CN110937880A - Integral alumina material and preparation method thereof - Google Patents
Integral alumina material and preparation method thereof Download PDFInfo
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- CN110937880A CN110937880A CN201811114226.9A CN201811114226A CN110937880A CN 110937880 A CN110937880 A CN 110937880A CN 201811114226 A CN201811114226 A CN 201811114226A CN 110937880 A CN110937880 A CN 110937880A
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- honeycomb
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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 55
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 amide compounds Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 claims description 4
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 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 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims 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 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000002243 precursor Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008131 herbal destillate Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses an integral alumina material and a preparation method thereof. The material is of a honeycomb structure, the wall of a honeycomb hole is provided with microscopic macroporous pores, the pore diameter of the macroporous is 50-1000nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macroporous to the corresponding wall thickness is 0.5-4.5. The preparation method of the material comprises the following steps: (1) uniformly dispersing boehmite powder in water to obtain a boehmite suspension, slowly adding a peptizing agent into the boehmite powder suspension, and heating and aging to obtain alumina sol; (2) inorganic aluminum salt, polyethylene glycol, alumina sol, amide compounds and low-carbon alcohol aqueous solution are mixed, then propylene oxide and/or pyridine are added, and the mixture is cast into a reverse honeycomb mould for molding. The method does not add an organic template, the preparation process is environment-friendly, the process is simple and easy to implement, and the product of the invention has macroscopic and microscopic macroporous structures, is very suitable to be used as a heterogeneous catalytic carrier, and is easy for industrial production.
Description
Technical Field
The invention relates to an integral aluminum oxide material and a preparation method thereof, belonging to the field of inorganic material preparation.
Background
The integral macroporous oxide has a larger pore channel structure, a higher specific surface area and good thermal stability, and is widely applied to the fields of heterogeneous catalysts, catalyst carriers, adsorption separation materials, chromatographic packing, electrode materials, acoustic resistance and thermal resistance materials and the like.
"Synthesis of Porous Silica and Metal Oxide particles used Emulsion-modified Polymer foams" (Chemical Material,2004,16:4245-2、Al2O3、TiO2And ZrO2After the precursor is converted, the template is finally roasted to remove the template to obtain the corresponding macroporous oxide material, and the pore diameter of the macropore can be controlled between a micron level and a millimeter level. In the method, the preparation of the template needs to use a surfactant and a stabilizer, the preparation process is complicated, the cost of the used raw materials including the surfactant is high, and the used acrylamide organic monomer has carcinogenicity. In addition, when the template is removed by baking, the emission irritation is strong, and the environmental pollution is large.
"Macroporos aluminum monolithins prepared by filing polymer foamswitch aluminum hydrosols" (J Mater. Sci.,2009,44: 931-938.) reported a technique of preparing a Macroporous polystyrene foam template by a high concentration emulsion polymerization method, then filling the template with an alumina hydrosol, converting, and removing the template by calcination to obtain the monolithic Macroporous alumina. The technology takes styrene as an organic monomer, divinyl benzene as a cross-linking agent, SPAN-80 as a surfactant and azodiisobutyronitrile as an initiator, and the cost of the used organic raw materials and the surfactant is relatively low.
CN101200297A discloses a preparation method of monolithic macroporous alumina: preparing an integral macroporous organic template by using styrene and divinylbenzene as monomers by adopting a reverse concentrated emulsion method; preparation of Al by using aluminium isopropoxide or pseudo-boehmite as precursor2O3Hydrosol; mixing Al2O3Filling the hydrosol into the integral macroporous organic template; and drying the filled integral organic/inorganic composite, and roasting at 600-900 ℃ to remove the template to obtain the integral macroporous alumina. The method has the advantages that the preparation process is simple and easy to implement, and the prepared integral macroporous alumina has micron-sized interconnected macroporous channels with the pore diameter of 1-50 mu m. The method for preparing the integral macroporous alumina is simple and easy to implement, but the volume fraction of the water phase in the method accounts for 75-90%, and correspondingly the volume fraction of the organic monomer is relatively low. The mechanical strength of the material is low. Meanwhile, similar to the other patents, the organic monomer has a certain toxicity, and when the template is removed by roasting, the emission has strong irritation, and the environment is polluted.
In a word, the existing preparation method of the integral macroporous alumina generally adopts an organic high polymer template method. The preparation of the macroporous alumina comprises at least three steps: (1) preparing an organic high polymer template by taking an organic matter as a raw material through a polymerization reaction: (2) filling a precursor of the integral macroporous oxide into a template, and converting the filled precursor in the template: (3) and (4) roasting to remove the template to obtain the integral macroporous oxide. The preparation of the integral macroporous alumina material has the problems of certain toxicity of the monomer for preparing the template, large template dosage, high preparation cost, complex process implementation and the like in the preparation of the integral macroporous alumina material. The resulting material has only one type of macroporous distribution, and the mechanical strength of the material is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an integral aluminum oxide material and a preparation method thereof. The method does not add an organic template, the preparation process is environment-friendly, the process is simple and easy to implement, and the product of the invention has macroscopic and microscopic macroporous structures, is very suitable to be used as a heterogeneous catalytic carrier, and is easy for industrial production.
The integral alumina material is a honeycomb structure, and the distribution number of honeycomb holes on the cross section is 1-50 holes/cm on the basis of the cross section vertical to the honeycomb pore passage2Preferably 2 to 25 pores/cm2An aperture; the shape of the opening of the honeycomb hole is round, clover-shaped, square or other special shapes, preferably round, clover-shaped and square; the walls of the honeycomb holes are provided with microscopic macroporous pores, the pore diameter of the macropores is 50-1000nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macropores to the corresponding wall thickness is 0.5-4.5, preferably 1-4.
The monolithic alumina materials of the present invention have a total porosity of 20% to 90%, preferably 30% to 75%; specific surface area of 100-450m2G, pore volume of 0.3-1.5cm3(ii) in terms of/g. The mechanical strength of the monolithic alumina material is 5-30N/mm, preferably 10-25N/mm.
Macroscopic appearances of the monolithic alumina materials of the present invention include, but are not limited to, cylindrical, bar-shaped, spherical, and other types of monolithic morphologies.
The preparation method of the monolithic alumina material comprises the following steps:
(1) uniformly dispersing boehmite powder in water to obtain a boehmite suspension, slowly adding a peptizing agent into the boehmite powder suspension, and after the addition is finished, heating and aging for a certain time to obtain clear alumina sol;
(2) uniformly mixing inorganic aluminum salt, polyethylene glycol, the alumina sol obtained in the step (1), an amide compound and a low-carbon alcohol aqueous solution, then adding propylene oxide and/or pyridine, uniformly mixing, casting the mixture into a reverse honeycomb mould, and waiting until gel is obtained; wherein the viscosity average molecular weight of the polyethylene glycol is 10000-;
(3) aging the gel obtained in the step (2) at 20-80 ℃ for 12-120 hours, and removing the die to obtain an aged product;
(4) and soaking the aged product in a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, and drying and roasting a solid phase to obtain the integral aluminum oxide material.
The solid content of the suspension liquid in the step (1) is 1-15 wt%.
The step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
The peptizing agent in the step (1) is a commonly used peptizing agent in the preparation process of the aluminum sol, and can be one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid. The peptizing agent (the dosage of which is H contained in the peptizing agent) in the step (1)+Calculated) with boehmite powder (in an amount calculated on the basis of Al contained)+The mol ratio of Al to Al is 0.05-1.
Based on the weight of the mixture obtained in the step (2), the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, the adding amount of the aluminum sol is 1-10 wt%, and the adding amount of the polyethylene glycol is 0.1-3.0 wt%, preferably 0.2-2.0 wt%; wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5; the addition amount of the amide compound is 0.1-5.0 wt%.
The order of adding the various materials in step (2) is not particularly limited, and is preferably: water, low carbon alcohol, inorganic aluminum salt, alumina sol, polyethylene glycol and organic compound containing amide group are added in sequence. Generally, before the latter material is added, the material added previously needs to be mixed uniformly.
The inorganic aluminum salt in the step (2) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
The lower alcohol in the steps (2) and (4) is generally C5The alcohol is preferably one or more of methanol, ethanol, n-propanol and isopropanol, and most preferably ethanol and/or propanol.
The amide compound in the step (2) can be one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide and 2-phenylacetamide.
The propylene oxide and/or pyridine and Al in the step (3)3+(not including Al in the alumina sol) in a molar ratio of 1.5 to 9.5, preferably 3.0 to 7.5. The propylene oxide and pyridine may be mixed in any proportion.
The shape of the reverse honeycomb mold in the step (3) can be selected or manufactured according to actual needs, and the material of the mold includes but is not limited to various plastic materials, metal materials, wood materials and other materials.
The soaking conditions in the step (4) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours.
The mass concentration of the lower alcohol aqueous solution used for soaking in the step (4) is not less than 50 wt%.
The drying in the step (4) is ordinary normal pressure drying, the drying temperature is not more than 120 ℃, and is preferably 20-100 ℃, and the drying is carried out until the product is not obviously reduced in weight. The roasting is carried out at 400-700 ℃ for 1-24 hours, preferably at 500-650 ℃ for 2-12 hours.
The invention casts the sol of inorganic aluminum salt on the reverse honeycomb mould to finally form a super large honeycomb pore structure. For the pore wall of the honeycomb super-large pore, the invention can obtain the three-dimensional through and uniformly distributed large pore by utilizing the sol-gel reaction characteristic of inorganic aluminum salt: the aluminum sol crystal seeds are introduced into the preparation system to induce the aluminum oxide precursor to evolve from the amorphous precursor to the crystalline precursor, so that the aluminum oxide precursor can be easily converted into the gamma crystalline state at a lower roasting temperature, and the energy consumption can be obviously saved. The introduction of the alumina sol crystal seed ensures that the wall of the macroporous hole generates a large amount of particles, and the wall of the macroporous hole is changed from a smooth compact state into a particle aggregate, which is beneficial to generating particle pores and improving the specific surface area of the material, thereby enlarging the contact area of the reaction material and the catalyst to improve the reaction activity. The addition of the amide compound can inhibit the generation of ultra-large pores, so that the large pores are more uniformly concentrated, and the stress effect caused by nonuniform pore sizes is favorably eliminated. The alumina material of the present invention ultimately forms a monolithic morphology having a macro-super macro pore structure.
The integral macroporous alumina can be used as a carrier of a heterogeneous catalyst, and is applied to various macromolecular catalytic reactions, such as hydrogenation reaction, alkylation reaction, desulfurization and denitration reaction, pollutant adsorption and degradation in the water treatment process and the like.
Drawings
Fig. 1 is a schematic view of the pore channel structure of the monolithic macroporous alumina material, and the right side in the figure is a scanning electron microscope image of the macroporous alumina prepared in example 1.
Figure 2 is an XRD pattern of the monolithic macroporous alumina prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. In the invention, the shape of the honeycomb super-large hole of the integral material is directly observed or photographed by an optical microscope or an optical camera, and the large hole on the wall of the honeycomb hole and the three-dimensional through condition of the large hole are observed by a scanning electron microscope. The crystalline state was tested by XRD. The porosity and the average pore diameter of the macroporous alumina are characterized and tested by a mercury intrusion method. The mechanical strength of the material was tested using a DL2 type strength tester manufactured by daintian scientific and technological development ltd. The boehmite powder is a product sold in the market or manufactured by self.
Example 1
Preparing aluminum sol: mixing boehmite powder and distilled water to form a suspension (solid content is 3 wt%), dropwise adding hydrochloric acid under the condition of continuous stirring to meet the acid/aluminum molar ratio of 0.07, and heating to 85 ℃ after the dropwise adding, and refluxing for 5 hours to form clear aluminum sol.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and formamide at room temperature (about 25 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 22% of water, 21% of ethanol, 18% of aluminum chloride, 0.3% of polyethylene glycol (viscosity average molecular weight is 100 ten thousand), 5% of alumina sol, 1% of formamide and 32.7% of pyridine. And after uniform mixing, casting the mixture into a selected reverse honeycomb mould, continuing aging for 48 hours at 40 ℃ after gelation, soaking the aged mixture for 48 hours by using 55wt% of ethanol aqueous solution after demoulding, drying at 40 ℃ until the product is not obviously reduced after soaking and removing a liquid phase, and then roasting for 3 hours at 550 ℃ to obtain the cylindrical integral aluminum oxide material.
The obtained monolithic alumina material had a total porosity of 81% and a specific surface area of 347m2G, pore volume 0.55cm3(ii) in terms of/g. The mechanical strength of the monolithic alumina material was 13N/mm. The shape of the hole opening of the honeycomb holes is that the diameter of a circular hole is 1mm, and the distribution number of the honeycomb holes on the cross section is 30 holes/cm2The honeycomb holes are distributed in order on the cross section. The walls of the honeycomb holes are provided with microscopic macroporous pores, the pore diameter of the macropores is 440nm, the macropores of the walls of the honeycomb holes are uniformly distributed and are communicated in a three-dimensional mode, and the ratio of the pore diameter of the macropores contained in the walls of the honeycomb holes to the corresponding wall thickness is 0.7.
Example 2
The preparation of the aluminum sol was the same as in example 1.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and acetamide at room temperature (about 25 ℃), and then adding propylene oxide, wherein the mixture comprises the following components in parts by weight: 23% of water, 20% of ethanol, 22% of aluminum chloride, 0.5% of polyethylene glycol (viscosity-average molecular weight is 100 ten thousand), 2% of alumina sol, 2.0% of formamide and 30.5% of propylene oxide. After even mixing, casting into a selected reverse honeycomb mould, continuously aging for 48 hours at 40 ℃ after gelation, soaking the aged mixture for 48 hours by ethanol after demoulding, and drying at 40 ℃ until the product is not obviously reduced in weight any more after soaking and removing a liquid phase. Then calcined at 450 ℃ for 5 hours and then cooled to room temperature to obtain square monolithic macroporous alumina.
The obtained monolithic alumina material had a total porosity of 84% and a specific surface area of 422m2/g，Pore volume of 0.62cm3(ii) in terms of/g. The mechanical strength of the monolithic alumina material was 11N/mm. The shape of the openings of the honeycomb holes is circular. The pore diameter is 1.5mm, and the honeycomb pores on the cross section are distributed at 20 pores/cm2The holes are distributed orderly, the wall of the honeycomb hole is provided with microscopic macroporous pores, the pore diameter of the macropores is 210nm, the macropores of the wall of the honeycomb hole are distributed uniformly and are communicated in a three-dimensional mode, and the ratio of the pore diameter of the macropores contained in the wall of the honeycomb hole to the corresponding wall thickness is 1.5.
Example 3
Preparing aluminum sol: mixing boehmite powder and distilled water to form suspension (solid content is 1.5 wt%), dropwise adding acetic acid under the condition of continuous stirring to meet the acid/aluminum molar ratio of 0.1, and heating to 90 ℃ after the dropwise adding is finished, and refluxing for 10 hours to form clear sol.
Uniformly mixing water, absolute ethyl alcohol, aluminum chloride, polyethylene glycol, aluminum sol and N, N-dimethylformamide at room temperature (about 25 ℃), and then adding pyridine, wherein the mixture comprises the following components in parts by weight: 20% of water, 20% of ethanol, 22% of aluminum chloride, 0.5% of polyethylene glycol (viscosity-average molecular weight is 100 ten thousand), 5% of alumina sol, 2.5% of formamide and 30.0% of pyridine. After uniform mixing, the sol is cast into a reverse honeycomb mould, after gelling, the sol is aged for 48 hours at 40 ℃, then the aged mixture is soaked in 80wt% ethanol water for 72 hours, after soaking and liquid phase removal, the mixture is dried at 40 ℃ until the product is not obviously reduced. Then roasting at 700 ℃ for 2.5 hours to obtain the cylindrical integral macroporous alumina.
The obtained monolithic alumina material had a total porosity of 79% and a specific surface area of 443m2G, pore volume 0.74cm3The mechanical strength of the monolithic alumina material was 17N/mm. The shape of the hole of the honeycomb holes is square. The side length of the square hole is 3mm, and the honeycomb holes on the cross section are distributed at 8 holes/cm2The holes are distributed orderly, the wall of the honeycomb hole is provided with microscopic macroporous pores, the pore diameter of the macropores is 184nm, the macropores of the wall of the honeycomb hole are distributed uniformly and are communicated in a three-dimensional mode, and the ratio of the pore diameter of the macropores contained in the wall of the honeycomb hole to the corresponding wall thickness is 1.2.
Example 4
The monolithic alumina obtained in example 1 was used as an adsorbent for adsorbing lead-containing wastewater. The adsorbent was added to the lead-containing wastewater at a ratio of 6 g/L. The lead content in the test wastewater is reduced to 0.8mg/L from 35mg/L by static adsorption for 10 minutes at room temperature, and the lead adsorption removal rate reaches 97.7 percent.
Comparative example 1
Macroporous alumina was prepared according to the method of Chemical materials, 2004,16: 4245-. The material obtained has only one type of macropore distribution and a mechanical strength of only 1N/mm.
Comparative example 2
Monolithic macroporous alumina was prepared according to the method of CN101200297A, and the obtained material had only one type of macroporous distribution and mechanical strength of only 2N/mm. When the material is used for the lead-containing wastewater in example 4, the lead adsorption removal rate is only 74.4%.
Claims (13)
1. A monolithic alumina material characterized by: the material is of a honeycomb structure, the wall of a honeycomb hole is provided with microscopic macroporous pores, the pore diameter of the macroporous is 50-1000nm, the macropores are uniformly distributed and are communicated in a three-dimensional way, and the ratio of the pore diameter of the macroporous to the corresponding wall thickness is 0.5-4.5.
2. The monolithic alumina material of claim 1 wherein: the total porosity of the monolithic alumina material is 20-90 percent, and the specific surface area is 100-450m2G, pore volume of 0.3-1.5cm3(iv) g, the mechanical strength is 5 to 30N/mm, preferably 10 to 25N/mm.
3. The monolithic alumina material of claim 1 wherein: the number of the honeycomb holes distributed on the cross section is 1-50 holes/cm by taking the cross section vertical to the honeycomb hole channel as the reference2Preferably 2 to 25 pores/cm2。
4. The method for preparing the monolithic alumina material of claim 1, comprising the steps of: (1) uniformly dispersing boehmite powder in water to obtain a boehmite suspension, slowly adding a peptizing agent into the boehmite powder suspension, and after the addition is finished, heating and aging for a certain time to obtain clear alumina sol; (2) uniformly mixing inorganic aluminum salt, polyethylene glycol, the alumina sol obtained in the step (1), an amide compound and a low-carbon alcohol aqueous solution, adding propylene oxide and/or pyridine, uniformly mixing, casting the mixture into a reverse honeycomb mold, and waiting until gel is obtained; (3) aging the gel obtained in the step (2) at 20-80 ℃ for 12-120 hours, and removing the die to obtain an aged product; (4) soaking the aged product in a low-carbon alcohol aqueous solution, then carrying out solid-liquid separation, and drying and roasting a solid phase to obtain an integral aluminum oxide material; wherein the viscosity average molecular weight of the polyethylene glycol is 10000-.
5. The method of claim 4, wherein: the solid content of the suspension liquid in the step (1) is 1-15 wt%; the step (1) is carried out under the condition of stirring, and the aging is carried out in a heating reflux mode, wherein the reflux temperature is 70-95 ℃, and the reflux time is 1-12 hours.
6. The method of claim 4, wherein: the peptizing agent in the step (1) is one or more of hydrochloric acid, nitric acid, sulfuric acid, formic acid or acetic acid; the dosage of the peptizing agent is calculated by the contained H + and the dosage of the boehmite powder is calculated by the contained Al+The mol ratio of Al to Al is 0.05-1.
7. The method of claim 4, wherein: based on the weight of the mixture obtained in the step (2), the adding amount of the lower alcohol aqueous solution is 10-80 wt%, the adding amount of the inorganic aluminum salt is 5-30 wt%, the adding amount of the aluminum sol is 1-10 wt%, and the adding amount of the polyethylene glycol is 0.1-3.0 wt%; wherein the mass ratio of water to the low-carbon alcohol in the low-carbon alcohol aqueous solution is 1.0-1.5; the addition amount of the amide compound is 0.1-5.0 wt%.
8. The method of claim 4, wherein: propylene oxide and/or pyridine with Al3+Is 1.5 to 9.5, and does not contain Al in the alumina sol.
9. The method of claim 4, wherein: the inorganic aluminum salt in the step (2) is one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
10. The method of claim 4, wherein: the lower alcohol in the steps (2) and (4) is C5The following alcohols.
11. The method of claim 4, wherein: the amide compound in the step (2) is one or more of formamide, acetamide, N-dimethylformamide, N-methylacetamide, benzamide or 2-phenylacetamide.
12. The method of claim 4, wherein: the soaking conditions in the step (4) are as follows: the soaking temperature is 10-80 ℃, and the soaking time is 12-60 hours; the mass concentration of the low-carbon alcohol aqueous solution used for soaking is not less than 50 wt%.
13. The application of the monolithic aluminum oxide material disclosed in any one of claims 1 to 3 in hydrogenation reaction, alkylation reaction, desulfurization and denitration reaction, and adsorption and degradation of pollutants in a water treatment process.
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