CN108525668A - The preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite - Google Patents
The preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite Download PDFInfo
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- CN108525668A CN108525668A CN201810359054.5A CN201810359054A CN108525668A CN 108525668 A CN108525668 A CN 108525668A CN 201810359054 A CN201810359054 A CN 201810359054A CN 108525668 A CN108525668 A CN 108525668A
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- 239000004113 Sepiolite Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 235000019355 sepiolite Nutrition 0.000 title claims abstract description 63
- 229910052624 sepiolite Inorganic materials 0.000 title claims abstract description 63
- 239000002121 nanofiber Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract 4
- 239000010941 cobalt Substances 0.000 claims abstract 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000003839 salts Chemical class 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 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
- 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 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 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 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 4
- 238000012805 post-processing Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 230000007547 defect Effects 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 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 8
- 239000002245 particle Substances 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
- 230000001788 irregular Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 238000011049 filling Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- UMWXOUAFWWUNGR-UHFFFAOYSA-N aluminum cobalt(2+) oxygen(2-) Chemical class [Co+2].[O-2].[Al+3] UMWXOUAFWWUNGR-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- 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
- YRVVJFGDXVSGCG-UHFFFAOYSA-I aluminum;cobalt(2+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2] YRVVJFGDXVSGCG-UHFFFAOYSA-I 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002940 palladium Chemical class 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
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229940105956 tea-dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J37/08—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
Description
技术领域technical field
本发明的技术方案涉及复合材料，具体地说是海泡石纳米纤维负载钴铝复合氧化物的制备方法。The technical proposal of the invention relates to composite materials, specifically a method for preparing cobalt-aluminum composite oxides supported by sepiolite nanofibers.
背景技术Background technique
钴铝氧化物作为催化剂和催化剂载体都有良好的催化性能，表现出较高的除碳烟和氮氧化物的催化活性。目前，钴铝氧化物的制备方法主要有固相法、共沉淀法、水热法和溶胶凝胶法。CN103943850A公开了一种采用低热固相反应制备锂镍钴铝氧化物材料的方法；CN105098171A公开了锂离子动力电池用钴铝氧化物的制备方法，是采用共沉淀法的制备方法；CN107170588A公开了一种碳氮掺杂钴铝氧化物复合材料及其制备方法，介绍了以硝酸钴、硝酸铝和尿素为原料，用水热法合成钴铝氢氧化物，然后在管式炉中进行高温煅烧得到碳氮掺杂钴铝氧化物。用上述现有技术制得的钴铝氧化物均存在产品为不规则状颗粒，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。Cobalt aluminum oxide has good catalytic performance as a catalyst and a catalyst carrier, and shows a high catalytic activity for removing soot and nitrogen oxides. At present, the preparation methods of cobalt aluminum oxide mainly include solid phase method, co-precipitation method, hydrothermal method and sol-gel method. CN103943850A discloses a method for preparing lithium-nickel-cobalt-aluminum oxide materials by low-heat solid-state reaction; CN105098171A discloses a method for preparing cobalt-aluminum oxides for lithium-ion power batteries, which is a preparation method using coprecipitation; CN107170588A discloses a A carbon-nitrogen-doped cobalt-aluminum oxide composite material and its preparation method, introduces the use of cobalt nitrate, aluminum nitrate and urea as raw materials, the hydrothermal synthesis of cobalt-aluminum hydroxide, and then high-temperature calcination in a tube furnace to obtain carbon Nitrogen doped cobalt aluminum oxide. The cobalt-aluminum oxides prepared by the above-mentioned prior art all have defects such as irregular particles, serious particle agglomeration, cumbersome preparation process, high energy consumption and high production cost.
海泡石是一种富镁硅酸盐粘土矿物，其理论化学式为Mg8Si12O30(OH)4(OH2)4·8H2O，其结构由两层硅氧四面体中间夹一层镁氧八面体组成，具有链状和层状过渡型结构、具有大的比表面积和具有独特的孔结构，还具有较强的吸附性和热稳定性，因而可用作催化剂的载体。海泡石作为催化剂的载体可以增大负载物的分散性与均匀性，因此，目前海泡石在催化剂的负载领域作为载体的研究成为热点。现有技术中制备海泡石基金属氧化物复合材料的方法主要有化学沉淀法、浸渍法和水热法。CN107344093A公开了一种多通道结构强吸附性能的海泡石/TiO2复合材料及其制备方法，采用以氨水为沉淀剂的共沉淀法，存在负载于海泡石纤维上的TiO2纳米颗粒在高温煅烧过程中会产生团聚现象的缺陷；CN106040278A公开了一种氮掺杂的酸活化海泡石负载Pd-Ni双金属催化剂的制备方法及应用，是以掺氮的酸化海泡石为载体，将镍盐和钯盐浸渍负载到海泡石载体上，得到Pd-Ni双金属催化剂，其存在在浸渍过程中活性组分易发生迁移，催化效果减弱的缺陷；CN106076422A公开了一种海泡石负载卟啉敏化Bi2WO6可见光催化剂的制备方法，采用水热法制备出海泡石负载卟啉敏化Bi2WO6可见光催化剂，该方法需要水热反应48h，存在制备周期长和成本高的缺陷。针对上述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不足和缺陷，创新海泡石基金属氧化物复合材料的制备方法对这类复合材料的研发和应用显得尤为重要。Sepiolite is a magnesium-rich silicate clay mineral. Its theoretical chemical formula is Mg 8 Si 12 O 30 (OH) 4 (OH 2 ) 4 8H 2 O. Its structure consists of two layers of silicon-oxygen tetrahedrons sandwiching a Composed of layer magnesium oxygen octahedron, it has a chain and layer transition structure, a large specific surface area and a unique pore structure, and also has strong adsorption and thermal stability, so it can be used as a catalyst carrier. Sepiolite as a catalyst carrier can increase the dispersion and uniformity of the load. Therefore, the research on sepiolite as a carrier in the field of catalyst loading has become a hot spot. The methods for preparing sepiolite-based metal oxide composite materials in the prior art mainly include chemical precipitation method, impregnation method and hydrothermal method. CN107344093A discloses a sepiolite/ TiO2composite material with multi-channel structure and strong adsorption performance and its preparation method. It adopts the co-precipitation method with ammonia water as precipitant, and the TiO2nanoparticles loaded on the sepiolite fiber exist at high temperature. The defect of agglomeration phenomenon can occur in the calcining process; CN106040278A discloses a preparation method and application of a nitrogen-doped acid-activated sepiolite loaded Pd-Ni bimetallic catalyst. Nickel salt and palladium salt are impregnated and loaded on the sepiolite carrier to obtain a Pd-Ni bimetallic catalyst, which has the defect that the active component is easy to migrate during the impregnation process and the catalytic effect is weakened; CN106076422A discloses a sepiolite-loaded The preparation method of porphyrin-sensitized Bi 2 WO 6 visible light catalyst uses hydrothermal method to prepare sepiolite-loaded porphyrin-sensitized Bi 2 WO 6 visible light catalyst. defect. In view of the deficiencies and defects in the methods for preparing sepiolite-based metal oxide composite materials in the above-mentioned prior art, it is particularly important to innovate the preparation method of sepiolite-based metal oxide composite materials for the development and application of such composite materials.
发明内容Contents of the invention
本发明所要解决的技术问题是：提供海泡石纳米纤维负载钴铝复合氧化物的制备方法，是利用微波水热法一步制备海泡石纳米纤维负载钴铝复合氧化物的复合材料，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 technical problem to be solved by the present invention is to provide a preparation method for cobalt-aluminum composite oxide supported by sepiolite nanofibers, which uses microwave hydrothermal method to prepare the composite material of sepiolite nanofibers loaded cobalt-aluminum composite oxide in one step, which not only overcomes The cobalt-aluminum oxides prepared by the prior art all have the defects 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, and the preparation of sepiolite by the prior art is overcome. The defects of long preparation cycle and high cost exist in the method of the base metal oxide composite material.
本发明解决该技术问题所采用的技术方案是：海泡石纳米纤维负载钴铝复合氧化物的制备方法，是利用微波水热法一步制备海泡石纳米纤维负载钴铝复合氧化物的复合材料，具体步骤如下：The technical scheme adopted by the present invention to solve the technical problem is: the preparation method of cobalt-aluminum composite oxide supported by sepiolite nanofibers is a composite material of cobalt-aluminum composite oxide supported by sepiolite nanofibers in one step by utilizing microwave hydrothermal method ,Specific steps are as follows:
第一步，配制溶液A：The first step is to prepare solution A:
称取所需用量的可溶性钴盐和可溶性铝盐溶于去离子水中，使Co离子的浓度为0.1mol/L～0.5mol/L，Co离子与Al离子的摩尔比为1～4∶2，恒温30～60℃下搅拌0.5～3h，配制得到溶液A；Take the required amount of soluble cobalt salt and soluble aluminum salt and dissolve them in deionized water, so that the concentration of Co ions is 0.1mol/L～0.5mol/L, and the molar ratio of Co ions to Al ions is 1～4:2, Stir at a constant temperature of 30-60°C for 0.5-3 hours to prepare solution A;
第二步，配制悬浮液B：The second step, preparation of suspension B:
取海泡石纳米纤维分散于去离子水中，使海泡石纳米纤维、去离子水和上述第一步中所用的可溶性钴盐和可溶性铝盐三者之间的质量比为1∶10∶10～15，恒温30～60℃下搅拌0.5～3h，配制得到悬浮液B；Get sepiolite nanofibers and disperse them in deionized water, so that the mass ratio between sepiolite nanofibers, deionized water and the soluble cobalt salt and soluble aluminum salt used in the above-mentioned first step is 1:10:10 ～15, stir at a constant temperature of 30～60°C for 0.5～3h, and prepare suspension B;
第三步，配制混合液C：The third step is to prepare the mixture C:
将上述第一步配制得到的溶液A和上述第二步配制得到的悬浮液B混合搅拌，然后调节混合液的pH＝9～13，恒温60～90℃下搅拌0.5～3h，配制得到混合液C；Mix and stir the solution A prepared in the first step above and the suspension B prepared in the second step above, then adjust the pH of the mixed solution to 9-13, stir at a constant temperature of 60-90°C for 0.5-3 hours, and prepare the mixed solution C;
第四步，配制前躯体混合液：The fourth step is to prepare the precursor mixture:
将有机物加入上述第三步配制得到的混合液C中，所加有机物的体积量为混合液C的体积的3％～15％，恒温30～60℃下搅拌0.5～3h，配制得到前躯体混合液；Add the organic matter to the mixed solution C prepared in the third step above, the volume of the added organic matter is 3% to 15% of the volume of the mixed solution C, stir at a constant temperature of 30-60°C for 0.5-3h, and prepare the precursor mixture liquid;
第五步，微波水热法反应：The fifth step, microwave hydrothermal reaction:
将上述第四步配制得到的前躯体混合液置于水热釜中，控制该水热釜的填充度为50％～70％，然后将水热釜放入微波水热设备中，温度设定为190～250℃，压力为3～4MPa，反应时间为2～5h，反应结束后自然冷却至室温，至此完成微波水热法反应；Place the precursor mixed solution prepared in the fourth step above in a hydrothermal kettle, control the filling degree of the hydrothermal kettle to 50% to 70%, then put the hydrothermal kettle into a microwave hydrothermal equipment, and set the temperature to The temperature is 190~250℃, the pressure is 3~4MPa, and the reaction time is 2~5h. After the reaction is completed, it is naturally cooled to room temperature, and the microwave hydrothermal reaction is completed so far;
第六步，后处理，制得海泡石纳米纤维负载钴铝复合氧化物的复合材料：The sixth step is post-treatment to prepare a composite material of sepiolite nanofiber loaded cobalt-aluminum composite oxide:
在完成上述第五步的微波水热法反应后，打开水热釜，取出产物，用去离子水抽滤洗涤至中性，再用无水乙醇洗涤，置于干燥箱中在60～90℃下干燥6～24h，研磨至粉末状，完成后处理，由此制得海泡石纳米纤维负载钴铝复合氧化物的复合材料。After completing the microwave hydrothermal reaction in the fifth step above, open the hydrothermal kettle, take out the product, filter and wash it with deionized water until it is neutral, then wash it with absolute ethanol, and place it in a drying oven at 60-90°C Drying for 6 to 24 hours, grinding to powder, and completing post-treatment, thereby preparing a composite material of cobalt-aluminum composite oxide supported by sepiolite nanofibers.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述可溶性钴盐为硝酸钴、硫酸钴或氯化钴。In the method for preparing cobalt-aluminum composite oxide supported on sepiolite nanofibers, the soluble cobalt salt is cobalt nitrate, cobalt sulfate or cobalt chloride.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述可溶性铝盐为硝酸铝、醋酸铝或氯化铝。In the preparation method of the cobalt-aluminum composite oxide supported on sepiolite nanofibers, the soluble aluminum salt is aluminum nitrate, aluminum acetate or aluminum chloride.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述有机物为乙二醇、三乙醇胺或十二烷基苯磺酸钠。In the preparation method of the cobalt-aluminum composite oxide supported by sepiolite nanofibers, the organic matter is ethylene glycol, triethanolamine or sodium dodecylbenzenesulfonate.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述微波水热设备为多用途微波化学合成仪、微波水热反应仪或微波水热平行合成仪。In the preparation method of the above-mentioned cobalt-aluminum composite oxide supported on sepiolite nanofibers, the microwave hydrothermal equipment is a multi-purpose microwave chemical synthesizer, a microwave hydrothermal reaction instrument or a microwave hydrothermal parallel synthesizer.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述填充度为填充物占水热釜的体积百分比。In the above method for preparing cobalt-aluminum composite oxide supported by sepiolite nanofibers, the filling degree is the volume percentage of the filler in the hydrothermal kettle.
上述海泡石纳米纤维负载钴铝复合氧化物的制备方法，所述原料海泡石纳米纤维是按照CN200910070297.8公开的方法所制备，其他原料均通过商购获得，所涉及的设备为本领域公知的，所涉及的工艺操作方法是本领域技术人员能够掌握的。The preparation method of the above-mentioned sepiolite nanofiber loaded cobalt-aluminum composite oxide, the raw material sepiolite nanofiber is prepared according to the method disclosed in CN200910070297.8, other raw materials are obtained through commercial purchase, and the equipment involved is the technical field It is well known that the process operation methods involved are within the grasp of those skilled in the art.
本发明的有益效果是：与现有技术相比，本发明具有如下突出的实质性特点和显著进步：The beneficial effects of the present invention are: compared with the prior art, the present invention has the following prominent substantive features and significant progress:
(1)如上所述由于海泡石的结构由两层硅氧四面体中间夹一层镁氧八面体组成，具有链状和层状过渡型结构、具有大的比表面积和具有独特的孔结构，还具有较强的吸附性和热稳定性，因而海泡石作为催化剂的载体可以增大负载物的分散性与均匀性，本发明通过将海泡石纳米纤维与钴铝复合氧化物进行复合，提高了钴铝复合氧化物的分散性、尺寸均匀性和催化性能，因而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，颗粒分散性差、团聚现象严重，产品性能得不到充分发挥的缺陷。(1) As mentioned above, the structure of sepiolite is composed of two layers of silicon-oxygen tetrahedron sandwiching a layer of magnesium-oxygen octahedron, which has a chain-like and layered transitional structure, a large specific surface area, and a unique pore structure. , also has strong adsorption and thermal stability, so sepiolite can increase the dispersion and uniformity of the load as the carrier of the catalyst. The present invention combines sepiolite nanofibers with cobalt-aluminum composite oxides , improve the dispersibility, size uniformity and catalytic performance of the cobalt-aluminum composite oxide, thereby overcoming the existence of products in the cobalt-aluminum oxide prepared by the prior art as irregular particles, poor particle dispersibility, serious agglomeration, and the product The defect that the performance is not fully utilized.
(2)本发明的海泡石纳米纤维负载钴铝复合氧化物与现有技术CN107170588A的碳氮掺杂钴铝氧化物复合材料本质不同。CN107170588A的碳氮掺杂钴铝氧化物，其本质上应该是一种化合物而非复合氧化物材料。同时，CN107170588A的缺陷在于，所得材料会由于团聚等因素影响其性能的充分发挥。本发明通过在微波水热的过程中引入海泡石纳米纤维，有效地调控了钴铝复合氧化物的形貌，并解决了因团聚影响其性能的缺陷。(2) The cobalt-aluminum composite oxide supported by sepiolite nanofibers of the present invention is essentially different from the carbon-nitrogen doped cobalt-aluminum oxide composite material of the prior art CN107170588A. The carbon-nitrogen-doped cobalt-aluminum oxide of CN107170588A should be essentially a compound rather than a composite oxide material. At the same time, the defect of CN107170588A is that the obtained material will affect its full performance due to factors such as agglomeration. The invention effectively regulates the morphology of the cobalt-aluminum composite oxide by introducing sepiolite nanofibers in the microwave hydrothermal process, and solves the defect that its performance is affected by agglomeration.
(3)本发明采用微波水热法一步制备海泡石纳米纤维负载钴铝复合氧化物的复合材料，该制备方法操作简单，制备周期短。(3) The present invention adopts a microwave hydrothermal method to prepare the composite material of cobalt-aluminum composite oxide loaded on sepiolite nanofibers in one step. The preparation method is simple in operation and short in preparation period.
(4)本发明通过添加有机物调控复合材料的形貌，所得复合材料的粒度小、纯度高、分散性好。(4) The present invention regulates the morphology of the composite material by adding organic matter, and the obtained composite material has small particle size, high purity and good dispersibility.
(5)本发明克服了一些现有技术，例如CN107344093A在高温煅烧过程中会产生严重团聚及烧结的现象。(5) The present invention overcomes some existing technologies, such as CN107344093A, which can produce severe agglomeration and sintering during high-temperature calcination.
具体实施方式Detailed ways
实施例1Example 1
第一步，配制溶液A：The first step is to prepare solution A:
称取所需用量的硝酸钴和硝酸铝溶于去离子水中，使Co离子的浓度为0.1mol/L，Co离子与Al离子的摩尔比为1∶2，恒温30℃下搅拌0.5h，配制得到溶液A；Weigh the required amount of cobalt nitrate and aluminum nitrate and dissolve them in deionized water so that the concentration of Co ions is 0.1mol/L, the molar ratio of Co ions to Al ions is 1:2, and stirred at a constant temperature of 30°C for 0.5h to prepare Obtain solution A;
第二步，配制悬浮液B：The second step, preparation of suspension B:
取海泡石纳米纤维分散于去离子水中，使海泡石纳米纤维、去离子水和上述第一步中所用的硝酸钴和硝酸铝三者之间的质量比为1∶10∶10，恒温30℃下搅拌0.5h，配制得到悬浮液B；Get sepiolite nanofiber and disperse in deionized water, make the mass ratio between sepiolite nanofiber, deionized water and the cobalt nitrate and aluminum nitrate used in the above-mentioned first step be 1: 10: 10, constant temperature Stir at 30°C for 0.5h to prepare suspension B;
第三步，配制混合液C：The third step is to prepare the mixture C:
将上述第一步配制得到的溶液A和上述第二步配制得到的悬浮液B混合搅拌，然后调节混合液的pH＝9，恒温60℃下搅拌0.5h，配制得到混合液C；Mix and stir the solution A prepared in the first step above and the suspension B prepared in the second step above, then adjust the pH of the mixed solution to 9, stir at a constant temperature of 60° C. for 0.5 h, and prepare the mixed solution C;
第四步，配制前躯体混合液：The fourth step is to prepare the precursor mixture:
将乙二醇加入上述第三步配制得到的混合液C中，所加乙二醇的体积量为混合液C的体积的3％，恒温30℃下搅拌0.5h，配制得到前躯体混合液；Add ethylene glycol to the mixed solution C prepared in the third step above, the volume of the added ethylene glycol is 3% of the volume of the mixed solution C, stir at a constant temperature of 30°C for 0.5h, and prepare the precursor mixed solution;
第五步，微波水热法反应：The fifth step, microwave hydrothermal reaction:
将上述第四步配制得到的前躯体混合液置于水热釜中，控制该水热釜的填充度为50％，然后将水热釜放入多用途微波化学合成仪中，温度设定为190℃，压力为3MPa，反应时间为2h，反应结束后自然冷却至室温，至此完成微波水热法反应；The precursor mixed solution prepared in the fourth step above is placed in a hydrothermal kettle, and the filling degree of the hydrothermal kettle is controlled to be 50%, and then the hydrothermal kettle is put into a multipurpose microwave chemical synthesizer, and the temperature is set at 190°C, pressure 3MPa, reaction time 2h, naturally cool to room temperature after the reaction, the microwave hydrothermal reaction is completed so far;
第六步，后处理，制得海泡石纳米纤维负载钴铝复合氧化物的复合材料：The sixth step is post-treatment to prepare a composite material of sepiolite nanofiber loaded cobalt-aluminum composite oxide:
在完成上述第五步的微波水热法反应后，打开水热釜，取出产物，用去离子水抽滤洗涤至中性，再用无水乙醇洗涤，置于干燥箱中在60℃下干燥6h，研磨至粉末状，完成后处理，由此制得海泡石纳米纤维负载钴铝复合氧化物的复合材料。After completing the microwave hydrothermal reaction in the fifth step above, open the hydrothermal kettle, take out the product, filter and wash it with deionized water until it is neutral, then wash it with absolute ethanol, and dry it in a drying oven at 60°C After 6 hours, it was ground to a powder state, and the post-treatment was completed, thereby preparing a composite material of cobalt-aluminum composite oxide supported by sepiolite nanofibers.
实施例2Example 2
第一步，配制溶液A：The first step is to prepare solution A:
称取所需用量的硫酸钴和醋酸铝溶于去离子水中，使Co离子的浓度为0.3mol/L，Co离子与Al离子的摩尔比为2∶2，恒温45℃下搅拌1.5h，配制得到溶液A；Weigh the required amount of cobalt sulfate and aluminum acetate and dissolve them in deionized water so that the concentration of Co ions is 0.3mol/L, the molar ratio of Co ions to Al ions is 2:2, and stirred at a constant temperature of 45°C for 1.5h to prepare Obtain solution A;
第二步，配制悬浮液B：The second step, preparation of suspension B:
取海泡石纳米纤维分散于去离子水中，使海泡石纳米纤维、去离子水和上述第一步中所用的硫酸钴和醋酸铝三者之间的质量比为1∶10∶12，恒温45℃下搅拌1.5h，配制得到悬浮液B；Get sepiolite nanofiber and disperse in deionized water, make the mass ratio between sepiolite nanofiber, deionized water and the cobalt sulfate used in the above-mentioned first step and aluminum acetate three be 1: 10: 12, constant temperature Stir at 45°C for 1.5h to prepare Suspension B;
第三步，配制混合液C：The third step is to prepare the mixture C:
将上述第一步配制得到的溶液A和上述第二步配制得到的悬浮液B混合搅拌，然后调节混合液的pH＝11，恒温75℃下搅拌1.5h，配制得到混合液C；Mix and stir the solution A prepared in the first step above and the suspension B prepared in the second step above, then adjust the pH of the mixed solution to 11, stir at a constant temperature of 75°C for 1.5 hours, and prepare the mixed solution C;
第四步，配制前躯体混合液：The fourth step is to prepare the precursor mixture:
将三乙醇胺加入上述第三步配制得到的混合液C中，所加有机物的体积量为混合液C的体积的9％，恒温45℃下搅拌1.5h，配制得到前躯体混合液；Add triethanolamine to the mixed solution C prepared in the third step above, the volume of the added organic matter is 9% of the volume of the mixed solution C, stir at a constant temperature of 45° C. for 1.5 h, and prepare the precursor mixed solution;
第五步，微波水热法反应：The fifth step, microwave hydrothermal reaction:
将上述第四步配制得到的前躯体混合液置于水热釜中，控制该水热釜的填充度为60％，然后将水热釜放入微波水热反应仪中，温度设定为220℃，压力为3.5MPa，反应时间为4h，反应结束后自然冷却至室温，至此完成微波水热法反应；Place the precursor mixed solution prepared in the fourth step above in a hydrothermal kettle, control the filling degree of the hydrothermal kettle to 60%, then put the hydrothermal kettle into a microwave hydrothermal reactor, and set the temperature to 220 ℃, the pressure is 3.5MPa, the reaction time is 4h, after the reaction is finished, it is naturally cooled to room temperature, and the microwave hydrothermal reaction is completed so far;
第六步，后处理，制得海泡石纳米纤维负载钴铝复合氧化物的复合材料：The sixth step is post-treatment to prepare a composite material of sepiolite nanofiber loaded cobalt-aluminum composite oxide:
在完成上述第五步的微波水热法反应后，打开水热釜，取出产物，用去离子水抽滤洗涤至中性，再用无水乙醇洗涤，置于干燥箱中在75℃下干燥15h，研磨至粉末状，完成后处理，由此制得海泡石纳米纤维负载钴铝复合氧化物的复合材料。After completing the microwave hydrothermal reaction in the fifth step above, open the hydrothermal kettle, take out the product, filter and wash it with deionized water until it is neutral, then wash it with absolute ethanol, and dry it in a drying oven at 75°C After 15 hours, it was ground to a powder state, and the post-treatment was completed, thereby preparing a composite material of cobalt-aluminum composite oxide supported by sepiolite nanofibers.
实施例3Example 3
第一步，配制溶液A：The first step is to prepare solution A:
称取所需用量的氯化钴和氯化铝溶于去离子水中，使Co离子的浓度为0.5mol/L，Co离子与Al离子的摩尔比为4∶2，恒温60℃下搅拌3h，配制得到溶液A；Weigh the required amount of cobalt chloride and aluminum chloride and dissolve them in deionized water so that the concentration of Co ions is 0.5mol/L, the molar ratio of Co ions to Al ions is 4:2, and stirred at a constant temperature of 60°C for 3h. Prepare solution A;
第二步，配制悬浮液B：The second step, preparation of suspension B:
取海泡石纳米纤维分散于去离子水中，使海泡石纳米纤维、去离子水和上述第一步中所用的氯化钴和氯化铝盐三者之间的质量比为1∶10∶15，恒温60℃下搅拌3h，配制得到悬浮液B；Get sepiolite nanofibers and disperse them in deionized water, so that the mass ratio between sepiolite nanofibers, deionized water and the cobalt chloride and aluminum chloride salt used in the above-mentioned first step is 1: 10: 15. Stir at a constant temperature of 60°C for 3 hours to prepare a suspension B;
第三步，配制混合液C：The third step is to prepare the mixture C:
将上述第一步配制得到的溶液A和上述第二步配制得到的悬浮液B混合搅拌，然后调节混合液的pH＝13，恒温90℃下搅拌3h，配制得到混合液C；Mix and stir the solution A prepared in the first step above and the suspension B prepared in the second step above, then adjust the pH of the mixed solution to 13, stir at a constant temperature of 90°C for 3 hours, and prepare the mixed solution C;
第四步，配制前躯体混合液：The fourth step is to prepare the precursor mixture:
将十二烷基苯磺酸钠加入上述第三步配制得到的混合液C中，所加有机物的体积量为混合液C的体积的15％，恒温60℃下搅拌3h，配制得到前躯体混合液；Add sodium dodecylbenzenesulfonate to the mixed solution C prepared in the third step above, the volume of the added organic matter is 15% of the volume of the mixed solution C, stir at a constant temperature of 60°C for 3 hours, and prepare the precursor mixture liquid;
第五步，微波水热法反应：The fifth step, microwave hydrothermal reaction:
将上述第四步配制得到的前躯体混合液置于水热釜中，控制该水热釜的填充度为70％，然后将水热釜放入微波水热平行合成仪中，温度设定为250℃，压力为4MPa，反应时间为5h，反应结束后自然冷却至室温，至此完成微波水热法反应；Place the precursor mixed solution prepared in the fourth step above in a hydrothermal kettle, control the filling degree of the hydrothermal kettle to 70%, then put the hydrothermal kettle into a microwave hydrothermal parallel synthesizer, and set the temperature to 250°C, pressure 4MPa, reaction time 5h, naturally cool to room temperature after the reaction, so far the microwave hydrothermal reaction is completed;
第六步，后处理，制得海泡石纳米纤维负载钴铝复合氧化物的复合材料：The sixth step is post-treatment to prepare a composite material of sepiolite nanofiber loaded cobalt-aluminum composite oxide:
在完成上述第五步的微波水热法反应后，打开水热釜，取出产物，用去离子水抽滤洗涤至中性，再用无水乙醇洗涤，置于干燥箱中在90℃下干燥24h，研磨至粉末状，完成后处理，由此制得海泡石纳米纤维负载钴铝复合氧化物的复合材料。After completing the microwave hydrothermal reaction in the fifth step above, open the hydrothermal kettle, take out the product, filter and wash it with deionized water until it is neutral, then wash it with absolute ethanol, and dry it in a drying oven at 90°C After 24 hours, it was ground to a powder state, and the post-treatment was completed, thereby preparing a composite material of cobalt-aluminum composite oxide supported by sepiolite nanofibers.
上述实施例中，所述填充度为填充物占水热釜的体积百分比，所述原料海泡石纳米纤维是按照CN200910070297.8公开的方法所制备，其他原料均通过商购获得，所涉及的设备为本领域公知的，所涉及的工艺操作方法是本领域技术人员能够掌握的。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 obtained commercially, and the involved The equipment is well known in the art, and the involved process operation methods are within the grasp of those skilled in the art.
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| CN111286217B (en) * | 2018-12-07 | 2021-06-15 | 中国科学院宁波材料技术与工程研究所 | Cobalt blue sepiolite nanocomposite pigment, its preparation method and application |
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| CN118515457B (en) * | 2024-07-23 | 2024-10-01 | 禹城市霞光建筑材料有限公司 | High-performance heat-resistant concrete and preparation method thereof |
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