CN1519201A - Method for preparing nano zirconia in high purity - Google Patents
Method for preparing nano zirconia in high purity Download PDFInfo
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- CN1519201A CN1519201A CNA031136354A CN03113635A CN1519201A CN 1519201 A CN1519201 A CN 1519201A CN A031136354 A CNA031136354 A CN A031136354A CN 03113635 A CN03113635 A CN 03113635A CN 1519201 A CN1519201 A CN 1519201A
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- purity nano
- urea
- nano zirconia
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 235000019270 ammonium chloride Nutrition 0.000 abstract 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A process for preparing high-purity nano-class zirconium oxide includes such steps as adding zirconium chloride oxide, urea and water to reactor, heating while stirring, holding the temp, automatic electrofluocculation, filtering, washing to remove NH4Cl, and drying the filtered cake. Its advantages are high purity (more than 99.9%), and high productivity.
Description
1. The technical field is as follows:
the invention relates to a preparation method of high-purity nano zirconia, belonging to an innovative technology of the preparation method of the high-purity nano zirconia.
2. Background art:
at present, the preparation method of the nano zirconia mainly comprises a gas phase method and a liquid phase method, wherein the gas phase method adopts ZrCl4Or Zr (OR)4(alkoxide) as raw material, passing through high-temperature waterDecomposing or pyrolyzing to obtain the nano zirconia. The method has the advantages of good product dispersibility, narrow particle size distribution and the like, but the raw material ZrCl exists4Or Zr (OR)4Difficult preparation and storage, complex equipment, high operation technical requirement, large investment, low productivity and the like. At present, the liquid phase method is mostly adopted for development and research, and mainly comprises a precipitation method, a sol-gel method, a hydrothermal method and an alkoxide hydrolysis method, and because the alkoxide hydrolysis method has the defects of large alcohol consumption, low production rate, poor safety, large investment, high cost and the like due to the addition of preparation and equipment of precursors such as alkoxide and the like, the industry mainly develops and researches the precipitation method, the sol-gel method and the hydrothermal method, and all the methods use cheap and easily obtained zirconium oxychloride as a raw material, use ammonia or strong base (NaOH or KOH) as a neutralizing precipitator, prepare a solution according to the stoichiometric proportion to prepare a precursorzirconium hydroxide gel, and remove NH through filtration and washing4Cl or NaCl (KCl), then is treated by absolute ethyl alcohol or other high molecular surfactants, and is roasted or hydrothermally dehydrated at a certain temperature to obtain the nano zirconia. These several methods have the following disadvantages: 1) the precursor solution and the zirconium hydroxide gel are prepared, so the process is long, the investment is large, and the energy consumption is high; 2) ammonia or strong alkali is used for neutralizing the precipitate and the filtering and washing process of zirconium hydroxide gel can cause ammonia gas to pollute the environment; 3) the surface properties of the zirconium hydroxide gel determine the NH in the reaction product4Cl or NaCl (KCl) is difficult to wash and brings much trouble to the subsequent procedures; 4) for precipitation methods and sol-gelsThe method has the advantages that the water content of the zirconium hydroxide gel is up to more than 90 percent, the roasting energy consumption is high, and the equipment productivity is low; for a hydrothermal method, the problems of a kettle material, a proper material for solid-liquid separation of products after hydrothermal dehydration and a filter medium exist; 5) the concentration of valuable components contained in the waste gas and waste water generated in the reaction process of the hydrothermal method is not high, and the waste gas and the waste water are difficult to recycle.
3. The invention content is as follows:
the invention aims to overcome the defects and provide a method for preparing high-purity nano zirconium oxide by adopting a hydrothermal-electrocoagulation method without preparing any precursor, and the method has the advantages of simple process and equipment, low investment, low energy consumption, high production rate and low production cost; and the product has high quality, controllable granularity and no environmental pollution. The invention is a preparation method of high-purity nano zirconia with remarkable social benefit and economic benefit.
The preparation method of the high-purity nano zirconia comprises the following steps:
1) directly adding zirconium oxychloride, urea and water into a reaction kettle;
2) heating under stirring, and performing heat preservation to ensure that the mixture is automatically electroflocculated;
3) filtering and washing the flocculated body to remove NH4Cl；
4) Drying the washed filter cake to obtain high-purity nano zirconium oxide ZrO2。
The urea is added in such an amount that Zr is converted into ZrO (OH)2The required theoretical amount is 1-8% of excess, and the addition amount of water is such that the concentration of Zr is 1-4 mol/L.
In the reaction process of the step 2), the pressure in the reaction kettle is controlled to be 2.0-5.0 Mpa, the heating temperature is controlled to be 190-250 ℃, and the heat preservation time is controlled to be 1-4 hours.
The drying temperature in the step 4) is 100-300 ℃.
The invention adopts hydrothermal-electric flocculation method to prepare high-purity nano zirconia without preparing any precursor, so it has the following advantages:
1) precursor solution and zirconium hydroxide gel are not required to be prepared, so that the process flow is shortened by about 40%, the equipment investment is reduced by 35%, and the energy consumption is reduced by more than 60%;
2) the physical and chemical process can be controlled, the equipment productivity is improved by 4 times, and the production cost is reduced by more than 80%;
3) the problems of solid-liquid separation and a filter medium are solved, and conditions are created for high purity of the product;
4) the waste gas generated in the reaction process and the valuable components contained in the waste water are recycled, and the zero-waste discharge is basically realized.
The invention has the advantages of simple process and equipment, low investment and low energy consumptionThe production efficiency is high, and the production cost is low; the purity of the product reaches more than 99.9 percent, the average particle size is 8-15 nm, and the specific surface area is 80-140 m2The grain size is controllable, and the environment is not polluted. Is a preparation method of high-purity nano zirconia with remarkable social benefit and economic benefit.
4. The specific implementation mode is as follows:
the preparation method of the high-purity nano zirconia comprises the following steps:
1) directly adding zirconium oxychloride, urea and water into a reaction kettle;
2) heating under stirring, and performing heat preservation to ensure that the mixture is automatically electroflocculated;
3) filtering and washing the flocculated body to remove NH4Cl；
4) Drying the washed filter cake to obtain high-purity nano zirconium oxide ZrO2。
The urea is added in such an amount that Zr is converted into ZrO (OH)2The required theoretical amount is 1-8% of excess, and the addition amount of water is such that the concentration of Zr is 1-4 mol/L.
In the reaction process of the step 2), the pressure in the reaction kettle is controlled to be 2.0-5.0 Mpa, the heating temperature is controlled to be 190-250 ℃, and the heat preservation time is controlled to be 1-4 hours.
The drying temperature in the step 4) is 100-300 ℃.
In the step 2), zirconium oxychloride (ZrOCl) is added in the heating and temperature rising process of the reaction kettle2.8H2O) and urea [ (NH)2)2CO]Dissolving and forming a homogeneous solution, wherein the decomposition speed of urea is accelerated along with the increase of the temperature, zirconium hydroxide sol is generated by the interaction of zirconium and the decomposition products of urea in the homogeneous solution through the control of the temperature increase speed, and the zirconium hydroxide sol is continuously converted into gel, so that the local nonuniformity and the environmental pollution caused by adding ammonia or alkali into the solution from the outside are avoided, and the process can be expressed by the following general reaction formula:
in the reverse directionIn the process, due to CO2The pressure in the kettle is raised by the precipitation, the temperature in the kettle is raised by the gas compression and gel formation heat release process, the dehydration, nucleation and crystallization of the zirconium hydroxide gel are promoted, and the process has the automatic catalysis effect, so the preparation method has the advantages of high product quality, narrow particle size distribution, controllable crystal particle size and shape, low energy consumption and cost, high equipment productivity and no environment pollution. The following are several embodiments of the invention:
example 1:
adding zirconium oxychloride 1.2Kg, urea 0.22Kg and water 0.5Kg directly into a reaction kettle, heating under stirring while controlling the pressure in the reaction kettle at 2.2MPa and the heating temperature at 190 deg.C for 4 hr, after the reaction product is electroflocculated, filtering the floccule under vacuum filtration, washing to remove NH4Cl, drying the washed filter cake at the temperature of 150 ℃ to constant weight to obtain the ZrO-containing powder299.93%, average particle diameter of 14.4nm, and specific surface area of 86.9m2ZrO of/g2434.2g of powder, ZrO 22The yield was found to be 98.8%.
Example 2:
adding zirconium oxychloride 1.2Kg, urea 0.215Kg and water 0.7Kg directly into a reaction kettle, heating under stirring, controlling the pressure in the reaction kettle at 3.5MPa and the heating temperature at 220 ℃, reacting for 2.5 hours, after the reaction product is electroflocculated, filtering the floccule under vacuum filtration condition, washing to remove NH4Cl, drying the washed filter cake at 200 ℃ to constant weight to obtain the ZrO-containing powder299.94%, average particle diameter of 12.7nm, and specific surface area of 127.5m2ZrO of/g2435.0g of powder, ZrO2The yield was found to be 99.0%.
Example 3:
adding zirconium oxychloride 1.2Kg, urea 0.23Kg and water 1.5Kg directly into a reaction kettle, heating under stirring, controlling the pressure in the reaction kettle at 4.5MPa and the heating temperature at 250 deg.C, reacting for 1 hr, after the reaction product is electroflocculated, filtering the floccule under vacuum filtration, washing to remove NH4Cl, washing the filter cake at 300 DEG CThen drying to constant weight to obtain the product containing ZrO299.93%, an average particle diameter of 8.7nm, and a specific surface area of 137.50m2ZrO of/g2432.5g of powder, ZrO2The yield was found to be 98.5%.
Claims (4)
1. A preparation method of high-purity nano zirconia is characterized by comprising the following steps:
1) directly adding zirconium oxychloride, urea and water into a reaction kettle;
2) heating under stirring, and performing heat preservation to ensure that the mixture is automatically electroflocculated;
3) filtering and washing the flocculated body to remove NH4Cl；
4) Drying the washed filter cake to obtain high-purity nano zirconium oxide ZrO2。
2. The method for preparing high purity nano zirconia according to claim 1, wherein the urea is added in an amount to convert Zr into ZrO (OH)2The required theoretical amount is 1-8% of excess, and the addition amount of water is such that the concentration of Zr is 1-4 mol/L.
3. The method for preparing high-purity nano zirconium oxide according to claim 1, wherein the pressure in the reaction kettle is controlled to be 2.0-5.0 MPa, the heating temperature is controlled to be 190-250 ℃, and the heat preservation time is controlled to be 1-4 hours in the reaction process of the step 2).
4. The method for preparing high-purity nano zirconia according to claim 1, wherein the drying temperature in the step 4) is 100 to 300 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031136354A CN1519201A (en) | 2003-01-22 | 2003-01-22 | Method for preparing nano zirconia in high purity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031136354A CN1519201A (en) | 2003-01-22 | 2003-01-22 | Method for preparing nano zirconia in high purity |
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| CN1519201A true CN1519201A (en) | 2004-08-11 |
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| CNA031136354A Pending CN1519201A (en) | 2003-01-22 | 2003-01-22 | Method for preparing nano zirconia in high purity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739014A (en) * | 2013-12-04 | 2014-04-23 | 首都师范大学 | Vapor phase method for controllable synthesis of biocompatible zirconium dioxide nano powder |
| CN107055609A (en) * | 2016-12-29 | 2017-08-18 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
-
2003
- 2003-01-22 CN CNA031136354A patent/CN1519201A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739014A (en) * | 2013-12-04 | 2014-04-23 | 首都师范大学 | Vapor phase method for controllable synthesis of biocompatible zirconium dioxide nano powder |
| CN107055609A (en) * | 2016-12-29 | 2017-08-18 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
| CN107055609B (en) * | 2016-12-29 | 2018-06-08 | 宣城晶瑞新材料有限公司 | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides |
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