CN102329959B - Separation method of palladium from silver electrolyte - Google Patents

Separation method of palladium from silver electrolyte Download PDF

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Publication number
CN102329959B
CN102329959B CN2011102602702A CN201110260270A CN102329959B CN 102329959 B CN102329959 B CN 102329959B CN 2011102602702 A CN2011102602702 A CN 2011102602702A CN 201110260270 A CN201110260270 A CN 201110260270A CN 102329959 B CN102329959 B CN 102329959B
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resin
silver
palladium
solution
desorb
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CN102329959A (en
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吴江华
杨天足
刘伟锋
谢祥林
张杜超
李俊
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Central South University
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Central South University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention relates to a wet metallurgic method for effectively separating palladium from silver electrolyte by adopting modified polyacrylonitrile resin, and the process is free from pollution. The method adopts a technical scheme that: polyacrylonitrile resin is modified by adopting a hydroxyl amine hydrochloride solution to obtain a novel chelating resin namely amidoxime polyacrylonitrile resin; silver electrolyte which is roughly purified to remove heavy metal impurities is adsorbed by adopting the amidoxime polyacrylonitrile resin, so that palladium in the solution is loaded onto the resin, and the resin is subjected to primary desorption by adopting an acidic thiourea solution to obtain a palladium-containing desorption liquid; the resin is subjected to secondary desorption by adopting a high-concentration hydrochloric acid solution to obtain a silver-containing desorption liquid; and the resin which is subjected to twice desorption is regenerated by adopting a hydroxyl amine hydrochloride solution, and is returned to adsorb the palladium-containing silver electrolyte. According to the method, palladium and silver can be effectively separated, the adsorbed solution can be directly returned to silver electrolysis, the operation is simple, the purification time is short, the recovery rate of noble metals is high, and the practicality is strong.

Description

A kind of from silver electrolyte the method for separate palladium
Technical field
The precious metal that the present invention relates in the hydrometallurgy field separates, especially effectively the method for separate palladium from silver electrolyte.
Background technology
Electrolytic refining process is mainly adopted in the refining of silver, and its electrolytic solution is silver nitrate solution.Along with the carrying out of electrorefining, the heavy metal in the silver anode plate can constantly dissolve, and causes Cu 2+, Pb 2+, Bi 3+, Sb 3+Plasma accumulates in silver electrolyte; Precious metal (like platinum, palladium) beyond the desilver in the silver anode plate also can be partly dissolved entering electrolytic solution in electrolytic process on the other hand, makes Pd 2+, Pt 2+Constantly accumulation in electrolytic solution, Pd in silver electrolyte 2+, Pt 2+Can separate out at negative electrode with silver when reaching finite concentration, cause electric silver amount to descend.Therefore, the electrolytic solution of electrorefining of silver except will removing the beavy metal impurity ion in the electrolytic solution, is also wanted outer precious metal impurity, the especially palladium of desilver in the free electrolyte.
At present, both at home and abroad from silver electrolyte the main method of separate palladium have four kinds:
Thermal decomposition method according to the difference of various metal nitrate heat decomposition temperatures, adopts the spissated method of direct heating, and the control decomposition temperature is 250-300 ℃, makes the nitrate salt of metal such as copper palladium be decomposed to form oxide compound, and Silver Nitrate then concentrates becomes crystallization.The thermolysis slag that is dissolved in water after decompose finishing makes the Silver Nitrate dissolving get into solution, finally obtains the slag of enriching noble metals palladium.But, can produce a large amount of oxides of nitrogen gas in the thermal decomposition process, be prone to environment is polluted, and also the wasteful water gaging of thermal decomposition method and the energy, long processing period.
The precipitator method progressively, a kind of is in silver electrolyte, to add saturated NaOH solution at normal temperatures, control pH value of solution=3-5 makes most of heavy metal ion precipitate and Ag with the form of oxyhydroxide +Separate, in filtrating, add HCl again and make Ag +Deposition leaches behind the AgCl with NaOH solution regulator solution pH value again and palladium is precipitated fully to 7-8; Another kind is in solution, to add earlier HCl to make Ag +With AgCl form deposition and separation, simultaneously excessive HCl and the HNO in the solution 3Form the chloroazotic acid system with Pd 2+Be oxidized to Pd 4+, add NH again 4Cl makes palladium be converted into the ammonium palladic chloride deposition.Progressively the precipitator method need add a lot of reagent, and valuable metal is progressively separated, and process is loaded down with trivial details, and cost is higher; And the ammonium palladic chloride precipitator method are only applicable to Pd 2+The solution that content is higher causes the direct yield of palladium not high.
The xanthate precipitator method generate the difference of sedimentary solubility product constant according to xanthate and precious metal ion, in Silver Nitrate electrolytic solution, are adding an amount of butyl xanthate under 80-85 ℃, and violent stirring precipitates palladium in the scope of pH=0.5-1.These precipitator method are simple to operate, and processing costs is low, but xanthate is only stable in the solution of pH=6.5-7.5; Acidity raises and then is decomposed into dithiocarbonic anhydride and alcohol; Cause in the silver electrolyte behind the heavy palladium and contain a large amount of organic impuritys, can not directly return silver-colored electrolysis, subsequent processes is loaded down with trivial details.
Active carbon adsorption, the gac after nitric acid oxidation is handled can selectivity preferentially adsorbed palladiums, and during activated carbon column after the silver nitrate solution that contains palladium flows through processing, about 98% palladium and about 15% silver can be adsorbed on the gac.To load type active carbon, adopt the industrial nitric acid of 1:1 to carry out desorb with reflux type, palladium, silver-colored desorption efficiency can both reach more than 90%, and the Ag-containing solution after the absorption can directly return silver-colored electrowinning process, and is easy to operate.But gac is low to the saturated adsorption capacity of palladium, is merely 23mgg -1, the gac demand is big in the adsorption process; The silver palladium is adsorption-desorption simultaneously, and the thoroughly separation of being unrealized; And adsorb used gac and need carry out oxide treatment with high density nitric acid, desorb also will be adopted the higher salpeter solution of concentration, and the liberating nitrogen oxide gas causes environmental pollution easily.In addition, adopt the gac fractionation by adsorption palladium metal from silver electrolyte after the thiocarbamide activation treatment in addition, its saturated adsorption capacity can reach 50-70 mgg -1, but make thiocarbamide get into silver electrolyte in the adsorption process easily, make that the electrolytic solution after the absorption palladium can not directly return silver-colored electrolysis.
Aforesaid method all can to a certain degree be isolated the platinum metals palladium from silver electrolyte, but sepn process is thorough inadequately, and the Ag-containing solution of after separating can not directly return silver-colored electrowinning process, makes that the subsequent disposal operation is loaded down with trivial details.
Summary of the invention
Summary of the invention
The present invention provides a kind of employing modified polyacrylonitrile resin separate palladium from silver electrolyte effectively, and the free of contamination Wet-process metallurgy method of process.The technical scheme that adopts is: adopt oxammonium hydrochloride solution that polyacrylonitrile resin is carried out modification and handle; Obtain novel chelate resin-amidoxim polyacrylonitrile resin; Adopt the amidoxim polyacrylonitrile resin that the silver electrolyte that rough purification removes beavy metal impurity is adsorbed; Palladium in the solution is loaded on the resin, adopt the sour sulfur urea solution to carry out a desorb afterwards and obtain containing the palladium stripping liquid, adopt the high salt concentration acid solution to carry out the secondary desorb again and obtain the argentiferous stripping liquid; Resin after twice desorb adopts oxammonium hydrochloride solution to carry out after the manipulation of regeneration again, returns resin absorption and contains palladium-silver electrolytic solution.
Concrete technological process and technical parameter are following:
1 resin modified:
It is 100-200gL that polyacrylonitrile resin is adopted behind the soaked in absolute ethyl alcohol 12-24h with concentration at normal temperatures -1, pH=6-8 oxammonium hydrochloride solution uniform mixing, the liquid-solid ratio (ml/g) of control oxammonium hydrochloride solution and polyacrylonitrile dried resin is 60-100:1, modification processing 5-10h obtains the amidoxim polyacrylonitrile resin under 60-100 ℃ temperature.
2 resin absorption:
Employing is handled resulting amidoxim polyacrylonitrile resin to containing Pd through modification 2+Silver electrolyte adsorb.Regulate the pH=0-0.5 of silver electrolyte, the liquid-solid ratio (ml/g) of control solution and amidoxim polyacrylonitrile resin is 100-200:1, and adsorption temp is 30-80 ℃, and adsorption time is 30-180min, and liquid can directly return silver-colored electrowinning process after the resulting absorption.
A desorb of 3 loaded resins:
Use 5-40 gL -1Thiocarbamide, 0.1-3 molL -1HNO 3Mixing solutions amidoxim polyacrylonitrile resin to supported palladium under 20-50 ℃ carries out desorb, and the liquid-solid ratio (ml/g) of controlling strippant and loaded resin is 100-500:1, and desorption time is 30-180min.
The secondary desorb of 4 loaded resins:
Use 5-12 molL -1HCl solution carries out the secondary desorb to loaded resin under 20-50 ℃, the liquid-solid ratio of secondary strippant and loaded resin (ml/g) is 100-500:1, and desorption time is 30-180min.
Regeneration of resin after 5 desorbs:
Resin after twice desorb adopts absolute ethyl alcohol after soaking 12-24 h under the room temperature, to use 100-200gL after washing is neutrality again -1Oxammonium hydrochloride solution in 60-100 ℃ of following activation treatment 5-10h, control liquid-solid ratio (ml/g) be 60-100:1, the resin after the activation can return the resin absorption process once more.
Oxammonium hydrochloride described in the present invention, thiocarbamide, nitric acid and hydrochloric acid are AR, and absolute ethyl alcohol is a technical grade reagent, and used resin is that degree of crosslinking is the commercially available polyacrylonitrile resin of 5-20%.
The present invention is suitable for handling the silver electrolyte that need purify, and its concentration range is (gL -1): Ag 30-100, Pd 0.10-2.00, Cu 0.50-5.00, pH value of solution=0-0.5.
The present invention with existing from silver electrolyte the method for separate palladium compare, following advantage is arranged:
Adopt the method for resin modified processings-resin absorption-substep desorb-resin regeneration, can realize separating of palladium and silver effectively, absorption back liquid can directly return silver-colored electrolysis, and is simple to operate, and clarification time weak point, and precious metal recovery height are practical; There is not the thermolysis of nitrate salt in the process, reduced the pollution problem of oxynitride in the traditional technology; Resin can activating and regenerating behind adsorption-desorption, continues to return adsorption operations, and cyclic utilization rate is high, non-wastewater discharge; Technology is low for equipment requirements, operational safety, and labour intensity is low, good operational environment.
Description of drawings
Fig. 1: process flow diagram of the present invention.
Embodiment
Embodiment
Commercially available polyacrylonitrile resin, degree of crosslinking are 10%; Technical grade absolute ethyl alcohol, wherein CH 3CH 2OH content is 99.7%; Analytical pure oxammonium hydrochloride, wherein HONH 2HCl content is 98.5%; Analytical pure soda ash light, wherein Na 2CO 3Content is 99.8%; Analytical pure thiocarbamide, wherein CS (NH 2) 2Content is 99.0%; Analytical pure nitric acid, wherein HNO 3Content is 65-68%; Analytical pure hydrochloric acid, wherein HCl content is 36-38%; Silver nitrate solution, wherein Pd 500mgL -1, Ag 80gL -1, Cu 4gL -1, pH=0.05.
The 10g polyacrylonitrile resin is with adding 100ml soaked in absolute ethyl alcohol 24h after the water-wet; Preparation 900ml 175 gL -1Oxammonium hydrochloride solution; Regulate pH=7 with yellow soda ash, add resin alcohol mixeding liquid (alcohol immersion liquid adds in the lump) again, after 8h is handled in 80 ℃ of following modifications, take out and clean; Obtain the flaxen amidoxim polyacrylonitrile resin of 15.5286g, corresponding itrile group transformation efficiency is up to 88.79%.
Get 25ml silver nitrate solution and 0.20g amidoxim polyacrylonitrile resin thorough mixing, separate behind the vibration absorption 120min down in 55 ℃, each ionic concn is respectively (gL in the liquid of gained absorption back -1): Pd 0.092, Ag 73.78, Cu 3.65, the adsorption rate of corresponding Pd, Ag, Cu is respectively: 81.55%, 7.76%, 8.73%.
Amidoxim polyacrylonitrile resin to supported palladium adds 50ml 20gL -1Thiocarbamide, 1.5molL -1HNO 3The mixing solutions desorb of under 35 ℃, vibrating separates behind the 120min and gets stripping liquid one time, and wherein various ionic concns are respectively (mgL -1): Pd 192.96, Ag 304.49, Cu 11.07, the desorption efficiency of then corresponding Pd, Ag, Cu is respectively: 94.64%, 9.79%, 6.34%.
Carry out the resin after the desorb one time, add 50ml 8molL -1HCl solution obtains the secondary stripping liquid at 30 ℃ of silver and copper that following desorb is remaining behind the 180min, wherein various ionic concns are respectively (mgL -1): Ag 2527.91, Cu 156.16, the desorption efficiency of then corresponding Ag, Cu is respectively: 90.11%, 95.49%.
Resin after the secondary desorb adopts 10ml soaked in absolute ethyl alcohol 12-24h through washing to be to wash water after neutral again, adopts 40ml 200gL again -1Oxammonium hydrochloride solution in 80 ℃ of following activation treatment 6h, obtain the amidoxim polyacrylonitrile dried resin after the 0.1748g regeneration.
0.1784g regenerating resin once more with 20ml silver nitrate solution uniform mixing after, separate behind the vibration absorption 120min down in 55 ℃ and to get absorption back liquid, wherein each ionic concn is respectively (gL -1): Pd 0.065, Ag 73.36, Cu 3.64, then activated resin is respectively the adsorption rate of Pd, Ag, Cu: 87.01%, 8.30%, 9.01%.

Claims (1)

1. the method for a separate palladium from silver electrolyte is characterized in that may further comprise the steps:
The A resin modified:
It is 100-200gL that polyacrylonitrile resin is adopted behind the soaked in absolute ethyl alcohol 12-24h with concentration at normal temperatures -1, pH=6-8 oxammonium hydrochloride solution uniform mixing, the volume milliliter of control oxammonium hydrochloride solution and polyacrylonitrile dried resin is 60-100:1 with the liquid-solid ratio that quality restrains, modification processing 5-10h obtains the amidoxim polyacrylonitrile resin under 60-100 ℃ temperature;
The B resin absorption:
Employing is handled resulting amidoxim polyacrylonitrile resin to containing Pd through modification 2+Silver electrolyte adsorb; Regulate the pH=0-0.5 of silver electrolyte; The liquid-solid ratio of control solution and amidoxim polyacrylonitrile resin volume milliliter and quality gram is 100-200:1; Adsorption temp is 30-80 ℃, and adsorption time is 30-180min, and liquid directly returns silver-colored electrowinning process after the resulting absorption;
A desorb of C loaded resin
Use 5-40 gL -1Thiocarbamide, 0.1-3 molL -1HNO 3Mixing solutions amidoxim polyacrylonitrile resin to supported palladium under 20-50 ℃ carries out desorb, and the liquid-solid ratio of controlling strippant and loaded resin volume milliliter and quality gram is 100-500:1, and desorption time is 30-180min;
The secondary desorb of D loaded resin
Use 5-12 molL -1HCl solution carries out the secondary desorb to loaded resin under 20-50 ℃, the liquid-solid ratio of secondary strippant and loaded resin volume milliliter and quality gram is 100-500:1, and desorption time is 30-180min;
Regeneration of resin after the E desorb
, washing adopt absolute ethyl alcohol after soaking 12-24 h under the room temperature, to use 100-200gL after being neutrality again -1Oxammonium hydrochloride solution in 60-100 ℃ of following activation treatment 5-10h, the liquid-solid ratio that resin volume milliliter after control oxammonium hydrochloride solution and twice desorb and quality restrain is 60-100:1, the resin after the activation returns the resin absorption process once more.
CN2011102602702A 2011-09-05 2011-09-05 Separation method of palladium from silver electrolyte Expired - Fee Related CN102329959B (en)

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CN102676837A (en) * 2012-05-25 2012-09-19 四会市鸿明贵金属有限公司 Method for recycling palladium from silver electrolyte by using dimethylglyoxime
CN103305700B (en) * 2013-06-27 2014-07-09 江苏省环境科学研究院 Method for recovering silver from silver-containing wastewater
CN103539283B (en) * 2013-10-11 2014-11-05 金川集团股份有限公司 Comprehensive treatment method for removing Sb and Bi impurities in Cu electrolyte
CN103820646B (en) * 2013-12-30 2016-04-27 中国神华能源股份有限公司 A kind of method extracting gallium from flyash
CN105695750A (en) * 2016-03-07 2016-06-22 紫金矿业集团股份有限公司 Method for removing platinum and palladium out of silver electrolyte and concentrating platinum and palladium
CN105819595A (en) * 2016-03-30 2016-08-03 深圳市世清环保科技有限公司 Method for recycling gold in situ from gold-containing wastewater
CN106086452B (en) * 2016-08-09 2017-11-07 成都虹华环保科技股份有限公司 A kind of Palladium recovery device
CN108149311A (en) * 2018-01-09 2018-06-12 重庆立道表面技术有限公司 Non-cyanide plating silvering solution purification method and device
CN109023421A (en) * 2018-08-15 2018-12-18 云南铜业股份有限公司西南铜业分公司 A kind of purifying treatment method of silver electrolyte
CN109402413B (en) * 2018-10-30 2020-11-03 中国工程物理研究院核物理与化学研究所 Method for recovering palladium in fission product of spent fuel element
CN110484747B (en) * 2019-09-02 2020-06-02 湖南省佳川冶金科技有限公司 Process for selectively extracting palladium from crude silver

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CN85100240A (en) * 1985-04-01 1986-07-16 武汉大学 With gold and the palladium in the mercapto-amine-type chelating resin recovery electroplating effluent
CN1400322A (en) * 2002-09-05 2003-03-05 北京矿冶研究总院 Method for separating platinum palladium iraurita
CN101215012A (en) * 2007-12-28 2008-07-09 河北工业大学 Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85100240A (en) * 1985-04-01 1986-07-16 武汉大学 With gold and the palladium in the mercapto-amine-type chelating resin recovery electroplating effluent
CN1400322A (en) * 2002-09-05 2003-03-05 北京矿冶研究总院 Method for separating platinum palladium iraurita
CN101215012A (en) * 2007-12-28 2008-07-09 河北工业大学 Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin

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