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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- sepiolite
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- composite oxide
- mixed liquor
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- 239000004113 Sepiolite 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
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000002121 nanofiber Substances 0.000 title claims abstract description 47
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 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 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 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
- 239000000725 suspension Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000012805 post-processing Methods 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 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
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 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
- 230000035484 reaction time Effects 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000007547 defect Effects 0.000 abstract description 12
- 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 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 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
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000395 magnesium oxide 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
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010037660 Pyrexia Diseases 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
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005245 sintering 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
- 239000004575 stone Substances 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
-
- 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
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite of the present invention, it is related to composite material, it is raw material with soluble cobalt, aluminum soluble salt and sepiolite nanofiber, it is configured to precursor mixed liquor with organic matter, recycles one step of microwave-hydrothermal method that the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made.It is irregular particle that the present invention, which had both overcome cobalt aluminum oxide made from the prior art to have product, agglomeration is serious, preparation process is cumbersome, required high energy consumption, the high defect of production cost, and overcome long preparation period present in the method for prior art preparation sepiolite metal oxides composite material and defect of high cost.
Description
Technical field
Technical scheme of the present invention is related to composite material, the specifically nano-fibre supported cobalt aluminum composite oxide of sepiolite
The preparation method of object.
Background technology
Cobalt aluminum oxide has good catalytic performance as catalyst and catalyst carrier, shows higher except soot
With the catalytic activity of nitrogen oxides.Currently, the preparation method of cobalt aluminum oxide mainly have solid phase method, coprecipitation, hydro-thermal method and
Sol-gal process.CN103943850A discloses a kind of side preparing lithium nickel cobalt aluminum oxide material using low fever solid phase reaction
Method；CN105098171A discloses the preparation method of lithium-ion-power cell cobalt aluminum oxide, is the system using coprecipitation
Preparation Method；CN107170588A discloses a kind of carbon-nitrogen doped cobalt aluminum oxide composite material and preparation method thereof, describe with
Cobalt nitrate, aluminum nitrate and urea are raw material, synthesize cobalt aluminium hydroxide with hydro-thermal method, high-temperature calcination is then carried out in tube furnace
Obtain carbon-nitrogen doped cobalt aluminum oxide.It is irregular that the cobalt aluminum oxide made from the above-mentioned prior art, which has product,
Grain, particle agglomeration phenomenon is serious, and preparation process is cumbersome, required high energy consumption, the high defect of production cost.
Sepiolite is a kind of rich magnesium silicate clay mineral, and theoretical chemistry formula is Mg8Si12O30(OH)4(OH2)4·
8H2O, structure are made of one layer of magnesia octahedron of folder among two layers oxygen-octahedron, have chain and stratiform transiens structure,
With big specific surface area and with unique pore structure, also there is stronger adsorptivity and thermal stability, thus can be used as urging
The carrier of agent.Sepiolite can increase the dispersibility and uniformity of loaded article as the carrier of catalyst, therefore, Hai Pao at present
Stone becomes hot spot in the load field of catalyst as the research of carrier.It is multiple that sepiolite metal oxides are prepared in the prior art
The method of condensation material mainly has chemical precipitation method, infusion process and hydro-thermal method.CN107344093A discloses a kind of multi-channel structure
Sepiolite/TiO of strong absorption property2Composite material and preparation method uses the coprecipitation using ammonium hydroxide as precipitating reagent, exists
The TiO being carried on sepiolite fibre2Nano particle will produce the defect of agglomeration in high-temperature burning process；
CN106040278A discloses a kind of preparation method of sepiolite supported Pd-Ni bimetallic catalysts of the acid activation of N doping and answers
With being, by nickel salt and palladium salt dip loading to sepiolite carrier, it is bis- to obtain Pd-Ni using the acidification sepiolite of nitrating as carrier
Metallic catalyst, presence active component in dipping process easily migrate, the defect that catalytic effect weakens；
CN106076422A discloses a kind of sepiolite supported porphyrin sensitization Bi2WO6The preparation method of visible light catalyst, using hydro-thermal
Method prepares out sepiolite supported porphyrin sensitization Bi2WO6Visible light catalyst, this method need hydro-thermal reaction 48h, there is preparation week
Phase grows and defect of high cost.It prepares and exists in the method for sepiolite metal oxides composite material for the above-mentioned prior art
Deficiency and defect, innovate the preparation method of sepiolite metal oxides composite material to the research and development of this kind of composite material and answer
With being particularly important.
Invention content
The technical problem to be solved by the present invention is to：The preparation of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is provided
Method is the composite material that the nano-fibre supported cobalt aluminum composite oxide of sepiolite is prepared using one step of microwave-hydrothermal method, both gram
It is irregular particle to have taken cobalt aluminum oxide made from the prior art to have product, and agglomeration is serious, and preparation process is numerous
It is trivial, required high energy consumption, the high defect of production cost, and overcome prior art preparation sepiolite metal oxides composite material
Method present in long preparation period and defect of high cost.
Technical solution is used by the present invention solves the technical problem：The nano-fibre supported cobalt aluminum composite oxide of sepiolite
The preparation method of object is the composite wood that the nano-fibre supported cobalt aluminum composite oxide of sepiolite is prepared using one step of microwave-hydrothermal method
Material, is as follows：
The first step prepares solution A：
It weighs desired amount of soluble cobalt and aluminum soluble salt is dissolved in deionized water, make a concentration of of Co ions
The molar ratio of 0.1mol/L~0.5mol/L, Co ion and Al ions is 1~4: 2, and 0.5~3h is stirred at 30~60 DEG C of constant temperature,
Preparation obtains solution A；
Second step, formulated suspension B：
It takes sepiolite nanofiber dispersion in deionized water, makes sepiolite nanofiber, deionized water and above-mentioned first
Mass ratio between soluble cobalt used in step and aluminum soluble salt three is 1: 10: 10~15, at 30~60 DEG C of constant temperature
0.5~3h is stirred, preparation obtains suspension B；
Third walks, and prepares mixed liquor C：
The solution A that the above-mentioned first step is prepared and the suspension B that above-mentioned second step is prepared are mixed, then
PH=9~13 of mixed liquor are adjusted, 0.5~3h is stirred at 60~90 DEG C of constant temperature, preparation obtains mixed liquor C；
4th step prepares precursor mixed liquor：
Above-mentioned third step is added in organic matter to prepare in obtained mixed liquor C, the volume of added organic matter is mixed liquor C
Volume 3%~15%, 0.5~3h is stirred at 30~60 DEG C of constant temperature, preparation obtains precursor mixed liquor；
5th step, microwave-hydrothermal method reaction：
The precursor mixed liquor that above-mentioned 4th step is prepared is placed in water heating kettle, the compactedness for controlling the water heating kettle is
50%~70%, then water heating kettle is put into microwave hydrothermal equipment, temperature is set as 190~250 DEG C, and pressure is 3~4MPa,
Reaction time is 2~5h, after reaction cooled to room temperature, so far completes microwave-hydrothermal method reaction；
The composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in 6th step, post-processing：
After completing the microwave-hydrothermal method reaction of above-mentioned 5th step, water heating kettle is opened, product is taken out, is filtered with deionized water
Washing is washed to neutrality, then with absolute ethyl alcohol, is placed in drying box at 60~90 DEG C dry 6~for 24 hours, be ground to it is powdered,
Post-processing is completed, the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is thus made.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the soluble cobalt are nitric acid
Cobalt, cobaltous sulfate or cobalt chloride.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the aluminum soluble salt are nitric acid
Aluminium, aluminum acetate or aluminium chloride.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the organic matter are ethylene glycol, three
Ethanol amine or neopelex.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the microwave hydrothermal equipment is multi-purpose
Way microwave chemosynthesis instrument, microwave hydrothermal reaction or microwave hydrothermal parallel projects instrument.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the compactedness are that filler accounts for water
The percent by volume of hot kettle.
The preparation method of the above-mentioned nano-fibre supported cobalt aluminum composite oxide of sepiolite, the raw material sepiolite nanofiber
It is according to prepared by method disclosed in CN200910070297.8, other raw materials are commercially available, and involved equipment is
It will appreciate that it is known in the art that involved process operation is those skilled in the art.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention has following substantive distinguishing features outstanding and shows
Write progress：
(1) as mentioned above due to the structure of sepiolite is made of one layer of magnesia octahedron of folder among two layers of oxygen-octahedron,
With chain and stratiform transiens structure, with big specific surface area and with unique pore structure, also have stronger absorption
Property and thermal stability, thus sepiolite can increase the dispersibility and uniformity of loaded article as the carrier of catalyst, the present invention
It is compound by carrying out sepiolite nanofiber with cobalt aluminum composite oxide, improve dispersibility, the ruler of cobalt aluminum composite oxide
Very little uniformity and catalytic performance, thus it is irregular to overcome cobalt aluminum oxide made from the prior art to have product
Grain, particle dispersion is poor, agglomeration is serious, the defect that properties of product are not in full use.
(2) carbon of sepiolite nano-fibre supported cobalt aluminum composite oxide and prior art CN107170588A of the invention
N doping cobalt aluminum oxide composite material essence is different.The carbon-nitrogen doped cobalt aluminum oxide of CN107170588A, is substantially answered
This is a kind of compound rather than composite oxide material.Meanwhile the defect of CN107170588A is, resulting materials can be due to group
The factors such as poly- influence giving full play to for its performance.The present invention by during microwave hydrothermal introduce sepiolite nanofiber,
Effectively regulate and control the pattern of cobalt aluminum composite oxide, and solves the defect because of its performance of influence of reuniting.
(3) present invention prepares the compound of the nano-fibre supported cobalt aluminum composite oxide of sepiolite using one step of microwave-hydrothermal method
Material, the preparation method is easy to operate, short preparation period.
(4) present invention regulates and controls the pattern of composite material by adding organic matter, and the granularity of gained composite material is small, purity
High, good dispersion.
(5) the present invention overcomes some prior arts, such as CN107344093A will produce in high-temperature burning process sternly
The phenomenon that reaggregation and sintering.
Specific implementation mode
Embodiment 1
The first step prepares solution A：
It weighs desired amount of cobalt nitrate and aluminum nitrate is dissolved in deionized water, make a concentration of 0.1mol/L of Co ions,
The molar ratio of Co ions and Al ions is 1: 2,0.5h is stirred at 30 DEG C of constant temperature, preparation obtains solution A；
Second step, formulated suspension B：
It takes sepiolite nanofiber dispersion in deionized water, makes sepiolite nanofiber, deionized water and above-mentioned first
Mass ratio between cobalt nitrate used in step and aluminum nitrate three is 1: 10: 10, stirs 0.5h at 30 DEG C of constant temperature, preparation obtains
Suspension B；
Third walks, and prepares mixed liquor C：
The solution A that the above-mentioned first step is prepared and the suspension B that above-mentioned second step is prepared are mixed, then
The pH=9 of mixed liquor is adjusted, 0.5h is stirred at 60 DEG C of constant temperature, preparation obtains mixed liquor C；
4th step prepares precursor mixed liquor：
Above-mentioned third step is added in ethylene glycol to prepare in obtained mixed liquor C, the volume of added ethylene glycol is mixed liquor C
Volume 3%, 0.5h is stirred at 30 DEG C of constant temperature, preparation obtains precursor mixed liquor；
5th step, microwave-hydrothermal method reaction：
The precursor mixed liquor that above-mentioned 4th step is prepared is placed in water heating kettle, the compactedness for controlling the water heating kettle is
50%, then water heating kettle is put into multipurpose microwave chemosynthesis instrument, temperature is set as 190 DEG C, pressure 3MPa, when reaction
Between be 2h, cooled to room temperature after reaction so far completes microwave-hydrothermal method reaction；
The composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in 6th step, post-processing：
After completing the microwave-hydrothermal method reaction of above-mentioned 5th step, water heating kettle is opened, product is taken out, is filtered with deionized water
Washing is washed to neutrality, then with absolute ethyl alcohol, is placed in drying box at 60 DEG C dry 6h, is ground to powdered, is located after the completion
Thus the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in reason.
Embodiment 2
The first step prepares solution A：
It weighs desired amount of cobaltous sulfate and aluminum acetate is dissolved in deionized water, make a concentration of 0.3mol/L of Co ions,
The molar ratio of Co ions and Al ions is 2: 2,1.5h is stirred at 45 DEG C of constant temperature, preparation obtains solution A；
Second step, formulated suspension B：
It takes sepiolite nanofiber dispersion in deionized water, makes sepiolite nanofiber, deionized water and above-mentioned first
Mass ratio between cobaltous sulfate used in step and aluminum acetate three is 1: 10: 12, stirs 1.5h at 45 DEG C of constant temperature, preparation obtains
Suspension B；
Third walks, and prepares mixed liquor C：
The solution A that the above-mentioned first step is prepared and the suspension B that above-mentioned second step is prepared are mixed, then
The pH=11 of mixed liquor is adjusted, 1.5h is stirred at 75 DEG C of constant temperature, preparation obtains mixed liquor C；
4th step prepares precursor mixed liquor：
Above-mentioned third step is added in triethanolamine to prepare in obtained mixed liquor C, the volume of added organic matter is mixing
The 9% of the volume of liquid C, 1.5h is stirred at 45 DEG C of constant temperature, and preparation obtains precursor mixed liquor；
5th step, microwave-hydrothermal method reaction：
The precursor mixed liquor that above-mentioned 4th step is prepared is placed in water heating kettle, the compactedness for controlling the water heating kettle is
60%, then water heating kettle is put into microwave hydrothermal reaction, temperature is set as 220 DEG C, pressure 3.5MPa, and the reaction time is
4h, cooled to room temperature, so far completes microwave-hydrothermal method reaction after reaction；
The composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in 6th step, post-processing：
After completing the microwave-hydrothermal method reaction of above-mentioned 5th step, water heating kettle is opened, product is taken out, is filtered with deionized water
Washing is washed to neutrality, then with absolute ethyl alcohol, is placed in drying box at 75 DEG C dry 15h, is ground to powdered, is located after the completion
Thus the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in reason.
Embodiment 3
The first step prepares solution A：
It weighs desired amount of cobalt chloride and aluminium chloride is dissolved in deionized water, make a concentration of 0.5mol/L of Co ions,
The molar ratio of Co ions and Al ions is 4: 2,3h is stirred at 60 DEG C of constant temperature, preparation obtains solution A；
Second step, formulated suspension B：
It takes sepiolite nanofiber dispersion in deionized water, makes sepiolite nanofiber, deionized water and above-mentioned first
Mass ratio between cobalt chloride used in step and chlorination aluminium salt three is 1: 10: 15, stirs 3h at 60 DEG C of constant temperature, preparation obtains
Suspension B；
Third walks, and prepares mixed liquor C：
The solution A that the above-mentioned first step is prepared and the suspension B that above-mentioned second step is prepared are mixed, then
The pH=13 of mixed liquor is adjusted, 3h is stirred at 90 DEG C of constant temperature, preparation obtains mixed liquor C；
4th step prepares precursor mixed liquor：
Above-mentioned third step is added in neopelex to prepare in obtained mixed liquor C, the volume of added organic matter
Amount is the 15% of the volume of mixed liquor C, and 3h is stirred at 60 DEG C of constant temperature, and preparation obtains precursor mixed liquor；
5th step, microwave-hydrothermal method reaction：
The precursor mixed liquor that above-mentioned 4th step is prepared is placed in water heating kettle, the compactedness for controlling the water heating kettle is
70%, then water heating kettle is put into microwave hydrothermal parallel projects instrument, temperature is set as 250 DEG C, pressure 4MPa, the reaction time
For 5h, cooled to room temperature, so far completes microwave-hydrothermal method reaction after reaction；
The composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in 6th step, post-processing：
After completing the microwave-hydrothermal method reaction of above-mentioned 5th step, water heating kettle is opened, product is taken out, is filtered with deionized water
Washing is washed to neutrality, then with absolute ethyl alcohol, be placed in drying box at 90 DEG C it is dry be ground to powdered for 24 hours, locate after the completion
Thus the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in reason.
In above-described embodiment, the compactedness is the percent by volume that filler accounts for water heating kettle, and the raw material sepiolite is received
Rice fiber is according to prepared by method disclosed in CN200910070297.8, other raw materials are commercially available, involved
What equipment was known in the art, involved process operation is that those skilled in the art will appreciate that.
Claims (5)
1. the preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite, it is characterised in that：It is to utilize microwave-hydrothermal method
One step prepares the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite, is as follows：
The first step prepares solution A：
It weighs desired amount of soluble cobalt and aluminum soluble salt is dissolved in deionized water, make a concentration of of Co ions
The molar ratio of 0.1mol/L~0.5mol/L, Co ion and Al ions is 1~4: 2, and 0.5~3h is stirred at 30~60 DEG C of constant temperature,
Preparation obtains solution A；
Second step, formulated suspension B：
It takes sepiolite nanofiber dispersion in deionized water, makes in sepiolite nanofiber, deionized water and the above-mentioned first step
Mass ratio between soluble cobalt and aluminum soluble salt three used is 1: 10: 10~15, is stirred at 30~60 DEG C of constant temperature
0.5~3h, preparation obtain suspension B；
Third walks, and prepares mixed liquor C：
The solution A that the above-mentioned first step is prepared and the suspension B that above-mentioned second step is prepared are mixed, then adjusted
PH=9~13 of mixed liquor, 0.5~3h is stirred at 60~90 DEG C of constant temperature, and preparation obtains mixed liquor C；
4th step prepares precursor mixed liquor：
Above-mentioned third step is added in organic matter to prepare in obtained mixed liquor C, the volume of added organic matter is the body of mixed liquor C
Long-pending 3%~15%, 0.5~3h is stirred at 30~60 DEG C of constant temperature, and preparation obtains precursor mixed liquor；
5th step, microwave-hydrothermal method reaction：
The precursor mixed liquor that above-mentioned 4th step is prepared is placed in water heating kettle, the compactedness for controlling the water heating kettle is 50%
~70%, then water heating kettle is put into microwave hydrothermal equipment, temperature is set as 190~250 DEG C, and pressure is 3~4MPa, reaction
Time is 2~5h, after reaction cooled to room temperature, so far completes microwave-hydrothermal method reaction；
The composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in 6th step, post-processing：
After completing the microwave-hydrothermal method reaction of above-mentioned 5th step, water heating kettle is opened, product is taken out, with deionized water filtering and washing
It is washed to neutrality, then with absolute ethyl alcohol, is placed in drying box at 60~90 DEG C dry 6~for 24 hours, be ground to powdered, completed
Thus the composite material of the nano-fibre supported cobalt aluminum composite oxide of sepiolite is made in post-processing.
2. the preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite according to claim 1, it is characterised in that：
The soluble cobalt is cobalt nitrate, cobaltous sulfate or cobalt chloride.
3. the preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite according to claim 1, it is characterised in that：
The aluminum soluble salt is aluminum nitrate, aluminum acetate or aluminium chloride.
4. the preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite according to claim 1, it is characterised in that：
The organic matter is ethylene glycol, triethanolamine or neopelex.
5. the preparation method of the nano-fibre supported cobalt aluminum composite oxide of sepiolite according to claim 1, it is characterised in that：
The microwave hydrothermal equipment is multipurpose microwave chemosynthesis instrument, microwave hydrothermal reaction or microwave hydrothermal parallel projects instrument.
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