 5792911 | 5723723 |
6160209 | 6111173 | 5990393 | 5905189 | 5792910 | 5723722 |
5717129 | 5541352 | 5159133 | 6495738 | 5451514 |
5706189 | 5534661 | 5159132 | 6410828 | |
5689036 | 5530184 | 5157208 | 6384207 | |
5689034 | 5527986 | 5157206 | 6331664 | |
5675066 | 5506368 | 5097096 | 6323395 | |
5639946 | 5506387 | 5097095 | 6166302 | |
5638637 | 5502272 | 5097093 | 6048838 | |
5633427 | 5495069 | 5097092 | 7799906 | |
5625133 | 5495066 | 5095174 | 7723584 | |
5625132 | 5495065 | 5082992 | 7709697 | |
5625130 | 5491295 | 5082991 | 7674951 | |
5625129 | 5491290 | 5049503 | 7663023 | |
5618987 | 5491289 | 4996049 | 7598430 | |
5608140 | 5491287 | 4812600 | 7288409 | |
5608139 | 5491286 | 4812599 | 7232941 | |
5608138 | 5478369 | 4806669 | 7148406 | |
5602318 | 5476999 | 480Θ652 | 7135618 | |
5602317 | 5463173 | 4737596 | 7087426 | |
5602312 | 5461171 | 4731499 | 7071384 | |
5585538 | 5453564 | 7820883 | 7071376 | |
5585537 | 5444178 | 7795395 | 7049485 | |
5583210 | 5436390 | 7728195 | 7012172 | |
5576472 | 5434346 | 7723582 | 6906239 | |
5574209 | 5432068 | 7723581 | 6855864 | |
5574206 | 5426041 | 7723580 | 6831208 | |
5569822 | 5416254 | 7723579 | 6703539 | |
5569821 | 5387758 | 7723578 | 6653528 | |
5569619 | 5387755 | 7723577 | 6635805 | |
5569816 | 5387754 | 7718852 | 6610908 | |
5569817 | 5367109 | 7709707 | 6489538 | |
5569816 | 5365014 | 7709623 | 6479732 | |
5587861 | 5356799 | 7671253 | 6476291 | |
5563326 | 5354941 | 7667100 | 6455762 | |
5563325 | 5349119 | 7635798 | 6441272 | |
5563323 | 5347081 | 7566818 | 6252135 | |
5563322 | 5347080 | 7456340 | 6242381 | |
5563321 | 5347079 | 7411117 | 6211432 | |
5563320 | 5316930 | 7371935 | 6204434 | |
5563055 | 5304720 | 7355100 | 6066780 | |
5557038 | 5304719 | 7348473 | 6015943 | |
5557035 | 5285004 | 7332657 | 5981837 | |
5557034 | 5276265 | 7179965 | 5959178 | |
5545814 | 5276264 | 7071386 | 5952486 | |
5545813 | 5260503 | 7071385 | 5922928 | |
5545812 | 5245125 | 6791013 | 5886243 | |
5545809 | 5220114 | 6753460 | 5850020 | |
5543575 | 5159134 | 6753459 | 5846333 |
20100071092 | 20100293639 | 20100275304 |
20100058498 | 20100293638 | 20100275303 |
20100058496 | 20100293637 | 20100275301 |
20090119796 | 20100293634 | 20100275300 |
20090106862 | 20100293633 | 20100275299 |
20090044294 | 20100293632 | 20100275298 |
20090019605 | 20100293630 | 20100275297 |
20080313774 | 20100293629 | 20100275296 |
20080235820 | 20100287653 | 20100275295 |
20080213871 | 20100287652 | 20100275294 |
20080118954 | 20100287651 | 20100275293 |
20080058510 | 20100287650 | 20100275292 |
20060206964 | 20100287649 | 20100275291 |
20060130183 | 20100287848 | 20100275290 |
20060101535 | 20100287647 | 20100275289 |
20050091707 | 20100287646 | 20100275288 |
20050076403 | 20100287645 | 20100275287 |
20040049802 | 20100287644 | 20100275286 |
20030163839 | 20100287643 | 20100273987 |
20030131373 | 20100287642 | 20100272880 |
20020138870 | 20100285202 | 20100269224 |
20020078477 | 20100281564 | 20100269211 |
20020078474 | 20100281563 | 20100269210 |
20100293661 | 20100281562 | 20100269209 |
20100293660 | 20100281561 | 20100269208 |
20100293659 | 20100281560 | 20100269207 |
20100293658 | 20100281559 | 20100269206 |
20100293657 | 20100281558 | 20100269205 |
20100293858 | 20100281557 | 20100269204 |
20100293655 | 20100278996 | 20100269203 |
20100293654 | 20100275332 | 20100269202 |
20100293653 | 20100275322 | 20100269201 |
20100293852 | 20100275318 | 20100269200 |
20100293651 | 20100275317 | 20100269199 |
20100293650 | 20100275316 | 20100269198 |
20100293649 | 20100275315 | 20100269197 |
20100293648 | 20100275314 | 20100269196 |
20100293647 | 20100275313 | 20100269195 |
20100293646 | 20100275312 | 20100263083 |
20100293645 | 20100275310 | 20100263082 |
20100293644 | 20100275309 | 20100263081 |
20100293643 | 20100275308 | 20100263080 |
20100293642 | 20100275307 | 20100263079 |
20100293640 | 20100275305 | 20100263078 |
20100263077 20100263076 20100263075 20100263074 20100263073 20100263072 20100263071 20100263070 20100263069 20100263066 20100260921 20100260920 20100257630 20100257629 20100257628 20100257627 20100257626 20100257625 20100257621 20100255175 20100251412 20100251411 20100251410 20100251406 20100251407 20100251406 20100251405 20100251403 20100251402 20100251401 20100251400 20100251399 20100251398 20100249389 20100248963 20100247733 20100242132 20100242130 20100242129 20100218269 20100196580 20100192245 20100173061 20100168455 20100146656 20100138953 20100115652
20100115649 20100115648 20100115647 20100115646 20100115645 20100115644 20100115643 20100112182 20100107272 20100107271 20100107270 20100107268 20100107267 20100100980 20100080887 20100064394 20100043094 20100043093 20100043091 20100043090 20100043088 20100043087 20100043086 20100037339 20100037336 20100037337 20100037336 20100037333 20100024064 20100024063 20100024062 20100024054 20100024052 20090288216 20090288215 20090288213 20090288212 20090288211 20090288210 20090288208 20090288207 20090288206 20090288205 20090288203 20090288202 20090288201 20090288200
20090288198 20090288197 20090288195 20090288194 20090288191 20090288189 20090288188 20090282575 20090282574 20090282573 20090282572 20090282571 20090282570 20090282569 20090282568 20090282567 20090282566 20090282565 20090282564 20090282563 20090282562 20090282561 20090282560 20090282559 20090282558 20090282557 20090282556 20090282555 20090282554 20090282553 20090282552 20090282551 20090282550 20090282549 20090282548 20090282547 20090282546 20090282545 20090282544 20090282543 20090282542 20090282541 20090282540 20090282539 20090282538 20090282536 20090282535
20090282534 | 20090276895 | 20090081353 |
20090282533 | 20090276894 | 20090077694 |
20090282532 | 20090276893 | 20090070902 |
20090282531 | 20090276892 | 20090070891 |
20090282530 | 20090276891 | 20090055957 |
20090282529 | 20090276885 | 20090055956 |
20090282528 | 20090276884 | 20090055955 |
20090282527 | 20090276883 | 20090031438 |
20090282528 | 20090276882 | 20090029861 |
20090282525 | 20090276881 | 20090019604 |
20090282523 | 20090276880 | 20090019603 |
20090282522 | 20090276879 | 20090019595 |
20090282521 | 20090276878 | 20090019594 |
20090282520 | 20090276871 | 20090019593 |
20090282519 | 20090276870 | 20090019592 |
20090202517 | 20090276869 | 20090019591 |
20090282516 | 20090275741 | 20090019590 |
20090282515 | 20090246350 | 20090019589 |
20090282514 | 20090241213 | 20090019588 |
20090282513 | 20090241212 | 20090019587 |
20090282512 | 20090241211 | 20090019586 |
20090282511 | 20090241210 | 20090019585 |
20090282510 | 20090235379 | 20090019584 |
20090282509 | 20090235378 | 20090019583 |
20090282508 | 20090235377 | 20090019582 |
20090282500 | 20090229004 | 20090019581 |
20090282499 | 20090229003 | 20090019580 |
20090282498 | 20090229002 | 20090019579 |
20090276916 | 20090210961 | 20090019578 |
20090276915 | 20090169709 | 20090019577 |
20090276914 | 20090165163 | 20090019576 |
20090276913 | 20090165162 | 20090019575 |
20090276910 | 20090165161 | 20090019574 |
20090276909 | 20090165159 | 20090019573 |
20090276908 | 20090165158 | 20090019572 |
20090276907 | 20090151020 | 20090019571 |
20090276906 | 20090138989 | 20090019570 |
20090276905 | 20090138985 | 20090019569 |
20090278904 | 20090133147 | 20090019568 |
20090276903 | 20090133146 | 20090019567 |
20090276902 | 20090133145 | 20090019565 |
20090276901 | 20090133144 | 20090019564 |
20090276900 | 20090133143 | 20090013429 |
20090276899 | 20090133142 | 20090013428 |
20090276898 | 20090100536 | 20090013427 |
20090276897 | 20090098099 | 20090013426 |
20090276896 | 20090083886 | 20090013425 |
20090007290 20090007289 20090007288 20090007287 20090007288 20080282422 20080282421 20080282420 20080282419 20080282418 20080282417 20080282416 20080282415 20080282414 20080282413 20080282412 20080282411 20080282410 20080282409 20080282408 20080282407 20080282406 20080282405 20080282404 20080282403 20080282402 20080282401 20080282400 20080282399 20080282398 20080282397 20080282396 20080282395 20080282394 20080282393 20080282392 20080282389 20080282388 20080282387 20080282386 20080282385 20080282384 20080262383 20080282382 20080282381 20080282380 20080282379
20080313765 20080313764 20080313763 20080313762 20080313761 20080282378 20080282377 20080282376 20080282375 20080282374 20080282373 20080282372 20080282371 20080282370 20080282366 20080280361 20080276330 20080271197 20080271196 20080271195 20080271194 20080271193 20080271192 20080271191 20080271190 20080271189 20080271188 20080271187 20080271186 20080271185 20080271184 20080271183 20080271182 20080271181 20080271180 20080271179 20080271178 20080271177 20080271176 20080271175 20080271174 20080271173 20080271172 20080271171 20080271170 20080271168 20080283713
20080313760 20080313759 20080313758 20080313757 20080282432 20080263712 20080263711 20080263706 20080263705 20080260929 20080256669 20080235819 20080227639 20080216190 20080216189 20080178345 20080178344 20080178343 20080178342 20080178341 20080178340 20080178338 20080178337 20080178336 20080178335 20080178334 20080178333 20080178332 20080178331 20080178330 20080178329 20080178328 20080178327 20080178326 20080178322 20080178320 20080178319 20080178318 20080178317 20080172781 20080172756 20080172755 20060172754 20080168576 20080155711 20080155710 20080155708
I «
20080155707 | 20060162007 | 20040237150 |
20080148428 | 20060111254 | 20040237149 |
20080148427 | 20060107340 | 20040237148 |
20000148426 | 20060101543 | 20040237139 |
20000148425 | 20060070140 | 20040221346 |
20080148424 | 20060064777 | 20040221344 |
20080148423 | 20060064776 | 20040221343 |
20080148422 | 20060059590 | 20040221342 |
20080148421 | 20060059589 | 20040221341 |
20080148420 | 20060021081 | 20040221339 |
20080070286 | 20060010530 | 20040221335 |
20000066202 | 20060010529 | 20040221329 |
20080064868 | 20060010528 | 20040221328 |
20080050506 | 20060010527 | 20040210958 |
20080022423 | 20060010526 | 20040205062 |
20070266456 | 20060010525 | 20040205861 |
20070256190 | 20060010524 | 20040205860 |
20070256187 | 20060010523 | 20040205859 |
20070256186 | 20060010522 | 20040205857 |
20070256105 | 20060010521 | 20040205856 |
20070256184 | 20050209664 | 20040205854 |
20070256182 | 20050193440 | 20040205849 |
20070256181 | 20050193430 | 20040168228 |
20070256180 | 20050193437 | 20040168225 |
20070256179 | 20050193436 | 20040168224 |
20070256171 | 20050183155 | 20040168223 |
20070256170 | 20050183154 | 20040168222 |
20070256155 | 20050183153 | 20040168219 |
20070250957 | 20050155114 | 20040148665 |
20070250955 | 20050155106 | 20040148664 |
20070250954 | 20050144680 | 20040148663 |
20070250952 | 20050144879 | 20040148662 |
20070250951 | 20050144678 | 20040148660 |
20070250950 | 20050144677 | 20040148659 |
20070250949 | 20050144676 | 20040148650 |
20070250947 | 20050144675 | 20040132975 |
20070214516 | 20050144674 | 20040111772 |
20070067871 | 20050132437 | 20040111770 |
20070054400 | 20050114929 | 20040093637 |
20070037700 | 20050114928 | 20040060002 |
20070022494 | 20050079494 | 20040055059 |
20070011761 | 20050071900 | 20040055058 |
20060288451 | 20050022272 | 20040055057 |
20060288447 | 20050022261 | 20040055056 |
20060202915 | 20050005332 | 20040055055 |
20060265778 | 20050005321 | 20040055054 |
20060174372 | 20040237152 | 20040055051 |
» a
20040055049 | 20100175149 | 20090089891 |
20040055048 | 20100162434 | 20090083882 |
20040055047 | 20100162432 | 20090075819 |
20040055045 | 20100162431 | 20090064374 |
20040055044 | 20100162430 | 20090055970 |
20040055043 | 20100162429 | 20090038025 |
20040049821 | 20100132071 | 20090031451 |
20040049820 | 20100115664 | 20090031446 |
20040049817 | 20100095404 | 20090031440 |
20040049816 | 20100095403 | 20090029860 |
20040049815 | 20100093715 | 20080307543 |
20040049814 | 20100088784 | 20080301835 |
20040016030 | 20100088783 | 20080263725 |
20040010824 | 20100088782 | 20080229453 |
20040010823 | 20100071093 | 20080229452 |
20030237111 | 20100071091 | 20080209588 |
20030233679 | 20100043100 | 20080201799 |
20030232757 | 20100037350 | 20080189806 |
20030195336 | 20100031392 | 20080178356 |
20030192072 | 20100011466 | 20080178355 |
20030182682 | 20100011465 | 20080172759 |
20030182678 | 20100005542 | 20080168585 |
20030172416 | 20090320158 | 20080168578 |
20030154524 | 20090320157 | 20080168577 |
20030131375 | 20090282580 | 20080163398 |
20030119158 | 20090276921 | 20080127369 |
20030101482 | 20090249514 | 20080120748 |
20030097672 | 20090241230 | 20080076179 |
20030068335 | 20090241227 | 20080072350 |
20030056243 | 20090235389 | 20080072347 |
20030005491 | 20090217417 | 20080052794 |
20020152496 | 20090217406 | 20080052792 |
20100293665 | 20090203094 | 20080050820 |
20100287665 | 20090188004 | 20080022427 |
20100287641 | 20090186762 | 20080005808 |
20100269219 | 20090172834 | 20070294783 |
20100263088 | 20090170173 | 20070261132 |
20100251416 | 20090165173 | 20070226842 |
20100229259 | 20090165170 | 20070209092 |
20100227924 | 20090158461 | 20070209087 |
20100205690 | 20090158454 | 20070199103 |
20100205689 | 20090144859 | 20070174927 |
20100199382 | 20090138987 | 20070118920 |
20100199380 | 20090113572 | 20070111311 |
20100199379 | 20090100541 | 20070033670 |
20100192254 | 20090100540 | 20070022497 |
20100190794 | 20090089896 | 20060206961 |
20060179515 | 20100192253 | 20090288217 |
20060174373 | 20100190707 | 20090282586 |
20060166684 | 20100186116 | 20090275473 |
20060162021 | 20100186115 | 20090265818 |
20060137043 | 20100186113 | 20090265802 |
20060112452 | 20100175150 | 20090264351 |
20060064784 | 20100167403 | 20090264290 |
20060037102 | 20100162440 | 20090260106 |
20060010514 | 20100162425 | 20090260105 |
20050241020 | 20100162424 | 20090235392 |
20040194163 | 20100154083 | 20090229018 |
20100293670 | 20100132072 | 20090227013 |
20100287669 | 20100132070 | 20090222954 |
20100287662 | 20100122367 | 20090222943 |
20100287656 | 20100115667 | 20090210970 |
20100287655 | 20100115662 | 20090205078 |
20100285591 | 20100115681 | 20090205067 |
20100281579 | 20100100985 | 20090205065 |
20100281578 | 20100100981 | 20090192117 |
20100281570 | 20100095401 | 20090192116 |
20100281569 | 20100088785 | 20090188008 |
20100269229 | 20100077508 | 20090188003 |
20100269228 | 20100077507 | 20090183285 |
20100269221 | 20100071087 | 20090183279 |
20100269218 | 20100058495 | 20090183278 |
20100269194 | 20100050293 | 20090183277 |
20100269193 | 20100037347 | 20090183276 |
20100269189 | 20100031391 | 20090178159 |
20100269188 | 20100029725 | 20090172841 |
20100269187 | 20100017915 | 20090165177 |
20100269186 | 20100017908 | 20090165174 |
20100269185 | 20100017907 | 20090158471 |
20100242138 | 20100017906 | 20090158459 |
20100242137 | 20100017905 | 20090158458 |
20100242131 | 20090328252 | 20090151022 |
20100236146 | 20090325804 | 20090151017 |
20100235944 | 20090320163 | 20090144843 |
20100235939 | 20090320162 | 20090138986 |
20100229257 | 20090320156 | 20090137395 |
20100223695 | 20090320155 | 20090136646 |
20100221238 | 20090313722 | 20090133161 |
20100218276 | 20090313721 | 20090119804 |
20100212049 | 20090307800 | 20090119799 |
20100199383 | 20090307797 | 20090113570 |
20100192263 | 20090300789 | 20090106860 |
20100192256 | 20090293147 | 20090106859 |
20100192255 | 20090293141 | 20090106857 |
» k
20090094713 | 20080256666 | 20060078004 |
20090094712 | 20080244767 | 20080072348 |
20090089897 | 20080244766 | 20080072345 |
20090089895 | 20080244765 | 20080072344 |
20090081354 | 20080241927 | 20080072343 |
20090077691 | 20080235827 | 20080060099 |
20090077690 | 20080234130 | 20080057564 |
20090077689 | 20080227091 | 20080051288 |
20090077688 | 20080222753 | 20080047031 |
20090069182 | 20080216200 | 20080040825 |
20090055966 | 20080216191 | 20080040824 |
20090055961 | 20080209582 | 20080034652 |
20090049571 | 20080200415 | 20080034448 |
20090049570 | 20080189810 | 20080034447 |
20090049569 | 20080178353 | 20080022426 |
20090038034 | 20080178350 | 20080020968 |
20090038028 | 20080178325 | 20080020967 |
20090038027 | 2ΟΟ8Ο17Θ323 | 20080020966 |
20090038026 | 20080172762 | 20080020123 |
20090036308 | 20080171321 | 20080016596 |
20090035765 | 20080168581 | 20080016595 |
20090031449 | 20080183402 | 20080016594 |
20090031448 | 20080163401 | 20070300323 |
20090025103 | 20080163400 | 20070294781 |
20090025102 | 20080141392 | 20070289030 |
20000007302 | 20080134362 | 20070283461 |
20090005306 | 20080134361 | 20070277256 |
20090000188 | 20080127377 | 20070274972 |
20090000187 | 20080127375 | 20070271628 |
20080320617 | 20080124804 | 20070266462 |
20080320613 | 20080124797 | 20070266458 |
20080313777 | 20080124796 | 20070281136 |
20080313770 | 20080120747 | 20070256198 |
20080305238 | 20080120746 | 20070250959 |
20080299658 | 20080120745 | 20070245430 |
20080288434 | 20080120744 | 20070245429 |
20080280018 | 20080120743 | 20070245428 |
20080280017 | 20080120742 | 20070245427 |
20080280016 | 20080120741 | 20070245425 |
20080280015 | 20080115241 | 20070240238 |
20080280014 | 20080109925 | 20070238179 |
20080260013 | 20080109924 | 20070234444 |
20080280012 | 20080108072 | 20070234443 |
20080280011 | 20080090294 | 20070231905 |
20080274261 | 20080090293 | 20070226837 |
20080274260 | 20080086783 | 20070226836 |
20080271198 | 20080083043 | 20070226835 |
20070226834 | 20070136866 | 20070107091 |
20070226833 | 20070136865 | 20070107090 |
20070226832 | 20070136864 | 20070107089 |
20070226831 | 20070136863 | 20070107088 |
20070220627 | 20070136862 | 20070107084 |
20070220626 | 20070136861 | 20070094747 |
20070214514 | 20070136860 | 20070089200 |
20070199105 | 20070136859 | 20070089181 |
20070192899 | 20070136858 | 20070079402 |
20070192897 | 20070136857 | 20070079397 |
20070180578 | 20070136856 | 20070079393 |
20070180577 | 20070136855 | 20070074311 |
20070180576 | 20070136854 | 20070074303 |
20070169227 | 20070136853 | 20070061926 |
20070169226 | 20070136852 | 20070044180 |
20070169225 | 20070136851 | 20070016980 |
20070169220 | 20070138850 | 20070011771 |
20070162999 | 20070136849 | 20070006350 |
20070157342 | 20070136848 | 20060294625 |
20070157341 | 20070136847 | 20060294624 |
20070157335 | 20070136846 | 20060293913 |
20070150980 | 20070136845 | 20060288453 |
20070150979 | 20070136844 | 20060288448 |
20070143880 | 20070136843 | 20060288440 |
20070136891 | 20070136842 | 20060282918 |
20070136888 | 20070136838 | 20060281910 |
20070136887 | 20070130653 | 20060272058 |
20070136886 | 20070130652 | 20060272057 |
20070136885 | 20070130651 | 20060272055 |
20070136884 | 20070130650 | 20060272054 |
20070136883 | 20070130649 | 20060272046 |
20070136882 | 20070130648 | 20060260006 |
20070136881 | 20070130647 | 20060242733 |
20070136880 | 20070130646 | 20060225161 |
20070136879 | 20070130642 | 20060225160 |
20070136878 | 20070118919 | 20060225152 |
2007013687Z | 20070107102 | 20060225151 |
20070136876 | 20070107101 | 20060223102 |
20070136875 | 20070107100 | 20060212971 |
20070136874 | 20070107099 | 20060212966 |
20070136873 | 20070107098 | 20060212964 |
20070136872 | 20070107097 | 20060206967 |
20070136871 | 20070107096 | 20060200874 |
20070136870 | 20070107095 | 20060195954 |
20070136869 | 20070107094 | 20060195953 |
20070136868 | 20070107093 | 20060195937 |
20070136887 | 20070107092 | 20060185039 |
20060174382 | 20060107413 | 20060107365 |
20060174381 | 20060107412 | 20060107384 |
20060168692 | 20060107411 | 20060107363 |
20060162030 | 20060107410 | 20060107362 |
20060162027 | 20060107409 | 20060107361 |
20060162015 | 20060107408 | 20060107360 |
20060162009 | 20060107407 | 20060107359 |
20060156439 | 20060107406 | 20060107358 |
20060150277 | 20060107405 | 20060107357 |
20060150275 | 20060107404 | 20060107356 |
20060150274 | 20060107403 | 20060107355 |
20060143744 | 20060107402 | 20060107354 |
20060143743 | 20060107401 | 20060107347 |
20060143733 | 20060107400 | 20060101546 |
20060143728 | 20060107399 | 20060095991 |
20060137035 | 20060107398 | 20060095990 |
20060137033 | 20060107397 | 20060090225 |
20060130190 | 20060107396 | 20060070143 |
20060130189 | 20060107395 | 20060070139 |
20060130188 | 20060107394 | 20060064789 |
20060130187 | 20060107393 | 20060064788 |
20060130184 | 20060107391 | 20060064779 |
20060112465 | 20060107390 | 20060064773 |
20060112464 | 20060107389 | 20060037109 |
20060112463 | 20060107388 | 20060037095 |
20060112462 | 20060107387 | 20060031962 |
20060112461 | 20060107386 | 20060026710 |
20060112460 | 20060107385 | 20060026709 |
20060112459 | 20060107384 | 20060026708 |
20060112458 | 20060107383 | 20060026707 |
20060112457 | 20060107382 | 20060021082 |
20060112458 | 20060107381 | 20060015988 |
20060112444 | 20060107380 | 20060010534 |
20060107427 | 20060107379 | 20060005287 |
20060107426 | 20060107378 | 20060005275 |
20060107425 | 20060107377 | 20060005274 |
20060107424 | 20060107376 | 20060005269 |
20060107423 | 20060107375 | 20050289670 |
20060107422 | 20060107374 | 20050283862 |
20060107421 | 20060107373 | 20050283314 |
20060107420 | 20060107372 | 20050278812 |
20060107419 | 20060107371 | 20050278811 |
20060107418 | 20060107370 | 20050278810 |
20060107417 | 20060107369 | 20050278805 |
20060107416 | 20060107368 | 20050278803 |
20060107415 | 20060107367 | 20050273889 |
20060107414 | 20060107366 | 20050273881 |
20050273879 | 20050150020 | 20050120404 |
20050257290 | 20050150019 | 20050114955 |
20050257209 | 20050150018 | 20050114954 |
20050240798 | 20050150017 | 20050114953 |
20050248796 | 20050144690 | 20050114952 |
20050235383 | 20050144689 | 20050114951 |
20050229483 | 20050144688 | 20050114950 |
20050229274 | 20050144687 | 20050114949 |
20050229271 | 20050144686 | 20050114948 |
20050223443 | 20050144685 | 20050114947 |
20050223439 | 20050144683 | 20050114946 |
20050223432 | 20050144682 | 20050114945 |
20050223426 | 20050144681 | 20050114944 |
20050216977 | 20050138697 | 20050114943 |
20050216974 | 20050138696 | 20050114942 |
20050216968 | 20050138695 | 20050114941 |
20050210551 | 20050138686 | 20050114940 |
20050210550 | 20050132453 | 20050114939 |
20050204418 | 20050132452 | 20050114938 |
20050202486 | 20050132451 | 20050114937 |
20050198706 | 20050132450 | 20050114936 |
20050198702 | 20050125866 | 20050114935 |
20050180441 | 20050120443 | 20050114934 |
20050188440 | 20050120442 | 20050114933 |
20050188439 | 20050120441 | 20050114932 |
20050188437 | 20050120440 | 20050114931 |
20050177898 | 20050120439 | 20050114930 |
20050177897 | 20050120438 | 20050108796 |
20050177892 | 20050120437 | 20050108795 |
20050172369 | 20050120436 | 20050108794 |
20050172368 | 20050120435 | 20050102717 |
20050172367 | 20050120434 | 20050097636 |
20050166291 | 20050120433 | 20050097634 |
20050166287 | 20050120432 | 20050097633 |
20050166286 | 20050120431 | 20050081265 |
20050168284 | 20050120430 | 20050076404 |
20050160506 | 20050120429 | 20050071901 |
20050160506 | 20050120428 | 20050070697 |
20050160496 | 20050120427 | 20050050590 |
20050160494 | 20050120426 | 20050039226 |
20050160488 | 20050120425 | 20050034193 |
20050155118 | 20050120424 | 20050028231 |
20050155102 | 20050120423 | 20050010975 |
20050150025 | 20050120422 | 20040248304 |
20050150023 | 20050120421 | 20040237147 |
20050150022 | 20050120420 | 20040231017 |
20050150021 | 20050120419 | 20040218192 |
20040210963 | 20040172707 | 20030200557 |
20040210960 | 20040172708 | 20030167532 |
20040210043 | 20040172705 | 20030167530 |
20040205864 | 20040172704 | 20030167528 |
20040205863 | 20040172703 | 20030167506 |
20040199965 | 20040172702 | 20030167504 |
20040199960 | 20040172701 | 20030166855 |
20040199959 | 20040172700 | 20030163840 |
20040194171 | 20040172699 | 20030163839 |
20040194170 | 20040172698 | 20030163838 |
20040194169 | 20040172697 | 20030159185 |
20040194168 | 20040172696 | 20030150016 |
20040194167 | 20040172695 | 20030150014 |
20040187179 | 20040172694 | 20030140381 |
20040181836 | 20040172693 | 20030140369 |
20040181835 | 20040172692 | 20030140368 |
20040181833 | 20040172691 | 20030131381 |
20040181832 | 20040172668 | 20030110528 |
20040181824 | 20040168212 | 20030101484 |
20040180436 | 20040166563 | 20030101483 |
20040177420 | 20040154059 | 20030097689 |
20040177419 | 20040148654 | 20030097680 |
20040177418 | 20040148652 | 20030088890 |
20040177417 | 20040143871 | 20030084486 |
20040177416 | 20040143870 | 20030084476 |
20040177415 | 20040123345 | 20030079251 |
20040177414 | 20040122592 | 20030079247 |
20040177413 | 20040118754 | 20030073239 |
20040177412 | 20040111761 | 20030041348 |
20040177411 | 20040098769 | 20030033632 |
20040177410 | 20040098760 | 20030033629 |
20040177409 | 20040083500 | 20030028921 |
20040177408 | 20040082770 | 20030028920 |
20040177407 | 20040073971 | 20030017566 |
20040177406 | 20040068767 | 20030009782 |
20040172728 | 20040064858 | 20030005482 |
20040172727 | 20040049804 | 20020166146 |
20040172726 | 20040040056 | 20020166143 |
20040172725 | 20040025206 | 20020166141 |
20040172724 | 20040019931 | 20020182142 |
20040172723 | 20040005713 | 20020148007 |
20040172722 | 20030228178 | 20020144307 |
20040172721 | 20030226167 | 20020124284 |
20040172711 | 20030221224 | 20020108149 |
20040172710 | 20030217387 | 20020083493 |
20040172709 | 20030213016 | 20020078475 |
20040172708 | 20030213014 | 20020069428 |
20020029392 20020004940 20010023501 20100281574 20100257638 20100235943 20100169999 20100168452 20100041610 20100037358 20100004177 20090320159 20090203612 20090158473 20090093366 20090029863 20090023782 20080295195 20080260933 20080178323 20080085856 20080058248 20070220629 20070143876 20060168683 20060070139 20060037095 20050216969 20050039226 20040194164
Claims (20)
1 o
22. The method of any of the above claims wherein the plant is a gcnetically modified alfalfa, potato corn, wheat, beet, cotton, rapeseed, rice, or sugarcane plant.
23. A product comprising sugar from a feedstock obtained at least in part from a plant that has been modified with respect to a wild type varîety of the plant.
24. A product comprising an irradiated feedstock obtained at least in part from a
1. A method of making a product comprising:
physically trcating a feedstock obtained at least in part from a plant that has been modifîed with respect to a wild type variety of the plant,
5
2. The method of claim 1 wherein the feedstock comprises lignocellulosic or cellulosic material.
3. The method of claim 1 or 2 wherein the plant has been genetically modifîed.
4. The method of any of the above claims wherein the plant comprises recombinant DNA.
5 comprises irradiation of the feedstock.
6. The method of any of the above claims wherein the plant expresses a recombinant protein.
7. The method of any of the above claims wherein the plant expresses onc or more
8. The method of claim 7 wherein the recombinant material is a polymer or a macromoleculc.
9. The method of any of the above claims further comprising obtaining from the feedstock a material selected from the group consisting of pharmaceuticals,
20 nutriceuticals, proteins, fats, vitamîns, oils, fiber, minerais, sugars, carbohydrates and alcohols.
10 15. The method of claim 12 wherein irradiatîng comprises applying a total dose of from about 5 Mrad to about 50 Mrad of radiation to the feedstock.
10. The method of any of the above claims further comprising treating the feedstock with an organism and/or enzyme to produce a product.
10 5. The method of any of the above claims wherein the plant comprises one or more recombinant genes.
11. The method of claim 10 wherein the product comprises a sugar.
12. The method of any of the above claims wherein the physical treatment
13. The method of claim 12 further comprising utilizing the irradiated feedstock as an animal feed.
14. The method of claim 12 wherein irradiatîng is performed using one or more électron beam devices.
15 plant that has been modified with respect to a wild type varicty of the plant.
25. The product of claim 24 further comprising a microorganism and/or an enzyme.
26. The product of claim 24 or 25 further comprising a liquid medium.
27. A product comprising a physically treated cellulosic or lignocellulosic
15 com stover.
15 recombinant materials.
16. The method of any of the above claims wherein the feedstock comprises a crop residue.
17. The method of claim 16 wherein the feedstock comprises corn cobs and/or
18. The method of claim 16 wherein the feedstock comprises wheat straw.
19. The method of any of the above claims wherein the plant comprises a genetically modified com or soybean plant.
20. The method of claim 11 further comprising fermenting the sugar.
i V
21. The method of any of the above claims wherein the plant has been modified with a modification selected from the group consisting of enhancement of résistance to insects, fungal diseases, and other pests and disease-causing agents; increased tolérance to herbicides; increased drought résistance; extended température range; enhanced 5 tolérance (o poor soil; enhanced stabilîty or shelf-life; greater yield; larger fruit size;
stronger stalks; enhanced shatter résistance; reduced time to crop maturity; more uniform germination times; higher or modified starch production; enhanced nutrient production,; modified lignin content; enhanced cellulose, hcmiccllulosc and/or lignin dégradation;; reduced recalcitrance and enhanced phytate metabolism.
20 feedstock obtained at least in part from a plant that has been modified with respect to a wild type varicty of the plant.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61/442,781 | 2011-02-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
OA16507A true OA16507A (en) | 2015-10-21 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20180179571A1 (en) | Processing biomass | |
US9353344B2 (en) | Processing biomass | |
AU2018201447B2 (en) | Processing Biomass | |
OA16507A (en) | Processing biomass. | |
NZ708603B2 (en) | Processing Biomass | |
NZ729489B2 (en) | Processing Biomass | |
NZ714143B2 (en) | Processing Biomass | |
NZ612186B2 (en) | Processing biomass | |
OA16578A (en) | Processing biomass. |