CN102489281B - Preparation method of mesoporous zirconia - Google Patents
Preparation method of mesoporous zirconia Download PDFInfo
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- CN102489281B CN102489281B CN201110423329.5A CN201110423329A CN102489281B CN 102489281 B CN102489281 B CN 102489281B CN 201110423329 A CN201110423329 A CN 201110423329A CN 102489281 B CN102489281 B CN 102489281B
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Abstract
The invention relates to a preparation method of mesoporous zirconia, and in particular to a preparation method of the mesoporous zirconia in the field of catalysts, belonging to the technical field of preparation of catalysts. The preparation method comprises the following steps: preparing an aqueous solution of water-soluble zirconium salt by deionized water; preparing a SO42- containing aqueous solution, and mixing the SO42- containing aqueous solution with the water-soluble zirconium salt solution uniformly; heating the mixed solution, and slowly dripping aqueous alkali to obtain a zirconium hydroxide containing suspension; aging the zirconium hydroxide suspension, filtering and separating to obtain a filter cake; eluting the filter cake, and filtering to obtain a high-purity zirconium hydroxidefilter cake; and thermally processing the zirconium hydroxidefilter cake to obtain the mesoporous zirconia. The preparation method of the mesoporous zirconia has mild technical conditions, and can realize industrial production easily; and after thermal processing, the aperture of the precursor zirconium hydroxide of the prepared zirconia is larger than that of the conventional zirconia.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous material, specifically, is the preparation method who is applied to the mesoporous zircite of catalyst field, belongs to catalyst preparation technical field.
Background technology
Zirconia, especially mesoporous zircite are a kind of normal adopted materials in catalyst field, as are used to hydrogen-storing material, SCR (SCR) catalyst, the fuel cell of tai-gas clean-up catalyst.Yet, when practical application, generally there is higher temperature (as higher than 500 ℃), compared with little zirconia, easily there is hole sintering and make catalyst activity reduction in aperture, and therefore, the larger zirconia in preparation aperture can effectively improve zirconic high-temperature stability.
At present, the zirconic method of known preparation is a lot, but is mainly alkaline precipitation and hydrothermal synthesis method for the zirconic method of preparation of industrialization.
Patent US2009/0005239A1 adds SO in zirconium salt solution
4 2-to optimize alkali precipitation process, SO
4 2-with Zr
4+molar ratio scope 0.40～0.52, under the condition lower than 25 ℃ (preferably lower than 2 ℃), add alkali to pH value higher than 11, then by the zirconium hydroxide obtaining hydrothermal treatment consists under the pressure condition lower than 3Barg, finally heat-treat and obtain all larger zirconias of pore volume and aperture.But because alkali precipitation process need is cooled to 25 ℃ even below 2 ℃ by mixed solution, this just needs special cooling device and very high energy consumption.Therefore, this preparation method is applied to the industrial production of scale not bery desirable.
Patent US7431910132 adds SO in zirconium salt solution
4 2-to optimize alkali precipitation process and follow-up washing and filtering process, SO
4 2-with Zr
4+molar ratio scope 0.42～0.7, under the condition lower than 50 ℃, alkaline chemical precipitation obtains zirconium hydroxide, this zirconium hydroxide as zirconic precursor for the preparation of cerium zirconium sosoloid.
Patent US2008/00907 adds SO in zirconium salt solution
4 2-be made into mixed solution, SO
4 2-with ZrO
2quality ratio range 0.3～0.6, (be SO
4 2-with Zr
4+molar ratio scope 0.38～0.77), then under the condition of 65 ℃, heat this mixed solution and make Zr being not less than
4+hydrolysis occurs and generate zirconium basic sulphate, this zirconium basic sulphate is the preparation for cerium zirconium sosoloid as zirconic precursor.
US2008/00907 is similar with patent, and patent CN100347092C adds SO in zirconium salt solution
4 2-be made into mixed solution, SO
4 2-with the quality ratio range of ZrO2 0.2～0.6, (be SO
4 2-with Zr
4+molar ratio scope 0.25～0.77), then heat this mixed solution and make Zr
4+there is hydrolysis and generate zirconium basic sulphate, then continue alkaline chemical precipitation, and repeatedly after washing, obtain nanometer zirconium hydroxide.
The hydrolysis that patent US2008/00907 and patent CN100347092C adopt generates the method for zirconium basic sulphate, at SO
4 2-with Zr
4+molar ratio lower than in 0.4 situation, need long time just can make hydrolysis occur.In addition,, due to the crystal grain of the zirconium basic sulphate obtaining large (0.5-2 μ m), the zirconic thermal stability finally obtaining is also poor.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of process conditions gentle, easily realize the method for preparing mesoporous zircite of suitability for industrialized production.The zirconia precursor zirconium hydroxide that this method prepares, through 450 ℃ of heat treatments 4 hours, the zirconic average pore size of gained reached 6～9nm; Through 550 ℃ of heat treatments 4 hours, the zirconic average pore size of gained reached 9～14nm.
Technical scheme of the present invention: a kind of preparation method of mesoporous zircite, the method comprises the following steps:
(1) preparation of zirconium salt solution: the aqueous solution that water-soluble zirconates is mixed with to 0.2～1mol/L by deionized water is standby;
Described water-soluble zirconates is ZrOCl
2, ZrO (NO
3)
2, Zr (NO
3)
4one of and various hydrates;
(2) SO
4 2-the preparation of the aqueous solution: preparation is containing SO
4 2-the aqueous solution, the water-soluble zirconium salt solution of preparing with step (1) mixes, and makes SO in mixed solution
4 2-with Zr
4+mol ratio be 0.10～0.30;
Described containing SO
4 2-the aqueous solution can be H
2sO
4, K
2sO
4, Na
2sO
4, Zr (SO
4)
2in one or more SO
4 2-mixed solution;
(3) preparation of zirconium hydroxide suspension: mixed solution prepared by step (2) is warming up to after 30 ℃～50 ℃, slowly drips aqueous slkali to pH value to 2.0～6.5, obtains hydrogeneous zirconic suspension;
Described aqueous slkali is that mass percent concentration is one or more mixed ammonium/alkali solutions in 10%～40% NaOH solution, KOH solution and ammoniacal liquor;
(4) post processing: under 30 ℃～90 ℃ temperature conditions, zirconium hydroxide suspension ageing prepared by step (3) filtered to isolate filter cake after 1～12 hour; By Washing of Filter Cake, filter 1～5 time, obtain highly purified zirconium hydroxide filter cake; Gained zirconium hydroxide filter cake is obtained to product mesoporous zircite through 400～600 ℃ of heat treatment 3～5h.
The described water-soluble zirconates of step (1) is ZrOCl
2hydrate.
Step (2) is described containing SO
4 2-the aqueous solution be H
2sO
4solution.
The described aqueous slkali of step (3) is the NaOH aqueous solution of mass concentration 10%～30%.
In step (4), zirconium hydroxide was through 450 ℃ of heat treatments 4 hours, and the average pore size of products obtained therefrom mesoporous zircite is 6～9nm; Through 550 ℃ of heat treatments 4 hours, the average pore size of products obtained therefrom mesoporous zircite was 9～14nm.
Beneficial effect of the present invention: process conditions of the present invention are gentle, easily realize suitability for industrialized production.The zirconia precursor zirconium hydroxide preparing is through heat treatment, and the more existing zirconia in aperture is larger, has better stability under hot conditions.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Take 790g ZrOCl
2.8H
2o, is mixed with the aqueous solution of 0.2mol/L, adds H
2sO
4solution, SO
4 2-with Zr
4+mol ratio be 0.1, by mixed solution be warming up to 50 ℃ and insulation, slowly splash into 30%NaOH solution to pH value to 6.5, obtain hydrogeneous zirconic suspension.Hydrogeneous zirconic suspension is warming up to 90 ℃ and insulation, and ageing was filtered after 1 hour.Filter cake is repeatedly washed, filtered, obtain highly purified zirconium hydroxide filter cake.By 450 ℃ of heat treatments of zirconium hydroxide 4 hours, the zirconic average pore size of gained was 7.2nm; Through 550 ℃ of heat treatments 4 hours, the zirconic average pore size of gained was 10.5nm.
Embodiment 2
Take 790g ZrOCl
2.8H
2o, is mixed with the aqueous solution of 0.5mol/L, adds H
2sO
4solution, SO
4 2-with Zr
4+mol ratio be 0.2, by mixed solution be warming up to 45 ℃ and insulation, slowly splash into 30%NaOH solution to pH value to 4.0, obtain hydrogeneous zirconic suspension.Hydrogeneous zirconic suspension is warming up to 50 ℃ of insulation ageings to be filtered after 5 hours.Filter cake is repeatedly washed, filtered, obtain highly purified zirconium hydroxide filter cake.By 450 ℃ of heat treatments of zirconium hydroxide 4 hours, the zirconic average pore size of gained was 8.4nm; Through 550 ℃ of heat treatments 4 hours, the zirconic average pore size of gained was 13.5nm.
Embodiment 3
Take 790g ZrOCl
2.8H
2o, is mixed with the aqueous solution of 1mol/L, adds H
2sO
4solution, SO
4 2-with Zr
4+mol ratio be 0.3, by mixed solution be warming up to 30 ℃ and insulation, slowly splash into 30%NaOH solution to pH value to 2.0, obtain hydrogeneous zirconic suspension.Hydrogeneous zirconic suspension is filtered after 12 hours 30 ℃ of insulation ageings.Filter cake is repeatedly washed, filtered, obtain highly purified zirconium hydroxide filter cake.By 450 ℃ of heat treatments of zirconium hydroxide 4 hours, the zirconic average pore size of gained was 6.6nm; Through 550 ℃ of heat treatments 4 hours, the zirconic average pore size of gained was 9.5nm.
Claims (1)
1. a preparation method for mesoporous zircite, is characterized in that, the method comprises the following steps:
(1) preparation of zirconium salt solution: the aqueous solution that water-soluble zirconates is mixed with to 0.2 ~ 1mol/L by deionized water is standby;
(2) SO
4 2-the preparation of the aqueous solution: preparation is containing SO
4 2-the aqueous solution, the water-soluble zirconium salt solution of preparing with step (1) mixes, and makes SO in mixed solution
4 2-with Zr
4+mol ratio be 0.10 ~ 0.30;
(3) preparation of zirconium hydroxide suspension: mixed solution prepared by step (2) is warming up to after 30 ℃ ~ 50 ℃, slowly drips aqueous slkali to pH value to 2.0 ~ 6.5, obtains hydrogeneous zirconic suspension;
(4) post processing: under 30 ℃ ~ 90 ℃ temperature conditions, zirconium hydroxide suspension ageing prepared by step (3) filtered to isolate filter cake after 1 ~ 12 hour; By Washing of Filter Cake, filter 1 ~ 5 time, obtain highly purified zirconium hydroxide filter cake;
The described water-soluble zirconates of step (1) is ZrOCl
2hydrate;
Step (2) is described containing SO
4 2-the aqueous solution be H
2sO
4solution;
The described aqueous slkali of step (3) is the NaOH aqueous solution of mass concentration 10% ~ 30%;
In step (4), resulting zirconium hydroxide filter cake was through 440 ~ 460 ℃ of heat treatments 3 ~ 5 hours, and the average pore size of products obtained therefrom mesoporous zircite is 6 ~ 9nm; Or through 550 ℃ of heat treatments 4 hours, the average pore size of products obtained therefrom mesoporous zircite was 9 ~ 14nm.
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|---|---|---|---|
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|---|---|---|---|
| CN201110423329.5A CN102489281B (en) | 2011-12-15 | 2011-12-15 | Preparation method of mesoporous zirconia |
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| CN102489281B true CN102489281B (en) | 2014-01-29 |
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| CN100347092C (en) * | 2006-04-04 | 2007-11-07 | 欧洲海赛有限公司 | Preparation method of ziroconium oxide composite nano crystal material |
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