CN102002589A - Method for three-phase extraction one-step separation of platinum, palladium and rhodium from leaching solution of precious metal catalyst - Google Patents
Method for three-phase extraction one-step separation of platinum, palladium and rhodium from leaching solution of precious metal catalyst Download PDFInfo
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Abstract
The invention relates to a method for three-phase extraction one-step separation of platinum, palladium and rhodium from leaching solution of a precious metal catalyst, which belongs to the technical field of solvent extraction and separation of the platinum, the palladium and the rhodium. The separation of the platinum, the palladium and the rhodium can be completed by adding hydrochloride, sulfate, nitrate or phosphate of sodium, potassium, lithium or ammonium into two non-polar and polar organic phases which can not be mixed and water solution containing the platinum, the palladium and the rhodium, and carrying out phase mixing under room temperature for obtaining a three-phase system. The separation of the platinum, the palladium and the rhodium can also be completed by adding a macromoleclar polymer and the hydrochloride, the sulfate, the nitrate or the phosphate containing the sodium, the potassium, the lithium or the ammonium into the water solution containing the platinum, the palladium and the rhodium according to proportion, further adding a non-polar organic solvent and carrying out the phase mixing under the room temperature for obtaining three phases. The method can simultaneously separate three phases of the platinum, the palladium and the rhodium with high separation selectivity from the failure extraction solution of a vehicle catalyst during the extraction process, and effectively simplify the existing lengthy and tedious two-phase extraction and separation process.
Description
Technical field
The invention belongs to solvent extraction and separation platinum, palladium, rhodium technical field, particularly relate to a kind of method that one step of three phase extraction is separated platinum, palladium, rhodium from the noble metal catalyst leach liquor.
Background technology
Precious metals such as platinum, palladium, rhodium are because of the various physicochemical property of its uniqueness, excellence, be widely used in modern high technology, defence and military, space flight navigation, new energy development, chemical industry, petrochemical industry, glass glass, electronic apparatus instrument, ecology and environmental pollution improvement and each major industry field of the development of the national economy, being described as " vitamin b6 usp of modern industry " and " primary high-technology metal ", is pillar industry in national economy development essential and irreplaceable " crucial strategic resource ".Because ore reserve is extremely rare in the world for it, and have problems such as grade is low, symbiont is complicated, separating difficulty is big, extraction recovery platinum, palladium, rhodium are the industries that countries in the world are attached great importance to always from the precious metal secondary resource that various uses were lost efficacy.
Cleaning catalyst for tail gases of automobiles is the Application Areas of precious metal maximums such as platinum, palladium, rhodium.At present, Quan Qiu platinum, palladium, rhodium have 1/3rd to be used for automotive industry approximately.Along with the day by day strictness of countries in the world to the motor vehicle exhaust rules, the automobile catalyst field increases day by day to the demand of platinum, palladium, rhodium.The assembling cleaning catalyst for tail gases of automobiles reduces pollutant discharge amount, is not only a mandatory rules of law of government, also is the inevitable choice of existence of automobile production producer and market competition.The recent statistics data showed in 2009, and global automobile manufacture industry increases 11% to the annual requirement strength of platinum, palladium, rhodium.Europe-III emission standard by European environmental requirement is in recent years calculated, the content summation of platinum, palladium, three kinds of metals of rhodium is up to 2000～3000ppm in the cellular purifying vehicle exhaust catalyst converter of trichroite type, is platinum, palladium, rhodium hundreds of times or thousands of times of content in its pay shoot.Calculate in view of the above, per 1,000,000 cars approximately will use 2～3 tons of platinum, palladium, rhodium metal.By about 400,000,000 calculating of present whole world car owning amount, if wherein about 1/2nd load onto exhaust gas cleaner, and by each 2g calculating, the platinum, palladium, the rhodium that overstock in automotive industry have reached 400 tons.In the face of huge numeral like this, Nan Gua the U.S. has the people that the automotive industry meaning is " mine, moving platinum metals ".Because its quantity is big, platinum, palladium, rhodium content is more much higher than the content of its pay shoot, the extraction recovery process is shorter relatively, a large amount of use spent automotive exhaust catalysts has become platinum, palladium, the most important recyclable secondary resource that utilizes of rhodium.
Solvent extraction is platinum, palladium, rhodium separates and the most promising method of purifying.Compare with substitution method with traditional precipitator method, Solvent Extraction Separation and purification platinum, palladium, rhodium have tangible advantage:, cycle simple as technology is short, speed of response is fast, metal direct yield height, to the adaptability of various materials with handiness is strong, energy consumption and tooling cost is low, easy handling and amplification, can realize large-scale continuous production and control etc. automatically.Therefore, Solvent Extraction Separation purification platinum, palladium, rhodium by each main precious-metal refiner of the world adopted (Yu Jianmin. the precious metal extraction chemistry. Beijing: Chemical Industry Press, 2005.).For example, the Acton refinery of International nickel Co. Ltd. Inco. Ltd. (INCO) uses di-n-octyl thioether DOS collection palladium earlier, and tributyl phosphate TBP collection platinum extracts rhodium with chemical precipitation method at last from raffinate then.The Mathey-Rusterburg refinery of Britain Royston with tri-n-octyl amine TOA collection platinum, extracts rhodium with ion exchange method then at last with the hydroxyoxime palladium that comes together from raffinate.China Jinchuan Nonferrous Metal Co. then earlier with isoamyl sulfide S201 collection palladium, then with trialkyl tertiary amine N 235 collection platinum, reclaims rhodium with the chemical method precipitation at last from the residual mother liquor that comes together.
Because platinum, palladium, rhodium physico-chemical property are very similar, and valence state is changeable, there is complex shape in species, how to improve its separation selectivity and be always the difficult problem in platinum, palladium, the rhodium lyometallurgy.When traditional organic phase/water two-phase solvent extraction and separation technology is handled the complicated feed liquid of a plurality of metal ions coexistence, general from selecting suitable selective extractant, determine optimum process condition, utilize the difference of each metal ion reactive behavior, with selectivity identification coordination between different extractant molecules, formulate suitable extraction procedure by the difficulty or ease order of its extraction.A plurality of metal target ionic selective extractions are separated, need to extract one by one with substep through the liquid-liquid biphase equilibrium of a plurality of steps.Optionally factor is very complicated but owing to influence extracting and separating in the actual procedure, the difference of metal coordination ion self character such as platinum, palladium, rhodium and the complicacy of coordination behavior in addition, the selectivity of tradition liquid-liquid two-phase solvent extracting and separating platinum, palladium, rhodium is not high, and the operation of the extraction equilibrium of multistep is because flow process is tediously long, separating step is many, easily causes platinum, palladium, the rhodium spread loss in extraction process.For improving the yield and the product purity of solvent extraction and separation platinum, palladium, rhodium, people have to by rule of thumb feed liquid be carried out various pre-treatment repeatedly to adjust its character, carry out biphase equilibrium then repeatedly to improve its extracting and separating selectivity.The consequence of doing like this is that artificial blindness is big, and the extractive reaction course is restive.Disclosed from platiniferous palladium deactivated rhodium automobile catalyst leach liquor the technology of extracting and separating platinum, palladium, rhodium must be before extraction reduce feed acidity earlier, with thioether kind of extractants elder generation selectivity collection palladium, feed acidity must be heightened again afterwards, be beneficial to tributyl phosphate TBP selective extraction separating platinum, from extract back liquid, extract rhodium at last with chemical precipitation method.Trivial operations, the human factor influence is big, restive, and the character that each section inter process is connected feed liquid requires high.
Liquid-liquid-liquid three phase extraction technology is based on micro emulsion phase abstraction technique and a kind of new and effective extraction separating method that grows up (Liu Huizhou etc., micro emulsion phase abstraction technique and application. Beijing: Science Press, 2005).Its principle is to utilize extractor body to be tied to form the difference of phase behavior, obtain the different coexistence macroscopic view liquid phase of three immiscible character and phase structure, utilize the otherness of different quilt collection species on physico-chemical property, realize that the different species that come together have different distribution behaviors in three different liquid phases.Because three phase extraction system separation selectivity height, can be implemented in that the step extraction three-phase to plurality of target composition in the COMPLEX MIXED system separates and purifying simultaneously in the single extraction process.Compare with traditional two-phase extraction, not only simplified original technical process greatly, and can improve the yield and the purity of target compound.Therefore, three phase extraction is as a kind of efficient new separation technology succinct, that have target selection, and is more and more in the research of biological, medicine, chemical field in recent years.Separation purification (Chinese invention patent ZL 00107655.8 " triphase one-step extraction process to purify penicillin ") as biological fermentation system penicillin, extract Potenlini and Liquiritin in the natural product Potenlini extracting solution, processing contains the trade effluent of multiple phenols etc., but disclosed three phase extraction system many be target to separate the polycomponent organic compound.
Comparatively speaking, it is considerably less that three phase extraction is used to handle the research report of multiple metal ion coexistence omplicated solution.Mojski M. etc. has reported and has used the acetonitrile solution (being called the acetonitrile phase) that contains pyridine or sulfonamide derivatives and contain monocarboxylic hexane solution (being called hexane mutually) and be extraction agent, can be from the aqueous solution of sodium-chlor, Repone K or ammonium sulfate one step extracting and separating chromium metal-copper-iron, or vanadium-copper-iron, or vanadium-nickel-cobalt (Journal of Analytical Chemistry, 1996,51 (4): 359-373).The kerosin of di-(2-ethylhexyl)phosphoric acid P204 and three-phase system one step extracting zinc and manganese from the old and useless battery leach liquor of polyoxyethylene glycol PEG 10000 double water-phase solution compositions such as Liu Huizhou, or zinc and copper, and realize zinc and manganese simultaneously, or zinc and copper separate (process engineering journal .2009,9 (4): 683-688) in the P204 organic phase in three-phase system and the PEG polymkeric substance water respectively.But disclosed at present document is at cationic three phase extraction separation systems of base metal such as cupric, nickel, cobalt, iron, zinc, and the medium solution acidity that is suitable for can not be too high, generally only is suitable in the pH scope.Since in the platiniferous palladium deactivated rhodium automobile catalyst leach liquor platinum, palladium, rhodium ion generally with chlorine complex anion form stable existence in high acidity (as, concentration of hydrochloric acid is higher than 1mol/L) in the media environment, present disclosed three phase extraction system is all inapplicable.
Summary of the invention
The object of the invention is to provide a kind of method that one step of three phase extraction is separated platinum, palladium, rhodium from the noble metal catalyst leach liquor.The precipitator method or substitution method with routine are removed the impurity base-metal ion (mainly being iron, silicon, aluminium, copper, nickel, tin, lead etc.) that coexists in the noble metal catalyst leach liquor in advance, and the solution that obtains containing platinum, palladium, rhodium is used for the present invention.
The present invention includes step has:
(1) selects the two kinds of extraction agents that can distinguish selective extraction platinum and palladium, be dissolved in respectively in the big and immiscible organic solvent of two kinds of polarity differences; The weight of platinum and palladium extraction agent accounts for the 10%-50% of organic weight of solvent separately respectively;
(2) a kind of hydrochloride, vitriol, nitrate or phosphoric acid salt that contains sodium, potassium, lithium or ammonium is joined in the aqueous solution that contains platinum, palladium, rhodium, this aqueous solution is for containing the free salt aqueous acid, or for containing the free sulphur aqueous acid, free acid concentration is 1mol/L-3mol/L; The weight of the salt that adds is the 10%-50% that contains platinum, palladium, rhodium aqueous solution weight;
(3) aqueous solution with (1) two kind of organic solvent of step and step (2) is first kind of organic solvent by volume: second kind of organic solvent: the aqueous solution=0.5-2: 0.5-2: 1, stirring at room temperature or vibration mixed phase 5 to 10 minutes, leave standstill then or centrifugal phase-splitting, obtain phase interface three not miscible coexistence liquid phases clearly.Wherein, platinum and palladium be concentration and separation in two immiscible organic phases respectively, and rhodium is enriched in lower floor's extraction back aqueous phase;
(4) resulting three the coexistence liquid phases of separating step (3) send follow-up back extraction operation to reclaim wherein platinum, palladium, rhodium respectively.
The extraction agent of the energy selective extraction platinum described in the step (1) is commercially available trialkyl tertiary amine N 235 or tri-n-octyl amine TOA; Perhaps be Tributyl phosphate ester TBP or commercially available trialkyl phosphine TRPO, the extraction agent of described energy selective extraction palladium is isoamyl sulfide S201 or di-n-octyl thioether DOS, described two kinds of immiscible organic solvents are that a non-polar organic solvent and a polar organic solvent are formed, wherein said non-polar organic solvent is alkane or the mixture that contains 6-12 carbon atom, perhaps is low polar organic solvent benzene, toluene, chloroform; Described polar organic solvent is acetonitrile, acetone, ethanol, Virahol, Nitromethane 99Min., oil of mirbane Huo diox.
The hydrochloride that contains sodium, potassium, lithium or ammonium, vitriol, nitrate or phosphoric acid salt described in the step (2) is ammonium sulfate, sodium sulfate, vitriolate of tartar, Lithium Sulphate, sodium-chlor, ammonium chloride, Repone K, lithium chloride, SODIUMNITRATE, saltpetre, ammonium nitrate, lithium nitrate or potassiumphosphate.
Further the palladium extraction agent in the preferred steps (1) is isoamyl sulfide S201, and the platinum extraction agent is commercially available trialkyl tertiary amine N 235, and non-polar organic solvent is hexane or nonane, and polar organic solvent is acetonitrile or Nitromethane 99Min..Further the salt that adds in the preferred steps (2) is ammonium sulfate, sodium sulfate or sodium-chlor.
The present invention can also realize with following step:
(1) a kind of high molecular polymer and a kind of hydrochloride, vitriol, nitrate or phosphoric acid salt that contains sodium, potassium, lithium or ammonium are joined in the aqueous solution that contains platinum, palladium, rhodium in proportion, this solution is for containing the free salt aqueous acid, or for containing the free sulphur aqueous acid, free acid concentration is 1mol/L-3mol/L, high molecular polymer, salt and the weight part ratio that contains platinum, palladium, rhodium solution are: in per 100 weight parts, high molecular polymer accounts for the 8-20 weight part, salt accounts for the 10-50 weight part, and all the other are the solution that contains platinum, palladium, rhodium;
(2) mixture of step (1) is at room temperature stirred or vibrated 5 to 10 minutes, leave standstill then or centrifugal phase-splitting, obtain a double-aqueous phase system of forming by two not miscible coexistence liquid phases;
(3) select a kind of palladium-selective extraction agent, be dissolved in the non-polar organic solvent, palladium extraction agent weight is the 10%-80% of non-polar organic solvent weight;
(4) double-aqueous phase system of step (2) and step organic solution are 3. at room temperature stirred or the mixed phase 5 to 10 minutes of vibrating, leave standstill then or centrifugal phase-splitting, obtain phase interface three not miscible coexistence liquid phases clearly, wherein, palladium and platinum is the high molecular polymer aqueous phase concentration and separation in organic phase, double-aqueous phase system respectively, and rhodium is enriched in lower floor's extraction back aqueous phase;
(5) resulting three the coexistence liquid phases of separating step (4) send follow-up back extraction operation to reclaim wherein platinum, palladium, rhodium respectively.
High molecular polymer described in the step (1) is a kind of of following high molecular polymer, polyoxyethylene glycol PEG, polypropylene glycol, methoxy poly (ethylene glycol), the methoxyl group polypropylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol-propylene glycol segmented copolymer, polypropylene glycol-polyoxyethylene glycol-mono, polyox-yethylene-polyoxypropylene block copolymer, PEP-101 EOPO, methylcellulose gum, Type 3U, hydroxypropyl dextran or ficoll, the described sodium that contains, potassium, the hydrochloride of lithium or ammonium, vitriol, nitrate or phosphoric acid salt are ammonium sulfate, sodium sulfate, vitriolate of tartar, Lithium Sulphate, sodium-chlor, ammonium chloride, Repone K, lithium chloride, SODIUMNITRATE, saltpetre, ammonium nitrate, lithium nitrate or potassiumphosphate.
Palladium-selective extraction agent described in the step (3) is isoamyl sulfide S201 or di-n-octyl thioether DOS, and described non-polar organic solvent is alkane or its mixture that contains 6-12 carbon atom.
Further high molecular polymer is polyoxyethylene glycol PEG or PEP-101 EOPO in the preferred steps (1).The salt that adds is ammonium sulfate, sodium sulfate, potassiumphosphate or its mixing salt in twos.Palladium-selective extraction agent described in the preferred steps (3) is isoamyl sulfide S201.Non-polar organic solvent is hexane or nonane.
The method that three phase extraction one step is separated platinum, palladium, rhodium from the inefficacy automobile catalyst leach liquor that contains platinum, palladium, rhodium provided by the invention can realize that platinum, palladium, rhodium distinguish enrichment and separate in three not miscible coexistence liquid phases (upper, middle and lower three-phase).Compare traditional liquid-liquid two-phase extraction method, the three phase extraction system can in the single extraction process, finish simultaneously platinum and palladium come together respectively the different coexistence organic phase of two polarity or respectively collection go into high molecular polymer water in organic phase and the double-aqueous phase system, and rhodium is strong because of hydration, stay lower floor's residual aqueous phase that comes together and be not extracted, separate with the platinum palladium.Therefore, the three phase extraction method can be implemented in while three phase separation platinum, palladium, rhodium in the step extraction process, and its separation selectivity height can effectively be simplified existing lengthy and tedious platinum, palladium, rhodium liquid-liquid two-phase extraction separation processes flow process.
Embodiment
Embodiment 1
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free hydrochloric acid concentration is 1mol/L, add ammonium sulfate by its weight percentage 30%, after the stirring and dissolving, by acetonitrile: platinum, palladium, rhodium mixed liquor volume ratio is 1: 1 adding acetonitrile.Then, the hexane solution that adds the isoamyl sulfide S201 identical again with preceding two phase liquid volume.Isoamyl sulfide S201 weight accounts for 50% of hexane solution weight.The said mixture system at room temperature stirred mixed phase 10 minutes, left standstill phase-splitting then, obtained three not miscible coexistence liquid phases (hexane phase-acetonitrile phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of hexane that contains isoamyl sulfide S201 accounts for 90.2 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, acetonitrile mutually in platinum weight account for 72.1 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 96.2 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.Three phase extraction can one the step realize platinum, palladium, rhodium respectively hexane phase, acetonitrile mutually and the enrichment of aqueous phase with separate.
Embodiment 2
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free hydrochloric acid concentration is 2mol/L, add sodium-chlor by its weight percentage 40%.After the stirring and dissolving, the Nitromethane 99Min. solution of 1: 1 by volume adding tributyl phosphate TBP.Tributyl phosphate TBP accounts for 20% of Nitromethane 99Min. solution weight.Then, the nonane solution that adds the isoamyl sulfide S201 identical again with preceding two phase liquid volume.Isoamyl sulfide S201 weight accounts for 30% of nonane solution weight.At room temperature vibrate mixed phase 5 minutes of said mixture system leaves standstill phase-splitting then, obtains three not miscible coexistence liquid phases (nonane phase-Nitromethane 99Min. phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of nonane that contains isoamyl sulfide S201 accounts for 92.4 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, the Nitromethane 99Min. of phosphoric acid tri-n-butyl TBP mutually in platinum weight account for 78.5 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 98.5 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.
Embodiment 3
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free sulfuric acid concentration is 1mol/L, add sodium sulfate by its weight percentage 40%.After the stirring and dissolving, the Nitromethane 99Min. solution of 1: 1 by volume adding trialkyl tertiary amine N 235.Trialkyl tertiary amine N 235 weight account for 30% of Nitromethane 99Min. solution weight.Then, the hexane solution that adds the isoamyl sulfide S201 identical again with preceding two phase liquid volume.Isoamyl sulfide S201 weight accounts for 50% of hexane solution weight.At room temperature vibrate mixed phase 10 minutes of said mixture system, centrifugal then phase-splitting obtains three not miscible coexistence liquid phases (hexane phase-Nitromethane 99Min. phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of hexane that contains isoamyl sulfide S201 accounts for 94.5 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, the Nitromethane 99Min. that contains trialkyl tertiary amine N 235 mutually in platinum weight account for 82.1 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 98.0 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.
Embodiment 4
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free hydrochloric acid concentration is 1mol/L, add ammonium sulfate by its weight percentage 30%.After the stirring and dissolving, the aqueous solution of 1: 1 by volume adding polyoxyethylene glycol PEG.Polyoxyethylene glycol PEG weight accounts for 10% of platinum, palladium, rhodium mixing solutions weight.Said mixture was at room temperature stirred 10 minutes, leave standstill phase-splitting then, obtain two not miscible coexistence liquid phases (double-aqueous phase system: PEG phase and water).Then, the hexane solution that adds the isoamyl sulfide S201 identical with preceding two aqueous phase solution volumes.Isoamyl sulfide S201 weight accounts for 50 weight % of hexane solution weight.The hexane solution of aforementioned double-aqueous phase system and isoamyl sulfide S201 is at room temperature stirred mixed phase 10 minutes, leave standstill phase-splitting then, obtain three not miscible coexistence liquid phases (hexane phase-PEG phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of hexane that contains isoamyl sulfide S201 accounts for 96.2 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, poly-second two PEG mutually in platinum weight account for 90.5 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 78.0 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.Three phase extraction can one the step realize platinum, palladium, rhodium respectively hexane phase, PEG mutually and the enrichment of aqueous phase with separate.
Embodiment 5
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free hydrochloric acid concentration is 2mol/L, add sodium sulfate by its weight percentage 40%.After the stirring and dissolving, the aqueous solution of 1: 1 by volume adding PEP-101 EOPO.PEP-101 EOPO weight accounts for 20 weight % of platinum, palladium, rhodium mixing solutions weight.Said mixture was at room temperature vibrated 5 minutes, and centrifugal then phase-splitting obtains two not miscible coexistence liquid phases (double-aqueous phase system: EOPO phase and water).Then, the nonane solution that adds the isoamyl sulfide S201 identical with preceding two aqueous phase solution volumes.Isoamyl sulfide S201 weight accounts for 80 weight % of nonane solution weight.With at room temperature vibrate mixed phase 10 minutes of the nonane solution of aforementioned double-aqueous phase system and S201, centrifugal then phase-splitting obtains three not miscible coexistence liquid phases (nonane phase-EOPO phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of nonane that contains isoamyl sulfide S201 accounts for 93.5 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, EOPO mutually in platinum weight account for 91.2 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 76.2 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.
Embodiment 6
Get 10mL and contain the platinum, palladium, rhodium mixing solutions that free hydrochloric acid concentration is 1mol/L, add the mixing solutions of sodium sulfate and potassiumphosphate by its weight percentage 40%.The weight ratio of sodium sulfate and sodium phosphate is 6: 1.After the stirring and dissolving, the aqueous solution of 1: 1 by volume adding polyoxyethylene glycol PEG.Polyoxyethylene glycol PEG weight accounts for 20% of platinum, palladium, rhodium mixing solutions weight.Said mixture was at room temperature vibrated 10 minutes, leave standstill phase-splitting then, obtain two not miscible coexistence liquid phases (double-aqueous phase system: PEG phase and water).Then, the nonane solution that adds the isoamyl sulfide S201 identical with preceding two aqueous phase solution volumes.Isoamyl sulfide S201 weight accounts for 70 weight % of nonane solution weight.With at room temperature vibrate mixed phase 10 minutes of the nonane solution of aforementioned double-aqueous phase system and S201, leave standstill phase-splitting then, obtain three not miscible coexistence liquid phases (nonane phase-PEG phase-water).Analyze three platinum, palladium, rhodium content in the liquid phase respectively as can be known, the middle mutually palladium weight of nonane that contains isoamyl sulfide S201 accounts for 95.0 weight % of palladium gross weight in the former platinum, palladium, rhodium aqueous solution, polyoxyethylene glycol PEG mutually in platinum weight account for 83.3 weight % of platinum gross weight in the former platinum, palladium, rhodium aqueous solution, and the rhodium of 89.0 weight % is stayed lower floor's residual aqueous phase that comes together in the former platinum, palladium, rhodium aqueous solution.
Claims (6)
1. method that three phase extraction one step is separated platinum, palladium, rhodium from the noble metal catalyst leach liquor is characterized in that step is as follows:
(1) selects the two kinds of extraction agents that can distinguish selective extraction platinum and palladium, be dissolved in respectively in the big and immiscible organic solvent of two kinds of polarity differences; The weight of platinum and palladium extraction agent accounts for the 10%-50% of organic weight of solvent separately respectively;
(2) a kind of hydrochloride, vitriol, nitrate or phosphoric acid salt that contains sodium, potassium, lithium or ammonium is joined in the aqueous solution that contains platinum, palladium, rhodium, this aqueous solution is for containing the free salt aqueous acid, or for containing the free sulphur aqueous acid, free acid concentration is 1mol/L-3mol/L; The weight of the salt that adds is the 10%-50% that contains platinum, palladium, rhodium aqueous solution weight;
(3) aqueous solution with (1) two kind of organic solvent of step and step (2) is first kind of organic solvent by volume: second kind of organic solvent: the aqueous solution=0.5-2: 0.5-2: 1, stirring at room temperature or vibration mixed phase 5 to 10 minutes, leave standstill then or centrifugal phase-splitting, obtain phase interface three not miscible coexistence liquid phases clearly.Wherein, platinum and palladium be concentration and separation in two immiscible organic phases respectively, and rhodium is enriched in lower floor's extraction back aqueous phase;
(4) resulting three the coexistence liquid phases of separating step (3) send follow-up back extraction operation to reclaim wherein platinum, palladium, rhodium respectively.
2. method according to claim 1 is characterized in that, the extraction agent of the energy selective extraction platinum described in the step (1) is trialkyl tertiary amine N 235 or tri-n-octyl amine TOA; Perhaps be Tributyl phosphate ester TBP or trialkyl phosphine TRPO, the extraction agent of described energy selective extraction palladium is isoamyl sulfide S201 or di-n-octyl thioether DOS, described two kinds of immiscible organic solvents are that a non-polar organic solvent and a polar organic solvent are formed, described non-polar organic solvent is alkane or the mixture that contains 6-12 carbon atom, perhaps is low polar organic solvent benzene, toluene, chloroform; Described polar organic solvent is acetonitrile, acetone, ethanol, Virahol, Nitromethane 99Min., oil of mirbane Huo diox.
3. method according to claim 1, it is characterized in that the hydrochloride that contains sodium, potassium, lithium or ammonium, vitriol, nitrate or the phosphoric acid salt described in the step (2) is ammonium sulfate, sodium sulfate, vitriolate of tartar, Lithium Sulphate, sodium-chlor, ammonium chloride, Repone K, lithium chloride, SODIUMNITRATE, saltpetre, ammonium nitrate, lithium nitrate or potassiumphosphate.
4. method that three phase extraction one step is separated platinum, palladium, rhodium from the noble metal catalyst leach liquor is characterized in that step is as follows:
(1) a kind of high molecular polymer and a kind of hydrochloride, vitriol, nitrate or phosphoric acid salt that contains sodium, potassium, lithium or ammonium are joined in the aqueous solution that contains platinum, palladium, rhodium in proportion, this solution is for containing the free salt aqueous acid, or for containing the free sulphur aqueous acid, free acid concentration is 1mol/L-3mol/L, high molecular polymer, salt and the weight part ratio that contains platinum, palladium, rhodium solution are: in per 100 weight parts, high molecular polymer accounts for the 8-20 weight part, salt accounts for the 10-50 weight part, and all the other are the solution that contains platinum, palladium, rhodium;
(2) mixture of step (1) is at room temperature stirred or vibrated 5 to 10 minutes, leave standstill then or centrifugal phase-splitting, obtain a double-aqueous phase system of forming by two not miscible coexistence liquid phases;
(3) select a kind of palladium-selective extraction agent, be dissolved in the non-polar organic solvent, palladium extraction agent weight is the 10%-80% of non-polar organic solvent weight;
(4) double-aqueous phase system of step (2) and step organic solution are 3. at room temperature stirred or the mixed phase 5 to 10 minutes of vibrating, leave standstill then or centrifugal phase-splitting, obtain three not miscible coexistence liquid phases, wherein, palladium and platinum is the high molecular polymer aqueous phase concentration and separation in organic phase, double-aqueous phase system respectively, and rhodium is enriched in lower floor's extraction back aqueous phase;
(5) resulting three the coexistence liquid phases of separating step (4) send follow-up back extraction operation to reclaim wherein platinum, palladium, rhodium respectively.
5. method according to claim 4, it is characterized in that, high molecular polymer described in the step (1) is a kind of of following high molecular polymer, polyoxyethylene glycol PEG, polypropylene glycol, methoxy poly (ethylene glycol), the methoxyl group polypropylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol-propylene glycol segmented copolymer, polypropylene glycol-polyoxyethylene glycol-mono, polyox-yethylene-polyoxypropylene block copolymer, PEP-101 EOPO, methylcellulose gum, Type 3U, hydroxypropyl dextran or ficoll, the described sodium that contains, potassium, the hydrochloride of lithium or ammonium, vitriol, nitrate or phosphoric acid salt are ammonium sulfate, sodium sulfate, vitriolate of tartar, Lithium Sulphate, sodium-chlor, ammonium chloride, Repone K, lithium chloride, SODIUMNITRATE, saltpetre, ammonium nitrate, lithium nitrate or potassiumphosphate.
6. method according to claim 4 is characterized in that, the palladium-selective extraction agent described in the step (3) is isoamyl sulfide S201 or di-n-octyl thioether DOS, and described non-polar organic solvent is alkane or its mixture that contains 6-12 carbon atom.
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