The method of processing of spent catalysts containing metals of platinum group

 

(57) Abstract:

The invention relates to the metallurgy of noble metals and can be used when extracting platinum group metals from spent catalysts based on alumina containing platinum or palladium. The technical result is to reduce losses of platinum metals and improve the quality of the final product is a concentrate of platinum metals. The method of processing of spent catalysts containing platinum metal based on aluminum oxide, is grinding, rihtovanie hydroxide of an alkali metal, sintering, water leaching SPECA with the transfer of sodium aluminate in solution, filtration and acid treatment of the solid residue with obtaining a concentrate of platinum metals. According to the invention the grinding lead to -3 mm, rihtovanie when the ratio of the hydroxide of alkaline metal catalyst (0,8 - 1,2) : 1, sintering at a temperature of 400 - 700oC for 1 to 2 h, water leaching in the presence of an alkaline reagent, and acid treatment at a pH of 1.5 - 2.0 with the introduction of the inorganic reducing agent. As a hydroxide of an alkali metal during sintering using sodium hydroxide or potassium. The quality is/l, as inorganic reductant use of copper compounds (I), for example, copper oxide (I) size -0,05 mm in relation to the platinum group metals 0.2 to 0.5 from the stoichiometry of reaction recovery. The solution after water leaching is neutralized with the subsequent receipt of the commodity aluminum compounds. Water leaching is carried out at T : W = 1 : (3 - 5) within 1 to 2 h, and acid treatment is carried out with hydrochloric or sulfuric acid at T : W = 1 : (3 - 5), a temperature of 50 - 90oC and stirring. 7 C. p. F.-ly, 3 tables.

The invention relates to the metallurgy of noble metals and can be used when extracting platinum group metals from spent catalysts, including automotive, on the basis of the oxides of aluminium, silicon and magnesium, containing platinum or palladium.

There is a method of processing of spent catalysts based on oxides of aluminum, silicon and magnesium containing platinum metals, including the opening of the foundations of the alkaline processing solution in the autoclave. The dissection is carried out at a temperature of 150oC, a pressure of 10 ATM for 4 hours. Extraction of platinum metals in the solid residue of 99%. About 1% of platinum goes into solution.

There is a method of processing waste of platinum-containing catalysts, including the opening of the fundamentals of sintering with sodium hydroxide in the recovery environment. Sintering is carried out at a temperature of 900-950oC with the introduction of the carbon. Spec leached with a solution of sulfuric acid in the presence of aluminum for cementation of platinum, passed into the solution. Platinum remains in the insoluble residue.

The disadvantages of the method are its high energy consumption and high consumption of reagents on stage leaching SPECA (see U.S. Pat. EN 2100072 C1 (Omsk state University) 27.12.97).

There is a method of processing of spent catalysts based on alumina containing platinum group metals, including sintering with caustic soda to convert the aluminum oxide to sodium aluminate. Spec leached with water, with sodium aluminate goes into solution, and the platinum group metals remain in the solid residue. The residue is separated by filtration, treated with hydrochloric acid to remove any remaining impurities, filtered off, washed and dried (see I. N. Martinovich metals sent for refining.

The disadvantages of the method are the inevitable losses of platinum metals on stage acid treatment and low enriched concentrate, because at the stage of water leaching SPECA possible hydrolysis of sodium aluminate.

The technical result of the claimed invention is to reduce losses of platinum metals and improve the quality of the final product is a concentrate of platinum metals.

This is achieved by a method for processing of spent catalysts containing platinum group metals, on the basis of aluminum oxide, including grinding, rihtovanie hydroxide of an alkali metal, sintering, water leaching SPECA with the transfer of sodium aluminate in solution, filtration and acid treatment of the solid residue with obtaining a concentrate of platinum metals, according to the invention the grinding lead to -3 mm, rihtovanie when the ratio of the hydroxide of alkaline metal catalyst (0,8-1,2):1, sintering at a temperature of 400-700oC for 1-2 hours, water leaching in the presence of an alkaline reagent, and acid treatment in the presence of inorganic reductant. As a hydroxide of an alkali metal during sintering use hydroc is sodium or potassium hydroxide with a concentration of 10-20 g/l, as a reducing agent in the processing of the remainder of the acid, the use of copper compounds (I) of size -0,05 mm in relation to the platinum group metals 0.2 to 0.5 from the stoichiometry of the reduction reaction of platinum metals; water leaching is carried out at T:W = 1:(3-5) for 1-2 hours, and the acid treatment is carried out with hydrochloric or sulfuric acid at T:W = 1:(3-5), the temperature of 50-90oC and stirring.

The invention consists in the following.

During sintering of the catalyst with alkali alumina goes into sodium aluminate. The declared parameters is the temperature of 400-700oWith the ratio of alkaline reagent and catalyst (0,8-1,2):1 and a process time of 1-2 hours to ensure complete opening of the base. Water leaching in the presence of an alkaline reagent prevents the hydrolysis of sodium aluminate and thereby provides the most complete transition of aluminum in the solution.

The introduction of the reductant at the stage acid treatment residue creates in the system redox potential, preventing oxidation and transfer of platinum metals in solution. Maintaining a pH of 1.5-2.0 stage acid treatment provides high performance cleaning from impurities and rata. The sodium aluminate solution can be neutralized and guide for various commodity aluminum compounds.

The combination of the claimed methods and modes allows you to get suitable for refining the concentrate with the PGM content of not less than 40%, while the extraction of platinum metals of 99.1 to 99.9%.

Substantiation of the parameters

The grinding of the catalyst to -3 mm is necessary for its full opening during sintering. The decrease of the ratio of alkaline agent to the catalyst in the mixture is less than 0.8: 1 does not provide for a full transition alumina in sodium aluminate, and an increase of more than 1.2:1 leads to unsustainable consumption of the reagent.

At temperatures below 400oC and time of sintering less than 1 hour does not fully opening the basics, and the temperature increase of more than 700oC and time more than 2 hours does not improve the performance of the autopsy process, but leads to waste of energy.

When the concentration of the alkaline reagent is less than 10 g/l at the stage of water leaching possible hydrolysis of sodium aluminate and the incomplete transition in a solution of aluminium, and concentrations above 20 g/l not intensifies its dissolution, and the reagent consumption is irrational.

Acid on the concentrating concentrate, as the pH decreases less than 1.5 does not increase the cleaning efficiency.

The use of copper oxide (I) as a reducing agent at a given its size and the flow creates a redox potential that prevented platinum metals found in high-level and fine form in the solution.

The ratio of T:W = 1:(3:5) in water and acid leaching of the most technologically advanced, because it creates the conditions most complete leaching of soluble components without irrational increase material flows.

The specified temperature acid treatment intensifies the process of dissolution.

Example

Spent palladium catalyst based on alumina, containing (wt. %): Pd 1,4; Fe, Ni, Cu, Si 1, Al2O3else, particle size 3 mm is mixed with sodium hydroxide in the ratio of 1:1 and is sintered at a temperature of 550oC for 1.5 hours. Spec leached water with the introduction of 15 g/l of sodium hydroxide at T:W = 1:4 for 1.5 hours and then filtered. The solid residue is treated with stirring with a solution of hydrochloric acid at a pH of 1.8 and a temperature of 70oC T:W = 1:4 in the presence of copper oxide (I). The copper oxide (I) particle size of 0.05 is trout, and the residue is dried.

Extraction of palladium in concentrate is 99,8%, and the content of palladium in concentrate - 53%.

The results of the method at other values of the declared parameters are presented in tables 1-3.

In table. 1 shows the results of extraction of platinum group metals at the opening of the catalysts with particle size of 3 mm by sintering with sodium hydroxide in the claimed values of the parameters.

Water leaching SPECA is carried out in the presence of alkali in amount of 15 g/l at T: W = 1:4, time 1.5 hours; acid treatment SPECA exercise solution of hydrochloric acid in the presence of copper oxide (I) in relation to the platinum group metals of 0.3 from the stoichiometry of reaction, recovery, temperature 70oC T:W = 1:4 with stirring.

In table. 2 results of the extraction of platinum group metals in the waste catalyst particle size 3 mm with an aqueous leaching SPECA in the presence of sodium hydroxide in the claimed values of the parameters. The original catalyst was shatavari with sodium hydroxide in the ratio of 1:1 and specaly at a temperature of 600oC.

The residue after water leaching was subjected to acid the and copper (I) in relation to the platinum group metals of 0.3 from the stoichiometry of reaction recovery.

In table. 3 results of the extraction of platinum group metals at the opening of the catalysts particle size -3 mm Sintering was carried out at the ratio of sodium hydroxide with catalyst 1:1, a temperature of 500oC, time of 1.5 hours.

Water leaching SPECA was implemented with the introduction of the sodium hydroxide solution with a concentration of 15 g/l, T:W = 1:4, time 1 hour. Acid treatment of the solid residue spent sulfuric acid solution at the stated values of the parameters in the presence of copper oxide (I).

1. The method of processing of spent catalysts containing platinum metal based on aluminum oxide, including grinding, rihtovanie hydroxide of an alkali metal, sintering, water leaching SPECA with the transfer of sodium aluminate in solution, filtration and acid treatment of the solid residue with obtaining a concentrate of platinum metals, characterized in that the grinding lead to -3 mm, rihtovanie when the ratio of the hydroxide of alkaline metal catalyst (0,8 - 1,2) : 1, sintering at a temperature of 400 - 700oC for 1 to 2 h, water leaching in the presence of an alkaline reagent, and acid treatment at a pH of 1.5 - 2.0 with the introduction of inorganic reductant.

led sodium or potassium.

3. The method according to p. 1 or 2, characterized in that as the alkaline reagent in aqueous leaching using sodium hydroxide or potassium hydroxide with a concentration of 10 - 20 g/L.

4. The method according to any of paragraphs.1 to 3, characterized in that the inorganic reductant use of copper compounds (I).

5. The method according to any of paragraphs.1 to 4, characterized in that compounds of copper (I) use the copper oxide (I) size -0,05 mm in relation to the platinum group metals 0.2 to 0.5 from the stoichiometry of reaction recovery.

6. The method according to any of paragraphs.1 to 5, characterized in that the solution after water leaching is neutralized with the subsequent receipt of the commodity aluminum compounds.

7. The method according to any of paragraphs.1 - 6, characterized in that the water leaching is carried out at T : W = 1 : (3 - 5) for 1 - 2 hours

8. The method according to any of paragraphs.1 to 7, characterized in that the acid treatment is carried out with hydrochloric or sulfuric acid at T : W = 1 : (3 - 5), a temperature of 50 - 90oC and stirring.

 

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