CN115340112A - Preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide - Google Patents
Preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide Download PDFInfo
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- CN115340112A CN115340112A CN202211138487.0A CN202211138487A CN115340112A CN 115340112 A CN115340112 A CN 115340112A CN 202211138487 A CN202211138487 A CN 202211138487A CN 115340112 A CN115340112 A CN 115340112A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F3/00—Compounds of beryllium
- C01F3/02—Oxides; Hydroxides
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Abstract
The invention discloses a preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide, wherein in the preparation process for producing beryllium oxide by a fluorination method, on the basis of producing beryllium oxide, ammonia water and a potassium permanganate solution are added into a first leaching solution, calcium ions and magnesium ions are separated out in the forms of calcium fluoride and magnesium fluoride, manganese elements are separated out in the form of manganese dioxide under the action of potassium permanganate, and silicon dioxide is separated out under the action of ammonia water without complete sintering of sodium hexafluorosilicate, so that a large amount of impurities are removed; and after the beryllium hydroxide precipitate is obtained primarily, removing silicon by concentrated sulfuric acid and bovine serum albumin again, and obtaining refined beryllium hydroxide through complex precipitation, thereby obtaining high-purity beryllium oxide through high-temperature calcination.
Description
Technical Field
The invention relates to the technical field of beryllium oxide preparation, in particular to a preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide.
Background
Beryllium oxide is an oxide of beryllium, is extremely toxic, has a chemical formula of BeO, has amphipathy, and can react with acid and strong base. Beryllium oxide is white powder, has high melting point and is used for alloys, catalysts, refractory materials and the like. Beryllium oxide with a purity of 95% or more is industrial-grade beryllium oxide and is mainly used in industry (for example, as a raw material for producing beryllium copper alloy), beryllium oxide with a purity of 99.5% or more is high-purity beryllium oxide and is mainly used in aviation, electronics, beryllium oxide ceramics and the like, and beryllium oxide with a purity of 99.85 or more is ultrahigh-purity beryllium oxide and is mainly used in military industry. At present, a sulfuric acid method and a fluorination method are two main processes for preparing beryllium oxide at present, and the beryllium oxide prepared by the fluorination method has high recovery rate and is favored. However, the conventional fluorination method can only produce industrial-grade beryllium oxide at the edge, and the purity of the high-purity beryllium oxide is difficult to achieve.
Disclosure of Invention
The invention provides a preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide, which can be used for preparing the high-purity beryllium oxide on the basis of the beryllium raw ore.
The invention is realized by the following technical scheme:
a preparation process for producing high-purity beryllium oxide by using beryllium raw ore comprises the following steps:
s1, crushing and grinding beryllium ores, adding ingredients, and stirring with pure water to prepare a blocky raw material; wherein the ingredients comprise 2.5-3.5 parts by weight and 17 parts by weight of beryllium ore, and the ingredients comprise sodium hexafluorosilicate and sodium carbonate;
s2, sintering and grinding the block raw materials, leaching the powder for multiple times by using pure water, and filtering leaching residues to obtain a first leaching solution;
s3, adding a proper amount of potassium permanganate solution into the first leaching solution, adding ammonia water to adjust the pH value to 8.5-9, boiling and oxidizing for at least 45min, and filtering to obtain a second leaching solution;
s4, adding a proper amount of sodium hydroxide solution into the 1/3 second leaching solution to dissolve the precipitate, heating and boiling, adding the rest 2/3 second leaching solution, adjusting the pH value to 10-11, and filtering to obtain beryllium hydroxide precipitate;
s5, adding concentrated sulfuric acid into the beryllium hydroxide precipitate for dissolving, mixing with bovine gelatin, evaporating at high temperature, adding water, and performing filter pressing;
s6, carrying out complex precipitation on the filtrate obtained in the step S5, and filtering to obtain refined beryllium hydroxide;
and S7, calcining the refined beryllium hydroxide at high temperature to obtain the high-purity beryllium oxide.
Further, the step S5 specifically includes: and (2) mixing the beryllium hydroxide precipitate with water, mixing into slurry, and mixing the beryllium hydroxide precipitate according to the weight ratio of the beryllium hydroxide precipitate: concentrated sulfuric acid is 1:4.5-5, adding concentrated sulfuric acid, stirring for at least 30min, and precipitating according to the weight ratio of beryllium hydroxide: the bovine gelatin is 1: adding bovine gelatin in a weight ratio of 0.008-0.012, heating to dry, adding pure water, and press filtering.
Further, the concentration of the concentrated sulfuric acid is 93-98%.
Further, in step S6, ammonia water is added to adjust the PH value to 3.5-4, the flow rate of the introduced liquid ammonia is 20kg/h under normal pressure, and the complexing agent is EDTA.
Further, the mass ratio of sodium hexafluorosilicate to sodium carbonate is 1.8-2.2:1.
further, the block-shaped raw material is honeycomb-shaped.
In a second aspect, the invention provides high-purity beryllium oxide, which is prepared by the preparation process for producing the high-purity beryllium oxide by using beryllium raw ore, wherein the purity of the high-purity beryllium oxide is greater than or equal to 99.5%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the preparation process of the high-purity beryllium oxide, on the basis of beryllium oxide production by a fluorination method, ammonia water and a potassium permanganate solution are added into a first leaching solution, calcium ions and magnesium ions are separated out in the forms of calcium fluoride and magnesium fluoride, manganese is separated out in the form of manganese dioxide under the action of potassium permanganate, and sodium hexafluorosilicate which is not completely sintered forms silicon dioxide separation under the action of ammonia water, so that a large amount of impurities are removed; and after the beryllium hydroxide precipitate is primarily obtained, removing silicon by concentrated sulfuric acid and bovine gelatin, and obtaining refined beryllium hydroxide through complex precipitation, so that high-purity beryllium oxide is obtained through high-temperature calcination.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
fig. 1 is a flow chart of a preparation process for producing high-purity beryllium oxide from beryllium raw ore according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and the accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limiting the present invention.
Examples
As shown in fig. 1, a preparation process for producing high-purity beryllium oxide by using beryllium raw ore comprises the following steps.
S1, crushing and grinding beryllium ores, adding ingredients, and stirring with pure water to prepare a blocky raw material; the beryllium ore comprises, by weight, 2.5-3.5 parts of ingredients and 17 parts of beryllium ore, wherein the ingredients comprise sodium hexafluorosilicate and sodium carbonate. Here, both sodium hexafluorosilicate and sodium carbonate are added as a powder, and for example, the fineness of sodium hexafluorosilicate and sodium carbonate and the fineness of beryllium ore ground may be 200 mesh or more.
S2, sintering and grinding the block raw materials, leaching the powder for multiple times by using pure water, and filtering leaching residues to obtain a first leaching solution. For example, the number of leaching may be three or more to filter out as much impurities as possible.
And S3, adding a proper amount of potassium permanganate solution into the first leaching solution, adding ammonia water to adjust the pH value to 8.5-9, boiling and oxidizing for at least 45min, and filtering to obtain a second leaching solution. Here, the addition of aqueous ammonia causes the calcium and magnesium ions in the first leach solution to precipitate as calcium fluoride and magnesium fluoride, while the manganese in the first leach solution is manganese ions and MnF 4 2+ By the action of potassium permanganate, mnF 4 2+ Manganese dioxide generated by the reaction is precipitated. Here, the concentration and the amount of the substance of the potassium permanganate solution may be determined based on MnF obtained by analyzing the composition of the first leachate 4 2+ It is also possible to add the potassium permanganate solution in excess on this basis.
S4, adding the 1/3 second leaching solutionAdding a proper amount of sodium hydroxide solution to dissolve the precipitate after precipitation, heating to boil, adding the rest 2/3 of the second leaching solution, adjusting the pH value to 10-11, and filtering to obtain beryllium hydroxide precipitate. Here, beryllium ions are precipitated as beryllium hydroxide by means of a sodium hydroxide solution, and the resulting beryllium hydroxide precipitate is then dissolved as Na when the sodium hydroxide solution is further added 2 BeO 2 Heating to boil, adding the rest of the second leachate, and adjusting the final pH to 10-11, na 2 BeO 2 Gradually hydrolyzing to obtain beryllium hydroxide precipitate.
And S5, adding concentrated sulfuric acid into the beryllium hydroxide precipitate for dissolving, mixing with the bovine gelatin, evaporating to dryness at high temperature, adding water, and performing filter pressing. Here, silicon-containing substances such as silica remaining in the beryllium hydroxide are removed by the bovine jelly.
And S6, carrying out complexing precipitation on the filtrate obtained in the step S5, and filtering to obtain the refined beryllium hydroxide. The fluorine content in the filtrate is higher, and the problem that the aluminum exceeds the standard often exists: F-to-Al in solution 3+ The influence of (2) is directly related to the excessive aluminum in the product quality and Al in the acidic sulfate solution 3+ Will combine with F-to form AlF 6 ] 3- (hexafluoroaluminate), the fluoroaluminium complex is further dissociated with the increase of the pH value, and aluminum and beryllium hydroxide are precipitated together, which seriously affects the product quality. [ AlF 6 ] 3- It is stable in chemical structure, its existence environment is estimated to be acidic, it is not allowed to exist in the form of complex by the regulation of temperature and the appropriate adjustment of complexing time at pH 1-5, it is convenient to combine with aluminum removing reagent directly, or it is allowed to exist in the form of other complex or ion in the solution at pH 5.2-8.5 so as to separate from beryllium hydroxide precipitate.
And S7, calcining the refined beryllium hydroxide at high temperature to obtain high-purity beryllium oxide.
According to the preparation process of the high-purity beryllium oxide, on the basis of beryllium oxide production by a fluorination method, ammonia water and a potassium permanganate solution are added into a first leaching solution, calcium ions and magnesium ions are separated out in the forms of calcium fluoride and magnesium fluoride, manganese is separated out in the form of manganese dioxide under the action of potassium permanganate, and sodium hexafluorosilicate which is not completely sintered forms silicon dioxide separation under the action of ammonia water, so that a large amount of impurities are removed; and after the beryllium hydroxide precipitate is primarily obtained, removing silicon by concentrated sulfuric acid and bovine gelatin, and obtaining refined beryllium hydroxide through complex precipitation, so that high-purity beryllium oxide is obtained through high-temperature calcination.
The measurement data of the components of beryllium oxide obtained by adopting the technical scheme are shown in the following table 1:
TABLE 1
In another embodiment, the step S5 specifically includes: and (3) mixing the beryllium hydroxide precipitate with water, adjusting the mixture into slurry, and mixing the beryllium hydroxide precipitate: concentrated sulfuric acid is 1:4.5-5, adding concentrated sulfuric acid, stirring for at least 30min, and precipitating according to the weight ratio of beryllium hydroxide: the bovine gelatin is 1: adding bovine gelatin in a weight ratio of 0.008-0.012, heating to dry, adding pure water, and press filtering.
In further embodiments, the concentrated sulfuric acid has a concentration of 93-98%.
In another embodiment, in step S6, ammonia is added to adjust the pH to 3.5-4, the flow rate of liquid ammonia is 20kg/h under normal pressure, and the complexing agent is EDTA.
In further examples, the ratio of the amount of sodium hexafluorosilicate to sodium carbonate species is 1.8-2.2:1.
in further embodiments, the feedstock pieces are honeycomb-shaped. By the arrangement, the heating surface of the block raw materials during sintering can be increased, and the sintering is more uniform and sufficient.
In a second aspect, the invention provides high-purity beryllium oxide, which is prepared by the preparation process for producing the high-purity beryllium oxide by using beryllium raw ore, wherein the purity of the high-purity beryllium oxide is greater than or equal to 99.5%.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation process for producing high-purity beryllium oxide by using beryllium raw ore is characterized by comprising the following steps:
s1, crushing and grinding beryllium ores, adding ingredients, and stirring with pure water to prepare a block-shaped raw material; wherein the ingredients comprise 2.5-3.5 parts by weight of beryllium ore and 17 parts by weight of sodium hexafluorosilicate and sodium carbonate;
s2, sintering and grinding the block raw materials, leaching the powder for multiple times by using pure water, and filtering leaching residues to obtain a first leaching solution;
s3, adding a proper amount of potassium permanganate solution into the first leaching solution, adding ammonia water to adjust the pH value to 8.5-9, boiling and oxidizing for at least 45min, and filtering to obtain a second leaching solution;
s4, adding a proper amount of sodium hydroxide solution into the 1/3 second leaching solution to dissolve the precipitate, heating to boil, adding the rest 2/3 second leaching solution, adjusting the pH value of the end point to 10-11, and filtering to obtain beryllium hydroxide precipitate;
s5, adding concentrated sulfuric acid into the beryllium hydroxide precipitate for dissolving, mixing with bovine gelatin, evaporating to dryness at high temperature, adding water, and performing filter pressing;
s6, carrying out complexing precipitation on the filtrate obtained in the step S5, and filtering to obtain refined beryllium hydroxide;
and S7, calcining the refined beryllium hydroxide at high temperature to obtain high-purity beryllium oxide.
2. The process for preparing high-purity beryllium oxide from beryllium raw ore according to claim 1, wherein the step S5 specifically comprises: and (3) mixing the beryllium hydroxide precipitate with water, adjusting the mixture into slurry, and mixing the beryllium hydroxide precipitate: concentrated sulfuric acid is 1:4.5-5, adding concentrated sulfuric acid, stirring for at least 30min, and precipitating according to the weight ratio of beryllium hydroxide: the bovine gelatin is 1: adding bovine gelatin in a weight ratio of 0.008-0.012, heating to dry, adding pure water, and press filtering.
3. The process for preparing high-purity beryllium oxide from beryllium raw ore according to claim 2, wherein the concentration of concentrated sulfuric acid is 93-98%.
4. The process for preparing high-purity beryllium oxide from beryllium raw ore according to claim 1, wherein in step S6, ammonia water is added to adjust the PH value to 3.5-4, the flow of the introduced liquid ammonia is 20kg/h under normal pressure, and the complexing agent is EDTA.
5. The process for preparing high-purity beryllium oxide from beryllium raw ore according to any one of claims 1 to 4, wherein the mass ratio of sodium hexafluorosilicate to sodium carbonate is 1.8-2.2:1.
6. the process for preparing high-purity beryllium oxide from beryllium raw ore according to any one of claims 1 to 4, wherein the raw block material is honeycomb-shaped.
7. The high-purity beryllium oxide is prepared by the preparation process for producing the high-purity beryllium oxide by using beryllium raw ore according to any one of claims 1 to 6, and the purity of the high-purity beryllium oxide is greater than or equal to 99.5%.
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| CN202211138487.0A CN115340112A (en) | 2022-09-19 | 2022-09-19 | Preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide |
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| CN202211138487.0A CN115340112A (en) | 2022-09-19 | 2022-09-19 | Preparation process for producing high-purity beryllium oxide by using beryllium raw ore and high-purity beryllium oxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116966470A (en) * | 2023-07-20 | 2023-10-31 | 中南大学 | Beryllium hyperstable mineralization reagent and method for hyperstable mineralization of dangerous beryllium elements in lithium slag |
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| GB423543A (en) * | 1934-02-06 | 1935-02-04 | Carlo Adamoli | Process for the production of beryllium compounds from beryllium-bearing minerals |
| CN1185486A (en) * | 1996-12-18 | 1998-06-24 | 水口山矿务局第六冶炼厂 | Process for preparing industrial beryllium oxide and mixed rare-earth hydroxy compound by using silicon-beryllium-yttium ore |
| CN1365948A (en) * | 2001-11-16 | 2002-08-28 | 水口山有色金属有限责任公司第六冶炼厂 | Process for preparing industrial beryllium oxide by sulfuric acid method |
| CN103088205A (en) * | 2011-11-02 | 2013-05-08 | 峨眉山市中山铁合金冶炼有限公司 | Beryllium oxide production process |
| CN103663506A (en) * | 2013-12-06 | 2014-03-26 | 富蕴恒盛铍业有限责任公司 | Preparation method for refined beryllium hydroxide and preparation method for reactor-quality metallic beryllium bead from refined beryllium hydroxide |
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- 2022-09-19 CN CN202211138487.0A patent/CN115340112A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB423543A (en) * | 1934-02-06 | 1935-02-04 | Carlo Adamoli | Process for the production of beryllium compounds from beryllium-bearing minerals |
| CN1185486A (en) * | 1996-12-18 | 1998-06-24 | 水口山矿务局第六冶炼厂 | Process for preparing industrial beryllium oxide and mixed rare-earth hydroxy compound by using silicon-beryllium-yttium ore |
| CN1365948A (en) * | 2001-11-16 | 2002-08-28 | 水口山有色金属有限责任公司第六冶炼厂 | Process for preparing industrial beryllium oxide by sulfuric acid method |
| CN103088205A (en) * | 2011-11-02 | 2013-05-08 | 峨眉山市中山铁合金冶炼有限公司 | Beryllium oxide production process |
| CN103663506A (en) * | 2013-12-06 | 2014-03-26 | 富蕴恒盛铍业有限责任公司 | Preparation method for refined beryllium hydroxide and preparation method for reactor-quality metallic beryllium bead from refined beryllium hydroxide |
Non-Patent Citations (1)
| Title |
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| 全俊: "氟化法生产工业氧化铍工艺研究", 湖南有色金属, vol. 27, no. 05, pages 20 - 23 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116966470A (en) * | 2023-07-20 | 2023-10-31 | 中南大学 | Beryllium hyperstable mineralization reagent and method for hyperstable mineralization of dangerous beryllium elements in lithium slag |
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