CN100503450C - Method for preparing powder of zirconium oxide in high purity - Google Patents
Method for preparing powder of zirconium oxide in high purity Download PDFInfo
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- CN100503450C CN100503450C CNB2007100678236A CN200710067823A CN100503450C CN 100503450 C CN100503450 C CN 100503450C CN B2007100678236 A CNB2007100678236 A CN B2007100678236A CN 200710067823 A CN200710067823 A CN 200710067823A CN 100503450 C CN100503450 C CN 100503450C
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- high purity
- zirconium oxide
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- mother liquor
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Abstract
This invention discloses a method for preparing high-purity ZrO2 nanopowder. The method utilizes ZrOCl2.8H2O as the precipitant, and adopts sol-gel method to prepare high-purity ZrO2 nanopowder. The method has such advantages as simple apparatus and process, low energy consumption, and high efficiency. The product purity is higher than 99.9%, and the particle sizes are distributed within 10-30 nm.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity nano zirconia material, particularly relating to the basic zirconium chloride is raw material, adopts sol-gel method to prepare zirconium oxide in high purity.
Background technology
Zirconium white has good physical and chemical stability, the characteristic that under the condition of high temperature, possesses solid electrolyte again, simultaneously because the singularity of its molecular structure, thereby possess certain katalysis, thereby have purposes widely at aspects such as material modification, sensor modification, transmitter preparation and fuel cells.And the zirconium white micro mist makes it show good prospects for application because of having the characteristics of high-specific surface area, good stability concurrently.At present, the preparation method of nano zircite mainly contains vapor phase process and liquid phase method, and vapor phase process is a raw material with zirconium chloride or pure zirconium, makes nano zircite through pyrohydrolysis or pyrolysis.These class methods have advantages such as good product dispersibility, narrow diameter distribution, but have equipment complexity, investment shortcoming such as big.Liquid phase method mainly contains the precipitator method, sol-gel method, hydrothermal method and alkoxide hydrolysis etc., because alkoxide cost height, therefore main exploitation is raw material, is the neutralization precipitation agent with alkali (ammoniacal liquor or highly basic) with the basic zirconium chloride of cheapness, make zirconium hydroxide gel, remove impurity through washing, handle through surfactant-dispersed, the dehydration of calcination at high temperature makes nano zircite.The shortcoming that these methods exist is: (1) equipment complexity, complicated process of preparation, length consuming time, energy consumption height, cost height; (2) with ammoniacal liquor as precipitation agent, or introduce (Chinese patent CN151902) such as other complicated organic reagents such as ureas in the process, in preparation process, can cause ammonia to pollute; (3) the highly basic positively charged ion (Na of Yin Ruing
+, K
+) (Chinese patent CN116875) be difficult to clean up, make cleaning step become loaded down with trivial details, and may influence the purity of nano zircite.
Summary of the invention
The object of the invention is to overcome above-mentioned shortcoming, provides that a kind of technology is simple, less investment, energy consumption be low, the preparation method of the zirconium oxide in high purity of environmental protection.
The invention provides the zirconium oxide in high purity material preparation method, with basic zirconium chloride (ZrOCl
28H
2O) be raw material, oxalic acid (H
2C
2O
42H
2O) be precipitation agent, adopt sol-gel method to prepare zirconium oxide in high purity (ZrO
2), preparation process is as follows:
1) be 0.5～0.8mol/L basic zirconium chloride ZrOCl with concentration
28H
2O solution is as mother liquor, and regulating its pH value with HCl is 4, adds mass percent concentration and be 1～2% PEG8000 as tensio-active agent;
2) compound concentration is the H of 0.4～0.5mol/L again
2C
2O
42H
2O solution, in the process that constantly stirs slowly will with above-mentioned ZrOCl
28H
2The H of O equimolar amount
2C
2O
42H
2O solution splashes into mother liquor, obtains vitreosol;
3) stir ageing 30 minutes, continue to drip accounting for ZrOCl in the mother liquor again
28H
2The above-mentioned H of O molar weight 3%～5%
2C
2O
42H
2O makes colloidal sol change transparent gel-form gradually into, and then coagulation is the opaque suspension liquid of oyster white;
4) centrifugally must precipitate ZrOC
2O
42H
2O, with deionized water wash for several times, the dehydrated alcohol ultra-sonic dispersion, the electric furnace oven dry, mortar grinds to form fine powder;
5) under 600 ℃, above-mentioned precursor is placed retort furnace calcining 2 hours, obtain nano zircite.
Above-mentioned steps 1) ZrOCl
28H
2The preferable concentration of O is 0.75mol/L, H
2C
2O
42H
2The preferable concentration of O is 0.4mol/L, and Surfactant PEG 8000 preferable concentration are 2%.
Above-mentioned steps 3) stirred digestion time 0.5 hour, drip excessive oxalic acid, preferable weight percent concentration is 4%, drips excessive H
2C
2O
42H
2O makes presoma easily washing and dehydration, with the HCl that produces in the flush away process, avoids making in follow-up drying process HCl volatilized and produce environmental pollution.
100～200 ℃ of the temperature of electric furnace oven dry above-mentioned steps 4), about 5 minutes of time.In mortar, grind through the exsiccant precipitation, help avoid the cohesion of powder in calcination process.
Mechanism of the present invention can describe with reaction equation once:
In step 2) in, following chemical reaction takes place in basic zirconium chloride and oxalic acid:
ZrOCl
2+H
2C
2O
4+2H
2O＝ZrOC
2O
4·2H
2O+2HCl
In step 3), add excessive oxalic acid, then can regulate the charge property of the sol system that back obtains, make colloidal sol generation retrogradation effect, precipitate then, thereby be convenient to subsequent washing and dehydration.So avoided by the direct ageing drying of wet gel,, made to form hard aggregation in the drying process, thereby cause the diameter of particle after the calcining very big owing to comprise a large amount of moisture in the gel.
Pyrolysis has taken place in retort furnace at step 5) mesoxalic acid oxygen zirconium:
2ZrOC
2O
4·2H
2O+O
2＝2ZrO
2+4CO
2+4H
2O
And, obtaining the ZrO2 nano-powder of cube phase through 600 ℃ of calcinings, particle diameter is evenly distributed in 10～30nm.Technique effect of the present invention
1) raw material basic zirconium chloride used in the present invention, oxalic acid are cheap raw material; The present invention need not specific installation such as reactor etc., need not high pressure, high temperature pyrolysis condition, and whole process all can be finished in common lab, makes material, facility investment and energy consumption far below existing nano zircite technology of preparing, can significantly reduce production costs;
2) do not introduce metallic cation impurity in the reaction process, for the high purifying of product has been created condition; Also avoid metal ion etc. to remain in aggressiveness before the product, finally caused hard aggregation;
3) do not produce waste gas in the reaction process, realized non-waste-emission, meet environment protection requirement as ammonia and so on.
4) preparation technology is simple, can finish within 4 hours, and weak point consuming time can be realized High-efficient Production.
The present invention not only equipment, technology is simple, less investment, energy consumption is low, the productivity height, production cost is low, and product purity can reach more than 99.9%, and particle diameter controllably is distributed between 10～30nm, the whole process of production environmental protection is a kind of energy-saving and cost-reducing preparation method that can produce the zirconium oxide in high purity of high benefit.
5) the prepared Zirconium oxide powder of the present invention can be used for the fields such as decorative material, specific function pottery, catalyzer or support of the catalyst of chemical sensor.
The present invention is a raw material with the basic zirconium chloride of cheapness, adopting oxalic acid cheap, that can not produce obnoxious flavour is precipitation agent, adopt sol-gel method to prepare the method for zirconium oxide in high purity, technology is simple, less investment, energy consumption are low, the process environmental protection, therefore the quality product height is all preparation methods of significant zirconium oxide in high purity of a kind of social benefit and economic benefit.
Embodiment
Embodiment 1
● with concentration is 0.75mol/L ZrOCl
28H
2O solution is as mother liquor, and regulating its pH value with HCl is about 4, and the PEG8000 of adding 1% is as tensio-active agent;
● compound concentration is the H of 0.4mol/L again
2C
2O
42H
2O solution, in the process that constantly stirs slowly will with ZrOCl
28H
2The H of amount of substances such as O
2C
2O
42H
2O solution splashes into mother liquor, obtains vitreosol;
● stir ageing 0.5 hour, continue to drip accounting for ZrOCl in the above-mentioned mother liquor
28H
2The above-mentioned H of O molar weight 3%～5%
2C
2O
42H
2O makes colloidal sol change transparent gel-form gradually into, and then coagulation is the opaque suspension liquid of oyster white;
● centrifugally must precipitate ZrOC
2O
42H
2O uses deionized water wash 3 times, and the dehydrated alcohol ultra-sonic dispersion places on the inherent 200 ℃ of electric furnaces of mortar and dries, and constantly grinds to form fine powder with grinding to precipitate in the drying process;
● under 600 ℃, above-mentioned precursor is placed retort furnace calcining 2 hours, obtain nano zircite.
Characterizing method: with Rigaku D/max type X-ray diffractometer (CuK
αLine, λ=1.5406 ') carry out the material material phase analysis, confirm that resulting nano zircite is cube phase.And to calculate the crystalline median size by Scherrer formula D=0.89 λ/β cos θ be 22nm.
Embodiment 2
Preparation process with reference to embodiment 1, different is: the basic zirconium chloride mother liquid concentration is 0.5mol/L, concentration of oxalic acid is 0.4mol/L, continuing to drip excessive concentration of oxalic acid is 5%, significantly agglomeration appears in the electric furnace drying process, through calcination, measurement calculates median size and is about 0.2 micron.
Claims (3)
1, a kind of zirconium oxide in high purity material preparation method is a raw material with the basic zirconium chloride, and oxalic acid is precipitation agent, adopts sol-gel method to prepare zirconium oxide in high purity, and preparation process is as follows:
● with concentration is the ZrOCl of 0.5～0.8mol/L
28H
2O solution is as mother liquor, and regulating its pH value with HCl is 4, adds mass percent concentration and be 1～2% PEG8000 as tensio-active agent;
● compound concentration is the H of 0.4～0.5mol/L again
2C
2O
42H
2O solution, in the process that constantly stirs slowly will with above-mentioned ZrOCl
28H
2The H of O equimolar amount
2C
2O
42H
2O solution splashes into mother liquor, obtains vitreosol;
● stir ageing 30 minutes, continue to drip accounting for ZrOCl in the mother liquor again
28H
2The above-mentioned H of O molar weight 3%～5%
2C
2O
42H
2O makes colloidal sol change transparent gel-form gradually into, and then coagulation is the opaque suspension liquid of oyster white;
● centrifugally must precipitate ZrOC
2O
42H
2O, with deionized water wash for several times, the dehydrated alcohol ultra-sonic dispersion, the electric furnace oven dry, mortar grinds to form fine powder;
● under 600 ℃, above-mentioned precursor is placed retort furnace calcining 2 hours, obtain nano zircite.
2, zirconium oxide in high purity material preparation method according to claim 1 is characterized in that the basic zirconium chloride mother liquid concentration is 0.75mol/L.
3, zirconium oxide in high purity material preparation method according to claim 1 is characterized in that 100～200 ℃ of the temperature of electric furnace oven dry, 5 minutes time.
Priority Applications (1)
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|---|---|---|---|
| CNB2007100678236A CN100503450C (en) | 2007-04-03 | 2007-04-03 | Method for preparing powder of zirconium oxide in high purity |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNB2007100678236A CN100503450C (en) | 2007-04-03 | 2007-04-03 | Method for preparing powder of zirconium oxide in high purity |
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|---|---|
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| CN100503450C true CN100503450C (en) | 2009-06-24 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851005B (en) * | 2010-05-17 | 2011-08-31 | 山东理工大学 | Preparation method of high-dispersion zirconium oxide nano powder |
| CN103011281B (en) * | 2012-12-12 | 2014-08-06 | 南昌大学 | Method for synthesizing sphere-like nano yttrium and cerium doped zirconia according to ethylene glycol sol-gel method |
| CN103058277B (en) * | 2013-02-05 | 2014-10-15 | 山东国瓷功能材料股份有限公司 | Supercritical hydrothermal synthesis method of nanometer zirconium oxide powder |
| CN107662945B (en) * | 2017-11-08 | 2020-03-13 | 山西新华化工有限责任公司 | Method for preparing nano zirconium oxide by using nonionic surfactant |
| CN108163888B (en) * | 2018-01-31 | 2019-10-29 | 南京信息工程大学 | The composite granule and its preparation process of a kind of recessed native nano zircite of high temperature resistant |
| CN109576820B (en) * | 2018-12-17 | 2020-11-24 | 北京航空航天大学 | Preparation method of high-strength high-toughness zirconia nanofiber |
| CN111377737B (en) * | 2018-12-27 | 2022-08-05 | 元颉新材料科技(浙江)有限公司 | Tetragonal phase nano-doped zirconia ceramic powder material and preparation method thereof |
| CN110467460B (en) * | 2019-09-12 | 2022-03-11 | 广东东方锆业科技股份有限公司 | Method for preparing composite zirconium oxide precursor by oxalate method |
| CN112919535B (en) * | 2021-02-25 | 2022-05-24 | 安徽景成新材料有限公司 | Preparation method of self-assembled flaky nano-zirconia |
| CN112919536A (en) * | 2021-03-08 | 2021-06-08 | 安徽景成新材料有限公司 | Method for synthesizing nano zirconia by rheological phase method |
| CN114477264A (en) * | 2022-03-03 | 2022-05-13 | 赣州湛海新材料科技有限公司 | Method for preparing nano cerium oxide by sol-gel method |
| CN116003901A (en) * | 2022-12-17 | 2023-04-25 | 重庆泛锐科技有限公司 | Wear-resistant anti-skid EVA composite material and preparation method thereof |
| CN116282144B (en) * | 2023-02-15 | 2024-04-12 | 吕梁学院 | Preparation method of zirconium dioxide |
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2007
- 2007-04-03 CN CNB2007100678236A patent/CN100503450C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 溶胶－凝胶法制备钇掺杂的纳米氧化锆粉体. 蒋银花等.无机盐工业，第38卷第2期. 2006 |
| 溶胶－凝胶法制备钇掺杂的纳米氧化锆粉体. 蒋银花等.无机盐工业，第38卷第2期. 2006 * |
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