Method for processing of loparite concentrate

 

(57) Abstract:

The invention relates to chemical technology of obtaining compounds of rare metals. Spend the decomposition of loparite concentrate 69-71% nitric acid at 100-110oWith over 38-42 including Separated precipitate hydrated titanium, niobium and tantalum. Process it with a reagent containing hydrogen fluoride, to obtain the solution of titanium, niobium and tantalum. Processing is carried out at a mass ratio of reagent (calculated on 100% HF) and dry hydrated sediment 0.9 to 1.0:1. As a reagent containing hydrogen fluoride, using hydrofluoric acid or a mixture of hydrogen fluoride and water vapor. Then carry out the extraction separation of niobium and tantalum from titanium aliphatic alcohols with translation of niobium and tantalum in the organic phase, and titanium in water. As the aliphatic alcohols used alcohols fraction7-WITH9mainly the octanol-1, octanol-2, or their mixture. In the aqueous phase is injected metallic zinc in an amount of not more than 5 wt.% in relation to the Titan in terms of TiO2and it is leading heat treatment at 500-750oWith obtaining titanium dioxide. Titanium dioxide is treated with a modifier with obtaining PI flow rate of 1-10% Al2O3and 1-5% SiO2with respect to the titanium dioxide. The result is a reduction of the flow rate of fluorine-containing reagent is more than 1.2 times and in improving the quality of titanium dioxide, representing pigmentary titanium dioxide rutile modification. 3 C.p. f-crystals, 1 table.

The invention relates to chemical technology of inorganic substances with obtaining compounds of rare metals used in metallurgy, in the creation of new structural materials with specific properties, as well as titanium dioxide, used in the manufacture of paints, plastics, paper.

There is a method of processing of loparite concentrate (see the Patent of Russia 2147621, IPC722 In 34/24, 59/00, 34/12; C 01 G 23/04, C 22 B 3/06, 2000), including the decomposition of its concentrated nitric acid to obtain a hydrated oxide oxides of refractory metals, dissolution of the oxide in hydrofluoric acid to obtain a solution of titanium, niobium and tantalum, extraction separation of niobium and tantalum from titanium tributyl phosphate with translation of niobium and tantalum in the organic phase, and titanium in water, evaporation of the aqueous phase in 1.5-2.0 times, the Stripping of hydrofluoric acid in the presence of concentrated sulfuric Kisarazu distillation of hydrofluoric acid.

The disadvantages of this method are its complexity, the complexity of recycling solutions, resulting from the extraction, insufficient utilization of HF (less than 93%), pollution by phosphorus oxides of niobium and tantalum due to hydrolysis of tributyl phosphate and toxicity of tributyl phosphate, low pigment properties of the obtained titanium dioxide, which is a technical product with a noticeable yellow-gray shade, which consists of a mixture of anatase and rutile.

Closest to the claimed technical solution is the method of processing of loparite concentrate (see the Patent of Russia 2149912, IPC722 In 34/24, 34/12, 3/06, 3/26, 2000), including decomposition crushed loparite concentrate concentrated nitric acid with the translation of rare earth elements in the solution, and titanium, niobium and tantalum in the hydrated precipitate, Department of hydrated sediment, the processing of hydrofluoric acid at a mass ratio of acid (calculated as 100% HF) and dry hydrated sediment than 1.1:1.0 by obtaining a solution of titanium, niobium and tantalum, extraction separation of niobium and tantalum from titanium oktilovom alcohol with translation of niobium and tantalum in the organic phase, and titanium in water ilen modifications and hydrofluoric acid.

The disadvantages of this method are the increased consumption of hydrofluoric acid for dissolving operation of hydrated sediment into force calculation flow of HF education fortechnology acid, H2TiF6low pigment properties of the obtained titanium dioxide, which is a technical product with a noticeable yellow-gray shade, which consists of a mixture of anatase and rutile.

The present invention is directed to solving the problem of reducing the flow rate of the reagent containing hydrogen fluoride, and improve the pigment properties of titanium dioxide.

The problem is solved in that in the method for processing of loparite concentrate, including its decomposition with nitric acid translation of rare earth elements in the solution, and titanium, niobium and tantalum in the hydrated precipitate, Department of hydrated sediment, the processing reagent containing hydrogen fluoride, to obtain the solution of titanium, niobium and tantalum, extraction separation of niobium and tantalum from titanium aliphatic alcohol with translation of niobium and tantalum in the organic phase, and titanium in water and its heat treatment to obtain titanium dioxide and hydrofluoric product according to the invention obrabotka 100% HF) and dry hydrated sediment 0.9-1.0:1, before heat treatment in the aqueous phase is injected metallic zinc in an amount of not more than 5 wt.% in relation to the Titan in terms of Tio2and heat treatment is conducted at 500-750oS, after which the titanium dioxide is treated with a modifier to obtain pigmentary rutile.

The problem is solved also by the fact that as a reagent containing hydrogen fluoride, using hydrofluoric acid or a mixture of hydrogen fluoride and water vapor.

The problem is solved and the fact that as an aliphatic alcohol use alcohol fraction7-C9mainly the octanol-1, octanol-2, isooctanol or their mixture.

The solution of this problem is achieved by the fact that, as a modifier, a mixture of aluminum phosphate and silicate in their mass flow rate of 1-10% Al2ABOUT3and 1-5% SiO2with respect to the titanium dioxide.

The reduction of the fluorine-containing reagent to the processing of hydrated sediment leads to a decrease in fluoride-containing solutions, concentrating them on the main components and parameters of thermal processing, provide almost 100% regeneration of HF. Improving dioxide is (II), which does not contaminate the titanium dioxide and initiates formation during thermal treatment of rutile and pigment properties are acquired with the operation surface treatment with a mixture of aluminum phosphate and silicate.

Carrying out processing of hydrated sediment when the mass ratio of the reagent containing hydrogen fluoride (calculated on 100% HF)? and dry hydrated sediment less than 0.9:1 accompanied by a decrease in the degree of transition of rare metals and titanium in fluoride solution and a significant increase in the duration of the process. To increase the mass ratio of the reagent containing hydrogen fluoride (calculated on 100% HF), and dry hydrated sediment greater than 1:1 has almost no influence on the dissolution rate and the degree of transition of rare metals and titanium in solution. In addition, if you increase the specified ratio greater than 1:1 decreases the efficiency of the separation of tantalum and niobium in the extraction step aliphatic alcohols.

The use of aliphatic alcohols due to their ability to extract niobium and tantalum from fluoride solutions in the absence of other mineral acids, higher resistance in the extraction process compared to tributary of niobium and tantalum, lower solubility in aqueous solutions and a lower fire hazard than cyclohexanone and the mixture. The use of aliphatic alcohols, which do not contain water-soluble compounds, in particular phosphorus, also improves the purity of the products.

As the aliphatic alcohols used alcohols WITH7-C9containing a mixture of isomers of octanol, heptanol and nonanol, mainly a mixture of isomers of octanol. The use of alcohols with carbon atoms is less than 7 leads to a sharp increase in the solubility of the extractant and the deterioration of technological and economic parameters of the process. The use of alcohols with carbon atoms of more than 9 significantly affects the delamination of organic and aqueous phase, which negatively affect the technological and economic indicators.

The introduction of metallic zinc in the aqueous phase before heat treatment promotes the translation of the anatase modification of titanium dioxide in rutelinae, and also allows you to lower the lower boundary heat treatment up to 500oC.

The amount of added zinc metal is not more than 5 wt.% on otoshiana.

The process of combustion at a temperature below 500oWith leads to an increase in the fluoride content in the pigment, which degrades its quality due to the increased content of water-soluble salts (HRV), having an acid reaction, and increases the share of the anatase form of the pigment. At temperatures above 750oWith decreasing the effectiveness of the modifier and significantly increase the cost of heat, necessary for the operation of combustion.

Treatment of the product of combustion of a mixture of aluminum phosphate and silicate, the mass flow rate which is less than 1% of Al2ABOUT3and less than 1% of SiO2leads to lower aggregate stability of paint and varnish materials (coatings), and decreases the service life of coatings. At the rate of more than 10% of Al2ABOUT3and more than 5% SiO2dramatically increases the measure of the opacity of the pigment and worsen the rheological properties of the ink based on it.

The method is as follows. Loparite concentrate process 69-71% nitric acid at 100-110oWith over 38-42 hours In the formed suspension add water and filtered under vacuum with the Department of hydrated precipitate, which is washed with water and treated with fluorine-containing reagent is, containing hydrogen fluoride, using hydrofluoric acid or a mixture of hydrogen fluoride and water vapor. The resulting fluoride solution of rare metals and titanium of the following composition, g/l: Tio2300, Nb2O560, TA2ABOUT54. It adds aliphatic alcohols and translate the extraction of niobium and tantalum in the organic phase. The ratio of the amounts of aliphatic alcohols: the solution is 1.1-1.3:1. Extraction into the organic phase in one step, %: TA2O595.0-95.2, Nb2O598.0-98.4, TiO24.7-4.8. Three-stage countercurrent extraction under the same conditions in the organic phase becomes about 5% of Tio2and more than 99.5% of TA2O5and Nb2ABOUT5when the content of phosphorus, in terms of P2O5, less than 0.01%. In the aqueous phase, which is a fluoride solution titanium, injected metallic zinc in an amount of not more than 5 wt.% in relation to the Titan in terms of TiO2and then in a special "combustion" installation is subjected to the heat treatment at 500-750oWith obtaining titanium dioxide and fluorinated product (hydrofluoric acid or a mixture of hydrogen fluoride and water vapor). The degree of regeneration of HF is not the MINIA and silicic acid, the mass flow rate which corresponds to 1-10% Al2O3and 1-5% SiO2no relation to the titanium dioxide. After processing, the product is dried at 250-300oWith obtaining of titanium dioxide pigment rutile modification. Properties of titanium dioxide pigment: dispersion (content of particles less than 1 Ám) - 100%, white - 94.6-96.8 srvc.ed., opacity - 30-35 g/m2the oil absorption of 25 to 30 g/100 g of pigment.

Hydrofluoric product (hydrofluoric acid or a mixture of hydrogen fluoride and water vapor) is used in circulation in the processing of hydrated sediment.

The essence of the proposed method can be explained by the following Examples.

Example 1. Take 1 kg of loparite concentrate composition, wt.%: TiO238.1, Nb2O58.14, TA2O50.57, REE 32.0, Na2O 8.48, CaO 4.74, Fe2O32.2, 2.5 SrO, SiO21.4, ThO20.54 process and its 70% nitric acid at T:W=1:1, 100-110oWith over 40 hours Then the suspension is diluted with water, the volume of which is equal to the original volume of nitric acid, cooled to 30-40oTo separate the hydrated precipitate, washed with water at T:W=1:3 and treated with hydrofluoric acid at a mass ratio of acid (in billaut octanol-1 from calculating the volume of octanol-1 : the solution equal to 1.3:1, and is transferred by the extraction of niobium and tantalum in the organic phase, and titanium in water. The degree of extraction in the organic phase in the three-stage countercurrent extraction is more than 99.5% of TA2O5and Nb2O5when the content of phosphorus, in terms of P2O5, less than 0.01%. To the aqueous phase add metallic zinc in the amount of 0.1 wt.% in relation to the Titan in terms of Tio2and then conducting heat treatment at 500oWith obtaining titanium dioxide and hydrofluoric acid. Titanium dioxide is treated with a mixture of aluminum phosphate and silicate, the mass flow rate which is 1% Al2ABOUT3and 5% SiO2with respect to the titanium dioxide, and after drying receive pigmentary titanium dioxide rutile modification with the following properties: dispersion (content of particles less than 1 Ám) - 100%, white - 94.6 srvc.ed., opacity - 30 g/m2the oil absorption of 25 g/100 g pigment. The obtained hydrofluoric acid is used in circulation during the processing of hydrated sediment.

Example 2. The process is conducted in accordance with the conditions of Example 1. The difference lies in the fact that the hydrated precipitate is treated with a mixture of hydrogen fluoride and water vapor gameternity solution add the octanol-2 from calculating the volume of octanol-2 : the solution equal to 1.1: 1, and is transferred by the extraction of niobium and tantalum in the organic phase, and titanium in water. The degree of extraction in the organic phase in the three-stage countercurrent extraction is more than 99.5% of TA2O5and Nb2O5when the content of phosphorus, in terms of P2ABOUT5, less than 0.01%. To the aqueous phase add metallic zinc in the amount of 2.5 wt.% in relation to the Titan in terms of TiO2and then conducting heat treatment at 650oWith obtaining of titanium dioxide and a mixture of hydrogen fluoride and water vapor. Titanium dioxide is treated with a mixture of aluminum phosphate and silicate, the mass flow rate which is 5% Al2O3and 2.5% SiO2with respect to the titanium dioxide, and after drying receive pigmentary titanium dioxide rutile modification with the following properties: dispersion (content of particles less than 1 Ám) -100%, white - 96.8 srvc.ed., opacity - 35 g/m2the oil absorption is 28 g/100 g pigment. The resulting mixture of hydrogen fluoride and water vapor used in the turnover during the processing of hydrated sediment.

Example 3. The process is conducted in accordance with the conditions of Example 1. The difference lies in the fact that the hydrated precipitate is treated with hydrofluoric this redomiciliation solution add isooctanol of calculating the volume of isooctanol : solution, equal to 1.25:1, and is transferred by the extraction of niobium and tantalum in the organic phase, and titanium in water. The degree of extraction in the organic phase in the three-stage countercurrent extraction is more than 99.5% of TA2O5and Nb2O5when the content of phosphorus, in terms of P2O5, less than 0.01%. To the aqueous phase add metallic zinc in an amount of 5 wt.% in relation to the Titan in terms of Tio2and then subjected to heat treatment at 750oWith obtaining titanium dioxide and hydrofluoric acid. Titanium dioxide is treated with a mixture of aluminum phosphate and silicate, the mass flow rate which is 10%Al2O3and 1% SiO2with respect to the titanium dioxide, and after drying receive pigmentary titanium dioxide rutile modification with the following properties: dispersion (content of particles less than 1 Ám) - 100%, white - 96.8 srvc.ed., opacity - 31 g/m2the oil absorption of 30 g/100 g of pigment.

The obtained hydrofluoric acid is used in circulation during the processing of hydrated sediment.

Example 4. The process is conducted in accordance with the conditions of Example 3. The difference lies in the fact that redomiciliation solution add the creative, equal to 1.22:1. The degree of extraction in the organic phase in the three-stage countercurrent extraction is more than 99.5% of TA2O5and Nb2O5when the content of phosphorus, in terms of P2O5, less than 0.01%. Next, a process similar to Example 3.

Example 5. The process is conducted in accordance with the conditions of Example 3. The difference lies in the fact that redomiciliation solution add aliphatic alcohols fraction7-C9from calculating amounts of aliphatic alcohols fraction7-C9: a solution of 1.18:1. The degree of extraction in the organic phase in the three-stage countercurrent extraction is more than 99.5% of TA2ABOUT5and Nb2O5when the content of phosphorus, in terms of P2O5, less than 0.01%. Next, a process similar to Example 3.

Summarized comparative information the nature and characteristics of the methods of processing of loparite concentrate according to the invention and taken as analogue and prototype shown in the Table.

Data Examples and Tables confirm the advantages of the proposed method lies in the reduction of the reagent hydrofluoric more than 1.2 times and improving the quality of the Method for processing of loparite concentrate, including its decomposition with nitric acid translation of rare earth elements in the solution, and titanium, niobium and tantalum in the hydrated precipitate, Department of hydrated sediment, the processing reagent containing hydrogen fluoride, to obtain the solution of titanium, niobium and tantalum, extraction separation of niobium and tantalum from titanium aliphatic alcohol with translation of niobium and tantalum in the organic phase, and titanium in water and its heat treatment to obtain titanium dioxide and hydrofluoric product, characterized in that the processing of hydrated sediment reagent containing hydrogen fluoride, carried out at a mass ratio of reagent and dry hydrated sediment 0,9-1,0: 1, before heat treatment in the aqueous phase is injected metallic zinc in an amount of not more than 5% with respect to titanium in terms of TiO2and heat treatment is conducted at 500-750oS, after which the titanium dioxide is treated with a modifier to obtain pigmentary rutile.

2. The method according to p. 1, characterized in that as a reagent containing hydrogen fluoride, using hydrofluoric acid or a mixture of hydrogen fluoride and water vapor.

3. The method according to p. 1, characterized in that as alipac is or their mixture.

4. The method according to any of paragraphs. 1-3, characterized in that as a modifier, a mixture of aluminum phosphate and silicate in their mass flow rate of 1-10% Al2O3and 1-5% SiO2with respect to the titanium dioxide.

 

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