CN114917923B - 一种负载型催化剂、制备方法及其应用 - Google Patents
一种负载型催化剂、制备方法及其应用 Download PDFInfo
- Publication number
- CN114917923B CN114917923B CN202110769256.9A CN202110769256A CN114917923B CN 114917923 B CN114917923 B CN 114917923B CN 202110769256 A CN202110769256 A CN 202110769256A CN 114917923 B CN114917923 B CN 114917923B
- Authority
- CN
- China
- Prior art keywords
- precursor
- catalyst
- supported catalyst
- solution
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 31
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 21
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 55
- 239000002243 precursor Substances 0.000 claims description 38
- 239000010931 gold Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- 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 14
- 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 14
- 239000011148 porous material Substances 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 229940076131 gold trichloride Drugs 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
- 229940033123 tannic acid Drugs 0.000 claims description 2
- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000003647 oxidation Effects 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 32
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910001020 Au alloy Inorganic materials 0.000 description 9
- 239000003353 gold alloy Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004323 potassium nitrate Substances 0.000 description 6
- 235000010333 potassium nitrate Nutrition 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PUCVSEVKFQLVKN-UHFFFAOYSA-N 2-methylpropan-2-ol;2-methylprop-1-ene Chemical compound CC(C)=C.CC(C)(C)O PUCVSEVKFQLVKN-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000006709 oxidative esterification reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种负载型催化剂、制备方法及其应用,所述负载型催化剂包括活性组分、载体;所述活性组分含有贵金属活性元素,所述贵金属活性元素包括Au、M;所述M选自Pt、Pd、Ru、Rh中的至少一种;所述载体为复合金属氧化物。将贵金属合金和氧化物载体以共沉积的方式生成催化剂。催化剂应用到叔丁醇(异丁烯)选择性氧化制甲基丙烯醛的反应中,可以在相对较低的温度下实现叔丁醇(异丁烯)到甲基丙烯醛的高效转化,转化率和选择性最高分别可达93%、96%,具有非常广阔的工业应用前景。
Description
技术领域
本发明涉及一种负载型催化剂、制备方法及其应用,属于催化剂制备与应用领域。
背景技术
甲基丙烯酸甲酯(MMA)由于其良好的物理化学性能,既是重要的有机化工原料,又可作为有机化工产品直接应用,因此被广泛应用于有机玻璃(PMMA)、涂料、皮革、甲基丙烯酸高级酯类等多种行业,市场前景十分广泛。
工业生产MMA的传统工艺主要是丙酮氰醇法(ACH法),其以丙酮和剧毒氢氰酸为原料,且反应过程中需使用高腐蚀性硫酸。因此此过程环境污染严重,原子利用率不高。以异丁烯(叔丁醇)为原料制MMA,由于其原子利用率高且工艺过程简单、绿色而展现出良好的工业应用前景。
而对于异丁烯选择性氧化制备甲基丙烯醛反应的催化剂,目前应用最为广泛的是Mo-Bi系列的复合氧化物催化剂。此类催化剂以Mo,Bi为主,同时添加了多种其他元素进行催化剂性能的调变。此催化剂虽然在异丁烯(叔丁醇)氧化中具有非常好的催化反应活性(~98%),但是甲基丙烯醛产物的选择性较低(~80%),副产物种类繁多且含量很高。这对后续的甲基丙烯醛一步氧化酯化到甲基丙烯酸甲酯(MMA)而言,较多的杂质不仅会影响反应的转化率和选择性,对催化剂的反应稳定性也有非常大的影响。因此异丁烯氧化的甲基丙烯醛产物需要经过较为复杂的提纯精制才能进一步用于氧化酯化过程。因此急需发展一种兼具高活性以及高选择性的异丁烯氧化到甲基丙烯醛催化剂,使得异丁烯可以高选择性的转化为甲基丙烯醛以降低后续分离精制过程的难度,并提升氧化酯化催化剂的反应性能。
专利文献CN103769159A、CN1647853A通过制备负载型催化剂的方式提高催化剂活性组分分布,用于异丁烯或叔丁醇氧化合成甲基丙烯醛的反应,但催化剂的活性仍然较低;CN1143946A、CN101385978A、CN102114427通过简单的共沉淀实现催化剂的制备,但催化剂活性选择性较低;专利文献CN101088608A提出用共沉淀并通过超声波和微波等外场强化,制备了分散效果较好的钼-铋-锑复合氧化物催化剂,专利文献CN101980781A、CN104437476A、CN104525242A等均通过后期外形制备来提高催化剂性能,但这些制备方法均未从根源上提高选择性。大多仅从酸碱性角度进行调节。
发明内容
本发明涉及一种以共沉淀方法将金合金纳米颗粒负载于复合氧化物载体上、制备复合氧化物负载金合金催化剂和应用。
本发明的主要目的是获得高转化率和高选择性的高效复合氧化物负载金合金催化剂,提出一种以共沉淀方法将金合金纳米颗粒负载于以Mo-Bi为主要组份的复合氧化物载体上制备复合氧化物负载金合金催化剂的方法,该方法制备的催化剂具有大的比表面积、有序的介孔结构,与传统催化剂相比,该催化剂具有更多的可参与反应的活性中心,传质效果好,在相对较低的温度下气催化效率高,同时贵金属负载量低,且通过此制备工艺可以诱导结构组装,这从根本上改变了催化剂的结构与性能,使其具有较好的转化率和极高的产物选择性。此催化剂的成功研制不仅将会打通两步法异丁烯制备甲基丙烯酸甲酯(MMA)反应的全部流程,使得石油炼制过程副产的大量异丁烯和叔丁醇得到充分利用,创造极高的经济效益。
本发明的目的之一是解决现有技术中用于异丁烯或叔丁醇氧化合成甲基丙烯醛反应的催化剂选择低的问题,提供一种用于合成甲基丙烯醛的复合金属氧化物催化剂,该催化剂在相对较低的反应温度下就可达到较高的选择性。
本发明的目的之二是提供一种用于解决上述问题的复合氧化物负载的贵金属合金粒子催化剂制备方法,该方法共沉淀方法将金合金纳米颗粒负载于复合氧化物载体上制备复合氧化物负载金合金催化剂的方法。
本发明的第三个方面涉及上述复合金属氧化物催化剂应用于异丁烯或叔丁醇氧化合成甲基丙烯醛的反应中。
本发明的一个方面,涉及一种负载型催化剂,所述催化剂包括活性组分、载体;
所述活性组分含有贵金属活性元素,所述贵金属活性元素包括金属元素Au和M;
所述M选自Pt、Pd、Ru、Rh中的至少一种;
所述活性元素以纳米颗粒形式负载于载体上;
所述载体为复合金属氧化物;
所述复合金属氧化物中金属元素包括Mo、Bi、Fe、Co、Ce、X元素;所述X选自K、Rb、Cs、Ni、Cu中的至少一种;
可选地,所述活性组分在所述载体上的负载量为0.0001~0.5,其中活性组分的质量以活性金属元素的质量计;
优选地,所述活性组分在所述载体上的负载量为0.001~0.1;
所述Au和M质量比为100~1;
优选地,所述Au和M质量比为20~10。
所述催化剂的比表面积为7.9~35.1m2/g;孔容为0.009~0.01mL/g;平均孔径为7.1~12.5nm。
可选地,所述负载型催化剂的基本组成为:
Au-M/MoaBibFecCodCeeXfOm;
所述a~f代表每种元素在一个催化剂团簇中的原子比。
其中:a=0.1~20;b=0.01~10;c=0.01~5;d=0.1~30;e=0.01~5;f=0.001~5;具体值根据助剂的种类变化;m=1~200具体值根据成分的数量发生变化。
优选地,a=1~15;b=0.5~7;c=0.1~3.5;d=3~22;e=0.1~3.5;f=0.01~2m=1~100。
本发明的另一个方面,提供一种所述负载型催化剂的制备方法,所述方法包括:将含有活性组分的溶液与钼元素的前驱体、铋元素的前驱体、铁元素的前驱体、钴元素的前驱体、铈元素的前驱体、X元素的前驱体以共沉淀的方法生成所述的负载型催化剂。
可选地,所述方法包括以下步骤:
(1)在含有贵金属前驱体的溶液中加入表面活性剂,搅拌,然后加入还原剂形成溶液I,搅拌0.2~2h后加入钼元素的前驱体,形成溶液A;
(2)将含铋元素的前驱体、铁元素的前驱体、钴元素的前驱体、铈元素的前驱体、X元素的前驱体的原料与酸性溶液混合,在60℃下搅拌半小时,得到溶液B;其中酸性溶液是为了溶解前驱体且调节溶液pH值;
(3)将溶液B与溶液A混合,老化、烘干、焙烧、还原得到所述负载型催化剂。
可选地,步骤(1)中,所述贵金属前驱体包括金源和M元素的前驱体;
所述金源选自氯金酸、三氯化金、纳米金溶液中的至少一种;
所述M元素的前驱体选自氯铂酸、氯钯酸、氯化钌、氯化铑、三氯化铑、四氯化铂中的至少一种;
所述表面活性剂选自聚乙烯醇、聚乙二醇、聚丙二醇中的至少一种;
所述还原剂选自硼氢化钠、柠檬酸钠、鞣酸、抗坏血酸、白磷中的至少一种;
所述表面活性剂与贵金属摩尔比为1~1000;所述还原剂与贵金属摩尔比为5~50;其中贵金属摩尔数以贵金属元素的摩尔数计算;
优选地,所述表面活性剂与贵金属摩尔比为50~400;
优选地,所述还原剂与贵金属摩尔比为8~25;
所述钼元素的前驱体选自钼酸铵、磷钼酸、钼酸钠中的至少一种。
可选地,步骤(2)中,
所述铋元素的前驱体选自硝酸铋、磷酸铋、碳酸铋、硫酸铋中的至少一种;
所述铁元素的前驱体选自硝酸铁、磷酸铁、碳酸铁、硫酸铁中的至少一种;
所述钴元素的前驱体选自硝酸钴、磷酸钴、碳酸钴、硫酸钴中的至少一种;
所述铈元素的前驱体选自硝酸铈、磷酸铈、碳酸铈、硫酸铈中的至少一种;
所述X元素的前驱体选自硝酸钾、硝酸钠、碳酸钠、碳酸钾、硝酸铜、碳酸铜中的至少一种;
所述酸性溶液选自硝酸、硫酸、盐酸、碳酸、醋酸、酒石酸中的至少一种;
所述酸性溶液的浓度5%~20%。
可选地,步骤(3)中,
所述老化温度为60~100℃,老化时间为2~6h;所述烘干温度为80~150℃;
进一步可选地,所述老化温度可独立选自60℃、70℃、80℃、90℃、100℃;
进一步可选地,所述老化时间可独立选自2h、2.5h、3h、3.5h、4h、4.5h、5h、5.5h、6h;
进一步可选地,所述烘干温度可独立选自80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃;
所述焙烧的条件为:在空气气氛下焙烧,焙烧温度为400~600℃,焙烧时间为2~6小时;
进一步可选地,所述焙烧温度可独立选自400℃、450℃、500℃、550℃、600℃;
进一步可选地,所述焙烧时间可独立选自2h、3h、4h、5h、6h;
所述还原的条件为:在氢气气氛下还原,还原温度为200~450℃,还原时间为0.5~4h,还原将减少负载型催化剂中复合金属氧化物载体的含量,增加金属活性组分的含量。
进一步可选地,所述还原温度可独立选自200℃、250℃、300℃、350℃、400℃、450℃;
进一步可选地,所述还原时间可独立选自0.5h、1h、1.5h、2h、2.5h、3h、3.5h、4h。
本发明的另一个方面,涉及一种异丁烯或叔丁醇氧化合成甲基丙烯醛的方法,所述方法包括将原料和水通入装有催化剂的固定床反应器中,在含有氧气的气氛下进行氧化反应,其中所述的催化剂选自上述的负载型催化剂、上述方法制备的负载型催化剂中的至少一种。
所述原料选自叔丁醇、异丁烯中的一种;
所述反应的条件为:反应温度为150~500℃,反应压力为0.05~1MPa,空速500~20000h-1,原料、水、氧气的体积摩尔比为1:1~5:5~20;
优选地,所述反应温度为200~360℃;所述反应压力为0.1~0.3MPa;所述原料气空速为2000~10000h-1,原料、水、氧气的体积摩尔比为1:2~4:8~11。
本申请能产生的有益效果包括:
1)本发明以共沉淀方法将金合金纳米颗粒负载于复合氧化物载体上、制备复合氧化物负载金合金催化剂,该方法制备的催化剂具有大的比表面积、有序的介孔结构,与传统催化剂相比,该催化剂具有更多的可参与反应的活性中心,传质效果好,在相对较低的温度下气催化效率高。
2)本发明解决现有技术中用于异丁烯或叔丁醇氧化合成甲基丙烯醛反应的催化剂选择低的问题,提供一种用于合成甲基丙烯醛的复合金属氧化物催化剂,现有催化剂是在360℃~400℃时,转化率和选择性分别在85%~92%、80%~87%,而该催化剂在250℃~320℃下就可达到较高的选择性,转化率和选择性分别最高可达93%、96%。
具体实施方式
下面结合实施例进一步说明本发明的技术方案,但本发明并不局限于这些实施例。
如无特别说明,本发明的实施例中的原料均通过商业途径在国药集团购买,其中聚乙烯醇(PVA)购自上海滨盛化工有限公司,分子量在300~400。
本申请的实施例中,反应产物用气相色谱在线分析。
异丁烯的转化率计算方法如下:
X(异丁烯)%=[1-(未反应的异丁烯的物质的量/供给的异丁烯的物质的量)]×100%
甲基丙烯醛的选择性计算方法如下:
S(甲基丙烯醛)%=[生成的甲基丙烯醛的物质的量/(供给的异丁烯的物质的量-未反应的异丁烯的物质的量)]×100%。
实施例1
催化剂制备:取0.2ml 10wt%的氯金酸以及0.2ml 5wt%的氯铂酸溶液到30ml的水中,保证金和铂的摩尔比为10:1,随后加入摩尔数为贵金属摩尔数30倍的聚乙烯醇(PVA),搅拌10min。快速加入摩尔数为贵金属摩尔数20倍的硼氢化钠,搅拌30min。随后将10.9g钼酸铵溶解到上述溶液中,制备得到pH值为2的溶液A。取2g硝酸铋、1.9g硝酸铈、2.0g硝酸铁、8.0g硝酸钴、0.4g硝酸铯、0.1g硝酸钾,溶解到30ml、质量浓度为15%、50℃的硝酸溶液中,制备得到溶液B。将B溶液在搅拌的状态下缓慢滴加到A溶液中,得到混合溶液。混合溶液在80℃老化3.5小时后,蒸干并在100℃干燥3小时。最后在550℃的空气气氛下焙烧5小时,并再400℃的氢气气氛下还原2h,得到催化剂A,催化剂A的组成为Au10Pt1Mo12Bi0.8Fe1Co5.5Ce0.9Cs0.4K0.2O28。
催化剂A粉体压制成20~40目的颗粒,取1.5ml装入固定床反应器,在叔丁醇:水:氧气=1:2:10(摩尔比)、空速为2500h-1且常压的条件下,进行选择性氧化反应(见表1)。
采用比表面积分析测量仪器(型号为:MicromeriticsASAP2020HD88),在氮气气氛条件下,测试获得催化剂A的氮吸附等温线,采用BET法分析得催化剂A的比表面积为7.9m2/g;采用BJH法计算得到孔容为0.009mL/g;平均孔径为7.1nm。
实施例2
催化剂制备:取0.2ml 10wt%的氯金酸溶液以及0.1ml 5wt%的氯钯酸溶液到30ml的水中,保证金和钯的摩尔比为10:1,随后加入摩尔数为贵金属摩尔量30倍的聚乙烯醇(PVA),搅拌10min。快速加入摩尔数为贵金属摩尔量20倍的硼氢化钠,搅拌30min。随后将10.9g钼酸铵溶解到上述溶液中,制备得到pH值为2的溶液A。取2g硝酸铋、1.9g硝酸铈、2.0g硝酸铁、8.0g硝酸钴、0.4g硝酸铯、0.1g硝酸钾,溶解到30ml、质量浓度为15%、50℃的硝酸溶液中,制备得到溶液B。将B溶液在搅拌的状态下缓慢滴加到A溶液中,得到混合溶液。混合溶液在80℃老化3.5小时后,蒸干并在100℃干燥3小时。最后在550℃的空气气氛下焙烧5小时,并再400℃的氢气气氛下还原2h,得到催化剂B,催化剂B的组成为Au10Pd1Mo12Bi0.8Fe1Co5.5Ce0.9Cs0.4K0.2O28。
催化剂B粉体压制成20~40目的颗粒,取1.5ml装入固定床反应器,在叔丁醇:水:氧气=1:2:10(摩尔比)、空速为2500h-1且常压的条件下,进行选择性氧化反应(见表2)。
采用比表面积分析测量仪器(型号为:MicromeriticsASAP2020HD88),在氮气气氛条件下,测试获得催化剂A的氮吸附等温线,采用BET法分析得催化剂B的比表面积为15.3m2/g;采用BJH法计算得到孔容为0.009mL/g;平均孔径为8.9nm。
实施例3
催化剂制备:取0.2ml 10wt%的氯金酸溶液以及0.2ml 5wt%的氯化钌溶液到30ml的水中,保证金和钌的摩尔比为10:1,随后加入摩尔数为贵金属摩尔数30倍的聚乙烯醇(PVA),搅拌10min。快速加入摩尔数为贵金属摩尔数20倍的硼氢化钠,搅拌30min。随后将10.9g钼酸铵溶解到上述溶液中,制备得到pH值为2的溶液A。取2g硝酸铋、1.9g硝酸铈、2.0g硝酸铁、8.0g硝酸钴、0.4g硝酸铯、0.1g硝酸钾,溶解到30ml、质量浓度为15%、50℃的硝酸溶液中,制备得到溶液B。将B溶液在搅拌的状态下缓慢滴加到A溶液中,得到混合溶液。混合溶液在80℃老化3.5小时后,蒸干并在100℃干燥3小时。最后在550℃的空气气氛下焙烧5小时,并再400℃的氢气气氛下还原2h,得到催化剂C,催化剂C的组成为Au10Ru1Mo12Bi0.8Fe1Co5.5Ce0.9Cs0.4K0.2O28。
催化剂C粉体压制成20~40目的颗粒,取1.5ml装入固定床反应器,在叔丁醇:水:氧气=1:2:10(摩尔比)、空速为2500h-1且常压的条件下,进行选择性氧化反应(见表3)。
采用比表面积分析测量仪器(型号为:MicromeriticsASAP2020HD88),在氮气气氛条件下,测试获得催化剂A的氮吸附等温线,采用BET法分析得催化剂C的比表面积为27m2/g;采用BJH法计算得到孔容为0.01mL/g;平均孔径为9.7nm。
实施例4
催化剂制备:取0.3ml 10wt%的氯金酸以及0.3ml 5wt%的氯铂酸溶液到30ml的水中,保证金和铂的摩尔比为10:1,随后加入摩尔数为贵金属摩尔数30倍的聚乙烯醇(PVA),搅拌15min。快速加入摩尔数为贵金属摩尔数20倍的硼氢化钠,搅拌30min。随后将10.9g钼酸铵溶解到上述溶液中,制备得到pH值为2的溶液A。取2g硝酸铋、1.9g硝酸铈、2.0g硝酸铁、8.0g硝酸钴、0.4g硝酸铯、0.1g硝酸钾,溶解到30ml、质量浓度为15%、50℃的硝酸溶液中,制备得到溶液B。将溶液B在搅拌的状态下缓慢滴加到溶液A中,得到混合溶液。混合在80℃老化3小时后,蒸干并在110℃干燥4小时。最后在550℃的空气气氛下焙烧4小时,并再400℃的氢气气氛下还原1.5h,得到催化剂D,催化剂D的组成为1-Au10Pt1Mo12Bi0.8Fe1Co5. 5Ce0.9Cs0.4K0.2O28。
催化剂D粉体压制成20~40目的颗粒,取1.5ml装入固定床反应器,在叔丁醇:水:氧气=1:2:10(摩尔比)、空速为2500h-1且常压的条件下,进行选择性氧化反应(见表4)。
采用比表面积分析测量仪器(型号为:MicromeriticsASAP2020HD88),在氮气气氛条件下,测试获得催化剂A的氮吸附等温线,采用BET法分析得催化剂D的比表面积为35.1m2/g;采用BJH法计算得到孔容为0.01mL/g;平均孔径为12.5nm。
对比例1
催化剂制备:将10.9g钼酸铵溶解到上述溶液中,制备得到溶液A。取2g硝酸铋、1.9g硝酸铈、2.0g硝酸铁、8.0g硝酸钴、0.4g硝酸铯、0.1g硝酸钾,溶解到30ml、质量浓度为15%、50℃的硝酸溶液中,制备得到溶液B。将溶液B在搅拌的状态下缓慢滴加到溶液A中,得到混合溶液。混合溶液在90℃老化4小时后,蒸干并在120℃干燥4小时。最后在500℃的空气气氛下焙烧4.5小时,得到催化剂E,催化剂E的组成为Mo12Bi0.8Fe1Co5.5Ce0.9Cs0.4K0.2O28。
催化剂E粉体压制成20~40目的颗粒,取1.5ml装入固定床反应器,在叔丁醇:水:氧气=1:2:10(摩尔比)、空速为2500h-1且常压的条件下,进行选择性氧化反应(见表5)。
采用比表面积分析测量仪器(型号为:MicromeriticsASAP2020HD88),在氮气气氛条件下,测试获得催化剂A的氮吸附等温线,采用BET法分析得催化剂E的比表面积为6.9m2/g;采用BJH法计算得到孔容为0.008mL/g;平均孔径为6.9nm。
表1催化剂A的催化反应活性
表2催化剂B催化反应活性
表3催化剂C的催化反应活性
表4催化剂D的催化反应活性
表5催化剂E的催化反应活性
根据表1~表4,可以看出,在叔丁醇(异丁烯)氧化合成甲基丙烯醛反应中,在相同的催化剂条件下,随着温度的升高,催化剂的活性增加,叔丁醇(异丁烯)的转化率也在升高,甲基丙烯醛的选择性随着温度的升高先增加而后降低;不同催化剂在同一温度下活性存在差距是因为添加贵金属的种类和剂量有所不同导致。
结合实施例1~4和对比例1可知,本发明的催化剂在200℃~300℃的温度下,异丁烯的转化率优于对比例1,甲基丙烯醛的选择性更高,对比例1在此温度范围内,异丁烯的转化率最高仅有3%,异丁烯几乎未发生转化。本发明的催化剂在320℃~360℃温度范围内中,异丁烯的转化率优于对比例1,甲基丙烯醛的选择性相当,其中在320℃时,本发明的异丁烯的转化率达到93%,而对比例1中,异丁烯的转化率仅有30%。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (7)
1.一种负载型催化剂,其特征在于,
所述负载型催化剂包括活性组分、载体;
所述活性组分含有贵金属活性元素,所述贵金属活性元素包括Au和M;
所述M选自Pt、Pd、Ru、Rh中的至少一种;
所述载体为复合金属氧化物;
所述复合金属氧化物中金属元素包括Mo、Bi、Fe、Co、Ce、X元素;
所述X选自K、Rb、Cs中的至少一种;
所述负载型催化剂的组成为:
Au-M/MoaBibFecCodCeeXfOm
其中,a=0.1~20;b=0.01~10;c=0.01~5;d=0.1~30;e=0.01~5;f=0.001~5; m=1~200;
所述Au和M质量比为20~10;
所述活性组分在所述载体上的负载量为0.0001~0.5,其中活性组分的质量以活性金属元素的质量计;
所述负载型催化剂的制备方法具体包括以下步骤:
(1)在含有贵金属前驱体、表面活性剂、还原剂的溶液中加入钼元素的前驱体,形成溶液A;
(2)将含铋元素的前驱体、铁元素的前驱体、钴元素的前驱体、铈元素的前驱体、X元素的前驱体的原料与酸性溶液混合,得到溶液B;
(3)将溶液B与溶液A混合,老化、烘干、焙烧、还原得到所述负载型催化剂。
2.根据权利要求1所述的负载型催化剂,其特征在于,
所述活性组分在所述载体上的负载量为0.001~0.1。
3.根据权利要求1所述的负载型催化剂,其特征在于,
所述负载型催化剂的比表面积为7.9~35.1m2/g;孔容为0.009~0.01mL/g;平均孔径为7.1~12.5nm。
4.根据权利要求1所述的负载型催化剂,其特征在于,步骤(1)中,
所述贵金属前驱体包括金源和M元素的前驱体;
所述金源选自氯金酸、三氯化金中的至少一种;
所述M元素的前驱体选自氯铂酸、氯钯酸、氯化钌、氯化铑、四氯化铂中的至少一种;
所述表面活性剂选自聚乙烯醇、聚乙二醇、聚丙二醇中的至少一种;
所述还原剂选自硼氢化钠、柠檬酸钠、鞣酸、抗坏血酸、白磷中的至少一种;
所述表面活性剂与贵金属摩尔比为1~1000,所述还原剂与贵金属摩尔比为5~50,其中贵金属摩尔量以贵金属元素的摩尔量计算;
所述钼元素的前驱体选自钼酸铵、磷钼酸 、钼酸钠中的至少一种。
5.根据权利要求1所述的负载型催化剂,其特征在于,步骤(2)中,
所述铋元素的前驱体选自硝酸铋、硫酸铋中的至少一种;
所述铁元素的前驱体选自硝酸铁、硫酸铁中的至少一种;
所述钴元素的前驱体选自硝酸钴、硫酸钴中的至少一种;
所述铈元素的前驱体选自硝酸铈、硫酸铈中的至少一种;
所述酸性溶液选自硝酸、硫酸、盐酸、醋酸、酒石酸中的至少一种;
所述酸性溶液的质量浓度5%~20%。
6.根据权利要求1所述的负载型催化剂,其特征在于,步骤(3)中,
所述老化温度为60~100℃,老化时间为2~6 h;所述烘干温度为80~150℃;
所述焙烧条件为:在空气气氛下焙烧,焙烧温度为400~600℃,焙烧时间为2~6h;
所述还原的条件为:在氢气气氛下还原,还原温度为200~450℃,还原时间为0.5~4h。
7.一种制备甲基丙烯醛的方法,其特征在于,将原料和水通入装有催化剂的固定床反应器中,在含有氧气的气氛下进行氧化反应,其中所述催化剂选自权利要求1~6任一项所述负载型催化剂;
所述原料选自叔丁醇、异丁烯中的一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110769256.9A CN114917923B (zh) | 2021-07-07 | 2021-07-07 | 一种负载型催化剂、制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110769256.9A CN114917923B (zh) | 2021-07-07 | 2021-07-07 | 一种负载型催化剂、制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114917923A CN114917923A (zh) | 2022-08-19 |
CN114917923B true CN114917923B (zh) | 2023-06-20 |
Family
ID=82804290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110769256.9A Active CN114917923B (zh) | 2021-07-07 | 2021-07-07 | 一种负载型催化剂、制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114917923B (zh) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101164694A (zh) * | 2006-10-20 | 2008-04-23 | 德古萨股份公司 | 用于催化气相氧化的混合氧化物催化剂 |
EP2121185A4 (en) * | 2007-01-19 | 2014-04-16 | Evernu Technology Llc | SELECTIVE OXIDATION OF ALKANES AND / OR ALKENES TO PRECIOUS OXYGENATES |
CN101850259B (zh) * | 2010-06-01 | 2013-03-20 | 上海华谊丙烯酸有限公司 | 一种高空速下丙烯氧化制丙烯醛的催化剂的制备方法 |
CN104801312B (zh) * | 2015-03-17 | 2017-07-07 | 烟台大学 | 一种复合氧化物催化剂及制备方法 |
JP6961358B2 (ja) * | 2017-02-27 | 2021-11-05 | 旭化成株式会社 | 酸化物触媒、酸化物触媒の製造方法及び不飽和アルデヒドの製造方法 |
-
2021
- 2021-07-07 CN CN202110769256.9A patent/CN114917923B/zh active Active
Non-Patent Citations (1)
Title |
---|
王蕾,张锁江,李增喜,张香平,王玉兰.制备条件对异丁烯选择性氧化催化剂性能的影响.燃料化学学报.2004,(04),第481-485页. * |
Also Published As
Publication number | Publication date |
---|---|
CN114917923A (zh) | 2022-08-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | MOF-derived CeO2 supported Ag catalysts for toluene oxidation: The effect of synthesis method | |
EP2116300B1 (en) | A method for alcohol production | |
EP3092072B1 (en) | A process for vapor-phase methanol carbonylation to methyl formate | |
CN104923225B (zh) | 一种负载型贵金属催化剂及其制备和应用 | |
CN103894208B (zh) | 用于乙炔氢氯化反应的低贵金属无汞催化剂、其制备方法及应用 | |
CN106540741A (zh) | 在室温下用于消除甲醛的催化剂及其制备方法 | |
JP2008503340A (ja) | 一酸化炭素の水素化によりc2−酸素化物を合成するための触媒および方法 | |
CN110102294B (zh) | 复合氧化物负载的Pd基催化剂及其制备方法和应用 | |
CN106964348A (zh) | 一种甲醛污染物室温催化氧化催化剂及其制备方法和应用 | |
Tian et al. | Nano-Au/MCeO x catalysts for the direct oxidative esterification of methylacrolein to methyl esters | |
CN103043773B (zh) | 一种烟气脱硫废液的催化湿式氧化方法 | |
CN112108145A (zh) | 一种氧化铝负载铱团簇催化剂及其制备与应用 | |
CN114853567B (zh) | 一种二氧化碳转化制备低碳醇催化剂及其制备方法和应用 | |
CN104959150B (zh) | 优先氧化CO的Au/CuO/CeO2‑TiO2催化剂及制备方法 | |
CN105435779B (zh) | 一氧化碳气相合成草酸酯催化剂 | |
CN106111154A (zh) | 用于降解VOCs的四元复合氧化物型催化剂及其制备方法 | |
CN113426457B (zh) | 一种酮加氢制备醇的催化剂及其制备方法和应用 | |
CN103170338B (zh) | 一种用于1,2‑丙二醇的催化剂及其制备方法 | |
CN109821529B (zh) | 一种钴基催化剂及其用于制备不饱和羧酸酯的方法 | |
CN114054034B (zh) | 多元铜基非贵金属加氢催化剂及其制备方法与应用 | |
CN114917923B (zh) | 一种负载型催化剂、制备方法及其应用 | |
CN109806881A (zh) | 一种用于甲醇氧化制甲醛的铁钼催化剂及其制备方法 | |
CN1113052C (zh) | 制备羧酸酯的方法及用于该方法的催化剂 | |
CN1281311C (zh) | 用于肉桂醛加氢制肉桂醇的猝冷骨架钴基催化剂及其制备方法 | |
CN111250098B (zh) | 一种用于费托合成反应水加氢催化剂及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |