The method of producing refractory oxides of metals of loparite concentrate

 

(57) Abstract:

The invention relates to the hydrometallurgical processing of ore concentrates, and more particularly to the processing of loparite concentrate. The method of producing refractory oxides of metals of loparite concentrate includes grinding of the concentrate to the size of particles of at least 0.075 mm classification, opening loparite concentrate concentrated nitric acid at atmospheric pressure and temperatures above 100C, the formation of the products autopsy concentrate fluoride compounds tantalum and niobium under the influence of hydrofluoric acid and extraction with tributyl phosphate. The formation of fluoride compounds tantalum and niobium ensure dissolution of hydrofluoric acid with a concentration of at least 40% hydrated oxide oxides of refractory metals, resulting from the opening of loparite concentrate concentrated nitric acid, with simultaneous formation as a result, the fluorine-Titanic acid. After extraction of tantalum and niobium extraction are oparka of raffinate 1.5-2.0 times at 105-108C, then the extraction of hydrofluoric acid by distillation using koncentrirane the Atka vykristallizovyvalas the titanyl sulphate monohydrate, from which they receive the finished product in the form of titanium dioxide, and the remaining mother liquor containing concentrated sulfuric acid to return into circulation for the extraction of hydrofluoric acid from one stripped off of the raffinate. The method allows to simplify the technology, improve its efficiency and effectiveness. 1 C.p. f-crystals, 2 tab.

The invention relates to the hydrometallurgical processing of ore concentrates, and more particularly to the processing of loparite concentrate.

Loparite concentrate is a complex raw material containing oxides of a large number of chemical elements. Used for processing of loparite concentrate brand CL-1 with the contents of loparite at least 95% in accordance with the applicable specifications contains, wt%: the oxide of tantalum (Ta2O5) - 0,57; the oxide of niobium (Nb2O5) - 8,14; titanium oxide (TiO2) - 38,1; oxides of rare earth metals cerium group, mainly oxides of lanthanum (La2O3), cerium oxide (Ce2O3) oxide, praseodymium (Pr2O3), neodymium oxide (Nd2O3) - 32; sodium oxide (Na2O) - 7,9-9,06; calcium oxide (CaO) - 4,2-5,7; strontium oxide (SrO) - 2,3-3,0; iron oxide (Fe2O3) - 2.0 to 2.5; the silicon oxide O5) - 0.15 to 0.22 and a source of alpha radiation - thorium oxide (ThO2) - 0,54.

From loparite concentrate extract the most valuable oxides of tantalum, niobium, titanium, and less valuable rare-earth metal oxides. This application for the recovery of oxides of refractory metals tantalum, niobium and titanium.

Up to the present time have been known and used two methods of processing of loparite concentrate, producing oxides of refractory metals, referred to as specialists of chlorine and sulfuric acid technologies.

Getting oxides of refractory metals by processing of loparite concentrate the chlorination is more simple from a technological point of view (see A. N. Zelikman and other "metallurgy of rare metals), metallurgy, 1991, S. 95-100). Its essence is that loparite concentrate previously subjected to dry grinding and mixed with coke. The mixture is exposed to 100% drained gaseous chlorine at 950-1050oC. differences in the volatility of the resulting chlorides components loparite concentrate allow you to split it on the main valuable components.

Chlorine technology of processing of loparite ptx2">

However, chlorine technology is very dangerous and harmful for operating personnel and the environment due to the applied large quantities of chlorine, and therefore today it is absolutely not acceptable for use with the point of view of environmental safety.

Safer and the closest analogue of the claimed invention is a method for oxides of refractory metals by processing of loparite concentrate using concentrated sulfuric acid for the opening of loparite (see A. N. Zelikman and other "metallurgy of rare metals), metallurgy, 1991, S. 101, 103-105).

This method is based on the decomposition of loparite concentrate with sulfuric acid and separating valuable components using differences in solubility of double sulfates of titanium, niobium and tantalum, rare earth elements with sulfates of alkali metals or ammonium. Source loparite concentrate is ground to a particle size of not less than 0.075 mm and subjected to classification. The opening of the concentrate is carried out using 95% sulfuric acid, spent based 2,78 t 1 t powdered concentrate. To prevent sintering of the reacting mass and improve recovery solution n the flow at a temperature reaching 270-280oC, niobium and tantalum in the presence of large quantities of titanium are part of the double sulfates of titanium in the form of isomorphic admixture. Rare earth elements are part of the double sulphates REE R2(SO4)3(NH4)2SO4. Product sulfatization - sulfate spec subjected to water leaching. As a result, in the solid phase remain double sulphates REE, and in the liquid phase remains sulfuric acid solution of titanium, niobium and tantalum. In this activity, due to the presence of loparite source of alpha-emitting thorium Th and mesochori MsTh, is divided between the solid and liquid phases by 50%. Removing oxides of refractory metals from their sulfate solution begins with the separation of titanium from niobium and tantalum. For the separation of titanium from niobium and tantalum using precipitation with ammonium sulfate soluble titanium salt (NH4)2TiO(SO4)2H2O). Bicrystalline the titanyl sulphate monohydrate carried out by heating VAT residue acute ferry to 140-150oC and shutter speed while moving it in a continuous stream over the 5.5 to 6.0 hours Under the influence of steam in addition to heating dilutes the pulp VAT residue 25-30% is lastnosti iron, remain in the solution, and the crystals have good filterability and otseivaemogo. Crystals STM is separated for further processing. In the processing of the crystals of the titanyl sulphate monohydrate is dissolved in water and neutralized with ammonia NH4OH. As a result, the sediment falls titanium hydroxide Ti(OH)4. Then perform filtering, washing and Stripping of the precipitate of titanium hydroxide. Then carry out the drying of the titanium hydroxide and calcining at a temperature of t=900-950oC. the result is titanium dioxide TiO2in rutile form, which is a ready-made product and is used as a pigment in paint industry and as a catalyst for the purification of gas emissions CHP. The remaining mother liquor contains concentrated sulfuric acid with a concentration of C=1200-1300 g/l and above the rest of HF. Sulfuric acid return for processing one stripped off of the raffinate with the HF Stripping. Return sulfuric acid is called current and is about 76% (38000 tons/year) from the total number of used sulfuric acid (50500 t/g). Updated warehouse volume of sulfuric acid is about 24% (12500 tons/year). Thanks to the release of titanium in the form of titanyl sulphate monohydrate turnover is their titanium is at least 95%.

Njezavisimij the method is illustrated by the concrete example of its implementation.

Reworked the way the nitrate opening 1000 kg loparite concentrate brand CL-1 of the above structure.

The opening of the concentrate was carried out under the following conditions.

1. After the initial wet grinding concentrate > 95% of the particles have a particle size of not more than 0,074 mm

2. The solid content in the pulp opening - 600 g/L.

3. Initial concentration of nitric acid - 700 g/l

4. Temperature autopsy - 115-118oC.

5. Autopsy - 40 p.m.

6. Intensive mixing with a mechanical stirrer (speed n= 200-220 rpm).

At the opening of loparite concentrate was consumed:

1. Nitric acid 70% - 1440 kg

2. Technical water - 400 kg.

3. Heating steam (deaf) - 550 kg.

4. Water for washing hydrate cake OTM - 3000 kg

In the nitrate processing reached the opening of loparite concentrate (total rare earth elements) - 95%.

Received the washed hydrate cake GCP - 575 kg (dry) of the following composition, %: Ta2O5- 0,99%; Nb2O5- 14.5cm; TiO2- 66,2;S="ptx2">

Deactivated nitrate solutions REE processed according to traditional extraction technology.

The washed hydrated oxide in the form of a slurry with a solid content ~ 800 g/l processed by fluoride technology, i.e., was dissolved in 40% hydrofluoric acid. Then clarified fluoride solution was applied for the extraction redistribution of obtaining paticia tantalum and niobium. The remaining refined processed with obtaining titanium dioxide and ammonium sulfate.

As a result of processing 575 kg of hydrated cake on fluoride technology was obtained:

- oxide of tantalum - 5.3 kg; end-to-end retrieval - 93,0% Ta2O5;

- patikis niobium - 75,3 kg; end-to-end retrieval - 93,5% Nb2O5;

- titanium dioxide - 362 kg; end-to-end retrieval - 95,0% TiO2.

The consumption of reagents to obtain the product in accordance with the inventive method compared to sulfuric acid technology are presented in table. 1.

The advantages of the proposed method of producing oxides of refractory metals from loparite concentrate compared with sulfuric acid method can be seen from the below table. 2 data on the example of the shop GAO "Silmet" (Estonia) processing 12 show the method compared with the method of the prototype are not only in higher end-to-end the extraction of valuable components into finished products, but in significantly lower cost of basic reagents for processing hydrate cake. This not only reduces the direct costs of the processing of loparite concentrate and reduces the cost of the finished product, but also reduces the cost of processing and disposal of waste and emissions of harmful substances into the environment.

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 of producing oxides of refractory metals from loparite concentrate provides a complete single branch of the most valuable components of tantalum, niobium and titanium from less valuable components and impurities. The most valuable components are extracted with virtually no losses and is absolutely clean from radioactivity. The method has high economic efficiency, because the most valuable and expensive plavica the bathroom sulfuric acid, consumption, which is very large, regenerated and recycled in the order of 76% of the total. The method is much simpler in hardware design compared to the way the prototype, because it has a significantly smaller volumes involved in the process of ingredients and easy to full automation because of the practical continuity of the process. The method creates a more gentle (less corrosive) conditions for operation of equipment due to lower temperatures and replacement of sulfate-fluoride environments on fluoride environment. Reduces the cost and complexity of maintaining equipment in working condition, and the number of staff.

1. The method of producing refractory oxides of metals of loparite concentrate, including the grinding of the concentrate to the size of particles of at least 0.075 mm classification, opening loparite concentrate concentrated inorganic acid at atmospheric pressure and a temperature of more than 100oC, the subsequent formation of fluoride compounds tantalum and niobium under the influence of hydrofluoric acid and extraction with tributyl phosphate and extraction of titanium dioxide, characterized in that the opening lead of kontsentrirovano the response of tantalum and niobium ensure dissolution of hydrofluoric acid with a concentration of at least 40% hydrated oxide oxides of refractory metals with simultaneous formation as a result, the fluorine-Titanic acid, after extraction of tantalum and niobium are oparka of raffinate 1.5 - 2.0 times at 105 - 108oC, then the extraction of hydrofluoric acid by distillation with the aid of concentrated sulfuric acid and the return of hydrofluoric acid on the dissolution of hydrated cake of the remaining VAT residue vykristallizovyvalas the titanyl sulphate monohydrate from which they receive the finished product in the form of titanium dioxide, and the remaining mother liquor containing concentrated sulfuric acid to return into circulation for the extraction of hydrofluoric acid from one stripped off of the raffinate.

2. The method according to p. 1, characterized in that bicrystalline of titanyl sulphate monohydrate carried out by heating VAT residue acute ferry to 140 - 150oC when it is moved in a continuous stream over the 5.5 to 6.0 hours

 

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