CN1232787A - Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature - Google Patents
Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature Download PDFInfo
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- CN1232787A CN1232787A CN 99107433 CN99107433A CN1232787A CN 1232787 A CN1232787 A CN 1232787A CN 99107433 CN99107433 CN 99107433 CN 99107433 A CN99107433 A CN 99107433A CN 1232787 A CN1232787 A CN 1232787A
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- zirconium dioxide
- sodium hydroxide
- dioxide powder
- superfine
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- 238000000034 method Methods 0.000 title claims abstract description 29
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 title claims abstract description 28
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 16
- 239000003513 alkali Substances 0.000 title claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- -1 add entry Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- BNXJSRUOQZHOGI-UHFFFAOYSA-N [O-2].[O-2].[Zr+4].[Cl+] Chemical compound [O-2].[O-2].[Zr+4].[Cl+] BNXJSRUOQZHOGI-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 238000007704 wet chemistry method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Analytically pure zirconium oxychloride and sodium hydroxide are mixed in the mole ratio of 1 to 2-20 inside one container for complete reaction; water is added into the product and the product is precipitated for 10-50 min; and the precipitate is processed through filtration, water washing, stoving and preheating into the superfine zirconium dioxide powder of the present invention. The superfine powder has high chemical purity and high reaction activity. The said process has the advantages of simple operation, short production period, less environmental pollution, low power consumption and reused material and is suitable and is suitable for industrial production.
Description
The present invention relates to a kind of superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature, belong to materials science field.
Zirconium dioxide has a wide range of applications at aspects such as high-temperature structural material, high temperature optical element, oxygen photosensitive elements, fuel cells owing to have good machinery, calorifics, electricity, optical property and studies.Because nano ceramics is that nano level particles solidify forms by yardstick, so the preparation of nano-ceramic powder just becomes the basis of nano ceramic material preparation.The purity of the shape of powder, particle size, size distribution, powder and degree of crystallization all are being subjected to the influence of preparation process.
Though the preparation method of nano level superfine zirconium dioxide powder is a lot; but some (as chemical Vapor deposition process, radio frequency sputtering method etc.) are owing to prices of raw and semifnished materials height, apparatus expensive are difficult to large-scale production in these methods; some method (as wet chemistry method, hydrothermal method, alkoxide hydrolysis) but owing to polluting the heavy waste that causes natural resources, aggravated environmental pollution.Many methods (as wet chemistry method, hydrothermal method, sol-gel method etc.) that prepare Zirconium dioxide powder all are that the sol-gel by the pre-burning zirconium obtains, thereby the environment of preparation gel and technological process have remarkably influenced to the Zirconium dioxide powder performance of final acquisition.For example, Tang Chaoqun etc. adopt sol-gel method, with homemade zirconium alkoxide and methyl alcohol is raw material, stir after constant temperature, constant humidity are placed and made gel in 8 days, the a large amount of organism of burning in the pre-burning process, emit obnoxious flavoures such as carbonic acid gas (seeing " Materials Science and Engineering ", 1997 the 5th phases, 49-52 page or leaf); Xu Dichun etc. add a large amount of organism such as tensio-active agent (seeing " silicate journal ", 1992 the 20th phases, the 48th～54 page) in order to change the aggregating state of wet chemistry method (is precipitation agent with ammoniacal liquor) preparation ultrafine powder in precipitation and treating processes.S.Nagasawa and H.Kishi have discussed in strong alkali environment in Japanese Patent JP62212224, utilize Ca, Mg, Y, Ce, H
2O
2The aqueous solution and initial feed such as chlorine zirconium dioxide, through 80～200 ℃ the thermal treatment and the technological process of other a series of complexity, the preparation method of synthetic zirconium dioxide sosoloid ultrafine powder.Although these methods have many advantages, a large amount of achievements in research is also arranged, the shortcoming that they all exist, and energy consumption is big, seriously polluted, the production cycle is long.Many researchs have all been adopted a large amount of, complicated raw material and technology owing to the performance of paying attention to the improvement reaction product, and this has aggravated the defective of technology itself undoubtedly.
The objective of the invention is to propose a kind of superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature, reduce in the wet chemistry method owing to clean Cl
-And consuming the consumption of a large amount of deionized waters, ammoniacal liquor reduces reunion degree and organic consumption to atmospheric pollution in the precipitator method to reduce, reduce the gel calcining temperature, cut down the consumption of energy, shorten the production cycle, reclaim and use byproduct, realize resources circulation regeneration etc.
Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature of the present invention comprises following each step:
(1) with analytical pure chlorine zirconium dioxide and sodium hydroxide is 1: 2～20 ratio weighing in molar ratio, earlier sodium hydroxide put into container, progressively add the chlorine zirconium dioxide then and stir, grind, after the chlorine zirconium dioxide adds, restir mixed 10～50 minutes, made to react completely, and mixed.
(2) in above-mentioned reactant, add entry, precipitate 10～50 minutes.
(3) throw out is after filtration, washing is placed in the baking oven, through 50～80 ℃ down oven dry 400～500 ℃ of pre-burnings 1～3 hour, cross 200 mesh sieves after 6～10 hours, be superfine zirconium dioxide powder of the present invention.
Superfine zirconium dioxide powder of the present invention can also prepare with another kind of method, and its step is as follows:
(1) with analytical pure chlorine zirconium dioxide and sodium hydroxide is 1: 2～20 ratio weighing in molar ratio, earlier sodium hydroxide put into container, progressively add the chlorine zirconium dioxide then and stir, grind, after the chlorine zirconium dioxide adds, restir mixed 10～50 minutes, made to react completely, and mixed.
(2) mixture with step (1) preparation after 1～24 hour, also is superfine zirconium dioxide powder of the present invention through washing after oven dry is sieved in thermal treatment under 70～200 ℃ the temperature.
Filtrate in the above-mentioned preparation process makes sodium-chlor powdery crystal after hydrochloric acid neutralization, drying, become byproduct and reclaim, and realizes the resources circulation regeneration.
Collision impact power in mechanical stirring is because particle mass and size factor are less, but because contact point area is littler, cause the very high stress in contact site in collision, collision time is very of short duration simultaneously, only allow few time distribute heat and discharge stress, thereby in the collision process time of particle from unstress state to high stressed condition very of short duration, produced high stress field gradient.In addition, most of collision energy blink internal consumption in minimum contact site, make energy density quite high, all of these factors taken together makes the temperature of local of short duration reflecting point rise, and makes surperficial point of contact atomic thermal motion aggravation, produces reaction, forms product.Because do not have the surface tension of water in the non-liquid state, perhaps very little, atomic migration speed is slow, thereby the product size is tiny, and structurally be different with the hydrogen zirconium dioxide of past method gained.This point can be used the dissolving with hydrochloric acid experimental verification easily.Because the hydrogen zirconium dioxide is soluble in hydrochloric acid, and the zirconium dioxide dissolution phenomena that reaction generates is not obvious.Its reactional equation process is as follows:
By to the discussion of reaction process and mechanism as can be known, the method for low temperature highly basic synthesize superfine zirconium dioxide powder is the green synthesis method different with additive method.Mix, in the reaction process, the zirconium dioxide nucleus just begins to take shape, just can grow up to form cube (four directions) phase superfine zirconium dioxide powder after Overheating Treatment.Owing to do not occur the normal chlorion problem that exists in the liquid phase method in the reaction product, do not comprise salt face bridges such as adsorbing chloride ions, thereby the cleaning of product be easy.Powder is loose, reunite less, the reactive behavior height.
Can directly at room temperature synthesize the zirconium dioxide nucleus with low temperature highly basic synthesis method of the present invention, its processing parameter has bigger adjustable capacity (the excessive 0%-900% of sodium hydroxide (weight ratio)).After Overheating Treatment, make nuclei growth, thereby forming complete, particle diameter is about≤10nm about, chemical purity height, superfine zirconium dioxide powder that reactive behavior is good.The byproduct that this method produces can pass through simple process, with filtrate in peracid and after, can obtain the high sodium chloride crystal of purity, recycle as industrial chemicals, have simple to operate, with short production cycle, environmental pollution is little, energy consumption is low, and resource can cyclic regeneration, is fit to the advantage of suitability for industrialized production.
Introduce embodiments of the invention below:
Embodiment 1:
Took by weighing analytical pure chlorine zirconium dioxide 32.275g in 1: 2 in molar ratio respectively, sodium hydroxide 8g (being excessive (weight ratio) 0% of sodium hydroxide) carries out X fluorescence spectrum chemical composition analysis, Cl to the oven dry material by the preparation of above-mentioned (1)～(3) step
-Detection less than promptly less than the accuracy of detection of instrument (＜l0ppm).Carry out X-ray diffraction analysis after will drying material pre-burning (400 ℃, 2 hours), find that its main crystalline phase is cube (four directions) phase, as calculated its primary particle size≤l0nm.
Embodiment 2:
Took by weighing analytical pure chlorine zirconium dioxide 32.275g in 1: 2.5 in molar ratio respectively, sodium hydroxide 10g (being excessive (weight ratio) 25% of sodium hydroxide) carries out X fluorescence spectrum chemical composition analysis, Cl to the oven dry material by the preparation of above-mentioned (1)～(3) step
-Detection less than, promptly less than the accuracy of detection of instrument (＜10ppm).Carry out X-ray diffraction analysis after will drying material pre-burning (500 ℃, 2 hours), find that its main crystalline phase is cube (four directions) phase, primary particle size≤10nm.
Embodiment 3:
The mixture that is prepared by excessive 25% sodium hydroxide among the embodiment 2 is carried out X-ray diffraction analysis after 70 ℃ of thermal treatments 24 hours, cleaning, oven dry, find that its main crystalline phase is cube (four directions) phase, this has proved that further the zirconium dioxide nucleus just forms behind low-temp reaction.
Embodiment 4:
Respectively take by weighing analytical pure chlorine zirconium dioxide 32.275g at 1: 20 with mol ratio, sodium hydroxide 80g (being excessive (weight ratio) 900% of sodium hydroxide) carries out X fluorescence spectrum chemical composition analysis, Cl to the oven dry material by the preparation of above-mentioned (1)～(3) step
-Detection less than promptly less than the accuracy of detection of instrument (＜10ppm).Carry out X-ray diffraction analysis after will drying material pre-burning (450 ℃, 2 hours), find that its main crystalline phase is cube (four directions) phase, primary particle size≤10nm.
Embodiment 5:
The mixture that is prepared by excessive 900% sodium hydroxide among the embodiment 4 is carried out X-ray diffraction analysis after 200 ℃ of thermal treatments 1 hour, cleaning, oven dry, find that its main crystalline phase is cube (four directions) phase, this has proved that further the zirconium dioxide nucleus just forms behind low-temp reaction.
This shows, sodium hydroxide concentration increase the increase do not cause chloride ion content on a large scale, promptly to the superfine zirconium dioxide powder of excessive 0% and 900% sodium hydroxide preparation, chlorion all detect less than.This is because this law structurally is different with the throw out that liquid phase method prepares.The consumption of sodium hydroxide does not need accurate control in this method, and noticeable change does not take place for product thing phase, chemical ingredients.The superfine zirconium dioxide powder of preparation is mainly based on cube mutually, the primary particle size is about≤10nm about.This has created favourable condition to scale operation.
Claims (2)
1. superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature is characterized in that this technology comprises following each step:
(1) with analytical pure basic zirconium chloride and sodium hydroxide is 1: 2～20 ratio weighing in molar ratio, earlier sodium hydroxide put into container, progressively add basic zirconium chloride then and stir, grind, after basic zirconium chloride adds, restir mixed 10～50 minutes, made to react completely, and mixed;
(2) in above-mentioned reactant, add entry, precipitate 10～50 minutes;
(3) throw out is after filtration, washing is placed in the baking oven, through 50～80 ℃ down oven dry 400～500 ℃ of pre-burnings 1～3 hour, cross 200 mesh sieves after 6～10 hours, be ultrafine zirconia powder of the present invention.
2, a kind of superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature is characterized in that this technology comprises following each step:
(1) with analytical pure basic zirconium chloride and sodium hydroxide is 1: 2～20 ratio weighing in molar ratio, earlier sodium hydroxide put into container, progressively add basic zirconium chloride then and stir, grind, after basic zirconium chloride adds, restir mixed 10～50 minutes, made to react completely, and mixed;
(2) mixture with step (1) preparation after 1～24 hour, also is ultrafine zirconia powder of the present invention through washing after oven dry is sieved in thermal treatment under 70～200 ℃ the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107433A CN1075467C (en) | 1999-05-21 | 1999-05-21 | Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99107433A CN1075467C (en) | 1999-05-21 | 1999-05-21 | Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature |
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| Publication Number | Publication Date |
|---|---|
| CN1232787A true CN1232787A (en) | 1999-10-27 |
| CN1075467C CN1075467C (en) | 2001-11-28 |
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| CN99107433A Expired - Fee Related CN1075467C (en) | 1999-05-21 | 1999-05-21 | Superstrong alkali process to synthesize superfine zirconium dioxide powder at low temperature |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU322961A1 (en) * | 1969-06-06 | 1988-01-23 | Rutman D S | Method of obtaining zirconium dioxide stabilized with calcium oxide |
| JPS6171943A (en) * | 1984-09-12 | 1986-04-12 | Tsugami Corp | Pallet exchanging device for machining center |
| FR2629072B1 (en) * | 1988-03-22 | 1990-11-30 | Produits Refractaires | PROCESS FOR THE MANUFACTURE OF HYDRATED ZIRCONIUM OXIDE FROM GRANULAR CRYSTALLIZED ZIRCONIUM OXIDE |
| CN1063268A (en) * | 1991-12-05 | 1992-08-05 | 广西冶金研究所 | Produce zirconium dioxide with the white lime sintering process |
| GB2280897B (en) * | 1993-08-09 | 1997-03-12 | Frank Pitts | Extraction of zirconium values from zircon |
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1999
- 1999-05-21 CN CN99107433A patent/CN1075467C/en not_active Expired - Fee Related
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