CN108330287A - A method of with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst - Google Patents

A method of with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst Download PDF

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CN108330287A
CN108330287A CN201810097457.7A CN201810097457A CN108330287A CN 108330287 A CN108330287 A CN 108330287A CN 201810097457 A CN201810097457 A CN 201810097457A CN 108330287 A CN108330287 A CN 108330287A
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alkali metal
ruthenium
catalyst
useless agent
salt form
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CN108330287B (en
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江莉龙
倪军
涂子龙
林建新
林炳裕
林科
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Beijing Haixin Energy Technology Co ltd
Fuzhou University National Engineering Research Center Of Chemical Fertilizer Catalyst
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CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
Beijing SJ Environmental Protection and New Material Co Ltd
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    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • C22B1/02—Roasting processes
    • 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

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  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention belongs to catalyst recovery technology fields, and in particular to a method of recycling ruthenium in the useless agent of catalyst in the form of alkali metal ruthenate.This method is first removed the activated carbon supported ruthenium catalyst alkali and alkaline earth metal ions in agent that give up by pickling, avoids the formation of insoluble alkaline earth ruthenate；Then alkali metal compound is added into catalyst again to be roasted, on the one hand alkali metal compound is capable of the oxidation of photocatalytic active carbon, it is substantially reduced calcination temperature, shorten roasting time, still further aspect catalyst can the give up ruthenium in agent is converted into soluble alkali metal ruthenate, alkali metal ruthenate can be directly thrown into the production technology of catalyst, be directly realized by the recycling of ruthenium.

Description

A method of with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst
Technical field
The invention belongs to catalyst recovery technology fields, and in particular to a kind of to recycle catalyst with alkali metal ruthenic acid salt form The method of ruthenium in useless agent.
Background technology
From BP companies of Britain in 1992 and Kellogg companies of the U.S. successfully develop activated carbon supported ruthenium ammonia synthesis catalyst with Come, since the catalyst can efficiently synthesize ammonia under the conditions ofs lower reaction temperature, pressure etc., it is considered to be after ferrum-based catalyst Later second generation ammonia synthesis catalyst.But the storage capacity of ruthenium is fewer in the world, and it is in addition expensive, limit ruthenium ammino At the development of catalyst, can ruthenium recycle the popularization and application for directly affecting catalyst.
For this purpose, Chinese patent literature CN106282581A discloses a kind of recycling side of ruthenium in activated carbon supported ruthenium catalyst Method, this method roast 4~20h after first drying activated carbon supported ruthenium catalyst under 400~800 DEG C of environment, remove activated carbon Then carrier is dissolved the remaining solid after roasting using acid solution, be filtered recycling after washing and obtain main component For the insoluble solid of ruthenic oxide, filtrate is directly recycled as the process water for preparing activated carbon supported ruthenium catalyst, the party Case step is simple, easy to operate.
But ruthenium recovery method needs disclosed in above patent document remove absorbent charcoal carrier under higher calcination temperature It goes, removal process high energy consumption；Secondly, ruthenium soluble-salt main component is potassium ruthenate in filtrate, and unstable chemcial property is easy to It is decomposed into insoluble ruthenic oxide, leads to the loss of ruthenium；And the content of potassium ruthenate is relatively low.Further, since in product of roasting Composition is more complex, and ruthenium can not recycle completely, and the solid ruthenic oxide that recycling obtains cannot be utilized directly, and the rate of recovery is relatively low. Based on this, if it is possible to a kind of method that low energy consumption, the rate of recovery is high, and direct recycling obtains the alkali metal salt of ruthenium is provided, it will The problem of energy waste and shortage of resources is effectively relieved.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome activated carbon supported ruthenium catalyst in the prior art to give up agent Recycling high energy consumption, the rate of recovery of middle ruthenium are low, and the solid ruthenic oxide recycled cannot be directly used to preparation of catalyst etc. and lack It falls into, to provide one kind, low energy consumption, the rate of recovery is high, and directly recycling obtains alkali gold in capable of giving up agent from activated carbon supported ruthenium catalyst Belong to the method for ruthenate.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A method of with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, the catalyst gives up agent as activated carbon Supported ruthenium catalyst gives up agent, includes the following steps：
Pre-treatment step：2-24h is impregnated into activated carbon supported ruthenium catalyst agent of giving up in acid solution, filtration washing obtains Filtrate and filter residue；Filter residue is the activated carbon supported ruthenium catalyst for removing alkali and alkaline earth metal ions, for not alkali metal containing and alkali The catalyst of earth metal then omits this step；If impregnating can repeatedly impregnate without fully removing alkali and alkaline earth metal ions；
Calcination steps：Alkali metal compound is added into filter residue, wherein alkali metal quality accounts for activated carbon supported ruthenium catalyst Useless agent quality 18-22%, 2-10h is roasted at 300-600 DEG C；
Post-processing step：It is then added to the solid water dissolution after roasting in polyhydroxy-alcohol solution, filters, washing, Filtrate is collected to get the polyhydroxy-alcohol solution of alkali metal ruthenate.Ruthenium tenor in filtrate can be measured by ICP, then It can put into the production technology of catalyst.
Further, the dosage of water is 8-12 times of calcined solids quality in the post-processing step.
Further, the dosage of polyhydroxy-alcohol is 8-12 times of calcined solids quality in the post-processing step.
Further, the mass concentration of the polyhydroxy-alcohol solution is 5-15%.The polyhydroxy-alcohol is ethylene glycol, the third three Alcohol, trimethylolethane or xylitol.
Further, the acid solution in the pre-treatment step is salpeter solution, hydrochloric acid solution, acetum or citric acid Solution.
Further, the mass concentration of the acid solution is 5-30%.
Further, in the calcination steps alkali metal compound be alkali metal nitrate, carbonate, acetate or Alkali.
Further, oxygen-containing gas is passed through when roasting.
Further, the volume content of oxygen is 8-40% in the oxygen-containing gas.
Further, contain base earth metal promoter in the activated carbon supported ruthenium catalyst；If activated carbon supported ruthenium is urged Alkaline including earth metal does not save pre-treatment step then in agent.
Technical solution of the present invention has the following advantages that：
1. the method for ruthenium, has step letter in the useless agent provided by the invention with alkali metal ruthenic acid salt form recycling catalyst It is single, removal process the advantages of low energy consumption.This method first gives up activated carbon supported ruthenium catalyst alkali metal and/or alkaline earth gold in agent Category is removed by pickling, avoids the formation of insoluble alkaline earth ruthenate；Then alkali metal chemical combination is added into catalyst again On the one hand object, alkali metal compound are capable of the oxidation of photocatalytic active carbon, hence it is evident that reduce calcination temperature, shorten roasting time, in addition On the one hand the ruthenium in agent that catalyst can give up is converted into soluble alkali metal ruthenate, and alkali metal ruthenate can directly be thrown Enter into the production technology of catalyst, is directly realized by the recycling of ruthenium.
2. the method for ruthenium in the useless agent provided by the invention with alkali metal ruthenic acid salt form recycling catalyst, in post-processing step It is middle to be handled using polyhydroxy-alcohol, stable polyhydroxy-alcohol ruthenium complex is formd with unstable alkali metal ruthenate, is kept away Exempt from unstable alkali metal ruthenate and be decomposed into ruthenic oxide, improves the rate of recovery of soluble alkali metal ruthenate.
Specific implementation mode
For convenience of description, the catalyst used in the embodiment of the present invention and comparative example the agent composition that gives up is as follows：
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and alkali metal, alkaline earth metal compound auxiliary agent in embodiment It is the 5.00% of catalyst quality that composition measures ruthenium content by micro-wave digestion-ICP, and potassium content is catalyst quality 4.00%, barium content is the 8.00% of catalyst quality.
The useless agent composition warp of activated carbon supported ruthenium catalyst containing metal Ru and alkaline earth metal compound auxiliary agent in embodiment It is the 5.00% of catalyst quality to cross micro-wave digestion-ICP and measure ruthenium content, and barium content is the 8.00% of catalyst quality.
The useless agent composition of the activated carbon supported ruthenium catalyst containing metal Ru measures ruthenium by micro-wave digestion-ICP in embodiment Content is the 5.00% of catalyst quality.
The activated carbon supported ruthenium catalyst of the alkali and alkaline earth metal ions compound auxiliary agent containing nitric acid ruthenium is useless in embodiment It is the 5.00% of catalyst quality that agent measures ruthenium content by micro-wave digestion-ICP, and potassium content is the 3.40% of catalyst quality, Barium content is the 8.10% of catalyst quality.
Embodiment 1
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in the glycerine water solution of 10ml 5% by 550 DEG C of roasting 6h.Filtering, gained filter Liquid is the glycerite of potassium ruthenate, and solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, A concentration of 8.23ppm of ruthenium, the rate of recovery 82.30% are measured with ICP.
Embodiment 2
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 4.66g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 9.42ppm of ruthenium, the rate of recovery 94.20%.
Embodiment 3
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 2h is impregnated in 5% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.70g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 6.41ppm of ruthenium, the rate of recovery 64.10%.
Embodiment 4
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist It impregnates for 24 hours in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 9.35ppm of ruthenium, the rate of recovery 93.50%.
Embodiment 5
Take the useless agent of activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkaline earth metal compound auxiliary agent in 30ml 10h is impregnated in 15% salpeter solution, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air 550 DEG C 6h is roasted, calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml.Filtering, gained filtrate are ruthenic acid Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, surveyed with ICP by the glycerite of potassium Obtain a concentration of 9.12ppm of ruthenium, the rate of recovery 91.20%.
Embodiment 6
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 2h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 82.2ppm of ruthenium, the rate of recovery 82.20%.
Embodiment 7
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 10h.Filtering, gained filtrate For the glycerite of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 8.73ppm of ruthenium, the rate of recovery 87.30%.
Embodiment 8
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkaline-earth metal, alkali metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% ethylene glycol solutions of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate For the ethylene glycol solutions of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, A concentration of 9.07ppm of ruthenium, the rate of recovery 90.70% are measured with ICP.
Embodiment 9
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% trihydroxy methyl ethane solution of 10ml by 550 DEG C of roasting 6h.Filtering, Gained filtrate is the trihydroxy methyl ethane solution of potassium ruthenate, and solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are used 100ml volumetric flasks are demarcated, and a concentration of 9.07ppm of ruthenium, the rate of recovery 90.70% are measured with ICP.
Embodiment 10
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% xylitol solutions of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate For the xylitol solutions of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, A concentration of 89.9ppm of ruthenium, the rate of recovery 89.90% are measured with ICP.
Embodiment 11
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% hydrochloric acid solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 9.31ppm of ruthenium, the rate of recovery 93.10%.
Embodiment 12
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% acetums of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 9.07ppm of ruthenium, the rate of recovery 90.70%.
Embodiment 13
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% citric acid solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air In 550 DEG C roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml.Filtering, gained filtrate For the glycerite of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 8.98ppm of ruthenium, the rate of recovery 89.80%.
Embodiment 14
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 20% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 8.52ppm of ruthenium, the rate of recovery 85.20%.
Embodiment 15
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 30% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 8.76ppm of ruthenium, the rate of recovery 87.60%.
Embodiment 16
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 3.54g K2CO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 9.08ppm of ruthenium, the rate of recovery 90.80%.
Embodiment 17
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 2.88g KOH, then in air Calcined solids are dissolved in 10ml water, are then added in 15% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate For the glycerite of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 8.81ppm of ruthenium, the rate of recovery 88.10%.
Embodiment 18
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 4.26g K2C2O4, then in air In 550 DEG C roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml.Filtering, gained filtrate For the glycerite of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 9.06ppm of ruthenium, the rate of recovery 90.60%.
Embodiment 19
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 300 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 6.58ppm of ruthenium, the rate of recovery 65.80%.
Embodiment 20
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 15% glycerites of 10ml by 600 DEG C of roasting 2h.Filtering, gained filtrate For the glycerite of potassium ruthenate, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 8.56ppm of ruthenium, the rate of recovery 85.60%.
Embodiment 21
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then oxygen-containing Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h in 8% atmosphere.Filtering, Gained filtrate is the glycerite of potassium ruthenate, and solution 100ml volumetric flasks are demarcated, 0.1ml are then taken again, with 100ml capacity Bottle calibration, a concentration of 8.34ppm of ruthenium, the rate of recovery 83.40% are measured with ICP.
Embodiment 22
10g is taken to contain the activated carbon supported ruthenium catalyst of metal Ru and alkali metal, alkaline earth metal compound auxiliary agent in 30ml 10h is impregnated in 15% salpeter solution, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in oxygen-containing 40% gas Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h in atmosphere.Filtering, gained filter Liquid is the glycerite of potassium ruthenate, and solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, A concentration of 9.09ppm of ruthenium, the rate of recovery 90.90% are measured with ICP.
Embodiment 23
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 400 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 8.83ppm of ruthenium, the rate of recovery 88.30%.
Embodiment 24
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 4.61g Na2CO3, then in air In 550 DEG C roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml.Filtering, gained filtrate For the glycerite of ruthenic acid sodium, solution 100ml volumetric flasks are demarcated, then take 0.1ml again, are demarcated with 100ml volumetric flasks, are used ICP measures a concentration of 9.12ppm of ruthenium, the rate of recovery 91.20%.
Embodiment 25
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains nitric acid ruthenium and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, are then added in 5% glycerites of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are Solution 100ml volumetric flasks are demarcated, then take 0.1ml again, demarcated with 100ml volumetric flasks, used by the glycerite of potassium ruthenate ICP measures a concentration of 8.53ppm of ruthenium, the rate of recovery 85.30%.
Comparative example 1
The useless agent of the activated carbon supported ruthenium catalyst that 10g contains metal Ru and alkali metal, alkaline earth metal compound auxiliary agent is taken to exist 10h is impregnated in 15% salpeter solutions of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air Calcined solids are dissolved in 10ml water, filtered, gained filtrate is the solution of potassium ruthenate, by solution 100ml by 550 DEG C of roasting 6h Volumetric flask is demarcated, and then takes 0.1ml again, is demarcated with 100ml volumetric flasks, is measured a concentration of 4.71ppm of ruthenium with ICP, the rate of recovery is 47.10%.
Comparative example 2
10g is taken to contain the activated carbon supported ruthenium catalyst of metal Ru and alkali metal, alkaline earth metal compound auxiliary agent in 30ml 10h is impregnated in 15% salpeter solution, is then filtered, washed.Dry filter residue, then 550 DEG C of roasting 6h in air, after roasting Solid is dissolved in 10ml water, is then added in 5% glycerites of 10ml.Filtering, gained filtrate are the glycerite of potassium ruthenate, will Solution is demarcated with 100ml volumetric flasks, then takes 0.1ml again, is demarcated with 100ml volumetric flasks, it is a concentration of to measure ruthenium with ICP 2.43ppm, the rate of recovery 24.30%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. the method for ruthenium, the useless agent of the catalyst are negative for activated carbon in a kind of useless agent with alkali metal ruthenic acid salt form recycling catalyst Carry the useless agent of ruthenium catalyst, which is characterized in that include the following steps：
Pre-treatment step：2-24h is impregnated into activated carbon supported ruthenium catalyst agent of giving up in acid solution, filtration washing obtains filtrate And filter residue；
Calcination steps：Alkali metal compound is added into filter residue, wherein alkali metal quality accounts for the useless agent of activated carbon supported ruthenium catalyst Quality 18-22% roasts 2-10h at 300-600 DEG C；
Post-processing step：It is then added to the solid water dissolution after roasting in polyhydroxy-alcohol solution, filters, wash, collects Filtrate to get alkali metal ruthenate polyhydroxy-alcohol solution.
2. the method for ruthenium, feature exist in the useless agent according to claim 1 with alkali metal ruthenic acid salt form recycling catalyst In the dosage of water is 8-12 times of calcined solids quality in the post-processing step.
3. the method for ruthenium, feature exist in the useless agent according to claim 1 with alkali metal ruthenic acid salt form recycling catalyst In the dosage of polyhydroxy-alcohol solution is 8-12 times of calcined solids quality in the post-processing step.
4. the method for ruthenium, feature exist in the useless agent according to claim 3 with alkali metal ruthenic acid salt form recycling catalyst In the mass concentration of the polyhydroxy-alcohol solution is 5-15%.
5. the method for ruthenium, feature exist in the useless agent according to claim 3 with alkali metal ruthenic acid salt form recycling catalyst In the polyhydroxy-alcohol is ethylene glycol, glycerine, trimethylolethane or xylitol.
6. the method for ruthenium, feature exist in the useless agent according to claim 1 with alkali metal ruthenic acid salt form recycling catalyst In the acid solution in the pre-treatment step is salpeter solution, hydrochloric acid solution, acetum or citric acid solution.
7. the method for ruthenium, feature exist in the useless agent according to claim 6 with alkali metal ruthenic acid salt form recycling catalyst In the mass concentration of the acid solution is 5-30%.
8. the method for ruthenium, feature exist in the useless agent according to claim 1 with alkali metal ruthenic acid salt form recycling catalyst In alkali metal compound is the nitrate of alkali metal, carbonate, acetate or alkali in the calcination steps.
9. the method for ruthenium, feature exist in the useless agent according to claim 1 with alkali metal ruthenic acid salt form recycling catalyst It is passed through oxygen-containing gas when, roasting.
10. the method for ruthenium, feature exist in the useless agent according to claim 9 with alkali metal ruthenic acid salt form recycling catalyst In the volume content of oxygen is 8-40% in the oxygen-containing gas.
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CN1872418A (en) * 2006-06-21 2006-12-06 浙江工业大学 Method for recovering ruthenium catalyst carried by active carbon
CN101638727A (en) * 2008-07-31 2010-02-03 中国石油天然气股份有限公司 Method for recovering ruthenium in activated carbon supported ruthenium catalyst
CN102796873A (en) * 2012-03-05 2012-11-28 阳光凯迪新能源集团有限公司 Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3
JP2013249494A (en) * 2012-05-30 2013-12-12 National Institute Of Advanced Industrial Science & Technology Method and apparatus for recovering noble metal by route of compound oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1872418A (en) * 2006-06-21 2006-12-06 浙江工业大学 Method for recovering ruthenium catalyst carried by active carbon
CN101638727A (en) * 2008-07-31 2010-02-03 中国石油天然气股份有限公司 Method for recovering ruthenium in activated carbon supported ruthenium catalyst
CN102796873A (en) * 2012-03-05 2012-11-28 阳光凯迪新能源集团有限公司 Method for comprehensively recovering metallic cobalt, ruthenium and aluminum from Fischer-Tropsch synthesis dead catalyst Co-Ru/Al2O3
JP2013249494A (en) * 2012-05-30 2013-12-12 National Institute Of Advanced Industrial Science & Technology Method and apparatus for recovering noble metal by route of compound oxide

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