A method of processing aluminium oxide-platinum catalysts, mainly containing rhenium

 

(57) Abstract:

The invention relates to rare metals and platinum group metals and can be used in enterprises, processing of the deactivated catalyst in various chemical and petrochemical industry. A method of processing aluminium oxide-platinum catalysts, mainly containing rhenium is in the initial firing of the catalyst in the temperature range 300-450oC for 2-3 h, leading to a more complete translation of the precious metals in solution with subsequent sulfide deposition of platinum and rhenium thioacetamide which would increase the degree of extraction of the metal. In addition, the proposed method are trademarks of crystalline aluminum TRIFLUORIDE, which is released from solution peraluminous acid at its neutralization of hydroxide of aluminum. The method increases the degree of extraction of precious metals in bulk concentrate, as well as simplifying the process steps subsequent to their separation and refining. 1 C.p. f-crystals.

The invention relates to rare metals and platinum group metals and can be used in enterprises, processing desactiver ucnai and patent literature, what methods are described relating to the processing of waste latinoreview catalysts can be divided into two types: 1) transfer of metals in the oxidized water-soluble state with separation of the solution from the insoluble cake [1]; 2) burning or dissolving the catalyst carrier with the separation of the resulting solution from the undissolved precipitate noble and rare metals [2]. Both methods have their positive and negative sides. Among the main disadvantages of the first type of the method include low completeness of extraction of precious metals due to the high sorption capacity of the fundamentals of catalysts. In the end, this leads to a large debt on their technological residual content and "improvement" using other methods more suitable for raw materials. The second disadvantage to be considered in the accumulation of large and small concentration of valuable components of solutions resulting from the repeated washing procedures.

The second group of methods based on the complete dissolution of the carrier in an alkaline or acid variants, undoubtedly leads to full access to the catalytic metals. However, has a limitation Sa in operation catalysts pumice, the spinels, silicates, zeolites, carbon-containing matrices, etc. However, the bulk of latinoreview reforming catalysts produced up to the present time on the basis of active aluminum oxide, and in the foreseeable future, this type of catalyst is a leading oil refineries.

The closest analogue is the prototype of the claimed method is a method described in the author's evidence [3], where the translation framework in a soluble state removed with hydrofluoric acid in a concentration range of 10-80 %. Valuable components - platinum and rhenium - stand out in the metallic state, and formed on the basis of the dissolution ferroaluminum acid is directed to the cryolite.

Solving the problem of complex processing of the deactivated catalysts Al2ABOUT3, the prototype method is not without some drawbacks, namely:

1. Input into refining catalyst is given, focusing only on the oxidative burning of organic deposits of the deactivated catalyst. While completely missing the entire recovery procedure of platinum and rhenium in the metallic state. In the above example 1 visualizando is enough for a partial translation of alumina-modification in the form, which is not soluble in hydrofluoric acid in any concentration.

2. The dissolution is carried out in the range of concentrated hydrofluoric acid 10-80%, although it is known that the medium is in the form-Al2ABOUT3in the hydrofluoric acid with a concentration of less than 20% insoluble. HF solution with a concentration of up to 40% are called hydrofluoric acid, and above this value is a solution of hydrogen fluoride in water. Even at room temperature, and even more so when heated to 60-70oWith these solutions lead to a strong outgassing of hydrogen fluoride, which is required to capture.

3. The conditions of example 3 precipitate of platinum and rhenium metal is platinum and rhenium. It is well known that during long-term operation and the regeneration of platinum and rhenium (up to 30-40% of the original content) becomes oxidized state. This part of the metal without the use of the recovery stage or precipitation, such as sulfide, will be irretrievably lost and the solution.

4. Further utilization hexafluoroaluminate acid cryolite requires its neutralization, filtration drum vacuum filters and drying pasta cryolite in rotary printing the technical result - increasing the degree of extraction of metals, simplify subsequent stages of refining and less time-consuming operations of the formed acid (H3lF6with getting as commercial production of aluminum fluoride as a raw material for production of aluminum by electrolysis, perform a method of processing aluminium oxide-platinum catalysts, mainly containing rhenium, including handling hydrofluoric acid. Thus, according to the invention, before treatment in hydrofluoric acid pre-exercise calcination of the catalyst in the range of 300-450oC for 2-3 h after dilution is introduced into the resulting solution dry thioacetamide in the amount of 2-3 g/l at a temperature of 30 - 60oWith separate sludge and conduct a subsequent allocation of a platinum and rhenium, and the solution after the precipitate was neutralized with aluminum hydroxide to form a crystalline precipitate of aluminum TRIFLUORIDE, which is filtered and dried.

Before the dissolution of the catalyst in the hydrofluoric acid, it is heated in air in the temperature range 300-450oC. such an operation is dictated primarily by the need to remove from the catalyst surface organic deposits and Y, because the ultimate goal of the firing process is the removal of coke that escapes platinum and rhenium, and having a high surface activity, adsorb these metals, making it difficult to later transfer them to the solution in the form of complex ions. The upper value of the temperature - 450oWith over substantially and rigidly defined. It must be strictly maintained to prevent the carrier to move in a different crystallographic type, namely-Al2ABOUT3that will not be dissolved and decapsulated catalytic metals inside the grain. At temperatures higher than 450oWith the possible transition rhenium voshon in a volatile oxide Re2O7that will result in significant irreversible loss of its or installation required equipment for his capture.

The second significant feature of the proposed method is to replace the cementation aluminum, for recovery of platinum from the solution and generate a large amount of hydrogen sulfide on the deposition of platinum and rhenium to the formation of insoluble sulfides produced by different sulfur-containing reagents. The absence of formation of gaseous hydrogen sulfide in sulfide deposition allowed in ecosnakes: initial firing, leading to a more complete translation of the precious metals in solution and subsequent sulfide deposition of platinum and rhenium thioacetamide, increase the degree of extraction of metals.

In addition, the proposed method of processing aluminium oxide-platinum catalysts are trademark crystalline aluminum TRIFLUORIDE, which is released from the solution peraluminous acid at its neutralization of the aluminum hydroxide and after filtering and drying, is directed to the production of aluminum.

Thus, the set of essential features aimed at achieving the main goal - increasing the degree of extraction of precious metals in bulk concentrate and simplify process steps subsequent to their separation and refining.

Example 1. Processing was subjected deactivated latinoreview catalyst brand CR-A after its use in cycles of catalytic reforming, of the following composition by macrocomponents, wt.%: platinum - 0,32; rhenium - 0,16; carbonaceous residues to 8.0; iron is 0.3; silica - 2,2; Nickel - 0,3; titanium - 0,58; aluminium oxide - rest.

The addition of catalyst at 1000 g load in a vertical tubular reactor of the firm resistance, set and maintained using estranho thermostat with an accuracy of 5oC. After reaching the set temperature 300oWith the firing continues in the mode of isotherms within 3 hours. After cooling, the catalyst was placed in the reactor ftoroplastory of 9 liters and filled in part 6 liters of 40% hydrofluoric acid with stirring. Analysis of the solution shows that the amount of water-soluble forms of platinum and rhenium is 22% and 48% respectively of their original content. In the obtained reaction solution was cooled to a temperature of 60oTo enter the hitch dry thioacetamide in the amount of 1.5 - 2 g based on the precipitation not only platinum and rhenium, but other metal components. After cooling the solution to room temperature, the precipitated sulphide is filtered off and washed with water. Platinum-rhenium cake weighing 11, 43 g, which corresponds to the concentration factor of not less than 80 times, directed to the selection of platinum and rhenium, and the solution to obtain aluminum fluoride.

Example 2. Suspension of catalyst in 1000 g of the composition described in example 1 is heated at a temperature of 450oC for 2 hours. Subsequent rentgenovskii analysis of the product of firing is not inte, conducted under the conditions of example 1, and subsequent analysis for platinum and rhenium indicate an increase in the content of oxidized forms of platinum and rhenium to the level of 56% and 84%, respectively. Platinum-rhenium concentrate obtained after carrying out sulfidization thioacetamide in the amount of 2.0-2.2 g filtered and washed with water. The residual content of platinum and rhenium in solution, determined by atomic absorption method is 1 mg/l and 3 mg/l, respectively. Deadweight losses platinum solution are equal to 7 mg, and rhenium - 21 mg, which is 0.22% and 1.3% of the initial content, the yield of platinum is 99.79% and rhenium 98,69%.

Thus, on the basis of the foregoing that the proposed method is compared with the prototype allows to significantly increase the degree of extraction of rhenium, without requiring additional equipment. The use of thioacetamide, and not other known sulfiding reagent, such as hydrogen sulfide, makes it a high-tech due to the receipt of sulphides, which are for platinum and rhenium weight forms. The proposed method is much safer to conduct, eliminates the use of hazardous and toxic substances, and more environmentally friendly, Oskolkova And, 63-203728, IPC From 22 In 11/04; a Method of extracting platinum group metals from spent catalyst is similar.

2. RF patent 2083705, IPC 22, 11/00, 7/00 Method of extracting precious metals from waste materials and alumina production is similar.

3. Copyright certificate 211655, the Czechoslovak socialist Republic, the IPC 01 J 23/40, 26.02.1982. The method of processing of spent catalysts containing precious metals - prototype.

1. A method of processing aluminium oxide-platinum catalysts, mainly containing rhenium, including the handling of hydrofluoric acid, characterized in that before the treatment in hydrofluoric acid pre-exercise calcination of the catalyst in the range of 300-450oC for 2-3 h after dilution is introduced into the resulting solution dry thioacetamide in the amount of 2-3 g/l at a temperature of 30-60oWith separate sludge and conduct a subsequent allocation of a platinum and rhenium.

2. The method according to p. 1, characterized in that the solution after the precipitate was neutralized with aluminum hydroxide to form a crystalline precipitate of aluminum TRIFLUORIDE, which is filtered and dried.

 

Same patents:

The invention relates to the field of demercurization of mercury wastes, but can be used to obtain mercury from mercury ores and mercury-containing materials

The invention relates to chemical technology, and in particular to methods of extracting sludge containing platinum, with the surfaces of the apparatuses of chemical technology installations, for example, apparatuses located along the gas for reactor conversion of ammonia on platinum catalyst, in installations for the production of has synthesis, nitrogen and hydrocyanic acid

The invention relates to metallurgy, in particular hydrometallurgy vanadium, and can be used for recycling and disposal of liquid vanadium-containing waste - sewage generated when receiving a different product of vanadium compounds: NH4VO3V2ABOUT5and others
The invention relates to the field of waste

The invention relates to the processing of waste in the form of metal shavings

The invention relates to the production of rare metals and, in particular, recycling of semiconductor compounds based on gallium
The invention relates to a method of dissolving zirconium in recycled materials, and can be used for the extraction of zirconium from construction materials and waste metallurgical and mechanical operations of the production of zirconium, its alloys and products

The invention relates to ferrous metallurgy, in particular to the production of aluminium and alumina, and may be used in the disposal of waste coal lining aluminium electrolysis cells

The invention relates to ferrous metallurgy, to methods for copper-phosphorous alloys used for the production of alloys, deoxidizers and solders

The invention relates to a method of extraction of technetium from a nitric acid solution of technetium using cathodic electrodeposition of technetium by electrolysis

The invention relates to metallurgical industry, namely the processing of molybdenum concentrates and middlings

The invention relates to the field of non-ferrous metallurgy, in particular to a method of processing lead waste containing precious and rare metals
The invention relates to hydrometallurgy and can be used for membrane extraction, concentration and purification of metals both in technology and analytical practice
The invention relates to hydrometallurgy rare metals and can be used for desorption of rhenium

The invention relates to waste latinoreview catalysts on AL2ABOUT3basis

The invention relates to the field of non-ferrous metallurgy

The invention relates to methods for extracting rare metals and can be used for separation of rhenium and other rare and precious metals from gas emissions from active volcanoes, fumaroles gases, gas emanations lava flows, lava lakes
The invention relates to a method for producing fine powder (3 - 5m) alloy of rhenium and molybdenum in the ratio 1 : 1

The invention relates to a method for production of metallic technetium from industrial concentrates pertechnitat potassium, including the dissolution of hanging pertechnitat potassium in water, ion exchange cleaning solution on the cation exchanger in the hydrogen form with obtaining a filtrate-technecally acid neutralization technecally acid ammonia solution, evaporation of the solution, deposition pertechnitat ammonium and restore it to the metal

The invention relates to the field of metallurgy, production of refractory materials - carbides of titanium
Up!