US20230250373A9 - Stillage solids concentration - Google Patents
Stillage solids concentration Download PDFInfo
- Publication number
- US20230250373A9 US20230250373A9 US17/673,655 US202217673655A US2023250373A9 US 20230250373 A9 US20230250373 A9 US 20230250373A9 US 202217673655 A US202217673655 A US 202217673655A US 2023250373 A9 US2023250373 A9 US 2023250373A9
- Authority
- US
- United States
- Prior art keywords
- recited
- acrylamide
- cationic polymer
- solids
- cationic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- 239000000701 coagulant Substances 0.000 claims abstract description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 20
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 20
- 235000005822 corn Nutrition 0.000 claims abstract description 20
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920001519 homopolymer Polymers 0.000 claims abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920003118 cationic copolymer Polymers 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 241000209149 Zea Species 0.000 claims 2
- 240000008042 Zea mays Species 0.000 abstract description 18
- 229920002472 Starch Polymers 0.000 abstract description 17
- 235000019698 starch Nutrition 0.000 abstract description 17
- 239000008107 starch Substances 0.000 abstract description 14
- 229920000642 polymer Polymers 0.000 abstract description 11
- 241000196324 Embryophyta Species 0.000 abstract description 7
- 241001465754 Metazoa Species 0.000 abstract description 6
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 description 23
- -1 dimethylaminoethyl Chemical group 0.000 description 22
- 238000000926 separation method Methods 0.000 description 17
- 125000002091 cationic group Chemical group 0.000 description 13
- 239000008394 flocculating agent Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000006188 syrup Substances 0.000 description 5
- 235000020357 syrup Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- WQHCGPGATAYRLN-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl prop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C=C WQHCGPGATAYRLN-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 3
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- MKRNVBXERAPZOP-UHFFFAOYSA-N Starch acetate Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OC(C)=O)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 MKRNVBXERAPZOP-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 2
- 238000009300 dissolved air flotation Methods 0.000 description 2
- 235000013804 distarch phosphate Nutrition 0.000 description 2
- 239000001245 distarch phosphate Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- DVROLKBAWTYHHD-UHFFFAOYSA-N hydroxy propyl distarch phosphate Chemical compound OC1C(O)C(OC)OC(CO)C1OC(O)CCOC1C(OC2C(C(O)C(OC3C(C(OP(O)(=O)OC4C(C(O)C(OC)OC4CO)O)C(C)OC3CO)O)OC2COC2C(C(O)C(OC)C(CO)O2)O)O)OC(CO)C(OC)C1O DVROLKBAWTYHHD-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920000107 Acetylated distarch adipate Polymers 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000416162 Astragalus gummifer Species 0.000 description 1
- 239000004370 Bleached starch Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920002148 Gellan gum Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920003012 Hydroxypropyl distarch phosphate Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 240000000968 Parkia biglobosa Species 0.000 description 1
- 229920002985 Phosphated distarch phosphate Polymers 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 235000013770 acetylated oxidized starch Nutrition 0.000 description 1
- 239000001073 acetylated oxidized starch Substances 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 235000019428 bleached starch Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- KCYQMQGPYWZZNJ-UHFFFAOYSA-N hydron;2-oct-1-enylbutanedioate Chemical compound CCCCCCC=CC(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-UHFFFAOYSA-N 0.000 description 1
- 235000013825 hydroxy propyl distarch phosphate Nutrition 0.000 description 1
- 239000001310 hydroxy propyl distarch phosphate Substances 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000252 konjac Substances 0.000 description 1
- 235000019823 konjac gum Nutrition 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 235000013807 monostarch phosphate Nutrition 0.000 description 1
- 239000001248 monostarch phosphate Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 235000013803 phosphated distarch phosphate Nutrition 0.000 description 1
- 239000001239 phosphated distarch phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12F—RECOVERY OF BY-PRODUCTS OF FERMENTED SOLUTIONS; DENATURED ALCOHOL; PREPARATION THEREOF
- C12F3/00—Recovery of by-products
- C12F3/10—Recovery of by-products from distillery slops
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0217—Separation of non-miscible liquids by centrifugal force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- coagulants and/or flocculants either alone or in combination to concentrate and separate solids from the stillage streams in the corn ethanol process.
- concentration and separation operations can be done at process temperatures.
- Stillage contains a mixture of solids, oil, and water.
- the corn kernels are ground, and the whole ground corn, without further separation of its constituents, is mixed with water, heated and processed to convert the starches into fermentable sugars; the resulting mixture is called mash.
- the mash is fermented to produce ethanol. Ethanol is separated from the fermented mash, called beer, by distillation in a stripper or distillation column.
- the residue of the distillation process, after the ethanol is removed, is called stillage or whole stillage.
- the whole stillage is then subjected to centrifuging or other separation methods to produce thin stillage and wet cake.
- the thin stillage is further processed in an evaporator or the like to remove excess water and produce “syrup” or evaporated thin stillage.
- this syrup has a moisture content of between about 55-75 wt %.
- part or all of the syrup stream is processed by mechanical and/or thermal and/or other separation techniques to separate corn oil for industrial use, such as manufacture of biodiesel.
- the wet cake is dried to make either distillers dried grains (DDG) or distillers dried grains with solubles (DDGS) which is sold as animal feed.
- DDG distillers dried grains
- DDGS distillers dried grains with solubles
- a method for concentrating solids in a corn to ethanol process wherein oil and solids are present in a process stream mixture.
- the method may comprise, for example, adding to the process stream mixture an effective amount of a solids concentration aid wherein the solids concentration aid is a polymeric treatment devoid of (meth)acrylic acid/2-acrylamido-2-methyl-1-propane sulfonic acid or salts thereof
- the solids concentration aid may be selected from the group consisting of a) a cationic polymer coagulant or flocculant, b) a starch coagulant or flocculant, or c) a biologically derived (plant and animal origin) coagulant or flocculant.
- the solids concentration aid is present in an amount of about 1-10,000 ppm based upon the weight of the process stream mixture.
- the solids concentration aid is a cationic polymer represented by the monomeric repeat units.
- q is present in a range of 1-99 parts
- r is present in a range of 1-99 parts
- the molecular weight of said cationic polymer being about 10,000-20,000,000 Dalton units, the combination of [A], [B], with or without [C] and with or without other monomers, being linear, branched, in block form, or in random form wherein [A] is chosen from acrylamide, methacrylamides, acrylic acid, methacrylic acid, and methyl methacrylic acid; [B] and [C] are cationic monomeric repeat units selected from the group consisting of: dimethylaminoethyl acrylate methyl chloride, dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate methyl sulfate quaternary salt, di
- the cationic polymer solids concentration aid is selected from:
- x:y is within the rage of 95:5 to 5:95;
- R 1 and R 2 may be the same or different and are chosen form H, and CH 3 ;
- Q is —C(O)O—, —OC(O)—, or —C(O)NH—,
- R 3 is branched or linear (C 1 -C 4 ) alkylene,
- R 4 , R 5 ,and R 6 are each independently chosen from H, C 1 -C 4 linear or branched alkyl, or a C 5 -C 8 aromatic or alkylaromatic group,
- A is an anion selected from Cl ⁇ , Br ⁇ , HSO 4 ⁇ or MeOSO 3 ⁇ wherein Me is methyl;
- Exemplary cationic polymer solids separation aids may comprise copolymers of acrylamide and a second monomeric repeat unit chosen from AETAC, MATAC, METAC, and AEDBAC.
- One particularly noteworthy cationic copolymer is a terpolymer of acrylamide/AETAC/AEDBAC.
- the solids concentration aid may comprise a coagulant such as homopolymeric polydiallyldimethyl ammonium chloride—(poly DADMAC).
- both a coagulant and flocculant are used conjointly as the solids concentration aid.
- coagulant and flocculant types of chemicals can be used alone or in combination to concentrate stillage solids.
- the chemicals can be added to the stillage stream at any point in the post-distillation phase of the corn ethanol process.
- the concentrated solids can be separated from the stillage stream by any one of numerous commercially available solid-liquid separation methods.
- solid-liquid separation methods include centrifugation, decantation, cyclonic separation, induced air flotation, dissolved air flotation, settling, thickening, clarifying and filtration. These methods can be used alone or in combination to facilitate the removal of the chemically concentrated solids.
- the coagulants can be either electrolytes (inorganic salts) such as alum, lime, ferric sulfate, ferric chloride, or polyelectrolytes, which can be either biologically derived (plant or animal) materials, such as starches and gums, or synthetic organic chemicals.
- electrolytes inorganic salts
- alum, lime, ferric sulfate, ferric chloride, or polyelectrolytes which can be either biologically derived (plant or animal) materials, such as starches and gums, or synthetic organic chemicals.
- the flocculants are polymeric and can be polyelectrolytes.
- Flocculants can be biologically derived (plant or animal) materials, such as starches, cellulose derivatives and gums; or synthetic organic chemicals.
- Polymers or polyelectrolytes in the molecular weight range 10,000 to 1,000,000 are generally classified as coagulants, and in the molecular weight range 1,000,000 to 20,000,000 are generally classified as flocculants. Depending on the specific chemistry, manufacturing process and end use there may be some overlap in the molecular weight range of either classification.
- one or more coagulants may be added to the process stream in the aggregate dosage range of 1 part per million (ppm) to 10,000 ppm by weight relative to the process stream. If more than one coagulant is being used the dosage may be apportioned among the different coagulant types, not to exceed the maximum dosage.
- the aggregate coagulant dosage range is 5 ppm to 5,000 ppm, and more preferably 10 ppm to 2,000 ppm.
- one or more flocculants may be added to the process stream in the aggregate dosage range of 1 part per million (ppm) to 10,000 ppm by weight relative to the process stream. If more than one flocculant is being used, the dosage may be apportioned among the different flocculant types, not to exceed the maximum dosage.
- the aggregate flocculant dosage range is 5 ppm to 5,000 ppm, and more preferably 10 ppm to 2,000 ppm.
- coagulants may be added first followed by flocculants; the method can also be practiced by adding flocculants first followed by coagulants. They can also be added concurrently.
- staged or multistep addition where the overall dosage of either the coagulant and/or the flocculant is divided into two or more portions and added to the stillage stream in several sequential or alternating steps at one or more points in the process.
- the concentrated solids may be separated from the stream by any one of numerous commercially available solid-liquid separation methods; some examples of solid/liquid separation methods include centrifugation, decantation, cyclonic separation, induced air flotation, dissolved air flotation, settling, thickening, clarifying and filtration. These methods can be used alone or in combination to facilitate the separation of chemically concentrated solids.
- the chemicals can be used in conjunction with an additional solid-liquid separation step utilizing a solid-liquid separation method that can include those mentioned above. Alternatively, the chemicals can be used in conjunction with existing solid-liquid separation steps and make those steps more efficient.
- the method of concentrating stillage solids by use of chemicals can be practiced at the normal process temperatures of the corn ethanol manufacturing, generally in the 30° C. to 120° C. range.
- the method of concentrating stillage solids by use of chemicals can be practiced at pH range of 2.5 to 10.0, preferably at pH range of 3.0 to 8.0. If necessary, the pH can be adjusted to accomplish the most effective concentration of solids, by use of a suitable alkalizing agent such as sodium hydroxide or lime; or acidifying agent such as sulfuric, sulfurous or hydrochloric acids.
- a suitable alkalizing agent such as sodium hydroxide or lime
- acidifying agent such as sulfuric, sulfurous or hydrochloric acids.
- Exemplary coagulants and flocculants for concentrating stillage solids are cationic in nature. Some examples of flocculants and coagulants are given below.
- homopolymer means a polymer with only one type of monomer.
- a copolymer means a polymer with two or more different monomeric repeat units.
- a multi-component copolymer is being used to describe a copolymer with three or more different monomeric repeat units.
- the polymers of the present invention can be copolymers, including multi-component copolymers, of acrylamide or functionalized acrylamides or acrylic acid or functionalized acrylic acids, or acrylates or functionalized acrylates, with other monomers.
- acrylamides and/or acrylates and/or acrylic acid can be polymerized with other monomers to impart cationic charge to the overall polymer molecule.
- Copolymers, including multi-component copolymers, of acrylamide, acrylate, and/or acrylic acid can include monomers [A], [B], and [C], in molar amounts of q, r, s, respectively.
- q, r, s represent the relative moles of the monomers relative to each other.
- q can be 1 to 99 parts
- r can be 1 to 99 parts
- s can be zero to 99 parts.
- the molecular weight of the resulting copolymers, including multi-component copolymers, is in the 10,000 to 20,000,000 range.
- the combination of [A], [B], with or without [C] and with or without other monomers can be linear, branched, in block form, or in random form.
- [A] can be chosen from acrylamide, methacrylamides, acrylic acid, methacrylic acid, methyl methacrylic acid.
- [B] and [C] can be cationic monomers selected from the group consisting of: dimethylaminoethyl acrylate methyl chloride, dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate methyl sulfate quaternary salt, dimethylaminoethyl (meth)acrylate benzyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate sulfuric acid salt, dimethylaminoethyl (meth)acrylate hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamides and their quaternary or acid salts, acrylamidopropyltrimethylammonium chloride, dimethylaminopropyl (meth)acrylamide methyl sulfate quaternary salt, and dimethylaminopropyl (meth)acrylamide hydrochloric acid salt,
- these polymers can include monomers which are cationic acrylamides and monomers which are quaternary ammonium salt monomers, or both, with or without other monomers as well.
- the polymer can be linear, branched, or crosslinked and can be a block copolymer or a random copolymer. More specifically, some of the monomeric repeat units can be represented by the following formulas:
- the amount of the monomer represented by Formula I (herein designated as x) and the amount of monomer represented by Formula II (herein designated as y) can have a ratio of x:y that varies from 95:5 to 5:95, including 50:50 to 70:30 with the molar ratio (x):(y) 60:40 being presently preferred.
- R 1 and R 2 may be the same or different and are chosen from H and CH 3 .
- Q is —C(O)O—, —OC(O)—, or
- R 3 is branched or linear (C 1 -C 4 ) alkylene;
- R 4 , R 5 , and R 6 are independently chosen from H, C 1 -C 4 linear or branched alkyl, or an C 5 -C 8 aromatic or alkylaromatic group;
- A is an anion selected from Cl ⁇ , Br ⁇ , HSO 4 ⁇ , or MeOSO 3 ⁇ wherein Me is methyl.
- Exemplary monomers which fall under Formula II can include:
- (AEDBAC)—2-acryloxyethyldimethylbenzyl ammonium chloride; in terms of Formula II, R 2 H, Q is —C(O)O—; R 3 is Et, R 4 and R 5 are Me, R 6 is benzyl, and A is Cl ⁇ .
- the present invention can also include additional starch based chemistries as coagulants and/or flocculants, as identified below, where the starch can be starch from corn, potato, rice, wheat and/or other plants.
- coagulants and/or flocculants include the following biologically derived (plant & animal origin) flocculant and coagulant chemistries:
- the coagulant is homopolymeric polydiallyldimethyl-ammonium chloride
- the flocculant is an acrylamide based copolymer comprising repeat units of acrylamide/(2-(acryloyloxy)ethyl trimethyl ammonium chloride [AETAC]/acryloxyethyl dimethyl benzyl ammonium chloride [AEDBAC].
- process stream mixture we mean that the coagulant and/or flocculant is brought into contact with any oil/solids/water mixture present in such corn to oil processes or into contact with any solids or liquids that will ultimately be brought into contact with such oil/solids/water mixture.
- process stream mixture includes whole stillage process streams, thin stillage process streams, evaporator streams, syrup streams, liquid/solid separators such as centrifuges, and the feed or make up to a corn to ethanol fermentation process such as fermentation feed addition to a beer well or the like.
- One combined coagulant/flocculant solids separation aid is:
- Coagulant Poly (diallyl dimethyl ammonium chloride); at dosage range of 200-400 ppm.
- Flocculant Cationic terpolymer of acrylamide, AETAC (2-(Acryloyloxy) ethyl trimethylammonium chloride) and AEDBAC (Acryloxyethyl dimethylbenzyl ammonium chloride); at a dosage range of 200-500.
- the temperature of the stillage stream was 150° F. (65.6° C.), and pH was adjusted from 3.0 to 6.4 with sodium hydroxide.
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Abstract
Description
- This application is a continuation of copending U.S. Patent Application No. 16/065,930 filed on June 25, 2018, which claims priority to PCT Appl. No. PCT/US2017/017619, filed February 13, 2017, and to U.S. Provisional Application No. 62/296,641 filed February 18, 2016.
- Use of coagulants and/or flocculants either alone or in combination to concentrate and separate solids from the stillage streams in the corn ethanol process. The concentration and separation operations can be done at process temperatures.
- Over the past few decades, ethanol has become increasingly important as an alternative fuel. One advantage to use of ethanol fuel is that it can be produced from corn in a milling process. The residue of the corn to ethanol process is referred to as stillage. Stillage contains a mixture of solids, oil, and water.
- In a corn milling operation, the corn kernels are ground, and the whole ground corn, without further separation of its constituents, is mixed with water, heated and processed to convert the starches into fermentable sugars; the resulting mixture is called mash. The mash is fermented to produce ethanol. Ethanol is separated from the fermented mash, called beer, by distillation in a stripper or distillation column. The residue of the distillation process, after the ethanol is removed, is called stillage or whole stillage. The whole stillage is then subjected to centrifuging or other separation methods to produce thin stillage and wet cake. The thin stillage is further processed in an evaporator or the like to remove excess water and produce “syrup” or evaporated thin stillage. Typically, this syrup has a moisture content of between about 55-75 wt %. Increasingly, part or all of the syrup stream is processed by mechanical and/or thermal and/or other separation techniques to separate corn oil for industrial use, such as manufacture of biodiesel.
- The wet cake, either by itself or combined with stillage and/or syrup and/or other by-product streams of the corn ethanol process, is dried to make either distillers dried grains (DDG) or distillers dried grains with solubles (DDGS) which is sold as animal feed.
- Currently saleable by-products of the corn ethanol process are DDG, DDGS and corn oil; this necessitates concentration of the solid fraction and removal of the water from stillage streams by mechanical and thermal methods, which use large amounts of energy. Therefore, it would result in significant energy savings to concentrate and facilitate the separation of the stillage solids by chemical addition; this method of concentrating and separating stillage solids may also lead to production of other commercially valuable products from the corn ethanol process.
- In certain aspects of the invention, a method for concentrating solids in a corn to ethanol process is disclosed wherein oil and solids are present in a process stream mixture. The method may comprise, for example, adding to the process stream mixture an effective amount of a solids concentration aid wherein the solids concentration aid is a polymeric treatment devoid of (meth)acrylic acid/2-acrylamido-2-methyl-1-propane sulfonic acid or salts thereof
- In other embodiments of the invention, the solids concentration aid may be selected from the group consisting of a) a cationic polymer coagulant or flocculant, b) a starch coagulant or flocculant, or c) a biologically derived (plant and animal origin) coagulant or flocculant. In some aspects of the invention, the solids concentration aid is present in an amount of about 1-10,000 ppm based upon the weight of the process stream mixture. In some embodiments, the solids concentration aid is a cationic polymer represented by the monomeric repeat units.
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[A]q [B]r and [C]s - wherein q is present in a range of 1-99 parts, r is present in a range of 1-99 parts and s can be present in an amount of 0-99 parts with the proviso that q, r, and s=100 molar percent. The molecular weight of said cationic polymer being about 10,000-20,000,000 Dalton units, the combination of [A], [B], with or without [C] and with or without other monomers, being linear, branched, in block form, or in random form wherein [A] is chosen from acrylamide, methacrylamides, acrylic acid, methacrylic acid, and methyl methacrylic acid;
[B] and [C] are cationic monomeric repeat units selected from the group consisting of: dimethylaminoethyl acrylate methyl chloride, dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate methyl sulfate quaternary salt, dimethylaminoethyl (meth)acrylate benzyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate sulfuric acid salt, dimethylaminoethyl (meth)acrylate hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamides and their quaternary or acid salts, acrylamidopropyltrimethylammonium chloride, dimethylaminopropyl (meth)acrylamide methyl sulfate quaternary salt, and dimethylaminopropyl (meth)acrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate, diallyldiethylammonium chloride, and diallyldimethyl ammonium chloride. - In some embodiments, the cationic polymer solids concentration aid is selected from:
-
- i) copolymers having monomeric repeat units of Formulae I and II
- wherein x:y is within the rage of 95:5 to 5:95; R1 and R2 may be the same or different and are chosen form H, and CH3; Q is —C(O)O—, —OC(O)—, or —C(O)NH—, R3 is branched or linear (C1-C4) alkylene, R4, R5,and R6 are each independently chosen from H, C1-C4 linear or branched alkyl, or a C5-C8 aromatic or alkylaromatic group, A is an anion selected from Cl−, Br−, HSO4 −or MeOSO3 −wherein Me is methyl;
-
- ii) copolymers of secondary amines and epichlorohydrin;
- iii) polymers formed from reaction of a lower dialkylamine, epichlorohydrin, and a member selected from ammonia, primary amines; alkylenediamines of from 2-6 carbon atoms and polyamines;
- iv) copolymers of adipic acid, diethylamine, and epichlorohydrin;
- v) copolymers of ethylenediamine and oxirane;
- vi) copolymers of acrylamide, dimethylamine, and formaldehyde;
- vii) copolymers of acrylamide and diallyl dialkyl ammonium chloride;
- viii) homopolymers of diallyl dialkyl ammonium chloride;
- ix) copolymers of tannin and a cationic monomer;
- x) and copolymers of chitin derivatives and/or chitosan with one or more cationic monomers.
- Exemplary cationic polymer solids separation aids may comprise copolymers of acrylamide and a second monomeric repeat unit chosen from AETAC, MATAC, METAC, and AEDBAC. One particularly noteworthy cationic copolymer is a terpolymer of acrylamide/AETAC/AEDBAC.
- In other exemplary embodiments, the solids concentration aid may comprise a coagulant such as homopolymeric polydiallyldimethyl ammonium chloride—(poly DADMAC).
- In some embodiments, both a coagulant and flocculant are used conjointly as the solids concentration aid.
- In one aspect of the invention, coagulant and flocculant types of chemicals can be used alone or in combination to concentrate stillage solids. The chemicals can be added to the stillage stream at any point in the post-distillation phase of the corn ethanol process. The concentrated solids can be separated from the stillage stream by any one of numerous commercially available solid-liquid separation methods. Some examples of solid-liquid separation methods include centrifugation, decantation, cyclonic separation, induced air flotation, dissolved air flotation, settling, thickening, clarifying and filtration. These methods can be used alone or in combination to facilitate the removal of the chemically concentrated solids.
- In certain embodiments, the coagulants can be either electrolytes (inorganic salts) such as alum, lime, ferric sulfate, ferric chloride, or polyelectrolytes, which can be either biologically derived (plant or animal) materials, such as starches and gums, or synthetic organic chemicals.
- In certain embodiments, the flocculants are polymeric and can be polyelectrolytes. Flocculants can be biologically derived (plant or animal) materials, such as starches, cellulose derivatives and gums; or synthetic organic chemicals.
- Polymers or polyelectrolytes in the molecular weight range 10,000 to 1,000,000 are generally classified as coagulants, and in the molecular weight range 1,000,000 to 20,000,000 are generally classified as flocculants. Depending on the specific chemistry, manufacturing process and end use there may be some overlap in the molecular weight range of either classification.
- In some embodiments, one or more coagulants may be added to the process stream in the aggregate dosage range of 1 part per million (ppm) to 10,000 ppm by weight relative to the process stream. If more than one coagulant is being used the dosage may be apportioned among the different coagulant types, not to exceed the maximum dosage. Preferably, the aggregate coagulant dosage range is 5 ppm to 5,000 ppm, and more preferably 10 ppm to 2,000 ppm.
- In some applications, one or more flocculants may be added to the process stream in the aggregate dosage range of 1 part per million (ppm) to 10,000 ppm by weight relative to the process stream. If more than one flocculant is being used, the dosage may be apportioned among the different flocculant types, not to exceed the maximum dosage. Preferably, the aggregate flocculant dosage range is 5 ppm to 5,000 ppm, and more preferably 10 ppm to 2,000 ppm.
- In practice, coagulants may be added first followed by flocculants; the method can also be practiced by adding flocculants first followed by coagulants. They can also be added concurrently.
- Irrespective of the order of addition or the number of chemicals used, it is possible to practice staged or multistep addition, where the overall dosage of either the coagulant and/or the flocculant is divided into two or more portions and added to the stillage stream in several sequential or alternating steps at one or more points in the process.
- After the addition of the chemicals to the process stream, in some embodiments, the concentrated solids may be separated from the stream by any one of numerous commercially available solid-liquid separation methods; some examples of solid/liquid separation methods include centrifugation, decantation, cyclonic separation, induced air flotation, dissolved air flotation, settling, thickening, clarifying and filtration. These methods can be used alone or in combination to facilitate the separation of chemically concentrated solids. The chemicals can be used in conjunction with an additional solid-liquid separation step utilizing a solid-liquid separation method that can include those mentioned above. Alternatively, the chemicals can be used in conjunction with existing solid-liquid separation steps and make those steps more efficient.
- In certain embodiments, the method of concentrating stillage solids by use of chemicals can be practiced at the normal process temperatures of the corn ethanol manufacturing, generally in the 30° C. to 120° C. range.
- In certain exemplary embodiments, the method of concentrating stillage solids by use of chemicals can be practiced at pH range of 2.5 to 10.0, preferably at pH range of 3.0 to 8.0. If necessary, the pH can be adjusted to accomplish the most effective concentration of solids, by use of a suitable alkalizing agent such as sodium hydroxide or lime; or acidifying agent such as sulfuric, sulfurous or hydrochloric acids.
- Exemplary coagulants and flocculants for concentrating stillage solids are cationic in nature. Some examples of flocculants and coagulants are given below.
- In the present description, the term homopolymer means a polymer with only one type of monomer. A copolymer means a polymer with two or more different monomeric repeat units. A multi-component copolymer is being used to describe a copolymer with three or more different monomeric repeat units.
- In some embodiments, the polymers of the present invention can be copolymers, including multi-component copolymers, of acrylamide or functionalized acrylamides or acrylic acid or functionalized acrylic acids, or acrylates or functionalized acrylates, with other monomers. For example, acrylamides and/or acrylates and/or acrylic acid can be polymerized with other monomers to impart cationic charge to the overall polymer molecule. Copolymers, including multi-component copolymers, of acrylamide, acrylate, and/or acrylic acid can include monomers [A], [B], and [C], in molar amounts of q, r, s, respectively. In other words, q, r, s, represent the relative moles of the monomers relative to each other. q can be 1 to 99 parts, r can be 1 to 99 parts, and s can be zero to 99 parts. It is possible to also have other monomers or to limit the monomers to [A] and [B] by themselves or [A], [B], and [C] by themselves. The molecular weight of the resulting copolymers, including multi-component copolymers, is in the 10,000 to 20,000,000 range. The combination of [A], [B], with or without [C] and with or without other monomers, can be linear, branched, in block form, or in random form.
- [A] can be chosen from acrylamide, methacrylamides, acrylic acid, methacrylic acid, methyl methacrylic acid.
- [B] and [C] can be cationic monomers selected from the group consisting of: dimethylaminoethyl acrylate methyl chloride, dimethylaminoethyl (meth)acrylate methyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate methyl sulfate quaternary salt, dimethylaminoethyl (meth)acrylate benzyl chloride quaternary salt, dimethylaminoethyl (meth)acrylate sulfuric acid salt, dimethylaminoethyl (meth)acrylate hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamides and their quaternary or acid salts, acrylamidopropyltrimethylammonium chloride, dimethylaminopropyl (meth)acrylamide methyl sulfate quaternary salt, and dimethylaminopropyl (meth)acrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate, diallyldiethylammonium chloride, and diallyldimethyl ammonium chloride.
- In certain aspects of the invention, these polymers can include monomers which are cationic acrylamides and monomers which are quaternary ammonium salt monomers, or both, with or without other monomers as well. The polymer can be linear, branched, or crosslinked and can be a block copolymer or a random copolymer. More specifically, some of the monomeric repeat units can be represented by the following formulas:
- The amount of the monomer represented by Formula I (herein designated as x) and the amount of monomer represented by Formula II (herein designated as y) can have a ratio of x:y that varies from 95:5 to 5:95, including 50:50 to 70:30 with the molar ratio (x):(y) 60:40 being presently preferred. R1 and R2 may be the same or different and are chosen from H and CH3. Q is —C(O)O—, —OC(O)—, or
- —C(O)NH—, R3 is branched or linear (C1-C4) alkylene; R4, R5, and R6 are independently chosen from H, C1-C4 linear or branched alkyl, or an C5-C8 aromatic or alkylaromatic group; A is an anion selected from Cl−, Br−, HSO4 −, or MeOSO3 − wherein Me is methyl.
- Exemplary monomers which fall under Formula II can include:
- 1. (AETAC)—2-acryloxyethyltrimethyl ammonium chloride; also referred to as dimethylaminoethylacrylate methyl chloride; in terms of Formula II above R2=H;
- Q is —C(O)O—, R3=Et; R4, R5, and R6 are all Me, and A is Cl—.
- 2. (MATAC)—3-(meth) acrylamidopropyltrimethyl ammonium chloride; in terms of Formula II above R2=CH3; Q is —C(O)NH—; R3=Pr; R4, R5, and R6 are all Me, and A is Cl—; Pr is propyl.
- 3. (METAC)—2-methacryloxyethyltrimethyl ammonium chloride; in terms of Formula II above R2=CH3; Q is —C(O)O—; R3 is Et and R4, R5, and R6 are all Me, and A is C1 −; Et is ethyl.
- 4. (AEDBAC)—2-acryloxyethyldimethylbenzyl ammonium chloride; in terms of Formula II, R2=H, Q is —C(O)O—; R3 is Et, R4 and R5 are Me, R6 is benzyl, and A is Cl−.
- Other exemplary chemistries for the polymers include the ones below (with or without other monomers):
- a) Copolymers of secondary amines, such as dimethylamine and epichlorohydrin;
b) Polymers formed via reaction of i) a lower dialkyl amine (C1-C3); an epoxy reactant such as epichlorohydrin, and iii) a member selected from ammonia, primary amines, alkylenediamines of from 2-6 C atoms and polyamines;
c) Copolymers of adipic acid, diethyltriamine and epichlorohydrin;
d) Copolymers of ethylenediamine and oxirane;
e) Copolymers of acrylamide, dimethylamine and formaldehyde;
f) Copolymers of acrylamide and diallyl dimethyl ammonium chloride and homopolymers of diallyldialkyl (C1-C3) ammonium chloride such as polydiallyl dimethyl ammonium chloride (polyDADMAC);
g) Copolymers of tannin and cationic monomer. Information on this can be obtained from U.S. Pat. No. 5,916,991, the disclosure of which is incorporated herein;
h) Copolymers of chitin derivatives and/or chitosan with one or more cationic monomers to impart an overall cationic charge to the copolymer molecule; an example of which is given in U.S. Pat. No. 8,557,125. The disclosure of this patent is incorporated by reference herein. - The present invention can also include additional starch based chemistries as coagulants and/or flocculants, as identified below, where the starch can be starch from corn, potato, rice, wheat and/or other plants.
-
Common Name Codex CAS No. number Acid treated starch INS 1401 65996-63-6 Alkaline treated starch INS 1402 Bleached starch INS 1403 977075-42-5 Oxidized starch INS 1404 65996-62-5 Monostarch phosphate INS 1410 11120-02-8 Distarch phosphate INS 1412 55963-33-2 Phosphated distarch phosphate INS 1413 977043-58-5 Acetylated distarch phosphate INS 1414 68130-14-3 Starch acetate INS 1420 9045-28-7 & 57456-08-3 Acetylated distarch adipate INS 1422 63798-35-6 & 68130-14-3 Hydroxypropyl starch INS 1440 9049-76-7 Hydroxypropyl distarch phosphate INS 1442 53124-00-8 Starch, hydrogen octenylbutanedioate INS 1450 52906-93-1 & 66829-29-6 Acetylated oxidized starch INS 1451 68187-08-6 Starch from corn, potato, rice, wheat or 9005-25-8 other plants Cationic starch: starch (2-hydroxypropyl) 56780-58-6 trimethylammonium chloride ether Cationic starch: Copolymer of starch and 3-chloro-2-hydroxypropyl trimethylammonium chloride (CTA) Cationic starch: Copolymer of starch and quaternary ammonium chloride monomer - Additional chemistries that can be used as coagulants and/or flocculants include the following biologically derived (plant & animal origin) flocculant and coagulant chemistries:
- e) Gum tragacanth
f) Gum karaya - l) Cellulose derivatives:
-
- a. Methyl cellulose
- b. Hydroxypropyl cellulose
- c. Hydroxyethyl cellulose
- d. Carboxymethyl cellulose
- e. Hydroxypropylmethyl cellulose
-
-
- a. Locust bean gum
- b. Guar gum
- c. Tara gum
- In one exemplary embodiment of the invention, the coagulant is homopolymeric polydiallyldimethyl-ammonium chloride, and the flocculant is an acrylamide based copolymer comprising repeat units of acrylamide/(2-(acryloyloxy)ethyl trimethyl ammonium chloride [AETAC]/acryloxyethyl dimethyl benzyl ammonium chloride [AEDBAC].
- The coagulants and flocculants used in accordance with the invention are applied to a process stream that is present in a corn to oil process. By process stream mixture, we mean that the coagulant and/or flocculant is brought into contact with any oil/solids/water mixture present in such corn to oil processes or into contact with any solids or liquids that will ultimately be brought into contact with such oil/solids/water mixture. The phrase “process stream mixture” includes whole stillage process streams, thin stillage process streams, evaporator streams, syrup streams, liquid/solid separators such as centrifuges, and the feed or make up to a corn to ethanol fermentation process such as fermentation feed addition to a beer well or the like.
- One combined coagulant/flocculant solids separation aid is:
- Coagulant: Poly (diallyl dimethyl ammonium chloride); at dosage range of 200-400 ppm.
- Flocculant: Cationic terpolymer of acrylamide, AETAC (2-(Acryloyloxy) ethyl trimethylammonium chloride) and AEDBAC (Acryloxyethyl dimethylbenzyl ammonium chloride); at a dosage range of 200-500.
- The temperature of the stillage stream was 150° F. (65.6° C.), and pH was adjusted from 3.0 to 6.4 with sodium hydroxide.
- It will be apparent to those skilled in the art that many modifications can be made in the methods and compositions herein disclosed without departing from the spirit of the invention. It is to be understood that the scope of the invention is to be limited solely by the scope of the appended claims.
Claims (17)
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US201662296641P | 2016-02-18 | 2016-02-18 | |
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US201816065930A | 2018-06-25 | 2018-06-25 | |
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