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 400-600°C air is treated with alkali solution with a concentration of not less than 40 wt.% in an autoclave at a temperature of 140-200°C 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 hoursStudies 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 hThe 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 hThe 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 hours2. 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.
FIELD: noble metal hydrometallurgy.
SUBSTANCE: invention relates to method for acid leaching of platinum method from secondary raw materials, in particular from ceramic support coated with platinum metal film. Target metals are leached with mixture of hydrochloric acid and alkali hypochlorite at mass ratio of OCl-/HCL = 0.22-0.25 and redox potential of 1350-1420 mV.
EFFECT: decreased leaching temperature, reduced cost, improved platinum metal yield.
FIELD: separation of palladium from waste mangani-palladium catalyst and cleaning of palladium.
SUBSTANCE: palladium-containing concentrate is treated with aqua regia solution and palladium is deposited in form of chloropalladate by means of treatment with aqua regia solution with solid ammonium chloride, pulp thus obtained is settled, cooled and filtered; sediment is treated with saturated hydrochloric acid solution of ammonium chloride. Then sediment thus treated is dissolved in water and solution is filtered and neutralized; pallarium is restored to metal by means of hydrochloric acid hydrazine at pH≥2 or formic acid solution at pH≥6; solution is filtered and metallic palladium is washed and dried at 90-100°C. Prior to treatment, mangani-palladium catalyst with aqua regia, it is dissolved in concentrated hydrochloric acid; solution is neutralized by asmmonia to pH=6-7 and treated with formic acid at flow rate no less than 1 l of HCOOH per kg of mangani-palladium catalyst; then mangani-palladium concentrate is filtered, washed and dried at 90-100ºC.
EFFECT: enhanced purity of metallic palladium at minimum losses of catalyst at all stages of chemical treatment.
FIELD: extraction of platinum and rhenium from decontaminated used platinum-rhenium catalysts; reworking of secondary raw materials of petrochemical industry.
SUBSTANCE: proposed method includes high-temperature oxidizing roasting at temperature of 1200-1300°C, wet trapping of rhenium by alkaline solution, leaching-out of cinder in hydrochloric acid solution at concentration of 100-150 g/dm3 in presence of oxidizing agent for setting the oxidizing-reducing potential of platinum electrode in pulp relative to saturated silver-chloride electrode equal to 850-1000 mV. Used as oxidizing agent is sodium hypochlorite or elementary chlorine or hydrogen peroxide.
EFFECT: enhanced efficiency of process.
1 tbl, 13 ex
FIELD: inorganic synthesis catalysts.
SUBSTANCE: ammonia synthesis catalyst includes, as catalytically active metal, ruthenium deposited on magnesium oxide having specific surface area at least 40 m2/g, while concentration of ruthenium ranges between 3 and 20 wt % and content of promoter between 0.2 and 0.5 mole per 1 mole ruthenium, said promoter being selected from alkali metals, alkali-earth metals, lanthanides, and mixtures thereof. Regeneration of catalytic components from catalyst comprises following steps: (i) washing-out of promoters from catalyst thereby forming promoter-depleted catalyst and obtaining solution enriched with dissolved promoter hydroxides; (ii) dissolution of magnesium oxide from promoter-depleted catalyst in acidic solvent wherein ruthenium is insoluble and thereby obtaining residual ruthenium metal in solution enriched with dissolved magnesium compound; and (iii) regeneration of residual ruthenium metal from solution enriched with dissolved magnesium compound via liquid-solids separation to form indicated solution enriched with dissolved magnesium compound and ruthenium metal.
EFFECT: increased catalyst activity.
6 cl, 6 ex
FIELD: hydrogenation-dehydrogenation catalysts.
SUBSTANCE: invention provides catalytic composition for dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprising: carrier consisting of alumina in δ phase or in θ phase, or in mixed δ+θ or θ+α, or δ+θ+α phase, modified with silicon oxide and having surface area less than 150 m2/g as measured by BET method; 0.1-35% gallium in the form of Ca2O3; 0.01-5% manganese in the form of Mn2O3; 0-100 ppm platinum; and 0.05-4% alkali or alkali-earth metal oxide, all percentages being based on the total weight of composition. Other variants of composition are also covered by invention. Methods of preparing such catalytic composition (options) envisage use of alumina-based carrier in the form of particles corresponding to group A of the Geldart Classification. Process of dehydration of alkylaromatic hydrocarbons optionally combined with ethane comprises: (i) dehydration of hydrocarbon stream optionally mixed with inert gas in fluidized-bed reactor in presence of catalytic composition consisted of alumina-supported and silica-modified gallium and manganese at temperature within a range of 400 to 700°C, total pressure within a range of 0.1 to 3 atmospheres, and gas hourly space velocity from 50 to 10000 h-1; and (ii) regeneration and heating of catalyst caused by catalytic oxidation of fuel in fluidized-bed reactor at temperature above 400°C.
EFFECT: increased activity of catalytic composition and prolonged lifetime thereof.
22 cl, 2 tbl, 16 ex
FIELD: methods of extraction and separation of platinum and rhenium in processing waste bimetallic reforming catalysts.
SUBSTANCE: proposed method includes alkali sintering and aqueous leaching-out for obtaining the solution containing sodium permeate and insoluble residue. Alkali sintering is carried out in presence of oxidant in form of agent generating the gaseous sulfur anhydride, sodium bisulfate or sodium permeate in particular. Insoluble residue is leached-out with hydrochloric acid for dissolving of platinum. Through extraction of rhenium and platinum into commercial product ranges from 96.6 to 99.2%, respectively. Proposed method requires no special equipment.
EFFECT: high degree of extraction of platinum and rhenium.
3 cl, 2 ex
SUBSTANCE: method of regeneration of the palladium catalyst of the hydrogenation of acetylenic hydrocarbons is described by processing it using an inert gas, then by mixture of an inert gas with an oxygen-containing gas at raised temperature till the content of CO2 in the outgoing regeneration gas is less than 0,05 % vol., cooling of the catalyst, the subsequent restoration of the catalyst from the oxidized form of palladium up to metal in an atmosphere of hydrogen containing gas and its cooling up to the temperature of the reaction of hydrogenation, and the catalyst after inert-gas flushing, additionally blow hydrogen-containing gas at the temperature 200-250°C and regeneration of the catalyst layer in adiabatic reactor is conducted separately, with a separate supply and outlet of regeneration gas for each catalyst layer.
EFFECT: improvement of restoration of operational characteristics of the palladium catalyst at carrying out the of process of regeneration.
3 cl, 2 tbl, 6 ex
SUBSTANCE: invention relates to methods of reducing platinum-rhenium reforming catalyst and can be used on oil-refining, petrochemical and gas production enterprises. A method is proposed for reducing platinum-rhenium reforming catalyst through high temperature treatment with a circulating reforming hydrogen-containing gas, containing an additive of sulphur compounds in amount of 0.05-0.30 % of the mass of catalyst (in terms of sulphur) in two stages. The method is distinguished by that, the platinum-rhenium catalyst is pre-treated only with hydrogen-containing gas at temperature 480-500°C for 2-4 hours, and treatment with sulphur compound additives at the first stage is done at temperature 480-400°C, and 280-260°C at the second stage.
EFFECT: significant increase of octane number of reformate, as well as inter-regeneration cycle of the catalyst.
4 cl, 2 ex
SUBSTANCE: invention refers to particles of metal oxide carrier of catalyst, method of such particle obtainment, waste gas treatment catalyst including metal oxide catalyst, and method of waste gas treatment catalyst recovery. Invention describes particle of metal oxide catalyst carrier, consisting of central part and external shell part, where both central and external shell parts include first metal oxide and second metal oxide, central part and external shell part differ in composition, molar fraction of first metal oxide is higher in central part than in external shell part, molar fraction of second metal oxide is higher in external shell part than in central part, and first metal oxide is aluminium or zirconium oxide while second metal oxide is selected out of group including neodymium, praseodymium, lanthanum, scandium and yttrium oxides. Invention describes waste gas treatment catalyst including the claimed particle of metal oxide carrier and platinum applied onto the particle of metal oxide catalyst carrier. Invention describes method of waste gas treatment catalyst recovery involving waste gas treatment catalyst heating at 500°C or higher in oxidation medium including oxygen. Also invention describes method of obtaining particle of metal oxide catalyst carrier, consisting of central part and external shell part, where both parts include first metal oxide and second metal oxide, central part and external shell part differ in composition. Method involves obtainment of material solution including at least colloid particles of first metal oxide and metal salts of second metal oxide, where first metal oxide is aluminium or zirconium oxide, second metal oxide is selected out of group including neodymium, praseodymium, lanthanum, scandium and yttrium oxides; achievement of solution pH close to isoelectric point of colloid particles of first metal oxide so as to coagulate colloid particles of the first metal oxide; solution pH increase so as to cause precipitation of colloid particles of the second metal oxide from metal salts and coagulate colloid particles of the second metal oxide around coagulated colloid particles of the first metal oxide, where isoelectric point of colloid particles of the second metal oxide is higher than isoelectric point of colloid particles of the first metal oxide; and coagulated product drying and calcination.
EFFECT: increased specific area of waste gas treatment catalyst surface, increased degree of platinum particle recovery.
10 cl, 19 ex, 2 tbl, 3 dwg
SUBSTANCE: invention relates to a catalyst for cleaning exhaust gases, a method of regenerating such a catalyst, as well as a device and a method of cleaning exhaust gases using the said catalyst. The invention describes a catalyst for cleaning exhaust gases where a noble metal is attached to a metal oxide support. In an oxidative atmosphere, the noble metal on the surface of the support is in a high oxidation state and the noble metal is bonded to the cation of the support though an oxygen atom on the surface of the support with formation of a surface oxide layer. In a reductive atmosphere, the noble metal on the surface of the support is metallic state and the amount of noble metal open on the surface of the support, measured through CO chemisorption, is equal to or greater than 10 at % of the total amount of noble metal attached to the support. Described is a method of regenerating a catalyst for cleaning exhaust gases in which the above described catalyst for cleaning exhaust gases undergoes oxidative treatment by heating in an oxidative atmosphere which contains oxygen, and reduction treatment. Described also are devices for cleaning exhaust gases (versions) and a method of cleaning exhaust gases, involving cleaning exhaust gases by bringing the exhaust gases into contact with the above described catalyst.
EFFECT: prevention of reduction of catalyst activity.
18 cl, 11 tbl, 46 ex, 10 dwg