CN107999119A - The hydrated alumina composition and catalyst and preparation method and hydroisomerization process of the molecular sieve of type containing ZSM-22 - Google Patents
The hydrated alumina composition and catalyst and preparation method and hydroisomerization process of the molecular sieve of type containing ZSM-22 Download PDFInfo
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- CN107999119A CN107999119A CN201610930280.5A CN201610930280A CN107999119A CN 107999119 A CN107999119 A CN 107999119A CN 201610930280 A CN201610930280 A CN 201610930280A CN 107999119 A CN107999119 A CN 107999119A
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- Prior art keywords
- hydrated alumina
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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 791
- 239000000203 mixture Substances 0.000 title claims abstract description 236
- 238000000034 method Methods 0.000 title claims abstract description 235
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 91
- 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 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 73
- 230000008569 process Effects 0.000 title claims abstract description 42
- 239000011240 wet gel Substances 0.000 claims abstract description 148
- 150000001875 compounds Chemical class 0.000 claims abstract description 100
- 238000001035 drying Methods 0.000 claims abstract description 52
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 43
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 67
- 239000000499 gel Substances 0.000 claims description 63
- 238000000926 separation method Methods 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 229910052782 aluminium Inorganic materials 0.000 claims description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 37
- 239000004411 aluminium Substances 0.000 claims description 35
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- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
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- 238000003756 stirring Methods 0.000 claims description 14
- 229920000926 Galactomannan Polymers 0.000 claims description 13
- 230000036571 hydration Effects 0.000 claims description 13
- 238000006703 hydration reaction Methods 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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- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-RWOPYEJCSA-N 0.000 claims description 4
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- -1 For boehmite) when Chemical compound 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 150000004645 aluminates Chemical class 0.000 description 7
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- 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
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- 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
- 239000003513 alkali Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 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
- 239000012065 filter cake Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 235000015424 sodium Nutrition 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 238000010009 beating Methods 0.000 description 5
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- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 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 3
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940009493 gel-one Drugs 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 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
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 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
- 230000036961 partial effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 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
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000014612 sandwich biscuits Nutrition 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 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
- 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/10—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28078—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28088—Pore-size distribution
- B01J20/2809—Monomodal or narrow distribution, uniform pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
- B01J20/28088—Pore-size distribution
- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/67—Pore distribution monomodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrated alumina composition of the 22 type molecular sieve containing ZSM and preparation method thereof and formed body and its preparation method and application, said composition contains hydrated alumina, 22 type molecular sieves of ZSM and the compound with least two proton acceptor sites, andIt is worth for less than 5.The invention also discloses using the hydroisomerisation catalysts and preparation method and hydroisomerization process by the formed body that the hydrated alumina composition is formed as carrier.The formed body with higher-strength is prepared by starting material of hydrated alumina wet gel in the present invention, eliminate for the step of drying hydrated alumina wet gel, simplify overall craft flow, reduce overall operation energy consumption, the dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, greatly improves operating environment.Catalyst according to the invention shows more preferable catalytic activity in hygrogenating isomerization reaction.
Description
Technical field
The present invention relates to aluminium oxide field shaping technique, in particular it relates to a kind of type containing ZSM-22 molecular sieve
Hydrated alumina composition and preparation method thereof, the invention further relates to the aqua oxidation formed by the hydrated alumina composition
Aluminium formed body and aluminium oxide formed body, the invention further relates to a kind of shaping to be formed by the hydrated alumina composition
The hydroisomerisation catalysts of body as carrier and preparation method thereof and the hydroisomerization process using the catalyst.
Background technology
ZSM-22 molecular sieves are a kind of System of Silica/Aluminum Microparticle hydrochlorates that Mobil companies of U.S. Dwyer et al. is developed the 1980s
Molecular screen material, belongs to rhombic system, space group Mmc21, cell parameter a=13.
ZSM-22 molecular sieves have TON structural topology frames, and topological structure includes five-membered ring, hexatomic ring and ten-ring.Main aperture road is
One-dimensional channels with ten-ring opening, duct are parallel to (001) direction, no intersection duct, port sizeIt is ellipse
Circular channel.ZSM-22 molecular sieves are due to the shape-selective isomerization reaction acted on thus be widely used in linear paraffin in space
In.
In conventional methods where, aluminium oxide formed body containing ZSM-22 type molecular sieves, particularly contain ZSM-22 type molecules
The gama-alumina formed body of sieve, because it is with preferable pore structure, suitable ratio surface and higher heat-resistant stability, often makees
Used for the carrier of adsorbent or loaded catalyst.This aluminium oxide usually by dried hydrated alumina, such as intends thin water
Aluminium stone etc. through being molded, it is dry after, high-temperature roasting obtains again.
Based on above-mentioned cognition, as shown in Figure 1, the hydrated alumina wet gel being prepared needs to be dried, intended
Boehmite dry glue powder, then using boehmite dry glue powder as starting point, adds ZSM-22 types molecular sieves, extrusion aid and can
The chemical peptizing agent (inorganic acid and/or organic acid) of choosing, through kneading aftershaping, molding is made after dry and optional roasting
Used for adsorbent or carrier.The main problem of this preparation method is that dust pollution is larger and high energy consumption.
In order to reduce dust pollution, improve operating environment, researcher recognizes that shaping raw material used should be changed, opens
Begin to attempt hydrated alumina wet gel or semiarid boehmite preparing aluminium oxide molding as raw material.
US4613585 discloses a kind of method for preparing alumina catalyst carrier, and this method comprises the following steps：
(a) aluminum sulfate solution and sodium aluminate solution are poured into the container equipped with deionized water at the same time, makes aluminum sulfate solution
Reacted with sodium aluminate solution, reaction condition pH6.0-8.5, temperature is 50-65 DEG C, thus prepares first containing amorphous
The aqueous slurry of aluminium hydroxide；
(b) sodium aluminate aqueous solution is added into the first aqueous slurry, the additive amount of the sodium aluminate aqueous solution is enough to neutralize institute
The first aqueous slurry is stated, the total amount of the sodium aluminate solution used in step (a) and step (b) is equivalent to the sulphur used in step (a)
Stoichiometric 0.95-1.05 of the amount of sour aluminium, thus prepares the second aqueous slurry, the Al of second aqueous slurry2O3Concentration is
7wt% or higher；
(c) amorphous hydroted alumina in the second aqueous slurry is filtered out, filter cake is obtained, is obtained first with dilute ammonia scrubbing
Filter cake, then washed with dilute nitric acid solution, finally washed again with dilute ammonium hydroxide, with remove sulfate anion and
Sodium cation impurity, while the pH of filter cake is adjusted in the range of 7.5-10.5；
(d) then, without the aging filter cake, on a filter press by the cake dewatering, and by its Al2O3Content improve to
28-35wt%, and in the range of pH is 7.5-10.5, mediate the filter cake in the mixer of a self-cleaning type, during stop
Between be 10s or longer, boehmite particle is grown up in a short time, thus obtain the dough containing these particles；
(e) dough for obtaining step (d) is extruded into extrudate, and then dry and roasting obtains extrudate.
From the point of view of method disclosed in US4613585, although hydrated alumina wet gel can be molded by this method, from
The preparation condition of amorphous hydroted alumina is all restricted to kneader device and kneading conditions, causes complex operation.Also, by
Carrier prepared by this method should be unable to have very high intensity, it is difficult to meet the requirement of commercial Application, its reason is by this
The content of Free water is high in extrudate prepared by method, and the extrudate obtained through dry and roasting is loose.Meanwhile using this method
Carrier is prepared, it is difficult to regulate and control to the pore structure of carrier, so as to it is difficult to meet the needs of a variety of use occasions.
CN103769118A discloses a kind of heavy-oil hydrogenation catalyst, including carrier and active ingredient, and carrier is aluminium oxide,
Active component is group VIII and/or the metal of group vib, and wherein group VIII metal is Co or Ni, and group vib metal is Mo or W, its
In, it is prepared by the boehmite shaping that the alumina support contents on dry basis is less than 50%.The contents on dry basis is 50%
The preparation process of following boehmite includes：(1) aluminum salt solution carries out neutralizing plastic reaction with precipitating reagent；(2) filter back
The solid product of harvest glue reaction；(3) solid product obtains contents on dry basis as less than 50% after drying.
CN103769118A uses contents on dry basis to prepare alumina support, contents on dry basis for less than 50% boehmite
Boehmite for less than 50% is then to be done the solid product separated from the mixture that plastic is reacted
Obtained from dry, in actual mechanical process, it is difficult the method carried out that this, which is one, and main cause is as follows：
(1) the boehmite viscosity not being completely dried is stronger, and transfer is difficult, easily causes secondary dust to pollute；
(2) dry all since surface, to the wet solid separated from the mixture that plastic is reacted
The drying that product carries out belongs to endless white drying, therefore there are sandwich biscuits phenomenon, the i.e. surface of part boehmite to be done
Dry (that is, Free water being substantially free of by dry surface), and internal wet state is still maintained (that is, for not by dry
Portion, the content of Free water keep dry substantially before level), since surface is dried, form hard particles, to it is this not
Peptizing agent and/or binding agent are added in the boehmite parched completely when through mediating aftershaping, is formed in drying process
Hard particles easily cause to block during extrusion, influence production efficiency；
(3) it is difficult to which the butt of stability contorting boehmite, butt is unstable to cause very big interference to shaping, make into
Type process is also highly unstable, causes the increase of substandard product amount, and production efficiency is low；
(4) CN103769118A in shaping using conventional moulding process, the boehmite used yet with it
Butt (for 35%-50%) far below conventional contents on dry basis (for 70% or so), i.e. water content height, in extrusion molding process
Extrusion pressure will not be substantially produced, therefore the carrier that extrudate obtains after drying and roasting does not have mechanical strength substantially, as long as
Apply some external force, will dusting, do not possess the possibility of commercial Application, this is the greatest problem that the technology faces.
In conclusion how to guarantee to be met the aluminium oxide containing ZSM-22 type molecular sieves of industrial application requirement
On the premise of carrier, simplify the preparation process flow of the alumina support containing ZSM-22 type molecular sieves and reduce operation energy consumption,
At the same time mitigate the alumina support preparation process containing ZSM-22 type molecular sieves in dust pollution be still one urgently
The technical problem of solution.
The content of the invention
It is an object of the invention to simplify the preparation process flow of the alumina support containing ZSM-22 type molecular sieves, mitigate
Dust pollution in alumina support preparation process containing ZSM-22 type molecular sieves, while the carrier prepared can also meet
Industrial application requirement.
For US4613585 and CN103769118A when preparing alumina support problem encountered, hair of the invention
A person of good sense is off the beaten track, by the compound containing at least two proton acceptor sites in molecular structure and arises directly from synthetic reaction
The mixing of hydrated alumina wet gel, the mixture of formation can not only be molded, and be obtained through dry and optional roasting
To shaping physical efficiency have and meet the intensity of industrial requirements.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of hydrated alumina group of the molecular sieve of type containing ZSM-22
Compound, said composition contain hydrated alumina, ZSM-22 types molecular sieve and the chemical combination with least two proton acceptor sites
Thing,
The compositionIt is worth for less than 5, it is describedValue is measured using following methods：By composition described in 10g at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
According to the second aspect of the invention, the present invention provides a kind of hydrated alumina group of the molecular sieve of type containing ZSM-22
The preparation method of compound, this method include mixing each component in a kind of feedstock composition, obtain the hydrated alumina group
Compound, the feedstock composition contain hydrated alumina wet gel, ZSM-22 types molecular sieve and with least two protons by
The compound of position point, the i values of the hydrated alumina wet gel be not less than 50%, it is described that there are at least two proton acceptors
The dosage of the compound in site causes the composition finally preparedIt is worth for less than 5,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will
Quality through dry composition is denoted as w1, calculated using Formulas IValue,
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention
The hydrated alumina composition of the standby molecular sieve of type containing ZSM-22.
According to the fourth aspect of the present invention, the present invention provides a kind of hydrated alumina formed body, the hydrated alumina
Hydrated alumina composition or the present invention the of the formed body as the molecular sieve of type containing ZSM-22 described in the first aspect of the present invention
The hydrated alumina composition of the molecular sieve of type containing ZSM-22 described in three aspects is formed.
According to the fifth aspect of the present invention, should the present invention provides a kind of preparation method of hydrated alumina formed body
Method is included the hydrated alumina composition or the present invention of the molecular sieve of type containing ZSM-22 described in the first aspect of the present invention
The hydrated alumina composition of the molecular sieve of type containing ZSM-22 described in 3rd aspect is molded, and obtained molding is carried out
It is dry.
According to the sixth aspect of the invention, the present invention provides a kind of method system as described in the 5th aspect of the present invention
Standby hydrated alumina formed body.
According to the seventh aspect of the present invention, the present invention provides a kind of aluminium oxide formed body, the aluminium oxide formed body by
The hydrated alumina composition or third aspect of the present invention of the molecular sieve of type containing ZSM-22 described in the first aspect of the present invention
The hydrated alumina composition of the molecular sieve of type containing ZSM-22 is formed.
According to the eighth aspect of the present invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method
Including by the hydrated alumina composition of the molecular sieve of type containing ZSM-22 described in the first aspect of the present invention or the present invention the 3rd
The hydrated alumina composition of the molecular sieve of type containing ZSM-22 described in a aspect is molded, and obtained molding is dried
And roasting.
According to the ninth aspect of the present invention, the present invention provides a kind of method system as described in the 8th aspect of the present invention
Standby aluminium oxide formed body.
According to the tenth aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, the party
Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and solid-liquid
Separation, obtains the first hydrated alumina wet gel, the condition of the separation of solid and liquid causes the first hydrated alumina wet gel
I values be not less than 50%；
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(2) using the method described in second aspect of the present invention by the first hydrated alumina wet gel and with least
The compound mixing in two proton acceptor sites, obtains hydrated alumina composition；
(3) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(4) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(5) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixing ZSM-22 type molecular sieves are carried out in step (1) and/or step (2),
So that the hydrated alumina composition contains ZSM-22 type molecular sieves.
According to the eleventh aspect of the present invention, should the present invention provides a kind of production forming method of hydrated alumina
Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains the second aqua oxidation
Aluminium wet gel,
(2-1) mixes the first hydrated alumina wet gel with water, forms slurries, and the slurries are carried out solid-liquid point
From obtaining the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are
Not less than 50%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(3) using the method described in second aspect of the present invention by the second hydrated alumina wet gel and with least two
The compound mixing in proton acceptor site, obtains hydrated alumina composition；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method be additionally included in one, two or three in step (1), step (2) and step (3) into
The operation of row mixing ZSM-22 type molecular sieves, so that the hydrated alumina composition contains ZSM-22 type molecular sieves.
According to the twelfth aspect of the present invention, the present invention provides one kind by the tenth aspect of the present invention or the 11st
Formed body prepared by the method described in a aspect.
13rd aspect according to the present invention, the present invention provides hydrated alumina formed body according to the present invention and oxygen
Change application of the aluminium formed body as carrier or adsorbent.
14th aspect according to the present invention, the present invention provides a kind of hydroisomerisation catalysts, which contains
There is the active ingredient of carrier and load on the carrier, wherein, carrier is the hydrated alumina formed body according to the present invention
Or aluminium oxide formed body according to the present invention.
15th aspect according to the present invention, the present invention provides a kind of preparation method of hydroisomerisation catalysts,
This method is included in supported on carriers active ingredient, wherein, this method is further included using the present invention the 5th aspect, the 8th side
The step of method described in face, the tenth aspect or the tenth one side prepares the formed body as carrier.
16th aspect according to the present invention, the present invention provides a kind of hydroisomerization process, this method is included in
Under the conditions of hydroisomerization, hydrocarbon ils is contacted with hydroisomerisation catalysts, wherein, the hydroisomerisation catalysts are this hair
Catalyst described in bright 14th aspect or the catalyst as the method preparation described in the 15th aspect of the present invention.
With the existing process that aluminium oxide formed body is prepared using boehmite dry glue powder as starting material (as schemed
Technique shown in 1) compare, the present invention is directly used as molding starting using the hydrated alumina wet gel that synthetic reaction is prepared
Raw material prepares the formed body containing ZSM-22 type molecular sieves, has the advantage that：
(1) the step of being used to dry hydrated alumina wet gel in existing process is eliminated, and is preparing shaping raw material
When, boehmite dry glue powder is modulated into plastic material without additionally introducing water, simplifies overall craft flow, is reduced
Overall operation energy consumption；
(2) dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, is greatly improved
Operating environment.
Existing process, such as US4613585 with directly preparing carrier using hydrated alumina wet gel as starting material
Compared with CN103769118A, technical process of the invention is more succinct, and operability is stronger, and can effectively improve final
The intensity of the formed body of preparation, while the pore-size distribution of the formed body finally prepared can be adjusted, it can meet a variety of uses
The requirement of occasion.The present invention can be prepared using hydrated alumina wet gel as starting material contains ZSM-22 types with higher-strength
The reason for formed body of molecular sieve, may is that：Compound and hydrated alumina with least two proton acceptor sites are wet solidifying
Free water in glue interacts to form hydrogen bond, adsorbs the Free water in hydrated alumina wet gel, while have at least two
Also with the hydroxyl in hydrated alumina molecular structure interaction of hydrogen bond can occur for the compound in proton acceptor site, play physics
The effect of peptization, so that hydrated alumina wet gel can not only be molded, and can be so that the formed body finally prepared has
Higher intensity.
The hydroisomerization that the formed body prepared using hydrated alumina composition according to the present invention is prepared as carrier is urged
Agent shows the catalytic activity of higher in hydrocarbon oil hydrogenation isomerization reaction.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is moulding process flow process usually used in current commercial Application.
Fig. 2 is a kind of preferred embodiment for the method for preparing hydrated alumina composition according to the present invention.
Fig. 3 is a kind of preferred embodiment of moulding process flow process according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of hydrated alumina composition, said composition to contain
Hydrated alumina, ZSM-22 types molecular sieve and the compound with least two proton acceptor sites.
The hydrated alumina can be more than one or both of gibbsite and a water aluminium oxide.It is described
The instantiation of hydrated alumina can include but is not limited to boehmite, gibbsite, unformed hydrated alumina and plan
Boehmite.The hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.In a kind of excellent of the present invention
In the embodiment of choosing, the hydrated alumina contains boehmite, more preferably boehmite.According to the preferable reality
The hydrated alumina composition of mode is applied particularly suitable for preparing the formed body as hydroisomerisation catalysts carrier.
Hydrated alumina composition according to the present invention, it is wet solidifying that the hydrated alumina is directed to hydrated alumina
Glue, is not originating from hydrated alumina dry glue powder.In the present invention, term " hydrated alumina wet gel " refers to pass through synthetic reaction
Obtain and do not live through the dehydration that its i value is reduced to less than 50% (being preferably less than 55%, more preferably less than 60%)
Aqueous alumina hydrate gel.In the present invention, i values are measured using following methods：10g hydrated alumina wet gels are existed
120 DEG C 240 minutes dry in air atmosphere, and the quality through dry sample is denoted as w2, i values are calculated using Formula II,
The synthetic reaction refers to the reaction for preparing gel aluminum hydroxide, can be aqua oxidation commonly used in the art
Alumina gel synthetic reaction, specific examples thereof include the precipitation method (including acid system and alkaline process), Hydrolyze method, kind point-score and fast dewatering
Method.The alumina hydrate gel of synthesis can be the alumina hydrate gel without going through aging, or live through aging
Alumina hydrate gel.The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method concrete operation method and condition can be with
For conventional selection, will hereinafter illustrate.The hydrated alumina wet gel can be by the hydration that obtains synthetic reaction
After alumina gel alternatively carries out aging, carry out washing and separation of solid and liquid and collect solid phase and obtain.
It is different from the hydrated alumina from dry glue powder, it is directed to the hydration oxygen of hydrated alumina wet gel
Change aluminium thing of hydrated alumina in storage process, which is met, to change.For example, it is small that 72 are placed under environment temperature and sealing condition
When, the thing of hydrated alumina, which is met, in the composition after placement changes.Depending on the environment temperature is with environment is placed, generally
It can be 5-50 DEG C, such as 20-40 DEG C.The sealing condition refers to the composition being placed in closed vessel, and the closing is held
Device can be closure container (such as tank, bucket or case), or the flexible coating (such as sealed bag) of sealing, the flexible bag
It can be paper and/or polymeric material to cover thing, be preferably polymeric material, such as plastics.
In an example, the hydrated alumina for being directed to hydrated alumina wet gel contains boehmite (such as
For boehmite) when, the composition is placed under environment temperature and sealing condition 72 it is small when, in the composition after placement
Gibbsite content higher than place before composition in gibbsite content.In this example, with the group before placement
On the basis of the content of gibbsite in compound, the gibbsite content in the composition after placement generally at least improves
0.5%, 1% is preferably at least improved, more preferably improves 1.1-1.5%.
Hydrated alumina composition according to the present invention, also contains the compound with least two proton acceptor sites.
Hydrated alumina composition according to the present invention, without being used as starting material using dry glue powder, you can (particularly extruded for being molded
Shaping), and there is obtained formed body the reason for higher intensity may is that：It is described that there are at least two proton acceptor sites
Compound and hydrated alumina wet gel in Free water interaction of hydrogen bond occurs, so as to adsorb Free water, while and water
The hydroxyl closed in alumina molecule structure interacts, and plays the role of peptization.
In the compound with least two proton acceptor sites, the proton acceptor site refers to the compound
Molecular structure in the position of hydrogen bond can be formed with water and hydroxyl.The instantiation in the proton acceptor site can include but
It is not limited to more than one or both of fluorine (F), oxygen (O) and nitrogen (N).The chemical combination with least two proton acceptor sites
The instantiation of thing can include but is not limited in molecular structure contain selected from hydroxyl, carboxyl, amino, ehter bond, aldehyde radical, carbonyl,
The compound of group more than one or both of amide groups and fluorine atom, is preferably hydroxyl and/or ehter bond.
The compound with least two proton acceptor sites can be organic compound, or inorganic chemical
Thing, can also be the combination of organic compound and inorganic compound.Using organising with least two proton acceptor sites
Compound, the organic compound can be removed by roasting process.Using the inorganic chemical with least two proton acceptor sites
Thing, the Partial Elements in the inorganic compound can be retained in the formed body finally prepared, it is possible thereby to inorganization by this
Compound introduces auxiliary element in formed body.
In a kind of preferred embodiment of the present invention, it is described there are at least two proton acceptor sites compound be
There is the polymer in multiple (such as more than three) proton acceptor sites in molecular structure.According to the preferred embodiment, can obtain
Physically better peptization is obtained, so that the intensity of the formed body finally prepared is further improved, particularly using extrusion work
When skill is molded, the intensity of the formed body finally prepared can be further improved.Preferably, the polymer is organic polymer
Thing.According to the preferred embodiment, the instantiation of the compound with least two proton acceptor sites can wrap
Include but be not limited to polyol, is more than one or both of polyethers and acrylic acid polymer.
The polyol can include but be not limited to polysaccharide, the etherate and polyalcohol of polysaccharide.
The polysaccharide can be homopolysaccharide, or heteroglycan, can also be the combination of homopolysaccharide and heteroglycan.It is described
Polysaccharide and its etherate specific examples thereof include but be not limited to glucan, galactan, mannosan, galactomannans, fibre
Dimension plain ether, starch, chitin, glycosaminoglycan and glycosaminoglycan.The cellulose ether refers to the part of hydroxyl in cellulosic molecule
On hydrogen atom substituted by one or more alkyl after the ether system derivative that is formed, wherein, multiple alkyl can be it is identical,
It can also be difference.The alkyl is selected from the alkyl of substitution and unsubstituted alkyl.The unsubstituted alkyl is preferably alkyl
(such as：C1-C5Alkyl).In the present invention, C1-C5The instantiation of alkyl include C1-C5Straight chained alkyl and C3-C5Branch
Alkyl group, can be but be not limited to：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, different
Amyl group and tertiary pentyl.The substituted alkyl for example can be substituted by hydroxyl, carboxyl, cyano group or aryl alkyl (such as：
C1-C5The alkyl being optionally substituted by a hydroxyl group, C1-C5The alkyl substituted by carboxyl, C1-C5The alkyl being substituted with aryl), the virtue
Base can be phenyl or naphthyl.The instantiation of the substituted alkyl can include but is not limited to：Cyano group, benzyl, benzene
Ethyl, methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.The instantiation of the cellulose ether
It can include but is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzyl fiber
Element, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose,
Carboxymethyl hydroxyethyl cellulose and benzyl cellulose.The polysaccharide and its etherate can provide in a variety of manners, such as：Gala
Mannosan can derive from sesbania powder.
The polyalcohol specific examples thereof include but be not limited to polyvinyl alcohol, part acetalation polyvinyl alcohol (acetalizing degree
Can be less than 95%, be preferably less than 80%, more preferably less than 70%, more preferably less than 50%), polyether polyols
It is more than one or both of alcohol and polyester polyol.
The polyethers specific examples thereof include but be not limited to polyethylene oxide, polypropylene oxide, epoxy ethane-epoxy propane
Block copolymer and PolyTHF.
The acrylic acid polymer refers to the polymer containing acrylic monomer unit, the acrylic monomer list
Member be specifically as follows but be not limited to acrylic monomer units and acrylate monomer units (be preferably C1-C5Alkyl acrylic
Monomeric unit, more preferably methacrylic acid monomer units).Specific examples thereof include polypropylene for the acrylic acid polymer
Acid, polymethylacrylic acid, copolymer of acrylic acid and methyl acrylate, acryl acid-methyl methacrylate copolymer, metering system
Acid-methyl acrylate copolymer and EUDRAGIT L100.
In the preferred embodiment, it is described there are at least two proton acceptor sites compound it is further preferably more
The etherate of sugar and/or polysaccharide, the more preferably etherate of polysaccharide and/or polysaccharide.
In a kind of embodiment being more highly preferred to of the present invention, the chemical combination with least two proton acceptor sites
Thing contains galactomannans and cellulose ether.The embodiment being more highly preferred to according to this, by composition shape according to the present invention
Into formed body have higher intensity.It is further preferred that it is described there are at least two proton acceptor sites compound it is excellent
Elect galactomannans and cellulose ether as.
In the embodiment that this is more highly preferred to, with the total amount of the compound with least two proton acceptor sites
On the basis of, the content of the galactomannans can be 10-70 weight %, be preferably 15-65 weight %, more preferably 25-
60 weight %；The content of the cellulose ether can be 30-90 weight %, be preferably 35-85 weight %, more preferably 40-75
Weight %.
Composition according to the present invention also contains ZSM-22 type molecular sieves.The ZSM-22 types molecular sieve can be Hydrogen
ZSM-22 molecular sieves (that is, H-ZSM-22 molecular sieves), Hydrogen ZSM-22 molecular sieves (such as La-H-ZSM-22, Ce-H- containing rare earth
ZSM-22, Pr-H-ZSM-22, Pm-H-ZSM-22, Sm-H-ZSM-22, Eu-H-ZSM-22), the Hydrogen of alkaline including earth metal element
ZSM-22 molecular sieves (such as 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) one or both of more than.
The silica alumina ratio (that is, the molar ratio of silica/alumina) of the ZSM-22 molecular sieves can be according to the aqua oxidation
The specifically used occasion of aluminium composition makes choice.In one embodiment, the silica alumina ratio of ZSM-22 molecular sieves can be 10-
200, it is preferably 30-150, is more preferably 40-100, such as 50-90.Combined according to the hydrated alumina of the preferred embodiment
Formed body prepared by thing, is particularly suitable as the carrier of hydroisomerisation catalysts.
The content of ZSM-22 types molecular sieve can be selected according to the concrete application occasion of said composition in the composition
Select.In a preferred embodiment, on the basis of the total amount of the composition after roasting, the content of ZSM-22 type molecular sieves can
Think 0.5-90 weight %, be preferably 5-88 weight %, more preferably 15-86 weight %, more preferably 30-85 weights
% is measured, is still more preferably 40-85 weight %；The content of aluminium oxide can be 10-99.5 weight %, be preferably 12-95 weights
%, more preferably 14-85 weight %, more preferably 15-70 weight % are measured, is still more preferably 15-60 weight %, institute
State roasting to carry out at a temperature of 600 DEG C, when the duration of the roasting is 3 small.According to the group of the preferred embodiment
Carrier of the compound particularly suitable for making hydroisomerisation catalysts.
Composition according to the present inventionIt is worth for less than 5, is preferably less than 4.5, more preferably less than 4, further preferably
For less than 3.5.Value can be more than 1.2, be preferably more than 1.3, more preferably more than 1.4, more preferably more than 1.5.
In an example, composition according to the present inventionValue can be 1.2-5, be preferably 1.2-4.5, more preferably 1.3-4,
More preferably 1.4-3.5, such as 1.5-3.5.
In the present invention,Value is measured using following methods：By composition described in 10g in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
Composition according to the present invention, the content of the compound with least two proton acceptor sites is can make institute
State compositionValue meets subject to above-mentioned requirements.Preferably, it is described to have extremely relative to hydrated alumina described in 100 parts by weight
The content of the compound in few two proton acceptor sites can be 1-25 parts by weight, be preferably 2-22 parts by weight, more preferably 3-
20 parts by weight.
Composition according to the present invention, can contain peptizing agent, can not also contain peptizing agent.The peptizing agent can be
The usually used reagent with gelatification of aluminium oxide formed body preparing technical field, its instantiation can include but unlimited
In Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.
Composition according to the present invention, the compound with least two proton acceptor sites, particularly described
It is described when compound with least two proton acceptor sites is containing polymer with least two proton acceptor sites
The compound with least two proton acceptor sites can play physics peptization, so as to reduce the use of peptizing agent
Amount, it might even be possible to without using peptizing agent.
In a kind of preferred embodiment of the present invention, relative to 100 parts by weight hydrated aluminas, the peptizing agent
Content is more preferably below 2 parts by weight below 5 parts by weight, to be preferably below 3 parts by weight.
In a kind of particularly preferred embodiment of the present invention, composition according to the present invention does not contain peptizing agent.Root
According to the composition of the particularly preferred embodiment, when being used to prepare formed body, even if the hydrated alumina formed body of preparation
Without roasting, aluminium oxide formed body is transformed into, can also be used as adsorbent or carrier to use, because unfired water
When conjunction aluminium oxide formed body contains peptizing agent, peptizing agent is being adsorbed and dissolved in dipping process, a large amount of to be lost in so that formed body goes out
Now dissolving, dusting and duct are caved in phenomenon, finally lose shape, thus adsorbent and carrier can not be used as to use.
According to the second aspect of the invention, should the present invention provides a kind of preparation method of hydrated alumina composition
Method includes mixing each component in a kind of feedstock composition, obtains the hydrated alumina composition, that is, is mixed to get
Mixture is the hydrated alumina composition.
The preparation method of hydrated alumina composition according to the present invention, it is wet that the raw mixture contains hydrated alumina
Gel, ZSM-22 types molecular sieve and the compound with least two proton acceptor sites.It is described that there are at least two protons
The compound and its species of acceptor site and the ZSM-22 types molecular sieve and its species have been carried out detailed above
Description, details are not described herein again.
The hydrated alumina wet gel can use conventional method to synthesize, for example with the precipitation method (including acid system and alkali
Method), Hydrolyze method, kind one or both of point-score and rapid dehydration method more than method be made.Usually by hydrated alumina
After gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from.
The precipitation method include acid system and alkaline process.The acid system is that aluminium salt is carried out precipitation reaction with alkali compounds.Institute
It is that aluminate is carried out precipitation reaction with acid compound to state alkaline process.In the precipitation method, the mixture that precipitation reaction obtains is optional
After ground carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, the solid phase isolated is washed, obtains the hydration
Aluminium oxide wet gel.
The aluminium salt and the species of the aluminate can be conventional selection.The instantiation of the aluminium salt can include but
It is not limited to more than one or both of aluminum sulfate, aluminium chloride, aluminum nitrate.The instantiation of the aluminate can be included but not
It is limited to more than one or both of sodium metaaluminate, potassium metaaluminate.
The alkali compounds and the acid compound can be conventional selection.The alkali compounds can be common
It is various can make water in alkalescence compounds, ammonium hydroxide, hydroxide and basic salt can be selected from.The hydroxide can be normal
The water soluble hydroxide seen, such as alkali metal hydroxide.The basic salt can be that common decomposition in water make it that water is in
The salt of alkalescence, such as meta-aluminate, carbonate and bicarbonate.The instantiation of the alkali compounds can include but is not limited to
Ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, sodium carbonate, carbonic acid
It is more than one or both of hydrogen potassium and potassium carbonate.The acid compound can be the common various changes that can make water in acidity
Compound, can be inorganic acid and/or organic acid.The instantiation of the acid compound can include but is not limited to sulfuric acid, salt
It is more than one or both of acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid.The carbonic acid can be by leading
Enter carbon dioxide and generation in situ.
The precipitation reaction can carry out under normal conditions, this is not particularly limited in the present invention.Usually, the alkali
The dosage of the property compound either acid compound causes the pH of the aluminum salt solution or the aluminate solution to be 6-10,
Preferably 7-9.The precipitation reaction can carry out at a temperature of 30-90 DEG C, preferably 40-80 DEG C.
The method of hydrated alumina wet gel is prepared using Hydrolyze method to be included：Aluminum contained compound is hydrolyzed instead
Should, after the mixture that hydrolysis is obtained alternatively carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, will be isolated
Solid phase washed, so as to obtain the hydrated alumina wet gel.
The aluminum contained compound can prepare the calorize that contains usually used in alumina hydrate gel technique for Hydrolyze method and close
Thing.The aluminum contained compound is preferably the organo-aluminum compound that hydrolysis can occur, more preferably aluminium alcoholates.It is described to contain calorize
The instantiation of compound can include but is not limited to aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and different
It is more than one or both of octanol aluminium.
The present invention is not particularly limited for the actual conditions of hydrolysis, can carry out under normal conditions.Usually,
The hydrolysis can be 3-11 in pH, be carried out under conditions of preferably 6-10.The hydrolysis can 30-90 DEG C,
It is preferred that carried out at a temperature of 40-80 DEG C.
In the precipitation method and Hydrolyze method, the condition of the aging is not particularly limited, and can carry out under normal conditions.One
As, the aging can carry out at a temperature of 35-98 DEG C, preferably 40-80 DEG C.The duration of the aging can be
When 0.2-6 is small.
The method of hydrated alumina wet gel is prepared using kind of point-score to be included：Added into supersaturated aluminate solution
Crystal seed, decomposes and produces aluminium hydroxide, and the mixture that decomposition is obtained carries out separation of solid and liquid, and the solid phase isolated is washed,
So as to obtain the hydrated alumina wet gel.
The instantiation of the aluminate can include but is not limited to one or both of sodium metaaluminate, potassium metaaluminate with
On.The degree of supersaturation of the aluminate solution can be conventional selection.
The method of hydrated alumina wet gel is prepared using rapid dehydration method to be included：By hydrated alumina in 600-
Roasted at a temperature of 950 DEG C, preferably 650-800 DEG C, product of roasting carries out hydro-thermal process, the mixing that hydro-thermal process is obtained
Thing carries out separation of solid and liquid, so as to obtain hydrated alumina wet gel.When the duration of the roasting can be 1-6 small, preferably
For 2-4 it is small when.The hydro-thermal process can carry out at a temperature of 120-200 DEG C, preferably 140-160 DEG C.The hydro-thermal process
Usually in closed container, carried out under self-generated pressure.
The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method in, the separation of solid and liquid can use conventional method into
OK, it is specifically as follows the combination of filtering, centrifugation or both.
The preparation method of hydrated alumina composition according to the present invention, the i values of the hydrated alumina wet gel is not
Less than 50%, 55% is preferably not lower than, more preferably not less than 60%, more preferably not less than 62%.The hydration
The i values of aluminium oxide wet gel are preferably not higher than 95%, more preferably not above 90%, more preferably not higher than 85%,
Still more preferably it is not higher than 82%.In one embodiment, the i values of the hydrated alumina wet gel are 50-95%,
Preferably 55-90%, more preferably 60-85%, more preferably 62-82%.The embodiment system being more highly preferred to according to this
For standby composition when for being molded, the formed body of acquisition has the intensity of higher.
Can be by the way that separation of solid and liquid bar during separation of solid and liquid be carried out containing alumina hydrate gel solution to being prepared
Part is controlled, so as to obtain the hydrated alumina wet gel that i values meet above-mentioned requirements.In one embodiment of the present invention
In, separation of solid and liquid is more than once or twice, at least last time separation of solid and liquid is pressure filtration and/or vacuum filter.At this
In embodiment, by adjusting the pressure of application and/or the size of vacuum, carried out to obtaining hydrated alumina wet gel i values
Control.The instantiation for the device that the pressure filtration uses can include but be not limited to plate and frame type filter-press, belt type filter
The combination of machine or both.In order to control the i values of the hydrated alumina wet gel of acquisition, natural wind or with pressure can also be used
Wind purges isolated solid phase, so as to improve the efficiency of moisture abjection.The pressure of the wind with pressure can be conventional
Selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.
The preparation method of hydrated alumina composition according to the present invention, the hydrated alumina wet gel that separation of solid and liquid obtains
It is general not live through the dehydration that its i value is reduced to less than 50% (being preferably less than 55%, more preferably less than 60%).
The preparation method of hydrated alumina composition according to the present invention, it is described that there are at least two proton acceptor sites
The dosage of compound enables to the hydrated alumina composition finally preparedIt is worth for less than 5, is preferably less than 4.5, it is more excellent
Elect less than 4 as, more preferably less than 3.5.The dosage of the compound with least two proton acceptor sites is preferred
So that the hydrated alumina composition finally preparedIt is worth for more than 1.2.The change with least two proton acceptor sites
The dosage of compound more preferably causes the hydrated alumina composition finally preparedIt is worth for more than 1.3, more preferably more than 1.4,
More preferably more than 1.5.Usually, it is described that there are at least two matter relative to 100 parts by weight hydrated alumina wet gels
The dosage of the compound of sub- acceptor site can be 1-25 parts by weight, be preferably 2-22 parts by weight, more preferably 3-20 parts by weight,
The hydrated alumina wet gel is in terms of hydrated alumina.
The preparation method of hydrated alumina composition according to the present invention, the raw mixture can contain peptizing agent,
Peptizing agent can not also be contained.Preferably, relative to 100 parts by weight hydrated alumina wet gels, the content of the peptizing agent is 5
Below parts by weight, it is preferably that more preferably below 2 parts by weight, the hydrated alumina wet gel is to be hydrated oxygen below 3 parts by weight
Change aluminium meter.It is highly preferred that the raw mixture does not contain peptizing agent.That is, hydrated alumina composition according to the present invention
Not the step of preparation method more preferably does not include adding peptizing agent into the raw mixture.
The preparation method of hydrated alumina composition according to the present invention, can use conventional method that hydrated alumina is wet
Gel is mixed with ZSM-22 types molecular sieve with the compound with least two proton acceptor sites.It can be incited somebody to action under shear action
Hydrated alumina wet gel is mixed with ZSM-22 types molecular sieve with the compound with least two proton acceptor sites.In one kind
In embodiment, the mode of the mixing is stirring.By hydrated alumina wet gel and ZSM-22 types molecular sieve and can have
Three is uniformly mixed by the compound at least two proton acceptor sites in the container with agitating device by stirring, from
And obtain hydrated alumina composition according to the present invention.The stirring can carry out in the container with agitating device,
It can be carried out in beater.In another embodiment, the mode of the mixing is kneading.Can be wet by hydrated alumina
Gel is mediated with ZSM-22 types molecular sieve with the compound with least two proton acceptor sites in kneader, so that
Obtain hydrated alumina composition according to the present invention.The type of the kneader is not particularly limited.Water according to the present invention
The preparation method of alumina composition is closed, stirring and hybrid combining can be used, by hydrated alumina wet gel with having
The compound mixing at least two proton acceptor sites.At this time, preferably first it is stirred, then is mediated.
The preparation method of hydrated alumina composition according to the present invention, can use various order by merging by the ZSM-
22 type molecular sieves, the compound with least two proton acceptor sites and the mixing of hydrated alumina wet gel.
In one embodiment, ZSM-22 type molecules can be mixed during hydrated alumina wet gel is prepared
ZSM-22 type molecular sieves, can also be added in the hydrated alumina wet gel being prepared by sieve, can also be hydrated preparing
Mixing portion ZSM-22 type molecular sieves during aluminium oxide wet gel, remainder ZSM-22 type molecular sieves, which are added to, to be prepared into
To hydrated alumina wet gel in, mixing ZSM-22 type molecular sieves operation can be in one of above-mentioned addition opportunity, two
Carried out in person or three., can be heavy when mixing ZSM-22 type molecular sieves during preparing hydrated alumina wet gel
One of shallow lake reaction process, ageing process, separation of solid and liquid process and washing process, both, carry out in three or four
Mix the operation of ZSM-22 type molecular sieves.It can be chosen whether preparing hydrated alumina wet gel according to the type of precipitation reaction
During mix ZSM-22 types molecular sieve and mixing opportunity so that the structure of ZSM-22 type molecular sieves will not or
Substantially subject to will not being destroyed, such as：It is excellent when adding ZSM-22 type molecular sieves during preparing hydrated alumina wet gel
It is non-strong basicity to be selected in preparation condition, if pH value is less than 10.Preferably, mixing ZSM-22 types are carried out in separation of solid and liquid process
The operation of molecular sieve.
In another embodiment, ZSM-22 type molecular sieves are mixed after the completion of the preparation of hydrated alumina wet gel.
In the embodiment, first ZSM-22 types molecular sieve can be mixed with hydrated alumina wet gel, then mixing has at least two
The compound in a proton acceptor site；Can also be first by compound and hydrated alumina with least two proton acceptor sites
Wet gel mixes, and then mixes ZSM-22 type molecular sieves；By ZSM-22 types molecular sieve and there can also be at least two matter at the same time
The compound of sub- acceptor site is mixed with hydrated alumina wet gel.
The preparation method of hydrated alumina composition according to the present invention, in mixed process, can supplement addition water,
Addition water can not be supplemented, as long as can be so that in the hydrated alumina composition preparedValue meets above-mentioned requirements.Generally
Ground, in the angle from the uniformity for improving mixing, can supplement addition water in mixed process.Usually, supplement addition
Water and the weight ratio of compound with least two proton acceptor sites can be 5-15：1.
According to the third aspect of the present invention, the present invention provides a kind of method system as described in second aspect of the present invention
Standby hydrated alumina composition.
Hydrated alumina composition according to the present invention can use conventional method to be molded, so as to obtain hydration oxygen
Change alumina supporter or alumina support.
According to the fourth aspect of the present invention, the present invention provides a kind of hydrated alumina formed body, the hydrated alumina
Formed body is as the hydrated alumina composition described in the first aspect of the present invention or the hydration described in third aspect of the present invention
Alumina composition is formed.
Hydrated alumina composition according to the present invention can be molded, obtained molding is dried, from
And obtain hydrated alumina formed body according to the present invention.
The molding mode is not particularly limited, and can use various molding modes commonly used in the art, such as：Squeeze
Bar, spraying, round as a ball, tabletting or combinations thereof.The present invention a kind of preferred embodiment in, by way of extrusion come
Shaping.
The temperature that the molding is dried can be the conventional selection of this area.Usually, the temperature of the drying
Degree can be preferably 65-300 DEG C for 60 DEG C less than 350 DEG C, more preferably 70-250 DEG C.The drying it is lasting when
Between can be made appropriate choice according to dry temperature, so as to so that volatilizing in the hydrated alumina formed body finally obtained
Point content meets subject to requirement.Usually, it is preferably 2-24 small when the duration of the drying can be 1-48 small
When, when more preferably 2-12 is small, when more preferably 2-6 is small.The drying can be in oxygen-containing atmosphere (such as air atmosphere)
Carry out, can also be carried out in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed), preferably in oxygen-containing atmosphere
Carry out.
Hydrated alumina formed body according to the present invention, can be had according to specifically used requirement it is variously-shaped, such as：Ball
Shape, bar shaped, annular, cloverleaf pattern, honeycombed, bird-nest-shaped, cylinder, Rasching ring or butterfly.
Hydrated alumina formed body according to the present invention has abundant pore structure, and pore-size distribution is adjustable.
In one embodiment, measured by mercury injection method, the pore-size distribution of hydrated alumina formed body is in bimodal distribution.Its
In, most probable pore size be respectively 4-20nm (be preferably 5-15nm, more preferably 6-10nm) and more than 20nm (such as 20.5-35nm,
Preferably 21-30nm, more preferably 21-25nm).
In another embodiment, measured by mercury injection method, the aperture of hydrated alumina formed body is in Unimodal Distribution.Its
In, most probable pore size 4-25nm, is preferably 5-20nm, more preferably 6-10nm.
Hydrated alumina formed body according to the present invention, the hydrated alumina formed body have higher intensity.Usually,
The radial direction crushing strength of hydrated alumina formed body according to the present invention is more than 15N/mm, is preferably 18N/ such as 15-40N/mm
More than mm, such as 18-35N/mm.In the present invention, crushed using the radial direction of method measure formed body specified in RIPP 25-90 strong
Degree.
According to the fifth aspect of the present invention, should the present invention provides a kind of preparation method of hydrated alumina formed body
Method is included the hydrated alumina composition described in the first aspect of the present invention or the water described in third aspect of the present invention
Close alumina composition to be molded, obtained molding is dried, so as to obtain the hydrated alumina formed body.
The shaping and the 4th aspect of dry method and condition and the present invention are described identical, are no longer described in detail herein.
In one embodiment of the invention, the hydrated alumina compositionIt is worth for not less than 1.8, such as can
Think 1.8-5.Preferably, the hydrated alumina compositionIt is worth for not less than 1.85, such as can is 1.85-4.It is more excellent
Selection of land, the hydrated alumina compositionIt is worth for not less than 1.9, such as can is 1.9-3.5.Measured by mercury injection method, according to
The aperture of hydrated alumina formed body prepared by the embodiment is in bimodal distribution.Most probable pore size be respectively 4-20nm (preferably
For 5-15nm, more preferably 6-10nm) and (such as 20.5-35nm, is preferably 21-30nm, more preferably 21- more than 20nm
25nm)。
In another embodiment of the invention, the hydrated alumina compositionIt is worth for less than 1.8, such as can
1.2 are thought to less than 1.8.Preferably, the hydrated alumina compositionIt is worth for not higher than 1.75 (as being not higher than 1.7), example
It such as can be 1.3-1.75, be preferably 1.5-1.7.Measured by mercury injection method, according to the embodiment prepare hydrated alumina into
The aperture of type body is in Unimodal Distribution.Most probable pore size is 4-25nm, is preferably 5-20nm, more preferably 6-10nm.
According to the sixth aspect of the invention, the present invention provides a kind of method system as described in the 5th aspect of the present invention
Standby hydrated alumina formed body.
The hydrated alumina formed body prepared by the method for the present invention has higher intensity.Usually, by the present invention's
The radial direction crushing strength of hydrated alumina formed body prepared by method is more than 15N/mm, is preferably 18N/mm such as 15-40N/mm
More than, such as 18-35N/mm.
According to the seventh aspect of the present invention, the present invention provides a kind of aluminium oxide formed body, the aluminium oxide formed body by
The hydrated alumina group described in hydrated alumina composition or third aspect of the present invention described in the first aspect of the present invention
Compound is formed.
Hydrated alumina composition according to the present invention can be molded, obtained molding is successively dried
And roasting, so as to obtain the aluminium oxide formed body.
The shaping and the 4th aspect of dry method and condition and the present invention are described identical, are no longer described in detail herein.
The present invention is not particularly limited for the condition of roasting, can be the conventional selection of this area.Specifically, the roasting
The temperature of burning can be 400-950 DEG C, be preferably 450-800 DEG C, more preferably 480-700 DEG C；The duration of the roasting
When can be 2-10 small, when being preferably 3-8 small.The roasting can carry out in oxygen-containing atmosphere, can also be in inert atmosphere
Carry out in (atmosphere that such as nitrogen and/or zero group gas are formed), carried out preferably in oxygen-containing atmosphere.
Aluminium oxide formed body according to the present invention, can be had according to specifically used requirement it is variously-shaped, such as：Spherical,
Bar shaped, annular, cloverleaf pattern, honeycombed, bird-nest-shaped, cylinder, Rasching ring or butterfly.
Aluminium oxide formed body according to the present invention has abundant pore structure, and pore-size distribution is adjustable.
In one embodiment, measured by mercury injection method, the pore-size distribution of aluminium oxide formed body is in bimodal distribution.Most probable
Aperture is respectively 4-20nm (being preferably 5-15nm, more preferably 6-10nm) and (such as 20.5-35nm, is preferably 21- more than 20nm
30nm, more preferably 21-25nm).
In another embodiment, measured by mercury injection method, the aperture of aluminium oxide formed body is in Unimodal Distribution.Most probable hole
Footpath is 4-20nm, is preferably 5-20nm, more preferably 6-10nm.
Aluminium oxide formed body according to the present invention, the aluminium oxide formed body have higher intensity.Usually, according to this hair
The radial direction crushing strength of bright aluminium oxide formed body is more than 15N/mm, is preferably more than 18N/mm, such as 18- such as 15-40N/mm
35N/mm。
According to the eighth aspect of the present invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method
Including by the hydrated alumina composition described in the first aspect of the present invention or the hydration oxygen described in third aspect of the present invention
Change aluminium composition to be molded, obtained molding is dried and roasted.
The shaping, dry and roasting method and the 7th aspect of condition and the present invention are described identical, no longer superfluous herein
State.
The preparation method of aluminium oxide formed body according to the present invention, can be by varying alumina compositionValue obtains
There must be the aluminium oxide formed body of different pore size distribution.
In one embodiment of the invention, the alumina compositionIt is worth for not less than 1.8, such as can is
1.8-5.Preferably, the hydrated alumina compositionIt is worth for not less than 1.85, such as can is 1.85-4.It is highly preferred that
The hydrated alumina compositionIt is worth for not less than 1.9, such as can is 1.9-3.5.Measured by mercury injection method, according to the reality
The aperture of aluminium oxide formed body prepared by the mode of applying is in bimodal distribution.Most probable pore size be respectively 4-20nm (be preferably 5-15nm,
More preferably 6-10nm) and more than 20nm (such as 20.5-35nm, is preferably 21-30nm, more preferably 21-25nm).
In another embodiment of the invention, the alumina compositionIt is worth for less than 1.8, such as can is
1.2 to less than 1.8.Preferably, the hydrated alumina compositionBe worth for not higher than 1.75 (as being not higher than 1.7), such as can
Think 1.3-1.75, be preferably 1.5-1.7.Measured by mercury injection method, the hole of the aluminium oxide formed body prepared according to the embodiment
Footpath is in Unimodal Distribution.Most probable pore size is 4-25nm, is preferably 5-20nm, more preferably 6-10nm.
According to the ninth aspect of the present invention, the present invention provides a kind of method system as described in the 8th aspect of the present invention
Standby aluminium oxide formed body.
The aluminium oxide formed body prepared by the method for the present invention has higher intensity.Usually, by the method for the present invention
The radial direction crushing strength of the aluminium oxide formed body of preparation is more than 15N/mm, is preferably more than 18N/mm, such as such as 15-40N/mm
18-35N/mm。
According to the tenth aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, such as Fig. 2
Shown in Fig. 3, this method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
Optionally (2), are handled the first hydrated alumina wet gel using (2-1) or (2-2),
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid
Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel；
(3) by hydrated alumina wet gel and there are at least two protons using the method described in second aspect of the present invention
The compound mixing of acceptor site, obtains hydrated alumina composition, and the hydrated alumina wet gel is the described first hydration
Aluminium oxide wet gel or the second hydrated alumina wet gel；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method be additionally included in one of step (1), step (2) and step (3), both or three into
The operation of row mixing ZSM-22 type molecular sieves, so that the hydrated alumina composition contains ZSM-22 type molecular sieves.This hair
In bright, " optional " expression " include or not comprising ", " including or not including ".
Forming method is produced according to the present invention, in second aspect of method and the present invention for mixing ZSM-22 type molecular sieves
The method is identical with order, is no longer described in detail herein.
In step (1), the alumina hydrate gel solution refers to alumina hydrate gel synthetic reaction obtains, process
Or the solution containing alumina hydrate gel without aging.The alumina hydrate gel solution can be prepared in situ
Alumina hydrate gel solution that is obtaining or coming from the transport of other production scenes.Preferably, the aqua oxidation
Alumina gel solution is the alumina hydrate gel solution being prepared in situ.The synthetic method and condition of alumina hydrate gel exist
Have been carried out being described in detail above, details are not described herein again.
Since the alumina hydrate gel solution that synthetic reaction obtains has an acid-base property, to hydrated alumina in step (1)
Wet gel is washed, and to remove acidic materials or alkaline matter therein, avoids the presence pair of acidic materials and alkaline matter
The adverse effect that alumina hydrate gel produces, while improve the solid content of alumina hydrate gel solution.Described in step (1)
Washing can carry out under normal conditions, as long as can be by the acidic materials and the amount of alkaline matter in alumina hydrate gel solution
Satisfaction is reduced to usually require that.
In step (1), separation of solid and liquid is directed in washing process, washings are extruded, obtain the first aqua oxidation
Aluminium wet gel.The i values of the first hydrated alumina wet gel can be meet the present invention second aspect described in with
The i values of the hydrated alumina wet gel of the compound mixing at least two proton acceptor sites, or higher than of the invention the
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in two aspects.
In one embodiment, the i values of the first hydrated alumina wet gel meet second aspect institute of the present invention
The i values for the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites stated, i.e., described first
The i values of hydrated alumina wet gel are not less than 50%, 55% are preferably not lower than, more preferably not less than 60%.In the reality
To apply in mode, the i values of the first hydrated alumina wet gel are preferably not higher than 95%, more preferably not above 90%, into
One step is preferably not higher than 85%, still more preferably for not higher than 82%.In an example, first hydrated alumina
The i values of wet gel are 50-95%, are preferably 55-90%, more preferably 60-85%, more preferably 62-82%.
According to the embodiment, the first hydrated alumina wet gel can be sent directly into step (3), and with extremely
The compound mixing in few two proton acceptor sites.This is especially suitable for meeting occasion claimed below：(A) in wash mill
Solid-liquid separating equipment has preferable separating capacity, it is sufficient to which the i values control of the first hydrated alumina wet gel is above-mentioned to meet
Scope；(B) wash mill compact can be set with mixing arrangement so that the discharging of wash mill can be directly entered mixing dress
Put.
According to the embodiment, the first hydrated alumina wet gel can also be sent into step (2), using (2-1)
Handled.This is especially suitable for meeting occasion claimed below：(A) solid-liquid separating equipment in wash mill has preferable
Separating capacity, it is sufficient to control the i values of the first hydrated alumina wet gel to meet above range；(B) wash mill is with mixing
Device compact can not be set, so that the discharging of wash mill can not be directly entered mixing arrangement.
In another embodiment, the i values of the first hydrated alumina wet gel are more than 95%, can not meet the present invention
The requirement mixed with the compound with least two proton acceptor sites described in second aspect.According to the embodiment,
The first hydrated alumina wet gel is sent into step (2), is handled using (2-1) or (2-2).The embodiment
Separating capacity or operating condition especially suitable for the solid-liquid separating equipment in wash mill are not enough to the first aqua oxidation
The i values of aluminium wet gel control to be filled for the occasion and wash mill of the requirement described in second aspect of the satisfaction present invention with mixing
Put can not compact setting occasion.
In step (2), the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains second
Hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water, slurries is formed, can so improve aqua oxidation
Aluminium wet gel transports performance.In (2-1), the additive amount of water, which is subject to the slurries to be formed, can meet to transport requirement, Ke Yigen
Made choice according to specific conveying equipment.
The i values for the second hydrated alumina wet gel that step (2) obtains meet described in second aspect of the present invention
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites, i.e., described aqua oxidation
The i values of aluminium wet gel are not less than 50%, are preferably not lower than 55%, more preferably not less than 60%, more preferably not
Less than 62%.The i values of the second hydrated alumina wet gel are preferably not higher than 95%, more preferably not above 90%, into
One step is preferably not higher than 85%, still more preferably for not higher than 82%.In one embodiment, the second hydration oxygen
The i values for changing aluminium wet gel are 50-95%, are preferably 55-90%, more preferably 60-85%, more preferably 62-82%.Can
Meet that the second hydrated alumina of above-mentioned requirements is wet with the condition by separation of solid and liquid described in rate-determining steps (2) to obtain i values
Gel.The method of the i values of hydrated alumina wet gel has been adjusted by selecting solid-liquid separating method and its condition above
It is described in detail, is no longer described in detail herein.
As shown in Figures 2 and 3, at least part ZSM-22 type molecular sieves can be mixed in step (2).For using (2-1)
When the mode carries out, as shown in Figures 2 and 3, ZSM-22 types can be mixed in dilution operation and/or separation of solid and liquid operation
Molecular sieve.
In step (3), using the method described in second aspect of the present invention by the first hydrated alumina wet gel or the
Two hydrated alumina wet gels are mixed with the compound with least two proton acceptor sites, so as to obtain hydrated alumina group
Compound.The i values of the first hydrated alumina wet gel and the second hydrated alumina wet gel of being sent into step (3) meet of the invention the
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in two aspects.
, can be according to expected hydrated alumina formed body or the pore-size distribution of aluminium oxide formed body, really in step (3)
Determine hydrated alumina compositionValue, this is the 8th in the method described in the 5th according to the present invention aspect and according to the present invention
It is illustrated in method described in a aspect, is no longer described in detail herein.
In step (4), the hydrated alumina composition that step (3) obtains is molded, obtains hydrated alumina shaping
Thing.The shape of the molding method and molding is referred to retouch on molding correlation in the first aspect of the present invention
State, details are not described herein again.
In step (5), the hydrated alumina forming matter that step (3) obtains is dried, obtains hydrated alumina shaping
Body.Hydrated alumina forming matter is dried to obtain the drying condition of hydrated alumina formed body, in the 5th side of the invention
Have been carried out being described in detail in method described in face, details are not described herein again.
According to the type of expected formed body, step (6) can be carried out, step (6) can not also be carried out.Carrying out step
(6) when, the whole hydrated alumina formed bodys that can obtain step (5) are sent into step (6), are roasted；It can also incite somebody to action
The partially hydrated aluminium oxide formed body that step (5) obtains is sent into step (6), can so prepare hydrated alumina shaping at the same time
Body and aluminium oxide formed body.The condition of the roasting has been carried out detailed in the method described in the 8th aspect of the present invention
Illustrate, details are not described herein again.
According to the eleventh aspect of the present invention, the present invention provides a kind of method as described in the tenth aspect of the present invention
The hydrated alumina formed body or aluminium oxide formed body of preparation.
Had as hydrated alumina formed body and aluminium oxide formed body prepared by the method described in the tenth aspect of the present invention
Higher intensity.Usually, the radial direction crushing strength of hydrated alumina formed body and aluminium oxide formed body can be each 15N/
More than mm, is preferably more than 18N/mm, such as 18-35N/mm such as 15-40N/mm.
Formation system can be produced in a kind of hydrated alumina according to the tenth aspect of the present invention to carry out, production shaping
System includes alumina hydrate gel production unit, separation of solid and liquid and washing unit, mixed cell, forming unit, drying unit
And optional roasting unit,
The alumina hydrate gel solution output port of the alumina hydrate gel production unit and the separation of solid and liquid
And the washing material input port to be separated of washing unit is connected, the solid-phase material output of the separation of solid and liquid and washing unit
Port is connected with the solid-phase material input port of the mixed cell, the mixed material output port of mixed cell with it is described into
The raw material input port of type unit is connected, the material to be dried input port of the drying unit and the forming unit into
Type thing output port is connected, and the dried material of the material input port to be roasted and the drying unit of the roasting unit is defeated
Exit port is connected.
The alumina hydrate gel production unit is used to generate alumina hydrate gel solution by synthetic reaction.Synthesis
The method of alumina hydrate gel can be conventional method, the precipitation method as previously described, Hydrolyze method, kind point-score and quick de-
Water law, is not described in detail herein.The alumina hydrate gel production unit can use conventional reactor to be synthesized
Reaction, so as to obtain alumina hydrate gel solution, this is not particularly limited in the present invention.
The separation of solid and liquid and washing unit are used for the aqua oxidation for exporting the alumina hydrate gel production unit
Alumina gel aqueous solution carries out separation of solid and liquid and washing, obtains hydrated alumina wet gel, the hydrated alumina wet gelValue
Meet the requirement that can be mixed with the compound with least two proton acceptor sites described in second aspect of the present invention.
The separation of solid and liquid and washing unit can use common various methods to carry out separation of solid and liquid and washing, so that
ArriveValue meets to mix desired alumina hydrate gel with the compound with least two proton acceptor sites.The solid-liquid
Separation and washing unit can use conventional equipment for separating liquid from solid, such as：The group of filtration apparatus, centrifugal device or both
Close.When separation of solid and liquid and washing unit include filtration apparatus, the filtration apparatus can be gravity filter device, pressurize
Filter one or more kinds of combinations in device and vacuum apparatus.Preferably, the filtration apparatus, which includes at least, adds
Press filtering device and/or vacuum apparatus.The instantiation of the pressure filter can include but be not limited to sheet frame
The combination of formula filter press, band filter or both.In order to control the hydrated alumina wet gel of acquisitionValue, it is described solid
Liquid separates and washing unit can also include blow device, and isolated solid phase is carried out using natural wind or wind with pressure
Purging, so as to improve the efficiency of moisture abjection.The pressure of the wind with pressure can be conventional selection, generally can be 0.1-
12MPa, is preferably 0.5-10MPa.
The separation of solid and liquid and washing unit can include one or more separation of solid and liquid subelement, preferably at least one
A separation of solid and liquid subelement and last separation of solid and liquid subelement are pressure filter and/or vacuum apparatus, so that
Obtain the solid-phase material (that is, hydrated alumina wet gel) that separation of solid and liquid and washing unit obtainValue can meet of the invention the
The requirement mixed with the compound with least two proton acceptor sites described in two aspects.By adjusting the pressure of application
Or the size of vacuum, can be to the hydrated alumina wet gel finally obtainedValue is adjusted.The separation of solid and liquid
And washing unit is when including two or more separation of solid and liquid subelement, except last separation of solid and liquid subelement is preferably used to press
Outside power is as the solid-liquid separation method of motive force, remaining separation of solid and liquid subelement can use pressure filter and/or true
Empty filtration apparatus, can not also use pressure filter and vacuum apparatus, it is preferred to use pressure filter and/or true
Empty filtration apparatus.
The separation of solid and liquid and washing unit can use conventional wash mill to wash the solid phase isolated.
It is for instance possible to use washings are sprayed to the solid phase surface isolated by spray equipment.In order to improve washing effect and washing
Efficiency, shearing and/or vibration can be applied to solid phase during the spray or after the completion of spray, by shower water with it is solid
Mix uniformly, the shearing is for example stirred.
For the trend of alumina hydrate gel material flow, separation of solid and liquid and washing unit are arranged on hydrated alumina
Between gel production unit and mixed cell, the gel solution for alumina hydrate gel production unit to be exported is divided
From obtainingValue meets the hydrated alumina wet gel that mixing requires, and raw material is provided for mixed cell.
On the premise of the alumina hydrate gel met the requirements being provided for mixed cell, from the conveying easy to material
Angle is set out, and in a preferred embodiment, the separation of solid and liquid and washing unit can include washing subelement, dilute
Monk unit, conveying subelement and the second separation of solid and liquid subelement,
The washing subelement is used for the alumina hydrate gel for collecting the alumina hydrate gel production unit output
Solid phase in solution is simultaneously washed；
The dilution subelement is used to the solid phase of the washing subelement output being diluted with water, obtains slurries；
The conveying subelement is used to the slurries of the dilution subelement output being sent into the second separation of solid and liquid subelement；
The second separation of solid and liquid subelement is used to the slurries carrying out separation of solid and liquid, and it is wet solidifying to obtain hydrated alumina
Glue.
The conveying subelement can use conventional various conveying devices, such as conveyer belt.The conveying subelement and institute
Stating washing subelement can integrate, such as integrate in one apparatus, so as to be washed during conveying, carry
High efficiency.Such as：Using the conveyer belt with solid-liquid separation function, while spray is set above the solid-phase material of conveyer belt
Shower device, so as to be washed during transporting and separation of solid and liquid.
The mixed cell includes the assistant feeding device that auxiliary agent is added into hydrated alumina wet gel, in the production system
During system operation, the assistant feeding device adds at least into hydrated alumina wet gel has at least two proton acceptor sites
Compound.The mixed cell can use conventional mixing arrangement, such as common various mixers, kneader or two
The combination of person.
The forming unit can use conventional molding machine, such as：Extrusion device, spraying device, circle rolling device, pressure
Sheet devices or two or more combinations.The drying unit can use conventional drying device, and the present invention is to this without spy
Do not limit.This is also not particularly limited in the conventional calciner that the roasting unit can use, the present invention.
Production formation system according to the present invention, on the basis of the flow direction of alumina hydrate gel, the production formation system
The solid-phase material of separation of solid and liquid and washing unit discharge port to mixed cell hydrated alumina wet gel input port it
Between be not provided with being enough the i values of hydrated alumina wet gel are reduced to less than 50% (preferably less than 55%, more preferably 60% with
Under) dewatering unit.
In the actual production process, mixing can be added on the basis of existing alumina hydrate gel process units
Unit, forming unit, drying unit and roasting unit, production and molding integration so as to fulfill alumina hydrate gel.
According to the twelfth aspect of the present invention, the present invention provides hydrated alumina formed body according to the present invention or
Application of the aluminium oxide formed body as carrier or adsorbent.
Hydrated alumina formed body and aluminium oxide formed body according to the present invention are particularly suitable as loaded catalyst
Carrier.The loaded catalyst can be it is commonly used in the art it is various can be with hydrated alumina formed body and/or aluminium oxide
Catalyst of the formed body as carrier.Preferably, the catalyst is hydroisomerisation catalysts.That is, water according to the present invention
Close aluminium oxide formed body and aluminium oxide formed body is particularly suitable as the carrier of hydroisomerisation catalysts.
Can use various methods commonly used in the art (such as：Dipping) it will be born with the active component that hydrogenation catalyst acts on
It is loaded on hydrated alumina formed body or aluminium oxide formed body according to the present invention, such as：Can be by using containing the activity
The formed body of the aqueous solution dipping present invention of component, then the formed body for being loaded with the active component is dried and can
The roasting of choosing, so as to obtain the catalyst.
13rd aspect according to the present invention, the present invention provides a kind of hydroisomerisation catalysts, which contains
There is the active ingredient of carrier and load on the carrier, wherein, carrier is the hydrated alumina formed body according to the present invention
And/or aluminium oxide formed body according to the present invention.
The active ingredient can be the common component to hydroisomerization with catalytic action.Usually, the work
Property component is selected from group VIII noble metals element.The group VIII noble metals element can be to be used as active ingredient using noble metal
The catalyst with hydroisomerization in common group VIII noble metals element, in ruthenium, osmium, palladium, platinum, rhodium and iridium
One or more.Preferably, the active ingredient is palladium and/or platinum.The active ingredient can be in the form of simple substance
It is supported on carrier, can also be supported in the form of compound on carrier.
The content of the active ingredient can be conventional selection.For example, on the basis of the total amount of catalyst, based on the element
The content of active ingredient can be 0.1-5 weight %, be preferably 0.2-2 weight %, more preferably 0.3-1 weight %.
14th aspect according to the present invention, the present invention provides a kind of preparation method of hydroisomerisation catalysts,
This method is included in supported on carriers active ingredient, wherein, this method is further included to be prepared using the previously described method of the present invention
The step of hydrated alumina formed body or aluminium oxide formed body as carrier.
The 13rd aspect of the species of the active ingredient and the present invention is described identical, and details are not described herein again.
Load capacity of the active ingredient on carrier can carry out appropriate choosing according to the concrete application occasion of catalyst
Select.For example, when the catalyst of preparation is used for the hydroisomerization of hydrocarbon ils, it is described on the basis of the total amount of the catalyst of preparation
The content of active ingredient disclosure satisfy that this hair in the catalyst that the load capacity of active ingredient on the carrier finally to prepare
Requirement described in bright 13rd aspect.
The preparation method of hydroisomerisation catalysts according to the present invention, can use various methods commonly used in the art will
Active ingredient loads on the carrier, such as：Dipping.The dipping can be that saturation impregnates, or excessive dipping.
The preparation method of hydroisomerisation catalysts according to the present invention, be able to will impregnate under conditions of commonly used in the art
Obtained carrier is dried and optionally roasts.Usually, the condition of the drying includes：Temperature can be 100-300
DEG C, it is preferably 100-280 DEG C；When duration can be 1-12 small, when being preferably 2-8 small.The condition of the roasting includes：Temperature
Degree can be 350-550 DEG C, be preferably 400-500 DEG C；When duration can be 1-10 small, when being preferably 2-8 small.
15th aspect according to the present invention, the present invention provides a kind of hydroisomerization process, this method is included in
Under hydroprocessing condition, hydrocarbon ils is contacted with hydroisomerisation catalysts, wherein, the hydroisomerisation catalysts are the present invention
Catalyst described in 13rd aspect or the catalyst as the method preparation described in the 14th aspect of the present invention.
The hydrocarbon ils can be the common various hydrocarbon ils for needing to carry out hydroisomerization processing, such as：It is hydrocracked tail
It is more than one or both of oil, distillate, solvent-refined oil, white oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.
Hydroisomerization process according to the present invention, the catalyst before the use, can be in the conventional strips of this area
Hydroisomerisation catalysts are activated under part, are such as reduced, the reduction can carry out outside reactor, can also be
Carried out in reactor.
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, the radial direction of the molding prepared using method measure specified in RIPP 25-90
Crushing strength.
In following embodiments and comparative example, measured using following methodsValue：By 10g hydrated aluminas composition at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
In following embodiments and comparative example, i values are measured using following methods：By 10g hydrated aluminas wet gel at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
In following embodiments and comparative example, the water absorption rate of the formed body prepared using following methods measure：By shaping to be measured
Then body is sieved with 40 the polished standard screens when 120 DEG C of dryings 4 are small, weighs 20g oversizes and (be denoted as sample to be tested
w3), sample to be tested 50g deionized waters are soaked 30 minutes, after filtering, solid phase are drained 5 minutes, what then weighing drained consolidates
The weight of phase (is denoted as w4), water absorption rate is calculated using formula III：
In following embodiments and comparative example, using U.S.'s Kang Ta companies Poremaster33 type mercury injection apparatuses, with reference to GB/T
Mercury injection method specified in 21650.1-2008 measures most probable pore size.
In following embodiments and comparative example, butt measures sample to be tested when 600 DEG C of roastings 4 are small, for roasting
Afterwards before the quality of sample and roasting the quality of sample ratio.
In following embodiments and comparative example, using the 3271 type x-ray fluorescence light of Japanese mechanics electric machine industry Co., Ltd.
Spectrometer, the composition of method measure catalyst with reference to specified in Petrochemical Engineering Analysis method RIPP133-90.
In following embodiments and comparative example, specific surface area and pore volume using multiple spot BET method commercially available from
The model of Quantachrome companiesSix stations automatically than being surveyed on surface and pore size distribution determining instrument
Examination.
Embodiment 1-11 is used to illustrate hydrated alumina composition, formed body of the present invention and preparation method thereof.
Embodiment 1
The hydrated alumina wet gel used in the present embodiment is that (sodium metaaluminate-aluminum sulfate method, is derived from Chinese stone by acid system
Change Chang Ling branch company) prepare alumina hydrate gel solution washed and be obtained by filtration boehmite wet cake (will
Wet cake numbering is SLB-1), after measured, the i values of the wet cake are 80.2%.
(1) 5.48kg H-ZSM-22 molecular sieves (Sinopec catalyst branch company is added into 50kg wet cakes SLB-1
Product, silica alumina ratio 50, butt 0.98), then add 10kg water and be mixed with beating 5 minutes, then by slurries belt type filter
Machine is filtered, and obtains 15.2kg wet cakes SLBZ-1.After measured, the i values of wet cake SLBZ-1 are 80.2%；By the wet filter
After cake SLBZ-1 is when 600 DEG C of roastings 3 are small, measure, the weight ratio of aluminium oxide and ZSM-22 type molecular sieves is 58：42.
(2) wet cake that 200g numberings are SLBZ-1 is placed in beaker, then adds 5g methylcellulose and (be purchased from Zhejiang
Hai Shen Chemical Co., Ltd.s, similarly hereinafter) and 3g sesbania powders (content of galactomannans is 80 weight %, is tried purchased from Beijing chemistry
Agent company), using mechanical agitator stirring after ten minutes, obtained mixture is hydrated alumina composition of the invention, its
Nature parameters are listed in table 1.
(3) the hydrated alumina composition for preparing step (2) is in F-26 types double screw extruder (section of South China Science ＆ Engineering University
On skill industry head factory system, similarly hereinafter) extrusion is carried out using the dish-shaped orifice plate of Ф 1.6mm.Wherein, extrusion process is smooth, extrudate table
Face Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
Hydrated alumina formed body HT-1 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 580 DEG C, air atmosphere 4 it is small when, obtain oxygen
Change aluminium formed body OT-1, its nature parameters is listed in table 1.
Comparative example 1
(1) wet cake that 100kg numberings are SLB-1 is spray-dried, obtains boehmite dry glue powder, the plan is thin
The butt of diaspore dry glue powder is 0.7.The boehmite powder (is placed in sealing in environment temperature (25-30 DEG C) and sealing condition
In polybag) under place 72 it is small when, do not detected after placement and form gibbsite.
(2) by boehmite dry glue powder prepared by 300g steps (1) and 162g ZSM-22 types molecular sieve (same to embodiments
1), 6.3g methylcellulose (with embodiment 1), 3.7g sesbania powders (with embodiment 1) and the 400mL (concentration of concentrated nitric acid containing 12mL
For 65 weight %) salpeter solution using mechanical agitator stir after ten minutes, obtain mixture.
(3) by step (2) prepare mixture on F-26 type double screw extruders using Ф 1.6mm dish-shaped orifice plate into
Row extrusion.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
Hydrated alumina formed body DHT-1 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 580 DEG C, air atmosphere 4 it is small when, obtain oxygen
Change aluminium formed body DOT-1, its nature parameters is listed in table 1.
Embodiment 2
(1) wet cake and 500g deionized waters that 5kg numberings are SLBZ-1 are mixed with beating 1 minute, then will obtained
Slurries are sent into plate and frame type filter-press, and the pressure of sheet frame is adjusted to 0.7MPa and is kept for 15 minutes, and obtaining wet cake, (numbering is
LBZ-1).After measured, the i values for the wet cake that numbering is LBZ-1 are 63%.
(2) wet cake that 300g numberings are LBZ-1 is placed in beaker, adds 4.3g hydroxyethylmethylcelluloses and (be purchased from
Shanghai Hui Guang Fine Chemical Co., Ltd, similarly hereinafter) and 1.7g sesbania powders (content of galactomannans is 85 weight %, is purchased from
Beijing chemical reagents corporation), using mechanical agitator stirring after ten minutes, the hydrated alumina composition of the present invention is obtained, its
Property is listed in table 1.
(3) the hydrated alumina composition for preparing step (2) utilizes Ф 2.0mm's on F-26 type double screw extruders
Circular orifice carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere,
Hydrated alumina formed body HT-2 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 480 DEG C, air atmosphere 8 it is small when, obtain oxygen
Change aluminium formed body OT-2, its nature parameters is listed in table 1.
Embodiment 3
Formed body is prepared using method same as Example 2, unlike, without using sesbania powder, hydroxyl second in step (2)
The dosage of ylmethyl cellulose is 5.7g, hydrated alumina composition, hydrated alumina formed body HT-3 and the oxidation of preparation
The property of aluminium formed body OT-3 is listed in table 1.
Embodiment 4
Formed body is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl in step (2)
Cellulose, the dosage of sesbania powder are 6.8g, hydrated alumina composition, hydrated alumina formed body HT-4 and the oxidation of preparation
The property of aluminium formed body OT-4 is listed in table 1.
Embodiment 5
Formed body is prepared using method same as Example 2, unlike, in step (2), in addition hydroxyethyl methyl
When cellulose and sesbania powder, 2.8g concentrated nitric acids (HNO is also added3Content be 65 weight %), the combination of the hydrated alumina of preparation
The property of thing, hydrated alumina formed body HT-5 and aluminium oxide formed body OT-5 is listed in table 1.
Comparative example 2
(1) by 300g numberings be LBZ-1 wet cake in 95 DEG C, air atmosphere it is dry 2 it is small when, obtain boehmite
Powder, the i values of the boehmite powder are 40%.The boehmite powder (is placed in environment temperature (25-30 DEG C) and sealing condition
In sealed plastic bag) under place 72 it is small when, do not detected after placement and form gibbsite.
(2) boehmite powder prepared by 185g steps (1) is placed in beaker, adds 4.3g hydroxyethylmethylcelluloses
(with embodiment 2) and 1.7g sesbania powders (with embodiment 2), using mechanical agitator stirring after ten minutes, obtain boehmite
Composition.
(3) boehmite combination of compositions thing prepared by step (2) is utilized into Ф on F-26 type double screw extruders
The circular orifice of 2.0mm carries out extrusion.Wherein, extruder Frequent trip during extrusion, extrudate surface are smooth.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere,
Hydrated alumina formed body DHT-2 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 480 DEG C, air atmosphere 8 it is small when, obtain oxygen
Change aluminium formed body DOT-2, its nature parameters is listed in table 1.
Comparative example 3
It is molded using the method identical with comparative example 2, unlike, without step (2), but by step (1)
The boehmite powder of preparation, which is sent directly into step (3), carries out extrusion.Wherein, extruder caloric value larger (performance during extrusion
It is hot for banded extruder fuselage, there are a large amount of hot gas to emerge), and extruder Frequent trip during extrusion, extrudate surface hairiness
Thorn.The hydrated alumina formed body being prepared is labeled as DHT-3, and the aluminium oxide formed body being prepared is labeled as DOT-3, its
Nature parameters are listed in table 1 respectively.
Comparative example 4
Hydrated alumina composition is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl
Cellulose and sesbania powder, but with 6.0g paraffin.As a result the hydrated alumina composition can not carry out extrusion molding.
Comparative example 5
Hydrated alumina composition is prepared using method same as Example 2, unlike, without using hydroxyethyl methyl
Cellulose and sesbania powder, but with 6.0g wood powders.As a result the hydrated alumina composition can not carry out extrusion molding.
Embodiment 6
(1) wet cake that 300g numberings are LBZ-1 is placed in beaker, adds 2.8g hydroxypropyl methyl celluloses and (be purchased from
Zhejiang Hai Shen Chemical Co., Ltd.s, similarly hereinafter) and 3.7g sesbania powders (content of galactomannans is 85 weight %), using machinery
Blender stirs the hydrated alumina composition for after ten minutes, obtaining the present invention, its property is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) is in SK132S/4 types single screw extrusion machine (U.S. BONNT
Company system) on using the orifice plate that the circular and middle cylinder with a 1.5mm for being Ф 4.5mm by overall diameter collectively constitutes into
Row extrusion.Wherein, extrusion process is smooth, extrudate (for Raschig ring) surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when drying 3 is small in 70 DEG C, air atmosphere by wet bar
Afterwards, when then drying 2 is small in 100 DEG C, air atmosphere, hydrated alumina formed body HT-6 is obtained, its nature parameters is in table 1
List.
(4) by step (4) prepare hydrated alumina formed body roasted in 650 DEG C, air atmosphere 3 it is small when, obtain oxygen
Change aluminium formed body OT-6, its nature parameters is listed in table 1.
Embodiment 7
(1) wet cake that 300g numberings are LBZ-1 is placed in beaker, adds 2.5g methylcellulose, 1.2g hydroxypropyls
Methylcellulose and 4g sesbania powders (content of galactomannans is 85 weight %), are stirred 10 minutes using mechanical agitator
Afterwards, the hydrated alumina composition of the present invention is obtained, its nature parameters is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 3.0mm's on F-26 type double screw extruders
Cloverleaf pattern orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 8mm, when by wet bar, drying 3 is small in 120 DEG C, air atmosphere,
Hydrated alumina formed body HT-7 is obtained, its nature parameters is listed in table 1.
(4) by step (4) prepare hydrated alumina formed body roasted in 600 DEG C, air atmosphere 4 it is small when, obtain oxygen
Change aluminium formed body OT-7, its nature parameters is listed in table 1.
Embodiment 8
(1) wet cake that 300g numberings are LBZ-1 is placed in beaker, adds 2.4g hydroxyethylmethylcelluloses and 1.8g
Hydroxypropyl methyl cellulose, using mechanical agitator stirring after ten minutes, obtains the hydrated alumina composition of the present invention, its property
Matter parameter is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 1.8mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 250 DEG C, air atmosphere,
Hydrated alumina formed body HT-8 is obtained, its nature parameters is listed in table 1.
(4) by step (4) prepare hydrated alumina formed body roasted in 650 DEG C, air atmosphere 3 it is small when, obtain oxygen
Change aluminium formed body OT-8, its nature parameters is listed in table 1.
Embodiment 9
Hydrated alumina composition, hydrated alumina formed body and aluminium oxide are prepared using method same as Example 2
Formed body, unlike, in step (1), the wet cake and 650g deionized waters, 30g Methyl celluloses that are SLBZ-1 by 5kg numberings
Element and 23g sesbania powders (content of galactomannans is 85 weight %) are mixed with beating 1 minute.
The property ginseng of the hydrated alumina composition of preparation, hydrated alumina formed body HT-9 and aluminium oxide formed body OT-9
Number is listed in table 1.
Embodiment 10
The hydrated alumina wet gel used in the present embodiment is by CO2Method (sodium aluminate-CO2Method, is derived from Shanxi Province Shan County
Emerging great catalyst new material Co., Ltd) the alumina hydrate gel solution thin water aluminium of plan that is washed and be obtained by filtration for preparing
Stone wet cake (being SLB-2 by wet cake numbering), after measured, the i values of the wet cake are 65.3%.
(1) (the Sinopec catalyst branch company production of 0.22kg H-ZSM-22 molecular sieves is added into 1kg wet cakes SLB-2
Product, silica alumina ratio 90, butt 0.98), then add 0.5kg water be mixed with beating 10 minutes, by slurries band filter into
Row filtering, obtains 1.12kg wet cakes SLBZ-2.After measured, the i values of wet cake SLBZ-2 are 68.6%；By the wet cake
After SLBZ-2 is when 600 DEG C of roastings 3 are small, the weight ratio of measure aluminium oxide and ZSM-22 type molecular sieves is 55：45.
(2) wet cake that 1.12kg numberings are SLBZ-2 is placed in beaker, then adds 16g methylcellulose and 20g
Sesbania powder (content of galactomannans is 80 weight %), using mechanical agitator stirring after ten minutes, obtained mixture
For the hydrated alumina composition of the present invention, its nature parameters is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion, and extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 130 DEG C, air atmosphere,
Hydrated alumina formed body HT-10 is obtained, its nature parameters is listed in table 1.
(4) by step (3) prepare hydrated alumina formed body roasted in 550 DEG C, air atmosphere 3 it is small when, obtain oxygen
Change aluminium formed body OT-10, its nature parameters is listed in table 1.
Comparative example 6
(1) wet cake that 100kg numberings are SLB-2 is spray-dried, obtains boehmite dry glue powder, the plan is thin
The butt of diaspore dry glue powder is 0.7.The boehmite powder (is placed in sealing in environment temperature (25-30 DEG C) and sealing condition
In polybag) under place 72 it is small when, do not detected after placement and form gibbsite.
(2) by boehmite dry glue powder prepared by 300g steps (1) and 175g H-ZSM-22 molecular sieve (same to embodiments
10), 4.4g methylcellulose (with embodiment 10), 5.6g sesbania powders (with embodiment 10) and 400mL concentrated nitric acids containing 12mL
The salpeter solution of (concentration is 65 weight %) is stirred after ten minutes using mechanical agitator, obtains mixture.
(3) by step (2) prepare mixture on F-26 type double screw extruders using Ф 1.6mm dish-shaped orifice plate into
Row extrusion.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 130 DEG C, air atmosphere,
Hydrated alumina formed body DHT-4 is obtained, its nature parameters is listed in table 1.
(5) by step (4) prepare hydrated alumina formed body roasted in 580 DEG C, air atmosphere 4 it is small when, obtain oxygen
Change aluminium formed body DOT-4, its nature parameters is listed in table 1.
Embodiment 11
The hydrated alumina wet gel used in the present embodiment is derived from the neat cyclopentadienyl catalyst Co., Ltd of Shandong Zibo, be by
Boehmite dry powder (butt is 70 weight %) prepared by 1000g acid systems (sodium aluminate-aluminum sulfate method) is in 700 DEG C, air gas
When roasting 3 is small in atmosphere, 700g aluminium oxide is obtained, 700g aluminium oxide is placed in 10L autoclaves, stirred with 5L deionized waters
After uniformly, autoclave is sealed, 6h is reacted under 150 DEG C, self-generated pressure, after reaction, by the temperature of autoclave
After being down to room temperature (for 25 DEG C), the slurries that reaction is obtained are sent into plate and frame type filter-press, by the sheet frame pressure of plate and frame filter
Power is adjusted to 0.5MPa and is kept for 10 minutes, and the filter cake 3 minutes in sheet frame, sheet frame pressure release are then swept with the wind with pressure of 10MPa
Obtain hydrated alumina wet cake LB-3.After measured, the thing of the wet cake is mutually boehmite, and the i values of the wet cake are
63.0%.
(1) (the Sinopec catalyst branch company production of 1.68kg H-ZSM-22 molecular sieves is added into 825g wet cakes LB-3
Product, silica alumina ratio 80, butt 0.75), then add 0.5kg water and be mixed with beating 10 minutes, then by slurries belt type filter
Machine is filtered, and obtains 1.12kg wet cakes SLBZ-3.After measured, the i values of wet cake SLBZ-3 are 65.3%；By the wet filter
After cake SLBZ-3 is when 600 DEG C of roastings 3 are small, the weight ratio of measure aluminium oxide and ZSM-22 type molecular sieves is 15：85.
(2) wet cake that 300g numberings are SLBZ-3 is placed in beaker, then adds 3.2g methylcellulose and 5g fields
Cyanines powder (content of galactomannans is 85 weight %), using mechanical agitator stirring after ten minutes, obtained mixture is
The hydrated alumina composition of the present invention, its nature parameters are listed in table 1.
(3) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, when by wet bar, drying 2 is small in 150 DEG C, air atmosphere,
Hydrated alumina formed body HT-11 is obtained, its nature parameters is listed in table 1.
(5) by step (3) prepare hydrated alumina formed body roasted in 590 DEG C, air atmosphere 4 it is small when, obtain oxygen
Change aluminium formed body OT-11, its nature parameters is listed in table 1.
Comparative example 7
Hydrated alumina wet cake LB-3 prepared by embodiment 11 is spray-dried, obtains boehmite dry glue powder
(butt 0.7).The boehmite dry glue powder is in environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag)
It is lower place 72 it is small when, do not detected after placement and form gibbsite.
By 300g step boehmite dry glue powders and 1587g H-ZSM-22 molecular sieves (with embodiment 11), 3.9g methyl
(concentration is 65 weights for cellulose (with embodiment 11), 6.1g sesbania powders (with embodiment 11) and 400mL concentrated nitric acids containing 12mL
Measure %) salpeter solution using mechanical agitator stir after ten minutes, obtain mixture.The mixture of preparation is used and implementation
After the identical method extrusion of example 11, hydrated alumina formed body DHT-5 and aluminium oxide formed body DOT-5, its property are prepared respectively
Parameter is listed in table 1.
Comparative example 8
Wet cake SLBZ-3 prepared by the method identical with 11 step of embodiment (1) will be used to use and 11 step of embodiment
(3) extruded with (4) identical method, as a result can not carry out extrusion molding.
Embodiment 1-11's as a result, it was confirmed that the present invention by hydrated alumina wet gel without being dried to dry glue powder, but directly
Connect and mixed with the compound with least two proton acceptor sites, obtained mixture is used directly for being molded, and obtains
Formed body there is higher intensity, so as to avoid it is existing prepare formed body using dry glue powder as starting material when existing work
The problem of industry bad environments and high energy consumption.Also, hydrated alumina composition according to the present invention by adjustingValue can be to system
The pore-size distribution of standby formed body is adjusted, and respectively obtains aperture in Unimodal Distribution or the formed body of bimodal distribution.
EXPERIMENTAL EXAMPLE 1-11 is used to illustrate hydroisomerisation catalysts according to the present invention and preparation method thereof.
EXPERIMENTAL EXAMPLE 1
(1) at a temperature of 25 DEG C, with four ammonia platinum solution of 127mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-1 prepared by embodiment 1, when dip time is 1 small.Obtained mixture will be impregnated in 120 DEG C dry 2
Hour, then when 150 DEG C of dryings 3 are small, catalyst OC-1 is obtained, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, using the hydration oxygen of the preparation of embodiment 1
Change aluminium formed body HT-1 to replace.The catalyst being prepared is denoted as HC-1, its composition is listed in table 2.
Experimental comparison's example 1
(1) catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, aluminium oxide formed body is contrast
Aluminium oxide formed body DOT-1 prepared by example 1.The catalyst being prepared is denoted as DOC-1, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with 1 step of EXPERIMENTAL EXAMPLE (2), unlike, using comparative example 1
The hydrated alumina formed body of preparation, as a result in dipping process formed body structural breakdown, preformed catalyst can not be obtained.
EXPERIMENTAL EXAMPLE 2
(1) it is real with four ammonia platinum solution of 86mL dichloros (mass content of Pt is 0.5%) dipping 100g at a temperature of 25 DEG C
The aluminium oxide formed body OT-2 of the preparation of example 2 is applied, when dip time is 1 small.It is small in 120 DEG C of dryings 2 by obtained mixture is impregnated
When, then when 150 DEG C of dryings 3 are small, catalyst OC-2 is obtained, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with step (1), unlike, using the hydration oxygen of the preparation of embodiment 2
Change aluminium formed body HT-2 to replace.The catalyst being prepared is denoted as HC-2, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 3
(1) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (1), unlike, aluminium oxide formed body
The aluminium oxide formed body OT-3 prepared for embodiment 3.The catalyst of preparation is denoted as OC-3, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (2), unlike, using embodiment 3
The hydrated alumina formed body HT-3 of preparation.The catalyst of preparation is denoted as HC-3, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 4
(1) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (1), unlike, aluminium oxide formed body
The aluminium oxide formed body OT-4 prepared for embodiment 4.The catalyst of preparation is denoted as OC-4, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (2), unlike, hydrated alumina into
Type body is hydrated alumina formed body HT-4 prepared by embodiment 4.The catalyst of preparation is denoted as HC-4, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 5
(1) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (1), unlike, aluminium oxide formed body
The aluminium oxide formed body OT-5 prepared for embodiment 5.The catalyst of preparation is denoted as OC-5, its composition is listed in table 2.
(2) catalyst is prepared using the method identical with 2 step of EXPERIMENTAL EXAMPLE (2), unlike, using embodiment 5
The hydrated alumina formed body of preparation, as a result in dipping process formed body structural breakdown, preformed catalyst can not be obtained.
EXPERIMENTAL EXAMPLE 6
At a temperature of 25 DEG C, implemented with four ammonia platinum solution of 83mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-6 prepared by example 6, when dip time is 1 small.Obtained mixture will be impregnated when 120 DEG C of dryings 2 are small,
Then when 150 DEG C of dryings 3 are small, catalyst OC-6 is obtained, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 7
At a temperature of 25 DEG C, implemented with four ammonia platinum solution of 93mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-7 prepared by example 7, when dip time is 1 small.Obtained mixture will be impregnated when 120 DEG C of dryings 2 are small,
Then when 150 DEG C of dryings 3 are small, catalyst OC-7 is obtained, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 8
At a temperature of 25 DEG C, implemented with four ammonia platinum solution of 86mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-8 prepared by example 8, when dip time is 1 small.Obtained mixture will be impregnated when 120 DEG C of dryings 2 are small,
Then when 150 DEG C of dryings 3 are small, catalyst OC-8 is obtained, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 9
At a temperature of 25 DEG C, implemented with four ammonia platinum solution of 93mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-9 prepared by example 9, when dip time is 1 small.Obtained mixture will be impregnated when 120 DEG C of dryings 2 are small,
Then when 150 DEG C of dryings 3 are small, catalyst OC-9 is obtained, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 10
At a temperature of 25 DEG C, implemented with four ammonia platinum solution of 38mL dichloros (mass content of Pt is 0.5%) dipping 100g
Aluminium oxide formed body OT-10 prepared by example 10, when dip time is 1 small.It is small in 120 DEG C of dryings 2 by obtained mixture is impregnated
When, then when 180 DEG C of dryings 2 are small, catalyst OC-10 is obtained, its composition is listed in table 2.
Experimental comparison's example 2
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 10, unlike, aluminium oxide formed body is comparative example 6
The aluminium oxide formed body of preparation.The catalyst being prepared is denoted as DOC-2, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 11
At a temperature of 25 DEG C, with four ammonia platinum solution of 38mL dichloros (mass content of Pt is 1%) dipping 100g embodiments
The 11 aluminium oxide formed body OT-11 prepared, when dip time is 1 small.Obtained mixture will be impregnated when 120 DEG C of dryings 2 are small,
Then when 150 DEG C of dryings 3 are small, finally when 350 DEG C roasting 2 is small in air atmosphere, catalyst OC-11 is obtained, it is formed
Listed in table 2.
Experimental comparison's example 3
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 11, unlike, aluminium oxide formed body is comparative example 7
The aluminium oxide formed body of preparation.The catalyst being prepared is denoted as DOC-3, its composition is listed in table 2.
Table 2
Testing example 1-11 is used to illustrate hydroisomerization process according to the present invention.
Testing example 1-11
Using the n-decane of 99 weight % of purity as raw material (analysis is pure), the evaluation experimental embodiment 1-11 in miniature fixed bed
The catalytic performance of the catalyst of preparation, wherein, the loadings of catalyst are 1.2 grams, and reaction condition is：330 DEG C of temperature, pressure
4.0MPa, feed space velocity 5h-1.Product gas-chromatography on-line analysis, calculates feed stock conversion and production according to the following formula respectively
Thing selectivity：
Feed stock conversion=the peak area ratio of n-decane (1- is unconverted) × 100%
Selectivity of product=(isoparaffin peak area ratio/(1- is unconverted n-decane peak area ratio)) × 100%
Experimental result is listed in table 3.
Test comparison example 1-3
Using the method identical with testing example 1-11 respectively to the catalytic of Experimental comparison's example 1-3 catalyst prepared
It can be evaluated, experimental result is listed in table 3.
Table 3
Testing example 1-11's as a result, it was confirmed that with hydrated alumina formed body according to the present invention and aluminium oxide formed body
The hydroisomerisation catalysts prepared as carrier, show the catalytic activity of higher in hygrogenating isomerization reaction.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (39)
1. a kind of hydrated alumina composition of the molecular sieve of type containing ZSM-22, said composition contain hydrated alumina, ZSM-22 types
Molecular sieve and the compound with least two proton acceptor sites,
The compositionIt is worth for less than 5, it is describedValue is measured using following methods：By composition described in 10g at 120 DEG C in sky
It is 240 minutes dry in gas atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
2. composition according to claim 1, wherein, it is describedIt is worth for less than 4.5, preferably less than 4, more preferably 3.5
Below；
It is it is highly preferred that describedBe worth for more than 1.2, be preferably more than 1.3, more preferably more than 1.4, more preferably 1.5 with
On；
It is it is further preferred that describedIt is worth for 1.2-5, preferably 1.3-4.5, more preferably 1.4-4, more preferably 1.5-
3.5。
3. composition according to claim 1 or 2, wherein, relative to hydrated alumina described in 100 parts by weight, the tool
The content for having the compound at least two proton acceptor sites is 1-25 parts by weight, is preferably 2-22 parts by weight, more preferably 3-
20 parts by weight.
4. according to the composition described in any one in claim 1-3, wherein, the hydrated alumina, which contains, intends thin water aluminium
Stone；
Preferably, the hydrated alumina is boehmite.
5. composition according to claim 4, wherein, the composition is placed 72 under environment temperature and sealing condition
Hour, the content of the gibbsite in composition after placement is higher than containing for the gibbsite in the composition before placing
Amount；
Preferably, on the basis of the content of the gibbsite in the composition before placement, three water in the composition after placement
Alumina content at least improves 0.5%；
It is highly preferred that on the basis of the content of the gibbsite in the composition before placement, three in composition after placement
The content of water aluminium oxide at least improves 1%, preferably improves 1.1-1.5%.
6. according to the composition described in any one in claim 1-5, wherein, the hydrated alumina is directed to hydration
Aluminium oxide wet gel.
7. according to the composition described in any one in claim 1-6, wherein, using the total amount of the composition after roasting as base
Standard, the content of ZSM-22 type molecular sieves is 0.5-90 weight %, is preferably 5-88 weight %, more preferably 15-86 weight %, into
One step is preferably 30-85 weight %, and the content of aluminium oxide is 10-99.5 weight %, is preferably 12-95 weight %, more preferably
14-85 weight %, more preferably 15-70 weight %, the roasting are carried out at a temperature of 600 DEG C, and the roasting is held
When the continuous time is 3 small.
8. according to the composition described in any one in claim 1-7, wherein, the composition is free of peptizing agent.
9. a kind of preparation method of the hydrated alumina composition of the molecular sieve of type containing ZSM-22, this method is included a kind of raw material group
Each component mixing in compound, obtains the hydrated alumina composition, it is wet solidifying that the feedstock composition contains hydrated alumina
Glue, ZSM-22 types molecular sieve and the compound with least two proton acceptor sites, the i of the hydrated alumina wet gel
It is worth for not less than 50%, the dosage of the compound with least two proton acceptor sites is so that the composition finally prepared
'sIt is worth for less than 5,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
It is describedValue is measured using following methods：10g compositions are dried 240 minutes at 120 DEG C in air atmosphere, will be through dry
The quality of dry composition is denoted as w1, calculated using Formulas IValue,
10. according to the method described in claim 9, wherein, the use of the compound with least two proton acceptor sites
Amount causes the hydrated alumina composition preparedIt is worth for less than 4.5, preferably less than 4, more preferably less than 3.5；
Preferably, the dosage of the compound with least two proton acceptor sites causes the hydrated alumina combination prepared
ThingIt is worth for more than 1.2, preferably more than 1.3, more preferably more than 1.4, more preferably more than 1.5；
It is highly preferred that the dosage of the compound with least two proton acceptor sites causes the hydrated alumina group prepared
CompoundIt is worth for 1.2-5, preferably 1.3-4.5, more preferably 1.4-4, more preferably 1.5-3.5.
11. the method according to claim 9 or 10, wherein, the i values of the hydrated alumina wet gel be not higher than
95%, more preferably 50-95%, more preferably 55-90%, are still more preferably 60-85%, particularly preferably 62-
82%.
12. according to the method described in any one in claim 9-11, wherein, the hydrated alumina wet gel is not undergo
Make the hydrated alumina wet gel for the dehydration that its i value is less than 50%.
13. according to the method described in any one in claim 9-12, wherein, the hydrated alumina wet gel is by least
After a kind of alumina hydrate gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from；
Preferably, the alumina hydrate gel solution is using one kind in the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method
Or two or more methods is prepared.
14. according to the method described in any one in claim 9-13, wherein, the feedstock composition is free of peptizing agent.
15. according to the method described in any one in claim 9-14, wherein, ZSM-22 types molecule in the raw mixture
The content of sieve make it that on the basis of the total amount of the hydrated alumina composition after roasting the content of ZSM-22 type molecular sieves is 0.5-
90 weight %, are preferably 5-88 weight %, more preferably 15-86 weight %, more preferably 30-85 weight %, aluminium oxide
Content be 10-99.5 weight %, be preferably 12-95 weight %, more preferably 14-85 weight %, more preferably 15-70
Weight %, the roasting carry out at a temperature of 600 DEG C, when the duration of the roasting is 3 small.
16. according to the method described in any one in claim 9-15, wherein, the method for the mixing for stirring and/or is pinched
Close.
17. according to the method described in any one in claim 9-16, wherein, it is wet relative to 100 parts by weight hydrated aluminas
Gel, the dosage of the compound with least two proton acceptor sites is 1-25 parts by weight, is preferably 2-22 parts by weight,
More preferably 3-20 parts by weight, the hydrated alumina wet gel is in terms of hydrated alumina.
18. in the composition or claim 9-17 according to any one in claim 1-8 described in any one
Method, wherein, in the compound with least two proton acceptor sites, proton acceptor site is can form hydrogen bond with water
One or both of F, O and N more than；
Preferably, the compound with least two proton acceptor sites is the compound containing hydroxyl in molecular structure；
It is highly preferred that the compound with least two proton acceptor sites is polyhydroxy organic compound；
It is further preferred that the compound with least two proton acceptor sites is polysaccharide and/or the etherate of polysaccharide；
It is further preferred that the compound with least two proton acceptor sites is galactan, mannosan, half
More than one or both of newborn mannosan and cellulose ether, the cellulose ether is preferably methylcellulose, ethoxy fibre
It is more than one or both of dimension element and hydroxypropyl cellulose；
It is particularly preferred that the compound with least two proton acceptor sites is galactomannans and cellulose ether,
Preferably, on the basis of the total amount of the compound with least two proton acceptor sites, the galactomannans
Content is 10-70 weight %, is preferably 15-65 weight %, more preferably 25-60 weight %；The content of the cellulose ether is
30-90 weight %, are preferably 35-85 weight %, more preferably 40-75 weight %.
19. the aqua oxidation of the molecular sieve of type containing ZSM-22 prepared by a kind of method in 9-18 as claim described in any one
Aluminium composition.
20. a kind of hydrated alumina formed body, the hydrated alumina formed body is as described in any one in claim 1-8 and 18
Hydrated alumina composition or claim 19 described in hydrated alumina composition formed.
21. a kind of preparation method of hydrated alumina formed body, this method includes will be by any one in claim 1-8 and 18
Hydrated alumina composition described in the hydrated alumina composition or claim 19 is molded, will obtain into
Type thing is dried.
A kind of 22. hydrated alumina formed body prepared by method as described in claim 21.
23. a kind of aluminium oxide formed body, the aluminium oxide formed body is as the hydration oxygen described in any one in claim 1-8 and 18
Hydrated alumina composition described in change aluminium composition or claim 19 is formed.
24. a kind of preparation method of aluminium oxide formed body, this method includes will be as described in any one in claim 1-8 and 18
Hydrated alumina composition or claim 19 described in hydrated alumina composition be molded, the molding that will be obtained
It is dried and roasts.
A kind of 25. aluminium oxide formed body prepared by method as described in claim 24.
26. appoint in the hydrated alumina formed body, claim 23 and 25 according to any one in claim 20 and 22
Aluminium oxide formed body described in meaning one, wherein, the radial direction pressure of the hydrated alumina formed body and the aluminium oxide formed body
Broken intensity is respectively 15-40N/mm, is preferably 18-35N/mm.
27. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed and separation of solid and liquid,
The first hydrated alumina wet gel is obtained, the condition of the separation of solid and liquid causes the i values of the first hydrated alumina wet gel
Not less than 50%, to be preferably not lower than 55%, more preferably not less than 60%, more preferably not above 95%, it is further excellent
Elect as not higher than 90%, more preferably not higher than 85%, still more preferably for not higher than 82%；
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(2) use the method in claim 9-18 described in any one by the first hydrated alumina wet gel with having extremely
The compound mixing in few two proton acceptor sites, obtains hydrated alumina composition；
(3) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(4) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(5) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, this method is additionally included in the operation that mixing ZSM-22 type molecular sieves are carried out in step (1) and/or step (2), so that
Obtain the hydrated alumina composition and contain ZSM-22 type molecular sieves.
28. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the first water
Close aluminium oxide wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), it is wet obtains the second hydrated alumina
Gel,
(2-1) mixes the first hydrated alumina wet gel with water, forms slurries, and the slurries are carried out separation of solid and liquid,
Obtain the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are not low
In 50%, 55% is preferably not lower than, more preferably not less than 60%, is more preferably not above 95%, more preferably not
Higher than 90%, more preferably not higher than 85%, still more preferably for not higher than 82%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(3) use the method in claim 9-18 described in any one by the second hydrated alumina wet gel with having at least two
The compound mixing in a proton acceptor site, obtains hydrated alumina composition；
(4) the hydrated alumina composition is molded, obtains hydrated alumina forming matter；
(5) hydrated alumina forming matter is dried, obtains hydrated alumina formed body；
(6) alternatively, at least partly described hydrated alumina formed body is roasted, obtains aluminium oxide formed body；
Wherein, mixed in this method is additionally included in step (1), step (2) and step (3) one, two or three
The operation of ZSM-22 type molecular sieves is closed, so that the hydrated alumina composition contains ZSM-22 type molecular sieves.
29. the method according to claim 27 or 28, wherein, the separation of solid and liquid carries out one or more times, at least most
A separation of solid and liquid is pressure filtration and/or vacuum filter afterwards.
30. according to the method described in any one in claim 27-29, wherein, the alumina hydrate gel solution is warp
Cross aging or without aging by more than the precipitation method, Hydrolyze method, kind one or both of point-score and rapid dehydration method
Method is prepared.
31. formed body prepared by a kind of method in 27-30 as claim described in any one.
32. formed body according to claim 31, wherein, the radial direction crushing strength of the formed body is 15-40N/mm, preferably
For 18-35N/mm.
33. in the hydrated alumina formed body, claim 23,25 and 26 in claim 20,22 and 26 described in any one
Formed body in aluminium oxide formed body or claim 31 and 32 described in any one described in any one as carrier or
The application of person's adsorbent.
34. application according to claim 33, wherein, the carrier is the carrier of loaded catalyst, is preferably loaded
The carrier of type hydrogenation catalyst.
35. a kind of hydroisomerisation catalysts, which contains the active ingredient of carrier and load on the carrier, its
In, the carrier is the hydrated alumina formed body described in any one in claim 20,22 and 26, claim 23,25
With 26 in formed body in aluminium oxide formed body described in any one or claim 31 and 32 described in any one.
36. catalyst according to claim 35, wherein, the active ingredient is selected from group VIII noble metals element, excellent
Elect platinum and/or palladium as；
Preferably, on the basis of the total amount of the catalyst, the content of the active ingredient based on the element is 0.1-5 weights
% is measured, is preferably 0.2-2 weight %, more preferably 0.3-1 weight %.
37. a kind of preparation method of hydroisomerisation catalysts, this method are included in supported on carriers active ingredient, wherein, should
Method is further included using the method preparation described in any one in claim 21,24 and 27-30 as the formed body of carrier
Step.
38. the preparation method according to claim 37, wherein, the active ingredient is selected from group VIII noble metals element,
Preferably platinum and/or palladium；
Preferably, load capacity of the active ingredient on carrier causes, on the basis of the total amount of the catalyst finally prepared, with
The content of the active ingredient of element meter is 0.1-5 weight %, is preferably 0.2-2 weight %, more preferably 0.3-1 weights
Measure %.
39. a kind of hydroisomerization process, this method are included under the conditions of hydroisomerization, by hydrocarbon ils and hydroisomerization catalytic
Agent contacts, wherein, the hydroisomerisation catalysts are for the catalyst described in any one in claim 35-36 or by weighing
Profit requires catalyst prepared by the method in 37-38 described in any one.
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