CN103406116B - High heat resistance modified aluminium oxide and preparation method thereof - Google Patents
High heat resistance modified aluminium oxide and preparation method thereof Download PDFInfo
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- CN103406116B CN103406116B CN201310311854.7A CN201310311854A CN103406116B CN 103406116 B CN103406116 B CN 103406116B CN 201310311854 A CN201310311854 A CN 201310311854A CN 103406116 B CN103406116 B CN 103406116B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 15
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 6
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 10
- 102220043159 rs587780996 Human genes 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 9
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008030 elimination Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- 229960005363 aluminium oxide Drugs 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- -1 rare earth modified aluminium oxide Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 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 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of high heat resistance modified aluminium oxide and preparation method thereof, described high heat resistance modified aluminium oxide, be made up of aluminium oxide and thermally-stabilised auxiliary agent, wherein the content of thermally-stabilised auxiliary agent is the 1%-5% of quality of alumina, and described thermally-stabilised auxiliary agent is selected from one or more in zirconia, barium monoxide or manganese dioxide.The present invention obtains activated alumina presoma by carrying out roasting pretreatment to boehmite, then pretreatment is carried out to activated alumina presoma with organic acid, adds the high heat resistance modified aluminium oxide of the preparations such as thermally-stabilised auxiliary agent and expanding agent, compare with technology with existing product, have with low cost, process is simple, be convenient to realize, reproducible, the product obtained has the features such as specific area is large, high temperature ageing resistance is good, is widely used in waste gas purification or the catalytic combustions such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion.
Description
Technical field
The present invention relates to a kind of Aluminium-oxide catalytic material and preparation method thereof, particularly a kind of Aluminium-oxide catalytic material being applicable to the waste gas purifications such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion or catalytic combustion.
Background technology
Reduce automobile exhaust pollution, environment protection quality, realizing the sustainable development of ecological environment and society, is one of important topic of China environmental protection in the current and following long duration.
For decreasing pollution, must break through from improving gasoline quality, improving engine combustion state and increasing exhaust purification catalytic efficiency three aspect.Up to the present, using cleaning catalyst for tail gases of automobiles to be most effective way is exactly reduced the content of HC, CO and NOx tri-kinds of toxic gases in tail gas by three-way catalytic apparatus.
Three-way catalyst mainly by catalytic action noble metal active component, containing CeO
2catalyst aid (hydrogen-storing material) and the alumina support composition for supporting active component.
Under high temperature, aluminium oxide easily sinters, and its specific area is obviously reduced, and the active component of load is assembled and catalytic activity decline.Along with developing rapidly of the technology such as catalytic combustion and environmental protection catalysis (catalytic purification and catalytic purification that is poisonous, harmful exhaust as vehicle exhaust); the carrier of catalyst is had higher requirement, needs carrier not only to have good heat endurance but also have larger specific area.Therefore, in the urgent need to the novel oxidized aluminum of research and development to the bigger serface of high-temperature stable.
For improving the heat endurance of carrier, all carry out many research both at home and abroad.
Patent CN1250455C discloses a kind of method prepared high temperature high surface area alumina and contain aluminium composite oxide.This invention describes with surfactant, cosurfactant, water-insoluble organic solvent, water, inorganic salts and alkaline matter as after raw material makes reverse micro emulsion, reaction is carried out in the mixing of two kinds of microemulsions and generates colloidal sol, after filtration, drying, roasting etc. can obtain the aluminium oxide of high thermal stability and contain aluminium composite oxide material after processing.
Patent CN102381722A discloses a kind of preparation method of activated alumina, the technical scheme of this invention introduction is: aluminium hydroxide fast dewatering obtains general active oxidation aluminium powder, in boehmite slurries, add aluminum nitrate, obtained crystal seed, again obtained general active oxidation aluminium powder and crystal seed are inserted in hydration reaction groove, carry out hydration reaction, final obtained active oxidation aluminium powder.
No matter be that reverse microemulsion process prepares aluminium oxide and the method containing aluminium composite oxide, or obtain crystal seed by boehmite, then carry out with general active oxidation aluminium powder the method that hydration reaction obtains activated alumina, have complex process, cost is higher, is unfavorable for the shortcoming of industrialized mass production.
Patent CN102701246A discloses the preparation method of the rare earth modified aluminium oxide of a kind of high heat stability, the preparation process of the method is: boehmite nitric acid reaction is made Alumina gel, make the aqueous solution by soluble in water for the soluble-salt of lanthanum element, then Alumina gel and lanthanum solution are mixed to get modified aluminium colloidal sol according to a certain percentage; Modified aluminium colloidal sol and modified alkaline precipitating reagent are carried out mixing co-precipitation, then obtain rare earth modified aluminium oxide after vacuum filtration, washing, calcining, pulverizing.
Patent CN102491389A discloses a kind of preparation method of high temperature resistant bigger serface aluminium oxide, it alkaline-earth metal or rare earth element is added to the water or makes stabiliser solution in ethanol water, then stabiliser solution is joined in the suspension made with boehmite, at activated alumina obtained after the operations such as dipping, evaporate to dryness, roasting.
Peptisation and infusion process prepare the conventional method of modified aluminas at present, but be all process and modification boehmite usually, and obtained modified aluminas specific area after high temperature ageing can significantly decline, and heat resistance is bad.
Summary of the invention
The object of the present invention is to provide a kind of high heat resistance modified aluminium oxide and preparation method thereof, overcome prior art Problems existing.
High heat resistance modified aluminium oxide of the present invention, is characterized in that, is made up of aluminium oxide and thermally-stabilised auxiliary agent, and wherein the content of thermally-stabilised auxiliary agent is the 1%-5% of quality of alumina.
One or more in the preferred autoxidation zirconium of described thermally-stabilised auxiliary agent, barium monoxide or manganese dioxide.
Described high heat resistance modified aluminium oxide, specific area is 200 ~ 260m
2/ g, after 1000 DEG C of roasting 4h, specific area is 150 ~ 190m
2/ g, medium particle diameter D50=3-6 μm.
Particle diameter corresponding when the cumulative particle sizes percentile that term " D50 " refers to a sample reaches 50%.Its physical significance is that the particle that particle diameter is greater than it accounts for 50%, and the particle being less than it also accounts for 50%.
The preparation method of described high heat resistance modified aluminium oxide, comprises the following steps:
(1) pretreatment in aluminium source: by boehmite at 400-500 DEG C of roasting 2-4h, obtain activated alumina presoma; Then activated alumina presoma is distributed in deionized water, is made into the suspension that mass fraction is 20%-50%, is heated to 50-70 DEG C, adds organic acid, stir 1-3h, obtain Alumina gel A;
Described organic acid is the one in sulfamic acid, glycolic acid or oxalic acid, and addition is the 10%-30% of activated alumina presoma quality.
(2) modification: by the diffusing soluble salts of thermally-stabilised auxiliary agent in deionized water, being made into thermally-stabilised auxiliary agent mass fraction is the 10%-30% aqueous solution, obtains solution B;
One or more preferably in zirconium nitrate, barium nitrate, manganese nitrate of the soluble-salt of described thermally-stabilised auxiliary agent; The addition of the soluble-salt of described thermally-stabilised auxiliary agent by percentage to the quality, is 1.7% ~ 15% of activated alumina presoma;
(3) solution B joined in Alumina gel A, stirring reaction 1-2h, adds expanding agent, continues to stir 1-2h, obtains slurries C;
Described expanding agent is selected from the one in ethylene glycol or oleic acid, and addition is the 50%-120% of activated alumina presoma weight;
(4) slurries C is put into the dry 2-4h of baking oven, baking temperature is 105-120 DEG C; Then roasting, obtains modified aluminas presoma; Wherein, roasting heating schedule for being first warming up to 200-350 DEG C of insulation 1-3h, then is warming up to 500-700 DEG C of insulation 2-4h, then modified aluminas precursor is broken to D50=3-6 μm, namely obtains described high heat resistance modified aluminium oxide;
The present invention obtains activated alumina presoma by carrying out roasting pretreatment to boehmite, then with organic acid, activated alumina is carried out to pretreatment, adds the high heat resistance modified aluminium oxide of the preparation such as heat stabilizer auxiliary agent and expanding agent, compare with technology with existing product, have with low cost, process is simple, be convenient to realize, reproducible, the product obtained has the features such as specific area is large, high temperature ageing resistance is good, is widely used in waste gas purification or the catalytic combustions such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1
Get the activated alumina presoma 1000g that boehmite obtains after 500 DEG C of roasting 2h, joined in 1000g deionized water, add the aqueous solution 1500g that sulfamic acid mass fraction is 20% under stirring, heating water bath to 50 DEG C, the obtained Alumina gel of reaction;
Barium nitrate 17g is joined in 50g deionized water, stir, obtain the barium nitrate aqueous solution of clear, joined in above-mentioned Alumina gel, reaction 1h;
In reacted slurries, add 500g oleic acid, stir;
Above-mentioned slurries are put into thermostatic drying chamber, 115 DEG C of dry 2h;
Desciccate is put into Muffle furnace, is warming up to 350 DEG C of insulation 1h, then is warming up to 500 DEG C of roasting 4h, roasting afterproduct is crushed to D50=3 μm, obtains described high heat resistance modified alumina material.
This material consist of barium monoxide 1%, aluminium oxide 95%.Recording specific area is 226m
2/ g, recording specific area after 1000 DEG C of aging 4h is 162m
2/ g.XRD figure is shown in Fig. 1.
Embodiment 2
Get the activated alumina presoma 1500g that boehmite obtains after 400 DEG C of roasting 4h, joined in 3500g deionized water, add the aqueous solution 600g that glycolic acid mass fraction is 50% under stirring, heating water bath to 60 DEG C, the obtained Alumina gel of reaction;
Barium nitrate 76.5g, manganese nitrate 50% solution 61.7g are joined in 430g deionized water, stirs, obtain the barium nitrate of clear, manganese nitrate mixed aqueous solution, joined in above-mentioned Alumina gel, reaction 2h;
In reacted slurries, add ethylene glycol 1200g, stir;
Above-mentioned slurries are put into thermostatic drying chamber, and 115 DEG C of dry 4h, obtain modified aluminas presoma;
Desciccate is put into Muffle furnace, is warming up to 200 DEG C of insulation 2h, then is warming up to 550 DEG C of roasting 4h, roasting afterproduct is crushed to D50=4.2 μm, obtains described high heat resistance modified alumina material.
This material consist of barium monoxide 3%, manganese dioxide 1%, aluminium oxide 96%.Recording specific area is 257m
2/ g, recording specific area after 1000 DEG C of aging 4h is 188m
2/ g.
Embodiment 3
Get the activated alumina presoma 1200g that boehmite obtains after 450 DEG C of roasting 3h, joined in 4800g deionized water, add the aqueous solution 800g that oxalic acid mass fraction is 15% under stirring, heating water bath to 70 DEG C, the obtained Alumina gel of reaction;
Zirconium nitrate 33g, manganese nitrate 50% solution 98.8g are joined in 530g deionized water, stir, obtain the zirconium nitrate of clear, manganese nitrate mixed aqueous solution, wherein zirconium nitrate needs under agitation slowly to be added in water to dissolve, joined in above-mentioned Alumina gel, reaction 1.5h;
In reacted slurries, add ethylene glycol 1200g, stir;
Above-mentioned slurries are put into thermostatic drying chamber, 105 DEG C of dry 4h;
Desciccate is put into Muffle furnace, is warming up to 250 DEG C of insulation 1.5h, then is warming up to 600 DEG C of roasting 3h, roasting afterproduct is crushed to D50=6 μm, obtains described high heat resistance modified alumina material.
This material consist of zirconia 1%, manganese dioxide 2%, aluminium oxide 97%.Recording specific area is 228m
2/ g, recording specific area after 1000 DEG C of aging 4h is 163m
2/ g.
Embodiment 4:
Get the activated alumina presoma 1600g that boehmite obtains after 500 DEG C of roasting 3h, joined in 2400g deionized water, add the aqueous solution 2400g that sulfamic acid mass fraction is 20% under stirring, heating water bath to 60 DEG C, the obtained Alumina gel of reaction;
Zirconium nitrate 220.3g is under agitation slowly joined in 1980g deionized water and dissolves, to the zirconium nitrate aqueous solution of clear, joined in above-mentioned Alumina gel, reaction 1h;
In reacted slurries, add 1920g oleic acid, stir;
Above-mentioned slurries are put into thermostatic drying chamber, 110 DEG C of dry 3h;
Desciccate is put into Muffle furnace, is warming up to 300 DEG C of insulation 2h, then is warming up to 700 DEG C of roasting 2h, roasting afterproduct is crushed to D50=5.3 μm, obtains described high heat resistance modified alumina material.
This material consist of zirconia 5%, aluminium oxide 95%.Recording specific area is 243m
2/ g, recording specific area after 1000 DEG C of aging 4h is 172m
2/ g.
Comparative example 1
Get the boehmite 1430g that alumina content is 70%, put into Muffle furnace, be warming up to 350 DEG C of insulation 1h, then be warming up to 500 DEG C of roasting 4h, roasting afterproduct is crushed to D50=3.4 μm, obtains activated alumina material.
This material consist of aluminium oxide 100%.Recording specific area is 157m
2/ g, recording specific area after 1000 DEG C of aging 4h is 69m
2/ g.
Comparative example 2
Get the boehmite 1430g that alumina content is 70%, joined in 1000g deionized water, under stirring, add the aqueous solution 600g that nitric acid mass fraction is 50%, the obtained Alumina gel of reaction;
Barium nitrate 17g is joined in 50g deionized water, stir, obtain the barium nitrate aqueous solution of clear, joined in above-mentioned Alumina gel, reaction 1h;
Above-mentioned slurries are put into thermostatic drying chamber, 115 DEG C of dry 2h;
Desciccate is put into Muffle furnace, is warming up to 350 DEG C of insulation 1h, then is warming up to 500 DEG C of roasting 4h, roasting afterproduct is crushed to D50=3 μm, obtains modified oxidized aluminum.
This material consist of barium monoxide 1%, aluminium oxide 95%.Recording specific area is 173m
2/ g, recording specific area after 1000 DEG C of aging 4h is 91m
2/ g.
More than show and describe general principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; the just principle of the present invention described in above-described embodiment and description; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in claimed scope of the present invention.The protection domain of application claims is defined by appending claims and equivalent thereof.
Accompanying drawing explanation
The XRD figure of Fig. 1 high heat resistance modified aluminium oxide prepared by the embodiment of the present invention 1.
Claims (4)
1. high heat resistance modified aluminium oxide, it is characterized in that, be made up of aluminium oxide and thermally-stabilised auxiliary agent, wherein the content of thermally-stabilised auxiliary agent is the 1%-5% of quality of alumina, described thermally-stabilised auxiliary agent is selected from one or more in zirconia, barium monoxide, manganese dioxide, described high heat resistance modified aluminium oxide, specific area is 200 ~ 260m
2/ g, after 1000 DEG C of roasting 4h, specific area is 150 ~ 190m
2/ g, described high heat resistance modified aluminium oxide, medium particle diameter D50=3-6 μm, preparation method comprises the following steps:
(1) by boehmite at 400-500 DEG C of roasting 2-4h, obtain activated alumina presoma, then activated alumina presoma be distributed in deionized water, be made into the suspension that mass fraction is 20%-50%, be heated to 50-70 DEG C, add organic acid, stir 1-3h, obtain Alumina gel A;
(2) by the diffusing soluble salts of thermally-stabilised auxiliary agent in deionized water, being made into thermally-stabilised promoter soluble salt mass fraction is the aqueous solution of 10%-30%, obtains solution B;
The soluble-salt of described thermally-stabilised auxiliary agent is selected from one or more in zirconium nitrate, barium nitrate, manganese nitrate;
(3) solution B joined in Alumina gel A, stirring reaction 1-2h, adds expanding agent, continues to stir 1-2h, obtains slurries C;
Described expanding agent is selected from the one in ethylene glycol or oleic acid, and addition is the 50%-120% of activated alumina presoma quality;
(4) slurries C is put into the dry 2-4h of baking oven, baking temperature is 105-120 DEG C; Then roasting, obtains modified aluminas presoma; Wherein, roasting heating schedule for being first warming up to 200-350 DEG C of insulation 1-3h, then is warming up to 500-700 DEG C of insulation 2-4h, then modified aluminas precursor is broken to D50=3-6 μm, namely obtains described high heat resistance modified aluminium oxide.
2. high heat resistance modified aluminium oxide according to claim 1, is characterized in that, described organic acid is the one in sulfamic acid, glycolic acid or oxalic acid.
3. high heat resistance modified aluminium oxide according to claim 2, is characterized in that, described organic acid addition is the 10%-30% of activated alumina presoma quality.
4. high heat resistance modified aluminium oxide according to claim 1, it is characterized in that, in step (3), the addition of the soluble-salt of the thermally-stabilised auxiliary agent in described solution B, in mass fraction, be the 1.7%-15% of activated alumina presoma weight.
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| CN112275258B (en) * | 2020-10-19 | 2023-01-10 | 西安建筑科技大学 | Rare earth modified aluminum-based adsorbent and preparation method and application thereof |
| CN115301231A (en) * | 2022-08-15 | 2022-11-08 | 中国科学院生态环境研究中心 | Noble metal catalyst for catalytic oxidation of formaldehyde and preparation method thereof |
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| JPH04277567A (en) * | 1991-03-06 | 1992-10-02 | Sekisui Chem Co Ltd | Alumina-zirconia coating composition |
| CN103008016A (en) * | 2012-10-31 | 2013-04-03 | 上海华明高纳稀土新材料有限公司 | High-thermostability aluminum oxide and preparation method thereof |
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| JPH04277567A (en) * | 1991-03-06 | 1992-10-02 | Sekisui Chem Co Ltd | Alumina-zirconia coating composition |
| CN103008016A (en) * | 2012-10-31 | 2013-04-03 | 上海华明高纳稀土新材料有限公司 | High-thermostability aluminum oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| "凝胶法制备改性活性氧化铝研究";顾伟伟;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20090415(第4期);4.3节、4.5.1节、表4.2 * |
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