CN108330287B - 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 PDFInfo
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- CN108330287B CN108330287B CN201810097457.7A CN201810097457A CN108330287B CN 108330287 B CN108330287 B CN 108330287B CN 201810097457 A CN201810097457 A CN 201810097457A CN 108330287 B CN108330287 B CN 108330287B
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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
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- 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
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- 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
Abstract
The invention belongs to catalyst recovery technology fields, and in particular to a method of ruthenium in the useless agent of catalyst is recycled in the form of alkali metal ruthenate.This method is first removed by pickling the activated carbon supported ruthenium catalyst alkali and alkaline earth metal ions that give up in agent, 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 maturing temperature, shorten calcining 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
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 technique
From BP companies, Britain in 1992 and Kellogg company, 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 first will roast 4~20h after activated carbon supported ruthenium catalyst drying under 400~800 DEG C of environment, remove active carbon
Then carrier is dissolved the remaining solid after roasting using acid solution, recycling obtains main component after being filtered washing
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 the needs of ruthenium recovery method disclosed in above patent document remove absorbent charcoal carrier under higher maturing temperature
It goes, removal process energy consumption is high；Secondly, ruthenium soluble-salt main component is potassium ruthenate in filtrate, 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 lower.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 lower.
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.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that activated carbon supported ruthenium catalyst in the prior art is overcome to give up agent
The recycling energy consumption of middle ruthenium is high, the rate of recovery is 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 the agent that can give up 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:
A method of with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, the catalyst gives up agent as active carbon
Supported ruthenium catalyst gives up agent, comprising 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 sufficiently 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%, roasts 2-10h at 300-600 DEG C；
Post-processing step: the solid after roasting is dissolved with water, is then added in polyhydroxy-alcohol solution, is filtered, 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 nitric acid 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 advantages that
1. the method provided by the invention with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, has step letter
It is single, removal process the advantages of low energy consumption.The alkali metal and/or alkaline earth gold that this method first gives up activated carbon supported ruthenium catalyst 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 maturing temperature, shorten calcining 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 provided by the invention with ruthenium in the useless agent of 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 embodiment
For ease of description, the agent composition that gives up of catalyst used in the embodiment of the present invention and comparative example 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, which 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
Crossing micro-wave digestion-ICP and measuring ruthenium content is the 5.00% of catalyst quality, and barium content is the 8.00% of catalyst quality.
The useless agent composition of activated carbon supported ruthenium catalyst in embodiment containing metal Ru measures ruthenium by micro-wave digestion-ICP
Content is the 5.00% of catalyst quality.
The activated carbon supported ruthenium catalyst of alkali and alkaline earth metal ions compound auxiliary agent in embodiment containing nitric acid ruthenium is useless
It is the 5.00% of catalyst quality that agent, which 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 for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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 flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask,
Measuring ruthenium concentration with ICP is 8.23ppm, the rate of recovery 82.30%.
Embodiment 2
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 9.42ppm, the rate of recovery 94.20% that ICP, which measures ruthenium concentration,.
Embodiment 3
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
2h is impregnated in 5% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 6.41ppm, the rate of recovery 64.10% that ICP, which measures ruthenium concentration,.
Embodiment 4
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
It impregnates for 24 hours in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 9.35ppm, the rate of recovery 93.50% that ICP, which measures ruthenium concentration,.
Embodiment 5
The useless agent of activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkaline earth metal compound auxiliary agent is in 30ml
10h is impregnated in 15% nitric acid 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% glycerite of 10ml.Filtering, gained filtrate are ruthenic acid
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, surveyed with ICP by the glycerite of potassium
Obtaining ruthenium concentration is 9.12ppm, the rate of recovery 91.20%.
Embodiment 6
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 2h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 82.2ppm, the rate of recovery 82.20% that ICP, which measures ruthenium concentration,.
Embodiment 7
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 10h.Filtering, gained filtrate
For the glycerite of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 8.73ppm, the rate of recovery 87.30% that ICP, which measures ruthenium concentration,.
Embodiment 8
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkaline-earth metal, alkali metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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 solution of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate
For the ethylene glycol solution of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask,
Measuring ruthenium concentration with ICP is 9.07ppm, the rate of recovery 90.70%.
Embodiment 9
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air
Calcined solids are dissolved in 10ml water by 550 DEG C of roasting 6h, are then added in 5% trihydroxy methyl ethane solution of 10ml.Filtering,
Gained filtrate is the trihydroxy methyl ethane solution of potassium ruthenate, and solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is used
The calibration of 100ml volumetric flask, measuring ruthenium concentration with ICP is 9.07ppm, the rate of recovery 90.70%.
Embodiment 10
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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 solution of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate
For the xylitol solution of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask,
Measuring ruthenium concentration with ICP is 89.9ppm, the rate of recovery 89.90%.
Embodiment 11
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% hydrochloric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 9.31ppm, the rate of recovery 93.10% that ICP, which measures ruthenium concentration,.
Embodiment 12
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% acetum 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 9.07ppm, the rate of recovery 90.70% that ICP, which measures ruthenium concentration,.
Embodiment 13
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% citric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air
In 550 DEG C of roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerite of 10ml.Filtering, gained filtrate
For the glycerite of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 8.98ppm, the rate of recovery 89.80% that ICP, which measures ruthenium concentration,.
Embodiment 14
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 20% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 8.52ppm, the rate of recovery 85.20% that ICP, which measures ruthenium concentration,.
Embodiment 15
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 30% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 8.76ppm, the rate of recovery 87.60% that ICP, which measures ruthenium concentration,.
Embodiment 16
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 9.08ppm, the rate of recovery 90.80% that ICP, which measures ruthenium concentration,.
Embodiment 17
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate
For the glycerite of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 8.81ppm, the rate of recovery 88.10% that ICP, which measures ruthenium concentration,.
Embodiment 18
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 4.26g K2C2O4, then in air
In 550 DEG C of roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerite of 10ml.Filtering, gained filtrate
For the glycerite of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 9.06ppm, the rate of recovery 90.60% that ICP, which measures ruthenium concentration,.
Embodiment 19
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 300 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 6.58ppm, the rate of recovery 65.80% that ICP, which measures ruthenium concentration,.
Embodiment 20
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 600 DEG C of roasting 2h.Filtering, gained filtrate
For the glycerite of potassium ruthenate, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 8.56ppm, the rate of recovery 85.60% that ICP, which measures ruthenium concentration,.
Embodiment 21
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then oxygen-containing
Calcined solids are dissolved in 10ml water by 550 DEG C of roasting 6h in 8% atmosphere, are then added in 5% glycerite of 10ml.Filtering,
Gained filtrate is the glycerite of potassium ruthenate, and solution 100ml volumetric flask is demarcated, 0.1ml is then taken again, with 100ml capacity
Bottle calibration, measuring ruthenium concentration with ICP is 8.34ppm, the rate of recovery 83.40%.
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% nitric acid 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 by 550 DEG C of roasting 6h in atmosphere, are then added in 5% glycerite of 10ml.Filtering, gained filter
Liquid is the glycerite of potassium ruthenate, and solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask,
Measuring ruthenium concentration with ICP is 9.09ppm, the rate of recovery 90.90%.
Embodiment 23
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 400 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 8.83ppm, the rate of recovery 88.30% that ICP, which measures ruthenium concentration,.
Embodiment 24
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 4.61g Na2CO3, then in air
In 550 DEG C of roasting 6h, calcined solids are dissolved in 10ml water, are then added in 5% glycerite of 10ml.Filtering, gained filtrate
For the glycerite of ruthenic acid sodium, solution 100ml volumetric flask is demarcated, then takes 0.1ml again, is demarcated with 100ml volumetric flask, is used
It is 9.12ppm, the rate of recovery 91.20% that ICP, which measures ruthenium concentration,.
Embodiment 25
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain nitric acid ruthenium and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution 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% glycerite of 10ml by 550 DEG C of roasting 6h.Filtering, gained filtrate are
Solution 100ml volumetric flask is demarcated, then takes 0.1ml again, demarcated with 100ml volumetric flask, used by the glycerite of potassium ruthenate
It is 8.53ppm, the rate of recovery 85.30% that ICP, which measures ruthenium concentration,.
Comparative example 1
The useless agent of the activated carbon supported ruthenium catalyst for taking 10g to contain metal Ru and alkali metal, alkaline earth metal compound auxiliary agent exists
10h is impregnated in 15% nitric acid solution of 30ml, is then filtered, washed.Dry filter residue, is added 5.17g KNO3, then in air
Calcined solids are dissolved in 10ml water by 550 DEG C of roasting 6h, and filtering, gained filtrate is the solution of potassium ruthenate, by solution 100ml
Volumetric flask calibration, then takes 0.1ml again, is demarcated with 100ml volumetric flask, measuring ruthenium concentration with ICP is 4.71ppm, and 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% nitric acid 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% glycerite of 10ml.Filtering, gained filtrate are the glycerite of potassium ruthenate, will
Solution is demarcated with 100ml volumetric flask, then takes 0.1ml again, is demarcated with 100ml volumetric flask, measuring ruthenium concentration with ICP is
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 (8)
1. a kind of method with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, the useless agent of the catalyst are negative for active carbon
Carry the useless agent of ruthenium catalyst, which comprises 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, and when roasting is passed through oxygen-containing gas, the body of oxygen in the oxygen-containing gas
Product content is 8-40%；
Post-processing step: the solid after roasting is dissolved with water, is then added in polyhydroxy-alcohol solution, is filtered, and is washed, and is collected
Filtrate to get alkali metal ruthenate polyhydroxy-alcohol solution.
2. the method according to claim 1 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the dosage of water is 8-12 times of calcined solids quality in the post-processing step.
3. the method according to claim 1 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the dosage of polyhydroxy-alcohol solution is 8-12 times of calcined solids quality in the post-processing step.
4. the method according to claim 3 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the mass concentration of the polyhydroxy-alcohol solution is 5-15%.
5. the method according to claim 3 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the polyhydroxy-alcohol is ethylene glycol, glycerine, trimethylolethane or xylitol.
6. the method according to claim 1 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the acid solution in the pre-treatment step is nitric acid solution, hydrochloric acid solution, acetum or citric acid solution.
7. the method according to claim 6 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In the mass concentration of the acid solution is 5-30%.
8. the method according to claim 1 with ruthenium in the useless agent of alkali metal ruthenic acid salt form recycling catalyst, feature exist
In alkali metal compound is the nitrate of alkali metal, carbonate, acetate or alkali in the calcination steps.
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Citations (4)
| 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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Patent Citations (4)
| 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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Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Patentee after: FUZHOU University NATIONAL ENGINEERING RESEARCH CENTER OF CHEMICAL FERTILIZER CATALYST Address before: 100044 Beijing Haidian District Xizhimen North Street a 43 Jinyun building A block 9. Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Patentee before: FUZHOU University NATIONAL ENGINEERING RESEARCH CENTER OF CHEMICAL FERTILIZER CATALYST |