CN1407120A - Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' - Google Patents
Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' Download PDFInfo
- Publication number
- CN1407120A CN1407120A CN01123699A CN01123699A CN1407120A CN 1407120 A CN1407120 A CN 1407120A CN 01123699 A CN01123699 A CN 01123699A CN 01123699 A CN01123699 A CN 01123699A CN 1407120 A CN1407120 A CN 1407120A
- Authority
- CN
- China
- Prior art keywords
- copper
- leaching
- follows
- cuprous chloride
- sulfide concentrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000012141 concentrate Substances 0.000 title claims abstract description 19
- 238000004070 electrodeposition Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000002386 leaching Methods 0.000 claims abstract description 36
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 23
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000005363 electrowinning Methods 0.000 claims abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 8
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical group [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000000049 pigment Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 239000012320 chlorinating reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 230000001180 sulfating effect Effects 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- -1 copper complex ion chloride salt Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- MPHXZVQYKBKSJV-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Cu+2].S(=O)=O Chemical compound S(=O)(=O)([O-])[O-].[Cu+2].S(=O)=O MPHXZVQYKBKSJV-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical class [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides a method for wet-process copper smelting of copper sulfide concentrate, which is characterized in that in the production process of 'oxidation leaching-cuprous chloride-electrowinning refined copper' of the copper sulfide concentrate, a leaching agent, an oxidizing agent and a reducing agent are regenerated in the production of a product in the next step, and the purposes of producing various products of cuprous chloride, electrolytic copper, pigment iron red and sulfur by using one raw material of the copper sulfide concentrate are basically achieved. Simple process, low investment, low energy consumption, no three-waste pollution and high comprehensive utilization benefit.
Description
The invention belongs to the field of wet metallurgy process, relates to the problems of comprehensive utilization of copper sulfide concentrate, environmental protection, energy consumption reduction, benefit improvement and the like, provides a production process flow of copper sulfide concentrate of 'oxidation leaching-cuprous chloride-electrodeposition copper refining', and is a new process for domestic and foreign wet copper smelting at present.
At present, with the rapid development of the petrochemical industry, the dosage of cuprous chloride is increased year by year. The copper chloride is used for producing phthalocyanine blue series pigments and synthesizing organic silicon in China, and the gap of high-purity and high-activity cuprous chloride is larger. At present, the traditional production methods are dozens of methods, which can be summarized as a copper sulfate sulfur dioxide method, a chlorine salt air oxidation method or a chlorine oxidation-hydrolysis method, and all adopt copper sulfate, electrolytic copper or electrolytic copper scraps, so that the raw material cost is high, the waste liquid amount of the hydrolysis method is large, the product direct recovery rate is low, the product quality is poor, the environment is polluted, and the raw materials are difficult to obtain. There is a problem of secondary processing from electrolytic copper. Compared with the new process flow of the invention, the copper sulfide concentrate directly produces cuprous chloride, and electrolytic copper is produced by electrodeposition of cuprous chloride electrolyte, so that the traditional production process has unreasonable raw material route and wastes materials and energy. Meanwhile, the production flow of sulfating roasting-leaching-electrodeposition adopted by the domestic wet copper smelting is a revolution. Copper sulfide concentrateThe "roasting-leaching-electrodeposition" method for producing electrolytic copper alone (as shown in figure 1) has the following problems:<a>The sulfating roasting process has complex process and comprises the working procedures of boiling roasting, dust collection, gas washing, acid making, tail gas recovery and the like. The equipment is huge, the investment cost is high, the technical operation difficulty is high, the production is unstable, and the labor environment is poor.<II>In the leaching process of the copper calcine, an oxidant is difficult to select, iron removal and filtration are difficult, and iron red slag is difficult to separate from liquid and solid, so that the copper calcine is washed and separated by adopting a countercurrent decantation method, and the solution of the whole copper system is seriously expanded.<III>The power consumption is large and the acid mist is serious. In the process of electrodeposition of copper alone: (
) The insoluble anode separates out oxygen, the oxygen overvoltage is 0.6V, the electric energy applied to the anode is not utilized completely, and in addition, the residual iron in the electrolyte reaches 4-6 g/L, the current efficiency of electrolysis is seriously influenced, the power consumption of one ton of copper reaches 1700-2250 KWh, and the oxygen separation causes serious acid mist.<Fourthly>The waste liquid is difficult to treat, the cost is high because of sulfating roasting, copper in the roasted product is mainly water-soluble copper, two thirds of electrolyte generated in the next step of electrolysis needs to be extracted for treatment, and a large amount of alkali neutralizer needs to be consumed. Based on the defects, the production cost of the wet electrolytic copper is high, and enterprises lose the defect, so that more than ten wet copper smelting plants in China are forced to be in a production stop state or a production transfer state.
Aiming at that the vast majority of copper ore resources in China are chalcopyrite (CuFeS)2) The invention aims to provide a novel process for wet treatment of copper sulfide concentrate, and the principle flow of the novel process is shown in the attached figure 2. The process only uses copper sulfide concentrate for secondary oxidation leaching, ferric sulfate leaching and chlorine and oxygen leaching, the primary leaching solution is divided into a crystallization part to produce iron oxide red by a dry method, and SO is decomposed at the same time3And SO2Two thirds of the primary leachate is oxidized by air or oxygen to absorb SO in the mixed gas3Making Fe2(SO4)3And (4) regenerating. Oxidizing the secondary leaching solution with chlorine and oxygen, and heating the SO by a sodium citrate method2Absorbing the liquid, removing the SO2Reduction to prepare cuprous chloride, complete separation of copper and iron, desorption, cooling and absorptionSO decomposed from iron oxide red produced2And (4) regenerating the reducing agent. Dissolving solid cuprous chloride with circulating electrolyte, electrowinning to refine copper, and chlorinating agent Cl2And (4) regenerating. Extracting sulfur from the leaching residue by high pressure leaching method, distillation method,(NH4)2S leaching, a flotation method and the like. The process comprises four main processes of 'oxidation leaching-copper precipitation-electrodeposition-regeneration', and can simultaneously obtain four products of cuprous chloride, electrolytic copper, pigment iron oxide red and sulfur. Has the following characteristics:<a>Because the copper sulfide concentrate does not need to be acidified and roasted, the process is greatly simplified, the equipment is simple, and the investment is small;<II>Due to leaching agent H2SO4An oxidizing agent Fe2(SO4)3Chlorinating agent Cl2Reducing agent SO2The regeneration is carried out in the production of the product in the next step, the process and the raw material route are more reasonable, and the production cost is greatly reduced;<III>Because the solid wet cuprous chloride with the concentration of more than 99 percent is used to be matched with the chloride electrolyte for electrodeposition, the interference of iron removal and other metals is avoided, the current efficiency is improved, and the electrolysis process is simplified. The electrolytic process with monovalent copper complex ion chloride salt has the largest power saving range, which is about 70% of the total power consumption. Meanwhile, chlorine is separated out from the anode by electrolysis of a diaphragm method, so that the comprehensive energy consumption is further reduced, and in a word, the energy consumption can be greatly reduced;<fourthly>In the process, all the solution and gas are in closed cycle, so that acid expansion and redundant gas discharge cannot be generated, only a small amount of sulfuric acid and hydrochloric acid needs to be supplemented due to loss, and no three-waste pollution is caused;<five of them>Basically, the copper sulfide concentrate is used as a single raw material to produce various products of cuprous chloride, electrolytic copper, pigment iron oxide red and sulfur, so that mineral resources are comprehensively utilized, and higher economic benefit and social benefit are obtained.
The technical features of the present invention are further described in detail below with reference to fig. 2: as shown in figure 2, the cuprous chloride is directly prepared by primary and secondary oxidation leaching of copper sulfide concentrate, and sulfur dioxide reduction of secondary oxidation leaching liquid; electrolytic copper and oxidant chlorine are prepared by electrolytic deposition of cuprous chloride electrolyte; oxidizing the liquid part separated from the primary oxidation leachate by oxygen or air, and absorbing sulfur trioxide decomposed by iron oxide red produced by the residual part of solid in a dry method to prepare ferric sulfate of the primary oxidation leachate; the sodium citrate method is used for removing and absorbing liquid by sulfur dioxide, absorbing sulfur dioxide decomposed by iron oxide red produced by ferrous sulfate dry method, preparing reducing agent sulfur dioxide, and the whole flow is in closed cycle, and the materials are basically balanced.
Primary oxidation leaching: the material proportion is according to the oxidation leaching agent Fe2(SO4)3Fe in solution3+The mol ratio of the Fe to the Fe in the copper sulfide concentrate feed is preferably 2-3: 1, and the Fe3+The concentration is 60-120 g/L, the temperature is 85-95 ℃, and the pH value of the end point of the reaction is controlled within the range of 3.0-4.0 by using copper sulfide concentrate. The primary leaching solution enters FeSO4And (5) a shunting treatment process.
The main reaction formula is as follows:
secondary oxidation leaching: taking partial mother liquor and washing liquor for producing cuprous chloride as leaching solutions, introducing chlorine gas for oxidizing leaching at the reaction temperature of 95-105 ℃, preferably introducing the chlorine gas to the primary oxidizing leaching and feeding ore, wherein the ratio of the chlorine gas to the Cu mol in the primary oxidizing leaching is 1-1.2: 2, then introducing pure oxygen or compressed air to supplement sulfuric acid for oxidizing leaching, preferably introducing 1: 2 of the amount of sulfuric acid and the Cu mol, and controlling the end-point pH value of the reaction to be within 1.5-2.5, wherein the excess oxygen is excessive. The main reaction formula is as follows:
and (3) reducing sulfur dioxide: controlling the temperature of the secondary oxidation leaching solution to be 60-80 ℃, and introducing SO2The color of the solution is faded,and CuCl precipitation is not generatedAnd (4) finishing. The precipitate is washed and dried, and then the precipitate is washed and dried,the CuCl mass can reach more than 99%, most of mother liquor returns to primary oxidation leaching, and a small part of mother liquor and washing liquor are used for secondary oxidation leaching, and the main reactions are as follows:
electro-deposition refining of copper: the precipitated CuCl is filtered, washed and filtered by water and dilute hydrochloric acid to remove Fe2+And SO2- 4After the test reaches the standard, the copper is dissolved by electrolyte chloride, the diaphragm electrolysis method is adopted for electrodeposition, the electrolyte enters from the upper part of a cathode and exits from the bottom of an anode, the temperature of a copper dissolving head tank is 60-70 ℃, and enough pure copper materials are always kept to reduce Cu generated by the anode negative reaction2+Closed-loop closed circulation electrolysis, electrolytic copper generated at the cathode and Cl separated out at the anode2The chlorinating agent is regenerated. The electrolyte comprises the following components: CuCl: 0.6-0.75M, HCl: 1-2M, NaCl: 1-2M, temperature of 35-60 ℃, cell voltage of 2-2.6V and cathode current density of 150-300A/M2The anode current density is 300-1200A/m2The main reaction formula is as follows:
anode negative reaction:
and (3) elevated tank reduction reaction:
regeneration of primary oxidation leachate: and oxidizing the liquid part separated from the primary oxidation leachate by oxygen or air, and absorbing sulfur trioxide decomposed from the residual part of the solid produced by the dry method to prepare ferric sulfate of the primary oxidation leachate. Oxidizing and hydrolyzing at pH>2.7 to obtain Fe (SO)4)3And Fe (OH)3To obtain a slurry mixture. Absorbing and decomposing SO in mixed gas3At 60-80 deg.C, controlling pH to be less than 2.7, and using SO2Desorption, multistage negative pressure absorption of its main reaction formula:
reducing agent SO2Regeneration, sodium citrate method SO2Cooling, absorbing, heating, desorbing, absorbing SO decomposed from iron oxide red by ferrous sulfate dry method2And preparing reducing agent sulfur dioxide. Absorption conditions are as follows: controlling the temperature to be 30-50 ℃, controlling the final pH value to be about 3, performing multi-stage negative pressure absorption, losing sodium citrate, supplementing sodium carbonate during absorption, and supplementing citric acid during desorption. The reaction formula is as follows:
wherein Ct is citrate (Citric acid)
Extracting sulfur from the leached slag by high pressure leaching method or distillation method, (NH)4)2S leaching, a flotation method and the like.
The invention comprehensively compares the defects of the roasting-leaching-electrodeposition process adopted in the domestic copper sulfide concentrate wet copper smelting process, and canbe seen that the invention has the advantages of simple process, low investment, low energy consumption, no three-waste pollution and high comprehensive utilization benefit. Aiming at the fact that most of copper ore resources in China are chalcopyrite (CuFeS)2) And the electrolytic refining of copper by using the monovalent copper complex ion chloride salt electrolyte has great potential for saving electricity, and the process has wide development prospect.
Claims (7)
1. A method for wet-process copper smelting of copper sulfide concentrate is characterized in that the copper sulfide concentrate is secondarily oxidized and leached by ferric sulfate solution and chlorine gas oxygen respectively, and heated by a sodium citrate method SO2Absorption liquid, SO2Reducing the secondary leachate to prepare cuprous chloride, preparing electrolytic copper and chlorine by electrodeposition of chloride electrolyte of the cuprous chloride by a diaphragm method, oxidizing the liquid part separated from the primary oxidation leachate by oxygen or air, and absorbing the residual part to produce SO decomposed from iron oxide red by a dry method3Preparing primary oxidation leaching liquid ferric sulfate and cooling sodium citrate method SO2Removing liquid absorption, absorbing SO decomposed from iron oxide red produced by dry method2Preparation of reducing agent SO2。
2. The method of claim 1, wherein the primary oxidation leaching conditions are: oxidant Fe2(SO4)3Fe in solution3+The mol ratio of the Fe to the Fe in the copper sulfide concentrate feed is preferably 2-3: 1, and the Fe3+The concentration is 60-120 g/L. The reaction temperature is 85-95 ℃, and the pH value of the end point of the reaction is controlled within the range of 3.0-4.0.
The main reaction formula is as follows:
3. the method of claim 1, wherein the secondary oxidation leaching conditions are: the reaction temperature is 95-105 ℃, chlorine is introduced for oxidizing leaching, the ratio of the amount of chlorine introduced to the molar ratio of Cu in ore fed by primary oxidizing leaching is 1-1.2: 2, then pure oxygen or compressed air is introduced for supplementing sulfuric acid for oxidizing leaching, the ratio of the amount of sulfuric acid to the molar ratio of Cu is 1: 2, oxygen is excessive, the end-point PH value of the reaction is controlled within the range of 1.5-2.5, and the main reaction formula is as follows:
4. the method of claim 1, wherein the conditions for producing cuprous chloride by reduction of sulfur dioxide are as follows: introducing SO at the reaction temperature of 60-80 DEG C2The end point was that the solution faded and no CuCl precipitate was formed. The mother liquor and the washing liquor return to the primary oxidation leaching and the secondary oxidation leaching of the ingredients, and the main reaction formula is as follows:
5. the method of claim 1, wherein the electrolytic copper and the oxidant chlorine are prepared by electrowinning of cuprous chloride using a chloride electrolyte membrane process under conditions such that: the temperature of the high-order copper dissolution tank is 60-70 ℃, enough pure copper materials are always kept, electrolyte enters from the upper part of a cathode to the bottom of an anode and is electrolyzed in a closed and closed cycle manner, and the electrolysis conditions are as follows: the electrolyte comprises the following components: CuCl: 0.6-0.75M, HCl; 1-2M, NaCl: 1-2M, temperature 35-60 ℃, cell voltage 2-2.6V, cathode current density 150-2Anodic current density 300-2. The main reaction formula is as follows:
anode negative reaction:
and (3) elevated tank reduction reaction:
6. the method according to claim 1, characterized in that the conditions for preparing the ferric sulphate of the primary oxidation leach solution are: the ferrous sulfate in the primary oxidation leaching solution is oxidized and hydrolyzed under the condition that the pH value is more than 2.7 to prepare Fe2(SO4)3And Fe (OH)3Absorbing the calcined FeSO in the slurry mixed solution4Decomposed SO3And free SO in the process of preparing CuCl3Controlling the mixed gas absorption condition: the temperature is 60-80 ℃, the pH value ofthe batch absorption liquid is controlled to be less than 2.7, which is beneficial to SO2Desorption and multistage negative pressure absorption.
The main reaction formula is as follows:
7. the method of claim 1, wherein the cooled Nafarinaceous SO is2Removing liquid and absorbing SO2Conditions for preparing reducing agent sulfur dioxide: absorbing FeSO by using sodium citrate desorption solution with pH value of about 54SO decomposed from iron oxide red produced by dry method2Controlling the temperature to be 30-50 ℃, controlling the pH value at the end point to be about 3, carrying out multi-stage negative pressure absorption, losing sodium citrate, supplementing sodium carbonate during absorption, and supplementing citric acid during desorption. The reaction formula is as follows: wherein Ct is citrate (citric acid Gitric, acid)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01123699A CN1407120A (en) | 2001-09-03 | 2001-09-03 | Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01123699A CN1407120A (en) | 2001-09-03 | 2001-09-03 | Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1407120A true CN1407120A (en) | 2003-04-02 |
Family
ID=4665225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01123699A Pending CN1407120A (en) | 2001-09-03 | 2001-09-03 | Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1407120A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014779A (en) * | 2012-03-18 | 2013-04-03 | 英德佳纳金属科技有限公司 | Multistage ore slurry decomposition-electrodeposition cell and decomposition-electrodeposition combined technique |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN103930598A (en) * | 2011-07-08 | 2014-07-16 | 化工学院 | Effect of operating parameters on the performance of electrochemical cell in copper-chlorine cycle |
| CN106430281A (en) * | 2016-09-26 | 2017-02-22 | 珠海格力电器股份有限公司 | Copper dissolving method and apparatus |
| CN107354482A (en) * | 2016-05-10 | 2017-11-17 | 日立金属株式会社 | The manufacture method and refined copper of refined copper and the manufacture method and electric wire of electric wire |
| CN110629252A (en) * | 2019-09-29 | 2019-12-31 | 昆明理工大学 | Method for preparing metal copper by electrolytic refining |
| CN111392944A (en) * | 2020-03-24 | 2020-07-10 | 宁波神化特种化学品集成有限公司 | Treatment method of cuprous cyanide production wastewater |
| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
-
2001
- 2001-09-03 CN CN01123699A patent/CN1407120A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930598A (en) * | 2011-07-08 | 2014-07-16 | 化工学院 | Effect of operating parameters on the performance of electrochemical cell in copper-chlorine cycle |
| CN103014779A (en) * | 2012-03-18 | 2013-04-03 | 英德佳纳金属科技有限公司 | Multistage ore slurry decomposition-electrodeposition cell and decomposition-electrodeposition combined technique |
| CN103014779B (en) * | 2012-03-18 | 2015-07-29 | 英德佳纳金属科技有限公司 | A kind of multistage ore pulp decomposes Winning cell and decomposes electrodeposition process integration |
| CN103422154A (en) * | 2012-05-24 | 2013-12-04 | 叶福祥 | Cuprous chloride (Cu+, cuCL) ion diaphragm electrodeposition regeneration of circuit board acidic waste etching solution |
| CN107354482A (en) * | 2016-05-10 | 2017-11-17 | 日立金属株式会社 | The manufacture method and refined copper of refined copper and the manufacture method and electric wire of electric wire |
| CN107354482B (en) * | 2016-05-10 | 2021-01-05 | 日立金属株式会社 | Method for producing refined copper, method for producing electric wire, and electric wire |
| CN106430281A (en) * | 2016-09-26 | 2017-02-22 | 珠海格力电器股份有限公司 | Copper dissolving method and apparatus |
| CN106430281B (en) * | 2016-09-26 | 2019-02-26 | 珠海格力电器股份有限公司 | Copper dissolving method and apparatus |
| CN110629252A (en) * | 2019-09-29 | 2019-12-31 | 昆明理工大学 | Method for preparing metal copper by electrolytic refining |
| CN110629252B (en) * | 2019-09-29 | 2021-05-04 | 昆明理工大学 | Method for preparing metal copper by electrolytic refining |
| CN111392944A (en) * | 2020-03-24 | 2020-07-10 | 宁波神化特种化学品集成有限公司 | Treatment method of cuprous cyanide production wastewater |
| CN113088722A (en) * | 2021-03-17 | 2021-07-09 | 磨名言 | Method for electrolytically recovering copper from copper sulfide ore |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108622943A (en) | A method of LITHIUM BATTERY nickel sulfate and cobaltous sulfate are produced with useless nickel cobalt (alloy) | |
| CN108624759B (en) | Method for comprehensively recovering valuable metals from white smoke | |
| CN107162067A (en) | A kind of method that high-purity sulphuric acid nickel is reclaimed from nickeliferous old and useless battery | |
| CN107354484A (en) | Method for removing chlorine in zinc electrolysis waste liquid | |
| CN103572313A (en) | Production method for mercury-free alkaline-manganese type electrolytic manganese dioxide | |
| CN108149015A (en) | A kind of method of valuable constituent element in oxygen-enriched Selectively leaching extraction vanadium titano-magnetite | |
| CN112708777B (en) | Method for recovering zinc sulfate from zinc-containing waste | |
| CN114318417B (en) | Method for producing electrolytic manganese by low-grade manganese oxide three-ore method | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| CN112410555B (en) | Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue | |
| CN108517425A (en) | A kind of method of calcium ions and magnesium ions in reduction electrolytic manganese qualifying liquid | |
| CN113511664A (en) | Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste | |
| CN111455189B (en) | Method for leaching copper from tin-copper slag | |
| CN109112560A (en) | A method of high purity tellurium is prepared using copper telluride | |
| CN114540641A (en) | Low-cost efficient open circuit and resource utilization method for arsenic in copper electrolysis | |
| CN1407120A (en) | Copper sulfide concentrate 'oxidation leaching-cuprous chloride-electro-deposition refined copper' | |
| CN107385220A (en) | A kind of method of the reclaiming high purity nickel from waste nickel catalyst | |
| CN106756008A (en) | The method that two sections of adverse current atmospheric pressure oxidations of sulfonic acid solutions leach lead in concentrate of lead sulfide ore | |
| CN106542506A (en) | A kind of method that selenium is reclaimed from heavy tellurium waste liquid | |
| CN109536992B (en) | Method for purifying copper electrolyte by two-removing and two-accumulating | |
| CN107245574A (en) | A kind of technique dechlorinated in zinc electrolyte | |
| CN113373314B (en) | Method for efficiently recycling scattered metal tellurium from cuprous telluride residues | |
| CN106591586A (en) | Method for recovering multiple kinds of metal from flue dust in copper smelting | |
| CN100590230C (en) | Method for synchronously electrolyzing metal lead and manganese dioxide in chloride medium | |
| CN109371245A (en) | Nickel refining system copper ashes recycling processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |