CN1159226C - Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction - Google Patents
Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction Download PDFInfo
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- CN1159226C CN1159226C CNB021136769A CN02113676A CN1159226C CN 1159226 C CN1159226 C CN 1159226C CN B021136769 A CNB021136769 A CN B021136769A CN 02113676 A CN02113676 A CN 02113676A CN 1159226 C CN1159226 C CN 1159226C
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Abstract
The present invention relates to a method for preparing rare-earth nanometer oxide by ball milling and solid-phase chemical reaction. Rare-earth inorganic salt and ligand thereof are used as raw materials. The processing steps orderly comprises: a predecessor is prepared by material matching, material mixing and ball milling solid phase chemical reaction; the predecessor carries out the trash extraction; the predecessor is dried; the predecessor is dissolved at a warm temperature. The rare-earth inorganic salt is cerium salt, lanthanum salt, praseodymium salt, neodymium salt or terbium salt. The ligand has inorganic ligand and organic ligand, the inorganic ligand is oxalic acid, sodium oxalate, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, potassium acetate or sodium acetate, and the organic ligand is 8-hydroxyquinoline, ethylenediamine tetraacetic acid disodium salt, potassium sodium tartrate, amino acid or dibenzoylmethane. The method prepares the predecessor by the ball milling solid state chemical reaction, so that the method not only can simplify the process, save solvent and protect the environment, but also enables a heat decomposition temperature to be reduced to 250 to 400 DEG C; the method is beneficial to energy saving and cost reducing. The powder size distribution of rare earth oxide prepared by the method is from 10 to 30 nm, and the purity can reach more than 99 %.
Description
One, technical field
The present invention relates to a kind of ball milling solid state reaction preparation method of oxide nano rare earth.
Two, background technology
Application number is the preparation method that 91110578.6 Chinese patent discloses a kind of cerium oxide, and this method is a raw material with the mishmetal that contains cerium, and processing step is followed successively by: (1) is with the Ce in the mishmetal
3+All be oxidized to Ce
4+, make the mishmetal sulfuric acid liquid with sulfuric acid dissolution then; (2) add sodium sulfate in the mishmetal sulfuric acid liquid, reaction generates few cerium RE
3+Double salt precipitation; (3) in the filtrate of filtering the double salt precipitation gained, add the ferrous sulfate reaction and generate cerous sulfate sodium double salt precipitation; (4) reaction of precipitation after the filtration and caustic soda changes into cerous hydroxide; (5) become cerium oxide to add oxalic acid again with dissolving with hydrochloric acid cerous hydroxide and generate oxalate precipitation; (6) oxalate precipitation after the filtration becomes cerium oxide 800 ℃ of calcinations.
Application number is that 98106748.4 Chinese patent application discloses a kind of fluorescent nanometer rare earth oxide powder and preparation method thereof, its technical scheme is to adopt the urea homogeneous precipitation method manufacturing presoma that combines with sonochemical method, this presoma decomposes in 900～1500 ℃ of air, calcination 0.5～3 hour can obtain nano-phosphor.
From the content of above-mentioned two parts of Chinese patent application as can be seen, they all are to prepare presoma or precursor by liquid-phase chemical reaction, and the thermolysis of precursor or presoma is at high temperature finished, thereby not only need a large amount of solvents, operation is various, and causes energy consumption to increase, and cost improves.
Three, summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of ball milling solid state reaction preparation method of oxide nano rare earth is provided, this kind method has not only been simplified technology, and heat decomposition temperature is middle temperature, helps save energy.
Mechanism of the present invention is: the broken solid-phase reactant of the mechanical force that produces in the mechanical milling process, increase the reactant specific surface, improve reactant contact surface and speed of reaction, therefore also just improved the ratio of nucleation rate and nuclear growth rate, can prepare fine, uniform precursor, obtain the very high nanometer level RE oxide powder of purity so that decompose under mesophilic condition.
Method provided by the invention is a raw material with inorganic salt of rare earth and part thereof, and processing step is as follows successively:
1, batching
The mol ratio of inorganic salt of rare earth and part is 1: 2～8;
2, batch mixing
Inorganic salt of rare earth, the part that will meet ratio mix, till evenly;
3, the ball milling solid state reaction prepares precursor
The mixture of inorganic salt of rare earth and part is carried out ball milling, make it issue biochemical reaction and generate precursor at the ball milling state, add lubricant during ball milling, the add-on of lubricant is to be kept dispersed to exceed by the ball milling thing, ball milling carries out under room temperature, normal pressure, till inorganic salt of rare earth and part fully solid state reaction take place;
4, precursor removal of impurities
The washing and filtering method is adopted in the precursor removal of impurities;
5, precursor drying
Precursor is dry to adopt natural air drying or 30～40 ℃ of oven dry;
6, warm decomposition in the precursor
Precursor pyrolysated temperature is controlled at 250～400 ℃, and the time is 2～4 hours, and its product is oxide nano rare earth.
In the aforesaid method, inorganic salt of rare earth is cerium salt or lanthanum salt or praseodymium salt or neodymium salt or terbium salt; Part has inorganic part and organic ligand, inorganic part is oxalic acid or sodium oxalate or sodium bicarbonate or saleratus or salt of wormwood or yellow soda ash or Potassium ethanoate or sodium-acetate, and organic ligand is oxine or sodium ethylene diamine tetracetate or Seignette salt or amino acid or dibenzoyl; The lubricant that is added during ball milling is ethanol or acetone.
The oxide nano rare earth of method preparation provided by the invention, its powder particle is a ball-type, and powder size is distributed as 10～30nm, and purity is (no any impurity peaks on the XRD figure spectrum) more than 99%.
The present invention has the following advantages and positively effect:
1, owing to carry out chemical reaction, reactant is pulverized fast, be increased the surface-area of reactant, improve the contact surface of reactant and the velocity of diffusion of solid phase particles, thereby chemical reaction velocity is accelerated the chemical time shortening at the ball milling state.
2, because the employing solid state reaction prepares precursor, thereby avoided reactant is mixed with solution, so not only simplified operation, saved solvent, and helped operator's work, and reduced environmental pollution.
3, solid state reaction can keep reactant concn constant, causes nucleation rate to be far longer than the nuclear growth rate, thereby easily forms the precursor of fine particles, has created condition for obtaining nano-powder.
4, the precursor that is obtained decomposes under 250～400 ℃ temperature condition, and compared with prior art, but save energy reduces cost.
Four, description of drawings
Fig. 1 is a kind of process flow sheet according to the ball milling solid state reaction preparation method of oxide nano rare earth provided by the present invention.
Five, embodiment
Embodiment 1:
In the present embodiment, inorganic salt of rare earth is a cerous nitrate, and part is a sodium oxalate, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of cerous nitrate and sodium oxalate is 1: 4;
(2) batch mixing
Cerous nitrate, sodium oxalate are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of cerous nitrate and sodium oxalate placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 230 rev/mins, ball milling carries out under room temperature, normal pressure, can make cerous nitrate and sodium oxalate that chemical reaction generation precursor Sedemesis takes place fully in 20 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the Sedemesis removal of impurities, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Sedemesis after the removal of impurities adopts natural air drying, and the time is 8 hours (10～15 ℃);
(6) warm decomposition in the precursor
Sedemesis after air-dry is placed retort furnace, and temperature is controlled at 310 ℃, and the time is can finish thermolysis in 3 hours, obtains nano-cerium oxide.
Embodiment 2:
In the present embodiment, inorganic salt of rare earth is a ceric ammonium nitrate, and part is an oxalic acid, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of ceric ammonium nitrate and oxalic acid is 1: 4;
(2) batch mixing
Ceric ammonium nitrate, oxalic acid are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of ceric ammonium nitrate and oxalic acid placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 270 rev/mins, ball milling carries out under room temperature, normal pressure, can make ceric ammonium nitrate and oxalic acid that chemical reaction generation precursor Sedemesis takes place fully in 15 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the Sedemesis removal of impurities, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Sedemesis after the removal of impurities adopts natural air drying, and the time is 6 hours (15～25 ℃);
(6) warm decomposition in the precursor
Sedemesis after air-dry is placed retort furnace, and temperature is controlled at 310 ℃, and the time is can finish thermolysis in 3 hours, obtains nano-cerium oxide.
Embodiment 3:
In the present embodiment, inorganic salt of rare earth is a Cerium II Chloride, and part is a sodium bicarbonate, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of Cerium II Chloride and sodium bicarbonate is 1: 8;
(2) batch mixing
Cerium II Chloride, sodium bicarbonate are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of Cerium II Chloride and sodium bicarbonate placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 250 rev/mins, ball milling carries out under room temperature, normal pressure, can make Cerium II Chloride and sodium bicarbonate that chemical reaction generation precursor hydrogen-carbonate cerium takes place fully in 25 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the removal of impurities of hydrogen-carbonate cerium, and washing composition is an acetone, and washing and filtering gets final product for three times;
(5) precursor drying
Hydrogen-carbonate cerium after the removal of impurities is 40 ℃ of oven dry, and the time is 3 hours;
(6) warm decomposition in the precursor
Hydrogen-carbonate cerium after the oven dry is placed retort furnace, and temperature is controlled at 340 ℃, and the time is can finish thermolysis in 3 hours, obtains nano-cerium oxide.
Embodiment 4:
In the present embodiment, inorganic salt of rare earth is a cerous sulfate, and part is an oxine, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of cerous sulfate and oxine is 1: 4;
(2) batch mixing
Cerous sulfate, oxine are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of cerous sulfate and oxine placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 270 rev/mins, ball milling carries out under room temperature, normal pressure, can make cerous sulfate and oxine that chemical reaction generation precursor cerium-8 hydroxyquinoline takes place fully in 20 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the removal of impurities of cerium-8 hydroxyquinoline, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Cerium after the removal of impurities-8 hydroxyquinoline is 40 ℃ of oven dry, and the time is 3 hours;
(6) warm decomposition in the precursor
Cerium-8 hydroxyquinoline after the oven dry is placed retort furnace, and temperature is controlled at 380 ℃, can finish thermolysis in 3 hours, obtains nano-cerium oxide.
Embodiment 5:
In the present embodiment, inorganic salt of rare earth is a Lanthanum trichloride, and part is an oxalic acid, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of Lanthanum trichloride and oxalic acid is 1: 3;
(2) batch mixing
Lanthanum trichloride, oxalic acid are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of Lanthanum trichloride and oxalic acid placed the star ball mill and add lubricant acetone carry out ball milling, the add-on of acetone is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 280 rev/mins, ball milling carries out under room temperature, normal pressure, can make Lanthanum trichloride and oxalic acid that chemical reaction generation precursor lanthanum oxalate takes place fully in 25 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the lanthanum oxalate removal of impurities, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Lanthanum oxalate after the removal of impurities is 30 ℃ of oven dry, and the time is 4 hours;
(6) warm decomposition in the precursor
Lanthanum oxalate after the oven dry is placed retort furnace, and temperature is controlled at 290 ℃, can finish thermolysis in 4 hours, obtains nano lanthanum oxide.
Embodiment 6:
In the present embodiment, inorganic salt of rare earth is a Lanthanum trichloride, and part is an oxine, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of Lanthanum trichloride and oxine is 1: 3;
(2) batch mixing
Lanthanum trichloride, oxine are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of Lanthanum trichloride and oxine placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 280 rev/mins, ball milling carries out under room temperature, normal pressure, can make Lanthanum trichloride and oxine that chemical reaction generation precursor lanthanum-8 hydroxyquinoline takes place fully in 25 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the removal of impurities of lanthanum-8 hydroxyquinoline, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Lanthanum after the removal of impurities-8 hydroxyquinoline adopts natural air drying, and the time is 6 hours (15～25 ℃ of temperature);
(6) warm decomposition in the precursor
Lanthanum-8 hydroxyquinoline after the oven dry is placed retort furnace, and temperature is controlled at 340 ℃, can finish thermolysis in 3 hours, obtains nano lanthanum oxide.
Embodiment 7:
In the present embodiment, inorganic salt of rare earth is a praseodymium chloride, and part is an oxalic acid, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of praseodymium chloride and oxalic acid is 1: 3;
(2) batch mixing
Praseodymium chloride, oxalic acid are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of praseodymium chloride and oxalic acid placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 270 rev/mins, ball milling carries out under room temperature, normal pressure, can make praseodymium chloride and oxalic acid that chemical reaction generation precursor praseodymium oxalate takes place fully in 25 minutes;
(4) precursor removal of impurities
The washing and filtering method is adopted in the praseodymium oxalate removal of impurities, and washing composition is an ethanol, and washing and filtering gets final product for three times;
(5) precursor drying
Praseodymium oxalate after the removal of impurities adopts natural air drying, 8 hours time (temperature is 10～15 ℃);
(6) warm decomposition in the precursor
Praseodymium oxalate after air-dry is placed retort furnace, and temperature is controlled at 320 ℃, can finish thermolysis in 3 hours, obtains nano oxidized praseodymium.
Embodiment 8:
In the present embodiment, inorganic salt of rare earth is a Neodymium trichloride, and part is a dibenzoyl, and technical process has following steps as shown in Figure 1 successively:
(1) batching
The mol ratio of Neodymium trichloride and dibenzoyl is 1: 3;
(2) batch mixing
Neodymium trichloride, dibenzoyl are mixed, till evenly;
(3) the ball milling solid state reaction prepares precursor
The mixture of Neodymium trichloride and dibenzoyl placed the star ball mill and add lubricant ethanol carry out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 240 rev/mins, ball milling carries out under room temperature, normal pressure, can make Neodymium trichloride and dibenzoyl that chemical reaction generation precursor Nd (DBM) takes place fully in 20 minutes
3
(4) precursor removal of impurities
Nd (DBM)
3The washing and filtering method is adopted in removal of impurities, and washing composition is a water, and washing and filtering gets final product for three times;
(5) precursor drying
Nd after the removal of impurities (DBM)
330 ℃ of oven dry, the time is 4 hours;
(6) warm decomposition in the precursor
With the Nd (DBM) after the oven dry
3Place retort furnace, temperature is controlled at 350 ℃, can finish thermolysis in 3 hours, obtains nano oxidized neodymium.
Embodiment 9:
In the present embodiment, inorganic salt of rare earth is Te (Ac)
34H
2O, part are dibenzoyl, and technical process has following steps as shown in Figure 1 successively:
(1) batching
Te (Ac)
34H
2The mol ratio of O and dibenzoyl is 1: 3;
(2) batch mixing
With Te (Ac)
34H
2O, dibenzoyl mix, till evenly;
(3) the ball milling solid state reaction prepares precursor
With Te (Ac)
34H
2The mixture of O and dibenzoyl places the star ball mill and adds lubricant ethanol and carries out ball milling, the alcoholic acid add-on is to be kept dispersed to exceed by the ball milling thing, the rotating speed of ball mill is controlled at 240 rev/mins, and ball milling carries out under room temperature, normal pressure, can make Te (Ac) in 25 minutes
34H
2Chemical reaction takes place and generates precursor Te (DBM) in O and dibenzoyl fully
3
(4) precursor removal of impurities
Te (DBM)
3The washing and filtering method is adopted in removal of impurities, and washing composition is a water, and washing and filtering gets final product for three times;
(5) precursor drying
Te after the removal of impurities (DBM)
3Adopt natural air drying, the time is 4 hours (about 30 ℃);
(6) warm decomposition in the precursor
With the Te (DBM) after the oven dry
3Place retort furnace, temperature is controlled at 360 ℃, can finish thermolysis in 3 hours, obtains nano oxidized terbium.
Claims (1)
1, a kind of ball milling solid state reaction preparation method of oxide nano rare earth, it is characterized in that with inorganic salt of rare earth and part thereof be raw material, inorganic salt of rare earth is cerium salt or lanthanum salt or praseodymium salt or neodymium salt or terbium salt, the part of inorganic salt of rare earth has inorganic part and organic ligand, inorganic part is oxalic acid or sodium oxalate or sodium bicarbonate or saleratus or salt of wormwood or yellow soda ash or Potassium ethanoate or sodium-acetate, organic ligand is oxine or sodium ethylene diamine tetracetate or Seignette salt or amino acid or dibenzoyl, and processing step is as follows successively:
(1) batching
The mol ratio of inorganic salt of rare earth and its part is 1: 2～8,
(2) batch mixing
The inorganic salt of rare earth and the part thereof that will meet ratio mix, till evenly,
(3) the ball milling solid state reaction prepares precursor
The mixture of inorganic salt of rare earth and its part is carried out ball milling, make it issue biochemical reaction and generate precursor at the ball milling state, add lubricant ethanol or acetone during ball milling, the add-on of ethanol or acetone is to be kept dispersed to exceed by the ball milling thing, ball milling carries out under room temperature, normal pressure, till solid state reaction takes place in inorganic salt of rare earth and part fully
(4) precursor removal of impurities
The washing and filtering method is adopted in the precursor removal of impurities, and used washing composition is ethanol or acetone or water,
(5) precursor drying
Precursor is dry to adopt natural air drying or 30～40 ℃ of oven dry,
(6) warm decomposition in the precursor
Precursor pyrolysated temperature is controlled at 250～400 ℃, and the time is 2～4 hours, and its product is oxide nano rare earth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021136769A CN1159226C (en) | 2002-04-29 | 2002-04-29 | Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021136769A CN1159226C (en) | 2002-04-29 | 2002-04-29 | Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction |
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|---|---|
| CN1386706A CN1386706A (en) | 2002-12-25 |
| CN1159226C true CN1159226C (en) | 2004-07-28 |
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| CNB021136769A Expired - Fee Related CN1159226C (en) | 2002-04-29 | 2002-04-29 | Process for preparing rare-earth nano oxide by ball grinding and solid-phase chemical reaction |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321896C (en) * | 2004-04-14 | 2007-06-20 | 北京方正稀土科技研究所有限公司 | Process for preparing nano cerium dioxide |
| CN102275971A (en) * | 2011-05-26 | 2011-12-14 | 哈尔滨工业大学 | Method for preparing nano-sized cerium dioxide through room temperature solid phase reaction |
| CN103553111B (en) * | 2013-10-28 | 2015-05-20 | 北京工业大学 | Method for preparing micron-order CeO2 by virtue of wet milling and low temperature dry coupling method |
| CN104291372A (en) * | 2014-09-10 | 2015-01-21 | 内江师范学院 | Cerium 8-hydroxyquinoline nano rare-earth crystal material and preparation method thereof |
| CN105733445B (en) * | 2016-03-21 | 2017-12-26 | 四川大学 | A kind of nano Ce O2The preparation method of polishing powder |
| CN109574061A (en) * | 2018-11-26 | 2019-04-05 | 新疆大学 | A kind of method for preparing solid phase with different-shape nano ceria |
| CN110194480B (en) * | 2019-06-11 | 2022-03-15 | 宜昌三峡中润纳米材料有限公司 | Nano cerium oxide and preparation method thereof |
| CN113233493A (en) * | 2021-05-31 | 2021-08-10 | 中南大学 | Method for synthesizing rare earth nano oxide particle material in batch |
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