CN113634252B - Preparation method of catalyst for preparing pyruvic acid ester by catalyzing lactate to be dehydrogenated - Google Patents
Preparation method of catalyst for preparing pyruvic acid ester by catalyzing lactate to be dehydrogenated Download PDFInfo
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- CN113634252B CN113634252B CN202111040274.XA CN202111040274A CN113634252B CN 113634252 B CN113634252 B CN 113634252B CN 202111040274 A CN202111040274 A CN 202111040274A CN 113634252 B CN113634252 B CN 113634252B
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- catalyst
- copper
- oxide
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- lactate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 25
- LCTONWCANYUPML-UHFFFAOYSA-N PYRUVIC-ACID Natural products CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229940107700 pyruvic acid Drugs 0.000 title claims abstract description 14
- -1 pyruvic acid ester Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 abstract description 8
- 229940076788 pyruvate Drugs 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002841 Lewis acid Substances 0.000 abstract description 6
- 150000007517 lewis acids Chemical class 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 229940116333 ethyl lactate Drugs 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000012691 Cu precursor Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000003903 lactic acid esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
- B01J23/72—Copper
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J23/825—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 gallium, indium or thallium
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- 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
- B01J23/83—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 rare earths or actinides
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- 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
- B01J23/835—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 germanium, tin or lead
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- 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
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst preparation technology, and aims to provide a preparation method of a catalyst for preparing pyruvic acid ester by catalyzing lactate to be dehydrogenated. Comprising the following steps: dissolving a copper metal precursor in a solvent, and adding ammonia water to carry out a complex reaction with the copper metal precursor to obtain a reaction solution; adding carrier powder into the reaction liquid, and treating for 0.5-24 hours at 100-220 ℃; and carrying out suction filtration, water washing and drying on the solid powder, and roasting to obtain the catalyst. The catalyst has very high copper dispersity, very high concentration of zero-valent copper sites and Lewis acid sites, very close space distance between the two sites and higher activity in catalyzing lactate dehydrogenation reaction. The special structure gives higher stability, and even if the activity is lowered due to carbon deposition during the reaction, the catalyst can be regenerated by a simple calcination procedure. The raw material price is low, and the preparation process is simple; provides a new option for preparing pyruvate for biomass routes.
Description
Technical Field
The invention belongs to a catalyst preparation technology, and particularly relates to a preparation method of a catalyst for preparing pyruvic acid ester by catalyzing lactate to be dehydrogenated.
Background
Pyruvic acid esters are important pharmaceutical intermediates and food additives. At present, pyruvic acid ester is mainly obtained by the reaction of tartaric acid and potassium hydrogen sulfite, so that the pollution is large, and the cost for separating and treating waste liquid is high. With the concept of sustainable development, the adoption of green routes instead of traditional routes for biomass raw materials becomes necessary.
Lactic acid ester can be obtained through cellulose fermentation or catalytic conversion, and is a more environment-friendly renewable resource. And the lactate can be simply catalyzed and oxidized and dehydrogenated to generate the pyruvate. Traditionally, air or oxygen is used as an oxidant, and a noble metal catalyst is used for oxidizing hydroxyl groups on the lactate into carbonyl groups in a high-temperature oxidation mode. The selectivity reported in the literature is generally below 85% because lactate is flammable and unstable in high temperature oxygen-containing atmospheres.
Therefore, the development of a high-efficiency catalyst for catalyzing the conversion of the lactate into the pyruvate has important research significance and practical value.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a preparation method of a catalyst for preparing pyruvic acid ester by catalyzing lactate to be dehydrogenated.
In order to solve the technical problems, the invention adopts the following solutions:
there is provided a method for preparing a catalyst for catalyzing lactate dehydrogenation to prepare pyruvic acid ester, comprising the steps of:
(1) Dissolving a copper metal precursor in a solvent to obtain a precursor solution; adding ammonia water and a copper metal precursor for complex reaction to obtain a reaction solution;
(2) Adding carrier powder into the reaction liquid in the step (1), and treating for 0.5-24 hours at 100-220 ℃;
(3) Carrying out suction filtration, water washing and drying on solid powder in the reaction liquid treated in the step (2); roasting at 200-500 ℃ for 1-10 hours to obtain a catalyst for catalyzing lactate dehydrogenation to prepare pyruvic acid ester; in the catalyst, the mass fraction of copper is 0.1-40%.
In a preferred embodiment of the present invention, the copper metal precursor is any one of copper sulfate, copper nitrate, copper acetate, copper chloride, and copper acetylacetonate.
As a preferable mode of the present invention, the solvent is any one of water, methanol, ethanol, acetone, acetylacetone, nitrogen-dimethylformamide, and valerolactone.
As a preferable embodiment of the present invention, the concentration of the precursor solution is 0.01 to 5mol/L.
As a preferable mode of the invention, the molar ratio of the ammonia water to the copper metal precursor is 1-10.
As a preferred embodiment of the present invention, the carrier is any one of silica, alumina, zinc oxide, tin dioxide, zirconium dioxide, magnesium oxide, titanium oxide, nickel oxide, cerium oxide, lanthanum oxide, iron oxide, cobalt oxide, indium oxide, and chromium oxide.
As a preferable mode of the invention, the volume-mass ratio of the reaction liquid to the carrier powder is 1-100 mL/g.
Description of the inventive principles:
direct catalytic alcohol dehydrogenation is a route of high atom economy, and the dehydrogenation products are the corresponding ketones (or aldehydes) and hydrogen. The hydrogen can be separated by a membrane to obtain ketone (or aldehyde) with high purity. Therefore, the invention provides a brand new copper-based catalytic material, which can realize the direct dehydrogenation of lactate to pyruvate in an anaerobic environment.
The principle of the invention at the microscopic level is as follows:
catalytic lactate requires two active sites to activate the alcohol hydroxyl groups and the hydrocarbon bond on the lactate alpha carbon, respectively. The former requires a zero-valent copper site and the latter requires a lewis acid site that act synergistically to efficiently catalyze the dehydrogenation of lactate to pyruvate. Zero-valent copper in the catalyst is generated from the copper precursor, while the lewis acid is generated from the interfacial atoms of copper and the oxide support. In order to increase the concentration of zero-valent copper and Lewis acid sites in the catalyst, the copper precursor is reacted with ammonia water to form copper-ammonia complex. Then dispersing the carrier powder into the cuprammonium complex, wherein hydroxyl groups on the carrier automatically interact with the cuprammonium complex; the mixture is then further heat treated to increase this effect so that the copper species are uniformly dispersed on the support. In the subsequent calcination treatment, copper particles are not sintered due to the high dispersity of copper species in the catalyst, so that zero-valent copper sites with small particle size and high dispersity can be obtained. The concentration of lewis acid sites is also high because of the high degree of dispersion of the copper particles, and the very large number of interfacial atoms between copper and the oxide support. The two are very close in space, so that the two can play a very good role in catalyzing the lactate dehydrogenation reaction.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts a special synthesis method, so that the dispersity of copper in the catalyst is very high, the concentration of zero-valent copper sites and Lewis acid sites is very high, the space between the two sites is very close, and the activity is higher in catalyzing the lactate dehydrogenation reaction.
2. The special structure of the catalyst synthesized by the method gives higher stability, and the catalyst can be regenerated by a simple roasting procedure even if the activity is reduced due to carbon deposition in the reaction process.
3. The raw materials adopted in the preparation process are low in price, and the preparation process is simple; provides a new option for preparing pyruvate for biomass routes.
Detailed Description
The following describes the content in detail by way of specific examples.
The preparation method of the catalyst for preparing pyruvic acid ester by catalyzing lactate to dehydrogenate comprises the following steps:
(1) Dissolving a copper metal precursor in a solvent to obtain a precursor solution; adding ammonia water and a copper metal precursor for complex reaction to obtain a reaction solution; the copper metal precursor is any one of copper sulfate, copper nitrate, copper acetate, copper chloride and copper acetylacetonate. The solvent is any one of water, methanol, ethanol, acetone, acetylacetone, nitrogen-dimethylformamide and valerolactone. The concentration of the precursor solution is 0.01-5 mol/L, and the molar ratio of ammonia water to copper metal precursor is 1-10.
(2) Adding carrier powder into the reaction liquid in the step (1), and treating for 0.5-24 hours at 100-220 ℃; the carrier is any one of silicon oxide, aluminum oxide, zinc oxide, tin dioxide, zirconium dioxide, magnesium oxide, titanium oxide, nickel oxide, cerium oxide, lanthanum oxide, iron oxide, cobalt oxide, indium oxide and chromium oxide. The volume mass ratio of the reaction solution to the carrier powder is 1-100 mL/g.
(3) Carrying out suction filtration, water washing and drying on solid powder in the reaction liquid treated in the step (2); roasting at 200-500 ℃ for 1-10 hours to obtain a catalyst for catalyzing lactate dehydrogenation to prepare pyruvic acid ester; in the catalyst, the mass fraction of copper is 0.1-40%.
The catalyst of the invention can be used for catalyzing lactate to be dehydrogenated to prepare pyruvic acid ester, and the effect of the catalyst of the invention is verified by the following example method:
(1) Diluting the catalyst with inert quartz sand with the same volume, filling the diluted catalyst into a quartz tube, and tightly fixing two ends of the diluted catalyst by using quartz tampons to obtain a fixed bed reaction tube; (2) Placing the quartz tube in a tube furnace, heating to 300 ℃, and introducing pure hydrogen for activation for 1 hour; then the reaction temperature is reduced to 275 ℃, and nitrogen is introduced instead; (3) Pumping ethyl lactate into a reaction tube by a sample injection pump, and gasifying before contacting with a catalyst; the gasified ethyl lactate is carried by nitrogen gas and enters a fixed bed, and the ethyl lactate reacts under the action of a catalyst to generate pyruvic acid ester.
The feed gas composition to the fixed bed was 1.3vol% ethyl lactate to 98.7vol% N 2 The space velocity of the feed gas is 1.0g Lactic acid esters /g Catalyst And/h. The catalyst was used in an amount of 200mg for a reaction time of 1 hour.
The gas passing through the catalyst bed was detected by gas chromatography (FID detector) and the specific results are shown in table 1 for ethyl lactate conversion and ethyl pyruvate selectivity data.
The catalyst was successfully prepared by 14 examples and was used in the preparation of pyruvate, respectively. The test data in each example are shown in Table 1 below.
TABLE 1 EXAMPLES data sheet
From the data in Table 1, the invention adopts cheap and easily available raw materials to prepare excellent co-catalyst through a simple process, shows higher activity and lactate selectivity in catalyzing lactate dehydrogenation reaction, and provides a new option for preparing pyruvate through a biomass route.
Finally, it should be noted that the above list is only specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (4)
1. A method for preparing a catalyst for catalyzing lactate dehydrogenation to prepare pyruvic acid ester, which is characterized by comprising the following steps:
(1) Dissolving a copper metal precursor in a solvent to obtain a precursor solution; adding ammonia water and a copper metal precursor for complex reaction to obtain a reaction solution;
the copper metal precursor is any one of copper sulfate, copper nitrate, copper acetate, copper chloride or copper acetylacetonate, the concentration of the precursor solution is 0.01-5 mol/L, and the molar ratio of ammonia water to the copper metal precursor is 1-10;
(2) Adding carrier powder into the reaction liquid in the step (1), and treating for 0.5-24 hours at 100-220 ℃;
(3) Carrying out suction filtration, water washing and drying on solid powder in the reaction liquid treated in the step (2); roasting at 200-500 ℃ for 1-10 hours to obtain a catalyst for catalyzing lactate dehydrogenation to prepare pyruvic acid ester; in the catalyst, the mass fraction of copper is 0.1-40%.
2. The method of claim 1, wherein the solvent is any one of water, methanol, ethanol, acetone, acetylacetone, nitrogen-dimethylformamide, or valerolactone.
3. The method of claim 1, wherein the support is any one of silica, alumina, zinc oxide, tin dioxide, zirconium dioxide, magnesium oxide, titanium oxide, nickel oxide, cerium oxide, lanthanum oxide, iron oxide, cobalt oxide, indium oxide, or chromium oxide.
4. The method according to claim 1, wherein the volume-mass ratio of the reaction solution to the carrier powder is 1 to 100mL/g.
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| CN108069850A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of method for being catalyzed lactic acid oxidative dehydrogenation and preparing pyruvic acid |
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| WO2016199174A1 (en) * | 2015-06-10 | 2016-12-15 | Council Of Scientific & Industrial Research | Oxidative dehydrogenation of lactate esters to pyruvate esters |
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