CN113368867A - 一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法 - Google Patents
一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法 Download PDFInfo
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- CN113368867A CN113368867A CN202110703956.8A CN202110703956A CN113368867A CN 113368867 A CN113368867 A CN 113368867A CN 202110703956 A CN202110703956 A CN 202110703956A CN 113368867 A CN113368867 A CN 113368867A
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- Prior art keywords
- catalyst
- ultrasonic
- nitrate
- silver
- methyl glycolate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims description 14
- 230000015572 biosynthetic process Effects 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 30
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 239000010931 gold Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 239000011591 potassium Substances 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- OMSFUHVZHUZHAW-UHFFFAOYSA-N [Ag].[Mo] Chemical compound [Ag].[Mo] OMSFUHVZHUZHAW-UHFFFAOYSA-N 0.000 claims description 11
- 239000012018 catalyst precursor Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical group [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 4
- 239000012752 auxiliary agent Substances 0.000 claims 4
- 150000002751 molybdenum Chemical class 0.000 claims 4
- 239000002243 precursor Substances 0.000 claims 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 2
- 238000002604 ultrasonography Methods 0.000 claims 2
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000428813 Gomphrena Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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Abstract
本发明公开了一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法,该方法首次采用超声波‑浸渍法制备乙醇酸甲酯催化剂,用于草酸二甲酯加氢合成乙醇酸甲酯催化剂。制备方法为,采用超声波辅助浸渍法制备主活性组分为银和钼,助活性组分为铁、钾、钠、钯、铂、钌、金、钡、铜、镁、镍、钴、锰、锌、钙、铈、镧、锆、铝、铬中的至少一种或多种,载体为硅、铝、钛源的草酸二甲酯加氢合成乙醇酸甲酯催化剂,方法操作简单,负载效果好,催化剂具有较高的稳定性和活性,在草酸二甲酯加氢合成乙醇酸甲酯过程中显现出良好的催化剂性能。
Description
技术领域
本发明属于化工用催化剂制备领域,具体涉及一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法。
背景技术
乙醇酸甲酯(MG)由于兼具醇和酯的化学性质,广泛应用于化工医药领域,引起了研究者的关注。多种生成MG的方法已有报道,但反应条件严苛,产量较低以及对依赖石油资源等缺点限制了它们的发展。相比而言,草酸二甲酯(DMO)部分加氢制MG凭借着简单的工艺,较低的成本以及环保的优势,最具发展前景。
乙醇酸甲酯分子中有一个羟基和一个羧基,同时具有有机酸和醇的性质。乙醇酸甲酯作为一种非常重要的有机合成和药物合成中间体,被广泛应用于化工、农药、医药、香料、饲料及染料等许多领域,还可作为一种纤维素、树脂、橡胶等的优良溶剂。
专利CN106944065A,专利申请号CN201710186879.7,发明人王斌,邢周昊,于克生,梁鹏,吴维果,胡晓鸣,吴晓金,《石墨烯负载镍加氢催化剂的制备方法和应用》制备方法为,在一定的有机胺插层剂存在的条件下超声剥离氧化石墨获得石墨烯,并通过蒸氨法负载镍,得到加氢催化剂,具有一定的催化活性和稳定性。
专利CN112209832A,专利申请号CN201910634942.8,发明人龚海燕,刘俊涛,孙凤侠,《一种草酸酯合成乙醇酸酯的方法》提供了一种草酸酯合成乙醇酸酯的方法,包括在催化剂的存在下,使草酸酯与包含氢气和一氧化碳的混合气体接触反应生成乙醇酸酯,气体进料为氢气和一氧化碳混合体。
专利CN111437828A,专利申请号CN202010217964.7,发明人姚元根,林凌,朱凌彬,李斐,陈冲冲,黄隆,杨锦霞,孙明玲,《一种合成乙醇酸甲酯用银基催化剂及其制备方法》公开了以硝酸银为银源、以硝酸镍为镍源、以稀土元素的硝酸盐为稀土元素来源,以正硅酸四乙本酯为硅源、在制备过程中引入有机物,采用溶胶凝胶法和浸渍法联用制备银基催化剂。
专利CN105363438A,专利申请号CN201410428723.1,发明人龚海燕,李蕾,《合成乙醇酸酯催化剂、制备方法及其用途》通过采用浸渍法制备包括以下组分活性组分银或其氧化物;选自钯、铂、钌、钡、铜、镁、镍、钴、锰或钼中的至少一种金属或氧化物;选自二氧化硅、氧化铝、二氧化锆、二氧化钛、分子筛中至少一种为载体。
专利CN105435810A,专利申请号CN201410427875.X,发明人龚海燕,宋海峰,《草酸酯加氢制乙醇酸酯催化剂活化方法》将浸渍烘干好的含银和二氧化硅的催化剂前体在含氧气体氛围下分段热处理;用氢气或含氢气的惰性气体进行程序升温还原。
专利CN110142048A,发明人***,赵传军,《一种用于草酸二甲酯加氢合成乙醇酸甲酯的银铜催化剂及其制备方法和使用方法》包括活性组分Ag、Cu和双金属氧化物载体,双金属氧化物分别为二价金属氧化物AO和三价金属氧化物B2O3,反应100h候测试结果为草酸二甲酯转化率为86.1%,乙醇酸甲酯选择性为84.8%。
因此综上所述,已公开的制备乙醇酸甲酯催化剂的专利多为单独浸渍法或沉淀制备,具有一定的催化活性和稳定性,但还需进一步提升催化剂的活性和稳定性,延长催化剂使用寿命,使其能更好的应用于工业化生产。
发明内容
本发明提供一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法,该催化剂用于草酸二甲酯加氢制备乙醇酸甲酯,进一步提升催化剂的活性和稳定性,延长催化剂使用寿命。
本发明的技术方案为:以硅、铝、钛源为载体,通过超声波辅助浸渍法将银-钼盐浸渍于载体上,再以超声波辅助浸渍活性组分盐类,得到催化剂前驱体,催化剂前驱体经水热法洗涤、烘箱干燥、程序焙烧,制得最终目标催化剂。
本发明采用超声波辅助浸渍法制备主活性组分为银-钼,助活性组分为铁、钾、钠、钯、铂、钌、金、钡、铜、镁、镍、钴、锰、锌、钙、铈、镧、锆、铝、铬中的至少一种或多种,载体为硅、铝、钛源的草酸二甲酯加氢合成乙醇酸甲酯催化剂。其中所述的银-钼所占总催化剂的质量分数为2~35%,助活性组分占比3~15%,载体占比50~95%,总计100%;主活性组分和助活性组分均以单质计重,载体以固体质量计重。该催化剂具有制备方法简单、催化剂活性和稳定性高特点。
本发明提供一种超声法辅助合成乙醇酸甲酯的催化剂及其制备方法,包括以下步骤:1)根据所需制备的目标催化剂的主活性组分,将选自硝酸银、醋酸银、草酸银、硫酸银或乳酸银中的一种或多种和硝酸钼溶于去离子水,充分搅拌形成均匀溶液,均匀溶液的浓度为0.2~2mol/L。
2)根据所需制备的目标催化剂的助活性组分,将选自硝酸铁、硝酸钾、硝酸钠、硝酸钯、氯铂酸、三氯化钌、氯金酸、硝酸钡、硝酸铜、硝酸镁、硝酸镍、硝酸钴、硝酸锰、硝酸锌、硝酸钙、硝酸铈、硝酸镧、硝酸锆、硝酸铝、硝酸铬中的至少一种或多种溶于去离子水,充分搅拌形成混合溶液,混合溶液浓度为0.3~3mol/L。
3)根据所需制备的目标催化剂的载体,将选自硅溶胶、硅铝分子筛、三氧化二铝、二氧化钛、气相二氧化硅中的一种或多种溶于碱性溶液,充分搅拌,载体与碱性溶液比为1g:2~10mL。
4)根据所需制备的目标催化剂的载体的碱性溶液,所述的碱性溶液为氢氧化钠、氢氧化铝、碳酸氢钠、氨水、氯化铵、碳酸铵、尿素溶液的一种或多种,其浓度为0.1~1mol/L。
5)根据所需制备的目标催化剂,将1)溶液置于超声波频率为50kHz,功率2000W,时间为10min;将2)溶液置于超声波频率为50kHz,功率2000W,时间为15min;将3)溶液置于超声波频率为50 kHz,功率2000W,时间为20min。
6)根据所需制备的目标催化剂,将5)中的3)溶液置于5)中的1)形成浸渍液,将浸渍液置于超声仪中,超声波频率为80kHz,功率3000W,时间为1h。
7)根据所需制备的目标催化剂,将5)中的2)加入6)浸渍液,将浸渍液置于超声仪中,超声波频率为80 kHz,功率3000W,时间为2h。
8)根据所需制备的目标催化剂,7)的浸渍液采用水热法洗至中性,得到目标催化剂前驱体,水热温度为60~100℃。
9)根据所需制备的目标催化剂,8)催化剂前驱体置于烘箱干燥,烘箱温度50~150℃,烘干时间为500~1000min。
10)根据所需制备的目标催化剂,9)程序焙烧,程序为室温至200℃,每min升1℃,200℃至350℃,每2min升1℃,温度达到350℃保持5h。
11)根据权所述的合成乙醇酸甲酯催化剂,其评价条件为催化剂装填至列式固定床反应器,以氢气流速50~80mL/min气氛下,以每分钟5℃从室温升温至260℃,再将温度降至进物料反应要求温度,通入配置好的质量体积数0.08%的DMO甲醇溶液,在2.0MPa***压力,草酸二甲酯的液时空速为0.8g(DMO)/g(cat)·h将反应温度控制在180~230℃。草酸二甲酯的转化率可达到99%以上,乙醇酸甲酯的选择性达到89%以上。
本发明在制备过程采用超声波辅助浸渍法的制备方法,在主活性组分溶解、助活性组分溶解过程中实现了主活性组分和助活性组分均匀分散;在高效均匀分散主和助活性组分的同时,并均匀地将主和助活性组分引入至载体表面和载体孔道,经粒度分析可知,其粒度小于只采用浸渍法制备的催化剂20%,同时超声波的辅助作用,抑制活性组分团聚,粒度颗粒均匀,而形成高性能负载型银-钼基催化剂,草酸二甲酯转化率可提高3%,乙醇酸甲酯的选择性可提高5%。银-钼盐作为主活性组分,在草酸二甲酯加氢合成乙醇酸甲酯过程中,利于草酸二甲酯中C-O和C=O键的断裂以及控制草酸二甲酯加氢的速率,控制反应进程。制备的催化剂前驱体再经程序焙烧形成稳定的氧化物,得到的目标催化剂表现出更好的活性和稳定性。在一定的评价条件下,该目标催化剂表现出,草酸二甲酯具有更高的转化率,可达99%以上,乙醇酸甲酯具有更高的选择性,可达89%以上。
具体实施方式
实施例1:
1)将0.5 mol/L硝酸银和硝酸钼溶液在超声的状态下加入0.2g/mL碱改性气相二氧化硅载体,超声波频率为80kHz,功率3000W,时间为1h。
2)将0.4mol/L硝酸镍溶液,在超声的状态下加入1)中,超声波频率为80 kHz,功率3000W,时间为2h。
3)将上述超声浸渍后的混合溶液置于60℃水浴锅中,加入等体积去离子水进行洗涤,直至将溶液洗至中性。
4)将上述洗至中性的溶液过滤,得到固体,置于125℃烘箱中烘干900min。
5)将烘干的固体置于马弗炉程序升温焙烧,程序为室温至200℃,每min升1℃,200℃至350℃,每2min升1℃,温度达到350℃保持5h,后取出降至室温,得到目标催化剂,标注催化剂01。
6)上述催化剂评价条件为催化剂装填至列式固定床反应器,以氢气流速50~80mL/min气氛下,以每min5℃从室温升温至260℃,再将温度降至进物料反应要求温度,通入配置好的质量体积数0.08%的DMO甲醇溶液,在2.0MPa***压力,草酸二甲酯的液时空速为0.8g(DMO)/g(cat)·h将反应温度控制在180~230℃。
实施例2:
同实施例1,不同的是将1)中的0.5mol/L硝酸银溶液替换为0.8mol/L硝酸银溶液,其它步骤一样,所得催化剂标注催化剂02。
实施例3:
同实施例1,不同的是将1)中的0.4mol/L硝酸镍溶液,替换为0.5mol/L硝酸镍溶液,其它步骤一样,所得催化剂标注催化剂03。
实施例4:
同实施例1,不同的是将1)中的0.4mol/L硝酸镍溶液,替换为0.4mol/L硝酸钴溶液,其它步骤一样,所得催化剂标注催化剂04。
实施例5:
同实施例1,不同的是将1)中的0.4mol/L硝酸镍溶液,替换为0.5mol/L硝酸钴溶液,其它步骤一样,所得催化剂标注催化剂05。
实施例6:
同实施例1,不同的是将1)中的0.5mol/L硝酸银,替换为0.5mol/L醋酸银溶液,其它步骤一样,所得催化剂标注催化剂06。
在相同的评价条件下,各例催化剂活性评价见表1。
表1各例催化剂活性评价结果
实施例 | 主活性组分(mol/L) | 助活性组分(mol/L) | 最佳反应温度(℃) | 最佳氢酯比(mL/min) | 草酸二甲酯转化率(%) | 乙醇酸甲酯选择性(%) |
1 | 0.5 | 0.4 | 195 | 66 | 99.6 | 89.9 |
2 | 0.8 | 0.4 | 190 | 66 | 99.9 | 88.3 |
3 | 0.5 | 0.5 | 190 | 70 | 99.2 | 89.6 |
4 | 0.5 | 0.4 | 200 | 70 | 99.5 | 88.9 |
5 | 0.5 | 0.5 | 205 | 72 | 98.8 | 88.5 |
6 | 0.5 | 0.4 | 208 | 72 | 99.1 | 89.2 |
表1 结果表明,本发明所制备的催化剂最佳反应温度为195℃,最佳氢酯比66 mL/min,并且草酸二甲酯的转化率不小于99%,乙醇酸甲酯的转化率不小于89%,催化剂具有较高的活性和稳定性。
本实施例仅仅是对本发明的解释,其并不是对本发明的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本发明的权利要求范围内都受到专利法的保护。
Claims (10)
1.一种超声法辅助合成乙醇酸甲酯的催化剂制备方法,其特征在于包括以下步骤:
(1)对载体进行碱性处理,得到碱性载体;银盐和钼盐配置成银盐和钼盐的混合水溶液,银-钼混合水溶液;助活性组分配置成助剂溶液,备用,所述碱性载体、混合水溶液、助剂溶液的配置过程中用一定频率、功率、时间的超声波;
(2)采用超声波辅助浸渍法在步骤(1)中的碱性载体负载银-钼盐:取步骤(1)中一定量的碱性载体超声分散于去离子水中,依次加入银-钼混合水溶液和助剂溶液,采用超声波辅助浸渍,在10~50℃下超声波辅助浸渍1~10h,得到催化剂前驱体;
(3)采用水热法将步骤(2)中的前驱体洗涤至中性后,在室温下进行过滤,烘箱烘干,程序焙烧,得到碱性载体负载银-钼基催化剂,所述前驱体洗涤时用一定频率、功率、时间的超声波;
所述碱性载体的质量与去离子水的体积比为1g:20~110mL;所述银-钼盐质量和去离子水的体积比为1~20g:100~200mL;所述银-钼盐质量比为7:3;所述助剂的质量和去离子水的体积比为2~10g:100~200mL;在不同步骤用一定频率、功率、时间的超声波。
2.一种超声法辅助合成乙醇酸甲酯的催化剂,其特征在于所述催化剂主活性组分为银和钼的氧化物,助活性组分为铁、钾、钠、钯、铂、钌、金、钡、铜、镁、镍、钴、锰、锌、钙、铈、镧、锆、铝、铬中的氧化物至少一种或多种,载体为硅、铝、钛源的草酸二甲酯加氢合成乙醇酸甲酯催化剂,所述的银和钼所占总催化剂的质量分数为2~35%;助活性组分的元素质量分数为3~15%;载体的质量分数为50~95%,所述主活性组分、助活性组分和载体总质量分数是100%。
3.根据权利要求2所述的一种超声法辅助合成乙醇酸甲酯的催化剂,其特征在于所述的主活性组分来源于银盐,所述银盐为硝酸银、醋酸银、草酸银、硫酸银或乳酸银中的若干种,钼盐为硝酸钼。
4.根据权利要求2所述的一种超声法辅助合成乙醇酸甲酯的催化剂,其特征在于所述的助活性组分来源于硝酸铁、硝酸钾、硝酸钠、硝酸钯、氯铂酸、三氯化钌、氯金酸、硝酸钡、硝酸铜、硝酸镁、硝酸镍、硝酸钴、硝酸锰、硝酸锌、硝酸钙、硝酸铈、硝酸镧、硝酸锆、硝酸铝、硝酸铬中的若干种。
5.根据权利要求2所述的一种超声法辅助合成乙醇酸甲酯的催化剂,其特征在于所述的载体选自硅溶胶、硅铝分子筛、三氧化二铝、二氧化钛、气相二氧化硅中的若干种。
6.根据权利要求2所述的一种超声法辅助合成乙醇酸甲酯的催化剂,其特征在于所述的碱性溶液为氢氧化钠、氢氧化铝、碳酸氢钠、氨水、氯化铵、碳酸铵、尿素溶液的若干种。
7.根据权利要求1所述的一种超声法辅助合成乙醇酸甲酯的催化剂制备方法,其特征在于所述的碱性载体用超声分散于去离子水中时,超声波的频率为50 kHz,功率2000W,时间为20min。
8.根据权利要求1所述的一种超声法辅助合成乙醇酸甲酯的催化剂制备方法,其特征在于用超声波浸渍银-钼盐溶液时,超声波频率为50kHz,功率2000W,时间为10min。
9.根据权利要求1所述的一种超声法辅助合成乙醇酸甲酯的催化剂制备方法,其特征在于用超声波浸渍助剂溶液时,超声波频率为50kHz,功率2000W,时间为15min。
10.根据权利要求3所述的一种超声法辅助合成乙醇酸甲酯的催化剂制备方法,其特征在于超声波辅助浸渍是指用超声波等体积浸渍法、超声波过量浸渍、超声波少量浸渍和超声波沉淀法任一种。
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