CN107051420A - A kind of normal butane isomerization catalyst and preparation method thereof - Google Patents
A kind of normal butane isomerization catalyst and preparation method thereof Download PDFInfo
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- CN107051420A CN107051420A CN201710362941.3A CN201710362941A CN107051420A CN 107051420 A CN107051420 A CN 107051420A CN 201710362941 A CN201710362941 A CN 201710362941A CN 107051420 A CN107051420 A CN 107051420A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 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 abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 30
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 2
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 2
- 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 claims description 2
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 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 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 150000002941 palladium compounds Chemical class 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000011017 operating method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000899793 Hypsophrys nicaraguensis Species 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NEBDODHTONKHGR-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O NEBDODHTONKHGR-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- 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
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- B01J37/024—Multiple impregnation or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- 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
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- B01J23/6525—Molybdenum
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
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- C07C5/2781—Acids of sulfur; Salts thereof; Sulfur oxides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
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- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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Abstract
The invention provides a kind of normal butane isomerization catalyst and preparation method thereof.The preparation method prepares the hydroxide of zirconium using coprecipitation, lanthanum salt is introduced to improve the ratio of Tetragonal, the zirconium oxide that abundant crystallization is Tetragonal is dried to obtain after hydro-thermal process, it is calcined after dip loading sulfate radical and molybdate, improve catalyst acid intensity, and aftershaping soaks group VIII metal again, synthesis has obtained the normal butane isomerization catalyst using tetragonal phase zirconium oxide as carrier.The normal butane isomerization catalyst is using nanometer grade tetragonal phase zircite as carrier；On the basis of the butt of tetragonal phase zirconium oxide carrier, the active component of the normal butane isomerization catalyst includes：The sulphur of 0.5 5.0 mass % lanthanum, 0.5 2.5 mass %, 0.5 2.5 mass % molybdenum and 0.01 5.0 mass % group VIII metal.The isomerization activity and selectivity of the catalyst are high, and repeatability and catalytic stability are good, and reaction temperature is low, and higher normal butane isomerization activity can be still kept under high temperature.
Description
Technical field
The present invention relates to a kind of normal butane isomerization catalyst and preparation method thereof, belong to catalyst preparation technical field.
Background technology
With increasingly strict, the specification of quality requirement more and more higher of mogas production of environmental requirement.Aromatic hydrocarbons, drop drop
Sulphur, Olefin decrease are that quality of gasoline improves the measure for having to take.Clean gasoline standard is towards low-sulfur, low alkene, low aromatic hydrocarbons
Direction is developed, and new process development, catalytic gasoline of the people constantly from pretreatment, the catalytic cracking of raw material is adopted in terms of post-processing
Measure is taken further to reduce catalytic gasoline sulfur content and alkene.And said from product blending angle, increase isoparaffin, research and development environmental protection
Type new technology can improve the octane number and reduction benzene and olefin(e) centent of its product.
Alkene, arene content are restricted in gasoline pool；Octane number wretched insufficiency, therefore exploitation antiknock component
It is most important.Iso-butane is the important source material of antiknock component MTBE (methyl tertiary butyl ether(MTBE)), while being also gasoline cleaning group
Point, the important source material of gasoline alkylate, thus exploitation normal butane isomerization catalyst is that the production to clean gasoline has
The research of significance.
Chloride oxidation aluminium profiles catalyst is used isomerization catalyst more.It is well known that chloride oxidation aluminium profiles catalyst is to anti-
Answer the requirement of raw material very strict, water, sulphur, nitrogen, the content of oxygen are less than 0.1ppm.Chloride oxidation aluminium profiles catalyst it is another
It is individual to have the disadvantage to regenerate, and chloride oxidation aluminium profiles catalyst, in catalytic reaction process, chlorine can be big with the process of reaction
Amount is lost in, in order to ensure that catalytic quantity needs constantly to mend chlorine into reaction.Because content of Cl element is higher, the corrosion ten to equipment
Divide it will be evident that this result in pays higher equipment repair and maintenance cost using chloride oxidation aluminium profiles catalyst needs again.Chlorination
Chlorine element in alumina catalyst can cause that the environment of the catalyst is unfriendly simultaneously, and it is impossible to meet Green Chemistry pair
The requirement of catalyst.Nanometer grade tetragonal phase zircite is above mentioned problem can then meet to the normal butane isomerization catalyst of carrier sword
Solution, requirement of the catalyst to raw material is loose；Chlorine need not be mended during catalytic production；And it can regenerate, meet greenization
Standard, is more efficient, more friendly normal butane isomerization catalyst.
The carrier property pore diameter range that for example specific surface area, average pore size and pore size distribution are mainly concentrated and ratio are to used
Catalyst activity, selectivity, stability and regenerability play an important role, therefore it is required that the ratio surface of carrier is big, to ensure
The selectivity and stability of catalyst.Therefore the nanometer grade tetragonal phase zircite used in above-mentioned normal butane isomerization catalyst compares table
Area is big, catalyst activity is high, stability and regenerability are good, and following patent reveals the preparation method of carrier or catalyst.
CN104117369A discloses a kind of preparation method of catalyst for normal paraffin isomerization, and it is with γ-Al2O3For
The aqueous solution dipping of carrier compound containing platinum, drying and roasting carries out reduction treatment with hydrogen, and under hydrogen and nitrogen respectively
Gasify aluminium chloride and the obtained catalyst of carbon tetrachloride.The aperture of aluminum oxide is all bigger than normal, is distributed relatively wide, chloride oxidation aluminium profiles catalysis
Agent can not regenerate, and chlorine can be lost in reaction process, and in order to ensure that the quality of catalyst needs constantly to mend chlorine, this to urge
Change can not meet environmental requirement, not environmentally type catalyst.
CN1524616A discloses a kind of preparation method of strong solid acid catalyst, and it is to mix zirconium saline solution and ammoniacal liquor
The hydroxide that zirconium is made in ageing, then oxide and the oxide mixed-forming of silicon with aluminium are closed, is calcined at a certain temperature.Should
The pH value that the method for patent application publication is controlled when preparing zirconium hydroxide is 6-10, and digestion time is longer, it is therefore an objective to make as far as possible
Zirconium hydroxide is converted into monoclinic phase.Higher it is easy to catalyst due to comparing shared by the oxide of aluminium in butt and the oxide of silicon
Shaping.The carrier of the catalyst adds the oxide of a large amount of silicon and the oxide of aluminium based on monoclinic phase in forming process,
Cause sulfate radical load capacity reduce the catalyst sulfur content it is low, only 1.0%-2.0% acidity is weak.
CN1170632A discloses a kind of metallic salt aqueous solution and is impregnated and prepare molecular sieve type ultrastrong acid type and urge
Agent, in the catalyst, the content of metallic element accounts for the 0.1-20% of molecular sieve, and binding agent is the oxide of silicon and the oxygen of aluminium
Compound weight accounts for the 25-45 of catalyst.The catalyst of molecular sieve type needs higher reaction temperature, and energy consumption is big.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of normal butane isomerization catalyst and its preparation
Method, the catalyst be the carrier that is prepared using zirconium oxide as carrier, using simple zirconates using hydro-thermal method and compound infusion process as
The catalyst of nanometer grade tetragonal crystalline phase zirconium oxide.
To reach above-mentioned purpose, the invention provides a kind of preparation method of normal butane isomerization catalyst, this method is
Normal butane isomerization is prepared by carrier of nanometer grade tetragonal phase zircite by compound pickling and leaching group VIII metal to be catalyzed
Agent, by raw material of simple zirconates by introduce lanthanum salt co-precipitation after hydro-thermal, washing, drying, crushing method obtain nanoscale
Tetragonal phase zirconium oxide carrier, then by compound pickling, shaping, drying, be calcined and soak group VIII metal again to prepare normal butane different
Structure catalyst.
On the basis of the butt of tetragonal phase zirconium oxide carrier, the active component of the normal butane isomerization catalyst includes：
0.5-5.0 mass % lanthanum, 0.5-2.5 mass % sulphur, 0.5-2.5 mass % molybdenum and 0.01-5.0 mass % VIII
Metal；Preferably, the content of group VIII metal is 0.05-5.0 mass %；
The preparation method comprises the following steps：
(1) zirconates and lanthanum salt are dissolved in deionized water, obtain mixture, adjust pH；
(2) feed the mixture into water heating kettle and carry out hydro-thermal reaction, reaction product is washed to neutrality；
(3) processing is dried to the filter cake that washing is obtained, obtains nanometer grade tetragonal phase zircite carrier；
(4) nanometer grade tetragonal phase zircite carrier is impregnated using the acid solution containing sulfate radical；
(5) using the solution containing molybdate to the leaching of nanometer grade tetragonal phase zircite carrier progress again by dipping
Stain；
(6) processing is dried to the nanometer grade tetragonal phase zircite carrier by dipping again；
(7) calcination process is carried out to dried nanometer grade tetragonal phase zircite carrier, the temperature of roasting is 350-750
℃；
(8) forming processes, the carrier being molded are carried out to product of roasting；
(9) carrier of shaping is impregnated using the maceration extract of the compound containing group VIII metal, then by drying, roasting
Burn the normal butane isomerization catalyst for obtaining that carrier is nanometer grade tetragonal phase zircite.
The emphasis of the present invention is to provide the normal butane isomery that a kind of stronger nanometer grade tetragonal phase zircite of acidity is carrier
Change the preparation method of catalyst.This method can be required according to isomerization catalyst difference, introduce different containing sulfate radicals solution, molybdenum
Acid group solution is to adjust the acid strength of catalyst, and appropriate adjustment sintering temperature condition, prepares the oxygen of different crystallization degrees in addition
Change zirconium carrier to use for preparing heterogeneous catalyst.
The technology of the present invention key is that the hydroxide that lanthanum salt prepares zirconium will be introduced in zirconates, then abundant crystallization is nanoscale four
Square phase zircite carrier, with containing sulfate radicals solution and solution impregnating carrier containing molybdate and adjusting sintering temperature obtains catalyst
Most beneficial for the acid strength of normal butane isomerization.The hydroxide of zirconium is suitably made with coprecipitation.Suitable zirconates
Including one or more kinds of combinations in zirconium oxychloride, zirconium sulfate, zirconyl nitrate etc., preferably zirconium oxychloride and nitric acid
Oxygen zirconium.Suitable lanthanum salt includes one kind or two in lanthanum nitrate, lanthanum chloride, lanthanum carbonate, lanthanum sulfate, lanthanum oxalate, lanthanum acetate etc.
The combination of the above is planted, most preferably lanthanum nitrate and lanthanum chloride., can after regulation pH to 7-8 after above-mentioned zirconates and lanthanum salt dissolving
Sufficiently to be stirred, to ensure the hydroxide for obtaining uniform zirconium.
The hydroxide (mixture i.e. in step (1)) of zirconium is moved into water heating kettle, it is natural after hydro-thermal reaction certain time
Room temperature is cooled down to, solution is removed into reactor, is removed after supernatant liquor, with Buchner funnel cyclic washing repeatedly up to neutrality,
The purpose of washing is to remove impurity (NO3 -And Cl-), being dried by conventional method at 50-150 DEG C after washing is converted into and received
Meter level tetragonal phase zirconium oxide carrier.The nanometer grade tetragonal phase zircite material is a kind of catalyst carrier with premium properties,
Sulphation can be carried out to the carrier and noble metal is supported, for preparing alkane isomerization catalyst.
In above-mentioned preparation method, it is preferable that the group VIII metal used includes platinum and/or palladium.Group VIII metal
Compound includes the compound and the/compound containing palladium of platiniferous, and the compound of the platiniferous includes chloroplatinic acid, ammonium chloroplatinate, dichloro
Change platinum or platinum tetrachloride etc., the compound containing palladium includes chlorine palladium acid, ammonium chloropalladate or palladium bichloride etc..
In above-mentioned preparation method, it is made after nanometer grade tetragonal phase zircite carrier, is stirred with the solution containing sulfate radical
Dipping makes sulfate radical fully be supported on nanometer grade tetragonal phase zircite carrier, washes away the sulfate radical on unsupported, waves solution
It is dry dry.Sulfate radical content in mixed liquor should reach the sulfur content needed for catalyst, dip time 0.5-10 hours.After filtering
Molybdate is fully supported on nanometer grade tetragonal phase zircite carrier with the solution stirring dipping containing molybdate, wash away and do not bear
Molybdate in load, dries solution evaporation.Molybdic acid radical content in mixed liquor should reach the molybdenum content needed for catalyst, dipping
Time 0.5-10 hour.Solid is calcined 2-4 hours at 350-750 DEG C after immersion filtration, obtains containing sulfate radicals and molybdate
Nanometer grade tetragonal phase zircite, by containing sulfate radicals and the nanometer grade tetragonal phase zircite extruded moulding of molybdate.Use predetermined amounts
The maceration extract impregnated carrier of preparation, makes active component content to reach the content needed for catalyst, dip time 0.5-10 hours.
Solid after immersion filtration obtains catalyst in 2-4 hours in 450-700 DEG C of roasting.
In above-mentioned preparation method, it is preferable that the acid solution containing sulfate radical used includes sulfuric acid or ammonium sulfate
Solution.The concentration of sulfate radical may be controlled to 0.1-5mol/L in acid solution containing sulfate radical.
In above-mentioned preparation method, it is preferable that the solution containing molybdate used includes molybdenum acid solution or ammonium molybdate
Solution.The concentration of Molybdenum in Solution acid group containing molybdate may be controlled to 0.1-5mol/L.
In above-mentioned preparation method, it is preferable that in step (4), needed for every gram of nanometer grade tetragonal phase zircite carrier
The amount of acid solution containing sulfate radical is 5-50ml.
In above-mentioned preparation method, it is preferable that in step (5), needed for every gram of nanometer grade tetragonal phase zircite carrier
The amount of solution containing molybdate is 5-50ml.
In above-mentioned preparation method, it is preferable that the particle diameter of nanometer grade tetragonal phase zircite carrier is 3-20nm, more preferably
3-10nm.Preferably, the specific surface area of nanometer grade tetragonal phase zircite carrier is 150-240m2/g。
In above-mentioned preparation method, it is preferable that in step (1), regulation pH is adjusting pH to adjust to 7-10
Stir 0.5-5 hours afterwards；Preferably, regulation pH operation is carried out under agitation.PH can be adjusted using weak aqua ammonia.
In above-mentioned preparation method, it is preferable that in step (2), the time of hydro-thermal reaction is 12-48 hours.
In above-mentioned preparation method, it is preferable that in step (3), (6), dry temperature is 50-150 DEG C, and the time is
12-36 hours.
In above-mentioned preparation method, it is preferable that in step (7), the time of roasting is 2-4 hours；
In above-mentioned preparation method, it is preferable that in step (9), the temperature of roasting is 450-700 DEG C, and the time is that 2-4 is small
When；
In above-mentioned preparation method, it is preferable that in step (4), (5), (6), the time of dipping is 0.5-10 hours.Leaching
Stain can be carried out using any conventional dipping method, preferably equi-volume impregnating.
According to specific embodiments of the present invention, the above-mentioned preparation method that the present invention is provided can be according to step in detail below
Carry out：
(1) zirconates and lanthanum salt are dissolved in deionized water, fully after dissolving, obtain mixture, weak aqua ammonia is added dropwise under agitation
PH is adjusted, after pH reaches 7-8, is stirred 0.5-5 hours；
(2) hydro-thermal reaction that water heating kettle is carried out 12-48 hours in 100-190 DEG C is fed the mixture into, reaction product is washed
Wash to neutrality, and remove chlorion；
(3) processing is dried in 50-150 DEG C to the filter cake that washing is obtained, obtains nanometer grade tetragonal phase zircite carrier；
(4) it is the 0.1-5mol/L acid solution containing sulfate radical to the nanometer grade tetragonal phase to use sulfate concentration
Zirconia carrier carries out the dipping of 0.5-10 hours；
(5) solution containing molybdate that molybdate concentration is 0.1-5mol/L is used again to the nanometer by impregnating
Level tetragonal phase zirconium oxide carrier carries out the dipping again of 0.5-10 hours；
(6) place is dried in 50-150 DEG C to the nanometer grade tetragonal phase zircite carrier by dipping again
Reason；
(7) to the dried nanometer grade tetragonal phase zircite carrier at the 350-750 DEG C of roasting for carrying out 2-4 hours
Reason；
(8) forming processes, the carrier being molded are carried out to product of roasting；
(9) carrier of the shaping is impregnated using the maceration extract of the compound containing group VIII metal, then passed through
Dry, 450-700 DEG C of roasting obtains the normal butane isomerization catalyst that carrier is nanometer grade tetragonal phase zircite for 2-4 hours.
Present invention also offers the normal butane isomery that carrier prepared by above-mentioned preparation method is nanometer grade tetragonal phase zircite
Change catalyst.
Technical scheme provided by the present invention prepares the hydroxide of zirconium using coprecipitation, introduces lanthanum salt to improve four directions
It is dried to obtain after the ratio of phase, hydro-thermal process after the zirconium oxide that abundant crystallization is Tetragonal, dip loading sulfate radical and molybdate
Roasting, improves catalyst acid intensity, and aftershaping soaks group VIII metal again, and synthesis has been obtained using tetragonal phase zirconium oxide as carrier
Normal butane isomerization catalyst.It is anti-that load sulfate radical and the tetragonal phase zirconium oxide carrier of molybdate can provide more isomerization
Site is answered, the isomerization activity and selectivity of the normal butane isomerization catalyst thus prepared are high, repeatability and catalytic stability
It is good, and reaction temperature is low, and higher normal butane isomerization activity can be still kept under high temperature.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph of nanometer grade tetragonal phase zircite carrier.
Fig. 2 is the XRD spectrum of nanometer grade tetragonal phase zircite.
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
A kind of preparation method of normal butane isomerization catalyst is present embodiments provided, it comprises the following steps：
(1) nanometer grade tetragonal phase zircite carrier is prepared
Taking zirconium oxychloride and lanthanum nitrate to be dissolved in deionized water, (concentration of zirconium is 0.4mol/L, and the content of lanthanum is 2%
(w) it is 10% ammoniacal liquor regulation pH that concentration), is added dropwise while stirring, makes pH value of solution=7-8, then moves into water heating kettle, in 170
DEG C hydro-thermal reaction 24 hours；Washed after cooling with filtered on buchner funnel, 110 DEG C of dryings obtained nanometer grade tetragonal phase oxidation in 24 hours
Zirconium carrier, Fig. 1 is that nanometer grade tetragonal phase zircite carrier obtains electromicroscopic photograph, and Fig. 2 is the XRD of nanometer grade tetragonal phase zircite
Spectrum.
(2) it is combined pickling shaping
Nanometer grade tetragonal phase zircite carrier predetermined amounts made from step (1) are configured into dilute sulfuric acid maceration extract, every gram is received
The dilute sulfuric acid stirring dipping that meter level tetragonal phase zirconium oxide carrier is 0.5mol/L with 20ml concentration 1 hour, is washed away on unsupported
Sulfate radical, then predetermined amounts configure dilute molybdic acid maceration extract, every gram of nanometer grade tetragonal phase zircite carrier is with 20ml concentration
0.5mol/L dilute molybdic acid stirring dipping 1 hour, washes away the molybdate on unsupported, and 650 DEG C are calcined after 110 DEG C of drying 24 hours
3 hours, it is extruded into strip or other shapes.
(3) dipping carries platinum
By containing sulfate radicals made from step (2) and the nanometer grade tetragonal phase zircite carrier predetermined amounts of molybdate configuration chlorine
Platinum content in platinic acid maceration extract, maceration extract should reach the platinum content (content of platinum is 0.2% (w)) needed for catalyst, stirring
Dipping 1 hour, washes away the platinum on unsupported, and 550 DEG C are calcined 3 hours obtainedization catalyst A after 110 DEG C of drying 24 hours.
Embodiment 2
It is identical with the operating method of embodiment 1, the difference is that (1) step takes zirconium oxychloride to be dissolved in the deionized water (concentration of zirconium
For 0.4mol/L, the content of lanthanum is 0% (w)) catalyst B is made, its active component content and normal butane isomerization rate are shown in Table 1.
Embodiment 3
It is identical with the operating method of embodiment 1, unlike (1) step take zirconium oxychloride to be dissolved in deionized water, stirring it is same
When be added dropwise concentration for 10% ammoniacal liquor regulation pH, make pH value of solution=7-8, then move into water heating kettle, it is small in 170 DEG C of hydro-thermal reactions 24
When；Lanthanum nitrate is made into aqueous solution dipping, then after filter washing, 110 DEG C of dryings after being washed after cooling with filtered on buchner funnel
Catalyst C, its active component content and normal butane is made in (concentration of zirconium is 0.4mol/L, and the content of lanthanum is 2% (w)) within 24 hours
Isomerization rate is shown in Table 1.
Embodiment 4
It is identical with the operating method of embodiment 1, the difference is that (1) step takes zirconium oxychloride and lanthanum nitrate to be dissolved in deionized water
(concentration of zirconium is 0.4mol/L, and the content of lanthanum is 2% (w)), it is 10% ammoniacal liquor regulation pH that concentration is added dropwise while stirring, is made
PH value of solution=7-8 it is still aging 24 when；Washed after cooling with filtered on buchner funnel, 110 DEG C of dryings obtain catalyst D in 24 hours, its
Active component content and normal butane isomerization rate are shown in Table 1.
Embodiment 5
It is identical with the operating method of embodiment 1, the difference is that (2) step predetermined amounts configuration dilute sulfuric acid maceration extract, every gram of nanometer
The dilute sulfuric acid stirring dipping that level tetragonal phase zirconium oxide carrier is 0.5mol/L with 20ml concentration 1 hour, washes away the sulphur on unsupported
Acid group, does not use molybdenum acid solution to be impregnated, and 650 DEG C are calcined 3 hours after 110 DEG C of dryings 24 hours, are extruded into strip or other shapes
Catalyst E is made in shape, and its active component content and normal butane isomerization rate are shown in Table 1.
Embodiment 6
It is identical with the operating method of embodiment 1, the difference is that (2) step predetermined amounts configure dilute molybdic acid maceration extract, every gram of nanometer
Dilute molybdic acid stirring dipping that level tetragonal phase zirconium oxide carrier is 0.5mol/L with 20ml concentration 1 hour, washes away the molybdenum on unsupported
650 DEG C are calcined 3 hours after acid group, 110 DEG C of dryings 24 hours, be extruded into strip or catalyst F, its active component is made in other shapes
Content and normal butane isomerization rate are shown in Table 1.
Embodiment 7
It is identical with the operating method of embodiment 1, the difference is that (2) step provides sulfate radical with ammonium sulfate is made catalyst G,
Its active component content and normal butane isomerization rate are shown in Table 1.
Embodiment 8
It is identical with the operating method of embodiment 1, the difference is that (2) step provides molybdate with ammonium molybdate solution is made catalyst H,
Its active component content and normal butane isomerization rate are shown in Table 1.
Embodiment 9
The present embodiment evaluates catalyst of the present invention to the performance of normal butane isomerization, specifically follows the steps below：Will
Isomerization catalyst is added in small fixed reactor, and raw material is normal butane, reaction condition：2.0MPa, 220 DEG C of feedstock qualities
Air speed is 2.0 hours-1, hydrogen/hydrocarbon molecule ratio is 1.2, and evaluation result is shown in Table 1.
Table 1
It can be seen that by the data of table 1：Catalyst carrier prepared by the present invention is nanoscale zirconia, and specific surface area is high,
Uniform particle sizes, fine holding effect is played to the acid group of load.Meanwhile, two kinds of strong acid to carrier impregnation are effectively raised
The acidity of catalyst, therefore under very low reaction temperatures (220 DEG C), the isomerization rate of normal butane can reach 39.7%.
Claims (10)
1. a kind of preparation method of normal butane isomerization catalyst, wherein, the normal butane isomerization catalyst is with nanoscale
Tetragonal phase zirconium oxide is carrier；
On the basis of the butt of tetragonal phase zirconium oxide carrier, the active component of the normal butane isomerization catalyst includes：0.5-
5.0 mass % lanthanum, 0.5-2.5 mass % sulphur, 0.5-2.5 mass % molybdenum and 0.01-5.0 mass % VIII gold
Category；Preferably, the content of the group VIII metal is 0.05-5.0 mass %；
The preparation method comprises the following steps：
(1) zirconates and lanthanum salt are dissolved in deionized water, obtain mixture, adjust pH；
(2) feed the mixture into water heating kettle and carry out hydro-thermal reaction in 100-190 DEG C, reaction product is washed to neutrality；
(3) processing is dried to the filter cake that washing is obtained, obtains nanometer grade tetragonal phase zircite carrier；
(4) the nanometer grade tetragonal phase zircite carrier is impregnated using the acid solution containing sulfate radical；
(5) using the solution containing molybdate to the leaching of nanometer grade tetragonal phase zircite carrier progress again by dipping
Stain；
(6) processing is dried to the nanometer grade tetragonal phase zircite carrier by dipping again；
(7) calcination process is carried out to the dried nanometer grade tetragonal phase zircite carrier, sintering temperature is 350-750 DEG C；
(8) forming processes, the carrier being molded are carried out to product of roasting；
(9) carrier of the shaping is impregnated using the maceration extract of the compound containing group VIII metal, then by drying, roasting
Burning obtains the normal butane isomerization catalyst.
2. preparation method as claimed in claim 1, wherein, the zirconates is included in zirconium oxychloride, zirconyl nitrate and zirconium sulfate
One or more kinds of combinations；
The lanthanum salt include lanthanum nitrate, lanthanum chloride, lanthanum carbonate, lanthanum sulfate, lanthanum oxalate and lanthanum acetate in one or two kinds of with
On combination, preferably lanthanum nitrate or lanthanum chloride；
The group VIII metal includes platinum and/or palladium, the compound of the group VIII metal compound including platiniferous and/containing palladium
Compound, wherein, the compound of the platiniferous includes chloroplatinic acid, ammonium chloroplatinate, platinous chloride or platinum tetrachloride, described containing palladium
Compound includes chlorine palladium acid, ammonium chloropalladate or palladium bichloride.
3. preparation method as claimed in claim 2, wherein, the acid solution containing sulfate radical includes sulfuric acid or ammonium sulfate
Solution；The solution containing molybdate includes molybdenum acid solution or ammonium molybdate solution.
4. preparation method as claimed in claim 3, wherein, the concentration of sulfate radical is in the acid solution containing sulfate radical
0.1-5mol/L, the concentration of the Molybdenum in Solution acid group containing molybdate is 0.1-5mol/L.
5. the preparation method as described in claim 1,3 or 4, wherein, in step (4), every gram of nanometer grade tetragonal phase oxygen
The amount of the acid solution containing sulfate radical needed for change zirconium carrier is 5-50ml；In step (5), every gram of nanometer grade tetragonal
The amount of the solution containing molybdate needed for phase zircite carrier is 5-50ml.
6. the preparation method as any one of claim 1-5, wherein, the grain of the nanometer grade tetragonal phase zircite carrier
Footpath is 3-20nm, preferably 3-10nm；Preferably, the specific surface area of the nanometer grade tetragonal phase zircite carrier is 150-
240m2/g。
7. the preparation method as any one of claim 1-6, wherein, in step (1), regulation pH is regulation to 7-
10, also, stir 0.5-5 hours after adjustment of ph；Preferably, regulation pH operation is carried out under agitation；It is highly preferred that using
Weak aqua ammonia adjusts pH.
8. the preparation method as any one of claim 1-7, wherein, in step (2), the time of the hydro-thermal reaction
For 12-48 hours；
In step (3), (6), the temperature of the drying is 50-150 DEG C, and the time is 12-36 hours；
In step (7), the time of the roasting is 2-4 hours；
In step (9), the temperature of the roasting is 450-700 DEG C, and the time is 2-4 hours；
In step (4), (5), (6), the time of the dipping is 0.5-10 hours.
9. the preparation method as any one of claim 1-8, wherein, the preparation method includes step in detail below：
(1) zirconates and lanthanum salt are dissolved in deionized water, fully after dissolving, obtain mixture, weak aqua ammonia regulation is added dropwise under agitation
PH, after pH reaches 7-8, is stirred 0.5-5 hours；
(2) feed the mixture into water heating kettle and carry out the hydro-thermal reaction of 12-48 hours in 100-190 DEG C, by reaction product wash to
Neutrality, and remove nitrate anion and/or chlorion；
(3) processing is dried in 50-150 DEG C to the filter cake that washing is obtained, obtains nanometer grade tetragonal phase zircite carrier；
(4) it is the 0.1-5mol/L acid solution containing sulfate radical to the nanometer grade tetragonal phase oxidation to use sulfate concentration
Zirconium carrier carries out the dipping of 0.5-10 hours；
(5) solution containing molybdate that molybdate concentration is 0.1-5mol/L is used to the nanometer grade tetragonal by impregnating
Phase zircite carrier carries out the dipping again of 0.5-10 hours；
(6) processing is dried in 50-150 DEG C to the nanometer grade tetragonal phase zircite carrier by dipping again；
(7) to the dried nanometer grade tetragonal phase zircite carrier in the calcination process of 350-750 DEG C of progress 2-4 hours；
(8) forming processes, the carrier being molded are carried out to product of roasting；
(9) carrier of the shaping is impregnated using the maceration extract of the compound containing group VIII metal, then by drying,
450-700 DEG C of roasting obtains the normal butane isomerization catalyst that carrier is nanometer grade tetragonal phase zircite for 2-4 hours.
10. carrier prepared by preparation method as claimed in any one of claims 1-9 wherein for nanometer grade tetragonal phase zircite just
Butane isomerization catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362941.3A CN107051420B (en) | 2017-05-22 | 2017-05-22 | N-butane isomerization catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710362941.3A CN107051420B (en) | 2017-05-22 | 2017-05-22 | N-butane isomerization catalyst and preparation method thereof |
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Cited By (8)
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| CN108772061A (en) * | 2018-06-04 | 2018-11-09 | 山东麟丰化工科技有限公司 | A kind of solid acid catalyst and normal butane-iso-butane isomerization method for isomerization reaction |
| CN109772287A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst carrier and preparation method thereof, and catalyst and preparation method thereof |
| CN110605125A (en) * | 2018-06-15 | 2019-12-24 | 国家能源投资集团有限责任公司 | Light alkane isomerization catalyst and preparation method thereof |
| CN112275309A (en) * | 2019-07-26 | 2021-01-29 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst carrier, carrier preparation method and obtained catalyst |
| CN113578354A (en) * | 2021-08-30 | 2021-11-02 | 南京克米斯璀新能源科技有限公司 | Catalyst and preparation method of heavy alkylbenzene |
| CN114258322A (en) * | 2019-08-20 | 2022-03-29 | 国际壳牌研究有限公司 | Methane oxidation catalyst and methods of making and using same |
| CN115501891A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof |
| CN115501890A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | N-butane skeletal isomerization catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109772287A (en) * | 2017-11-15 | 2019-05-21 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst carrier and preparation method thereof, and catalyst and preparation method thereof |
| CN108772061B (en) * | 2018-06-04 | 2021-02-12 | 山东麟丰化工科技有限公司 | Solid acid catalyst for isomerization reaction and n-butane-isobutane isomerization method |
| CN108772061A (en) * | 2018-06-04 | 2018-11-09 | 山东麟丰化工科技有限公司 | A kind of solid acid catalyst and normal butane-iso-butane isomerization method for isomerization reaction |
| CN110605125B (en) * | 2018-06-15 | 2022-08-12 | 国家能源投资集团有限责任公司 | Light alkane isomerization catalyst and preparation method thereof |
| CN110605125A (en) * | 2018-06-15 | 2019-12-24 | 国家能源投资集团有限责任公司 | Light alkane isomerization catalyst and preparation method thereof |
| CN112275309A (en) * | 2019-07-26 | 2021-01-29 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst carrier, carrier preparation method and obtained catalyst |
| CN112275309B (en) * | 2019-07-26 | 2023-05-26 | 中国石油天然气股份有限公司 | Alkane isomerization catalyst carrier, carrier preparation method and catalyst obtained by carrier preparation method |
| CN114258322A (en) * | 2019-08-20 | 2022-03-29 | 国际壳牌研究有限公司 | Methane oxidation catalyst and methods of making and using same |
| CN115501891A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | N-tetracarbon hydrocarbon isomerization catalyst and preparation method and application thereof |
| CN115501890A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | N-butane skeletal isomerization catalyst and preparation method and application thereof |
| CN115501891B (en) * | 2021-06-23 | 2023-09-29 | 中国石油化工股份有限公司 | N-carbon tetra-alkane isomerization catalyst and preparation method and application thereof |
| CN115501890B (en) * | 2021-06-23 | 2024-03-29 | 中国石油化工股份有限公司 | N-butane skeleton isomerization catalyst and its preparation method and application |
| CN113578354A (en) * | 2021-08-30 | 2021-11-02 | 南京克米斯璀新能源科技有限公司 | Catalyst and preparation method of heavy alkylbenzene |
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