CN108070712B - A kind of silver is electrolysed the recovery method of valuable metal in mother liquor purification slag - Google Patents
A kind of silver is electrolysed the recovery method of valuable metal in mother liquor purification slag Download PDFInfo
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- CN108070712B CN108070712B CN201711348569.7A CN201711348569A CN108070712B CN 108070712 B CN108070712 B CN 108070712B CN 201711348569 A CN201711348569 A CN 201711348569A CN 108070712 B CN108070712 B CN 108070712B
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- slag
- valuable metal
- mother liquor
- recovery
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- 239000002893 slag Substances 0.000 title claims abstract description 58
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 49
- 238000000746 purification Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 239000012452 mother liquor Substances 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000002386 leaching Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 3
- 229910000367 silver sulfate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000009867 copper metallurgy Methods 0.000 description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical group [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 238000009491 slugging Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—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
- 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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B30/06—Obtaining bismuth
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- 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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a kind of recovery methods of valuable metal in silver electrolysis mother liquor purification slag, comprising: the purification slag is calcined to 1-3h at 450-550 DEG C of temperature except nitre；Sulfuric acid solution is added in except the purification slag after nitre, stirs, leachate and leached mud is obtained by filtration in heating；Leachate and leached mud are handled, recycling obtains valuable metal.The rate of recovery of each valuable metal is all higher, the rate of recovery of copper is 97% or more, silver, bismuth, lead the rate of recovery respectively 99%, 97%, 96% or more, method environmental pollution of the invention is small, discharges without " three wastes ", and process is simple, it is easy to operate, operating cost is low, and synthetical recovery degree is high, has stronger practicability.
Description
Technical field
The invention belongs to smelting field of nonferrous metal, and in particular to a kind of silver is electrolysed time of valuable metal in mother liquor purification slag
Receiving method.
Background technique
The electrorefining processes of silver, are to make anode with thick silver, titanium plate makees cathode, silver nitrate AgNO3Aqueous solution makees electrolyte,
In DC voltage 2-3V, electric current 250-300A/m2Under conditions of refine available 99.99% silver, while the pH value of electrolyte
It is by addition acid adjustment.Thick silver before electrolysis, generally all containing the various metals such as a small amount of lead Pb, copper Cu, bismuth Bi, antimony Sb at
Divide impurity.In electrolytic process, these impurity enter electrolyte, and with the extension of electrolysis activity duration, impurity is constantly assembled
Electrolyte is polluted in the electrolytic solution.Therefore people are dedicated to controlling the pollution of electrolyte and changing its component always, but are derived from
The complex chemical composition of thick silver and cannot completely effectively avoid, during entire electrolyte use, pollution level can be increasingly
Greatly, after impurity is more than certain content in the electrolytic solution, electrolyte cannot then reuse and it is to be replaced fall.Using dirty
The shortcomings that electrolyte of dye, also resides in, and the impurity in electrolyte can be absorbed in the lattice for being mixed into and silver-colored crystal being precipitated, to reduce
The quality of electrolytic silver requires contaminated electrolyte carrying out purified treatment thus.
Traditional silver electrolysis mother liquor purification method is that alkali or silver oxide tune pH are added into mother liquor, makes lead, bismuth, copper, palladium etc.
Most impurity hydrolytic precipitations, also hydrolytic precipitation, such slag charge are electrolysed mother liquor purification slag we term it silver-colored to part silver therewith,
Above-mentioned metal mainly exists in the form of hydroxide and oxide in this purification slag.Valuable metal in purification slag is returned
It receives to recycle and not only reduces production cost, also economize on resources, it is environmentally friendly.
Country's Processing Ag electrolysis mother liquor purification slag usually directly returns to big converter and lead anode slurry mixed smelting at present, should
For technique on the one hand there are the production cycle is long, valuable metal synthetical recovery degree is low, on the other hand, does not open a way, causes to copper
Copper is constantly accumulated in system, is seriously affected the electrorefining processes of silver, is seriously threatened quality of cathode silver power.Therefore one kind is developed
Silver electrolysis mother liquor purification slag is effectively treated, the technique for making copper be opened a way has important practical significance.
Grant number CN104962749A patent of invention discloses a kind of processing method of heavy copper ashes of silver electrolysis mother liquor alkalinity, should
The technology path of technique is that hydrochloric acid is added into heavy copper ashes, and copper, bismuth are with the leachate that enters of chlorate, and silver, lead are with silver chlorate, chlorine
The form for changing lead enters in silver-colored slag, then adds the heavy copper of piece alkali neutralization to obtain copper ashes into leachate, copper metallurgy industry is sent to recycle copper.Silver
Slag is by entering silver converter recycling silver after conversion dechlorination.Being evaporated to the waste liquid containing villaumite generated in the process crystallizes industrial
Salt.The technique there are process flows long, trivial operations, high production cost, metal recovery rate are low etc., and only carry out to silver and copper
Recycling, other metals are not recycled, enter the features such as system is high to equipment anticorrosion requirement additionally, due to chloride ion.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide valuable metal in a kind of silver electrolysis mother liquor purification slag
Recovery method.
The present invention provides a kind of silver-colored recovery method for being electrolysed valuable metal in mother liquor purification slag, includes the following steps:
A) purification slag is calcined except nitre at 450-550 DEG C of temperature, is obtained except nitre slag；
B) it to except sulfuric acid solution is added in nitre slag, stirs, leachate and leached mud is obtained by filtration, and the sulfuric acid is molten in heating
Liquid concentration is 120-180g/L, and sulfuric acid solution is 4-6mL:1g with the volume mass ratio except nitre slag, and heating temperature is 40-85 DEG C；
C) leachate directly send eddy flow electrodeposition process to carry out the heavy copper of electrodeposition, obtains cathode copper products, leached mud is sent to silver
Valuable metal of the smelting system synthetical recovery including Pb, Ag, Bi.
Preferably, purification slag described in step a) includes the substance of following weight percent content: Cu15-40%, Ag8-
45%, Bi0.2-8.0%, Pb0.1-2%.
Preferably, calcination time described in step a) is 1-3h.
Preferably, mixing speed described in step b) is 500-700r/min.
Preferably, the reaction time described in step b) is 1-1.5h.
The beneficial effects of the present invention are:
1. replacing the hydrochloric acid solution in patent CN104962749A to leach using sulfuric acid solution in the present invention, it is omitted
Subsequent dechlorination reaction realizes the separation of metallic copper and the valuable metal including bismuth, and the metal ion in leachate is only
There is copper, it is simple to the post-processing of leachate.
2. method of the invention is suitable for recycling valuable metal, the recycling of each valuable metal from silver electrolysis mother liquor purification slag
Rate is all higher, the rate of recovery of copper 97% or more, silver, bismuth, lead the rate of recovery respectively 99%, 97%, 96% or more.
3. method environmental pollution of the invention is small, to be discharged without " three wastes ", process is simple, and easy to operate, operating cost is low,
Synthetical recovery degree is high, has stronger practicability.
Reaction principle of the invention are as follows: using silver electrolysis mother liquor purification slag as raw material, carry out calcining except nitre, pass through control technology
Condition makes the silver nitrate contained in purification slag, copper nitrate remove nitrate ion therein by pyrolytic.It will be calcined
Purification slag is leached with sulfuric acid, and copper oxide and sulfuric acid reaction generate copper sulphate and enter in leachate, and silver, bismuth, lead are respectively with sulphur
Sour silver, bismuth sulfate, lead sulfate form stay in leached mud.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference
Technical solution of the present invention is clearly and completely described in attached drawing.
Embodiment 1
Process flow chart is as shown in Figure 1, the specific steps are as follows:
200g silver is electrolysed mother liquor purification slag (Cu32.05%；Ag12.33%；Bi1.51%；Pb0.83%) it is packed into oxidation
In aluminium crucible, be then placed in Muffle furnace and calcined, adjust 480 DEG C of temperature, calcine to take out after 1.5h and obtain except nitre slag, then plus
Enter the sulfuric acid solution that concentration is 120g/L to be leached, sulfuric acid solution is 6:1, i.e. 1g with the volume mass ratio (mL/g) except nitre slag
Except 6mL sulfuric acid solution is added in nitre slag, under temperature 45 C, leaching is obtained by filtration after reacting 1.25h in mixing speed 600r/min
Liquid and leached mud.
Copper in purification slag enters leachate in the form of copper sulphate, and silver, bismuth, lead are respectively with silver sulfate, bismuth sulfate, sulfuric acid
The form of lead stays in leached mud, obtains copper leaching rate through assay and is up to 98.75%, cupric leachate directly send eddy flow electrodeposition
Process carries out the heavy copper of electrodeposition and obtains cathode copper products, and purity 99.972% meets the requirement of national standard 1# tough cathode product quality, electricity
Product waste liquid returns to leaching tanks and is recycled as leaching solvent.Leached mud returns silver-colored smelting system recycling Ag, Bi, Pd valuable element.
Embodiment 2
200g silver is electrolysed mother liquor purification slag (Cu35.09%；Ag11.79%；Bi1.05%；Pb0.67%) it is packed into oxidation
It in aluminium crucible, is then placed in Muffle furnace and is calcined, adjust 550 DEG C of temperature, taking-up obtains then being added except nitre slag after calcining 1h
Concentration is that the sulfuric acid solution of 180g/L is leached, and sulfuric acid solution is 4:1 with the volume mass ratio (mL/g) except nitre slag, i.e. 1g is removed
In nitre slag be added 4mL sulfuric acid solution, at 85 DEG C of temperature, mixing speed 700r/min, react 1h after be obtained by filtration leachate and
Leached mud.
Copper in purification slag enters leachate in the form of copper sulphate, and silver, bismuth, lead are respectively with silver sulfate, bismuth sulfate, sulfuric acid
The form of lead stays in leached mud, obtains copper leaching rate through assay and is up to 98.93%, cupric leachate directly send eddy flow electrodeposition
Process carries out the heavy copper of electrodeposition and obtains cathode copper products, and purity 99.967% meets the requirement of national standard 1# tough cathode product quality, electricity
Product waste liquid returns to leaching tanks and is recycled as leaching solvent.Leached mud returns silver-colored smelting system recycling Ag, Bi, Pd valuable element.
Embodiment 3
200g silver is electrolysed mother liquor purification slag (Cu28.63%；Ag33.26%；Bi6.44%；Pb1.64%) it is packed into oxidation
It in aluminium crucible, is then placed in Muffle furnace and is calcined, adjust 450 DEG C of temperature, taking-up obtains then being added except nitre slag after calcining 3h
Concentration is that the sulfuric acid solution of 150g/L is leached, and sulfuric acid solution is 5:1 with the volume mass ratio (mL/g) except nitre slag, i.e. 1g is removed
5mL sulfuric acid solution is added in nitre slag, at 40 DEG C of temperature, leachate is obtained by filtration after reacting 1.5h in mixing speed 500r/min
And leached mud.
Copper in purification slag enters leachate in the form of copper sulphate, and silver, bismuth, lead are respectively with silver sulfate, bismuth sulfate, sulfuric acid
The form of lead stays in leached mud, obtains copper leaching rate through assay and is up to 97.96%, cupric leachate directly send eddy flow electrodeposition
Process carries out the heavy copper of electrodeposition and obtains cathode copper products, and purity 99.979% meets the requirement of national standard 1# tough cathode product quality, electricity
Product waste liquid returns to leaching tanks and is recycled as leaching solvent.Leached mud returns silver-colored smelting system recycling Ag, Bi, Pd valuable element.
Comparative example 1
Mother liquor purification slag (Cu20.56% is electrolysed to 200g silver；Ag37.34%；Bi1.59%；Pb0.74% it is added in) dense
Degree is that the hydrochloric acid solution of 20g/L is leached, and the volume mass ratio (mL/g) of hydrochloric acid solution and purification slag slag is 10:1, i.e. 1g is net
10mL hydrochloric acid solution is added in slugging, at 40 DEG C of temperature, leachate is obtained by filtration after reacting 0.5h in mixing speed 700r/min
And leached mud.
Kocide SD in purification slag, which reacts to obtain copper chloride with hydrochloric acid, to be stayed in leachate, and silver oxide is reacted with hydrochloric acid
It obtains silver nitride precipitation to stay in leached mud, is added sodium hydroxide into leachate, keep pH of leaching solution in 6-7, it is to be precipitated
Gained filter residue is Kocide SD by filtering after completely, is sent to copper metallurgy industry recycling copper, gained filtrate evaporative crystallization obtains industry
Salt；Sodium carbonate liquor is added into leached mud, wherein the quality of sodium carbonate be theoretically with quality needed for chlorination silver reaction,
It is 2:1 that liquid, which consolidates mass ratio, and reaction temperature is 30 DEG C, is filtered after reacting 1h, obtains dechlorination silver slag silver carbonate, gained filtrate evaporation knot
Crystalline substance obtains Nacl；What obtained dechlorination silver slag was added to the precious metals containing lead that blows divides silver stove to blow, and obtains meeting electrorefining
Thick silver.
It is used from the rate of recovery and comparative example 1 for recycling each metal in silver electrolysis mother liquor purification slag using method of the invention
Process ration such as the following table 1.
1 silver medal of table is electrolysed the comparison of each recovery rate of valuable metals in mother liquor purification slag
It can be seen that using each metal in method recycling silver electrolysis mother liquor purification slag of the invention, respectively from data in upper table
The rate of recovery of metal has all reached 96% or more, and compared with comparative example 1, the rate of recovery of copper and silver increases, and further
The lead and bismuth in purification slag are recycled.
Claims (3)
1. the recovery method of valuable metal in a kind of silver electrolysis mother liquor purification slag, which is characterized in that include the following steps:
A) purification slag is calcined except nitre, calcination time 1-3h at 550 DEG C of temperature, is obtained except nitre slag, the purification slag
Substance including following weight percent content: Cu15-40%, Ag8-45%, Bi0.2-8.0%, Pb0.1-2%；
B) it to except sulfuric acid solution is added in nitre slag, stirs, leachate and leached mud is obtained by filtration, and the sulfuric acid solution is dense in heating
Degree is 120-180g/L, and sulfuric acid solution is 4-6mL:1g with the volume mass ratio except nitre slag, and heating temperature is 40-85 DEG C；
C) leachate directly send eddy flow electrodeposition process to carry out the heavy copper of electrodeposition, obtains cathode copper products, leached mud is sent to silver and is smelted
Valuable metal of the system synthetical recovery including Pb, Ag, Bi.
2. the recovery method of valuable metal in silver electrolysis mother liquor purification slag as described in claim 1, which is characterized in that step b)
Described in mixing speed be 500-700r/min.
3. such as the recovery method of valuable metal in the described in any item silver electrolysis mother liquor purification slags of claim 1-2, feature exists
In the reaction time is 1-1.5h in step b).
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| CN102690947A (en) * | 2012-05-24 | 2012-09-26 | 赤峰中色锌业有限公司 | Smelting process of silver concentrate |
| CN103352116A (en) * | 2013-04-07 | 2013-10-16 | 昆明理工大学 | Method for recovering zinc from high iron and high lead leaching residue through microwave-ultrasonic wave combination |
| CN104451172A (en) * | 2014-08-26 | 2015-03-25 | 云南罗平锌电股份有限公司 | Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags |
| CN105543479A (en) * | 2015-12-16 | 2016-05-04 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method of bismuth matte |
| CN106756069A (en) * | 2017-02-08 | 2017-05-31 | 陕西理工学院 | A kind of method that valuable metal is reclaimed in the waste residue from zinc abstraction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4312969B2 (en) * | 2001-03-02 | 2009-08-12 | 東京電力株式会社 | Reprocessing method of spent nuclear fuel |
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|---|---|---|---|---|
| CN101440434A (en) * | 2008-12-17 | 2009-05-27 | 昆明金湖冶金有限公司 | Technique for extracting copper from high-calcium high-magnesium cupric sulfide by wet method |
| CN102690947A (en) * | 2012-05-24 | 2012-09-26 | 赤峰中色锌业有限公司 | Smelting process of silver concentrate |
| CN103352116A (en) * | 2013-04-07 | 2013-10-16 | 昆明理工大学 | Method for recovering zinc from high iron and high lead leaching residue through microwave-ultrasonic wave combination |
| CN104451172A (en) * | 2014-08-26 | 2015-03-25 | 云南罗平锌电股份有限公司 | Method for comprehensively recovering valuable metals from zinc hydrometallurgy high-temperature purification slags |
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