CN106995887B - A kind of copper sulfide produces the technique and its system of metallic copper or copper compound - Google Patents
A kind of copper sulfide produces the technique and its system of metallic copper or copper compound Download PDFInfo
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- CN106995887B CN106995887B CN201710321053.7A CN201710321053A CN106995887B CN 106995887 B CN106995887 B CN 106995887B CN 201710321053 A CN201710321053 A CN 201710321053A CN 106995887 B CN106995887 B CN 106995887B
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- copper
- slag
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- sulfide
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 141
- 239000010949 copper Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 121
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000005749 Copper compound Substances 0.000 title claims abstract description 79
- 150000001880 copper compounds Chemical class 0.000 title claims abstract description 79
- 239000002893 slag Substances 0.000 claims abstract description 93
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 62
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003546 flue gas Substances 0.000 claims abstract description 43
- 230000019086 sulfide ion homeostasis Effects 0.000 claims abstract description 40
- 239000005864 Sulphur Substances 0.000 claims abstract description 28
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 21
- 230000023556 desulfurization Effects 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 17
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005751 Copper oxide Substances 0.000 claims abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 50
- UXNBTDLSBQFMEH-UHFFFAOYSA-N [Cu].[Zn].[Pb] Chemical compound [Cu].[Zn].[Pb] UXNBTDLSBQFMEH-UHFFFAOYSA-N 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 28
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 27
- 239000001110 calcium chloride Substances 0.000 claims description 26
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 24
- 229910052737 gold Inorganic materials 0.000 claims description 24
- 239000010931 gold Substances 0.000 claims description 24
- 238000006386 neutralization reaction Methods 0.000 claims description 24
- 238000000605 extraction Methods 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000011133 lead Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000012141 concentrate Substances 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 238000005201 scrubbing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000010306 acid treatment Methods 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000012320 chlorinating reagent Substances 0.000 claims description 4
- 235000019504 cigarettes Nutrition 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 239000013590 bulk material Substances 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 2
- 235000001508 sulfur Nutrition 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 230000001698 pyrogenic effect Effects 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 238000005188 flotation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- -1 ferrous sulfides Chemical class 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 1
- JLKFUGXSXNYLPC-UHFFFAOYSA-N [S].[S].[Cu] Chemical compound [S].[S].[Cu] JLKFUGXSXNYLPC-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000010852 non-hazardous waste Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/08—Chloridising roasting
-
- 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
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0008—Preliminary treatment without modification of the copper constituent 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
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0019—Chloridizing roasting
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Treating Waste Gases (AREA)
Abstract
The present invention provides the technique and its system of a kind of copper sulfide production metallic copper or copper compound, which includes the following steps：(1) desulphurizing roasting processing is carried out to copper sulfide under nonoxidizing atmosphere, to obtain desulfurization slag and the thick sulphur containing cuprous sulfide and ferrous sulfide；(2) wet oxidation process is carried out to desulfurization slag, so that ferrous sulfide is converted into iron oxide and elemental sulfur, to obtain the first mixed material containing cuprous sulfide, iron oxide and elemental sulfur；(3) simple substance sulphuring treatment is extracted to the first mixed material, to obtain the second mixed material containing cuprous sulfide, iron oxide；(4) chloridising roasting processing is carried out to the second mixed material, obtains flue gas and chlorination slag, flue gas is further processed, prepares metallic copper or copper compound；Copper compound can be copper chloride or copper oxide；Metallic copper can be tough cathode.Scheme provided by the invention has many advantages, such as small investment, and production cost is low, high financial profit, environmentally protective.
Description
Technical field
The invention belongs to mine smelting technical fields, and in particular to a kind of copper sulfide produces the work of metallic copper or copper compound
Skill and its system.
Background technology
The vulcanization pyrometallurgical copper smelting plant in one 100,000 tons of copper/year of investment takes around investment hundred million RMB of 12-15 at present,
It invests huge, has not only increased considerably the cost of factory, also increased the cost of investment of factory；Existing vulcanization pyrometallurgical copper
Smeltery due to must output sulfur dioxide, so, extracting sulfuric acid is necessary technique, still, is difficult in many area sulfuric acid
Therefore sale, storage and transport become a problem of puzzlement vulcanization copper smelting plant addressing；Existing vulcanization pyrometallurgical copper
Smeltery is due to using slagging process, metallurgical slag to take away a large amount of valuable element, to have lost prodigious income, meanwhile,
The processing of metallurgical slag is also a problem；Environmental issue is also the major issue of the existing vulcanization pyrometallurgical copper smelting plant of puzzlement.
Invention content
To solve the above problems, the purpose of the present invention is to provide the works of a kind of copper sulfide production metallic copper or copper compound
Skill.
It is a further object of the present invention to provide the systems of a kind of copper sulfide production metallic copper or copper compound.
In order to achieve the above objectives, the present invention provides the technique of a kind of copper sulfide production metallic copper or copper compound, the works
Skill includes the following steps：
(1) desulphurizing roasting processing is carried out to copper sulfide under nonoxidizing atmosphere, it is sub- containing cuprous sulfide and vulcanization to obtain
The desulfurization slag of iron and thick sulphur；The nonoxidizing atmosphere is the environmental protection that non-oxidized gas is formed, or is negative pressure ring
Border；
(2) wet oxidation process is carried out to the desulfurization slag, ferrous sulfide is made to be converted into iron oxide and elemental sulfur, with
To the first mixed material containing cuprous sulfide, iron oxide and elemental sulfur；
(3) simple substance sulphuring treatment is extracted to first mixed material, with obtain containing cuprous sulfide, iron oxide
Two mixed materials；
(4) chloridising roasting processing is carried out to second mixed material, obtains flue gas and chlorination slag, and carry out to flue gas
It is further processed, to prepare metallic copper or copper compound.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the copper compound is copper chloride
Or copper oxide；The metallic copper is tough cathode.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (1)
The condition of desulphurizing roasting processing is to be roasted 10-150 minutes at 500-1200 DEG C；90-120 points are roasted at preferably 650-700 DEG C
Clock.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (1)
Non-oxidized gas can be selected from non-oxide gas commonly used in the art, either pure gas, or several gas shapes
At gaseous mixture.In preferred embodiment provided by the invention, non-oxidized gas includes nitrogen, carbon dioxide and inert gas
The combination of one or more of (helium, neon, argon gas etc.).
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in above-mentioned steps (1), the party
Method further includes being further processed thick sulphur, and then obtain sulphur and the step of impurity；The impurity is preferably arsenic.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (2)
The process of wet oxidation process includes：Water is added to be made slurry the desulfurization slag, the quality hundred of desulfurization slag in the slurry
It is 1-79.9% to divide specific concentration；Oxidation processes are carried out to the slurry, the containing cuprous sulfide, iron oxide and elemental sulfur is made
One mixed material.The wet process oxidation technology that the present invention uses can make ferrous sulfide be converted into iron oxide and elemental sulfur, and energy
Enough good controlling reaction temperatures, to ensure progress that oxidation can be uniform and stable.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (2)
The condition of oxidation processes condition is：It is aoxidized 2-60 hours at 50-99 DEG C；It is aoxidized 40-50 hours at preferably 90-95 DEG C.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (3)
The concrete mode of extraction simple substance sulphuring treatment is to be evaporated in vacuo；Preferably, the condition of vacuum distillation is to be distilled at 160-300 DEG C
10-120 minutes.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (4)
Chloridising roasting processing includes that chloridising roasting process, the condition of chloridising roasting are that 10-120 points are roasted at 500-1300 DEG C at least once
Clock.Used chlorinating agent can be conventional reagent, such as chlorine and/or calcium chloride.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in above-mentioned steps (4), the work
Skill further includes the steps that preparing iron ore concentrate or sponge iron using the chlorination slag.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in above-mentioned steps (4), to cigarette
Gas is further processed, and the process to prepare metallic copper includes：
A. washing recycling is carried out to flue gas with cleaning solution, solution after being washed；
B. dense washing filtration treatment is carried out to solution after the washing, obtains gold and silver filter residue and chlorination copper-lead zinc feed liquid
The chloride solution of lead, zinc (copper)；
C. the chlorination copper-lead zinc feed liquid (containing a certain amount of ferro element in the feed liquid) is carried out in calcium hydroxide gradient
And processing, obtain in the iron of solid phase and slag, copper in and slag, lead zinc in and slag and liquid phase calcium chloride solution；
D. from extracting in the copper and further metallic copper in slag.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in above-mentioned steps (4), to cigarette
Gas is further processed, and the process to prepare copper chloride includes：
On the basis of stating step a to step b on the implementation, concentration is carried out to the chlorination copper-lead zinc feed liquid of acquisition, is obtained
It to chlorination copper-lead zinc solid, is then accurately distilled and separating treatment, copper chloride is made.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in above-mentioned steps (4), to cigarette
Gas is further processed, and the process to prepare copper oxide includes：
On the basis of stating step a to step c on the implementation, in the copper of acquisition and slag is filtered drying process, roasting
Copper oxide is made afterwards.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in step (4) chlorination copper-lead zinc material
During liquid gradient neutralizes, which further includes to further being located in the gold and silver filter residue, iron and with slag in slag, lead zinc
Reason, the step of to extract respective metal.For example, the production of cyaniding carbon-impregnated technique remanufacture gold and silver may be used for gold and silver filter residue
Product can also use other gold and silver production technologies to produce gold and silver product；For in lead zinc and slag, lead-zinc production work may be used
Skill produces lead zinc product or lead cadmia.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that detached from flue gas in step (4)
During copper and mixed metal, which further includes in the calcium chloride solution return to step a for obtaining step c, as washing
The step of washing liquid.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that in step (4) to flue gas into traveling
The processing of one step, during preparing metallic copper, which further includes extracting calcium chloride from the calcium chloride solution that step c is obtained
Or chlorine is prepared, and the step of calcium chloride or chlorine are used as chlorinating agent in chloridising roasting processing.It is further preferred that logical
It crosses the calcium chloride solution and prepares the mode of chlorine and be：Calcium chloride is extracted from the calcium chloride solution, by calcium chloride and oxygen
SiClx carries out reaction and prepares chlorine and calcium silicates, or calcium chloride with sulfur dioxide react to prepare chlorine and calcium sulfate.
In the technique that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that described in above-mentioned steps (4)
To carry out, chloridising roasting process, second of chloridising roasting process are obtained to first time chloridising roasting twice for chloridising roasting processing
Chlorination slag carries out chloridising roasting again and handles.It is further preferred that the technique will also be in first time chloridising roasting process steps c
In the iron that process obtains and chlorination slag that slag and first time chloridising roasting process obtain is mixed includes after closing, and progress is for the second time together
The step of chloridising roasting.Preferably, the material of first time chloridising roasting can be granular material, can also be pelletizing shape material；
The material of second of chloridising roasting is pelletizing shape material.
When it is tough cathode that above-mentioned copper sulfide, which produces copper described in the technique of metallic copper or copper compound, above-mentioned steps d's
Process includes：To in the copper in above-mentioned steps d and slag is purged chlorion and sulfuric acid treatment, then being produced with extraction electrodeposition method
Tough cathode；The extraction electrodeposition method includes copper ion extraction step, organic phase washing step, stripping steps and copper electrodeposition step
Suddenly.
In the technique of above-mentioned a kind of copper sulfide production metallic copper or copper compound, wherein the copper sulfide includes copper sulfide
Ore, copper sulfide concentrate contain copper sulfide mixture material.
In a kind of preferred embodiment provided by the invention, copper sulfide produces metallic copper or the technique of copper compound is specific
For：The technique carries out copper sulfide desulphurizing roasting using nonoxidizing atmosphere, and output contains the de- of the elements such as cuprous sulfide, ferrous sulfide
Sulphur slag, and output contains the thick sulphur of the impurity such as arsenic, dust, thick sulphur carries out refining and distilling, produces sulfur product, arsenic can give birth to
Output arsenic product.The desulfurization slag containing elements such as cuprous sulfide, ferrous sulfides of output is subjected to wet oxidation, sulphur therein
Change ferrous iron and be oxidized to iron oxide and elemental sulfur, first containing elements such as cuprous sulfide, iron oxide, elemental sulfurs of output is mixed
Close material dewatering drying；The first mixed material after dehydration and drying carries out elemental sulfur distillation using vacuum distillation mode, produces
Sulfur product and the second mixed material containing elements such as cuprous sulfide, iron oxide.Second mixed material is subjected to first time chlorine
Change roasting, chloridising roasting flue gas carries out washing recycling；Chlorination slag after chloridising roasting can produce iron ore concentrate or sponge iron,
Can carry out second of chloridising roasting, output iron ore pellets and flue gas, flue gas caused by second of chloridising roasting with for the first time
The merging of chloridising roasting flue gas carries out washing recycling.Chloridising roasting flue gas washing generate containing elements such as copper, gold, silver, lead, zinc
Cleaning solution is respectively processed；Chloridising roasting flue gas washing liquid is first carried out dense washing to filter, obtains gold and silver filter residue and chlorination
Copper-lead zinc feed liquid；Wherein gold and silver filter residue produces gold and silver product using gold and silver production technology；Chlorination copper-lead zinc feed liquid uses hydroxide
Calcium carries out gradient neutralization, respectively in output iron and in slag, copper and in slag and lead zinc and slag and calcium chloride solution；Wherein output
In copper and slag carries out thickening and washing dehydration, after removing chlorion, uses sulfuric acid treatment；And it is qualified using the production of extraction electrodeposition method
Cathode copper products；In the lead zinc of institute's output and slag produces lead zinc product or lead cadmia using lead-zinc production technique；The iron of output
It neutralizes slag and returns to second of chlorination Pelletizing Process；The calcium chloride solution of output returns to chloridising roasting flue gas washing operation, when
When calcium chloride solution is close to saturated concentration, calcium chloride precipitation is produced using falling temperature method, is dehydrated after filtering and produces anhydrous calcium chloride；Nothing
Water calcium chloride is used for chloridising roasting operation.
The present invention also provides the system of a kind of copper sulfide production metallic copper or copper compound, which includes：Connect successively
Logical desulphurizing roasting device, wet oxidation device, extraction elemental sulfur device, chloridising roasting device, flue gas washing retracting device, chlorine
Change copper-lead zinc feed liquid gradient neutralisation treatment device and copper, lead, zinc Metal Production device；
The desulphurizing roasting device is used to carry out desulphurizing roasting processing to copper sulfide under nonoxidizing atmosphere, to be contained
The desulfurization slag and thick sulphur of cuprous sulfide and ferrous sulfide；
The wet oxidation device is used to carry out wet oxidation process to the desulfurization slag, and ferrous sulfide is made to be converted into oxygen
Change iron and elemental sulfur, to obtain the first mixed material containing cuprous sulfide, iron oxide and elemental sulfur；
The extraction elemental sulfur device to first mixed material for extracting simple substance sulphuring treatment, to be contained
The second mixed material and sulphur of cuprous sulfide, iron oxide；
The chloridising roasting device is used to carry out chloridising roasting processing to second mixed material, obtains flue gas and chlorination
Slag；
The flue gas washing retracting device is used to recycle copper chloride and chlorination mixed metal from the flue gas, is contained
Solution after the washing of copper chloride and chlorination mixed metal；
The dense washing filtration treatment of solution after the washing, to obtain gold and silver filter residue and chlorination copper-lead zinc feed liquid；
The chlorination copper-lead zinc feed liquid gradient neutralisation treatment device carries out calcium hydroxide gradient for chlorination copper-lead zinc feed liquid
Neutralisation treatment, obtain in the iron of solid phase and slag, copper in and slag, lead zinc in and slag and liquid phase calcium chloride solution；
The copper, lead, zinc Metal Production device are respectively used to from producing metallic copper or copper compound in the copper and in slag,
From in lead zinc and slag in produce lead zinc metal.
Can be directly to be connected in the system that above-mentioned copper sulfide produces metallic copper or copper compound, between each device,
Can be indirect communication, it may be necessary to increase necessary auxiliary device between related device.Those skilled in the art can basis
Necessary connecting line and valve is arranged in actual needs.Used device can select the conventional equipment of this field substantially, respectively
Mode of communicating between device can be determined according to mutual material relationships.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, desulphurizing roasting device can be suitably modified
The routine calciner such as rotary kiln carries out desulphurizing roasting.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, the wet oxidation device can be agitator
Or flotation device, slurry preparation can be prepared in dedicated slot or directly be carried out in wet method agitator or flotation device.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the system further includes for handling
The thick sulphur refining plant of the thick sulphur of output in desulphurizing roasting device.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the extraction elemental sulfur device is
Vacuum distillation plant.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the flue gas washing retracting device
Including washing liquid bath, scrubbing tower, concentrator, filter, calcium hydroxide solution slot and the gradient being directly or indirectly connected to successively
Neutralisation treatment device；The washing liquid bath is for preparing and storing cleaning solution；The scrubbing tower is used for using cleaning solution to flue gas
Washing recycling is carried out, with solution after being washed；The concentrator is dense for being carried out to solution after the washing, and uses
Filter processing, to obtain gold and silver filter residue and chlorination copper-lead zinc feed liquid；The calcium hydroxide solution slot is for preparing and storing hydrogen-oxygen
Change calcium solution；The chlorination copper-lead zinc feed liquid gradient neutralisation treatment device is used to carry out hydroxide to the chlorination copper-lead zinc feed liquid
Calcium gradient neutralisation treatment, in the iron to obtain solid phase and in slag, copper and in slag, lead zinc and the calcium chloride solution of slag and liquid phase.
It is further preferred that the chlorination copper-lead zinc feed liquid gradient neutralisation treatment device is provided with for conveying calcium chloride to washing liquid bath
The pipeline and calcium hydroxide solution slot of solution, the calcium hydroxide solution slot is for preparing and storing calcium hydroxide solution.More
Preferably, which further includes calcium chloride precipitation equipment, for obtaining chlorination from the calcium chloride solution in gradient and in device
Calcium solid.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the production tough cathode device is
Electrodeposition produces tough cathode device, which includes sulfuric acid treatment equipment and extraction electrodeposition component.
In the system that above-mentioned copper sulfide produces metallic copper or copper compound, it is preferable that the copper sulfide includes copper sulfide
Ore, copper sulfide concentrate or the mixed material containing copper sulfide；The copper compound is copper chloride or copper oxide；The metallic copper
For tough cathode.
The major advantage of scheme provided by the present invention is：
(1) present invention carries out copper sulfide desulfurization with roasting technique using the sulfur removal technology under nonoxidizing atmosphere so that in copper sulfide
Sulphur produces sulfur product in the form of elemental sulfur, and the problem of sulfuric acid must be produced by avoiding conventional pyrogenic process copper smelting plant, to solve
Certainly conventional copper pyrometallurgy addressing caused by sulfuric acid marketing problem limits.
(2) the present invention program is used to invest very low, only conventional pyrogenic process Copper making using copper sulfide production tough cathode
The 20-30% of the investment of factory so that the investment of copper sulfide production tough cathode factory is greatly lowered.
(3) the present invention program is compared with conventional pyrogenic process Copper making technique, most valuable elements in copper sulfide
It is recycled, and product sale can be done, only a small amount of non-hazardous waste of output.
(4) for the present invention program compared with conventional pyrogenic process Copper making technique, the production cost of tough cathode is about conventional pyrogenic process copper
The 70-80% of smelting process；Simultaneously because can fecund go out sulfur product, iron product and lead zinc product, it is remote in economic benefit
Higher than conventional pyrogenic process copper smelting plant.
(5) sulfur dioxide, nitrogen oxides etc. can be greatly reduced compared with conventional pyrogenic process Copper making technique in the present invention program
Output, while wastewater zero discharge can be made, therefore it is more environmentally-friendly.
(6) the present invention program is adapted to low-grade and high impure vulcanization compared with conventional pyrogenic process Copper making technique
Copper, copper sulfide concentrate and therefore the copper sulfide of various complexity can be handled containing copper sulfide mixture material.It is technically economical
On all have feasibility, and there is stronger exploitativeness.
Description of the drawings
Fig. 1 is the epimere flow diagram that copper sulfide concentrate prepares tough cathode in embodiment 1；
Fig. 2 is the hypomere flow diagram that copper sulfide concentrate prepares tough cathode in embodiment 1.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
A kind of copper sulfide production metallic copper or copper compound device are present embodiments provided, and is produced using the device cloudy
The technique of pole copper, specifically：
The copper sulfide produces metallic copper or the system of copper compound includes：Desulphurizing roasting device, the wet method oxygen being sequentially communicated
Makeup, which sets, extract the dense washing of solution after elemental sulfur device, chloridising roasting device, flue gas washing retracting device, washing filters and sets
Standby, chlorination copper-lead zinc feed liquid gradient neutralisation treatment device and production copper, lead, zinc metal device；The system further includes following depth
Processing unit (plant) or auxiliary device：Drying device, thick sulphur refining plant, calcium chloride precipitation equipment, calcium chloride preparing chlorine gas device etc.；
Desulphurizing roasting device is used to carry out desulphurizing roasting processing to copper sulfide under nonoxidizing atmosphere, to obtain containing vulcanization
Cuprous and ferrous sulfide desulfurization slag and thick sulphur；Wet oxidation device is used to carry out wet oxidation process to desulfurization slag,
Ferrous sulfide is set to be converted into iron oxide and elemental sulfur, to obtain the first mixture containing cuprous sulfide, iron oxide and elemental sulfur
Material；Extraction elemental sulfur device to the first mixed material for extracting simple substance sulphuring treatment, to obtain containing cuprous sulfide, oxidation
The second mixed material and sulfur product of iron；Chloridising roasting device is used to carry out chloridising roasting processing to the second mixed material, obtains
To flue gas and chlorination slag；Flue gas washing retracting device is used to recycle copper chloride and chlorination mixed metal from the flue gas, obtains
Solution after must washing；The dense washing filtration treatment of solution after the washing, to obtain gold and silver filter residue and chlorination copper-lead zinc feed liquid；
The chlorination copper-lead zinc feed liquid gradient neutralisation treatment device carries out calcium hydroxide gradient with chlorination in copper-lead zinc feed liquid
Neutralisation treatment, obtain in the iron of solid phase and slag, copper in and slag, lead zinc in and slag and liquid phase calcium chloride solution；
The production copper, lead, zinc metal device are respectively used to produce copper metal from the copper and in slag, are neutralized from lead zinc
Extraction production lead zinc metal in slag.
Desulphurizing roasting device is the rotary kiln that can be passed through non-oxidized gas；Wet oxidation device is mineral dressing flotation；Extraction
Elemental sulfur device is vacuum distillation plant；Chloridising roasting device is conventional chlorinating roasting apparatus；Thick sulphur refining plant is for handling
The thick sulphur of output in desulphurizing roasting device；It is that electrodeposition produces tough cathode device to produce tough cathode device, which includes at sulfuric acid
Manage equipment and extraction electrodeposition component；
Flue gas washing retracting device include the washing liquid bath for being sequentially communicated (directly or indirectly connection), scrubbing tower, concentrator,
Filter, calcium hydroxide solution slot and chlorination copper-lead zinc feed liquid gradient neutralisation treatment device；Liquid bath is washed to wash for storing
Liquid；Scrubbing tower carries out washing recycling for cleaning solution to flue gas, with solution after being washed；Concentrator is used for solution after washing
Carry out dense processing；De- liquid of the filter for solution after the washing after dense, to obtain gold and silver filter residue and chlorination copper-lead zinc material
Liquid；Calcium hydroxide solution slot is for preparing and storing calcium hydroxide solution；Chlorination copper-lead zinc feed liquid gradient neutralisation treatment device is used
In carrying out calcium hydroxide gradient neutralisation treatment to chlorination copper-lead zinc feed liquid, in the iron to obtain solid phase and in slag, copper and slag, lead zinc
Neutralize slag and the calcium chloride solution of liquid phase；Gradient neutralisation treatment device is provided with for molten to washing liquid bath conveying calcium chloride
The pipeline of liquid；
Calcium chloride precipitation equipment is used to obtain calcium chloride solid from the calcium chloride solution in gradient and in device；
Calcium chloride preparing chlorine gas device is used to convert partial oxidation calcium solid to chlorine；
Necessary connecting line and valve are provided between each device.
Concrete technology is (detailed process is shown in Fig. 1 and Fig. 2)：It is non-to enter the progress of desulphurizing roasting device after copper sulfide concentrate drying
Oxidation sweetening roasts, and the desulfurization slag containing elements such as cuprous sulfide, ferrous sulfides of output and contains the impurity such as arsenic, dust
Thick sulphur, thick sulphur carry out refining and distilling, produce sulfur product, and arsenic produces arsenic product；Non-oxidative desulfurization calcination temperature is 670 DEG C, roasting
It is 100 minutes to burn the time, using nitrogen and carbon dioxide gas mixture as protective gas.Output contains cuprous sulfide, sulphur
The desulfurization slag for changing the elements such as ferrous iron is aoxidized using wet process oxidation technology, ferrous sulfide therein be oxidized to iron oxide with
Elemental sulfur forms the first mixed material (i.e. mixed material in Fig. 1) containing elements such as cuprous sulfide, iron oxide, elemental sulfurs；
Using mineral dressing flotation as wet oxidation equipment, a concentration of the 50% of material oxidation, oxidization time is 50 hours.By described
One mixed material deviates from elemental sulfur after dewatered drying, using vacuum distillation plant, produces sulfur product, and output contains sulphur
Change the second mixed material (i.e. distillation slag in Fig. 1) of the metals such as cuprous, iron oxide；190 DEG C of temperature, distillation time is evaporated in vacuo
90 minutes.Chloridising roasting is carried out to second mixed material using chloridising roasting device, using chlorine as first time chlorination
The chlorinating agent of roasting；Roasting generate flue gas handled using flue gas washing retracting device, obtain contain copper, gold, silver, lead,
The cleaning solution and chlorination slag of the elements such as zinc；1050 DEG C of the temperature of first time chloridising roasting, roasting time 60 minutes.To for the first time
Chlorination slag after chloridising roasting carries out second of chlorination pellet roasting, the iron ball group's product and flue gas of output qualification；To second
Flue gas caused by secondary chloridising roasting merges with first time chloridising roasting flue gas carries out washing recycling；Second of chloridising roasting temperature
1200 DEG C, roasting time 45 minutes.The cleaning solution containing elements such as copper, gold, silver, lead, zinc that washing is collected into is carried out
Dense washing filtration treatment obtains gold and silver filter residue and chlorination copper-lead zinc feed liquid；Wherein gold and silver filter residue is given birth to using gold and silver production technology
Pan silver products；Chlorination copper-lead zinc feed liquid carries out gradient neutralization using calcium hydroxide, obtain in iron and slag, copper in and slag and lead zinc
Neutralize slag and calcium chloride solution；Sulfuric acid treatment is used wherein in copper and after slag removing chloride ion, then uses extraction electrodeposition method
Produce qualified tough cathode；In the lead zinc of institute's output and slag produces lead zinc product using lead-zinc production technique；In the iron of output
Second of chlorination Pelletizing Process is returned with slag；The calcium chloride solution of output returns to chloridising roasting flue gas washing operation, works as chlorine
Change calcium solution close to saturated concentration, taking-up partial oxidation calcium is molten to produce calcium chloride precipitation using falling temperature method, and filtering means dehydration produces nothing
Water calcium chloride；Anhydrous calcium chloride can be used for producing chlorine, and calcium chloride can be used for chloridising roasting.
As can be seen from the above-described embodiment, copper sulfide provided by the invention produces the technique of metallic copper or copper compound and is
System, effectively can be produced as copper products, and the valuable metal of recyclable copper sulfide association by copper sulfide.With existing technology phase
Than the present invention has many advantages, such as that production cost is low, low energy consumption, comprehensive benefit is good and environmental friendly.As it can be seen that the present invention has
High economic value and the value of environmental protection and practical value.
Claims (31)
1. the technique of a kind of copper sulfide production metallic copper or copper compound, which is characterized in that the technique includes the following steps：
(1) desulphurizing roasting processing is carried out to copper sulfide under nonoxidizing atmosphere, to obtain containing cuprous sulfide and ferrous sulfide
Desulfurization slag and thick sulphur；The nonoxidizing atmosphere is the environmental protection that non-oxidized gas is formed, or is subnormal ambient；
(2) wet oxidation process is carried out to the desulfurization slag, so that ferrous sulfide is converted into iron oxide and elemental sulfur, to be contained
There is the first mixed material of cuprous sulfide, iron oxide and elemental sulfur；
(3) simple substance sulphuring treatment is extracted to first mixed material, with obtain containing cuprous sulfide, iron oxide it is second mixed
Close material；
(4) chloridising roasting processing is carried out to second mixed material, obtains flue gas and chlorination slag, and to flue gas into advancing one
Step processing, to prepare metallic copper or copper compound.
2. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (1), the condition of the desulphurizing roasting processing is to be roasted 10-120 minutes at 500-1200 DEG C.
3. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (1), the condition of the desulphurizing roasting processing is to be roasted 90-120 minutes at 650-700 DEG C.
4. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (1), the non-oxidized gas includes the combination of one or more of nitrogen, carbon dioxide and inert gas gas.
5. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that in above-mentioned step
Suddenly further include being further processed thick sulphur, and then obtain sulphur and the step of impurity in (1).
6. the technique of copper sulfide production metallic copper according to claim 5 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (1), the impurity is arsenic.
7. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (2), the process of the wet oxidation process includes：
Water is added to be made slurry the desulfurization slag, the mass percent concentration of desulfurization slag is 1-79.9% in the slurry；
Oxidation processes are carried out to the slurry, the first mixed material containing cuprous sulfide, iron oxide and elemental sulfur is made.
8. the technique of copper sulfide production metallic copper according to claim 7 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (2), the condition of the oxidation processes is：It is aoxidized 2-60 hours at 50-99 DEG C.
9. the technique of copper sulfide production metallic copper according to claim 7 or copper compound, which is characterized in that in above-mentioned step
Suddenly in (2), the condition of the oxidation processes is：It is aoxidized 40-50 hours at 90-95 DEG C.
10. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that above-mentioned
In step (3), the concrete mode of the extraction simple substance sulphuring treatment is to be evaporated in vacuo.
11. the technique of copper sulfide production metallic copper according to claim 10 or copper compound, which is characterized in that above-mentioned
In step (3), the condition of vacuum distillation is to be distilled 10-120 minutes at 160-300 DEG C.
12. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that above-mentioned
In step (4), the chloridising roasting processing includes chloridising roasting process at least once, and the condition of chloridising roasting is 500-1300 DEG C
Lower roasting 10-120 minutes.
13. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that above-mentioned
In step (4), which further includes the steps that preparing iron ore concentrate or sponge iron using the chlorination slag.
14. the technique of copper sulfide production metallic copper according to claim 1 or copper compound, which is characterized in that above-mentioned
In step (4), flue gas is further processed, the process to prepare metallic copper includes：
A. washing recycling is carried out to flue gas with cleaning solution, obtains solution after the washing containing copper chloride and chlorination mixed metal；
B. dense washing filtration treatment is carried out to solution after the washing, obtains gold and silver filter residue and chlorination copper-lead zinc feed liquid；
C. calcium hydroxide gradient neutralisation treatment is carried out to the chlorination copper-lead zinc feed liquid, obtains in the iron of solid phase and slag, copper neutralizes
In slag, lead zinc and the calcium chloride solution of slag and liquid phase；
D. from extracting in the copper and further metallic copper in slag.
15. the technique of copper sulfide production metallic copper according to claim 14 or copper compound, which is characterized in that above-mentioned
In step (4), the copper compound is copper chloride or copper oxide；The metallic copper is tough cathode.
16. the technique of copper sulfide production metallic copper according to claim 15 or copper compound, which is characterized in that above-mentioned
In step (4), flue gas is further processed, the process to prepare copper chloride includes：
On the basis of stating step a to step b on the implementation, concentration is carried out to the chlorination copper-lead zinc feed liquid of acquisition, obtains chlorine
Change copper-lead zinc solid, then accurately distilled and separating treatment, copper chloride is made.
17. the technique of copper sulfide production metallic copper according to claim 15 or copper compound, which is characterized in that above-mentioned
In step (4), flue gas is further processed, the process to prepare copper oxide includes：
On the basis of stating step a to step c on the implementation, in the copper of acquisition and slag is filtered drying process, being made after roasting
Obtain copper oxide.
18. the technique of copper sulfide production metallic copper according to claim 14 or copper compound, which is characterized in that above-mentioned
In step (4), which further includes to being further processed in the gold and silver filter residue, iron and with slag in slag, lead zinc, with extraction
The step of respective metal.
19. the technique of copper sulfide production metallic copper according to claim 14 or copper compound, which is characterized in that above-mentioned
In step (4), the step of which further includes in the calcium chloride solution return to step a for obtaining step c, be used as cleaning solution.
20. the technique of copper sulfide production metallic copper according to claim 14 or copper compound, which is characterized in that above-mentioned
In step (4), which further includes extracting calcium chloride from the calcium chloride solution that step c is obtained or preparing chlorine, and will be described
Calcium chloride or chlorine are used as the step of chlorinating agent in chloridising roasting processing.
21. the technique of copper sulfide production metallic copper according to claim 20 or copper compound, which is characterized in that above-mentioned
In step (4), it is in such a way that the calcium chloride solution prepares chlorine：Calcium chloride is extracted from the calcium chloride solution,
Calcium chloride with silica react and prepares chlorine and calcium silicates, or calcium chloride with sulfur dioxide react to prepare chlorine
And calcium sulfate.
22. the technique of copper sulfide production metallic copper according to claim 20 or copper compound, which is characterized in that above-mentioned
In step (4), to carry out chloridising roasting process twice, second of chloridising roasting process is to for the first time for the chloridising roasting processing
The chlorination slag that chloridising roasting obtains carries out chloridising roasting again and handles.
23. the technique of copper sulfide production metallic copper according to claim 22 or copper compound, which is characterized in that above-mentioned
In step (4), which further includes in the iron that will be obtained in first time chloridising roasting process steps c and slag is roasted with first time chlorination
After burning the chlorination slag mixing of output, the step of carrying out second of chloridising roasting together.
24. the technique of copper sulfide production metallic copper according to claim 23 or copper compound, which is characterized in that above-mentioned
In step (4), the material of first time chloridising roasting is granular material or pelletizing shape material；The material of second of chloridising roasting is ball
Bulk material.
25. the technique of copper sulfide production metallic copper according to claim 15 or copper compound, which is characterized in that the copper
For tough cathode when, the process of above-mentioned steps d includes：
To in copper and slag is purged chlorion and sulfuric acid treatment, then producing tough cathode with extraction electrodeposition method；The extraction electricity
Area method includes copper ion extraction step, organic phase washing step, stripping steps and copper electrodeposition step.
26. the system of a kind of copper sulfide production metallic copper or copper compound, which is characterized in that the system includes：
Desulphurizing roasting device, wet oxidation device, extraction elemental sulfur device, chloridising roasting device, the flue gas washing being sequentially communicated
The dense washing filter plant of solution, chlorination copper-lead zinc feed liquid gradient neutralisation treatment device and copper after retracting device, washing, lead,
Zinc Metal Production device；
The desulphurizing roasting device is used to carry out desulphurizing roasting processing to copper sulfide under nonoxidizing atmosphere, to obtain containing vulcanization
Cuprous and ferrous sulfide desulfurization slag and thick sulphur；
The wet oxidation device is used to carry out wet oxidation process to the desulfurization slag, and ferrous sulfide is made to be converted into iron oxide
And elemental sulfur, to obtain the first mixed material containing cuprous sulfide, iron oxide and elemental sulfur；
The extraction elemental sulfur device to first mixed material for extracting simple substance sulphuring treatment, to obtain containing vulcanization
Cuprous, iron oxide the second mixed material and sulphur；
The chloridising roasting device is used to carry out chloridising roasting processing to second mixed material, obtains flue gas and chlorination is burnt
Slag；
The flue gas washing retracting device is used to recycle copper chloride and chlorination mixed metal from the flue gas, and acquisition contains chlorination
Solution after the washing of copper and chlorination mixed metal；
The dense washing filtration treatment of solution after the washing, to obtain gold and silver filter residue and chlorination copper-lead zinc feed liquid；
The chlorination copper-lead zinc feed liquid gradient neutralisation treatment device carries out calcium hydroxide gradient neutralization for chlorination copper-lead zinc feed liquid
Processing, obtain in the iron of solid phase and slag, copper in and slag, lead zinc in and slag and liquid phase calcium chloride solution；
The copper, lead, zinc Metal Production device are respectively used to produce metallic copper or copper compound from the copper and in slag, from lead
Lead zinc metal is produced in zinc and in slag.
27. the system of copper sulfide production metallic copper according to claim 26 or copper compound, which is characterized in that the system
It further include the thick sulphur refining plant for handling the thick sulphur of output in desulphurizing roasting device.
28. the system of copper sulfide production metallic copper according to claim 26 or copper compound, which is characterized in that the cigarette
Gas washing retracting device includes washing liquid bath, scrubbing tower, concentrator, the filter being sequentially communicated；
The washing liquid bath is for storing cleaning solution；
The scrubbing tower is used to using cleaning solution carry out washing recycling to flue gas, with solution after being washed；
The concentrator is used to carry out dense dehydration to solution after the washing, so using filter plant handled with
Obtain gold and silver filter residue and chlorination copper-lead zinc feed liquid；
The chlorination copper-lead zinc feed liquid gradient neutralisation treatment device is used to carry out calcium hydroxide ladder to the chlorination copper-lead zinc feed liquid
Neutralisation treatment is spent, in the iron to obtain solid phase and in slag, copper and in slag, lead zinc and the calcium chloride solution of slag and liquid phase.
29. the system of copper sulfide production metallic copper according to claim 28 or copper compound, which is characterized in that the chlorine
Change copper-lead zinc feed liquid gradient neutralisation treatment device to be provided with for the pipeline and hydrogen-oxygen to washing liquid bath conveying calcium chloride solution
Change calcium solution slot, the calcium hydroxide solution slot is for preparing and storing calcium hydroxide solution.
30. the system of copper sulfide production metallic copper according to claim 29 or copper compound, which is characterized in that the system
Further include calcium chloride precipitation equipment, for obtaining calcium chloride solid from the calcium chloride solution in gradient neutralization pond.
31. the system of copper sulfide production metallic copper according to claim 26 or copper compound, which is characterized in that the sulphur
Change copper-clad and includes copper sulfide ore, copper sulfide concentrate or the mixed material containing copper sulfide；The copper compound is copper chloride or oxygen
Change copper；The metallic copper is tough cathode.
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| CN1575346A (en) * | 2001-10-24 | 2005-02-02 | 奥托库姆普联合股份公司 | Method for purifying the solution in the hydrometallurgical processing of copper |
| CN106676284A (en) * | 2016-12-08 | 2017-05-17 | 中南大学 | Method for preparing raw material for preparation of nickel-base anode material precursor by using copper-nickel ores |
| CN206721329U (en) * | 2017-05-09 | 2017-12-08 | 刘慧南 | A kind of system of copper sulfide production metallic copper or copper compound |
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|---|---|---|---|---|
| CN1077497A (en) * | 1992-04-14 | 1993-10-20 | 刘秉贤 | Technology for wet-process cupper smelting |
| CN1575346A (en) * | 2001-10-24 | 2005-02-02 | 奥托库姆普联合股份公司 | Method for purifying the solution in the hydrometallurgical processing of copper |
| CN106676284A (en) * | 2016-12-08 | 2017-05-17 | 中南大学 | Method for preparing raw material for preparation of nickel-base anode material precursor by using copper-nickel ores |
| CN206721329U (en) * | 2017-05-09 | 2017-12-08 | 刘慧南 | A kind of system of copper sulfide production metallic copper or copper compound |
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