CN1286555C - 基于ZrO2的催化剂载体及其制备方法 - Google Patents
基于ZrO2的催化剂载体及其制备方法 Download PDFInfo
- Publication number
- CN1286555C CN1286555C CNB038099535A CN03809953A CN1286555C CN 1286555 C CN1286555 C CN 1286555C CN B038099535 A CNB038099535 A CN B038099535A CN 03809953 A CN03809953 A CN 03809953A CN 1286555 C CN1286555 C CN 1286555C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- silane
- zirconium dioxide
- weight
- dioxide powder
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 title description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004756 silanes Chemical class 0.000 claims abstract description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 20
- -1 alkoxy silane Chemical compound 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 239000001294 propane Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract 3
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- GRJISGHXMUQUMC-UHFFFAOYSA-N silyl prop-2-enoate Chemical class [SiH3]OC(=O)C=C GRJISGHXMUQUMC-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000013464 silicone adhesive Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- XWRLQRLQUKZEEU-UHFFFAOYSA-N ethyl(hydroxy)silicon Chemical class CC[Si]O XWRLQRLQUKZEEU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- YKIAZARODMJWBV-UHFFFAOYSA-N formic acid;lanthanum Chemical compound [La].OC=O YKIAZARODMJWBV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
-
- 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B01J35/60—
-
- 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
-
- 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)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- 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
-
- B01J35/30—
-
- B01J35/69—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
本发明涉及一种制备催化剂载体的方法，其中二氧化锆粉末与粘合剂、非必要的成孔剂、非必要的酸、水以及非必要的其它添加剂混合，得到可捏合的组合物，将该组合物均化以形成成型体，干燥和煅烧。所述粘合剂是单体、低聚或聚合的有机硅化合物。合适的粘合剂是单体的、低聚的或聚合的硅烷、烷氧基硅烷、芳氧基硅烷、酰氧基硅烷、肟基硅烷、卤代硅烷、胺氧基硅烷、氨基硅烷、酰氨基硅烷、硅氮烷或硅氧烷。本发明还涉及如此制备的催化剂载体，含有所述载体的催化剂以及它们作为脱氢催化剂的用途。
Description
本发明涉及一种催化剂载体，涉及其制备方法，和涉及包含该载体的脱氢催化剂以及脱氢催化剂的用途。
公知的是二氧化锆可以用作脱氢催化剂的催化剂载体。
EP-A 0 716 883公开了一种基本上由单斜晶二氧化锆组成的催化剂载体。它是通过将硝酸氧锆或二氯氧化锆溶液加入氨水溶液制备的，这导致pH从14降到6，洗涤沉淀产物，干燥，煅烧和造粒。以此方式生产的催化剂载体包含85-100重量％的单斜晶二氧化锆。
DE-A 196 54 391描述了通过将基本单斜晶二氧化锆用Pt(NO3)2和Sn(OAc)2的溶液浸渍或通过将二氧化锆先用Cr(NO3)3的第一溶液浸渍和然后用La(NO3)3的第二溶液浸渍来制备脱氢催化剂。浸渍的载体进行干燥，随后煅烧。以此方式获得的催化剂用作丙烷脱氢制备丙烯的脱氢催化剂。
现有技术的催化剂在其活性和其操作寿命方面仍然需要改进。
本发明的目的是提供一种用于生产脱氢催化剂的催化剂载体，它具有改进的性能，特别是改进的催化剂活性，和相应的脱氢催化剂本身。
我们已经发现该目的可以通过一种制备催化剂载体的方法实现，其中二氧化锆粉末与粘合剂、非必要的成孔剂、非必要的酸、水以及非必要的其它添加剂混合，得到可捏合的组合物，将该组合物均化，成型以生产成型体，干燥和煅烧，其中粘合剂是单体、低聚或聚合的有机硅化合物。
该目的还特别通过该方法获得的催化剂载体实现。
根据本发明，已经发现将具有高表面积的基本单斜晶二氧化锆粉末与有机硅化合物混合(其中有机硅化合物在作为粘合剂煅烧时形成SiO2)，将该混合物成型以生产成型体例如粒料、挤出物和球体，并煅烧成型体，这样能制得具有高机械稳定性和非常适合链烷脱氢的孔结构的催化剂载体。本发明的催化剂载体具有足够的稳定性来经受数百次氧化再生循环，且没有机械损坏和活性降低。
用作粘合剂的有机硅化合物通常是液体。结果，高表面积的二氧化锆在混合时被有机硅化合物均匀地润湿，使得二氧化锆颗粒被封闭和部分被有机硅化合物浸渍。这导致二氧化锆颗粒之间的高结合强度和所得成型催化剂载体的优异机械稳定性。在催化剂载体成型体进行煅烧时，有机硅粘合剂的有机基团被燃烧。这形成了非常细地分散在二氧化锆基体中的SiO2。有机硅粘合剂的有机基团的燃烧形成了额外的孔。由于有机硅粘合剂在二氧化锆基体中的均匀分布，这些孔也相似地非常均匀地分布。结果，催化剂的总孔隙度增加。另外，SiO2的存在对二氧化锆抗热烧结性起到稳定作用。二氧化硅分布得越均匀，这种作用就越显著。
适合作为有机硅粘合剂的化合物是单体的、低聚的或聚合的硅烷、烷氧基硅烷、芳氧基硅烷、酰氧基硅烷、肟基硅烷、卤代硅烷、胺氧基硅烷、氨基硅烷、酰氨基硅烷、硅氮烷和硅氧烷，例如描述在Ullmann’sEncyclopedia of Industrial Chemistry，第A24卷，21-56页。这些特别包括式(I)至式(VI)的单体化合物：
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal各自独立地是卤素(F、Cl、Br或I)，
R各自独立地是H或取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基，
R1、R2自独立地是H或取代或未取代的烷基、酰基、芳基烷基或芳基，和
x是0-4。
R、R1和R2各自独立地是H或烷基，优选C1-C6烷基，其可以是直链或支化的。如果R是烷基，R特别优选是甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基，特别是甲基或乙基。R、R1和R2也可以是芳基，优选苯基，或芳基烷基，优选苄基。
R还可以是链烯基，优选C2-C6链烯基，特别是乙烯基或烯丙基，或炔基，优选乙炔基。
R1和R2也可以是酰基，优选C2-C6酰基，特别是乙酰基。
合适的式(I)有机硅化合物例如是SiCl4、MeSiCl3、Me2SiCl2和Me3SiCl。
合适的式(IV)有机硅化合物是例如Si(OEt)4、MeSi(OEt)3、Me2Si(OEt)2和Me3SiOEt。
合适的式(V)化合物是例如Me3Si(NMeCOMe)和MeSi(NMeCOCH2C6H5)。
合适的式(VI)化合物是例如(MeO)3SiNMe2。
合适的低聚和聚合的有机硅化合物的例子是甲基硅氧烷和乙基硅氧烷。
非常特别优选的有机硅粘合剂是甲基硅氧烷，例如从Wacker获得的Silres产品。
在本发明方法的第一步中，二氧化锆粉末与有机硅粘合剂、非必要的成孔剂、非必要的酸、水以及非必要的其它添加剂混合，得到可捏合的组合物。优选将以下组分混合：
a)50-98重量％的二氧化锆粉末，
b)2-50重量％、特别优选5-20重量％的有机硅化合物，
c)0-48重量％、特别优选0-10重量％的成孔剂，和
d)0-48重量％、特别优选0-10重量％的其它添加剂，
其中组分a)至d)的总和是100重量％，
并且添加水和酸，得到可捏合的组合物。
二氧化锆粉末是具有高表面积的二氧化锆粉末，通常是基本单斜晶的二氧化锆粉末。在E P-A 0 716 883中描述了基本单斜晶的二氧化锆粉末，它包含85-100重量％、优选90-100重量％的基本单斜晶二氧化锆，是通过锆盐用氨沉淀制备的。这是如下进行的：将硝酸氧锆或二氯氧化锆溶液加入氨水溶液，这导致pH从14降到6，沉淀产物进行洗涤，干燥和煅烧。为此，先从碳酸锆和盐酸制备高度浓缩的、通常2-5摩尔％的氯化锆溶液，或从碳酸锆和硝酸制备高度浓缩的、通常2-5摩尔％的硝酸锆溶液。该溶液通常于20-60℃加入到氨水溶液中(约15摩尔％的NH3)，同时监控pH值；添加操作在pH为6-8时停止，且pH不能低于6。然后再搅拌通常30-600分钟。
沉淀产物例如在过滤压机上洗涤且基本上不含氨盐，干燥和于300-600℃、优选400-500℃和0.05-1巴压力下在空气中煅烧。以此方式制备的基本单斜晶二氧化锆偶尔仍然含有少量的四方形或立体改性结构。四方形或立体改性结构的比例可以通过在煅烧之前在0.2-0.9巴的水蒸汽分压下干燥产物而降低到X-射线结晶检测极限。这种干燥例如需要在120℃进行约16小时。
通常将水加入二氧化锆粉末和有机硅化合物中以获得可捏合的组合物。
此外，酸可以加入催化剂载体组合物中。这用于使可捏合的组合物造粒。合适的酸例如是硝酸和乙酸，优选硝酸。
催化剂载体组合物通常还包含成孔剂。合适的成孔剂例如是聚氧化烯，例如聚氧乙烯，烃例如纤维素和糖，天然纤维，浆料或合成聚合物，例如聚乙烯醇。
催化剂载体组合物可以进一步含有额外的添加剂。其它添加剂的例子是能影响流变学的公知化合物。
组分a)至f)在常规混合装置中混合和均化。合适的装置例如是捏合机、轮碾机、能确保初始非均相可捏合组合物被良好混合和均化的Mix-Mullers。催化剂载体组合物随后成型得到成型体，例如通过挤出形成棒状或空心载体来进行。
催化剂成型体然后通常进行干燥。干燥例如在90-120℃下进行10-100小时。
干燥的催化剂成型体然后进行煅烧。煅烧通常在300-800℃、优选400-600℃进行0.5-6小时。煅烧优选在空气中和在大气压下进行。
本发明的催化剂载体适合于生产氢化和脱氢催化剂，如DE-A 196 54391所述。这些包括在催化剂载体上的选自过渡族VIII和VI元素的一种或多种元素，如果需要的话包括选自主族I和II、包括镧系元素在内的过渡族III、主族III、铼、锌和锡的一种或多种其它元素。
特别有用的脱氢活性元素是过渡族VIII的金属，优选贵金属铂和钯，特别优选铂。
如果贵金属用作脱氢活性元素，可以存在能减慢贵金属烧结的其它金属，例如Re和/或Sn。
可能的其它元素是公知能影响催化剂表面的酸性或能使贵金属对烧结稳定的那些元素。这些其它元素是主族I和II的元素，即Li、Na、K、Rb、Cs、Mg、Ca、Sr和Ba，以及包括镧系元素在内的过渡族III的元素，特别是Y和La。Zn也是有效的。
代替贵金属，还可以在催化剂载体上存在过渡族VI的脱氢活性金属，特别是铬或钼。
脱氢活性金属通常通过用相应金属的合适化合物浸渍来施用。合适的化合物是能通过煅烧转化成相应金属氧化物的那些。金属氧化物还可以喷涂。合适的金属盐是例如金属的硝酸盐、乙酸盐和氯化物，金属的配合阴离子也是可能的。优选使用H2PtCl6或Pt(NO3)2涂覆铂，和使用 Cr(NO3)3或(NH4)2CrO4涂覆铬。为了施用碱金属和碱土金属，有利地使用能通过煅烧转化成相应氧化物的化合物的水溶液。合适的化合物是例如碱金属和碱土金属的氢氧化物、碳酸盐、草酸盐、乙酸盐或碱性碳酸盐。如果催化剂载体用主族或过渡族III的金属掺杂，则通常使用能通过煅烧转化成相应氧化物的氢氧化物、碳酸盐、硝酸盐、甲酸盐、乙酸盐或草酸盐，例如La(OH)3、La3(CO3)2、La(NO3)3、乙酸镧、甲酸镧或草酸镧。
用相应金属盐溶液浸渍的本发明催化剂载体的煅烧通常在350-650℃进行0.5-6小时。
本发明还提供使用本发明催化剂载体获得的催化剂。这些催化剂优选用作氢化催化剂或脱氢催化剂。
特别优选使用本发明的催化剂进行丙烷向丙烯的脱氢反应。
本发明通过以下实施例说明。
实施例
催化剂载体的制备
实施例1
将已经预先在450℃热处理3小时的200g ZrO2粉末与41.7g的3-甲基丙烯酰氧基丙基三甲氧基硅烷(硅烷MEMO，从Sivento获得)、6g的ZusoplastPS1(从Zshimmer & Schwarz获得)、6ml的65％重量浓度的HNO3和92ml的水一起捏合30分钟。所得的团状组合物在柱塞式挤出机中成型，得到外径为3mm的挤出物。该挤出物在120℃干燥，然后在560℃煅烧4小时。所得的载体的BET表面积是109m2/g，孔隙度是0.48ml/g(通过水银孔隙率检测计检测)，具有最大为20和1100nm的双模态孔直径分布。载体的切割硬度是25N。
实施例2
将已经预先在450℃热处理3小时的3680g ZrO2粉末与262.6g的甲氧基硅烷(Silres MSE 100，从Wacker获得)、110.4g的聚氧乙烯(Alkox E100)、110.4g的65％重量浓度的HNO3和1270g的水一起在轮碾机中捏合20分钟。所得的团状组合物在螺杆挤出机中成型，得到外径为3mm的挤出物。该挤出物在120℃干燥，然后在560℃热处理4小时。所得的载体的BET表面积是95m2/g，孔隙度是0.36ml/g(通过水银孔隙率检测计检测)，具有最大为20和450nm的双模态孔直径分布。载体的切割硬度是35N。
实施例3
将已经预先在450℃热处理3小时的200g ZrO2粉末与6g的聚氧乙烯(Alkox E100)、10.1g的Aerosil 200(从Degussa获得)、6ml的65％重量浓度的HNO3和100ml的水一起捏合30分钟。所得的团状组合物在柱塞式挤出机中成型，得到外径为3mm的挤出物。该挤出物在120℃干燥，然后在560℃煅烧4小时。所得的载体的BET表面积是75m2/g，孔隙度是0.49ml/g(通过水银孔隙率检测计检测)，载体的切割硬度是22N。
催化剂前体的制备
实施例4
将在实施例3中制备的载体材料切碎，得到1.6-2mm的筛分级分。切碎的载体用活性组分Pt/Sn/K/Cs和La按照下述方法涂覆。
将0.1814g的H2PtCl6·6H2O和0.2758g的SnCl2·2H2O溶解在138ml的乙醇中，并加入在旋转蒸发器中的23g从实施例3获得的ZrO2/SiO2载体材料中。上层的乙醇从旋转蒸发器上在水泵真空(20毫巴)和在40℃的水浴温度下取出。固体随后在100℃干燥15小时，然后在560℃煅烧3小时，在各情况下在静态空气中进行。将0.1773g的CsNO3、0.3127g的KNO3和2.2626g的La(NO3)3·6H2O在55ml水中的溶液倒在干固体上。上层的水从旋转蒸发器上在水泵真空(20毫巴)和在85℃的水浴温度下取出。固体随后在100℃干燥15小时，然后在560℃煅烧3小时，在各情况下在静态空气中进行。以此方式获得的催化剂前体在下面称为催化剂前体1。
实施例5
将在实施例2中制备的载体材料切碎，得到1.6-2mm的筛分级分。切碎的载体用活性组分Pt/Sn/K/Cs和La按照下述方法涂覆。
将0.2839g的H2PtCl6·6H2O和0.4317g的SnCl2·2H2O溶解在216ml的乙醇中，并加入在旋转蒸发器中的36g从实施例2获得的ZrO2/SiO2载体材料中。上层的乙醇从旋转蒸发器上在水泵真空(20毫巴)和在40℃的水浴温度下取出。固体随后在100℃干燥15小时，然后在560℃煅烧3小时，在各情况下在静态空气中进行。将0.2784g的CsNO3、0.4894g的KNO3和3.5399g的La(NO3)3·6H2O在86ml水中的溶液倒在干固体上。上层的水从旋转蒸发器上在水泵真空(20毫巴)和在85℃的水浴温度下取出。固体随后在100℃干燥15小时，然后在560℃煅烧3小时，在各情况下在静态空气中进行。以此方式获得的催化剂前体在下面称为催化剂前体2。
催化剂的活化
在实施例4和5中制备的用于丙烷脱氢的催化剂在实验室反应器中在以下条件下进行活化：
在各情况下向立式管反应器中加入20ml的催化剂前体1或2(反应器长度是520mm，壁厚是2mm，内径是20mm，反应器材料是内部合金化的(alonized)、即氧化铝涂覆的不锈钢管；加热采用在管长度中间处450mm上的电加热(BASF的炉，室内结构)，催化剂床的长度是60mm，催化剂床的位置是管式反应器长度的中间处；在顶部和底部处的剩余反应器体积用直径4-5mm的滑石球填充(惰性材料)，位于底部载体之上)。
随后将9.3标准l/h的氢气通过反应管30分钟，沿着加热区的外壁温度调节到500℃(基于其中通过相同惰性气流的管计)。氢气流然后在相同的壁温度下先被23.6标准l/h的80体积％氮气和20体积％空气的混合物料流代替30分钟，然后被纯空气的相同料流代替30分钟。在保持壁温度的同时，然后用N2的相同气流将该管吹扫15分钟，催化剂最后用9.3标准l/h的氢气还原30分钟。如此完成催化剂前体的活化。
粗丙烷的脱氢
在实施例4和5中制备的活化催化剂前体1和2的催化实验在各种情况下在相同反应器中活化催化剂之后进行，使用20标准l/h的粗丙烷、18g/h的水蒸汽和1标准L/h的氮气的混合物进行。粗丙烷通过从Brooks获得的质流调节器计量加入，同时通过HPLC泵(从Bischoff获得)将液体形式的水先加入蒸发器中，在其中蒸发，然后与粗丙烷和氮气混合。气体混合物然后经过催化剂。壁温度是622℃。
通过位于反应器出口的压力调节器(从REKO获得)将反应器出口的压力设定在1.5绝对巴。
已经在压力调节器下游解压到大气压的产物气体被冷却，使得在其中存在的水蒸气冷凝出来。剩余的未冷凝的气体通过GC分析(HP 6890，Chemical Station，检测器：FID、WLD，分离柱：Al2O3/KCl(Chrompack)，Carboxen 1010(Supelco))。反应气体也按照相似的方式分析。
下表显示了作为操作时间函数的结果。报道的数字是基于“干”气体计的体积百分数，即存在的水蒸气的量在所有情况下都不考虑。
表1
实施例4的活化的催化剂前体1(对比)
| 反应气体体积％ | 产品气体(1小时后)体积％ | 产品气体(9小时后)体积％ | |
| 丙烷 | 96.408 | 39.198 | 42.764 |
| 丙烯 | 0.014 | 24.598 | 23.741 |
| H2 | 0 | 30.942 | 29.281 |
| N2 | 3.5 | 2.648 | 2.875 |
| 乙烷 | 0.078 | 0.544 | 0.450 |
| 乙烯 | 0 | 0.234 | 0.258 |
| CH4 | 0 | 0.836 | 0.631 |
表2
实施例5的活化的催化剂前体2(根据本发明)
| 反应气体体积％ | 产品气体(1小时后)体积％ | 产品气体(9小时后)体积％ | |
| 丙烷 | 96.408 | 28.924 | 31.934 |
| 丙烯 | 0.014 | 26.574 | 27.953 |
| H2 | 0 | 38.530 | 36.011 |
| N2 | 3.5 | 2.386 | 2.490 |
| 乙烷 | 0.078 | 1.159 | 0.734 |
| 乙烯 | 0 | 1.166 | 0.677 |
| CH4 | 0 | 0.261 | 0.201 |
从上表可见，与对比催化剂相比，根据本发明的催化剂具有显著更高的活性。
Claims (6)
1.一种催化剂，包含在催化剂载体上的选自过渡族VIII和VI元素中的一种或多种元素，和在需要时包含选自主族I和II、包括镧系元素在内的过渡族III、主族III、铼、锌和锡中的一种或多种其它元素，其中所述催化剂载体是如下制备的：将二氧化锆粉末与作为粘合剂的单体、低聚或聚合的有机硅化合物、非必要的成孔剂、非必要的酸、水以及非必要的其它添加剂混合，得到可捏合的组合物，将该组合物均化，成型以生产成型体，干燥和煅烧，
其中所述单体、低聚或聚合的有机硅化合物是单体的、低聚的或聚合的硅烷、烷氧基硅烷、芳氧基硅烷、酰氧基硅烷、肟基硅烷、卤代硅烷、胺氧基硅烷、氨基硅烷、酰氨基硅烷、硅氮烷或硅氧烷。
2、根据权利要求1的催化剂，其中粘合剂是选自式(I)至式(VI)的化合物：
(Hal)xSiR4-x (I)
(Hal)xSi(OR1)4-x (II)
(Hal)xSi(NR1R2)4-x (III)
RxSi(OR1)4-x (IV)
RxSi(NR1R2)4-x (V)
(R1O)xSi(NR1R2)4-x (VI)
其中
Hal各自独立地是卤素，
R各自独立地是H或取代或未取代的烷基、链烯基、炔基、环烷基、环烯基、芳基烷基或芳基，
R1、R2各自独立地是H或取代或未取代的烷基、酰基、芳基烷基或芳基，和
x是0-4。
3、根据权利要求1或2的催化剂，其中以下组分在添加水和酸的情况下混合，得到可捏合的组合物：
a)50-98重量％的二氧化锆粉末，
b)2-50重量％的作为粘合剂的有机硅化合物，
c)0-48重量％的成孔剂，和
d)0-48重量％的其它添加剂，
其中组分a)至d)的总和是100重量％。
4、根据权利要求1或2的催化剂，其中二氧化锆粉末基本上由单斜晶二氧化锆粉末组成。
5、权利要求1或2的催化剂用作脱氢催化剂的用途。
6、权利要求5的用途，用于将丙烷脱氢为丙烯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10219879.9 | 2002-05-03 | ||
| DE10219879A DE10219879A1 (de) | 2002-05-03 | 2002-05-03 | Katalysatorträger und Verfahren zu seiner Herstellung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1649668A CN1649668A (zh) | 2005-08-03 |
| CN1286555C true CN1286555C (zh) | 2006-11-29 |
Family
ID=29265056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038099535A Expired - Fee Related CN1286555C (zh) | 2002-05-03 | 2003-05-02 | 基于ZrO2的催化剂载体及其制备方法 |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US7850842B2 (zh) |
| EP (1) | EP1503855B1 (zh) |
| JP (1) | JP4413134B2 (zh) |
| KR (1) | KR100944476B1 (zh) |
| CN (1) | CN1286555C (zh) |
| AT (1) | ATE505265T1 (zh) |
| AU (1) | AU2003240591B2 (zh) |
| BR (1) | BR0309653B1 (zh) |
| CA (1) | CA2482790A1 (zh) |
| DE (2) | DE10219879A1 (zh) |
| EA (1) | EA008478B1 (zh) |
| ES (1) | ES2363218T3 (zh) |
| MX (1) | MXPA04010296A (zh) |
| MY (1) | MY141278A (zh) |
| NO (1) | NO327435B1 (zh) |
| TW (1) | TWI266648B (zh) |
| WO (1) | WO2003092887A1 (zh) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10356184A1 (de) | 2003-12-02 | 2005-07-07 | Basf Ag | Zeolithisches Material vom Pentasil-Strukturtyp, seine Herstellung und seine Verwendung |
| DE102004029544A1 (de) | 2004-06-18 | 2006-01-05 | Basf Ag | Formkörper enthaltend ein mikroporöses Material und mindestens ein siliciumhaltiges Bindemittel, Verfahren zu seiner Herstellung und seine Verwendung als Katalysator, insbesondere in einem Verfahren zur Herstellung von Triethylendiamin (TEDA) |
| DE502005010622D1 (de) * | 2004-06-18 | 2011-01-13 | Basf Se | Verfahren zur kontinuierlichen synthese von methylaminen |
| US7572749B2 (en) * | 2004-08-31 | 2009-08-11 | Exxonmobil Research And Engineering Company | Structured bodies with siliceous binder |
| US20070004926A1 (en) | 2005-06-29 | 2007-01-04 | Basf Aktiengesellschaft | Process for producing propylene oxide |
| WO2007033934A2 (de) * | 2005-09-20 | 2007-03-29 | Basf Se | Verfahren zur ermittlung der tortuosität, katalysatorträger, katalysator und verfahren zur dehydrierung von kohlenwasserstoffen |
| DE102005052016B4 (de) * | 2005-10-31 | 2009-05-20 | Süd-Chemie AG | Verfahren zur Herstellung poröser Formkörper und Formkörper erhältlich durch das Verfahren |
| DE102005059711A1 (de) | 2005-12-12 | 2007-06-14 | Basf Ag | Formkörper enthaltend ein mikroporöses Material und mindestens ein siliciumhaltiges Bindemittel, Verfahren zu seiner Herstellung und seine Verwendung als Katalysator, insbesondere in einem Verfahren zur kontinuierlichen Synthese von Methylaminen |
| DE102007006647A1 (de) | 2007-02-06 | 2008-08-07 | Basf Se | Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts |
| DE102008036724A1 (de) * | 2008-08-07 | 2010-02-11 | Uhde Gmbh | Hochporöse Schaumkeramiken als Katalysatorträger zur Dehydrierung von Alkanen |
| EP2610318A1 (en) * | 2011-12-30 | 2013-07-03 | Essilor International (Compagnie Générale D'Optique) | Coating composition for an optical article, comprising a colloidal suspension of zirconia particles |
| IN2014DN09620A (zh) | 2012-06-22 | 2015-07-31 | Praxair Technology Inc ; | |
| EP3002058A1 (de) * | 2014-10-02 | 2016-04-06 | Evonik Degussa GmbH | Katalysatorsystem zur Herstellung von Ketonen aus Epoxiden |
| DK3227019T3 (en) | 2014-12-03 | 2019-04-23 | Basf Se | RHODIUM CATALYST FOR THE DEGRADATION OF LATTERY GAS, PREPARATION AND USE thereof |
| DE102015112612A1 (de) | 2015-07-31 | 2017-02-02 | Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock | Verfahren zur Herstellung von Olefinen sowie Katalysator |
| JP7472014B2 (ja) | 2017-07-27 | 2024-04-22 | ビーエーエスエフ コーポレーション | リーン／リッチシステムのための自動車排気からのｎ２ｏ除去 |
| CN108067211A (zh) * | 2017-12-13 | 2018-05-25 | 南京大学扬州化学化工研究院 | 一种甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法 |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159569A (en) * | 1961-03-30 | 1964-12-01 | Union Oil Co | Hydrocracking process and catalysts |
| GB1356249A (en) * | 1970-11-05 | 1974-06-12 | Zirconal Processes Ltd | Ethyl silicate binder |
| US4631267A (en) * | 1985-03-18 | 1986-12-23 | Corning Glass Works | Method of producing high-strength high surface area catalyst supports |
| FR2590887B1 (fr) * | 1985-12-02 | 1990-09-07 | Rhone Poulenc Spec Chim | Composition a base d'oxyde de zirconium et procede de preparation |
| US5032556A (en) * | 1989-02-21 | 1991-07-16 | Tosoh Corporation | Preparation method for zircon powder |
| DE59003114D1 (de) * | 1989-05-02 | 1993-11-25 | Lonza Ag | Sinterfähiges Zirkonoxidpulver und Verfahren zu seiner Herstellung. |
| JP2651332B2 (ja) * | 1992-09-21 | 1997-09-10 | 松下電工株式会社 | ジルコニア系複合セラミック焼結体及びその製法 |
| US5633217A (en) * | 1994-09-12 | 1997-05-27 | Corning Incorporated | Method of making a high strength catalyst, catalyst support or adsorber |
| DE4445142A1 (de) | 1994-12-17 | 1996-06-20 | Basf Ag | Katalysatoren oder Träger die im wesentlichen aus monoklinem Zirconiumdioxid bestehen |
| JP2703207B2 (ja) * | 1995-01-30 | 1998-01-26 | 松下電工株式会社 | ジルコニア系複合セラミック焼結体及びその製法 |
| GB2305430B (en) * | 1995-09-21 | 1997-08-27 | Matsushita Electric Works Ltd | Zirconia based ceramic material and process of making the same |
| US5667674A (en) * | 1996-01-11 | 1997-09-16 | Minnesota Mining And Manufacturing Company | Adsorption medium and method of preparing same |
| DE19654391A1 (de) | 1996-12-27 | 1998-07-02 | Basf Ag | Katalysator zur selektiven Herstellung von Propylen aus Propan |
| DE19743100A1 (de) * | 1997-09-30 | 1999-04-01 | Degussa | Verfahren zur Herstellung eines Schalenkatalysators |
| DE19832087A1 (de) * | 1998-07-16 | 2000-01-20 | Basf Ag | Verfahren zur Umsetzung von organischen Verbindungen mit boroxidhaltigen, makroporösen Trägerkatalysatoren |
| JP3643948B2 (ja) * | 1999-03-15 | 2005-04-27 | 株式会社豊田中央研究所 | チタニア−ジルコニア系粉末およびその製造方法 |
| DE19937107A1 (de) * | 1999-08-06 | 2001-02-08 | Basf Ag | Katalysator mit bimodaler Porenradienverteilung |
| US6376590B2 (en) * | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
| KR100679001B1 (ko) * | 2000-12-22 | 2007-02-07 | 바스프 악티엔게젤샤프트 | 이봉 세공 반경 분포를 갖는 촉매 |
-
2002
- 2002-05-03 DE DE10219879A patent/DE10219879A1/de not_active Withdrawn
-
2003
- 2003-04-15 MY MYPI20031407A patent/MY141278A/en unknown
- 2003-04-21 TW TW092109217A patent/TWI266648B/zh active
- 2003-05-02 BR BRPI0309653-0A patent/BR0309653B1/pt not_active IP Right Cessation
- 2003-05-02 ES ES03729967T patent/ES2363218T3/es not_active Expired - Lifetime
- 2003-05-02 EA EA200401445A patent/EA008478B1/ru not_active IP Right Cessation
- 2003-05-02 WO PCT/EP2003/004625 patent/WO2003092887A1/de active Application Filing
- 2003-05-02 JP JP2004501063A patent/JP4413134B2/ja not_active Expired - Fee Related
- 2003-05-02 AT AT03729967T patent/ATE505265T1/de active
- 2003-05-02 MX MXPA04010296A patent/MXPA04010296A/es active IP Right Grant
- 2003-05-02 US US10/513,041 patent/US7850842B2/en not_active Expired - Fee Related
- 2003-05-02 EP EP03729967A patent/EP1503855B1/de not_active Expired - Lifetime
- 2003-05-02 AU AU2003240591A patent/AU2003240591B2/en not_active Ceased
- 2003-05-02 CA CA002482790A patent/CA2482790A1/en not_active Abandoned
- 2003-05-02 KR KR1020047017612A patent/KR100944476B1/ko not_active IP Right Cessation
- 2003-05-02 DE DE50313615T patent/DE50313615D1/de not_active Expired - Lifetime
- 2003-05-02 CN CNB038099535A patent/CN1286555C/zh not_active Expired - Fee Related
-
2004
- 2004-10-22 NO NO20044561A patent/NO327435B1/no not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE50313615D1 (de) | 2011-05-26 |
| BR0309653A (pt) | 2005-03-01 |
| EA200401445A1 (ru) | 2005-06-30 |
| AU2003240591A1 (en) | 2003-11-17 |
| KR100944476B1 (ko) | 2010-03-03 |
| WO2003092887A1 (de) | 2003-11-13 |
| EA008478B1 (ru) | 2007-06-29 |
| CN1649668A (zh) | 2005-08-03 |
| US7850842B2 (en) | 2010-12-14 |
| JP2005528976A (ja) | 2005-09-29 |
| NO20044561L (no) | 2004-11-26 |
| TW200408445A (en) | 2004-06-01 |
| TWI266648B (en) | 2006-11-21 |
| ES2363218T3 (es) | 2011-07-27 |
| CA2482790A1 (en) | 2003-11-13 |
| AU2003240591B2 (en) | 2009-06-18 |
| ATE505265T1 (de) | 2011-04-15 |
| KR20040104687A (ko) | 2004-12-10 |
| MXPA04010296A (es) | 2005-03-31 |
| JP4413134B2 (ja) | 2010-02-10 |
| BR0309653B1 (pt) | 2013-03-19 |
| EP1503855B1 (de) | 2011-04-13 |
| EP1503855A1 (de) | 2005-02-09 |
| MY141278A (en) | 2010-04-16 |
| US20060046929A1 (en) | 2006-03-02 |
| DE10219879A1 (de) | 2003-11-20 |
| NO327435B1 (no) | 2009-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1286555C (zh) | 基于ZrO2的催化剂载体及其制备方法 | |
| CN1829676A (zh) | 羰基化合物的脱氢方法 | |
| KR20080096678A (ko) | 올레핀 산화 촉매용 담체, 그 제조 방법 및 적용 | |
| KR101647243B1 (ko) | 아크릴로니트릴의 제조 방법 | |
| CN109499558B (zh) | 一种α-氧化铝载体、银催化剂及烯烃环氧化方法 | |
| WO2012035637A1 (ja) | シリカ系材料及びその製造方法、並びに貴金属担持物及びそれを触媒として用いるカルボン酸類の製造方法 | |
| TW201231158A (en) | An alumina support, a preparation method for the same, and a silver catalyst prepared from the same, and use thereof | |
| US10695750B2 (en) | Catalyst for decomposition of nitrous oxide | |
| TW201522301A (zh) | 不飽和羧酸之製造方法及載持觸媒 | |
| CN1160151C (zh) | 甲醇蒸汽重整催化剂及用该催化剂制备氢气的方法 | |
| EP3738670A1 (en) | Catalyst, method for producing same, and method for producing diene compound using said catalyst | |
| JP6812620B2 (ja) | 酸化的脱水素化反応用触媒システム、それを含むブタジエン製造用反応器及び１，３−ブタジエンの製造方法 | |
| KR101431578B1 (ko) | 메타크릴산 제조 촉매의 제조 방법 및 메타크릴산의 제조 방법 | |
| KR102602129B1 (ko) | 불균일 촉매 | |
| JP5020514B2 (ja) | 流動層用触媒の製造方法およびニトリル類の製造方法 | |
| JP7197507B2 (ja) | 触媒及びその製造方法並びに前記触媒を用いたジエン化合物の製造方法 | |
| CN111939884A (zh) | 一种α-氧化铝载体及其制备方法和银催化剂及应用 | |
| CN107812542B (zh) | 一种α-氧化铝载体及其制备方法与应用 | |
| CN112007625A (zh) | 一种α-氧化铝载体及制备方法和银催化剂与应用 | |
| RU2779498C1 (ru) | Катализатор, способ получения катализатора и способ получения акрилонитрила | |
| KR102640090B1 (ko) | 불균일 촉매를 사용하여 산화적 에스터화에 의해 메틸 메타크릴레이트를 제조하는 방법 | |
| JP2023537205A (ja) | 機械的強度が高くかつ化学的に耐性のある触媒による酸化的エステル化のためのプロセス及び触媒 | |
| JP2011115683A (ja) | メタクリル酸製造用触媒の製造方法 | |
| WO2008077835A2 (de) | Trägerkatalysator für die metathese | |
| JP2008229511A (ja) | ジメチルエーテル製造用触媒とその製造方法およびこれを用いたジメチルエーテルの製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061129 Termination date: 20180502 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |