CN1556037A - Preparation method of nano rare earth oxide - Google Patents
Preparation method of nano rare earth oxide Download PDFInfo
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- CN1556037A CN1556037A CNA2003101103064A CN200310110306A CN1556037A CN 1556037 A CN1556037 A CN 1556037A CN A2003101103064 A CNA2003101103064 A CN A2003101103064A CN 200310110306 A CN200310110306 A CN 200310110306A CN 1556037 A CN1556037 A CN 1556037A
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Abstract
A process for preparing nano-class RE oxide includes preparing the solution of ammonium citrate, preparing RE nitrate, adding alkaline solution of ammonium citrate to RE nitrate, reacting, measuring pH value, filtering, washing the filtered cake, baking and calcining in muffle furnace.
Description
Technical field:
The invention belongs to the compound of rare earth metal group of the lanthanides.
Background technology:
Behind the Bining and Rohrer invention tunnel microscope of Zurich institute of IBM Corporation in 1981, just be born one be the front subject of research object---nanoscale science and technology with 0.1～100nm yardstick.From then on, the whole world has started the research boom of nanotechnology.Nano material has the characteristic different with other size material because of the microcosmic of its size: small-size effect, surface and interfacial effect, quantum size effect and macro quanta tunnel effect.These characteristics make nano material be widely used in various fields, as coating, catalyzer, electrochemistry, photochemistry, structured material (as opto-electronic device) and biological field.At present, one of greatest problem that is restricting Nano-technology Development is the preparation of nano material.
In the rare earth field, according to preparation method's difference, the preparation of nano-oxide can be divided into physical method and chemical process.Physical method is a raw material with solid-state oxide compound or metal carbonate normally, and ball milling is after high temperature solid state reaction obtains composite oxide powder through pulverizing again.Its concrete grammar comprises vapor condensing method, physics crush method, mechanical ball milling method, amorphous crystallization method, plasma-deposited method and sputtering method.Physical method usually will be through pyroreaction, and the product particle diameter of preparation big, distribute widely, some component is easy to volatilization or segregation takes place, thereby this method generally should not be used for preparing the nano rareearth oxidate powder body; And chemical process normally adopts softening chemical method, and promptly the liquid-phase mixing by reaction raw materials makes each metallic element high dispersing, thereby can prepare nano material under lower temperature of reaction and chemical environment.Its concrete grammar comprises sol-gel processing, microemulsion method, spray pyrolysis, metal alkoxide hydrolysis method, chemical precipitation method.Sol-gel processing is that rare earths salt and precipitation agent effect are produced precipitation, and the precipitation that obtains is made colloidal sol, to obtain clear gel behind the organic solvent replacement water wherein, makes super-fine powder through thermal treatment again.From it building-up process as can be seen the gel specific surface area greatly, easily harden therefore become relatively difficulty of super-fine powder, this has just determined sol-gel method to prepare the complex manufacturing of powder, the production cost height.In addition, the defective of this method maximum is that the product that obtains easily reunites.Add dispersion agent in the preparation later stage and help preventing the generation of reuniting, but the affiliation that adds of dispersion agent has a negative impact to product property; Microemulsion method is to utilize the chemical reaction in the emulsion droplet of microemulsion to generate solid, to make required ultra-micro powder.Because volume of water and the reactant concn of micro emulsion in dripping can be controlled, monodispersity is good, may command nucleation and growth thereof, thereby can obtain the monodispersed ultramicron of various particle diameters; Spray pyrolysis is that metal salt solution is sprayed in the high-temperature atmosphere, and solvent evaporation and metal-salt pyrolysis moment that coexists is finished, and is called for short EDS or SP method.It is easy that spray pyrolysis has technological process, and system is adjustable, and whole process is once decomposed and finished, and powder is spherical in shape, good uniformity, and process has continuity, can realize automatic control; Alkoxide process is that the hydrolysis by metal alkoxide prepares ultra-micro powder, the metal alkoxide organometallics that to be metal generate with the alcohol reaction.All there is the synthetic high shortcoming of cost in above-mentioned back three kinds of chemical synthesiss.
Advantages such as compare with the physics method, it is fairly simple that chemical process has building-up process, and the synthesis condition ratio is easier to control, and synthetic cost is lower.The material that the precipitator method in the chemical synthesis are normally formed different chemical composition under solution state mixes mutually, in mixed solution, add suitable precipitation agent and prepare the presoma throw out, again throw out is carried out drying or calcining, thereby make the corresponding powder particle.The precipitator method of preparation nano rare earth compound powder comprise direct precipitation method, coprecipitation method and homogeneous precipitation method etc.Direct precipitation method is the method that directly prepares nano rare earth oxalate, carbonate and hydroxide particle in precipitant solution; Coprecipitation method is that precipitation agent is joined in the mixed salt solution, impels each component uniform mixing precipitation, and thermal degradation is to obtain powder then.Therefore many with oxalic acid, carbonate and ammoniacal liquor when preparing oxide nano rare earth as the research of precipitation agent with the precipitator method, and separately advantage is also respectively arranged with these three kinds of precipitation agents.The research of making precipitation agent with alkaline ammonium citrate is not seen in report as yet.Coming the synthesis of nano rare earth oxide with alkaline ammonium citrate as precipitation agent, both had the advantage with chemical synthesis, is again a kind of method of new synthesis of nano rare earth oxide.
Summary of the invention:
The present invention relates to the technological process of a kind of alkaline ammonium citrate solution precipitation agent and preparation oxide nano rare earth thereof, one of purpose of the present invention provides the method that a kind of alkaline ammonium citrate system prepares oxide nano rare earth.
Another purpose of the present invention provides a kind of method of producing oxide nano rare earth.
The present invention relates to the technological process of a kind of alkaline ammonium citrate solution precipitation agent and preparation oxide nano rare earth thereof, the preparation of its neutral and alkali ammonium citrate solution is to make 0.5～8M solution with the analytically pure citric acid of deionized water dissolving, adds strong aqua then and is made into 0.01～1M ammonium citrate solution; The preparation of rare earth nitrate is to be 90%～99.9999% RE oxide powder with 1: 1 concentrated nitric acid dissolving purity, in this process, need with excessive concentrated nitric acid dissolving RE oxide powder, the solution that makes is concentrated, the deionized water dilution can be made into the rare earth nitrate solution that concentration is 0.1～1.0M.Ammonium citrate solution with 0.01～1M joins in the rare earth nitrate solution as the speed of precipitation agent with per minute 1～50ml, and keeping the stirring velocity of reaction system in this process is 80～600 rev/mins.The pH value of reaction system terminal point is controlled at 6～10, and the precipitation that reaction is generated is with the deionized water wash of 300ml～2400ml 1～8 time, through oven for drying.Simultaneously entire reaction course all is to carry out under 10～50 ℃ condition, core promptly of the present invention be a kind of be the technological process that precipitation agent prepares oxide nano rare earth with alkaline ammonium citrate solution.
Calcining 1～5 hour in 700～1200 ℃ of high temperature muffle furnaces after, last procedure of this oxide nano rare earth preparation makes, therefore the rare earth oxide of preparation is preserved also very important, suction easily under the environment of humidity, the nano-scale particle that makes is reunited once more form material, and do not reach expected effect greater than nanoscale.
Oxide nano rare earth is widely used at aspects such as catalyzer, solid electrolytes as important rare earth oxide.Especially use in hydrogenation, isomerization, dehydration, dehydrogenation reaction as basic catalyst, make katalysis have some singularity.
The preparation of several key reagents of the present invention:
The preparation of alkalescence ammonium citrate precipitation agent.With the solution of analytically pure citric acid preparation 0.5～8M, and then in this solution, add the ammonium citrate solution that strong aqua is made 0.01～1M.
The preparation of rare earth nitrate solution.The present invention is to be 90%～99.9999% RE oxide powder with 1: 1 excessive concentrated nitric acid dissolving purity, in the dissolved process, liquid heated up to RE oxide powder and dissolve fully, filtering and impurity removing is made into the solution that concentration is 0.1～1.0M after cooling.
The control of various conditions in the reaction process.At the uniform velocity add in the adding of reaction process neutral and alkali ammonium citrate precipitation agent speed with per minute 1～50ml.The rotating speed of agitator is controlled at per minute 80～600 commentaries on classics in the reaction process simultaneously.React at the end, the pH value of system remains on 6～10.
The flocks of Sheng Chenging at last is through deionized water wash (1～8 time), suction filtration, 105 ℃ baking oven baking 2～4 hours, advances in 700～1200 ℃ the muffle furnace and calcines 1～5 hour, promptly can be made into the nano rareearth oxidate powder body.In preparation process, shorten filter cake after later filter cake of oven dry and the calcining exposed time in air as far as possible, the time kept 0.5～1 hour.
Advantage of the present invention is as follows:
1. the oxide nano rare earth of the present invention's preparation mainly is based on RE oxide powder.Because rare-earth mineral itself
Come from nature, so RE oxide powder is can not cause detrimentally affect to soil and environment.And
In the process of preparation oxide nano rare earth, have advantages such as safe, stable, nontoxic, harmless.
2. the oxide nano rare earth of the present invention's preparation can be the powdery solid granules of a kind of white, brown, greyish-green,
Production and storage process are more convenient.And during as catalyzer, solid electrolyte, use also relatively side
Just.
3. the oxide nano rare earth of the present invention preparation, be with alkaline ammonium citrate solution as precipitation agent, whole synthesizing
Journey is fairly simple, operation is also than being easier to, and it is 6～10 that reaction end is controlled at the pH value.
The present invention is in the process of preparation oxide nano rare earth, the selecting for use of the pH value that the temperature of reaction system, reaction end, precipitation agent, the concentration of precipitation agent and the temperature and time of the oven dry in the aftertreatment technology, the temperature and time of high-temperature calcination etc. have all passed through strict test.Now some test-results are illustrated:
1. the selection of precipitation agent.Respectively as precipitation agent synthesizing rare-earth oxide powder, wherein use ammonium citrate less with ammonium citrate, oxalic acid, carbon ammonium, urea and ammoniacal liquor as precipitation agent synthetic particle diameter ratio.
2. system temperature is to the influence of synthetics particle diameter.The thermograde of selecting for use is 10 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃, the concentration of the precipitated thing of control reaction simultaneously is that result that 0.1～1.0M the measures particle diameter ratio when showing 30 ℃ and 90 ℃ is less, again because 30 ℃ the relatively good control of temperature condition is the temperature of reaction system so chosen 30 ℃.
3. pH value of reaction system is to the influence of synthetics particle diameter.The temperature of reaction that system has been chosen in test is 10～50 ℃, and the concentration of precipitated thing is 0.1～1.0M, and the concentration of precipitation agent is 0.01～1M.From test-results as can be known: the pH value of reaction system there is not difference to the influence of synthetic materials particle diameter under sour environment, and the particle diameter under alkaline environment is significantly greater than the particle diameter under the sour environment, promptly when the pH value more than or equal to 8 the time, the particle diameter of synthetic materials obviously increases.
4. precipitation agent concentration is to the influence of synthetics particle diameter.Test-results shows: when precipitation agent concentration is any concentration between 0.1～1.0M, do not have significant difference between the particle diameter of synthetic materials.The precipitation agent concentration that is the synthesis of nano rare earth oxide preferably is controlled between 0.01～1.0M.
Embodiment:
Be the embodiment of two kinds of oxide nano rare earths below:
Embodiment 1:
Precipitation solution La (NO
3)
3Concentration be 0.5M:
La (the NO of preparation 1M
3)
3Solution, at first weighing 162.92 gram purity are 99.99% La
2O
3,, treat the La (NO of the fixed molten 1M of being made into of adding distil water when solution is 300ml with 1: 1 concentrated nitric acid 480ml heating for dissolving
3)
3Solution.Get the 33ml 1M La (NO for preparing in advance
3)
3Be diluted to 66ml, be made into the solution of 0.5M;
The concentration of alkalescence ammonium citrate solution is 0.015M:
Get 3M Citric 11ml, be diluted to 2200ml, add the 9.9ml strong aqua then, be made into the alkaline ammonium citrate solution of 0.015M, and splash into La (NO with the speed of per minute 10ml
3)
3In the solution.
The pH value of ammonium citrate solution is 8.79 when reacting initial.
Stirring velocity in the reaction process remains per minute 380 changes.
The pH value that system ends is 7.8.
Question response at the end continues to stir 20 minutes again.
The deionized water wash 3 times of 500ml is used in the white flocks that suction filtration reaction generates simultaneously.
Filter cake behind the suction filtration was dried by the fire 2 hours in 105 ℃ baking oven.
Dried filter cake high-temperature calcination 1 hour in 850 ℃ muffle furnace.
Can make the nano rareearth oxidate powder body.
Embodiment 2:
Precipitation solution La (NO
3)
3Concentration be 0.2M:
Get the 1M La (NO for preparing in advance
3)
3Solution 30ml is diluted to 150ml and makes 0.2M solution.
Homemade 0.015M alkalescence ammonium citrate solution is splashed into La (NO with the speed of per minute 10ml
3)
3In the solution.
The pH value of ammonium citrate solution is 9.31 when reacting initial.
Stirring velocity in the reaction process remains a constant speed and is per minute 330 commentaries on classics.
The pH value that system ends is 8.0.
Question response at the end continues to stir 20 minutes again.
The white flocks that the suction filtration reaction generates is used the 500ml deionized water wash 3 times simultaneously.
The filter cake that suction filtration is obtained dried by the fire 2 hours in 105 ℃ baking oven.
Dried filter cake high-temperature calcination 1 hour in 850 ℃ muffle furnace.
The nano rareearth oxidate powder body that can make.
Claims (5)
1. the preparation method of oxide nano rare earth is characterized in that: at first be the preparation of ammonium citrate solution, and the alkaline ammonium citrate solution made from itself and strong aqua reaction then, this solution can be used as a kind of precipitation agent; Next is the preparation of rare earth nitrate, makes rare earth nitrate solution with 1: 1 concentrated nitric acid dissolving 90%～99.9999% rare earth oxide powder; Finally join in the rare earth nitrate with the speed of the precipitation agent for preparing with per minute 1～50ml, in reaction process, the stirring velocity of reaction system is that per minute 80～600 changes; When reaction was finished, the pH value of system was controlled at 6～10, and the precipitate with deionized water that reaction generates is washed 1～8 time, and after oven for drying, 700～1200 ℃ of calcinings of high temperature are 1～5 hour in muffle furnace, can make the nano rareearth oxidate powder body.
2. the preparation method of oxide nano rare earth according to claim 1 is characterized in that process is as follows:
(1) preparation of alkaline ammonium citrate solution: analytically pure citric acid powder spends the ionized water dissolving, makes the solution of 0.5～8M, adds the alkaline ammonium citrate solution that 0.01～1M is made in the strong aqua reaction then;
(2) preparation of rare earth nitrate: the concentrated nitric acid dissolving purity with 1: 1 is the rare earth nitrate solution that 90%～99.9999% rare earth oxide powder is made 0.1～1.0M, filters and remove impurity, is made into required solution;
(3) reaction process: the speed of the ammonium citrate solution of the 0.01～1M for preparing with per minute 1～50ml is joined in the rare earth nitrate solution of 0.1～1.0M, in this process, the rotating speed of agitator is controlled at per minute 80～600 to be changeed, simultaneously, the assaying reaction system pH, when the pH of reaction system value reaches 6～10, stop to add precipitation agent, after finishing, question response left standstill 5～30 minutes, the pH value of assaying reaction system once more, if do not reach 6～10, then need continue to add precipitation agent, so repeated multiple times;
(4) filter and washing: the flocks of adopting the suction filtration processing reaction to obtain, use the deionized water wash 1～8 time of 300ml～2400ml simultaneously, make filter cake;
(5) filter cake that makes is put into 105 ℃ baking oven and dried by the fire 2～4 hours, dry fully up to moisture;
(6) dried filter cake is changed in 700～1200 ℃ the muffle furnace calcined 1～5 hour.
3. the preparation method of oxide nano rare earth according to claim 1 is characterized in that adopting alkaline ammonium citrate as precipitation agent synthesis of nano powder.
4. the preparation method of oxide nano rare earth according to claim 1 is characterized in that it is 10～50 ℃ that this production technique keeps the temperature of reaction system.
5. the preparation method of oxide nano rare earth according to claim 1 is characterized in that in the preparation process of this production technique, shortens filter cake after later filter cake of oven dry and the calcining exposed time in air as far as possible, and the time kept 0.5～1 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107867726A (en) * | 2016-09-27 | 2018-04-03 | 北京化工大学 | A kind of preparation method of nano oxidized ruthenium |
| CN108408757A (en) * | 2018-03-15 | 2018-08-17 | 益阳鸿源稀土有限责任公司 | A kind of preparation method of high pure and ultra-fine scandium oxide powder |
| CN108654604A (en) * | 2017-03-31 | 2018-10-16 | 北京化工大学 | A kind of preparation method and application of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material |
| CN110137510A (en) * | 2019-04-28 | 2019-08-16 | 江苏大学 | A kind of preparation method and applications of nano oxidized ruthenium |
| CN114014646A (en) * | 2021-12-09 | 2022-02-08 | 营口理工学院 | Method for preparing nano gadolinium aluminate powder material by citric acid chelation method |
-
2003
- 2003-12-30 CN CNB2003101103064A patent/CN1281505C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107867726A (en) * | 2016-09-27 | 2018-04-03 | 北京化工大学 | A kind of preparation method of nano oxidized ruthenium |
| CN107867726B (en) * | 2016-09-27 | 2019-07-12 | 北京化工大学 | A kind of preparation method of nano oxidized ruthenium |
| CN108654604A (en) * | 2017-03-31 | 2018-10-16 | 北京化工大学 | A kind of preparation method and application of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material |
| CN108408757A (en) * | 2018-03-15 | 2018-08-17 | 益阳鸿源稀土有限责任公司 | A kind of preparation method of high pure and ultra-fine scandium oxide powder |
| CN110137510A (en) * | 2019-04-28 | 2019-08-16 | 江苏大学 | A kind of preparation method and applications of nano oxidized ruthenium |
| CN114014646A (en) * | 2021-12-09 | 2022-02-08 | 营口理工学院 | Method for preparing nano gadolinium aluminate powder material by citric acid chelation method |
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