Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B11/00—Obtaining noble metals
  • C22B11/04—Obtaining noble metals by wet processes
  • C22B11/042—Recovery of noble metals from waste materials
  • C22B11/048—Recovery of noble metals from waste materials from spent catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
  • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
  • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
  • B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B1/00—Preliminary treatment of ores or scrap
  • C22B1/005—Preliminary treatment of scrap
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
  • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
  • C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
• • A—HUMAN NECESSITIES
  • A62—LIFE-SAVING; FIRE-FIGHTING
  • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
  • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
  • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
  • A62D3/36—Detoxification by using acid or alkaline reagents
• • A—HUMAN NECESSITIES
  • A62—LIFE-SAVING; FIRE-FIGHTING
  • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
  • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
  • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling

Definitions

• This invention relates to the recovery and reuse of platinum group metals, and more particularly to a process for preparing solid nitrosyl nitrate nitrite using a spent catalyst. Background technique
• Patent CN101638727A discloses a process for the recovery of ruthenium in an activated carbon supported ruthenium catalyst, which involves the preparation of nitrosyl nitrate.
• the obtained cesium hydroxide or RuO 2H 2 0 is stirred and dissolved in a reflux apparatus with a slightly boiling nitric acid by a series of steps such as alkali fusion to obtain a nitric acid solution of Ru(NO)(N0 3 ) 3 .
• the products obtained by the above methods are all acid solutions of nitrosyl nitrate, but because of their high acidity, they are not easy to store and transport.
• Patent CN102167405A discloses a method for preparing solid nitrosyl nitrate nitrate, which reacts ruthenium trichloride and sodium nitrite to synthesize a nitrosylguanidinium intermediate, and an intermediate and silver nitrate to obtain a nitrosyl nitrate solution. Then, nitrosyl nitrate was extracted with diethyl ether, and finally the ether extract was evaporated to obtain a nitrosyl nitrate solid.
• the method can produce solid nitrosyl nitrate, there are still disadvantages: First, due to the introduction of chloride during the preparation process, the product contains impurity chlorine, It is easy to cause catalyst poisoning; Secondly, the method needs to prepare the ruthenium intermediate to obtain the final product in the implementation process, resulting in low product yield; Third, the raw material RuCl 3 .xH 2 0 used in the method can be directly used. As a catalyst, the crystallization of nitrosyl nitrate is prepared by using the crystalline hydrate as a raw material, and the cost is high. Summary of the invention
• the method is simple and efficient, and the high-purity solid nitrosyl nitrate can be directly prepared from the supported ruthenium-containing catalyst, and the obtained solid nitrosyl nitrate can be used as a raw material to prepare the ruthenium-containing catalyst again.
• the method for preparing solid nitrosyl nitrate using the spent catalyst is designed according to the present invention, comprising the following steps:
• cerium-containing black solid obtained in the step 1) is ground to a powder, placed in a fluidized bed reactor, replaced with nitrogen or an inert gas for 0.5 to 2 hours, then switched to hydrogen, and heated to 100 to 600 ° C. Reducing cerium oxide in the spent catalyst to metal ruthenium;
• step 5 adding sodium nitrite solid to the acid solution of cerium nitrate obtained in step 4), stirring appropriately, heating to a slight boiling reflux of the solution to obtain a solution containing nitrosyl nitrate;
• the nitrosyl nitrate-containing solution obtained in the step 5) is extracted with anhydrous diethyl ether, and the ethyl ether extract is collected, and the diethyl ether is evaporated to obtain a nitrosyl nitrate solid.
• the drying condition of the spent catalyst is selected to be heated to 100 ⁇ 150 ° C in a nitrogen or inert gas atmosphere, dried for 1 ⁇ 2 h, and the spent catalyst can be placed in a muffle furnace. Calcination.
• the flow rate of the hydrogen gas during the reduction reaction is not particularly limited, but is preferably 1200 to 400011-1, and the reduction time is 1 to 12 hours, preferably 6 to 12 hours.
• the oxidized ruthenium in the spent catalyst is reduced by hydrogen, and the chemical equation of the reaction is as follows:
• the flow rate of the mixed gas of ozone and air is not particularly limited, but is preferably 1200 to 4000 IT 1 , and the volume fraction of ozone in the mixed gas is 1 to 20%, preferably 15%, oxidized.
• the time is from l to 12 h, preferably from 8 to 12 h.
• the metal ruthenium is oxidized by the mixed gas to osmium tetroxide gas, and the chemical equation of the reaction is as follows:
• Ru + 20 2 Ru0 4 ⁇
• 3Ru + 40 3 3Ru0 4 ⁇
• the temperature of the nitric acid solution is 50 to 95 ° C, and the mass concentration is 45 to 68%.
• the theoretical amount of the nitric acid solution is calculated according to the loading amount of ruthenium in the spent catalyst, and the theoretical amount is 1.2. ⁇ 2.0 times the actual amount used as a nitric acid solution.
• the tertiary absorption device is three brown containers in series. The osmium tetroxide gas is introduced into the nitric acid solution, and the osmium tetroxide gas is absorbed, and a cerium nitrate solution is formed under heating, and the chemical equation of the reaction is as follows:
• the theoretical amount of the sodium nitrite solid is calculated according to the loading amount of ruthenium in the spent catalyst, and the theoretical amount of 1.5 to 2.0 times is taken as the actual amount of the sodium nitrite solid.
• the sodium nitrite solid is suitably added slowly to the acid solution of cerium nitrate with appropriate stirring to uniformly diffuse it in the acid solution of cerium nitrate, and the solution is heated to a slight boiling for reflux, and the reflux time of the reaction is 1 to 8 h. It is preferably 4 to 8 hours.
• the reaction vessel which is heated and refluxed is a commonly used three-necked round bottom flask, which is a common technical means in the art and will not be described herein.
• the chemical equation for the reaction of nitric acid in nitric acid with sodium nitrite is as follows:
• the ruthenium-containing catalyst is a supported ruthenium-containing catalyst having a wide range of supports and may be a combination of one or a mixture of alumina, silica, zirconia, titania and zeolite.
• the carrier can be of any shape, common spherical, cylindrical, clover, four-leaf, ring, honeycomb The type or the like can be used to recover hydrazine by the method of the present invention.
• the invention has the beneficial effects: First, the solid nitrosyl nitrate can be directly prepared from the supported ruthenium-containing spent catalyst by the method of the invention, the recovery cost is low, and the obtained solid product is convenient for storage and transportation;
• the solid nitrosyl nitrate nitrate obtained by the invention method does not contain halogen, and avoids poisoning caused by halogen in the reaction process of the ruthenium-containing catalyst;
• the method of the invention has simple operation steps and does not involve introduction of ruthenium intermediate, The yield of the solid product nitrosyl nitrate is effectively increased.
• the method of the invention realizes the reuse of the cesium resources, has low recovery cost, simple operation, high product yield, high purity, and is suitable for large-scale production.
• Figure 1 is a schematic illustration of a process for the preparation of solid nitrosyl nitrate nitrite using a spent catalyst. detailed description
• ruthenium-containing catalyst (spherical type, Ru/Al 2 0 3 , Ru loading 5%) in a crucible, place it in a muffle furnace, pass N 2 , dry at 120 °C for 2 h, then After calcination at 450 ° C for 3 h, the organic matter remaining in the spent catalyst was removed, and cooled to room temperature to obtain 58.6 g of a solid.
• the solid was triturated in a uniform black powder was transferred to a fluidized bed reactor, purged with nitrogen through for 30min switched to hydrogen gas, a space velocity 120011-1, warmed to 300 ° C, temperature reduction 12h, continue to heat up to 600 ° C , then enter the mixture 15vol%0 3 /air, keep the mixture airspeed 1200 h 1 circulation for 12h.
• the produced Ru0 4 gas was sequentially introduced into three absorption bottles containing 40 g of a 68% by mass nitric acid solution, and the temperature of the nitric acid solution was controlled to be around 75 ° C to obtain an acid solution of Ru(N0 3 ) 3 .
• ruthenium-containing catalyst (cylindrical type, Ru/Si0 2 , Ru loading 3%), place it in a crucible, place it in a muffle furnace, pass N 2 , dry at 120 ° C for 2 h, then at 450 ° C was calcined for 3 h, cooled to room temperature and weighed to give 48.9 g of a solid.
• the black solid was ground into a uniform powder, transferred to a fluidized bed reactor, and replaced with hydrogen gas after being replaced by nitrogen for 30 minutes.
• the space velocity of hydrogen was 2500 IT 1 , the temperature was raised to 350 ° C, the temperature was reduced for 10 h, and the temperature was further increased to 620 ° C.
• ruthenium-containing catalyst (clover type, Ru/Zr0 2 , Ru loading 4%.), put it in a crucible, place it in a muffle furnace, pass N 2 , dry at 120 ° C for 2 h, then at 450 It was calcined at ° C for 3 h, cooled to room temperature and weighed to give 118.2 g of a solid.
• the black solid was ground into a uniform powder, transferred to a fluidized bed reactor, and replaced with hydrogen gas after being replaced by nitrogen for 30 minutes.
• the space velocity of hydrogen was 4000 IT 1 , the temperature was raised to 350 ° C, the temperature was reduced for 6 hours, and the temperature was further increased to 650 ° C.
• ruthenium-containing catalyst (Clover type, Ru/Ti0 2 , Ru load 5%), put it in a crucible, place it in a muffle furnace, pass N 2 , dry at 120 ° C for 2 h, then After calcination at 450 ° C for 3 h, the organic matter remaining in the spent catalyst was removed, and cooled to room temperature to obtain 58.1 g of a solid.
• the black solid was ground into a uniform powder, transferred to a fluidized bed reactor, and replaced with hydrogen gas after being replaced by nitrogen for 30 minutes.
• the space velocity of hydrogen gas was OOO!T 1 , the temperature was raised to 350 ° C, the temperature was reduced for 8 hours, and the temperature was further increased to 620 °.
• the produced Ru0 4 gas was sequentially introduced into three absorption bottles containing 27 g of a 68% by mass nitric acid solution, and the temperature of the nitric acid solution was controlled to be around 75 ° C to obtain an acid solution of Ru(N0 3 ) 3 .
• the mixture gas was introduced into 15 vol% 0 3 /air, and the air-fuel mixture was kept at a space velocity of 3000 h - 1 for 8 hours.
• the produced Ru0 4 gas was sequentially introduced into three absorption bottles containing 16 g of a 45% by mass nitric acid solution, and the temperature of the nitric acid solution was controlled to be around 75 ° C to obtain an acid solution of Ru(N0 3 ) 3 .
• the Ru(N0 3 ) 3 acid solution obtained above was collected in a three-necked round bottom flask, and a NaN0 2 powder of 1.5 times (1.2 g) of the theoretical amount was slowly added, stirred and heated to reflux for 6 hours, and the solution gradually turned into a deep red black. .
• the solution was cooled, extracted with EtOAc (EtOAc) EtOAc.
• EtOAc EtOAc
• Infrared analysis by KBr tableting showed that the characteristic peak was at 1924 cm" 1 , which was consistent with the characteristic structure parameters of RuCNO)CN0 3 ) 3 , and the calculated yield was 96.6%, and the impurity metal content was ⁇ 30 ppm.
• ruthenium-containing catalyst honeycomb type, Ru/Al 2 0 3 -Si0 2 , Ru loading 2%.
• put it in a crucible place it in a muffle furnace, pass N 2 , dry at 120 ° C.
• calcination at 450 ° C for 3 h
• the residual organic matter in the spent catalyst was removed, and cooled to room temperature to obtain 156.4 g of a solid.
• the black solid was ground into a uniform powder, transferred to a fluidized bed reactor, and replaced with hydrogen gas after being replaced by nitrogen for 30 minutes.
• the space velocity of hydrogen gas was SOOO!T 1 , the temperature was raised to 350 ° C, the temperature was reduced for 8 hours, and the temperature was further increased to 620 °. C, then enter the mixture of 15vol%0 3 /air, keep the mixture airspeed 2500 h- 1 for 8h.
• the produced Ru0 4 gas was sequentially introduced into three absorption bottles containing 8.6 g of a 45% by mass nitric acid solution, and the temperature of the nitric acid solution was controlled to be around 75 ° C to obtain an acid solution of Ru(N0 3 ) 3 .
• the Ru(N0 3 ) 3 acid solution obtained above was collected in a three-necked round bottom flask, and a theoretical amount of 1.5 times (0.64 g) of NaN 2 2 powder was slowly added thereto, stirred and heated to reflux for 8 hours, and the solution gradually became dark reddish black.
• the solution was cooled, extracted with EtOAc (3 mL) EtOAc.
• EtOAc 3 mL
• EtOAc Infrared analysis by KBr compression, the characteristic peak is located at 1924cm- 1 , which is consistent with the characteristic structure parameters of Ru(NO)(N0 3 ) 3 .
• the calculated yield is 97.2%, and the impurity metal content is ⁇
• the solid nitrosyl nitric acid prepared by using the spent catalyst containing ruthenium as a raw material according to the method for preparing solid nitrosyl nitrate nitrate by using a spent catalyst is prepared according to the present invention.
• the yields are all above 90%, and under preferred conditions, the yield can be over 95%.
• the obtained solid nitrosyl nitrate can be used as a raw material to prepare a ruthenium-containing catalyst again, thereby realizing the effective utilization of ruthenium resources.
• the method of the invention has low recovery cost and simple operation, and the obtained product has high yield and high purity, and is suitable for large-scale production.

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• 2012
  • 2012-03-05 CN CN201210055796.1A patent/CN102616868B/zh active Active
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