CN114774700B - Method for efficiently extracting platinum-palladium resources in silver electrolysis system - Google Patents
Method for efficiently extracting platinum-palladium resources in silver electrolysis system Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 246
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 192
- 239000004332 silver Substances 0.000 title claims abstract description 192
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 164
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000003792 electrolyte Substances 0.000 claims abstract description 80
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 72
- 238000001179 sorption measurement Methods 0.000 claims abstract description 61
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 17
- 239000010931 gold Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- -1 palladium modified carbon fiber Chemical class 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002386 leaching Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 24
- 238000011084 recovery Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000284 extract Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 238000000605 extraction Methods 0.000 description 16
- 238000004064 recycling Methods 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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Abstract
The invention discloses a method for efficiently extracting platinum-palladium resources in a silver electrolysis system, which can simultaneously extract palladium and platinum from a silver electrolyte and a silver anode slime leaching solution, wherein for the silver electrolyte, platinum-palladium in the silver electrolyte is adsorbed to a low value through a platinum-palladium adsorption material to form a purified electrolyte, for the silver anode slime, platinum-palladium in the silver electrolyte is dissolved by nitric acid and separated into separated gold liquid, and the separated gold liquid is used as acid liquor and silver resources to be supplemented into the purified electrolyte, and the separated gold liquid and the silver electrolyte are returned to the silver electrolysis system together to participate in silver electrolysis reaction. The method for recovering platinum and palladium resources by silver electrolysis not only can meet the condition that the platinum and palladium in silver powder is out of standard, but also solves the problem of resource utilization of silver anode slime nitric acid leaching solution, and simultaneously only extracts the platinum and palladium resources in silver electrolyte and silver anode slime leaching solution by one step, thereby achieving the purposes of short process flow, high recovery rate and high resource utilization, and having good economical efficiency and environmental protection.
Description
Technical Field
The invention relates to a method for efficiently extracting platinum and palladium resources in a silver electrolysis system, in particular to an environment-friendly scheme for efficiently extracting platinum and palladium in the silver electrolysis system, belonging to the hydrometallurgy industry.
Background
Platinum-palladium resources of a silver anode plate in a silver electrolysis system are dispersed in silver electrolyte and silver anode slime along with the electrolysis process, wherein about 30% of the platinum-palladium resources exist in the silver electrolyte, and about 70% of the platinum-palladium resources exist in the silver anode slime. And along with the continuous occurrence of silver electrolysis reaction, platinum and palladium ions in the silver electrolyte enter the silver powder product along with electrolysis, and when the concentration exceeds a certain degree, the palladium content in the silver powder exceeds the standard, so that the quality of silver is affected, and the value of platinum and palladium is reduced.
According to the conditions of two different components of silver electrolyte and silver anode slime, generally, platinum and palladium extraction in different processes are respectively carried out, and the problems of open circuit and concentration of the electrolyte, neutralization of anode slime leaching liquid, silver precipitation and the like are involved.
The process of extracting platinum and palladium from silver electrolyte is as disclosed in CN201610126617.7, and the process includes adsorbing and filtering coconut shell carbon with platinum and palladium as adsorbent, desorbing with nitric acid as desorbing agent, and adding the coconut shell carbon to desorbing agent to eliminate platinum and palladium. The method has poor selectivity under a high-concentration nitric acid system and is easy to consume silver components.
Silver anode slime is generally leached by nitric acid, such as silver platinum palladium, and the like, gold still keeps an elemental state, and the anode slime leaching liquid is obtained by filtering and separating gold. The conventional platinum-palladium recovery method for the silver anode slime nitric acid leaching solution after gold separation comprises the steps of obtaining platinum-palladium concentrate by adopting a sodium sulfite reduction method or a zinc powder replacement or butyl xanthate precipitation method, and separating and purifying by utilizing the characteristic that ammonium chloropalladate or dichlorodiammine palladium is easy to selectively precipitate after acid dissolution; the zinc powder replacement method has large material consumption and poor selectivity under the environment of high acid and high impurity; the butyl xanthate precipitation method has long flow, very strict control requirements on operation technical conditions, easy incomplete palladium precipitation and complex subsequent treatment.
The above methods all cause the change of solution components, nitric acid and silver resources which are the main components in the silver anode slime leaching solution can not be recycled, and the selective extraction effect on platinum and palladium is low.
Platinum and palladium are rare noble metals, are present in the ore in a trace amount in a concomitant form, and have different sources and large differences in content. For silver electrolysis working sections of some smelting plants, the existing technology only extracts platinum and palladium from the silver electrolyte and the silver anode slime which are out of standard and open, and under the condition that copper and bismuth are out of standard before platinum and palladium, low-concentration platinum and palladium can be lost along with the process of removing copper and bismuth by precipitation, so that the recovery rate of platinum and palladium resources is low due to dispersion and even cannot be recovered. How to shorten the extraction flow process is an effective way to reduce resource dispersion.
Disclosure of Invention
The invention solves the technical problems that: aiming at the problems of long dispersion and low recovery rate of the platinum-palladium noble metal recovery process in the existing silver electrolysis process, the method for efficiently extracting the platinum-palladium resources in the silver electrolysis system is provided.
The invention is realized by adopting the following technical scheme:
A method for efficiently extracting platinum-palladium resources in a silver electrolysis system comprises the steps of adsorbing platinum-palladium in a silver electrolyte to a low value through a platinum-palladium adsorption material to form a purified electrolyte, dissolving the platinum-palladium in silver anode slime through nitric acid and separating gold to obtain a separated gold solution, supplementing the separated gold solution serving as acid liquor and silver resources into the purified electrolyte, and returning the separated gold solution to the silver electrolyte of the silver electrolysis system together to participate in silver electrolysis reaction.
In the method for efficiently extracting the platinum-palladium resources in the silver electrolysis system, the platinum-palladium adsorption material is further a platinum-palladium adsorption modified carbon fiber containing an organic chelating group.
In the method for efficiently extracting platinum-palladium resources in the silver electrolysis system, the platinum-palladium-absorbing modified carbon fiber further comprises a carbon fiber and an organic chelating group bonded to the carbon fiber, wherein the organic chelating group is mainly obtained by condensation reaction of an active group and an amino-containing organic matter, and the active group at least comprises a carboxyl group.
In the method for efficiently extracting platinum-palladium resources in the silver electrolysis system, the amino-containing organic matter further comprises one or more of tetraethylenepentamine, diethylenetriamine, ethylenediamine and N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine.
In the method for efficiently extracting platinum-palladium resources in the silver electrolysis system, further, the adsorption rate of the platinum-palladium-absorbing modified carbon fiber containing the organic chelating group to platinum ions and palladium ions in the acidic aqueous solution containing the platinum-palladium ions is more than 99%, and the saturated adsorption amounts are respectively as follows: 60 mg/g-100 mg/g of platinum and 80-120 mg/L of palladium.
In the method for efficiently extracting platinum-palladium resources in the silver electrolysis system, further, the silver anode slime is leached by using 65-68% industrial nitric acid, and gold-separated liquid is obtained by filtering and gold-separating.
In the method for efficiently extracting the platinum-palladium resources in the silver electrolysis system, further, the minimum value of the platinum-palladium adsorption material for platinum-palladium adsorption in the silver electrolyte is not more than 10mg/L.
The method for efficiently extracting platinum-palladium resources in a silver electrolysis system, according to claim 1, wherein the platinum-palladium adsorption material adsorbs and enriches platinum-palladium, and high-grade platinum-palladium concentrate/noble slag with the mass ratio of more than 60% is obtained through pyrolysis.
Aiming at the fact that nitric acid is continuously consumed in the silver electrolysis process, the high-acid high-silver solution is obtained after gold separation by combining the nitric acid leaching solution of the silver anode slime, the silver anode slime leaching solution is creatively utilized to replace the traditional acid supplementing form, and the nitric acid is fed into the silver electrolyte in a batch supplementing mode to participate in the silver electrolysis reaction of a silver electrolysis system; after platinum and palladium resources in the silver anode slime enter silver electrolyte, the silver electrolyte is subjected to electrolysis accumulation until the platinum and palladium content reaches a certain concentration, and then unified extraction and enrichment are carried out through a platinum and palladium adsorption material, so that the comprehensive utilization of the silver anode slime is realized. The scheme has short flow, high resource recycling rate and recovery rate, and no other material consumption and three wastes.
The method disclosed by the invention has the advantages that the silver electrolyte and the platinum and palladium of the silver anode slime in the silver electrolysis system are all merged into the silver electrolyte to be comprehensively recycled, the quality of the electrolytic silver is not affected, the whole extraction process flow is short, the platinum and palladium are not easy to disperse, the recovery rate is high, the three wastes are not generated in the extraction process, and the method has the characteristics of environmental friendliness and economy.
The platinum-palladium adsorption material for extracting and enriching platinum and palladium takes carbon fiber as a matrix, active groups (mainly carboxyl groups) obtained by oxidation on the carbon fiber are subjected to chemical reaction with small molecules of amino-containing organic matters, and platinum-adsorbing organic chelating groups are obtained by organic condensation reaction, and are bonded on the carbon fiber, so that the platinum-adsorbing organic chelating groups have very outstanding selectivity on platinum and palladium ions, and unreacted monomers on the surface of the adsorption material are washed away, so that pollution of the un-bonded chelating groups to adsorbed liquid is avoided. The platinum-palladium-absorbing modified carbon fiber containing the organic chelating group has strong selectivity to platinum and palladium, and has high saturated adsorption capacity to platinum and palladium ions in an acidic solution, and can reach 60 mg/g-120 mg/g. Meanwhile, the platinum-palladium adsorption material can selectively enrich and refine high, medium and low concentration platinum-palladium ions (0.5-1700 mg/L) under a complex multi-ion environment, especially, trace platinum-palladium ion waste liquid still keeps high enrichment times, adsorption rate and saturated adsorption quantity, can be applied to further adsorption recovery of low concentration platinum-palladium ions by acid leaching liquid, precipitation method or waste liquid after enrichment by extraction method, and can purify the platinum-palladium containing grade after purification and purification is greatly improved by the selectivity of the material. The platinum-absorbing modified carbon fiber is a carbon-based material, and the group playing a role in metal chelation is also an organic group, so that the platinum-absorbing modified carbon fiber does not introduce metal or inorganic salt refractory substances, is environment-friendly and is easy to process.
The platinum-palladium adsorption material is suitable for recovering platinum and palladium in an acidic high-salt solution of silver electrolyte, the lower limit of extraction of the platinum-palladium adsorption material can be less than 1mg/L under the premise of continuous adsorption purification, and the platinum-palladium adsorption capacity of the platinum-palladium adsorption material is about 100 times higher than that of active carbon and 10 times higher than that of commercial ion exchange resin under the same experimental condition of real wastewater, and simultaneously exceeds that of foreign resin adsorption materials. In practical production application, in consideration of the combination cost, the minimum value of the platinum-palladium adsorption material for platinum-palladium adsorption in the silver electrolyte is set to be not more than 10 mg/L.
The method has the following beneficial effects in the application of recovering platinum and palladium resources of the silver electrolyte:
(1) According to the invention, platinum and palladium can be selectively extracted to extremely low concentration through the platinum and palladium adsorption material, the concentration of silver and nitric acid is not influenced, the yield of high-quality silver powder is effectively improved, the silver electrolyte of low platinum and palladium has the capacity of containing platinum and palladium resources of the nitric acid leaching solution of silver anode slime, the quality of silver powder is not influenced, and the recycling of silver and nitric acid in the silver anode slime and the synchronous recycling of platinum and palladium are realized.
(2) The method has wide application conditions, can be directly applied to the technical process liquid of the acid electrolyte, does not need open-circuit treatment, has high selectivity extraction rate of platinum and palladium, does not consume silver and nitric acid, and can directly recycle the silver electrolyte after platinum and palladium extraction.
(3) The method has the advantages of short process flow, difficult dispersion of platinum and palladium, high recovery rate and higher economy.
(4) The process of the invention has no three wastes and has high environmental protection.
In summary, according to the scheme for efficiently extracting the platinum-palladium resources in the silver electrolysis system, the rare noble metals are efficiently recovered and other resources are efficiently recycled into a whole, the platinum-palladium resources in the silver electrolyte and the silver anode slime nitric acid leaching solution are synchronously extracted, the purposes of short recovery flow, high recovery and recycling of the platinum-palladium resources in the silver electrolysis system are realized, and the method has good economical efficiency and environmental friendliness.
The invention is further described below with reference to the drawings and detailed description.
Drawings
FIG. 1 is a process flow diagram in an embodiment.
Detailed Description
Examples
As shown in fig. 1, a method for efficiently extracting platinum-palladium resources in a silver electrolysis system in the diagram has the following process route: the process takes silver electrolyte and silver anode slime leaching liquid generated in the silver electrolysis process as platinum-palladium resource extraction objects. Wherein 70% of palladium on the silver anode plate is concentrated in silver anode mud and 30% is concentrated in silver electrolyte in the silver electrolysis process.
The silver anode slime is generally leached by industrial nitric acid with the concentration of 65-68%, platinum, palladium and silver are dissolved, and gold separating liquid is obtained by filtering and separating gold, namely, the silver anode slime leaching liquid. At this time, the silver anode slime leaching solution contains a large amount of nitric acid and is a high-acidity solution; at the moment, the silver anode slime leaching liquid is utilized to replace nitric acid to supplement acid to the silver electrolyte, and the silver electrolyte is returned to the silver electrolysis system in a segmented mode to participate in silver electrolysis reaction, so that platinum and palladium resources are collected in the silver electrolyte to be collected uniformly, meanwhile, effective recycling of silver and nitric acid in the silver anode slime can be guaranteed, and silver production by electrolysis is carried out.
When the content of platinum and palladium in the silver electrolyte is accumulated to reach a certain concentration or reaches a concentration which leads the silver powder to exceed the standard in the silver electrolysis process, the platinum and palladium in the silver electrolyte are adsorbed and collected through a platinum and palladium adsorption material, the extraction of the platinum and palladium is concentrated in a platinum and palladium extraction section of the silver electrolyte, and the platinum and palladium content in the silver electrolyte is purified to be less than 10mg/L through the platinum and palladium adsorption material. The platinum-palladium resources in the silver electrolyte and the silver anode slime are concentrated, extracted and enriched through the working section, the silver electrolyte after adsorption and purification returns to a silver electrolysis system to continuously participate in silver electrolysis reaction, the generated low platinum-palladium-silver electrolyte is subjected to electrolysis to produce silver, the purity of silver powder is ensured, the platinum-palladium adsorption material is separated after adsorption and enrichment of platinum-palladium, and high-grade platinum-palladium concentrate/noble slag with the purity of more than 60% is obtained through pyrolysis.
The platinum-palladium adsorption material of the embodiment adopts HSJ-APP-Pd platinum-palladium adsorption material developed by Changsha Chemicals technology development Co., ltd (specific components and preparation method can refer to patent application document with application number of CN 202110342506.0), and the platinum-palladium adsorption material of the model is a high-selectivity extraction material for platinum-palladium, is suitable for recovering low-concentration platinum-palladium in acidic high-salt solution such as silver electrolyte, and has the lower extraction limit of below 1 mg/L. In the application of the silver electrolyte, platinum and palladium can be selectively extracted to be less than 10mg/L, the concentration of silver and nitric acid is not influenced, and the yield of high-quality silver powder is effectively improved; meanwhile, the silver electrolyte with low platinum and palladium content has the capability of containing platinum and palladium resources of the nitric acid leaching solution of the silver anode slime, the quality of silver powder is not affected, and the recycling of silver and nitric acid in the silver anode slime and the synchronous recycling of platinum and palladium are realized.
Specifically, the platinum-palladium-absorbing modified carbon fiber of the HSJ-APP-Pd platinum-palladium adsorption material comprises carbon fiber and an organic chelating group bonded on the carbon fiber, wherein the organic chelating group is obtained by condensation reaction of an active group and an amino-containing organic matter, the active group is mainly carboxyl, the amino-containing organic matter is tetraethylenepentamine, and one or more of diethylenetriamine, ethylenediamine, N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine and the like can be adopted in practical application. The adsorption rate of the HSJ-APP-Pd platinum-palladium adsorption material to platinum-palladium ions in the acidic aqueous solution containing platinum-palladium ions is over 99 percent, and the saturated adsorption amounts are respectively as follows: 60-100 mg/L of platinum and 80-120 mg/g of palladium.
The technical effects of the present invention will be described below by way of specific examples of recovery of platinum and palladium resources in a silver electrolysis system in a certain factory.
Adsorption Properties of HSJ-APP-Pd platinum palladium adsorbent Material
Firstly, the adsorption effect of the HSJ-APP-Pd platinum palladium adsorption material adopted in the embodiment is verified.
The silver electrolyte of a certain factory is adsorbed by adopting an HSJ-APP-Pd platinum-palladium adsorption material, the silver electrolyte before adsorption and the silver electrolyte after adsorption are shown in the following table 1, the silver electrolyte used in the method is pure electrolyte without acid supplementation of a silver anode slime nitric acid leaching solution, wherein the silver content is about 100g/L, the nitric acid content is about 8g/L, the platinum-palladium content is only 8.40mg/L and 61.69mg/L, and the silver electrolyte can be selectively adsorbed to 0.21mg/L of platinum and 0.277mg/L of palladium, namely less than 1mg/L, and the concentration of silver and nitric acid is kept unchanged through the HSJ-APP-Pd platinum-palladium adsorption material.
TABLE 1 composition of silver electrolyte stock solution before and after adsorption
2. Example platinum palladium extraction of super-standard silver electrolyte
The platinum-palladium super-standard silver electrolyte and the silver anode slime nitric acid leaching solution of a certain factory have the components shown in the following table 2, and the silver electrolyte before adsorption applied here is a mixed silver electrolyte adopting the silver anode slime nitric acid leaching solution for acid supplementing, wherein the platinum-palladium content of the silver electrolyte reaches 14.32mg/L and 166.8mg/L.
TABLE 2 composition of silver electrolyte and silver anode mud nitric acid leachate
According to economy, the platinum and palladium in the silver electrolyte is collected and purified by using an HSJ-APP-Pd platinum and palladium adsorption material in actual operation until the platinum and palladium content is reduced to below 10 mg/L. As shown in Table 2, the platinum and palladium contents in the purified electrolyte after adsorption are respectively reduced to 4.46mg/L and 5.78mg/L, and the silver and copper contents are not obviously reduced compared with those before purification (the data belong to the detection error range), and the adsorbed silver electrolyte is directly returned to a silver electrolysis system to participate in silver electrolysis reaction.
As can be seen from Table 2, the content of the silver electrolyte HNO 3 in the electrolytic reaction under the working condition is kept between 8 and 10g/L, but the content of the nitric acid is continuously consumed and volatilized in the electrolytic process, and the pure nitric acid needs to be intermittently supplemented. While Table 2 shows that the HNO 3 content of the nitric acid leaching solution of the silver anode slime is up to 356.2g/L, and the nitric acid leaching solution of the silver anode slime is used for replacing pure nitric acid to carry out acid supplementing on the silver electrolyte in the continuous electrolysis process of the silver electrolyte system.
3. Electrolytic silver production of silver electrolyte after adsorption
Table 3 shows the results of the electrolysis of the two ways of supplementing pure nitric acid and supplementing silver anode slime leachate in the simulated continuous electrolysis process of the absorbed silver electrolyte, respectively, in order to compare the effects of supplementing the acid with the pure nitric acid in the present example.
TABLE 3 silver electrolyte electrolytic silver after acid make-up
In the continuous electrolytic reaction process, the pure nitric acid and the silver anode slime leaching solution are respectively supplemented, the nitric acid content of the silver electrolyte is kept at 8-10 g/L, and two periods are respectively supplemented, in the embodiment, 50L of silver electrolyte is supplemented with about 20-50 mL of pure nitric acid every 10 hours, and the silver anode slime leaching solution is about 100-200 mL. And respectively taking electrolytic silver production of each period for content detection, wherein the content of impurity palladium is below 3g/t, and meets the requirements of qualified silver powder. The silver anode slime nitric acid leaching solution is proved to replace pure nitric acid to supplement silver electrolyte, so that the quality of silver is not affected, and silver ions in the silver electrolyte are supplemented, so that the silver content is basically maintained at about 100 g/L.
4. Pyrolysis to obtain high-grade platinum palladium concentrate/noble slag
The high-grade platinum-palladium concentrate/noble slag obtained by pyrolyzing the saturated material after the concentrated adsorption of platinum-palladium ions is subjected to component analysis, and specific data are shown in the following table 4.
TABLE 4 composition of platinum palladium concentrate/noble slag after pyrolysis
Wherein the platinum content of the ash after pyrolysis is about 1/10 of that of palladium, and the platinum and palladium in the ash mainly exist in the forms of oxide and simple substance. The main metal impurity is silver, accounting for about 6%, and the content of other metal ions is lower. The high selectivity of the HSJ-APP-Pd platinum-palladium adsorption material is proved, and high-grade platinum-palladium concentrate can be formed by pyrolysis after one-step adsorption.
Experimental data prove that the method and the process for taking the platinum-palladium resources in the silver electrolysis system can realize the recycling of the platinum-palladium resources in the silver electrolysis system in a short process and high efficiency, have no output of other harmful products, and have high economical efficiency and environmental protection.
The above is merely a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described with reference to the preferred embodiments, it is not intended to limit the scope of the invention. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (6)
1. A method for efficiently extracting platinum-palladium resources in a silver electrolysis system is characterized by comprising the following steps of: for silver electrolyte, platinum and palladium in the silver electrolyte are adsorbed to a low value through a platinum and palladium adsorption material to form purified electrolyte, for silver anode slime, platinum and palladium in the silver electrolyte are dissolved through nitric acid and separated into separated gold liquid, and the separated gold liquid is used as acid liquor and silver resources to be supplemented into the purified electrolyte, and the separated gold liquid and the silver electrolyte are returned to a silver electrolysis system together to participate in silver electrolysis reaction; the platinum-palladium adsorption material is a platinum-palladium adsorption modified carbon fiber containing an organic chelating group; the platinum-absorbing palladium modified carbon fiber comprises carbon fiber and an organic chelating group bonded to the carbon fiber, wherein the organic chelating group is mainly obtained by condensation reaction of an active group and an amino-containing organic matter, and the active group at least comprises carboxyl.
2. The method for efficiently extracting platinum-palladium resources in a silver electrolysis system according to claim 1, wherein the amino-containing organic matter comprises one or more of tetraethylenepentamine, diethylenetriamine, ethylenediamine and N, N' -tetra (2-hydroxyethyl) ethylenediamine.
3. The method for efficiently extracting platinum-palladium resources in a silver electrolysis system according to claim 1 or 2, wherein the adsorption rate of the platinum-palladium-absorbing modified carbon fiber containing organic chelating groups to platinum ions and palladium ions in the acidic aqueous solution containing platinum-palladium ions is more than 99%, and the saturated adsorption amounts are respectively: 60-mg/g to 100-mg/g of platinum and 80-120-mg/L of palladium.
4. The method for efficiently extracting platinum and palladium resources in a silver electrolysis system according to claim 1, wherein the silver anode slime is leached by using 65-68% industrial nitric acid, and gold-separated liquid is obtained by filtering and separating gold.
5. The method for efficiently extracting platinum-palladium resources in a silver electrolysis system according to claim 1, wherein the minimum value of platinum-palladium adsorption of the platinum-palladium adsorption material in the silver electrolyte is not more than 10 mg/L.
6. The method for efficiently extracting platinum-palladium resources in a silver electrolysis system, according to claim 1, wherein the platinum-palladium adsorption material adsorbs and enriches platinum-palladium, and high-grade platinum-palladium concentrate/noble slag with the mass ratio of more than 60% is obtained through pyrolysis.
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