CN108097200B - Method for preparing modified alumina - Google Patents
Method for preparing modified alumina Download PDFInfo
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- CN108097200B CN108097200B CN201611052881.7A CN201611052881A CN108097200B CN 108097200 B CN108097200 B CN 108097200B CN 201611052881 A CN201611052881 A CN 201611052881A CN 108097200 B CN108097200 B CN 108097200B
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- alumina
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- deionized water
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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 226
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000001035 drying Methods 0.000 claims abstract description 85
- 238000002156 mixing Methods 0.000 claims abstract description 72
- 238000003756 stirring Methods 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000008367 deionised water Substances 0.000 claims abstract description 54
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 54
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 16
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000002715 modification method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 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
- 238000011068 loading method Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 230000008021 deposition Effects 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
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- IOLQAHFPDADCHJ-POHAHGRESA-N (e)-5-methyl-2-propan-2-ylhex-2-enal Chemical compound CC(C)C\C=C(\C=O)C(C)C IOLQAHFPDADCHJ-POHAHGRESA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- 101710083129 50S ribosomal protein L10, chloroplastic Proteins 0.000 description 1
- 101710114762 50S ribosomal protein L11, chloroplastic Proteins 0.000 description 1
- 101710082414 50S ribosomal protein L12, chloroplastic Proteins 0.000 description 1
- 101710164994 50S ribosomal protein L13, chloroplastic Proteins 0.000 description 1
- 101710177347 50S ribosomal protein L15, chloroplastic Proteins 0.000 description 1
- 101710125690 50S ribosomal protein L17, chloroplastic Proteins 0.000 description 1
- 101710149636 50S ribosomal protein L18, chloroplastic Proteins 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 101001075055 Spinacia oleracea 50S ribosomal protein L19, chloroplastic Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates 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
- 229910021502 aluminium hydroxide Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging 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
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 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
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 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
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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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
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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
- B01J20/28057—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
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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
- B01J20/28071—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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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
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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- B01J35/615—
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- B01J35/633—
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- B01J35/635—
Abstract
The invention discloses a method for preparing modified alumina, wherein the crystal structure of the modified alumina is gamma-alumina, and the surface area of the modified alumina is 100-500 m2A pore volume of 0.1 to 0.6cm3The preparation method comprises the steps of mixing, stirring and drying aluminum oxide and deionized water; mixing with ethanol, stirring, drying, and treating at certain temperature; then mixing with auxiliary agent and deionized water, stirring, directly filtering, separating and drying; finally, the modified alumina product is obtained by high-temperature treatment. The alumina provided by the invention has the characteristic of adjustable alkalinity, and meets the requirements of adsorbents and carriers on different alkaline properties of alumina.
Description
Technical Field
The invention relates to a preparation method of modified alumina, in particular to a preparation method of alumina with adjustable alkaline property.
Background
Alumina is an industrially important porous material and is widely used as a catalyst carrier, an adsorbent, and the like. In the prior art, the preparation and modification technology of alumina mainly aims at improving the acidity of alumina, adjusting the pore structure, improving the structural stability and the like. The patent CN104588011A alkane dehydrogenation catalyst and the preparation method thereof adopt an alcohol modification method to treat alumina. The specific process is as follows: heating and vacuumizing the Sn-containing alumina carrier, then adding an alcohol solvent in a vacuum state, recovering the normal pressure, and heating and refluxing the mixture. The patent describes that an alcohol solvent is used for carrying out surface modification on an alumina carrier loaded with Sn, molecules of the alcohol solvent can preferentially occupy adsorption sites on the surface of the alumina carrier containing Sn, and active metal Pt can be directionally anchored to the surface of exposed Sn, so that Pt-Sn generates a synergistic effect, and the selectivity of propylene and the activity stability of a catalyst are improved. Meanwhile, the modification can omit the dechlorination process and avoid the aggregation and growth of Pt particles; and the acidity of the surface of the catalyst can be reduced, carbon deposition can be inhibited, and the stability of the catalyst can be improved.
Patent CN103693771A multistage serial drinking water adsorption defluorination device and method, discloses a modification method of alumina. Filling active alumina into the device, filtering and washing the filter material by using clear water, circularly filtering by using polymeric ferric sulfate and/or ferric sulfate aqueous solution, and then discharging ferric salt solution; and then washing the filter material with clear water to obtain the ferric salt modified adsorbent. The method can improve the efficiency of fluorine removal. The inventor explains the modification principle of ferric sulfate in 'continuous experimental research on adsorption and fluorine removal of modified activated alumina' (journal university of chemical industry (Nature science), third phase 39 of 2012), and considers that Fe only forms amorphous deposition on the surface of activated alumina, and the modified activated alumina adsorbent has the advantages of reduced surface particles, increased surface free energy, enhanced adsorption performance and promotion of surface precipitation of fluorine ions.
Patent CN102847541A coal tar hydrodemetallization catalyst and preparation method thereof, discloses a modification method of alumina. The whole operation steps are that firstly, an alumina carrier is taken or prepared; treating alumina with organic acid solution, impregnating alumina with aluminum nitrate solution, drying and roasting to obtain modified alumina carrier; then loading a hydrogenation active component to obtain the hydrogenation demetalization catalyst. The activity and activity stability of the catalyst can be improved by the modification method, and the running period of the catalyst is delayed.
The patent CN102850175B discloses an alumina modification method in the purification method of coking benzene, which comprises the steps of flushing active alumina by using ethanol solution with the concentration of 50-70%, drying at 110-150 ℃, and then putting into aluminum sulfate solution with the concentration of 0.5-1.0 mol/L for treatment; washing with pure water for multiple times; and finally, drying and roasting to obtain the aluminum sulfate modified acidic alumina. When the modified alumina is used for purifying the coking benzene, impurities such as sulfur compounds, nitrides, moisture, trace tar heavy components, solid residues and the like in the raw material coking benzene can be well removed, and the quality of the coking benzene is improved.
Patent CN1953806A relates to a process for preparing active chromium/alumina catalysts by treatment with sulfate and polymers produced using the chromium/alumina catalysts, both to alumina modification technology. These patents all use sulfate to treat the alumina support by reacting the sulfate with chromium and then calcining it with alumina, or by treating the alumina with sulfate and then reacting it with chromium. And it is believed that the sulfate provides acidity to the chromium and causes little or no sintering of the alumina.
Patent CN100431964C discloses a spherical alumina with high hydrothermal stability and a preparation method thereof, relating to a modification method of alumina. The method comprises the steps of dissolving phosphorus-containing species such as ammonium phosphate, ammonium hydrogen phosphate or phosphoric acid in deionized water, soaking alumina in the solution, and drying and roasting to obtain the modified spherical alumina. The invention introduces phosphate ions to react with hydroxyl on the pore wall of alumina, reduces the number of hydroxyl, prevents sintering and phase change of alumina pore channels and achieves the aim of improving hydrothermal stability of alumina.
The patent CN1063099C for preparing propylene glycol ether discloses a modification method of alumina. The method comprises the steps of carrying out pore-expanding modification on alumina by using acid or alkali, and then soaking alkali metal fluoride. The specific acid-base treatment method comprises the steps of dipping alumina in acid or alkali liquor, cooling, washing with deionized water until the pH value is 7, and drying. The purpose of the acid-base treatment is to enlarge the pores of the alumina.
In the patent CN1331605C, an alumina carrier containing silicon and titanium and a preparation method thereof, auxiliary agent silicon is introduced in the gelling process of aluminum hydroxide, and the specific surface area, the aperture and the pore volume can be improved; the assistant titanium is added after gelling and before aging, so that the acid content on the surface of the carrier and the acid content B are greatly improved. The surface of the alumina is modified by titanium, so that the interaction between the active metal and the carrier is weakened, and the dispersibility of the active metal is improved.
Patent CN101069832 is a production method of modified alumina. The main modification method is to treat aluminium hydroxide with acetic acid and palladium chloride and then make it into aluminium oxide, so as to improve specific surface area and increase filtration speed.
' modification of alumina and application thereof in reaction for directly preparing dimethyl ether from synthesis gas ' (catalytic science, 2006) ' gamma-Al is modified by oxoacid radical anion of boron, phosphorus and sulfur2O3When the method is used for methanol dehydration reaction, the sulfate radical modification can obviously improve the gamma-Al2O3The dehydration activity of methanol is reduced by boron modification, and the dehydration activity is improved by phosphorus modification, but the improvement range is small.
In the chemical industry, alumina is mainly used as an acidic carrier or adsorbent. But actually, alumina is an acid-base amphoteric compound, and is relatively weak in alkalinity compared with acid. Alumina generally has been modified in its basic properties by loading it with some basic material. For example, mixing KOH and K2CO3When alkaline substance is supported on Al2O3On the surface, better alkaline sites can be generated; loading alkaline Cs carbonate or acetate to Al2O3On the surface, super-strong alkali sites can be generated by pyrolysis. Patent CN103508864A is a preparation method of 2-isopropyl-5-methyl-2-hexenal, relating to a method for improving the alkalinity of alumina by modification. The modification method is to load alkali metal hydroxide or alkali metal carbonate by using alumina as a carrier.
Patent CN103691437A discloses a supported metal palladium catalyst and a preparation method thereof, relating to a method for improving the alkalinity of alumina by modification. The modification method comprises the steps of adding alumina into a lanthanum salt solution for dipping, carrying out adsorption and drying under the vacuum condition, and carrying out high-temperature calcination to obtain the modified catalystA reagent carrier. The modification can inhibit Al during high temperature treatment2O3The growth of crystal grains, the surface alkalinity of the carrier, the surface area increase, the Pd concentration on the surface of the catalyst is improved, and the thickness of the Pd layer is reduced, thereby improving the hydrogenation activity and the selectivity of the catalyst.
In the chemical industry, alumina is a very important industrial carrier and adsorption material. Although the preparation and modification of alumina have made great progress, increasingly severe green chemistry and environment-friendly chemistry have made higher requirements on catalytic materials such as alumina, and thus new alumina preparation and modification technologies need to be developed to meet different application requirements and environmental requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing modified alumina. The modified alumina prepared by the method is alumina with adjustable alkalinity, the preparation method is simple and easy to implement, and the production cost is low.
The invention provides a method for preparing modified alumina, wherein the crystal structure of the modified alumina is gamma-alumina, and the surface area of the modified alumina is 100-500 m2A pore volume of 0.1 to 0.6cm3The alkali content of the modified alumina is 0.1-99% lower than that of the original alumina raw material; the preparation method comprises the following steps:
(1) mixing and uniformly stirring aluminum oxide and deionized water, and then drying at 100-180 ℃ for 10-20 h;
(2) mixing the alumina obtained in the step (1) with ethanol, uniformly stirring, drying at 100-180 ℃ for 10-20 h, and then treating at 200-320 ℃ for 1-7 h;
(3) mixing the alumina obtained in the step (2), an auxiliary agent and deionized water, uniformly stirring, and then directly filtering, separating and drying;
(4) and (4) roasting the substance obtained in the step (3) at 400-650 ℃ for 1-12 h in a nitrogen atmosphere, and then obtaining a modified alumina product.
In the method, the alumina in the step (1) is gamma-alumina, and the gamma-alumina can be a commercially available product or a self-made product.
In the method, the mass ratio of the alumina to the deionized water in the step (1) is 0.5-5: 10, preferably 1-4: 10.
in the method, the drying temperature in the step (1) is 110-170 ℃, and the drying time is 12-18 h.
In the method, the ethanol in the step (2) is absolute ethanol.
In the method, the mass ratio of the alumina to the ethanol in the step (2) is 0.5-5: 10, preferably 1-4: 10.
in the method, the drying temperature in the step (2) is 110-170 ℃; the drying time is 12-18 h.
In the method, the auxiliary agent in the step (3) is one of magnesium sulfate, ammonium chloride, ferrous sulfate and ferric nitrate.
In the method, the mass ratio of the alumina, the auxiliary agent and the deionized water in the step (3) is 1-30: 0.05-55: 100, preferably 1.5 to 28: 0.1-50: 100.
in the method, the direct separation in the step (3) is directly carried out by filtration without washing with water or other solvent.
In the method, the drying temperature in the step (3) is 100-180 ℃, and preferably 110-170 ℃; the drying time is 10-20 h, preferably 12-18 h.
In the method, the treatment temperature in the step (4) is 450-600 ℃, and the treatment time is 2-10 h.
The alumina provided by the invention adopts carbon dioxide temperature programmed desorption (CO) for alkalinity2TPD) method, the apparatus used being an AutoChem model 2920 chemisorption apparatus from Michkok, USA. The specific characterization process is as follows: treating the sample for 1h at 300 ℃ in a helium atmosphere of 30 mL/min; then cooling to 70 ℃ at 30mL/min CO2-He（CO25% of He and 95% of He) for 2 h; then treating for 1h at 70 ℃ in a He atmosphere of 30 mL/min; finally at 10mL/minCO of the sample in He atmosphere at a rate of 10 ℃/min2-TPD characterization. The alkali amount is calculated by adopting a peak area integration method, taking the alkali amount of the original alumina as 100%, and calculating the alkali amount of the alumina by peak area comparison.
Other physicochemical properties of the alumina provided by the invention are characterized by other conventional characterization methods.
The alumina provided by the invention is the adjustable-alkalinity alumina, and the alkalinity of the alumina can be adjusted according to actual requirements. Can be used as an adsorbent and a catalyst carrier to meet the requirements of the adsorbent and the carrier on different alkali properties of alumina.
Compared with the existing alumina material, the modified alumina prepared by the method has the characteristic of adjustable alkaline property. The preparation method mainly utilizes the auxiliary agent to modify the alumina, and the auxiliary agent adopted in the invention can accurately and selectively react with the alkaline site of the alumina, thereby playing a role in reducing the alkalinity of the alumina; but not physically or chemically reacting with other active sites of the alumina, thus not changing the crystal structure, pore structure and other physicochemical properties of the alumina, and therefore, only adjusting the alkali property without basically changing other characteristics of the alumina. The method is different from other alumina modifying technologies, and other technologies introduce other elements into alumina to change the morphological characteristics of the alumina, the pore structure thermal properties and the like. The preparation method of the alumina provided by the invention has the advantages of simple and feasible operation steps, cheap and easily-obtained raw materials, low production cost and easy industrial production.
Drawings
FIG. 1 is a CO comparison of a sample prepared in example 1 with a starting alumina material2-TPD spectrum.
FIG. 2 CO of sample prepared in example 6 and original alumina feedstock2-TPD spectrum.
FIG. 3 is a CO comparison of the sample prepared in example 11 with the original alumina feedstock2-TPD spectrum.
FIG. 4 CO of sample prepared in example 16 and original alumina feedstock2-TPD spectrum.
Detailed Description
The method for producing alumina of the present invention will be described in detail below with reference to specific examples, but it is not limited thereto.
Example 1
(1) Mixing 10g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 150 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 150 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2), 7.5 magnesium sulfate and 100mL of deionized water, stirring for 5 hours, directly filtering and separating, and drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL1, and the basic properties of the obtained sample are shown in FIG. 1, and other properties are shown in Table 1. As can be seen from FIG. 1 and Table 1, the modified alumina had an alkali content of 1.0% of that of the original alumina and a surface area of 207m2The method can effectively reduce the alkalinity of the alumina without basically changing other properties of the alumina.
Example 2
(1) 10g of alumina was mixed with 90mL of deionized water, stirred for 30 min and then dried at 140 ℃ for 15 h.
(2) The alumina obtained in step (1) was mixed with 90mL of ethanol, stirred for 30 min, then dried at 140 ℃ for 15h, and then treated at 265 ℃ for 4 h.
(3) The alumina obtained in step (2) was mixed with 5.5g magnesium sulfate, 90mL deionized water, stirred for 4h, then directly filtered for separation, and then dried at 150 ℃ for 15 h.
(4) And (4) treating the substance obtained in the step (3) for 5 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL2, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 3
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 2g of magnesium sulfate and 100mL of deionized water, stirring for 6 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 450 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL3, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 4
(1) Mixing 18g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 235 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 1g of magnesium sulfate and 100mL of deionized water, stirring for 8 hours, directly filtering and separating, and then drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 600 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL4, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 5
(1) Mixing 12g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 0.35g of magnesium sulfate and 100mL of deionized water, stirring for 7 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 550 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL5, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 6
(1) Mixing 10g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 150 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 150 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 6.5 ferrous sulfate and 100mL of deionized water, stirring for 5 hours, directly filtering and separating, and drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL6, and the basic properties of the obtained sample are shown in FIG. 2, and other properties are shown in Table 1. As can be seen from FIG. 2 and Table 1, the modified alumina had an alkali content of 1.2% of that of the original alumina and a surface area of 207m2The method can effectively reduce the alkalinity of the alumina without basically changing other properties of the alumina.
Example 7
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 265 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 5g of ferrous sulfate and 90mL of deionized water, stirring for 4 hours, directly filtering and separating, and drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 5 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL7, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 8
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 2.3g of ferrous sulfate and 100mL of deionized water, stirring for 6 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 450 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL8, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 9
(1) Mixing 18g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 235 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 0.5g of ferrous sulfate and 100mL of deionized water, stirring for 8 hours, directly filtering and separating, and drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 600 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL9, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 10
(1) Mixing 12g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 0.35g of ferrous sulfate and 100mL of deionized water, stirring for 7 hours, directly filtering and separating, and drying for 15 hours at 150 ℃;
(4) and (4) treating the substance obtained in the step (3) for 6h at 550 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL10, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 11
(1) Mixing 10g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 150 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 150 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing 20g of ferric nitrate with 100mL of deionized water, filtering, mixing the clear solution with the alumina obtained in the step (2), stirring for 5 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL11, and the basic properties of the obtained sample are shown in FIG. 3, and other properties are shown in Table 1. As can be seen from FIG. 3 and Table 1, the modified alumina had an alkali content of 67.1% of that of the original alumina and a surface area of 212m2The method can effectively reduce the alkalinity of the alumina without basically changing other properties of the alumina.
Example 12
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 265 ℃ for 4 h;
(3) mixing 15.5g of ferric nitrate with 100mL of deionized water, filtering, mixing the clear solution with the alumina obtained in the step (2), stirring for 4 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 5 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL12, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 13
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing 13.5g of ferric nitrate with 100mL of deionized water, filtering, mixing the clear solution with the alumina obtained in the step (2), stirring for 6 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 450 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL13, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 14
(1) Mixing 18g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 235 ℃ for 4 h;
(3) mixing 5g of ferric nitrate with 100mL of deionized water, filtering, mixing the clear solution with the alumina obtained in the step (2), stirring for 8 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 600 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL14, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 15
(1) Mixing 12g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing 3.5g of ferric nitrate with 100mL of deionized water, filtering, mixing the clear solution with the alumina obtained in the step (2), stirring for 7 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 550 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL15, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 16
(1) Mixing 10g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 150 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 150 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2), 22 ammonium chloride and 100mL of deionized water, stirring for 5h, directly filtering and separating, and drying at 150 ℃ for 15 h;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL16, and the basic properties of the obtained sample are shown in FIG. 4, and other properties are shown in Table 1. As can be seen from FIG. 4 and Table 1, the modified alumina had an alkali content of 50.8% of that of the original alumina and a surface area of 210m2The method can effectively reduce the alkalinity of the alumina without basically changing other properties of the alumina.
Example 17
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 265 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 20g of ammonium chloride and 90mL of deionized water, stirring for 4 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 5 hours at 500 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL17, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 18
(1) Mixing 10g of alumina with 90mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 90mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 12.6g of ammonium chloride and 100mL of deionized water, stirring for 6 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 450 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL18, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 19
(1) Mixing 18g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 235 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 5.5g of ammonium chloride and 100mL of deionized water, stirring for 8 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6 hours at 600 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL19, and the physicochemical properties of the obtained sample are shown in Table 1.
Example 20
(1) Mixing 12g of alumina with 100mL of deionized water, stirring for 30 min, and then drying for 15h at 140 ℃;
(2) mixing the alumina obtained in the step (1) with 100mL of ethanol, stirring for 30 min, drying at 140 ℃ for 15h, and then treating at 260 ℃ for 4 h;
(3) mixing the alumina obtained in the step (2) with 3.5g of ammonium chloride and 100mL of deionized water, stirring for 7 hours, directly filtering and separating, and drying at 150 ℃ for 15 hours;
(4) and (4) treating the substance obtained in the step (3) for 6h at 550 ℃ in a nitrogen atmosphere to finally obtain the modified alumina. The obtained sample was designated as CL20, and the physicochemical properties of the obtained sample are shown in Table 1.
Table 1 shows properties of the samples obtained in the examples
Note: CL0 in Table 1 is the original alumina before modification, and the amount of alkali in the sample is referenced to CL 0.
Claims (15)
1. The method for preparing the modified alumina has a crystal structure of gamma-alumina and a surface area of 100-500 m2A pore volume of 0.1 to 0.6cm3The alkali content of the modified alumina is 0.1-99% lower than that of the original alumina raw material; the method for preparing the modified alumina comprisesThe method comprises the following steps:
(1) mixing and uniformly stirring aluminum oxide and deionized water, and then drying at 100-180 ℃ for 10-20 h;
(2) mixing the alumina obtained in the step (1) with ethanol, uniformly stirring, drying at 100-180 ℃ for 10-20 h, and then treating at 200-320 ℃ for 1-7 h;
(3) mixing the alumina obtained in the step (2), an auxiliary agent and deionized water, uniformly stirring, and then directly filtering, separating and drying;
(4) roasting the substance obtained in the step (3) at 400-650 ℃ for 1-12 h in a nitrogen atmosphere, and then obtaining a modified alumina product;
the auxiliary agent in the step (3) is one of magnesium sulfate, ammonium chloride, ferrous sulfate and ferric nitrate.
2. The method of claim 1, wherein: the alumina in the step (1) is gamma-alumina.
3. The method of claim 1, wherein: the mass ratio of the alumina to the deionized water in the step (1) is 0.5-5: 10.
4. the method of claim 1, wherein: the mass ratio of the alumina to the deionized water in the step (1) is 1-4: 10.
5. the method of claim 1, wherein: the drying temperature in the step (1) is 110-170 ℃, and the drying time is 12-18 h.
6. The method of claim 1, wherein: the ethanol in the step (2) is absolute ethanol.
7. The method of claim 1, wherein: the mass ratio of the alumina to the ethanol in the step (2) is 0.5-5: 10.
8. the method of claim 1, wherein: the mass ratio of the alumina to the ethanol in the step (2) is 1-4: 10.
9. the method of claim 1, wherein: the drying temperature in the step (2) is 110-170 ℃; the drying time is 12-18 h.
10. The method of claim 1, wherein: the mass ratio of the alumina to the auxiliary agent to the deionized water in the step (3) is 1-30: 0.05-55: 100.
11. the method of claim 1, wherein: the mass ratio of the alumina to the auxiliary agent to the deionized water in the step (3) is 1.5-28: 0.1-50: 100.
12. the method of claim 1, wherein: and (4) directly filtering and separating in the step (3) without washing with water or other solvents.
13. The method of claim 1, wherein: and (4) drying at 100-180 ℃ for 10-20 h.
14. The method of claim 1, wherein: the drying temperature in the step (3) is 110-170 ℃; the drying time is 12-18 h.
15. The method of claim 1, wherein: in the step (4), the treatment temperature is 450-600 ℃, and the treatment time is 2-10 h.
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| CN102513044A (en) * | 2011-12-16 | 2012-06-27 | 黑龙江省科学院高技术研究院 | Surface modification method of nanometer aluminum oxide |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| EP2823888A1 (en) * | 2012-03-05 | 2015-01-14 | Sunshine Kaidi New Energy Group Co., Ltd | Surface modification method of aluminum oxide carrier |
| CN104445317A (en) * | 2014-11-12 | 2015-03-25 | 中国海洋石油总公司 | Method for preparing modified pseudo-boehmite |
| CN105617978A (en) * | 2016-01-04 | 2016-06-01 | 武汉理工大学 | Preparation method of loaded type MgO/gamma-Al2O3 adsorbent capable of adsorbing CO2 at room temperature |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513044A (en) * | 2011-12-16 | 2012-06-27 | 黑龙江省科学院高技术研究院 | Surface modification method of nanometer aluminum oxide |
| EP2823888A1 (en) * | 2012-03-05 | 2015-01-14 | Sunshine Kaidi New Energy Group Co., Ltd | Surface modification method of aluminum oxide carrier |
| CN103357436A (en) * | 2012-03-28 | 2013-10-23 | 中国石油化工股份有限公司 | Alkali treatment modification method of alumina carrier as well as preparation method and application of silver catalyst supported by alumina carrier |
| CN104445317A (en) * | 2014-11-12 | 2015-03-25 | 中国海洋石油总公司 | Method for preparing modified pseudo-boehmite |
| CN105617978A (en) * | 2016-01-04 | 2016-06-01 | 武汉理工大学 | Preparation method of loaded type MgO/gamma-Al2O3 adsorbent capable of adsorbing CO2 at room temperature |
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