CN101029353A - Comprehensive extraction of valent metal from bismuth-containing polymetallic material - Google Patents
Comprehensive extraction of valent metal from bismuth-containing polymetallic material Download PDFInfo
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- CN101029353A CN101029353A CNA2007100346669A CN200710034666A CN101029353A CN 101029353 A CN101029353 A CN 101029353A CN A2007100346669 A CNA2007100346669 A CN A2007100346669A CN 200710034666 A CN200710034666 A CN 200710034666A CN 101029353 A CN101029353 A CN 101029353A
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- China
- Prior art keywords
- bismuth
- copper
- tellurium
- slag
- metal
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- Granted
Links
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 59
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims description 31
- 238000000605 extraction Methods 0.000 title claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 24
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 9
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 6
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 16
- 239000004332 silver Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 4
- 229940073609 bismuth oxychloride Drugs 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 2
- 238000010304 firing Methods 0.000 abstract 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910021607 Silver chloride Inorganic materials 0.000 abstract 1
- 229910052924 anglesite Inorganic materials 0.000 abstract 1
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- 239000010931 gold Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 230000001698 pyrogenic effect Effects 0.000 description 5
- 239000010944 silver (metal) Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 229910000563 Arsenical copper Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QQHJESKHUUVSIC-UHFFFAOYSA-N antimony lead Chemical compound [Sb].[Pb] QQHJESKHUUVSIC-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen sodium hydroxide Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- 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 method for extracting metal from bismuth-contained multi-metal material is carried out by leaching out copper and tellurium from bismuth-contained multi-metal by sulfuric acid, adding into chlorinating agent and oxidant to leach out metal bismuth, extracting silver from leaching-out slag with AgCl, PbSO4 and PbC12, adding ammonia water into leaching-out liquid, adjusting pH value to 1.5 to obtain bismuth oxychloride slag with 70% bismuth content, smelting into coarse bismuth by firing method or machining to obtain high-purity bismuth sesquioxide, adjusting pH value to 4.5 by Na2CO3, depositing tellurium to obtain tellurium dioxide and copper-contained solution, and electrically depositing to obtain copper powder with copper-contained content90%. It adopts wetting and firing metallurgical technology, has higher metal recovery rate and excellent leaching-out separation effect and effluent circulating utilization and no environmental pollution.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, relate in particular to a kind of employing hydrometallurgy, pyrometallurgy and electrochemical metallurgical technology and combine, the comprehensive technology of extracting valuable metal from the many metalliferous materials of bismuth-containing.
Background technology
Prior art is the many metalliferous materials of bismuth-containing such as meeting output wet method slag, pyrogenic process slag, flue dust in the process of handling lead anode slurry recovery production gold and silver, and its main component content is: Pb 35-40%; Cu 10-15%; Bi 15-20%; Fe 1-1.5%; Ag 3-5%; Te 10-20%.The many metalliferous materials of bismuth-containing for such complicated component comprehensively recycle, and present most producers adopt traditional converter mixed smelting---pyrorefining flow process, make tellurium slag enrichment tellurium, output bismuth slag, copper ashes and lead skim simultaneously in the converter during pyrogenic process desilver.The silver direct yield is low only to be 10%, and reason is that material bismuth-containing tellurium copper is too high, and the quantity of slag is too big, and the oxidation order of bismuth tellurium copper and silver is near the also oxidized and mechanical entrapments of silver a large amount of when making bismuth slag, tellurium slag and copper ashes.The bismuth slag that this technology is produced, tellurium slag, the bad again processing of copper ashes separate undesirablely, and added value of product is low.Therefore, be necessary in time to work out a kind of novel process to address the above problem.
Existing reference technique related to the present invention is as follows:
1, on June 2nd, 1992 is by " treatment method of high arsonium lead anode mud wet process " patents of invention that the people proposed such as the Hu Xuming of Kunming Precious Metals Research Inst., China Nonferrous Metals Gen. Corp, Xie Bin, the patent No. 92104421.6; Its method is to place 3～5N hydrochloric acid medium to lead to the chlorination of people's chlorine CONTROLLED POTENTIAL material.The enrichment of gained leach liquor arsenic, antimony, bismuth, copper, tellurium, the enrichment of gained leached mud silver, golden; Method-the electrolysis of starting to exchange fire after chloride slag available hydrogen sodium hydroxide solution is handled gets fine silver, gold; After also can wet gold extraction again with wet method or pyrogenic process desilver.Leach liquor leads to SO
2Reduction or catalytic reduction are settled out the tellurium concentrate, and distillation method reclaims arsenic, and the vinasse hydrolysis method reclaims antimony, and the neutralization of antimony hydrolysising mother liquid adds sodium carbonate solution neutralization precipitation bismuth and gets the bismuth concentrate, and control terminal point pH value is 2～4; Heavy bismuth mother liquor oxidation post neutralization precipitate copper ore concentrates.
2, on January 15th, 2000 is by " new process for treating electrolytic anode mud " patents of invention that the people proposed such as the Zhang Xu of Kunming University of Science and Technology, Liu Zhonghua, the patent No. 00112636.9; Be a kind of non-ferrous metal wet extraction process, the wet processing process of employing sulfuric acid system separates arsenic, copper, antimony, bismuth, the silver in the electrolysis anode sludge; To the effect of normal pressure oxygen and catalyzer, make arsenical copper enter leach liquor in pressure 500 millimeter water column, wherein antimony, bismuth are converted into oxide compound, and lead is converted into lead sulfate, and silver is converted into silver suboxide and enters leached mud; Extraction temperature 95-100 ℃, catalyzer is made up of ferrous sulfate, nitric acid, hydrochloric acid, nitrite or nitrate, and leach liquor obtains arsenical copper slag and displaced liquid with the iron displacement, and displaced liquid obtains ferrous sulfate through crystallisation by cooling, and mother liquor returns oxidation and leaches.
3, on December 2nd, 2005, " valuable metal reclaims technology in the thick bismuth " applications for a patent for invention that the people proposed such as the light gold plumbous Zhai Ju of limited-liability company in Henan, effluent south pays, Ni Hengfa, application number 200510125630.2; This process using wet method, the pyrogenic process comprehensive recovery of carrying out valuable metal linked together, at first material is carried out shrend, ball milling, leach, washing and filtration, obtain antimony lead slag and leach liquor, the antimony lead slag that produces changes plumbous smelting system after returning pyrogenic process system recoveries antimony, the leach liquor that produces with copper sponge displacement Au wherein, Ag output gold and silver mud, output gold and silver mud returns the precious metal smelting system, to the heavy bismuth that is hydrolyzed of the liquid behind the displacement gold and silver mud, with lime and water neutralization, obtain chlorine oxygen bismuth after the filtration, become thick bismuth further to be refined into smart bismuth again, to filtering leach liquor iron powder replacement Cu through retailoring, heavy Cu, output copper sponge, the liquid behind the heavy Cu add lime and neutralize, through 2～3 grades of post precipitation qualified discharges.
Summary of the invention
Technical problem to be solved of the present invention is to overcome the deficiencies in the prior art, a kind of technology of comprehensively extracting valuable metal from the many metalliferous materials of bismuth-containing is provided, this process synthesis utilizes hydrometallurgy, pyrometallurgy and electrochemical metallurgical technology, the metal recovery rate height, argentalium is gone into slag rate height, copper, bismuth, tellurium leach separator well, the waste liquid recycle, and no waste residue produces Environmental Safety.
Technical thinking of the present invention is such: leach copper, tellurium with sulfuric acid from the many metalliferous materials of bismuth-containing earlier; Add chlorizating agent and oxygenant again the metallic state bismuth also leached, and Ag with AgCl form Pb with PbSO
4, PbCl
2Form is stayed in the leached mud, and desilver from this leached mud in leach liquor, adds ammoniacal liquor earlier and adjusts the bismuth oxychloride slag that pH value to 1.5 obtains bismuth-containing 70%, and this bismuth slag becomes thick bismuth or directly is processed into high-purity bismuthous oxide bismuth trioxide with pyrometallurgical smelting; In the leach liquor, during copper and the ammoniacal liquor complexing do not deposit, use Na
2CO
3Transfer PH to 4.5, heavy tellurium gets tellurium dioxide.Obtain copper-containing solution at last, again with big 90% copper powder of copper electrodeposition output cupric.
The technical scheme that the present invention deals with problems is as follows:
A kind of technology of from the many metalliferous materials of bismuth-containing, comprehensively extracting valuable metal, its step is as follows:
A, oversize material through crusher in crushing to particle line footpath less than 2cm;
B, the material after fragmentation carry out grinding by raymond mill, and the raw meal particle size of control 80% reaches below-120 orders;
C, first with the many metalliferous materials behind the sulfuric acid immersion grinding therefrom leaches copper, tellurium; Adding chlorizating agent and oxygenant is more also leached the metallic state bismuth; Filter residue, at this moment, Ag is with the AgCl form, and Pb is with PbSO
4, PbCl
2Form is stayed in the leached mud, desilver from this leached mud;
In this step, the sulfuric acid concentration of immersion is Cl in 3M, the chlorizating agent
-Concentration is that 4M, oxygenant choosing are add-on, 95 ℃ of extraction temperatures, extraction time 5h by 8% of many metalliferous materials weight;
D, feed ammoniacal liquor in the leach liquor of c step, adjusting PH is 1.5, and bismuth is sunk in the bismuth slag with the form of chlorine oxygen bismuth, filters the bismuth slag, gets the bismuth slag and proposes the bismuth deep processing with pyrometallurgical smelting;
E, in the leach liquor of d step, add Na
2CO
3, transfer PH to 4.5, heavy tellurium filters, and gets filter residue and gets tellurium dioxide;
F, send electrochemical workshop to carry out the copper electrodeposition leach liquor of d step, the electrodeposition temperature is controlled at temperature 45-50 ℃; Obtain out at last cupric greater than 90% copper powder;
Waste water behind g, the electrodeposition is under the not high situation of sulfur acid ammonium and sodium sulfate concentration, directly return the leaching operation, after circulation for some time, re-use after needing crystallisation by cooling to separate out vitriol, after harmful impurity A s, Sb, Fe are accumulated to a certain degree, do open circuit and handle, promptly add ferrous sulfate method and make the foreign metal precipitation, and make discharged wastewater met the national standard with lime.
The present invention utilizes hydrometallurgy, pyrometallurgy and electrochemical metallurgical technology to combine, comprehensively recovering valuable metal from the many metalliferous materials of bismuth-containing, and prior art has following advantage relatively:
1, metal recovery rate height, silver is gone into the slag rate greater than 98% in force, and lead is gone into the slag rate greater than 95%, and copper leaching rate is greater than 99%, and the bismuth leaching yield is greater than 98%, tellurium leaching yield 88%.Separation of lead, silver and tellurium, bismuth, copper, the silver ingot that produces, bismuth ingot, lead pig all can reach GB 1# standard, the copper powder of the direct output of copper electrodeposition also can reach 90% again, economic target is good; In the technology silver with AgCl form Pb with PbSO
4, PbCl
2Form is stayed in the leached mud, and this leached mud is an ideal desilver material, helps next process and handles the added value of product height;
2, the present invention does not have waste water, waste residue produces, but qualified discharge after only a small amount of waste water passes through to handle, and most of waste water can return use, Environmental Safety;
3, the present invention removes extraction temperature and requires in that other all can utilize reaction heat and waste heat to react completely more than 95 ℃, in addition the power consumption source.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
With concrete embodiment the present invention is described below in conjunction with accompanying drawing.
The bismuth-containing material that present embodiment adopts, composition is as follows:
Pb38% Cu12% Bi18% Fe1.2% Ag3.5% Te15% other 12.8%;
This material is smeltery's waste residue, becomes block, and metalluster is arranged after the fragmentation, and what value was higher in the material is silver and tellurium, and other can reclaim from byproduct.
Comprehensive processing step such as the accompanying drawing 1 that extracts valuable metal from above-mentioned bismuth-containing material;
A, fragmentation: oversize material through crusher in crushing to particle line footpath less than 2cm;
B, grinding: the material after fragmentation carries out grinding by raymond mill, and the raw meal particle size of control 80% reaches below-120 orders; The abrasive dust process is a mechanical activation process, can effectively improve leaching yield;
C, leaching: with the many metalliferous materials behind the sulfuric acid immersion grinding, therefrom leach copper, tellurium earlier; Add chlorizating agent and oxygenant again the metallic state bismuth also leached, filter residue, at this moment, Ag with AgCl form Pb with PbSO
4, PbCl
2Form is stayed in the leached mud, desilver from this leached mud;
In this step, the chlorizating agent here is a sodium-chlor, and oxygenant is hydrogen peroxide or Manganse Dioxide, a kind of during sodium chlorate is several.Sulfuric acid concentration is that C1-concentration is that 4M, oxygenant choosing are add-on, 95 ℃ of extraction temperatures, extraction time 5h by 8% of many metalliferous materials weight in 3M, the chlorizating agent;
D, the heavy bismuth of neutralization: in the leach liquor of c step, feed ammoniacal liquor, adjusting PH is 1.5, bismuth is sunk in the bismuth slag with the form of the chlorine oxygen bismuth of bismuth-containing 70%, filter the bismuth slag, get the bismuth slag and propose the bismuth deep processing with pyrometallurgical smelting and become thick bismuth or directly be processed into high-purity bismuthous oxide bismuth trioxide; When the ammoniacal liquor that adds simultaneously formed complex copper and makes next step heavy tellurium, copper did not deposit;
E, the heavy tellurium of neutralization: in the leach liquor of d step, add Na
2CO
3, transfer PH to 4.5, heavy tellurium filters, and gets filter residue and gets tellurium dioxide;
F, electro deposited copper: send electrochemical workshop to carry out the copper electrodeposition cupric leach liquor of d step, the electrodeposition temperature is controlled at temperature 45-50 ℃, about copper material per ton power consumption 2300 degree; Obtain out at last cupric greater than 90% copper powder;
G, wastewater treatment: the waste water behind the electrodeposition is under the not high situation of sulfur acid ammonium and sodium sulfate concentration, directly return the leaching operation, after circulation for some time, re-use after needing crystallisation by cooling to separate out vitriol, after harmful impurity A s, Sb, Fe are accumulated to a certain degree, must do open circuit and handle, promptly add ferrous sulfate method and make the foreign metal precipitation, and make discharged wastewater met the national standard with lime.
Claims (1)
1, a kind of technology of from the many metalliferous materials of bismuth-containing, comprehensively extracting valuable metal, its step is as follows:
A, oversize material through crusher in crushing to particle line footpath less than 2cm;
B, the material after fragmentation carry out grinding by raymond mill, and the raw meal particle size of control 80% reaches below-120 orders;
C, first with the many metalliferous materials behind the sulfuric acid immersion grinding therefrom leaches copper, tellurium; Adding chlorizating agent and oxygenant is more also leached the metallic state bismuth; Filter residue, at this moment, Ag is with the AgCl form, and Pb is with PbSO
4, PbCl
2Form is stayed in the leached mud, desilver from this leached mud;
In this step, the sulfuric acid concentration of immersion is Cl in 3M, the chlorizating agent
-Concentration is that 4M, oxygenant choosing are add-on, 95 ℃ of extraction temperatures, extraction time 5h by 8% of many metalliferous materials weight;
D, feed ammoniacal liquor in the leach liquor of c step, adjusting PH is 1.5, and bismuth is sunk in the bismuth slag with the form of chlorine oxygen bismuth, filters the bismuth slag, gets the bismuth slag and proposes the bismuth deep processing with pyrometallurgical smelting;
E, in the leach liquor of d step, add Na
2CO
3, transfer PH to 4.5, heavy tellurium filters, and gets filter residue and gets tellurium dioxide;
F, send electrochemical workshop to carry out the copper electrodeposition leach liquor of d step, the electrodeposition temperature is controlled at temperature 45-50 ℃; Obtain out at last cupric greater than 90% copper powder;
Waste water behind g, the electrodeposition is under the not high situation of sulfur acid ammonium and sodium sulfate concentration, directly return the leaching operation, after circulation for some time, re-use after needing crystallisation by cooling to separate out vitriol, after harmful impurity A s, Sb, Fe are accumulated to a certain degree, do open circuit and handle, promptly add ferrous sulfate method and make the foreign metal precipitation, and make discharged wastewater met the national standard with lime.
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