CN108097201A - A kind of modified aluminas and preparation method thereof - Google Patents
A kind of modified aluminas and preparation method thereof Download PDFInfo
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- CN108097201A CN108097201A CN201611052885.5A CN201611052885A CN108097201A CN 108097201 A CN108097201 A CN 108097201A CN 201611052885 A CN201611052885 A CN 201611052885A CN 108097201 A CN108097201 A CN 108097201A
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- Prior art keywords
- aluminium oxide
- preparation
- accordance
- modified aluminas
- method described
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 363
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000019441 ethanol Nutrition 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 47
- 238000012545 processing Methods 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 32
- 239000003463 adsorbent Substances 0.000 abstract description 6
- 239000003643 water by type Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 16
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- -1 sulphur compound Chemical class 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004939 coking Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 101710083129 50S ribosomal protein L10, chloroplastic Proteins 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28—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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of modified aluminas and preparation method thereof, and the modified aluminas is gamma-alumina, and the surface area of modified aluminas is 100~500m2/ g, pore volume are 0.1~0.6cm3/g.Aluminium oxide with deionized water is mixed, stirred, is dry by the preparation method；It mixes, stir with ethyl alcohol again, is dry, then handling at a certain temperature；It mixes, stir with auxiliary agent, deionized water again, be then directly separated drying；Final high temperature handles to obtain modified aluminas product.Aluminium oxide provided by the invention have alkalescence can modulation feature, meet adsorbent and carrier to aluminium oxide Bu Tong alkalescence matter the needs of.
Description
Technical field
The present invention relates to a kind of aluminium oxide and preparation method thereof, particularly a kind of alkaline matter can modulation aluminium oxide and its system
Preparation Method.
Background technology
Aluminium oxide is a kind of industrial important porous material, is widely used as catalyst carrier and adsorbent etc..It is existing
In technology, prepared on aluminium oxide and modified technology is primarily directed to the acidity for improving aluminium oxide, adjust pore structure, Yi Jigai
Kind structural stability etc..Patent CN104588011A alkane dehydrogenating catalysts and preparation method thereof, using alcohols modification side
Method handles aluminium oxide.Detailed process is：Sn alumina supports heating vacuumize process will be contained, then add in alcohol under vacuum conditions
Class solvent recovers normal pressure, is heated to reflux handling.The patent describes, and alcohols solvent carries out surface to the alumina support for loading Sn
Modified, alcohol solvent molecules can preferentially occupy the adsorption potential of alumina carrier surface containing Sn, the anchor that active metal Pt can be oriented
Surely exposed Sn surfaces are arrived, Pt-Sn is made to generate synergistic effect, improves the selectivity of propylene and the activity stability of catalyst.Together
When modification can save dechlorination process, avoid the agglomeration of Pt particles；Catalyst surface acidity can be also reduced, inhibits carbon distribution,
Improve catalyst stability.
The drinking water adsorption-defluorination device and method of patent CN103693771A plural serial stages, discloses a kind of aluminium oxide
Method of modifying.Its method of modifying is by activated alumina filling device, with clear water filtration and washing filtrate, then uses bodied ferric sulfate
And/or ferric sulfate aqueous solution circulating filtration, then exhaust iron salt solutions；Then filtrate is rinsed with clear water, obtains modification with Fe suction
Attached dose.This method can improve the efficiency of fluorine removal.The inventor is " long run test of modified activated aluminum oxide adsorption-defluorination is ground
Study carefully "（Beijing University of Chemical Technology's journal (natural science edition), the third phases of volume 39 in 2012）, the modification theory of ferric sulfate is done and is understood
It releases, it is believed that Fe only forms unformed deposition on the surface of activated alumina, and modified activated alumina adsorbents surface particles become
Small, surface free energy increases, absorption property enhancing, promotes the surface precipitation of fluorine ion.
Patent CN102847541A Coal tar hydrodemetalization catalysts and preparation method thereof, disclose a kind of aluminium oxide
Method of modifying.Whole operation step is first to take or prepare alumina support；Aluminium oxide is handled with organic acid soln again, then uses nitre
The aluminium oxide of sour aluminum solutions dipping, finally dry, roasting obtain modified aluminium oxide supports；Then hydrogenation active component is loaded, is obtained
To Hydrodemetalation catalyst.The activity and activity stability of catalyst can be improved by modified method, delays catalysis
The service cycle of agent.
A kind of alumina modified method is disclosed in the method for purification of patent CN102850175B coking benzenes, method is to use
The ethanol solution that concentration is 50%~70% rinses activated alumina, and concentration is put into after dry at 110~150 DEG C as 0.5~1.0
It is handled in the aluminum sulfate solution of mol/L；It is multiple with pure water rinsing again；Finally drying roasting obtains the acidic oxidation of aluminum sulfate modification
Aluminium.When modified aluminium oxide purifies for coking benzene, it can preferably remove the sulphur compound in raw material coking benzene, nitrogenize
The impurity such as object, moisture, micro tar heavy constituent, solid residue improve the quality of coking benzene.
Patent CN1953806A prepares method and the use of active chromium/aluminium oxide catalyst by using sulfuric acid salt treatment
The polymer of the chromium/aluminium oxide catalyst production is directed to the modification technology of aluminium oxide.These patents are all with sulfuric acid salt treatment
Alumina support, the method are that sulfate with aluminium oxide effect is roasted or aoxidized with sulfuric acid salt treatment simultaneously with chromium again
Acted on again with chromium after aluminium roasting etc..And think that sulfate provides acidity for chromium, and cause aluminium oxide a small amount of or be not sintered.
A kind of alumina in high hydrothermal stability of patent CN100431964C and preparation method thereof, is related to aluminium oxide
Method of modifying.Its method is that phosphorous species such as ammonium phosphate, ammonium hydrogen phosphate or phosphoric acid are dissolved in deionized water, and aluminium oxide is impregnated
Modified ball-aluminium oxide is obtained in solution, then through drying and roasting.The invention introduces phosphate anion, makes itself and aluminium oxide
The hydroxyl reaction of hole wall reduces the quantity of hydroxyl, prevents the sintering and phase transformation in aluminium oxide duct, and it is steady to reach raising aluminium oxide hydro-thermal
Qualitatively purpose.
The catalyst that patent CN1063099C is used to prepare propylene glycol discloses a kind of method of modifying of aluminium oxide.It is described
Aluminium oxide is first carried out reaming modification by method with acid or alkali, then impregnates alkali metal fluoride.Wherein specific soda acid processing side
Method is acid or soda-dip processing aluminium oxide, is after cooling 7 with deionised water to pH value, then dries.Soda acid processing
Purpose expands the duct of aluminium oxide.
A kind of alumina supports of siliceous and titanium of patent CN1331605C and preparation method thereof, in the patent auxiliary agents of silicon be
It is introduced during aluminium hydroxide plastic, specific surface area, aperture and the pore volume that can be improved；Auxiliary agent titanium is after plastic, aging
Preceding addition, can greatly improve carrier surface acid amount and B acid amounts.This external application titanium modifies oxidation aluminium surface, weakens activity gold
Belong to the interaction with carrier, improve the dispersiveness of active metal.
A kind of production methods of modified aluminas of patent CN101069832.Its main method of modifying is with acetic acid and chlorination
Palladium handles aluminium hydroxide, and aluminium oxide is then made, and improves large specific surface area with this, increases the rate of filtration.
" modification of aluminium oxide and its application in directed preparing dimethyl ether by synthetic gas reaction "（Catalysis journal, 2006）With
Anion-modified γ-the Al of oxygen-containing acid group of boron, p and s2O3, for Dehydration of methanol, it is found that modified by sulfate radicle can be notable
Improve γ-Al2O3Methanol dehydration activity, boron modification then reduces methanol dehydration activity, and although P Modification improves dehydration anti-
The activity answered, but the amplitude very little improved.
In chemical engineering industry, aluminium oxide is used mainly as acid carrier or adsorbent.But actually aluminium oxide is a kind of
Soda acid amphoteric compound, compared to Acidity, alkalescence is weaker.So aluminium oxide is carried generally by some alkaline matters are loaded
Its high alkaline matter.Such as by KOH and K2CO3Alkaline matters is waited to load to Al2O3Surface, so that it may generate preferable basic sites；By alkali
The carbonate or acetate of the Cs of property loads to Al2O3Surface, pyrolytic can generate super base position.Patent CN103508864A
A kind of preparation method of 2- isopropyls -5- methyl -2- hexenoic aldehydes, the modified method for improving aluminium oxide alkalescence being related to.It is modified
Method is carrying alkali metal hydroxide or alkali carbonate using aluminium oxide as carrier.
A kind of Supported palladium catalysts of patent CN103691437A and preparation method thereof, the modified raising oxygen being related to
Change the method for aluminium alkalescence.Method of modifying is to add in aluminium oxide in lanthanum salt solution to impregnate, and is adsorbed and is done under vacuum
Dry, high-temperature calcination obtains modified catalyst carrier.Modification can inhibit Al during high-temperature process2O3The growth of crystal grain, enhancing
Carrier surface alkalescence, increases surface area, improves the Pd concentration of catalyst surface, reduces Pd layer thickness, so as to improve catalyst
Hydrogenation activity and selectivity.
In present chemical industry, aluminium oxide is a kind of very important industrial carrier and sorbing material.Although aluminium oxide
It prepares and is modified the significant progress having been achieved with, but increasingly harsh Green Chemistry and environmentally friendly chemistry urge aluminium oxide etc.
That changes material proposes higher requirement, this just needs to develop new aluminium oxide preparation and modification technology, to meet different answer
With demand and environmental requirement.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of modified aluminas and preparation method thereof.The method of the present invention
The modified aluminas being prepared be a kind of alkaline matter can modulation aluminium oxide, while there is alkalescent position and strong basicity position, make
Preparation Method is simple and practicable, low production cost.
The present invention provides a kind of modified aluminas, and the crystal structure of the modified aluminas is gama-alumina, modified oxidized
The surface area of aluminium is 100~500m2/ g, pore volume are 0.1~0.6cm3/ g, the modified aluminas have simultaneously strong basicity position and
Alkalescent position, the scope of the strong basicity position is 310~660 DEG C, and the scope of the alkalescent position is 80~300 DEG C, described to change
Property aluminium oxide alkalescent position alkali number reduce by 0.1~75% than the alkalescent position alkali number of alumina raw material；The modified aluminas
Strong basicity position alkali number increases by 0.1~7% than the strong basicity position alkali number of alumina raw material.
The present invention provides a kind of preparation method of above-mentioned modified aluminas, and the preparation method comprises the following steps：
（1）Aluminium oxide and deionized water are mixed and stirred for uniformly, then dry 10~20 h at 100~180 DEG C；
（2）By step（1）Obtained aluminium oxide is mixed and stirred for uniformly with ethyl alcohol, dry 10~20 h at 100~180 DEG C,
Then processing is 1~7 h at 200~320 DEG C；
（3）By step（2）Aluminium oxide, auxiliary agent, deionized water is obtained to be mixed and stirred for uniformly, being then directly separated by filtration drying；
（4）By step（3）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere, then obtains
Alumina product.
In the method for the present invention, step（1）Described in aluminium oxide for gama-alumina, the gama-alumina can be commercially available
Commodity or self-control.
In the method for the present invention, step（1）Described in aluminium oxide and deionized water mass ratio be 0.5~5：10, preferably
For 1~4：10.
In the method for the present invention, step（1）Described in drying temperature for 110~170 DEG C, drying time is 12~18h.
In the method for the present invention, step（2）Described in ethyl alcohol be absolute ethyl alcohol.
In the method for the present invention, step（2）Described in aluminium oxide and ethyl alcohol mass ratio be 0.5~5：10, it is preferably 1~4：
10。
In the method for the present invention, step（2）The drying temperature is 110~170 DEG C；Drying time is 12~18h.
In the method for the present invention, step（3）Described in auxiliary agent be frerrous chloride, one or both of titanium sulfate.
In the method for the present invention, step（3）Described in aluminium oxide, auxiliary agent, deionized water mass ratio be 1~30：0.05
~55：100, it is preferably 1.5~28：0.1~50：100.
In the method for the present invention, step（3）It is described to be directly separated as without washing or other solvent washing operations, directly
It is filtered separation.
In the method for the present invention, step（3）The drying temperature is 100~180 DEG C, preferably 110~170 DEG C；When dry
Between for 10~20 h, be preferably 12~18h.
In the method for the present invention, step（4）Described in treatment temperature be 450~600 DEG C, processing time be 2~10h.
Aluminium oxide alkalescence provided by the invention uses carbon dioxide temperature programmed desorption (CO2- TPD) method characterization, it is used
Instrument is the 2920 type chemical adsorption instruments of AutoChem of Merck ＆ Co., Inc of U.S. production.Embodiments process is：Sample is existed
300 DEG C of processing 1h in 30mL/min helium atmospheres；Then 70 DEG C are cooled to, in 30mL/min CO2-He（CO25%, He is accounted for account for
95%）2h is handled in atmosphere；Then in 30mL/min He atmosphere, 70 DEG C of processing 1h；Finally in the He atmosphere of 10mL/min,
The CO of sample is carried out with 10 DEG C/min rates2- TPD is characterized.The calculating of alkali number uses integrating peak areas method, with native aluminum oxide
Alkali number is 100%, passes through the alkali number of peak area comparing calculation aluminium oxide of the present invention.
Other physico-chemical properties of aluminium oxide provided by the invention are using other conventional characterizing method characterizations.
Aluminium oxide provided by the invention is alkaline adjustable alumina oxide, and the alkali of aluminium oxide can be adjusted according to actual demand
Property.Adsorbent and catalyst carrier are may be used as, meets the needs of adsorbent and carrier to the different alkaline matter of aluminium oxide.
Compared with existing alumina material, modified aluminas prepared by the method for the present invention have alkaline matter can modulation spy
Point.For preparation method of the present invention mainly using additive modification aluminium oxide, the auxiliary agent that is used in the present invention can accurately and high selection
Property have an effect with the basic sites of aluminium oxide, so as to play the effect for reducing aluminium oxide alkalescence；Without with the other work of aluminium oxide
Property position occur physically or chemically to act on, because of the crystal structure without change aluminium oxide, physico-chemical properties such as pore structure, therefore can be only
Alkaline matter is adjusted, does not change the other feature of aluminium oxide substantially.This puts, other technologies different from the modification technology of other aluminium oxide
It is that other other elements are introduced in aluminium oxide, has change to shape characteristic pore structure thermal property of aluminium oxide etc..The present invention
The preparation method of the aluminium oxide of offer, operating procedure is simple and practicable, raw materials used cheap and easy to get, and low production cost is easy to work
Industry metaplasia is produced.
Description of the drawings
Fig. 1 is the CO of sample and native oxide aluminum feedstock that embodiment 1 is prepared2- TPD spectrograms.
The CO of the sample that Fig. 2 positions embodiment 6 is prepared and native oxide aluminum feedstock2- TPD spectrograms.
Specific embodiment
The preparation method of aluminium oxide of the present invention is described in detail below by specific embodiment, but is not limited to
Embodiment.
Embodiment 1
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 20g frerrous chlorides, 100mL deionized waters, stirs 5h, then directly filter
It separates, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL1, the alkaline matter of gained sample are shown in Fig. 1, and other properties are shown in Table 1.It was found from Fig. 1 and table 1, the alkali of modified aluminium oxide
It measures as the 29.2% of native aluminum oxide, surface area 208m2/ g illustrates that the method for the present invention can effectively reduce the alkalescence of aluminium oxide,
And other properties of aluminium oxide are not changed substantially.
Embodiment 2
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
265 DEG C of processing 4h；
（3）By step（2）Aluminium oxide, 15g frerrous chlorides, the mixing of 90mL deionized waters are obtained, stirs 4h, then directly filtering point
From then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 5h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL2, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 3
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 8g frerrous chlorides, 100mL deionized waters, stirs 6h, then directly filter
It separates, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 450 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL3, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 4
（1）18g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
235 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 3.5g frerrous chlorides, 100mL deionized waters, stirs 8h, then direct mistake
Filter separates, then 150 DEG C of dry 15h；
（4）By step（3）600 DEG C of processing 6h of obtained substance, finally obtain modified aluminas.Gained sample number into spectrum CL4, gained
The physico-chemical property of sample is shown in Table 1.
Embodiment 5
（1）12g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）It obtains aluminium oxide to mix with 1.8g frerrous chlorides, 100mL deionized waters, stirs 7h, then direct mistake
Filter separates, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL5, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 6
（1）10g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 150 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 150 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）Obtain aluminium oxide and 7mL titanium sulfates（Mass content wt20%）, 100mL deionized waters mixing, stirring
Then 5h is directly separated by filtration, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL6, the alkaline matter of gained sample are shown in Fig. 2, and other properties are shown in Table 1.It was found from Fig. 2 and table 1, modified aluminium oxide it is weak
Alkali number is the 1.5% of native aluminum oxide, surface area 207m2/ g illustrates that the method for the present invention can effectively reduce the alkali of aluminium oxide
Property, and do not change other properties of aluminium oxide substantially.
Embodiment 7
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
265 DEG C of processing 4h；
（3）By step（2）Obtain aluminium oxide and 4mL titanium sulfates（Mass content wt20%）, 90mL deionized waters mixing, stir 4h,
Then directly it is separated by filtration, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 500 DEG C of processing 5h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL7, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 8
（1）10g aluminium oxide with 90mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 90mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）Obtain aluminium oxide and 2.5mL titanium sulfates（Mass content wt20%）, 100mL deionized waters mixing, stirring
Then 6h is directly separated by filtration, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 450 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL8, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 9
（1）18g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
235 DEG C of processing 4h；
（3）By step（2）Obtain aluminium oxide and 1mL titanium sulfates（Mass content wt20%）, 100mL deionized waters mixing, stirring
Then 8h is directly separated by filtration, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 600 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL9, the physico-chemical property of gained sample are shown in Table 1.
Embodiment 10
（1）12g aluminium oxide with 100mL deionized waters is mixed, stirs 30 min, then 140 DEG C of dry 15h；
（2）By step（1）It obtains aluminium oxide to mix with 100mL ethyl alcohol, stirs 30 min, then 140 DEG C of dry 15h, then exist
260 DEG C of processing 4h；
（3）By step（2）Obtain aluminium oxide and 0.8mL titanium sulfates（Mass content wt20%）, 100mL deionized waters mixing, stirring
Then 7h is directly separated by filtration, then 150 DEG C of dry 15h；
（4）By step（3）Obtained substance 550 DEG C of processing 6h in nitrogen atmosphere, finally obtain modified aluminas.Gained sample
Number CL10, the physico-chemical property of gained sample are shown in Table 1.
The property of the sample obtained by embodiment of table 1
| Sample ID | Crystalline phase | Alkalescent position alkali number, % | Strong basicity position alkali number, % | Surface area, m2/g |
| CL0 | Gama-alumina | 100 | 0 | 213 |
| CL1 | Gama-alumina | 29.2 | 4.9 | 208 |
| CL2 | Gama-alumina | 36.5 | 3.6 | 210 |
| CL3 | Gama-alumina | 51.8 | 2.0 | 211 |
| CL4 | Gama-alumina | 62.7 | 0.8 | 213 |
| CL5 | Gama-alumina | 70.6 | 0.6 | 213 |
| CL6 | Gama-alumina | 1.5 | 6.9 | 207 |
| CL7 | Gama-alumina | 2.0 | 6.5 | 208 |
| CL8 | Gama-alumina | 3.6 | 5.9 | 208 |
| CL9 | Gama-alumina | 31.5 | 2.3 | 213 |
| CL10 | Gama-alumina | 38.7 | 2.1 | 213 |
Note：CL0 is native aluminum oxide before modified in table 1, and the alkali number of sample is using the alkali number of CL0 as reference.
Claims (13)
1. a kind of modified aluminas, the crystal structure of the modified aluminas is gama-alumina, and the surface area of modified aluminas is
100~500m2/ g, pore volume are 0.1~0.6cm3/ g, the modified aluminas has strong basicity position and alkalescent position simultaneously, described
The scope of strong basicity position is 310~660 DEG C, and the scope of the alkalescent position is 80~300 DEG C, the weak base of the modified aluminas
Property position alkali number reduce by 0.1~75% than the alkalescent position alkali number of alumina raw material；The strong basicity position alkali number ratio of the modified aluminas
The strong basicity position alkali number of alumina raw material increases by 0.1~7%.
2. the preparation method of modified aluminas as described in claim 1, it is characterised in that：The preparation comprises the following steps：
（1）Aluminium oxide and deionized water are mixed and stirred for uniformly, then dry 10~20 h at 100~180 DEG C；
（2）By step（1）Obtained aluminium oxide is mixed and stirred for uniformly with ethyl alcohol, dry 10~20 h at 100~180 DEG C,
Then processing is 1~7 h at 200~320 DEG C；
（3）By step（2）Aluminium oxide, auxiliary agent, deionized water is obtained to be mixed and stirred for uniformly, being then directly separated by filtration drying；
（4）By step（3）Obtained substance 1~12 h of calcination process at 400~650 DEG C in a nitrogen atmosphere, then obtains
Alumina product.
3. preparation method described in accordance with the claim 2, it is characterised in that：Step（1）Described in aluminium oxide be gamma oxidation
Aluminium.
4. preparation method described in accordance with the claim 2, it is characterised in that：Step（1）Described in aluminium oxide and deionized water
Mass ratio be 0.5~5：10, it is preferably 1~4：10.
5. preparation method described in accordance with the claim 2, it is characterised in that：Step（1）Described in drying temperature for 110~
170 DEG C, drying time is 12~18h.
6. preparation method described in accordance with the claim 2, it is characterised in that：Step（2）Described in ethyl alcohol be absolute ethyl alcohol.
7. preparation method described in accordance with the claim 2, it is characterised in that：Step（2）Described in aluminium oxide and ethyl alcohol quality
Than for 0.5~5：10, it is preferably 1~4：10.
8. preparation method described in accordance with the claim 2, it is characterised in that：Step（2）The drying temperature is 110~170
℃；Drying time is 12~18h.
9. preparation method described in accordance with the claim 2, it is characterised in that：Step（3）Described in auxiliary agent for frerrous chloride, sulphur
One or both of sour titanium.
10. preparation method described in accordance with the claim 2, it is characterised in that：Step（3）Described in aluminium oxide, auxiliary agent, go from
The mass ratio of sub- water is 1~30：0.05~55：100, it is preferably 1.5~28：0.1~50：100.
11. preparation method described in accordance with the claim 2, it is characterised in that：Step（3）Described is directly separated as without water
It washes or other solvent washing operations, is directly filtered separation.
12. preparation method described in accordance with the claim 2, it is characterised in that：Step（3）The drying temperature is 100~180
DEG C, preferably 110~170 DEG C；Drying time is 10~20 h, is preferably 12~18h.
13. preparation method described in accordance with the claim 2, it is characterised in that：Step（4）Described in treatment temperature be 450~600
DEG C, processing time is 2~10h.
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