CN1078104C - 载体型催化剂及其制备方法和用途 - Google Patents
载体型催化剂及其制备方法和用途 Download PDFInfo
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- CN1078104C CN1078104C CN94119933A CN94119933A CN1078104C CN 1078104 C CN1078104 C CN 1078104C CN 94119933 A CN94119933 A CN 94119933A CN 94119933 A CN94119933 A CN 94119933A CN 1078104 C CN1078104 C CN 1078104C
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- supported catalyst
- catalyst
- water
- hydrogenation
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- 238000000034 method Methods 0.000 claims abstract description 17
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- GCOWAJWTRQQHAI-UHFFFAOYSA-H [Ru+3].C(C)(=O)[O-].[Ru+3].[N+](=O)(O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound [Ru+3].C(C)(=O)[O-].[Ru+3].[N+](=O)(O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] GCOWAJWTRQQHAI-UHFFFAOYSA-H 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- SVEIXENKLWYGIZ-UHFFFAOYSA-J aluminum;sodium;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Al+3] SVEIXENKLWYGIZ-UHFFFAOYSA-J 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- XPVHUBFHKQQSDA-UHFFFAOYSA-N ammonium arsenate Chemical compound [NH4+].[NH4+].O[As]([O-])([O-])=O XPVHUBFHKQQSDA-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- RQAWMKTZSKTIHN-UHFFFAOYSA-N cyano thiocyanate;silver Chemical compound [Ag].N#CSC#N RQAWMKTZSKTIHN-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- OQURWADGXKZUIH-UHFFFAOYSA-N osmium(4+) Chemical compound [Os+4] OQURWADGXKZUIH-UHFFFAOYSA-N 0.000 description 1
- IHUHXSNGMLUYES-UHFFFAOYSA-J osmium(iv) chloride Chemical compound Cl[Os](Cl)(Cl)Cl IHUHXSNGMLUYES-UHFFFAOYSA-J 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- GVPLVOGUVQAPNJ-UHFFFAOYSA-M potassium;hydron;trioxido(oxo)-$l^{5}-arsane Chemical compound [K+].O[As](O)([O-])=O GVPLVOGUVQAPNJ-UHFFFAOYSA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- BSGFBYZRPYAMRQ-UHFFFAOYSA-H tetrabromoplatinum(2+) dibromide Chemical compound Br[Pt](Br)(Br)(Br)(Br)Br BSGFBYZRPYAMRQ-UHFFFAOYSA-H 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
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- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
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- C—CHEMISTRY; METALLURGY
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
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- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
一种可由下述方法得到的载体型催化剂：
a)将一种催化活性成份或其中间产物溶于溶剂，
b)向所述溶液中加入一种能结合其本身重量至少十倍水的有机高聚物，
C)使高聚物与催化剂载体混合，
d)使如此得到的物料成型、干燥和焙烧，
一种制备催化剂的方法及催化剂的应用。
Description
本发明是关于载体型催化剂，其制备方法及用该催化剂进行的加氢方法。
催化活性成分在载体型催化剂中的分布对催化剂的活性，选择性和寿命起决定性作用。如果采用使含催化活性成份或其中间产物的溶液浸渍多孔催化剂载体的方法，或者采用使活性成份与载体共沉淀的方法制备载体型催化剂，活性成份均匀分布在整个催化剂上，或者形成含活性成份的涂层。一般而言，由于直径＜20nm的微孔构成催化剂内表面积的主要部分，活性成份大部分存在于这些微孔中。尽管如此，与中孔或大孔(直径分别为20-100nm和＞100nm)相比，反应物更难进入微孔。特别对由扩散控制的反应，上述情况导致活性和选择性都较低，因为不希望出现的二级反应优先在微孔中进行。在大分子的催化反应中，可能由于催化剂中活性成份的催化有效量问题，转化率或活性降低，因为这些分子不能进入微孔。
JP-A-84/104678涉及制备载体型催化剂的方法，将交联聚丙烯酸、水作为载体的硅藻土和作为活性成份的氧化钒混合，挤出该混合物，并将挤出物切割成环，在550℃下焙烧。如此制出的催化剂在挤出时具有良好的加工性。
本发明的目的是提供一种载体型催化剂，其中活性成份主要分布在中孔和大孔内。
我们发现，这一目的可由下述方法制成的载体型催化剂实现：a)将催化活性成份或其中间产物溶于溶剂，b)向该溶液加入一种有机高聚物，该高聚物能够结合其本身重量至少十倍的水，c)使该高聚物与催化剂载体混合，d)使获得的物质成型，干燥和焙烧。
亦发现制备这些载体型催化剂的方法及催化剂的用途。
下面描述制备新催化剂的各个步骤。步骤a)
将催化活性成份或其中间体溶于溶剂，所述中间体须经进一步处理或活化后才能转化成活性成份。溶剂优选极性，水互溶性溶剂，如醇，醚和胺。特别适用的醇是C1-C4醇，如甲醇、乙醇、异丙醇和正丁醇。适用的具体的一种醚是四氢呋喃。本发明可用的胺是氨，一元胺如二甲胺，甲胺，三甲胺，乙胺，丙胺和丁胺。但特别优选水或氨/水混合物。
催化活性成份一般是过渡金属的水溶性盐，如硝酸钯，乙酸钯，六氯钯(IV)酸铵，四氯钯(II)酸铵，二氯二胺合钯(II)，六氯钯(IV)酸钾，四氯钯(II)酸钾，四氯钯(II)酸钠，乙酰丙酮合钯，氯化钯(II)，硫酸钯(II)，二氯四氨合钯(II)，硝酸四氨合钯，氯化铂，六溴铂酸铵，六氯铂(IV)酸铵，四氯铂(II)酸铵，四氰铂(II)酸钡，六氯铂(IV)酸，六溴铂(IV)酸钾，六氯铂(IV)酸钾，四氯铂(II)酸钾，四氰铂(II)酸钾，六氯铂(IV)酸钠，氯化二氨合铂(II)，氯化四氨合铂(II)，及硝酸四氨合铂(II)；硝酸银，乙酸银，硫酸银，氰化银，碳酸银，和硫氰酸银；硝酸铜，乙酸铜，硫酸铜和氯化铜；硝酸锌，乙酸锌，硫酸锌，氯化锌，和碳酸锌；氯化铁(II)，氯化铁(III)，硝酸铁和硫酸铁；氯化铬和硫酸铬，重铬酸钾和铬酸钾；硝酸镍，乙酸镍，硫酸镍，和氯化镍；硫酸锰，和氯化锰，高锰酸钾；硝酸钴，乙酸钴，硫酸钴和氯化钴；六氯铑(III)酸铵，和六氯铑(III)酸钠；氯化铑(III)，乙酸铑，硝酸铑(III)和硫酸铑(III)；硝酸釕乙酸釕和亚硝酰基硝酸钌 ；氧化铼(VII)，高铼酸铵，高铼酸钠，高铼酸钾，和高铼酸；氯化锇，六氯锇酸铵，氧化锇(VIII)；六氯锇(IV)酸钾和锇(VI)酸钾。
这些化合物都可商购到。可由，例如据Angew.Chem.103(1991)，852获得，或者，在某些情况下可商购到的金属钯、铂、银和铜的溶胶也适用。
优选化合物是铂、银、镍、铜和钯的盐，特别优选乙酸钯，硝酸钯和氯化钯。
如果除实际的活性成份外，还想在载体型催化剂中进一步加入可能影响催化剂活性或选择性的促进剂或调节剂，向过渡金属盐或溶胶中直接或以其中间体形式加入这些成份较好。促进剂或其中间体的具体实例是：
碱金属锂、钠、钾和铯以及碱土金属镁、钙、钡和锶的销酸盐，乙酸盐，氯化物，硫酸盐和氢氧化物，以及碱金属和镁、钙的硫酸盐，碱金属碳酸盐和碳酸镁。磷酸盐，如磷酸钠，砷酸盐，如砷酸铵，砷酸钠和砷酸钾，铅化合物，如乙酸铅，氯化铅，和硝酸铅，铋化合物，如硝酸铋和氯氧化铋，锡化合物，如氯化锡，或碱金属锡酸盐，及锑化合物，如铵、钠和钾的锑酸盐。
过渡金属盐溶液或溶胶的浓度一方面取决于相应化合物的溶解度。一般而言，应至少0.1g/l且可直到使溶液泡和。一般溶液含0.01-5wt％过渡金属离子。此外，活性成份含量取决于新载体型催化剂的目的浓度。所述溶液通常在室温下制备。步骤b)将有机高聚物加到如上所述的活性成份或其中间体的溶液中，即可将溶液加到高聚物中，也可将高聚物加到溶液中。
该有机高聚物能够结合其本身重量十倍的水。这类化合物被称作水凝胶(参见，B、D、Rathmer等人的Hydrogels forMedical and related Applications，ACS Symposium SeriesNo.31(1976))。这些化合物是交联的高聚物，其中交联可由离子的相互作用或氢桥键形成或通过化学交联形成。例如，淀粉和丙烯腈的接枝共聚物(例如，G.F.Fanta等人，Starch34(1982)95)，淀粉和丙烯酸(EP-A83022)，多糖和丙烯酸(DE-A4105000)，聚乙烯醇和丙烯酸钠的共聚物(US-A4155893)，丙烯酰胺和丙烯酸的共聚物(EP-A72214)，交联的聚环氧乙烷(US-A3264202)，交联的聚丙烯酰胺(US-A3669103)，交联的聚-N-乙烯基吡咯烷酮(US-A3669103)，交联的聚乙烯醇(Walter等人，Biomaterials9(1988)150)，交联的羧纤维素纤维(US-A-3826711)，聚乙酸乙烯酯/丙烯酸共聚物的水解产物(GB 20 30 990)和聚丙烯腈的水解产物(US-A 43 66 206)。
优选丙烯酸或丙烯酸和丙烯酰胺的交联聚合物以及丙烯酰胺的交联聚合物。尤其优选略微交联的部分中和的聚丙烯酸钠。适用的化学交联剂的实例是二元醇，如乙二醇，聚乙二醇，和多元醇，二胺和二烯，其用量为以高聚物为基准0.1-5wt％。这类聚合物可结合其本身重量直到1000倍的水。通常是在水溶液中通过自由基聚合制成，并可作为增稠剂或超吸收剂商购到(F.L.Buchholz，Preparation and Structure of Polyacrylates inAbsorbent Polymer Technology，Studies in PolymerScience 8，Elzevier，Amsterdam 1990，page23).
通常，将活性成份的溶液加到高聚物上，其加入量要使后者能完全吸收所述溶液。其结果是高聚物膨胀。该过程一般在60min内完成。高聚物的膨胀一般在室温下进行。聚丙烯酸盐膨胀期间，PH应至少6，否则吸收的溶液不够。
步骤c)使膨胀的高聚物与粉末状催化剂载体混合，其中两种成份相互混合的顺序并不重要。
适宜的载体是在催化反应条件下惰性的化合物，优选氧化铝，氧化硅，硅藻土，硅胶，矿物粘土，如蒙托土，硅酸盐，与氧化铝形成混合物的沸石，氧化锆，氧化钛，及这些化合物彼此的混合物，其中特别优选氧化铝和氧化硅。
亦可采用下列化合物：Mg、Ca、Sr、Ba的氧化物，Ca、Ba、Sr和Pb的硫酸盐，Mg、Ca、Sr、Ba、Ni、Co、Mn、Fe、和Cu的碳酸盐，Mo、W、Co、Ni、Fe、Pb、Ag、Cr、Cu、Cd、Sn和Zn的硫化物，B、Si和W的碳化物，及B和Si的氮化物。
载体用量一般为未膨胀高聚物用量的10-1000倍，优选20-200倍。可向溶液中加入常规胶溶剂，以改进制成的成型物的机械稳定性，例如用氧化铝载体时加氨，用二氧化硅时加氢氧化钠溶液。用量一般0.1-5wt％，以载体为基准。
对各成份进行混合，可用捏和机或混合-研磨机进行混合。步骤d)进一步的处理手段本身对所属领域技术人员是公知的。
如用挤出机挤出对由步骤c)制出的物质进行成型加工，制成具有所需尺寸的挤出物。成型物经干燥，一般100-150℃下2-24hr.。
成型物一般在300-800℃，优选300-550℃焙烧2-24小时，从载体基质上脱除高聚物，并将活性成份的高温下不稳定的盐转化成氧化物，混合氧化物(mixed oxides)或卤化物。根据活性成份的情况，可再进行一步活化处理，催化活性成份只在该阶段形成。在加氢催化剂的情况下，活化在如80-400℃下，一般常压下，在氢气流中用氢处理实现。
也可取消干燥步骤，但已发现干燥有利于温和地脱除溶剂。
还可按常规方式，将如此制成的载体型催化剂进一步施涂到无孔型载体包括如，滑石或玻璃环，石英环或高温烧结的氧化铝环。为此，将研磨的载体型催化剂颗粒及一种成粒状的液体施涂到该无孔载体上。该液体可是硝酸铝溶液，乙酸铝溶液或氢氧化铝钠溶液，涂复的无孔载体干燥焙烧后，上述每一液体在无孔载体与催化剂颗粒之间形成牢固的结合。
新型载体催化剂是高度多孔性的，具有较小的堆积密度。电子显微照片清楚显示出大部分，一般大于80％的活性成份处于大孔中。只有通过估算整个催化剂挤出物的多个有代表性的断面，即利用扫描电镜，借据反散射电子可见到重金属元素，可以确定大孔中活性成份的比例。
新型催化剂中，反应物可以很容易地到达反应中心，反应产物可很容易地脱离。通过使活性成份分布在大孔中，制备出的催化剂具有与常规催化剂相同的活性，却只需要活性成份常规用量的一部分。
新载体型催化剂特别适用于加氢反应，尤其是液相加氢反应。这些反应(特别优选的活性成份列于括号内)的实例是：——在精炼厂或蒸汽裂化装置内催化或热裂解或高温分解方法中
形成的C2-C10烃物料中多不饱和烃的选择加氢，尤其是——C2物料中乙炔的加氢(Pd、Pt、Cu)，——C3物料中丙炔和丙二烯的加氢(Pd、Pt、Cu、Ag)，——C4物料中丁二烯、丁炔和乙烯基乙炔的加氢(Pd、Pt、Cu)，——C5物料中环戊二烯、戊二烯和异戊二烯的加氢(Pd、Pt、Cu、Ni)，以及——C5-C10物料(热解汽油)中二烯类和苯乙烯的加氢(Pd、Pt、Cu、Ni)，——来自精炼物料的长链烃的加氢精制，尤其是——加氢条件下，轻石脑油，重石脑油，瓦斯油，真空瓦斯油，
残渣油中氧、硫、氮和芳烃化合物的降解，尤其是在加氢
条件下，溶剂精制的和脱蜡真空瓦斯油精制成技术级和医药
级白油(Ni、Mo、W、Pt、Pd)及在加氢条件下，石蜡的精
制(Ni、Mo、W、Pt、Pd)——食用油脂的加氢(油脂肪的加氢)(Ni，Pd，Pt)，——高聚物中官能团的选择加氢，尤其是苯乙烯/丁二烯共聚物中
烯双键的加氢(Ni，Pd，Pt)，——异构化，尤其是正丁烷骨架异构化制异丁烷(Pd、Pt)，——利用含Pd或Cr的催化剂进行C3-C15烃物料的脱氢反应，特别
是——异丁烯脱氢——丁烷脱氢制丁烯和丁二烯——丙烷脱氢制丙烯——异戊烷脱氢制异戊二烯——C6-C15链烷烃脱氢，——选择氧化，特别是——乙烯选择氧化制环氧乙烷(Ag，Cu)和——乙二醇选择氧化制乙二醛(Ag，Cu)。
脱氢反应中，新载体型催化剂因在大孔中传质较快及在表面较短的停留时间而不易结焦或寿命较长(参见A.Wheeler，Adv.Catal.3(1951)，317)。
实例1
新载体型催化剂的制备(Pd/Al2O3)
将150ml水和3g结合其本身重量300倍水的大分子量聚丙烯酸钠(90％的酸基被中和，用分子量1500的0.4mol％的聚乙二醇交联)加到5.47g硝酸钯水溶液中(11wt％的Pd)。0.5hr后，胶状物与280g氧化铝捏和(假勃姆石，600℃焙烧后表面积：300m2/g)。加入200ml氨溶液后(含50ml浓氨)，捏和1hr.。物料在挤出机中6.5×106pa压力下挤出形成3.8mm挤出物，120℃干燥16hr.，330℃焙烧6hr.。
催化剂的分析数据：
重量/升 383g/l
BET表面积 298m2/mg
孔容积(DIN66132) 1.17ml/g
(利用汞孔率计测定，J.v.Brakel等人，PowderTechnology 29(1991)，1)
微孔直径＜20nm，中孔直径20-100nm，大孔直径＞100nm。
新催化剂具有下列分析数据：大孔的平均直径(nm)： 600微孔和中孔的平径直径(nm)： 4大孔的比例(V％)： 33
实例2
对比催化剂的制备(Pd/Al2O3)
在捏和机中，将3g结合其本身重量300倍水的大分子量聚丙烯酸钠(90％的酸基被中和，用0.4％的分子量1500的聚乙二醇交联)与280g假勃姆石混合(粉末A)。
将5.47g硝酸钯水溶液(11wt％的Pd)溶于150ml水。将该含pd溶液加到粉末A上。加入200ml氨溶液(含50ml浓氨)后，捏和一小时。物料挤出成3.8mm挤出物，120℃干燥16hr.，330℃焙烧6hr.。
例1与2的区别只在于例1中用硝酸钯溶液使高聚物预膨胀。例2中，将硝酸钯水溶液与假勃姆石和高聚物混合。
例2催化剂的分析数据：重量/升(g/l)： 376BET表面积(m2/g)： 276孔容积(DIN 66 132)(ml/g)： 1.09采用汞孔率计测定(J.V.Brakel等人，Powder Technology 29(1991)，1)大孔平均直径(nm)： 500微孔和中孔平均直径(nm)： 4.5大孔比例(V％)： 35
对例1和例2制备的催化剂的断面的电子显微图进行的比较表明：新型催化剂中，活性成份大部分(＞80％)存在于大孔内。而对比催化剂中，活性成份主要存在于微孔内，而大孔内只有约10％的活性成份。
实例3
用例1和2的载体型催化剂对C4物料进行选择加氢。采用喷淋床法，使下表所示的C4物料在例1和2的催化剂上反应，温度50℃，压力1.4×106Pa，空速6.41/l.hr.，以C4物料为基准。
加氢反应前，催化剂在氢气流中还原(大气压，150℃，8hr.，20升的H2/l.hr.)。
下表示出C4物料组成及加氢产物：
组成 mol％
C4物料 加氢产物
例1 例2丁二烯 45.6 3.2 3.3丁烯-1 15.9 38.7 36.6反丁烯-2 4.9 20.2 20.1顺丁烯-2 3.7 7.3 7.5异丁烯 24.2 24.2 24.2异丁烷 1.5 1.5 1.5正丁烷 4.2 4.9 6.8
新型催化剂对丁二烯加氢制丁烯的选择性明显较高，这一点可由正丁烷生成率明显较少反映出来。
在常规催化剂上(0.3wt％Pd/α-Al2O3，重量/升为1100g/l)，在相同的丁二烯转化率情况下，只能得到较低的选择性(正丁烷生成率约1％)。新催化剂的优点还在于，由于其每升重量较轻，其空速提高到2.8倍(以催化剂物料为基准)，而活性成份含量减少到2.8倍。
实例4
制备Pd/Ag涂复催化剂
将3.72g硝酸钯水溶液(11(wt)％Pd)和6.44g硝酸银溶于150ml稀氨水。将该含Pd和Ag的溶液加到6g高分子量聚丙烯酸钠上(90％酸基被中和，与0.4％分子量1500的聚乙二醇交联)，该高聚物可结合其本身重量300倍的水。
1Hr后，将胶状物与280g假勃姆石(600°焙烧后表面积：300m2/g)捏合。加入175ml水后，捏合1hr.。物料在6.0×106Pa压力下挤出成4.0mm挤出物，120℃干燥16hr.，400℃焙烧4hr.。
将焙烧的挤出物在球磨机中研磨。用该物料涂复滑石球(直径4.3-4.7mm)。使用的成粒液体为4.2％浓度硝酸铝溶液。涂复的球在90°干燥16hr.，530℃焙烧3hr。
制成的球Pd含量0.02(wt)％，Ag含量0.2(wt)％。该法制出的催化剂其活性组份载于大孔涂复层中，且活性成份集中在涂复层的大孔内。
实例5
用例4催化剂对C2物料中乙炔选择加氢。
用例4的Pd/Ag涂复催化剂对C2物料中乙炔进行气相选择加氢。
向催化剂容积66ml的反应器通入200升/hr的C2物料(组成：99％(V)乙烯，1％(V)乙炔)和2.2升/hr.的氢。在2.0×106Pa压力和反应器入口温度31℃下，乙炔转化率90％，选择性78％。
实例6
用例1的新催化剂对C3物料中丙炔和丙二烯进行液相选择加氢。
利用液相法，在入口温度4℃，压力2.0×106Pa及空速9.5kg/l·hr.(以C3物料为基准)条件下，使下表的C3物料在例1的新催化剂上反应。氢与丙炔/丙二烯的摩尔比是1.1∶1。
加氢反应前，例1制备的催化剂在氢气(大气压，150℃，3hr.，20升的H2/l·hr.)中还原。丙炔/丙二烯含量从4.07％减少到＜140ppm。
组成 mol％
C3物料 加氢产物丙炔 2.32 ＜20ppm丙二烯 1.75 120ppm丙烯 90.78 93.69丙烷 5.13 5.8未知化合物 0.02 0.5
Claims (9)
1.一种由下列a-d步骤得到的载体型催化剂：a)将一种过渡金属的盐或者一种Pd、Pt、Ag或Cu或其中间产物的溶液作为活性成分溶于水可混溶的溶剂中；b)向上述溶液中加入能够结合其本身重量至少十倍水的一种有机高聚物；c)将所述高聚物与催化剂载体混合；和d)使由此得到的物料成型，干燥和焙烧。
2.如权利要求1所述的载体型催化剂，其制备时用水或水与氨的混合物作溶剂。
3.如权利要求1所述的载体型催化剂，其制备时用交联的聚丙烯酸钠作为有机高聚物。
4.如权利要求2所述的载体型催化剂，其制备时用交联的聚丙烯酸钠作为有机高聚物。
5.如权利要求1所述的载体型催化剂，其制备时用水溶性钯盐作为活性成份的中间产物。
6.一种制备权利要求1所述载体型催化剂的方法，其中a)将一种催化剂活性成份或其中间产物溶于溶剂，b)向上述溶液中加入能结合其本身重量至少十倍水的一种有机高聚物，c)使所述高聚物与催化剂载体混合，d)使由此得到的物料成型，干燥和焙烧。
7.一种丁炔、丁二烯或这些化合物的混合物选择加氢制丁烯的方法，其中加氢反应在权利要求1所述的载体型催化剂上进行。
8.一种乙炔选择加氢制乙烯的方法，其中加氢反应在权利要求1所述的载体型催化剂上进行。
9.一种丙炔、丙二烯或这些化合物的混合物选择加氢制丙烯的方法，其中加氢反应在权利要求1所述的载体型催化剂上进行。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4339138.9 | 1993-11-16 | ||
| DE4339138A DE4339138A1 (de) | 1993-11-16 | 1993-11-16 | Trägerkatalysatoren |
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| CN1078104C true CN1078104C (zh) | 2002-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN94119933A Expired - Fee Related CN1078104C (zh) | 1993-11-16 | 1994-11-16 | 载体型催化剂及其制备方法和用途 |
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| Country | Link |
|---|---|
| US (1) | US5516851A (zh) |
| EP (1) | EP0653243B1 (zh) |
| CN (1) | CN1078104C (zh) |
| CA (1) | CA2135733C (zh) |
| DE (2) | DE4339138A1 (zh) |
| ES (1) | ES2154660T3 (zh) |
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| DE19528942A1 (de) * | 1995-08-07 | 1997-02-13 | Basf Ag | Verfahren zur Herstellung von halogenfreiem, reaktivem Polyisobuten |
| DE19602710A1 (de) * | 1996-01-26 | 1997-07-31 | Basf Ag | Verfahren zur selektiven Hydrierung von Vinyloxiran zu 1,2-Butylenoxid an Heterogenkatalysatoren |
| US6248924B1 (en) | 1996-06-19 | 2001-06-19 | Basf Aktiengesellschaft | Process for reacting an organic compound in the presence of a supported ruthenium catalyst |
| DE19635893A1 (de) * | 1996-09-04 | 1998-03-05 | Basf Ag | Katalysatorzusammensetzung und Verfahren zu selektiven Reduktion von NO¶x¶ bei gleichzeitiger weitgehender Vermeidung der Oxidation von SO¶x¶ in sauerstoffhaltigen Verbrennungsabgasen |
| DE19636064A1 (de) * | 1996-09-05 | 1998-03-12 | Basf Ag | Verfahren zur Hydrierung |
| DE19645047A1 (de) * | 1996-10-31 | 1998-05-07 | Basf Ag | Katalysatoren für die Aminierung von Alkylenoxiden, Alkoholen, Aldehyden und Ketonen |
| DE19651129A1 (de) * | 1996-12-09 | 1998-06-10 | Basf Ag | Verfahren zur Hydrierung einer aromatischen Verbindung in Gegenwart eines Trägerkatalysators |
| US5859304A (en) * | 1996-12-13 | 1999-01-12 | Stone & Webster Engineering Corp. | Chemical absorption process for recovering olefins from cracked gases |
| DE19757297A1 (de) | 1997-12-22 | 1999-06-24 | Basf Ag | Verfahren zur Herstellung oxidischer Katalysatoren, die Kupfer in einer Oxidationsstufe > 0 enthalten |
| DE19832087A1 (de) * | 1998-07-16 | 2000-01-20 | Basf Ag | Verfahren zur Umsetzung von organischen Verbindungen mit boroxidhaltigen, makroporösen Trägerkatalysatoren |
| DE19839459A1 (de) | 1998-08-29 | 2000-03-02 | Basf Ag | Katalysator und Verfahren zur Selektivhydrierung ungesättigter Verbindungen in Kohlenwasserstoffströmen |
| DE19840372A1 (de) * | 1998-09-04 | 2000-03-09 | Basf Ag | Katalysator und Verfahren zur Reinigung von Stoffströmen |
| US6127588A (en) * | 1998-10-21 | 2000-10-03 | Phillips Petroleum Company | Hydrocarbon hydrogenation catalyst and process |
| GB9826486D0 (en) * | 1998-12-03 | 1999-01-27 | Johnson Matthey Plc | Improvements in coatings |
| US6297414B1 (en) | 1999-10-08 | 2001-10-02 | Stone & Webster Process Technology, Inc. | Deep selective hydrogenation process |
| EP1145763B1 (en) | 1999-10-27 | 2012-07-04 | Idemitsu Kosan Co., Ltd. | Hydrotreating catalyst for hydrocarbon oil, carrier for the same and method for hydrotreating of hydrocarbon oil |
| DE19962907A1 (de) * | 1999-12-23 | 2001-07-05 | Basf Ag | Verfahren zur Herstellung von C¶10¶-C¶30¶-Alkenen durch partielle Hydrierung von Alkinen an Festbett-Palladium-Trägerkatalysatoren |
| CN1090997C (zh) * | 2000-04-30 | 2002-09-18 | 中国石油化工集团公司 | 一种选择加氢除炔多金属催化剂 |
| DE10040091A1 (de) | 2000-08-16 | 2002-02-28 | Basf Ag | Verbessertes Verfahren zur Herstellung von Polytetrahydrofuran mit niedriger Farbzahl |
| US6465391B1 (en) * | 2000-08-22 | 2002-10-15 | Phillips Petroleum Company | Selective hydrogenation catalyst and processes therefor and therewith |
| US6734130B2 (en) | 2001-09-07 | 2004-05-11 | Chvron Phillips Chemical Company Lp | Hydrocarbon hydrogenation catalyst composition, a process of treating such catalyst composition, and a process of using such catalyst composition |
| DE10223067A1 (de) | 2002-05-24 | 2003-12-11 | Basf Ag | Verfahren zur Herstellung von Polytetrahydrofuran mit niedrigen Farbzahlen |
| JP4883162B2 (ja) | 2009-10-02 | 2012-02-22 | トヨタ自動車株式会社 | Ｃｏ又はｈｃ浄化用の排ガス浄化触媒 |
| FR2968578B1 (fr) | 2010-12-14 | 2013-06-28 | IFP Energies Nouvelles | Nouveau procede de preparation de catalyseurs a base de palladium et utilisation de ces catalyseurs en hydrogenation selective |
| EP2570470A1 (en) * | 2011-09-19 | 2013-03-20 | Shell Internationale Research Maatschappij B.V. | Hydrogenation catalyst |
| EP2610366A3 (en) * | 2011-12-31 | 2014-07-30 | Rohm and Haas Electronic Materials LLC | Plating catalyst and method |
| CN104768646B (zh) * | 2012-10-10 | 2017-12-08 | 阿尔比马尔欧洲有限公司 | 具有增强的活性的负载型加氢处理催化剂 |
| CN103736507B (zh) * | 2014-01-08 | 2015-11-18 | 常州大学 | 一种粘土基c22-环脂肪三酸酯合成用催化剂及其制备方法 |
| DE102019121084A1 (de) * | 2019-08-05 | 2021-02-11 | Umicore Ag & Co. Kg | Katalysatorsubstrate mit poröser Beschichtung |
| US20220105501A1 (en) * | 2019-09-30 | 2022-04-07 | Lg Chem, Ltd. | Catalyst for hydrogenation reaction and method for producing same |
| EP3903934A4 (en) * | 2019-09-30 | 2022-05-11 | LG Chem, Ltd. | HYDROGENATION REACTION CATALYST AND PROCESS FOR THE PREPARATION THEREOF |
| CN114524787B (zh) * | 2020-11-23 | 2023-10-13 | 中国科学院大连化学物理研究所 | 一种糠酸甲酯催化氧化偶联的方法 |
| CN114308065B (zh) * | 2021-12-24 | 2024-03-08 | 苏州知益微球科技有限公司 | 一种单分散Fe30Mo1-Pt催化剂微球的制备方法 |
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| EP0569077A1 (en) * | 1992-04-23 | 1993-11-10 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Process for preparing a supported metal catalyst |
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| US4762956A (en) * | 1983-04-13 | 1988-08-09 | Beijing Research Institute Of Chemical Industry He Ping Li | Novel catalyst and process for hydrogenation of unsaturated hydrocarbons |
| JPS60248237A (ja) * | 1984-05-25 | 1985-12-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | 成型触媒の製造方法 |
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- 1994-11-08 ES ES94117574T patent/ES2154660T3/es not_active Expired - Lifetime
- 1994-11-08 EP EP94117574A patent/EP0653243B1/de not_active Expired - Lifetime
- 1994-11-08 DE DE59409647T patent/DE59409647D1/de not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0569077A1 (en) * | 1992-04-23 | 1993-11-10 | Ministero Dell' Universita' E Della Ricerca Scientifica E Tecnologica | Process for preparing a supported metal catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111251A (zh) | 1995-11-08 |
| CA2135733C (en) | 2005-03-22 |
| ES2154660T3 (es) | 2001-04-16 |
| US5516851A (en) | 1996-05-14 |
| CA2135733A1 (en) | 1995-05-17 |
| DE59409647D1 (de) | 2001-03-08 |
| DE4339138A1 (de) | 1995-05-18 |
| EP0653243B1 (de) | 2001-01-31 |
| EP0653243A1 (de) | 1995-05-17 |
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