CN1043216C - Rare earth oxide with large specific surface area and preparation method thereof - Google Patents
Rare earth oxide with large specific surface area and preparation method thereof Download PDFInfo
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- CN1043216C CN1043216C CN96116316A CN96116316A CN1043216C CN 1043216 C CN1043216 C CN 1043216C CN 96116316 A CN96116316 A CN 96116316A CN 96116316 A CN96116316 A CN 96116316A CN 1043216 C CN1043216 C CN 1043216C
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- rare earth
- hydrazine
- specific surface
- surface area
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Abstract
本发明涉及一种大比表面积稀土氧化物REO及其制备方法，本发明的大比表面积稀土氧化物是通过含肼稀土草酸盐的热分解而制得的，其比表面积可达5～50m2/g，且灼减量小于1%。The invention relates to a rare earth oxide REO with a large specific surface area and a preparation method thereof. The rare earth oxide with a large specific surface area is prepared by thermal decomposition of hydrazine-containing rare earth oxalate, and its specific surface area can reach 5-50m 2 /g, and the loss on ignition is less than 1%.
Description
The present invention relates to a kind of large specific surface area earth-rare oxides and preparation method thereof.Specifically the present invention relates to a kind of specific surface area and can reach 5～50m
2The rare earth oxide of/g; This large specific surface area earth-rare oxides contains the hydrazine rare-earth oxalate by thermolysis and makes.
" rare earth element " is meant the general name of lanthanon (from La to Lu) with scandium (Sc) and yttrium 17 kinds of elements such as (Y) of III B family in the periodic table of elements in general.Because scandium and other rare earth elements difference on chemical property are bigger, and the content of scandium is very low in many rare-earth minerals, therefore when mentioning rare earth element usually, do not comprise scandium.(Pm) is artificial radioelement in view of promethium, so also often be not included in wherein.
The total abundance of rare earth element in the earth's crust is 211g/t, than the abundance (g/t) of some common elements as Cu (63), Pb (12), Zn (94), Ni (21), Co (25) etc. are also high.The rare earth reserves of China account for the No. 1 in the world.
Rare earth metal is burning or rare-earth hydroxide, oxalate, carbonate, nitrate and most of rare earth organic compounds in air, can make the oxide compound of corresponding rare earth after calcination.The normal rare-earth oxalate thermal degradation that adopts changes into corresponding oxide compound in industrial production.The specific surface area of these oxide compounds only reaches 2～4m
2/ g (with B.E.T nitrogen determining adsorption, down together).
Specific surface area is one of important parameter of weighing the active size of solid powder material, the performance close association of it and material, large specific surface area earth-rare oxides can improve material activity, is the new function material in fields such as catalysis, magnetic, luminous, pottery, is the new trend of present rare earth research.
At present industrial common employing rare-earth oxalate thermolysis process is produced rare earth oxide.Rare-earth oxalate by the oxalic acid solution precipitation generates becomes rare earth oxide 400～745 ℃ of beginning thermolysiss.In order to guarantee to change into fully oxide compound, generally be 800～950 ℃ of calcinations 0.5～1 hour.At high temperature long-time calcination, the crystal that helps oxide compound is grown up, but the crystalline surface-area is reduced, and generally only is 2～4m
2/ g; And if calcination at a lower temperature, though can obtain oxide compound than bigger serface, the igloss amount is bigger, can not reach product quality indicator.
The purpose of this invention is to provide a kind of specific surface area greater than 5m
2The large specific surface area earth-rare oxides of/g and manufacture method thereof.
Another object of the present invention provides the big (＞5m of a kind of not only specific surface area
2/ g), and the rare earth oxide of its igloss amount little (＜1%) and preparation method thereof.
Large specific surface area earth-rare oxides REO of the present invention is characterised in that its surface-area can reach 5～50m
2/ g, the RE among this rare earth oxide REO comprises La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, one or more rare earth element such as Y.
The feature of large specific surface area earth-rare oxides of the present invention is that also its igloss amount is less than 1%.
Large specific surface area earth-rare oxides REO of the present invention is by adopting hydrazine or hydrazine compound as additive, and the first step generates earlier and contains the hydrazine rare-earth oxalate, again by containing the rare earth oxide that the thermolysis of hydrazine rare-earth oxalate makes bigger serface.
Because containing the hydrazine rare-earth oxalate discharges a large amount of heats and gas in thermal decomposition process, make the crystal of its degradation production-rare earth oxide become loose like this, the a large amount of heats that produced have simultaneously quickened decomposition course again, make the rare earth oxide specific surface area that makes increase (＞5m
2/ g), maximum can reach 50m
2/ g, its igloss amount (1000 ℃ calcination 1 hour) and can satisfying less than 1%.
The present invention can make the rare earth oxide of different specific surface areas by the dosage of control additive hydrazine.
Obtain containing the hydrazine rare-earth oxalate and can preparing of large specific surface area earth-rare oxides in order to thermolysis in the inventive method by number of ways such as coprecipitation method, hybrid systems.
1. coprecipitation method is added to hydrazine in the oxalic acid solution earlier before being meant and using oxalic acid precipitation in rare earth chloride or rare earth nitrate solution; Or hydrazine added respectively in oxalic acid solution and the earth solution:
2. hybrid system is to add hydrazine or hydrazine compound and mixing in rare-earth oxalate:
The hydrazine rare-earth oxalate that contains of above-mentioned coprecipitation method or hybrid system gained is placed in the crucible,, be cooled to room temperature,, just can obtain large specific surface area earth-rare oxides of the present invention through pulverizing, sieving through high temperature sintering.Adopt its specific surface area of B.E.T determination of nitrogen adsorption.
In order to further specify the effect of hydrazine in rare-earth oxalate in the inventive method, be example with the yttrium oxide below, in conjunction with subordinate list, accompanying drawing elaborates:
The adding mode of hydrazine is to the influence of rare earth oxide specific surface area: large specific surface area earth-rare oxides preparation method of the present invention is characterised in that it can carry out by various feed way, 1. in rare earth chloride or rare earth nitrate solution, earlier hydrazine (or compound of hydrazine) is added in the oxalic acid solution before with oxalic acid precipitation, generates with rare earth chloride (or rare earth nitrate) solution reaction then and contain the hydrazine rare-earth oxalate; 2. or with hydrazine (or compound of hydrazine) be added to respectively in oxalic acid and rare earth chloride (or rare earth nitrate) solution, then these two kinds of solution mixed, obtain containing the hydrazine rare-earth oxalate; 3. or directly be added to hydrazine (or compound of hydrazine) in the rare-earth oxalate;
Add hydrazine (or compound of hydrazine) with above-mentioned three kinds of modes and all can obtain containing hydrazine rare-earth oxalate precipitation, after thermolysis, can both obtain large specific surface area earth-rare oxides again, below table 1 listed experimental data with the resulting bigger serface yttrium oxide of adding mode of three kinds of different hydrazines:
Table 1: hydrazine adds the influence of mode to the rare earth oxide specific surface area
| The adding mode | Y 2O 3Specific surface area m 2/g | |
| 1 hydrazine (or hydrazine compound) adds in the oxalic acid solution | The HCl system | 16.8 |
| HNO 3System | 14.3 | |
| 2 hydrazines (or hydrazine compound) add respectively in oxalic acid solution and the yttrium chloride solution | 18.8 | |
| 3 hydrazines (or hydrazine compound) add in the yttrium oxalate | 17.4 | |
As shown in Table 1, at HCl system or HNO
3When using the oxalic acid precipitation yttrium in the system, no matter add hydrazine (or compound of hydrazine) in the oxalic acid solution earlier; Or hydrazine (or compound of hydrazine) added to respectively in oxalic acid solution and the yttrium solution earlier; Or hydrazine (or compound of hydrazine) directly added in the yttrium oxalate mix, all can obtain containing the hydrazine yttrium oxalate, contain the hydrazine yttrium oxalate and after thermolysis, all can obtain the bigger serface yttrium oxide.
The numerical value of the specific surface area of rare earth oxide of the present invention is also directly relevant with factors such as the add-on of hydrazine, the calcination time that contains the hydrazine oxalate and calcination temperatures.
Below further specify each factor of preparation process of the present invention to the influence of rare earth oxide specific surface area and the character of rare earth oxide of the present invention by accompanying drawing 1-5.
Fig. 1-a and 1-b are the influence of the dosage of hydrazine to the yttrium oxide specific surface area
Wherein Fig. 1-a is that hydrazine adds to oxalic acid solution
Fig. 1-b is that hydrazine compound adds to yttrium oxalate.
Fig. 2 contains the influence of hydrazine yttrium oxalate calcination temperature to the yttrium oxide specific surface area.
Fig. 3 contains the influence of hydrazine rare-earth oxalate calcination time to the rare earth oxide specific area.
Fig. 4-a is the x-diffractogram of yttrium oxide of the present invention.
Fig. 4-b is yttrium oxide standard diagram (25-1200)
Fig. 5-a is the stereoscan photograph of yttrium oxide of the present invention.
Fig. 5-b is the stereoscan photograph of the existing yttrium oxide of producing (not adding hydrazine).
As shown in Figure 1, the specific area of yittrium oxide is along with the dosage of hydrazine increases and increases. Owing to contain the specific surface area size that hydrazine content in the hydrazine rare-earth oxalate directly has influence on resulting oxide after the thermal decomposition, thereby can by the addition of control additive hydrazine, produce the rare earth oxide of various different specific areas.
As shown in Figure 2, along with calcination temperature raises, the yittrium oxide specific area reduces gradually, though temperature up to 1000 ℃, specific area is still greater than 5.0m2/g。
As shown in Figure 3, contain the at a certain temperature calcination of hydrazine yttrium oxalate, increase in time, the yittrium oxide specific area reduces gradually. Even calcination time grows to 4 hours, specific area still can be greater than 15m2/g。
As seen from Figure 4, yittrium oxide collection of illustrative plates of the present invention is consistent with yittrium oxide standard diagram (25-1200).
As seen from Figure 5, yittrium oxide of the present invention is the powder of porous, and specific area is large, and is formed by the fine grained reunion. And existing yttria particles of producing is larger, and specific area is little.
Further specify rare earth oxide difference with the prior art of the present invention below by embodiment and comparative example.Embodiment 1:
Take by weighing 10 gram yttrium oxide (Y
2O
3) in the 500ml beaker, adding 100ml 1+1 hydrochloric acid, the heat of solution of heating is extremely clear, regulator solution pH=1～3; Other gets 300ml 100g/L oxalic acid (H
2C
2O
4) solution, slowly add 5ml 80% hydrazine.Above-mentioned two solution are heated to respectively boil, again that they are mixed and stir to make and carry out precipitin reaction, throw out is filtered, use absolute ethanol washing, obtain white depositions, promptly contain the hydrazine yttrium oxalate.
The above-mentioned hydrazine yttrium oxalate that contains is placed crucible, and 800 ℃ of calcinations are 1.5 hours in High Temperature Furnaces Heating Apparatus, are cooled to room temperature, obtain white Y
2O
3Powder behind crushing screening, adopts its specific surface area of B.E.T determination of nitrogen adsorption.Embodiment 2～5:
Be that dosage with hydrazine among the embodiment 1 changes 10ml, 20ml, 25ml, 30ml respectively into, all the other are with embodiment 1.Embodiment 6:
Getting 200L concentration is 102g Y
2O
3The yttrium chloride solution of/L; Other gets 600L 100g/L oxalic acid solution, and slowly adds 40L 80% hydrazine in this oxalic acid solution, and is mixed with above-mentioned yttrium chloride solution again.The resulting hydrazine yttrium oxalate that contains is placed in the crucible,, obtain white Y 1000 ℃ of calcinations 1 hour
2O
3Powder.All the other are with embodiment 1.Embodiment 7:
Take by weighing 10g CeO
2In the 500ml beaker, add 100ml 1+1 nitric acid dissolve, obtain cerous nitrate solution, other gets the 300ml100g/L oxalic acid solution, slowly adds the 10ml80% hydrazine therein.All the other are with embodiment 1.That obtain is faint yellow CeO
2Powder.Embodiment 8:
Change the dosage of hydrazine among the embodiment 7 into 15ml, all the other are with embodiment 7.Embodiment 9:
Getting 15L concentration is 101g Y
2O
3/ L yttrium chloride solution adds 1L 80% hydrazine and mixes; Other prepares 45L 100g/L oxalic acid solution, slowly adds 2L 80% hydrazine and mixes.Contain the hydrazine yttrium chloride solution and contain the hydrazine oxalic acid solution and mix above-mentioned again, make to generate to contain the hydrazine yttrium oxalate.The hydrazine yttrium oxalate that contains that is generated is placed in the High Temperature Furnaces Heating Apparatus,, obtain white powder 850 ℃ of calcinations 2 hours.All the other are with embodiment 1.
Comparative Examples 1: for not adding hydrazine, all the other are with embodiment 1.
The sample testing of embodiment 1～9 and Comparative Examples 1 be the results are shown in table 2.
The specific surface area and the igloss of table 2: embodiment 1～9 and Comparative Examples 1 rare earth oxide
Embodiment 10:
| Sequence number | Specific surface area m 2/g | Igloss (1000 ℃, 1h) % |
| Embodiment 1 | 17.1 | 0.95 |
| | 28.4 | 0.97 |
| Embodiment 3 | 38.2 | 0.98 |
| Embodiment 4 | 44.2 | 0.98 |
| Embodiment 5 | 50.1 | 0.99 |
| Embodiment 6 | 18.3 | 0.94 |
| Embodiment 7 | 28.3 | 0.93 |
| Embodiment 8 | 43.8 | 0.95 |
| Embodiment 9 | 26.0 | 0.96 |
| Comparative Examples 1 | 3.2 | 0.93 |
Get yttrium oxalate throw out 15g, placed the interior 100 ℃ of dryings of baking oven 1 hour, after the taking-up cooling, add 2.5ml800g/L hydrazine hydrochloride solution, mix, stir evenly.This is contained the hydrazine yttrium oxalate place in the crucible, 850～900 ℃ of calcination 0.5h are cooled to room temperature in High Temperature Furnaces Heating Apparatus, obtain white Y
2O
3Powder.Behind crushing screening, measure.Embodiment 11～12:
Be that dosage with the hydrazine hydrochloride solution among the embodiment 10 changes 5ml respectively into, 6ml, all the other are with embodiment 10.Obtain Y
2O
3Powder.Embodiment 13:
Get Sedemesis throw out 20g, add 6ml 1400g/L hydrazine nitrate solution, all the other are with embodiment 10.Obtain CeO
2Powder.Embodiment 14:
Get gadolinium oxalate throw out 20g, add 7ml 1400g/L hydrazine nitrate solution, all the other are with embodiment 10.Obtain Gd
2O
3Powder.Embodiment 15～16:
Get the oxalic acid dysprosium respectively, each 20g of erbium oxalate throw out, each adds 6ml 800g/L hydrazine hydrochloride solution, and all the other are with embodiment 10.Obtain Dy respectively
2O
3And Er
2O
3Powder.Embodiment 17:
Get yttrium oxalate europium coprecipitate 20g, add 7ml 1400g/L hydrazine nitrate solution, all the other are with embodiment 10.Obtain (YEu)
2O
3Powder.Embodiment 18:
Get the oxalate 20g of thulium ytterbium lutetium enriched substance, add 6ml 800g/L hydrazine hydrochloride solution, all the other are with embodiment 10.Obtain (Tm Yb Lu)
2O
3Powder.
Comparative Examples 2～8: for not adding hydrazine compound, all the other are respectively with embodiment 12～18.Embodiment 10～18 lists in table 3 with the sample measurement result of Comparative Examples 2～8.
Table 3: embodiment 10-18 and
Comparative Examples 2-8 rare earth oxide specific surface area and igloss
| Sequence number | Specific surface area m 2/g | Igloss (1000C 1h) % | Sequence number | Specific surface area m 2/g | Igloss (1000 ℃, 1h) |
| Embodiment | |||||
| 10 | 14.4 | 0.95 | |||
| Embodiment 11 | 17.4 | 0.90 | |||
| Embodiment 12 | 21.7 | 0.91 | Comparative Examples 2 | 2.6 | 0.92 |
| Embodiment 13 | 20.1 | 0.91 | Comparative Examples 3 | 2.4 | 0.90 |
| Embodiment 14 | 21.4 | 0.92 | Comparative Examples 4 | 1.3 | 0.93 |
| Embodiment 15 | 8.9 | 0.97 | Comparative Examples 5 | 3.5 | 0.96 |
| Embodiment 16 | 10.1 | 0.96 | Comparative Examples 6 | 2.3 | 0.97 |
| Embodiment 17 | 12.9 | 0.94 | Comparative Examples 7 | 3.8 | 0.95 |
| Embodiment 18 | 5.0 | 0.92 | Comparative Examples 8 | 1.3 | 0.94 |
From the foregoing description and comparative example as can be seen: adopt the technology of the present invention can obtain specific surface area greater than 5m
2The rare earth oxide of/g, and its igloss＜1%.Compared with prior art, effect of the present invention is fairly obvious.Production technique of the present invention is simple and feasible, easily integrates with existing production; And can prepare the rare earth oxide of different specific surface areas to satisfy the domestic and international market demand by the dosage of control hydrazine.
The above embodiment of the present invention is just in order to illustrate content of the present invention rather than the present invention to be limited specifically to illustrated specific embodiment mode.Those skilled in the art can understand and the present invention includes various change and the corrections of doing for specific embodiment that do not deviate from essence of the present invention and scope.
Claims (14)
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| CN1043216C true CN1043216C (en) | 1999-05-05 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348496C (en) * | 2004-09-15 | 2007-11-14 | 北京有色金属研究总院 | Low bulk specific weight and large specific surface rare-earth oxide REO and its preparing method |
| CN100417599C (en) * | 2006-10-23 | 2008-09-10 | 浙江理工大学 | A kind of preparation method of tetragonal phase zirconia nanopowder |
| CN105603223B (en) * | 2016-03-02 | 2018-09-28 | 中铝广西国盛稀土开发有限公司 | A method of preparing bigger serface neodymia |
| CN107603490B (en) * | 2017-09-27 | 2020-06-26 | 甘肃稀土新材料股份有限公司 | Samarium-cerium-based polishing powder and preparation process thereof |
| CN108456219B (en) * | 2018-05-04 | 2020-06-16 | 中国工程物理研究院化工材料研究所 | Method for preparing ultra-pure volatile rare earth cerium chelate |
| CN108746656B (en) * | 2018-06-15 | 2021-11-26 | 威海职业学院 | Pre-alloyed powder for diamond products and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100388A (en) * | 1988-02-02 | 1988-11-23 | 中国科学院化工冶金研究所 | Rare-earth oxalate oxidizing roasting technology and device |
| CN1056098A (en) * | 1990-05-04 | 1991-11-13 | 罗纳·布朗克化学公司 | Process for the production of rare earth ammonium bisoxalates and their use in the production of rare earth oxides Bisoxalates and oxides obtained |
| CN1061402A (en) * | 1990-11-13 | 1992-05-27 | 罗纳·布朗克化学公司 | The production method of double oxalate of rare earth ammonium and be used for producing rare earth oxide |
| US5332558A (en) * | 1990-11-22 | 1994-07-26 | Shin-Etsu Chemical Co., Ltd. | Rare earth oxide powder and method for the preparation thereof |
-
1996
- 1996-04-11 CN CN96116316A patent/CN1043216C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88100388A (en) * | 1988-02-02 | 1988-11-23 | 中国科学院化工冶金研究所 | Rare-earth oxalate oxidizing roasting technology and device |
| CN1056098A (en) * | 1990-05-04 | 1991-11-13 | 罗纳·布朗克化学公司 | Process for the production of rare earth ammonium bisoxalates and their use in the production of rare earth oxides Bisoxalates and oxides obtained |
| CN1061402A (en) * | 1990-11-13 | 1992-05-27 | 罗纳·布朗克化学公司 | The production method of double oxalate of rare earth ammonium and be used for producing rare earth oxide |
| US5332558A (en) * | 1990-11-22 | 1994-07-26 | Shin-Etsu Chemical Co., Ltd. | Rare earth oxide powder and method for the preparation thereof |
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