CN108914157B - A kind of technique that high antimonial lead separates lead, antimony, silver - Google Patents

A kind of technique that high antimonial lead separates lead, antimony, silver Download PDF

Info

Publication number
CN108914157B
CN108914157B CN201810765556.8A CN201810765556A CN108914157B CN 108914157 B CN108914157 B CN 108914157B CN 201810765556 A CN201810765556 A CN 201810765556A CN 108914157 B CN108914157 B CN 108914157B
Authority
CN
China
Prior art keywords
lead
antimony
silver
anode
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810765556.8A
Other languages
Chinese (zh)
Other versions
CN108914157A (en
Inventor
唐磊
杨建广
李陵晨
南天翔
丁龙
闫万鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shiny Materials Science And Technology Inc
Original Assignee
Shiny Materials Science And Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shiny Materials Science And Technology Inc filed Critical Shiny Materials Science And Technology Inc
Priority to CN201810765556.8A priority Critical patent/CN108914157B/en
Publication of CN108914157A publication Critical patent/CN108914157A/en
Application granted granted Critical
Publication of CN108914157B publication Critical patent/CN108914157B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
    • 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
    • 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • 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
    • C22B7/007—Wet processes by acid leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

A kind of technique that high antimonial lead separates lead, antimony, silver, alloy made of the technique is cast using high antimony-lead anode mud is as anode, it is loaded into anode and carries out pulse electrolysis in lead methanesulfonate system, antimony and silver, which fall off, when electrolysis forms the earth of positive pole in anode, the first pass into solution in the form of lead methanesulfonate of lead, it is precipitated later with simple substance form in cathode, electric lead and antimony silver powder is respectively obtained after electrolysis；Antimony silver powder is separated by filtration after using nitric acid to dissolve again, obtains silver nitrate solution and antimony trichloride, after iron powder and hydrochloric acid reaction is added in silver nitrate, solid-liquor separation obtains silver powder and iron nitrate solution.The technique can carry out classification extraction to lead, antimony, the silver in high antimonial lead, have the advantages that process flow is simple, the valuable element rate of recovery is high, clean and environmental protection.

Description

A kind of technique that high antimonial lead separates lead, antimony, silver
Technical field
The invention belongs to field of hydrometallurgy, and in particular to a kind of technique that high antimonial lead separates lead, antimony, silver.
Background technique
When lead bullion electrorefining, because the metals such as Sb, As, Bi, Cu, Ag, Au standard electrode potential ratio Pb just, these metals It is seldom dissolved to enter electrolyte but adhere to anode surface in solid form or fall off and forms the earth of positive pole in electrolytic cell, due to Wherein it is enriched 5~30% bismuth, 5~45% antimony, 1~10% copper, 1~20% bismuth, the gold of 10~1500g/t, 1~ The elements such as 20% silver and 5~30% lead, 0.1~30% arsenic, it is achieved that its cleaning treatment and high efficiente callback utilize It is significant.In recent years, high antimony lead raw material accounting gradually increases, and antimony content also rises therewith in the earth of positive pole that lead bullion obtains when being electrolysed Height, antimony content even reaches 30% or more in the lead bullion electrolysis anode sludge of some firms outputs, how more effectively to handle height The antimony-lead anode mud attention more and more by each enterprise.
The method of lead anode slurry recycling lead, antimony, silver etc. can be divided into thermal process and wet processing.Thermal process has place The advantages that reason amount is big, adaptability to raw material is strong, technical maturity, mainly by lead anode slurry through reduction melting, divide silver stove refinement oxide, Antimony flue dust reduction smelting in reverberatory furnace and refining, respectively obtain the products such as thick silver, stibium trioxide.The method is still what lead anode slurry was handled at present Main method, but still have the deficiencies of separation of antimony bismuth silver is not thorough, the rate of recovery is low, recovery process is complicated, smoke contamination is serious.
The method of lead anode slurry wet-treating mainly uses NaCl+CaCl2It leaching, salt Ore Leaching or nitration mixture leach, FeCl is usually added into leaching process3、NaClO3、Cl2、H2O2Wait oxidants to improve the leaching rate of antimony, leachate passes through water again The solution precipitation method obtain the products such as antimony oxide respectively.These methods avoid smoke contamination during pyrogenic process, improve labour item Part, but there are still complex procedures, anodes to be easily passivated, reagent consumes the disadvantages of more, wastewater flow rate is big.Therefore, a kind of energy cleaning is found The method for efficiently separating lead, antimony, silver etc. in recycling lead anode slurry wet process is of great significance.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of recycling, clean place Manage high antimonial lead made of high antimony-lead anode mud (antimony content > 20wt% lead anode slurry is known as high antimony-lead anode mud) casting New process, to realize that lead in high antimony lead anode alloy, antimony, silver efficiently separate extraction.
The technical solution adopted by the present invention to solve the technical problems is: a kind of high antimonial lead separates the work of lead, antimony, silver Skill is: alloy made of being cast first using high antimony-lead anode mud is loaded into anode as anode in lead methanesulfonate system Pulse electrolysis is carried out, antimony and silver, which fall off, when electrolysis forms the earth of positive pole in anode, and lead first dissolves in the form of lead methanesulfonate molten Liquid is precipitated in cathode in the form of elementary lead later, electric lead and antimony silver powder is respectively obtained after electrolysis, antimony silver powder uses nitric acid molten again It is separated by filtration after solution, obtains silver nitrate solution and antimony trichloride, after iron powder and hydrochloric acid reaction is added in silver nitrate, solid-liquor separation is obtained Silver powder and iron nitrate solution.Antimony content is greater than 20wt% in the high antimony-lead anode mud.
The technique of the high antimonial lead separation lead, antimony, silver, specifically includes the following steps:
Step 1: high antimonial lead lead methanesulfonate system pulse electrolysis prepares electric lead
High antimonial lead made of being cast using high antimony-lead anode mud carries out pulse electricity as anode in lead methanesulfonate system Solution；Anode is fitted into the canvas material anode of acid corrosion-resistant when electrolysis, the anode insoluble matter to fall off when accepting anode electrolysis, First the pass into solution in the form of lead methanesulfonate respectively obtains electricity after electrolysis later again in the form of elementary lead in cathode precipitation to lead Antimony silver powder in lead and anode；
Selection is the reason of lead methanesulfonate system carries out pulse electrolysis to high antimonial lead anode, appropriate by controlling Pulse electrolysis condition, the lead in anode can be well soluble in lead methanesulfonate electrolyte under the function of current forms Pb (CH3SO3)2, while Pb2+It can be precipitated well in cathode as elementary lead again, antimony, silver and (Me is represented with MeS in anode alloy Cu in anode, Sb, Ag etc.) component existing for form then falls off and forms the earth of positive pole in anode；Meanwhile impulse electric field is answered With can apply bigger anode current under the same conditions makes anode be easier to occur anodic solution without customary DC electricity " anodic passivity " phenomenon that solution is also easy to produce avoids the problem that conventional anodes electrolysis need to frequently stop reaction and carry out anode brush board；
Step 2: antimony silver powder extracts silver powder
Using concentrated nitric acid as leaching agent, the antimony silver powder that step 1 is obtained carries out oxidising acid leaching, and liquid is solid after leaching Separation, respectively obtains silver nitrate leachate and antimony trichloride leached mud；Iron powder is added in silver nitrate leachate and hydrochloric acid carries out Solid-liquor separation after displacement reaction, respectively obtains the higher silver powder of purity and ferrous nitrate solution.
Further, in step 1, when pulse electrolysis, the pulse frequency of impulse electric field is 50~2000Hz, and duty ratio is 50%~80%, average pulse current density is 200~1000A/m2, temperature is 20~60 DEG C, and lead methanesulfonate is dense in electrolyte Degree is 0.1~0.8mol/L.
Further, in step 1, when pulse electrolysis, anode and cathode spacing is 3~12cm, and cathode material is lead, titanium, stainless steel One of.
Further, in step 1, the terminal of pulse electrolysis is as Bi in electrolyte3+Ion is (because in these lead anode slurries A small amount of bismuth is usually contained, enters solution when anode electricity is molten and forms Bi3+.Its concentration is controlled in pulse electrolysis, otherwise can Deposited on cathode plate) concentration enrichment to 3g/L when, terminate electrolytic process, and lead powder replacement Treatment, lead powder are carried out to electrolyte 10~90 DEG C of reaction temperature when displacement, 10~120min of time swap, lead powder dosage are all to replace bismuth ion in electrolyte For theoretical amount needed for bismuth with elementary 1.0~1.5 times (for control solution in Bi3+Concentration, be not higher than 3g/L), displaced liquid return For configuring electrolyte.
Further, in step 2, when antimony silver powder extracts silver powder, the condition of nitric acid leaching are as follows: concentration of nitric acid is 1~5mol/ L, temperature are 30~90 DEG C, and nitric acid dosage is theory needed for antimony and silver in antimony silver powder are completely converted into antimony trichloride and silver nitrate 1.0~1.5 times of amount, extraction time are 1~5h.
Further, in step 2, the iron powder amount that when silver nitrate leachate displacement silver powder is added is that silver ion in solution is complete Portion is reduced to 1~3 times of theoretical amount needed for elemental silver, and the amount that hydrochloric acid is added is theoretical amount needed for the iron powder that will be added all dissolves 1~2 times.Iron powder is added separately to hydrochloric acid when displacement, and hydrochloric acid is added after being spaced 60~180min after addition iron powder.Reaction temperature It is 10~80 DEG C, the reaction time is 10~240min.
The present invention exist for existing high antimony-lead anode mud pyrogenic process, wet processing process " metal recovery rate is low, it is at high cost, The status of pollution weight " is proposed high antimony-lead anode mud founding at high antimonial lead, and with " methane sulfonic acid lead system pulse electrolysis The technical combinations of separation lead-antimony silver powder nitric acid oxidation-iron replacement extraction silver powder " handle high antimonial lead technique.The invention work Skill on the basis of barium plumbate problem, obtains electric lead, antimony trichloride, silver powder in solving high antimonial lead from high antimonial lead Equal products.
Each step is effectively connected in the present invention, coordinated, and research practice shows the pulse electrolysis of methane sulfonic acid lead and antimony Silver powder nitric acid oxidation-iron replacement combines, and can efficiently separate the lead recycled in high antimonial lead anode, antimony and recycling silver.
Specific embodiment
The invention will be further described with reference to embodiments, but the present invention is not limited to the following embodiments.
Embodiment 1
Yunnan company provide cast with high antimony-lead anode mud made of anode alloy ingredient are as follows: Pb 72.6%, Sb 21.5%, Ag 1.1%, Bi 2.0%, Cu 1.2%.
It is cathode in lead methanesulfonate using stainless steel plate using this high antimonial lead as anode (long 12cm × wide 8cm × thickness 2cm) Pulse electrolysis is carried out in system, anode is placed in canvas anode.The pulse frequency of impulse electric field is 1000Hz, duty when electrolysis Than being 70%, average pulse current density is 300A/m2, temperature is 30 DEG C, and anode and cathode spacing is 5cm, electrolyte volume 1L, electricity Solving lead methanesulfonate concentration in liquid is 0.3mol/L.It is electrolysed with this condition, every 30min, sampling analysis is wherein from electrolyte Bi3+Concentration, as Bi in electrolyte3+When ion concentration is enriched to 3g/L, terminate electrolytic process.Pattern is received in cathode at this time Fine and close electric lead flake 109.7g, purity 99.4%, cathode efficiency 96.4%.Insoluble matter warp is collected into anode It is weighed as 39.4g after washing is dry, analyzes wherein argentiferous 4.2%, contains antimony 82.4%.The antimony silver powder being collected into anode is used Nitric acid leaching process, concentration of nitric acid is 2.5mol/L when leaching, and temperature is 80 DEG C, and nitric acid dosage is that antimony and silver in antimony silver powder is complete 1.1 times of theoretical amount needed for portion is converted into antimony trichloride and silver nitrate, extraction time 3h.Solid-liquor separation after leaching, obtains To residue washing after drying weigh and analyze its ingredient, be determined as 41.8g purity be 99.7% SbO2.Later, above-mentioned Iron powder is added in filtered fluid and hydrochloric acid carries out displacement reaction.The iron powder amount of addition is that silver ion in solution is all reduced to simple substance 1.5 times of theoretical amount needed for silver, the amount that hydrochloric acid is added are 1.1 times of theoretical amount needed for the iron powder that will be added all dissolves.Displacement When iron powder be added separately to hydrochloric acid, be added iron powder after be spaced 90min after hydrochloric acid is added.Reaction temperature is 40 DEG C, and the reaction time is 60min.Solid-liquor separation after reaction, filter residue drying weigh and analyze its ingredient, are determined as the silver of 1.67g purity 99.5%. To electrolyte carry out lead powder replacement Treatment, 30 DEG C of reaction temperature, time swap 60min, lead powder dosage be by bismuth in electrolyte from Sub 1.1 times for being all replaced into theoretical amount needed for bismuth with elementary.Solid-liquor separation, displaced liquid analysis are wherein led after reaction for displacement Want the concentration of metal ion are as follows: Pb2+67.4g/L Bi3+0.1g/L, Sb3+0.3g/L can return to and use for configuring electrolyte. Drying weighs and analyzes its ingredient after filter residue then washs, and is confirmed as the Sponge bismuth powder displacement that 3.17g purity is 98.9%.
Embodiment 2
Henan company provide cast with high antimony-lead anode mud made of anode alloy ingredient are as follows: Bi 3.3%, Cu 0.6%, Pb 55.7%, Sb 37.2%, Ag 2.8%.
It is cathode in lead methanesulfonate body using titanium plate using this high cerrobase alloy as anode (long 20cm × wide 16cm × thickness 3cm) Pulse electrolysis is carried out in system, lead methanesulfonate concentration is that 0.3mol/L (has used reality when configuration lead methanesulfonate electrolyte in electrolyte Resulting displaced liquid is replaced through lead powder after applying in example 1 electrolysis and terminating).Anode is placed in canvas anode.The arteries and veins of impulse electric field Rushing frequency is 500Hz, and duty ratio 60%, average pulse current density is 600A/m2, temperature is 30 DEG C, and anode and cathode spacing is 7cm, electrolyte volume 1.5L.Be electrolysed with this condition, every 30min from electrolyte sampling analysis wherein Bi3+Concentration, when Bi in electrolyte3+When ion concentration is enriched to 3g/L, terminate electrolytic process.The electric lead flake of pattern densification is received in cathode at this time 76.1g, purity 99.7%, cathode efficiency 95.1%.Claim after being collected into the washed drying of insoluble matter in anode Weight is 58.7g, analyzes wherein argentiferous 6.5%, contains antimony 86.4%.At the antimony silver powder nitric acid leaching being collected into this anode Reason, concentration of nitric acid is 2.5mol/L when leaching, and temperature is 85 DEG C, and nitric acid dosage is that antimony and silver in antimony silver powder are completely converted into two 1.3 times of theoretical amount needed for antimony oxide and silver nitrate, extraction time 2h.Solid-liquor separation after leaching, obtained filter residue are washed Drying weighs and analyzes its ingredient after washing, and is determined as the SbO that 63.2g purity is 99.2%2.Later, add in above-mentioned filtered fluid Enter iron powder and hydrochloric acid carries out displacement reaction.The iron powder amount of addition is that silver ion in solution is all reduced to theory needed for elemental silver 1.2 times of amount, the amount that hydrochloric acid is added are 1.5 times of theoretical amount needed for the iron powder that will be added all dissolves.Iron powder and salt when displacement Acid is added separately to, and hydrochloric acid is added after being spaced 60min after addition iron powder.Reaction temperature is 30 DEG C, reaction time 120min.Reaction After solid-liquor separation, filter residue drying weigh simultaneously analyzes its ingredient, be determined as the silver of 3.87g purity 99.8%.To electrolyte into The processing of quadrat powder substitution, 50 DEG C of reaction temperature, time swap 90min, lead powder dosage is all to replace bismuth ion in electrolyte It is 1.2 times of theoretical amount needed for bismuth with elementary.Solid-liquor separation, displaced liquid analyze wherein primary metal ion after reaction for displacement Concentration are as follows: Pb2+70.1g/L Bi3+0.12g/L, Sb3+0.24g/L can return to and use for configuring electrolyte.Filter residue is then washed Drying weighs and analyzes its ingredient after washing, and is confirmed as the Sponge bismuth powder displacement that 5.1g purity is 94.2%.
(methanesulfonic acid is added, then antimony, bi content increase in lead, cathode efficiency decline, solution in comparative example 1 in electrolyte Middle antimony ion content increases)
Using high antimonial lead described in above-described embodiment 1 as anode (long 12cm × wide 8cm × thickness 2cm), with stainless steel Plate is that cathode carries out pulse electrolysis in methanesulfonic acid-lead methanesulfonate system, and anode is placed in canvas anode.Pulse electricity when electrolysis The pulse frequency of field is 1000Hz, and duty ratio 70%, average pulse current density is 300A/m2, temperature is 30 DEG C, anode and cathode Spacing is 5cm, electrolyte volume 1L, and lead methanesulfonate concentration is 0.3mol/L, methanesulfonic acid 0.3mol/L in electrolyte.At this Be electrolysed under part, every 30min from electrolyte sampling analysis wherein Bi3+Concentration, as Bi in electrolyte3+Ion concentration enrichment When to 3g/L, terminate electrolytic process.Electric lead flake 87.1g, purity 79.3% are received in cathode at this time, cathode efficiency is 65.7%.Lead powder replacement Treatment is carried out to electrolyte, 30 DEG C of reaction temperature, time swap 60min, lead powder dosage is by electrolyte Middle bismuth ion is all replaced into 1.1 times of theoretical amount needed for bismuth with elementary.Solid-liquor separation, displaced liquid return after reaction for displacement For configuring electrolyte.Drying weighs and analyzes its ingredient after filter residue then washs, and is confirmed as the sponge that 3.11g purity is 96.2% Bismuth meal analyzes the content of primary metal ion in displaced liquid: Pb2+59.7g/L Bi3+0.33g/L, Sb3+Concentration 5.4g/L.
Comparative example 2 (is electrolysed) using customary DC pressure stabilizing
Using high cerrobase alloy described in above-described embodiment 2 as anode (long 20cm × wide 16cm × thickness 3cm), it is with titanium plate Cathode carries out direct current under the conditions of conventional DC regulated power supply in lead methanesulfonate system, and lead methanesulfonate concentration is in electrolyte 0.3mol/L is (after having used in embodiment 1 electrolysis when configuration lead methanesulfonate electrolyte and terminating after lead powder replaces resulting displacement Liquid).But electrolysis is only after 15min, and slot pressure just increases to 3.8V from 0.5V, continues growing electrolysis time, and slot pressure continues to increase.Anode Surface adhesion has a large amount of bulk earth of positive pole, and cathode is also unable to get fine and close stereotype, but is in lead sponge powdery, easily from cathode table Emaciated face is fallen, and is electrolysed after 3h because slot pressure rises to 4.5v, current efficiency only 67.1%.

Claims (7)

1. the technique of a kind of high antimonial lead separation lead, antimony, silver, it is characterised in that: cast first with high antimony-lead anode mud Alloy as anode, be loaded into anode and carry out pulse electrolysis in lead methanesulfonate system, when electrolysis antimony and silver fall off into The earth of positive pole is formed in anode, the first pass into solution in the form of lead methanesulfonate of lead is precipitated in the form of elementary lead in cathode later, Electric lead and antimony silver powder are respectively obtained after electrolysis, antimony silver powder is separated by filtration after using nitric acid to dissolve again, obtains silver nitrate solution and two Antimony oxide, after iron powder and hydrochloric acid reaction is added in silver nitrate, solid-liquor separation obtains silver powder and iron nitrate solution；In the high antimony lead Antimony content is greater than 20 wt%.
2. the technique of high antimonial lead separation lead according to claim 1, antimony, silver, which is characterized in that specifically include following Step:
Step 1: high antimonial lead lead methanesulfonate system pulse electrolysis prepares electric lead
High antimonial lead made of being cast using high antimony-lead anode mud carries out pulse electrolysis as anode in lead methanesulfonate system；Electricity Anode is fitted into the canvas material anode of acid corrosion-resistant when solution, the anode insoluble matter to fall off when accepting anode electrolysis, and lead is first The pass into solution in the form of lead methanesulfonate, later again in the form of elementary lead cathode be precipitated, respectively obtained after electrolysis electric lead and Antimony silver powder in anode；
Step 2: antimony silver powder extracts silver powder
Using concentrated nitric acid as leaching agent, the antimony silver powder progress oxidising acid leaching that step 1 is obtained, solid-liquor separation after leaching, Respectively obtain silver nitrate leachate and antimony trichloride leached mud；Iron powder is added in silver nitrate leachate and hydrochloric acid replace instead Solid-liquor separation after answering, respectively obtains the higher silver powder of purity and ferrous nitrate solution；The concentrated nitric acid concentration is 1~5 mol/ L。
3. the technique of high antimonial lead separation lead according to claim 2, antimony, silver, which is characterized in that in step 1, arteries and veins When punching electrolysis, the pulse frequency of impulse electric field is 50~2000 Hz, and duty ratio is 50%~80%, and average pulse current density is 200~1000 A/m2, temperature is 20~60 DEG C, and lead methanesulfonate concentration is 0.1~0.8 mol/L in electrolyte.
4. the technique of high antimonial lead separation lead according to claim 2 or 3, antimony, silver, which is characterized in that in step 1, Anode and cathode spacing is 3~12 cm when pulse electrolysis, and cathode material is one of lead, titanium, stainless steel.
5. the technique of high antimonial lead separation lead according to claim 2 or 3, antimony, silver, which is characterized in that in step 1, The terminal of pulse electrolysis is as Bi in electrolyte3+When ion concentration is enriched to 3 g/L, terminate electrolytic process, and to electrolyte into The processing of quadrat powder substitution, 10~90 DEG C of reaction temperature, 10~120 min of time swap when lead powder is replaced, lead powder dosage is will be electric Bismuth ion is all replaced into 1.0~1.5 times of theoretical amount needed for bismuth with elementary in solution liquid, and displaced liquid is returned for configuring electrolysis Liquid.
6. the technique of high antimonial lead separation lead according to claim 2 or 3, antimony, silver, which is characterized in that in step 2, The condition that nitric acid leaches when antimony silver powder extracts silver powder are as follows: temperature is 30~90 DEG C, and nitric acid dosage is that antimony and silver in antimony silver powder is complete 1.0~1.5 times of theoretical amount needed for portion is converted into antimony trichloride and silver nitrate, extraction time are 1~5 h.
7. the technique of high antimonial lead separation lead according to claim 2 or 3, antimony, silver, which is characterized in that in step 2 The iron powder amount being added when silver nitrate leachate displacement silver powder is that silver ion in solution is all reduced to theoretical amount needed for elemental silver 1~3 times, the amount that hydrochloric acid is added is 1~2 times of theoretical amount needed for the iron powder that will be added all dissolves, iron powder and salt when displacement Acid is added separately to, and is added after iron powder after being spaced 60~180 min and is added hydrochloric acid, and reaction temperature is 10~80 DEG C, and the reaction time is 10~240 min.
CN201810765556.8A 2018-07-12 2018-07-12 A kind of technique that high antimonial lead separates lead, antimony, silver Active CN108914157B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810765556.8A CN108914157B (en) 2018-07-12 2018-07-12 A kind of technique that high antimonial lead separates lead, antimony, silver

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810765556.8A CN108914157B (en) 2018-07-12 2018-07-12 A kind of technique that high antimonial lead separates lead, antimony, silver

Publications (2)

Publication Number Publication Date
CN108914157A CN108914157A (en) 2018-11-30
CN108914157B true CN108914157B (en) 2019-08-30

Family

ID=64411831

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810765556.8A Active CN108914157B (en) 2018-07-12 2018-07-12 A kind of technique that high antimonial lead separates lead, antimony, silver

Country Status (1)

Country Link
CN (1) CN108914157B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1141966A (en) * 1995-05-15 1997-02-05 北美埃尔夫爱托化学股份有限公司 Electrolytic metallurgy of lead
CN104746098A (en) * 2015-03-24 2015-07-01 昆明理工大学 Electrolyte and method for electrolyzing and refining crude lead

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101343691B (en) * 2008-09-01 2010-06-02 中南大学 Pollution-free separation method for plumbum and silver
CN102676822B (en) * 2011-03-11 2014-01-01 深圳市格林美高新技术股份有限公司 Burning-free non-cyaniding method for treating waste printed circuit board
CN102690951B (en) * 2012-06-20 2014-06-04 郴州市金贵银业股份有限公司 Method for removing lead and antimony from alkaline-leaching dearsenification solution of lead anode slime
CN103290429A (en) * 2013-06-17 2013-09-11 湖南省桂阳银星有色冶炼有限公司 Method for electrolyzing high-content low-grade lead bullion
CN104141057B (en) * 2014-07-28 2015-08-05 蒙自矿冶有限责任公司 The method of bismuth is reclaimed in a kind of precious metals containing lead
CN107177865B (en) * 2017-06-13 2018-09-28 中南大学 Process for separating lead and bismuth from high-bismuth lead alloy
CN107574300A (en) * 2017-08-29 2018-01-12 山东恒邦冶炼股份有限公司 A kind of mixed processing technique of copper, lead anode slurry

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1141966A (en) * 1995-05-15 1997-02-05 北美埃尔夫爱托化学股份有限公司 Electrolytic metallurgy of lead
CN104746098A (en) * 2015-03-24 2015-07-01 昆明理工大学 Electrolyte and method for electrolyzing and refining crude lead

Also Published As

Publication number Publication date
CN108914157A (en) 2018-11-30

Similar Documents

Publication Publication Date Title
JP5469157B2 (en) Electrochemical process for recovering valuable metal iron and sulfuric acid from iron-rich sulfate waste, mining residues, and pickling liquors
CN101575715B (en) Method for extracting valuable metals from electronic waste
CN104630826B (en) Technique for recovering tin from tin anode sludge
AU2016318302B2 (en) Optimized ore processing using molten salts for leaching and thermal energy source
CN102041393A (en) Silver anode mud treatment process
CN107177865B (en) Process for separating lead and bismuth from high-bismuth lead alloy
CN104046785A (en) Method for processing waste copper/iron-based diamond tool bit
CN107557589B (en) A method of recycling valuable metal from zinc hydrometallurgy copper-cadmium slag
CN104831315A (en) Novel process for recovering antimony from antimony-containing gold concentrate
JP5250683B2 (en) Recovery method of valuable metals from Pb-free waste solder
JPH11506808A (en) Copper matte electrowinning method
CN108193046B (en) The optimal recovery method of metal in a kind of tin anode mud
CN109971964A (en) A kind of processing method of the high tin high-copper regeneration tin anode mud of high palladium
PL111879B1 (en) Method of recovery of copper from diluted acid solutions
CN104087971B (en) Method for treating lead matte
CN106978538B (en) Treatment method of high-bismuth lead anode mud or bismuth slag
JP2009167451A (en) Method for electrolytically extracting copper
CN108517410A (en) A kind of method of metallic copper in hydrometallurgical recovery printed wiring board (PCB)
CN104746105A (en) Device and method for separating antimony-containing alloy
CN108914157B (en) A kind of technique that high antimonial lead separates lead, antimony, silver
US11566333B2 (en) Method for cleanly extracting metallic silver
CN108034821B (en) A kind of wet processing process of earth of positive pole smelting slag
RU2510669C2 (en) Method of extracting noble metals from wastes
Yang et al. The separation and electrowinning of bismuth from a bismuth glance concentrate using a membrane cell
JP2007224400A (en) Method of recovering electrolytic iron from aqueous ferric chloride solution

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A process for separating lead, antimony and silver from high antimony lead alloy

Effective date of registration: 20210319

Granted publication date: 20190830

Pledgee: Bank of Changsha Limited by Share Ltd. Yiyang branch

Pledgor: SHINY MATERIALS SCIENCE & TECHNOLOGY Inc.

Registration number: Y2021980001851

PC01 Cancellation of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20220411

Granted publication date: 20190830

Pledgee: Bank of Changsha Limited by Share Ltd. Yiyang branch

Pledgor: SHINY MATERIALS SCIENCE & TECHNOLOGY Inc.

Registration number: Y2021980001851