CN107051420B - N-butane isomerization catalyst and preparation method thereof - Google Patents
N-butane isomerization catalyst and preparation method thereof Download PDFInfo
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- CN107051420B CN107051420B CN201710362941.3A CN201710362941A CN107051420B CN 107051420 B CN107051420 B CN 107051420B CN 201710362941 A CN201710362941 A CN 201710362941A CN 107051420 B CN107051420 B CN 107051420B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 50
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 142
- 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 45
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 13
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 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
- 238000000465 moulding Methods 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 46
- 238000004519 manufacturing process Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005470 impregnation Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 13
- 150000003754 zirconium Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003929 acidic solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 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
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 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
- 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 3
- 239000002245 particle Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 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
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 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
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000005554 pickling Methods 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
- 239000007787 solid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B01J35/40—
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- B01J35/613—
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- B01J35/615—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C5/2781—Acids of sulfur; Salts thereof; Sulfur oxides
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- 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
- C07C2523/652—Chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
Abstract
The invention provides a normal butane isomerization catalyst and a preparation method thereof. The preparation method comprises the steps of preparing zirconium hydroxide by a coprecipitation method, introducing lanthanum salt to improve the proportion of a tetragonal phase, drying after hydrothermal treatment to obtain fully crystallized tetragonal-phase zirconium oxide, impregnating and loading sulfate radicals and molybdate radicals, roasting to improve the acid strength of the catalyst, then molding, and then impregnating VIII-group metal, thus synthesizing the n-butane isomerization catalyst taking the tetragonal-phase zirconium oxide as a carrier. The n-butane isomerization catalyst takes nano-scale tetragonal zirconia as a carrier; the active components of the n-butane isomerization catalyst comprise the following components based on the dry basis of a tetragonal zirconia carrier: 0.5-5.0 mass% lanthanum, 0.5-2.5 mass% sulfur, 0.5-2.5 mass% molybdenum and 0.01-5.0 mass% group VIII metal. The catalyst has high isomerization activity and selectivity, good repeatability and catalytic stability, low reaction temperature and high n-butane isomerization activity at high temperature.
Description
Technical Field
The invention relates to a normal butane isomerization catalyst and a preparation method thereof, belonging to the technical field of catalyst preparation.
Background
With the stricter environmental protection requirements, the quality specification requirements of the motor gasoline products are higher and higher. The reduction of aromatics, sulfur and olefins is a measure which must be taken to improve the quality of gasoline. The standard of clean gasoline is developed towards the direction of low sulfur, low olefin and low aromatic hydrocarbon, so that people continuously take measures to further reduce the sulfur content and the olefin of the catalytic gasoline from the aspects of pretreatment of raw materials, development of a new catalytic cracking process, aftertreatment of the catalytic gasoline and the like. From the aspect of product blending, the isoparaffin is added, and the octane number of the product can be improved and the contents of benzene and olefin can be reduced by researching and developing an environment-friendly new process.
The contents of olefin and aromatic hydrocarbon in the gasoline pool are limited; gasoline octane is severely deficient and it is therefore of paramount importance to develop high octane components. Isobutane is an important raw material for high octane number component MTBE (methyl tert-butyl ether) and also an important raw material for gasoline cleaning component and alkylated gasoline, so that the development of n-butane isomerization catalyst is a research with important significance for the production of clean gasoline.
The isomerization catalyst is usually a chlorinated alumina type catalyst. It is known that the requirements of the chlorided alumina type catalyst on the reaction raw materials are very strict, and the contents of water, sulfur, nitrogen and oxygen are all less than 0.1 ppm. Another disadvantage of the chloridized alumina catalyst is that it cannot be regenerated, and during the catalytic reaction of the chloridized alumina catalyst, a great amount of chlorine is lost along with the progress of the reaction, and the chlorine needs to be continuously supplemented into the reaction in order to ensure the catalytic quality. The corrosion to equipment is obvious due to the high content of chlorine element, which causes higher equipment maintenance cost for using the chloridized alumina type catalyst. Chlorine element in the chloridized alumina type catalyst can cause the environment of the catalyst to be unfriendly, and the requirement of green chemistry on the catalyst cannot be met. The problem can be solved easily by the n-butane isomerization catalyst using nano-scale tetragonal zirconia as a carrier, and the requirement of the catalyst on raw materials is loose; chlorine supplementation is not needed in the catalytic production process; and the catalyst can be regenerated, meets the standard of green chemistry, and is a more efficient and friendly n-butane isomerization catalyst.
The range and proportion of pore diameters in which the properties of the carrier, such as specific surface area, average pore diameter and pore distribution, are mainly concentrated play an important role in the activity, selectivity, stability and regeneration performance of the catalyst used, and therefore the specific surface of the carrier is required to be large to ensure the selectivity and stability of the catalyst. Therefore, the nano-scale tetragonal zirconia used in the n-butane isomerization catalyst has large specific surface area, high catalyst activity, good stability and regeneration performance, and the following patents disclose the preparation method of the carrier or the catalyst.
CN104117369A discloses a preparation method of a normal paraffin isomerization catalyst, which is gamma-Al2O3The carrier is soaked in water solution containing platinum compound, dried and roasted, and then is reduced by hydrogen, and under the condition of hydrogen and nitrogen the aluminium chloride and carbon tetrachloride are respectively gasified to obtain the catalyst. The pore diameter of the alumina is large, the distribution is wide, the chloridized alumina catalyst can not be regenerated, the chlorine can be lost in the reaction process, and the chlorine is required to be continuously supplemented for ensuring the quality of the catalyst, so that the catalysis can not meet the environmental protection requirement, and the catalyst is not environment-friendly.
CN1524616A discloses a method for preparing a solid strong acid catalyst, which is to mix and age a zirconium salt aqueous solution and ammonia water to prepare zirconium hydroxide, mix and form the zirconium hydroxide with aluminum oxide and silicon oxide, and calcine the zirconium hydroxide at a certain temperature. The process disclosed in this patent application controls the pH in the range of 6 to 10 during the preparation of zirconium hydroxide and the aging time is long in order to try to convert the zirconium hydroxide into a monoclinic phase. The catalyst is easy to shape because the aluminum oxide and the silicon oxide account for higher proportion in a dry basis. The carrier of the catalyst is mainly monoclinic phase, and a large amount of silicon oxide and aluminum oxide are added in the forming process, so that the sulfur content of the catalyst is reduced due to the reduction of sulfate radical loading, and the catalyst is only weak in acidity of 1.0-2.0%.
CN1170632A discloses a molecular sieve type super strong acid catalyst prepared by impregnating a metal salt aqueous solution, wherein in the catalyst, the content of metal elements accounts for 0.1-20% of the molecular sieve, and the weight of a binder is that the weight of silicon oxide and aluminum oxide accounts for 25-45% of the catalyst. The molecular sieve type catalyst requires a high reaction temperature and consumes a large amount of energy.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a normal butane isomerization catalyst and a preparation method thereof, wherein the catalyst takes zirconia as a carrier, and the carrier prepared by a simple zirconium salt by a hydrothermal method and a composite impregnation method is a catalyst of nano tetragonal crystal phase zirconia.
In order to achieve the purpose, the invention provides a preparation method of an n-butane isomerization catalyst, which comprises the steps of preparing the n-butane isomerization catalyst by taking nano-scale tetragonal-phase zirconia as a carrier through composite pickling and VIII-group metal leaching, taking simple zirconium salt as a raw material, obtaining the nano-scale tetragonal-phase zirconia carrier through introducing lanthanum salt for coprecipitation, hydrothermal, washing, drying and crushing, and preparing the n-butane isomerization catalyst by composite pickling, molding, drying, roasting and leaching the VIII-group metal.
The active components of the n-butane isomerization catalyst comprise the following components based on the dry basis of a tetragonal zirconia carrier: 0.5-5.0 mass% lanthanum, 0.5-2.5 mass% sulfur, 0.5-2.5 mass% molybdenum and 0.01-5.0 mass% group VIII metal; preferably, the content of the group VIII metal is 0.05 to 5.0 mass%;
the preparation method comprises the following steps:
(1) dissolving zirconium salt and lanthanum salt in deionized water to obtain a mixture, and adjusting the pH value;
(2) adding the mixture into a hydrothermal kettle for hydrothermal reaction, and washing a reaction product to be neutral;
(3) drying the washed filter cake to obtain a nanoscale tetragonal-phase zirconia carrier;
(4) dipping the nano-scale tetragonal-phase zirconia carrier by adopting an acid solution containing sulfate radicals;
(5) adopting a solution containing molybdate radicals to dip the dipped nanoscale tetragonal-phase zirconia carrier again;
(6) drying the impregnated nanoscale tetragonal-phase zirconia carrier;
(7) roasting the dried nanoscale tetragonal-phase zirconia carrier at the roasting temperature of 350-750 ℃;
(8) molding the roasted product to obtain a molded carrier;
(9) dipping the formed carrier by dipping liquid containing VIII group metal compound, drying and roasting to obtain the normal butane isomerization catalyst with nano-scale tetragonal zirconia as the carrier.
The invention is characterized in that the preparation method of the normal butane isomerization catalyst which takes nano tetragonal zirconia with stronger acidity as a carrier is provided. According to different requirements of the isomerization catalyst, different sulfate-containing solutions and molybdate solutions can be introduced to adjust the acid strength of the catalyst, and in addition, the roasting temperature condition is properly adjusted to prepare zirconia carriers with different crystallization degrees for preparing the isomerization catalyst.
The technological key point of the present invention is that lanthanum salt is introduced into zirconium salt to prepare zirconium hydroxide, which is then crystallized into nanometer level tetragonal phase zirconia carrier, the carrier is soaked with sulfate radical containing solution and molybdate radical containing solution and the roasting temperature is regulated to make the catalyst obtain acid strength favorable to n-butane isomerization. Preferably, the hydroxide of zirconium is prepared by coprecipitation. Suitable zirconium salts include one or a combination of two or more of zirconium oxychloride, zirconium sulfate, zirconyl nitrate, and the like, preferably zirconium oxychloride and zirconyl nitrate. Suitable lanthanum salts include one or a combination of two or more of lanthanum nitrate, lanthanum chloride, lanthanum carbonate, lanthanum sulfate, lanthanum oxalate, lanthanum acetate, and the like, with lanthanum nitrate and lanthanum chloride being preferred. After the zirconium salt and the lanthanum salt are dissolved, the pH is adjusted to 7-8, and then the zirconium salt and the lanthanum salt can be fully stirred to ensure that uniform zirconium hydroxide is obtained.
Transferring zirconium hydroxide (i.e. the mixture in the step (1)) into a hydrothermal kettle, performing hydrothermal reaction for a certain time, naturally cooling to room temperature, transferring the solution out of the reaction kettle, removing supernatant, repeatedly washing with a Buchner funnel for multiple times until the solution is neutral, wherein the purpose of washing is to remove impurities (NO)3 -And Cl-) And drying the washed zirconium oxide at 50-150 ℃ according to a common method to convert the zirconium oxide into the nano-scale tetragonal phase zirconium oxide carrier. The nanometer isThe tetragonal zirconia material is a catalyst carrier with excellent performance, and can be sulfated and loaded with noble metals for preparing alkane isomerization catalysts.
In the above preparation method, preferably, the group VIII metal used includes platinum and/or palladium. The group VIII metal compound includes a platinum-containing compound including chloroplatinic acid, ammonium chloroplatinate, platinum dichloride, platinum tetrachloride or the like, and/or a palladium-containing compound including chloropalladic acid, ammonium chloropalladate, palladium chloride or the like.
In the preparation method, after the nano-scale tetragonal-phase zirconia carrier is prepared, a solution containing sulfate radicals is used for stirring and dipping to fully load the sulfate radicals on the nano-scale tetragonal-phase zirconia carrier, and the sulfate radicals which are not loaded are washed off to volatilize and dry the solution. The sulfate radical content in the mixed liquid should reach the sulfur content needed by the catalyst, and the dipping time is 0.5-10 hours. After filtering, the solution containing molybdate radical is stirred and dipped to make molybdate radical fully loaded on the nano-scale tetragonal phase zirconia carrier, and the unloaded molybdate radical is washed off to make the solution volatilize and dry. The content of molybdate radical in the mixed liquid is required to reach the molybdenum content required by the catalyst, and the soaking time is 0.5-10 hours. The solid after dipping and filtering is roasted for 2 to 4 hours at the temperature of 350-750 ℃ to obtain the nano-scale tetragonal-phase zirconia containing sulfate radicals and molybdate radicals, and the nano-scale tetragonal-phase zirconia containing the sulfate radicals and the molybdate radicals is extruded and formed. Impregnating the carrier with an impregnating solution prepared according to a predetermined amount to make the content of the active component reach the required content of the catalyst, wherein the impregnating time is 0.5-10 hours. The solid after the dipping and filtration is roasted for 2 to 4 hours at the temperature of 450 ℃ and 700 ℃ to obtain the catalyst.
In the above production method, preferably, the sulfate group-containing acidic solution used includes a sulfuric acid or ammonium sulfate solution. The concentration of sulfate radical in the sulfate radical-containing acidic solution can be controlled to be 0.1-5 mol/L.
In the above production method, preferably, the molybdate-containing solution used includes a molybdic acid solution or an ammonium molybdate solution. The concentration of the molybdate in the solution containing the molybdate can be controlled to be 0.1-5 mol/L.
In the above production method, preferably, in the step (4), the amount of the sulfate group-containing acidic solution required per gram of the nanosized tetragonal zirconia support is 5 to 50 ml.
In the above production method, preferably, in step (5), the amount of the solution containing molybdate is required to be 5 to 50ml per gram of the nanosized tetragonal zirconia support.
In the above production method, preferably, the nano-sized tetragonal zirconia carrier has a particle diameter of 3 to 20nm, more preferably 3 to 10 nm. Preferably, the specific surface area of the nanoscale tetragonal phase zirconia support is 150-240m2/g。
In the above production method, preferably, in the step (1), the pH is adjusted to 7 to 10, and stirring is performed for 0.5 to 5 hours after the pH is adjusted; preferably, the operation of adjusting the pH is carried out under stirring. The pH can be adjusted with dilute ammonia.
In the above production method, preferably, in the step (2), the hydrothermal reaction time is 12 to 48 hours.
In the above production method, it is preferable that in the steps (3) and (6), the drying temperature is 50 to 150 ℃ and the time is 12 to 36 hours.
In the above production method, preferably, in the step (7), the time of calcination is 2 to 4 hours;
in the above preparation method, preferably, in the step (9), the temperature of the calcination is 450-700 ℃ for 2-4 hours;
in the above production method, preferably, in the steps (4), (5), (6), the time of immersion is 0.5 to 10 hours. The impregnation can be carried out by any conventional impregnation method, preferably by an equal volume impregnation method.
According to a specific embodiment of the present invention, the preparation method provided by the present invention can be performed according to the following specific steps:
(1) dissolving zirconium salt and lanthanum salt in deionized water, fully dissolving to obtain a mixture, dropwise adding dilute ammonia water under stirring to adjust the pH, and stirring for 0.5-5 hours when the pH reaches 7-8;
(2) adding the mixture into a hydrothermal kettle for hydrothermal reaction at the temperature of 100-190 ℃ for 12-48 hours, washing the reaction product to be neutral, and removing chloride ions;
(3) drying the washed filter cake at 50-150 ℃ to obtain a nano-scale tetragonal phase zirconia carrier;
(4) dipping the nanoscale tetragonal-phase zirconia carrier for 0.5-10 hours by using an acid solution containing sulfate radicals with the sulfate radical concentration of 0.1-5 mol/L;
(5) then, carrying out secondary impregnation on the impregnated nanoscale tetragonal-phase zirconia carrier for 0.5 to 10 hours by adopting a solution containing molybdate radicals with the molybdate radical concentration of 0.1 to 5 mol/L;
(6) drying the impregnated nanoscale tetragonal zirconia carrier at 50-150 ℃;
(7) roasting the dried nanoscale tetragonal-phase zirconia carrier at the temperature of 350-750 ℃ for 2-4 hours;
(8) molding the roasted product to obtain a molded carrier;
(9) dipping the formed carrier by using dipping liquid containing VIII group metal compounds, and then drying and roasting at 450-700 ℃ for 2-4 hours to obtain the n-butane isomerization catalyst with the carrier of nano-scale tetragonal zirconia.
The invention also provides a normal butane isomerization catalyst with the carrier of nano-scale tetragonal zirconia, which is prepared by the preparation method.
The technical scheme provided by the invention is that zirconium hydroxide is prepared by a coprecipitation method, lanthanum salt is introduced to improve the proportion of a tetragonal phase, the zirconium oxide fully crystallized into the tetragonal phase is obtained by drying after hydrothermal treatment, sulfate radicals and molybdate radicals are impregnated and loaded and then roasted to improve the acid strength of the catalyst, and VIII group metal is impregnated after post-forming, so that the n-butane isomerization catalyst taking the tetragonal phase zirconium oxide as a carrier is synthesized. The sulfate radical and molybdate loaded tetragonal zirconia carrier can provide more isomerization reaction sites, so that the prepared n-butane isomerization catalyst has high isomerization activity and selectivity, good repeatability and catalytic stability, low reaction temperature and high n-butane isomerization activity at high temperature.
Drawings
FIG. 1 is an electron micrograph of a nanoscale tetragonal zirconia support.
Fig. 2 is an XRD spectrum of nano-sized tetragonal phase zirconia.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides a method for preparing an n-butane isomerization catalyst, comprising the steps of:
(1) preparation of nanoscale tetragonal phase zirconia support
Dissolving zirconium oxychloride and lanthanum nitrate in deionized water (the concentration of zirconium is 0.4mol/L, the content of lanthanum is 2% (w)), dropwise adding ammonia water with the concentration of 10% while stirring to adjust the pH value of the solution to 7-8, then transferring the solution into a hydrothermal kettle, and carrying out hydrothermal reaction at 170 ℃ for 24 hours; and (3) after cooling, filtering and washing by using a Buchner funnel, and drying for 24 hours at 110 ℃ to obtain the nano-scale tetragonal phase zirconia carrier, wherein figure 1 is a photograph of the obtained electron microscope of the nano-scale tetragonal phase zirconia carrier, and figure 2 is an XRD (X-ray diffraction) spectrum of the nano-scale tetragonal phase zirconia.
(2) Composite pickling forming
Preparing a dilute sulphuric acid impregnation solution for the nanoscale tetragonal-phase zirconia carrier prepared in the step (1) according to a preset amount, stirring and impregnating each gram of the nanoscale tetragonal-phase zirconia carrier with 20ml of dilute sulphuric acid with the concentration of 0.5mol/L for 1 hour, washing off unsupported sulfate radicals, then preparing a dilute molybdic acid impregnation solution according to a preset amount, stirring and impregnating each gram of the nanoscale tetragonal-phase zirconia carrier with 20ml of dilute molybdic acid with the concentration of 0.5mol/L for 1 hour, washing off unsupported molybdate radicals, drying at 110 ℃ for 24 hours, roasting at 650 ℃ for 3 hours, and extruding into strips or other shapes.
(3) Impregnated platinum support
Preparing chloroplatinic acid impregnation liquid from the nanoscale tetragonal-phase zirconia carrier containing sulfate radicals and molybdate radicals prepared in the step (2) according to a preset amount, wherein the platinum content in the impregnation liquid is required to reach the platinum content (the platinum content is 0.2 percent (w)) required by the catalyst, stirring and impregnating for 1 hour, washing off the platinum which is not loaded, drying at 110 ℃ for 24 hours, and roasting at 550 ℃ for 3 hours to prepare the chemical catalyst A.
Example 2
The same procedure as in example 1 was followed, except that (1) zirconium oxychloride was dissolved in deionized water (the concentration of zirconium was 0.4mol/L and the content of lanthanum was 0% (w)) to obtain catalyst B, whose active component content and n-butane isomerization ratio were as shown in Table 1.
Example 3
The same operation method as that of example 1, except that (1) step of dissolving zirconium oxychloride in deionized water, stirring and simultaneously dripping 10% ammonia water to adjust the pH value of the solution to 7-8, then transferring the solution into a hydrothermal kettle, and carrying out hydrothermal reaction at 170 ℃ for 24 hours; after cooling, lanthanum nitrate is filtered and washed by a Buchner funnel, prepared into aqueous solution to be soaked, then filtered and washed, and dried for 24 hours at 110 ℃ (the concentration of zirconium is 0.4mol/L, the content of lanthanum is 2% (w)) to prepare the catalyst C, and the content of active components and the isomerization rate of n-butane are shown in Table 1.
Example 4
The same operation method as that of example 1 is carried out except that in the step (1), zirconium oxychloride and lanthanum nitrate are dissolved in deionized water (the concentration of zirconium is 0.4mol/L, the content of lanthanum is 2% (w)), ammonia water with the concentration of 10% is added dropwise while stirring to adjust the pH, and the solution is kept standing and aged for 24 hours until the pH is 7-8; after cooling, the mixture was filtered and washed by a Buchner funnel and dried at 110 ℃ for 24 hours to obtain catalyst D, the active component content and the n-butane isomerization rate of which are shown in Table 1.
Example 5
The same operation as in example 1 was conducted except that (2) a dilute sulfuric acid impregnation solution was prepared in predetermined amounts, 20ml of dilute sulfuric acid having a concentration of 0.5mol/L was stirred and impregnated into each gram of the nano-sized tetragonal zirconia support for 1 hour, the unsupported sulfate group was washed off, impregnation was not carried out with a molybdic acid solution, drying was carried out at 110 ℃ for 24 hours, then calcination was carried out at 650 ℃ for 3 hours, and extrusion into a bar or other shape to obtain catalyst E, the active component content and the n-butane isomerization ratio of which are shown in Table 1.
Example 6
The same procedure as in example 1 was followed, except that (2) a diluted molybdic acid impregnation solution was prepared in predetermined amounts, 20ml of diluted molybdic acid having a concentration of 0.5mol/L was stirred and impregnated into each gram of the nano-sized tetragonal zirconia support for 1 hour, the unsupported molybdate group was washed off, the support was dried at 110 ℃ for 24 hours and then calcined at 650 ℃ for 3 hours, and the catalyst F was extruded into a bar or other shape to obtain a catalyst F, the active component content and the n-butane isomerization ratio of which are shown in Table 1.
Example 7
The same procedure as in example 1 was followed, except that the sulfate group was supplied as an ammonium sulfate solution in step (2), to obtain catalyst G whose active component content and n-butane isomerization ratio were as shown in Table 1.
Example 8
The same procedure as in example 1 was followed, except that in the step (2), ammonium molybdate solution was used to provide molybdate groups, to obtain catalyst H, the active component content and the n-butane isomerization ratio of which are shown in Table 1.
Example 9
This example evaluates the performance of the catalyst of the invention for the isomerization of n-butane, in particular according to the following steps: adding an isomerization catalyst into a small fixed bed reactor, wherein the raw material is n-butane, and the reaction conditions are as follows: 2.0MPa, 220 ℃ feeding mass space velocity of 2.0 hours-1The hydrogen/hydrocarbon molecular ratio was 1.2, and the evaluation results are shown in Table 1.
TABLE 1
As can be seen from the data in table 1: the catalyst carrier prepared by the invention is nano-grade zirconia, has high specific surface area and uniform particle size, and plays a good role in keeping the loaded acid radicals. Meanwhile, the carrier is impregnated with two strong acids, so that the acidity of the catalyst is effectively improved, and the isomerization rate of n-butane can reach 39.7% at a very low reaction temperature (220 ℃).
Claims (14)
1. A preparation method of a normal butane isomerization catalyst, wherein the normal butane isomerization catalyst takes nano-scale tetragonal zirconia as a carrier;
the active components of the n-butane isomerization catalyst comprise the following components based on the dry basis of a tetragonal zirconia carrier: 2.0 mass% lanthanum, 1.9-2.3 mass% sulfur, 1.9-2.1 mass% molybdenum and 0.2 mass% group VIII metal; the group VIII metal is platinum;
the preparation method comprises the following steps:
(1) dissolving zirconium salt and lanthanum salt in deionized water to obtain a mixture, and adjusting the pH value;
(2) adding the mixture into a hydrothermal kettle for hydrothermal reaction at the temperature of 100 ℃ and 190 ℃, and washing a reaction product to be neutral;
(3) drying the washed filter cake to obtain a nanoscale tetragonal-phase zirconia carrier; the particle size of the nano-scale tetragonal phase zirconia carrier is 5-10 nm;
(4) impregnating the nanoscale tetragonal zirconia support with an acidic solution containing sulfate radicals;
(5) adopting a solution containing molybdate radicals to perform secondary impregnation on the impregnated nanoscale tetragonal-phase zirconia carrier;
(6) drying the impregnated nanoscale tetragonal-phase zirconia carrier;
(7) roasting the dried nanoscale tetragonal-phase zirconia carrier at the roasting temperature of 350-750 ℃; the specific surface area of the nano-scale tetragonal phase zirconia carrier is 208-232m2/g；
(8) Molding the roasted product to obtain a molded carrier;
(9) and (3) impregnating the formed carrier by using impregnation liquid containing VIII group metal compounds, and then drying and roasting to obtain the n-butane isomerization catalyst.
2. The production method according to claim 1, wherein the zirconium salt comprises one or a combination of two or more of zirconium oxychloride, zirconium oxynitrate, and zirconium sulfate;
the lanthanum salt comprises one or the combination of more than two of lanthanum nitrate, lanthanum chloride, lanthanum carbonate, lanthanum sulfate, lanthanum oxalate and lanthanum acetate;
the group VIII metal compound comprises a platinum-containing compound, wherein the platinum-containing compound comprises chloroplatinic acid, ammonium chloroplatinate, platinum dichloride, or platinum tetrachloride.
3. The production method according to claim 2, wherein the sulfate group-containing acidic solution comprises a sulfuric acid or ammonium sulfate solution; the solution containing molybdate groups comprises a molybdic acid solution or an ammonium molybdate solution.
4. The method of claim 2, wherein the lanthanum salt comprises lanthanum nitrate or lanthanum chloride.
5. The production process according to claim 3, wherein the sulfate group concentration in the sulfate group-containing acidic solution is 0.1 to 5mol/L, and the concentration of the molybdate group in the molybdate group-containing solution is 0.1 to 5 mol/L.
6. The production method as claimed in claim 1, wherein, in the step (4), the amount of the sulfate group-containing acidic solution required per gram of the nano-sized tetragonal zirconia support is 5 to 50 ml; in step (5), the amount of the solution containing molybdate is required to be 5 to 50ml per gram of the nanoscale tetragonal-phase zirconia support.
7. The production method as claimed in claim 3, wherein, in the step (4), the amount of the sulfate group-containing acidic solution required per gram of the nano-sized tetragonal zirconia support is 5 to 50 ml; in step (5), the amount of the solution containing molybdate is required to be 5 to 50ml per gram of the nanoscale tetragonal-phase zirconia support.
8. The production method as claimed in claim 5, wherein, in the step (4), the amount of the sulfate group-containing acidic solution required per gram of the nano-sized tetragonal zirconia support is 5 to 50 ml; in step (5), the amount of the solution containing molybdate is required to be 5 to 50ml per gram of the nanoscale tetragonal-phase zirconia support.
9. The production process according to claim 1, wherein in the step (1), the pH is adjusted to 7 to 10, and stirring is carried out for 0.5 to 5 hours after the pH adjustment.
10. The method of claim 9, wherein the operation of adjusting the pH is performed under stirring.
11. The method of claim 9, wherein the pH is adjusted using dilute ammonia.
12. The preparation method according to claim 1, wherein, in the step (2), the hydrothermal reaction is carried out for 12 to 48 hours;
in the steps (3) and (6), the drying temperature is 50-150 ℃, and the drying time is 12-36 hours;
in the step (7), the roasting time is 2-4 hours;
in the step (9), the roasting temperature is 450-700 ℃, and the roasting time is 2-4 hours;
in the steps (4), (5) and (6), the immersion time is 0.5 to 10 hours.
13. The method of any one of claims 1-12, wherein the method comprises the specific steps of:
(1) dissolving zirconium salt and lanthanum salt in deionized water, fully dissolving to obtain a mixture, dropwise adding dilute ammonia water under stirring to adjust the pH, and stirring for 0.5-5 hours when the pH reaches 7-8;
(2) adding the mixture into a hydrothermal kettle for hydrothermal reaction at the temperature of 100 ℃ and 190 ℃ for 12-48 hours, washing the reaction product to be neutral, and removing nitrate and/or chloride ions;
(3) drying the washed filter cake at 50-150 ℃ to obtain a nano-scale tetragonal phase zirconia carrier;
(4) dipping the nanoscale tetragonal-phase zirconia carrier for 0.5-10 hours by using an acid solution containing sulfate radicals with the sulfate radical concentration of 0.1-5 mol/L;
(5) carrying out secondary impregnation on the impregnated nanoscale tetragonal-phase zirconia carrier for 0.5-10 hours by adopting a solution containing molybdate radicals with molybdate radical concentration of 0.1-5 mol/L;
(6) drying the impregnated nanoscale tetragonal zirconia carrier at 50-150 ℃;
(7) roasting the dried nanoscale tetragonal-phase zirconia carrier at the temperature of 350-750 ℃ for 2-4 hours;
(8) molding the roasted product to obtain a molded carrier;
(9) dipping the formed carrier by using dipping liquid containing VIII group metal compounds, and then drying and roasting at 450-700 ℃ for 2-4 hours to obtain the n-butane isomerization catalyst with the carrier of nano-scale tetragonal zirconia.
14. The support produced by the production method according to any one of claims 1 to 13 is a normal butane isomerization catalyst of nano-sized tetragonal zirconia.
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| 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 |
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| CA3150386A1 (en) * | 2019-08-20 | 2021-02-25 | Shell Internationale Research Maatschappij B.V. | A methane oxidation catalyst and a method of making and using 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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| KR101306814B1 (en) * | 2011-06-01 | 2013-09-10 | 금호석유화학 주식회사 | Catalysts based on Zirconia for Direct dehydrogenation, Preparing method thereof, and Preparing method of Butenes using the same |
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| CN1541764A (en) * | 2003-04-29 | 2004-11-03 | 中国石油化工股份有限公司 | Catalyst for isomerizing low-carbon paraffin and its preparing process |
| CN1583256A (en) * | 2004-06-09 | 2005-02-23 | 中国科学院大连化学物理研究所 | Nobel metal catalyst for treating industrial waste water, preparing method and use thereof |
| CN103373743A (en) * | 2013-07-12 | 2013-10-30 | 南京宇热材料科技有限公司 | Polyol assisted hydrothermal method for synthesis of zirconium oxide nano-powder |
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