CN111004580A - Rare earth fluoride polishing powder and preparation method of rare earth fluoride polishing solution - Google Patents
Rare earth fluoride polishing powder and preparation method of rare earth fluoride polishing solution Download PDFInfo
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- CN111004580A CN111004580A CN201911291538.1A CN201911291538A CN111004580A CN 111004580 A CN111004580 A CN 111004580A CN 201911291538 A CN201911291538 A CN 201911291538A CN 111004580 A CN111004580 A CN 111004580A
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- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Abstract
The invention discloses a rare earth fluoride polishing powder and a preparation method of rare earth fluoride polishing solution, comprising the following steps: 1) adding water and acid into a rare earth raw material for dissolving to prepare a rare earth acid solution, and controlling the concentration of the rare earth acid solution to be less than or equal to 100 g/L; 2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for more than 90% and 4-8% of the total weight of the rare earth contained in the rare earth acidic solution; 3) dropwise adding the modified solution into a rare earth acid solution, reacting, separating out precipitate, calcining, and grinding to obtain powder with the maximum particle size of less than or equal to 20 μm; and mixing the prepared polishing powder with water to prepare rare earth fluoride polishing solution; after the polishing powder prepared by the invention is applied to surface treatment, high cutting rate is realized on the premise of ensuring that the surface of optical glass has no surface defects such as scratches, the preparation method is simpler, and the purpose of synchronously carrying out precipitation and fluorination is completely realized.
Description
Technical Field
The invention belongs to the technical field of optical glass surface ultra-leveling treatment, and particularly relates to rare earth fluoride polishing powder and a preparation method of rare earth fluoride polishing solution.
Background
In recent years, with the vigorous development of the optical industry, the requirement on the surface planarization of materials is higher and higher, and the rare earth polishing powder products in the market gradually tend to be diversified, so that the requirements on the variety and polishing performance of the rare earth cerium-based polishing powder are stricter and stricter. Pure CeO on the market2The cutting efficiency of the high-cerium polishing powder is lower than that of fluorine-containing rare earth cerium-based polishing powderTherefore, for optical glass with a hard material, the fluorine-containing rare earth cerium-based polishing powder has a large market share.
At present, in the fluorine-containing rare earth cerium-based polishing powder synthesized traditionally in the market, lanthanum oxyfluoride and cerium carbonate are used as main components, wherein the ratio of lanthanum to cerium is about 25: 75, most of the raw materials are dissolved by acid, a precipitator is added for precipitation after the solution is prepared, and then fluorination treatment is carried out, wherein the fluorinating agent is usually hydrofluoric acid, and the hydrofluoric acid has great damage to the environment and instruments; for example, the method for producing cerium-rich rare earth polishing powder disclosed in chinese invention patent CN100497508C, comprising the steps of preparing cerium lanthanum carbonate, adding hydrofluoric acid for fluorination, and calcining to obtain cerium-rich rare earth polishing powder, wherein the method is divided into two steps, the synthesis process is complex, the time consumption is long, the benefit is low, the treatment cost of the generated waste water and waste gas is high, and the pollution to the environment is easy to cause; meanwhile, the wet synthesis of rare earth polishing materials has strict requirements on production and processing equipment, and the yield and fluorination efficiency are also poor.
In order to solve the above problems, chinese patent CN106978090A provides an improved solution, which discloses a method for preparing rare earth fluoride polishing powder, comprising the following steps: s1, adding a certain amount of light rare earth acid solution with the concentration of 100g/L into the reaction kettle, heating and stirring to 75 ℃, and keeping the temperature constant; s2, preparing oxalic acid accounting for 115% of the total weight of the rare earth in the reaction kettle into a saturated solution at the temperature of 45-55 ℃; s3, dropwise adding the oxalic acid saturated solution into the reaction kettle at a speed of 50 drops/min; s4, when the oxalic acid saturated solution is dripped to 1/5 of the total amount, dripping 35-50 wt% of hydrofluoric acid solution which accounts for 5-10 wt% of the total weight of the rare earth in the reaction kettle at a dripping speed of 15 seconds per droplet into the reaction kettle; s5, after the hydrofluoric acid solution is dripped, taking the supernatant solution in the reaction kettle, dripping the oxalic acid saturated solution, stopping dripping the oxalic acid saturated solution in the reaction kettle if no precipitate is generated, keeping the temperature of the reaction kettle for 2 hours, aging, and continuing dripping the oxalic acid saturated solution in the reaction kettle if the precipitate is generated until no precipitate is generated after dripping the oxalic acid saturated solution in the supernatant solution taken out of the reaction kettle; s6, taking out the precipitate in the reaction kettle, washing with water until the pH value is 6-8, drying at 120 ℃, calcining at 800-1150 ℃ for 5-8 hours, and finally adding a dispersing agent to grind until the average particle size is 1.0-2.5 mu m to obtain the rare earth fluoride polishing powder. According to the method, after a period of precipitation, oxalic acid and hydrofluoric acid are simultaneously added to perform precipitation and fluorination at the same time, although the steps are simplified to a certain extent, two kinds of acid liquid still need to be added separately, more equipment is needed, and the polishing effect of the polishing powder obtained in the mode still needs to be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an improved preparation method of rare earth fluoride polishing powder, the prepared polishing powder is applied to surface treatment, high cutting rate is realized on the premise of ensuring that the surface of optical glass is not scratched and other surface defects, the preparation method is simpler, the aim of synchronously carrying out precipitation and fluorination is completely fulfilled, and the number of required devices is reduced.
The invention also provides a preparation method of the rare earth fluoride polishing solution.
In order to solve the technical problems, the invention adopts a technical scheme as follows: a preparation method of rare earth fluoride polishing powder comprises the following steps:
(1) adding water and acid into a rare earth raw material for dissolving to prepare a rare earth acidic solution, and controlling the concentration of the rare earth acidic solution to be less than or equal to 100 g/L;
(2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for more than 90% and 4-8% of the total weight of the rare earth in the rare earth acidic solution treated in the step (1);
(3) and (3) dropwise adding the modified solution prepared in the step (2) into the rare earth acidic solution treated in the step (1), reacting, separating out precipitate, calcining, and grinding to obtain powder with the maximum particle size of less than or equal to 20 microns, thus obtaining the rare earth fluoride polishing powder.
According to some specific aspects of the present invention, in the step (1), the rare earth raw material is a rare earth carbonate including cerium carbonate and a lanthanum salt-based rare earth or lanthanum cerium carbonate.
According to some specific and preferred aspects of the present invention, in the step (1), the acid is a combination of one or more selected from hydrochloric acid, nitric acid and sulfuric acid.
According to some preferred aspects of the present invention, in the step (2), the ammonium carbonate and the ammonium fluoride in the modification solution respectively account for more than 93% and 5-7% of the total weight of the rare earth contained in the rare earth acidic solution after the treatment in the step (1).
According to some preferred aspects of the present invention, in the step (3), the temperature of the reaction is controlled to be 60 to 75 ℃. More preferably, in step (3), the temperature of the reaction is controlled to be 65 to 70 ℃.
According to some specific aspects of the invention, in the step (3), before the precipitate is separated, after the modified solution is added dropwise, the supernatant of the reaction mixed solution is taken, ammonium carbonate is added, if no precipitate is generated, the precipitate is complete, if the precipitate is generated, ammonium carbonate is added into the reaction mixed solution until the precipitate is complete, and then the reaction mixed solution is subjected to heat preservation and standing ageing.
According to some specific aspects of the present invention, in the step (3), the separated precipitate is washed with water until a pH of a washing liquid obtained after the washing with water is 6 to 9, and then the calcination is performed.
According to some specific and preferred aspects of the present invention, in step (3), the calcination is carried out at 800-.
According to the invention, the average grain diameter of the prepared rare earth fluoride polishing powder is controlled to be 1.0-2.5 μm.
The invention provides another technical scheme that: the preparation method of the rare earth fluoride polishing solution comprises the step of preparing the rare earth fluoride polishing powder according to the preparation method, and then mixing the prepared rare earth fluoride polishing powder with water to prepare the rare earth fluoride polishing solution, wherein the rare earth fluoride polishing powder accounts for 5-60% of the mass of the rare earth fluoride polishing solution in percentage by mass.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the method creatively adopts ammonium carbonate and ammonium fluoride as modifying reagents, and mixes the modifying reagents and applies the mixing reagents to modify the rare earth raw materials, so that precipitation and fluorination can be synchronously carried out, and the operations of precipitation and fluorination are completed without separating steps, thereby greatly simplifying the process steps; meanwhile, the addition of the amino can also play a role in neutralizing the pH value of the solution, so that the water consumption for regulating the pH value by washing is reduced, a strong alkali substance is not required to be added for regulating the pH value, and the water consumption or the wastewater discharge amount is reduced.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in routine experiments.
In the following, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
Example 1
The embodiment provides a preparation method of rare earth fluoride polishing powder, which comprises the following steps:
(1) dissolving a rare earth raw material (specifically lanthanum cerium carbonate, purchased from baotoxin rare earth) in water and hydrochloric acid (the mass fraction can be 20%, other mass fractions can be adopted in other embodiments, and the actual requirements are met) to prepare a rare earth acid solution, controlling the concentration of the rare earth acid solution to be 100g/L, and controlling the temperature of the rare earth acid solution to be 68 +/-2 ℃;
(2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for 94% and 6% of the total weight of the rare earth in the rare earth acidic solution treated in the step (1) by weight percentage;
(3) dropwise adding the modified solution prepared in the step (2) into the rare earth acidic solution treated in the step (1), keeping the temperature at 68 +/-2 ℃ for reaction, separating out precipitates, washing the separated precipitates with water until the pH value of a cleaning solution obtained after washing with water is about 7 +/-0.3, calcining for 5 hours at 1100 +/-50 ℃, and grinding to obtain powder with the average particle size of 2.0 +/-0.3 mu m and the maximum particle size of less than or equal to 20 mu m, thereby preparing the rare earth fluoride polishing powder;
before separating out the precipitate, after the modification solution is dripped, taking supernatant liquor of the reaction mixed liquor, adding ammonium carbonate, if no precipitate is generated, indicating that the precipitate is complete, if the precipitate is generated, adding ammonium carbonate into the reaction mixed liquor until the precipitate is complete, then preserving heat, and standing and aging for 2 hours.
Example 2
The embodiment provides a preparation method of rare earth fluoride polishing powder, which comprises the following steps:
(1) adding water and hydrochloric acid (the mass fraction of which can be 20%) into a rare earth raw material (specifically, lanthanum cerium carbonate purchased from baoticin rare earth) to dissolve the rare earth raw material to prepare a rare earth acid solution, controlling the concentration of the rare earth acid solution to be 95g/L, and controlling the temperature of the rare earth acid solution to be 68 +/-1 ℃;
(2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for 95% and 6% of the total weight of the rare earth in the rare earth acidic solution treated in the step (1);
(3) dropwise adding the modified solution prepared in the step (2) into the rare earth acidic solution treated in the step (1), keeping the temperature at 68 +/-1 ℃ for reaction, separating out a precipitate, washing the separated precipitate with water until the pH value of a washing liquid obtained after washing with water is about 6.8 +/-0.3, calcining at 1100 +/-30 ℃ for 5 hours, and grinding to obtain powder with the average particle size of 2.2 +/-0.3 mu m and the maximum particle size of less than or equal to 20 mu m, thereby preparing the rare earth fluoride polishing powder;
before separating out the precipitate, after the modification solution is dripped, taking supernatant liquor of the reaction mixed liquor, adding ammonium carbonate, if no precipitate is generated, indicating that the precipitate is complete, if the precipitate is generated, adding ammonium carbonate into the reaction mixed liquor until the precipitate is complete, then preserving heat, and standing and aging for 2 hours.
Example 3
The embodiment provides a preparation method of rare earth fluoride polishing powder, which comprises the following steps:
(1) adding water and nitric acid (the mass fraction of the nitric acid can be 20%) into a rare earth raw material (specifically lanthanum cerium carbonate purchased from baotoxin aventurine) for dissolving to prepare a rare earth acid solution, controlling the concentration of the rare earth acid solution to be 90g/L, and controlling the temperature of the rare earth acid solution to be 68 +/-2 ℃;
(2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for 93 percent and 6 percent of the total weight of the rare earth in the rare earth acidic solution treated in the step (1);
(3) dropwise adding the modified solution prepared in the step (2) into the rare earth acidic solution treated in the step (1), keeping the temperature at 68 +/-2 ℃ for reaction, separating out a precipitate, washing the separated precipitate with water until the pH value of a washing liquid obtained after washing with water is about 7.3 +/-0.3, calcining at 1050 +/-50 ℃ for 5 hours, and grinding to obtain powder with the average particle size of 2.0 +/-0.3 mu m and the maximum particle size of less than or equal to 20 mu m, thereby preparing the rare earth fluoride polishing powder;
before separating out the precipitate, after the modification solution is dripped, taking supernatant liquor of the reaction mixed liquor, adding ammonium carbonate, if no precipitate is generated, indicating that the precipitate is complete, if the precipitate is generated, adding ammonium carbonate into the reaction mixed liquor until the precipitate is complete, then preserving heat, and standing and aging for 2 hours.
Examples of the applications
The polishing powder prepared in examples 1 to 3 was mixed with water to prepare a polishing solution (solid content about 10%) for polishing optical glass, and the specific polishing process was: polishing at a high speed; the results of the specific performance tests are shown in table 1 below.
TABLE 1
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the rare earth fluoride polishing powder is characterized by comprising the following steps:
(1) adding water and acid into a rare earth raw material for dissolving to prepare a rare earth acid solution, and controlling the concentration of the rare earth acid solution to be less than or equal to 100 g/L;
(2) mixing ammonium carbonate and ammonium fluoride to prepare a modified solution, wherein the ammonium carbonate and the ammonium fluoride in the modified solution respectively account for more than 90% and 4-8% of the total weight of the rare earth in the rare earth acidic solution treated in the step (1);
(3) and (3) dropwise adding the modified solution prepared in the step (2) into the rare earth acidic solution treated in the step (1), reacting, separating out precipitate, calcining, and grinding to obtain powder with the maximum particle size of less than or equal to 20 microns, thus obtaining the rare earth fluoride polishing powder.
2. The method for preparing rare earth fluoride polishing powder as claimed in claim 1, wherein in the step (1), the rare earth raw material is rare earth carbonate, and the rare earth carbonate comprises cerium carbonate and/or lanthanum cerium carbonate.
3. The method for preparing rare earth fluoride polishing powder according to claim 1, wherein in the step (1), the acid is one or a combination of more selected from hydrochloric acid, nitric acid and sulfuric acid.
4. The method according to claim 1, wherein in the step (2), the ammonium carbonate and the ammonium fluoride respectively account for more than 93% and 5-7% of the total weight of the rare earth contained in the rare earth acidic solution treated in the step (1).
5. The method of claim 1, wherein the reaction temperature in step (3) is controlled to be 60-75 ℃.
6. The method according to claim 1, wherein in the step (3), before the precipitate is separated, after the modification solution is added dropwise, the supernatant of the reaction mixture is taken, ammonium carbonate is added, if no precipitate is formed, the precipitate is completely precipitated, and if the precipitate is formed, ammonium carbonate is added to the reaction mixture until the precipitate is completely precipitated, and then the reaction mixture is subjected to heat preservation and standing for aging.
7. The method of producing a rare earth fluoride polishing powder as claimed in claim 1, wherein in the step (3), the separated precipitate is washed with water until a pH of a washing liquid obtained after the washing with water is 6 to 9, and then the calcination is carried out.
8. The method as claimed in claim 1, wherein the calcination is performed at 800-1200 ℃ for 3-8h in step (3).
9. The method of claim 1, wherein the average particle size of the rare earth fluoride polishing powder is controlled to be 1.0 to 2.5 μm.
10. A method for preparing rare earth fluoride polishing solution, characterized in that the method comprises the steps of preparing the rare earth fluoride polishing powder according to the preparation method of any one of claims 1 to 9, and then mixing the prepared rare earth fluoride polishing powder with water to prepare the rare earth fluoride polishing solution, wherein the rare earth fluoride polishing powder accounts for 5 to 60 percent of the mass of the rare earth fluoride polishing solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539928A (en) * | 2022-03-16 | 2022-05-27 | 深圳市瑞来稀土材料有限公司 | Rare earth polishing powder for optical glass polishing treatment and preparation method thereof |
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| CN103571335A (en) * | 2013-11-05 | 2014-02-12 | 上海华明高纳稀土新材料有限公司 | Rare earth polishing powder and preparation method thereof |
| CN104387988A (en) * | 2014-10-30 | 2015-03-04 | 包头市金蒙研磨材料有限责任公司 | Preparation method of superfine fluorine-containing cerium-based polishing powder |
| CN104419378A (en) * | 2013-09-06 | 2015-03-18 | 北京有色金属研究总院 | Fluorine doping method of cerium-based rare earth polishing powder |
| CN109111854A (en) * | 2018-08-24 | 2019-01-01 | 甘肃稀土新材料股份有限公司 | A kind of yttrium cerium mischmetal polishing powder and its preparation process |
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- 2019-12-16 CN CN201911291538.1A patent/CN111004580A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104419378A (en) * | 2013-09-06 | 2015-03-18 | 北京有色金属研究总院 | Fluorine doping method of cerium-based rare earth polishing powder |
| CN103571335A (en) * | 2013-11-05 | 2014-02-12 | 上海华明高纳稀土新材料有限公司 | Rare earth polishing powder and preparation method thereof |
| CN104387988A (en) * | 2014-10-30 | 2015-03-04 | 包头市金蒙研磨材料有限责任公司 | Preparation method of superfine fluorine-containing cerium-based polishing powder |
| CN109111854A (en) * | 2018-08-24 | 2019-01-01 | 甘肃稀土新材料股份有限公司 | A kind of yttrium cerium mischmetal polishing powder and its preparation process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539928A (en) * | 2022-03-16 | 2022-05-27 | 深圳市瑞来稀土材料有限公司 | Rare earth polishing powder for optical glass polishing treatment and preparation method thereof |
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Application publication date: 20200414 |