CN111495390B - Supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compound and preparation and application thereof - Google Patents
Supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compound and preparation and application thereof Download PDFInfo
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- CN111495390B CN111495390B CN202010319132.6A CN202010319132A CN111495390B CN 111495390 B CN111495390 B CN 111495390B CN 202010319132 A CN202010319132 A CN 202010319132A CN 111495390 B CN111495390 B CN 111495390B
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- hydrotalcite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 239000010931 gold Substances 0.000 title claims abstract description 104
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 90
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 89
- -1 aldehyde compound Chemical class 0.000 title claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000002148 esters Chemical class 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title description 20
- 238000007254 oxidation reaction Methods 0.000 title description 20
- 238000005886 esterification reaction Methods 0.000 title description 19
- 230000032050 esterification Effects 0.000 title description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- 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 abstract description 45
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 45
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 45
- 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 26
- 238000000034 method Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 20
- 235000018417 cysteine Nutrition 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 238000006709 oxidative esterification reaction Methods 0.000 claims description 16
- 150000003573 thiols Chemical class 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 13
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 6
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims description 5
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052759 nickel 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
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 claims description 4
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 4
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 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
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001816 cooling Methods 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 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
- 238000011049 filling Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 43
- 239000002245 particle Substances 0.000 description 29
- 239000003223 protective agent Substances 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 2
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910052745 lead Inorganic materials 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
- 238000004519 manufacturing process Methods 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
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 238000010276 construction Methods 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
- 238000005034 decoration Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 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
- 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
- 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
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 compound, and a preparation method and application thereof, wherein the supported gold catalyst takes chloroauric acid aqueous solution as a raw material, hydrotalcite as a carrier and a thiol compound as a stabilizer, the gold catalyst can efficiently and highly selectively convert the alcohol/aldehyde compound into the ester compound in one step, the preparation process of the catalyst is simple, the catalyst can keep stable structure in the reaction process, has a certain sulfur resistance effect, and is favorable for industrial production and application in the future.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a supported gold catalyst for synthesizing esters by oxidizing and esterifying alcohol/aldehyde compounds, and preparation and application thereof.
Background
The reaction of synthesizing esters by one-step oxidative esterification of alcohol/aldehyde compounds is a very important chemical reaction because ester compounds are chemicals for synthesizing various fragrances, essences and copolymers. Taking Methyl Methacrylate (MMA) produced by oxidative esterification of methanol and Methacrolein (MAL) as an example, it is an important organic polymer monomer mainly used for the synthesis of polymethyl methacrylate (PMMA, organic glass). In recent years, with the rapid development of the domestic decoration industry, the construction industry and the IT industry, the market demand for PMMA has been increasing.
At present, the industrial MMA production mainly adopts an Acetone Cyanohydrin (ACH) method. The method uses hydrocyanic acid, sulfuric acid and caustic soda as raw materials, and generates a large amount of ammonium bisulfate byproducts, so that the atomic utilization rate is low, and the method is a typical non-environment-friendly process. Isobutene can be obtained from the petroleum cracking process, and MMA produced by using the isobutene as a raw material has the advantages of simple process, high atomic utilization rate, environmental protection and energy conservation. The method mainly comprises two routes: oxidation and direct methylation. The former is oxidized from isobutylene to MAL, which is then oxidized to methacrylic acid (MAA), which is then reacted with methanol to produce MMA. The direct methylation method avoids the direct generation of MAA, and reduces the problems of equipment corrosion, environmental pollution, product separation and the like.
MAL oxidative esterification studies initially employed H 2 O 2 Or a homogeneous reaction system catalyzed by peracetic acid [ R.Gopinath, B.K.Patel, org.Lett.,2000,2,577-579 ].]After oxygen-containing gas is introduced as an oxidant, the catalyst is gradually transferred to a heterogeneous catalyst which takes noble metal Pd or Au as an active component and is added with different auxiliary agents. Compared with homogeneous catalyst, the heterogeneous catalyst has the advantages of less side products, mild reaction condition, easy separation and reuse, continuous operation, etc.
A series of palladium-based catalysts developed by Asahi Kasei Corp have been studied in laboratory to obtain a good catalytic effect [ CN 108607550A ], but Pd as an active ingredient has a high catalytic activity but the selectivity of the target product is not high, so that it is necessary to add auxiliaries such as Pb and Bi to improve the selectivity [ C.Liu, J.Wang, L.Meng, angew.Chem.Int.Ed.,2011,50,5144-5148 ]. However, the addition of additives such as Pb and Bi causes environmental pollution, so that the need for efficient and highly selective green heterogeneous catalysts is a problem to be solved.
The Japan Xudio chemical company developed a nano gold catalyst (Au@NiO) having a core-shell structure in later studies x )[K.Suzuki,T.Yamaguchi,K.Matsushita,et al.ACS Catal.,2013,3,1845-1849.]They found that the catalyst can efficiently catalyze the oxidation and 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 conversion rate of the catalyst in application is low, about 60%, and the preparation technology and the catalyst cost are high, so that the catalyst is not suitable for industrial production.
Based on the analysis, the one-step oxidation and esterification reaction of the methacrolein and the methanol is a key link of the process for preparing the methyl methacrylate from the isobutene, and the development of the green and high-efficiency supported catalyst for synthesizing the ester by the oxidation and esterification of the alcohol/aldehyde compound has 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 be used for efficiently and selectively converting the alcohol/aldehyde compound into an 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 favorable for industrial production and application in the future.
In order to realize the scheme, the invention adopts the following technical scheme:
the supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compounds takes chloroauric acid aqueous solution as a raw material, takes hydrotalcite as a carrier, takes a thiol 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 0.1-20wt% and the mass fraction of the sulfur is 0.01-10wt%.
Preferably, the thiol-containing compound is selected from one or more of cysteine, homocysteine, glutathione, captopril, dodecyl mercaptan, phenethyl mercaptan or hexyl mercaptan.
Preferably, the gold catalyst has an average particle diameter of 1 to 5nm.
The invention also relates to a preparation method of the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound, which adopts the following technical scheme:
a preparation method of a supported gold catalyst for synthesizing esters by oxidative esterification of alcohol/aldehyde compounds, the method one comprises the following steps: taking a proper amount of chloroauric acid aqueous solution, regulating the pH value to 7-10 by using NaOH solution, adding a hydrotalcite carrier, stirring for reaction, carrying out suction filtration and washing on the suspension, then dispersing a filter cake in a proper amount of ultrapure water, adding a certain amount of thiol compound under stirring, carrying out suction filtration and washing on the liquid after stirring for reaction, and drying and roasting the obtained filter cake to obtain the supported gold catalyst, wherein the molar ratio of hydrotalcite to thiol compound to chloroauric acid is 100-500: 0.01 to 1.0:1, preferably 100 to 200:0.1 to 0.5:1.
or a second method: dissolving chloroauric acid, thiol compound, naOH solution and NaBH by sol-gel method 4 Sequentially adding the solution into a container, and controlling the thiol compound, naOH and NaBH 4 The molar ratio of the gold and the Au is 1 to 4 respectively: 50-100: 1 to 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, V Ethanol /V Water and its preparation method =2 to 6:1, freeze-drying the obtained black solid, dissolving the dried crystal (thiol-stabilized gold atom clusters) in water or acetone solution, then soaking or adsorbing the solution on a hydrotalcite carrier, and drying and roasting the solution to obtain the supported gold catalyst.
The hydrotalcite carrier is prepared through adding water into zinc nitrate, magnesium nitrate, nickel nitrate, cobalt nitrate or aluminum nitrate in certain weight proportion of zinc, magnesium, nickel or cobalt to aluminum in the molar ratio of 1 to 3-3 to 1 to prepare solution A, and taking certain amount of NaOH and Na 2 CO 3 Adding deionized water into the solid to prepare a mixed solution which is denoted as a solution B, and stirring the solution B and the solution A in a water bath according to a ratio of 1:1, stirring and aging at the temperature, carrying out suction filtration and washing on the aged solution by using a large amount of deionized water, drying the obtained filter cake in an oven, and grinding the dried solid into fine powder with 100 meshes; the total mass of the metal nitrate accounts for 10-30wt% of the solution A, and the mol ratio of NaOH to nitrate is 5-7: 1, na 2 CO 3 The mole ratio of the solid to the nitrate is 1-3: 1.
the invention also relates to application of the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound, which adopts the following technical scheme:
the application of supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compound includes such steps as adding aldehyde compound and alcohol compound to reactor, adding supported gold catalyst, displacing air in reactor with nitrogen, filling oxygen-containing gas, heating reactor, monitoring temp, magnetic stirring or mechanical stirring, mixing solution with gas, cooling, releasing residual gas, separating catalyst from reaction liquid, and analyzing reactant and product by chromatography.
Preferably, the temperature is 50-120 ℃, the oxygen partial pressure is 0.1-1MPa, and the molar ratio of the aldol is 8-50:1, the molar ratio of aldehyde to gold in the catalyst is 1-10 3 ：1。
The application of supported gold catalyst for synthesizing ester by using alcohol/aldehyde compound oxidation and esterification includes adding a certain quantity of supported gold catalyst into fixed bed reactor, then 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, using heat sensor to monitor internal and external temp. of the reactor, after the temp. is raised to the specified temp., making a certain quantity of aldehyde compound and alcohol compound into reaction solution, using double-plunger liquid pump to make the reaction solution be injected into reaction system, after a certain period of reaction, the reaction solution is cooled from fixed bed reactor to a cold tank, and the product is discharged from cold tank and analyzed by means of gas chromatograph.
Preferably, the temperature is 50-120 ℃, the oxygen partial pressure is 0.1-1MPa, and the molar ratio of the aldol is 8-50:1, the molar ratio of aldehyde to gold in the catalyst is 1-10 3 ：1。
Preferably, 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.
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 and esterification reaction of alcohol/aldehyde compounds, and can obtain the aldehyde conversion rate of more than 90 percent and the ester selectivity of more than 80 percent. And the catalyst can keep stable structure without aggregation when being applied to reaction.
Drawings
FIG. 1 is a graph showing the particle diameter distribution of the supported gold catalysts prepared in examples 1, 6, 34 and 35, (a) Au-S/Zn 3 Al-HT；(b)Au-S/Mg 3 Al-HT；(c)Au 25 /Zn 3 Al-HT；(d)Au 25 /Mg 3 Al-HT。
FIG. 2 shows the conversion of MAL and the selectivity of MMA at different reaction times in example 5.
FIG. 3 is a graph showing the effect of oxygen pressure on reaction rate and selectivity to target product in example 5.
Detailed Description
The following examples illustrate the invention further without limiting the scope of the invention.
Example 1:
the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound takes zinc-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 3:1; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
Preparation of hydrotalcite carrier: zn (NO) 3 ) 2 ·6H 2 O(0.21mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol) was added to a beaker, 200mL of deionized water was added to prepare solution A, and NaOH (0.438 mol) and Na were taken 2 CO 3 (0.113 mol) was added to a beaker, and 200mL of deionized water was taken and dissolved with stirring to prepare solution B. Slowly dropwise adding the solution A into the solution B by using a constant flow pump under the condition of stirring in a water bath at 70 ℃, controlling the flow rate to be 3mL/min, stirring and aging for 24 hours at the temperature, washing with a large amount of deionized water after aging, filtering, drying the obtained filter cake at 70 ℃, and grinding into 100-mesh powder for later use.
Preparation of the catalyst: taking 1.02mL of chloroauric acid solution (0.1 mol/L), diluting with 20mL of deionized water, adjusting the pH value to about 9, adding 2g of zinc-aluminum hydrotalcite carrier (molar ratio Zn: al=3:1), stirring for reaction for 12h, obtaining a solid through suction filtration and washing, dispersing the solid in the deionized water, adding 9.5mg of cysteine, stirring for 1h, drying and roasting the solid obtained through suction filtration, and finally obtaining the supported gold catalyst with the average particle size of 1.1nm.
Application of supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compound
Oxidation and esterification reaction: the one-step oxidation esterification of alcohol/aldehyde is carried out in a 15mL stainless steel high-pressure reaction kettle, 5mL (123.6 mmol) of methanol, 396 mu L (4.8 mmol) of 95% methacrolein, 121 mu L of internal standard o-xylene and Au-S/Zn are added into the kettle 3 0.1g of Al-HT catalyst (molar quantity of gold 0.005 mmol). Oxygen is filled in to 0.3MPa, the reaction is carried out under the stirring of 80 ℃ water bath, the reaction is carried out for 2 hours, the product is detected by a gas chromatograph after the reaction is finished, the conversion rate of the obtained methacrolein is 90%, and the selectivity of the methyl methacrylate is 95%.
The cysteine in example 1 may be replaced by homocysteine, glutathione, captopril, dodecyl mercaptan, phenethyl mercaptan or hexyl mercaptan.
Example 2:
the supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 2:1; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Zn (NO 3 ) 2 ·6H 2 O(0.14mol g)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal mole ratio of the obtained zinc-aluminum hydrotalcite is Zn/Al=2:1, the average particle size of the prepared supported gold catalyst is 1.3nm, the conversion rate of the obtained methacrolein is 92%, and the selectivity of the methyl methacrylate is 96%.
Example 3:
the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound takes zinc-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1:1; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Zn (NO 3 ) 2 ·6H 2 O(0.07mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal mole ratio of the obtained zinc-aluminum hydrotalcite is Zn/Al=1:1, the average particle size of the prepared supported gold catalyst is 1.5nm, the conversion rate of the obtained methacrolein is 85%, and the selectivity of the methyl methacrylate is 92%.
Example 4:
the supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1:2; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Zn (NO 3 ) 2 ·6H 2 O(0.035mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal mole ratio of the obtained zinc-aluminum hydrotalcite is Zn/Al=1:2, the average particle size of the prepared supported gold catalyst is 1.6nm, the conversion rate of the obtained methacrolein is 82%, and the selectivity of the methyl methacrylate is 90%.
Example 5:
the supported gold catalyst for synthesizing ester by oxidation and esterification of alcohol/aldehyde compounds takes zinc-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of zinc to aluminum is 1:3; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Zn (NO 3 ) 2 ·6H 2 O(0.023mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal mole ratio of the obtained zinc-aluminum hydrotalcite is Zn/Al=1:3, the average particle size of the prepared supported gold catalyst is 1.9nm, the conversion rate of the obtained methacrolein is 65%, and the selectivity of the methyl methacrylate is 81%.
Example 6:
the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound takes magnesium aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of magnesium to aluminum is 3:1; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Mg (NO 3 ) 2 ·6H 2 O(0.021mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal molar ratio of the obtained magnesium aluminum hydrotalcite is Mg/Al=3:1, and the obtained catalyst is expressed as Au-S/Mg 3 Al-HT, with an average particle size of 1.1nm, gave a conversion of 88% of methacrolein and a selectivity of 77% of methyl methacrylate.
Example 7:
the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound takes nickel-aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of nickel to aluminum is 3:1; the mass fraction of active component gold is 1.0wt%, and the mass fraction of sulfur is 0.1wt%
In comparison with example 1, the difference is that Ni (NO 3 ) 2 ·6H 2 O(0.021mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), the metal molar ratio of the obtained nickel aluminum hydrotalcite is Ni/Al=3:1, and the obtained catalyst is expressed as Au-S/Ni 3 Al-HT, with an average particle size of 2.1nm, gave a conversion of 92% of methacrolein and a selectivity of 65% for methyl methacrylate.
Example 8:
the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound takes cobalt aluminum hydrotalcite as a carrier, cysteine as a stabilizer, and the molar ratio of cobalt to aluminum is 3:1; the mass fraction of the active component gold is 1.0wt% and the mass fraction of the sulfur is 0.1wt%.
In comparison with example 1, the difference is that Co (NO 3 ) 2 ·6H 2 O(0.021mol)、Al(NO 3 ) 3 ·9H 2 O (0.07 mol), gold of the obtained cobalt aluminum hydrotalciteThe generic molar ratio was Co/al=3:1, and the catalyst obtained was expressed as Au-S/Co 3 Al-HT, with an average particle size of 2.0nm, gave a conversion of methacrolein of 86% and a selectivity to methyl methacrylate of 85%.
Example 9:
compared with example 1, the difference is that no thiol-containing protective agent is 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 example 2, the difference is that no thiol-containing protective agent is 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 example 3, the difference is that no thiol-containing protective agent is added in the catalyst preparation process, the particle size of the obtained supported gold catalyst is 4.2nm, the conversion rate of methacrolein is 20%, and the selectivity of methyl methacrylate is 39%.
Example 12:
compared with example 6, the difference is that no thiol-containing protective agent is added in the catalyst preparation process, 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 no thiol-containing protective agent is added in the catalyst preparation process, 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 example 8, the difference is that no thiol-containing protective agent is 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 adding amount of cysteine in the catalyst preparation process is 4.5mg, the mass fraction of sulfur is 0.05wt%, the average particle diameter of the prepared supported gold catalyst is 2.0nm, the conversion rate of the obtained methacrolein is 90%, and the selectivity of methyl methacrylate is 92%.
Example 16:
compared with example 1, the difference is that the adding amount of cysteine in the catalyst preparation process is 19.2mg, the mass fraction of sulfur is 0.25wt%, the average particle diameter of the prepared supported gold catalyst is 1.6nm, the conversion rate of the obtained methacrolein is 88%, and the selectivity of methyl methacrylate is 90%.
Example 17:
compared with example 1, the difference is that the adding amount of cysteine in the catalyst preparation process is 45.1mg, the mass fraction of sulfur is 0.5wt%, the average particle diameter of the prepared supported gold catalyst is 1.5nm, the conversion rate of the obtained methacrolein is 42%, and the selectivity of methyl methacrylate is 88%.
Example 18:
compared with example 1, the difference is that the thiol protecting agent added in the catalyst preparation process is 5.0mg of homocysteine, the mass fraction of sulfur is 0.1wt%, the average particle diameter of the prepared supported gold catalyst is 1.8nm, the conversion rate of the obtained methacrolein is 91%, and the selectivity of methyl methacrylate is 92%.
Example 19:
compared with example 1, the difference is that the thiol protecting agent added in the catalyst preparation process is 11.4mg of glutathione, the mass fraction of sulfur is 0.1wt%, 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 methyl methacrylate is 88%.
Example 20:
compared with example 1, the difference is that the thiol protecting agent added in the catalyst preparation process is captopril 8.1mg, the mass fraction of sulfur is 0.1wt%, 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 methyl methacrylate is 85%.
Example 21:
compared with example 1, the difference is that 5.1mL of chloroauric acid solution (0.1 mol/L) and 47.5mg of cysteine are added in the preparation process of the catalyst, the mass fraction of active component gold is 5.0wt%, the mass fraction of sulfur is 0.5wt%, the average particle size of the prepared supported gold catalyst is 1.9nm, 0.05g of the catalyst is taken in the oxidation and esterification reaction process, the conversion rate of the obtained methacrolein is 87%, and the selectivity of methyl methacrylate is 90%.
Example 22:
compared with example 1, the difference is that 20.4mL of chloroauric acid solution (0.1 mol/L) and 190mg of cysteine are added in the preparation process of the catalyst, the mass fraction of active component gold is 20wt%, the mass fraction of sulfur is 2wt%, the average particle size of the prepared supported gold catalyst is 2.6nm, 0.025g of catalyst is taken in the oxidation esterification reaction process, the conversion rate of the obtained methacrolein is 76%, and the selectivity of methyl methacrylate is 90%.
Example 23:
compared with example 22, the difference is that 950mg of cysteine, 20wt% of active component gold and 10wt% of sulfur are added in the preparation process of the catalyst, the average particle size of the prepared supported gold catalyst is 2.5nm, 0.025g of the catalyst is taken 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:
the difference compared with example 1 was that the amount of the catalyst added in the oxidative esterification reaction was 0.05g, the conversion of methacrolein was 62%, and the selectivity for methyl methacrylate was 91%.
Example 25:
the difference from example 1 is that the oxygen pressure charged in the oxidative esterification reaction was 0.5MPa, the conversion of methacrolein was 92%, and the selectivity for methyl methacrylate was 94%.
Example 26:
the difference compared with example 1 is that the oxygen pressure charged in the oxidative esterification reaction is 0.2MPa, the conversion of methacrolein is 88%, and the selectivity of methyl methacrylate is 90%.
Example 27:
the difference from example 1 is that the reaction temperature in the oxidative esterification reaction was 60℃and the conversion of methacrolein was 80% and the selectivity for methyl methacrylate was 93%.
Example 28:
the difference from example 1 is that the reaction temperature in the oxidative esterification reaction was 100℃and the conversion of methacrolein was 96% and the selectivity for methyl methacrylate was 94%.
Example 29:
the difference compared with example 1 is that the aldehyde added in the oxidative esterification reaction is 450. Mu.L of isobutyraldehyde, the obtained isobutyraldehyde conversion is 95%, and the selectivity of methyl isobutyrate is 98.5%.
Example 30:
the difference compared with example 1 is that the aldehyde added in the oxidative esterification reaction is 660. Mu.L of cinnamaldehyde, the conversion rate of the obtained cinnamaldehyde is 75%, and the selectivity of methyl cinnamate is 80%.
Example 31:
the difference compared with example 1 is that 660. Mu.L of benzaldehyde was added in the oxidative esterification reaction, the conversion of benzaldehyde was 80% and the selectivity of methyl benzoate was 65%.
Example 32:
the difference compared with example 1 is that the aldehyde added in the oxidative esterification reaction is crotonaldehyde 395. Mu.L, the conversion of crotonaldehyde is 75% and the selectivity of methyl crotonate is 65%.
Example 33:
the difference compared with example 1 is that the oxidative esterificationThe reaction is carried out in a continuous fixed bed reactor, the reaction liquid is 10 percent of methylacrolein/methanol solution with volume fraction, and Au-S/Zn 3 Al-HT (obtained from example 1) catalyst 0.5g, oxygen partial pressure 0.2MPa, gas flow rate 20mL/min, reaction temperature 80 ℃, reaction time 12h were sampled, and the product was detected by gas chromatograph, resulting in a methacrolein conversion of 95% and a methyl methacrylate selectivity of 95%.
Example 34:
in comparison with example 30, the difference is that the catalyst is Au/Zn without thiol protecting agent 3 0.5g of Al-HT catalyst, 75% conversion of methacrolein and 90% selectivity to methyl methacrylate were obtained.
Example 35:
in comparison with example 30, the difference is that the catalyst is Au-S/Mg 3 Al-HT (from example 6) catalyst 0.5g, gives a conversion of methacrolein of 90% and a selectivity to methyl methacrylate of 75%.
Example 36:
in comparison with example 30, the difference is that the catalyst is Au-S/Ni 3 Al-HT (from example 7) catalyst 0.5g, gives a conversion of methacrolein of 95% and a selectivity of methyl methacrylate of 77%.
Example 37:
in comparison with example 30, the difference is that the catalyst is Au-S/Co 3 Al-HT (from example 8) catalyst 0.5g, gives a conversion of methacrolein of 85% and a selectivity to methyl methacrylate of 86%.
Example 38:
in comparison with example 30, the difference is that the catalyst is Au 25 /Zn 3 0.5g of Al-HT, wherein Au 25 /Zn 3 Al-HT catalysts are prepared by impregnating gold clusters (Au 25 ) Carried by Zn 3 Drying and roasting the Al-HT carrier to obtain Au 25 The atomic cluster is obtained by taking cysteine as a stabilizer and sodium borohydride as a reducing agent, and the specific preparation method comprises the following steps: taking 0.5mL of prepared chlorine in advanceGold acid solution (19.12 g) Au (L) was added with 20mL of ultrapure and 15mL of cysteine solution, the color of the solution was observed to change from pale yellow to deep yellow and finally to milky white, then 3mL of 1M NaOH solution was rapidly added to the flask, and after the solution became clear, freshly prepared NaBH was added 4 (0.2M NaOH) solution, stirring at room temperature for reaction for 3 hr to obtain brown black solution, centrifuging with 3/1 ethanol/water solution to obtain black solid, and lyophilizing for 12 hr to obtain Au 25 The average particle size of the supported gold catalyst prepared by the method is 1.7nm, the conversion rate of the methacrolein obtained by using the catalyst in the oxidation and esterification reaction of the methacrolein and the methanol is 95%, and the selectivity of the methyl methacrylate is 96%.
Example 39:
in comparison with example 35, the difference is that the catalyst is Au 25 /Mg 3 0.5g of Al-HT, wherein Au 25 /Mg 3 The Al-HT catalyst is prepared by impregnating Au 25 The clusters are supported on Mg 3 The catalyst is obtained by drying and roasting an Al-HT carrier, and in the oxidation and esterification reaction of methacrolein/methanol on a fixed bed, the average particle diameter of a 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 only intended to illustrate the invention and other embodiments of the invention are possible. But all technical schemes formed by adopting equivalent substitution or equivalent deformation are within the protection scope of the invention.
Claims (5)
1. The application of the supported gold catalyst for synthesizing the ester by oxidizing and esterifying the alcohol/aldehyde compound is characterized by comprising the steps of adding a certain amount of aldehyde compound and alcohol compound into a reaction kettle, adding a certain amount of supported gold catalyst, then replacing air in the kettle by nitrogen, then filling a certain amount of oxygen-containing gas into the kettle, heating the reaction kettle in heating equipment, monitoring the temperature in the kettle by a heat sensor, starting magnetic stirring or mechanical stirring after the temperature is raised to a specified temperature, fully mixing the solution in the kettle with the gas, cooling the kettle body in a cooling medium after a period of reaction, discharging the residual gas in the kettle, separating the catalyst from a reaction liquid, and analyzing reactants and products by using chromatography;
the catalyst takes chloroauric acid aqueous solution as a raw material, hydrotalcite as a carrier and a thiol-containing compound as a stabilizer, 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 active component gold is 0.1-20wt% and the mass fraction of sulfur is 0.01-10wt%, the catalyst is prepared by adopting a first method or a second method,
the method comprises the following steps: taking a proper amount of chloroauric acid aqueous solution, regulating the pH value to 7-10 by using a NaOH solution, adding a hydrotalcite carrier, stirring for reaction, carrying out suction filtration and washing on the suspension, then dispersing a filter cake in a proper amount of ultrapure water, adding a certain amount of thiol compound under the stirring condition, carrying out suction filtration and washing on the liquid after stirring for reaction, and drying and roasting the obtained filter cake to obtain the supported gold catalyst, wherein the molar ratio of hydrotalcite to thiol compound to chloroauric acid is 100-500: 0.01 to 1.0:1, a step of;
the second method is as follows: dissolving chloroauric acid, thiol compound, naOH solution and NaBH by sol-gel method 4 Sequentially adding the solution into a container, and controlling the thiol compound, naOH and NaBH 4 The molar ratio of the gold and the Au is 1 to 4 respectively: 50-100: 1 to 10:1, centrifugally washing the obtained product with a mixed solution of ethanol and water, V Ethanol /V Water and its preparation method =2 to 6: and 1, freeze-drying the obtained black solid, obtaining crystal of thiol-stable gold cluster after drying, dissolving the crystal in water or acetone solution, then dipping or adsorbing the crystal on a hydrotalcite carrier, and obtaining the supported gold catalyst after drying and roasting.
2. The application of the supported gold catalyst for synthesizing ester by oxidizing and esterifying alcohol/aldehyde compound comprises the steps of adding a certain amount of supported gold catalyst into a fixed bed reactor, then replacing gas in a pipeline by nitrogen, then introducing a certain amount of oxygen-containing gas into the reactor, controlling the pressure and flow of the gas through a back pressure valve and a mass flowmeter, monitoring the internal and external temperature of the reactor through a heat sensor, preparing a reaction solution by a certain amount of aldehyde compound and alcohol compound into a reaction solution after the temperature is increased to a specified temperature, injecting the reaction solution into a reaction system through a double-plunger liquid pump, cooling the reaction solution from the fixed bed reactor to a cold tank, taking out a product from the cold tank, and analyzing the reactant and the product through a gas chromatograph;
the catalyst takes chloroauric acid aqueous solution as a raw material, hydrotalcite as a carrier and a thiol-containing compound as a stabilizer, 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 active component gold is 0.1-20wt% and the mass fraction of sulfur is 0.01-10wt%, the catalyst is prepared by adopting a first method or a second method,
the method comprises the following steps: taking a proper amount of chloroauric acid aqueous solution, regulating the pH value to 7-10 by using a NaOH solution, adding a hydrotalcite carrier, stirring for reaction, carrying out suction filtration and washing on the suspension, then dispersing a filter cake in a proper amount of ultrapure water, adding a certain amount of thiol compound under the stirring condition, carrying out suction filtration and washing on the liquid after stirring for reaction, and drying and roasting the obtained filter cake to obtain the supported gold catalyst, wherein the molar ratio of hydrotalcite to thiol compound to chloroauric acid is 100-500: 0.01 to 1.0:1, a step of;
the second method is as follows: dissolving chloroauric acid, thiol compound, naOH solution and NaBH by sol-gel method 4 Sequentially adding the solution into a container, and controlling the thiol compound, naOH and NaBH 4 The molar ratio of the gold and the Au is 1 to 4 respectively: 50-100: 1 to 10:1, centrifugally washing the obtained product with a mixed solution of ethanol and water, V Ethanol /V Water and its preparation method =2 to 6:1, freeze-drying the black solid to obtain crystal of thiol stable gold atom cluster, dissolving in water or acetone solution, soaking or adsorbing on hydrotalcite carrier, drying, and roasting to obtain loadA gold-type catalyst.
3. The use of a supported gold catalyst for the oxidative esterification of alcohol/aldehyde compounds to esters according to claim 1 or 2, wherein the thiol-containing compound is selected from one or more of cysteine, homocysteine, glutathione, captopril, dodecyl mercaptan, phenethyl mercaptan or hexyl mercaptan.
4. The use of the supported gold catalyst for the oxidative esterification of alcohol/aldehyde compounds to esters according to claim 1 or 2, characterized in that the temperature is 50-120 ℃, the partial pressure of oxygen is 0.1-1MPa, the molar ratio of aldol is 8-50:1, the molar ratio of aldehyde to gold in the catalyst is 1-10 3 ：1。
5. The use of a supported gold catalyst for the oxidative esterification of alcohol/aldehyde compounds to synthesize esters according to claim 1 or 2, wherein the aldehyde compounds comprise one or more of isobutyraldehyde, methacrolein, crotonaldehyde, cinnamaldehyde, benzaldehyde, and the alcohol compounds comprise one or more of methanol, ethanol, isopropanol, isobutanol, butanol, cinnamyl alcohol, benzyl alcohol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029228A1 (en) * | 2008-09-15 | 2010-03-18 | Ifp | Method for preparing alcohol esters from triglycerides and alcohols using a heterogeneous catalyst containing a mesostructured zinc silicic solid |
| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
| CN107857692A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of efficient catalytic unsaturation aldehyde ketone selection is hydrogenated to the gold atom cluster catalyst of unsaturated alcohol |
| CN107899575A (en) * | 2017-11-20 | 2018-04-13 | 山东理工大学 | Nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010029228A1 (en) * | 2008-09-15 | 2010-03-18 | Ifp | Method for preparing alcohol esters from triglycerides and alcohols using a heterogeneous catalyst containing a mesostructured zinc silicic solid |
| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
| CN107857692A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of efficient catalytic unsaturation aldehyde ketone selection is hydrogenated to the gold atom cluster catalyst of unsaturated alcohol |
| CN107899575A (en) * | 2017-11-20 | 2018-04-13 | 山东理工大学 | Nano catalyst for one step oxidative esterification of aldehyde and alcohol generation ester and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 催化剂的制备及其氧化酯化反应催化性能研究;李冰等;《中国化学会第30届学术年会摘要集-第三十七分会：纳米催化》;20160731;第80页 * |
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