CN103627902A - Method for recovering rhodium from inactive noble metal catalyst - Google Patents
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Abstract
A method for recovering rhodium from an inactive noble metal catalyst comprises: mixing the preliminary-processed inactive noble metal catalyst with tin powder and a surface covering agent according to a certain ratio; heating in a medium-frequency induction furnace to fragmenting the mixture; cooling the obtained mixture and immersing with hydrochloric acid with a concentration of 6 N for 3 hours; filtering out rhodium-containing insoluble substances; putting the rhodium-containing insoluble substances in aqua regia, stirring for dissolving; repeatedly performing extraction on the above solution with an extraction agent, merging obtained organic-phase solution; performing back-extraction on the organic-phase solution with an aqueous solution to obtain an aqueous solution containing high-concentration rhodium; and performing ammonium chloride precipitation, washing, calcining, hydrogen reduction on the rhodium-containing aqueous solution to obtain high-purity rhodium powder. The beneficial effects comprise that the method has the advantages of being simple in technology, convenient to operate, high in recovery rate, recyclable in all reagents and the like.
Description
Technical field
The present invention relates to noble metal catalyst and reclaim field, especially a kind of method that reclaims rhodium from inefficacy noble metal catalyst.
Background technology
Noble metal catalyst is widely used in chemical industry, petroleum refining and automotive field.But use after for some time, due to carbon distribution, oxidation or other reason, can cause the inactivation of catalyzer, cyclic regeneration several times after, become spent catalyst and can not continue to use.The spent catalyst that this bullion content is high has now become the secondary resource with high recovery value.
The method of existing recovery rhodium is for reclaiming rhodium the spent catalyst solution from rhodium-containing mostly, mainly contain following several method: the first is the precipitator method of introducing as in Chinese patent CN102910720, the method is to using highly basic as precipitation agent, join in the catalyst solution of rhodium-containing, heated and stirred 1～5h under the condition of 80～100 ℃, make it that precipitin reaction occur, obtain solid hydrogen rhodium oxide, more moisture solid hydrogen rhodium oxide is dried 120 ℃ time and obtained anhydrous rhodium hydroxide, the second is the ion exchange method of introducing as in Chinese patent CN101177306, the method is respectively at 30 ℃ by the spent catalyst of rhodium-containing, 100 ℃, 150 ℃, 200 ℃ and 230 ℃ remove the high boiling point by-products produced rhodium that makes in raw material through underpressure distillation and are concentrated, in the rhodium spent catalyst after concentrated, add oxidizing acid, make organic matter carbonizing wherein, add again a kind of strong acid dissolved carbon compound, organism is removed from system, now, rhodium is present in acid solution with complex anion form, rhodium pH is adjusted to 1～6, thickening filtration, remove most of salt, regulate again mother liquor pH value that rhodium is precipitated with aqua oxidation rhodium, dissolving with hydrochloric acid rhodium oxide precipitation with 2～6N, be diluted to rhodium content 200～450ppm, speed process ion-exchange with 4～6m/h, by the concentrated rhodium chloride crystal that obtains of the solution evaporation after exchange, the third is intensification burning method, as recorded in Chinese patent CN1273278, rhodium-containing catalyst waste liquid is put into crucible oven or incinerator, by waste liquid at 600 ℃ by waste liquid ashing, also having a kind of method is extraction process, and acid adding and superoxide in rhodium-containing spent catalyst destroy rhodium complex, make rhodium enter water, thereby are reclaimed.
Above several method for be the recovery method of the useless catalytic liquid of rhodium-containing, and it is less for discarded, invalid solid catalyst recovery method, a kind of is the fragmentation dissolving methof of a kind of precious metal as introduced in Chinese patent CN1048238, under the condition of 700～1200 ℃, with a kind of aluminium-zinc alloy fragmentation agent, treat together the mixing of materials melting containing precious metal of fragmentation, with hydrochloric acid soln, leach fragmentation material, leached mud is carried out to aqueous solution ammonification dissolving; Another kind be as in Chinese patent CN102796877, introduce a kind of from the organic spent catalyst of rhodium-containing the method for enrichment rhodium, the organic spent catalyst of rhodium-containing and trapping agent, reductive agent and additive are mixed to the rear ball processed of profit mill by a certain percentage, pelletizing after profit mill is put into plumbago crucible and be placed in chamber type electric resistance furnace, at 1100～1350 ℃, reduce 4～12h, after reduction, grind choosing, make the micro-base alloy of rhodium-containing iron-based separated with slag, finally the micro-base alloy of rhodium-containing iron-based is placed in to 10%～30% diluted acid selectivity and leaches base metal wherein, obtain rhodium enriched substance.
Summary of the invention
For solving the deficiencies in the prior art, the object of this invention is to provide a kind of method that reclaims rhodium from inefficacy noble metal catalyst, possess skills simple, the advantage such as easy to operate, the rate of recovery is high, agents useful for same reusable edible.
The present invention is achieved through the following technical solutions:
A method that reclaims rhodium from inefficacy noble metal catalyst, comprises the following steps,
1. fragmentation: the inefficacy noble metal catalyst after preliminary treatment is mixed by a certain percentage with glass putty and surface dopant, mixture is placed in medium-frequency induction furnace and is heated, make it become fragmentation particle, described surface dopant is the mixture of sodium-chlor and Repone K;
2. dissolve: by gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving;
3. acetic acid ethyl acetate extract extraction: with containing certain proportion TOPO(trioctyl-phosphine oxide) repeatedly extracts above-mentioned solution, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains certain proportion solubilizing agent, obtain the aqueous solution that contains high density rhodium;
4. reduction is purified: the aqueous solution of above-mentioned rhodium-containing, through chloride precipitation, washing, calcining, hydrogen reducing, obtains highly purified rhodium powder.
Further, described step 1. in preliminary treatment be to leach insolubles after stripping platinum, gained insolubles is processed as aforesaid method.
Further, described step 1. in the consumption of glass putty and the weight ratio of catalyzer be 7.5～9:1, the consumption of described surface dopant and the weight ratio of catalyzer are 0.5～1:1, in surface dopant, sodium-chlor and Repone K weight ratio are 1:1.
Further, described step 3. in solubilizing agent be a kind of in alkyl polyoxyethylene glycol, alkylbenzene polyoxyethylene glycol and acyl group polyoxyethylene glycol, its consumption be step 1. in insolubles weight 0.1%～1%.
Further, described step 3. in the content in extraction phase of TOPO be 0.05mol/L～0.1mol/L.
Further, the described step 4. chloride precipitation thing of middle rhodium is calcined through three steps, and the first step initial temperature is 150～250 ℃, calcination time 2～4h, second step temperature is 400～750 ℃, calcination time 0.5～2h, the 3rd Buwen's degree is 600～800 ℃, calcination time 6～12h.
Further, the shielding gas that described step passes into before hydrogen reducing in 4., described shielding gas is a kind of in nitrogen, argon gas, carbonic acid gas.
Further, described step 4. middle hydrogen reducing temperature is 600～900 ℃, and the recovery time is 1～3h.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
In order to make technique means of the present invention, creation characteristic, reach object and effect is easy to understand, below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.
Embodiment 1
By the inefficacy noble metal catalyst 100g after preliminary treatment and glass putty 750g and surface dopant 50g(sodium-chlor and each 25g of Repone K) mix to be placed in medium-frequency induction furnace and heat, gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving, with containing 0.05mol/L concentration TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains 1g solubilizing agent, obtain the aqueous solution that contains high density rhodium, the acetic acid ethyl acetate extract that contains TOPO can be reused by Distillation recovery in reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 150 ℃, calcination time 2h, second step temperature is 400 ℃, calcination time 1h, and the 3rd Buwen's degree is 600 ℃, calcination time 6h, hydrogen reducing 1h at 600 ℃, obtains highly purified rhodium powder 70.84g, and yield is 98.4%.
Embodiment 2
By the inefficacy noble metal catalyst 100g after preliminary treatment and glass putty 800g and surface dopant 80g(sodium-chlor and each 40g of Repone K) mix to be placed in medium-frequency induction furnace and heat, gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving, with containing 0.01mol/L concentration TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains 1g solubilizing agent, obtain the aqueous solution that contains high density rhodium, the acetic acid ethyl acetate extract that contains TOPO can be reused by Distillation recovery in reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 200 ℃, calcination time 2h, second step temperature is 500 ℃, calcination time 1h, and the 3rd Buwen's degree is 700 ℃, calcination time 6h, hydrogen reducing 2h at 700 ℃, obtains highly purified rhodium powder 70.56g, and yield is 98%.
Embodiment 3
By the inefficacy noble metal catalyst 100g after preliminary treatment and glass putty 900g and surface dopant 100g(sodium-chlor and each 50g of Repone K) mix to be placed in medium-frequency induction furnace and heat, gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving, with containing 0.05mol/L concentration TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains 1g solubilizing agent, obtain the aqueous solution that contains high density rhodium, the acetic acid ethyl acetate extract that contains TOPO can be reused by Distillation recovery in reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 150 ℃, calcination time 4h, second step temperature is 500 ℃, calcination time 2h, and the 3rd Buwen's degree is 800 ℃, calcination time 12h, hydrogen reducing 1h at 900 ℃, obtains highly purified rhodium powder 71.56g, and yield is 99.4%.
Embodiment 4
By the inefficacy noble metal catalyst 500g after preliminary treatment and glass putty 4000g and surface dopant 500g(sodium-chlor and each 250g of Repone K) mix to be placed in medium-frequency induction furnace and heat, gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving, with containing 0.1mol/L concentration TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains 2.5g solubilizing agent, obtain the aqueous solution that contains high density rhodium, the acetic acid ethyl acetate extract that contains TOPO can be reused by Distillation recovery in reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 250 ℃, calcination time 2h, second step temperature is 750 ℃, calcination time 1h, and the 3rd Buwen's degree is 800 ℃, calcination time 6h, hydrogen reducing 3h at 900 ℃, obtains highly purified rhodium powder 356.76g, and yield is 99.1%.
Embodiment 5
By the inefficacy noble metal catalyst 500g after preliminary treatment and glass putty 3750g and surface dopant 400g(sodium-chlor and each 200g of Repone K) mix to be placed in medium-frequency induction furnace and heat, gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving, with containing 0.1mol/L concentration TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains 5g solubilizing agent, obtain the aqueous solution that contains high density rhodium, the acetic acid ethyl acetate extract that contains TOPO can be reused by Distillation recovery in reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 250 ℃, calcination time 3h, second step temperature is 650 ℃, calcination time 2h, and the 3rd Buwen's degree is 800 ℃, calcination time 8h, hydrogen reducing 2h at 900 ℃, obtains highly purified rhodium powder 354.2g, and yield is 98.4%.
Claims (9)
1. from inefficacy noble metal catalyst, reclaim a method for rhodium, it is characterized in that, comprise the following steps,
1. fragmentation;
2. dissolve;
3. extraction;
4. reduction is purified,
Its concrete steps feature is: 1. the inefficacy noble metal catalyst after preliminary treatment is mixed by a certain percentage with glass putty and surface dopant, mixture is placed in medium-frequency induction furnace and is heated, make it become fragmentation particle, described surface dopant is the mixture of sodium-chlor and Repone K; 2. by gained mixture cooling rear by concentration, be 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in to chloroazotic acid stirring and dissolving; 3. with containing certain proportion TOPO(trioctyl-phosphine oxide) acetic acid ethyl acetate extract above-mentioned solution is repeatedly extracted, gained organic phase solution merges, above-mentioned organic phase solution is stripped with the aqueous solution that contains certain proportion solubilizing agent, obtain the aqueous solution that contains high density rhodium; 4. the aqueous solution of above-mentioned rhodium-containing, through chloride precipitation, washing, calcining, hydrogen reducing, obtains highly purified rhodium powder.
2. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, is characterized in that, described step 1. in preliminary treatment be to leach insolubles after stripping platinum, gained insolubles is processed as aforesaid method.
3. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, it is characterized in that, described step 1. in the consumption of glass putty and the weight ratio of catalyzer be 7.5～9:1, the consumption of described surface dopant and the weight ratio of catalyzer are 0.5～1:1.
4. according to a kind of method that reclaims rhodium from inefficacy noble metal catalyst described in claim 1 or 3, it is characterized in that, in described surface dopant, sodium-chlor and Repone K weight ratio are 1:1.
5. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, is characterized in that, the described step 3. content in extraction phase of middle TOPO is 0.05mol/L～0.1mol/L.
6. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1; it is characterized in that; described step 3. in solubilizing agent be a kind of in alkyl polyoxyethylene glycol, alkylbenzene polyoxyethylene glycol and acyl group polyoxyethylene glycol, its consumption be step 1. in insolubles weight 0.1%～1%.
7. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, it is characterized in that, the described step 4. chloride precipitation thing of middle rhodium is calcined through three steps, the first step initial temperature is 150～250 ℃, calcination time 2～4h, second step temperature is 400～750 ℃, calcination time 0.5～2h, the 3rd Buwen's degree is 600～800 ℃, calcination time 6～12h.
8. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, is characterized in that, the shielding gas that described step passes into before hydrogen reducing in 4., and described shielding gas is a kind of in nitrogen, argon gas, carbonic acid gas.
9. a kind of method that reclaims rhodium from inefficacy noble metal catalyst according to claim 1, is characterized in that, described step 4. middle hydrogen reducing temperature is 600～900 ℃, and the recovery time is 1～3h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724822A (en) * | 2019-11-27 | 2020-01-24 | 北京科技大学 | Method for recovering platinum group metals by trapping-crushing iron-based alloy |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| CN114427996A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for dissolving rhodium in rhodium-containing waste liquid and application thereof |
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| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| CN101230469A (en) * | 2007-11-02 | 2008-07-30 | 北京科技大学 | Method for directly reclaiming metals from electron wastes |
| WO2012029379A1 (en) * | 2010-09-03 | 2012-03-08 | Jx日鉱日石金属株式会社 | Recovery method for high purity platinum |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1031567A (en) * | 1987-08-13 | 1989-03-08 | 中国有色金属工业总公司昆明贵金属研究所 | The dissolving and the purification of thick rhodium and high rhodium-containing alloyed scrap |
| CN101230469A (en) * | 2007-11-02 | 2008-07-30 | 北京科技大学 | Method for directly reclaiming metals from electron wastes |
| WO2012029379A1 (en) * | 2010-09-03 | 2012-03-08 | Jx日鉱日石金属株式会社 | Recovery method for high purity platinum |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724822A (en) * | 2019-11-27 | 2020-01-24 | 北京科技大学 | Method for recovering platinum group metals by trapping-crushing iron-based alloy |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| CN111054933B (en) * | 2019-12-09 | 2022-08-02 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
| CN114427996A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for dissolving rhodium in rhodium-containing waste liquid and application thereof |
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