CN111495390A - Supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compound and preparation and application thereof - Google Patents
Supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compound and preparation and application thereof Download PDFInfo
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- CN111495390A CN111495390A CN202010319132.6A CN202010319132A CN111495390A CN 111495390 A CN111495390 A CN 111495390A CN 202010319132 A CN202010319132 A CN 202010319132A CN 111495390 A CN111495390 A CN 111495390A
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- aldehyde
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 239000010931 gold Substances 0.000 title claims abstract description 97
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 150000002148 esters Chemical class 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 28
- -1 aldehyde compound Chemical class 0.000 title claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 32
- 238000006709 oxidative esterification reaction Methods 0.000 title claims description 28
- 150000001298 alcohols Chemical class 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 92
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 44
- 229960001545 hydrotalcite Drugs 0.000 claims description 44
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 44
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 20
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 19
- 235000018417 cysteine Nutrition 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 150000003573 thiols Chemical class 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001299 aldehydes Chemical class 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 4
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 108010024636 Glutathione Proteins 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 claims description 4
- 229960000830 captopril Drugs 0.000 claims description 4
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 4
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 229960003180 glutathione Drugs 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 42
- 239000002245 particle Substances 0.000 description 29
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 10
- 239000003223 protective agent Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds, and preparation and application thereof.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a supported gold catalyst for synthesizing ester by oxidative esterification of an alcohol/aldehyde compound, and preparation and application thereof.
Background
The reaction of synthesizing ester by one-step oxidative esterification of alcohol/aldehyde compound is a very important chemical reaction, because the ester compound is a chemical product for synthesizing various perfumes, essences and copolymers, taking Methyl Methacrylate (MMA) generated by oxidative esterification of methanol and methacrolein (MA L) as an example, the methyl methacrylate is an important organic polymer monomer and is mainly used for synthesizing polymethyl methacrylate (PMMA, organic glass).
The method mainly comprises two routes, namely an oxidation method and a direct methylation method, wherein the oxidation method is used for oxidizing isobutene into MA L by the aid of isobutene, then the oxidation method is used for oxidizing MA L into methacrylic acid (MAA), and the MAA is reacted with methanol to generate MMA, and the direct methylation method avoids direct generation of the MAA and solves the problems of equipment corrosion, environmental pollution, product separation and the like.
MA L oxidative esterification studies originally used H2O2Or a homogeneous reaction system catalyzed by peracetic acid [ R.Gopinath, B.K. Patel, Org. L ett, 2000,2, 577-.]After oxygen-containing gas is introduced as oxidant, the catalyst is gradually transited to a heterogeneous catalyst which takes noble metal Pd or Au as active component and is added with different assistants. Compared with homogeneous catalysts, heterogeneous catalysts have the advantages of few byproducts, mild reaction conditions, easy separation and reutilization, continuous operation and the like.
A series of palladium-based catalysts developed by asahi chemicals co., ltd, japan have achieved a good catalytic effect [ CN 108607550 a ], but when Pd is used as an active component, the catalytic activity is high, but the selectivity of the target product is not high, so that it is necessary to add auxiliary agents such as Pb and Bi to improve the selectivity [ c. L iu, j.wang, &ttttransfer = L "&tttl &ttt/t &ttt. Meng, angew.chem. int.ed.,2011,50,5144-.
The Japan Asahi formation company developed a nanogold catalyst (Au @ NiO) having a core-shell structure in subsequent studiesx) [K.Suzuki,T.Yamaguchi,K.Matsushita,et al.ACS Catal.,2013,3,1845-1849.]The catalyst can efficiently catalyze the oxidative esterification of methacrolein and methanol to form MMA, the selectivity of MMA is as high as more than 99%, and the catalyst shows excellent stability when applied to a fixed bed reactor. However, the catalyst has low conversion rate of about 60 percent when in use, and the preparation technology and the catalyst have high cost and are not suitable for industrial production.
Based on the analysis, the one-step oxidation esterification reaction of methacrolein and methanol is a core link of the process for preparing methyl methacrylate from isobutene, and the development of a green and efficient supported catalyst for synthesizing ester by the oxidation esterification of alcohol/aldehyde compounds has very strong practical significance.
Disclosure of Invention
The invention aims to provide a supported gold catalyst for synthesizing ester by oxidizing and esterifying an alcohol/aldehyde compound, which can efficiently and selectively convert the alcohol/aldehyde compound into the ester compound in one step, has a simple preparation process, can keep a stable structure in the reaction process, has a certain sulfur-resistant effect, and is beneficial to industrial production and application in the future.
In order to realize the scheme, the technical scheme adopted by the invention is as follows:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds is prepared by taking chloroauric acid aqueous solution as a raw material, taking hydrotalcite as a carrier and taking thiol-containing compound as a stabilizer to control the particle size of gold and keep the stability of the gold catalyst, wherein the hydrotalcite comprises zinc-aluminum hydrotalcite, magnesium-aluminum hydrotalcite, nickel-aluminum hydrotalcite or cobalt-aluminum hydrotalcite, and the molar ratio of zinc, magnesium, nickel or cobalt to aluminum is 1: 3-3: 1; the mass fraction of the active component gold is 0.1-20 wt%, and the mass fraction of the sulfur is 0.01-10 wt%.
Preferably, the thiol-containing compound is one or more selected from cysteine, homocysteine, glutathione, captopril, dodecanethiol, phenethylthiol or hexanthiol.
Preferably, the average particle size of the gold catalyst is 1-5 nm.
The invention also relates to a preparation method of the supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds, which adopts the following technical scheme:
a preparation method of a supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compounds comprises the following steps: taking a proper amount of chloroauric acid aqueous solution, adjusting the pH value to 7-10 by using NaOH solution, adding a hydrotalcite carrier, performing stirring reaction, performing suction filtration and washing on the suspension, then dispersing the filter cake in a proper amount of ultrapure water again, adding a certain amount of thiol-containing compound under the stirring condition, performing stirring reaction, performing suction filtration and washing on the liquid, drying and roasting the obtained filter cake to obtain the supported gold catalyst, wherein the molar ratio of the hydrotalcite to the thiol compound to the chloroauric acid is 100-500: 0.01-1.0: 1, preferably 100 to 200: 0.1-0.5: 1.
or the second method: adopting a sol-gel method to mix chloroauric acid solution, thiol compound-containing solution, NaOH solution and NaBH4The solution is added into a container in sequence to control the mercaptan compound, NaOH and NaBH4The molar ratio of Au to Au is 1-4: 50-100: 1-10: 1, preferably 1.5 to 3: 50-65: 5-10: 1, centrifugally washing the obtained product with a mixed solution of ethanol and water, VEthanol/VWater (W)2-6: and 1, freeze-drying the obtained black solid, dissolving the dried crystal (gold atom cluster with stable mercaptan) in water or acetone solution, impregnating or adsorbing the crystal on a hydrotalcite carrier, drying and roasting to obtain the supported gold catalyst.
The preparation method of the hydrotalcite carrier comprises the steps of adding water into zinc nitrate, magnesium nitrate, nickel nitrate, cobalt nitrate or aluminum nitrate with certain mass according to the molar ratio of the zinc to the magnesium to the nickel to the cobalt to the aluminum of 1: 3-3: 1 to prepare a solution A, and taking a certain amount of NaOH and Na2CO3Solid deionizationPreparing a mixed solution by water, recording as a solution B, and mixing the solution B and the solution A in a water bath stirring mode according to the weight ratio of 1:1, stirring and aging at the temperature, performing suction filtration and washing on the aged solution by using a large amount of deionized water, placing the obtained filter cake in an oven for drying, and grinding the dried solid into fine powder of 100 meshes; the total mass of the metal nitrate accounts for 10-30 wt% of the solution A, and the molar ratio of NaOH to the nitrate is (5-7): 1, Na2CO3The molar ratio of the solid to the nitrate is 1-3: 1.
the invention also relates to an application of the supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds, which adopts the following technical scheme:
the application of supported gold catalyst for synthesizing ester by using alcohol/aldehyde compound through oxidative esterification includes adding a certain quantity of aldehyde compound and alcohol compound into reaction still, adding a certain quantity of supported gold catalyst, then using nitrogen gas to displace air in the reaction still, then filling a certain quantity of oxygen-containing gas into the reaction still, placing the reaction still in heating equipment to raise temperature, monitoring temperature in the reaction still by means of heat sensor, when the temperature is raised to a defined temperature, starting magnetic stirring or mechanical stirring to make the solution in the reaction still be fully mixed with gas, after a period of reaction, placing the reaction still in cooling medium to lower temperature, discharging residual gas in the reaction still, then separating catalyst and reaction liquor, and using chromatography to analyze reactant and product.
Preferably, the temperature is 50-120 ℃, the oxygen partial pressure is 0.1-1MPa, and the molar ratio of the alcohol aldehyde is 8-50: 1, the molar ratio of aldehyde to gold in the catalyst is 1-103：1。
The application of supported gold catalyst for synthesizing ester by using alcohol/aldehyde compound through oxidative esterification includes adding a certain quantity of supported gold catalyst into fixed bed reactor, using nitrogen gas to make displacement of gas in pipeline, then introducing a certain quantity of oxygen-containing gas into the reactor, using back pressure valve and mass flowmeter to control pressure and flow rate of gas, using heat sensor to monitor internal and external temp. of reactor, when the temp. is raised to a defined temp., using a certain quantity of aldehyde compound and alcohol compound to prepare reaction liquor, injecting the reaction liquor into reaction system by means of double-plunger liquid pump, after a period of reaction, making the reaction liquor flow into a cold tank from fixed bed reactor and cooling, and using gas chromatograph to analyze reactant and product.
Preferably, the temperature is 50-120 ℃, the oxygen partial pressure is 0.1-1MPa, and the molar ratio of the alcohol aldehyde is 8-50: 1, the molar ratio of aldehyde to gold in the catalyst is 1-103：1。
Preferably, the aldehyde compound includes one or more of isobutyraldehyde, methacrolein, crotonaldehyde, cinnamaldehyde and benzaldehyde, and the alcohol compound includes one or more of methanol, ethanol, isopropanol, isobutanol, butanol, cinnamyl alcohol and benzyl alcohol.
The gold catalyst prepared by the invention has small particle size and strong sulfur resistance, has better activity and selectivity when being applied to the oxidation esterification reaction of alcohol/aldehyde compounds, and can obtain over 90 percent of aldehyde conversion rate and over 80 percent of ester selectivity. And the catalyst can keep the structure stable without aggregation when being applied to reaction.
Drawings
FIG. 1 is a graph showing the particle size distribution of the supported gold catalysts prepared in examples 1, 6, 34 and 35, (a) Au-S/Zn3Al-HT； (b)Au-S/Mg3Al-HT；(c)Au25/Zn3Al-HT；(d)Au25/Mg3Al-HT。
FIG. 2 shows the conversion of MA L and the selectivity for MMA at different reaction times in example 5.
FIG. 3 is a graph showing the effect of oxygen pressure on the reaction rate and selectivity to the desired product in example 5.
Detailed Description
The following examples illustrate the invention in more detail without limiting the scope of the invention.
Example 1:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 3: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Preparation of hydrotalcite carrier: taking Zn (NO)3)2·6H2O(0.21mol)、Al(NO3)3·9H2Adding O (0.07mol) into a beaker, adding 200m L deionized water to prepare solution A, and taking NaOH (0.438mol) and Na2CO3(0.113mol) is added into a beaker, 200m L deionized water is stirred and dissolved to prepare solution B, the solution A is slowly dripped into the solution B by a constant flow pump under the stirring of 70 ℃ water bath, the flow rate is controlled to be 3m L/min, the solution A is stirred and aged for 24h at the temperature, a large amount of deionized water is used for washing and suction filtration after aging, the obtained filter cake is dried at 70 ℃, and the dried filter cake is ground into 100-mesh powder for standby.
The preparation of the catalyst comprises the steps of taking 1.02m L chloroauric acid solution (0.1 mol/L), diluting with 20m L deionized water, adjusting the pH value to about 9, adding 2g of zinc-aluminum hydrotalcite carrier (the molar ratio of Zn to Al is 3:1), stirring for reaction for 12 hours, carrying out suction filtration and washing to obtain a solid, dispersing the solid in deionized water, adding 9.5mg of cysteine, stirring for 1 hour, drying and roasting the solid obtained by suction filtration, and finally obtaining the supported gold catalyst, wherein the average particle size of the supported gold catalyst is 1.1 nm.
Application of supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compound
Oxidation esterification reaction, alcohol/aldehyde one-step oxidation esterification reaction is carried out in a 15m L stainless steel high-pressure reaction kettle, methanol 5m L (123.6mmol), 95% methacrolein 396 mu L (4.8mmol), internal standard o-xylene 121 mu L, Au-S/Zn30.1g of Al-HT catalyst (0.005 mmol of gold in mol). Introducing oxygen of 0.3MPa, carrying out the reaction for 2h under the stirring of water bath at 80 ℃, detecting the product by using a gas chromatograph after the reaction is finished, wherein the conversion rate of the obtained methacrolein is 90 percent, and the selectivity of the methyl methacrylate is 95 percent.
The cysteine in example 1 may be replaced by homocysteine, glutathione, captopril, dodecanethiol, phenethylthiol or hexanthiol.
Example 2:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 2: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Zn (NO) is adopted in the preparation of hydrotalcite carrier3)2·6H2O(0.14molg)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the obtained zinc-aluminum hydrotalcite was Zn/Al 2:1, the average particle diameter of the prepared supported gold catalyst was 1.3nm, the conversion of methacrolein obtained was 92%, and the selectivity of methyl methacrylate was 96%.
Example 3:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Zn (NO) is adopted in the preparation of hydrotalcite carrier3)2·6H2O(0.07mol)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the obtained zinc-aluminum hydrotalcite was 1:1, the average particle diameter of the prepared supported gold catalyst was 1.5nm, the conversion of methacrolein was 85% and the selectivity of methyl methacrylate was 92%.
Example 4:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1: 2; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Zn (NO) is adopted in the preparation of hydrotalcite carrier3)2·6H2O(0.035mol)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the obtained zinc-aluminum hydrotalcite was 1:2, the average particle diameter of the obtained supported gold catalyst was 1.6nm,the conversion of methacrolein obtained was 82% and the selectivity for methyl methacrylate was 90%.
Example 5:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1: 3; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Zn (NO) is adopted in the preparation of hydrotalcite carrier3)2·6H2O(0.023mol)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the obtained zinc-aluminum hydrotalcite was 1:3, the average particle size of the prepared supported gold catalyst was 1.9nm, the conversion of methacrolein was 65%, and the selectivity of methyl methacrylate was 81%.
Example 6:
a supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compounds takes magnesium-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of magnesium to aluminum is 3: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Mg (NO) is adopted in the preparation of the hydrotalcite carrier3)2·6H2O(0.021mol)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the resulting magnesium aluminum hydrotalcite was 3:1, and the resulting catalyst was expressed as Au-S/Mg3Al-HT with an average particle size of 1.1nm gave a methacrolein conversion of 88% and a methyl methacrylate selectivity of 77%.
Example 7:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes nickel-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of nickel to aluminum is 3: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%
Compared with example 1, the difference lies in the preparation of hydrotalcite carrierUsing Ni (NO)3)2·6H2O(0.021mol)、 Al(NO3)3·9H2O (0.07mol), the metal molar ratio of the resulting nickel-aluminum hydrotalcite was 3:1, and the resulting catalyst was expressed as Au-S/Ni3Al-HT with an average particle size of 2.1nm gives a methacrolein conversion of 92% and a methyl methacrylate selectivity of 65%.
Example 8:
a supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds takes cobalt-aluminum hydrotalcite as a carrier and cysteine as a stabilizer, and the molar ratio of cobalt to aluminum is 3: 1; the mass fraction of the active component gold is 1.0 wt%, and the mass fraction of the sulfur is 0.1 wt%.
Compared with example 1, the difference is that Co (NO) is adopted in the preparation of the hydrotalcite carrier3)2·6H2O(0.021mol)、 Al(NO3)3·9H2O (0.07mol), the resulting cobalt aluminum hydrotalcite had a metal molar ratio of Co/Al of 3:1, and the resulting catalyst was expressed as Au-S/Co3Al-HT with an average particle size of 2.0nm gave a methacrolein conversion of 86% with a methyl methacrylate selectivity of 85%.
Example 9:
compared with the example 1, the difference is that the thiol-containing protective agent is not added in the catalyst preparation process, the particle size of the obtained supported gold catalyst is 3.5nm, the conversion rate of methacrolein is 26%, and the selectivity of methyl methacrylate is 45%.
Example 10:
compared with the example 2, the difference is that the thiol-containing protective agent is not added in the catalyst preparation process, the particle size of the obtained supported gold catalyst is 3.8nm, the conversion rate of methacrolein is 22%, and the selectivity of methyl methacrylate is 48%.
Example 11:
compared with the example 3, the difference is that the thiol-containing protective agent is not added in the catalyst preparation process, the particle size of the obtained supported gold catalyst is 4.2nm, the conversion rate of the methacrolein is 20%, and the selectivity of the methyl methacrylate is 39%.
Example 12:
compared with example 6, the difference is that the catalyst preparation process does not add the thiol-containing protective agent, the particle size of the obtained supported gold catalyst is 4.5nm, the conversion rate of methacrolein is 21%, and the selectivity of methyl methacrylate is 44%.
Example 13:
compared with example 7, the difference is that the catalyst preparation process does not add a thiol-containing protective agent, the particle size of the obtained supported gold catalyst is 10.5nm, the conversion rate of methacrolein is 5%, and the selectivity of methyl methacrylate is 22%.
Example 14:
compared with the example 8, the difference is that the thiol-containing protective agent is not added in the catalyst preparation process, the particle size of the obtained supported gold catalyst is 6.5nm, the conversion rate of methacrolein is 36%, and the selectivity of methyl methacrylate is 46%.
Example 15:
compared with example 1, the difference is that the addition amount of cysteine in the catalyst preparation process is 4.5mg, the mass fraction of sulfur is 0.05 wt%, the average particle size of the prepared supported gold catalyst is 2.0nm, the conversion rate of the obtained methacrolein is 90%, and the selectivity of the methyl methacrylate is 92%.
Example 16:
compared with example 1, the difference is that the addition amount of cysteine in the catalyst preparation process is 19.2mg, the mass fraction of sulfur is 0.25 wt%, the average particle size of the prepared supported gold catalyst is 1.6nm, the conversion rate of the obtained methacrolein is 88%, and the selectivity of the methyl methacrylate is 90%.
Example 17:
compared with example 1, the difference is that the addition amount of cysteine in the catalyst preparation process is 45.1mg, the mass fraction of sulfur is 0.5 wt%, the average particle size of the prepared supported gold catalyst is 1.5nm, the conversion rate of the obtained methacrolein is 42%, and the selectivity of the methyl methacrylate is 88%.
Example 18:
compared with example 1, the difference is that the thiol protectant added in the catalyst preparation process is 5.0 mg of homocysteine, the mass fraction of sulfur is 0.1 wt%, the average particle size of the prepared supported gold catalyst is 1.8nm, the conversion rate of the obtained methacrolein is 91%, and the selectivity of the methyl methacrylate is 92%.
Example 19:
compared with example 1, the difference is that 11.4 mg of glutathione is added as the mercaptan protective agent in the preparation process of the catalyst, the mass fraction of sulfur is 0.1 wt%, the average particle size of the prepared supported gold catalyst is 2.1nm, the conversion rate of the obtained methacrolein is 87%, and the selectivity of the methyl methacrylate is 88%.
Example 20:
compared with example 1, the difference is that the mercaptan protective agent added in the catalyst preparation process is captopril 8.1mg, the mass fraction of sulfur is 0.1 wt%, the average particle size of the prepared supported gold catalyst is 2.2nm, the conversion rate of the obtained methacrolein is 82%, and the selectivity of the methyl methacrylate is 85%.
Example 21:
compared with example 1, the difference is that 5.1m L chloroauric acid solution (0.1 mol/L) and 47.5mg cysteine are added in the catalyst preparation process, the mass fraction of active components gold is 5.0 wt%, the mass fraction of sulfur is 0.5 wt%, the average particle size of the prepared supported gold catalyst is 1.9nm, 0.05g of the catalyst is taken in the oxidation esterification reaction process, the conversion rate of the obtained methacrolein is 87%, and the selectivity of methyl methacrylate is 90%.
Example 22:
compared with the example 1, the difference is that 20.4m L chloroauric acid solution (0.1 mol/L) and 190mg cysteine are added in the catalyst preparation process, the mass fraction of the active component gold is 20 wt%, the mass fraction of sulfur is 2 wt%, the average particle size of the prepared supported gold catalyst is 2.6nm, 0.025g of the catalyst is taken in the oxidation esterification process, the conversion rate of the obtained methacrolein is 76%, and the selectivity of the methyl methacrylate is 90%.
Example 23:
compared with the example 22, the difference is that 950mg of cysteine is added in the preparation process of the catalyst, the mass fraction of the active component gold is 20 wt%, the mass fraction of sulfur is 10 wt%, the average particle size of the prepared supported gold catalyst is 2.5nm, the catalyst is 0.025g in the oxidation esterification reaction process, the conversion rate of the obtained methacrolein is 26%, and the selectivity of methyl methacrylate is 84%.
Example 24:
compared with example 1, the difference is that the amount of the catalyst added in the oxidative esterification reaction is 0.05g, the conversion rate of the obtained methacrolein is 62%, and the selectivity of the methyl methacrylate is 91%.
Example 25:
compared with example 1, the difference is that the oxygen pressure charged in the oxidative esterification reaction is 0.5MPa, the conversion rate of the obtained methacrolein is 92%, and the selectivity of the methyl methacrylate is 94%.
Example 26:
compared with example 1, the difference is that the oxygen pressure charged in the oxidative esterification reaction is 0.2MPa, the conversion rate of the obtained methacrolein is 88 percent, and the selectivity of the methyl methacrylate is 90 percent.
Example 27:
compared with example 1, the difference is that the reaction temperature in the oxidative esterification reaction is 60 ℃, the conversion rate of the obtained methacrolein is 80%, and the selectivity of the methyl methacrylate is 93%.
Example 28:
compared with example 1, the difference is that the reaction temperature in the oxidative esterification reaction is 100 ℃, the conversion rate of the obtained methacrolein is 96%, and the selectivity of the methyl methacrylate is 94%.
Example 29:
the difference from example 1 is that isobutyraldehyde 450. mu. L was used as the aldehyde added in the oxidative esterification reaction, and the conversion of isobutyraldehyde was 95% and the selectivity to methyl isobutyrate was 98.5%.
Example 30:
compared with example 1, the difference is that the aldehyde added in the oxidative esterification reaction is cinnamaldehyde 660 mu L, the conversion rate of the obtained cinnamaldehyde is 75%, and the selectivity of methyl cinnamate is 80%.
Example 31:
compared with the example 1, the difference is that the aldehyde added in the oxidative esterification reaction is benzaldehyde 660 mu L, the conversion rate of the obtained benzaldehyde is 80%, and the selectivity of the methyl benzoate is 65%.
Example 32:
compared with example 1, the difference is that the aldehyde added in the oxidative esterification reaction is butenal 395 mu L, the conversion rate of the butenal is 75 percent, and the selectivity of the methyl crotonate is 65 percent.
Example 33:
compared with the example 1, the difference is that the oxidative esterification reaction is carried out in a continuous fixed bed reactor, and the reaction solution is 10 percent by volume of methylacrolein/methanol solution, Au-S/Zn30.5g of Al-HT (obtained in example 1) catalyst, 0.2MPa of oxygen partial pressure, 20m L/min of gas flow rate, 80 ℃ of reaction temperature, 12h of reaction time, sampling, detecting a product by a gas chromatograph, wherein the conversion rate of the obtained methacrolein is 95 percent, and the selectivity of the methyl methacrylate is 95 percent.
Example 34:
compared with the example 30, the difference is that the catalyst is Au/Zn without adding the thiol protective agent30.5g of Al-HT catalyst, the conversion of methacrolein obtained was 75%, and the selectivity for methyl methacrylate was 90%.
Example 35:
compared with the example 30, the difference is that the catalyst is Au-S/Mg30.5g of Al-HT (from example 6) catalyst gave a conversion of methacrolein of 90% and a selectivity for methyl methacrylate of 75%.
Example 36:
compared with example 30, with the difference that the catalyst is Au-S @Ni30.5g of Al-HT (from example 7) catalyst gave a conversion of methacrolein of 95% and a selectivity for methyl methacrylate of 77%.
Example 37:
compared with the example 30, the difference is that the catalyst is Au-S/Co30.5g of Al-HT (from example 8) catalyst gave a methacrolein conversion of 85% and a methyl methacrylate selectivity of 86%.
Example 38:
compared with the example 30, the difference is that the catalyst is Au25/Zn3Al-HT 0.5g, wherein Au25/Zn3The Al-HT catalyst is prepared by adopting an impregnation method to cluster gold atoms (Au)25) Carried on Zn3Drying and roasting the Al-HT carrier to obtain Au25The atomic cluster is obtained by using cysteine as stabilizer and sodium borohydride as reducing agent, and is prepared by preparing 0.5m L pre-prepared chloroauric acid solution (19.12 g)Au/L), adding 20M L ultrapure and 15M L cysteine solution, observing the color of the solution changing from light yellow to dark yellow and finally to milky white, then taking 3M L1M NaOH solution, quickly adding the solution into the flask, adding freshly prepared NaBH after the solution becomes clear4(0.2M NaOH) solution, finding that the solution turns into brownish red, stirring at room temperature for reaction for 3h, finally turning the solution into brownish black, centrifugally washing the brownish black liquid by using ethanol/water solution with the volume ratio of 3/1, placing the obtained black solid under freeze drying for 12h to obtain Au25The average particle diameter of the supported gold catalyst prepared by the method is 1.7nm, the conversion rate of methacrolein obtained by using the catalyst in the oxidation esterification reaction of methacrolein/methanol is 95%, and the selectivity of methyl methacrylate is 96%.
Example 39:
compared with example 35, the difference is that the catalyst is Au25/Mg3Al-HT 0.5g, wherein Au25/Mg3The Al-HT catalyst is prepared by dipping Au25Cluster carried on Mg3Drying and roasting the Al-HT carrier on a fixed bedIn the oxidation esterification reaction of methacrolein and methanol, the average particle diameter of the supported gold catalyst is 2.2nm, the conversion rate of the obtained methacrolein is 90%, and the selectivity of methyl methacrylate is 85%.
The above examples are merely illustrative of the present invention, and other embodiments of the present invention are possible. But all the technical solutions formed by equivalent alternatives or equivalent modifications fall within the protection scope of the present invention.
Claims (7)
1. A supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compounds is characterized in that chloroauric acid aqueous solution is used as a raw material, hydrotalcite is used as a carrier, and thiol-containing compounds are used as stabilizers, wherein the hydrotalcite comprises zinc-aluminum hydrotalcite, magnesium-aluminum hydrotalcite, nickel-aluminum hydrotalcite or cobalt-aluminum hydrotalcite, wherein the molar ratio of zinc, magnesium, nickel or cobalt to aluminum is 1: 3-3: 1; the mass fraction of the active component gold is 0.1-20 wt%, and the mass fraction of the sulfur is 0.01-10 wt%.
2. The supported gold catalyst for the oxidative esterification of alcohol/aldehyde compounds to synthesize esters according to claim 1, wherein the thiol-containing compound is one or more selected from cysteine, homocysteine, glutathione, captopril, dodecanethiol, phenethyl thiol, and hexanthiol.
3. A preparation method of a supported gold catalyst for synthesizing ester by oxidative esterification of alcohol/aldehyde compounds is characterized in that the first method comprises the following steps: taking a proper amount of chloroauric acid aqueous solution, adjusting the pH value to 7-10 by using NaOH solution, adding a hydrotalcite carrier, performing stirring reaction, performing suction filtration and washing on the suspension, then dispersing the filter cake in a proper amount of ultrapure water again, adding a certain amount of thiol-containing compound under the stirring condition, performing stirring reaction, performing suction filtration and washing on the liquid, drying and roasting the obtained filter cake to obtain the supported gold catalyst, wherein the molar ratio of the hydrotalcite to the thiol compound to the chloroauric acid is 100-500: 0.01-1.0: 1;
or the second method: by sol-gel methodChloroauric acid solution, thiol compound-containing solution, NaOH solution, and NaBH4The solution is added into a container in sequence to control the mercaptan compound, NaOH and NaBH4The molar ratio of Au to Au is 1-4: 50-100: 1-10: 1, centrifugally washing the obtained product with a mixed solution of ethanol and water, VEthanol/VWater (W)2-6: and 1, freeze-drying the obtained black solid to obtain a mercaptan-stable gold atom cluster crystal, dissolving the mercaptan-stable gold atom cluster crystal in water or an acetone solution, impregnating or adsorbing the mercaptan-stable gold atom cluster crystal on a hydrotalcite carrier, and drying and roasting the hydrotalcite carrier to obtain the supported gold catalyst.
4. The application of supported gold catalyst for synthesizing ester by using alcohol/aldehyde compound through oxidative esterification is characterized by that it includes adding a certain quantity of aldehyde compound and alcohol compound into reaction still, adding a certain quantity of supported gold catalyst, then using nitrogen gas to displace air in the reaction still, then charging a certain quantity of oxygen-containing gas into the reaction still, placing the reaction still in heating equipment to raise temperature, and monitoring the temperature in the reaction still by means of heat sensor, when the temperature is raised to a defined temperature, starting magnetic stirring or mechanical stirring to fully mix the solution in the reaction still with gas, after a period of reaction, placing the reaction still in cooling medium to lower temperature, and discharging residual gas from the reaction still, then separating catalyst from reaction liquor, and using chromatography to analyze reactant and product.
5. The application of supported gold catalyst for synthesizing ester by using alcohol/aldehyde compound through oxidative esterification includes adding a certain quantity of supported gold catalyst into fixed bed reactor, using nitrogen gas to make displacement of gas in pipeline, then introducing a certain quantity of oxygen-containing gas into the reactor, using back pressure valve and mass flowmeter to control pressure and flow rate of gas, using heat sensor to monitor internal and external temp. of reactor, when the temp. is raised to a defined temp., using a certain quantity of aldehyde compound and alcohol compound to prepare reaction liquor, injecting the reaction liquor into reaction system by means of double-plunger liquid pump, after a period of reaction, making the reaction liquor flow into a cold tank from fixed bed reactor and cooling, and using gas chromatograph to analyze reactant and product.
6. The use of the supported gold catalyst for the oxidative esterification synthesis of esters from alcohol/aldehyde compounds according to claim 4 or 5, wherein the temperature is 50-120 ℃, the oxygen partial pressure is 0.1-1MPa, and the molar ratio of the alcohol to the aldehyde is 8-50: 1, the molar ratio of aldehyde to gold in the catalyst is 1-103：1。
7. The use of the supported gold catalyst for the oxidative esterification synthesis of esters from alcohol/aldehyde compounds according to claim 4 or 5, wherein the aldehyde compound comprises one or more of isobutyraldehyde, methacrolein, crotonaldehyde, cinnamaldehyde and benzaldehyde, and the alcohol compound comprises one or more of methanol, ethanol, isopropanol, isobutanol, butanol, cinnamyl alcohol and benzyl alcohol.
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