CN100346873C - Method for preparing large pore capacity, high specific surface area alumina - Google Patents
Method for preparing large pore capacity, high specific surface area alumina Download PDFInfo
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- CN100346873C CN100346873C CNB2005100863810A CN200510086381A CN100346873C CN 100346873 C CN100346873 C CN 100346873C CN B2005100863810 A CNB2005100863810 A CN B2005100863810A CN 200510086381 A CN200510086381 A CN 200510086381A CN 100346873 C CN100346873 C CN 100346873C
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- surface area
- specific surface
- alumina
- cyclodextrin
- large pore
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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 89
- 239000011148 porous material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 19
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 23
- 229960004853 betadex Drugs 0.000 claims description 23
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 17
- 239000001099 ammonium carbonate Substances 0.000 claims description 17
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 159000000013 aluminium salts Chemical class 0.000 claims description 7
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 6
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [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 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 4
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000001116 FEMA 4028 Substances 0.000 description 21
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IDMTXBAVGGZUEV-UHFFFAOYSA-E S(=O)(=O)([O-])[O-].[Al+3].[Al](Cl)(Cl)Cl.[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Al+3].[Al](Cl)(Cl)Cl.[Al+3].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] IDMTXBAVGGZUEV-UHFFFAOYSA-E 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal aluminate Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- JQZHRRRYJXSQFC-UHFFFAOYSA-N propane-1,2-diol;propane-1,2,3-triol Chemical compound CC(O)CO.CC(O)CO.OCC(O)CO JQZHRRRYJXSQFC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a method for preparing alumina with large pore volume and high specific surface area, which belongs to the technical field of inorganic oxide preparation. In order to solve the problems of complicated technology and difficult realization of both high specific surface area and large pore volume in the alumina preparing process, the present invention provides a method for preparing activated alumina with simple technology, large pore volume and high specific surface area, which comprises the steps that alkaline solution precipitating agents are added into a mixed solution containing aluminum salt and cyclodextrin, and the obtained precipitates are washed, dried and calcined at high temperature to obtain activated alumina. The specific surface area of the alumina prepared by the method of the present invention can reach 220 to 480 m<2>/g, and the pore volume is from 0.7 to 1.55 ml/g. As a catalyst carrier or an adsorbing agent with good performance, the alumina can be used in the industries of petrifaction, medicine, chemical engineering, etc.
Description
Technical field
The present invention relates to the particularly preparation method of large pore capacity, high specific surface area alumina of a kind of activated alumina, belong to the preparing technical field of inorganic oxide.
Background technology
Aluminium oxide is a kind of commercial Application inorganic oxide very widely.As carrier, it is the important component part of many catalyst, coating as honeycomb substrate surface in the catalyst for catalytic purifying car tail gas is used aluminium oxide, and the hydrofining catalyst carrier in the petrochemical process is exactly an aluminium oxide, and the carrier of many catalyst for hydrogenation is also used aluminium oxide.In addition, aluminium oxide also can be used as adsorbent and drier.Specific area and pore volume are two important parameters that influence the aluminium oxide performance.Preparation about the different specific area aluminium oxide of different pore volumes both at home and abroad has a lot of patented methods.U.S. Pat 4248852 (Process for theproduction of alumina suitable for use as a catalyst carrier, a kind of preparation method who is suitable for alumina as catalyst carrier, on February 3rd, 1981 is open) disclosed alumina preparation method is the pH swing method, can control aperture, pore volume and the pore size distribution of gained aluminium oxide by this method.But the method complex process, production efficiency are low.Chinese patent CN1164563A (a kind of preparation method of alumina as catalyst carrier, on November 12nd, 1997 is open) provides a kind of catalyst carrier γ-Al that does
2O
3The preparation method, it is base stock with aqueous slkali or alkali metal aluminate that this method adopts aluminum salt solution or acid solution, and two kinds of solution are alternately added in the reactor, makes its pH value by acid to alkaline, is replaced to acid under the situation of variation by alkali to become glue, prepared γ-Al again
2O
3Specific area can reach 250～350m
2/ g, but pore volume only is 0.55～0.75ml/g.The preparation method of the disclosed activated alumina of Chinese patent CN1254684A (a kind of method of process for preparing active alumina by sodium metaaluminate-carbon dioxide, on May 31st, 2000 is open) is sodium metaaluminate and CO
2Neutralisation, the prepared activated alumina pore volume of this method is 0.88ml/g to the maximum.CN1425612A (the preparation method of activated alumina, on June 25th, 2003 is open) preparation method of disclosed activated alumina is, with aluminium chloride, ammoniacal liquor and expanding agent ammonium oxalate or ammonium citrate etc. is raw material, be made into mixed aqueous solution, heating concentrates this solution to generate aluminum hydroxide precipitation, drying, roasting can obtain activated alumina again, though the aluminium oxide pore volume that this method obtains can be up to 1.225ml/g, specific area is lower than 190m
2/ g.CN1528668A (the preparation method of acinous activated alumina, on September 15th, 2004) preparation method of disclosed a kind of acinous activated alumina, be that industrial aluminium hydroxide is calcined under stirring condition, the screening of cooling back makes, and this method gained aluminium oxide specific area is 150～280m
2/ g, but pore volume is lower, is 0.38～0.45ml/g.Above-mentioned preparation method of alumina exists complex process, made aluminium oxide to be difficult to have shortcomings such as high-specific surface area and large pore volume simultaneously.
Summary of the invention
Be difficult to satisfactory to both parties problem for solving the complex process, high-specific surface area and the large pore volume that exist in the aluminium oxide preparation process, it is simple to the invention provides a kind of technology, not only has large pore volume but also have the preparation method of the activated alumina of high-specific surface area.
Concrete steps of the present invention are as follows:
1) with water, organic alcohol, perhaps a kind of solvent of doing in the aqueous solution of the organic solvent that dissolves each other with water is dissolved in aluminium salt and cyclodextrin wherein, is made into mixed solution.The concentration of cyclodextrin is 0.005～1.6mol/L in the mixed solution, is preferably 0.006～0.1mol/L, and the concentration of aluminium salt is counted 0.1～3.0mol/L with aluminium; Described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride, is preferably aluminum nitrate; Described cyclodextrin is α, β or γ cyclodextrin, is preferably beta cyclodextrin.Described organic alcohol is selected from a kind of in ethylene glycol, propane diols, the glycerine, and the described organic solvent that dissolves each other with water is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, glycerine, dimethyl formamide, the dimethyl sulfoxide (DMSO).
2) under constantly stirring, in step 1) gained mixed solution, add aqueous slkali to pH value 〉=6, obtain containing the slurry of solid precipitate.Described aqueous slkali is selected from one or more of the aqueous solution of ammoniacal liquor, ammonium carbonate, carbonic hydroammonium, alkali-metal hydroxide and alkali-metal carbonate, is preferably ammonium carbonate solution.
3) with step 2) slurries filtration that obtains, spend deionised water;
4) filter cake that step 3) is obtained is in 80～150 ℃ of drying 4～12h;
5) pressed powder that step 4) is obtained promptly obtains large pore capacity, high specific surface area alumina in 400～1000 ℃ of roasting 2～6h.
The present invention compared with prior art has following advantage:
1) production technology is simple, environmental friendliness;
2) the prepared activated alumina of the present invention has large pore volume and high-specific surface area simultaneously, is 220-480m by the prepared aluminium oxide specific area of the present invention
2/ g, pore volume are 0.7～1.55ml/g.
The specific embodiment
Further illustrate the present invention with embodiment below.
Embodiment 1
Take by weighing the 4.0g beta cyclodextrin and 37.51 the gram aluminum nitrates be dissolved in the 100ml ethylene glycol, being made into beta cyclodextrin concentration is that 0.035mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 1.
Embodiment 2
Take by weighing 8.0g α cyclodextrin and 37.51 the gram aluminum nitrates be dissolved in the 100ml ethylene glycol, being made into the α cyclodextrin concentration is that 0.08mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 1.
Embodiment 3
Take by weighing 3.3g γ cyclodextrin and 18.75 the gram aluminum nitrates be dissolved in the 500ml ethanol water (ethanol and water volume ratio are 1: 1), being made into the γ cyclodextrin concentration is that 0.005mol/L, aluminum concentration are the mixed solution of 0.10mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 1.
Embodiment 4
The preparation method is similar to embodiment 1, and difference is to add ammonium carbonate solution, and to make the pH value be 6.0, and gained the results are shown in table 1.
Embodiment 5
The preparation method is similar to embodiment 1, and difference is to add potassium hydroxide aqueous solution, and to make the pH value be 11.0, and gained the results are shown in table 1.
Embodiment 6
Take by weighing the 4.0g beta cyclodextrin and 37.51 the gram aluminum nitrates be dissolved in the 100ml aqueous propanol solution (30ml propyl alcohol and 70ml water), being made into beta cyclodextrin concentration is that 0.035mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 80 ℃ of baking 12h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 2.
Embodiment 7
Take by weighing 103.8g γ cyclodextrin and 36.25 the gram aluminium chloride be dissolved in the 50ml aqueous propanol solution (30ml propyl alcohol and 70ml water), being made into the γ cyclodextrin concentration is that 1.6mol/L, aluminum concentration are the mixed solution of 3.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 150 ℃ of baking 4h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 2.
Embodiment 8
Take by weighing the 4.0g beta cyclodextrin and 34.21 the gram aluminum sulfate be dissolved in the 100ml aqueous propanol solution (30ml propyl alcohol and 70ml water), being made into beta cyclodextrin concentration is that 0.035mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 2.
Embodiment 9
Take by weighing the 8.0g beta cyclodextrin and 37.51 the gram aluminum nitrates be dissolved in the 100ml ethylene glycol, being made into beta cyclodextrin concentration is that 0.07mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stirring down to dropping ammonia solution wherein is 9.0 to the pH value, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 3.
Embodiment 10
The preparation method is similar to embodiment 9, and difference is that used alkali lye is sodium hydrate aqueous solution, and gained the results are shown in table 3.
Embodiment 11
The preparation method is similar to embodiment 9, and difference is that used alkali lye is aqueous sodium carbonate, and gained the results are shown in table 3.
Embodiment 12
The preparation method is similar to embodiment 9, and difference is that used alkali lye is the mixed aqueous solution of sodium carbonate and NaOH, and gained the results are shown in table 3.
Embodiment 13
Take by weighing the 8.0g beta cyclodextrin and 37.51 the gram aluminum nitrates be dissolved in the 100ml ethylene glycol, being made into beta cyclodextrin concentration is that 0.07mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 400 ℃ of roasting 6h promptly get activated alumina, and its main character is listed in table 4.
Embodiment 14
The preparation method is similar to embodiment 13, and sintering temperature is respectively 500,650,800 and 1000 ℃, and roasting time is 2h, and gained the results are shown in table 4.
Embodiment 15
Take by weighing the 1.5g beta cyclodextrin and 24.15 the gram aluminium chloride be dissolved in the 100ml water, being made into beta cyclodextrin concentration is that 0.013mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 5.
Embodiment 16
Take by weighing the 1.5g beta cyclodextrin and 24.15 the gram aluminium chloride be dissolved in the 100ml glycerine, being made into beta cyclodextrin concentration is that 0.013mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 5.
Embodiment 17
Take by weighing the 1.5g beta cyclodextrin and 24.15 the gram aluminium chloride be dissolved in the 100ml propane diols, being made into beta cyclodextrin concentration is that 0.013mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 650 ℃ of roasting 2h promptly get activated alumina, and its main character is listed in table 5.
Embodiment 18
The preparation method is similar to embodiment 15, and difference is that solvent for use is that (volume ratio of propane diols and water is 50: 50 to aqueous solution of propylene glycol, and gained the results are shown in table 5.
Embodiment 19
The preparation method is similar to embodiment 15, and difference is that solvent for use is that (volume ratio of glycerine and water is 50: 50 to glycerine water solution, and gained the results are shown in table 5.
Embodiment 20
Take by weighing the 8.0g beta cyclodextrin and 24.15 the gram aluminium chloride be dissolved in the 100ml dimethyl sulphoxide aqueous solution (volume ratio of dimethyl sulfoxide (DMSO) and water is 60: 40), being made into beta cyclodextrin concentration is that 0.07mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 400 ℃ of roasting 6h promptly get activated alumina, and its main character is listed in table 5.
Embodiment 21
Take by weighing the 8.0g beta cyclodextrin and 24.15 the gram aluminium chloride be dissolved in the aqueous solution (volume ratio of dimethyl formamide and water is 50: 50) of 100ml dimethyl formamide, being made into beta cyclodextrin concentration is that 0.07mol/L, aluminum concentration are the mixed solution of 1.0mol/L, constantly stir is 9.0 to wherein dripping the 0.1mol/L ammonium carbonate solution to the pH value down, the gained slurry after filtration, deionized water washing, 90 ℃ of baking 6h, 400 ℃ of roasting 6h promptly get activated alumina, and its main character is listed in table 5.
Table 6 has been listed the character contrast situation of prepared aluminium oxide of the present invention and similar products at home and abroad, and comparing result shows that the prepared aluminium oxide of the present invention had both had big pore volume, had high specific area again.
Table 1 embodiment 1～5 product main character
| Sample | The cyclodextrin kind | The pH value | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| Embodiment 1 embodiment 2 | β α | 9.0 9.0 | 1.46 1.35 | 262.1 245.6 | γ-Al 2O 3 γ-Al 2O 3 |
| Embodiment 3 embodiment 4 embodiment 5 | γ β β | 9.0 6.0 11.0 | 1.40 1.30 1.38 | 256.2 240.5 250.4 | γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 |
Table 2 embodiment 6～8 product main character
| Sample | Aluminium salt kind | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| Embodiment 6 embodiment 7 embodiment 8 | Aluminum nitrate aluminium chloride aluminum sulfate | 1.27 1.20 1.26 | 259.1 250.2 255.6 | γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 |
Table 3 embodiment 9～12 product main character
| Sample | Aqueous slkali | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| Embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 1 | Ammoniacal liquor NaOH Na 2CO 3 Na 2CO 3+ NaOH ammonium carbonate | 1.15 1.20 1.44 1.40 1.46 | 238.2 240.5 258.0 251.0 262.1 | γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 |
Table 4 embodiment 13～14 product main character
| Sample | Sintering temperature/℃ | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| Embodiment 13 embodiment 14-1 embodiment 14-2 embodiment 14-3 embodiment 14-4 | 400 500 650 800 1000 | 1.01 0.98 1.27 0.87 0.70 | 236.6 484.3 285.3 220.9 124.2 | Unformed γ-Al 2O 3 γ-Al 2O 3 α+γAl 2O 3 |
Table 5 embodiment 15～21 product main character
| Sample | Solvent species | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| Embodiment 15 embodiment 16 embodiment 17 embodiment 18 embodiment 19 embodiment 20 embodiment 21 embodiment 6 embodiment 1 | Water glycerine propylene glycol propylene glycol aqueous solution glycerine water solution methyl-sulfoxide aqueous solution dimethyl formamide aqueous solution aqueous propanol solution ethylene glycol | 1.03 0.93 1.21 1.11 1.30 1.20 1.23 1.27 1.46 | 274.9 254.4 280.6 276.5 283.5 255.0 260.6 259.1 262.1 | γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 γ-Al 2O 3 |
Table 6 compares with similar products at home and abroad
| Sample | Sintering temperature/℃ | Pore volume/ml/g | Specific area/m 2/g | The thing phase |
| The high-temperature roasting of aluminium oxide SB powder is produced in embodiment 14-1 embodiment 14-2 Tianjin | 500 650 650 500 | 0.98 1.27 0.78 0.54 | 484.3 285.3 228.5 243.8 | Unformed γ-Al 2O 3 γAl 2O 3 γ-Al 2O 3 |
Claims (1)
1. the preparation method of a large pore capacity, high specific surface area alumina is characterized in that, this preparation method's concrete steps are as follows:
1) with water, organic alcohol, perhaps a kind of solvent of doing in the aqueous solution of the organic solvent that dissolves each other with water is dissolved in aluminium salt and cyclodextrin wherein, is made into mixed solution, the concentration of cyclodextrin is 0.005～1.6mol/L in the mixed solution, and the concentration of aluminium salt is counted 0.1～3.0mol/L with aluminium; Described organic alcohol is a kind of in ethylene glycol, propane diols or the glycerine; The organic solvent that described and water dissolve each other is selected from a kind of in methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propane diols, glycerine, dimethyl formamide or the dimethyl sulfoxide (DMSO); Described aluminium salt is aluminum nitrate, aluminum sulfate or aluminium chloride; Described cyclodextrin is α, β or γ cyclodextrin;
2) under constantly stirring, in step 1) gained mixed solution, add aqueous slkali to pH value 〉=6, obtain containing the slurry of solid precipitate; Described aqueous slkali is one or more in the aqueous solution of ammoniacal liquor, ammonium carbonate, carbonic hydroammonium, alkali-metal hydroxide and alkali-metal carbonate;
3) with step 2) slurries filtration that obtains, spend deionised water, obtain filter cake;
4) filter cake that step 3) is obtained obtains pressed powder in 80～150 ℃ of drying 4～12h;
5) pressed powder that step 4) is obtained promptly obtains large pore capacity, high specific surface area alumina in 400～1000 ℃ of roasting 2～6h.
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| CN102838142B (en) * | 2011-06-23 | 2014-04-16 | 中国石油化工股份有限公司 | Three-dimensional ordered macroporous alumina and preparation method thereof |
| CN102515229B (en) * | 2011-12-09 | 2015-03-11 | 沈阳工业大学 | Preparation method for activated alumina oxide with large pore volume and high specific surface area |
| CN103536625B (en) * | 2013-09-27 | 2016-01-06 | 安徽师范大学 | A kind of nanometer cerium oxide composite and preparation method thereof, antioxidant |
| CN104190391B (en) * | 2014-07-02 | 2016-08-17 | 上海应用技术学院 | A kind of catalyst and the purposes in preparing thymol method thereof |
| CN106276993B (en) * | 2015-05-27 | 2017-08-11 | 裕祥化工（大连）有限公司 | A kind of nano aluminium oxide thickened pulp and preparation method thereof |
| CN106669850B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of preparation method of macropore alumina supporter |
| CN106955744B (en) * | 2016-01-08 | 2019-09-27 | 中国石油化工股份有限公司 | The alpha-alumina supports and its preparation and application of alkene epoxidation silver catalyst |
| CN111068706A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Preparation method of denitration catalyst |
| CN110255594B (en) * | 2019-06-20 | 2022-02-18 | 萍乡市华顺环保化工填料有限公司 | Preparation method of active alumina |
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