CN113831248A - Method for preparing 3-hydroxy propionate derivatives - Google Patents
Method for preparing 3-hydroxy propionate derivatives Download PDFInfo
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- CN113831248A CN113831248A CN202010586985.6A CN202010586985A CN113831248A CN 113831248 A CN113831248 A CN 113831248A CN 202010586985 A CN202010586985 A CN 202010586985A CN 113831248 A CN113831248 A CN 113831248A
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- 238000000034 method Methods 0.000 title claims abstract description 64
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical class OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 127
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical class OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims abstract description 31
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims abstract description 30
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 26
- -1 alcohol compound Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 148
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910002785 ReO3 Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 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
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 46
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 45
- 238000010438 heat treatment Methods 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 239000008247 solid mixture Substances 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000011049 filling Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 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
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000011160 research Methods 0.000 description 3
- 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 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- UKDLORMZNPQILV-UHFFFAOYSA-N ethyl 3-hydroxypropanoate Chemical compound CCOC(=O)CCO UKDLORMZNPQILV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004811 liquid chromatography 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
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 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 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 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
- 229910021012 Co2(CO)8 Inorganic materials 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
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 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
- 230000009286 beneficial effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 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
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000002815 homogeneous catalyst Substances 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
- 230000007483 microbial process Effects 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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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-hydroxypropionate 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 green and environment-friendly, and the yield of the 3-hydroxy propionate derivatives is high.
Description
Technical Field
The invention relates to a method for preparing ester derivatives, in particular to a method for preparing 3-hydroxypropionate ester derivatives from renewable biomass-based raw materials.
Background
3-hydroxypropionate derivatives, such as methyl 3-hydroxypropionate, 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) by using methyl 3-hydroxypropionate avoids the toxicity, instability and other negative factors in the preparation process of another intermediate 3-hydroxypropionaldehyde. Methyl 3-hydroxypropionate is expensive in price, and the synthesis method thereof is less discussed at present, so the research of the synthesis process thereof is highly concerned by the polyester academia (remainder. research of synthesizing methyl 3-hydroxypropionate from ethylene oxide catalyzed by sodium cobalt tetracarbonyl [ D ]. university of Dow. Resulter. 2012.).
The 3-hydroxy propionic acid lipid derivative can be obtained by esterification reaction of 3-hydroxy propionic acid and alcohol molecules. The synthesis process of 3-hydroxy propionic acid includes chemical process and microbial process, and the chemical process includes adding 3-hydroxy propionitrile into sodium hydroxide solution to react at 30 deg.c, adding sulfuric acid and stirring, and extracting with ether to produce 3-hydroxy propionic acid in 28-31% yield. 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 source such as glycerol and glucose. Although the microbiological method uses renewable resources as raw materials and has low pollution, the method also has the problems of low production efficiency, harsh reaction conditions and the like (the chemical engineering progresses, 2018, 37 (11): 4427-4436). Therefore, the method for green and efficient synthesis of the 3-hydroxypropionate derivatives by the heterogeneous catalysis starts from renewable biomass-based raw materials, and 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, widely participates in chemical reactions such as polymerization and condensation, and is an important intermediate and multifunctional reagent for chemical synthesis (Anhui agricultural science, 2017, 45 (36): 116-. Glyceric acid can be prepared by oxidizing glycerol which is a main byproduct in the production process of biodiesel and has the characteristics of greenness, renewability, wide sources and the like, and the great development of downstream high-value transformation of glycerol and derivatives thereof has very important significance for the sustainable development of chemical industry in China
CN108329203A discloses a method for preparing 3-hydroxypropionic acid by a two-step method starting from glyceric acid. In the first step of the method, glyceric acid and HI are mixed according to a certain proportion, and an intermediate product, namely 3-iodopropionic acid is obtained under the condition that other catalysts or a certain amount of metal catalysts are not added. And in the second step, reacting the organic phase obtained in the first step with water, and separating and acidifying the organic phase under the condition of adding a basic catalyst to obtain the 3-hydroxypropionic acid. This method has several problems: firstly, hydroiodic acid with extremely strong corrosivity is used in the first step, so that the requirement on the corrosion resistance of the device is enhanced, and the cost and the environmental protection risk of the device are increased; secondly, salts of the 3-hydroxypropionic acid are directly obtained in the second step, and finally, the 3-hydroxypropionic acid product can be obtained through acidification and separation; thirdly, the process flow is long, and complex processes such as extraction and separation of the solvent are involved.
Using ethylene oxide, CO and methanol as raw materials, Co2(CO)8The catalyst can also be synthesized into the methyl 3-hydroxypropionate by methyl hydrogen esterification (natural gas chemical industry, 2011, 36 (03): 34-36), the non-renewable petroleum-based ethylene oxide is used as a raw material in the process, the reaction raw materials such as CO, methanol and the like which are flammable, explosive and have high toxicity are involved, and the used cobalt carbonyl and other homogeneous catalysts are difficult to recycle, so that the process has high cost and low environmental friendliness and is not beneficial to the chemical industry in ChinaCan be developed continuously.
Disclosure of Invention
The invention provides a method for preparing 3-hydroxypropionate derivatives, which is used for efficiently converting glyceric acid into a target product, namely the 3-hydroxypropionate derivatives in an alcoholic solution in one step.
The invention provides a method for preparing 3-hydroxy propionate derivatives, which comprises the following steps:
reacting glyceric acid with hydrogen and alcohol in the presence of an alcohol compound neutralization hydrodeoxygenation catalyst to obtain the 3-hydroxypropionate 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, and specifically can be a mixture of a supported metal catalyst and at least one supported metal oxide catalyst, can also 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 loaded on the carrier, wherein the carrier is selected from one or more of activated 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 amount of the metal is 0.5-45%, preferably 1-35%, based on the total mass of the carrier. 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 a catalyst carrier supported on the carrierThe metal oxide on the carrier takes the total mass of the carrier as a reference, and the loading amount of the metal oxide is 1-50%, preferably 2-40%, and more preferably 5-30%; the carrier is selected from one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon aluminum oxide or molecular sieve; the metal oxide is MoO3、WO3Or ReO3One or more of (a).
The supported heteropolyacid catalyst comprises a carrier and heteropolyacid loaded on the carrier, wherein the loading amount of the heteropolyacid is 1% -50%, preferably 2-40%, and more preferably 5-30% based on the total mass of the carrier; the carrier is one or more of activated 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, the hetero atom is selected from one or more of Si or P, preferably one or more of tungstenic heteropoly acid, molybdenic heteropoly acid or rhenium heteropoly acid, and more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphothrenic acid and the like.
The alcohol compound is selected from one or more of C1-C6 aliphatic alcohol or alicyclic alcohol, and is preferably methanol, ethanol or n-propanol.
In the solution formed by glyceric acid and alcohol compound, the mass percentage content of glyceric acid can be 0.1-60%, preferably 0.5-30%, and more preferably 1-20%.
The molar ratio of the metal in the supported metal catalyst to the glyceric acid in the hydrodeoxygenation catalyst can 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 2MPa 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, and 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, and can be formulated by simple mechanical mixing.
The supported metal catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method. During the specific preparation, after metal deposition, the solid powder is placed in an oven at 100-140 ℃ for drying for about 6-24 hours, the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for a period of time, and then the calcination is carried out in a reducing atmosphere (such as H)2Or H2And N2Mixed atmosphere) at a temperature of 200-500 ℃ for about 6-24 hours to obtain the supported metal catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method; during the preparation, after the deposition of the metal oxide precursor or the heteropoly acid precursor, the solid powder is placed in an oven at 100-140 ℃ for drying for about 6-24 hours, and the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for about 6-24 hours to obtain the supported metal oxide catalyst or the supported heteropoly acid catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst and the supported metal catalyst can be uniformly ground according to a certain proportion before reaction and then added into a reaction system, and can also be respectively added into the reaction system according to a certain proportion.
When the method is used for preparing the 3-hydroxypropionate derivative, the preparation 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 pressure of the reaction kettle is relieved, after 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. The method of the invention can also adopt other conventional reactors, such as fixed bed reactors and the like.
The method for preparing the 3-hydroxypropionate derivative provided by the invention is carried out in an alcohol solution, other miscellaneous elements are not introduced except for a used heterogeneous catalyst, and the yield of the 3-hydroxypropionate derivative is higher, so that the method not only further reduces the production cost, but also is more environment-friendly.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. Wherein the glyceric acid is derived from Ikaty technologies, Inc. of Beijing.
Preparation example 1
Hydrogenation catalyst 10% Ni/Al2O3The preparation of (1):
1mol/L of Ni (NO3)21.7mL of hydrochloric acid solution and 3.0mL of deionized water are mixed and stirred uniformly, and then SiO is added2Adding 0.9g of carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. The loading amount of Ni was 10% (mass%). Putting the precursor prepared in the step into a quartz tube, firstly calcining for 4H at 500 ℃ in the air, and then calcining for 20% H2+N2Reducing for 3h at the temperature of 500 ℃ to obtain the load type 10 percent Ni/Al2O3A catalyst.
Preparation of 20% Co/SiO according to the above method2，5％Pd/TiO2And 1% Pt/C catalyst.
Preparation example 2
Supported metal oxide catalyst 10% MoO3/TiO2The preparation of (1):
0.2g of ammonium molybdate is mixed with 5.0mL of water, the mixture is stirred evenly, and then TiO is added2Adding 1.00g of carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. MoO3The supporting amount of (B) is 10 mass%. The precursor prepared in the above steps is placed in a quartz tube, firstly calcined for 3 hours at 500 ℃ in the air,10% MoO was obtained3/TiO2。
The supported metal oxide catalyst is prepared according to the method, and 5 percent of ReO is loaded respectively3C and 20% WO3/ZrO2. Different supported metal oxide catalysts are prepared by selecting precursors corresponding to supported components, for example, the supported component is ReO3When the precursor is ammonium perrhenate, the precursor can be selected; the load component is WO3When the precursor is ammonium metatungstate, ammonium metatungstate can be selected as the precursor.
Preparation example 3
Preparation of the supported heteropolyacid catalyst:
the preparation method of different supported heteropolyacid catalysts is similar to that of supported metal oxides, and the precursors corresponding to the supported components are selected to prepare the supported heteropolyacid catalysts according to the examples, if the supported components are tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like, the corresponding tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like can be selected as the precursors; when the load component is a molybdenum-containing heteropoly acid, the corresponding molybdenum-containing heteropoly acid, such as phosphomolybdic acid, silicomolybdic acid and the like, can be selected as a precursor.
The supported heteropolyacid catalyst is prepared according to the method, and 20 percent of PWO is loaded respectivelyx/SiO2， 10％SiMoOx/ZrO2And 5% PReOx/C。
Example 1 preparation of methyl 3-hydroxypropionate from Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, 2MPa hydrogen is filled in the reaction kettle to replace residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled in 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 carried out for 20 hours under the rotation speed of 700rpm by stirring. After the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, and putting the kettle intoAnd (3) reducing the pressure to normal pressure, opening a 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.
Example 2 preparation of methyl 3-hydroxypropionate from Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 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 200 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 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 220 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. 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, performing suction filtration and separation, and using the obtained liquid as a liquid phaseThe chromatography was analyzed and the conversion and product yield were calculated. The reaction results are shown in Table 1.
Example 4 preparation of methyl 3-hydroxypropionate from Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 6MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 4MPa 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 carried out for 20 hours under the rotation speed of 700rpm by stirring. 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 5 preparation of ethyl 3-hydroxypropionate from Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 20% Co/SiO2+20％WO3/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 20% Co/SiO2Catalyst, 0.1g 20% WO3/ZrO2The catalyst and 10g of methanol are added, 2MPa hydrogen is filled in the reaction kettle to replace residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled in 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 carried out for 20 hours under the rotation speed of 700rpm by stirring. 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 5% Pd/TiO2+5％ReO3The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.5g glyceric acid and 0.05g 5% Pd/TiO were added2Catalyst, 0.4g 5% ReO3And C, catalyst and 20g of methanol, filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 1% Pt/C + 20% PWOx/SiO2As a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.2g glyceric acid, 0.1g 1% Pt/C catalyst was addedAgent, 0.5g 20% PWOx/SiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is sealed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 180 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 5% Pd/TiO2+10％SiMoOx/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 0.2g glyceric acid and 0.05g 5% Pd/TiO were added2Catalyst, 0.2g 10% SiMoOx/ZrO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is sealed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 Glycerol
With 1% Pt/C + 5% PReOxThe catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
In a 30mL autoclave, 1g of glyceric acid, 0.1g of 1% Pt/C catalyst, 0.2g of 5% PReO were chargedxThe catalyst/C and 10g of methanol are added, 2MPa hydrogen is filled for replacing residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled into the reaction kettle, and the reaction kettle is placedThe mixture was heated in a heating furnace to a reaction temperature of 180 ℃ and stirred at 700rpm for 20 hours. 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, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, 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 added2O3Catalyst without addition of 10% MoO3/TiO2A 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 added3/TiO2Catalyst without addition of 10% Ni/Al2O3A catalyst. The reaction results are shown in Table 1.
Comparative example 3
The reaction was carried out according to the procedure of example 4, except that "0.2 g of 10% MoO" was added3/TiO2Catalyst "replacement by" 0.2g MoO3Catalyst ". The reaction results are shown in Table 1.
Comparative example 4
The procedure of preparation 1 was followed at 10% MoO3/TiO2Further loading 10% Ni component on the catalyst to obtain 10% Ni/10% MoO3/TiO2Co-supported catalyst
The reaction was carried out according to the procedure of example 4, except that "0.2 g 10% Ni/Al" was added2O3Catalyst, 0.2g 10% MoO3/TiO2Catalyst "replacement" 0.2g 10% Ni/10% MoO3/TiO2Co-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-hydroxypropionate derivative provided by the invention can well realize the conversion of glyceric acid to the important chemical raw material 3-hydroxypropionate derivative in an alcohol solvent. Starting from glyceric acid, a yield of methyl 3-hydroxypropionate of 92% or a yield of ethyl 3-hydroxypropionate of 90% can be obtained.
As can be seen from comparative examples 1 and 2, the 3-hydroxypropionate derivative product could not be obtained by adding the supported metal catalyst or the supported metal oxide catalyst alone. As can be seen from comparative examples 3 and 4, the use of the combination of the supported metal catalyst and the metal oxide or the metal and metal oxide co-supported catalyst failed to achieve the yield level of the 3-hydroxypropionate derivative of the catalyst system of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
TABLE 1 reaction conditions, conversion and 3-hydroxypropionic acid yield of examples and comparative examples
Claims (15)
1. A method for preparing a 3-hydroxypropionate derivative, 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-hydroxypropionate 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.
2. The process according to claim 1, wherein the alcohol compound is selected from the group consisting of C1-C6 aliphatic or alicyclic alcohols, preferably methanol, ethanol or n-propanol.
3. The method according to claim 1, wherein the content of the glyceric acid in the solution of the glyceric acid and the alcohol compound is 0.1 to 60% by mass, preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass.
4. 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: 0.1 to 100, preferably 1:0.2 to 10, more preferably 1:0.5 to 5.
5. The process according to claim 1, wherein the supported metal catalyst comprises a support and a metal selected from one or more of group VIII and IB metals, preferably Co, Ni, Ru, Pd or Pt, supported on the support.
6. The process according to claim 5, wherein the supported metal catalyst has a metal loading of 0.5 to 45%, preferably 1 to 35%, based on the total mass of the carrier.
7. The process of claim 6, 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%.
8. The process according to claim 1, wherein the supported metal oxide catalyst comprises a carrier and a metal oxide selected from MoO supported on the carrier3、WO3Or ReO3One or more of (a).
9. The process according to claim 8, wherein the supported metal oxide catalyst has a metal oxide loading of 1 to 50%, preferably 2 to 40%, more preferably 5 to 30%, based on the total mass of the carrier.
10. A process according to claim 1, wherein the supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support, the heteropolyacid having metal atoms selected from one or more of W, Mo, Re, V, Nb and Ta and heteroatoms selected from one or more of Si or P, preferably one or more of a tungstenic, molybdenic or rhenium-containing heteropolyacid, more preferably phosphotungstic, silicotungstic, phosphomolybdic, silicomolybdic and phosphotrhenic acid.
11. A process according to claim 10, wherein the supported heteropolyacid catalyst is loaded at a level of from 1% to 50%, preferably from 2% to 40%, more preferably from 5% to 30% based on the total mass of the support.
12. A process according to claim 5, 8 or 10 wherein the support is selected from one or more of activated carbon, silica, alumina, zirconia, titania, silica alumina or molecular sieves.
13. The process of claim 1 wherein the molar ratio of metal in said supported metal catalyst to said glyceric acid is from 1: 1 to 1000, preferably 1:3 to 800, more preferably 1:5 to 500.
14. The process according to claim 1, wherein the reaction is carried out at a pressure of 1 to 10MPa, preferably 2 to 6 MPa.
15. The process according to claim 1, wherein the reaction temperature is 160 ℃ to 300 ℃, preferably 180 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.
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