CA2482790A1 - Zr02-based catalyst carrier and method for the production thereof - Google Patents
Zr02-based catalyst carrier and method for the production thereof Download PDFInfo
- Publication number
- CA2482790A1 CA2482790A1 CA002482790A CA2482790A CA2482790A1 CA 2482790 A1 CA2482790 A1 CA 2482790A1 CA 002482790 A CA002482790 A CA 002482790A CA 2482790 A CA2482790 A CA 2482790A CA 2482790 A1 CA2482790 A1 CA 2482790A1
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- weight
- zirconium dioxide
- binder
- 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.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000001294 propane Substances 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 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
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000003795 chemical substances by application Substances 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
- 239000012018 catalyst precursor Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 alkyl radical Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 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
- 238000002459 porosimetry Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000005245 sintering Methods 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 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
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium nitrate Inorganic materials [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000004148 curcumin Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002823 nitrates Chemical class 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
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 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
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002339 La(NO3)3 Inorganic materials 0.000 description 1
- 229910020854 La(OH)3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 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
- PLOSEKHZRPLNLO-UHFFFAOYSA-K lanthanum(3+);triformate Chemical compound [La+3].[O-]C=O.[O-]C=O.[O-]C=O PLOSEKHZRPLNLO-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000006200 vaporizer Substances 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
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium 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
The invention relates to a method for the production of a catalyst carrier, wherein Zirconium dioxide powder is mixed with a binding agent, optionally a pore forming agent, optionally an acid, water and optionally other additives to form a kneadable mass, said mass is homogenized in order to form shaped bodies, dried and calcinated. The binding agent is a monomer, oligomer or polymer organosilicon compound.Suitable binding agents are monomer, oligomer or polymer silanes, alkoxysilanes, aryloxysilanes, acryloxysilanes, oximinosilanes, halogensilanes, aminoxysilanes, aminosilanes, amidosilanes, silazanes or silicones. The invention also relates to a catalyst carrier thu s produced, a catalyst containing said carrier and the use thereof as a dehydrogenation catalyst.
Description
THE PRODUCTION THEREOF
The invention relates to a catalyst support, to a process for its preparation, to a dehydrogenation catalyst comprising the support and to the use of the dehydrogenation catalyst.
It is known that zirconium dioxide can be used as catalyst support for dehydrogenation catalysts.
EP-A 0 716 883 discloses a catalyst support consisting essentially of monoclinic zirconium dioxide. This is prepared by addition of a zirconyl nitrate or zirconyl chloride solution to an aqueous ammonia solution, which results in the pH dropping from 14 to 6, washing the precipitated product, drying, calcination and tableting. The catalyst support produced in this way comprises from 85 to 100% by weight of monoclinic zirconium dioxide.
DE-A 196 54 391 describes the preparation of a dehydrogenation catalyst by impregnation of essentially monoclinic Zr02 with a solution of Pt(N03)2 and Sn(OAc)2 or by impregnation of the Zr02 with a first solution of Cr(N03)3 and subsequently a second solution of La.(N03)3. The impregnated supports are dried and subsequently calcined. The catalysts obtained in this way are used as dehydrogenation catalyst for the dehydrogenation of propane to propene.
The catalysts of the prior art are still capable of improvement in respect of their activity and their operating life.
It is an object of the present invention to provide a catalyst support for the production of dehydrogenation catalysts having improved properties, in particular an improved catalyst activity, and the corresponding dehydrogenation catalysts themselves.
We have found that this object is achieved by a process for preparing a catalyst support, in which zirconium dioxide powder is mixed with a binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition and the composition is homogenized, shaped to produce shaped bodies, dried and calcined, wherein the binder is a monomeric, oligomeric or polymeric organosilicon compound.
The object is also achieved by, in particular, the catalyst support obtainable by this process.
According to the present invention, it has been found that mixing essentially monoclinic zirconium dioxide powder which has a high surface area with an organosilicon compound which forms Si02 on calcination as binder, shaping the mixture to produce shaped bodies such as pellets, extrudates and spheres and calcining the shaped bodies enables catalyst supports having a high mechanical stability and a pore structure which is very well suited to the dehydrogenation of alkanes to be prepared. The catalyst supports of the present invention have sufficient stability to withstand several hundred oxidative regeneration cycles without mechanical damage and a drop in activity.
The organosilicon compounds used as binder are generally liquid. As a result, the high surface area zirconium dioxide is uniformly wetted with the organosilicon compound on mixing, so that the zirconium dioxide particles are enclosed and partially impregnated by the organosilicon compound. This results in a high bond strength between the zirconium 2o dioxide particles and a very good mechanical stability of the shaped catalyst support bodies obtained. On calcination of the shaped catalyst support bodies, the organic radicals of the organosilicon binder are burnt. This forms SiOz which is very finely dispersed in the zirconium dioxide matrix. The combustion of the organic radicals of the organosilicon binder forms additional pores. Due to the uniform distribution of the organosilicon binder in the zirconium dioxide matrix, these pores are likewise very uniformly distributed. As a result, the total porosity of the catalyst support is increased. In addition, the presence of Si02 stabilizes the zirconium dioxide against thermal sintering. This becomes increasingly pronounced, the more uniformly the silicon dioxide is distributed.
Compounds suitable as organosilicon binder are monomeric, oligomeric or polymeric silanes, alkoxysilanes, aryloxysilanes, acyloxysilanes, oximinosilanes, halosilanes, aminoxysilanes, aminosilanes, amidosilanes, silazanes and silicones, as are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A24, on pages 21 to 56.
These include, in particular, the monomeric compounds of the formulae (I) to (VI):
The invention relates to a catalyst support, to a process for its preparation, to a dehydrogenation catalyst comprising the support and to the use of the dehydrogenation catalyst.
It is known that zirconium dioxide can be used as catalyst support for dehydrogenation catalysts.
EP-A 0 716 883 discloses a catalyst support consisting essentially of monoclinic zirconium dioxide. This is prepared by addition of a zirconyl nitrate or zirconyl chloride solution to an aqueous ammonia solution, which results in the pH dropping from 14 to 6, washing the precipitated product, drying, calcination and tableting. The catalyst support produced in this way comprises from 85 to 100% by weight of monoclinic zirconium dioxide.
DE-A 196 54 391 describes the preparation of a dehydrogenation catalyst by impregnation of essentially monoclinic Zr02 with a solution of Pt(N03)2 and Sn(OAc)2 or by impregnation of the Zr02 with a first solution of Cr(N03)3 and subsequently a second solution of La.(N03)3. The impregnated supports are dried and subsequently calcined. The catalysts obtained in this way are used as dehydrogenation catalyst for the dehydrogenation of propane to propene.
The catalysts of the prior art are still capable of improvement in respect of their activity and their operating life.
It is an object of the present invention to provide a catalyst support for the production of dehydrogenation catalysts having improved properties, in particular an improved catalyst activity, and the corresponding dehydrogenation catalysts themselves.
We have found that this object is achieved by a process for preparing a catalyst support, in which zirconium dioxide powder is mixed with a binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition and the composition is homogenized, shaped to produce shaped bodies, dried and calcined, wherein the binder is a monomeric, oligomeric or polymeric organosilicon compound.
The object is also achieved by, in particular, the catalyst support obtainable by this process.
According to the present invention, it has been found that mixing essentially monoclinic zirconium dioxide powder which has a high surface area with an organosilicon compound which forms Si02 on calcination as binder, shaping the mixture to produce shaped bodies such as pellets, extrudates and spheres and calcining the shaped bodies enables catalyst supports having a high mechanical stability and a pore structure which is very well suited to the dehydrogenation of alkanes to be prepared. The catalyst supports of the present invention have sufficient stability to withstand several hundred oxidative regeneration cycles without mechanical damage and a drop in activity.
The organosilicon compounds used as binder are generally liquid. As a result, the high surface area zirconium dioxide is uniformly wetted with the organosilicon compound on mixing, so that the zirconium dioxide particles are enclosed and partially impregnated by the organosilicon compound. This results in a high bond strength between the zirconium 2o dioxide particles and a very good mechanical stability of the shaped catalyst support bodies obtained. On calcination of the shaped catalyst support bodies, the organic radicals of the organosilicon binder are burnt. This forms SiOz which is very finely dispersed in the zirconium dioxide matrix. The combustion of the organic radicals of the organosilicon binder forms additional pores. Due to the uniform distribution of the organosilicon binder in the zirconium dioxide matrix, these pores are likewise very uniformly distributed. As a result, the total porosity of the catalyst support is increased. In addition, the presence of Si02 stabilizes the zirconium dioxide against thermal sintering. This becomes increasingly pronounced, the more uniformly the silicon dioxide is distributed.
Compounds suitable as organosilicon binder are monomeric, oligomeric or polymeric silanes, alkoxysilanes, aryloxysilanes, acyloxysilanes, oximinosilanes, halosilanes, aminoxysilanes, aminosilanes, amidosilanes, silazanes and silicones, as are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A24, on pages 21 to 56.
These include, in particular, the monomeric compounds of the formulae (I) to (VI):
(Hal)XSiRa_X
(Hal)XSi(ORl)a-X (II) (H~)XSi(~1R2)a-X
RXSi(ORi)a_X (IV) RXSi(NR1R2)a-X (V) (R10)xSi(NR1R2)a-X
where to Hal are each, independently of one another, halogen (F, Cl, Br or I), R are each, independently of one another, H or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl or aryl radical, Rl, R2 are each, independently of one another, H or a substituted or unsubstituted alkyl, acyl, arylalkyl or aryl radical, and x is from 0 to 4.
R, Rl and R2 can each be H or an alkyl radical, preferably a Cl-C6-alkyl radical, which may be linear or branched. If R is an alkyl radical, R is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, especially methyl or ethyl. R, Rl and R2 2o can also be an aryl radical, preferably phenyl, or an arylalkyl radical, preferably benzyl.
R can also be an alkenyl radical, preferably a Cz-C6-alkenyl radical, in particular vinyl or allyl, or an alkynyl radical, preferably ethynyl.
Rl and R2 can also each be an acyl radical, preferably a CZ-C6-acyl radical, in particular an acetyl radical.
Examples of suitable organosilicon compounds of the formula (n are SiCla, MeSiCl3, Me2SiCl2 and Me3SiCl.
Suitable organosilicon compounds of the formula (IV) are, for example, Si(OEt)a, MeSi(OEt)3, MeZSi(OEt)2 and Me3Si0Et.
Suitable compounds of the formula (V) are, for example, Me3Si(NMeCOMe) and MeSi(NMeCOCH2C6H5).
(Hal)XSi(ORl)a-X (II) (H~)XSi(~1R2)a-X
RXSi(ORi)a_X (IV) RXSi(NR1R2)a-X (V) (R10)xSi(NR1R2)a-X
where to Hal are each, independently of one another, halogen (F, Cl, Br or I), R are each, independently of one another, H or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl or aryl radical, Rl, R2 are each, independently of one another, H or a substituted or unsubstituted alkyl, acyl, arylalkyl or aryl radical, and x is from 0 to 4.
R, Rl and R2 can each be H or an alkyl radical, preferably a Cl-C6-alkyl radical, which may be linear or branched. If R is an alkyl radical, R is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, especially methyl or ethyl. R, Rl and R2 2o can also be an aryl radical, preferably phenyl, or an arylalkyl radical, preferably benzyl.
R can also be an alkenyl radical, preferably a Cz-C6-alkenyl radical, in particular vinyl or allyl, or an alkynyl radical, preferably ethynyl.
Rl and R2 can also each be an acyl radical, preferably a CZ-C6-acyl radical, in particular an acetyl radical.
Examples of suitable organosilicon compounds of the formula (n are SiCla, MeSiCl3, Me2SiCl2 and Me3SiCl.
Suitable organosilicon compounds of the formula (IV) are, for example, Si(OEt)a, MeSi(OEt)3, MeZSi(OEt)2 and Me3Si0Et.
Suitable compounds of the formula (V) are, for example, Me3Si(NMeCOMe) and MeSi(NMeCOCH2C6H5).
An example of a suitable compound of the formula (VI) is (Me0)3SiNMez.
Examples of suitable oligomeric and polymeric organosilicon compounds are methylsilicones and ethylsilicones.
Very particularly preferred organosilicon binders are methylsilicones, for example the Silres~ products from Wacker.
In a first step of the process of the present invention, zirconium dioxide powder is mixed to with the organosilicon binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition. Preference is given to mixing a) from 50 to 98% by weight of zirconium dioxide powder, b) from 2 to 50% by weight, particularly preferably from 5 to 20% by weight, of the organosilicon compound, c) from 0 to 48% by weight, particularly preferably from 0 to 10% by weight, of pore formers, and d) from 0 to 48% by weight, particularly preferably from 0 to 10% by weight, of further additives, where the sum of the components a) to d) is 100% by weight, with addition of water and an acid to give a kneadable composition.
The zirconium dioxide powder is zirconium dioxide powder having a high surface area, usually an essentially monoclinic zriconium dioxide powder. Essentially monoclinic 3o zirconium dioxide powder comprising from 85 to 100% by weight, preferably from 90 to 100% by weight, of monoclinic zirconium dioxide can, as described in EP-A 0 716 883, be prepared by precipitation of zirconium salts with ammonia. This is achieved by adding a zirconyl nitrate or zirconyl chloride solution to an aqueous ammonia solution, resulting in the pH dropping from 14 to 6, and washing, drying and calcining the precipitated product.
For this purpose, a highly concentrated, generally from 2 to 5 mol%, zirconium chloride solution is firstly prepared from zirconium carbonate and hydrochloric acid or a highly concentrated, generally from 2 to 5 mol%, zirconium nitrate solution is prepared from zirconium carbonate and nitric acid. This solution is generally added to an aqueous ammonia solution (about 15 mol% of NH3) at from 20 to 60°C while monitoring the pH;
the addition is stopped at a pH of 6-8 and the pH must not drop below 6. This is followed by further stirring for a time of generally from 30 to 600 minutes.
The precipitated product is, for example, washed on a filter press and substantially freed of ammonia salts, dried and calcined in air at from 300 to 600°C, preferably from 400 to 500°C and a pressure of from 0.05 to 1 bar. The essentially monoclinic zirconium dioxide prepared in this way occasionally still contains small amounts of the tetragonal or cubic modification. The proportion of the tetragonal or cubic modification can be reduced to the X-ray crystallographic detection limit by drying the product at a partial pressure of water vapor of from 0.2 to 0.9 bar before calcination. This drying takes, for example, about 16 hours at 120°C.
Water is usually added to the zirconium dioxide powder and the organosilicon compound in order to obtain a kneadable composition.
Furthermore, an acid can be added to the catalyst support composition. This serves to 2o peptize the kneadable composition. Examples of suitable acids are nitric acid and acetic acid; preference is given to nitric acid.
The catalyst support composition usually further comprises a pore former.
Suitable pore formers are, for example, polyalkylene oxides such as polyethylene oxide, carbohydrates such as cellulose and sugar, natural fibers, pulp or synthetic polymers such as polyvinyl alcohol.
The catalyst support composition can further comprise additional additives.
Examples of additional additives are known compounds which influence the rheology.
The components a) to f) are mixed and homogenized in customary mixing apparatuses.
Suitable apparatuses are, for example, kneaders, edge runner mills, Mix-Mullers which ensure good mixing and homogenization of the initially inhomogeneous kneadable composition. The catalyst support composition is subsequently shaped to produce shaped bodies, for example by extrusion to form rods or hollow supports.
Examples of suitable oligomeric and polymeric organosilicon compounds are methylsilicones and ethylsilicones.
Very particularly preferred organosilicon binders are methylsilicones, for example the Silres~ products from Wacker.
In a first step of the process of the present invention, zirconium dioxide powder is mixed to with the organosilicon binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition. Preference is given to mixing a) from 50 to 98% by weight of zirconium dioxide powder, b) from 2 to 50% by weight, particularly preferably from 5 to 20% by weight, of the organosilicon compound, c) from 0 to 48% by weight, particularly preferably from 0 to 10% by weight, of pore formers, and d) from 0 to 48% by weight, particularly preferably from 0 to 10% by weight, of further additives, where the sum of the components a) to d) is 100% by weight, with addition of water and an acid to give a kneadable composition.
The zirconium dioxide powder is zirconium dioxide powder having a high surface area, usually an essentially monoclinic zriconium dioxide powder. Essentially monoclinic 3o zirconium dioxide powder comprising from 85 to 100% by weight, preferably from 90 to 100% by weight, of monoclinic zirconium dioxide can, as described in EP-A 0 716 883, be prepared by precipitation of zirconium salts with ammonia. This is achieved by adding a zirconyl nitrate or zirconyl chloride solution to an aqueous ammonia solution, resulting in the pH dropping from 14 to 6, and washing, drying and calcining the precipitated product.
For this purpose, a highly concentrated, generally from 2 to 5 mol%, zirconium chloride solution is firstly prepared from zirconium carbonate and hydrochloric acid or a highly concentrated, generally from 2 to 5 mol%, zirconium nitrate solution is prepared from zirconium carbonate and nitric acid. This solution is generally added to an aqueous ammonia solution (about 15 mol% of NH3) at from 20 to 60°C while monitoring the pH;
the addition is stopped at a pH of 6-8 and the pH must not drop below 6. This is followed by further stirring for a time of generally from 30 to 600 minutes.
The precipitated product is, for example, washed on a filter press and substantially freed of ammonia salts, dried and calcined in air at from 300 to 600°C, preferably from 400 to 500°C and a pressure of from 0.05 to 1 bar. The essentially monoclinic zirconium dioxide prepared in this way occasionally still contains small amounts of the tetragonal or cubic modification. The proportion of the tetragonal or cubic modification can be reduced to the X-ray crystallographic detection limit by drying the product at a partial pressure of water vapor of from 0.2 to 0.9 bar before calcination. This drying takes, for example, about 16 hours at 120°C.
Water is usually added to the zirconium dioxide powder and the organosilicon compound in order to obtain a kneadable composition.
Furthermore, an acid can be added to the catalyst support composition. This serves to 2o peptize the kneadable composition. Examples of suitable acids are nitric acid and acetic acid; preference is given to nitric acid.
The catalyst support composition usually further comprises a pore former.
Suitable pore formers are, for example, polyalkylene oxides such as polyethylene oxide, carbohydrates such as cellulose and sugar, natural fibers, pulp or synthetic polymers such as polyvinyl alcohol.
The catalyst support composition can further comprise additional additives.
Examples of additional additives are known compounds which influence the rheology.
The components a) to f) are mixed and homogenized in customary mixing apparatuses.
Suitable apparatuses are, for example, kneaders, edge runner mills, Mix-Mullers which ensure good mixing and homogenization of the initially inhomogeneous kneadable composition. The catalyst support composition is subsequently shaped to produce shaped bodies, for example by extrusion to form rods or hollow supports.
The shaped catalyst bodies are then usually dried. Drying is carried out, for example, at from 90 to 120°C for a period of from 10 to 100 hours.
The dried shaped catalyst support body is subsequently calcined. Calcination is usually carried out at from 300 to 800°C, preferably from 400 to 600°C, for a period of from 0.5 to 6 hours. Calcination is preferably carried out in air and at atmospheric pressure.
The catalyst supports of the present invention are suitable for producing hydrogenation and dehydrogenation catalysts as are described, for example, in DE-A 196 54 391.
These l0 comprise, on the catalyst support, one or more elements selected from the group consisting of the elements of transition groups VIII and VI, if desired together with one or more further elements selected from the group consisting of the elements of main groups I and II, transition group III including the lanthanides, main group III, rhenium, zinc and tin.
Particularly useful dehydrogenation-active elements are metals of transition group VIII, preferably the noble metals platinum and palladium, particularly preferably platinum.
If a noble metal is used as dehydrogenation-active element, it is possible for additional metals which slow the sintering of the noble metal, e.g. Re and/or Sn, to be present.
Possible further elements are ones which are known to be able to influence the acidity of the catalyst surface or stabilize the noble metals against sintering. Such further elements are elements of main groups I and II, namely Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba and also elements of transition group III including the lanthanides, in particular Y and La. Zn has also been found to be effective.
In place of a noble metal, it is also possible for dehydrogenation-active metals of transition group VI, in particular chromium or molybdenum, to be present on the catalyst support.
3o The dehydrogenation-active metals) are generally applied by impregnation with suitable compounds of the metals concerned. Suitable compounds are those which can be converted into the corresponding metal oxide by calcination. The metal compounds) can also be sprayed on. Suitable metal salts are, for example, the nitrates, acetates and chlorides of the metals, and complex anions of the metals are also possible. Preference is given to using HZPtCI6 or Pt(N03)2 for applying platinum and Cr(N03)3 or (NH4)2Cr04 for applying chromium. To apply alkali metals and alkaline earth metals, use is advantageously made of _7_ aqueous solutions of compounds which can be converted into the corresponding oxides by calcination. Suitable compounds are, for example, hydroxides, carbonates, oxalates, acetates or basic carbonates of the alkali metals and alkaline earth metals.
If the catalyst support is doped with metals of main or transition group III, use is frequently made of the hydroxides, carbonates, nitrates, acetates, formates or oxalates which can be converted into the corresponding oxides by calcination, for example La(OH)3, La3(C03)2, La(N03)3, lanthanum acetate, lanthanum formate or lanthanum oxalate.
The calcination of the catalyst supports of the present invention impregnated with the to metal salt solution concerned is usually carried out at from 350 to 650°C for a period of from 0.5 to 6 hours.
The present invention also provides the catalysts obtainable using the catalyst supports of the present invention. These are preferably used as hydrogenation catalysts or dehydrogenation catalysts.
Particular preference is given to using the catalysts of the present invention for the dehydrogenation of propane to propene.
2o The invention is illustrated by the following examples.
Examples Preparation of the catalyst supports Example 1 200 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are kneaded together with 41.7 g of 3-methacryloxypropyltrimethoxysilane (silane MEMO
from Sivento), 6 g of Zusoplast PS1 (from Zschimmer & Schwarz), 6 ml of 65%
strength 3o by weight HN03 and 92 ml of water for 30 minutes. The doughy composition obtained is shaped in a ram extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C and subsequently calcined at 560°C
for 4 hours. The support obtained has a BET surface area of 109 m2/g and a porosity of 0.48 mllg (measured by mercury porosimetry) and has a bimodal pore diameter distribution with maxima at 20 and 1100 nm. The cutting hardness of the support is 25 N.
_g_ Example 2 3680 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are mixed with 262.6 g of methoxysilane (Silres MSE 100 from blacker), 110.4 g of polyethylene oxide (Alkox E100), 110.4 g of 65% strength by weight HN03 and 1270 g of water for 20 minutes in an edge runner mill. The resulting doughy composition is shaped in a screw extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C and subsequently heat-treated at 560°C for 4 hours. The support obtained has a BET surface area of 95 m2/g and a porosity of 0.36 ml/g (measured by mercury porosimetry) and has a bimodal pore diameter distribution with maxima at 20 and 450 nm. The cutting hardness of the support is 35 N.
Example 3 200 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are kneaded together with 6 g of polyethylene oxide (Alkox E100), 10.1 g of Aerosil 200 (from Degussa), 6 ml of 65% strength by weight HN03 and 100 ml of water for 30 minutes. The doughy composition obtained is shaped in a ram extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C
and subsequently calcined at 560°C for 4 hours. The support obtained has a BET surface area of 75 m2/g, a porosity measured by means of Hg porosimetry of 0.49 ml/g and a cutting hardness of 22 N.
Preparation of the catalyst precursors Example 4 The support material prepared as described in Example 3 is crushed and a sieve fraction of 1.6-2 mm is obtained. The crushed support is coated with the active components PtlSn/K/Cs and La by the method described below.
0.1814 g of HZPtCI6 ~ 6 H20 and 0.2758 g of SnCl2 ~ 2 H20 are dissolved in 138 ml of ethanol and added to 23 g of the Zr02/Si02 support material from Example 3 in a rotary evaporator. The supernatant ethanol is taken off on the rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 40°C. The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case in stationary air. A
solution of 0.1773 g of CsN03, 0.3127 g of KN03 and 2.2626 g of La(N03)3 ~ 6 H20 in 55 ml of H20 is then poured over the dried solid. The supernatant water is taken off on a rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 85°C.
The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case under stationary air. The catalyst precursor obtained in this way will hereinafter be referred to as catalyst precursor 1.
Example 5 The support material prepared as described in Example 2 is crushed and a sieve fraction of 1.6-2 mm is obtained. The crushed support is coated with the active components Pt/Sn/K/Cs and La by the method described below.
0.2839 g of HZPtCI6 ~ 6 H20 and 0.4317 g of SnCl2 ~ 2 H20 are dissolved in 216 ml of ethanol and added to 36 g of the Zr02/Si02 support material from Example 2 in a rotary evaporator. The supernatant ethanol is taken off on the rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 40°C. The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case in stationary air. A
solution of 0.2784 g of CsN03, 0.4894 g of KN03 and 3.5399 g Of La(NO3)3 ~ 6 H20 in 86 ml of H20 is then poured over the dried solid. The supernatant water is taken off on a rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 85°C.
The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case under stationary air. The catalyst precursor obtained in this way will hereinafter be referred to as catalyst precursor 2.
Catalyst Activation The activation of the catalysts prepared in Examples 4 and 5 for the dehydrogenation of propane is carned out in a laboratory reactor under the following conditions:
An upright tube reactor is charged in each case with 20 ml of catalyst precursor 1 or 2 (reactor length: 520 mm; wall thickness 2 mm; internal diameter: 20 mm;
reactor material:
internally alonized, i.e. aluminum oxide-coated steel tube; heating: electric (furnace of BASF in-house construction) over a length of 450 mm in the middle of the length of the tube; length of the catalyst bed: 60 mm; position of the catalyst bed: in the middle of the length of the tube reactor; filling of the remaining reactor volume at the top and bottom with steatite spheres (inert material) having a diameter of 4-5 mm, resting on a support at the bottom).
9.3 standard I/h of hydrogen are subsequently passed through the reaction tube for 30 minutes with the external wall temperature along the heating zone being regulated to 500°C (based on a tube through which an identical inert gas stream is passed). The hydrogen stream is subsequently replaced at the same wall temperature firstly by a stream of 23.6 standard 1/h of a mixture of 80% by volume of nitrogen and 20% by volume of air for 30 minutes and then by an identical stream of pure air for 30 minutes.
While 1o maintaining the wall temperature, the tube is then flushed with an identical stream of NZ
for 15 minutes and the catalyst is finally reduced with 9.3 standard 1ih of hydrogen for 30 minutes. The activation of the catalyst precursor is thus concluded.
Dehydrogenation of crude propane Catalytic testing of the activated catalyst precursors 1 and 2 prepared in Examples 4 and 5 was in each case carned out subsequent to the activation of the catalyst in the same reactor using a mixture of 20 standard 1/h of crude propane, 18 g/h of water vapor and 1 standard 1/h of nitrogen. Crude propane was metered in by means of a mass flow regulator from 2o Brooks, while the water was initially introduced in liquid form by means of an HPLC
pump (from Bischoffj into the vaporizer, vaporized in this and then mixed with the crude propane and nitrogen. The gas mixture was subsequently passed over the catalyst. The wall temperature was 622°C.
The pressure at the outlet of the reactor was set to 1.5 bar absolute by means of a pressure regulator (from REKO) located at the reactor outlet.
The product gas which had been depressurized to atmospheric pressure downstream of the pressure regulator was cooled, resulting in the water vapor present in it condensing out.
3o The remaining uncondensed gas was analyzed by means of GC (HP 6890 with Chem-Station, detectors: Fm, WLD, separation columns: A1203/KCl (Chrompack), Carboxen 1010 (Supelco)). The reaction gas was also analyzed in an analogous fashion.
The tables below show the results achieved as a function of the operating time. The figures reported are in percent by volume based on "dry" gas, i.e. the amount of water vapor present was in all cases disregarded.
Table 1:
Activated catalyst precursor 1 from Example 4 (comparison) Reaction gas Product gas Product gas (after % b volume (after 1 h) 9 h) % b volume % b volume Pro ane 96.408 39.198 42.764 Pro ne 0.014 24.598 23.741 H2 0 30.942 29.281 NZ 3.5 2.648 2.875 Ethane 0.078 0.544 0.450 Ethene 0 0.234 0.258 CH4 0 0.836 0.631 Table 2:
1o Activated catalyst precursor 2 from Example 5 (according to the present invention) Reaction gas Product gas Product gas (after % b volume (after 1 h) 9 h) % b volume % b volume Pro ane 96.408 28.924 31.934 Pro ene 0.014 26.574 27.953 H2 0 38.530 36.011 N2 3.5 2.386 2.490 Ethane 0.078 1.159 0.734 Ethene 0 1.166 0.677 CH4 0 0.261 0.201 As can be seen from the tables, the catalyst according to the present invention has a significantly higher activity than the comparative catalyst.
The dried shaped catalyst support body is subsequently calcined. Calcination is usually carried out at from 300 to 800°C, preferably from 400 to 600°C, for a period of from 0.5 to 6 hours. Calcination is preferably carried out in air and at atmospheric pressure.
The catalyst supports of the present invention are suitable for producing hydrogenation and dehydrogenation catalysts as are described, for example, in DE-A 196 54 391.
These l0 comprise, on the catalyst support, one or more elements selected from the group consisting of the elements of transition groups VIII and VI, if desired together with one or more further elements selected from the group consisting of the elements of main groups I and II, transition group III including the lanthanides, main group III, rhenium, zinc and tin.
Particularly useful dehydrogenation-active elements are metals of transition group VIII, preferably the noble metals platinum and palladium, particularly preferably platinum.
If a noble metal is used as dehydrogenation-active element, it is possible for additional metals which slow the sintering of the noble metal, e.g. Re and/or Sn, to be present.
Possible further elements are ones which are known to be able to influence the acidity of the catalyst surface or stabilize the noble metals against sintering. Such further elements are elements of main groups I and II, namely Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba and also elements of transition group III including the lanthanides, in particular Y and La. Zn has also been found to be effective.
In place of a noble metal, it is also possible for dehydrogenation-active metals of transition group VI, in particular chromium or molybdenum, to be present on the catalyst support.
3o The dehydrogenation-active metals) are generally applied by impregnation with suitable compounds of the metals concerned. Suitable compounds are those which can be converted into the corresponding metal oxide by calcination. The metal compounds) can also be sprayed on. Suitable metal salts are, for example, the nitrates, acetates and chlorides of the metals, and complex anions of the metals are also possible. Preference is given to using HZPtCI6 or Pt(N03)2 for applying platinum and Cr(N03)3 or (NH4)2Cr04 for applying chromium. To apply alkali metals and alkaline earth metals, use is advantageously made of _7_ aqueous solutions of compounds which can be converted into the corresponding oxides by calcination. Suitable compounds are, for example, hydroxides, carbonates, oxalates, acetates or basic carbonates of the alkali metals and alkaline earth metals.
If the catalyst support is doped with metals of main or transition group III, use is frequently made of the hydroxides, carbonates, nitrates, acetates, formates or oxalates which can be converted into the corresponding oxides by calcination, for example La(OH)3, La3(C03)2, La(N03)3, lanthanum acetate, lanthanum formate or lanthanum oxalate.
The calcination of the catalyst supports of the present invention impregnated with the to metal salt solution concerned is usually carried out at from 350 to 650°C for a period of from 0.5 to 6 hours.
The present invention also provides the catalysts obtainable using the catalyst supports of the present invention. These are preferably used as hydrogenation catalysts or dehydrogenation catalysts.
Particular preference is given to using the catalysts of the present invention for the dehydrogenation of propane to propene.
2o The invention is illustrated by the following examples.
Examples Preparation of the catalyst supports Example 1 200 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are kneaded together with 41.7 g of 3-methacryloxypropyltrimethoxysilane (silane MEMO
from Sivento), 6 g of Zusoplast PS1 (from Zschimmer & Schwarz), 6 ml of 65%
strength 3o by weight HN03 and 92 ml of water for 30 minutes. The doughy composition obtained is shaped in a ram extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C and subsequently calcined at 560°C
for 4 hours. The support obtained has a BET surface area of 109 m2/g and a porosity of 0.48 mllg (measured by mercury porosimetry) and has a bimodal pore diameter distribution with maxima at 20 and 1100 nm. The cutting hardness of the support is 25 N.
_g_ Example 2 3680 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are mixed with 262.6 g of methoxysilane (Silres MSE 100 from blacker), 110.4 g of polyethylene oxide (Alkox E100), 110.4 g of 65% strength by weight HN03 and 1270 g of water for 20 minutes in an edge runner mill. The resulting doughy composition is shaped in a screw extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C and subsequently heat-treated at 560°C for 4 hours. The support obtained has a BET surface area of 95 m2/g and a porosity of 0.36 ml/g (measured by mercury porosimetry) and has a bimodal pore diameter distribution with maxima at 20 and 450 nm. The cutting hardness of the support is 35 N.
Example 3 200 g of Zr02 powder which has been heat-treated beforehand at 450°C
for 3 hours are kneaded together with 6 g of polyethylene oxide (Alkox E100), 10.1 g of Aerosil 200 (from Degussa), 6 ml of 65% strength by weight HN03 and 100 ml of water for 30 minutes. The doughy composition obtained is shaped in a ram extruder to give extrudates having an external diameter of 3 mm. The extrudates are dried at 120°C
and subsequently calcined at 560°C for 4 hours. The support obtained has a BET surface area of 75 m2/g, a porosity measured by means of Hg porosimetry of 0.49 ml/g and a cutting hardness of 22 N.
Preparation of the catalyst precursors Example 4 The support material prepared as described in Example 3 is crushed and a sieve fraction of 1.6-2 mm is obtained. The crushed support is coated with the active components PtlSn/K/Cs and La by the method described below.
0.1814 g of HZPtCI6 ~ 6 H20 and 0.2758 g of SnCl2 ~ 2 H20 are dissolved in 138 ml of ethanol and added to 23 g of the Zr02/Si02 support material from Example 3 in a rotary evaporator. The supernatant ethanol is taken off on the rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 40°C. The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case in stationary air. A
solution of 0.1773 g of CsN03, 0.3127 g of KN03 and 2.2626 g of La(N03)3 ~ 6 H20 in 55 ml of H20 is then poured over the dried solid. The supernatant water is taken off on a rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 85°C.
The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case under stationary air. The catalyst precursor obtained in this way will hereinafter be referred to as catalyst precursor 1.
Example 5 The support material prepared as described in Example 2 is crushed and a sieve fraction of 1.6-2 mm is obtained. The crushed support is coated with the active components Pt/Sn/K/Cs and La by the method described below.
0.2839 g of HZPtCI6 ~ 6 H20 and 0.4317 g of SnCl2 ~ 2 H20 are dissolved in 216 ml of ethanol and added to 36 g of the Zr02/Si02 support material from Example 2 in a rotary evaporator. The supernatant ethanol is taken off on the rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 40°C. The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case in stationary air. A
solution of 0.2784 g of CsN03, 0.4894 g of KN03 and 3.5399 g Of La(NO3)3 ~ 6 H20 in 86 ml of H20 is then poured over the dried solid. The supernatant water is taken off on a rotary evaporator in a water pump vacuum (20 mbar) at a water bath temperature of 85°C.
The solid is subsequently dried at 100°C for 15 hours and then calcined at 560°C for 3 hours, in each case under stationary air. The catalyst precursor obtained in this way will hereinafter be referred to as catalyst precursor 2.
Catalyst Activation The activation of the catalysts prepared in Examples 4 and 5 for the dehydrogenation of propane is carned out in a laboratory reactor under the following conditions:
An upright tube reactor is charged in each case with 20 ml of catalyst precursor 1 or 2 (reactor length: 520 mm; wall thickness 2 mm; internal diameter: 20 mm;
reactor material:
internally alonized, i.e. aluminum oxide-coated steel tube; heating: electric (furnace of BASF in-house construction) over a length of 450 mm in the middle of the length of the tube; length of the catalyst bed: 60 mm; position of the catalyst bed: in the middle of the length of the tube reactor; filling of the remaining reactor volume at the top and bottom with steatite spheres (inert material) having a diameter of 4-5 mm, resting on a support at the bottom).
9.3 standard I/h of hydrogen are subsequently passed through the reaction tube for 30 minutes with the external wall temperature along the heating zone being regulated to 500°C (based on a tube through which an identical inert gas stream is passed). The hydrogen stream is subsequently replaced at the same wall temperature firstly by a stream of 23.6 standard 1/h of a mixture of 80% by volume of nitrogen and 20% by volume of air for 30 minutes and then by an identical stream of pure air for 30 minutes.
While 1o maintaining the wall temperature, the tube is then flushed with an identical stream of NZ
for 15 minutes and the catalyst is finally reduced with 9.3 standard 1ih of hydrogen for 30 minutes. The activation of the catalyst precursor is thus concluded.
Dehydrogenation of crude propane Catalytic testing of the activated catalyst precursors 1 and 2 prepared in Examples 4 and 5 was in each case carned out subsequent to the activation of the catalyst in the same reactor using a mixture of 20 standard 1/h of crude propane, 18 g/h of water vapor and 1 standard 1/h of nitrogen. Crude propane was metered in by means of a mass flow regulator from 2o Brooks, while the water was initially introduced in liquid form by means of an HPLC
pump (from Bischoffj into the vaporizer, vaporized in this and then mixed with the crude propane and nitrogen. The gas mixture was subsequently passed over the catalyst. The wall temperature was 622°C.
The pressure at the outlet of the reactor was set to 1.5 bar absolute by means of a pressure regulator (from REKO) located at the reactor outlet.
The product gas which had been depressurized to atmospheric pressure downstream of the pressure regulator was cooled, resulting in the water vapor present in it condensing out.
3o The remaining uncondensed gas was analyzed by means of GC (HP 6890 with Chem-Station, detectors: Fm, WLD, separation columns: A1203/KCl (Chrompack), Carboxen 1010 (Supelco)). The reaction gas was also analyzed in an analogous fashion.
The tables below show the results achieved as a function of the operating time. The figures reported are in percent by volume based on "dry" gas, i.e. the amount of water vapor present was in all cases disregarded.
Table 1:
Activated catalyst precursor 1 from Example 4 (comparison) Reaction gas Product gas Product gas (after % b volume (after 1 h) 9 h) % b volume % b volume Pro ane 96.408 39.198 42.764 Pro ne 0.014 24.598 23.741 H2 0 30.942 29.281 NZ 3.5 2.648 2.875 Ethane 0.078 0.544 0.450 Ethene 0 0.234 0.258 CH4 0 0.836 0.631 Table 2:
1o Activated catalyst precursor 2 from Example 5 (according to the present invention) Reaction gas Product gas Product gas (after % b volume (after 1 h) 9 h) % b volume % b volume Pro ane 96.408 28.924 31.934 Pro ene 0.014 26.574 27.953 H2 0 38.530 36.011 N2 3.5 2.386 2.490 Ethane 0.078 1.159 0.734 Ethene 0 1.166 0.677 CH4 0 0.261 0.201 As can be seen from the tables, the catalyst according to the present invention has a significantly higher activity than the comparative catalyst.
Claims (7)
We claim:
1. A catalyst comprising one or more elements selected from the group consisting of the elements of transition groups VIII and VI and, if desired, one or more further elements selected from the group consisting of the elements of main groups I
and II, transition group III including the lanthanides, main group III, rhenium, zinc and tin on a catalyst support, wherein said catalyst support is prepared by mixing zirconium dioxide powder with a monomeric, oligomeric or polymeric organosilicon compound as a binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition, homogenizing the composition, shaping the composition to produce shaped bodies, drying and calcining.
and II, transition group III including the lanthanides, main group III, rhenium, zinc and tin on a catalyst support, wherein said catalyst support is prepared by mixing zirconium dioxide powder with a monomeric, oligomeric or polymeric organosilicon compound as a binder, if desired a pore former, if desired an acid, water and, if desired, further additives to give a kneadable composition, homogenizing the composition, shaping the composition to produce shaped bodies, drying and calcining.
2. A catalyst as claimed in claim 1, wherein the binder is a monomeric, oligomeric or polymeric silane, alkoxysilane, aryloxysilane, acyloxysilane, oximinosilane, halosilane, aminoxysilane, aminosilane, amidosilane, silazane or silicone.
3. A catalyst as claimed in claim 2, wherein the binder is selected from among the compounds of the formulae (I) to (VII) (Hal)x SiR4-x (I) (Hal)x Si(OR1)4-x (II) (Hal)x Si(NR1R2)4-x (III) R x Si(OR1)4-x (IV) R x Si(NR1R2)4-x (V) (R1O)x Si(NR1R2)4-x (VI) where Hal are each, independently of one another, halogen (F, Cl, Br or I), R are each, independently of one another, H or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, arylalkyl or aryl radical, R1, R2 are each, independently of one another, H or a substituted or unsubstituted alkyl, acyl, arylalkyl or aryl radical, and x is from 0 to 4.
4. A catalyst as claimed in any of claims 1 to 3, wherein a) from 50 to 98% by weight of zirconium dioxide powder, b) from 2 to 50% by weight of the organosilicon compound as binder, c) from 0 to 48% by weight of pore formers, and d) from 0 to 48% by weight of further additives, where the sum of the components a) to d) is 100% by weight, are mixed with addition of water and an acid to give a kneadable composition.
5. A catalyst as claimed in any of claims 1 to 4, wherein the zirconium dioxide powder consists essentially of monoclinic zirconium dioxide powder.
6. The use of a catalyst as claimed in any of claims 1 to 5 as dehydrogenation catalyst.
7. The use as claimed in claim 6 for the dehydrogenation of propane to propene.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10219879.9 | 2002-05-03 | ||
DE10219879A DE10219879A1 (en) | 2002-05-03 | 2002-05-03 | Catalyst support and process for its manufacture |
PCT/EP2003/004625 WO2003092887A1 (en) | 2002-05-03 | 2003-05-02 | Zr02-based catalyst carrier and method for the production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2482790A1 true CA2482790A1 (en) | 2003-11-13 |
Family
ID=29265056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002482790A Abandoned CA2482790A1 (en) | 2002-05-03 | 2003-05-02 | Zr02-based catalyst carrier and method for the production thereof |
Country Status (17)
Country | Link |
---|---|
US (1) | US7850842B2 (en) |
EP (1) | EP1503855B1 (en) |
JP (1) | JP4413134B2 (en) |
KR (1) | KR100944476B1 (en) |
CN (1) | CN1286555C (en) |
AT (1) | ATE505265T1 (en) |
AU (1) | AU2003240591B2 (en) |
BR (1) | BR0309653B1 (en) |
CA (1) | CA2482790A1 (en) |
DE (2) | DE10219879A1 (en) |
EA (1) | EA008478B1 (en) |
ES (1) | ES2363218T3 (en) |
MX (1) | MXPA04010296A (en) |
MY (1) | MY141278A (en) |
NO (1) | NO327435B1 (en) |
TW (1) | TWI266648B (en) |
WO (1) | WO2003092887A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10356184A1 (en) | 2003-12-02 | 2005-07-07 | Basf Ag | Pentasil-type zeolitic material, its preparation and its use |
DE102004029544A1 (en) | 2004-06-18 | 2006-01-05 | Basf Ag | Shaped body containing a microporous material and at least one silicon-containing binder, process for its preparation and its use as catalyst, in particular in a process for the preparation of triethylenediamine (TEDA) |
JP2008502637A (en) * | 2004-06-18 | 2008-01-31 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for continuously synthesizing methylamines |
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 (en) * | 2005-09-20 | 2007-03-29 | Basf Se | Method for determining tortuosity, catalyst support, catalyst, and method for dehydrogenating hydrocarbons |
DE102005052016B4 (en) * | 2005-10-31 | 2009-05-20 | Süd-Chemie AG | Process for the preparation of porous moldings and moldings obtainable by the process |
DE102005059711A1 (en) | 2005-12-12 | 2007-06-14 | Basf Ag | Shaped body containing a microporous material and at least one silicon-containing binder, process for its preparation and its use as a catalyst, in particular in a process for the continuous synthesis of methylamines |
DE102007006647A1 (en) | 2007-02-06 | 2008-08-07 | Basf Se | Process for the regeneration of a catalyst bed deactivated in the context of a heterogeneously catalyzed partial dehydrogenation of a hydrocarbon |
DE102008036724A1 (en) * | 2008-08-07 | 2010-02-11 | Uhde Gmbh | Highly porous foam ceramics as catalyst supports for the dehydrogenation of alkanes |
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 |
MX2014016112A (en) * | 2012-06-22 | 2015-09-21 | Praxair Technology Inc | Novel adsorbent compositions. |
EP3002058A1 (en) * | 2014-10-02 | 2016-04-06 | Evonik Degussa GmbH | Catalyst system for the production of ketones from epoxides |
DK3227019T3 (en) * | 2014-12-03 | 2019-04-23 | Basf Se | RHODIUM CATALYST FOR THE DEGRADATION OF LATTERY GAS, PREPARATION AND USE thereof |
DE102015112612A1 (en) | 2015-07-31 | 2017-02-02 | Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock | Process for the preparation of olefins and catalyst |
KR102644446B1 (en) | 2017-07-27 | 2024-03-07 | 바스프 코포레이션 | N₂O removal from automotive emissions for lean/rich systems |
CN108067211A (en) * | 2017-12-13 | 2018-05-25 | 南京大学扬州化学化工研究院 | A kind of glycerine hydrogenation prepares the zirconia-based catalyst preparation method of 1,3- propylene glycol |
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 (en) | 1985-12-02 | 1990-09-07 | Rhone Poulenc Spec Chim | ZIRCONIUM OXIDE COMPOSITION AND PROCESS FOR THE PREPARATION |
US5032556A (en) * | 1989-02-21 | 1991-07-16 | Tosoh Corporation | Preparation method for zircon powder |
DE59003114D1 (en) * | 1989-05-02 | 1993-11-25 | Lonza Ag | Sinterable zirconium oxide powder and process for its production. |
JP2651332B2 (en) * | 1992-09-21 | 1997-09-10 | 松下電工株式会社 | Zirconia-based composite ceramic sintered body and method for producing the same |
US5633217A (en) | 1994-09-12 | 1997-05-27 | Corning Incorporated | Method of making a high strength catalyst, catalyst support or adsorber |
DE4445142A1 (en) | 1994-12-17 | 1996-06-20 | Basf Ag | Catalysts or supports consisting essentially of monoclinic zirconia |
JP2703207B2 (en) * | 1995-01-30 | 1998-01-26 | 松下電工株式会社 | Zirconia-based composite ceramic sintered body and method for producing the same |
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 (en) | 1996-12-27 | 1998-07-02 | Basf Ag | Catalyst for the selective production of propylene from propane |
DE19743100A1 (en) * | 1997-09-30 | 1999-04-01 | Degussa | Process for the production of a coated catalyst |
DE19832087A1 (en) * | 1998-07-16 | 2000-01-20 | Basf Ag | Process for the conversion of organic compounds with boron oxide-containing, macroporous supported catalysts |
JP3643948B2 (en) * | 1999-03-15 | 2005-04-27 | 株式会社豊田中央研究所 | Titania-zirconia powder and method for producing the same |
DE19937107A1 (en) * | 1999-08-06 | 2001-02-08 | Basf Ag | Catalyst with bimodal pore radius distribution |
US6376590B2 (en) * | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
EP1351765B1 (en) * | 2000-12-22 | 2005-01-05 | Basf Aktiengesellschaft | Catalyst with bimodal pore radius distribution |
-
2002
- 2002-05-03 DE DE10219879A patent/DE10219879A1/en not_active Withdrawn
-
2003
- 2003-04-15 MY MYPI20031407A patent/MY141278A/en unknown
- 2003-04-21 TW TW092109217A patent/TWI266648B/en active
- 2003-05-02 US US10/513,041 patent/US7850842B2/en not_active Expired - Fee Related
- 2003-05-02 EP EP03729967A patent/EP1503855B1/en not_active Expired - Lifetime
- 2003-05-02 JP JP2004501063A patent/JP4413134B2/en not_active Expired - Fee Related
- 2003-05-02 EA EA200401445A patent/EA008478B1/en not_active IP Right Cessation
- 2003-05-02 AT AT03729967T patent/ATE505265T1/en active
- 2003-05-02 KR KR1020047017612A patent/KR100944476B1/en not_active IP Right Cessation
- 2003-05-02 WO PCT/EP2003/004625 patent/WO2003092887A1/en active Application Filing
- 2003-05-02 MX MXPA04010296A patent/MXPA04010296A/en active IP Right Grant
- 2003-05-02 BR BRPI0309653-0A patent/BR0309653B1/en not_active IP Right Cessation
- 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 ES ES03729967T patent/ES2363218T3/en not_active Expired - Lifetime
- 2003-05-02 CN CNB038099535A patent/CN1286555C/en not_active Expired - Fee Related
- 2003-05-02 DE DE50313615T patent/DE50313615D1/en not_active Expired - Lifetime
-
2004
- 2004-10-22 NO NO20044561A patent/NO327435B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
BR0309653B1 (en) | 2013-03-19 |
EP1503855A1 (en) | 2005-02-09 |
NO327435B1 (en) | 2009-06-29 |
KR100944476B1 (en) | 2010-03-03 |
JP4413134B2 (en) | 2010-02-10 |
US7850842B2 (en) | 2010-12-14 |
AU2003240591B2 (en) | 2009-06-18 |
WO2003092887A1 (en) | 2003-11-13 |
TWI266648B (en) | 2006-11-21 |
DE50313615D1 (en) | 2011-05-26 |
TW200408445A (en) | 2004-06-01 |
KR20040104687A (en) | 2004-12-10 |
NO20044561L (en) | 2004-11-26 |
US20060046929A1 (en) | 2006-03-02 |
BR0309653A (en) | 2005-03-01 |
JP2005528976A (en) | 2005-09-29 |
AU2003240591A1 (en) | 2003-11-17 |
CN1649668A (en) | 2005-08-03 |
EA008478B1 (en) | 2007-06-29 |
ES2363218T3 (en) | 2011-07-27 |
EA200401445A1 (en) | 2005-06-30 |
MXPA04010296A (en) | 2005-03-31 |
CN1286555C (en) | 2006-11-29 |
DE10219879A1 (en) | 2003-11-20 |
EP1503855B1 (en) | 2011-04-13 |
ATE505265T1 (en) | 2011-04-15 |
MY141278A (en) | 2010-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2003240591B2 (en) | ZR02-based catalyst carrier and method for the production thereof | |
JP4611298B2 (en) | Method for producing unsaturated carbonyl compound | |
US6670303B1 (en) | Catalyst having a bimodal pore radius distribution | |
CN1299298A (en) | Prodn. of unsaturated acids or esters thereof and catalysts therefor | |
BR112013005598B1 (en) | silica-based material, process for producing the same, material supported with a noble metal, process for producing a carboxylic acid ester, and, process for producing a carboxylic acid | |
JPH09502129A (en) | Epoxidation catalyst and method | |
US10695750B2 (en) | Catalyst for decomposition of nitrous oxide | |
JP4777891B2 (en) | Catalyst and process for producing cycloolefin | |
JP4296430B2 (en) | Catalyst for water gas shift reaction and process for producing the same | |
JP4148775B2 (en) | Catalyst with bimodal pore radius distribution | |
JP2014514996A (en) | Mixed oxide composition and method for producing isoolefin | |
JP3730792B2 (en) | Hydrocarbon isomerization process | |
CA1094533A (en) | Reforming catalyst and a hydrocarbon catalytic reforming process using the catalyst | |
KR20210061711A (en) | Shaped Dehydrogenation Catalysts and Process for Converting Paraffins to Corresponding Olefins Using the Same | |
US4913886A (en) | Production of improved copper aluminum borate | |
JP2007054685A (en) | Catalyst for water gas shift reaction | |
JP2002301372A (en) | Solid acid catalyst, method for producing the same and method for hydrodesulfurizing and isomerizing light hydrocarbon oil using the same | |
JP3973176B2 (en) | Acid-catalyzed reaction method | |
EP3689452A1 (en) | Catalyst, device for manufacturing conjugated diene, and method for manufacturing conjugated diene | |
WO2004094357A1 (en) | Method for producing ether using solid acid catalyst | |
JP2008229511A (en) | Catalyst for preparing dimethylether, method for preparing the same, and method for preparing dimethylether using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |