CN100528344C - Process for the preparation of a paraffin isomerisation catalyst - Google Patents
Process for the preparation of a paraffin isomerisation catalyst Download PDFInfo
- Publication number
- CN100528344C CN100528344C CNB2006101625208A CN200610162520A CN100528344C CN 100528344 C CN100528344 C CN 100528344C CN B2006101625208 A CNB2006101625208 A CN B2006101625208A CN 200610162520 A CN200610162520 A CN 200610162520A CN 100528344 C CN100528344 C CN 100528344C
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- China
- Prior art keywords
- catalyst
- oxide
- family metal
- isomerization
- cellulose
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims abstract description 12
- 239000012188 paraffin wax Substances 0.000 title abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- -1 VIB metal oxide Chemical class 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 52
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 229930195733 hydrocarbon Natural products 0.000 claims description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 229920005594 polymer fiber Polymers 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000006210 lotion Substances 0.000 claims description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 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 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 235000010980 cellulose Nutrition 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229920003064 carboxyethyl cellulose Polymers 0.000 claims description 2
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000010944 ethyl methyl cellulose Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920003087 methylethyl cellulose Polymers 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229920003086 cellulose ether Polymers 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000005336 cracking Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910001593 boehmite Inorganic materials 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- WGECXQBGLLYSFP-UHFFFAOYSA-N (+-)-2,3-dimethyl-pentane Natural products CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2,4-trimethyl-butane Natural products CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 3
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 3
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- AEXMKKGTQYQZCS-UHFFFAOYSA-N Dimethyl-diaethyl-methan Natural products CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
- C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
Process for preparation of a paraffin isomerisation catalyst comprising a mixture of a Group IVB metal oxide, a Group VIB metal oxide, a Group IIIA metal oxide and a Group VIII metal, the process comprising the steps of (a) contacting a hydroxide of the Group IVB metal with an aqueous solution of an oxyanion of the Group VIB metal to provide a mixture, (b) drying the mixture to provide a dry powder, (c) kneading the powder with a Group IIIA hydroxide gel and a polymeric cellulose ether compound to form a paste, (d) shaping the paste to form a shaped material, (e) calcining the shaped material to form a calcined material, (f) impregnating the calcined material with an aqueous solution of a Group VIII metal salt to provide the catalyst, and (g) calcining the catalyst.
Description
Technical field
The present invention relates to prepare the method for alkane (paraffin) isomerization catalyst, described catalyst comprises: aluminium and the oxide of zirconium and the hydrogenation/dehydrogenation component of VIII group metal of using the tungsten oxide modification that mixes.This catalyst is used for by containing C
4+The hydrocarbon incoming flow of hydrocarbon-fraction prepares high octane gasoline.
Background technology
The alkane of highly branched chain is desirable high-octane blended into gasoline component that has.For environment reason, need to seek the substitute of aromatic component in gasoline.Therefore, exist to develop and to be used to increase C
4-C
12The motivation of the method for the octane number of cut (cuts).Although C
5/ C
6Isomerization of paraffinic hydrocarbons is common refinery practice, contains senior fraction (fractions) (C
7+The commercialization of technology hydrocarbon) has run into the remarkable difficulty that is caused by highly being cracked into gaseous products usually, and this is unfavorable.
K.Arata and M.Hino are at Proceedings 9
ThInternational Congress onCatalysis (1988, volume 4,1727-1735 page or leaf) put down in writing a kind of in based on IVB family metal oxide (for example particularly by the oxo-anions of the group vib zirconia of tungstate modified particularly) catalyst and the purposes in isomerization of paraffinic hydrocarbons thereof.
Further research activities shows, the catalytic performance of wolframic acid salinization zirconia catalyst can be by adding the hydrogenation/dehydrogenation function in the solid acid catalyst that mixes in isomerization of paraffinic hydrocarbons, preferred noble metal and being improved.In isomerization of paraffinic hydrocarbons, use wolframic acid salinization zirconia to be recorded in for example following open source literature: S.L.Soled, S.Miseo, J.E.Baumgartner, W.E.Gates, D.G.Barton and E.Iglesia, Proc.13 with noble metal promoted
ThInt.Conf.Catal. (The Taniguchi Foundation, Kobe, Japan, 1994) 17 pages; E.Iglesia D.G.Barton, S.L.Soled, S.Miseo, J.E.Baumgartner, W.E.Gates, G.A.Feuntes and G.D.Meitzner, Stud.Surf.Sci.Catal.101 (1996) 533; G.Larsen, E.Lotero, S.Raghavan, R.D.Parra and C.A.Querini, Appl.Catal.A 139 (1996) 201.
One group of United States Patent (USP) about the solid acid isomerization catalyst has transferred Mobil OilCorporation.US patent No.5510309 provides a kind of method of acid solid of the IVB family metal oxide that is used to prepare the oxo-anions modification that contains useful group vib metal.The example of this acid solid is the zirconia with tungstate modified.This soild oxide through modification can be used as such as being used to make C
4-C
8The catalyst of isomerization of paraffinic hydrocarbons.Soild oxide through modification preferably prepares by the oxo-anions codeposition with IVB family metal oxide and vib metal.After filtration, this coprecipitate is 825 ℃ of calcinings down.
US patent No.5780382 provides a kind of method of acid solid of the IVB family metal oxide that is used to prepare the oxo-anions modification that contains useful group vib metal.
US patent No.5854170 has put down in writing a kind of preparation method who contains the acidic solid catalyst of noble metal, and this preparation method comprises: the aqueous solution with the oxo-anions that contains the group vib metal floods the hydroxide of IVB family metal or the oxide of hydrate.Noble metal (preferred Pt) can flood by the oxo-anions with the group vib metal or add in the impregnation steps of separating jointly.
US patent No.6080904 has put down in writing a kind of C that utilizes isomerization catalyst
4-C
8Isomerization process, this isomerization catalyst have hydrogenation/dehydrogenation component (preferred Pt) and have the solid acid component of the IVB family metal oxide that comprises the oxo-anions modification of using the group vib metal.
In all above-mentioned patents, aluminium is for example mentioned when aluminium oxide, silica-alumina and silica as just the host material of routine, and preferred silica.
The zirconia of wolframic acid salinization often is recited as and is used for C
5+Isomerized catalyst.It is platinum that this catalyst contains tungsten oxide and the hydrogenation component that concentration is lower than 20wt% usually.Yet, by these materials provide to isomerized catalytic selectivity deficiency.Following patent is the flexible program of above-mentioned prior art.
US patent No.5422327 has put down in writing a kind of carbon monoxide-olefin polymeric of the VIII family metal in the carrier of being made up of zirconia and purposes in isomerization of paraffinic hydrocarbons thereof of being attached to, and described carrier is further used the impregnation mixture of silica and tungsten oxide.
The claimed a kind of catalytic isomerization metallization processes of US patent No.5648589 is included under the isomerisation conditions and makes C
5+Charging with contact by VIII family metal and the carbon monoxide-olefin polymeric formed with the Zirconia carrier of tungsten oxide and silica dipping.
US patent No.5837641 has put down in writing isomerization reaction on the zirconia of wolframic acid salinization and the water facilitation to this catalyst.
US patent No.6767859 has put down in writing a kind of alkane isomerization technology of using carbon monoxide-olefin polymeric, the metal oxide of this carbon monoxide-olefin polymeric for mixing with metal dopant (IVB family metal and hydrogenation/dehydrogenation function thing), described metal-doped metal oxide is by prepared by co-precipitation from solution, and metal dopant is attached in the crystal lattices of metal oxide by calcining under high enough temp.Described metal dopant is attached in the crystal lattices of metal oxide and verifies by X-ray diffraction.This carbon monoxide-olefin polymeric has shown the high activity that transforms for alkane, but has for the low selectivity of alkane isomerization with for the C with low commercial value
1-C
4The high cracking of gaseous products is shortcoming optionally.
Come the stable sulfation zirconia catalyst of processing machinery for example on the books among the US patent No.6326328 by adding aluminium oxide at patent documentation.
When aluminium oxide was present in the zirconia catalyst of wolframic acid salinization, it can be used as aluminium ion (Al
3+) be attached in the crystal of zirconium oxide lattice.The traditional catalyst that has been found that this form has the low selectivity of isomerization product and is unfavorable gaseous products with prepared highly branched chain hydrocarbon cracking often.
General purpose of the present invention provides the method for the following catalyst of preparation, and this catalyst is applicable to by isomerization and improves C
4+The octane number of hydrocarbon mixture and can be not gaseous products with the remarkable cracking of highly branched chain hydrocarbon that is produced.
Another object of the present invention provides a kind of catalyst, and this catalyst is suitable for improving C by isomerization
4+The octane number of hydrocarbon mixture and can be not gaseous products with the remarkable cracking of highly branched chain hydrocarbon that is produced.
Another purpose of the present invention provides a kind of catalyst, and this catalyst contains the aluminium oxide of reduction and demonstrates the isomerization character of improvement and the cracking character of minimizing.
Summary of the invention
Above-mentioned purpose realizes that by following method prepared a kind of isomerization of paraffinic hydrocarbons catalyst thus, this catalyst comprises the combination of three kinds of oxides that are selected from IVB family metal oxide, group vib metal oxide and IIIA family metal oxide.This catalyst is used for by containing C
4+The hydrocarbon incoming flow of hydrocarbon-fraction prepares high octane gasoline.
The present invention includes a kind of method for preparing the isomerization of paraffinic hydrocarbons catalyst, this catalyst comprises the mixture of IVB family metal oxide, group vib metal oxide, IIIA family metal oxide and VIII family metal, and this method comprises the following steps:
(a) hydroxide of IVB family metal is contacted so that mixture to be provided with the aqueous solution of the oxo-anions of group vib metal,
(b) dry this mixture to be providing dried powder,
(c) mediate the plain ether compound of this dried powder and IIIA family hydroxide gel and polymer fiber with the formation lotion,
(d) to this lotion moulding forming moulding material,
(e) calcine this moulding material with the formation calcined materials,
(f) with the aqueous solution of VIII family slaine flood this calcined materials with provide catalyst and
(g) calcine this catalyst.
The invention still further relates to by isomerization of paraffinic hydrocarbons catalyst method for preparing and that comprise IVB family metal oxide, group vib metal oxide, IIIA family metal oxide and VIII family metal, this catalyst has X-ray powder diffraction (XRPD) 2 θ that are lower than 30.20 °.
At last, the present invention relates to from comprising C
5+The method of the hydrocarbon feed preparation high octane gasoline of hydrocarbon-fraction, wherein this hydrocarbon charging contacts with above-mentioned isomerization of paraffinic hydrocarbons catalyst.
The specific embodiment
Catalyst by the inventive method preparation is to be applicable to by isomerization to improve C
4+The octane number of hydrocarbon mixture and can be not the solid acid catalyst of gaseous products with the remarkable cracking of prepared highly branched chain hydrocarbon.
Highly-branched chain isomerous in this case body is defined as containing more than a carbon atom that is connected to other three adjacent carbon atoms at least or at least one and is connected to the compound of the carbon atom of four adjacent carbon atoms.Single branched chain isomer is defined as only containing a compound that is connected to three carbon atoms on the adjacent carbon atom.
Catalyst prepared according to the methods of the invention can be applied to C
7+Fraction or contain following fraction (C for example
4-C
7, C
5-C
9, C
7-C
9, C
6-C
7, C
7, C
8Or C
9, C
7-C
12) and the cut mainly formed by alkane and possible naphthalene, aromatic compounds and alkene in.
Method of the present invention has a plurality of advantages:
The raw material of-Preparation of catalysts utilization cheapness carry out, thus with respect to provide advantage economically for the Preparation of Catalyst of the parent material of halogenation.
-avoided using the parent material of metal halides, avoided the expensive step of taking-up halide anions from catalyst material thus.Getting rid of halide anions on catalyst material provides technological merit, and this is because this has been avoided the etching problem in the industrial equipment of isomerization reactor unit and has increased catalyst service life.
-aluminium content in catalyst is low, and mechanically firm catalyst extrudates is provided simultaneously.
Catalyst prepared according to the methods of the invention comprises the carrier based on the combination of three kinds of oxides that are selected from IVB family metal oxide, group vib metal oxide and IIIA family metal oxide.Then this carrier through VIII family metal impregnation so that final catalyst to be provided.
The mixture of IVB family metal hydroxides and the anionic aqueous solution of group vib metal oxygen-containing can carry out drying by for example spray-drying or other drying means.Moulding can be for example by extruding or other moulding process carries out.This catalyst can be at the temperature lower calcination that is high enough to decompose this VIII family slaine.
In one embodiment of the invention, comprise that the spray-drying mixt of oxide of IVB family metal and group vib metal is 600-800 ℃ of following precalcining.
In a preferred embodiment of the invention, comprise zirconia, aluminium oxide and tungsten oxide by the catalyst of the inventive method preparation, these oxides are through calcining and with VIII family metal impregnation.
Have in the preferred embodiment of the present invention, the method that is used to prepare catalyst comprises that the mixture of mediating zirconia, aluminium oxide and tungsten oxide and the plain ether compound of polymer fiber are suitable for the lotion of moulding with formation, succeeded by calcining with flood with VIII family slaine subsequently and catalyst is provided.
The plain ether compound of polymer fiber that is fit to use is in the methods of the invention obtained by being selected from the following cellulose that substituting group replaced: alkyl, carboxyl, hydroxyl and their combination, and alkyl substituent is selected from methyl, ethyl, propyl group and their combination.
The plain ether compound of preferred polymer fiber is carboxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methyl hydroxy propyl cellulose, methylcellulose, ethyl cellulose, propyl cellulose, ethyl carboxymethyl cellulose, methylethylcellulose and HYDROXY PROPYL METHYLCELLULOSE.
Most preferably, the plain ether compound of described polymer fiber is a methylcellulose.
In one embodiment of the invention, this method is fit to the catalyst that preparation contains the hydrogenation/dehydrogenation component of the oxide of the aluminium of mixing of useful tungsten oxide modification and zirconium and VIII family metal.
In the methods of the invention, the moulding material that contains the oxo-anions of IVB family metal hydroxides, group vib metal and IIIA family metal of calcining is simultaneously also given catalyst with mechanical strength with the plain ether compound of polymer fiber simultaneously so that the amount of the IIIA family metal hydroxides gel that will use descends.
Yet the plain ether compound of described polymer fiber is not present in the catalyst that is obtained by the inventive method, and this is because it burnedly during calcining falls.This catalyst is with different based on other conventional catalyst of IVB family metal oxide, group vib metal oxide, IIIA family metal oxide and VIII family metal, and IIIA family metal is incorporated in the crystal lattices of IVB family metal oxide in other conventional catalyst.The catalyst that obtains by the inventive method does not have the IIIA family metal that is attached in the ivb metal oxide crystal lattices, and this catalyst is characterised in that to have the X-ray powder diffraction 2 θ values that are lower than 30.20 °.This causes the selectivity and the active advantage of improvement for isomerization.
In one embodiment of the invention, X-ray diffraction 2 θ values be 30.10 ° to being lower than 30.20 °.
When implementing X-ray powder diffraction and measure, for the D[101 of IVB family metal oxide] line position is suitable as the sign of the combination degree of IIIA family metal.IIIA family metal is (as Al
3+Thereby) combination cause the lattice parameter of IVB family metal to descend and 2 higher θ values.
In one embodiment of the invention, the calcining of moulding material is carried out to being lower than under 800 ℃ of temperature at 600 ℃.Can not obtain X-ray powder diffraction 2 θ values at 800 ℃ or the temperature lower calcination that is higher than this temperature and be lower than 30.20 ° catalyst.
The calcining heat of the zirconium/tungsten/aluminum oxide carrier that mixes also is an important parameters for activity of such catalysts that is prepared by the inventive method and selectivity.Cause having optionally catalyst of zirconium at 600 ℃ to being lower than 800 ℃ of temperature lower calcinations, the remarkable economic advantages of comparing with the catalyst of prior art are provided thus for isomerization.
In a preferred embodiment of the invention, the calcining of moulding material is carried out under 625-700 ℃ of temperature.
In one embodiment of the invention, the plain ether compound of polymer fiber adds in the lotion with the amount of 0.1-5wt%.Preferred addition is 0.6-1.2wt%.
In one embodiment of the invention, the addition of IIIA family metal oxide is reduced to and is lower than 10wt%, for example is reduced to 2wt%.As a comparison, when not using polymer fiber element ether compound, the amount of IIIA family metal oxide can be up to 22wt%.
Most typical aluminium source is a hydrated alumina, for example boehmite (pseudoboehmite).Because aluminum halide is preferably avoided for example AlCl of aluminum halide for the corrosivity character of extensive steel equipment and with respect to the higher price of boehmite
36H
2O.
The quality of ivb metal oxide is extremely important for total catalyst performance.Can use for example tetrahydrochysene zirconia of IVB family metal oxide in one embodiment of the invention.Zirconium hydroxide can be for example by making zirconyl nitrate and ammonia precipitation process under high pH value, succeeded by add hot preparation under refluxing, this preparation method is similar to A.Calafat, and Stud.Surf.Sci.Catal.118 (1998) 837.The example that is suitable as the zirconium hydroxide of the inventive method has the particle size of 10 μ m and has greater than 300m
2The surface area of/g.
In one embodiment of the invention, the group vib metal oxide is the oxide of tungsten.Most typical tungsten precursor is an ammonium metatungstate, and ammonium metatungstate is for its high stability and low heating but useful.
VIII family metal can be selected from any VIII family metal and composition thereof.Preferred metal is palladium and platinum, and its concentration is 0.01wt%-5wt%, most preferably 0.05wt%-1wt%.
In embodiment of the present invention, catalyst prepared according to the methods of the invention comprises that this method comprises the following steps: with the aluminium of tungsten oxide modification and the hydrogenation/dehydrogenation component of Zirconium oxide oxide and VIII family metal
(a) make the tetrahydrochysene zirconia be suspended in mixture spray-drying in the aqueous solution of ammonium metatungstate to form spray-dried mixture and randomly at the 650-700 ℃ of mixture that following precalcining is spray-dried.
(b) will be kneaded into lotion through the spray-drying product (oxide/hydroxide of zirconium and tungsten) of calcining in advance and the mixture of alumina gel, boehmite and methylcellulose,
(c) make the lotion moulding form extrudate by extruding,
(d) 600-800 ℃, most preferably 625-700 ℃ down the calcining extrudate forming through calcined materials,
(e) with VIII family metal impregnation through calcined materials so that catalyst to be provided,
(f) under 300-500 ℃, preferably calcine the gained catalyst down at 350-450 ℃.
In embodiments of the invention, described catalyst through calcining contains the tungsten oxide of 10-50wt%, aluminium oxide and the surplus of 2-40wt% is the residue of zirconia and VIII family metal.
Total can compensate by the temperature that increases isomerization reaction than the low catalyst activity.This has increased catalytic conversion and has not significantly increased the cracking selectivity.
For the typical operation conditions of isomerization reaction is 150-300 ℃ temperature, the gross pressure and the 0.1-30h of 1-100 crust
-1Liquid air speed (LHSV).Preferred condition is 130-250 ℃ a temperature, 0.5-5h
-1LHSV, the pressure and the 0.1-5 hydrogen of 5-50 crust: hydrocarbon ratio.
Charging can also randomly comprise shorter alkane, aromatic compounds or cyclic-paraffins.When with this charging when the reactor beds, shorter alkane is also by isomerization, and aromatic compounds is hydrogenated and is corresponding cycloalkane.The reaction rate of ring-opening reaction will be very slow usually.
Being used for preparing the specific embodiments of the present invention with high research octane number (RON) (reseurch octane number) high liquid yield gasoline (RON) is described in more detail below.
Selectivity is defined as 2, the 2-dimethyl pentane (2,2-DMP), 2, the 4-dimethyl pentane (2,4-DMP) and 2,2, the 3-triptane (2,2, total amount 3-TMB) and with the weight of all products and ratio.
The cracking factor is defined as gaseous products (C
1-C
4) weight and with isomers 2, the 2-dimethyl pentane (2,2-DMP), 2, the 4-dimethyl pentane (2,4-DMP) and 2,2, the 3-trimethylpentane (2,2, weight 3-TMB) and ratio.
During X-ray powder diffraction is measured, for the zirconic D[101 of tetragonal system] position of line mixes the sign of degree as aluminium.
Embodiment
Embodiment 1
The spray-drying of zirconium hydroxide and ammonium metatungstate is carried out in the following manner:
With 12.0kg (NH
4)
6H
6W
12O
40Be dissolved in 180 liters of deionized waters.Make 28.0kgZr (OH)
4Mix with solution.This mixture is that 250 ℃, outlet temperature are that 90 ℃ and charging flow velocity are dry in the spray dryer of 29kg/h in inlet temperature.
Embodiment 2
The comparative example:
Preparation contains the isomerization catalyst of the aluminium oxide of 22wt%:
Spray-dried product that 1.432kg is obtained in embodiment 1 and 1.400kg alumina gel (30% boehmite) and 112g boehmite powder 10 minutes, and as 1/16 " cylinder extrudes.These extrudates were calcined 3 hours down 110 ℃ of following dried overnight and at 650 ℃.By initial stage wetness impregnation [Pd (NH
3)
4] (NO
3)
2The aqueous solution is introduced the Pd of 0.5wt%.Before catalyst is inserted reactor, the catalyst that obtains was thus being calcined 6 hours in air stream (4l/minkg catalyst) under 400 ℃.
Isoversion:
Before isoversion test, this catalyst under 200 ℃ and atmospheric pressure by H
2(200Nml/min) reduction.The catalyst that utilization prepares in embodiment 2 makes gross pressure and the 2.03h of heptane isomerization at 6atm
-1LHSV under in fixed bed reactors, carry out.
Charging is that hydrogen/heptane mixture of 4.95: 1 is formed by mol ratio.Catalytic result is shown in Table 1.
Embodiment 3
The comparative example:
To 52.7g zirconyl chloride (ZrOCl
28H
2O, 30% solution in hydrochloric acid) add dense NH
4OH (aq) is about 9 up to pH value of solution.The slurry Zr (OH) of gained
4Wash through the deionized water of distillation after filtration and with 500g.This solid was dry 160 hours of 130 ℃ of following air.The product of this drying (11.9g) is by containing 2.12g ammonium metatungstate, (NH with 8.9g
4)
6H
6W
12O
40The aqueous solution carry out initial wetting and flood.The gained material is at air drying and calcined 3 hours 7.0g desciccate 55mg (NH then under 825 ℃ in air
4)
2PdCl
4Aqueous solution initial wetting flood.Then, this catalyst under 300 ℃ air drying 2 hours.
Isoversion test (contrast):
Before catalytic test, this catalyst is used H under 200 ℃ and atmospheric pressure
2(200Nml/min) reduction.The catalyst that is used in preparation among the embodiment 6 makes the heptane isomerization at 6atm gross pressure and 1.14h
-1LHSV under in fixed bed reactors, carry out.Charging is that hydrogen/hydrocarbon mixture of 4.41: 1 is formed by mol ratio.Catalytic result is shown in the table 1.
Embodiment 4
The comparative example
In the 600ml glass beaker, mix 0.161mol ZrOCl
28H
2O and 0.0082molAlCl
36H
2O.Under agitation add 320ml H then
2O is with dissolving salt.Then under the strong agitation condition with 25%NH
4OH is added drop-wise in the solution, reaches 9.0 up to the final pH value of precipitation mixture.After stirring reached above 1 hour, this sediment washed with distilled water, and reclaims by centrifugation.This material is through washing 6 times to remove chlorion.This sediment in stove 120 ℃ of following dried overnight.Then, add in the mixed hydroxides by the aqueous solution of incipient wetness technology ammonium metatungstate (3.13g).After calcining 3 hours under 800 ℃, the Al that is obtained with the wolframic acid salinization
3+The zirconia that mixes [Pd (NH
3)
4(NO
3)
2The aqueous solution flood 0.5wt%Pd.Before inserting this catalyst in the reactor, this catalyst was calcined 3 hours down at 450 ℃.
The isoversion test:
Before catalytic test, this catalyst is used H under 200 ℃ and atmospheric pressure
2(200Nml/min) reduction.The catalyst that is used in preparation among the embodiment 8 makes the heptane isomerization at 6atm gross pressure and 2.14h
-1LHSV under in fixed bed reactors, carry out.Charging is that hydrogen/hydrocarbon mixture of 4.93: 1 is formed by mol ratio.Catalytic result is shown in the table 1.
All the test in measured with wt% represent to 2,2-DMP, 2,4-DMP and 2,2, the selectivity of 3-TMB.
Table 1
The result who provides in table 1 has shown C
7The catalyzed conversion chlorine and the cracking factor are for the correlation of carrier calcining heat.Temperature is low more, then C
7Catalytic conversion is low more and the cracking factor is low more.
It can also be seen that calcining heat is increased to 800 ℃ from 650 ℃ and causes aluminium to be attached to the zirconia crystal lattice.
Although the result of embodiment 2 shows that under 650 ℃ low calcining heat, aluminium still is attached in the zirconia crystal lattice, this is because aluminium exists with high-load (22wt%).
Comparative example 4 shows that when using traditional handicraft, even used aluminium content very low (3.2wt%), aluminium still is attached in the zirconia crystal lattice.
Embodiment 5
Use the plain ether compound of polymer fiber to prepare isomerization catalyst.
The spray-dried product that 167.6g is obtained in embodiment 1 mixes with 33.4g alumina gel (30% boehmite), 3.0g methylcellulose and 68g water.It is 1/16 that described lotion is extruded " cylinder.This extrudate was also calcined 1 hour down at 650 ℃ down at 110 ℃ in dry 6 hours on the net.By using [Pd (NH
3)
4] (NO
3)
2Aqueous solution incipient wetness flood the Pd that introduces 0.5wt%.Thus obtained catalyst was calcined 6 hours down at 400 ℃ in air stream (4l/minkg catalyst) before being introduced into reactor.
Before isoversion test, this catalyst is used H under 200 ℃ and atmospheric pressure
2(200Nml/min) reduction.Make the heptane isomerization at 20atm gross pressure and 2.03h with catalyst
-1LHSV under in fixed bed reactors, carry out.Charging is that hydrogen/heptane mixture of 2.2: 1 is formed by mol ratio.Catalytic result is shown in the table 2.
Figure 1 illustrates X-ray diffractogram.Therefrom as can be seen, 2 θ (2 θ) are moved at the zirconia peak and are lower than 30.2 °, show that aluminium is not attached in the crystal of zirconium oxide lattice and aluminium mainly is present in outside the crystal of zirconium oxide lattice with the amorphous state form.
Embodiment 6
Use the plain ether compound of polymer fiber to prepare isomerization catalyst.
The spray-dried product that 335.2g is obtained in embodiment 1 mixes with 66.8g alumina gel (30% boehmite), 6.0g methylcellulose and 130g water.It is 1/16 that this lotion is extruded " cylinder.Described extrudate 110 ℃ dry 6 hours and have in the open containers of 5cm extrudate bed height down 650 ℃ of calcinings 3 hours down.By using [Pd (NH
3)
4] (NO
3)
2Aqueous solution incipient wetness flood the Pd that introduces 0.5wt%.Thus obtained catalyst was calcined 6 hours down at 400 ℃ in air stream (4l/minkg catalyst) before being introduced into reactor.
Before isoversion test, this catalyst is used H under 200 ℃ and atmospheric pressure
2(200Nml/min) reduction.Make the heptane isomerization at 20atm gross pressure and 2.14h with catalyst
-1LHSV under in fixed bed reactors, carry out.Charging is that hydrogen/heptane mixture of 2.1: 1 is formed by mol ratio.Catalytic result is shown in the table 2.
Table 2
| Embodiment: | 2θ[101] ZrO 2(°) | Temperature (℃) | C 7Conversion ratio (%) | The cracking factor (%) | Selectivity (%) |
| 5 | 30.183 | 209.6 220.4 225.9 | 43.5 61.4 74.4 | 4.5 7.2 10.3 | 3.13 6.88 11.19 |
| 6 | 30.18 | 200.0 | 68.8 | 13.0 | 8.66 |
Obtained as can be seen to be lower than 30.2 ° 2 θ values from the result, this shows that aluminium is not attached in the crystal of zirconium oxide lattice.
Claims (11)
1. the method for preparing the isomerization of paraffinic hydrocarbons catalyst, this catalyst comprise the mixture of zirconia, group vib metal oxide, aluminium oxide and VIII family metal, and this method comprises the following steps:
(a) hydroxide of zirconium is contacted so that mixture to be provided with the aqueous solution of the oxo-anions of group vib metal,
(b) dry this mixture to be providing dried powder,
(c) mediate the plain ether compound of this powder and IIIA family hydroxide gel and polymer fiber to form lotion, the addition of IIIA family metal oxide is lower than 10wt%, and described IIIA family metal is an aluminium,
(d) make this lotion moulding with the formation moulding material,
(e) calcine this moulding material with the formation calcined materials,
(f) with the aqueous solution of VIII family slaine flood this calcined materials with provide catalyst and
(g) calcine this catalyst, to obtain the isomerization of paraffinic hydrocarbons catalyst, this catalyst comprises the tetragonal system zirconia, and this tetragonal system zirconia has X-ray powder diffraction (XRPD) the reflection 2 θ scopes that are lower than 30.20 °.
2. the method for claim 1, the plain ether compound of wherein said polymer fiber is obtained by being selected from the cellulose that following substituting group replaces: alkyl, carboxyl, hydroxyl and their combination, and alkyl substituent is selected from methyl, ethyl, propyl group and their combination.
3. the method for claim 2, the plain ether compound of wherein said polymer fiber is selected from carboxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, methyl hydroxy propyl cellulose, methylcellulose, ethyl cellulose, propyl cellulose, ethyl carboxymethyl cellulose, methylethylcellulose and HYDROXY PROPYL METHYLCELLULOSE.
4. the process of claim 1 wherein the precalcining before mediating of described dried powder.
5. the process of claim 1 wherein that described moulding material is at 600-800 ℃ of temperature lower calcination.
6. the process of claim 1 wherein that described group vib metal is that the plain ether of tungsten and described polymer fiber is methylcellulose.
7. the process of claim 1 wherein that described catalyst through calcining contains the aluminium oxide of tungsten oxide, 2-10wt% of 10-50wt% and all the other are zirconia and VIII family metal.
8. the process of claim 1 wherein that described VIII family metal is palladium and/or platinum, its amount is 0.01-5wt%.
9. by the isomerization of paraffinic hydrocarbons catalyst of the method for claim 1 preparation, comprise Zirconium oxide, group vib metal oxide, be lower than IIIA family metal oxide and the VIII family metal of 10wt%, described IIIA family metal is an aluminium, comprise the tetragonal system zirconia with this catalyst, and this tetragonal system zirconia have X-ray powder diffraction (XRPD) the reflection 2 θ scopes that are lower than 30.20 °.
10. from containing C
5+The method for preparing high octane gasoline in the hydrocarbon charging of hydrocarbon-fraction, wherein said charging contacts with the isomerization of paraffinic hydrocarbons catalyst of claim 9.
11. the method for claim 10, wherein, described hydrocarbon charging contains C
7+Hydrocarbon-fraction or contain the cut of this fraction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/287,206 US20070119748A1 (en) | 2005-11-28 | 2005-11-28 | Process for the preparation of a paraffin isomerization catalyst |
| US11/287206 | 2005-11-28 | ||
| US11/486056 | 2006-07-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1981926A CN1981926A (en) | 2007-06-20 |
| CN100528344C true CN100528344C (en) | 2009-08-19 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101625208A Expired - Fee Related CN100528344C (en) | 2005-11-28 | 2006-11-27 | Process for the preparation of a paraffin isomerisation catalyst |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20070119748A1 (en) |
| CN (1) | CN100528344C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2486005C1 (en) * | 2012-02-03 | 2013-06-27 | Федеральное Государственное Автономное Образовательное Учреждение Высшего Профессионального Образования "Сибирский Федеральный Университет" | Oxide catalyst for isomerisation of light gasoline fractions |
| GB2609806B (en) * | 2020-04-14 | 2024-08-14 | Kellogg Brown & Root Llc | Method for catalyst production for C5-C12 paraffin's isomerization |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2103876A1 (en) * | 1992-08-27 | 1994-02-28 | Stuart Leon Soled | Group viii metal containing tungsten oxide silica modified zirconia as acid catalyst |
| US5854170A (en) * | 1993-07-22 | 1998-12-29 | Mobil Oil Corporation | Method for preparing a modified solid oxide |
| US6080904A (en) * | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| JP3769293B2 (en) * | 1993-07-22 | 2006-04-19 | モービル オイル コーポレイション | Process for producing modified solid oxide catalyst |
| US5510309A (en) * | 1994-05-02 | 1996-04-23 | Mobil Oil Corporation | Method for preparing a modified solid oxide |
| US5453556A (en) * | 1994-06-22 | 1995-09-26 | Mobil Oil Corporation | Oligomerization process for producing synthetic lubricants |
| US5608133A (en) * | 1995-10-23 | 1997-03-04 | Mobil Oil Corporation | Catalytic oligomerization |
| US5837641A (en) * | 1996-01-16 | 1998-11-17 | Uop Llc | Method of promoting the activity of solid strong acid catalysts |
| ATE211947T1 (en) * | 1996-09-05 | 2002-02-15 | Japan Energy Corp | ACIDIC CATALYST IN SOLID FORM AND METHOD FOR PRODUCING THE SAME |
| WO2003013722A1 (en) * | 2001-08-07 | 2003-02-20 | Massachusetts Institute Of Technology | Non-zeolitic nanocomposite materials for solid acid catalysis |
| US6818589B1 (en) * | 2002-06-18 | 2004-11-16 | Uop Llc | Isomerization catalyst and processes |
| US7414007B2 (en) * | 2002-09-13 | 2008-08-19 | Uop Llc | Isomerization catalyst and process |
| AU2003272375A1 (en) * | 2002-09-13 | 2004-04-30 | Uop Llc | Isomerization catalyst and process |
| ES2341950T3 (en) * | 2002-09-25 | 2010-06-30 | Haldor Topsoe A/S | PROCESS OF ISOMERIZATION OF C7 + PARFINES AND CATALYST FOR THE SAME. |
| US7494953B2 (en) * | 2003-09-17 | 2009-02-24 | Haldor Topsoe A/S | Process for the preparation of an isomerisation catalyst |
| WO2005066101A1 (en) * | 2003-12-23 | 2005-07-21 | Exxonmobil Chemical Patents Inc. | Selective decomposition of ethers |
-
2005
- 2005-11-28 US US11/287,206 patent/US20070119748A1/en not_active Abandoned
-
2006
- 2006-11-27 CN CNB2006101625208A patent/CN100528344C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| US20070119748A1 (en) | 2007-05-31 |
| CN1981926A (en) | 2007-06-20 |
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