CN101108340B - Preparation method of zirconium manganese doped hexa- aluminate catalyzer - Google Patents
Preparation method of zirconium manganese doped hexa- aluminate catalyzer Download PDFInfo
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- CN101108340B CN101108340B CN200710029455A CN200710029455A CN101108340B CN 101108340 B CN101108340 B CN 101108340B CN 200710029455 A CN200710029455 A CN 200710029455A CN 200710029455 A CN200710029455 A CN 200710029455A CN 101108340 B CN101108340 B CN 101108340B
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Abstract
The invention discloses a preparation method of manganese zirconium mixing hexaaluminate catalysts, which mixes and stirs cyclohexane, Isobutanol, OP-10 emulsifier and water according certain volume ratio to prepare reverse microemulsion system; the invention adopts zirconium nitrate, manganous nitrate, aluminium nitrate and carbowax as material to mix and dissolve in deionized water, add into the prepared reverse microemulsion system, drip urea and ammonia precipitant according to certain volume ratio, to produce lodgment; prepare catalyst forequarter by high pressure kettle critical drying agent, manganese zirconium mixing hexaaluminate catalyst of good dispersing, less block and of platy shape is ahcieved after being baked in muffle furnace; the preparation method has simple technics, low cost, small size of crystal grain and stable high temperature.
Description
Technical field
The present invention relates to a kind of preparation method of zirconium manganese doped hexa-aluminate catalyzer.
Background technology
The catalyst that is used for catalytic combustion mainly contains noble metal carrier catalyst, metal oxide catalyst and doping type hexa-aluminate etc.Noble metal has good active, but itself costs an arm and a leg, and has limited further developing of noble metal catalyst.The heat endurance of metal oxide catalyst is higher, raw material is cheap easily asks, and can be used as the substitute of noble metal, but the metal oxide catalyst series is easy and carrier generation high temperature solid state reaction, and this limits it and uses in the high-temp combustion reaction.Hexa-aluminate is alternately to pile up the crystal of the six side's layer structures that form by spinel structure unit and minute surface.Compare with other combustion catalysts, the catalytic activity of catalytic activity of (1) hexa-aluminate and noble metal carrier catalyst, metal oxide catalyst is approaching, by introducing transition metal ions or allotment minute surface heavy ion, can improve the hexa-aluminate catalyzer activity.(2) owing in the crystal structure of hexa-aluminate, mix suitable metal ion, can partly replace the Al in the tetrahedron space
3+With the Al in the octahedral interstices
3+, make its stable existence in the hexa-aluminate lattice, reach inlaying of active specy and the constant purpose of skeleton structure.From its crystal structure, β-Al no matter
2O
3Type still is the Magnetoplumbate-type hexa-aluminate, be lamellar structure compound and be that the spinelle piece that is mutually the mirror phase forms along the C uranium pile is long-pending, minute surface contains the bigger cation of radius, cause this lamellar structure compound crystallite comparatively slow, make it possess good heat endurance along the axial growth rate of the C vertical with minute surface.Therefore at high temperature, the heat endurance of hexa-aluminate, mechanical strength and thermal shock resistance are all than the height of noble metal carrier catalyst, metal oxide catalyst.(3) price of hexa-aluminate is more cheap than noble metal carrier catalyst, and raw material is easily tried to achieve.Thus, just become to be rich in most the high-temperature catalytic material of prospect at the doping type hexa-aluminate.Zirconium has high high-temp stability, and manganese has good catalytic activity, so the present invention has prepared a kind of zirconium manganese doped hexa-aluminate catalyzer.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of zirconium manganese doped hexa-aluminate catalyzer.
The present invention makes the reverse microemulsion system after cyclohexane, n-butanol, OP-10 emulsifying agent and water are mixed stirring by certain volume ratio.Adopting zirconium nitrate, manganese nitrate, aluminum nitrate and polyethylene glycol is raw material, with it mixed dissolution in deionized water, then add in the reverse microemulsion system for preparing, drip the urea and the ammonia precipitation process agent of certain volume ratio, generate precipitation, make catalyst precursor by the autoclave supercritical drying, then in Muffle furnace, this presoma is carried out roasting and promptly obtain zirconium manganese doped hexa-aluminate particle.
The volume ratio of the reverse microemulsion system of preparation is: 10～60% cyclohexanes, 10～30% n-butanols, 10～30%OP-10 emulsifying agent, 10～30% water; The concentration of zirconium nitrate is at 0.1～1mol/L, and the concentration of manganese nitrate is at 0.1～1mol/L, and the concentration of aluminum nitrate is at 1～3mol/L, and the amount of the polyethylene glycol of adding is 1～5g, and the concentration of urea is 1～3mol/L, and the concentration of ammoniacal liquor is 2～5mol/L; Zirconium nitrate: manganese nitrate: aluminum nitrate (mol ratio) is 0.5～1.5: 0.5～1.5: between 10～12, urea: ammoniacal liquor (volume ratio) is between 1: 1～1: 4.
Process conditions: 10～60% cyclohexanes, 10～30% n-butanols, 10～30%OP-10 emulsifying agent, 10～30% water mix the back and add in the there-necked flask, stirred 10 hours with 600 rev/mins rotating speeds, left standstill 12 hours, make transparent or semitransparent stable reverse microemulsion system.Zirconium nitrate: manganese nitrate: aluminum nitrate (mol ratio) is 0.5～1.5: 0.5～1.5: between 10～12, mix the back and be added dropwise in the reverse micro emulsion in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s, the amount that adds polyethylene glycol is 1～5g.Stop water-bath and stirring, leave standstill 1～3h.Being ratio that 1～3mol/L urea and 2～5mol/L ammoniacal liquor homogeneous mixture solotion between 1: 1～1: 4 is added dropwise in the microemulsion system with 0.5d/s in 80 ℃ of water-baths then, producing precipitation, is 8～10 up to pH.Precipitation ageing 24h filters out precipitation.Precipitation is used the autoclave supercritical drying with behind the industrial alcohol washing and filtering, pressure 8MPa, drying time 2h.The time of presoma roasting is 2～8h, and sintering temperature is 800～1400 ℃.
The zirconium manganese doped hexa-aluminate catalyzer nanoparticle features of preparation: grain diameter is little, good dispersion, and it is few to reunite, and mainly is shaped as sheet.
Preparation method's technology of the present invention is simple, with low cost; Little, the high-temperature stable of crystal particle scale.
Description of drawings
Fig. 1: the XRD figure of prepared zirconium manganese doped hexa-aluminate catalyzer sample
Fig. 2: the TEM figure of prepared zirconium manganese doped hexa-aluminate catalyzer sample
The specific embodiment
Following embodiment further proves the present invention, the invention is not restricted to this.
Embodiment 1:
Reverse micro emulsion mixes the back by 50% cyclohexane, 16% n-butanol, 20%OP-10 emulsifying agent and 14% water (volume ratio) and adds in the there-necked flask, stirs 10 hours with 600 rev/mins rotating speeds, leaves standstill 12 hours.The zirconium nitrate solution of preparation 0.4mol/L, the manganese nitrate solution of 0.6mol/L, the aluminum nitrate solution of 2mol/L.Zirconium nitrate: manganese nitrate: aluminum nitrate is that 1: 1.5: 10.5 (mol ratio) mixing back speed with 0.5d/s in 80 ℃ of water-baths is added dropwise in the reverse micro emulsion, and the amount that adds polyethylene glycol is 4g, stops water-bath and stirring, leaves standstill 1～3h.Being ratio the 3mol/L urea of 1: 2 (volume ratio) and 5mol/L ammoniacal liquor in 80 ℃ of water-baths then splashes in the microemulsion system with the speed of 0.5d/s, produces precipitation, is 8 up to pH.Precipitation ageing 24h filters out precipitation.Use the industrial alcohol washing precipitation, filter the back by the autoclave supercritical drying, pressure 8MPa, drying time 2h.Presoma is at 800 ℃ of roasting 2h.
Embodiment 2:
Reverse micro emulsion mixes the back by 60% cyclohexane, 20% n-butanol, 20%OP-10 emulsifying agent and 10% water (volume ratio) and adds in the there-necked flask, stirs 10 hours with 600 rev/mins rotating speeds, leaves standstill 12 hours.The zirconium nitrate solution of preparation 0.5mol/L, the manganese nitrate solution of 1.0mol/L, the aluminum nitrate solution of 1.5mol/L.Zirconium nitrate: manganese nitrate: aluminum nitrate is to be added dropwise in the reverse micro emulsion in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s after 1: 2: 10 (mol ratio) mixes, and the amount that adds polyethylene glycol is to stop water-bath and stirring behind the 3g, leaves standstill 3h.Being ratio the 3mol/L urea of 1: 1 (volume ratio) and 5mol/L ammoniacal liquor in 80 ℃ of water-baths then splashes in the microemulsion system with the speed of 0.5d/s, produces precipitation, is 8.5 up to pH.Precipitation ageing 24h filters out precipitation.Use the industrial alcohol washing precipitation, filter the back by the autoclave supercritical drying, pressure 8MPa, drying time 2h.Presoma is at 1000 ℃ of roasting 4h.
Embodiment 3:
Reverse micro emulsion mixes the back by 40% cyclohexane, 15% n-butanol, 25%OP-10 emulsifying agent and 30% water (volume ratio) and adds in the there-necked flask, stirs 10 hours with 600 rev/mins rotating speeds, leaves standstill 12 hours.The zirconium nitrate solution of preparation 0.5mol/L, the manganese nitrate solution of 1.0mol/L, the aluminum nitrate solution of 1.5mol/L.Zirconium nitrate: manganese nitrate: aluminum nitrate is to be added dropwise in the reverse micro emulsion in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s after 1: 1: 12 (mol ratio) mixes, and the amount that adds polyethylene glycol is to stop water-bath and stirring behind the 2g, leaves standstill 2h.Being ratio the 2mol/L urea of 2: 1 (volume ratio) and 3.5mol/L ammoniacal liquor in 80 ℃ of water-baths then splashes in the microemulsion system with the speed of 0.5d/s, produces precipitation, is 10 up to pH.Precipitation ageing 24h filters out precipitation.Use the industrial alcohol washing precipitation, filter the back by the autoclave supercritical drying, pressure 8MPa, drying time 2h.Presoma is at 1200 ℃ of roasting 4h.
Embodiment 4:
Reverse micro emulsion mixes the back by 55% cyclohexane, 15% n-butanol, 18%OP-10 emulsifying agent and 12% water (volume ratio) and adds in the there-necked flask, stirs 10 hours with 600 rev/mins rotating speeds, leaves standstill 12 hours.The zirconium nitrate solution of preparation 0.5mol/L, the manganese nitrate solution of 1.0mol/L, the aluminum nitrate solution of 3mol/L.Zirconium nitrate: manganese nitrate: aluminum nitrate is to be added dropwise in the reverse micro emulsion in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s after 1: 1: 11 (mol ratio) mixes, and the amount that adds polyethylene glycol is to stop water-bath and stirring behind the 3.5g, leaves standstill 2h.Being ratio the 2mol/L urea of 2: 1 (volume ratio) and 5mol/L ammoniacal liquor in 80 ℃ of water-baths then splashes in the microemulsion system with the speed of 0.5d/s, produces precipitation, is 9.5 up to pH.Precipitation ageing 24h filters out precipitation.Use the industrial alcohol washing precipitation, filter the back by the autoclave supercritical drying, pressure 8MPa, drying time 2h.Presoma is at 1200 ℃ of roasting 2h.
Embodiment 5:
Reverse micro emulsion mixes the back by 55% cyclohexane, 15% n-butanol, 18%OP-10 emulsifying agent and 12% water (volume ratio) and adds in the there-necked flask, stirs 10 hours with 600 rev/mins rotating speeds, leaves standstill 12 hours.The zirconium nitrate solution of preparation 0.5mol/L, the manganese nitrate solution of 1.0mol/L, the aluminum nitrate solution of 3mol/L.Zirconium nitrate: manganese nitrate: aluminum nitrate is to be added dropwise in the reverse micro emulsion in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s after 1: 1: 11 (mol ratio) mixes, and the amount that adds polyethylene glycol is to stop water-bath and stirring behind the 4.5g, leaves standstill 2h.Being ratio the 2mol/L urea of 2: 1 (volume ratio) and 5mol/L ammoniacal liquor in 80 ℃ of water-baths then splashes in the microemulsion system with the speed of 0.5d/s, produces precipitation, is 9.5 up to pH.Precipitation ageing 24h filters out precipitation.Use the industrial alcohol washing precipitation, filter the back by the autoclave supercritical drying, pressure 8MPa, drying time 2h.Presoma is at 1200 ℃ of roasting 2h.
Claims (2)
1. the preparation method of a zirconium manganese doped hexa-aluminate catalyzer is characterized in that this preparation method's step is as follows:
1) with volume ratio be: 10～60% cyclohexanes, 10～30% n-butanols, 10～30%OP-10,10～30% water, the rotating speed with 600 rev/mins after mixing stirred 10 hours, left standstill 12 hours, made transparent or semitransparent stable reverse microemulsion system;
2) adopting zirconium nitrate, manganese nitrate, aluminum nitrate and polyethylene glycol is raw material, in deionized water, then adds in the reverse microemulsion system for preparing it mixed dissolution; The concentration of described zirconium nitrate is at 0.1～1mol/L, and the concentration of manganese nitrate is at 0.1～1mol/L, and the concentration of aluminum nitrate is at 1～3mol/L; Zirconium nitrate: manganese nitrate: aluminum nitrate is with 0.5～1.5: 0.5～1.5: the molar ratio between 10～12 mixes the back and is added dropwise in the reverse microemulsion system for preparing in the speed of 80 ℃ of waters bath with thermostatic control with 0.5d/s, and the amount that adds polyethylene glycol is 1～5g; Stop water-bath and stirring then, left standstill 1～3 hour;
3) in 80 ℃ of water-baths, be volume ratio that 1～3mol/L urea and 2～5mol/L ammoniacal liquor homogeneous mixture solotion between 1: 1～1: 4 is added dropwise to step 2 with 0.5d/s) in the microemulsion system that obtains, produce precipitation, up to pH is 8～10, precipitation ageing 24 hours, filter out post precipitation and make presoma, in Muffle furnace, this presoma is carried out roasting then and promptly obtain zirconium manganese doped hexa-aluminate particle by the autoclave supercritical drying.
2. by the preparation method of the described zirconium manganese doped hexa-aluminate catalyzer of claim 1, it is characterized in that: after the filtration,, use the autoclave supercritical drying, pressure 8MPa, 2 hours drying times with the precipitation that the industrial alcohol washing and filtering comes out; The time of presoma roasting is 2～8 hours, and sintering temperature is 800～1400 ℃.
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| CN102358826B (en) * | 2011-08-19 | 2013-08-07 | 湖南皓志新材料股份有限公司 | Method for preparing aluminum-doped zirconium oxide compound polishing powder |
| CN103537286B (en) * | 2013-10-28 | 2015-06-17 | 湛江师范学院 | Single-step hydrothermal micro-emulsion method for preparing iron-doped nano titanium dioxide powder |
| CN106032284B (en) * | 2015-03-09 | 2017-06-30 | 中国科学院大连化学物理研究所 | A kind of preparation method that temperature hexa-aluminate is formed with low phase |
| CN106582618A (en) * | 2016-12-08 | 2017-04-26 | 中国科学技术大学 | W-doped hexaaluminate, preparation method thereof and application thereof in biodiesel catalytic combustion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030176278A1 (en) * | 2002-03-05 | 2003-09-18 | David Wickham | Thermally stable catalysts for methane combustion |
| CN1680020A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院生态环境研究中心 | Preparation of transition metal substituted hexaaluminate as catalyst for natural gas combustion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030176278A1 (en) * | 2002-03-05 | 2003-09-18 | David Wickham | Thermally stable catalysts for methane combustion |
| CN1680020A (en) * | 2004-04-05 | 2005-10-12 | 中国科学院生态环境研究中心 | Preparation of transition metal substituted hexaaluminate as catalyst for natural gas combustion |
Non-Patent Citations (2)
| Title |
|---|
| YU Qian et al..Study on hexaaluminate MnLaAll1O19-δ catalyst for catalyticcombustive reaction of dimethyl ether as a new fuel.RARE METALS25 Spec..2006,25(Spec.),p333,334. |
| YU Qian et al..Study on hexaaluminate MnLaAll1O19-δ catalyst for catalyticcombustive reaction of dimethyl ether as a new fuel.RARE METALS25 Spec..2006,25(Spec.),p333,334. * |
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