CN103764698B - 制备丙烯酸或其衍生物的方法 - Google Patents
制备丙烯酸或其衍生物的方法 Download PDFInfo
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- CN103764698B CN103764698B CN201380002854.7A CN201380002854A CN103764698B CN 103764698 B CN103764698 B CN 103764698B CN 201380002854 A CN201380002854 A CN 201380002854A CN 103764698 B CN103764698 B CN 103764698B
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- mixture
- propionic acid
- catalyzer
- acid
- hydroxy
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- 238000000034 method Methods 0.000 title claims abstract description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 133
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 37
- 150000004712 monophosphates Chemical class 0.000 claims abstract description 33
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 97
- 239000003054 catalyst Substances 0.000 claims description 56
- 150000002500 ions Chemical class 0.000 claims description 50
- 150000001768 cations Chemical class 0.000 claims description 45
- 235000014655 lactic acid Nutrition 0.000 claims description 44
- 239000004310 lactic acid Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 28
- 239000008246 gaseous mixture Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000009466 transformation Effects 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000006227 byproduct Substances 0.000 abstract description 10
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 229960000448 lactic acid Drugs 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 32
- 229910019142 PO4 Inorganic materials 0.000 description 25
- 239000007788 liquid Substances 0.000 description 25
- 239000010452 phosphate Substances 0.000 description 25
- -1 phosphate radical Chemical class 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 239000011575 calcium Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 229910052622 kaolinite Inorganic materials 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000008247 solid mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 239000005388 borosilicate glass Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 229940001447 lactate Drugs 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920000247 superabsorbent polymer Polymers 0.000 description 4
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 230000004941 influx Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 241001012508 Carpiodes cyprinus Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910004856 P—O—P Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- RZOBLYBZQXQGFY-UHFFFAOYSA-N ammonium lactate Chemical compound [NH4+].CC(O)C([O-])=O RZOBLYBZQXQGFY-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229940107700 pyruvic acid Drugs 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- BYPIKLIXBPMDBY-UHFFFAOYSA-N 2-hydroxypropanoic acid;potassium Chemical compound [K].CC(O)C(O)=O BYPIKLIXBPMDBY-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical group C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCTNAFQDPQLRRG-UHFFFAOYSA-H O[Cr](O)(=O)=O.O[Cr](O)(=O)=O.O[Cr](O)(=O)=O.P.P Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O.O[Cr](O)(=O)=O.P.P UCTNAFQDPQLRRG-UHFFFAOYSA-H 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- SMHNUIFHMAGAFL-UHFFFAOYSA-N calcium;2-hydroxypropanoic acid Chemical compound [Ca].CC(O)C(O)=O SMHNUIFHMAGAFL-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- TXTCTCUXLQYGLA-UHFFFAOYSA-L calcium;prop-2-enoate Chemical compound [Ca+2].[O-]C(=O)C=C.[O-]C(=O)C=C TXTCTCUXLQYGLA-UHFFFAOYSA-L 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
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Classifications
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- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
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Abstract
本发明提供了将羟基丙酸、羟基丙酸衍生物、或它们的混合物催化脱水成丙烯酸、丙烯酸衍生物、或它们的混合物的方法,所述方法具有高收率和选择率,但没有向非期望副产物如乙醛、丙酸和乙酸的显著转化。所述催化剂为混合的单磷酸盐。
Description
技术领域
本发明一般涉及将羟基丙酸、羟基丙酸衍生物、或它们的混合物催化转化成丙烯酸、丙烯酸衍生物、或它们的混合物的方法。更具体地讲,本发明涉及方法,所述方法使用可用于将羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水成丙烯酸、丙烯酸衍生物、或它们的混合物的催化剂,对丙烯酸、丙烯酸衍生物、或它们的混合物具有高收率和选择性,停留时间短,并且没有显著的羟基丙酸、羟基丙酸衍生物、或它们的混合物向非期望副产物如乙醛、丙酸、乙酸、2,3-戊二酮、二氧化碳和一氧化碳的转化。
背景技术
丙烯酸、丙烯酸衍生物、或它们的混合物具有多种工业用途,通常以聚合物形式使用。继而,这些聚合物通常用于生产粘结剂、粘合剂、涂料、漆料、抛光剂、洗涤剂、絮凝剂、分散剂、触变剂、多价螯合剂、和超吸收聚合物等,所述超吸收聚合物用于一次性吸收制品中,包括例如尿布和卫生产品。丙烯酸通常由石油源制得。例如,丙烯酸一直通过丙烯的催化氧化制得。由石油源制备丙烯酸的这些和其它方法描述于“Kirk-OthmerEncyclopediaofChemicalTechnology”第1卷第342-369页(第5版,JohnWiley&Sons,Inc.,2004)中。石油基丙烯酸由于其石油衍生的碳含量高而助长了温室气体排放。此外,石油是不可再生的材料,因为它自然形成需要数十万年,而消耗仅需短时间。由于石化资源变得日益匮乏,更加昂贵,并且受到CO2排放规定的制约,因此逐渐需要可用作石油基丙烯酸、丙烯酸衍生物、或它们混合物的替代物的生物基丙烯酸、丙烯酸衍生物、或它们的混合物。
在过去40至50年里已进行了许多尝试,由非石油源制备生物基丙烯酸、丙烯酸衍生物、或它们的混合物,如乳酸(还被称为2-羟基丙酸)、3-羟基丙酸、甘油、一氧化碳和环氧乙烷、二氧化碳和乙烯、以及巴豆酸。在这些非石油源中,当前仅乳酸以高收率(≥90%的理论收率,或换句话讲,≥0.9g乳酸/g糖)以及高纯度和经济性由糖制得,这可以对石油基丙烯酸富有竞争力的成本支持制备丙烯酸。因此,乳酸或乳酸酯提供用作生物基丙烯酸、丙烯酸衍生物、或它们混合物的给料的实际机会。而且,3-羟基丙酸预计在几年内以商业规模生产,因此3-羟基丙酸将提供用作生物基丙烯酸、丙烯酸衍生物、或它们混合物的给料的另一个实际机会。硫酸盐、磷酸盐、硫酸盐和磷酸盐的混合物、碱、沸石或改性沸石、金属氧化物或改性的金属氧化物、以及超临界水是过去已用于将乳酸或乳酸酯脱水成丙烯酸、丙烯酸衍生物、或它们的混合物成主要催化剂,取得了不同程度的成功。
例如,美国专利4,786,756(公布于1988年)描述了使用用含水无机碱处理过的磷酸铝(AlPO4)作为催化剂,将乳酸或乳酸铵气相脱水成丙烯酸。例如,‘756专利公开了在约大气压下将乳酸加入到反应器时43.3%的丙烯酸最大收率,和将乳酸铵加入到反应器中时61.1%的相应收率。在两个例子中,乙醛分别以34.7%和11.9%的收率产生,并且还呈现大量其它副产物,如丙酸、CO和CO2。略除碱处理,造成副产物量增加。另一个例子为Hong等人(2011)“Appl.Catal.A:General”396:194-200,其研发并且测试了用浆液混合方法,由Ca3(PO4)2和Ca2(P2O7)盐制得的复合催化剂。由乳酸甲酯以最高收率获得丙烯酸的催化剂为50%-50%(按重量计)催化剂。它在390℃下生成68%的丙烯酸,约5%的丙烯酸甲酯,和约14%的乙醛。相同的催化剂由乳酸获得54%收率的丙烯酸,14%收率的乙醛,和14%收率的丙酸。
密歇根州立大学(MSU)D.Miller教授的课题组公布了许多关于乳酸或乳酸酯脱水成丙烯酸和2,3-戊二酮的文章,如Gunter等人(1994)J.Catalysis148:252-260;和Tam等人(1999)Ind.Eng.Chem.Res.38:3873-3877。该课题组报导的最佳丙烯酸收率为在350℃下,在NaOH饱和的低表面积和孔体积的二氧化硅上将乳酸脱水时的约33%。在相同的实验中,乙醛收率为14.7%,并且丙酸收率为4.1%。该课题组测试的其它催化剂例子为Na2SO4、NaCl、Na3PO4、NaNO3、Na2SiO3、Na4P2O7、NaH2PO4、Na2HPO4、Na2HAsO4、NaC3H5O3、NaOH、CsCl、Cs2SO4、KOH、CsOH和LiOH。在所有情况下,上文引用的催化剂均以单独组分形式而不是以混合物形式测试。最后,该课题组提出,当二氧化硅载体表面积低、反应温度高、反应压力低、并且反应物在催化剂床中的停留时间短时,丙烯酸的收率得到改善,并且副产物收率被抑制。
最后,中国专利申请200910054519.7公开了用含水碱(如NH3、NaOH、和Na2CO3)或磷酸盐(如NaH2PO4、Na2HPO4、LiH2PO4、LaPO4等)改性的ZSM-5分子筛的用途。乳酸脱水中获得的丙烯酸最佳收率为83.9%,然而该收率是在非常长的停留时间下获得的。
因此,经由方法如上述文献中所述那些由乳酸或乳酸酯制备丙烯酸、丙烯酸衍生物、或它们的混合物,已表明:1)丙烯酸、丙烯酸衍生物、或它们的混合物的收率不超过70%;2)丙烯酸、丙烯酸衍生物、或它们的混合物的选择性低,即大量非期望的副产物如乙醛、2,3-戊二酮、丙酸、CO和CO2;3)在催化剂床中的停留时间长;以及4)催化剂在短反应时间(TOS)内失活。副产物可沉积在催化剂上,致使催化剂污损并且过早快速钝化。此外,沉积后,这些副产物可催化其它非期望的反应如聚合反应。除了沉积在催化剂上以外,这些副产物即使仅少量存在,也在生产例如超吸收聚合物(SAP)时,占据加工丙烯酸(当存在于反应产物流出物中时)的额外成本。现有技术工业和催化剂的这些缺陷使得它们在商业上是不可行的。
因此,需要用于将羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水成丙烯酸、丙烯酸衍生物、或它们的混合物的催化剂和方法,具有高收率、选择率和效率(即短停留时间)以及长寿命的催化剂。
发明内容
本发明提供了制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法。在本发明的一个实施例中,所述方法包括使包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流与催化剂接触,所述催化剂包含:
a.由式(I)描述的单磷酸一氢根阴离子:
[HPO4]2-(I),
b.和由式(II)描述的单磷酸二氢根阴离子:
[H2PO4]-(II),以及
c.至少两种不同的阳离子,
其中所述催化剂基本上是电中性的;并且进一步地,其中所述催化剂中所述单磷酸一氢根阴离子与所述单磷酸二氢根阴离子的摩尔比介于约0.1和约10之间。
在本发明的另一个实施例中,制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法包括使包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流与催化剂接触,所述催化剂包含由式(III)和(IV)描述的单磷酸盐:
MIIHPO4(III),
MIH2PO4(IV),并且
其中MI为一价阳离子,并且MII为二价阳离子。
在本发明的另一个实施例中,制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法包括使包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流与催化剂接触,所述催化剂包含由式(V)描述的单磷酸盐:
MII 2-xMI xHx(HPO4)2(V),
其中MI为一价阳离子,并且MII为二价阳离子;并且其中x大于约0.2并且小于约1.8。
在本发明的一个实施例中,制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法包括接触:(a)气体混合物,所述气体混合物包含:(i)乳酸,(ii)水,和(iii)氮气,其中所述乳酸以基于所述气体混合物的总摩尔数计约2.5mol%的量存在,并且其中所述水以约50mol%的量存在;与(b)由方法制得的催化剂,所述方法包括以介于约3:2和约2:3之间的摩尔比混合BaHPO4和KH2PO4以形成固体混合物,并且碾磨所述固体混合物以制得所述催化剂,并且其中反应器中所述气体混合物与所述催化剂的所述接触在约300℃至约450℃的温度,约7,200h-1至约3,600h-1的GHSV,和约360psig的压力下进行,所述反应器具有内表面,所述内表面具有选自石英和硼硅酸盐玻璃的材料,从而由于所述乳酸与所述催化剂接触而制得丙烯酸。
通过结合实施例阅读以下具体实施方式,本发明的其它特征对于本领域的技术人员而言可变得显而易见。
具体实施方式
I定义
如本文所用,术语“单磷酸盐”或“正磷酸盐”是指其阴离子单元[PO4]3-由围绕中心磷原子近似规则四面体阵列排列的四个氧原子组成的任何盐。
如本文所用,术语“缩聚磷酸盐”是指包含一个或多个通过PO4四面体角共享产生的P-O-P键的任何盐。
如本文所用,术语“多磷酸盐”是指通过PO4四面体角共享致使形成有限链的包含线性P-O-P键的任何缩聚磷酸盐。
如本文所用,术语“低聚磷酸盐”是指包含五个或更少的PO4单元的任何聚磷酸盐。
如本文所用,术语“环磷酸盐”是指由两个或更多个角共享PO4四面体构成的任何环状缩聚磷酸盐。
如本文所用,术语“过磷酸盐”是指其中阴离子单元中至少两个PO4四面体与邻近四面体共享它们三个角的任何缩聚磷酸盐。
如本文所用,术语“阳离子”是指具有正电荷的任何原子或共价键合的原子组。
如本文所用,术语“阴离子”是指具有负电荷的任何原子或共价键合的原子组。
如本文所用,术语“一价阳离子”是指具有+1正电荷的任何阳离子。
如本文所用,术语“多价阳离子”是指具有等于或大于+2正电荷的任何阳离子。
如本文所用,术语“杂多阴离子”是指具有共价键合的XOp和YOr多面体的任何阴离子,从而包含X-O-Y和可能的X-O-X和Y-O-Y键,其中X和Y代表任何原子,并且其中p和r为任何正整数。
如本文所用,术语“杂多磷酸根”是指任何杂多阴离子阴离子,其中X代表磷(P),并且Y代表任何其它原子。
如本文所用,术语“磷酸根加合物”是指具有未共价连接的一个或多个磷酸根阴离子和一个或多个非磷酸根阴离子的任何化合物。
如本文所用,术语“LA”是指乳酸,“AA”是指丙烯酸,“AcH”是指乙醛,而“PA”是指丙酸。
如本文所用,术语“颗粒跨度”是指给定颗粒样品的统计表示,并且等于(Dv,0.90-Dv,0.10)/Dv,0.50。术语“中值粒度”或Dv,0.50是指50%颗粒的总体积在低于其的颗粒直径。此外,Dv,0.10是指区分10%体积份数颗粒样品的粒度,而Dv,0.90为区分90%体积份数颗粒样品的粒度。
如本文所用,以%表示的术语“转化率”定义为[羟基丙酸、羟基丙酸衍生物、或它们的混合物的流入量(mol/min)-羟基丙酸、羟基丙酸衍生物、或它们的混合物的流出量(mol/min)]/[羟基丙酸、羟基丙酸衍生物、或它们的混合物的流入量(mol/min)]*100。对于本发明目的,除非另外指明,术语“转化率”是指摩尔转化率。
如本文所用,以%表示的术语“收率”定义为[产物流出量(mol/min)/羟基丙酸、羟基丙酸衍生物、或它们的混合物的流入量(mol/min)]*100。对于本发明目的,除非另外指明,术语“收率”是指摩尔收率。
如本文所用,以%表示的术语“选择率”定义为[收率/转化率]*100。对于本发明目的,除非另外指明,术语“选择率”是指摩尔选择率。
如本文所用,以h-1为单位的术语“气时空速”或“GHSV”定义为60×[总气体流量(mL/min)/催化剂床体积(mL)]。总气体流量在标准温度和压力条件(STP;0℃和1atm)下计算。
如本文所用,以h-1为单位的术语“液时空速”或“LHSV”定义为60×[总液体流量(mL/min)/催化剂床体积(mL)]。
II催化剂
已出乎意料地发现,包含混合的单磷酸根阴离子的催化剂将羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水成丙烯酸、丙烯酸衍生物、或它们的混合物,具有:1)对丙烯酸、丙烯酸衍生物、或它们的混合物的高收率和选择率,即副产物量少并且不多;2)高效率,即在短停留时间内完成;和3)长寿命。虽然不愿受任何理论的束缚,但是申请人猜测,包含至少单磷酸一氢根和单磷酸二氢根阴离子和两种不同阳离子的催化剂如下起作用:羟基丙酸、羟基丙酸衍生物、或它们的混合物的羧酸根基团通过一个或两个氧原子与一个或多个阳离子缔合(在一个实施例中所述阳离子是多价的),将所述分子保留在催化剂表面上,使其失活以避免脱羰,并且活化C-OH键以进行消去。然后,所得质子化单磷酸根阴离子通过羟基协同质子化,从甲基上移除质子,并且以水分子形式消去质子化羟基,使羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水,生成丙烯酸、丙烯酸衍生物、或它们的混合物,并且重新活化催化剂。此外,申请人相信,单磷酸根阴离子的特殊质子化态对促进羟基丙酸、羟基丙酸衍生物、或它们的混合物的脱水是重要的。
在一个实施例中,所述催化剂包含:
a.由式(I)描述的单磷酸一氢根阴离子:
[HPO4]2-(I),
b.和由式(II)描述的单磷酸二氢根阴离子:
[H2PO4]-(II),以及
c.至少两种不同的阳离子,
其中所述催化剂基本上是电中性的;并且进一步地,其中所述催化剂中所述单磷酸一氢根阴离子与所述单磷酸二氢根阴离子的摩尔比介于约0.1和约10之间。在另一个实施例中,单磷酸一氢根阴离子与单磷酸二氢根阴离子的摩尔比介于约0.2和约5之间。在另一个实施例中,单磷酸一氢根阴离子与单磷酸二氢根阴离子的摩尔比为约1。
在本发明的一个实施例中,所述催化剂包含由式(III)和(IV)描述的单磷酸盐:
MIIHPO4(III),
MIH2PO4(IV),并且
其中MI为一价阳离子,并且MII为二价阳离子。在另一个实施例中,MIIHPO4与MIH2PO4的摩尔比介于约0.1和约10之间。在另一个实施例中,MIIHPO4与MIH2PO4的摩尔比介于约0.2和约5之间。在另一个实施例中,MIIHPO4与MIH2PO4的摩尔比为约1。
在本发明的一个实施例中,所述催化剂包含由式(V)描述的单磷酸盐:
MII 2-xMI xHx(HPO4)2(V),
其中MI为一价阳离子,并且MII为二价阳离子;并且其中x大于约0.2并且小于约1.8。在本发明的另一个实施例中,x为约1。
在另一个实施例中,由式(I)描述的单磷酸一氢根阴离子被由式[H(1- v)P(1+v)O(4+3v)]2(1+v)-描述的一个或多个磷酸根阴离子替代,其中v大于或等于零并且小于或等于1。
在另一个实施例中,由式(II)描述的单磷酸二氢根阴离子被由式[H2(1-v)PO4-v]-描述的一个或多个磷酸根阴离子替代,其中v大于或等于零并且小于或等于1。
所述阳离子可为一价或多价的。在一个实施例中,一个阳离子为一价的,而另一个阳离子为多价的。在另一个实施例中,一价阳离子与多价阳离子的摩尔比介于约0.1和约10之间。在另一个实施例中,一价阳离子与多价阳离子的摩尔比介于约0.5和约5之间。在本发明的另一个实施例中,一价阳离子与多价阳离子的摩尔比为约1。
在一个实施例中,多价阳离子选自二价阳离子、三价阳离子、四价阳离子、五价阳离子、以及它们的混合物。一价阳离子的非限制性例子为Li+、Na+、K+、Rb+、Cs+、Ag+、Rb+、Tl+、以及它们的混合物。在一个实施例中,一价阳离子选自Li+、Na+、K+、Rb+、Cs+、以及它们的混合物;在另一个实施例中,一价阳离子为Na+或K+;并且在另一个实施例中,一价阳离子为K+。多价阳离子的非限制性例子为下列的阳离子:碱土金属(即Be、Mg、Ca、Sr、Ba和Ra),过渡金属(例如Y、Ti、Zr、V、Nb、Cr、Mo、Mn、Re、Fe、Ru、Co、Rh、Ni、Pd、Pt、Cu、Ag和Au),贫金属(例如Zn、Ga、Si、Ge、B、Al、In、Sb、Sn、Bi和Pb),镧系元素(例如La和Ce),和锕系元素(例如Ac和Th)。在一个实施例中,多价阳离子选自Be2+、Mg2+、Ca2+、Sr2+、Ba2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Sn2+、Pb2+、Ti3+、Cr3+、Mn3+、Fe3+、Al3+、Ga3+、Y3+、In3+、Sb3+、Bi3+、Si4+、Ti4+、V4+、Ge4+、Mo4+、Pt4+、V5+、Nb5+、Sb5+、以及它们的混合物。在一个实施例中,多价阳离子选自Ca2+、Ba2+、Cu2+、Mn2+、Mn3+、以及它们的混合物;在另一个实施例中,多价阳离子选自Ca2+、Ba2+、Mn2+、以及它们的混合物;并且在另一个实施例中,多价阳离子为Ba2+。
所述催化剂可包含阳离子:(a)Li+、Na+、K+、Rb+、Cs+、或它们的混合物;和(b)Be2+、Mg2+、Ca2+、Sr2+、Ba2+、Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+、Sn2+、Pb2+、Ti3+、Cr3+、Mn3+、Fe3+、Al3+、Ga3+、Y3+、In3+、Sb3+、Bi3+、Si4+、Ti4+、V4+、Ge4+、Mo4+、Pt4+、V5+、Nb5+、Sb5+、或它们的混合物。在一个实施例中,所述催化剂包含Li+、Na+或K+作为一价阳离子,并且包含Ca2+、Ba2+、Mn2+或Mn3+作为多价阳离子;在另一个实施例中,所述催化剂包含K+作为一价阳离子,并且包含Ca2+、Ba2+或Mn2+作为多价阳离子;并且在另一个实施例中,所述催化剂包含K+作为一价阳离子,并且包含Ba2+作为多价阳离子。
所述催化剂可包含惰性载体,所述载体由包括硅酸盐、铝酸盐、碳、金属氧化物、以及它们的混合物的材料组成。作为另外一种选择,所述载体相对于预计接触催化剂的反应混合物是惰性的。在本文明确描述的反应背景下,在一个实施例中,所述载体为低表面积的二氧化硅或氧化锆。当存在时,所述载体的含量以所述催化剂的总重量计为约5重量%至约98重量%。一般来讲,包含惰性载体的催化剂可由两种示例性方法之一制得:浸渍或共沉淀。在浸渍方法中,用预催化剂溶液处理固体惰性载体的悬浮液,然后在将所述预催化剂转变成更活性状态的条件下活化所得材料。在共沉淀方法中,通过加入附加成分,使催化剂成分的均一化溶液沉淀。
III催化剂制备方法
在本发明的一个实施例中,制备催化剂的方法包括混合至少两种含磷化合物,其中每种所述化合物由式(VI)至(XXV)之一描述,或为所述式的任何水合形式:
MI a(H3-aPO4)(VI)
MII a(H3-aPO4)2(VII)
MIII a(H3-aPO4)3(VIII)
MIV a(H3-aPO4)4(IX)
MII b(OH)c(PO4)d(X)
MIII e(OH)f(PO4)g(XI)
MIIMIPO4(XII)
MIIIMI 3(PO4)2(XIII)
MIV 2MI(PO4)3(XIV)
MI hH4-hP2O7(XV)
MII iH(4-2i)P2O7(XVI)
MIVP2O7(XVII)
MIIIMIP2O7(XVIII)
MIHj(PO3)(1+j)(XIX)
MIIHj(PO3)(2+j)(XX)
MIIIHj(PO3)(3+j)(XXI)
MIVHj(PO3)(4+j)(XXII)
MII kMI l(PO3)r(XXIII)
MIII qMI p(PO3)s(XXIV)
P2O5(XXV)
其中MI为一价阳离子;其中MII为二价阳离子;其中MIII为三价阳离子;
其中MIV为四价阳离子;其中a为0、1、2或3;其中h为0、1、2、3或4;其中i为0、1或2;其中j为0或任何正整数;并且其中b、c、d、e、f、g、k、l、m、n、p和q是任何正整数,使得满足公式:2b=c+3d,3e=f+3g,r=2k+l,和s=3q+p。在另一个实施例中,制备催化剂的方法包括混合后使含磷化合物与包含水的气体混合物接触。
在一个实施例中,所述催化剂通过混合一种或多种式(VI)的含磷化合物(其中所述a等于1)与一种或多种式(VII)的含磷化合物(其中所述a等于2)来制备。在另一个实施例中,所述催化剂通过混合KH2PO4与BaHPO4或CaHPO4来制备。
在另一个实施例中,所述催化剂经由包括下列的步骤制得:(a)混合一种或多种式(VI)的含磷化合物(其中所述a等于1)与一种或多种式(XVI)的含磷化合物(其中所述i等于2);以及(b)使含磷化合物的混合物与包含水的气体混合物接触。在另一个实施例中,所述含磷化合物为KH2PO4和Ba2P2O7或Ca2P2O7。
在另一个实施例中,所述催化剂经由包括下列的步骤制得:(a)混合一种或多种式(VII)的含磷化合物(其中所述a等于2)与一种或多种式(XIX)的含磷化合物(其中所述j等于0);以及(b)使含磷化合物的混合物与包含水的气体混合物接触。在另一个实施例中,所述含磷化合物为(KPO3)w和BaHPO4或CaHPO4;其中w为大于2的整数。
在另一个实施例中,所述催化剂经由包括下列的步骤制得:(a)混合一种或多种式(XVI)的含磷化合物(其中所述i等于2)与一种或多种式(XIX)的含磷化合物(其中所述j等于0),以及(b)使含磷化合物的混合物与包含水的气体混合物接触。在另一个实施例中,所述含磷化合物为(KPO3)w和Ba2P2O7或Ca2P2O7;其中w为大于2的整数。
在本发明的一个实施例中,制备催化剂的方法包括混合并且加热:(a)至少一种含磷化合物,其中每种所述化合物由式(VI)至(XXV)之一描述,或为所述式的任何水合形式:
MI a(H3-aPO4)(VI)
MII a(H3-aPO4)2(VII)
MIII a(H3-aPO4)3(VIII)
MIV a(H3-aPO4)4(IX)
MII b(OH)c(PO4)d(X)
MIII e(OH)f(PO4)g(XI)
MIIMIPO4(XII)
MIIIMI 3(PO4)2(XIII)
MIV 2MI(PO4)3(XIV)
MI hH4-hP2O7(XV)
MII iH(4-2i)P2O7(XVI)
MIVP2O7(XVII)
MIIIMIP2O7(XVIII)
MIHj(PO3)(1+j)(XIX)
MIIHj(PO3)(2+j)(XX)
MIIIHj(PO3)(3+j)(XXI)
MIVHj(PO3)(4+j)(XXII)
MII kMI l(PO3)r(XXIII)
MIII qMI p(PO3)s(XXIV)
P2O5(XXV)
其中MI为一价阳离子;其中MII为二价阳离子;其中MIII为三价阳离子;其中MIV为四价阳离子;其中a为0、1、2或3;其中h为0、1、2、3或4;其中i为0、1或2;其中j为0或任何正整数;并且其中b、c、d、e、f、g、k、l、m、n、p和q是任何正整数,使得满足公式:2b=c+3d,3e=f+3g,r=2k+l,和s=3q+p;和(b)至少一种不含磷化合物,所述化合物选自硝酸盐、碳酸盐、乙酸盐、金属氧化物、氯化物盐、硫酸盐、和金属氢氧化物,其中每种所述化合物由式(XXVI)至(L)之一描述,或为所述式的任何水合形式:
MINO3(XXVI)
MII(NO3)2(XXVII)
MIII(NO3)3(XXVIII)
MI 2CO3(XXIX)
MIICO3(XXX)
MIII 2(CO3)3(XXXI)
(CH3COO)MI(XXXII)
(CH3COO)2MII(XXXIII)
(CH3COO)3MIII(XXXIV)
(CH3COO)4MIV(XXXV)
MI 2O(XXXVI)
MIIO(XXXVII)
MIII 2O3(XXXVIII)
MIVO2(XXXIX)
MICl(XL)
MIICl2(XLI)
MIIICl3(XLII)
MIVCl4(XLIII)
MI 2SO4(XLIV)
MIISO4(XLV)
MIII 2(SO4)3(XLVI)
MIV(SO4)2(XLVII)
MIOH(XLVIII)
MII(OH)2(XLIX)
MIII(OH)3(L)。
在另一个实施例中,所述不含磷的化合物可选自羧酸衍生的盐、卤化物盐、乙酰基丙酮酸金属盐、和金属醇盐。
在另一个实施例中,制备催化剂的方法包括混合后使含磷化合物和不含磷的化合物与包含水的气体混合物接触。
在一个实施例中,所述催化剂通过包括下列的步骤制得:混合并且加热一种或多种式(VI)的含磷化合物(其中所述a等于2)、式(VI)的含磷化合物(其中所述a等于0)(即磷酸)、和一种或多种式(XXVII)的硝酸盐。在另一个实施例中,所述催化剂通过混合并且加热K2HPO4、H3PO4和Ba(NO3)2制得。在另一个实施例中,所述催化剂通过混合并且加热K2HPO4、H3PO4和Ca(NO3)2制得。在又一个实施例中,所述催化剂通过混合并且加热K2HPO4、H3PO4和Mn(NO3)2×4H2O制得。
在本发明的一个实施例中,制备催化剂的方法包括接触:(a)包含水的气体混合物,与(b)包含至少一种选自式(LI)至(LIII)的缩聚磷酸盐阴离子的化合物的混合物,
[PnO3n+1](n+2)-(LI)
[PnO3n]n-(LII)
[P(2m+n)O(5m+3n)]n-(LIII)
其中n为至少2;其中m为至少1;其中所述化合物的混合物基本上是电中性的;并且进一步地,其中催化剂中磷与一价和多价阳离子的摩尔比介于约0.7和约1.7之间。在另一个实施例中,磷与一价和多价阳离子的摩尔比为约1。
在另一个实施例中,所述催化剂经由包括下列的步骤制得:接触(a)包含水的气体混合物,与(b)包含缩聚磷酸盐的化合物的混合物,所述缩聚磷酸盐选自Ba2-y-zK2yH2zP2O7、Ca2-y-zK2yH2zP2O7、Mn1-y-zK1+3yH3zP2O7、Mn1-y-zK2+2yH2zP2O7、以及它们的混合物;和(KPO3)w;其中y和z大于或等于0并且小于约0.5,并且w为大于2的整数。
在一个实施例中,所述催化剂可包含惰性载体,所述载体由包括硅酸盐、铝酸盐、碳、金属氧化物、以及它们的混合物的材料组成。作为另外一种选择,所述载体相对于预计接触催化剂的反应混合物是惰性的。在另一个实施例中,制备催化剂的方法还可包括在混合含磷化合物之前、期间或之后,使惰性载体与所述催化剂混合,其中所述惰性载体包括硅酸盐、铝酸盐、碳、金属氧化物、以及它们的混合物。在另一个实施例中,制备催化剂的方法还可包括在混合并且加热含磷化合物与不含磷化合物之前、期间或之后,使惰性载体与所述催化剂混合,其中所述惰性载体包括硅酸盐、铝酸盐、碳、金属氧化物、以及它们的混合物。
所述催化剂中含磷化合物或含磷和不含磷化合物的混合可通过本领域技术人员已知的任何方法来实现,如但不限于:固体混合和共沉淀。在固体混合方法中,采用本领域技术人员已知的任何方法将各种组分物理混合在一起,并且任选碾磨,所述方法如但不限于剪切、压延、捏合、挤出等。在共沉淀方法中,制备包括一种或多种磷酸盐化合物在内的各种组分的水溶液或悬浮液,然后任选过滤并且加热,以移除溶剂和挥发性物质(例如水、硝酸、二氧化碳、氨、或乙酸)。通常采用本领域技术人员已知的任何方法进行加热,如但不限于对流、传导、辐射、微波加热等。
混合后,在一个实施例中将所述催化剂碾磨并且筛分以提供更均匀的产物。催化剂颗粒的粒度分布包括在一个实施例中小于约3的颗粒跨度;在另一个实施例中,催化剂颗粒的粒度分布包括小于约2的颗粒跨度;并且在另一个实施例中,催化剂颗粒的粒度分布包括小于约1.5的颗粒跨度。在本发明的另一个实施例中,将所述催化剂筛分至约50μm至约500μm的中值粒度。在本发明的另一个实施例中,将所述催化剂筛分至约100μm至约200μm的中值粒度。
所述催化剂可用于催化多个化学反应。反应的非限制性例子为:羟基丙酸脱水成丙烯酸(如下文更详细描述的),甘油脱水成丙烯醛,脂肪族醇脱水成链烯或烯烃,脂肪族醇脱氢成醚,其它脱氢反应,水解反应,烷基化反应,脱烷基化反应,氧化反应,歧化反应,酯化反应,环化反应,异构化反应,缩合反应,芳构化反应,聚合反应,以及对本领域普通技术人员而言可能显而易见的其它反应。
在本发明的一个实施例中,所述催化剂通过包括下列的步骤制得:将BaHPO4和KH2PO4以介于约3:2和约2:3之间的摩尔比混合,以形成固体混合物,并且将所述固体混合物碾磨以制得所述催化剂。
在本发明的另一个实施例中,所述催化剂通过包括下列的步骤制得:(a)将BaHPO4和KH2PO4以介于约3:2和约2:3之间的摩尔比混合,以形成固体混合物;(b)将所述固体混合物碾磨以制得混合粉末;(c)将所述混合粉末在约550℃下煅烧以制得缩聚磷酸盐混合物;以及(d)在约350℃温度和约25巴总压力下使所述缩聚磷酸盐混合物与包含水和乳酸的气体混合物接触,以制得所述催化剂,并且其中水在所述气体混合物中的分压为约12.5巴。
在本发明的另一个实施例中,所述催化剂通过包括下列的步骤制得:(a)使K2HPO4、Ba(NO3)2、H3PO4和水混合形成湿混合物,其中Ba(NO3)2、K2HPO4和H3PO4的摩尔比为约3:1:4;(b)搅拌下将所述湿混合物加热至约80℃,直至接近干燥,形成湿固体;(c)将所述湿固体在约50℃、约80℃、约120℃和约450℃至约550℃下逐步干燥,以制得干燥的固体;以及(d)在约350℃温度和约25巴总压力下使所述干燥固体与包含水和乳酸的气体混合物接触,以制得所述催化剂,并且其中水在所述气体混合物中的分压为约12.5巴。
IV制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法
提供了将羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水成丙烯酸、丙烯酸衍生物、或它们的混合物的方法。
可使用供替代的包含阴离子和至少两种不同阳离子的催化剂将羟基丙酸、羟基丙酸衍生物、或它们的混合物脱水成丙烯酸、丙烯酸衍生物、或它们的混合物,所述阴离子选自不含磷的阴离子、杂多阴离子和磷酸根加合物,其中所述催化剂基本上是电中性的。不含磷的阴离子的非限制性例子为砷酸根、缩聚砷酸根、硝酸根、硫酸根、硼酸根、碳酸根、铬酸根、钒酸根、铌酸根、钽酸根、硒酸根、以及对本领域普通技术人员而言可能显而易见的其它单体含氧负离子或多氧阴离子。杂多阴离子的非限制性例子为杂多磷酸根,如砷磷酸根、磷铝酸根、磷硼酸根、磷铬酸根、磷钼酸根、磷硅酸根、磷硫酸根、磷钨酸根、以及对本领域普通技术人员而言可能显而易见的其它例子。磷酸根加合物的非限制性例子为磷酸根阴离子与碲酸、卤离子、硼酸根、碳酸根、硝酸根、硫酸根、铬酸根、硅酸根、草酸根、它们的混合物的加合物,以及对本领域普通技术人员而言可能显而易见的其它例子。
羟基丙酸可为3-羟基丙酸、2-羟基丙酸(还称为乳酸)、或它们的混合物。在一个实施例中,羟基丙酸为乳酸。羟基丙酸的衍生物可为羟基丙酸的金属盐或铵盐、羟基丙酸烷基酯、羟基丙酸低聚物、羟基丙酸环状二酯、羟基丙酸酐、或它们的混合物。羟基丙酸金属盐的非限制性例子为羟基丙酸钠、羟基丙酸钾、和羟基丙酸钙。羟基丙酸烷基酯的非限制性例子为羟基丙酸甲酯、羟基丙酸乙酯、羟基丙酸丁酯、羟基丙酸2-乙基己酯、或它们的混合物。羟基丙酸环状二酯的非限制性例子为丙交酯。
丙烯酸衍生物可为丙烯酸的金属盐或铵盐、丙烯酸烷基酯、丙烯酸低聚物、或它们的混合物。丙烯酸金属盐的非限制性例子为丙烯酸钠、丙烯酸钾、和丙烯酸钙。丙烯酸烷基酯的非限制性例子为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、或它们的混合物。
包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流可包含液体流和惰性气体(即在所述方法条件下对反应混合物呈惰性的气体),所述液体流和惰性气体可分开或合并加入到催化剂反应器上游的蒸发容器中,以使流变成气态。所述液体流可包含羟基丙酸、羟基丙酸衍生物、或它们的混合物,和稀释剂。稀释剂的非限制性例子为水、甲醇、乙醇、丙酮、C3至C8直链和支链醇、C5至C8直链和支链烷烃、乙酸乙酯、非挥发性醚(包括二苯基醚)、以及它们的混合物。在一个实施例中,所述稀释剂包括水。在另一个实施例中,所述液体流包含乳酸或乳酸衍生物的水溶液,所述乳酸衍生物选自丙交酯、乳酸低聚物、乳酸的盐、和乳酸烷基酯。在一个实施例中,所述液体流包含以所述液体流的总重量计约2重量%至约95重量%的乳酸或乳酸衍生物。在另一个实施例中,所述液体流包含以所述液体流的总重量计约5重量%至约50重量%的乳酸或乳酸衍生物。在另一个实施例中,所述液体流包含以所述液体流的总重量计约10重量%至约25重量%的乳酸或乳酸衍生物。在另一个实施例中,所述液体流包含以所述液体流的总重量计约20重量%的乳酸或乳酸衍生物。在另一个实施例中,所述液体流包含乳酸以及乳酸衍生物的水溶液。在另一个实施例中,所述液体流包含以所述液体流的总重量计小于约30重量%的乳酸衍生物。在另一个实施例中,所述液体流包含以所述液体流的总重量计小于约10重量%的乳酸衍生物。在另一个实施例中,所述液体流包含以所述液体流的总重量计小于约5重量%的乳酸衍生物。
惰性气体为在所述方法条件下对反应混合物呈惰性的气体。惰性气体的非限制性例子为氮气、空气、氦气、氩气、二氧化碳、一氧化碳、水蒸气、以及它们的混合物。在一个实施例中,所述惰性气体为氮气。
包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在接触催化剂时可为气体混合物形式。在一个实施例中,羟基丙酸、羟基丙酸衍生物、或它们的混合物的浓度以所述流的总摩尔数计(在STP条件下计算)为约0.5mol%至约50mol%。在另一个实施例中,羟基丙酸、羟基丙酸衍生物、或它们的混合物的浓度以所述流的总摩尔数计(在STP条件下计算)为约1mol%至约10mol%。在另一个实施例中,羟基丙酸、羟基丙酸衍生物、或它们的混合物的浓度以所述流的总摩尔数计(在STP条件下计算)介于约1.5mol%至约3.5mol%之间。在另一个实施例中,羟基丙酸、羟基丙酸衍生物、或它们的混合物的浓度以所述流的总摩尔数计(在STP条件下计算)为约2.5mol%。
在一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的所述流与催化剂接触时的温度介于约120℃和约700℃之间。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的所述流与催化剂接触时的温度介于约150℃和约500℃之间。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的所述流与催化剂接触时的温度介于约300℃和约450℃之间。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的所述流与催化剂接触时的温度介于约325℃和约400℃之间。
在一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在介于约720h-1和约36,000h-1之间的GHSV下接触催化剂。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在介于约1,800h-1至约7,200h-1之间的GHSV下接触催化剂。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在约3,600h-1的GHSV下接触催化剂。
在一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在介于约0psig和约550psig之间的压力下接触催化剂。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在约360psig的压力下接触催化剂。
在一个实施例中,所述稀释剂包括水,并且水在气体混合物中的分压介于约10psi和约500psi之间。在另一个实施例中,水在气体混合物中的分压介于约15psi和约320psi之间。在另一个实施例中,水在气体混合物中的分压为约190psi。
在一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在具有内表面的反应器内与催化剂接触,所述内表面包含选自石英、硼硅酸盐玻璃、硅、哈司特镍合金、铬镍铁合金、人造蓝宝石、不锈钢、以及它们混合物的材料。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在具有内表面的反应器内与催化剂接触,所述内表面包含选自石英或硼硅酸盐玻璃的材料。在另一个实施例中,包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流在具有内表面的反应器内与催化剂接触,所述内表面包含硼硅酸盐玻璃。
在一个实施例中,所述方法包括在足以以至少50%收率生成丙烯酸、丙烯酸衍生物、或它们的混合物的条件下,使催化剂与包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的气体混合物接触。在另一个实施例中,所述方法包括在足以以至少约70%收率生成丙烯酸、丙烯酸衍生物、或它们的混合物的条件下,使催化剂与包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的气体混合物接触。在另一个实施例中,所述方法包括在足以以至少约80%收率生成丙烯酸、丙烯酸衍生物、或它们的混合物的条件下,使催化剂与包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的气体混合物接触。在另一个实施例中,所述方法条件足以以至少约50%的选择率生成丙烯酸、丙烯酸衍生物、或它们的混合物。在另一个实施例中,所述方法条件足以以至少约70%的选择率生成丙烯酸、丙烯酸衍生物、或它们的混合物。在另一个实施例中,所述方法条件足以以至少约80%的选择率生成丙烯酸、丙烯酸衍生物、或它们的混合物。在另一个实施例中,所述方法条件足以生成丙烯酸、丙烯酸衍生物、或它们的混合物,以及为杂质的丙酸,其中所述丙酸的选择率小于约5%。在另一个实施例中,所述方法条件足以生成丙烯酸、丙烯酸衍生物、或它们的混合物,以及为杂质的丙酸,其中所述丙酸的选择率小于约1%。在另一个实施例中,所述方法条件足以以大于约50%的所述羟基丙酸、羟基丙酸衍生物、或它们的混合物的转化率,生成丙烯酸、丙烯酸衍生物、或它们的混合物。在另一个实施例中,所述方法条件足以以大于约80%的所述羟基丙酸、羟基丙酸衍生物、或它们的混合物的转化率,生成丙烯酸、丙烯酸衍生物、或它们的混合物。
在所述有益效果中,由前述实施例可获得的是低副产物收率。在一个实施例中,所述条件足以以小于约6%的收率由气体混合物中存在的乳酸生成丙酸。在另一个实施例中,所述条件足以以小于约1%的收率由气体混合物中存在的乳酸生成丙酸。在一个实施例中,所述条件足以以各自小于约2%的收率由气体混合物中存在的乳酸生成乙酸、丙酮酸、1,2-丙二醇和2,3-戊二酮。在另一个实施例中,所述条件足以以各自小于约0.5%的收率由气体混合物中存在的乳酸生成乙酸、丙酮酸、1,2-丙二醇和2,3-戊二酮。在一个实施例中,所述条件足以以小于约8%的收率由气体混合物中存在的乳酸生成乙醛。在另一个实施例中,所述条件足以以小于约4%的收率由气体混合物中存在的乳酸生成乙醛。在另一个实施例中,所述条件足以以小于约3%的收率由气体混合物中存在的乳酸生成乙醛。在此之前,据信这些收率是达不到如此之低的。然而这些有益效果实际上是可获得的,由下文所示例子进一步展示。
提供了将甘油脱水成丙烯醛的方法。所述方法包括使包含甘油的流与催化剂接触,所述催化剂包含:(a)由式(I)和(II)描述的单磷酸一氢根和单磷酸二氢根阴离子:
[HPO4]2-(I),
[H2PO4]-(II),以及
(b)至少两种不同的阳离子,其中所述催化剂基本上是电中性的;并且进一步地,其中催化剂中所述单磷酸一氢根阴离子与所述单磷酸二氢根阴离子的摩尔比介于约0.1和约10之间,从而由于所述甘油与所述催化剂接触而制得丙烯醛。丙烯醛是中间体,可采用与当前丙烯至丙烯酸方法中的第二氧化步骤所用相类似的条件,将所述丙烯醛转化成丙烯酸。
V实例
给出下述实例是为了举例说明本发明,而不是旨在限制其范围。实例1至3描述了根据上述各个实施例所述的不同混合缩聚磷酸盐催化剂的制备。
实例1
催化剂制备:
将磷酸一氢钡BaHPO4(20g,85.7mmol,Sigma–AldrichCo.(St.Louis,MO);目录号31139)与磷酸二氢钾KH2PO4(7.8g,57.1mmol,Sigma–AldrichCo.(St.Louis,MO);目录号60216)混合。使用研钵和研杵研磨所述混合物,直至获得细粉。使用重力对流烘箱将所述材料在105℃下干燥2h,制得催化剂。最后,由X射线衍射(XRD)分析所述材料,能够识别预期的BaHPO4和KH2PO4。
催化剂测试:
在部分VI中描述的反应体系下,使所述催化剂接触包含L-乳酸(2.4mol%)、水(49.6mol%)和氮气(48.0mol%)的气体混合物。反应在350℃和360psig下进行,达到186psi的水分压。结果总结于部分VII的表1中。
实例2
催化剂制备:
将磷酸一氢钡BaHPO4(20g,85.7mmol,Sigma–AldrichCo.(St.Louis,MO);目录号31139)与磷酸二氢钾KH2PO4(7.8g,57.1mmol,Sigma–AldrichCo.(St.Louis,MO);目录号60216)混合。使用研钵和研杵研磨所述混合物,直至获得细粉。使用重力对流烘箱将所述材料在550℃下煅烧27h。煅烧后,使所述材料保留于所述烘箱内,直至其自身冷却下来。最后将所述催化剂碾磨并且筛分至约100μm至约200μm。由XRD分析所述材料,能够识别α-Ba2P2O7和KPO3。
催化剂测试:
在部分VI中描述的反应体系下,使所述催化剂接触包含L-乳酸(2.4mol%)、水(49.6mol%)和氮气(48.0mol%)的气体混合物。反应在350℃和360psig下进行,达到186psi的水分压。结果总结于部分VII的表1中。
实例3
催化剂制备:
室温下将硝酸钡Ba(NO3)2的水溶液(3414mL0.08g/mL的原液,1.04mol,99.999%;Sigma–AldrichCo.(St.Louis,MO);目录号202754)加入到固体磷酸氢二钾K2HPO4(60.7g,0.35mol,≥98%;Sigma–AldrichCo.(St.Louis,MO);目录号P3786)中。将磷酸H3PO4(98mL85重量%,密度=1.684g/mL,1.44mol;AcrosOrganics(Geel,Belgium);目录号295700010)加入到所述浆液中,提供包含钾(K+,MI)和钡(Ba2+,MII)阳离子的溶液。所述悬浮液的最终pH为约1.6。然后使用加热板,将玻璃烧杯中包含酸的悬浮液在80℃下缓慢干燥,同时磁力搅拌所述悬浮液,直至液体蒸发,并且所述材料几乎完全干燥。蒸发后,将所述材料转移到可压碎陶瓷器皿中。在具有空气环流的烘箱(N30/80HA;NaberthermGmbH(Lilienthal,Germany))中持续加热,在50℃下2h,然后在80℃下10h(0.5℃/min阶升),在120℃下2小时(0.5℃/min阶升),以移除残余的水,然后在450℃下煅烧4小时(2℃/min阶升)。煅烧后,使所述材料保留于烘箱内,直至它自身冷却至低于100℃的温度,之后将它从烘箱中取出。最后将所述催化剂碾磨并且筛分至约100μm至约200μm。由XRD和能量分散光谱结合扫描电镜(EDS/SEM)分析所述材料,能够识别σ-Ba2P2O7、α-Ba3P4O13、Ba(NO3)2、(KPO3)w、以及大概由具有显著量钾和钡的缩聚磷酸盐组成的附加相。还在所有包含Ba的相中检测出一些K的掺入。XRD识别出的缩聚磷酸盐中磷(P)与阳离子(MI和MII)之间的摩尔比为约1至约1.3。
催化剂测试:
在部分VI中描述的反应体系下,使所述催化剂接触包含L-乳酸(2.3mol%)、水(49.9mol%)和氮气(47.8mol%)的气体混合物。反应在350℃和360psig下进行,达到187psi的水分压。结果总结于部分VII的表1中。
在反应结束后,使催化剂冷却至236℃,同时使总压保持在360psig,并且使包含水(50.6mol%)和氮气(49.4mol%)的气体混合物流动。然后在200psig总压下将温度降至213℃,同时使相同气体混合物流动,接着是100psig总压下降至180℃和10psig总压下降至125℃的附加步骤。冷却后,由XRD和EDS/SEM分析所述催化剂,能够识别BaHPO4(具有Ba2- xKxHx(HPO4)2以及少量Ba(H2PO4)2和(KPO3)w表观化学组成的混合相),其中x为约1,并且w为大于2的整数。
VI测试方法
XRD:在STADI-P透射型衍射计(Stoe&CieGmbH(Darmstadt,Germany))上收集广角数据(WAXS)。发生器在40kV/40mA下工作,向铜阳极细长聚焦Cux-射线管供电。所述衍射计并入入射光束曲面锗单晶单色器、标准入射光束狭缝体系、和具有约124°2θ角度范围的图像板位置灵敏检测器。数据以透射模式收集。如果需要,使用研钵和研杵,用手将样品轻轻研磨至细粉稠度,然后加载到仪器的标准样品夹持器中。采用最新的粉末衍射数据库(得自ICDD),使用Jade中搜索/匹配途径(MaterialsData,Inc.,v9.4.2),识别结晶相。
SEM/EDS:将干粉分散在已经安装在金属扫描电镜(SEM)基板上的双面铜或碳带上。使用GatanAlto2500Cryo制备室,将用Au/Pd将每个样品涂覆约65-80s。采用均对EDS配备BrukerXFlash30mm2SDD检测器(Quantax2000体系,具有5030检测器;BrukerCorp.(Billerica,MA))的HitachiS-4700FE-SEM或HitachiS-5200in-lensFE-SEM(HitachiLtd.(Tokyo,Japan)),将SEM成像和能量分散光谱(EDS)进行作图。采用分析探针电流模式的10kV加速电压,进行EDS作图。使用Hypermap模块内的BrukerEspritV1.9软件,产生所有绘图。
反应器:向具有4.0mm内径(ID)13英寸(330mm)长不锈钢玻璃内衬管(SGEAnalyticalSciencePtyLtd.(Ringwood,Australia))填塞玻璃棉(3英寸/76mm床长),顶部填塞催化剂(1.6cm3床体积,5英寸/127mm床长),以获得2.55cm3填充床(8英寸/203mm)和反应器顶部1.6cm3(5英寸/127mm)的自由空间。将所述管放入到铝块内,并且放入贝壳式加热炉系列3210(AppliedTestSystems(Butler,PA))中,使得填充床顶部与铝块顶部平齐。将反应器设置为顺流排列,并且配备KnauerSmartline100进料泵(Berlin,Germany)、Brooks0254气流控制器(Hatfield,PA)、Brooks背压调节器和收集槽。将贝壳式加热炉加热,使得反应过程期间,反应器壁温恒定保持在约350℃。向反应器提供单独的液体和气体给料,它们在到达催化剂床之前混合在一起。气体给料由约360psig和45mL/min流量的氮气分子(N2)组成。液体给料为乳酸水溶液(20重量%L-乳酸),并且以0.045mL/min流量进料。流动通过反应器后,将气体混合物冷却,并且将液体收集于收集槽中,以采用本领域普通技术人员通常已知的方法,由离线HPLC分析,所述HPLC使用Agilent1100体系(SantaClara,CA),配备二极管阵列检测器(DAD)和WatersAtlantisT3柱(目录号186003748;(Milford,MA))。气体混合物由GC在线分析,所述GC使用Agilent7890体系(SantaClara,CA),配备FID检测器和VarianCP-ParaBondQ柱(目录号CP7351;(SantaClara,CA))。
反应器进料:将生物质衍生的乳酸溶液(113.6g)(88重量%,PuracCorp.(Lincolnshire,IL))溶于蒸馏水(386.4g)中,以提供具有20重量%预期乳酸浓度的溶液。将该溶液在95℃至100℃下加热12-30小时。使所得混合物冷却,并且经由HPLC(上述),相对于已知重量的标准物进行分析。
VII结果
表1总结了由部分V中所述不同催化剂获得的催化参数。
表1
给出以上描述仅用于理解清楚,并且不应从中理解为不必要的限制,因为本发明范围内的修改对本领域普通技术人员而言是显而易见的。
本文所公开的量纲和值不旨在被理解为严格地限于所述的精确值。相反,除非另外指明,每个这样的量纲旨在表示所引用的值和围绕该值功能上等同的范围。例如,公开为“40mm”的尺寸旨在表示“约40mm”。
本文引用的每一文件,包括任何交叉引用的或相关的专利或专利申请,均特此以其全文引入本文,除非明文予以排除或以其他方式受限。对任何文献的引用均不是承认其为本文公开的或受权利要求书保护的任何发明的现有技术、或承认其独立地或以与任何其它一个或多个参考文献的任何组合的方式传授、提出建议或公开任何此类发明。此外,当本文献中术语的任何含义或定义与引入本文以供参考的文献中相同术语的任何含义或定义冲突时,将以赋予本文献中那个术语的含义或定义为准。
尽管已用特定实施例举例说明和描述了本发明,但对于本领域的技术人员显而易见的是,在不背离本发明的实质和范围的情况下可做出许多其它改变和变型。因此,随附权利要求书旨在涵盖本发明范围内的所有这些改变和变型。
[权利要求前的最后段落]虽然已经举例说明和描述了本发明的具体实施例,但是对于本领域技术人员来说显而易见的是,在不脱离本发明的实质和范围的情况下可作出多种其它的改变和变型。因此,随附权利要求书旨在涵盖本发明范围内的所有这些改变和变型。
Claims (15)
1.一种制备丙烯酸、丙烯酸衍生物、或它们的混合物的方法,包括使包含羟基丙酸、羟基丙酸衍生物、或它们的混合物的流与催化剂接触,所述催化剂包含:
a.由式(I)描述的单磷酸一氢根阴离子:
[HPO4]2-(I),
b.和由式(II)描述的单磷酸二氢根阴离子:
[H2PO4]-(II),以及
c.至少两种不同的阳离子,
其中所述催化剂基本上是电中性的;并且进一步地,其中所述催化剂中所述单磷酸一氢根阴离子与所述单磷酸二氢根阴离子的摩尔比介于0.1和10之间。
2.根据权利要求1所述的方法,其中所述流还包含:
(a)稀释剂;和
(b)惰性气体,所述惰性气体选自空气、氮气、氦气、氩气、二氧化碳、一氧化碳、水蒸气、以及它们的混合物。
3.根据权利要求1所述的方法,其中所述流在接触所述催化剂时为气体混合物形式。
4.根据权利要求2所述的方法,其中所述稀释剂包括水。
5.根据权利要求1所述的方法,其中所述羟基丙酸为乳酸。
6.根据权利要求5所述的方法,其中所述乳酸至所述丙烯酸的选择率为至少80%。
7.根据权利要求5所述的方法,其中所述乳酸至杂质丙酸的选择率小于1%。
8.根据权利要求5所述的方法,其中所述乳酸的转化率大于80%。
9.根据权利要求1所述的方法,其中所述流在150℃至500℃的温度下接触所述催化剂。
10.根据权利要求5所述的方法,其中所述乳酸在300℃至450℃的温度下接触所述催化剂。
11.根据权利要求1所述的方法,其中所述羟基丙酸、羟基丙酸衍生物、或它们的混合物以基于所述流的总摩尔数计介于1mol%和10mol%之间的量存在。
12.根据权利要求1所述的方法,其中所述流在介于720h-1和36,000h-1之间的GHSV下接触所述催化剂。
13.根据权利要求1所述的方法,其中所述流在介于0psig和550psig之间的压力下接触所述催化剂。
14.根据权利要求3所述的方法,其中水在所述气体混合物中的分压为10psi至500psi。
15.根据权利要求1所述的方法,其中所述至少两种不同的阳离子包括:
(a)至少一种一价阳离子;和
(b)至少一种多价阳离子。
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