The method of producing refractory oxides of metals of loparite concentrate

 

(57) Abstract:

The invention relates to the hydrometallurgical processing of loparite concentrate. The method includes 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 temperatures above 100C, the subsequent formation of the products autopsy concentrate fluoride compounds tantalum and niobium under the influence of hydrofluoric acid and extraction. Subsequent extraction of titanium dioxide. When the opening lead with concentrated nitric acid to obtain a hydrated oxide oxides of refractory metals, the formation of fluoride compounds tantalum and niobium ensure dissolution of hydrated cake hydrofluoric acid with a concentration of at least 40% with the formation of the fluorine-Titanic acid, extraction of tantalum and niobium is performed using oktilovom alcohol, and removing oxides from their reextractors carried out by high-temperature pyrolysis at a temperature of 600-650C , followed by oparka of raffinate 1.5-2.0 times and subsequent extraction of titanium dioxide by viscotester the oho hydrogen water to obtain hydrofluoric acid, you return to the dissolution of hydrated cake. The method allows us to simplify the process, improve its efficiency and effectiveness. table 1.

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 weight. %:

The oxide of tantalum (Ta2O5) - 0,57

The oxide of niobium (Nb2O5) - 8,14

The titanium oxide (TiO2) of 38.1

The oxides of rare earth metals cerium group, mainly oxides of lanthanum (La2O3), cerium oxide (CE2ABOUT3) oxide, praseodymium (Pr2O3), neodymium oxide (Nd2O3) - 32

The sodium oxide (Na2O) - 7,9-9,06

Calcium oxide (CaO) - 4,2-5,7

The strontium oxide (Sr) - 2,3-3,0

Iron oxide (Fe2O3) - 2,0-2,5

Silicon oxide (SiO2) - 1,95-2,5

Aluminum oxide (Al2O3) - 0,6-0,7

The oxide of potassium (K2O) - 0,26-0,75

The phosphorus oxide is first 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.- M.: 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 a temperature of 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 extracts 93-94% of niobium and 86-88% of tantalum in technical oxides of 96.5-97% of the titanium in technical tetrachloride.

However, chlorine those who isih quantities of chlorine, and so 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.- M.: 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 of niobium and tantalum to sulfuric acid is added ammonium sulfate (0.2 tons per 1 ton of concentrate). In the opening, occurring at a range of temperatures up to 270-2802(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)210 g/l Sulfuric acid is neutralized to pH 4-6. Then carry out the binding and precipitation of fluoride with milk of lime with a concentration of Cao=200 g/l in the form of insoluble sludge CaF2. Neutralized raffinate is subjected to filtration, resulting in a separate cake containing Ti(OH)4CaF2, CaO. KEK are disposed in the slurry tank (pit). The leachate concentration (NH4)2SO4=300 g/l evaporated and disposed in the form of maroccolo refractory metals from loparite concentrate for the opening of the concentrate is used in more environmentally friendly chemical reagent compared to chlorine technology. However, this method has several significant disadvantages. The main of them are significant losses of oxides of refractory metals in the process of their extraction. This is because immediately at the first stage - the showdown concentrate showdown and the release of the most valuable components that go into sulphate solution and distributed among the less valuable components in the solid phase. As a result of this we have to separate from the most valuable components of the less valuable the double sulphate of REE, which takes in various forms up to 25-30% of tantalum and niobium. To return tantalum and niobium is necessary to carry out additional processing of the dump cake remaining after the processing of double sulphates REE. In addition, there irretrievable loss of tantalum and niobium with crystals of titanium salt when salting out from sulfuric acid solution of tantalum, niobium and titanium. Use as extractant of tributyl phosphate makes the extraction process of the oxides of tantalum and niobium fluoride from their solutions time-consuming and laborious. The selection of titanium sulfate solutions in the form of dual titanium salt leads to large losses of titanium due to the considerable dissolve yet not more than 72%. Extracted this way oxides of refractory metals have increased activity due to a shift in their sulfuric acid solution of about 50% of the original activity. Moreover, scarce and expensive hydrofluoric acid is used for sulfate-fluoride extraction of tantalum and niobium, in this way is not utilized because the fluoride concentration in the raffinate after extraction is only 25-30 g/l, which makes recycling economically feasible. When implementing the method has a high consumption of sulfuric acid, because the acid from ratinov is removed, and only disposed of as low ammonium sulfate. All this makes the method complicated, inefficient and uneconomical.

The present invention was based on the objective to develop a method of producing oxides of refractory metals from loparite concentrate, in which the extraction and processing of refined would be carried out under such conditions to prevent loss recoverable valuable components, provided the return to the technology of hydrofluoric acid, provided the receiving radioactively pure products, which provides a simplified way, an increase in the efficiency of metals from 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 the products autopsy concentrate fluoride compounds tantalum and niobium under the influence of hydrofluoric acid and extraction, and the extraction of titanium dioxide, it is new that the opening lead with concentrated nitric acid to obtain a hydrated oxide oxides of refractory metals, 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 with simultaneous formation as a result of this fortechnology acid, extraction of fluoride compounds tantalum and niobium are carried out with oktilovom alcohol, and removing oxides from their reextractors carried out by high-temperature pyrolysis at a temperature of 600-650oC, followed by oparka of raffinate 1.5-2.0 times and subsequent extraction of titanium dioxide by high-temperature pyrolysis, while gaseous PE this hydrofluoric acid, you return to the dissolution of hydrated cake.

This solution hydrated cake, which is completely 100% focused extractable oxides of refractory metals is dissolved in hydrofluoric acid. Subsequent extraction of tantalum and niobium oksanalove alcohol use resulting fortechnology acid provides full lossless their removal in the finished product. Reextracted tantalum and niobium with oktanovogo alcohol, carried out with clean water, provides the reextractors in the form of pure (without impurities) fortunelounge and Tornionjoki acids, each of which, as well as the raffinate, containing fortechnology acid, are subjected to high-temperature pyrolysis. Due to pyrolysis occurs simultaneous production of pure oxides of refractory metals and highlighting together with gaseous products of pyrolysis of hydrogen fluoride HF, which is easily absorbed by water, turning into hydrofluoric acid, is returned into circulation (by dissolving hydrated cake GCP). This allows you to recycle up to 98% expensive hydrofluoric acid used in the production cycle. Thanks to all of this and provides a simplified way, the above is from loparite concentrate is carried out as follows. Source loparite concentrate is ground to a particle size at least 95% of particles of not more than 0.075 mm wet grinding with the classification of the particles and the thickening of the pulp loparite concentrate. Then carry out attackone opening of the pulp loparite at atmospheric pressure nitric acid HNO3with concentration C=650-700 g/l at temperature t=115-118oC. Because the process azotnokislogo of pulp exposure are discussed in detail in the previously filed application by the same applicant, in this application it is disclosed in the aggregated form. After azotnokislogo opening receive the pulp opening - nitrate slurry of hydrated oxide oxides of refractory metals (GCP). In the opening in the solution passed all the oxides of rare earth metals into soluble form nitrates of rare-earth elements R(NO3)3. At the same time in the process of opening under the influence of nitric acid in the solution is passed in the form of nitrates and all impurities loparite, including the source of the alpha-activity of the oxide of thorium, mesochori. The most valuable of allocated components of loparite - oxides of tantalum, niobium and titanium is practically not dissolved by nitric acid, and therefore, completely, 100% remain in the solid part of the slurry, the pre is in fact Keke these components are in a mixture of the same as they were in the loparite. Thus in the opening loparite concentrate nitric acid is full of single branch of the most valuable components (tantalum, niobium), remaining hydrated Keke without any losses from the less valuable components that have fallen into the solution. When hydrated, the cake is almost free from radioactivity, since ~95% of thorium oxide and mesochori is a nitric acid solution of nitrates of rare-earth elements and impurities, and therefore, if further processing is not required, a special process of decontamination cake ELEVATION. Then nitrate hydrate slurry cake is diluted with water to 1.5-2.0 times and cool. After cooling are filtered solution of nitrate slurry of hydrated oxide and its subsequent washing from nitric acid solutions of nitrates of rare-earth elements and impurities. In the hillshade get pure hydrated cake MARK in the form of a slurry with a concentration of nitrates NO32 g/l and the concentration of solid WITHTV=150-200 g/l of Pure hydrate cake is the starting product for the issuance of oxides of refractory metals, which are completely left in him.

Removing oxides of refractory metals from pure hydrat the Dissolution is more heat. To reduce the temperature of the heat from the reaction vessel is performed by the water flowing through the coil. After the dissolution of fluoride slurry is subjected to sedimentation and filtration for removal of fluoride solution of tantalum, niobium and titanium undissolved part of the cake ELEVATION, consisting mainly of REE fluorides, calcium and silicon. The amount does not exceed 10% of the initial mass of hydrated cake. Sediment otdovat on the moisture filter the air. Sediment Rasulova lime milk, resulting fluorine transformed into an insoluble precipitate, and pumped to the tailings pond. Pure fluoride solution of tantalum, niobium and titanium is directed to the extraction of tantalum and niobium with 100% oktilovom alcohol, also known as the octanol-1,1-axiostar or octanol. The octanol as the extractant exceeds tributyl phosphate used in the method prototype for such basic indicators as the selectivity of the extractant, the capacity of the extractant, chemical resistance, it has a lower density and solubility in water. In the present method fortiana acid (H2TiF6formed from titanium under the influence of hydrofluoric acid, facilitates the transition fluoride compounds tancesindicate opening. The octanol-rich tantalum and niobium, is directed to 2-contour alternately reextraction (flush with octanol) of niobium and tantalum with clean water. As a result of this get ferniany and fortuntely the reextractors in the form of pure pornoviejas acid HNbF6and percentlevel acid HTaF6and portianoy the raffinate as fortechnology acid. Extracted with pure octanol tornieria and protentially acid is then subjected to high-temperature pyrolysis at a temperature of 600-650oC, resulting in a gain oxides (pentoxide) tantalum and niobium Ta2O5and Nb2O5, which is the finished product resulting from implementation of the proposed method. The use of high temperature pyrolysis in the present method it has become possible thanks to the use as a solvent octanol, reextraction which is pure water. If, as in the method prototype extraction of tantalum and niobium was performed using tributyl phosphate, then reextraction busy extractant have been carried out with a solution of ammonium fluoride. In this case, the reextractors subjected to pyrolysis would be impossible because of the formation during the oxidation complex task. In the present method the percentage of extraction of oxides of tantalum and niobium from loparite concentrate reaches at least 95% and they are almost completely devoid of radioactivity, because it does not contain thorium Th and mesochori MsTh. This is explained by the fact that about 5% of the radioactivity passing in hydrated cake at the opening of loparite concentrate nitric acid, remain bound in the sediment remaining from the cake after its dissolution with hydrofluoric acid. This finished product is particularly valuable source product for metallurgy, electronics and semiconductor technology.

After extraction of tantalum and niobium, the raffinate is subjected to processing to extract the remaining Dookie titanium. Almost all of the titanium present in the raffinate as fortechnology acid HaTiF6. Before processing the raffinate evaporated 1.5-2.0 to increase the concentration of TiO2to=350-400 g/l Processing the raffinate is in high-temperature pyrolysis one stripped off fortechnology acid at a temperature of 600-650oC. In the pyrolysis of getting titanium dioxide. If necessary, it can be calcined at a temperature of t=900-950oC and put it in rutilio form, which privaet high degree of selection of titanium in the finished product. This end-to-end extraction of titanium is at least 98%.

High temperature pyrolysis is carried out in a known tower spray pyrolysis furnaces powered by natural gas or fuel oil. Subjected to pyrolysis concentrated portentosa, tornieria and fortiana acid spray nozzles in the upper parts of the furnace. Oxides of refractory metals formed by pyrolysis, remove from baking ovens. Hot gaseous products of pyrolysis containing hydrogen fluoride HF, directed from the upper parts of the furnace first to clear the solid products of pyrolysis in the cyclone, and then cooling and absorption of HF pure water. As a result of this get 40% hydrofluoric acid, which in return turnover by dissolving hydrated cake. Thanks to the pyrolysis allocation hydrogen fluoride is carried out without using any chemical reagent, and the absorbance of hydrogen fluoride with getting expensive hydrofluoric acid is a very simple technology. When this is returned into circulation hydrofluoric acid up to 98% of the total amount of acid used in technology.

Below, the inventive method is illustrated by a concrete example of its assisatance 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 hours.

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

Nb2O3- 14,5

TiO2- 66,2

The amount of oxides REE - 2,78

ThO2- 0,05

CaO - 0,4

Na2O - 0,75

Fe2O3- 0,35

SiO2- 3,5

NO3- 0,1

Deactivated nitrate dissolve the slurry with a solid content of 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 patootie tantalum and niobium. The remaining refined processed with obtaining titanium dioxide. Disposed after pyrolysis hydrofluoric acid is returned to the dissolution of hydrated cake.

As a result of processing 575 kg of hydrated cake for the claimed fluoride technology was obtained:

- pentoxide tantalum - 5,407 kg; through removing -95,0% Ta2O5;

- niobium pentoxide - 79,2 kg; end-to-end retrieval - 95,0% Nb2O5;

- titanium dioxide - 373 kg; end-to-end retrieval - 98,0% TiO2.

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

From the above examples and data the table shows that the advantages of the proposed 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 a much smaller expenditure of the main reagents for processing hydrate cake. This not only reduces the direct costs of processing the Saami waste disposal 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, which, however, 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, as particularly environmentally harmful and expensive hydrofluoric acid is almost completely regenerated after use and recycled. The method is much simpler in hardware design in comparison with the method of the prototype, because it has a significantly smaller volumes involved in the process of ingredients and easy to full automation because virtually the Oia 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.

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 the products autopsy concentrate fluoride compounds tantalum and niobium under the action of hydrofluoric acid and extraction of the t reextraction, extract, titanium dioxide, characterized in that the opening lead with concentrated nitric acid to obtain a hydrated oxide oxides of refractory metals, the formation of fluoride compounds tantalum and niobium carried out by dissolving hydrated cake hydrofluoric acid with a concentration of at least 40% while gaining fortechnology acid, extraction of tantalum and niobium is performed using oktilovom alcohol, and removing the oxides of tantalum and niobium is carried out reextract by high-temperature pyrolysis at a temperature of 600 560oC, Rapin the temperature of pyrolysis, when this gaseous products of pyrolysis are subjected to cooling for absorption of vapors of hydrogen fluoride with water to obtain hydrofluoric acid, which return to the dissolution of hydrated cake.

 

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