The method of extraction of platinum and/or palladium from spent catalysts

 

(57) Abstract:

The invention can be used in the field of oil refining and petrochemistry, namely the processing of spent catalysts containing platinum and/or palladium on the basis of aluminum oxide formed during refining. Describes how to extract platinum and/or palladium, in which the platinum and/or palladium spent catalysts after the preliminary burning of coke in an environment heated to 400-600C air is treated with alkali solution with a concentration of not less than 40 wt.% in an autoclave at a temperature of 140-200C With supplementation of aqueous solutions of hydroxylamine, aluminum nitrate, an alcohol solution of isobutyl alcohol, taken in the ratio of 1-2:1-2:1 in the amount of 0.5-2% by weight of the catalyst. The technical result is to increase the degree of extraction of platinum and/or palladium. 1 C.p. f-crystals, 1 table.

The present invention relates to the field of petrochemistry and oil refining, and in particular to the field of processing of the deactivated catalysts containing platinum and/or palladium on aluminium oxide.

During operation aluminium oxide-platinum (palladium) catalysts containing from 0.1 to 0.7 wt.% blogarchive they derive from the process of refining and sent as waste (deactivated) in processing, along with the waste catalyst production.

The simplest method of disposal of decontaminated, aromaplastie (palladium) catalysts recognized them melting in the ore-thermal furnaces together with copper-Nickel raw material at a temperature of 1350oC. the platinum group Metals are lost in large quantities because of their distribution in the products of melting, the volumes are significant /I. W. Sataev and other "non-Waste technology platinum palladium catalysts," C. 95/.

Numerous methods of extraction of platinum and palladium contained in the directories /M. Sittich. Extraction of metals and inorganic compounds from waste. TRANS. from English., M, metallurgy, 1985, S. 288; M. A. meretukov, A. M. Orlov. Metallurgy of noble metals (foreign experience), M, metallurgy, 1991 ; Noble metals, References:. ed. Ed. by E. M. Savitsky, M., metallurgy, 1984/.

Known methods hydrometallurgical hydrochloric opening of the deactivated catalysts: the processing solution of 1 to 12 N. hydrochloric acid and 30% hydrogen peroxide /the Japanese patent class. C (22 11/04) N 53-28849/, the solution of 1 to 12 N. HCl with addition of chloride acid /Japanese patent class. C N 28-28850/.

To the acidic ways autopsy of rare-metal ores and placers, Proceedings of Irgiredmet, M., 1967, vol. 16/.

Acidic methods often involve the use of high temperatures, which leads to the decomposition of the acids, the release of gases, vapors, harmful for staff, the environment, corrosive to the equipment used. This should include the main weaknesses of the acid methods. In addition, the concentration of platinum (palladium) in solutions insignificant and for their allocation requires an increased consumption of reagents, such as iron, aluminum powder (chip) for cementation. Loss of platinum is 3-5 % /M. Sittich. Extraction of metals and inorganic compounds from waste. TRANS. from English., M, metallurgy, 1985, S. 288/.

Known combined, the acid-alkaline methods of processing of spent catalysts. According to the patent U.S. CL 75-83 N 3332771 raw materials are treated with nitric acid or nitric acid with the addition of hydrofluoric acid. The residue leaching alloy with caustic soda at a temperature of more than 750oC., the Melt then leached with water. The use of such methods is associated with high energy consumption.

There are many alkaline processing methods deactivated catalization (aluminium oxide) in solution, for example, in the form of sodium aluminate. Platinum (palladium) mainly concentrated in the insoluble residue leaching. These methods can be done in different ways: by fusing with caustic soda /patents RU CL 01 J 23/96 N 96119021/04, N 96115639/02, N 2083705; patent Czechoslovakia N 91468/, sintering with soda /Processing gold, diamond, and rare-metal ores and placers, proceedings of Irgiredmet, M., 1967, vol. 16/ with subsequent leaching SPECA water.

In addition, it is known that the basis deactivated aluminium oxide-platinum (palladium) catalysts (alumina) is dissolved in autoclaves in solutions of caustic soda /metallurgy of noble metals, ed. 2 Ed. by A. C. Chuguev, M. , metallurgy, 1987, S. 426/. The temperature in autoclaves offer support 160-170oC /France, patent N 1156974/ or 200oC for 3 h, the ratio of T:W=1:1.5 and thus obtain a concentrate containing precious metals to 7.4%.

The disadvantages of alkaline ways of "opening" of spent catalysts, i.e. the dissolution of their framework is the partial transition of platinum (palladium) in the liquid phase of the slurry of sodium aluminate. Loss of platinum group metals in this case will be determined by the concentration and volume paciana apply the reducing agent, for example, metallic aluminum, hydrazine, formalin.

Closest to the proposed method according to the technical solution is the prototype, described in the book "the metallurgy of noble metals, ed. 2 Ed. by A. C. tchugaev, M., metallurgy, 1987, page 426".

The prototype is proposed to autoclave leaching of the deactivated catalysts containing platinum or palladium, in an aqueous solution of alkali at a temperature of 160-170oC, you get a 7 wt.% the concentrate of precious metals.

At the specified method does not assume the introduction of additives into the autoclave to prevent transition in the solution of various compounds of platinum metals (up to 1 - 3 wt.%), formed during operation of the catalyst and during the pre-firing, which entails additional cementation formed pulp different reducing agents.

Therefore, the objective of the proposed invention is to provide a method for processing deactivated platinum, palladium catalysts, and mixtures thereof with minimum losses of precious metals from solution after autoclave leaching with the possibility of further use of the sodium aluminate solution to pry the result is achieved by after the preliminary regeneration from coke handling spent catalyst is conducted in the following way.

In a pre-heated in the autoclave up to 40-70oC 46% alkali solution is poured exhaust catalyst, and additives are introduced: hydroxylamine hydrochloric acid, aluminum nitrate, isobutyl alcohol, taken in the mass ratio of 1-2:1-2:1 and in a total amount of 0.5-2% by weight of the catalyst. The solution is incubated for 2-5 hours at a temperature of 40-70oC. After cooling, the autoclave is heated to a temperature of 140-200oC and carry out the leaching within 3-8 hours

Studies have shown that the proposed method autoclave leaching allows to achieve extraction for platinum 99.70-99.80% palladium 97.0-99.0%.

Supplementation allows on stage preheating and entry mode to minimize partial transition metals in solution. The complete elimination of one of the substances significantly reduces the effectiveness of the additive in General, the flow compensating component increases, which complicates the processing of aluminate solution, reduces economic indicators.

The quantity of additives and their ratio depends on the type and content of the 1000 g, loaded into an autoclave filled with 46 wt.% aqueous alkali solution (mass ratio of Na2O:Al2O3amounted to 1.7:1), heated to a temperature of 160oC and incubated for 6 h

The resulting slurry is diluted with 9 times the water volume filtered off the insoluble precipitate in the mother solution, determined in a known manner, the output of platinum with an insoluble precipitate, which was 98.73% by weight (table 1).

Example 2 (prototype). A portion of the catalyst containing 0.50% of palladium in the amount of 1000 g, loaded into an autoclave filled with 46 wt.% aqueous alkali solution (mass ratio of Na2O:Al2O was 1.7:1), heated to a temperature of 170oC and incubated for 6 h

The resulting slurry is diluted with 9 times the water volume filtered off the insoluble precipitate in the mother solution in a known manner to determine the output of palladium, which amounted to 97,31 wt.% (table 1).

Example 3. In the autoclave preheated to 50oC 46% alkali solution (mass ratio of Na2O:Al2O31.7-1.8:1) sleep 1000 g of spent catalyst with a platinum content 0.51 wt.% and enter the additives: hydroxylamine hydrochloric acid, azo who s spent catalyst, and maintained at a temperature of 50oC and stirring for 3 hours the Reaction mass is heated to a temperature of 170-180oC, incubated for 5 hours the resulting slurry is diluted 9 times with water, filtered off the insoluble precipitate in the mother solution in a known manner to determine the loss of solution. The output of platinum was 99.80 wt.% (table 1).

Examples 4 through 12. Carried out analogously to example 3, except that changing the mass ratio of additives: hydroxylamine hydrochloric acid, aluminum nitrate, isobutyl alcohol, and the total amount of additives. Received the degree of extraction of precious metals is given in table 1.

The results of our experiments show that, on the one hand, reducing the number of one of the components of the additive leads to a noticeable increase in the losses of precious metals from the mother liquor (more than 0.3 wt.% for platinum - examples N 4, 7, 9; more than 3 wt.% for palladium - examples N 15, 17, 19), on the other hand, the increase in the number of one of the additives does not lead to further reduction of the losses of precious metals with the mother solution (examples N 6, 8, 10, 14, 16, 20).

Thus, for carrying out the leaching of the deactivated catalyst solution SEL is about, nitrate aluminum, isobutyl alcohol) is 1-2:1-2:1 when the total number of additives 0.5-2% by weight of the deactivated catalyst.

The method of extraction of platinum and/or palladium from spent catalysts containing chemical processing of spent catalyst with an aqueous solution of alkali in the autoclave, characterized in that the chemical treatment of spent catalysts containing platinum and/or palladium, conduct heated to 40-70oC alkali concentration of at least 40 wt.% aged 2-5 h and supplementation: hydroxylamine hydrochloric acid, aluminum nitrate, isobutyl alcohol, taken in the mass ratio of 1-2:1-2:1 and in a total amount of 0.5-2% by weight of spent catalyst, followed by heating to a temperature of 140-200oC and leaching within 3-8 hours

2. The method according to p. 1, characterized in that after leaching and separation of insoluble precipitate containing platinum and/or palladium, the sodium aluminate solution is directed to the production of catalysts, adsorbents, gas dehydrators.

 

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