CN107999119B - Hydrated alumina composition containing ZSM-22 type molecular sieve, catalyst, preparation method and hydroisomerization method - Google Patents
Hydrated alumina composition containing ZSM-22 type molecular sieve, catalyst, preparation method and hydroisomerization method Download PDFInfo
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- CN107999119B CN107999119B CN201610930280.5A CN201610930280A CN107999119B CN 107999119 B CN107999119 B CN 107999119B CN 201610930280 A CN201610930280 A CN 201610930280A CN 107999119 B CN107999119 B CN 107999119B
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- hydrated alumina
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- wet gel
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 644
- 238000000034 method Methods 0.000 title claims abstract description 250
- 239000000203 mixture Substances 0.000 title claims abstract description 242
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 98
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011240 wet gel Substances 0.000 claims abstract description 172
- 150000001875 compounds Chemical class 0.000 claims abstract description 110
- 230000008569 process Effects 0.000 claims abstract description 72
- 238000001035 drying Methods 0.000 claims abstract description 46
- 238000000926 separation method Methods 0.000 claims description 93
- 239000007788 liquid Substances 0.000 claims description 89
- 239000000499 gel Substances 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 57
- 238000005406 washing Methods 0.000 claims description 53
- 239000012298 atmosphere Substances 0.000 claims description 45
- 238000004519 manufacturing process Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000004480 active ingredient Substances 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 25
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 claims description 24
- 229920000926 Galactomannan Polymers 0.000 claims description 24
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
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- 208000005156 Dehydration Diseases 0.000 claims description 13
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract description 41
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- 238000009826 distribution Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
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- 238000003786 synthesis reaction Methods 0.000 description 10
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- 239000002253 acid Substances 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000002902 bimodal effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
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- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
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- 239000004033 plastic Substances 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 229940024545 aluminum hydroxide Drugs 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
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- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QVRVXSZKCXFBTE-UHFFFAOYSA-N n-[4-(6,7-dimethoxy-3,4-dihydro-1h-isoquinolin-2-yl)butyl]-2-(2-fluoroethoxy)-5-methylbenzamide Chemical compound C1C=2C=C(OC)C(OC)=CC=2CCN1CCCCNC(=O)C1=CC(C)=CC=C1OCCF QVRVXSZKCXFBTE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000014612 sandwich biscuits Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005563 spheronization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B01J20/28078—Pore diameter
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/28088—Pore-size distribution
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The invention discloses a hydrated alumina composition containing ZSM-22 type molecular sieve, a preparation method thereof, a formed body, a preparation method and application thereof, wherein the composition contains the hydrated alumina, the ZSM-22 type molecular sieve and a compound with at least two proton acceptor sites, and
the value is 5 or less. The invention also discloses a hydroisomerization catalyst using a formed body formed by the hydrated alumina composition as a carrier, a preparation method and a hydroisomerization method. The invention prepares the forming body with higher strength by taking the hydrated alumina wet gel as the initial raw material, omits the step of drying the hydrated alumina wet gel, simplifies the overall process flow, reduces the overall operation energy consumption, avoids the dust pollution caused by adopting the pseudoboehmite dry glue powder as the raw material, and greatly improves the operation environment. The catalyst according to the invention shows better catalytic activity in the hydroisomerization reaction.
Description
Technical Field
The invention relates to the technical field of alumina forming, in particular to a hydrated alumina composition containing a ZSM-22 type molecular sieve and a preparation method thereof, a hydrated alumina forming body and an alumina forming body formed by the hydrated alumina composition, and further relates to a hydroisomerization catalyst taking the forming body formed by the hydrated alumina composition as a carrier, a preparation method thereof and a hydroisomerization method adopting the catalyst.
Background
The ZSM-22 molecular sieve is a novel aluminosilicate molecular sieve material developed by Mobil corporation Dwyer et al in the 80 th century in the United states, belongs to an orthorhombic system, has a space group of Mmc21 and a unit cell parameter of a ═ 13.
The ZSM-22 molecular sieve has a TON structural topological framework, and the topological structure comprises five-membered rings, six-membered rings and ten-membered rings. The main channel is a one-dimensional channel with ten-membered ring opening, the channel is parallel to the (001) direction, no cross channel exists, and the size of the orifice is
Of the elliptical channel. ZSM-22 molecular sieve has space shape-selective effect and is widely applied to isomerization reaction of straight-chain alkane.
In the conventional method, an alumina compact containing a ZSM-22 type molecular sieve, particularly a γ -alumina compact containing a ZSM-22 type molecular sieve, is often used as an adsorbent or a carrier of a supported catalyst because it has a good pore structure, a suitable specific surface area, and a high thermal stability. The alumina is usually prepared from dried hydrated alumina, such as pseudoboehmite, by molding, drying and high-temperature roasting.
Based on the above knowledge, as shown in fig. 1, the prepared wet alumina gel needs to be dried to obtain pseudo-boehmite dry gel powder, and then the ZSM-22 type molecular sieve, the extrusion assistant and the optional chemical peptizing agent (inorganic acid and/or organic acid) are added with the pseudo-boehmite dry gel powder as a starting point, and are kneaded and molded, and the molded product is dried and optionally calcined to be used as an adsorbent or a carrier. The main problems of this preparation method are the high dust pollution and the high energy consumption.
In order to reduce dust pollution and improve working environment, researchers have realized that raw materials used for forming should be changed, and have begun to try to prepare alumina formed products using hydrated alumina wet gel or semi-dried pseudo-boehmite as raw materials.
US4613585 discloses a process for preparing an alumina catalyst support, which comprises the steps of:
(a) pouring an aluminum sulfate solution and a sodium aluminate solution simultaneously into a vessel containing deionized water to react the aluminum sulfate solution and the sodium aluminate solution under reaction conditions of pH6.0 to 8.5 and a temperature of 50 to 65 ℃, thereby preparing a first aqueous slurry containing amorphous aluminum hydroxide;
(b) adding an aqueous sodium aluminate solution to the first aqueous slurry in an amount sufficient to neutralize the first aqueous slurry, the total amount of sodium aluminate solution used in steps (a) and (b) corresponding to 0.95-1.05 of the stoichiometric amount of aluminum sulfate used in step (a), thereby preparing a second aqueous slurry having Al in the second aqueous slurry2O3A concentration of 7 wt% or more;
(c) filtering amorphous aluminum hydroxide in the second water slurry to obtain a filter cake, washing the obtained filter cake with dilute ammonia water, washing with dilute nitric acid solution, washing with dilute ammonia water to remove sulfate radical anions and sodium cation impurities, and adjusting the pH value of the filter cake to be within the range of 7.5-10.5;
(d) then, without aging the filter cake, on a filter pressDehydrating the filter cake and subjecting it to Al2O3Is increased to 28 to 35% by weight and the filter cake is kneaded in a self-cleaning type mixer at a pH in the range of 7.5 to 10.5 for a residence time of 10s or more to grow the pseudoboehmite particles in a short time, thereby obtaining agglomerates containing these particles;
(e) extruding the dough obtained in step (d) to form an extrudate, and then drying and roasting to obtain the extrudate.
From the method disclosed in US4613585, although the hydrated alumina wet gel can be shaped, there are limitations from the conditions for preparing amorphous aluminum hydroxide to kneading equipment and kneading conditions, resulting in complicated process operations. Also, the support prepared by the method should not have high strength and hardly meet the requirements for industrial applications because of high content of free water in the extrudate prepared by the method and the porosity of the extrudate obtained by drying and firing. Meanwhile, the carrier prepared by the method is difficult to regulate and control the pore structure of the carrier, so that the requirements of various use occasions are difficult to meet.
CN103769118A discloses a heavy oil hydrogenation catalyst, which comprises a carrier and an active component, wherein the carrier is alumina, the active component is metal of VIII group and/or VIB group, the VIII group metal is Co or Ni, the VIB group metal is Mo or W, and the alumina is prepared by molding pseudo-boehmite with a dry basis content of below 50%. The preparation process of the pseudo-boehmite with the dry basis content of less than 50 percent comprises the following steps: (1) carrying out neutralization gelling reaction on an aluminum salt solution and a precipitator; (2) filtering and recovering a solid product of the gelling reaction; (3) the solid product is dried to obtain the product with the dry content of below 50 percent.
CN103769118A adopts pseudoboehmite with a dry content of less than 50% to prepare an alumina carrier, and the pseudoboehmite with a dry content of less than 50% is obtained by drying a solid product separated from a mixture obtained by gelling reaction, which is a method difficult to implement in the actual operation process, mainly because:
(1) the incompletely dried pseudo-boehmite has strong viscosity and difficult transfer, and is easy to cause secondary dust pollution;
(2) drying is started from the surface, and the drying of a wet solid product separated from a mixture obtained by the gelling reaction belongs to incomplete drying, so that a sandwich biscuit phenomenon exists, namely, the surface of part of the pseudo-boehmite is dried (namely, the dried surface is basically free of free water), the inner part is still kept in a wet state (namely, the content of the free water in the non-dried inner part is basically kept at the level before drying), hard particles are formed because the surface is dried, and when the pseudo-boehmite which is not completely dried through is added with a peptizer and/or a binder and the like and is kneaded and formed, the hard particles formed in the drying process are easy to cause blockage in the extrusion process, so that the production efficiency is influenced;
(3) the dry basis of the pseudo-boehmite is difficult to be stably controlled, the instability of the dry basis can cause great interference to the forming, so that the forming process is also very unstable, the unqualified product quantity is increased, and the production efficiency is low;
(4) CN103769118A adopts a conventional forming process during forming, however, because the dry basis (35-50%) of the pseudo-boehmite adopted by the method is far lower than the conventional dry basis content (about 70%), namely the water content is high, extrusion pressure is not generated basically in the extrusion forming process, the carrier obtained after drying and roasting an extrudate has basically no mechanical strength, and the carrier can be pulverized only by applying a little external force, so that the possibility of industrial application is not provided, and the problem is the biggest problem faced by the technology.
In conclusion, how to simplify the preparation process of the alumina carrier containing the ZSM-22 type molecular sieve and reduce the operation energy consumption while reducing the dust pollution during the preparation process of the alumina carrier containing the ZSM-22 type molecular sieve is still an urgent technical problem to be solved on the premise of ensuring that the alumina carrier containing the ZSM-22 type molecular sieve which meets the industrial use requirements can be obtained.
Disclosure of Invention
The invention aims to simplify the preparation process flow of the alumina carrier containing the ZSM-22 type molecular sieve, reduce the dust pollution in the preparation process of the alumina carrier containing the ZSM-22 type molecular sieve, and simultaneously, the prepared carrier can also meet the industrial use requirement.
Aiming at the problems of the preparation of alumina carriers of US4613585 and CN103769118A, the inventor of the present invention has a new approach to mix a compound containing at least two proton acceptor sites in the molecular structure with hydrated alumina wet gel directly from the synthesis reaction, and the formed mixture can be shaped, and the shaped body obtained by drying and optional roasting can have the strength meeting the industrial requirements. The present invention has been completed based on this finding.
According to a first aspect of the present invention there is provided a hydrated alumina composition containing a ZSM-22 type molecular sieve, the composition containing hydrated alumina, a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites,
of said composition
A value of 5 or less, said
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was recorded as w1Is calculated by formula I
The value of the one or more of,
according to a second aspect of the present invention there is provided a process for the preparation of a hydrated alumina composition containing a ZSM-22 type molecular sieve, which process comprises mixing the components of a feedstock composition comprising a wet hydrated alumina gel having an i value of not less than 50%, a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites, to give the hydrated alumina composition, the i value of the wet hydrated alumina gel being not less than 50%, and the ZSM-22 type molecular sieveThe compound having at least two proton acceptor sites is used in an amount such that the composition finally prepared is
The value of the amount of the organic acid is 5 or less,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the above-mentioned
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w1Is calculated by formula I
The value of the one or more of,
according to a third aspect of the present invention there is provided a hydrated alumina composition containing a molecular sieve of the ZSM-22 type prepared by the process of the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided a hydrated alumina compact formed from a hydrated alumina composition containing a molecular sieve of the ZSM-22 type according to the first aspect of the present invention or a hydrated alumina composition containing a molecular sieve of the ZSM-22 type according to the third aspect of the present invention.
According to a fifth aspect of the present invention, there is provided a process for producing a hydrous alumina compact, which comprises molding a hydrous alumina composition containing a ZSM-22 type molecular sieve according to the first aspect of the present invention or a hydrous alumina composition containing a ZSM-22 type molecular sieve according to the third aspect of the present invention, and drying the resulting molded article.
According to a sixth aspect of the present invention, there is provided a hydrated alumina molded body produced by the method of the fifth aspect of the present invention.
According to a seventh aspect of the present invention there is provided alumina shapes formed from a hydrated alumina composition containing a molecular sieve of the ZSM-22 type according to the first aspect of the present invention or a hydrated alumina composition containing a molecular sieve of the ZSM-22 type according to the third aspect of the present invention.
According to an eighth aspect of the present invention, there is provided a process for producing an alumina compact, which comprises forming a hydrated alumina composition containing a ZSM-22 type molecular sieve according to the first aspect of the present invention or a hydrated alumina composition containing a ZSM-22 type molecular sieve according to the third aspect of the present invention, and drying and calcining the obtained formed product.
According to a ninth aspect of the present invention, there is provided an alumina compact produced by the method of the eighth aspect of the present invention.
According to a tenth aspect of the present invention, there is provided a method for producing a hydrous alumina, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 50%;
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(2) mixing the first hydrated alumina wet gel with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a hydrated alumina composition;
(3) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(4) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(5) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the process further comprises mixing the molecular sieve of the ZSM-22 type in step (1) and/or step (2) such that the hydrated alumina composition contains the molecular sieve of the ZSM-22 type.
According to an eleventh aspect of the present invention, there is provided a method for producing a hydrous alumina, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel,
(2-1) and (2-2), the solid-liquid separation conditions being such that the second hydrated alumina wet gel has an i value of not less than 50%,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(3) mixing a second wet hydrated alumina gel with a compound having at least two proton acceptor sites using the method of the second aspect of the invention to obtain a hydrated alumina composition;
(4) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(5) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(6) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the process further comprises mixing the ZSM-22 type molecular sieve in one, two or three of step (1), step (2) and step (3) such that the hydrated alumina composition contains the ZSM-22 type molecular sieve.
According to a twelfth aspect of the present invention, there is provided a molded body produced by the method according to the tenth or eleventh aspect of the present invention.
According to a thirteenth aspect of the present invention, the present invention provides a hydrated alumina molded body according to the present invention and use of the alumina molded body as a carrier or an adsorbent.
According to a fourteenth aspect of the present invention, there is provided a hydroisomerization catalyst comprising a support and an active ingredient supported on the support, wherein the support is a hydrous alumina compact according to the present invention or an alumina compact according to the present invention.
According to a fifteenth aspect of the present invention, there is provided a process for producing a hydroisomerization catalyst, which comprises supporting an active ingredient on a support, wherein the process further comprises the step of producing a shaped body as a support by the process according to the fifth, eighth, tenth or eleventh aspect of the present invention.
According to a sixteenth aspect of the present invention, there is provided a hydroisomerization process comprising contacting, under hydroisomerization conditions, a hydrocarbon oil with a hydroisomerization catalyst, wherein said hydroisomerization catalyst is a catalyst according to the fourteenth aspect of the present invention or a catalyst prepared by the process according to the fifteenth aspect of the present invention.
Compared with the prior process method (shown as a process in figure 1) for preparing the alumina forming body by taking the pseudo-boehmite dry glue powder as the starting raw material, the invention directly takes the hydrated alumina wet gel prepared by the synthesis reaction as the forming starting raw material to prepare the forming body containing the ZSM-22 type molecular sieve, and has the following advantages that:
(1) the step of drying the hydrated alumina wet gel in the prior art is omitted, and when the forming raw material is prepared, the pseudo-boehmite dry glue powder is prepared into a formable material without additionally introducing water, so that the overall process flow is simplified, and the overall operation energy consumption is reduced;
(2) avoids dust pollution caused by adopting the pseudo-boehmite dry glue powder as a raw material, and greatly improves the operation environment.
Compared with the prior art, such as US4613585 and CN103769118A, which directly takes the hydrated alumina wet gel as the starting material to prepare the carrier, the process of the invention is simpler and has stronger operability, and can effectively improve the strength of the finally prepared formed body, and simultaneously can adjust the pore size distribution of the finally prepared formed body, thereby meeting the requirements of various use occasions. The reason that the present invention can prepare the molded body containing the ZSM-22 type molecular sieve with higher strength by using the hydrated alumina wet gel as the starting material may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel interact to form hydrogen bonds to adsorb the free water in the hydrated alumina wet gel, and simultaneously, the compound with at least two proton acceptor sites and the hydroxyl in the molecular structure of the hydrated alumina can also perform hydrogen bond interaction to play a role of physical peptization, so that the hydrated alumina wet gel can be molded, and the finally prepared molded body has higher strength.
The hydroisomerization catalyst prepared by using the molded body prepared from the hydrated alumina composition according to the present invention as a carrier shows higher catalytic activity in the hydroisomerization reaction of hydrocarbon oil.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of a molding process commonly used in current industrial applications.
FIG. 2 is a preferred embodiment of a method of making a hydrated alumina composition in accordance with the present invention.
Fig. 3 is a preferred embodiment of a molding process flow according to the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention there is provided a hydrated alumina composition comprising hydrated alumina, a molecular sieve of the ZSM-22 type and a compound having at least two proton acceptor sites.
The hydrated alumina may be one or more selected from alumina trihydrate and alumina monohydrate. Specific examples of the hydrated alumina may include, but are not limited to, boehmite, alumina trihydrate, amorphous hydrated alumina, and pseudo-boehmite. The hydrated alumina preferably comprises alumina monohydrate, more preferably alumina monohydrate. In a preferred embodiment of the invention, the hydrated alumina contains pseudoboehmite, more preferably pseudoboehmite. The hydrated alumina composition according to this preferred embodiment is particularly suitable for the preparation of shaped bodies for use as supports for hydroisomerization catalysts.
According to the hydrated alumina composition of the present invention, the hydrated alumina is directly derived from the hydrated alumina wet gel and not from the hydrated alumina dry gel powder. In the present invention, the term "hydrated alumina wet gel" refers to an aqueous hydrated alumina gel which is obtained by a synthesis reaction and has not undergone a dehydration process for reducing its i value to 50% or less (preferably 55% or less, more preferably 60% or less). In the present invention, the value of i is determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
the synthesis reaction refers to a reaction for preparing an aluminum hydroxide gel, and may be a synthesis reaction of a hydrated alumina gel commonly used in the art, and specifically, a precipitation method (including an acid method and an alkaline method), a hydrolysis method, an seeded precipitation method, and a rapid dehydration method may be mentioned. The synthesized hydrated alumina gel may be either a hydrated alumina gel that has not undergone aging or a hydrated alumina gel that has undergone aging. The specific operating methods and conditions for the precipitation, hydrolysis, seeding and flash dehydration processes may be routinely selected and will be described hereinafter. The hydrated alumina wet gel can be obtained by optionally aging the hydrated alumina gel obtained by the synthesis reaction, washing and performing solid-liquid separation, and collecting the solid phase.
Unlike hydrated alumina derived from dry gelatine powder, the hydrated alumina directly derived from hydrated alumina wet gel undergoes a phase change during storage. For example, when the composition is left at ambient temperature and under closed conditions for 72 hours, the phase of the hydrated alumina in the composition after the standing is changed. The ambient temperature depends on the environment in which it is placed and may typically be in the range of 5-50 deg.C, such as 20-40 deg.C. The closed condition means that the composition is placed in a closed container, which may be a closed container (such as a can, pail or box) or a closed flexible wrap (such as a lidded bag), which may be paper and/or a polymeric material, preferably a polymeric material such as plastic.
In one example, where the hydrated alumina directly derived from the hydrated alumina wet gel contains pseudoboehmite (e.g., is pseudoboehmite), the composition is left at ambient temperature and under closed conditions for 72 hours, the alumina trihydrate content in the composition after placement being greater than the alumina trihydrate content in the composition prior to placement. In this example, the alumina trihydrate content of the composition after placement is generally increased by at least 0.5%, preferably by at least 1%, more preferably by from 1.1 to 1.5%, based on the alumina trihydrate content of the composition before placement.
The hydrated alumina composition according to the present invention further contains a compound having at least two proton acceptor sites. The hydrated alumina composition according to the present invention can be used for molding (particularly extrusion molding) without using a dry rubber powder as a starting material, and the reason why the obtained molded article has a higher strength may be that: the compound with at least two proton acceptor sites and the free water in the hydrated alumina wet gel generate hydrogen bond interaction, so that the free water is adsorbed, and simultaneously, the compound and the hydroxyl in the molecular structure of the hydrated alumina generate interaction to play a role in peptization.
In the compound having at least two proton acceptor sites, the proton acceptor sites are sites capable of forming hydrogen bonds with water and hydroxyl groups in the molecular structure of the compound. Specific examples of the proton acceptor site include, but are not limited to, one or two or more of fluorine (F), oxygen (O), and nitrogen (N). Specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, compounds having one or more groups selected from hydroxyl groups, carboxyl groups, amino groups, ether linkages, aldehyde groups, carbonyl groups, amide groups, and fluorine atoms in the molecular structure, preferably hydroxyl groups and/or ether linkages.
The compound having at least two proton acceptor sites may be an organic compound, an inorganic compound, or a combination of an organic compound and an inorganic compound. An organic compound having at least two proton acceptor sites is employed, which can be removed by a calcination process. By using an inorganic compound having at least two proton acceptor sites, part of the elements in the inorganic compound can remain in the finally produced shaped body, whereby auxiliary elements can be introduced into the shaped body by means of the inorganic compound.
In a preferred embodiment of the present invention, the compound having at least two proton acceptor sites is a polymer having a plurality of (e.g., three or more) proton acceptor sites in a molecular structure. According to this preferred embodiment, a better physical peptization effect is obtained, which further increases the strength of the finally produced shaped body, in particular when shaping is carried out by an extrusion process. Preferably, the polymer is an organic polymer. According to the preferred embodiment, specific examples of the compound having at least two proton acceptor sites may include, but are not limited to, one or more of polyhydroxy compounds, polyethers, and acrylic-type polymers.
The polyol compound may be exemplified by, but not limited to, polysaccharides, etherified polysaccharides and polyols.
The polysaccharide can be a homopolysaccharide, a heteropolysaccharide or a combination of the homopolysaccharide and the heteropolysaccharide. Specific examples of the polysaccharide and its etherified product include, but are not limited to, dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide. The cellulose ether is an ether derivative in which hydrogen atoms of partial hydroxyl groups in a cellulose molecule are substituted with one or more hydrocarbon groups, and the hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl and unsubstituted hydrocarbyl. The unsubstituted hydrocarbon group is preferablyIs selected from alkyl (e.g. C)1-C5Alkyl groups of (ii). In the present invention, C1-C5Specific examples of the alkyl group of (1) include C1-C5Straight chain alkyl of (2) and C3-C5The branched alkyl group of (a), may be, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and tert-pentyl. The substituted hydrocarbon group may be, for example, an alkyl group substituted with a hydroxyl group, a carboxyl group, a cyano group or an aryl group (e.g., C)1-C5Alkyl substituted by hydroxy, C1-C5Alkyl substituted by carboxyl, C1-C5Aryl-substituted alkyl) which may be phenyl or naphthyl. Specific examples of the substituted hydrocarbon group may include, but are not limited to: cyano, benzyl, phenethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl. Specific examples of the cellulose ether may include, but are not limited to, methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, and phenyl cellulose. The polysaccharides and etherified products thereof may be provided in various forms, for example: the galactomannan may be derived from sesbania powder.
Specific examples of the polyol include, but are not limited to, one or more of polyvinyl alcohol, partially acetalized polyvinyl alcohol (the acetalization degree may be 95% or less, preferably 80% or less, more preferably 70% or less, and further preferably 50% or less), polyether polyol, and polyester polyol.
Specific examples of the polyether include, but are not limited to, polyethylene oxide, polypropylene oxide, an ethylene oxide-propylene oxide block copolymer, and polytetrahydrofuran.
The acrylic acid-type polymer refers to a polymer containing acrylic acid-type monomer units, which may be specifically, but not limited to, acrylic acid monomer units and alkyl acrylic acid monomer units (preferably, C)1-C5Alkyl propylene of (2)Acid monomer units, more preferably methacrylic acid monomer units). Specific examples of the acrylic polymer include polyacrylic acid, polymethacrylic acid, acrylic acid-methyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, methacrylic acid-methyl acrylate copolymer, and methacrylic acid-methyl methacrylate copolymer.
In this preferred embodiment, the compound having at least two proton acceptor sites more preferably contains a polysaccharide and/or an etherified polysaccharide, and still more preferably a polysaccharide and/or an etherified polysaccharide.
In a more preferred embodiment of the invention, the compound having at least two proton acceptor sites comprises a galactomannan and a cellulose ether. According to this more preferred embodiment, the moulded body formed from the composition according to the invention has a higher strength. Further preferably, the compound having at least two proton acceptor sites is preferably a galactomannan and a cellulose ether.
In this more preferred embodiment, the galactomannan may be present in an amount of 10 to 70 wt.%, preferably 15 to 65 wt.%, more preferably 25 to 60 wt.%, based on the total amount of the compound having at least two proton acceptor sites; the cellulose ether may be present in an amount of 30 to 90 wt%, preferably 35 to 85 wt%, more preferably 40 to 75 wt%.
The composition according to the present invention may further comprise a ZSM-22 type molecular sieve, and the ZSM-22 type molecular sieve may Be one or more of a hydrogen type ZSM-22 molecular sieve (i.e., H-ZSM-22 molecular sieve), a hydrogen type ZSM-22 molecular sieve containing rare earth (e.g., L a-H-ZSM-22, Ce-H-ZSM-22, Pr-H-ZSM-22, Pm-H-ZSM-22, Sm-H-ZSM-22, Eu-H-ZSM-22), and a hydrogen type ZSM-22 molecular sieve containing an alkaline earth metal element (e.g., Mg-H-ZSM-22, Ni-H-ZSM-22, Ca-H-ZSM-22, Sr-H-ZSM-22, Ba-H-ZSM-22, Al-H-ZSM-22In-H-ZSM-22, Be-H-ZSM-22).
The silica to alumina ratio (i.e., the silica to alumina molar ratio) of the ZSM-22 molecular sieve may be selected according to the particular application of the hydrated alumina composition. In one embodiment, the ZSM-22 molecular sieve may have a silica to alumina ratio of 10 to 200, preferably 30 to 150, more preferably 40 to 100, such as 50 to 90. The hydrated alumina composition according to this preferred embodiment produces shaped bodies that are particularly suitable as supports for hydroisomerization catalysts.
The amount of ZSM-22 type molecular sieve in the composition may be selected according to the particular application of the composition. In a preferred embodiment, the molecular sieve of the ZSM-22 type may be present in an amount of from 0.5 to 90 wt%, preferably from 5 to 88 wt%, more preferably from 15 to 86 wt%, even more preferably from 30 to 85 wt%, and even more preferably from 40 to 85 wt%, based on the total weight of the calcined composition; the content of alumina may be 10 to 99.5% by weight, preferably 12 to 95% by weight, more preferably 14 to 85% by weight, further preferably 15 to 70% by weight, still further preferably 15 to 60% by weight, and the calcination is carried out at a temperature of 600 ℃ and the duration of the calcination is 3 hours. The composition according to this preferred embodiment is particularly suitable for making a support for a hydroisomerization catalyst.
Of the compositions according to the invention
The value is 5 or less, preferably 4.5 or less, more preferably 4 or less, and further preferably 3.5 or less.
The value may be 1.2 or more, preferably 1.3 or more, more preferably 1.4 or more, and further preferably 1.5 or more. In one example, of a composition according to the invention
The value may be 1.2 to 5, preferably 1.2 to 4.5, more preferably 1.3 to 4, still more preferably 1.4 to 3.5, such as 1.5 to 3.5.
In the present invention,
the values were determined using the following method: drying 10g of the composition at 120 ℃ for 240 minutes in an air atmosphereThe mass of the composition is denoted as w1Is calculated by formula I
The value of the one or more of,
the compound having at least two proton acceptor sites is contained in an amount enabling the composition according to the invention
The value meets the above requirements. Preferably, the compound having at least two proton acceptor sites may be contained in an amount of 1 to 25 parts by weight, preferably 2 to 22 parts by weight, more preferably 3 to 20 parts by weight, relative to 100 parts by weight of the hydrated alumina.
The composition according to the invention may or may not contain a peptizing agent. The peptizing agent may be an agent having a gelling effect, which is generally used in the technical field of preparation of alumina moldings, and specific examples thereof may include, but are not limited to, alumina sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid, and trichloroacetic acid.
According to the composition of the present invention, the compound having at least two proton acceptor sites can perform a physical peptization effect, particularly when the compound having at least two proton acceptor sites is a polymer containing at least two proton acceptor sites, so that the amount of a peptizing agent can be reduced, and even the peptizing agent can be omitted.
In a preferred embodiment of the present invention, the content of the peptizing agent is 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, with respect to 100 parts by weight of the hydrated alumina.
In a particularly preferred embodiment of the invention, the composition according to the invention does not contain a peptizing agent. According to the composition of this particularly preferred embodiment, when used for the production of a shaped body, the produced hydrated alumina shaped body can be used as an adsorbent or a carrier even if it is converted into an alumina shaped body without calcination, because when the unfired hydrated alumina shaped body contains a peptizing agent, the peptizing agent is dissolved during adsorption and impregnation, and is lost in a large amount, so that the shaped body is dissolved, pulverized, and collapsed in the channels, and finally loses its shape, and thus cannot be used as an adsorbent or a carrier.
According to a second aspect of the present invention, there is provided a process for preparing a hydrated alumina composition, which comprises mixing the components of a feedstock composition to obtain the hydrated alumina composition, i.e. the mixture obtained by mixing is the hydrated alumina composition.
According to the method of preparing a hydrated alumina composition of the present invention, the raw material mixture contains a hydrated alumina wet gel, a ZSM-22 type molecular sieve, and a compound having at least two proton acceptor sites. The compound having at least two proton acceptor sites and the species thereof, and the ZSM-22 type molecular sieve and the species thereof have been described in detail above and will not be described herein again.
The hydrated alumina wet gel can be synthesized by a conventional method, for example, by one or more of precipitation (including acid and alkaline methods), hydrolysis, seed separation, and flash dehydration. Generally, the hydrated alumina gel solution is obtained by optionally aging, washing and solid-liquid separation.
The precipitation method comprises an acid method and an alkali method. The acid method is to precipitate aluminum salt with alkaline compound. The alkaline method is to carry out precipitation reaction on aluminate by using an acidic compound. In the precipitation method, after the mixture obtained by the precipitation reaction is optionally aged (preferably, aged), solid-liquid separation is performed, and the separated solid phase is washed to obtain the hydrated alumina wet gel.
The kind of the aluminum salt and the aluminate may be conventionally selected. Specific examples of the aluminum salt may include, but are not limited to, one or two or more of aluminum sulfate, aluminum chloride, and aluminum nitrate. Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate and potassium metaaluminate.
The basic compound and the acidic compound may be conventionally selected. The alkaline compound can be various common compounds capable of making water alkaline, and can be selected from ammonia, hydroxide and alkaline salt. The hydroxide may be a common water-soluble hydroxide such as an alkali metal hydroxide. The basic salt may be a common salt that decomposes in water to make the water basic, such as meta-aluminates, carbonates and bicarbonates. Specific examples of the basic compound may include, but are not limited to, one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate. The acidic compound can be various common compounds capable of making water acidic, and can be inorganic acid and/or organic acid. Specific examples of the acidic compound may include, but are not limited to, one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, and oxalic acid. The carbonic acid may be generated in situ by the introduction of carbon dioxide.
The precipitation reaction may be carried out under conventional conditions, and the present invention is not particularly limited thereto. Generally, the alkaline compound or the acidic compound is used in such an amount that the pH of the aluminium salt solution or the aluminate solution is 6-10, preferably 7-9. The precipitation reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.
The method for preparing the hydrated alumina wet gel by the hydrolysis method may include: subjecting an aluminum-containing compound to hydrolysis reaction, optionally aging (preferably aging) the mixture obtained by the hydrolysis reaction, then performing solid-liquid separation, and washing the separated solid phase to obtain the hydrated alumina wet gel.
The aluminum-containing compound may be an aluminum-containing compound generally used in a process for preparing a hydrated alumina gel by a hydrolysis method. The aluminum-containing compound is preferably an organoaluminum compound which can undergo hydrolysis reaction, and more preferably an aluminum alkoxide. Specific examples of the aluminum-containing compound may include, but are not limited to, one or more of aluminum isopropoxide, aluminum isobutoxide, aluminum triisopropoxide, aluminum tri-t-butoxide, and aluminum isooctanolate.
The hydrolysis reaction of the present invention is not particularly limited, and may be carried out under conventional conditions. Generally, the hydrolysis reaction may be carried out at a pH of 3 to 11, preferably 6 to 10. The hydrolysis reaction may be carried out at a temperature of 30 to 90 deg.C, preferably 40 to 80 deg.C.
In the precipitation method and the hydrolysis method, the aging conditions are not particularly limited and may be carried out under conventional conditions. In general, the ageing can be carried out at temperatures of from 35 to 98 deg.C, preferably from 40 to 80 deg.C. The duration of the aging may be 0.2 to 6 hours.
The method for preparing the hydrated alumina wet gel by the seed precipitation method can comprise the following steps: adding seed crystals into the supersaturated aluminate solution, decomposing to generate aluminum hydroxide, carrying out solid-liquid separation on a mixture obtained by decomposition, and washing a separated solid phase to obtain the hydrated alumina wet gel.
Specific examples of the aluminate may include, but are not limited to, one or more of sodium metaaluminate and potassium metaaluminate. The supersaturation of the aluminate solution may be conventionally selected.
The method for preparing the hydrated alumina wet gel by the rapid dehydration method may include: roasting the hydrated alumina at the temperature of 600-950 ℃, preferably 650-800 ℃, carrying out hydrothermal treatment on the roasted product, and carrying out solid-liquid separation on the mixture obtained by the hydrothermal treatment, thereby obtaining the hydrated alumina wet gel. The duration of the calcination may be 1 to 6 hours, preferably 2 to 4 hours. The hydrothermal treatment may be carried out at a temperature of 120-200 deg.C, preferably 140-160 deg.C. The hydrothermal treatment is usually carried out under autogenous pressure in a closed vessel.
In the precipitation method, the hydrolysis method, the seed precipitation method and the rapid dehydration method, the solid-liquid separation can be performed by a conventional method, and specifically, the solid-liquid separation can be performed by filtration, centrifugation or a combination of the two.
According to the method for producing a hydrated alumina composition of the present invention, the i value of the hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%, and further preferably not less than 62%. The i value of the hydrated alumina wet gel is preferably not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, and further preferably not higher than 82%. In one embodiment, the hydrated alumina wet gel has an i value of 50 to 95%, preferably 55 to 90%, more preferably 60 to 85%, and even more preferably 62 to 82%. The composition prepared according to this more preferred embodiment, when used for molding, gives a molded article having higher strength.
The hydrated alumina wet gel with the value i meeting the requirement can be obtained by controlling the solid-liquid separation conditions when the prepared hydrated alumina gel-containing solution is subjected to solid-liquid separation. In one embodiment of the present invention, the solid-liquid separation is performed once or twice or more, and at least the last solid-liquid separation is performed by pressure filtration and/or vacuum filtration. In this embodiment, the value of the hydrated alumina wet gel i obtained is controlled by adjusting the magnitude of the applied pressure and/or vacuum. Specific examples of the apparatus used for the pressure filtration include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. In order to control the i value of the obtained hydrated alumina wet gel, natural wind or pressurized wind can be adopted to blow the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.
According to the method for producing a hydrated alumina composition of the present invention, the hydrated alumina wet gel obtained by solid-liquid separation is generally not subjected to a dehydration treatment for reducing the i value thereof to 50% or less (preferably 55% or less, more preferably 60% or less).
According to the method for preparing a hydrated alumina composition of the present invention, the compound having at least two proton acceptor sites is used in an amount such that the hydrated alumina composition finally prepared
The value is 5 or less, preferably 4.5 or less, more preferably 4 or less, and further preferably 3.5 or less. The compound having at least two proton acceptor sites is preferably used in an amount such that the final prepared hydrated alumina composition is
The value is 1.2 or more. The amount of the compound having at least two proton acceptor sites is more preferably such that the final hydrated alumina composition is prepared
The value is 1.3 or more, more preferably 1.4 or more, and still more preferably 1.5 or more. Generally, the compound having at least two proton acceptor sites may be used in an amount of 1 to 25 parts by weight, preferably 2 to 22 parts by weight, more preferably 3 to 20 parts by weight, based on the hydrated alumina, relative to 100 parts by weight of the hydrated alumina wet gel.
According to the method for preparing the hydrated alumina composition of the present invention, the raw material mixture may or may not contain a peptizing agent. Preferably, the peptizing agent is present in an amount of 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less, relative to 100 parts by weight of the hydrated alumina wet gel, based on the hydrated alumina. More preferably, the raw material mixture does not contain a peptizing agent. That is, the method for producing a hydrated alumina composition according to the present invention more preferably does not include a step of adding a peptizing agent to the raw material mixture.
According to the method for preparing the hydrated alumina composition of the present invention, the hydrated alumina wet gel may be mixed with the ZSM-22 type molecular sieve and the compound having at least two proton acceptor sites by a conventional method. The hydrated alumina wet gel may be mixed under shear with a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites. In one embodiment, the mixing is by stirring. The hydrated alumina composition according to the present invention can be obtained by uniformly mixing the hydrated alumina wet gel with a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites in a vessel having a stirring device by stirring. The stirring can be carried out in a vessel with a stirring device or in a beater. In another embodiment, the mixing is by kneading. The hydrated alumina wet gel may be kneaded with a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites in a kneader to obtain the hydrated alumina composition according to the present invention. The type of the kneader is not particularly limited. According to the method for preparing the hydrated alumina composition of the present invention, stirring and mixing may be used in combination to mix the hydrated alumina wet gel with a compound having at least two proton acceptor sites. In this case, it is preferable to perform stirring and kneading.
According to the method of preparing the hydrated alumina composition of the present invention, the ZSM-22 type molecular sieve, the compound having at least two proton acceptor sites, and the hydrated alumina wet gel may be mixed in various mixing orders.
In one embodiment, the ZSM-22 type molecular sieve may be mixed during the preparation of the hydrated alumina wet gel, the ZSM-22 type molecular sieve may be added to the prepared hydrated alumina wet gel, a part of the ZSM-22 type molecular sieve may be mixed during the preparation of the hydrated alumina wet gel, the remaining part of the ZSM-22 type molecular sieve may be added to the prepared hydrated alumina wet gel, and the mixing of the ZSM-22 type molecular sieve may be performed at one, two, or three of the above-mentioned addition timings. When the ZSM-22 type molecular sieve is mixed in the process of preparing the hydrated alumina wet gel, the operation of mixing the ZSM-22 type molecular sieve may be performed in one, two, three or four of the precipitation reaction process, the aging process, the solid-liquid separation process and the washing process. Whether the ZSM-22 type molecular sieve is mixed in the preparation of the hydrated alumina wet gel, and the timing of mixing may be selected according to the type of precipitation reaction so that the structure of the ZSM-22 type molecular sieve is not or substantially not destroyed, for example: when the ZSM-22 type molecular sieve is added during the preparation of the hydrated alumina wet gel, it is preferably not strongly basic under the preparation conditions, e.g., pH less than 10. Preferably, the operation of mixing the ZSM-22 type molecular sieve is carried out in a solid-liquid separation process.
In another embodiment, the ZSM-22 type molecular sieve is mixed after the hydrated alumina wet gel preparation is complete. In this embodiment, the ZSM-22 type molecular sieve may be first mixed with the wet gel of hydrated alumina, followed by mixing the compound having at least two proton acceptor sites; or mixing a compound having at least two proton acceptor sites with the wet gel of hydrated alumina and then mixing the ZSM-22 type molecular sieve; it is also possible to mix a ZSM-22 type molecular sieve and a compound having at least two proton acceptor sites with the hydrated alumina wet gel simultaneously.
According to the method for producing a hydrated alumina composition of the present invention, water may or may not be added during the mixing process, as long as the hydrated alumina composition can be produced
The value satisfies the above requirements. In general, water may be additionally added during the mixing process from the viewpoint of improving the homogeneity of the mixing. Generally, the weight ratio of the supplemental added water to the compound having at least two proton acceptor sites may be from 5 to 15: 1.
according to a third aspect of the present invention there is provided a hydrated alumina composition prepared by the process of the second aspect of the present invention.
The hydrated alumina composition according to the present invention can be shaped by a conventional method to obtain a hydrated alumina carrier or an alumina carrier.
According to a fourth aspect of the present invention, there is provided a hydrated alumina molded body formed from the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention.
The hydrated alumina composition according to the present invention may be molded, and the resulting molded article may be dried to obtain a hydrated alumina molded article according to the present invention.
The molding method is not particularly limited, and various molding methods commonly used in the art may be employed, for example: extrusion, spraying, spheronization, tableting or a combination thereof. In a preferred embodiment of the invention, the shaping is carried out by means of extrusion.
The temperature at which the shaped article is dried may be a conventional choice in the art. Generally, the temperature of the drying may be 60 ℃ or more and less than 350 ℃, preferably 65 to 300 ℃, more preferably 70 to 250 ℃. The duration of the drying can be properly selected according to the drying temperature so as to enable the volatile content in the finally obtained hydrated alumina forming body to meet the use requirement. Generally, the duration of the drying may be 1 to 48 hours, preferably 2 to 24 hours, more preferably 2 to 12 hours, and further preferably 2 to 6 hours. The drying may be carried out in an oxygen-containing atmosphere (e.g., air atmosphere) or in an inert atmosphere (e.g., an atmosphere formed by nitrogen and/or a group-zero gas), preferably in an oxygen-containing atmosphere.
The hydrated alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, bird's nest, cylindrical, raschig ring, or butterfly.
The hydrated alumina formed body has abundant pore structure and adjustable pore size distribution.
In one embodiment, the hydrated alumina shaped bodies have a bimodal pore size distribution as measured by mercury intrusion. Wherein the most probable pore size is 4-20nm (preferably 5-15nm, more preferably 6-10nm) and more than 20nm (e.g. 20.5-35nm, preferably 21-30nm, more preferably 21-25nm), respectively.
In another embodiment, the hydrated alumina shaped bodies have a monomodal distribution of pore diameters as determined by mercury intrusion. Of these, the most probable pore diameter is 4 to 25nm, preferably 5 to 20nm, and more preferably 6 to 10 nm.
According to the hydrated alumina molded body of the present invention, the hydrated alumina molded body has high strength. In general, the hydrated alumina moulded body according to the invention has a radial crush strength of 15N/mm or more, such as 15 to 40N/mm, preferably 18N/mm or more, such as 18 to 35N/mm. In the present invention, the radial crush strength of the molded article was measured by the method specified in RIPP 25-90.
According to a fifth aspect of the present invention, there is provided a method for producing a hydrated alumina molded body, which comprises molding the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention, and drying the obtained molded body to obtain the hydrated alumina molded body.
The methods and conditions for the shaping and drying are the same as those described for the fourth aspect of the present invention and will not be described in detail here.
In one embodiment of the invention, the hydrated alumina composition is
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of the hydrated alumina composition
The value is not less than 1.85, and may be, for example, 1.85 to 4. More preferably, of the hydrated alumina composition
The value is not less than 1.9, and may be, for example, 1.9 to 3.5. The pore size of the hydrated alumina shaped bodies prepared according to this embodiment is bimodal as determined by mercury intrusion. The most probable pore diameters are 4 to 20nm (preferably 5 to 15nm, more preferably 6 to 10nm) and more than 20nm (e.g., 20.5 to 35nm, preferably 21 to 30nm, more preferably 21 to 25nm), respectively.
In another embodiment of the present invention, the hydrated alumina composition is
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of the hydrated alumina composition
The value is not higher than 1.75 (e.g., not higher than 1.7), and for example, may be 1.3 to 1.75, preferably 1.5 to 1.7. The pore diameter of the hydrated alumina molded body prepared according to this embodiment is unimodal as measured by mercury intrusion method. The most probable pore size is 4 to 25nm, preferably 5 to 20nm, more preferably 6 to 10 nm.
According to a sixth aspect of the present invention, there is provided a hydrated alumina molded body produced by the method of the fifth aspect of the present invention.
The hydrated alumina formed body prepared by the method of the invention has higher strength. In general, the hydrated alumina moulded bodies prepared by the process of the invention have a radial crush strength of 15N/mm or more, such as 15 to 40N/mm, preferably 18N/mm or more, such as 18 to 35N/mm.
According to a seventh aspect of the present invention, there is provided an alumina molded body formed from the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention.
The hydrated alumina composition according to the present invention may be molded, and the obtained molded article may be dried and calcined in sequence to obtain the alumina molded body.
The methods and conditions for the shaping and drying are the same as those described for the fourth aspect of the present invention and will not be described in detail here.
The conditions for calcination in the present invention are not particularly limited, and may be selected conventionally in the art. Specifically, the temperature of the roasting may be 400-950 ℃, preferably 450-800 ℃, and more preferably 480-700 ℃; the duration of the calcination may be 2 to 10 hours, preferably 3 to 8 hours. The calcination may be carried out in an oxygen-containing atmosphere, or may be carried out in an inert atmosphere (e.g., an atmosphere formed of nitrogen and/or a group-zero gas), and is preferably carried out in an oxygen-containing atmosphere.
The alumina molded body according to the present invention may have various shapes according to specific use requirements, for example: spherical, bar, annular, clover, honeycomb, bird's nest, cylindrical, raschig ring, or butterfly.
The alumina formed body has abundant pore structure and adjustable pore size distribution.
In one embodiment, the pore size distribution of the alumina compact is bimodal as determined by mercury intrusion. The most probable pore diameters are 4 to 20nm (preferably 5 to 15nm, more preferably 6 to 10nm) and more than 20nm (e.g., 20.5 to 35nm, preferably 21 to 30nm, more preferably 21 to 25nm), respectively.
In another embodiment, the pore size of the aluminum oxide shaped body is unimodal as determined by mercury intrusion. The most probable pore size is 4 to 20nm, preferably 5 to 20nm, more preferably 6 to 10 nm.
According to the alumina formed body of the present invention, the alumina formed body has high strength. In general, the alumina shaped bodies according to the invention have a radial crush strength of above 15N/mm, such as 15-40N/mm, preferably above 18N/mm, such as 18-35N/mm.
According to an eighth aspect of the present invention, there is provided a method for producing an alumina molded body, which comprises molding the hydrated alumina composition of the first aspect of the present invention or the hydrated alumina composition of the third aspect of the present invention, and drying and firing the resulting molded body.
The methods and conditions for forming, drying and firing are the same as those described in the seventh aspect of the present invention and will not be described in detail herein.
According to the method for producing the alumina formed body of the present invention, the alumina composition can be changed
To obtain alumina shaped bodies with different pore size distributions.
In one embodiment of the invention, the alumina composition is
The value is not less than 1.8, and may be, for example, 1.8 to 5. Preferably, of the hydrated alumina composition
The value is not less than 1.85, and may be, for example, 1.85 to 4. More preferably, of the hydrated alumina composition
The value is not less than 1.9, and may be, for example, 1.9 to 3.5. The pore diameters of the alumina moldings produced according to this embodiment are bimodal, as determined by mercury intrusion. The most probable pore diameters are 4 to 20nm (preferably 5 to 15nm, more preferably 6 to 10nm) and more than 20nm (e.g., 20.5 to 35nm, preferably 21 to 30nm, more preferably 21 to 25nm), respectively.
In another embodiment of the present invention, the alumina composition is
The value is less than 1.8, and may be, for example, from 1.2 to less than 1.8. Preferably, of the hydrated alumina composition
The value is not higher than 1.75 (e.g., not higher than 1.7), and for example, may be 1.3 to 1.75, preferably 1.5 to 1.7. The pore diameter of the aluminum oxide shaped bodies produced according to this embodiment is unimodal as determined by mercury intrusion. The most probable pore size is 4 to 25nm, preferably 5 to 20nm, more preferably 6 to 10 nm.
According to a ninth aspect of the present invention, there is provided an alumina compact produced by the method of the eighth aspect of the present invention.
The alumina formed body prepared by the method has higher strength. In general, the alumina shaped bodies produced by the process of the invention have a radial crush strength of 15N/mm or more, such as 15 to 40N/mm, preferably 18N/mm or more, such as 18 to 35N/mm.
According to a tenth aspect of the present invention, there is provided a method for producing and molding hydrated alumina, as shown in fig. 2 and 3, comprising the steps of:
(1) providing a hydrated alumina gel solution, and washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel;
optionally (2), treating the first hydrated alumina wet gel with (2-1) or (2-2),
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel;
(3) mixing a hydrated alumina wet gel with a compound having at least two proton acceptor sites by using the method of the second aspect of the present invention to obtain a hydrated alumina composition, wherein the hydrated alumina wet gel is the first hydrated alumina wet gel or the second hydrated alumina wet gel;
(4) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(5) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(6) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the process further comprises mixing a ZSM-22 type molecular sieve in one, two or three of step (1), step (2) and step (3) such that the hydrated alumina composition contains a ZSM-22 type molecular sieve. In the present invention, "optional" means "including or not including", "including or not including".
The method for producing the shaped form, the ZSM-22 type molecular sieve, according to the present invention is the same as the method and sequence described in the second aspect of the present invention, and will not be described in detail herein.
In the step (1), the hydrated alumina gel solution is a hydrated alumina gel-containing solution which is obtained by a hydrated alumina gel synthesis reaction and is aged or not aged. The hydrated alumina gel solution can be prepared on site or transported from other production sites. Preferably, the hydrated alumina gel solution is a hydrated alumina gel solution prepared in situ. The synthesis method and conditions of the hydrated alumina gel have been described in detail above and will not be described herein.
Because the hydrated alumina gel solution obtained by the synthesis reaction has acidity and alkalinity, the hydrated alumina wet gel is washed in the step (1) to remove acidic substances or alkaline substances in the hydrated alumina wet gel, so that the adverse effect of the presence of the acidic substances and the alkaline substances on the hydrated alumina gel is avoided, and meanwhile, the solid content of the hydrated alumina gel solution is increased. The washing in step (1) may be carried out under conventional conditions as long as the amounts of acidic substances and basic substances in the hydrated alumina gel solution can be reduced to meet the usual requirements.
In step (1), solid-liquid separation is also involved in the washing process to squeeze out the wash water to give a first hydrated alumina wet gel. The i value of the first hydrated alumina wet gel may be a value satisfying the i value of the hydrated alumina wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention, or may be higher than the i value of the hydrated alumina wet gel mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention.
In one embodiment, the first hydrated alumina wet gel has an i value which satisfies the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention, i.e., the i value of the first hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%. In this embodiment, the first hydrated alumina wet gel preferably has an i value of not higher than 95%, more preferably not higher than 90%, still more preferably not higher than 85%, and still more preferably not higher than 82%. In one example, the first hydrated alumina wet gel has an i value of 50 to 95%, preferably 55 to 90%, more preferably 60 to 85%, and still more preferably 62 to 82%.
According to this embodiment, the first hydrated alumina wet gel may be fed directly to step (3) to be mixed with a compound having at least two proton acceptor sites. This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device can be compactly arranged, so that the discharge of the washing device can directly enter the mixing device.
According to this embodiment, the first hydrated alumina wet gel may also be sent to step (2) for treatment with (2-1). This applies in particular to situations in which the following requirements are satisfied: (A) the solid-liquid separation equipment in the washing device has better separation capacity, and the value i of the first hydrated alumina wet gel is controlled to meet the range; (B) the washing device and the mixing device cannot be compactly arranged, so that the discharge of the washing device cannot directly enter the mixing device.
In another embodiment, the first hydrated alumina wet gel has an i value of 95% or greater and fails to meet the requirements of the second aspect of the invention for mixing with a compound having at least two proton acceptor sites. According to this embodiment, the first hydrated alumina wet gel is sent to step (2) and treated with either (2-1) or (2-2). This embodiment is particularly suitable for the case where the separation capacity or the operating conditions of the solid-liquid separation device in the washing apparatus are insufficient to control the i value of the first hydrated alumina wet gel to satisfy the requirements described in the second aspect of the present invention, and the case where the washing apparatus and the mixing apparatus cannot be compactly arranged.
In the step (2), the first hydrated alumina wet gel is treated by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water to form a slurry, which can improve the transport properties of the hydrated alumina wet gel. In (2-1), the amount of water added is selected according to the specific transportation equipment, so that the formed slurry can meet the transportation requirement.
The second hydrated alumina wet gel obtained in the step (2) has an i value satisfying the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention, that is, the i value of the hydrated alumina wet gel is not less than 50%, preferably not less than 55%, more preferably not less than 60%, and further preferably not less than 62%. The second hydrated alumina wet gel preferably has an i value of not higher than 95%, more preferably not higher than 90%, further preferably not higher than 85%, further preferably not higher than 82%. In one embodiment, the second hydrated alumina wet gel has an i value of 50 to 95%, preferably 55 to 90%, more preferably 60 to 85%, and even more preferably 62 to 82%. The second hydrated alumina wet gel having an i value satisfying the above requirements can be obtained by controlling the conditions of the solid-liquid separation in the step (2). The method for adjusting the i value of the hydrated alumina wet gel by selecting the solid-liquid separation method and the conditions thereof has been described in detail above and will not be described in detail herein.
As shown in fig. 2 and 3, at least a portion of the ZSM-22 type molecular sieve may be mixed in step (2). For the case of carrying out the process in the manner described in (2-1), the ZSM-22 type molecular sieve may be mixed in the dilution operation and/or the solid-liquid separation operation as shown in FIGS. 2 and 3.
In step (3), the first hydrated alumina wet gel or the second hydrated alumina wet gel is mixed with a compound having at least two proton acceptor sites by the method according to the second aspect of the present invention to obtain a hydrated alumina composition. The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel fed to the step (3) satisfy the i value of the hydrated alumina wet gel mixed with the compound having at least two proton acceptor sites according to the second aspect of the present invention.
In the step (3), the hydrated alumina composition can be determined based on the intended pore size distribution of the hydrated alumina molded body or the alumina molded body
This is illustrated in the method according to the fifth aspect of the invention and in the method according to the eighth aspect of the invention and will not be described in detail here.
In the step (4), the hydrated alumina composition obtained in the step (3) is molded to obtain a hydrated alumina molded product. The forming method and the shape of the formed object can refer to the description related to the forming in the first aspect of the invention, and are not repeated herein.
In the step (5), the hydrated alumina molded product obtained in the step (3) is dried to obtain a hydrated alumina molded product. The drying conditions for drying the shaped hydrated alumina product to obtain the shaped hydrated alumina product have been described in detail in the method of the fifth aspect of the present invention, and are not described herein again.
Depending on the type of shaped body to be expected, step (6) may or may not be carried out. In the case of performing step (6), the whole hydrated alumina compact obtained in step (5) may be fed to step (6) and calcined; the partially hydrated alumina formed body obtained in the step (5) may also be fed to the step (6), so that the hydrated alumina formed body and the alumina formed body can be simultaneously produced. The conditions for the calcination have been described in detail in the method of the eighth aspect of the present invention, and are not described herein again.
According to an eleventh aspect of the present invention, there is provided a hydrated alumina compact or an alumina compact produced by the method of the tenth aspect of the present invention.
The hydrated alumina formed body and the alumina formed body produced by the method according to the tenth aspect of the present invention have high strength. In general, the radial crush strength of the hydrated alumina compact and the alumina compact may each be 15N/mm or more, such as 15 to 40N/mm, preferably 18N/mm or more, such as 18 to 35N/mm.
The tenth aspect according to the present invention may be carried out in a hydrated alumina production molding system comprising a hydrated alumina gel production unit, a solid-liquid separation and washing unit, a mixing unit, a molding unit, a drying unit and optionally a calcining unit,
the hydrated alumina gel production unit is characterized in that an output port of a hydrated alumina gel solution of the hydrated alumina gel production unit is communicated with an input port of a washing material to be separated of the solid-liquid separation and washing unit, an output port of a solid-phase material of the solid-liquid separation and washing unit is communicated with an input port of a solid-phase material of the mixing unit, an output port of a mixed material of the mixing unit is communicated with an input port of a raw material of the forming unit, an input port of a material to be dried of the drying unit is communicated with an output port of a formed product of the forming unit, and an input port of a material to be calcined of the.
The hydrated alumina gel production unit is used for generating a hydrated alumina gel solution through a synthesis reaction. The method for synthesizing the hydrated alumina gel may be a conventional method such as the precipitation method, the hydrolysis method, the seed precipitation method, and the rapid dehydration method described above, and will not be described in detail herein. The hydrated alumina gel production unit may perform a synthesis reaction using a conventional reactor to obtain a hydrated alumina gel solution, which is not particularly limited in the present invention.
The solid-liquid separation and washing unit is used for carrying out solid-liquid separation and washing on the hydrated alumina gel aqueous solution output by the hydrated alumina gel production unit to obtain hydrated alumina wet gel
The value satisfies the requirement of being able to be mixed with a compound having at least two proton acceptor sites according to the second aspect of the present invention.
The solid-liquid separation and washing unit can adopt various common methods to carry out solid-liquid separation and washing, thereby obtaining
A hydrated alumina gel having a value that satisfies the mixing requirements with a compound having at least two proton acceptor sites. The solid-liquid separation and washing unit can adoptConventional solid-liquid separation devices, for example: a filtration device, a centrifugation device, or a combination of both. When the solid-liquid separation and washing unit includes a filtering device, the filtering device may be one or a combination of two or more of a gravity filtering device, a pressure filtering device, and a vacuum filtering device. Preferably, the filtration means comprises at least a pressure filtration means and/or a vacuum filtration means. Specific examples of the pressure filtration device include, but are not limited to, a plate and frame filter press, a belt filter, or a combination of both. For controlling the hydrated alumina wet gel obtained
The solid-liquid separation and washing unit can further comprise a blowing device, and natural wind or pressurized wind is adopted to blow the separated solid phase, so that the efficiency of water removal is improved. The pressure of the pressurized air can be selected conventionally, and generally can be 0.1-12MPa, and preferably 0.5-10 MPa.
The solid-liquid separation and washing unit may comprise one or more solid-liquid separation subunits, preferably at least one solid-liquid separation subunit and the last solid-liquid separation subunit being a pressure filtration device and/or a vacuum filtration device, so as to allow solid-liquid separation and washing of the solid phase material (i.e. hydrated alumina wet gel) obtained by the unit
The value is such that the requirements for mixing with a compound having at least two proton acceptor sites according to the second aspect of the invention are met. By adjusting the magnitude of the applied pressure or vacuum, the final hydrated alumina wet gel can be treated
The value is adjusted. When the solid-liquid separation and washing unit comprises more than two solid-liquid separation subunits, the other solid-liquid separation subunits can adopt a pressurizing and filtering device and/or a vacuum filtering device except that the last solid-liquid separation subunit preferably adopts a solid-liquid separation mode taking pressure as driving forceIt is also possible to dispense with the pressure filtration device and the vacuum filtration device, preferably with the pressure filtration device and/or the vacuum filtration device.
The solid-liquid separation and washing unit can wash the separated solid phase by adopting a conventional washing device. For example, a spray device may be used to spray wash water onto the surface of the separated solid phase. In order to improve the washing effect and the washing efficiency, shearing and/or oscillation may be applied to the solid phase during or after the spraying, and the spray water and the solid phase may be mixed uniformly with the shearing, such as stirring.
The solid-liquid separation and washing unit is arranged between the hydrated alumina gel production unit and the mixing unit in terms of the material flow direction of the hydrated alumina gel, and is used for separating the gel solution output by the hydrated alumina gel production unit to obtain
The hydrated alumina wet gel, which has a value that meets the mixing requirements, provides the raw materials for the mixing unit.
In a preferred embodiment, the solid-liquid separation and washing unit may comprise a washing subunit, a diluting subunit, a conveying subunit and a second solid-liquid separation subunit, from the viewpoint of facilitating the transportation of the material, on the premise that the mixing unit is provided with the hydrated alumina gel satisfying the requirements,
the washing subunit is used for collecting and washing a solid phase in the hydrated alumina gel solution output by the hydrated alumina gel production unit;
the diluting subunit is used for diluting the solid phase output by the washing subunit with water to obtain slurry;
the conveying subunit is used for conveying the slurry output by the diluting subunit into a second solid-liquid separation subunit;
and the second solid-liquid separation subunit is used for carrying out solid-liquid separation on the slurry to obtain hydrated alumina wet gel.
The conveying subunit may employ any of a variety of conventional conveying devices, such as a conveyor belt. The delivery sub-unit and the washing sub-unit may be integrated together, for example in one device, so that washing is performed during delivery, improving production efficiency. For example: a conveying belt with a solid-liquid separation function is adopted, and a spraying device is arranged above solid-phase materials of the conveying belt, so that washing and solid-liquid separation are carried out in the conveying process.
The mixing unit comprises an auxiliary agent adding device for adding an auxiliary agent to the hydrated alumina wet gel, wherein the auxiliary agent adding device at least adds a compound with at least two proton acceptor sites to the hydrated alumina wet gel when the production system is in operation. The mixing unit may employ conventional mixing devices such as various conventional mixers, kneaders, or a combination of both.
The forming unit may employ conventional forming devices, such as: an extrusion device, a spraying device, a rounding device, a tabletting device or a combination of more than two. The drying unit may employ a conventional drying device, and the present invention is not particularly limited thereto. The baking unit may employ a conventional baking apparatus, and the present invention is not particularly limited thereto.
According to the production molding system of the present invention, the production molding system is not provided with a dehydration unit sufficient to reduce the i value of the hydrated alumina wet gel to 50% or less (preferably 55% or less, more preferably 60% or less) between the solid phase material discharge port of the solid-liquid separation and washing unit and the hydrated alumina wet gel input port of the mixing unit, based on the flow direction of the hydrated alumina gel.
In the actual production process, a mixing unit, a forming unit, a drying unit and a roasting unit can be additionally arranged on the basis of the existing hydrated alumina gel production device, so that the production and the forming of the hydrated alumina gel are integrated.
According to a twelfth aspect of the present invention, the present invention provides the use of the hydrated alumina formed body or the alumina formed body according to the present invention as a carrier or an adsorbent.
The hydrated alumina molded bodies and alumina molded bodies according to the present invention are particularly suitable as a carrier for a supported catalyst. The supported catalyst may be any of various catalysts commonly used in the art that can have a hydrated alumina molded body and/or an alumina molded body as a support. Preferably, the catalyst is a hydroisomerization catalyst. That is, the hydrated alumina formed body and the alumina formed body according to the present invention are particularly suitable as a support of a hydroisomerization catalyst.
The active component having a hydrocatalytic effect can be supported on the hydrated alumina shaped body or alumina shaped body according to the invention by various methods customary in the art (e.g. impregnation), for example: the catalyst may be obtained by impregnating the shaped bodies according to the invention with an aqueous solution containing the active component, and then drying and optionally calcining the shaped bodies loaded with the active component.
According to a thirteenth aspect of the present invention, there is provided a hydroisomerization catalyst comprising a support and an active ingredient supported on the support, wherein the support is a hydrous alumina compact according to the present invention and/or an alumina compact according to the present invention.
The active ingredient may be a conventional ingredient having a catalytic effect on hydroisomerization. Typically, the active ingredient is selected from the group VIII noble metal elements. The group VIII noble metal element may be one or more of group VIII noble metal elements commonly used in a catalyst having a hydroisomerization effect, which contains a noble metal as an active ingredient, such as ruthenium, osmium, palladium, platinum, rhodium, and iridium. Preferably, the active ingredient is palladium and/or platinum. The active ingredient may be supported on the carrier in the form of a simple substance or may be supported on the carrier in the form of a compound.
The content of the active ingredient may be conventionally selected. For example, the active ingredient may be present in an amount of 0.1 to 5 wt%, preferably 0.2 to 2 wt%, more preferably 0.3 to 1 wt% on an elemental basis, based on the total amount of the catalyst.
According to a fourteenth aspect of the present invention, there is provided a method for producing a hydroisomerization catalyst, comprising supporting an active ingredient on a carrier, wherein the method further comprises the step of producing a hydrated alumina compact or an alumina compact as a carrier by the method described hereinbefore.
The active ingredient is of the same kind as described in the thirteenth aspect of the invention and will not be described in further detail herein.
The amount of the active ingredient supported on the carrier may be appropriately selected depending on the specific application of the catalyst. For example, when the prepared catalyst is used for the hydroisomerization of hydrocarbon oil, the amount of the active component supported on the carrier is such that the content of the active component in the finally prepared catalyst can satisfy the requirements of the thirteenth aspect of the present invention, based on the total amount of the prepared catalyst.
According to the preparation method of the hydroisomerization catalyst of the present invention, the active ingredient may be supported on the carrier by various methods commonly used in the art, for example: and (4) dipping. The impregnation may be a saturated impregnation or an excess impregnation.
According to the preparation process of the hydroisomerization catalyst of the present invention, the support obtained by impregnation may be dried and optionally calcined under the conditions customary in the art. Generally, the drying conditions include: the temperature can be 100-300 ℃, and preferably 100-280 ℃; the duration may be from 1 to 12 hours, preferably from 2 to 8 hours. The roasting conditions comprise: the temperature can be 350-550 ℃, and preferably 400-500 ℃; the duration may be from 1 to 10 hours, preferably from 2 to 8 hours.
According to a fifteenth aspect of the present invention, there is provided a hydroisomerization process comprising contacting, under hydrotreating conditions, a hydrocarbon oil with a hydroisomerization catalyst, wherein said hydroisomerization catalyst is a catalyst according to the thirteenth aspect of the present invention or a catalyst prepared by the process according to the fourteenth aspect of the present invention.
The hydrocarbon oil may be any of various hydrocarbon oils that require hydroisomerization treatment, such as: hydrocracking tail oil, distillate oil, solvent refined oil, white oil, coal liquefied oil, light deasphalted oil and heavy deasphalted oil.
According to the hydroisomerization process of the present invention, the catalyst may be activated, for example, reduced, under conditions conventional in the art, before use, either outside the reactor or inside the reactor.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the radial crush strength of the molded articles prepared was measured by the method specified in RIPP 25-90.
In the following examples and comparative examples, the following methods were used to measure
The value: 10g of the hydrated alumina composition are dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition is recorded as w1Is calculated by formula I
The value of the one or more of,
in the following examples and comparative examples, the value of i was determined by the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
in the following examples and comparative examples, the water absorption of the molded articles prepared were measured by the following method: drying the molded body to be tested at 120 ℃ for 4 hours, then sieving by using a 40-mesh standard sieve, and weighing 20g of oversize as a sample to be tested (marked as w)3) Soaking a sample to be detected in 50g of deionized water for 30 minutes, filtering, and then, mixing the solid phaseDrained for 5 minutes, then the drained solid phase was weighed (noted as w)4) Calculating the water absorption by using formula III:
in the following examples and comparative examples, the best possible pore size was determined using a mercury intrusion instrument model Poremaster33, Congta, USA, with reference to the mercury intrusion method specified in GB/T21650.1-2008.
In the following examples and comparative examples, the dry basis is determined by baking a sample to be tested at 600 ℃ for 4 hours, and is the ratio of the mass of the sample after baking to the mass of the sample before baking.
In the following examples and comparative examples, the composition of the catalyst was measured by using a 3271X-ray fluorescence spectrometer manufactured by Nippon mechanical electric machines Co., Ltd. in accordance with the method specified in the petrochemical analysis method RIPP 133-90.
In the following examples and comparative examples, the specific surface area and pore volume were measured by the multipoint BET method in a model number commercially available from Quantachrome
The test is carried out on a six-station full-automatic specific surface and aperture distribution tester.
Examples 1 to 11 are intended to illustrate the hydrated alumina composition, the shaped body and the process for producing the same of the present invention.
Example 1
The hydrated alumina wet gel used in this example was a pseudoboehmite wet cake (the wet cake was designated as S L B-1) obtained by washing and filtering a hydrated alumina gel solution prepared by an acid method (sodium metaaluminate-aluminum sulfate method, obtained from the tommy of petrochemical, china, long-distance division), and the i value of the wet cake was determined to be 80.2%.
(1) 5.48kg of H-ZSM-22 molecular sieve (product of China petrochemical catalyst division, the silica-alumina ratio is 50, and the dry basis is 0.98) is added into 50kg of wet filter cake S L B-1, 10kg of water is added for mixing and pulping for 5 minutes, then the slurry is filtered by a belt filter to obtain 15.2kg of wet filter cake S L BZ-1, the i value of the wet filter cake S L BZ-1 is determined to be 80.2%, and the weight ratio of alumina to ZSM-22 type molecular sieve is determined to be 58: 42 after the wet filter cake S L BZ-1 is roasted at 600 ℃ for 3 hours.
(2) 200g of the wet cake numbered S L BZ-1 was placed in a beaker, then 5g of methylcellulose (purchased from Zhejiang Haishi chemical Co., Ltd., the same applies hereinafter) and 3g of sesbania powder (having a galactomannan content of 80% by weight, purchased from Beijing chemical Co., Ltd.) were added and stirred for 10 minutes using a mechanical stirrer, and the resulting mixture was the hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(3) And (3) extruding the hydrated alumina composition prepared in the step (2) into strips on an F-26 type double-screw extruder (general factory of science and technology industry of southern China university, the same below) by using a disc-shaped orifice plate with the diameter of 1.6 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 120 ℃ for 3 hours in an air atmosphere to give hydrated alumina moldings HT-1, the property parameters of which are shown in Table 1.
(5) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 580 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-1, wherein the property parameters are listed in Table 1.
Comparative example 1
(1) 100kg of wet filter cake with the serial number of S L B-1 is subjected to spray drying to obtain pseudo-boehmite dry glue powder, the dry basis of the pseudo-boehmite dry glue powder is 0.7, the pseudo-boehmite powder is placed for 72 hours at the ambient temperature (25-30 ℃) under a closed condition (placed in a sealed plastic bag), and alumina trihydrate is not detected to be formed after the placement.
(2) 300g of the pseudoboehmite dry glue powder prepared in the step (1), 162g of a ZSM-22 type molecular sieve (same as in example 1), 6.3g of methylcellulose (same as in example 1), 3.7g of sesbania powder (same as in example 1), and 400m of L nitric acid solution containing 12m L concentrated nitric acid (65 wt%) were stirred for 10 minutes by a mechanical stirrer to obtain a mixture.
(3) And (3) extruding the mixture prepared in the step (2) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.6 mm.
(4) The extrudate was cut into wet strips having a length of about 6mm, and the wet strips were dried at 120 ℃ for 3 hours in an air atmosphere to obtain DHT-1 which is a hydrated alumina molded body and has the property parameters shown in Table 1.
(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 580 ℃ for 4 hours in an air atmosphere to obtain alumina forming body DOT-1, wherein the property parameters of the alumina forming body DOT-1 are listed in Table 1.
Example 2
(1) 5kg of the wet cake numbered S L BZ-1 was mixed with 500g of deionized water and beaten for 1 minute, and the resulting slurry was fed to a plate and frame filter press, the pressure of the plate and frame was adjusted to 0.7MPa and held for 15 minutes to obtain a wet cake (numbered L BZ-1). The i value of the wet cake numbered L BZ-1 was determined to be 63%.
(2) 300g of the wet cake numbered L BZ-1 was placed in a beaker, 4.3g of hydroxyethyl methylcellulose (purchased from Shanghai Huikang Fine chemical Co., Ltd., the same below) and 1.7g of sesbania powder (having a galactomannan content of 85% by weight, purchased from Beijing chemical Co., Ltd.) were added, and after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention was obtained, the properties of which are listed in Table 1.
(3) And (3) extruding the hydrated alumina composition prepared in the step (2) on an F-26 type double-screw extruder by using a round orifice plate with the phi of 2.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-2, the property parameters of which are shown in Table 1.
(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain an alumina forming body OT-2, wherein the property parameters are listed in Table 1.
Example 3
A molded body was produced in the same manner as in example 2, except that sesbania powder was not used in the step (2) and the amount of hydroxyethyl methylcellulose was 5.7g, and properties of the produced hydrated alumina composition, the hydrated alumina molded body HT-3 and the alumina molded body OT-3 were as shown in Table 1.
Example 4
A molded body was produced in the same manner as in example 2, except that hydroxyethyl methylcellulose was not used in step (2) and that sesbania powder was used in an amount of 6.8g, and properties of the produced hydrated alumina composition, the hydrated alumina molded body HT-4 and the alumina molded body OT-4 were as shown in Table 1.
Example 5
A molded body was produced in the same manner as in example 2, except that in the step (2), 2.8g of concentrated nitric acid (HNO) was further added to the mixture of hydroxyethyl methylcellulose and sesbania powder3Content of 65 wt.%), the properties of the prepared hydrated alumina composition, hydrated alumina molded body HT-5 and alumina molded body OT-5 are listed in table 1.
Comparative example 2
(1) 300g of the wet filter cake numbered L BZ-1 was dried at 95 ℃ for 2 hours in an air atmosphere to obtain pseudo-boehmite powder having an i value of 40%, which was left to stand at ambient temperature (25-30 ℃) under closed conditions (in a sealed plastic bag) for 72 hours, and no formation of alumina trihydrate was detected after standing.
(2) 185g of the pseudo-boehmite powder prepared in the step (1) was put in a beaker, and 4.3g of hydroxyethyl methyl cellulose (same as in example 2) and 1.7g of sesbania powder (same as in example 2) were added and stirred for 10 minutes by a mechanical stirrer to obtain a pseudo-boehmite composition.
(3) And (3) extruding the pseudo-boehmite composition prepared in the step (2) into strips on an F-26 type double-screw extruder by using a circular orifice plate with the phi of 2.0 mm. Wherein, the extruder frequently trips in the extrusion process, and the surface of the extruded material is smooth.
(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give DHT-2 as a hydrated alumina molded body, the property parameters of which are shown in Table 1.
(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 480 ℃ for 8 hours in an air atmosphere to obtain an alumina forming body DOT-2, wherein the property parameters of the alumina forming body DOT-2 are listed in Table 1.
Comparative example 3
The molding was carried out in the same manner as in comparative example 2, except that the pseudo boehmite powder prepared in step (1) was directly fed to the step (3) for bar extrusion without carrying out the step (2). The extruder has large heat productivity during extrusion (the extruder body is hot and a large amount of hot air is emitted), and the extruder frequently trips during extrusion, so that burrs are formed on the surface of an extruded material. The prepared hydrated alumina forming body is marked as DHT-3, the prepared alumina forming body is marked as DOT-3, and the property parameters are respectively listed in Table 1.
Comparative example 4
A hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethyl methylcellulose and sesbania powder were not used, and 6.0g of paraffin was used. As a result, the hydrated alumina composition cannot be extrusion-molded.
Comparative example 5
A hydrated alumina composition was prepared in the same manner as in example 2, except that hydroxyethyl methylcellulose and sesbania powder were not used, but 6.0g of wood flour was used. As a result, the hydrated alumina composition cannot be extrusion-molded.
Example 6
(1) 300g of the wet cake numbered L BZ-1 was placed in a beaker, and 2.8g of hydroxypropylmethylcellulose (available from Hakka chemical Co., Zhejiang, the same applies hereinafter) and 3.7g of sesbania powder (having a galactomannan content of 85% by weight) were added and stirred with a mechanical stirrer for 10 minutes to obtain a hydrated alumina composition of the present invention, the properties of which are listed in Table 1.
(2) The alumina hydrate composition prepared in the step (1) was extruded on a single screw extruder of SK132S/4 type (manufactured by BONNT, USA) using an orifice plate composed of a circular shape having an outer diameter of phi 4.5mm and a cylinder having a diameter of 1.5mm in the middle. Wherein, the extrusion process is smooth, and the surface of the extrusion material (Raschig ring) is smooth and has no burrs.
(3) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 70 ℃ for 3 hours in an air atmosphere and then at 100 ℃ for 2 hours in an air atmosphere to obtain a hydrated alumina molded article HT-6, the property parameters of which are shown in Table 1.
(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 650 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-6, wherein the property parameters are listed in Table 1.
Example 7
(1) 300g of the wet cake numbered L BZ-1 were placed in a beaker and 2.5g of methylcellulose, 1.2g of hydroxypropyl methylcellulose and 4g of sesbania powder (galactomannan content 85% by weight) were added and after stirring for 10 minutes with a mechanical stirrer, the hydrated alumina composition of the present invention was obtained with the property parameters listed in Table 1.
(2) Extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a clover-shaped orifice plate with the phi of 3.0 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strands having a length of about 8mm, and the wet strands were dried at 120 ℃ for 3 hours in an air atmosphere to give hydrated alumina moldings HT-7, the property parameters of which are shown in Table 1.
(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 600 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-7, wherein the property parameters are listed in Table 1.
Example 8
(1) 300g of the wet cake numbered L BZ-1 were placed in a beaker, 2.4g of hydroxyethyl methylcellulose and 1.8g of hydroxypropyl methylcellulose were added and after stirring for 10 minutes with a mechanical stirrer, a hydrated alumina composition according to the invention was obtained, the properties of which are given in Table 1.
(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.8 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(3) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 250 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-8, the property parameters of which are shown in Table 1.
(4) And (3) roasting the alumina hydrate formed body prepared in the step (4) at 650 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-8, wherein the property parameters are listed in Table 1.
Example 9
A hydrated alumina composition, a hydrated alumina molded body and an alumina molded body were prepared in the same manner as in example 2, except that in the step (1), 5kg of the wet cake numbered S L BZ-1 was mixed and beaten for 1 minute with 650g of deionized water, 30g of methyl cellulose and 23g of sesbania powder (the content of galactomannan was 85% by weight).
The properties of the prepared hydrated alumina composition, the hydrated alumina compact HT-9 and the alumina compact OT-9 are shown in Table 1.
Example 10
The hydrated alumina wet gel used in this example was prepared by mixing CO2Method (sodium aluminate-CO)2The method is that the i value of the pseudo-boehmite wet filter cake (the wet filter cake is numbered as S L B-2) obtained by washing and filtering a hydrated alumina gel solution prepared by Xinghao catalyst new material Co., Ltd., Shanxi province) is measured to be 65.3%.
(1) 0.22kg of H-ZSM-22 molecular sieve (a product of China petrochemical catalyst division, the silica-alumina ratio is 90, and the dry basis is 0.98) is added into 1kg of the wet filter cake S L B-2, then 0.5kg of water is added for mixing and pulping for 10 minutes, the slurry is filtered by a belt filter to obtain 1.12kg of the wet filter cake S L BZ-2, the i value of the wet filter cake S L BZ-2 is determined to be 68.6%, and the weight ratio of alumina to the ZSM-22 type molecular sieve is determined to be 55: 45 after the wet filter cake S L BZ-2 is roasted at 600 ℃ for 3 hours.
(2) 1.12kg of the wet cake numbered S L BZ-2 was placed in a beaker, followed by the addition of 16g of methylcellulose and 20g of sesbania powder (galactomannan content 80% by weight), and after stirring for 10 minutes using a mechanical stirrer, the resulting mixture was a hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(2) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the diameter of 2.4mm, wherein the strip extruding process is smooth, and the surface of an extruded product is smooth and has no burrs.
(3) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 130 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-10, the property parameters of which are shown in Table 1.
(4) And (3) roasting the alumina hydrate formed body prepared in the step (3) at 550 ℃ for 3 hours in an air atmosphere to obtain an alumina formed body OT-10, wherein the property parameters are listed in Table 1.
Comparative example 6
(1) 100kg of wet filter cake with the serial number of S L B-2 is subjected to spray drying to obtain pseudo-boehmite dry glue powder, the dry basis of the pseudo-boehmite dry glue powder is 0.7, the pseudo-boehmite powder is placed for 72 hours at the ambient temperature (25-30 ℃) under a closed condition (placed in a sealed plastic bag), and alumina trihydrate is not detected to be formed after the placement.
(2) 300g of the pseudoboehmite dry glue powder prepared in the step (1), 175g H-ZSM-22 molecular sieve (same as the example 10), 4.4g of methylcellulose (same as the example 10), 5.6g of sesbania powder (same as the example 10) and 400m L of nitric acid solution containing 12m L concentrated nitric acid (the concentration is 65 weight percent) are stirred for 10 minutes by a mechanical stirrer to obtain a mixture.
(3) And (3) extruding the mixture prepared in the step (2) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 1.6 mm.
(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 130 ℃ for 2 hours in an air atmosphere to give DHT-4 as a hydrated alumina molded body, the property parameters of which are shown in Table 1.
(5) And (3) roasting the hydrated alumina forming body prepared in the step (4) at 580 ℃ for 4 hours in an air atmosphere to obtain an alumina forming body DOT-4, wherein the property parameters of the alumina forming body DOT-4 are listed in Table 1.
Example 11
The hydrated alumina wet gel used in this example is obtained from Shandong Zibo zimao catalyst Co., Ltd, 1000g of a dry pseudo-boehmite powder (dry basis is 70 wt%) prepared by an acid process (sodium aluminate-aluminum sulfate process) is calcined at 700 ℃ for 3 hours in an air atmosphere to obtain 700g of alumina, 700g of alumina is placed in a 10L high-pressure reaction vessel, and is uniformly stirred with 5L deionized water, the high-pressure reaction vessel is sealed, and is reacted at 150 ℃ under an autogenous pressure for 6 hours, after the reaction is finished, the temperature of the high-pressure reaction vessel is reduced to room temperature (25 ℃), the slurry obtained by the reaction is sent to a plate and frame filter press, the plate and frame pressure of the plate and frame filter is adjusted to 0.5MPa and is kept for 10 minutes, then the filter cake in the plate and frame is blown with 10MPa of pressure air for 3 minutes, and the plate and frame is decompressed to obtain a hydrated alumina wet filter cake L B-3.
(1) 1.68kg of H-ZSM-22 molecular sieve (a product of China petrochemical catalyst division, the silica-alumina ratio is 80, and the dry basis is 0.75) is added into 825g of the wet filter cake L B-3, then 0.5kg of water is added for mixing and pulping for 10 minutes, then the slurry is filtered by a belt filter to obtain 1.12kg of wet filter cake S L BZ-3, the i value of the wet filter cake S L BZ-3 is determined to be 65.3%, and the weight ratio of alumina to the ZSM-22 type molecular sieve is determined to be 15: 85 after the wet filter cake S L BZ-3 is roasted at 600 ℃ for 3 hours.
(2) 300g of the wet cake numbered S L BZ-3 were placed in a beaker, and then 3.2g of methylcellulose and 5g of sesbania powder (galactomannan content 85% by weight) were added, and after stirring for 10 minutes with a mechanical stirrer, the resulting mixture was a hydrated alumina composition of the present invention, the property parameters of which are listed in Table 1.
(3) And (2) extruding the hydrated alumina composition prepared in the step (1) on an F-26 type double-screw extruder by using a disc-shaped orifice plate with the phi of 2.4 mm. Wherein, the extrusion process is smooth, and the surface of the extruded material is smooth and has no burrs.
(4) The extrudate was cut into wet strands having a length of about 6mm, and the wet strands were dried at 150 ℃ for 2 hours in an air atmosphere to give hydrated alumina moldings HT-11, the property parameters of which are shown in Table 1.
(5) And (3) roasting the alumina hydrate formed body prepared in the step (3) at 590 ℃ for 4 hours in an air atmosphere to obtain an alumina formed body OT-11, wherein the property parameters are listed in Table 1.
Comparative example 7
The wet alumina hydrate cake L B-3 prepared in example 11 was spray dried to give a powder of pseudoboehmite dry glue (dry basis 0.7). The powder was allowed to stand at ambient temperature (25-30 ℃ C.) in a closed condition (in a sealed plastic bag) for 72 hours, after which no formation of alumina trihydrate was detected.
300g of the dried powder of the pseudo-boehmite was mixed with 1587g H-ZSM-22 molecular sieve (same as in example 11), 3.9g of methylcellulose (same as in example 11), 6.1g of sesbania powder (same as in example 11) and 400m of a solution of L in nitric acid containing 12m of L concentrated nitric acid (concentration of 65 wt%) by means of a mechanical mixer for 10 minutes to obtain a mixture, and the obtained mixture was extruded in the same manner as in example 11 to prepare a hydrated alumina formed body DHT-5 and an alumina formed body DOT-5, respectively, the properties of which are shown in Table 1.
Comparative example 8
The wet cake S L BZ-3 prepared by the same method as in step (1) of example 11 was extruded by the same method as in steps (3) and (4) of example 11, and as a result, extrusion molding could not be carried out.
The results of examples 1-11 demonstrate that the present invention mixes wet hydrated alumina gel directly with a compound having at least two proton acceptor sites without drying the wet hydrated alumina gel to form dry gel powder, the resulting mixture can be used directly for molding, and the resulting molded article has high strength, thereby avoiding the problems of harsh working environment and high energy consumption of the conventional process for preparing molded articles from dry gel powder as a starting material. And, the hydrated alumina composition according to the present invention is prepared by adjusting
The pore size distribution of the shaped bodies produced can be adjusted to give shaped bodies having a monomodal or bimodal distribution of pore sizes, respectively.
Experimental examples 1 to 11 are illustrative of hydroisomerization catalysts and methods for preparing the same according to the present invention.
Experimental example 1
(1) 100g of the alumina compact OT-1 prepared in example 1 were impregnated with 127m L-tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, followed by drying at 150 ℃ for 3 hours to obtain catalyst OC-1, the composition of which is shown in Table 2.
(2) A catalyst was prepared in the same manner as in the step (1) except that the hydrated alumina formed body HT-1 prepared in example 1 was used instead. The catalyst prepared was designated HC-1 and its composition is given in Table 2.
Experimental comparative example 1
(1) A catalyst was prepared in the same manner as in Experimental example 1, except that the alumina compact was DOT-1, which was the alumina compact prepared in comparative example 1. The catalyst prepared was designated DOC-1 and its composition is set forth in Table 2.
(2) The catalyst was prepared in the same manner as in the step (2) of experimental example 1, except that the hydrated alumina molded body prepared in comparative example 1 was used, and as a result, the structure of the molded body collapsed during impregnation, and a molded catalyst could not be obtained.
Experimental example 2
(1) 100g of the alumina compact OT-2 prepared in example 2 were impregnated with 86m L-tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, followed by drying at 150 ℃ for 3 hours to obtain catalyst OC-2, the composition of which is shown in Table 2.
(2) A catalyst was prepared in the same manner as in the step (1) except that the hydrated alumina formed body HT-2 prepared in example 2 was used instead. The catalyst prepared was designated HC-2 and its composition is given in Table 2.
Experimental example 3
(1) A catalyst was prepared in the same manner as in the step (1) of Experimental example 2, except that the alumina compact was OT-3 which was prepared in example 3. The catalyst prepared was designated as OC-3 and its composition is listed in table 2.
(2) A catalyst was prepared in the same manner as in the step (2) of Experimental example 2, except that the hydrated alumina formed body HT-3 prepared in example 3 was used. The catalyst prepared was designated HC-3 and its composition is given in Table 2.
Experimental example 4
(1) A catalyst was prepared in the same manner as in the step (1) of Experimental example 2, except that the alumina compact was the alumina compact OT-4 prepared in example 4. The catalyst prepared was designated as OC-4 and its composition is listed in table 2.
(2) A catalyst was prepared in the same manner as in the step (2) of Experimental example 2, except that the hydrated alumina compact was the hydrated alumina compact HT-4 prepared in example 4. The catalyst prepared was designated HC-4 and its composition is given in Table 2.
Experimental example 5
(1) A catalyst was prepared in the same manner as in the step (1) of Experimental example 2, except that the alumina compact was OT-5 which was prepared in example 5. The catalyst prepared was designated as OC-5 and its composition is listed in table 2.
(2) A catalyst was prepared in the same manner as in the step (2) of experimental example 2, except that the hydrated alumina molded body prepared in example 5 was used, and as a result, the structure of the molded body collapsed during impregnation, and a molded catalyst could not be obtained.
Experimental example 6
100g of the alumina compact OT-6 prepared in example 6 were impregnated with 83m L parts by mass of tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours and then at 150 ℃ for 3 hours to obtain catalyst OC-6, the composition of which is shown in Table 2.
Experimental example 7
100g of the alumina compact OT-7 prepared in example 7 were impregnated with 93m L of a tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours and then at 150 ℃ for 3 hours to obtain a catalyst OC-7, the composition of which is shown in Table 2.
Experimental example 8
100g of the alumina compact OT-8 prepared in example 8 were impregnated with 86m L-tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, followed by drying at 150 ℃ for 3 hours to obtain catalyst OC-8, the composition of which is shown in Table 2.
Experimental example 9
100g of the alumina compact OT-9 prepared in example 9 were impregnated with 93m L of a tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours and then at 150 ℃ for 3 hours to obtain a catalyst OC-9, the composition of which is shown in Table 2.
Experimental example 10
100g of the alumina compact OT-10 prepared in example 10 were impregnated with 38m L-tetraammineplatinum dichloride solution (Pt content 0.5% by mass) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, followed by drying at 180 ℃ for 2 hours to obtain catalyst OC-10, the composition of which is shown in Table 2.
Experimental comparative example 2
A catalyst was prepared in the same manner as in experimental example 10, except that the alumina formed body was the alumina formed body prepared in comparative example 6. The catalyst prepared was designated DOC-2 and its composition is set forth in Table 2.
Experimental example 11
100g of the alumina compact OT-11 prepared in example 11 were impregnated with 38m L-tetraammineplatinum dichloride solution (Pt content by mass: 1%) at a temperature of 25 ℃ for 1 hour, and the impregnated mixture was dried at 120 ℃ for 2 hours, then at 150 ℃ for 3 hours, and finally at 350 ℃ for 2 hours in an air atmosphere to obtain a catalyst OC-11, the composition of which is shown in Table 2.
Experimental comparative example 3
A catalyst was prepared in the same manner as in experimental example 11, except that the alumina formed body was the alumina formed body prepared in comparative example 7. The catalyst prepared was designated DOC-3 and its composition is set forth in Table 2.
TABLE 2
Test examples 1-11 are intended to illustrate the hydroisomerization process according to the invention.
Test examples 1 to 11
The catalytic performance of the catalysts prepared in experimental examples 1-11 was evaluated on a mini-fixed bed using n-decane having a purity of 99% by weight (analytical grade), wherein the loading of the catalyst was 1.2g, and the reaction conditions were: the temperature is 330 ℃, the pressure is 4.0MPa, and the space velocity of the raw material is 5h-1. The product is analyzed on line by gas chromatography, and the conversion rate of the raw material and the selectivity of the product are respectively calculated according to the following formulas:
conversion of starting Material- × 100% (peak area ratio of 1-unconverted n-decane)
Product selectivity [ isoalkane peak area ratio/(1-unconverted n-decane peak area ratio) ] × 100%
The results of the experiment are listed in table 3.
Testing of comparative examples 1-3
The catalysts prepared in experimental comparative examples 1 to 3 were evaluated for their catalytic performance in the same manner as in test examples 1 to 11, respectively, and the results of the experiments are shown in Table 3.
TABLE 3
The results of test examples 1 to 11 confirmed that the hydroisomerization catalysts prepared using the hydrated alumina molded bodies and the alumina molded bodies according to the present invention as supports show higher catalytic activity in the hydroisomerization reaction.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (93)
1. A production and forming method of hydrated alumina comprises the following steps:
(1) providing a hydrated alumina gel solution, and washing and carrying out solid-liquid separation on the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the solid-liquid separation condition is that the i value of the first hydrated alumina wet gel is not less than 50%, and the hydrated alumina gel solution is prepared by one or more than two methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method, and is aged or not aged;
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(2) contacting the first hydrated alumina wet gel with a catalyst having at least two proton acceptor sitesMixing the compounds to obtain a hydrated alumina composition, wherein the compound with at least two proton acceptor sites is one or more than two of glucan, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, and the compound with at least two proton acceptor sites is used in an amount of the finally prepared composition
A value of 1.2 or more and 5 or less,
the above-mentioned
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w1Is calculated by formula I
The value of the one or more of,
(3) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(4) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(5) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the process comprises mixing a molecular sieve of the ZSM-22 type in step (1) and/or step (2) such that the hydrated alumina composition contains a molecular sieve of the ZSM-22 type.
2. The process of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 55%.
3. The method of claim 2, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not less than 60%.
4. The method of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 95%.
5. The method of claim 4, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no more than 90%.
6. The method of claim 5, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of not greater than 85%.
7. The method of claim 6, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of no greater than 82%.
8. The method of claim 1, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 50-95%.
9. The method of claim 8, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 55-90%.
10. The method of claim 9, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 60-85%.
11. The method of claim 10, wherein the solid-liquid separation conditions are such that the first hydrated alumina wet gel has an i value of 62-82%.
12. The method of any of claims 1-11, wherein the first hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 50% or less.
13. The method according to any one of claims 1-11, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.
14. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4.5 or less.
15. The method of claim 14, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4 or less.
16. The method of claim 15, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 3.5 or less.
17. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3 or more.
18. The method of claim 17, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.4 or more.
19. The method of claim 18, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.5 or more.
20. The method of claim 1, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3-4.5.
21. The method of claim 20, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.4-4.
22. The method of claim 21, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.5-3.5。
23. The method of any of claims 1 and 14-22, wherein the hydrated alumina composition is free of a peptizing agent.
24. The process of claim 1, wherein the ZSM-22-type molecular sieve is present in the feed mixture in an amount of from 0.5 to 90 wt% and the alumina is present in an amount of from 10 to 99.5 wt%, based on the total amount of the calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ for a duration of 3 hours.
25. The process of claim 24, wherein the ZSM-22-type molecular sieve content of the feed mixture is such that the ZSM-22-type molecular sieve content is from 5 to 88 wt% and the alumina content is from 12 to 95 wt% based on the total calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the calcination is carried out for a duration of 3 hours.
26. The process of claim 25, wherein the ZSM-22-type molecular sieve content of the feed mixture is such that the ZSM-22-type molecular sieve content is 15-86 wt% and the alumina content is 14-85 wt% based on the total calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the calcination is carried out for a duration of 3 hours.
27. The process of claim 26, wherein the ZSM-22-type molecular sieve content of the feed mixture is such that the ZSM-22-type molecular sieve content is 30-85 wt% and the alumina content is 15-70 wt% based on the total calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ for a duration of 3 hours.
28. The method of any of claims 1 and 14-22, wherein the compound having at least two proton acceptor sites is used in an amount of 1 to 25 parts by weight relative to 100 parts by weight of the first hydrated alumina wet gel, based on hydrated alumina.
29. The method of claim 28, wherein the compound having at least two proton acceptor sites is used in an amount of 2 to 22 parts by weight relative to 100 parts by weight of the first hydrated alumina wet gel, the first hydrated alumina wet gel being based on hydrated alumina.
30. The method of claim 29, wherein the compound having at least two proton acceptor sites is used in an amount of 3 to 20 parts by weight relative to 100 parts by weight of the first hydrated alumina wet gel, the first hydrated alumina wet gel being based on hydrated alumina.
31. The method of claim 30, wherein the compound having at least two proton acceptor sites is one or more of a galactan, a mannan, a galactomannan, and a cellulose ether.
32. The method of claim 31, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
33. The method of any one of claims 1 and 14-22, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
34. The method of claim 33, wherein the galactomannan is present in an amount of 10 to 70 wt% and the cellulose ether is present in an amount of 30 to 90 wt%, based on the total amount of the compound having at least two proton acceptor sites.
35. The method of claim 34, wherein the galactomannan is present in an amount of 15 to 65 wt% and the cellulose ether is present in an amount of 35 to 85 wt%, based on the total amount of the compound having at least two proton acceptor sites.
36. The method of claim 35, wherein the galactomannan is present in an amount of 25 to 60 wt% and the cellulose ether is present in an amount of 40 to 75 wt%, based on the total amount of the compound having at least two proton acceptor sites.
37. The process of any one of claims 1 and 14-22, wherein in step (2), the mixing is by stirring and/or kneading.
38. A production and forming method of hydrated alumina comprises the following steps:
(1) providing a hydrated alumina gel solution, washing the hydrated alumina gel solution to obtain a first hydrated alumina wet gel, wherein the hydrated alumina gel solution is prepared by one or more methods of a precipitation method, a hydrolysis method, a seed precipitation method and a rapid dehydration method after aging or not aging;
(2) treating the first hydrated alumina wet gel by adopting (2-1) or (2-2) to obtain a second hydrated alumina wet gel,
(2-1) mixing the first hydrated alumina wet gel with water to form slurry, and carrying out solid-liquid separation on the slurry to obtain a second hydrated alumina wet gel;
(2-2) carrying out solid-liquid separation on the first hydrated alumina wet gel to obtain a second hydrated alumina wet gel,
(2-1) and (2-2), the solid-liquid separation conditions being such that the second hydrated alumina wet gel has an i value of not less than 50%,
the i value is determined using the following method: 10g of the hydrated alumina wet gel were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried sample was recorded as w2The value of i is calculated by adopting the formula II,
(3) mixing the second hydrated alumina wet gel with a compound having at least two proton acceptor sites, the compound having at least two proton acceptor sites being one or more than two selected from the group consisting of dextran, galactan, mannan, galactomannan, cellulose ether, starch, chitin, glycosaminoglycan and aminopolysaccharide, in an amount to provide a final composition of hydrated alumina
A value of 1.2 or more and 5 or less,
the above-mentioned
The values were determined using the following method: 10g of the composition were dried at 120 ℃ for 240 minutes in an air atmosphere, and the mass of the dried composition was designated as w1Is calculated by formula I
The value of the one or more of,
(4) forming the hydrated alumina composition to obtain a hydrated alumina forming product;
(5) drying the hydrated alumina forming product to obtain a hydrated alumina forming body;
(6) optionally, roasting at least part of the hydrated alumina forming body to obtain an alumina forming body;
wherein the process comprises mixing a molecular sieve of the ZSM-22 type in one, two or three of step (1), step (2) and step (3) such that the hydrated alumina composition contains a molecular sieve of the ZSM-22 type.
39. The method as claimed in claim 38, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 55%.
40. A process as claimed in claim 39, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not less than 60%.
41. The method as claimed in claim 38, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not higher than 95%.
42. The method as claimed in claim 41, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not higher than 90%.
43. The method of claim 42, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not more than 85%.
44. The method of claim 43, wherein in steps (2-1) and (2-2), the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of not higher than 82%.
45. The method of claim 38, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 50-95%.
46. The method of claim 45, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 55-90%.
47. The method of claim 46, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 60-85%.
48. The method of claim 47, wherein the solid-liquid separation conditions are such that the second hydrated alumina wet gel has an i value of 62-82%.
49. The method of any of claims 38-48, wherein the second hydrated alumina wet gel is a hydrated alumina wet gel that has not been subjected to a dehydration treatment such that its i value is 50% or less.
50. The method according to any one of claims 38-48, wherein the solid-liquid separation is performed one or more times, at least the last solid-liquid separation being pressure filtration and/or vacuum filtration.
51. The method of claim 38, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4.5 or less.
52. A process according to claim 51, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 4 or less.
53. The method of claim 52, wherein the compound having at least two proton acceptor sites is used in an amount to produce hydrationOf compositions of aluminium oxide
The value is 3.5 or less.
54. The method of claim 38, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3 or more.
55. The method of claim 54, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.4 or more.
56. The method of claim 55, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.5 or more.
57. The method of claim 38, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.3-4.5.
58. The method of claim 57, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.4-4.
59. The method of claim 58, wherein the compound having at least two proton acceptor sites is used in an amount to produce a hydrated alumina composition
The value is 1.5-3.5.
60. The method of any of claims 38 and 51-59, wherein the hydrated alumina composition is peptizing agent free.
61. The process of claim 38, wherein the ZSM-22-type molecular sieve is present in the feed mixture in an amount of from 0.5 to 90 wt% and the alumina is present in an amount of from 10 to 99.5 wt%, based on the total amount of the calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ for a duration of 3 hours.
62. The process of claim 61, wherein the ZSM-22 type molecular sieve is present in the feed mixture in an amount of 5 to 88 wt% and the alumina is present in an amount of 12 to 95 wt% based on the total calcined hydrated alumina composition, the calcination being carried out at a temperature of 600 ℃ and the calcination being carried out for a duration of 3 hours.
63. The process of claim 62, wherein the ZSM-22 type molecular sieve is present in the feed mixture in an amount of 15 to 86 wt% and the alumina in an amount of 14 to 85 wt% based on the total calcined hydrated alumina composition, and the calcination is carried out at a temperature of 600 ℃ and the calcination is carried out for a duration of 3 hours.
64. The process of claim 63, wherein the ZSM-22 type molecular sieve is present in the feed mixture in an amount of 30 to 85 wt% and the alumina is present in an amount of 15 to 70 wt% based on the total calcined hydrated alumina composition, the calcination being carried out at a temperature of 600 ℃ and the calcination being carried out for a duration of 3 hours.
65. The method of claim 38, wherein the compound having at least two proton acceptor sites is used in an amount of 1 to 25 parts by weight relative to 100 parts by weight of a second wet gel of hydrated alumina, based on hydrated alumina.
66. The method of claim 65, wherein the compound having at least two proton acceptor sites is used in an amount of 2 to 22 parts by weight relative to 100 parts by weight of a second wet gel of hydrated alumina, based on hydrated alumina.
67. The method of claim 66, wherein the compound having at least two proton acceptor sites is used in an amount of 3 to 20 parts by weight relative to 100 parts by weight of a second wet gel of hydrated alumina, based on hydrated alumina.
68. The method of any one of claims 38 and 65-67, wherein the compound having at least two proton acceptor sites is one or more of a galactan, mannan, galactomannan, and cellulose ether.
69. The method of claim 68, wherein the cellulose ether is one or more of methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose.
70. The method of any one of claims 38 and 65-67, wherein the compound having at least two proton acceptor sites is a galactomannan and a cellulose ether.
71. The method of claim 70, wherein the galactomannan is present in an amount of 10 to 70 wt.% and the cellulose ether is present in an amount of 30 to 90 wt.%, based on the total amount of the compound having at least two proton acceptor sites.
72. The method of claim 71, wherein the galactomannan is present in an amount of 15 to 65 wt.% and the cellulose ether is present in an amount of 35 to 85 wt.%, based on the total amount of the compound having at least two proton acceptor sites.
73. The method of claim 72, wherein the galactomannan is present in an amount of 25 to 60 wt.% and the cellulose ether is present in an amount of 40 to 75 wt.%, based on the total amount of the compound having at least two proton acceptor sites.
74. The process of any one of claims 38 and 65 to 67, wherein in step (3), the mixing is by stirring and/or kneading.
75. A shaped body produced by the method of any one of claims 1-74.
76. The shaped body according to claim 75, wherein the shaped body has a radial crush strength of from 15 to 40N/mm.
77. The shaped body according to claim 76, wherein the shaped body has a radial crush strength of from 18 to 35N/mm.
78. Use of the shaped bodies according to any of claims 75 to 77 as supports or adsorbents.
79. The use according to claim 78, wherein the support is a support for a supported catalyst.
80. The use according to claim 79, wherein the support is a support for a supported hydrogenation catalyst.
81. A hydroisomerization catalyst comprising a support and an active ingredient supported on said support, wherein said support is the shaped body according to any of claims 75 to 77.
82. The catalyst according to claim 81, wherein the active ingredient is selected from the group VIII noble metal elements.
83. The catalyst of claim 82, wherein the active ingredient is platinum and/or palladium.
84. A catalyst as claimed in any one of claims 81 to 83, wherein the active ingredient is present in an amount of from 0.1 to 5% by weight calculated as element on the total catalyst.
85. The catalyst of claim 84, wherein the active ingredient is present in an amount of 0.2-2% by weight, calculated as element, based on the total amount of the catalyst.
86. A catalyst as claimed in claim 85, wherein the active ingredient is present in an amount of 0.3 to 1% by weight calculated as element on the total catalyst.
87. A process for the preparation of a hydroisomerization catalyst comprising supporting an active ingredient on a support, wherein the process further comprises the step of preparing a shaped body as support by the process according to any of claims 1 to 74.
88. The method of claim 87 wherein the active ingredient is selected from the group consisting of group VIII noble metal elements.
89. The method of claim 88, wherein the active ingredient is platinum and/or palladium.
90. The production method according to any one of claims 87 to 89, wherein the active ingredient is supported on the carrier in such an amount that the content of the active ingredient in terms of element is 0.1 to 5% by weight based on the total amount of the finally produced catalyst.
91. The production method according to claim 90, wherein a supporting amount of the active ingredient on the carrier is such that the content of the active ingredient in terms of element is 0.2 to 2% by weight based on the total amount of the finally produced catalyst.
92. The production method according to claim 91, wherein a supporting amount of the active ingredient on the carrier is such that the content of the active ingredient in terms of element is 0.3 to 1% by weight based on the total amount of the finally produced catalyst.
93. A hydroisomerization process comprising contacting a hydrocarbon oil under hydroisomerization conditions with a hydroisomerization catalyst, wherein the hydroisomerization catalyst is a catalyst according to any of claims 81-86 or prepared by the process according to any of claims 87-92.
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| CN102451765B (en) * | 2010-10-15 | 2013-10-09 | 中国石油化工股份有限公司 | Preparation method for composite oxide carrier |
| CN102861618B (en) * | 2011-07-07 | 2014-05-21 | 中国石油化工股份有限公司 | Preparation method of alumina supporter |
| CN102861590A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
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