Method for processing of loparite concentrate

 

The invention relates to the hydrometallurgical processing of ore concentrates, and more particularly to the processing of loparite concentrate and can be used in complex extraction of compounds of titanium, niobium and tantalum. Method for processing of loparite concentrate includes opening of hydrochloric acid with getting chloride solutions, the separation of compounds of titanium, niobium and tantalum compounds from rare earth elements and the subsequent receipt of a solution of fluorides of titanium, niobium and tantalum. While the Department of titanium, niobium and tantalum carry out their extraction from chloride solutions using organic mixtures containing alkylphosphoric acid, and fluoride solutions of these rare metals is produced by Stripping them from the extract with concentrated hydrofluoric acid. The method allows us to simplify the process of dividing the amount of rare metals and rare earth elements. 5 C.p. f-crystals, 1 table.

The invention relates to the hydrometallurgical processing of ore concentrates, and more particularly to the processing of loparite concentrate and can be used in complex extraction of titanium compounds, nocause opening it with concentrated nitric acid to obtain a solution of the nitrates of rare-earth elements and hydrated pulp cake containing oxides of titanium, niobium and tantalum. Then nitrate hydrate slurry cake is diluted with water to 1.5-2 times, cooled, filtered with getting hydrated cake, which is washed from nitric acid solutions of nitrates of rare-earth elements and impurities and dissolved in 40% hydrofluoric acid HF obtaining fluoride solutions of titanium, niobium and tantalum, with subsequent extraction of niobium and tantalum 100% of tributyl phosphate fluoride solution and crystallization of the monohydrate titanylsulphate of VAT residue.

The disadvantages of this method include the need for additional dissolution of hydrated cake to get fluoride solutions of titanium, niobium and tantalum and the associated need for additional operations: diluting the pulp with water, filtering, washing hydrate cake from the nitrates of rare-earth elements and impurities. When the filtration rate of the slurry is low because of the presence of the gel formed from compounds of silicon, the impurity contained in the minerals quartz and aegirine, and released during their decomposition.

More advanced and closest to the claimed method is a method of processing of loparite concentrate his autopsy salt, Kieu acid at atmospheric pressure for 8-10 hours at a temperature of 100-105oC. the Precipitate containing unopened loparite and aegirine, share. From the separated liquid phase of the pulp hydrolysis, subject to certain conditions, are precipitated hydroxides of titanium, niobium and tantalum. The precipitate hydroxides of titanium, niobium and tantalum is separated by filtration from the chlorides of rare earth elements and other impurity metals and elements thoroughly washed. The purified precipitate hydroxides of titanium, niobium and tantalum (hydrated cake) served on dissolution in hydrofluoric acid. The resulting solution contains a mixture formetanate acid titanium, niobium and tantalum. He is referred for extraction separation of titanium, niobium and tantalum using octanol. The result is individual fluoride solutions of titanium, niobium and tantalum. Further, these solutions are sent to individual pyrohydrolysis installation to obtain titanium oxide, niobium and tantalum.

This method is the most perfect and therefore selected as the closest analogue. However, he in obtaining fluoride solutions of titanium, niobium and tantalum is no different from the above analog. Therefore, the disadvantages of this method include the need for additional dissolution hydrate additional operations.

The present invention was used to develop the method for processing of loparite concentrate, in which the extraction of valuable components would be carried out using such reagents and under such conditions that the valuable components were extracted from solutions formed at the opening of loparite concentrate, due to which there is no need to dissolve hydrated cake and concomitant operations, which is the technical result of the claimed invention.

The technical result is achieved by the fact that in the present method of processing of loparite concentrate, including the opening of hydrochloric acid with getting chloride solutions, the separation of compounds of titanium, niobium and tantalum compounds from rare earth elements and the subsequent receipt of a solution of fluorides of titanium, niobium and tantalum, what's new is that the Department of titanium, niobium and tantalum carry out their extraction from chloride solutions using organic mixtures containing alkylphosphoric acid, and fluoride solutions of these rare metals is produced by Stripping them from the extract with concentrated hydrofluoric acid.

The implementation of the method under these conditions Zemelny elements, as well as getting fluoride solutions of titanium, niobium and tantalum, suitable for subsequent efficient processing. Due to this, unlike the prototype, there is no need to dissolve hydrated cake and its operations and, accordingly, is provided to facilitate the method by reducing the number of operations.

New is also that before extraction separation of compounds of titanium (Ti), niobium (Nb) and tantalum (TA) from rare earth elements are cleaned chloride solutions from iron impurities by extraction or adsorption.

The cleaning solutions provides further receiving fluoride solutions of Ti, Nb and TA, practically free from iron impurities that interfere with the production of clean titanium compounds.

Also new is the fact that the extraction of titanium, niobium and tantalum carried out from solutions 5-8 molar (M) hydrochloric acid (Hcl).

The process from solutions of 5-8 M Hcl promotes selective extraction of Ti, Nb and TA from chloride solutions and provides at the same time reducing the consumption of hydrochloric acid on the opening of loparite concentrate.

Also new is the fact that the extraction of titanium, niobium and tantalum from chloride is tributylphosphate (TBP) in an inert diluent.

Application for the extraction of Ti, Nb and TA organic compounds such structure provides a high degree of extraction from a solution of titanium, niobium and tantalum and at the same time a good hydrodynamics of the process.

Also new is the fact that the extraction of titanium, niobium and tantalum from chloride solutions spend an organic mixture containing from 0.6 to 1.2 mol of di-2-ethylhexylamine acid in octanol.

Application for the extraction of Ti, Nb and TA organic compounds such composition also provides a high degree of extraction from a solution of titanium, niobium and tantalum and at the same time a good hydrodynamics of the process and, in addition, contributes to the reduction of pollution reextractors impurities of phosphorus.

Also new is that reextraction titanium, niobium and tantalum spend 40-71% hydrofluoric acid with getting their fluoride solutions containing not less than 200 g/l in terms of the amount of their oxides.

Getting fluoride solutions of Ti, Nb and TA with a concentration of not less than 200 g/l in terms of the amount of their oxides provides carrying out the subsequent separation of these elements in fluoride media without prior podarki solutions.

The inventive method is carried out as follows.

Loparite the om paramasivan and temperatures below 100oTo his complete decomposition to obtain the combined solution of chlorides of rare metals titanium, niobium and tantalum chlorides of rare earth elements and inevitable impurities, such as iron impurities. The specific parameters of the process of opening loparite concentrate hydrochloric acid, developed by the applicant shall be subject to a separate application for the invention, therefore, in this application they are not.

After opening loparite concentrate spend cleaning chloride solution from the iron by solvent extraction or adsorption of iron using reagents from among neutral oxygen-containing extractants, such as aliphatic alcohols, tributyl phosphate; or anion-exchange extractants - secondary or tertiary amines in diluents; or the sorption of iron on the anion exchange resin, such as the brand of AMP. The cleaning solutions provides further receiving fluoride solutions of Ti, Nb and TA, practically free from iron impurities that interfere with the production of clean titanium compounds.

In a purified from the iron chloride solution containing 5-8 M Hcl , introducing organic reagent containing 0.6 to 1.2 M di-2 ethylhexylamine acid (D2EGFK) in the diluent and proposesthat using concentrated 40-71% hydrofluoric acid HF, This way, fluoride solutions containing at least 200 g/l by the sum of the oxides of Ti, Nb and TA, suitable for subsequent selective extraction of fluoride, niobium and tantalum without prior evaporation.

Using as extractant di-2-ethylhexylamine acid of a concentration higher than 1.2 M in diluent increases the viscosity of the organic solution and, consequently, to reduce the hydrodynamic characteristics of the process (to reduce the speed and separation).

When using organic gas concentration D2EGFK < 0.6 M decreases the extraction of titanium, niobium and tantalum in the organic phase due to the lower capacity of the used extractant, which requires a significant increase of the flows of organic and aqueous phases (a:) in the extraction step.

The introduction of tributyl phosphate TBP in the organic solution in the amount of 0.18-0,37 M allows you to remove the film on the phase boundary, resulting in extraction systems based on alkylphosphoric acids and increase the speed of separation of phases. The increase in the content of TBP in the mixture > 0,37 M has no significant impact on the process of separation of phases, and a decrease in the content TBP < 0.18 M increases the breaking time. Introduction to the organization is of use both as a modifier, to remove the film on the phase boundary and to achieve almost instantaneous separation of phases.

The decrease in the initial solution concentration model HC1 < 5 M is undesirable because of the instability of such solutions is caused by the hydrolysis of titanium, niobium and tantalum. In addition, when the concentration of Hcl < 5 M there is coextracted REE in the organic phase.

The high concentration of Hcl > 8 M does not reduce the extraction of characteristics of the process, but it is undesirable because of the reduction of the environmental parameters of the process, because concentrated Hcl fumes in the air due to vapor emissions of gaseous hydrogen chloride.

Use on stage Stripping 40-71% concentrated HF is determined by the concentrations produced in industrial scale HFconc.different brands. Reduction of the concentration of HF leads to incomplete extraction of titanium, niobium and tantalum fluoride in the solution due to the scarcity of F-ion required for binding of titanium, niobium and tantalum in a solid fluoride complexes.

Further processing of the concentrated metal fluoride reextractors carried out by known methods, for example by selective extraction of aliphatic alcohols, in particular - octanol.

lankily solution with a concentration of 5 M Hcl, received in the opening means of hydrochloric acid loparite concentrate, containing (g/l): Nb2About5- 5,0; Tio2- 30,0; Ta2O5to 0.3; Fe2About3to 1.4; the amount of oxides REE - 25,1, enter the extractant - TBP and carry out extraction cleaning chloride solution from the iron when the ratio of organic and aqueous phase A:B=1:10. Separate organic and aqueous phase. The residual content of Fe2About3the solution is 0.003 g/l In solution, free from iron, enter the extractant containing 0.6 M D2EGFK and 0.18 M TBP in an inert diluent, and carry out the extraction of titanium, niobium and tantalum when the ratio of organic and aqueous phase A: B= 1:1. Separate organic and aqueous phase. Coextracted REE in the organic phase is less than 1%.

The organic phase containing rare metals, introducing a solution of 40% HF and carry out their reextraction when the ratio of phase a:=5:1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%): Nb2About5- 98,8; TiO2- 98,7; Ta2O5at 99.1. The total concentration of oxides of rare metals in fluoride solution of 200 g/L. the Main parameters of the Department of titanium, niobium and tantalum from redkozemelami the present method, and Examples 5-6 from beyond the values given in the table.

Example 2. In hydrochloric acid solution with a concentration of 6 M Hcl, the resulting opening means of hydrochloric acid loparite concentrate, containing (g/l): Nb2O5- 6,7; TiO2- 48,8; Ta2O5to 0.5; Fe2About3- 1.6 and the amount of oxides REE - 43,4, enter the extractant - octanol and carry out extraction cleaning chloride solution from the iron when the ratio of organic and aqueous phase A:B=1:5. Separate organic and aqueous phase. The residual content of Fe2About3the solution is 0.002 g/l In solution, free from iron, enter the extractant containing 0.9 M D2EGFK in octanol, and carry out the extraction of titanium, niobium and tantalum when the ratio of organic and aqueous phase A:B=1:1. Separate organic and aqueous phase. Coextracted REE in the organic phase is less than 1%.

The organic phase containing rare metals, introducing a solution of 50% HF and are reextraction rare metals at a ratio of phase a:=5:1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%): Nb2O5- 99,4; TiO2- 99,6; Ta2O5- 99,6. The total concentration is concentratie 8 M Hcl, received in the opening means of hydrochloric acid loparite concentrate, containing (g/l): Nb2About5- 25,1; TiO2- 79,8; TA2O5- 2,0; Fe2O3to 1.9; the amount of oxides REE - 72,2, is passed through the sorption column containing anion exchange resin, such as the brand of AMP. The residual content of Fe2About3the solution is 0.0002 g/l In solution, free from iron, enter the extractant containing 1.2 M D2EGFK and 0.37 M TBP in an inert diluent, and carry out the extraction of titanium, niobium and tantalum when the ratio of organic and aqueous phase a:=a 2.2:1. Separate organic and aqueous phase. Coextracted REE in the organic phase is less than 1%.

The organic phase containing rare metals, introducing a solution of 50% HF and are reextraction rare metals at a ratio of phase a:=5:1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%): Nb2About5- 99,0; Tio2- 99,3; TA2O5with 97.1. The total concentration of oxides of rare metals in fluoride solution is 250 g/L.

Example 4. In hydrochloric acid solution composition as in example 1, enter the extractant, containing 20% of a secondary amine in an inert diluent and exercise are organic and aqueous phase. The residual content of Fe2About3the solution is 0.0004 g/l In solution, free from iron, enter the extractant containing 1.0 M D2EGFK and 0.26 M TBP in an inert diluent, and carry out the extraction of titanium, niobium and tantalum when the ratio of organic and aqueous phase A:B=1:1. Separate organic and aqueous phase. Coextracted REE in the organic phase is less than 1%.

The organic phase containing rare metals, introducing a solution of 70% HF and are reextraction rare elements in the correlation of phases A:B=10: 1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%): Nb2O5- 99,4; TiO22 - 99,7; TA2O5- 99,5. The total concentration of oxides of rare metals in fluoride solution of 350 g/L.

Example 5. In hydrochloric acid solution composition as in example 2, enter the extractant containing 20% of tertiary amine in tributylphosphate and carry out extraction cleaning chloride solution from the iron when the ratio of organic and aqueous phase A:B=1:10. Separate organic and aqueous phase. The residual content of Fe2About3the solution is 0.003 g/l In solution, free from iron, enter the extractant containing 0.5 M DEGF the political and aqueous phase A:B=1:1, Separate organic and aqueous phase. Sexcrazy REE in the organic phase is less than 1%.

The organic phase containing rare metals, introducing a solution of 50% HF and are reextraction when the ratio of phase a:=5:1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%); Nb2O5- 75,4; TiO2- 68,8; TA3About5- 70,1. The total concentration of oxides of rare metals in fluoride solution is 156 g/L.

Example 6. In hydrochloric acid solution with a concentration of 4 M Hcl obtained by means of hydrochloric acid of opening loparite concentrate, containing (g/l): Nb2O5- 4,8; TiO2- 23,4; TA2O5to 0.2, Fe2About3to 1.3, the amount of oxides REE - 20,5 , enter the extractant containing 20% of tertiary amine in octanol, and perform extraction cleaning chloride solution from the iron when the ratio of organic and aqueous phase A:B=1:10. Separate organic and aqueous phase. The residual content of Fe2About3the solution is 0.004 g/L.

In solution, free from iron, enter the extractant containing 0.6 M D2EGFK in octanol, and carry out the extraction of titanium, niobium and tantalum when the ratio of organic and aq the organic phase, containing rare metals, introducing a solution of 40% HF and are reextraction when the ratio of phase a:=5:1. Separate organic and aqueous phase. The degree of extraction in fluoride solution from the source is (%): Nb2O5reached 98.9; TiO2- 98,5; TA2O5- 99,0. The total concentration of oxides of rare metals in fluoride solution is 139 g/L.

From the specific embodiments of the claimed invention for any specialist in this field are obvious possibilities for its realization with the simultaneous solution of the set task. However it is also clear that the invention can be made small changes, but which will not exceed the scope of the invention defined by the following claims.

The inventive method is easy to implement. It allows, in comparison with the prototype, to simplify the process of dividing the amount of rare metals and rare earth elements, making it in the solution obtained after opening means of hydrochloric acid loparite concentrate. This allows you to exclude the operation of dissolution of loparite concentrate and related operations. The method allows to obtain purified the x oxides, suitable for further extraction processing without prior evaporation.

Claims

1. Method for processing of loparite concentrate, including the opening of hydrochloric acid with getting chloride solutions, the separation of compounds of titanium, niobium and tantalum compounds from rare earth elements and the subsequent receipt of a solution of fluorides of titanium, niobium and tantalum, wherein the separation of titanium, niobium and tantalum carry out their extraction from chloride solutions using organic mixtures containing alkylphosphoric acid, and fluoride solutions of these rare metals is produced by Stripping them from the extract with concentrated hydrofluoric acid.

2. The method according to p. 1, characterized in that before the extraction of the Department of compounds of titanium, niobium and tantalum from rare earth elements are cleaned chloride solutions from iron impurities by extraction or adsorption.

3. The method according to p. 1 or 2, characterized in that the extraction of titanium, niobium and tantalum carried out from solutions 5-8 molar hydrochloric acid.

4. The method according to any of paragraphs. 1-3, characterized in that the extraction of titanium, niobium and tantalum from chloridi is tributylphosphate in an inert diluent.

5. The method according to any of paragraphs. 1-3, characterized in that the extraction of titanium, niobium and tantalum from chloride solutions spend an organic mixture containing from 0.6 to 1.2 mol of di-2-ethylhexylamine acid in octanol.

6. The method according to any of paragraphs. 1-5, characterized in that reextraction titanium, niobium and tantalum spend 40-71% hydrofluoric acid with getting their fluoride solutions containing not less than 200 g/l in terms of the amount of their oxides.

 

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