CN113831248B - Method for preparing 3-hydroxy propionate derivative - Google Patents
Method for preparing 3-hydroxy propionate derivative Download PDFInfo
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- CN113831248B CN113831248B CN202010586985.6A CN202010586985A CN113831248B CN 113831248 B CN113831248 B CN 113831248B CN 202010586985 A CN202010586985 A CN 202010586985A CN 113831248 B CN113831248 B CN 113831248B
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- catalyst
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- metal
- heteropolyacid
- acid
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- 238000000034 method Methods 0.000 title claims abstract description 70
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical class OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 140
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 47
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 alcohol compound Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 142
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical class OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 34
- 229910010413 TiO 2 Inorganic materials 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 21
- 238000011049 filling Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000000926 separation method Methods 0.000 description 15
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000004811 liquid chromatography Methods 0.000 description 13
- 239000008247 solid mixture Substances 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- KMRNTNDWADEIIX-UHFFFAOYSA-N 3-Iodopropanoic acid Chemical compound OC(=O)CCI KMRNTNDWADEIIX-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- MENWVOUYOZQBDM-UHFFFAOYSA-N butyl 3-hydroxypropanoate Chemical compound CCCCOC(=O)CCO MENWVOUYOZQBDM-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UKDLORMZNPQILV-UHFFFAOYSA-N ethyl 3-hydroxypropanoate Chemical compound CCOC(=O)CCO UKDLORMZNPQILV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- KNCDNPMGXGIVOM-UHFFFAOYSA-N propyl 3-hydroxypropanoate Chemical compound CCCOC(=O)CCO KNCDNPMGXGIVOM-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/883—Molybdenum and nickel
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J35/19—
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Abstract
The invention discloses a method for preparing 3-hydroxy propionate derivatives, which comprises the following steps: reacting glyceric acid with hydrogen and an alcohol compound in the presence of an alcohol compound and a hydrodeoxygenation catalyst to obtain the 3-hydroxy propionate derivative; wherein the hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst. The method is environment-friendly, and the yield of the 3-hydroxy propionate derivative is high.
Description
Technical Field
The invention relates to a method for preparing an ester derivative, in particular to a method for preparing a 3-hydroxy propionate derivative from renewable biomass-based raw materials.
Background
3-hydroxy propionate derivatives, such as methyl 3-hydroxy propionate, are important chemical raw materials, and are often used as chemical reagents, pharmaceutical intermediates and material intermediates. The reaction process for synthesizing 1, 3-propanediol (key raw material for producing novel polyester fiber PTT with great development prospect) from 3-hydroxy methyl propionate avoids the negative factors such as toxicity, instability and the like in the preparation process of another intermediate 3-hydroxy propyl aldehyde. Methyl 3-hydroxypropionate is expensive, and the research on the synthesis method is little at present, so that the research on the synthesis process is highly focused by the polyester academy (Yu Wenli. Research on the synthesis of methyl 3-hydroxypropionate by catalyzing ethylene oxide with sodium cobalt tetracarbonyl [ D ]. Chengdu university, 2012.).
The 3-hydroxy propionic acid lipid derivative can be obtained by esterification reaction of 3-hydroxy propionic acid and alcohol molecules. The synthesis method of 3-hydroxy propionic acid mainly includes chemical method and microbiological method, the chemical method is that 3-hydroxy propionitrile is added into sodium hydroxide solution to react at 30 ℃, then sulfuric acid is added and stirred, and diethyl ether is used to extract the generated 3-hydroxy propionic acid, and the yield is 28-31%. At present, the chemical method uses non-renewable resources, has a plurality of byproducts, is difficult to separate and is easy to cause environmental pollution. The microorganism method is obtained by fermenting engineering Escherichia coli with carbon sources such as glycerol and glucose. Although the microbial method uses renewable resources as raw materials and has low pollution, the microbial method has the problems of low production efficiency, harsh reaction conditions and the like (chemical progress, 2018, 37 (11): 4427-4436). Therefore, the green and efficient synthesis of the 3-hydroxypropionate derivative from renewable biomass-based raw materials by a heterogeneous catalysis method has very important scientific research and application values.
On the other hand, glyceric acid (CAS: 473-81-4), also known as 2, 3-dihydroxypropionic acid, is an active organic compound containing three functional groups, and widely participates in chemical reactions such as polymerization, condensation, etc., and is an important intermediate for chemical synthesis and a multifunctional reagent (Anhui agricultural science, 2017, 45 (36): 116-118). The glyceric acid can be prepared by oxidizing glycerol, and the glycerol is a main byproduct in the biodiesel production process, has the characteristics of green and renewable properties, wide sources and the like, and has great significance for the sustainable development of chemical industry in China by greatly developing the downstream high-value conversion of the glycerol and the derivatives thereof
CN108329203a discloses a method for preparing 3-hydroxy propionic acid from glyceric acid by a two-step method. In the first step of the method, glyceric acid and HI are mixed in a certain proportion, and an intermediate product 3-iodopropionic acid is obtained under the condition of adding no other catalyst or adding a certain amount of metal catalyst. And secondly, reacting the organic phase obtained in the first step with water, and separating and acidifying under the condition of adding an alkaline catalyst to obtain the 3-hydroxy propionic acid. The method has the following problems: firstly, in the first step, hydroiodic acid with extremely strong corrosiveness is used, so that the requirement on corrosion resistance of the device is enhanced, and the cost and environmental protection risk of the device are improved; secondly, the salt of the 3-hydroxy propionic acid is directly obtained in the second step, and finally the 3-hydroxy propionic acid product can be obtained through acidification and separation; thirdly, the process flow is longer, and the complex processes of extraction and separation of the solvent and the like are involved.
Ethylene oxide, CO and methanol are used as raw materials, co 2 (CO) 8 The catalyst can be used for synthesizing the methyl 3-hydroxypropionate (natural gas chemical industry, 2011, 36 (03): 34-36) through the hydro-methyl esterification reaction, the process uses non-renewable petroleum-based ethylene oxide as a raw material, and the process involves the reaction raw materials with inflammable and explosive properties such as CO, methanol and the like and larger toxicity, and the used homogeneous catalyst such as cobalt carbonyl and the like is difficult to recycle, so that the process has higher cost and lower environmental friendliness, and is unfavorable for sustainable development of the chemical industry in China.
Disclosure of Invention
The invention provides a method for preparing 3-hydroxy propionate derivatives, which is characterized by simple process, environment protection and high efficiency by efficiently converting glyceric acid into target product 3-hydroxy propionate derivatives in one step in alcohol solution.
The invention provides a method for preparing 3-hydroxy propionate derivatives, which comprises the following steps:
in the presence of alcohol compounds and hydrodeoxygenation catalysts, glyceric acid reacts with hydrogen and alcohol to obtain the 3-hydroxy propionate derivatives.
The hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst, and specifically, the hydrodeoxygenation catalyst can be a mixture of a supported metal catalyst and at least one supported metal oxide catalyst, can be a mixture of a supported metal catalyst and at least one supported heteropolyacid catalyst, and can also be a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and at least one supported heteropolyacid catalyst.
Wherein, (mass of supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1: 0.1 to 100, preferably 1:0.2 to 10, more preferably 1:0.5 to 5.
The supported metal catalyst comprises a carrier and metal supported on the carrier, wherein the carrier is selected from one or more of active carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon aluminum oxide or molecular sieve; the metal is selected from one or more of group VIII and IB metals, preferably Co, ni, ru, pd or Pt. The loading of the metal is 0.5-45%, preferably 1-35% based on the total mass of the carrier. Wherein when the metal is a noble metal, the loading is more preferably 1-5%, and when the metal is a non-noble metal, the loading is more preferably 5-25%.
The supported metal oxide catalyst comprises a carrier and metal oxide supported on the carrier, wherein the loading amount of the metal oxide is 1% -50%, preferably 2% -40%, more preferably 5% -30% based on the total mass of the carrier; the carrier is selectedFrom one or more of activated carbon, silica, alumina, zirconia, titania, silica alumina or molecular sieves; the metal oxide is MoO 3 、WO 3 Or ReO (R) 3 One or more of the following.
The supported heteropolyacid catalyst comprises a carrier and heteropolyacid supported on the carrier, wherein the load capacity of the heteropolyacid is 1% -50%, preferably 2% -40%, more preferably 5% -30% based on the total mass of the carrier; the carrier is one or more of active carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon aluminum oxide or molecular sieve; the metal atom in the heteropoly acid is selected from one or more of W, mo, re, V, nb and Ta, and the heteroatom is selected from one or more of Si or P, preferably one or more of tungsten-containing heteropoly acid, molybdenum-containing heteropoly acid or rhenium-containing heteropoly acid, more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphorhenic acid and the like.
The alcohol compound is selected from one or more of C1-C6 aliphatic alcohol or alicyclic alcohol, preferably methanol, ethanol or n-propanol.
The mass percentage of the glyceric acid in the solution formed by the glyceric acid and the alcohol compound can be 0.1-60%, preferably 0.5-30%, more preferably 1-20%.
The molar ratio of metal in the supported metal catalyst to glyceric acid in the hydrodeoxygenation catalyst may be 1:1 to 1000, preferably 1:3 to 800, more preferably 1:5 to 500.
The reaction is carried out at a pressure of 1MPa to 10MPa, preferably 2 to 6 MPa.
The temperature of the reaction may be 160 ℃ to 300 ℃, preferably 180 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.
The reaction time may be 1 to 40 hours, preferably 5 to 30 hours, more preferably 10 to 20 hours.
The hydrodeoxygenation catalyst used in the process of the invention is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst or at least one supported heteropolyacid catalyst, which can be formulated by simple mechanical mixing.
The supported metal catalyst can be prepared according to the existing method, such as an isovolumetric impregnation method, a incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method, a vacuum impregnation method, or the like. In the specific preparation, after metal deposition, solid powder is dried in an oven at 100-140 ℃ for about 6-24 hours, and the obtained supported catalyst precursor is calcined in air at 300-800 ℃ for a period of time and then is subjected to a reducing atmosphere (such as H 2 Or H 2 And N 2 The mixed atmosphere of (2) is reduced for about 6 to 24 hours at a temperature of between 200 and 500 ℃ to obtain the supported metal catalyst.
The supported metal oxide catalyst or supported heteropolyacid catalyst can be prepared according to the existing method, such as isovolumetric impregnation, incipient wetness impregnation, ion exchange, deposition-precipitation or vacuum impregnation; in the specific preparation, after the metal oxide precursor or the heteropoly acid precursor is deposited, solid powder is placed in a baking oven at 100-140 ℃ to be dried for about 6-24 hours, and the obtained supported catalyst precursor is calcined in air at 300-800 ℃ for about 6-24 hours, so that the supported metal oxide catalyst or the supported heteropoly acid catalyst is obtained.
The supported metal oxide catalyst or the supported heteropoly acid catalyst and the supported metal catalyst can be added into the reaction system after being uniformly ground according to a certain proportion before the reaction, or can be added into the reaction system respectively according to a certain proportion.
When the method is used for preparing the 3-hydroxy propionate derivatives, the method can be carried out in a reaction kettle, after the reaction is finished, the reaction kettle is taken out, cooled to room temperature, the reaction kettle is decompressed, a kettle cover is opened, a liquid-solid mixture is taken out for suction filtration and separation, the obtained liquid is analyzed by liquid chromatography, and the conversion rate and the product yield are calculated. Other conventional reactors, such as fixed bed reactors, etc., may also be employed in the process of the present invention.
The method for preparing the 3-hydroxy propionate derivative is carried out in an alcohol solution, other hetero elements are not introduced except the used heterogeneous catalyst, and the yield of the 3-hydroxy propionate derivative is higher, so that the method not only further reduces the production cost, but also is more environment-friendly.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. Wherein the glyceric acid is obtained from Beijing Inocover technology Co.
Preparation example 1
Hydrogenation catalyst 10% Ni/Al 2 O 3 Is prepared from the following steps:
ni (NO 3) in an amount of 1mol/L 2 1.7mL of hydrochloric acid solution and 3.0mL of deionized water are mixed and stirred uniformly, and then SiO is added 2 0.9g of carrier is added into the mixed solution, stirred and immersed for 10 hours at room temperature, then the water is evaporated, and then the catalyst precursor is obtained after drying for 12 hours in a 110 ℃ oven. The loading of Ni was 10% (mass percent). Placing the precursor prepared by the above steps into a quartz tube, calcining for 4 hours at 500 ℃ in air, and then calcining for 20% H 2 +N 2 Reducing for 3h at the temperature of 500 ℃ to obtain the supported 10 percent Ni/Al 2 O 3 A catalyst.
Preparation of 20% Co/SiO according to the method described above 2 ，5％Pd/TiO 2 And 1% Pt/C catalyst.
Preparation example 2
Supported metal oxide catalyst 10% MoO 3 /TiO 2 Is prepared from the following steps:
0.2g of ammonium molybdate and 5.0mL of water were mixed and stirred well before TiO was added 2 1.00g of a carrier was added to the mixed solution, followed by stirring and immersing at room temperature for 10 hours, evaporating the water, and then drying in an oven at 110℃for 12 hours to obtain a catalyst precursor. MoO (MoO) 3 The loading of (2) was 10% by mass. Placing the precursor prepared by the steps in a quartz tube, and calcining for 3 hours at 500 ℃ in air to obtain 10% MoO 3 /TiO 2 。
The supported metal oxide catalysts were prepared according to the above method, each supported with 5% ReO 3 C and 20% WO 3 /ZrO 2 . The different supported metal oxide catalysts are prepared by selecting the precursors corresponding to the supported components, for example, if the supported components are ReO 3 When ammonium perrhenate is used as a precursor, ammonium perrhenate can be selected; the loading component is WO 3 When the ammonium metatungstate is used as a precursor, the ammonium metatungstate can be selected.
Preparation example 3
Preparation of supported heteropolyacid catalyst:
the preparation method of the different supported heteropolyacid catalysts is similar to that of the supported metal oxide, and the preparation is carried out by selecting the precursor corresponding to the supported component of the supported heteropolyacid catalyst according to the example, if the supported component is a tungsten-containing heteropolyacid, such as phosphotungstic acid, silicotungstic acid and the like, the corresponding tungsten-containing heteropolyacid, such as phosphotungstic acid, silicotungstic acid and the like, can be selected as the precursor; when the supporting component is molybdenum-containing heteropoly acid, corresponding molybdenum-containing heteropoly acid, such as phosphomolybdic acid, silicomolybdic acid and the like, can be selected as a precursor.
The supported heteropolyacid catalyst was prepared according to the above method, and 20% PWO was supported separately x /SiO 2 ， 10％SiMoO x /ZrO 2 And 5% PReO x /C。
Example 1 preparation of methyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield.The reaction results are shown in Table 1.
Example 2 preparation of methyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 3 preparation of methyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 220 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 4 preparation of methyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 6MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 4MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 5 preparation of ethyl 3-hydroxy propionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 6 preparation of propyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 7 preparation of n-butyl 3-hydroxypropionate from glyceric acid
At 10% Ni/Al 2 O 3 +10％MoO 3 /TiO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 10% Ni/Al was charged 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 8 preparation of methyl 3-hydroxypropionate from glyceric acid
At 20% Co/SiO 2 +20％WO 3 /ZrO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.2g of 20% Co/SiO was added 2 Catalyst, 0.1g of 20% WO 3 /ZrO 2 After the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 9 preparation of methyl 3-hydroxypropionate from glyceric acid
In 5% Pd/TiO 2 +5％ReO 3 The catalyst obtained by mechanical mixing of the catalyst and the catalyst is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid, 0.05g of 5% Pd/TiO were added 2 Catalyst, 0.4g of 5% ReO 3 And (2) after the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 10 preparation of methyl 3-hydroxypropionate from glyceric acid
In 1% Pt/C+20% PWO x /SiO 2 As hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.2g of glyceric acid, 0.1g of 1% Pt/C catalyst, 0.5g of 20% PWO was added x /SiO 2 The catalyst and 20g of methanol are filled with hydrogen of 2MPa to replace the residual air in the reaction kettle after the reaction kettle is closed,2MPa hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is stirred for 20 hours at the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 11 preparation of methyl 3-hydroxypropionate from glyceric acid
In 5% Pd/TiO 2 +10％SiMoO x /ZrO 2 The catalyst obtained by mechanical mixing is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.2g of glyceric acid, 0.05g of 5% Pd/TiO were added 2 Catalyst, 0.2g of 10% SiMoO x /ZrO 2 The catalyst and 20g of methanol are put into a reaction kettle, after the reaction kettle is closed, the residual air in the reaction kettle is replaced by 2MPa of hydrogen, the reaction kettle is repeatedly filled with 2MPa of hydrogen for three times, and the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 200 ℃ and stirred for reaction for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture for suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 12 preparation of methyl 3-hydroxypropionate from glyceric acid
In 1% Pt/C+5% PReO x The catalyst obtained by mechanical mixing of the catalyst and the catalyst is used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 1g of glyceric acid, 0.1g of 1% Pt/C catalyst, 0.2g of 5% PReO were added x And (2) after the reaction kettle is closed, filling 2MPa hydrogen to replace residual air in the reaction kettle, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, heating the reaction kettle on a heating furnace to the reaction temperature of 180 ℃, and stirring and reacting for 20 hours at the rotation speed of 700 rpm. After the reaction is finished, the reaction kettle is taken out from the heating furnace and cooled to room temperatureAnd (3) reducing the pressure in the kettle to normal pressure, opening the kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Comparative example 1
The reaction was carried out according to the procedure of example 4, except that only 10% Ni/Al was added 2 O 3 Catalyst without addition of 10% MoO 3 /TiO 2 A catalyst. The reaction results are shown in Table 1.
Comparative example 2
The reaction was carried out according to the procedure of example 4, except that only 10% MoO was added 3 /TiO 2 Catalyst without addition of 10% Ni/Al 2 O 3 A catalyst. The reaction results are shown in Table 1.
Comparative example 3
The reaction was carried out in accordance with the procedure of example 4, except that "0.2g of 10% MoO was added 3 /TiO 2 Catalyst "replacement with" 0.2g MoO 3 A catalyst. The reaction results are shown in Table 1.
Comparative example 4
According to the method of preparation example 1, at 10% MoO 3 /TiO 2 The catalyst is further loaded with 10% Ni component to obtain 10% Ni/10% MoO 3 /TiO 2 Co-supported catalyst
The reaction was carried out in accordance with the procedure of example 4, except that "0.2g of 10% Ni/Al was added 2 O 3 Catalyst, 0.2g of 10% MoO 3 /TiO 2 The catalyst was "replaced with" 0.2g of 10% Ni/10% MoO 3 /TiO 2 Co-supported catalyst). The reaction results are shown in Table 1.
As can be seen from the data in Table 1, the method for preparing the 3-hydroxy propionate derivatives can well realize the conversion from glyceric acid to important chemical raw materials 3-hydroxy propionate derivatives in alcohol solvents. Starting from glyceric acid, a yield of 92% of methyl 3-hydroxypropionate, or a yield of 90% of ethyl 3-hydroxypropionate, can be obtained.
As can be seen from comparative examples 1 and 2, the 3-hydroxypropionate derivative product could not be obtained by adding either the supported metal catalyst or the supported metal oxide catalyst alone. As can be seen from comparative examples 3 and 4, the use of a combination of supported metal catalyst and metal oxide or a co-supported metal and metal oxide catalyst does not allow the level of yield of 3-hydroxypropionate ester derivative of the catalyst system of the present invention to be achieved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
TABLE 1 reaction conditions, conversion and 3-hydroxypropionic acid yield for examples and comparative examples
。
Claims (23)
1. A process for preparing 3-hydroxypropionate derivatives comprising:
reacting glyceric acid with hydrogen and an alcohol compound in the presence of an alcohol compound and a hydrodeoxygenation catalyst to obtain the 3-hydroxy propionate derivative;
wherein the hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst;
the alcohol compound is selected from C1-C6 aliphatic alcohol or alicyclic alcohol;
in the hydrodeoxygenation catalyst, (mass of the supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1: 0.1 to 100;
the supported metal catalyst comprises a carrier and a metal supported on the carrier, wherein the metal is selected from Co, ni, ru, pd or Pt; the loading amount of the metal is 0.5% -45% based on the total mass of the carrier; the supported metal oxide catalyst comprises a carrier and a metal oxide supported on the carrier, wherein the metal oxide is selected from MoO 3 、WO 3 Or ReO (R) 3 One or more of the following; in the supported metal oxide catalyst, the load of the metal oxide is 1% -50% based on the total mass of the carrier; the supported heteropolyacid catalyst comprises a carrier and heteropolyacid supported on the carrier, wherein the heteropolyacid is selected from one or more of tungstic heteropolyacid, molybdenum-containing heteropolyacid or rhenium-containing heteropolyacid, and hetero atoms in the heteropolyacid are selected from one or more of Si or P; in the supported heteropoly acid catalyst, the load of the heteropoly acid is 1-50% based on the total mass of the carrier.
2. The method of claim 1, wherein the alcohol compound is methanol, ethanol, or n-propanol.
3. The method according to claim 1, wherein the glyceric acid and the alcohol compound form a solution, and the glyceric acid accounts for 0.1-60% by mass.
4. A method according to claim 3, wherein the glyceric acid is present in an amount of 0.5 to 30% by mass.
5. The method according to claim 4, wherein the glyceric acid is 1-20% by mass.
6. The process according to claim 1, wherein, in the hydrodeoxygenation catalyst, (mass of supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1:0.2-10.
7. The process according to claim 6, wherein, in the hydrodeoxygenation catalyst, (mass of supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) =1:0.5-5.
8. The method according to claim 1, wherein the supported metal catalyst has a metal loading of 1 to 35% based on the total mass of the support.
9. The method according to claim 8, wherein the metal is a noble metal at a loading of 1 to 5% and the metal is a non-noble metal at a loading of 5 to 25%.
10. The process according to claim 1, wherein the supported metal oxide catalyst has a loading of 2 to 40% of the metal oxide based on the total mass of the support.
11. The process according to claim 10, wherein the supported metal oxide catalyst has a loading of 5 to 30% of the metal oxide based on the total mass of the support.
12. The process of claim 1, wherein the heteropolyacid is selected from one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphorhenic acid.
13. The process according to claim 1, wherein the supported heteropolyacid catalyst has a loading of from 2 to 40% based on the total mass of the support.
14. The process according to claim 13, wherein the supported heteropolyacid catalyst has a loading of 5 to 30% based on the total mass of the support.
15. The method of claim 1, wherein the support is selected from one or more of activated carbon, silica, alumina, zirconia, titania, silica alumina, or molecular sieves.
16. The process of claim 1, wherein the molar ratio of metal in the supported metal catalyst to glyceric acid is 1:1 to 1000.
17. The process according to claim 16, wherein the molar ratio of metal in the supported metal catalyst to glyceric acid is from 1:3 to 800.
18. The process according to claim 17, wherein the molar ratio of metal in the supported metal catalyst to glyceric acid is from 1:5 to 500.
19. The process according to claim 1, wherein the reaction is carried out at a pressure of 1 to 10 MPa.
20. The process according to claim 19, wherein the reaction is carried out at a pressure of 2 to 6 MPa.
21. The process according to claim 1, wherein the temperature of the reaction is 160 ℃ to 300 ℃.
22. The process according to claim 21, wherein the temperature of the reaction is 180 ℃ to 240 ℃.
23. The process according to claim 22, wherein the temperature of the reaction is 180 ℃ to 220 ℃.
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