CN108525668B - Preparation method of sepiolite nanofiber loaded cobalt-aluminum composite oxide - Google Patents
Preparation method of sepiolite nanofiber loaded cobalt-aluminum composite oxide Download PDFInfo
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- CN108525668B CN108525668B CN201810359054.5A CN201810359054A CN108525668B CN 108525668 B CN108525668 B CN 108525668B CN 201810359054 A CN201810359054 A CN 201810359054A CN 108525668 B CN108525668 B CN 108525668B
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 64
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 64
- 239000002121 nanofiber Substances 0.000 title claims abstract description 44
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229940105956 tea-dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 11
- LTXHKPDRHPMBKA-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2] LTXHKPDRHPMBKA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000001788 irregular Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 3
- 229940009827 aluminum acetate Drugs 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- YRVVJFGDXVSGCG-UHFFFAOYSA-I aluminum;cobalt(2+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2] YRVVJFGDXVSGCG-UHFFFAOYSA-I 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- UMWXOUAFWWUNGR-UHFFFAOYSA-N aluminum cobalt(2+) oxygen(2-) Chemical class [Co+2].[O-2].[Al+3] UMWXOUAFWWUNGR-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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Abstract
本发明海泡石纳米纤维负载钴铝复合氧化物的制备方法，涉及复合材料，用可溶性钴盐、可溶性铝盐和海泡石纳米纤维为原料，与有机物配制成前躯体混合液，再利用微波水热法一步制得海泡石纳米纤维负载钴铝复合氧化物的复合材料。本发明既克服了现有技术制得的钴铝氧化物均存在产品为不规则状颗粒，团聚现象严重，制备工艺繁琐，所需能耗高，生产成本高的缺陷，又克服了现有技术制备海泡石基金属氧化物复合材料的方法中存在的制备周期长和成本高的缺陷。The preparation method of the sepiolite nanofiber-supported cobalt-aluminum composite oxide of the present invention relates to a composite material. The soluble cobalt salt, the soluble aluminum salt and the sepiolite nanofiber are used as raw materials, and the organic matter is prepared into a precursor mixed solution, and then microwave The cobalt-aluminum composite oxide composite material supported by sepiolite nanofibers was prepared in one step by hydrothermal method. The invention not only overcomes the defects of the cobalt aluminum oxide prepared by the prior art that the products are irregular particles, the agglomeration phenomenon is serious, the preparation process is cumbersome, the required energy consumption is high, and the production cost is high, but also the prior art is overcome. The method for preparing the sepiolite-based metal oxide composite material has the defects of long preparation cycle and high cost.
Description
Technical Field
The technical scheme of the invention relates to a composite material, in particular to a preparation method of sepiolite nanofiber loaded cobalt-aluminum composite oxide.
Background
The cobalt aluminum oxide has good catalytic performance as a catalyst and a catalyst carrier, and shows higher catalytic activity for removing soot and nitrogen oxide. At present, the preparation methods of cobalt aluminum oxide mainly comprise a solid phase method, a coprecipitation method, a hydrothermal method and a sol-gel method. CN103943850A discloses a method for preparing lithium nickel cobalt aluminum oxide material by using low thermal solid phase reaction; CN105098171A discloses a preparation method of cobalt-aluminum oxide for lithium ion power batteries, which is a preparation method adopting a coprecipitation method; CN107170588A discloses a carbon and nitrogen doped cobalt aluminum oxide composite material and a preparation method thereof, which introduces that cobalt nitrate, aluminum nitrate and urea are used as raw materials, cobalt aluminum hydroxide is synthesized by a hydrothermal method, and then the cobalt aluminum hydroxide is calcined at high temperature in a tubular furnace to obtain the carbon and nitrogen doped cobalt aluminum oxide. The cobalt-aluminum oxide prepared by the prior art has the defects of irregular particle, serious particle agglomeration phenomenon, complicated preparation process, high required energy consumption and high production cost.
Sepiolite is a magnesium-rich silicate clay mineral with a theoretical chemical formula of Mg8Si12O30(OH)4(OH2)4·8H2The structure of O is composed of two layers of silicon-oxygen tetrahedrons, a layer of magnesium-oxygen octahedron is sandwiched between the two layers of silicon-oxygen tetrahedrons, and the O has chain-shaped and layered transition structures, has large specific surface area and unique pore structure, and also has stronger adsorbability and thermal stability, thereby being used as a carrier of a catalyst. Sepiolite as a carrier of a catalyst can increase the dispersibility and uniformity of a supported substance, and therefore, research on sepiolite as a carrier in the field of catalyst supporting is a hot spot at present. The methods for preparing the sepiolite-based metal oxide composite material in the prior art mainly comprise a chemical precipitation method, an impregnation method and a hydrothermal method. CN107344093A discloses sepiolite/TiO with multichannel structure and strong adsorption performance2The composite material is prepared through coprecipitation process with ammonia water as precipitant and TiO supported on sepiolite fiber2The nano particles can generate the defect of agglomeration phenomenon in the high-temperature calcination process; CN106040278A discloses a preparation method and application of a nitrogen-doped acid-activated sepiolite-loaded Pd-Ni bimetallic catalyst, wherein the method comprises the steps of taking nitrogen-doped acidified sepiolite as a carrier, and impregnating and loading nickel salt and palladium salt on the sepiolite carrier to obtain the Pd-Ni bimetallic catalyst, wherein the Pd-Ni bimetallic catalyst has the defects that active components are easy to migrate in the impregnation process and the catalytic effect is weakened; CN106076422A discloses sepiolite-loaded porphyrin-sensitized Bi2WO6The preparation method of the visible light catalyst adopts a hydrothermal method to prepare sepiolite-loaded porphyrin-sensitized Bi2WO6The visible light catalyst needs hydrothermal reaction for 48 hours, and has the defects of long preparation period and high cost. Aiming at the defects of the method for preparing the sepiolite-based metal oxide composite material in the prior art, the preparation method of the sepiolite-based metal oxide composite material is innovatedThe development and application of the composite material are particularly important.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method of the sepiolite nanofiber-loaded cobalt-aluminum composite oxide is characterized in that the composite material of the sepiolite nanofiber-loaded cobalt-aluminum composite oxide is prepared in one step by a microwave hydrothermal method, and not only are the defects that all the cobalt-aluminum oxides prepared in the prior art are irregular particles, serious in agglomeration phenomenon, complex in preparation process, high in required energy consumption and high in production cost overcome, but also the defects of long preparation period and high cost in the method for preparing the sepiolite-based metal oxide composite material in the prior art are overcome.
The technical scheme adopted by the invention for solving the technical problem is as follows: the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide is to prepare the composite material of the sepiolite nanofiber loaded cobalt-aluminum composite oxide by one step by using a microwave hydrothermal method, and comprises the following specific steps:
step one, preparing a solution A:
weighing soluble cobalt salt and soluble aluminum salt with required dosage, dissolving the soluble cobalt salt and the soluble aluminum salt in deionized water to ensure that the concentration of Co ions is 0.1-0.5 mol/L and the molar ratio of the Co ions to Al ions is 1-4: 2, stirring for 0.5-3 h at constant temperature of 30-60 ℃, and preparing to obtain a solution A;
secondly, preparing a suspension B:
dispersing sepiolite nanofibers in deionized water, enabling the mass ratio of the sepiolite nanofibers to the deionized water to the soluble cobalt salt and the soluble aluminum salt used in the first step to be 1: 10-15, stirring at the constant temperature of 30-60 ℃ for 0.5-3 hours, and preparing a suspension B;
step three, preparing a mixed solution C:
mixing and stirring the solution A prepared in the first step and the suspension B prepared in the second step, then adjusting the pH of the mixed solution to 9-13, and stirring at the constant temperature of 60-90 ℃ for 0.5-3 h to prepare a mixed solution C;
step four, preparing precursor mixed liquid:
adding organic matters into the mixed solution C prepared in the third step, wherein the volume of the added organic matters is 3-15% of the volume of the mixed solution C, and stirring at the constant temperature of 30-60 ℃ for 0.5-3 h to prepare a precursor mixed solution;
fifthly, microwave hydrothermal reaction:
placing the precursor mixed solution prepared in the fourth step into a hydrothermal kettle, controlling the filling degree of the hydrothermal kettle to be 50% -70%, then placing the hydrothermal kettle into microwave hydrothermal equipment, setting the temperature to be 190-250 ℃, the pressure to be 3-4 MPa, and the reaction time to be 2-5 h, and naturally cooling to room temperature after the reaction is finished, so as to finish the microwave hydrothermal reaction;
sixthly, post-treating to obtain the sepiolite nanofiber loaded cobalt-aluminum composite oxide composite material:
and (3) after the microwave hydrothermal method reaction in the fifth step is finished, opening the hydrothermal kettle, taking out a product, performing suction filtration and washing by using deionized water until the product is neutral, washing by using absolute ethyl alcohol, drying in a drying oven at 60-90 ℃ for 6-24 hours, grinding to be powder, and finishing post-treatment, thereby preparing the sepiolite nanofiber supported cobalt-aluminum composite oxide composite material.
In the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide, the soluble cobalt salt is cobalt nitrate, cobalt sulfate or cobalt chloride.
In the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide, the soluble aluminum salt is aluminum nitrate, aluminum acetate or aluminum chloride.
According to the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide, the organic matter is ethylene glycol, triethanolamine or sodium dodecyl benzene sulfonate.
According to the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide, the microwave hydrothermal equipment is a multipurpose microwave chemical synthesizer, a microwave hydrothermal reaction instrument or a microwave hydrothermal parallel synthesizer.
According to the preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide, the filling degree is the volume percentage of the filler in the hydrothermal kettle.
According to the preparation method of the sepiolite nanofiber-supported cobalt-aluminum composite oxide, the raw material sepiolite nanofiber is prepared according to the method disclosed in CN200910070297.8, other raw materials are obtained commercially, the related equipment is well known in the art, and the related process operation method can be mastered by a person skilled in the art.
The invention has the beneficial effects that: compared with the prior art, the invention has the following prominent substantive characteristics and remarkable progress:
(1) as the structure of the sepiolite consists of two layers of silicon-oxygen tetrahedrons sandwiching one layer of magnesium-oxygen octahedron, the sepiolite has chain and layered transition structures, has large specific surface area and unique pore structure, and also has stronger adsorbability and thermal stability, the sepiolite can be used as a carrier of a catalyst to increase the dispersity and uniformity of a load.
(2) The sepiolite nanofiber loaded cobalt-aluminum composite oxide is different from carbon-nitrogen doped cobalt-aluminum oxide composite materials of CN107170588A in the prior art in nature. CN107170588A carbon nitrogen doped cobalt aluminum oxide, which should be a compound and not a composite oxide material in nature. Meanwhile, CN107170588A has a disadvantage that the obtained material may affect the full exertion of its properties due to agglomeration and other factors. The invention effectively controls the appearance of the cobalt-aluminum composite oxide by introducing the sepiolite nanofibers in the microwave hydrothermal process, and overcomes the defect that the performance of the cobalt-aluminum composite oxide is influenced by agglomeration.
(3) The composite material of the sepiolite nanofiber loaded cobalt-aluminum composite oxide is prepared in one step by adopting a microwave hydrothermal method, and the preparation method is simple to operate and short in preparation period.
(4) According to the invention, the morphology of the composite material is regulated by adding the organic matters, and the obtained composite material has small granularity, high purity and good dispersibility.
(5) The invention overcomes the defects of serious agglomeration and sintering in the high-temperature calcination process of CN107344093A in the prior art.
Detailed Description
Example 1
Step one, preparing a solution A:
weighing cobalt nitrate and aluminum nitrate with required dosage, dissolving in deionized water to ensure that the concentration of Co ions is 0.1mol/L and the molar ratio of the Co ions to the Al ions is 1: 2, and stirring at constant temperature of 30 ℃ for 0.5h to prepare a solution A;
secondly, preparing a suspension B:
dispersing sepiolite nano fibers into deionized water, enabling the mass ratio of the sepiolite nano fibers to the deionized water to the cobalt nitrate and the aluminum nitrate used in the first step to be 1: 10, and stirring at constant temperature of 30 ℃ for 0.5h to prepare suspension B;
step three, preparing a mixed solution C:
mixing and stirring the solution A prepared in the first step and the suspension B prepared in the second step, then adjusting the pH of the mixed solution to 9, and stirring at the constant temperature of 60 ℃ for 0.5h to prepare a mixed solution C;
step four, preparing precursor mixed liquid:
adding ethylene glycol into the mixed solution C prepared in the third step, wherein the volume of the added ethylene glycol is 3% of the volume of the mixed solution C, and stirring at the constant temperature of 30 ℃ for 0.5h to prepare a precursor mixed solution;
fifthly, microwave hydrothermal reaction:
placing the precursor mixed solution prepared in the fourth step into a hydrothermal kettle, controlling the filling degree of the hydrothermal kettle to be 50%, then placing the hydrothermal kettle into a multipurpose microwave chemical synthesizer, setting the temperature to be 190 ℃, the pressure to be 3MPa and the reaction time to be 2h, and naturally cooling to room temperature after the reaction is finished, so as to finish the microwave hydrothermal reaction;
sixthly, post-treating to obtain the sepiolite nanofiber loaded cobalt-aluminum composite oxide composite material:
and (3) after the microwave hydrothermal method reaction in the fifth step is finished, opening the hydrothermal kettle, taking out a product, performing suction filtration and washing by using deionized water until the product is neutral, washing by using absolute ethyl alcohol, drying in a drying oven at 60 ℃ for 6 hours, grinding to powder, and finishing post-treatment, thereby preparing the sepiolite nanofiber supported cobalt-aluminum composite oxide composite material.
Example 2
Step one, preparing a solution A:
weighing cobalt sulfate and aluminum acetate with required dosage, dissolving in deionized water to ensure that the concentration of Co ions is 0.3mol/L and the molar ratio of the Co ions to the Al ions is 2: 2, stirring at constant temperature of 45 ℃ for 1.5h, and preparing to obtain a solution A;
secondly, preparing a suspension B:
dispersing sepiolite nano fibers in deionized water to ensure that the mass ratio of the sepiolite nano fibers to the deionized water to the cobalt sulfate and the aluminum acetate used in the first step is 1: 10: 12, and stirring at the constant temperature of 45 ℃ for 1.5 hours to prepare a suspension B;
step three, preparing a mixed solution C:
mixing and stirring the solution A prepared in the first step and the suspension B prepared in the second step, then adjusting the pH value of the mixed solution to 11, and stirring for 1.5h at the constant temperature of 75 ℃ to prepare a mixed solution C;
step four, preparing precursor mixed liquid:
adding triethanolamine into the mixed solution C prepared in the third step, wherein the volume of the added organic matters is 9 percent of the volume of the mixed solution C, and stirring at the constant temperature of 45 ℃ for 1.5 hours to prepare a precursor mixed solution;
fifthly, microwave hydrothermal reaction:
placing the precursor mixed solution prepared in the fourth step into a hydrothermal kettle, controlling the filling degree of the hydrothermal kettle to be 60%, then placing the hydrothermal kettle into a microwave hydrothermal reactor, setting the temperature to be 220 ℃, the pressure to be 3.5MPa and the reaction time to be 4h, and naturally cooling to room temperature after the reaction is finished, so as to finish the microwave hydrothermal reaction;
sixthly, post-treating to obtain the sepiolite nanofiber loaded cobalt-aluminum composite oxide composite material:
and (3) after the microwave hydrothermal method reaction in the fifth step is finished, opening the hydrothermal kettle, taking out a product, performing suction filtration and washing by using deionized water until the product is neutral, washing by using absolute ethyl alcohol, drying in a drying oven at 75 ℃ for 15 hours, grinding to be powder, and finishing post-treatment, thereby preparing the sepiolite nanofiber supported cobalt-aluminum composite oxide composite material.
Example 3
Step one, preparing a solution A:
weighing cobalt chloride and aluminum chloride with required dosage, dissolving in deionized water to ensure that the concentration of Co ions is 0.5mol/L and the molar ratio of the Co ions to the Al ions is 4: 2, stirring at constant temperature of 60 ℃ for 3 hours, and preparing to obtain a solution A;
secondly, preparing a suspension B:
dispersing sepiolite nanofibers in deionized water to enable the mass ratio of the sepiolite nanofibers to the deionized water to the cobalt chloride and the aluminum chloride salt used in the first step to be 1: 10: 15, and stirring for 3 hours at a constant temperature of 60 ℃ to prepare suspension B;
step three, preparing a mixed solution C:
mixing and stirring the solution A prepared in the first step and the suspension B prepared in the second step, then adjusting the pH of the mixed solution to 13, and stirring for 3 hours at a constant temperature of 90 ℃ to prepare a mixed solution C;
step four, preparing precursor mixed liquid:
adding sodium dodecyl benzene sulfonate into the mixed solution C prepared in the third step, wherein the volume of the added organic matters is 15% of the volume of the mixed solution C, and stirring at the constant temperature of 60 ℃ for 3 hours to prepare a precursor mixed solution;
fifthly, microwave hydrothermal reaction:
placing the precursor mixed solution prepared in the fourth step into a hydrothermal kettle, controlling the filling degree of the hydrothermal kettle to be 70%, then placing the hydrothermal kettle into a microwave hydrothermal parallel synthesizer, setting the temperature to be 250 ℃, the pressure to be 4MPa and the reaction time to be 5h, and naturally cooling to room temperature after the reaction is finished, so as to finish the microwave hydrothermal reaction;
sixthly, post-treating to obtain the sepiolite nanofiber loaded cobalt-aluminum composite oxide composite material:
and (3) after the microwave hydrothermal method reaction in the fifth step is finished, opening the hydrothermal kettle, taking out a product, performing suction filtration and washing by using deionized water until the product is neutral, washing by using absolute ethyl alcohol, drying in a drying oven at 90 ℃ for 24 hours, grinding to powder, and finishing post-treatment, thereby preparing the sepiolite nanofiber supported cobalt-aluminum composite oxide composite material.
In the above examples, the filling degree is the volume percentage of the filler in the hydrothermal kettle, the raw material sepiolite nanofiber is prepared according to the method disclosed in CN200910070297.8, other raw materials are commercially available, the related equipment is well known in the art, and the related process operation method can be grasped by those skilled in the art.
Claims (3)
1. The preparation method of the sepiolite nanofiber loaded cobalt-aluminum composite oxide is characterized by comprising the following steps of: the method is characterized by preparing the sepiolite nanofiber-loaded cobalt-aluminum composite oxide composite material by one step by using a microwave hydrothermal method, and comprises the following specific steps:
step one, preparing a solution A:
weighing soluble cobalt salt and soluble aluminum salt with required dosage, dissolving the soluble cobalt salt and the soluble aluminum salt in deionized water to ensure that the concentration of Co ions is 0.1-0.5 mol/L and the molar ratio of the Co ions to Al ions is 1-4: 2, stirring for 0.5-3 h at constant temperature of 30-60 ℃, and preparing to obtain a solution A;
secondly, preparing a suspension B:
dispersing sepiolite nanofibers in deionized water, enabling the mass ratio of the sepiolite nanofibers to the deionized water to the soluble cobalt salt and the soluble aluminum salt used in the first step to be 1: 10-15, stirring at the constant temperature of 30-60 ℃ for 0.5-3 hours, and preparing a suspension B;
step three, preparing a mixed solution C:
mixing and stirring the solution A prepared in the first step and the suspension B prepared in the second step, then adjusting the pH = 9-13 of the mixed solution, and stirring for 0.5-3 h at a constant temperature of 60-90 ℃ to prepare a mixed solution C;
step four, preparing precursor mixed liquid:
adding an organic matter into the mixed solution C prepared in the third step, wherein the volume of the added organic matter is 3% -15% of the volume of the mixed solution C, stirring at the constant temperature of 30-60 ℃ for 0.5-3 h, and preparing a precursor mixed solution, wherein the organic matter is ethylene glycol, triethanolamine or sodium dodecyl benzene sulfonate;
fifthly, microwave hydrothermal reaction:
placing the precursor mixed solution prepared in the fourth step into a hydrothermal kettle, controlling the filling degree of the hydrothermal kettle to be 50% -70%, then placing the hydrothermal kettle into microwave hydrothermal equipment, setting the temperature to be 190-250 ℃, the pressure to be 3-4 MPa, and the reaction time to be 2-5 h, and naturally cooling to room temperature after the reaction is finished, so as to finish the microwave hydrothermal reaction;
sixthly, post-treating to obtain the sepiolite nanofiber loaded cobalt-aluminum composite oxide composite material:
and (3) after the microwave hydrothermal method reaction in the fifth step is finished, opening the hydrothermal kettle, taking out a product, performing suction filtration and washing by using deionized water until the product is neutral, washing by using absolute ethyl alcohol, drying in a drying oven at 60-90 ℃ for 6-24 hours, grinding to be powder, and finishing post-treatment, thereby preparing the sepiolite nanofiber supported cobalt-aluminum composite oxide composite material.
2. The preparation method of the sepiolite nanofiber supported cobalt-aluminum composite oxide according to claim 1, characterized in that: the microwave hydrothermal equipment is a multipurpose microwave chemical synthesizer, a microwave hydrothermal reaction instrument or a microwave hydrothermal parallel synthesizer.
3. The preparation method of the sepiolite nanofiber supported cobalt-aluminum composite oxide according to claim 1, characterized in that: the sepiolite nanofibers are compounded with the cobalt-aluminum composite oxide, so that the dispersity, size uniformity and catalytic performance of the cobalt-aluminum composite oxide are improved.
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