CN107794376A - The recovery method of Metal Palladium in a kind of thin powdered carbon carrier palladium-carbon catalyst - Google Patents
The recovery method of Metal Palladium in a kind of thin powdered carbon carrier palladium-carbon catalyst Download PDFInfo
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- CN107794376A CN107794376A CN201710944100.3A CN201710944100A CN107794376A CN 107794376 A CN107794376 A CN 107794376A CN 201710944100 A CN201710944100 A CN 201710944100A CN 107794376 A CN107794376 A CN 107794376A
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- palladium
- carbon catalyst
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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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- 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 discloses a kind of recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst, includes roasting, reducing agent reduction, inorganic acid and oxidant leaching, leachate removal of impurities, ammonia complexing, ammonia complexing acidification of filtrate successively and obtains the step of ammino Asia palladium of dichloro two precipitates, precipitation roasting reduction obtains Metal Palladium；The bulk or bulk calcining matter composition being placed in calcining process in roaster include calcium gluconate, waste palladium carbon catalyst and water by weight percentage, and the percentage by weight of its reclaimed water is not higher than 10%, and sintering temperature is 750~800 DEG C.Calcium gluconate is added to mix with palladium-carbon catalyst, calcium gluconate decomposes the stable foam calcium carbonate of generation under incineration temperature, the effect of filtering enriched palladium using being acted on covering of the foam calcium carbonate to palladium-carbon catalyst and to flue gas, reduce the loss of palladium in roasting process, the final rate of recovery for improving precious metal palladium.
Description
Technical field
The present invention relates to natural drug purification technique field, and in particular to metal in a kind of thin powdered carbon carrier palladium-carbon catalyst
The recovery method of palladium.
Background technology
Palladium catalyst has the function that important as the catalyst commonly used in Chemical Manufacture in chemical reaction.But by
It is expensive in palladium, and resource-constrained, its recovery process have just obtained the attention of people.Recover palladium is normal from dead palladium catalyst
That sees has two kinds of lixiviation process and roasting method.
Lixiviation process such as 201210428269.0 in the prior art, from economical and practical angle, palladium-carbon catalyst recovery
Method focuses mostly in roasting method, and such as 03126465.4,91104385.3,201610792867.4,200610097872.Roasting
As the committed step in recovery process, appropriate air should be passed through during roasting, so as to organic in catalyst
Thing impurity and activated carbon sufficiently and oxygen reaction carries out combustion decomposition, while can be also convenient for formic acid and palladium oxide gone back
Original, but the ascending air in roasting process in Muffle furnace can take away ash content, cause the loss of palladium, be unfavorable for that your higher gold ensured
Belong to the rate of recovery.
In order to overcome the technological deficiency that dust-firing shifts with air-flow, improved technical scheme such as periodical " urge by useless palladium platinum carbon
Three kinds of improvement projects described in the oxidizing roasting method of agent ", the first scheme are by 25% clay, 25% inflammable charcoal and 50%
Dead catalyst mix break into coal briquette, second scheme is by solid-to-liquid ratio 1 in waste material:0.5 adds water glass solution, after mixing
Pinch it is agglomerating be put into electric kiln roasting, the third scheme be in dead catalyst add 25% white lime, agglomerating be placed on is pinched after mixing
Electric kiln roasting, experiment show that there is the white lime of the third scheme combustion-supporting effect and the adsorbing and trapping to noble metal to act on, and
And calcium carbonate dissolves in acid, will not be had an impact for the subsequent step of noble metal recovery.
In the heavy metals emission control technology of coal, in coal combustion process, the calcium oxide and a huge sum of money of calcium carbonate roasting generation
Category or non-hole can be generated during other substance reactions, fine and close thing is covered in calcium oxide grain surface, so as to reach the effect of trapping metal
Fruit.But the roasting of catalyst is generally carried out as in crucible, above-mentioned non-hole densification thing is unfavorable for air and non-calcined catalyst
Abundant contact, and then cause the rate of roasting of dead catalyst to slow down, and catalyst spreads out roasting and further increase can risen
The ash amount that air-flow is taken away, increase the loss amount of palladium.
The content of the invention
An object of the present invention is to overcome defect present in prior art, there is provided a kind of thin powdered carbon carrier palladium carbon is urged
The recovery method of Metal Palladium in agent, the palladium incineration loss amount of above-mentioned recovery method are small.
To achieve the above object, the technical scheme is that：Metal Palladium in a kind of thin powdered carbon carrier palladium-carbon catalyst
Recovery method, include roasting, reducing agent reduction, inorganic acid and oxidant leaching, leachate removal of impurities, ammonia complexing, ammino successively
Close the step of acidification of filtrate obtains the ammino Asia palladium precipitation of dichloro two, precipitation roasting reduction obtains Metal Palladium；
Characterized in that, the bulk or bulk calcining matter composition that are placed in calcining process in roaster include by weight percentage
Calcium gluconate, waste palladium carbon catalyst and water, the percentage by weight of its reclaimed water are not higher than 10%, and sintering temperature is 750~800 DEG C.
First, the waste palladium carbon catalyst of fine-powdered is made into block or bulk helps to reduce the stream of roasting powder at initial stage
Lose；Calcium gluconate decomposes generation foam calcium carbonate at a lower temperature and carbon dioxide, the bulging of foam calcium carbonate simultaneously coat
On the surface of calcining matter, calcining matter from outward appearance to inner essence in fully burn, roasting gained ascending air need it is swollen through foam calcium carbonate
Body discharges, and foam calcium carbonate has filtration for roasting gained flue gas, and part palladium is trapped in calcium carbonate, and with roasting
Product reacts with formic acid in the lump, further, since object to be burned part moisture evaporation after roasting, fine-powdered palladium carbon come off, is covered in roasting
The varicosity for burning thing surface has barrier effect for the air stream for being blown into roaster, further reduces the powder flow in roasting process
Vector.
Solubility of the calcium gluconate in water is smaller under normal temperature, therefore the mixing of above-mentioned calcining matter can directly at normal temperatures
Complete.Above-mentioned bulk or bulk are not limited to the regular character such as spherical strip, and fine-powdered palladium-carbon catalyst is agglomerating.
Preferable technical scheme is the bulk or bulk calcining matter composition by weight hundred being placed in calcining process in roaster
Divide and include calcium gluconate 20~35%, waste palladium carbon catalyst 60~75% and water 2~8% than meter.Calcium gluconate too high levels are not
Beneficial to the entrance of oxygen in air, slow down roasting process, it is insufficient that appreciation causes catalyst to be calcined, and gluconic acid calcium content is too low
It is then poor for the trapping effect for the palladium that volatilizees.
Preferable technical scheme be the composition for the bulk or bulk calcining matter being placed in the calcining process in roaster also
Comprising organic thickening agent, the percentage by weight of organic thickening agent is 0.5~3%.Organic thickening agent is added in calcining matter, is increased
The bonding force of calcium gluconate and palladium-carbon catalyst, reduce the fine-powdered caused by object to be burned part moisture evaporation after roasting
The phenomenon that palladium carbon comes off.
In theory, not being introduced into the organic thickening agent of new impurity element can be introduced into calcining matter, include but is not limited to have
Machine thickener is selected from least one of CMS class thickener, chitosan and carboxymethyl cellulose class thickener.
Palladium-carbon catalyst is calcined and the carbon dioxide density of calcium gluconate decomposition generation is big, is easily collected on calcining matter week
Enclose, the abundant release of importing and carbon dioxide for the ease of air, preferable technical scheme is calcining matter container in roaster
Material be Alumina Foam Ceramics.Object to be burned container can be foamed ceramics pipe, or the foamed ceramics part of crucible shape.
Position-limiting action is played in the bulging of the foamed ceramics part pair and foam calcium carbonate of above two structure, and least a portion of foam calcium carbonate enters
Enter the inside of foamed ceramics part, cause roasting to start the accumulation of foam calcium carbonate in the rear short time, extend combustion-gas flow in foam
Filtration channel in calcium carbonate, further reduce palladium loss.Foamed ceramics part can also play to the combustion-gas flow oozed out via it
Filter effect.
In order that the palladium in product of roasting and calcining matter container fully reacts with formic acid, preferable technical scheme is to go back
Former agent extract technology is：Product of roasting and calcining matter container are placed in soak in reducing agent and reacted.
For the ease of the quick stripping of calcination vessel surface and internal product of roasting ash content, preferable technical scheme is to go back
Reaction solution and calcination vessel in former agent leaching process reaction vessel are handled using ultrasonic oscillation.
Conventional reducing agent includes hydrazine hydrate, formic acid, sodium formate, due to introducing calcium gluconate in calcining matter, therefore
Calcium carbonate is contained in product of roasting, in order to fully dissolve calcium carbonate and reduction-oxidation palladium, preferable technical scheme is reducing agent
For formic acid, the weight ratio of product of roasting and formic acid is 1:（5.5~7）.
In order to promote the separation of product of roasting and object to be burned container, further preferred technical scheme is ultrasonic frequency
For 25~40KHZ.
The advantages of the present invention are：
Change the burning form of fine-powdered waste palladium carbon catalyst, reduce powder number of dropouts；
Add calcium gluconate to mix with palladium-carbon catalyst, calcium gluconate decomposes the stable foamy carbon of generation under incineration temperature
Sour calcium, roasted using with covering effect of the foam calcium carbonate to palladium-carbon catalyst and the effect of the filtering enriched palladium to flue gas, reduction
The loss of palladium during burning, the final rate of recovery for improving precious metal palladium.
Embodiment
With reference to embodiment, the embodiment of the present invention is further described.Following examples are only used for more
Add and clearly demonstrate technical scheme, and can not be limited the scope of the invention with this.
Embodiment 1
Using the recovery process with Chinese patent 200610097872.X embodiments 1, difference is burning process embodiment 1
In, by waste palladium carbon catalyst（It is 0.33wt% content）Mixed with calcium gluconate it is agglomerating after as being calcined in crucible（Expense palladium is urged
Agent is with calcium gluconate with weight than 1:1 mixing, mixes a small amount of moisture）, sintering temperature is 750 DEG C, fully supply, roasting ash
Add formic acid reduction, product of roasting（Palladium ash）Addition ratio with formic acid is 1:4,70 DEG C are heated to, is kept for 3 hours, filtering,
The aqueous solution for filtering hydrochloric acid for dreg, sodium hypochlorite and hydrogen peroxide leaches, wherein palladium ash：Hydrochloric acid：Sodium hypochlorite：Hydrogen peroxide：Water is 1:
5:5:5:3, temperature is 75 DEG C, 4 hours time, filtering, filter residue recovery, and filtrate carries out ion exchange, ammonia complexing, filtered, complexing
Slag is reclaimed, complex liquid acidifying, and acidifying tail acid is collected, and is put into roaster after acid precipitation drying, is calcined 4 hours at 600 DEG C, uses hydrogen
Gas reduces, and obtains Metal Palladium.
Technological parameter in embodiment 1 can also be substituted with the technological parameter of palladium ash Recover palladium of the prior art, and not only
It is limited to technological parameter disclosed in embodiment 1.
Embodiment 2-4
The difference of embodiment 2 and embodiment 1 is, the bulk that is placed in calcining process in roaster or bulk calcining matter composition by
Percentage by weight meter includes calcium gluconate 20%, waste palladium carbon catalyst 75% and water 5%,
The difference of embodiment 3 and embodiment 1 is, the bulk that is placed in calcining process in roaster or bulk calcining matter composition by
Percentage by weight meter includes calcium gluconate 32%, waste palladium carbon catalyst 60% and water 8%.
The difference of embodiment 4 and embodiment 1 is, bulk or the bulk calcining matter group being placed in calcining process in roaster
Into including calcium gluconate 35%, waste palladium carbon catalyst 63% and water 2% by weight percentage.
Embodiment 5-6
The difference of embodiment 5 and embodiment 4 is, the bulk or the composition of bulk calcining matter being placed in calcining process in roaster
Organic thickening agent CMS is also included, the percentage by weight of organic thickening agent is 0.5%.
The organic thickening agent of embodiment 6 is chitosan and sodium carboxymethylcellulose 1:1 mixes, the weight of organic thickening agent
Percentage is 3%.
Embodiment 7
The difference of embodiment 7 and embodiment 6 is, by calcining matter as being calcined in Alumina Foam Ceramics pipe.
Embodiment 8
The difference of embodiment 8 and embodiment 7 is that reducing agent leaches reaction solution and calcination vessel use in process reaction vessel
Ultrasonic oscillation processing, ultrasonic frequency is 25~40KHZ.
Embodiment 9-10
The difference of embodiment 9 and embodiment 8 is that the weight ratio of product of roasting and formic acid is 1:5.5.
The difference of embodiment 10 and embodiment 9 is that the weight ratio of product of roasting and formic acid is 1:7.
Comparative example
Comparative example 1 is directly used in roasting using fine-powdered palladium carbon, and the addition of formic acid is every kilogram of product of roasting（Palladium ash）Add
300ml formic acid；
Fine-powdered palladium carbon is used to be calcined by comparative example 2 after white lime mixes；
Palladium recovery rate is divided into primary recovery and ult rec：
The percent value of corresponding palladium simple substance quality and Pd in palladium-carbon catalyst gross weight is calculated as once reclaiming in formic acid reduzate
Rate；
The percent value of end-product Metal Palladium and Pd in palladium-carbon catalyst gross weight is calculated as ult rec；
The palladium recovery rate of embodiment and comparative example see the table below：
| Primary recovery（%） | Ult rec（%） | |
| Embodiment 1 | 94.2 | 94.0 |
| Embodiment 2 | 96.0 | 95.5 |
| Embodiment 3 | 96.1 | 95.5 |
| Embodiment 4 | 96.5 | 96.1 |
| Embodiment 5 | 97.2 | 96.8 |
| Embodiment 6 | 97.0 | 96.7 |
| Embodiment 7 | 97.0 | 96.6 |
| Embodiment 8 | 97.3 | 97 |
| Embodiment 9 | 99.0 | 98.5 |
| Embodiment 10 | 99.2 | 98.8 |
| Comparative example 1 | 87.7 | 87.2 |
| Comparative example 2 | 92.8 | 91.3 |
The fine-powdered palladium-carbon catalyst rate of recovery is generally less than the granular palladium-carbon catalyst rate of recovery, Chinese patent
200610097872.X the recovery rate score of embodiment part is consistent with the granular palladium-carbon catalyst rate of recovery.
The roasting speed of calcining matter is fast compared with embodiment 6 in embodiment 7, and it is thorough to burn.
Formic acid addition is very few in formic acid embodiment 1-8, and the reduction of palladium oxide is not thorough, causes primary recovery relatively low.
Processing for product of roasting, formic acid it can also be reacted first under normal temperature with product of roasting, it is solid obtained by separation of solid and liquid
State residue and reducing agent（Optional formic acid, sodium formate or hydrazine hydrate）Heating carries out redox reaction, i.e., in product of roasting
Calcium carbonate distribution process.
Only it is the preferred embodiment of the present invention described in upper, it is noted that for those skilled in the art
For, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (9)
1. the recovery method of Metal Palladium in a kind of thin powdered carbon carrier palladium-carbon catalyst, includes roasting, reducing agent reduces, be inorganic successively
Strong acid and oxidant leaching, leachate removal of impurities, ammonia complexing, ammonia complexing acidification of filtrate obtain the ammino Asia palladium precipitation of dichloro two, precipitation roasting
Burning reduce Metal Palladium the step of；
Characterized in that, the bulk or bulk calcining matter composition that are placed in calcining process in roaster include by weight percentage
Calcium gluconate, waste palladium carbon catalyst and water, the percentage by weight of its reclaimed water are not higher than 10%, and sintering temperature is 750~800 DEG C.
2. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 1, it is characterised in that roasting
Burn process in be placed in roaster bulk or bulk calcining matter composition by weight percentage comprising calcium gluconate 20~
35%th, waste palladium carbon catalyst 60~75% and water 2~8%.
3. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 1, it is characterised in that institute
The composition for stating the bulk being placed in calcining process in roaster or bulk calcining matter also includes organic thickening agent, organic thickening agent
Percentage by weight is 0.5~3%.
4. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 2, it is characterised in that have
Machine thickener is selected from least one of CMS class thickener, chitosan and carboxymethyl cellulose class thickener.
5. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 1, it is characterised in that roasting
The material for burning kiln roasting thing container is Alumina Foam Ceramics.
6. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 4, it is characterised in that also
Former agent extract technology is：Product of roasting and calcining matter container are placed in soak in reducing agent and reacted.
7. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 5, it is characterised in that also
Reaction solution and calcination vessel in former agent leaching process reaction vessel are handled using ultrasonic oscillation.
8. the recovery method of Metal Palladium, its feature exist in the thin powdered carbon carrier palladium-carbon catalyst according to Claims 2 or 3
It is formic acid in, reducing agent, the weight ratio of product of roasting and formic acid is 1:（5.5~7）.
9. the recovery method of Metal Palladium in thin powdered carbon carrier palladium-carbon catalyst according to claim 6, it is characterised in that super
Frequency of sound wave is 25~40KHZ.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111334663A (en) * | 2018-12-19 | 2020-06-26 | 中国科学院过程工程研究所 | Method for recovering precious metal from spent automobile exhaust catalyst |
| KR20210021077A (en) * | 2018-06-21 | 2021-02-24 | 헤레우스 도이칠란트 게엠베하 운트 코. 카게 | Noble metal catalyst briquette, preparation and incineration method thereof |
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| KR20210021077A (en) * | 2018-06-21 | 2021-02-24 | 헤레우스 도이칠란트 게엠베하 운트 코. 카게 | Noble metal catalyst briquette, preparation and incineration method thereof |
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| CN111334663B (en) * | 2018-12-19 | 2021-05-18 | 中国科学院过程工程研究所 | Method for recovering precious metal from spent automobile exhaust catalyst |
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