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
  • C22B11/06—Chloridising
• • 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
  • C22B11/02—Obtaining noble metals by dry processes
  • C22B11/021—Recovery of noble metals from waste materials
  • C22B11/026—Recovery of noble metals from waste materials from spent catalysts
• • 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
• • 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

• the invention belongs to the technical field of precious metal recovery in waste catalysts, and specifically relates to a method for recovering ruthenium in an alumina-supported spent catalyst. Background technique
• Bismuth is an extremely expensive rare metal with excellent catalytic properties. It is widely used in the catalyst industry. It is widely used in the production of synthetic ammonia, selective hydrogenation of benzene to cyclohexene and fuel cells. The annual output of the world is only tens of tons. China's plutonium resources are scarce, with an annual output of only a few kilograms, less than 1% of the total demand. Therefore, most of the plutonium used in China's production of catalysts relies on imports, which ultimately leads to high cost of antimony catalysts.
• the content of antimony in natural ore in China is only 0.028g/t
• the content of antimony in the catalyst is generally not less than 500g/t, which is much higher than the content of antimony in natural ore
• the composition of spent catalyst is far more than natural ore.
• the composition is simple. Therefore, the recovery of plutonium from spent catalyst can not only realize the recycling of plutonium resources, but also have important significance for resource conservation and environmental protection, and also have important economic value.
• the Chinese invention patent No. 200610052073.0 discloses a method for recovering a ruthenium catalyst supported by activated carbon, comprising the following steps: an activated carbon supported ruthenium catalyst containing no or already removed alkali metal or alkaline earth metal compound auxiliaries at 600 ⁇ 1000 ° C calcined for 2 ⁇ 20h, the obtained gray-black mixture is mixed with KOH and KN0 3 , and the temperature is kept at 300 ⁇ 950 °C for 1 ⁇ 5h, and the alkali melt is obtained by cooling, and the alkali melt is dissolved in hot water of 50 ⁇ 90 °C to obtain K.
• Chinese Patent Application No. 200610106338.0 discloses a method for efficiently preparing a high-quality cerium powder from a cerium-containing solution, which is a step of preparing cerium powder by calcining (NH 4 ) 3 RuCl 6
• the crude crucible obtained by calcining (NH 4 ) 3 RuCl 6 at 500 to 800 ° C is then calcined again at 800 to 1000 ° C, whereby the chlorine content in the niobium powder is 100 ppm by mass or less.
• Ru(III) is directly precipitated by using ammonium chloride in a hydrochloric acid solution containing hydrazine to form (NH 4 ) 3 RuCl 6 , which is calcined and reduced with hydrogen to obtain cerium powder.
• this method can obtain high-quality tantalum powder, the (NH 4 ) 3 RuCl 6 obtained by precipitation of Ru(III) is highly water-soluble, resulting in incomplete precipitation of ruthenium in the solution, and the recovery rate is extremely low.
• An object of the present invention is to provide a process for recovering ruthenium from an alumina supported spent catalyst which is simple in operation, low in cost, short in recovery period, and high in recovery.
• the method for recovering rhodium in the alumina-supported spent catalyst of the present invention comprises the following steps in sequence:
• the alumina-supported spent catalyst to be treated is heated to 100 to 150 ° C in a N 2 atmosphere, dried for 1 to 2 hours, and then heated to 300 to 500 ° C. After calcination for 2 to 4 hours, it is cooled to room temperature and then ground. , obtaining a black powder containing cerium oxide;
• the flow rate of the mixture of the step 3) is 1000 OO! T ⁇
• the volume fraction of ozone is 1 to 20%.
• the concentration of hydrochloric acid in the step 4) is 6 mol/L.
• the weight of NH 4 C1 added in step 5) is controlled to be 1.2 to 2.5 times the theoretical value required for the reaction with H 2 RuCl 6 .
• the soluble chlorate in step 5) is one or more of ammonium chlorate, potassium chlorate, sodium chlorate or magnesium chlorate.
• the filter cake is washed with an ethanol solution in step 5).
• step 5 when NH 4 C1 is added, it is stirred at a rate of 100 to 400 r/min for 1 to 3 hours; further preferably, it is stirred at a rate of 200 r/min for 1.5 to 2.5 hours.
• the mixture is dried in a N 2 atmosphere and then calcined at a high temperature, whereby the water in the spent catalyst and the residual organic substance impurities can be effectively removed, and the main component of the product is cerium oxide.
• step 2) the cerium oxide in the spent catalyst is reduced to a free state by hydrogen gas, and the reaction process is:
• step 3 The reaction that occurs in step 3) is:
• Ru+20 2 Ru0 4 ⁇
• 3Ru+40 3 3Ru0 4 ⁇
• oxygen can be used as oxygen in the mixture, and pure oxygen can also be used.
• step 4 the ruthenium tetroxide gas is introduced into a sufficient amount of 3 ⁇ 8 mol/L hydrochloric acid, and the osmium tetroxide gas is absorbed and reduced to a solution of hexachloroiridium(III) acid (H 3 RuCl 6 ). for:
• step (5) an oxidizing agent is used for the oxidation reaction, and the hexachloroiridium (III) acid (H 3 RuCl 6 ) is oxidized to hexachloroiridium (IV) acid (H 2 RuCl 6 ), and then an excess of ammonium chloride is added.
• the precipitation of ammonium hexachloroiridium (IV) hydride [(NH 4 ) 2 RuCl 6 ] is obtained, and the reaction principle is as follows:
• Step 6 The metal ruthenium is obtained by hydrogen reduction of the ammonium hexachloroiridium (IV) hydride [i.e., (NH 4 ) 2 RuCl 6 ] solid at a high temperature. After the metal crucible is further processed, the crucible powder for the target can be obtained.
• IV ammonium hexachloroiridium
• the method of the present invention obtains a solution of Ru(III)-containing hexachloroiridium(III) acid (H 3 RuCl 6 ) in a recovery step, and then hexachlorine is added by adding an oxidizing agent.
• the ruthenium (III) acid (H 3 RuCl 6 ) is sufficiently oxidized to hexachloroiridium (IV) acid (H 2 RuCl 6 ), and the corresponding ammonium hexachloroantimonate (IV ) is obtained by adding an excess of ammonium chloride [ie The precipitation of (NH 4 ) 2 RuCl 6 ] increases the precipitation rate of cerium in the solution, and the obtained ammonium hexachloroantimonate precipitate can directly produce the cerium powder meeting the target requirements by the calcination hydrogen reduction method.
• the recovery process of the method of the invention has simple operation and low reaction energy consumption, and realizes efficient recycling of the ruthenium in the alumina-supported spent catalyst, thereby improving economic benefits and facilitating recycling of the ruthenium. detailed description
• a method for recovering ruthenium in an alumina supported spent catalyst comprises the following steps:
• the Ru recovery in this example was 98.03%.
• a method for recovering ruthenium in an alumina supported spent catalyst comprises the following steps:
• the Ru recovery in this example was 99.2%.
• a method for recovering ruthenium in an alumina supported spent catalyst comprises the following steps:
• a method for recovering ruthenium in an alumina supported spent catalyst comprises the following steps:
• the Ru recovery was 96.7%.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
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• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Catalysts (AREA)
• Manufacture And Refinement Of Metals (AREA)

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Citations (5)

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• 2012
  • 2012-03-05 CN CN2012100558061A patent/CN102560128B/zh not_active Expired - Fee Related
• 2013
  • 2013-03-04 EP EP13758628.5A patent/EP2824201B1/en not_active Not-in-force
  • 2013-03-04 MX MX2014010726A patent/MX342580B/es active IP Right Grant
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  • 2013-03-04 WO PCT/CN2013/072114 patent/WO2013131453A1/zh not_active Ceased
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  • 2013-03-04 AU AU2013230405A patent/AU2013230405B2/en not_active Ceased
• 2014
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