CN1114361A - Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime - Google Patents
Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime Download PDFInfo
- Publication number
- CN1114361A CN1114361A CN94107754A CN94107754A CN1114361A CN 1114361 A CN1114361 A CN 1114361A CN 94107754 A CN94107754 A CN 94107754A CN 94107754 A CN94107754 A CN 94107754A CN 1114361 A CN1114361 A CN 1114361A
- Authority
- CN
- China
- Prior art keywords
- leaching
- silver
- residue
- lead
- liquid
- 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.)
- Pending
Links
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 18
- 229910052745 lead Inorganic materials 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 238000002386 leaching Methods 0.000 claims description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 37
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000382 dechlorinating effect Effects 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- LIRDHUDRLFDYAI-UHFFFAOYSA-H iron(3+);trisulfite Chemical compound [Fe+3].[Fe+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O LIRDHUDRLFDYAI-UHFFFAOYSA-H 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229960000443 hydrochloric acid Drugs 0.000 claims 4
- 235000011167 hydrochloric acid Nutrition 0.000 claims 4
- 230000008569 process Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 3
- MKKUILJGMGDMRS-UHFFFAOYSA-L [Cl-].[Na+].Cl.Cl(=O)(=O)[O-].[Na+] Chemical compound [Cl-].[Na+].Cl.Cl(=O)(=O)[O-].[Na+] MKKUILJGMGDMRS-UHFFFAOYSA-L 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 239000011133 lead Substances 0.000 description 20
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002140 antimony alloy Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The process for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime features use of hydrochloric acid to extract Sb and Cu, sodium chlorate-hydrochloric acid-sodium chloride to extract Au and ammonia to extract sponge Ag with Ag content of 99.3% for direct production of analytically pure silve nitrate. Its advantages include shorter extraction period, high extraction effect, low cost, high direct yield of sponge silver up to over 96% and low pollution.
Description
The invention relates to a method for recovering silver, gold, antimony, copper and lead from lead anode slime, belonging to the technical field of hydrometallurgy.
The recovery of associated silver from anode slime of nonferrous metals such as lead, copper, nickel and the like has become an important source of silver, and China always adopts the traditional pyrometallurgical treatment of the anode slime for many years. The pyrogenic process has the characteristics of high processing capacity, strong raw material adaptability and the like. But also has the defects of long process flow, more return slag, large investment, long production period and the like. And a large amount of flue gas such as arsenic, lead, antimony, selenium and the like is discharged in the process of reducing smelting and oxidizing refining by a pyrogenic process, so that the environment is seriously polluted. In recent years, a plurality of scientific research institutes and smelting plants in China research out the method for treating the anode mud by the wet method, the process flow is simpler, the number of intermediate products is less, the investment for building the plant is less, the capital turnover is fast, and the useful metals in the anode mud can be effectively and comprehensively utilized. For example, chinese patent 90109944.9 discloses a method for preparing silver nitrate and recovering copper, lead and antimony from lead anode slime, which comprises leaching the filter residue after nitric acid leaching with hydrochloric acid, precipitating lead with sulfuric acid, hydrolyzing hydrochloric acid leaching solution, washing the filter residue obtained by hydrolysis with alkali, precipitating silver with hydrochloric acid, ammonia leaching, complexing, reducing, etc. It also has the defects of complex working procedure, large consumption of nitric acid, high cost, low recovery rate of silver and the like.
The invention aims to provide a method for recovering silver, gold, antimony, copper and lead from various lead anode slime, which has the advantages of low acid consumption, low cost, high silver recovery rate and low pollution and can overcome the defects in the prior art.
The purpose of the invention is realized by the following technical solution: the method is carried out according to the following steps in sequence:
1. leaching for 1-2 hours at 60-90 ℃ by using hydrochloric acid with the liquid-solid ratio of 3: 1-6: 1 and the 3N-5.5N, removing copper and antimony in the anode mud, recovering antimony through hydrolysis, and replacing copper with scrap iron;
2. adding sodium chlorate accounting for 3-10% of the weight of the residue into the filter residue, leaching the filter residue for 1-3 hours at 60-90 ℃ by using hydrochloric acid accounting for 0.3-1N and sodium chloride accounting for 2-12% of the weight of the residue in a liquid-solid ratio of 3: 1-5: 1, filtering, and reducing the filtrate by using oxalic acid or ferric sulfite or sulfur dioxide to obtain sponge gold;
3. leaching the sodium chlorate leaching residue for 1-3 hours at 20-60 ℃ by using 3-5N ammonia water with the liquid-solid ratio of 3: 1-6: 1, filtering, adding 1.2-2 times of excessive hydrazine hydrate into the filtrate, and reducing to obtain sponge silver, wherein the filter residue is lead dichloride containing 56-70% of lead.
4. Dissolving sponge silver in reagent-grade nitric acid, adsorbing with dechlorinating agent such as activated carbon or activated aluminum, filtering, evaporating, crystallizing, filtering, and oven drying to obtain analytically pure silver nitrate.
The attached drawing is a process flow chart of the invention.
The technical solution of the present invention will now be further described with reference to the accompanying drawings.
First, hydrochloric acid soaks antimony, copper
The antimony in the lead anode slime is mainly in the form of metallic antimony and antimony trioxide, and only a small amount of antimony exists in the form of antimony alloy. Adding hydrochloric acid with the liquid-solid ratio of 5: 1 and the concentration of 4N into the lead anode slime, and leaching for 1-1.5 hours at the temperature of 75-90 ℃. In the leaching process, antimony trioxide reacts with hydrochloric acid to form an antimony trichloride solution such as
Metallic antimony also reacts with hydrochloric acid to form an antimony trichloride solution, e.g.
The copper in the anode slime is mainly present as metallic copper and partly as basic copper carbonate, the copper and basic copper carbonate react with hydrochloric acid to form cuprous chloride solution, e.g. copper chloride
In the process, more than 95 percent of antimony and copper are leached, and antimony and copper chloride are separated from silver-containing filter residue through vacuum filtration, wherein the leaching rate of silver is lower than 1 percent.
Chlorination gold leaching
After antimony and copper are leached by hydrochloric acid, the leaching residue mainly contains silver, gold and lead compounds, sodium chlorate accounting for 4-6% of the weight of the residue is added into hydrochloric acid medium, sodium chloride accounting for 6-10% of the weight of the residue and hydrochloric acid with the concentration of 0.5-0.6N and the liquid-solid ratio of 4: 1 are added to leach gold, the leaching temperature is 75-35 ℃, and the leaching time is 1.5-2.5 hours. The following reactions take place in the process:
the action of sodium chlorate and hydrochloric acid produces hypochlorous acid, which is immediately decomposed to produce active oxygen to oxidize gold and silver. At the moment, gold forms complex ions to enter the solution, and oxidized silver is combined with chlorine to generate silver chloride precipitate with low solubility product to enter slag. The concentration of industrial sodium chloride is about 40g/L and the concentration of hydrochloric acid medium is 0.5N-0.6N when gold leaching is carried out by chlorination, so that the [ AgCl]is difficult to form2]So silver is hardly leached out. During chlorination, the copper content in the slag is further reduced. The purpose of chlorination is to convert substantially all of the silver to silver chloride.
Three, ammonia leaching process
After chlorination, most of silver in the slag is converted into silver chloride, lead is converted into lead dichloride, ammonia water with the concentration of 3-4N and the liquid-solid ratio of 5: 1 is added into the slag for secondary ammonia leaching, the leaching temperature is 40-55 ℃, and the time is 1.2-1.8 hours. And (3) carrying out secondary ammonia leaching on the filter residue after the primary ammonia leaching to ensure that the silver chloride is completely converted into silver-ammonia complex ions, wherein the reaction is as follows:
since the lead dichloride is not complexed with the ammonia water, the ammonia leaching solution is Ag (NH)3)2 +And the filtrate is lead dichloride containing 56-70% of lead.
Four, silver reduction process
Ag (NH) produced after complexing reaction of silver chloride3)2Reducing hydrazine hydrate (also called hydrazine hydrate) with 1.5 times excess in a stainless steel reaction kettleReaction under
Filtering the reduced sponge silver, washing the sponge silver by secondary distilled water, and drying the sponge silver to obtain the sponge silver with the silver content of more than 99.0 percent.
The sponge silver is washed and then reacts with reagent-grade nitric acid to generate silver nitrate, and the reaction formula is as follows:
adding 11-13 liters of 65% reagent-grade nitric acid into 20 liters of secondary distilled water in a reaction kettle to react with 8-11 kilograms of sponge silver, adsorbing impurities such as chloride ions in the solution by dechlorinating agents such as activated carbon or activated aluminum, and evaporating, crystallizing, filtering and drying to obtain the reagent-grade silver nitrate.
The results of the pilot test are shown in the following table:
| name of material | Weight of material Kg | Filtrate L | Filtering residue Kg | Grade of slag (%) | Content of solution (%) | Leaching rate (%) | Recovery (%) | ||||||||
| Cu | Sb | Ag | Au (g/r) | Cu | Sb | Ag | Au | Cu | Sb | Ag | Au | ||||
| Anode mud | 100 | 6.1 | 9.5 | 16.4 | 252 | ||||||||||
| Copper-leaching antimony slag | 43.7 | 0.04 | 0.34 | 37.6 | 538 | ||||||||||
| Copper and antimony leaching solution | 490 | 12.4 | 19.1 | 99.7 | 98.4 | ||||||||||
| Chlorination slag | 40 | 0.04 | 0.31 | 21 | |||||||||||
| Chlorination solution | 380 | 0.64 | 96.5 | ||||||||||||
| Ammonia leaching residue | 25.3 | Pb 62.1 | 0.1 | ||||||||||||
| Ammonia leaching solution | 470 | 33.5 | |||||||||||||
| Sponge silver | 15.9 | 99.3 | 96.3 | ||||||||||||
| Reducing liquid | 460 | 0.1 | |||||||||||||
The invention overcomes the defects in the background technology, improves the leaching effect of copper and antimony by using hydrochloric acid as a leaching agent, does not need to add an oxidant, and can effectively separate the copper and the antimony from silver, gold and lead. In the process of leaching gold by sodium chlorate-hydrochloric acid-sodium chloride, hypochlorous acid generated after the action of sodium chlorate and hydrochloric acid is immediately decomposed into active oxygen, gold and silver are oxidized, gold forms complex ions and enters the solution, crude gold is reduced by ferric sulfite, the recovery rate of gold is 96.5%, silver and chlorine are combined to generate silver chloride precipitate with low solubility product, and the silver chloride precipitate exists in slag and is ready for ammine complexing silver. And reducing the silver-ammonia complex generated after complexing the silver chloride into sponge silver by using hydrazine hydrate which is excessive by 1.5 times, wherein the direct recovery rate of the silver is more than 96 percent, and the ammonia leaching residue is lead dichloride containing 56 to 70 percent of lead. The sponge silver is washed, dissolved in nitric acid, and adsorbed and filtered by dechlorinating agent such as active carbon or active aluminum to obtain analytically pure or industrial pure silver nitrate. The method has the advantages of short leaching time, good leaching effect, low acid consumption, low cost, less pollution, capability of producing the silver nitrate of analytical pure grade meeting the GB 670-86 standard, and capability of producing the silver nitrate of the sponge silver with the silver content of more than 99.3 percent, and is suitable for treating various lead anode slime.
Claims (4)
1. A method for recovering silver, gold, antimony, copper and lead from lead anode slime is characterized by comprising the following steps in sequence:
1.1, leaching for 1-2 hours at 60-90 ℃ by using hydrochloricacid with the liquid-solid ratio of 3: 1-6: 1 and the 3N-5.5N, removing copper and antimony in anode mud, recovering antimony through hydrolysis, and replacing copper with scrap iron;
1.2 adding sodium chlorate accounting for 3-10% of the weight of the residue into the filter residue, leaching the filter residue for 1-3 hours at 60-90 ℃ by using hydrochloric acid accounting for 0.3-1N and sodium chloride accounting for 2-12% of the weight of the residue in a liquid-solid ratio of 3: 1-5: 1, filtering, and reducing the filtrate into sponge gold by using oxalic acid, ferric sulfite or sulfur dioxide;
1.3, leaching sodium chlorate leaching residue for 1-3 hours at 20-60 ℃ for two times by using ammonia water with a liquid-solid ratio of 3: 1-6: 1 and 3N-5N, filtering, adding 1.2-2 times of excessive hydrazine hydrate into filtrate, reducing to obtain sponge silver, and obtaining filter residue which is lead dichloride containing 56-70% of lead;
1.4 dissolving sponge silver in reagent-grade nitric acid, adsorbing and filtering with dechlorinating agent such as activated carbon or activated aluminum, evaporating, crystallizing, filtering, and oven drying to obtain analytically pure silver nitrate.
2. The method as claimed in claim 1, wherein the liquid-solid ratio of the hydrochloric acid leaching in 1.1 is 4: 1-6: 1, the concentration is 4N-5N, and the leaching temperature is preferably 75-90 ℃.
3. The method as set forth in claim 1, wherein the weight of said sodium chlorate in 1.2 is 5-10% of the weight of the residue, the concentration of hydrochloric acid is 0.5-0.8N, the liquid-solid ratio is 3.5: 1-4.5: 1, the amount of sodium chloride is 4-11% of the weight of the residue, the leaching temperature is 70-90 ℃, and the leaching time is 1-2.5 hours.
4. The method according to claim 1, wherein the ammonia water concentration of 1.3 is 3 to 4N, the liquid-solid ratio is 4: 1 to 5: 1, and the ammonia leaching is carried out at 30 to 55 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107754A CN1114361A (en) | 1994-06-28 | 1994-06-28 | Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94107754A CN1114361A (en) | 1994-06-28 | 1994-06-28 | Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114361A true CN1114361A (en) | 1996-01-03 |
Family
ID=5033196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107754A Pending CN1114361A (en) | 1994-06-28 | 1994-06-28 | Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1114361A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045794C (en) * | 1996-09-16 | 1999-10-20 | 昆明贵金属研究所 | Method for extracting gold, silver and valuable metals from high-arsenic lead anode mud |
| EP1061143A1 (en) * | 1999-06-18 | 2000-12-20 | W.C. Heraeus GmbH & Co. KG | Method for solubilizing noble metalls |
| EP1061142A1 (en) * | 1999-06-18 | 2000-12-20 | W.C. Heraeus GmbH & Co. KG | Method for dissolving metals |
| CN101787440A (en) * | 2010-03-29 | 2010-07-28 | 广西华锡集团股份有限公司 | Method for wet processing of high antimony-lead anode mud |
| CN102305843A (en) * | 2011-03-11 | 2012-01-04 | 肇庆理士电源技术有限公司 | Method for quickly identifying whether plumbum or plumbum and calcium alloy contains antimony |
| CN102925703A (en) * | 2012-11-22 | 2013-02-13 | 湖南稀土金属材料研究院 | Method for recycling valuable metals from lead anode slime |
| CN101760624B (en) * | 2009-11-09 | 2013-05-29 | 广东奥美特集团有限公司 | Method for extracting gold by using circuit board anode mud |
| CN103954524A (en) * | 2013-12-11 | 2014-07-30 | 西部矿业股份有限公司 | Simple and rapid method for accurate determination of silver in lead anode mud |
| CN107746955A (en) * | 2017-11-01 | 2018-03-02 | 北京工业大学 | A kind of method of rough lead chloride atom economy method separating-purifying |
| CN110205500A (en) * | 2019-06-18 | 2019-09-06 | 山东黄金冶炼有限公司 | The removal methods of impurity in a kind of reduction bronze |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN116103506A (en) * | 2021-11-10 | 2023-05-12 | 上颍股份有限公司 | Environment-friendly water-soluble gold reducing agent and gold refining treatment method |
| CN117385187A (en) * | 2023-10-31 | 2024-01-12 | 中节能工程技术研究院有限公司 | A comprehensive treatment method for waste circuit board fire smelting smoke and soot |
| CN117431407A (en) * | 2023-10-20 | 2024-01-23 | 福建紫金矿冶测试技术有限公司 | A method for processing and recovering silver from gold smelting silver slag |
-
1994
- 1994-06-28 CN CN94107754A patent/CN1114361A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045794C (en) * | 1996-09-16 | 1999-10-20 | 昆明贵金属研究所 | Method for extracting gold, silver and valuable metals from high-arsenic lead anode mud |
| EP1061143A1 (en) * | 1999-06-18 | 2000-12-20 | W.C. Heraeus GmbH & Co. KG | Method for solubilizing noble metalls |
| EP1061142A1 (en) * | 1999-06-18 | 2000-12-20 | W.C. Heraeus GmbH & Co. KG | Method for dissolving metals |
| US6440376B1 (en) | 1999-06-18 | 2002-08-27 | W. C. Heraeus Gmbh & Co. Kg. | Method for dissolving noble metals out of segregated ores containing noble metals |
| CN101760624B (en) * | 2009-11-09 | 2013-05-29 | 广东奥美特集团有限公司 | Method for extracting gold by using circuit board anode mud |
| CN101787440A (en) * | 2010-03-29 | 2010-07-28 | 广西华锡集团股份有限公司 | Method for wet processing of high antimony-lead anode mud |
| CN101787440B (en) * | 2010-03-29 | 2011-08-10 | 广西华锡集团股份有限公司 | Method for wet processing of high antimony-lead anode mud |
| CN102305843A (en) * | 2011-03-11 | 2012-01-04 | 肇庆理士电源技术有限公司 | Method for quickly identifying whether plumbum or plumbum and calcium alloy contains antimony |
| CN102925703A (en) * | 2012-11-22 | 2013-02-13 | 湖南稀土金属材料研究院 | Method for recycling valuable metals from lead anode slime |
| CN103954524A (en) * | 2013-12-11 | 2014-07-30 | 西部矿业股份有限公司 | Simple and rapid method for accurate determination of silver in lead anode mud |
| CN103954524B (en) * | 2013-12-11 | 2017-02-15 | 西部矿业股份有限公司 | Simple and rapid method for accurate determination of silver in lead anode mud |
| CN107746955B (en) * | 2017-11-01 | 2019-03-22 | 北京工业大学 | A kind of method for separating and purifying crude lead chloride atomic economic method |
| CN107746955A (en) * | 2017-11-01 | 2018-03-02 | 北京工业大学 | A kind of method of rough lead chloride atom economy method separating-purifying |
| CN110205500A (en) * | 2019-06-18 | 2019-09-06 | 山东黄金冶炼有限公司 | The removal methods of impurity in a kind of reduction bronze |
| CN110205500B (en) * | 2019-06-18 | 2021-09-17 | 山东黄金冶炼有限公司 | Method for removing impurities in reduced gold powder |
| CN116103506A (en) * | 2021-11-10 | 2023-05-12 | 上颍股份有限公司 | Environment-friendly water-soluble gold reducing agent and gold refining treatment method |
| CN114892007A (en) * | 2022-05-18 | 2022-08-12 | 云南锡业股份有限公司铜业分公司 | Method for recovering valuable metals from selenium steaming slag of complex copper anode slime |
| CN117431407A (en) * | 2023-10-20 | 2024-01-23 | 福建紫金矿冶测试技术有限公司 | A method for processing and recovering silver from gold smelting silver slag |
| CN117385187A (en) * | 2023-10-31 | 2024-01-12 | 中节能工程技术研究院有限公司 | A comprehensive treatment method for waste circuit board fire smelting smoke and soot |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7479262B2 (en) | Method for separating platinum group element | |
| CN1114361A (en) | Method for recovering Ag, Au, Sb, Cu and Pb from Pb anode slime | |
| JP3616314B2 (en) | Method for treating copper electrolytic deposits | |
| EP0049169A2 (en) | Hydrometallurgical processing of precious metal-containing materials | |
| EP0259454B1 (en) | Preparation of ultra-pure silver nitrate | |
| CN113308606A (en) | Method for leaching and separating valuable metals from silver-gold-rich selenium steaming slag | |
| US5797977A (en) | Method of platinum recovery | |
| JP2012246198A (en) | Method for purifying selenium by wet process | |
| CN1119678A (en) | Method for recovering silver, gold, antimony, copper and lead from lead anode mud | |
| CN1045796C (en) | Method for extracting gold, silver and valuable metals from high-arsenic copper anode mud | |
| CN1195085C (en) | Amminochloride process of purifying gold | |
| CN109280772B (en) | Method for leaching and gradient separating enriched antimony, bismuth and arsenic from copper anode slime | |
| EP1577408B1 (en) | Method for separating platinum group elements from selenum/tellurium bearing materials | |
| JP4269693B2 (en) | Process for treating selenium mixture | |
| CN1271781A (en) | Process for preparing gold by reduction of gold-contained chlorated liquid | |
| US3996046A (en) | Extraction and purification of silver from sulfates | |
| CN111235396B (en) | A kind of wet processing method of copper smelting acid-making acid sludge | |
| CN1162650A (en) | Method for smelting sodium sulfate from refined complex antimony ore | |
| JP2011195935A (en) | Method for separating and recovering platinum group element | |
| JPH10265863A (en) | Precious metal recovery method from smelting residue | |
| CN101033505A (en) | Method of leaching valuable metal from anode sludge with high content of antimony, bismuth and copper | |
| JP3407600B2 (en) | Silver extraction and recovery method | |
| CN1254025A (en) | Antimony and impurity removing method for copper electrolyte | |
| CN1200407A (en) | Process for extracting and recovering silver | |
| CN1064087C (en) | Low-temperature cobalt-eliminating antimonate technology for zonc smelting wet process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |