CN108531732B - A kind of activated carbon supported ruthenium catalyst gives up the recovery method of ruthenium in agent - Google Patents
A kind of activated carbon supported ruthenium catalyst gives up the recovery method of ruthenium in agent Download PDFInfo
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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
- 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
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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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- 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
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Abstract
The invention belongs to catalyst recovery technology fields, more particularly to a kind of recovery method of ruthenium in activated carbon supported ruthenium catalyst, it is the following steps are included: by alkali metal promoter is added in activated carbon supported ruthenium dead catalyst, base earth metal promoter or acid assistant, in 350-600 DEG C of roasting 2-10h, roasting remaining solid is dissolved in the aqueous solution of polyhydroxy-alcohol or polyhydroxy-acid, it adds in nitric acid solution, it is filtered again, obtaining filtrate main ingredient is ruthenium, alkali metal ion, the aqueous solution of alkaline-earth metal ions, obtain the alkali salt that filter residue is mainly ruthenium, by restoring to obtain ruthenium metal.The invention has the advantages that maturing temperature is low, operational sequence is easy, can directly recovery section ruthenium solution into the dipping process of catalyst, Product recycling form multiselect, the rate of recovery is high, energy saving.
Description
Technical field
The invention belongs to catalyst recovery technology fields, and in particular to a kind of activated carbon supported ruthenium catalyst gives up ruthenium in agent
Recovery method.
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
Activity can be lost in use for some time at the development of catalyst, especially catalyst, and the shortage of ruthenium resource just needs
Effectively recycling obtains ruthenium in dead 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 ruthenic oxide insoluble solid, filtrate is recycled as the process water for preparing activated carbon supported ruthenium catalyst, program step
Simply, 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；Further, since composition is more complex in product of roasting, ruthenium can not be complete
Full recycling, the rate of recovery are lower.Based on this, if it is possible to provide a kind of ruthenium recovery method that low energy consumption, the rate of recovery is high, will have
Effect alleviates the problem of energy waste and shortage of resources.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is that overcoming energy consumption height in ruthenium removal process in the prior art, returning
The defects such as yield is low, to provide the recovery method that a kind of activated carbon supported catalyst that low energy consumption, the rate of recovery is high gives up ruthenium in agent.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of activated carbon supported ruthenium catalyst gives up the recovery method of ruthenium in agent, comprising the following steps:
Calcination process: catalyst is given up agent dry 2-24h at 100-130 DEG C, then with account for catalyst and give up agent quality 5-
20% alkali metal promoter, base earth metal promoter or acid assistant mixing, in 350-600 DEG C of roasting 2-10h；
Pickling processes: the agent of giving up of the catalyst after roasting is added to the water dissolution, then addition polyhydroxy-alcohol or polyhydroxy
The aqueous solution of acid, is eventually adding nitric acid solution, is filtered, washed, obtain filtrate and insoluble solid；
Reduction treatment: insoluble solid is restored to obtain metal Ru.
In order to accurately control the additional amount of auxiliary agent, it is useless that micro-wave digestion-ICP measurement catalyst can be first passed through before recycling
The content of ruthenium, alkali metal, alkaline-earth metal in agent.Ruthenium barium potassium content has an impact for the additive amount of alkali metal.
Further, the filtrate is directly used in the preparation of activated carbon supported ruthenium catalyst.
Further, the dosage of water is 8-12 times of calcined catalyst quality in the pickling processes step.
Further, the dosage of polyhydroxy-alcohol or polyhydroxy-acid is calcined catalyst quality in the pickling processes step
8-12 times.
Further, the nitric acid solution is added to reaction system there is no bubble generation, then excess 10-25%.
Further, the filtrate is directly used in the preparation of activated carbon supported ruthenium catalyst, and filtrate is carried out ICP characterization,
Its main component is measured as the content of ruthenium, the soluble-salt of alkali and alkaline earth metal ions.
Further, the insoluble solid hydrogen, carbon monoxide or hydrazine hydrate reduction.
The temperature of the reduction treatment is 300-500 DEG C when further, with hydrogen or Carbon monoxide reduction.Use hydrazine hydrate
The reduction temperature is 80-90 DEG C when reduction.
Further, the alkali metal in the alkali metal promoter is sodium and/or potassium.
Further, the alkali metal promoter is nitrate, carbonate, acetate, oxalates or the alkali of alkali metal.
Further, the alkaline-earth metal in the base earth metal promoter is strontium and/or barium.
Further, the base earth metal promoter is the nitrate or alkali of alkaline-earth metal.
Further, the acid assistant is nitric acid, citric acid or acetic acid.
Further, the polyhydroxy-alcohol is ethylene glycol, glycerol, trimethylolethane or xylitol.
Further, the polyhydroxy-acid is oxalic acid, tartaric acid or citric acid.
Further, the gas that oxygen volume content is 8-40% is continually fed into when the roasting.
Further, the useless agent of the catalyst is the activity of the alkali and alkaline earth metal ions compound auxiliary agent containing nitric acid ruthenium
The useless agent of charcoal supported ruthenium catalyst or the activated carbon supported ruthenium catalysis of the alkali and alkaline earth metal ions compound auxiliary agent containing metal Ru
Agent is given up agent.
Technical solution of the present invention has the advantages that
1. the recovery method of ruthenium in activated carbon supported ruthenium catalyst provided by the invention, by calcination process step to
Auxiliary agent is added in the useless agent of catalyst, is on the one hand capable of the oxidizing fire of photocatalytic active carbon, hence it is evident that reduces maturing temperature, shortens roasting
Time；On the other hand, enough alkali metal promoters are added, the recycling of ruthenium and the preparation flow of ruthenium catalyst, energy can be organically combined
It is enough to convert the ruthenium in catalyst to soluble alkali metal salt, it can be directly thrown into the production technology of catalyst, directly
Realize the recycling of ruthenium, the direct recovery rate of ruthenium is up to 50% or more.It gives up to catalyst and alkaline-earth metal is added in agent, can make to roast
Product becomes the ruthenate of insoluble alkaline-earth metal, improves the content of ruthenium in insoluble solid, increases the rate of recovery of metal Ru.
Acid assistant, which is added, can be realized the redistribution for being supported on auxiliary agent in the useless agent of catalyst, can be improved original in the useless agent of catalyst
The dispersion degree of alkali and alkaline earth metal ions can accelerate reaction rate, reduce maturing temperature.
2. the recovery method of ruthenium in activated carbon supported ruthenium catalyst provided by the invention, when alkali metal promoter is added, roasting
The ruthenate comparision contents of soluble alkali metal are high in product afterwards, when base earth metal promoter is added, after roasting in product not
The ruthenate of soluble alkaline-earth metal is relatively more, therefore can pass through the amount of addition alkali metal or alkaline-earth metal into catalyst
The existence form of recovery product is adjusted, meets actual production demand；Finally the insoluble solid ruthenium that recycling obtains is reduced to
Metal Ru has widened use scope.
3. the recovery method of ruthenium in activated carbon supported ruthenium catalyst provided by the invention, using more in pickling processes step
Carboxylic acid or polyhydroxy-alcohol are handled, and unstable nitric acid ruthenium is converted for stable polyhydroxy (alcohol) ruthenium complex, is kept away
The alkali metal salt for having exempted from unstable ruthenium is decomposed into ruthenic oxide, improves the rate of recovery of ruthenium.In addition, polyhydroxy-acid can dissolve admittedly
Remaining barium carbonate etc. in body improves the rate of recovery of barium in filtrate.
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 activated carbon supported ruthenium catalyst of alkali and alkaline earth metal ions compound auxiliary agent in embodiment containing metal Ru is useless
It is the 10.0% of catalyst quality that agent, which measures ruthenium content by micro-wave digestion-ICP, and potassium content is the 3.60% of catalyst quality,
Barium content is the 8.30% 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 9.80% 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 activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10, adds in the nitric acid solution that 10ml concentration is 10% and have no obvious dissolution to remaining solid, it will
Solution filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 17.35% in solution, and the barium rate of recovery is 43.44%, and the potassium rate of recovery is 87.83%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.71g, the rate of recovery of ruthenium are 71%.Comprehensive solution and solid, the rate of recovery of ruthenium are 88.35%.
Embodiment 2
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 3.53g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 52.34% in solution, and the barium rate of recovery is 57.66%, and the potassium rate of recovery is 92.37%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.39g, the recycling of ruthenium after then washing
Rate is 39%.Comprehensive solution and solid, the rate of recovery of ruthenium are 91.34%.
Embodiment 3
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 1.29g KNO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 19.63% in solution, and the barium rate of recovery is 45.46%, and the potassium rate of recovery is 88.96%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru after then washing
0.68g, the rate of recovery of ruthenium are 68%.Comprehensive solution and solid, the rate of recovery of ruthenium are 87.63%.
Embodiment 4
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 5.17g KNO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 57.67% in solution, and the barium rate of recovery is 55.46%, and the potassium rate of recovery is 94.96%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.35g, the recycling of ruthenium after then washing
Rate is 35%.Comprehensive solution and solid, the rate of recovery of ruthenium are 92.67%.
Embodiment 5
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 1.44g KOH, is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 17.41% in solution, and the barium rate of recovery is 46.64%, and the potassium rate of recovery is 87.16%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru after then washing
0.67g, the rate of recovery of ruthenium are 67%.Comprehensive solution and solid, the rate of recovery of ruthenium are 84.41%.
Embodiment 6
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 5.74g KOH, is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 52.64% in solution, and the barium rate of recovery is 56.41%, and the potassium rate of recovery is 95.16%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.38g, the recycling of ruthenium after then washing
Rate is 38%.Comprehensive solution and solid, the rate of recovery of ruthenium are 90.64%.
Embodiment 7
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 1.31g CH3COOK is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 15.44% in solution, and the barium rate of recovery is 45.72%, and the potassium rate of recovery is 85.56%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.69g, the rate of recovery of ruthenium are 69%.Comprehensive solution and solid, the rate of recovery of ruthenium are 84.44%.
Embodiment 8
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 5.23g CH3COOK is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 53.42% in solution, and the barium rate of recovery is 52.34%, and the potassium rate of recovery is 95.27%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.36g, ruthenium after then washing
The rate of recovery be 36%.Comprehensive solution and solid, the rate of recovery of ruthenium are 89.42%.
Embodiment 9
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 1.06g K2C2O4, it is placed on 550 DEG C
It is passed through under the atmosphere of air and roasts 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, quality is then added
Than the glycerine water solution for 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution
Filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 14.64% in solution, and the barium rate of recovery is 43.74%, and the potassium rate of recovery is 85.64%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.69g, the rate of recovery of ruthenium are 69%.Comprehensive solution and solid, the rate of recovery of ruthenium are 83.64%.
Embodiment 10
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 4.26g K2C2O4, it is placed on 550 DEG C
It is passed through under the atmosphere of air and roasts 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, quality is then added
Than the glycerine water solution for 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution
Filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 54.74% in solution, and the barium rate of recovery is 53.14%, and the potassium rate of recovery is 93.41%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.36g, ruthenium after then washing
The rate of recovery be 36%.Comprehensive solution and solid, the rate of recovery of ruthenium are 90.74%.
Embodiment 11
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.62g Ba (OH)2, it is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 9.62% in solution, and the barium rate of recovery is 63.74%, and the potassium rate of recovery is 82.61%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.76g, the rate of recovery of ruthenium are 76%.Comprehensive solution and solid, the rate of recovery of ruthenium are 85.62%.
Embodiment 12
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.50g Ba (OH)2, it is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 5.65% in solution, and the barium rate of recovery is 93.74%, and the potassium rate of recovery is 72.61%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.82g, ruthenium after then washing
The rate of recovery be 82%.Comprehensive solution and solid, the rate of recovery of ruthenium are 87.65%.
Embodiment 13
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.95g Ba (NO3)2, it is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 9.87% in solution, and the barium rate of recovery is 66.14%, and the potassium rate of recovery is 81.23%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.77g, the rate of recovery of ruthenium are 77%.Comprehensive solution and solid, the rate of recovery of ruthenium are 86.87%.
Embodiment 14
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 3.81g Ba (NO3)2, it is placed on 550
It DEG C is passed through under the atmosphere of air and to roast 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, matter is then added
Amount adds 10ml than the glycerine water solution for being 1:10, has no obvious dissolution to remaining solid in 10% nitric acid solution, will be molten
Liquid filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 5.37% in solution, and the barium rate of recovery is 96.34%, and the potassium rate of recovery is 65.23%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.79g, ruthenium after then washing
The rate of recovery be 79%.Comprehensive solution and solid, the rate of recovery of ruthenium are 84.37%.
Embodiment 15
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.3g Na2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, sodium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 35.37% in solution, and the barium rate of recovery is 46.34%, and the potassium rate of recovery is 87.23%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.53g, the rate of recovery of ruthenium are 53%.Comprehensive solution and solid, the rate of recovery of ruthenium are 88.37%.
Embodiment 16
The useless agent of activated carbon supported ruthenium catalyst containing nitric acid ruthenium and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 3.28g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 42.14% in solution, and the barium rate of recovery is 47.64%, and the potassium rate of recovery is 87.37%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 90 DEG C of reduction in hydrazine hydrate, obtain metal Ru 0.43g after then washing,
The rate of recovery of ruthenium is 43%.Comprehensive solution and solid, the rate of recovery of ruthenium are 85.14%.
Embodiment 17
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 3.28g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 42.24% in solution, and the barium rate of recovery is 46.14%, and the potassium rate of recovery is 84.97%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 80 DEG C of reduction in hydrazine hydrate, obtain metal Ru 0.44g after then washing,
The rate of recovery of ruthenium is 44%.Comprehensive solution and solid, the rate of recovery of ruthenium are 86.24%.
Embodiment 18
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 350 DEG C and leads to
Enter and roasts 10h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, quality is then added
Than the glycerine water solution for 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution
Filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 25.71% in solution, and the barium rate of recovery is 42.51%, and the potassium rate of recovery is 83.73%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.56g, the rate of recovery of ruthenium are 56%.Comprehensive solution and solid, the rate of recovery of ruthenium are 81.71%.
Embodiment 19
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 600 DEG C and leads to
Enter and roasts 2h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 34.21% in solution, and the barium rate of recovery is 44.72%, and the potassium rate of recovery is 86.31%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru after then washing
0.51g, the rate of recovery of ruthenium are 51%.Comprehensive solution and solid, the rate of recovery of ruthenium are 85.21%.
Embodiment 20
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
It is dried for 24 hours under 100 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 3.53g K2CO3, it is placed on 550 DEG C
It is passed through under the atmosphere of air and roasts 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, quality is then added
Than the glycerine water solution for 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution
Filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 49.71% in solution, and the barium rate of recovery is 56.3%, and the potassium rate of recovery is 93.3%.It is insoluble solid
Body main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.37g after then washing, ruthenium
The rate of recovery is 37%.Comprehensive solution and solid, the rate of recovery of ruthenium are 86.71%.
Embodiment 21
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 17.35% in solution, and the barium rate of recovery is 43.44%, and the potassium rate of recovery is 87.83%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% carbon monoxide, obtain metal Ru after then washing
0.66g, the rate of recovery of ruthenium are 66%.Comprehensive solution and solid, the rate of recovery of ruthenium are 83.35%.
Embodiment 22
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 17.15% in solution, and the barium rate of recovery is 43.44%, and the potassium rate of recovery is 87.83%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 500 DEG C of reduction in 10% hydrogen, obtain metal Ru after then washing
0.67g, the rate of recovery of ruthenium are 67%.Comprehensive solution and solid, the rate of recovery of ruthenium are 84.15%.
Embodiment 23
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under the atmosphere of air；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 17.53% in solution, and the barium rate of recovery is 43.44%, and the potassium rate of recovery is 87.83%.Insoluble solids master
Wanting ingredient is ruthenic acid barium and ruthenic oxide.By solid, 300 DEG C of reduction in 10% hydrogen, obtain metal Ru after then washing
0.64g, the rate of recovery of ruthenium are 64%.Comprehensive solution and solid, the rate of recovery of ruthenium are 81.53%.
Embodiment 24
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added dilute nitre that 10ml mass fraction is 10%
Acid solution is placed under the atmosphere that 550 DEG C are passed through air and roasts 8h；Solid after roasting is added to molten in 10ml water
Then 10ml is added in solution, mass ratio is the glycerine water solution of 1:10, adds 10ml, and extremely residue is solid in 10% nitric acid solution
Body has no obvious dissolution, and solution is filtered, and obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the life of catalyst
In production. art.Filtrate 100ml volumetric flask constant volume, 0.1ml constant volume in 100ml volumetric flask is then taken to carry out ICP characterization again,
Ruthenium barium potassium content will be measured convert, the rate of recovery of ruthenium is 27.15% in solution, and the barium rate of recovery is 47.24%, potassium recycling
Rate is 86.73%.Insoluble solids main component is ruthenic acid barium and ruthenic oxide.400 DEG C of reduction in 10% hydrogen by solid, so
Metal Ru 0.54g is obtained after washing afterwards, the rate of recovery of ruthenium is 54%.Comprehensive solution and solid, the rate of recovery of ruthenium are 81.15%.
Embodiment 25
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, it is 10% citric acid that 10ml mass fraction, which is then added,
Solution is placed under the atmosphere that 550 DEG C are passed through air and roasts 8h；Solid after roasting is added in 10ml water and is dissolved,
Then it is added 10ml, mass ratio is the glycerine water solution of 1:10, adds 10ml, in 10% nitric acid solution not to remaining solid
See obvious dissolution, solution is filtered, obtains the aqueous solution that filtrate is ruthenium, barium, potassium, the production work of catalyst can be directly thrown into
In skill.Filtrate 100ml volumetric flask constant volume, then takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will survey
It obtains ruthenium barium potassium content convert, the rate of recovery of ruthenium is 24.25% in solution, and the barium rate of recovery is 41.34%, and the potassium rate of recovery is
84.71%.Insoluble solids main component is ruthenic acid barium and ruthenic oxide.Solid is restored for 400 DEG C in 10% hydrogen, then water
Metal Ru 0.56g is obtained after washing, the rate of recovery of ruthenium is 56%.Comprehensive solution and solid, the rate of recovery of ruthenium are 80.25%.
Embodiment 26
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 10ml, 10% acetum is placed
8h is roasted under being passed through the atmosphere of air at 550 DEG C；Solid after roasting is added in 10ml water and is dissolved, is then added
10ml, mass ratio are the glycerine water solution of 1:10, add 10ml, have no obvious molten to remaining solid in 10% nitric acid solution
Solution, solution is filtered, and is obtained the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.?
Then filtrate 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium
Potassium content convert, and the rate of recovery of ruthenium is 25.54% in solution, and the barium rate of recovery is 45.34%, and the potassium rate of recovery is
84.33%.Insoluble solids main component is ruthenic acid barium and ruthenic oxide.Solid is restored for 400 DEG C in 10% hydrogen, then water
Metal Ru 0.55g is obtained after washing, the rate of recovery of ruthenium is 55%.Comprehensive solution and solid, the rate of recovery of ruthenium are 80.54%.
Embodiment 27
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under oxygen-containing 8% gas atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added,
Mass ratio is the glycerine water solution of 1:10, adds 10ml, has no obvious dissolution to remaining solid in 10% nitric acid solution, will
Solution filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 27.21% in solution, and the barium rate of recovery is 47.24%, and the potassium rate of recovery is 86.73%.It is insoluble
Solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal after then washing
Ruthenium 0.56g, the rate of recovery of ruthenium are 56%.Comprehensive solution and solid, the rate of recovery of ruthenium are 83.21%.
Embodiment 28
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 0.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under oxygen-containing 40% gas atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added,
Mass ratio is the glycol water of 1:10, adds 10ml, has no obvious dissolution to remaining solid in 10% nitric acid solution,
Solution is filtered, the aqueous solution that filtrate is ruthenium, barium, potassium is obtained, can be directly thrown into the production technology of catalyst.Filtrate
With 100ml volumetric flask constant volume, then takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, ruthenium barium potassium will be measured and contained
Amount convert, and the rate of recovery of ruthenium is 24.15% in solution, and the barium rate of recovery is 47.24%, and the potassium rate of recovery is 86.73%.No
Molten solid main component is ruthenic acid barium and ruthenic oxide.By solid, 400 DEG C of reduction in 10% hydrogen, obtain gold after then washing
Belong to ruthenium 0.55g, the rate of recovery of ruthenium is 55%.Comprehensive solution and solid, the rate of recovery of ruthenium are 79.15%.
Embodiment 29
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The glycerine water solution of 1:10, adds 10ml, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 44.25% in solution, and the barium rate of recovery is 48.14%, and the potassium rate of recovery is 87.63%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.45g, the recycling of ruthenium after then washing
Rate is 45%.Comprehensive solution and solid, the rate of recovery of ruthenium are 89.25%.
Embodiment 30
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The trimethylolethane aqueous solution of 1:10, adds 10ml, has no obvious dissolution to remaining solid in 10% nitric acid solution, will
Solution filtering obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 44.17% in solution, and the barium rate of recovery is 49.31%, and the potassium rate of recovery is 88.17%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.44g, ruthenium after then washing
The rate of recovery be 44%.Comprehensive solution and solid, the rate of recovery of ruthenium are 88.17%.
Embodiment 31
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The xylose alcohol solution of 1:10, adds 10ml, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 43.75% in solution, and the barium rate of recovery is 47.98%, and the potassium rate of recovery is 86.27%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.46g, the recycling of ruthenium after then washing
Rate is 46%.Comprehensive solution and solid, the rate of recovery of ruthenium are 89.75%.
Embodiment 32
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The oxalic acid aqueous solution of 1:10, adds 10ml, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 46.55% in solution, and the barium rate of recovery is 48.18%, and the potassium rate of recovery is 87.16%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.44g, the recycling of ruthenium after then washing
Rate is 44%.Comprehensive solution and solid, the rate of recovery of ruthenium are 90.55%.
Embodiment 33
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The aqueous tartaric acid solution of 1:10, adds 10ml, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 47.24% in solution, and the barium rate of recovery is 46.25%, and the potassium rate of recovery is 85.24%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.43g, the recycling of ruthenium after then washing
Rate is 43%.Comprehensive solution and solid, the rate of recovery of ruthenium are 90.24%.
Embodiment 34
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.88g K2CO3, it is placed on 550 DEG C and leads to
Enter and roasts 8h under air atmosphere environment；Solid after roasting is added in 10ml water and is dissolved, 10ml is then added, mass ratio is
The aqueous citric acid solution of 1:10, adds 10ml, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the production technology of catalyst.Filtrate is used 100ml
Then volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content and change
It calculates, the rate of recovery of ruthenium is 45.12% in solution, and the barium rate of recovery is 48.18%, and the potassium rate of recovery is 87.57%.Insoluble solids master
Wanting ingredient is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.44g, the recycling of ruthenium after then washing
Rate is 44%.Comprehensive solution and solid, the rate of recovery of ruthenium are 89.12%.
Embodiment 35
The useless agent of activated carbon supported ruthenium catalyst containing metal Ru and potassium compound auxiliary agent, barium compound auxiliary agent is placed on
Dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is then added 2.08g SrCO3, it is placed on 550 DEG C
It is passed through under air atmosphere environment and roasts 8h；Solid after roasting is added in 10ml water and is dissolved, 10ml, mass ratio is then added
For the glycerine water solution of 1:10,10ml is added, obvious dissolution is had no to remaining solid in 10% nitric acid solution, by solution mistake
Filter obtains the aqueous solution that filtrate is ruthenium, barium, potassium, strontium, can be directly thrown into the production technology of catalyst.Filtrate is used
Then 100ml volumetric flask constant volume takes 0.1ml constant volume in 100ml volumetric flask to carry out ICP characterization again, will measure ruthenium barium potassium content
Convert, the rate of recovery of ruthenium is 15.72% in solution, and the barium rate of recovery is 46.13%, and the potassium rate of recovery is 85.24%.It is insoluble
Solid main component is ruthenic acid barium.By solid, 400 DEG C of reduction in 10% hydrogen, obtain metal Ru 0.66g, ruthenium after then washing
The rate of recovery be 66%.Comprehensive solution and solid, the rate of recovery of ruthenium are 81.72%.
Comparative example 1
The useless agent of the activated carbon supported ruthenium catalyst of alkali and alkaline earth metal ions compound auxiliary agent containing metal Ru is placed
The dry 2h under 130 DEG C of environment；The useless agent of catalyst after taking 10.00g dry, is placed on 550 DEG C and is passed through under air atmosphere environment
Roast 8h；Solid after roasting is added in the water of 10mL and is dissolved, be then added 10mL, 10% nitric acid solution in remaining solid
Body has no obvious dissolution, and solution is filtered, and obtains the aqueous solution that filtrate is ruthenium, barium, potassium, can be directly thrown into the life of catalyst
In production. art.Filtrate 100ml volumetric flask constant volume, 0.1ml constant volume in 100ml volumetric flask is then taken to carry out ICP characterization again,
Ruthenium barium potassium content will be measured convert, the rate of recovery of ruthenium is 12.32% in solution, and the barium rate of recovery is 46.44%, potassium recycling
Rate is 85.61%, and insoluble solids main component is ruthenic acid barium and ruthenic oxide, and the rate of recovery of ruthenium is 65% in solid.Synthesis is molten
Liquid and solid, the rate of recovery of ruthenium are 77.32%.
From the data of the embodiment of the present invention it is found that addition alkali metal promoter, base earth metal promoter and acid assistant can be obvious
It reduces maturing temperature, shorten calcining time；In addition, when alkali metal promoter is added, soluble alkali metal in the product after roasting
Ruthenate comparision contents it is high, when base earth metal promoter is added, after roasting in product insoluble alkaline-earth metal ruthenate ratio
It is more, thus can be adjusted by the way that the amount of alkali metal or alkaline-earth metal is added into catalyst recovery product there are shapes
Formula.Compared with the data of comparative example 1, technical solution of the present invention can significantly improve the rate of recovery of ruthenium.
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 (11)
1. the recovery method of ruthenium in a kind of useless agent of activated carbon supported ruthenium catalyst, which comprises the following steps:
Calcination process: catalyst is given up agent dry 2-24h at 100-130 DEG C, then with account for catalyst and give up agent quality 5-20%
Alkali metal promoter, base earth metal promoter or acid assistant mixing, in 350-600 DEG C of roasting 2-10h；
Pickling processes: the agent of giving up of the catalyst after roasting is added to the water dissolution, then addition polyhydroxy-alcohol or polyhydroxy-acid
Aqueous solution is eventually adding nitric acid solution, is filtered, washed, and obtains filtrate and insoluble solid；
Reduction treatment: insoluble solid is restored to obtain metal Ru；
Wherein, the alkali metal promoter is nitrate, carbonate, acetate, oxalates or the alkali of alkali metal；
The base earth metal promoter is the nitrate or alkali of alkaline-earth metal；
The acid assistant is nitric acid, citric acid or acetic acid；
The useless agent of the catalyst is that the activated carbon supported ruthenium of the alkali and alkaline earth metal ions compound auxiliary agent containing nitric acid ruthenium is catalyzed
The useless agent of agent or the useless agent of activated carbon supported ruthenium catalyst of the alkali and alkaline earth metal ions compound auxiliary agent containing metal Ru.
2. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
The dosage of water is 8-12 times of the useless agent quality of calcined catalyst in pickling processes step.
3. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
The dosage of polyhydroxy-alcohol or polyhydroxy-acid is 8-12 times of the useless agent quality of calcined catalyst in pickling processes step.
4. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
Nitric acid solution is added to reaction system there is no bubble generation, then excess 10-25%.
5. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
Insoluble solid hydrogen, carbon monoxide or hydrazine hydrate reduction.
6. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 5, which is characterized in that use
The temperature of hydrogen reducing or Carbon monoxide reduction is 300-500 DEG C, uses the temperature of hydrazine hydrate reduction for 80-90 DEG C.
7. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
Alkali metal in alkali metal promoter is sodium and/or potassium.
8. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
Alkaline-earth metal in base earth metal promoter is strontium and/or barium.
9. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that described
Polyhydroxy-alcohol is ethylene glycol, glycerine, trimethylolethane or xylitol.
10. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that institute
Stating polyhydroxy-acid is oxalic acid, tartaric acid or citric acid.
11. the recovery method of ruthenium in the useless agent of activated carbon supported ruthenium catalyst according to claim 1, which is characterized in that institute
State the gas for being continually fed into that oxygen volume content is 8-40% when roasting.
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| EP2339594A1 (en) * | 2008-10-22 | 2011-06-29 | Tosoh Corporation | Composition for producing metal film, method for producing metal film, and method for producing metal powder |
| CN102643175A (en) * | 2005-07-04 | 2012-08-22 | 赞南科技(上海)有限公司 | Ruthenium complex ligand, ruthenium complex, supported ruthenium complex catalyst and preparation method and application thereof |
| CN103157446A (en) * | 2013-03-11 | 2013-06-19 | 浙江大学 | Adsorbent for separating palladium from alkali metals and alkaline-earth metals and its preparation method and use |
| CN103380219A (en) * | 2011-02-18 | 2013-10-30 | 三菱瓦斯化学株式会社 | Method for collection of ruthenium or ruthenium compound |
| CN106282581A (en) * | 2016-11-01 | 2017-01-04 | 福州大学 | A kind of recovery method of ruthenium in activated carbon supported ruthenium catalyst |
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| CN102643175A (en) * | 2005-07-04 | 2012-08-22 | 赞南科技(上海)有限公司 | Ruthenium complex ligand, ruthenium complex, supported ruthenium complex catalyst and preparation method and application thereof |
| EP2339594A1 (en) * | 2008-10-22 | 2011-06-29 | Tosoh Corporation | Composition for producing metal film, method for producing metal film, and method for producing metal powder |
| CN103380219A (en) * | 2011-02-18 | 2013-10-30 | 三菱瓦斯化学株式会社 | Method for collection of ruthenium or ruthenium compound |
| CN103157446A (en) * | 2013-03-11 | 2013-06-19 | 浙江大学 | Adsorbent for separating palladium from alkali metals and alkaline-earth metals and its preparation method and use |
| CN106282581A (en) * | 2016-11-01 | 2017-01-04 | 福州大学 | A kind of recovery method of ruthenium in activated carbon supported ruthenium catalyst |
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