CN101717115B - Organic acid method for preparing ultrafine partial stable zirconia - Google Patents
Organic acid method for preparing ultrafine partial stable zirconia Download PDFInfo
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- CN101717115B CN101717115B CN2009101129023A CN200910112902A CN101717115B CN 101717115 B CN101717115 B CN 101717115B CN 2009101129023 A CN2009101129023 A CN 2009101129023A CN 200910112902 A CN200910112902 A CN 200910112902A CN 101717115 B CN101717115 B CN 101717115B
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- zirconyl chloride
- active agent
- yttrium salt
- stable zirconia
- soluble yttrium
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Abstract
The invention provides an organic acid method for preparing ultrafine-part stable zirconia. The ultrafine partial stable zirconia is prepared by a tartaric acid or a malic acid, ZrOCl2.8H2O, a surface active agent and soluble yttrium salt, wherein the mole ratio of the ZrOCl2.8H2O to the soluble yttrium salt is 1 to 0.03; the mole ratio of the ZrOCl2.8H2O to the tartaric acid or the malic acid is 1 to 3; the mole ratio of the ZrOCl2.8H2O to the surface active agent is 1 to 0.004-0.01; the reaction temperature of the tartaric acid or the malic acid and the ZrOCl2.8H2O and the soluble yttrium salt can be controlled between 65 DEG C and 95 DEG C; the adding temperature of the surface active agent is 95 DEG C, and the roasting temperature is controlled between 750 DEG C and 1000 DEG C so that the partial stable zirconia with the grain diameter of 30-85 nm is obtained. The invention solves the technical problems of high sintering temperature, low sintering finished product ratio, the low breaking strength, the poor fracture toughness and the insufficient abrasive resistance of products, and the like in the technology production of zirconia powder.
Description
Technical field
The present invention relates to the synthetic and field of new of inorganic chemical, be specifically related to a kind of method of utilizing the organic acid method for preparing ultrafine partial stable zirconia powder.
Background technology
Zirconium powder is a kind of high temperature resistant, wear-resistant, corrosion resistant ceramic.At present preparation superfine Zirconium powder enterprise adopts coprecipitation method, hydrothermal method mostly, and the prepared Zirconium powder process of these several kinds of technologies is difficult to control, and the goods that use the powder of this explained hereafter to produce have many defectives.Show that mainly sintering temperature is high, burn till that yield rate is low, the goods folding strength is low, fracture toughness property is poor, wear resistance is not enough etc.The major cause that produces these defectives is: the bad control of powder granule size, it is clean that impurity is difficult for washing, is easy to generate powder reuniting.Use simultaneously in this explained hereafter powder process, the water, electricity, gas consumption is big, and energy consumption is high.Waste water is difficult to handle, not only uneconomical but also not environmental protection.Have part enterprise to explore alkoxide hydrolysis at present and prepare superfine zirconium white production technique, but most of enterprise rests on lab scale or pilot scale level.This technology produces that to also have many deficiencies, major cause be that alkoxide hydrolysis consumption alcohol amount is big in batches, and has increased the preparation and the equipment of alkoxide precursor, exists to produce that long reaction time, productivity are low, the problem of poor stability.Difficulty is handled in energy consumption height, waste gas, wastewater collection in this prepared powder process of use simultaneously, makes this technology cost high, big to environmental disruption.
Summary of the invention
The object of the present invention is to provide a kind of organic acid method for preparing ultrafine partial stable zirconia that utilizes, to solve sintering temperature height in the Zirconium powder explained hereafter, to burn till technical problems such as yield rate is low, the goods folding strength is low, fracture toughness property is poor, wear resistance is not enough.
To achieve these goals, solution of the present invention is following:
Organic acid method for preparing ultrafine partial stable zirconia is by tartrate or oxysuccinic acid, zirconyl chloride ZrOCl
28H
2O, tensio-active agent and the preparation of soluble yttrium salt, the mol ratio of zirconyl chloride and soluble yttrium salt is 1: 0.03, and the mol ratio of zirconyl chloride and tartrate or oxysuccinic acid is 1: 3, and the mol ratio of zirconyl chloride and tensio-active agent is 1: 0.004-0.01; The temperature of reaction of tartrate or oxysuccinic acid and zirconyl chloride and soluble yttrium salt is controlled at 65 ℃-95 ℃; The interpolation temperature of tensio-active agent is at 95 ℃, pH=3-6, and calcination temperature is controlled at 750 ℃-1000 ℃, obtains the PSZ that particle diameter is 30-85nm.
Said soluble yttrium salt is YCl
3, Y (NO
3)
3
Said tensio-active agent is peregal, 16 Phenylsulfonic acids or both mixing.
The concrete preparation process of this organic acid method for preparing ultrafine partial stable zirconia powder is: tartrate or oxysuccinic acid are dissolved in water, in reaction kettle, stir (300-500r/min) and be heated to 65 ℃ of adding zirconyl chloride ZrOCl
28H
2O and soluble yttrium salt treat that zirconyl chloride dissolves fully, control pH=1-2; Slowly be heated to 95 ℃ and insulation; When the aqueous solution becomes to glue and pH=3-6, add tensio-active agent, continue heating evaporate to dryness moisture content; Under 750 ℃ of-1000 ℃ of temperature calcination 4-10 hour, obtain soft ultrafine partial stable zirconia powder.
It is water-soluble that the present invention passes through basic zirconium chloride and tartrate or oxysuccinic acid, replaces the Cl in the raw material with acid group
-, HCl is got rid of in heating, adds tensio-active agent simultaneously, prevents to reunite.Warp sateen burns the back and generates uniform particles, soft zirconia powder, and reaction mechanism is following:
Prepare superfine zirconia powder technology with organic acid among the present invention and compare with other technologies and have many advantages, mainly show: after 1, adding acid, acid group replaces the Cl in the raw material
-, HCl is got rid of in heating, can remove washing from and remove Cl
-Process has significantly reduced the consumption of water like this, and the generation of having exempted from great amount of wastewater again can be with Cl
-Remove totallyer.Reduced water washing process simultaneously, can prevent to wash influence, prevented that particle from growing up the crystal grain size.2, organic acid system can better be controlled particulate size in the reaction process.3, yttrium is more evenly distributed in zirconium powder.4, the soft difficult formation of zirconia powder that calcining is good is reunited.Organic acid is produced superfine zirconia powder body technology and is compared with coprecipitation method, and water consumption reduces 80%, and waste water has reduced 83%, and energy consumption has reduced by 45%, and powder characteristic improves more than 35%.Compare with hydrolysis method, water consumption reduces 70%, and waste water has reduced 75%, and energy consumption has reduced by 50%, and powder characteristic has only descended 7%.
Embodiment
Ultrafine partial stable process for producing zirconia provided by the invention is following:
Embodiment 1:
(1) takes by weighing tartrate (method for making of oxysuccinic acid is identical, as not giving unnecessary details), zirconyl chloride (ZrOCl
28H
2O), peregal, 16 Phenylsulfonic acids, Yttrium trinitrate.Wherein to get mol ratio be 1: 0.03 for zirconyl chloride and Yttrium trinitrate, zirconyl chloride (ZrOCl
28H
2O) be 1: 3 with tartaric mol ratio, zirconyl chloride (ZrOCl
28H
2O), the mol ratio of tensio-active agent is 1: 0.004, peregal is 1: 3 with 16 sulfonic acid ratio.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) tartaric acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add peregal, the 16 Phenylsulfonic acid solution prepared, continue heating evaporate to dryness moisture content, 750 ℃ of-900 ℃ of temperature lower calcinations 10 hours, the particle diameter of powder was at 40-60nm.
Embodiment 2:
(1) like embodiment 1, peregal is 2: 2 with 16 sulfonic acid ratio.
(2) preparation 1.5mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) tartaric acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add peregal, the 16 Phenylsulfonic acid solution prepared, continue heating evaporate to dryness moisture content, 750 ℃ of-900 ℃ of temperature lower calcinations 10 hours, the particle diameter of powder was at 50-65nm.
Embodiment 3:
(1) like embodiment 1.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add the peregal, the 16 Phenylsulfonic acid solution that have prepared, continue heating evaporate to dryness moisture content, calcined 6 hours down at 750 ℃-900 ℃, the particle diameter of powder is at 30-48nm.
Embodiment 4
(1) like embodiment 1, zirconyl chloride (ZrOCl
28H
2O), the mol ratio of tensio-active agent is 1: 0.008, peregal is 1: 3 with 16 sulfonic acid ratio.
(2) preparation 1.5mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) tartaric acid solution is heated with stirring to 65 ℃ in reaction kettle and adds zirconyl chloride, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add peregal, the 16 Phenylsulfonic acid solution prepared, continue heating evaporate to dryness moisture content, 750 ℃ of-900 ℃ of temperature lower calcinations 6 hours, the particle diameter of powder was at 70-85nm.
Embodiment 5:
(1) like embodiment 1.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add the peregal, the 16 Phenylsulfonic acid solution that have prepared, continue heating evaporate to dryness moisture content, calcined 10 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 45-58nm.
Embodiment 6:
(1) like embodiment 1.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add the peregal, the 16 Phenylsulfonic acid solution that have prepared, continue heating evaporate to dryness moisture content, calcined 6 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 40-52nm.
Embodiment 7:
(1) like embodiment 1, peregal is 2: 2 with 16 sulfonic acid ratio.
(2) preparation 1.5mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.During to pH=4-5, add the peregal, the 16 Phenylsulfonic acid solution that have prepared, continue heating evaporate to dryness moisture content, calcined 10 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 58-69nm.
Embodiment 8:
(1) like embodiment 1.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.To peregal, the 16 Phenylsulfonic acid solution that pH=3-4 has prepared, continue heating evaporate to dryness moisture content, to calcine 6 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 55-70nm.
Embodiment 9:
(1) like embodiment 1, zirconyl chloride (ZrOCl
28H
2O), the mol ratio of tensio-active agent is 1: 0.008, peregal is 1: 3 with 16 sulfonic acid ratio.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.To peregal, the 16 Phenylsulfonic acid solution that the pH=5-6 adding has prepared, continue heating evaporate to dryness moisture content, to calcine 6 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 70-85nm.
Embodiment 10:
(1) like embodiment 1.
(2) preparation 1mol/L tartaric acid solution is subsequent use, and peregal, 16 Phenylsulfonic acid compound concentrations are 10% solution for standby.
(3) mixed acid solution is stirred (300-500r/min) in reaction kettle and be heated to 65 ℃ of adding zirconyl chlorides, wait zirconyl chloride to dissolve fully, control pH=1-2.Slowly be heated to 95 ℃ and insulation.To peregal, the 16 Phenylsulfonic acid solution that the pH=5-6 adding has prepared, continue heating evaporate to dryness moisture content, to calcine 4 hours down at 850 ℃-1000 ℃, the particle diameter of powder is at 50-67nm.
Comparing embodiment 1 to embodiment 10, the proportioning of peregal and 16 Phenylsulfonic acids, the pH value during dissolving; The variation of calcining temperature and calcination time is to the influence of particle diameter, can draw preferred processing condition to be: the mol ratio of peregal, 16 Phenylsulfonic acids is 1: 3 o'clock, during interpolation during pH=3-4; 750 ℃-900 ℃ of calcining temperatures; Calcination time was at 6 hours, and the particle diameter of powder is 30-48nm, and the diameter of particle under these processing condition is less.
This organic acid is produced superfine zirconia powder body technology and is compared with coprecipitation method, and water consumption reduces 80%, and waste water has reduced 83%, and energy consumption has reduced by 45%, and powder characteristic improves more than 35%.Compare with hydrolysis method, water consumption reduces 70%, and waste water has reduced 75%, and energy consumption has reduced by 50%, and powder characteristic has only descended 7%.
More than being merely preferred embodiment of the present invention, is not the qualification to protection scope of the present invention, and all various modifications, combination, parts of making according to the mentality of designing of this case combine and replacement, all fall into the protection domain of this case.
Claims (3)
1. the method for organic acid method for preparing ultrafine partial stable zirconia is characterized in that: by tartrate or oxysuccinic acid, zirconyl chloride ZrOCl
28H
2O, tensio-active agent and the preparation of soluble yttrium salt, the mol ratio of zirconyl chloride and soluble yttrium salt is 1: 0.03, and the mol ratio of zirconyl chloride and tartrate or oxysuccinic acid is 1: 3, and the mol ratio of zirconyl chloride and tensio-active agent is 1: 0.004-0.01; Tartrate or oxysuccinic acid are dissolved in water, in reaction kettle, are heated with stirring to 65 ℃ and add zirconyl chloride ZrOCl
28H
2O and soluble yttrium salt, and stir, treat that zirconyl chloride dissolves fully; Control pH=1-2, the temperature of reaction of tartrate or oxysuccinic acid and zirconyl chloride and soluble yttrium salt is controlled at 65 ℃-95 ℃, slowly is heated to 95 ℃ and insulation; When the aqueous solution becomes to gluey and control pH=3-6; Add tensio-active agent, tensio-active agent is peregal, 16 Phenylsulfonic acids or both mixing, continues heating evaporate to dryness moisture content; Under 750 ℃ of-1000 ℃ of temperature calcination 4-10 hour, obtaining particle diameter was the ultrafine partial stable zirconia powder of 30-85nm.
2. the method for organic acid method for preparing ultrafine partial stable zirconia as claimed in claim 1, it is characterized in that: said soluble yttrium salt is YCl
3Or Y (NO
3)
3
3. the method for organic acid method for preparing ultrafine partial stable zirconia as claimed in claim 1, it is characterized in that: said stirring velocity is 300-500r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915836A (en) * | 2006-09-01 | 2007-02-21 | 清华大学 | Method for preparting Nano powder of zirconia |
| CN101275212A (en) * | 2008-03-31 | 2008-10-01 | 中国地质大学（武汉） | Preparation for nanostructured Yt-stable spherical zircite powder for thermal spraying |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915836A (en) * | 2006-09-01 | 2007-02-21 | 清华大学 | Method for preparting Nano powder of zirconia |
| CN101275212A (en) * | 2008-03-31 | 2008-10-01 | 中国地质大学（武汉） | Preparation for nanostructured Yt-stable spherical zircite powder for thermal spraying |
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Denomination of invention: Organic acid method for preparing ultrafine partial stable zirconia Effective date of registration: 20140707 Granted publication date: 20120418 Pledgee: Bank of China Limited by Share Ltd Xianyou branch Pledgor: Fujian Johnson Mining Co., Ltd. Registration number: 2014350000028 |
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Date of cancellation: 20170426 Granted publication date: 20120418 Pledgee: Bank of China Limited by Share Ltd Xianyou branch Pledgor: Fujian Johnson Mining Co., Ltd. Registration number: 2014350000028 |