The method of extraction of cerium (options)

 

(57) Abstract:

The invention proposes a method of recovery of cerium increased its output from fluoride containing ores, such as the latest. The ore is disintegrated, made red-hot and leached using diluted hydrochloric acid for the formation of ore concentrate. The concentrate is treated with a solution of hydrochloric and boric acid for dissolving cerium and conversion of the fluoride ion tetrafluoroborate. Tetrafluoroborate is removed from the solution, for example by sedimentation, and the solution is subjected to further processing for recovery of cerium. Due to the removal of tetrafluoroborate to prevent loss of cerium in the form of insoluble tetrafluoroborate cerium during the specified additional processing. 7 C. and 49 C.p. f-crystals.

The invention relates to metallurgy, and in particular to methods for rare-earth metals, and can be used in the processing of fluorine-containing cerium ore.

The main source of rare earth metals is a mineral latest, representing a mixture of florocarbon lanthanides. The latest processing involves operations of grinding, flotation, roasting and leaching, which allows the RA to perform the selection of the pure cerium.

There is a method of extraction of cerium fluoride-containing ores [1], which includes contacting the crushed ore with a leaching solution containing a strong acid and an additive in the form of a source of Floriana. Also known is a method of processing the latest [2], which includes contacting the solid material obtained from the latest by roasting and leaching of impurities and containing cerium ions and fluorine, with a solution of a strong acid, followed by separation of the solution of the lanthanides, including cerium. The disadvantage of this method should recognize the low yield of cerium.

The technical objective is to develop a new highly effective method of extraction of cerium. The technical result obtained as a result of implementation of the method is to increase the yield of cerium in the processing of fluoride containing mixtures.

To obtain the technical result of the cerium oxide process leach solution containing a strong acid and a fluorine-containing additive, and leaching solution further contains a boron-containing additive to form a leachate containing cerium. In the case of treatment of a mixture of cerium oxide and fluoride of cerium leaching solution contains St hydrochloric acid. When processing the latest solid concentrate, derived from the latest and containing cerium ions and fluorine, are treated with a solution of a strong acid containing boron compounds are able to bind ions of fluorine to obtain a solution containing cerium ions and the reaction product of compounds of boron and fluoride ion.

During the processing of leach solutions containing soluble compounds of boron, is the binding of fluoride ion tetrafluoroborate that catalyze the solubility of cerium oxide. The insoluble residue depleted cerium, can be removed and enriched in cerium solution is subjected to further processing, aimed, in particular, to the removal of tetrafluoroborate. The removal may be effected by the introduction into the solution of potassium ions, which causes the precipitation of insoluble tetrafluoroborate potassium, which is separated from the solution. Enriched in cerium and depleted fluoride solution is treated with traditional methods of recovery of cerium.

Mineral latest contains 5 to 8 (usually around 6) wt.% rare earth elements (in terms of oxide of lanthanum). In the processing of the ore crushed to particle size of 1 to 100 μm, mostly 5 - 25 µm. Milled ore platinuum, poet expose the first acid leaching action of dilute hydrochloric acid (pH of about 1.0) for partial removal of the concentrate alkaline earth metals. This allows you to improve the content of oxides of rare earth metals, about 70 wt.% . Rich concentrate is calcined in air at a temperature of 400 - 800oC. When the cerium goes in the tetravalent state, and the residual alkaline earth metals pass into oxides. The calcined ore is re-treated with acidic solution, and is used mainly hydrochloric acid of 0.1 - 0.5 N, in particular about 0.2 N, which leads to the removal of residual alkaline earth metals and the separation of cerium oxide other oxides of rare earth metals. The main part of the cerium remains in the form of insoluble concentrate, and a smaller part in the form of a solution goes to the solvent extraction. Insoluble cerium concentrate typically contains a cerium oxide and a fluoride of cerium (in particular, fluoride cerium (II) fluoride cerium (IV) and fluoride hydrate of cerium (IV)), as well as impurities such as iron, thorium, alkaline earth elements, lead and calcium. Then the concentrate is treated with a concentrated solution of a strong acid, to which was added boron compound, in particular boric acid. The boron compound should be capable of interacting with fluorides to form a soluble complex compounds of boron that the resulting perborate (in particular, tetrafluoroborate) catalyzes the process of dissolution of cerium oxide in a solution of a strong acid. The content of perborate should be at least 0.05 M on one mol of cerium oxide, and mostly not less than 0.1 M per one mol of cerium oxide. Perborate should contain at least about 0.1 mole of boron per 4 mol of fluorine present in the cerium concentrate, preferably about 0.5 mol of boron to 4 mol of fluorine. It is more preferable to use the ratio of boron to fluorine as 1 : 4, more preferably 2 : 4, but not more than 4 : 4. When this is dissolved at least 10 wt.%, more preferably at least 25 wt.%, and even more preferably at least 50 wt. % of all those present in the concentrate fluoride cerium. As boron compounds, it is preferable to use boric acid and its salts, in particular potassium borate and sodium borate, while the use of borates is necessary to use a mineral acid. Typically, the ratio of atoms of cerium oxide to atoms of cerium fluoride is 1 : 9 to 9 : 1, preferably 1 : 5 to 5 : 1, more preferably 1 : 2 to 2 : 1. In cerium concentrate it usually is 1 : 1.

In the implementation of a solid mixture usually crushed to particle size of neenie 2 - 3 h to a suspension add the required amount of concentrated hydrochloric acid. Originally leaching acid solution contains at least 50 wt.% hydrochloric acid, predominantly at least 60 wt.%, more preferably at least 70 wt.% usually not more than 85 wt.%, preferably not more than 80 wt.%. The leaching process can proceed at any temperature ranging from 20oC to the boiling temperature of the liquid. It is preferable to use a temperature of 40 -90oC, mostly 50 - 80oC, even more preferably 60 to 70oC, for example, 65oC. the Leaching is carried out under stirring for 3 to 12 hours, mostly 5 - 9 p.m. At the completion of the leaching solution should be a sufficient amount of hydrochloric acid to prevent precipitation from a solution of cerium compounds. The solution should contain hydrochloric acid in an amount of about 4N.

In another embodiment of the method, the solution containing ions of cerium and tetrafluoroborate, treated in this way to remove from solution only ions tetrafluoroborate. This may increase the pH value of the solution for the rapid deposition of impurities without concomitant osazuwa with ion tetrafluoroborate insoluble precipitate. To do this usually use acid-soluble potassium compounds, in particular potassium salts of strong acids. It is preferable to use potassium chloride. The potassium salt is added in an amount to provide removal from a solution of at least 25%, mostly at least 40%, and most preferably 60%. Mainly add enough potassium compounds to provide at least 0.5 mol of potassium, and more preferably at least 1 mole of potassium per mole of boron present in the solution.

The connection of potassium can be added at any stage of leaching. Mostly it is added to the beginning of the process.

It is desirable to maximize the concentration of cerium ions in the leaching solution. But in the leaching solution of cerium concentrate, obtained by treatment of the latest, the concentration of cerium ions should be maintained at a relatively low level not exceeding 60 g/l of cerium per liter of solution. However, the introduction of potassium ions in the solution at the beginning of the leaching allows you to bring the concentration of cerium ions in the solution to a content of at least 90 g/l, mostly at least 120 g/l, and most preferably at mi filtering. The purified solution is treated by known methods to identify cerium. For example, the solution can be processed to obtain a solid carbonate, cerium, similarly to spend processing solutions leaching latest hydrochloric acid. In particular, the pH of the solution significantly increased until precipitation of iron salts, for example the pH is brought to a value of 2.6 use of alkali, such as sodium hydroxide. The solution is filtered and added soluble sulfide, in particular acidic sodium sulfide, which causes the precipitation of lead sulfide. The solution is again filtered. Then increase the acidity of the solution, preferably to a pH of 1.0 and added slowly soluble carbonate, predominantly carbonate of an alkali metal such as sodium carbonate. When this occurs, the allocation of cerium carbonate, which is removed, in particular by filtration on a continuous belt filter. Adding carbonate of an alkali metal stop to start the selection in the precipitate of impurities. This usually occurs when the pH of the solution exceeds a magnitude of 4.9. The cerium carbonate is removed from the filter and dried. The precipitate contains at least about 90% pure substances, mainly at least the s cerium in the latest and at least one compound of fluorine in the latest. Material process leach solution containing concentrated hydrochloric acid, the desired compound of boron and a source of potassium ions. The material may include burnt and unburnt (original) bastnasite and leftovers from previous stages of processing, cerium compounds and fluorides. The compound of cerium can be represented by an oxide or carbonate. As fluoride can be used fluoride cerium.

Example. Suspension of 24.5 g of cerium concentrate and 4.6 g of boric acid in 99 ml of water was heated to 70oC. In the heated suspension for 2 h was added 105 ml of concentrated hydrochloric acid. The suspension was passed in the 70oC for 2.5 h and then the solid fraction was removed by filtration. To the filtrate was added 5.6 g of potassium chloride dissolved in water. Tetrafluoroborate potassium was removed by filtration. To the filtrate was added hydrochloric sodium to a pH of 2.6 to remove iron. The resulting solution was processed in order to obtain cerium carbonate. The output amounted to approximately 82% of the total content of cerium concentrate.

1. The method of extraction of cerium oxide cerium, including the processing of cerium oxide leach solution containing a strong acid and a fluorine-containing additive, from the products of leaching, containing dissolved cerium.

2. The method according to p. 1, characterized in that after treatment with cerium oxide leach solution in the solution impose additional source of potassium ions.

3. The method according to p. 1, characterized in that use leachate solution containing 50-85 wt.% of hydrochloric acid.

4. The method according to p. 1, characterized in that the processing of the leach solution is carried out at 40-90oC.

5. The method according to p. 1, characterized in that the processing of the leach solution is carried out at 60-90oC.

6. The method according to p. 1, wherein the used washing solution containing the fluoride ion, the resulting leaching, and a compound selected from the group of boric acid or its compounds.

7. The method according to p. 6, characterized in that use one of the forms of perborate.

8. The method according to p. 7, characterized in that use a form of perborate not less than 1 mol per 1 mol of cerium oxide.

9. The method according to p. 7, characterized in that use a form of perborate in the amount of not less than 0.5 mol per 1 mol of cerium oxide.

10. The method according to p. 6, characterized in that use ions tetrafluoroborate.

11. How WPI is living solution containing a strong acid and a boron compound capable of reacting with fluoride.

12. The method according to p. 11, characterized in that it further after processing leaching solution in the solution is injected source of potassium ions.

13. The method according to p. 11, wherein the boron compound is chosen from the group consisting of boric acid and its salts.

14. The method according to p. 11, characterized in that the mixture contains fluoride cerium.

15. The method according to p. 11, wherein the leaching solution contains not more than 50-85 wt.% of hydrochloric acid.

16. The method according to p. 11, characterized in that the content of boron compounds is not more than 4 mol of boron to 4 mol of fluoride.

17. The method according to p. 11, characterized in that the content of boron compounds is 1 mol of boron to 4 mol of fluoride.

18. The method according to p. 11, characterized in that the content of boron compounds is 2 mol of boron to 4 mol of fluoride.

19. The method according to p. 11, characterized in that the reaction is carried out in conditions that lead to the award of one of the forms of perborate.

20. The method according to p. 11, characterized in that the reaction is carried out under conditions leading to the ion tetrafluoroborate.

21. The method of extraction of cerium from the MCA which contains hydrochloric acid and boron compounds able to react with fluoride with the formation of soluble compounds of cerium with one of the forms of perborate.

22. The method according to p. 21, wherein after the processing of leach solution in the solution impose additional source of potassium ions.

23. The method according to p. 21, wherein the boron compound is chosen from the group consisting of boric acid and its salts.

24. The method according to p. 21, characterized in that the boron compounds enter in the quantity, ensure the receipt of the ratio of boron and fluorine, at least about 1:4.

25. The method according to p. 21, characterized in that the boron compounds enter in the quantity, ensure the receipt of the ratio of boron and fluorine, at least about 1:2.

26. The method according to p. 21, characterized in that after leaching from the solution remove perborate.

27. The method according to p. 26, characterized in that the solution after leaching contains about 90 g/l soluble form of cerium.

28. The method according to p. 26, characterized in that the solution after leaching contains about 120 g/l soluble form of cerium.

29. The method according to p. 26, characterized in that the solution after leaching contains about 150 g/l soluble form of cerium.

30. The way of the future in the original mixture.

31. The method according to p. 26, characterized in that the solution after leaching contains at least about 80% of the cerium present in the original mixture.

32. The method according to p. 26, characterized in that the solution after leaching contains at least about 90% of the cerium present in the original mixture.

33. The method according to any of paragraphs. 22 and 26, characterized in that the removal of perborate carried out by introducing into the solution an ion source of potassium.

34. The method according to p. 21, wherein the initial mixture contains at least about 30% of cerium in terms of cerium oxide and at least 5% of fluoride.

35. The method according to p. 21, wherein the initial mixture contains at least about 45% of cerium in terms of cerium oxide and not less than 7.5% of fluoride.

36. The method according to p. 21, wherein the initial mixture contains at least about 60% of cerium in terms of cerium oxide and at least 10% of fluoride.

37. The method of extraction of cerium from the latest, including the treatment of solid concentrate, derived from the latest and containing ions of cerium fluoride, a strong acid, wherein the treatment is carried out with the introduction of the boron compounds able to react with the specified ion fluoride with obrazovano by p. 37, characterized in that in the solution after treatment in a strong acid impose additional source of potassium ions.

39. The method according to p. 37, characterized in that use hydrochloric acid.

40. The method according to p. 37, characterized in that use sulfuric acid.

41. The method according to p. 37, characterized in that the nitric acid.

42. The method according to p. 37, characterized in that the concentrate contains the oxide and fluoride of cerium.

43. The method according to p. 37, characterized in that the boron compounds is administered in an amount to provide a ratio of boron and fluorine, at least about 1:4.

44. The method of extraction of cerium from the latest, including the calcination of finely latest in the presence of oxygen, the processing of calcined latest diluted acid to obtain a solution of alkaline earth component and a solid residue containing cerium and fluorine, and treatment of the solid residue more concentrated acid, characterized in that the second treatment is carried out with a solution of hydrochloric acid containing a boron compound selected from the group consisting of boric acid and its salts, to obtain the solution containing the soluble form of cerium and one form of perborate.

46. The method according to p. 44, characterized in that the hydrochloric acid solution is added potassium ions in a quantity sufficient to precipitate tetrafluoroborate-ion battery.

47. The method according to p. 46, characterized in that the solution contains at least about 70% of cerium present in the solid residue.

48. The method according to p. 46, characterized in that the solution contains at least about 80% of the cerium present in the solid residue.

49. The method according to p. 46, characterized in that the solution contains at least about 90% of the cerium present in the solid residue.

50. The method according to p. 44, characterized in that the treatment with hydrochloric acid is carried out at 40-90oC.

51. The method according to p. 44, characterized in that the treatment with hydrochloric acid is carried out at 50-80oC.

52. The method according to p. 44, characterized in that the treatment with hydrochloric acid is carried out at 60-70oC.

53. The method according to p. 44, wherein the boron compound is administered in an amount to provide a ratio of boron and fluoride solid precipitate at least about 1:4.

54. The method according to p. 44, wherein the boron compound is administered in an amount to provide a ratio of boron and fluoride TWA processing solid strong acid, characterized in that the solid substance use fluoride cerium, and the treatment is carried out with a solution of a strong acid with addition of boric acid or its salts with the formation of a solution containing cerium ions, and one of the forms of perborate, and the resulting solution is treated with a soluble compound with potassium deposition of tetrafluoroborate potassium and sludge separation.

56. The method of extraction of cerium from the solution, wherein the solution containing cerium ions and form perborate injected soluble compound of potassium, followed by deposition of tetrafluoroborate potassium and sludge separation.

 

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FIELD: ear-earth element compounds, in particular cerium dioxide.

SUBSTANCE: invention relates to simplified method for production of cerium dioxide having high specific surface useful for catalyst preparation. Method includes blending of (mass %) cerium carbonate 44-58; ammonia acetate 25-34; and water 14-25. Obtained mixture is dried in air and baked at 7000C.

EFFECT: simplified method for production of cerium dioxide.

2 cl, 1 tbl, 1 ex

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