CN114045392A - Method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite - Google Patents
Method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite Download PDFInfo
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- CN114045392A CN114045392A CN202111282353.1A CN202111282353A CN114045392A CN 114045392 A CN114045392 A CN 114045392A CN 202111282353 A CN202111282353 A CN 202111282353A CN 114045392 A CN114045392 A CN 114045392A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 70
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011701 zinc Substances 0.000 title claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 58
- 229910052951 chalcopyrite Inorganic materials 0.000 title claims abstract description 57
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 86
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 17
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052595 hematite Inorganic materials 0.000 claims abstract description 10
- 239000011019 hematite Substances 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052745 lead Inorganic materials 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 8
- 235000020679 tap water Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002893 slag Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 abstract description 2
- 229960001763 zinc sulfate Drugs 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 238000009853 pyrometallurgy Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052947 chalcocite Inorganic materials 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910001779 copper mineral Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- BUGICWZUDIWQRQ-UHFFFAOYSA-N copper iron sulfane Chemical compound S.[Fe].[Cu] BUGICWZUDIWQRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
-
- 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
-
- 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
-
- 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
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
The invention discloses a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite, and relates to the technical field of metallurgical engineering. According to the method for extracting copper and zinc and separating lead and iron from the low-grade multi-metal complex chalcopyrite, the sulfide in the low-grade multi-metal complex chalcopyrite is converted into sulfuric acid in a hydrothermal system under the oxygen atmosphere, copper and zinc in the sulfide in the low-grade multi-metal complex chalcopyrite are converted into zinc sulfate and copper sulfate to enter a solution, and lead and iron in the sulfide are converted into lead sulfate and hematite to enter leaching slag, so that the aims of efficiently leaching copper and zinc and separating lead and iron under the acid-free condition are fulfilled. The invention has the advantages of simple technical scheme, less reagent consumption, low energy consumption, no generation of greenhouse gases, low production cost and accordance with the era development theme of cleanness, high efficiency, low carbon and environmental protection.
Description
Technical Field
The invention relates to a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite, and relates to the technical field of metallurgical engineering.
Background
Copper ore resources in nature mainly exist in the form of sulfides, and can be divided into sulfide copper ores and oxide copper ores according to the generation conditions and chemical composition of copper minerals, and the sulfide copper ores are abundant. Sulfide ore is mainly extracted and treated by adopting a pyrometallurgical process, and oxide ore is mainly extracted by adopting a hydrometallurgical method. Chalcopyrite (CuFeS2) is the most widely distributed and most abundant mineral in primary sulfide copper minerals, and most of the chalcopyrite exists in the form of associated minerals and multi-metal complex minerals, and accounts for about 70% of the total copper ore resource amount in the world. The high-grade chalcopyrite is mainly prepared by matte smelting, air refining, fire refining and electrolytic refining, and valuable metals in the high-grade chalcopyrite are extracted by the traditional high-temperature fire process; however, the pyrometallurgical process has high energy consumption and large device investment, and poisonous and harmful flue gas containing sulfur dioxide, arsenic, mercury and the like generated in the process has large pollution to the environment; moreover, due to the characteristics of low grade of the low-grade chalcopyrite, fine disseminated particle size and multi-metal concomitance, the recovery rate of copper is low and the production cost is high when the traditional pyrometallurgical process is adopted for treatment. Aiming at the characteristics of low-grade chalcopyrite resource, such as low grade, poor grade, fine embedded particle size and complex components, the method explores an energy-saving, environment-friendly, economic and efficient wet extraction technology, and becomes a necessary trend for sustainable development and utilization of the copper sulfide resource.
Researchers at home and abroad carry out a great deal of research work aiming at the hydrometallurgical technology of high-grade chalcopyrite concentrate, and direct treatment technologies such as high-valence iron salt leaching, acidic condition oxidative leaching, acidic condition oxygen pressure leaching and the like are mostly adopted at the present stage. The main disadvantages of the leaching process of the high-valence ferric salt are that the reaction mechanism of the process is complex, the flow path is long, the loss of the high-valence ferric salt is large, the regeneration is difficult, and the distance from the realization of industrialization is large; the chloride leaching process in the high-valence iron salt has strong corrosion and is fresh to popularize and apply. The oxidative leaching under the acidic condition needs to be added with an expensive oxidant, the oxidant is difficult to regenerate and has high cost, and the leaching rate of copper is not high. The oxygen pressure leaching under acidic condition is mostly implemented in a sulfuric acid solution system, more than 90% of sulfur in sulfides is converted into elemental sulfur in the process, the obtained leaching residue contains a large amount of harmful jarosite and other components besides the elemental sulfur, and the defect that elemental sulfur and the harmful jarosite are incompletely separated and are mixed with harmful components exists in the sulfur selection process of the leaching residue. In addition, aiming at the research reports that the processing technology of low-grade multi-metal complex chalcopyrite is less researched and the similar processing technology of high-grade brass concentrate is not transplanted, microbial leaching (Yi sublimation and the like, the research progress of the copper mine microbial leaching technology in China [ J ] engineering science bulletin, 2019,41(2):143 to 158; Dong Ying Bo, Linhai, the research progress of the low-grade copper mine microbial leaching technology [ J ] metal mine: 2010, (1), 11 to 15; Wu Ying and the like; the low-grade secondary copper sulfide ore heap bioleaching process optimizes and researches [ J ] nonferrous metals (smelting part), 2018, (1) to 5.) and ultrasonic enhanced leaching (Wangming and the like; the ultrasonic enhanced leaching experiment and mechanism analysis of low-grade copper sulfide ore [ J ] Chinese non-ferrous metal bulletin: 2013,23(7):2019 to 2025) and the like are directly used for copper ore extraction to sulfide (chalcopyrite) or sulfide copper blue, chalcocite, chalcocite) low-grade multi-metal complex copper sulfide ore. The microbial leaching technology has the problems of long leaching period, long microbial culture and domestication period, low copper leaching rate (the copper leaching rate is only 62.67 percent) and the like, and limits the industrial popularization and application of the technology. When the low-grade primary copper sulfide ore, namely the chalcopyrite, is leached by adopting ultrasonic reinforcement, although the leaching rate of copper is improved by 5.6 to 14.8 percent compared with that of the chalcopyrite without the ultrasonic, the highest leaching rate of copper is only 6.2 percent, and the leaching time is up to 24 hours.
In summary, the prior art has a series of problems in processing low-grade multi-metal complex chalcopyrite: the extraction efficiency of the valuable metals of copper and zinc is low; lead and iron are easy to combine, so that lead-iron-alum slag which is difficult to separate and utilize is formed, and the lead-iron-alum slag belongs to dangerous solid waste and has great harm to the environment; most of iron in the raw materials and valuable metals copper and zinc enter a leaching solution, an additional treatment reagent is required to be added when copper and zinc are separated and extracted, the process of purifying and removing iron is long, the treatment cost is increased, the loss of copper and zinc is increased, the industrial utilization is not easy, and the environment-friendly degree is low. The research and development of the environment-friendly technology for effectively separating lead and iron while selectively extracting copper and zinc from the chalcopyrite has stronger practical significance.
Disclosure of Invention
The invention aims to provide a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite, which converts sulfur in sulfide in the low-grade multi-metal complex chalcopyrite into sulfuric acid in a hydrothermal system under oxygen atmosphere, converts copper and zinc in the sulfide in the low-grade multi-metal complex chalcopyrite into zinc sulfate and copper sulfate to enter a solution, converts lead and iron in the sulfide into lead sulfate and hematite to enter leaching slag, and achieves the aims of efficiently leaching copper and zinc and separating lead and iron under an acid-free condition.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) activation and fine grinding: adding tap water into the low-grade multi-metal complex chalcopyrite according to the mass ratio of 1: 6-10, and adding sodium dodecyl sulfate according to 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite; finely grinding and activating by a wet mill until the mineral content with the granularity less than 0.075mm reaches more than 90%, and obtaining ore pulp for leaching;
(2) hydrothermal leaching: adding the ore pulp into a reaction kettle, heating to 180-220 ℃ under stirring at a speed of 400-700 r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 1.0-3.0 h at the oxygen partial pressure of 0.8-1.2 MPa;
(3) liquid-solid separation: and after leaching is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, and performing liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and leaching residues mainly comprising hematite, lead sulfate and elemental sulfur.
Further, the low-grade multi-metal complex chalcopyrite comprises the following components in percentage by mass: 8 to 12.0 percent of Cu, 20 to 30 percent of Fe, 8 to 15 percent of Pb, 2 to 5 percent of Zn, 30 to 40 percent of S, 21 to 3 percent of SiO, 0.1 to 1.0 percent of CaO, 0.1 to 1.0 percent of MgO and 30.1 to 1.0 percent of Al2O30.
Furthermore, the addition amount of the sodium dodecyl sulfate is 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite.
Further, the wet mill is a wet ball mill or a wet rod mill.
The invention has the beneficial effects that:
(1) the invention relates to a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite, which belongs to the all-wet method technology, does not generate flue gas containing sulfur dioxide and lead which pollutes the environment, and is a method for directly extracting valuable metals of copper and zinc from low-grade multi-metal complex chalcopyrite;
(2) the method for extracting copper and zinc and separating lead and iron from the low-grade multi-metal complex chalcopyrite can efficiently realize the selective extraction of valuable components of copper and zinc in the low-grade multi-metal complex chalcopyrite, the leaching rates of copper and zinc in the leaching solution are both more than 98.0 wt%, the leaching rate of iron is less than 10.0%, and lead is completely added into slag;
(3) the method for extracting copper and zinc and separating lead and iron from the low-grade multi-metal complex chalcopyrite makes full use of the element sulfur in the minerals to oxidize and convert the element sulfur into the sulfuric acid required by leaching copper and zinc, thereby abandoning the jiong state that the sulfuric acid needs to be added in the leaching process while producing a large amount of sulfur in the traditional oxygen pressure acid leaching industry.
(4) According to the method for extracting copper and zinc and separating lead and iron from the low-grade multi-metal complex chalcopyrite, after fine grinding and activation, no acid is added in the leaching process, the corrosion to equipment is small, the operation condition is mild, the cost is low, and the industrialization is easy to realize;
(5) the invention has the advantages of simple technical scheme, less reagent consumption, low energy consumption, no generation of greenhouse gases, low production cost and accordance with the era development theme of cleanness, high efficiency, low carbon and environmental protection.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is a flow chart of a method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite according to an embodiment of the invention;
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
activation and fine grinding: adding tap water into the low-grade multi-metal complex chalcopyrite according to the mass ratio of 1: 6-10, and adding sodium dodecyl sulfate according to 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite; finely grinding and activating by a wet mill until the mineral content with the granularity less than 0.075mm reaches more than 90%, and obtaining ore pulp for leaching;
hydrothermal leaching: adding the ore pulp into a reaction kettle, heating to 180-220 ℃ under stirring at a speed of 400-700 r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 1.0-3.0 h at the oxygen partial pressure of 0.8-1.2 MPa;
liquid-solid separation: and after leaching is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, and performing liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and leaching residues mainly comprising hematite, lead sulfate and elemental sulfur.
The low-grade multi-metal complex chalcopyrite comprises the following components in percentage by mass: 8 to 12.0 percent of Cu, 20 to 30 percent of Fe, 8 to 15 percent of Pb, 2 to 5 percent of Zn, 30 to 40 percent of S, 21 to 3 percent of SiO, 0.1 to 1.0 percent of CaO, 0.1 to 1.0 percent of MgO and 30.1 to 1.0 percent of Al2O30.
The addition amount of the sodium dodecyl sulfate is 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite.
The wet mill is a wet ball mill or a wet rod mill.
The technical scheme of the invention is explained by combining the specific embodiment as follows:
example 1
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) fine grinding and activating: 100g of low-grade multi-metal complex chalcopyrite (the components in percentage by mass are Cu 8%, Fe 30%, Pb 12%, Zn 2%, S30%, SiO 2)23%, CaO 1.0%, MgO 1.0% and Al2O31.0 percent), 600g of tap water and 0.2g of sodium dodecyl sulfate are added into a ball mill, fine grinding is carried out by a wet ball mill until the proportion of minerals with the granularity of less than 0.075mm reaches more than 90 percent, and the materials are dried to be used as leached mineral aggregates;
(2) hydrothermal leaching: adding the ore pulp obtained in the step (1) into a reaction kettle, heating to 180 ℃ under stirring at the speed of 400r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 1.0h at the oxygen partial pressure of 0.8 MPa;
(3) liquid-solid separation: and (3) after leaching in the step (2) is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, carrying out liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and a filter cake, and drying the filter cake in a drying oven for 2 hours at 105 ℃. The volume of the obtained leachate is 615mL, and the volume of the leachate contains 12.99g/L, Zn 3.23.23 g/L, Fe 4.66.66 g/L Cu; the dried filter cake weighed 66.1g, and the main components were the leached residues of hematite and lead sulfate, containing Fe 41.06% and Pb 18.15%.
In the present example, the leaching rates of copper and zinc were 99.88% and 99.25%, respectively, and the leaching rate of iron was 9.55%, and the impurity element lead was completely introduced into the leaching residue in the form of lead sulfate.
Example 2
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) fine grinding and activating: 100g of low-grade multi-metal complex chalcopyrite (the components in percentage by mass are Cu 12.0%, Fe 30%, Pb 15%, Zn 5%, S40% and SiO)21.0%, CaO 0.1%, MgO 0.1%, and Al2O30.1 percent), 1000g of tap water and 1.5g of sodium dodecyl sulfate are added into a ball mill, finely ground by a wet ball mill until the proportion of minerals with the granularity of less than 0.075mm reaches more than 90 percent, and dried to be used as leached oreFeeding;
(2) hydrothermal leaching: adding the ore pulp obtained in the step (1) into a reaction kettle, heating to 220 ℃ under stirring at a speed of 700r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 3.0h at the oxygen partial pressure of 1.2 MPa;
(3) liquid-solid separation: and (3) after leaching in the step (2) is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, carrying out liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and a filter cake, and drying the filter cake in a drying oven for 2 hours at 105 ℃. The volume of the obtained leachate is 1152mL, and the volume of the leachate contains 10.30g/L, Zn 4.28.28 g/L, Fe 2.09.09 g/L Cu; the dried filter cake weighs 65.2g, and the main components of the filter cake are the leaching residues of hematite and lead sulfate, and contain 42.31% of Fe and 23.01% of Pb.
In this example, leachate rich in valuable metals copper and zinc and hematite residue containing a small amount of lead sulfate are obtained, wherein the leaching rates of copper and zinc are respectively 98.88% and 98.75%, the leaching rate of iron is 8.05%, and lead as an impurity element is completely added into the residue in the form of lead sulfate.
Example 3
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) fine grinding and activating: 100g of low-grade multi-metal complex chalcopyrite (the components in percentage by mass are Cu 10%, Fe 25.5%, Pb 12.0%, Zn 2.97%, S34.2%, SiO21.5%, CaO 0.5%, MgO 0.4%, and Al2O30.6 percent), 700g of tap water and 1.0g of sodium dodecyl sulfate are added into a ball mill, fine grinding is carried out by a wet ball mill until the proportion of minerals with the granularity of less than 0.075mm reaches more than 90 percent, and the materials are dried to be used as leached mineral aggregates;
(2) hydrothermal leaching: adding the ore pulp obtained in the step (1) into a reaction kettle, heating to 200 ℃ under stirring at a speed of 600r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 2.0h at the oxygen partial pressure of 1.0 MPa;
(3) liquid-solid separation: and (3) after leaching in the step (2) is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, carrying out liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and a filter cake, and drying the filter cake in a drying oven for 2 hours at 105 ℃. The volume of the obtained leachate is 690mL, and the leachate contains 14.38g/L, Zn 4.29.29 g/L, Fe 3.40.40 g/L Cu; the dried filter cake weighed 65.6g, and the main components were the leached residues of hematite and lead sulfate, containing 35.29% Fe and 18.29% Pb.
In this example, leachate rich in valuable metals copper and zinc and hematite residue containing a small amount of lead sulfate are obtained, wherein the leaching rates of copper and zinc are 99.28% and 99.65%, respectively, the leaching rate of iron is 9.20%, and lead as an impurity element is completely added into the residue in the form of lead sulfate.
Example 4
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) fine grinding and activating: 100g of low-grade multi-metal complex chalcopyrite (the components in percentage by mass are 11.5 percent of Cu, 28.2 percent of Fe, 8.90 percent of Pb, 3.4 percent of Zn, 34.6 percent of S and SiO)21.4%, CaO 0.2%, MgO 0.21%, and Al2O30.3 percent), 800g of tap water and 0.6g of sodium dodecyl sulfate are added into a ball mill, fine grinding is carried out by a wet ball mill until the proportion of minerals with the granularity of less than 0.075mm reaches more than 90 percent, and the materials are dried to be used as leached mineral aggregates;
(2) hydrothermal leaching: adding the ore pulp obtained in the step (1) into a reaction kettle, heating to 190 ℃ under stirring at the speed of 500r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 2.5 hours at the oxygen partial pressure of 0.9 MPa;
(3) liquid-solid separation: and (3) after leaching in the step (2) is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, carrying out liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and a filter cake, and drying the filter cake in a drying oven for 2 hours at 105 ℃. The volume of the obtained leaching solution is 892mL, and the leaching solution contains 12.88g/L, Zn 3.80.80 g/L, Fe 3.0.0 g/L Cu; the dried filter cake weighed 66.3g, and the main components were the leached residues of hematite and lead sulfate, containing Fe 38.49% and Pb 13.42%.
In the present example, the leaching rates of copper and zinc were 99.92% and 99.85%, respectively, and the leaching rate of iron was 9.50%, and the impurity elements of lead were all introduced into the slag in the form of lead sulfate.
Example 5
A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite comprises the following steps:
(1) fine grinding and activating: 100g of low-grade multi-metal complex chalcopyrite (the components in percentage by mass are 11.1 percent of Cu, 28.2 percent of Fe, 8.90 percent of Pb, 3.4 percent of Zn, 36.2 percent of S and SiO)21.86%, CaO 0.38%, MgO 0.43%, and Al2O30.3 percent), 800g of tap water and 0.8g of sodium dodecyl sulfate are added into a ball mill, fine grinding is carried out by a wet ball mill until the proportion of minerals with the granularity of less than 0.075mm reaches more than 90 percent, and the materials are dried to be used as leached mineral aggregates;
(2) hydrothermal leaching: adding the ore pulp obtained in the step (1) into a reaction kettle, heating to 205 ℃ under stirring at the speed of 500r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 1.5h at the oxygen partial pressure of 1.0 MPa;
(3) liquid-solid separation: and (3) after leaching in the step (2) is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, carrying out liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and a filter cake, and drying the filter cake in a drying oven for 2 hours at 105 ℃. The volume of the obtained leachate is 902mL, and the leachate contains 12.30g/L, Zn 3.76.76 g/L, Fe 2.83.83 g/L Cu; the dried filter cake weighed 66.1g, and the main components were the leached residues of hematite and lead sulfate, containing 38.80% Fe and 13.45% Pb.
In the present example, the leaching rates of copper and zinc were 99.95% and 99.90%, respectively, and the leaching rate of iron was 9.05%, and the impurity elements, lead, were all introduced into the slag in the form of lead sulfate.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. A method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite is characterized by comprising the following steps:
(1) activation and fine grinding: adding tap water into the low-grade multi-metal complex chalcopyrite according to the mass ratio of 1: 6-10, and adding sodium dodecyl sulfate according to 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite; finely grinding and activating by a wet mill until the mineral content with the granularity less than 0.075mm reaches more than 90%, and obtaining ore pulp for leaching;
(2) hydrothermal leaching: adding the ore pulp into a reaction kettle, heating to 180-220 ℃ under stirring at a speed of 400-700 r/min, introducing industrial oxygen with the content of more than 90%, and leaching for 1.0-3.0 h at the oxygen partial pressure of 0.8-1.2 MPa;
(3) liquid-solid separation: and after leaching is finished, stopping heating, introducing cooling water to cool the reactant to a temperature lower than 80 ℃, releasing the pressure, taking out ore pulp, and performing liquid-solid separation and washing to obtain leaching liquid rich in valuable metals copper and zinc and leaching residues mainly comprising hematite, lead sulfate and elemental sulfur.
2. The method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite according to claim 1, wherein the method comprises the following steps: the low-grade multi-metal complex chalcopyrite comprises the following components in percentage by mass: 8 to 12.0 percent of Cu, 20 to 30 percent of Fe, 8 to 15 percent of Pb, 2 to 5 percent of Zn, 30 to 40 percent of S, 21 to 3 percent of SiO, 0.1 to 1.0 percent of CaO, 0.1 to 1.0 percent of MgO and 30.1 to 1.0 percent of Al2O30.
3. The method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite according to claim 1, wherein the method comprises the following steps: the addition amount of the sodium dodecyl sulfate is 0.2-1.5% of the mass of the low-grade multi-metal complex chalcopyrite.
4. The method for extracting copper and zinc and separating lead and iron from low-grade multi-metal complex chalcopyrite according to claim 1, wherein the method comprises the following steps: the wet mill is a wet ball mill or a wet rod mill.
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| US20080023342A1 (en) * | 2004-10-29 | 2008-01-31 | Phelps Dodge Corporation | Process for recovery of copper from copper-bearing material using pressure leaching, direct electrowinning and solution extraction |
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| US20080023342A1 (en) * | 2004-10-29 | 2008-01-31 | Phelps Dodge Corporation | Process for recovery of copper from copper-bearing material using pressure leaching, direct electrowinning and solution extraction |
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| CN115772606A (en) * | 2022-12-12 | 2023-03-10 | 昆明理工大学 | Method for leaching chalcopyrite by ultrasonically strengthening persulfate oxidation in hydrochloric acid system |
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