CN103627902B - A kind of method reclaiming rhodium from inactive noble metal catalyst - Google Patents
A kind of method reclaiming rhodium from inactive noble metal catalyst Download PDFInfo
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 70
- 239000010948 rhodium Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000002019 doping agent Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000011521 glass Substances 0.000 claims abstract description 10
- 238000013467 fragmentation Methods 0.000 claims abstract description 9
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 230000006698 induction Effects 0.000 claims abstract description 8
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 4
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002024 ethyl acetate extract Substances 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- IDAKEVGCRYXPBQ-UHFFFAOYSA-N [Rh]=O.Cl Chemical compound [Rh]=O.Cl IDAKEVGCRYXPBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
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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
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- Manufacture And Refinement Of Metals (AREA)
- Catalysts (AREA)
Abstract
A kind of method reclaiming rhodium from inactive noble metal catalyst, inactive noble metal catalyst after preliminary treatment is mixed by a certain percentage with glass putty and surface dopant, in medium-frequency induction furnace, heating makes its fragmentation, it is 6N salt acid soak 3 hours that gained mixture is cooled rear concentration, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with extraction liquid, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the above-mentioned organic phase solution aqueous solution is stripped, obtain the aqueous solution containing high density rhodium, the aqueous solution of rhodium-containing is through chloride precipitation, washing, calcining, hydrogen reducing, obtain highly purified rhodium powder.Beneficial effect: the present invention possesses skills simply, the advantages such as easy to operate, the rate of recovery is high, agents useful for same reusable edible.
Description
Technical field
The present invention relates to noble metal catalyst and reclaim field, especially a kind of method reclaiming rhodium from inactive 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, the inactivation of catalyzer can be caused, cyclic regeneration several times after, then 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 reclaim rhodium for from the spent catalyst solution of rhodium-containing mostly, mainly contain following several method: the first is the precipitator method as introduced in Chinese patent CN102910720, the method is 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 DEG C, make it that precipitin reaction occur, obtain solid hydrogen rhodium oxide, more moisture solid hydrogen rhodium oxide is dried 120 DEG C time obtain anhydrous rhodium hydroxide, the second is the ion exchange method as introduced in Chinese patent CN101177306, the method is respectively at 30 DEG C by the spent catalyst of rhodium-containing, 100 DEG C, 150 DEG C, 200 DEG C and 230 DEG C remove the high boiling point by-products produced rhodium that makes in raw material through underpressure distillation and are concentrated, oxidizing acid is added in the rhodium spent catalyst after concentrated, make organic matter carbonizing wherein, add a kind of strong acid dissolution carbide again, organism is removed from system, now, rhodium is present in acid solution with complex anion form, rhodium solution ph is adjusted to 1 ~ 6, thickening filtration, remove most of salt, regulate mother liquor pH value that rhodium is precipitated with aqua oxidation rhodium again, precipitate with the dissolving with hydrochloric acid rhodium oxide of 2 ~ 6N, be diluted to rhodium content 200 ~ 450ppm, with the speed of 4 ~ 6m/h through ion-exchange, rhodium chloride crystal is obtained by concentrated for 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 DEG C by waste liquid ashing, also have a kind of method to be extraction process, acid adding and superoxide in rhodium-containing spent catalyst, rhodium complex is destroyed, makes rhodium enter aqueous phase, thus 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 fragmentation dissolving methof as a kind of precious metal introduced in Chinese patent CN1048238, with the same mixing of materials melting containing precious metal treating fragmentation of a kind of aluminium-zinc alloy fragmentation agent under the condition of 700 ~ 1200 DEG C, leach fragmentation material with hydrochloric acid soln, aqueous solution ammonification dissolving is carried out to leached mud; Another kind is the method as a kind of enrichment rhodium from rhodium-containing organic waste catalyzer introduced in Chinese patent CN102796877, rhodium-containing organic waste catalyzer and trapping agent, reductive agent and additive are mixed by a certain percentage moisten grind after ball processed, pelletizing after profit mill is put into plumbago crucible and is placed in chamber type electric resistance furnace, reduction 4 ~ 12h at 1100 ~ 1350 DEG C, mill choosing is carried out after reduction, the micro-base alloy of rhodium-containing iron-based is separated with slag, finally micro-for rhodium-containing iron-based base alloy is placed in the diluted acid Selectively leaching base metal wherein of 10% ~ 30%, obtains 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 reclaiming rhodium from inactive noble metal catalyst, possessing skills simple, the advantages 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:
From inactive noble metal catalyst, reclaim a method for rhodium, it is characterized in that, comprise the following steps,
1. fragmentation;
2. dissolve;
3. extract;
4. purification is reduced,
Its concrete steps feature is: 1. the inactive noble metal catalyst after preliminary treatment mixed by a certain percentage with glass putty and surface dopant, mixture is placed in medium-frequency induction furnace and heats, it is made to become fragmentation particle, described surface dopant is the mixture of sodium-chlor and Repone K, the consumption of glass putty and the weight ratio of catalyzer are 7.5 ~ 9:1, the consumption of described surface dopant and the weight ratio of catalyzer are 0.5 ~ 1:1, and in surface dopant, sodium-chlor and Repone K weight ratio are 1:1; 2. gained mixture being cooled rear concentration is 6N salt acid soak 3 hours, leaches the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving; 3. with the acetic acid ethyl acetate extract containing certain proportion trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing certain proportion solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, the content of trioctyl-phosphine oxide in extraction phase is 0.05mol/L ~ 0.1mol/L; 4. the aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, calcining, hydrogen reducing, obtains highly purified rhodium powder.
Further, described step 1. middle preliminary treatment is leach insolubles after stripping platinum, and gained insolubles is as aforesaid method process.
Further, described step 3. in solubilizing agent be one in alkyl polyoxyethylene glycol, alkylbenzene polyoxyethylene glycol and acyl group polyoxyethylene glycol, its consumption be step 2. in rhodium-containing insolubles weight 0.1% ~ 1%.
Further, described step 4. in the chloride precipitation thing of rhodium calcine through three steps, the first step initial temperature is 150 ~ 250 DEG C, calcination time 2 ~ 4h, second step temperature is 400 ~ 750 DEG C, calcination time 0.5 ~ 2h, 3rd Buwen's degree is 600 ~ 800 DEG C, calcination time 6 ~ 12h.
Further, described step 4. in pass into shielding gas before hydrogen reducing, described shielding gas is the one in nitrogen, argon gas, carbonic acid gas.
Further, described step 4. middle hydrogen reducing temperature is 600 ~ 900 DEG C, and the recovery time is 1 ~ 3h.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet.
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
Inactive noble metal catalyst 100g after preliminary treatment is mixed with glass putty 750g and surface dopant 50g (sodium-chlor and each 25g of Repone K) be placed in medium-frequency induction furnace and heat, the rear concentration of gained mixture cooling is 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with the acetic acid ethyl acetate extract containing 0.05mol/L concentration trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing 1g solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, acetic acid ethyl acetate extract containing trioctyl-phosphine oxide can be reused through Distillation recovery after reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 150 DEG C, calcination time 2h, second step temperature is 400 DEG C, calcination time 1h, and the 3rd Buwen's degree is 600 DEG C, calcination time 6h, hydrogen reducing 1h at 600 DEG C, obtain highly purified rhodium powder 70.84g, yield is 98.4%.
Embodiment 2
Inactive noble metal catalyst 100g after preliminary treatment is mixed with glass putty 800g and surface dopant 80g (sodium-chlor and each 40g of Repone K) be placed in medium-frequency induction furnace and heat, the rear concentration of gained mixture cooling is 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with the acetic acid ethyl acetate extract containing 0.01mol/L concentration trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing 1g solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, acetic acid ethyl acetate extract containing trioctyl-phosphine oxide can be reused through Distillation recovery after reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 200 DEG C, calcination time 2h, second step temperature is 500 DEG C, calcination time 1h, and the 3rd Buwen's degree is 700 DEG C, calcination time 6h, hydrogen reducing 2h at 700 DEG C, obtain highly purified rhodium powder 70.56g, yield is 98%.
Embodiment 3
Inactive noble metal catalyst 100g after preliminary treatment is mixed with glass putty 900g and surface dopant 100g (sodium-chlor and each 50g of Repone K) be placed in medium-frequency induction furnace and heat, the rear concentration of gained mixture cooling is 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with the acetic acid ethyl acetate extract containing 0.05mol/L concentration trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing 1g solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, acetic acid ethyl acetate extract containing trioctyl-phosphine oxide can be reused through Distillation recovery after reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 150 DEG C, calcination time 4h, second step temperature is 500 DEG C, calcination time 2h, and the 3rd Buwen's degree is 800 DEG C, calcination time 12h, hydrogen reducing 1h at 900 DEG C, obtain highly purified rhodium powder 71.56g, yield is 99.4%.
Embodiment 4
Inactive noble metal catalyst 500g after preliminary treatment is mixed with glass putty 4000g and surface dopant 500g (sodium-chlor and each 250g of Repone K) be placed in medium-frequency induction furnace and heat, the rear concentration of gained mixture cooling is 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with the acetic acid ethyl acetate extract containing 0.1mol/L concentration trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing 2.5g solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, acetic acid ethyl acetate extract containing trioctyl-phosphine oxide can be reused through Distillation recovery after reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 250 DEG C, calcination time 2h, second step temperature is 750 DEG C, calcination time 1h, and the 3rd Buwen's degree is 800 DEG C, calcination time 6h, hydrogen reducing 3h at 900 DEG C, obtain highly purified rhodium powder 356.76g, yield is 99.1%.
Embodiment 5
Inactive noble metal catalyst 500g after preliminary treatment is mixed with glass putty 3750g and surface dopant 400g (sodium-chlor and each 200g of Repone K) be placed in medium-frequency induction furnace and heat, the rear concentration of gained mixture cooling is 6N salt acid soak 3 hours, leach the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving, with the acetic acid ethyl acetate extract containing 0.1mol/L concentration trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing 5g solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, acetic acid ethyl acetate extract containing trioctyl-phosphine oxide can be reused through Distillation recovery after reextraction.The aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, three step calcinings, the first step initial temperature is 250 DEG C, calcination time 3h, second step temperature is 650 DEG C, calcination time 2h, and the 3rd Buwen's degree is 800 DEG C, calcination time 8h, hydrogen reducing 2h at 900 DEG C, obtain highly purified rhodium powder 354.2g, yield is 98.4%.
Claims (6)
1. from inactive noble metal catalyst, reclaim a method for rhodium, it is characterized in that, comprise the following steps,
1. fragmentation;
2. dissolve;
3. extract;
4. purification is reduced,
Its concrete steps feature is: 1. the inactive noble metal catalyst after preliminary treatment mixed by a certain percentage with glass putty and surface dopant, mixture is placed in medium-frequency induction furnace and heats, it is made to become fragmentation particle, described surface dopant is the mixture of sodium-chlor and Repone K, the consumption of glass putty and the weight ratio of catalyzer are 7.5 ~ 9:1, the consumption of described surface dopant and the weight ratio of catalyzer are 0.5 ~ 1:1, and in surface dopant, sodium-chlor and Repone K weight ratio are 1:1; 2. gained mixture being cooled rear concentration is 6N salt acid soak 3 hours, leaches the insolubles of rhodium-containing, the insolubles of rhodium-containing is placed in chloroazotic acid stirring and dissolving; 3. with the acetic acid ethyl acetate extract containing certain proportion trioctyl-phosphine oxide, above-mentioned solution is repeatedly extracted, gained organic phase solution merges, the aqueous solution of above-mentioned organic phase solution containing certain proportion solubilizing agent is stripped, obtain the aqueous solution containing high density rhodium, the content of trioctyl-phosphine oxide in extraction phase is 0.05mol/L ~ 0.1mol/L; 4. the aqueous solution of above-mentioned rhodium-containing is through chloride precipitation, washing, calcining, hydrogen reducing, obtains highly purified rhodium powder.
2. a kind of method reclaiming rhodium from inactive noble metal catalyst according to claim 1, is characterized in that, described step 1. middle preliminary treatment is leach insolubles after stripping platinum, the method process as claimed in claim 1 of gained insolubles.
3. a kind of method reclaiming rhodium from inactive noble metal catalyst according to claim 1; it is characterized in that; described step 3. in solubilizing agent be one in alkyl polyoxyethylene glycol, alkylbenzene polyoxyethylene glycol and acyl group polyoxyethylene glycol, its consumption be step 2. in rhodium-containing insolubles weight 0.1% ~ 1%.
4. a kind of method reclaiming rhodium from inactive noble metal catalyst according to claim 1, it is characterized in that, described step 4. in the chloride precipitation thing of rhodium calcine through three steps, the first step initial temperature is 150 ~ 250 DEG C, calcination time 2 ~ 4h, second step temperature is 400 ~ 750 DEG C, calcination time 0.5 ~ 2h, 3rd Buwen's degree is 600 ~ 800 DEG C, calcination time 6 ~ 12h.
5. a kind of method reclaiming rhodium from inactive noble metal catalyst according to claim 1, is characterized in that, described step 4. in pass into shielding gas before hydrogen reducing, described shielding gas is the one in nitrogen, argon gas, carbonic acid gas.
6. a kind of method reclaiming rhodium from inactive noble metal catalyst according to claim 1, is characterized in that, described step 4. middle hydrogen reducing temperature is 600 ~ 900 DEG C, and the recovery time is 1 ~ 3h.
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| CN110724822B (en) * | 2019-11-27 | 2020-10-23 | 北京科技大学 | Method for recovering platinum group metals by trapping-crushing iron-based alloy |
| 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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| 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 |
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| JP5399510B2 (en) * | 2010-09-03 | 2014-01-29 | Ｊｘ日鉱日石金属株式会社 | High-purity platinum recovery method |
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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 |
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