CN117535517A - Method for comprehensively utilizing copper sulfide ore base hydrogen reduction short process - Google Patents
Method for comprehensively utilizing copper sulfide ore base hydrogen reduction short process Download PDFInfo
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- CN117535517A CN117535517A CN202311253403.2A CN202311253403A CN117535517A CN 117535517 A CN117535517 A CN 117535517A CN 202311253403 A CN202311253403 A CN 202311253403A CN 117535517 A CN117535517 A CN 117535517A
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- base
- copper
- sulfide
- hydrogen
- hydrogen reduction
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 69
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 43
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006722 reduction reaction Methods 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000007885 magnetic separation Methods 0.000 claims abstract description 16
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 239000002918 waste heat Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 71
- 239000002893 slag Substances 0.000 claims description 22
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 15
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052947 chalcocite Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003546 flue gas Substances 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 16
- 239000000126 substance Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 6
- 229910001950 potassium oxide Inorganic materials 0.000 description 6
- 238000009853 pyrometallurgy Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052948 bornite Inorganic materials 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 flux Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0073—Selection or treatment of the reducing gases
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- 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
- C22B15/0026—Pyrometallurgy
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
Abstract
A method for comprehensively utilizing copper sulfide ore base hydrogen reduction short process belongs to the technical field of comprehensive utilization of copper sulfide ore, and comprises the following steps: 1) Copper sulfide and base oxide are used as raw materials, and hydrogen is used as a reducing agent to carry out base hydrogen reduction reaction in a continuous packed bed; 2) The base sulfide in the solid product generated by the continuous packed bed reactor is oxidized by utilizing self waste heat to obtain base sulfate; alternatively, the base sulfide in the solid product produced in a continuous packed bed reactor is converted with waterForming hydrogen sulfide and a water conversion solution, carrying out catalytic electrolysis on the hydrogen sulfide to obtain elemental sulfur and hydrogen, and recycling the hydrogen for the first-stage reduction reaction, wherein sulfur is used as a product; 3) Magnetically separating the reaction product to obtain elemental iron powder; 4) And melting and separating the residual materials of the low-temperature oxidation magnetic separation to obtain copper ingots and base sulfate. The invention realizes the multi-element comprehensive utilization of copper sulfide ores and eliminates SO 2 The problems of flue gas pollution and sulfuric acid treatment are an efficient and pollution-free copper sulfide ore utilization method.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of copper sulfide ores, and particularly relates to a method for short-process comprehensive utilization of base hydrogen reduction of copper sulfide ores.
Background
Copper sulphide accounts for 80% of copper ore resources. Copper sulphide minerals mainly include chalcocite, chalcopyrite, cerulous copper and bornite. Wherein, chalcocite is easy to oxidize, which can cause that ore pulp contains a large amount of copper ions and cause difficulty for the subsequent separation of copper zinc and copper matte. The existing extraction method of valuable components of copper sulfide ore mainly comprises two modes of pyrometallurgy and wet leaching.
Patent CN201710321053.7 provides a process for producing metallic copper or copper compounds from copper sulphide and a system therefor, the process comprising the steps of: (1) Desulfurizing and roasting copper sulfide in a non-oxidizing atmosphere to obtain desulfurizing cinder containing cuprous sulfide and ferrous sulfide and coarse sulfur; (2) Wet oxidation treatment is carried out on the desulfurization sintering slag, so that ferrous sulfide is converted into ferric oxide and elemental sulfur, and a first mixed material containing cuprous sulfide, ferric oxide and elemental sulfur is obtained; (3) Extracting elemental sulfur from the first mixed material to obtain a second mixed material containing cuprous sulfide and ferric oxide; (4) Performing base hydrogen reduction roasting treatment on the second mixed material to obtain flue gas and base hydrogen reduction cinder, and further treating the flue gas to prepare metallic copper or copper compounds; the copper compound can be base hydrogen reduced copper or copper oxide; the metallic copper may be cathodic copper.
Patent CN200910094542.9 provides a process for copper smelting with a midt furnace, which comprises the following steps: (1) Copper sulfide concentrate, flux, fuel and the like are put into a hearth of a dtex metallurgical furnace, a spray gun is inserted into a molten pool and blown into oxygen-enriched air for smelting, and the produced matte is reserved in the hearth; (2) Performing heat preservation, clarification and separation on the waste slag mixture discharged from the slag port in a high-temperature container to obtain waste slag and matte with copper content less than 0.5%; (3) Continuously blowing by adding flux, matte and the like, wherein molten products are blister copper and slag rich in magnetic iron oxide; (4) The slag is sent into another hearth which is being subjected to the reaction of (1) for depletion, and the blister copper is discharged from a copper discharge port at the lower part of the hearth.
Patent CN202211218243.3 provides a method for enriching germanium and indium from copper sulphide ores and co-producing blister copper, the method comprising the steps of: (1) Mixing copper sulfide ore containing germanium and indium, a reducing agent and a fluxing agent in proportion, and grinding; (2) Smelting the ground mixture by reducing the matte to obtain volatile smoke dust and copper matte containing germanium and indium respectively, and collecting the volatile matters containing germanium and indium by using a cloth bag; (3) Volatilizing germanium and indium from the copper matte by oxygen-enriched converting to obtain blister copper and volatilizing smoke dust containing germanium and indium respectively; (4) The fume discharged from the cloth bag dust collection is oxidized by ozone and then is absorbed by spraying alkali liquor, so that the standard emission is achieved.
In summary, the prior extraction process of valuable components of copper sulfide ore adopts a pyrometallurgy mode. Two defects which cannot be overcome by the pyrometallurgy process per se: (1) valuable components in copper sulphide ores are not effectively utilized. The pyrometallurgy process must go through a slag-making process, and the slag ash takes away a large amount of valuable elements, so that the pyrometallurgy benefit is reduced, and the valuable components such as copper, iron and the like are wasted; (2) SO (SO) 2 Flue gas pollution and sulfuric acid treatmentThe questions are given. SO-containing produced in the pyrometallurgy of copper sulphide ores 2 The tail gas, although purified, still contains a certain amount of SO 2 Emissions, and in addition, the selling price of sulfuric acid is related to the radius of transportation, and the sales area, storage and transportation problems of sulfuric acid have become a problem for copper sulfide ore smelting enterprises.
Disclosure of Invention
A method for comprehensively utilizing a short flow of base hydrogen reduction of copper sulfide ore, as shown in figure 1, comprises the following steps:
(1) The method comprises the steps of (1) taking copper sulfide-containing minerals and base oxides as raw materials, and taking hydrogen as a reducing agent to carry out base hydrogen reduction reaction in a continuous packed bed;
(2) The base sulfide in the solid product generated by the continuous packed bed reactor is oxidized by utilizing self waste heat to obtain base sulfate; or alternatively
The base sulfide and water in the solid product generated by the continuous packed bed reactor are converted into hydrogen sulfide and water conversion solution, the hydrogen sulfide is catalyzed and electrolyzed to obtain elemental sulfur (sulfur) and hydrogen, the hydrogen is recycled for the first-stage reduction reaction, and the sulfur is used as a product;
(3) Magnetically separating the reaction product to obtain elemental iron powder;
(4) And smelting and separating the magnetic separation residue to obtain copper ingots and base sulfate.
In the step (1), the copper sulfide-containing mineral refers to one or more of chalcopyrite, chalcocite, bornite and matte. The base oxide is one or more of a calcium-based compound, a sodium-based compound and a potassium-based compound.
In the step (1), the addition amount of the base oxide is calculated according to 1-3 times of the stoichiometric number of the alkaline metal and sulfur in copper sulfide ore in the base hydrogen reduction reaction, and the base oxide is added.
In the step (1), the reaction temperature of the base hydrogen reduction reaction is 500-1200 ℃ and the reaction time is 10-120 min.
In the step (2), a continuous packed bed reactor adopted in the base hydrogen reduction reaction comprises a multi-hearth reaction furnace, a multi-stage countercurrent cyclone, a polymerization type stirring fluidized bed, a fixed bed and a moving bed, wherein the top of the multi-hearth reaction furnace is provided with a feeding air seal device, the bottom of the multi-hearth reaction furnace is provided with a discharging air seal device, and the continuous reduction reaction is realized by utilizing the feeding air seal device and the discharging air seal device; the multi-stage countercurrent cyclone can be carried out by adopting a 2-N multi-stage countercurrent cyclone according to the actual requirement of the base hydrogen reduction process, copper sulfide ore, base oxide and hydrogen in the multi-stage countercurrent cyclone are subjected to base hydrogen reduction reaction in a countercurrent mode in the heat exchange process, and compared with a conventional fluidized bed reactor, the system heat utilization rate is more than 70%; the hydrogen utilization efficiency reaches more than 99 percent; the polymerization type stirring fluidized bed is provided with a top stirring paddle and a lateral stirring paddle, wherein the top stirring shaft separates fine particles back into the bed by utilizing centrifugal force, so that the escape of the small particles is prevented, the internal structure of the lateral stirring shaft is hollow, solid particles are ensured to enter the fluidized bed from the bottom of the stirring paddle, the large bubble rate is reduced by more than 60 percent compared with the conventional fluidized bed, the heat transfer efficiency is improved by more than 30 percent, the dust carrying rate is reduced by less than 2 percent, and the adhesion of metal powder generated by reduction is prevented.
Oxidizing the base sulfide in the solid slag generated after the base hydrogen reduction reaction by utilizing self waste heat to obtain base sulfate, keeping the temperature of the solid slag at 50-300 ℃ and the oxidation time at 10-120 min, and obtaining S in the solid slag 2- The content is less than or equal to 0.1 percent.
In the step (3), the elemental iron powder is recovered through magnetic separation, the magnetic separation strength is 0.1-1T, and the recovery rate of iron is more than 95%.
In the step (4), the magnetic separation residual material is placed into a heating furnace for melting, the melting temperature is 1000-1250 ℃, and the copper ingot product and the base sulfate are obtained, and the recovery rate of copper is more than 95%.
The recovery rate of copper and iron in copper sulfide ores is more than 95 percent; s in the obtained solid slag 2- The content is less than or equal to 0.1 percent.
The invention relates to a method for comprehensively utilizing a short flow of base hydrogen reduction of copper sulfide ore, taking calcium oxide as an example, reducing components in the copper sulfide ore into metal simple substance and calcium sulfide through base hydrogen reduction reaction, wherein metal iron powder is recovered through magnetic separation, copper powder is smelted and cast to obtain copper ingots, and the calcium sulfide is oxidized at a low temperature to prepare calcium sulfate, and the chemical reaction formula of the reaction process comprises the following steps:
base hydrogen reduction process:
CuS+CaO+H 2 (g)＝Cu+CaS+H 2 O(g)
FeS 2 +2CaO+2H 2 (g)＝Fe+2CaS+2H 2 O(g)
calcium sulfide conversion process
(1) Low-temperature oxidation reaction:
CaS+2O 2 (g)＝CaSO 4
(2) Water conversion and electrolysis reaction:
CaS+H 2 O＝H 2 S(g)+Ca(OH) 2
H 2 S(g)＝H 2 (g) +S (catalytic electrolysis)
Compared with the prior art, the invention has the beneficial effects that:
(1) The multiple components in the copper sulphide ore are effectively utilized. The invention adopts base hydrogen reduction reaction to reduce metal components in copper sulphide ore into metal simple substance, sulfur is converted into sulfide to enter solid phase, sulfide is oxidized into sulfate at low temperature, thus achieving the purpose of sulfur fixation. The base sulfide in the solid product generated by the continuous packed bed reactor can be converted into hydrogen sulfide and alkali with water, the hydrogen sulfide is catalyzed and electrolyzed to obtain elemental sulfur (sulfur) and hydrogen, the hydrogen is recycled for reduction in the first stage, and the sulfur is used as a product. The metal iron powder is recovered by magnetic separation, copper powder is melted and separated to obtain copper ingots, SO that SO is eliminated 2 Smoke pollution and sulfuric acid treatment.
(2) The multi-hearth reaction furnace and the continuous packed bed realize continuous base hydrogen reduction reaction by using a feeding air seal device and a discharging air seal device; the solid phase and the gas phase in the multi-stage countercurrent cyclone are subjected to base hydrogen reduction reaction in a countercurrent mode in the heat exchange process, and compared with a conventional fluidized bed, the heat utilization rate of the system is more than 70%; the utilization rate of chlorine reaches more than 99%; the polymerization type stirring fluidized bed is provided with the top stirring paddle and the lateral stirring paddle, compared with the conventional fluidized bed, the high bubble rate is reduced by more than 60%, the heat transfer efficiency is improved by more than 30%, the dust carrying rate is reduced by less than 2%, and the metal powder generated by reduction is prevented from being adhered.
(3) The invention realizes the multi-element comprehensive utilization of copper sulfide ores and eliminates SO 2 The problems of flue gas pollution and sulfuric acid treatment are an efficient and pollution-free copper sulfide ore utilization method.
Drawings
FIG. 1 is a schematic diagram of a process flow of a method for short-process comprehensive utilization of base hydrogen reduction of copper sulfide ores.
Detailed Description
The present invention will be described in further detail with reference to examples.
The copper sulfide ores adopted in the embodiments 1 and 5 are chalcopyrite, and the main components of the copper sulfide ores are Cu 30.20%, fe 32.34%, S34.2% and the balance of other components;
the copper sulfide ore adopted in the embodiment 2 of the invention is chalcocite, the main components of which are Cu 53.55%, fe 4.23%, S15.26% and the balance of other components;
copper sulfide ores adopted in the embodiments 3 and 4 are chalcopyrite, and the main components of the copper sulfide ores are Cu 60.0%, fe 9.12%, S19.26% and the balance of other components;
example 1
(1) Mixing chalcopyrite and calcium oxide in proportion, wherein the addition amount of the calcium oxide is 1 time of the stoichiometric number of calcium and sulfur in the chalcopyrite base hydrogen reduction reaction;
(2) The method comprises the steps of (1) performing base hydrogen reduction reaction on chalcopyrite, calcium oxide and hydrogen in a continuous packed bed, reducing metal components in the chalcopyrite into metal simple substances, converting sulfur into calcium sulfide, and performing base hydrogen reduction at a reaction temperature of 600 ℃ for 20min;
(3) The calcium sulfide in the solid slag generated by the continuous packed bed is preheated and oxidized by the calcium sulfide to obtain the calcium sulfate, the temperature of the solid slag is 50 ℃, the oxidizing time is 120min, and S in the material is obtained after the separation after the reaction is completed 2－ The content is 0.1%;
(4) Separating and separating the reacted material to recover the metal simple substance, wherein the magnetic field strength is 0.1T, and the recovery rate of iron is 95%;
(5) And (3) placing the magnetic separation residue into a heating furnace for melting, wherein the melting temperature is 1000 ℃, and obtaining copper ingot products and calcium sulfate, and the recovery rate of copper is 95%.
Example 2
(1) Mixing chalcocite and sodium oxide in proportion, wherein the adding amount of the sodium oxide is 1 time of the stoichiometric number of sodium and sulfur in the hydrogen reduction reaction of chalcocite base;
(2) Performing base hydrogen reduction reaction on chalcocite, sodium oxide and hydrogen in a continuous packed bed, reducing metal components in the chalcocite into metal simple substances, converting sulfur into sodium sulfide, and performing base hydrogen reduction reaction for 10min at a reaction temperature of 700 ℃;
(3) Sodium sulfide in solid slag generated by the continuous packed bed is preheated and oxidized by self to obtain sodium sulfate, the temperature of the solid slag is 300 ℃, the oxidizing time is 20min, and S in the material is obtained after the separation after the reaction is completed 2－ The content is 0.06%;
(4) Separating and separating the reacted material to recover the metal simple substance, wherein the magnetic field strength is 0.1T, and the recovery rate of iron is 96%;
(5) And (3) placing the magnetic separation residue into a heating furnace for melting, wherein the melting temperature is 1200 ℃, and obtaining copper ingot products and calcium sulfate, and the recovery rate of copper is 97%.
Example 3
(1) Mixing the chalcopyrite and the potassium oxide in proportion, wherein the adding amount of the potassium oxide is 1 time of the stoichiometric number of the potassium and the sulfur in the base hydrogen reduction reaction of the chalcopyrite;
(2) Performing base hydrogen reduction reaction on the chalcopyrite, potassium oxide and hydrogen in a continuous packed bed, reducing metal components in the chalcopyrite into metal simple substances, converting sulfur into potassium sulfide, and performing base hydrogen reduction reaction for 20min at the reaction temperature of 600 ℃;
(3) The potassium sulfide in the solid slag generated by the continuous packed bed is preheated and oxidized by self to obtain potassium sulfate, the temperature of the solid slag is 200 ℃, the oxidizing time is 60min, and S in the material is obtained after the separation after the reaction is completed 2－ The content is 0.05%;
(4) Separating and separating the reacted material to recover the metal simple substance, wherein the magnetic field strength is 0.1T, and the recovery rate of iron is 96%;
(5) And (3) placing the magnetic separation residue into a heating furnace for melting, wherein the melting temperature is 1100 ℃, and obtaining copper ingot products and calcium sulfate, and the recovery rate of copper is 96%.
Example 4
(1) Mixing the bankoite and the calcium oxide in proportion, wherein the addition amount of the calcium oxide is 1 time of the stoichiometric number of potassium and sulfur in the base hydrogen reduction reaction of the copper sulfide ore;
(2) Performing base hydrogen reduction reaction on copper sulfide ore, calcium oxide and hydrogen in a continuous packed bed, reducing metal components in the copper spotted ore into metal simple substances, converting sulfur into calcium sulfide, and performing base hydrogen reduction reaction for 10min at a reaction temperature of 800 ℃;
(3) The calcium sulfide in the solid slag generated by the continuous packed bed is preheated and oxidized by self to obtain the calcium sulfate, the temperature of the solid slag is 200 ℃, the oxidizing time is 60min, and S in the material is obtained after the separation after the reaction is completed 2－ The content is 0.07%;
(4) Separating and separating the reacted material to recover the metal simple substance, wherein the magnetic field strength is 0.1T, and the recovery rate of iron is 96%;
(5) And (3) placing the magnetic separation residue into a heating furnace for melting, wherein the melting temperature is 1050 ℃, and obtaining copper ingot products and calcium sulfate, and the recovery rate of copper is 96%.
Example 5
(1) Mixing chalcopyrite and potassium oxide in proportion, wherein the addition amount of the potassium oxide is 1 time of the stoichiometric number of potassium and sulfur in the chalcopyrite base hydrogen reduction reaction;
(2) Performing base hydrogen reduction reaction on the chalcopyrite, potassium oxide and hydrogen in a continuous packed bed, reducing metal components in the chalcopyrite into metal simple substances, converting sulfur into potassium sulfide, and performing base hydrogen reduction reaction for 30min at the reaction temperature of 900 ℃;
(3) Conversion of base sulfide with water in solid product produced in continuous packed bed reactorTo form hydrogen sulfide and alkali, the hydrogen sulfide is catalyzed and electrolyzed to obtain elemental sulfur (sulfur) and hydrogen, the hydrogen is recycled for the first stage reduction, and the sulfur is used as a product. After the reaction is completed, S in the obtained material 2－ The content is 0.07%;
(4) Separating and separating the material obtained in the step (3) to recover the metal simple substance, wherein the magnetic field strength is 0.1T, and the recovery rate of iron is 97%;
(5) And (3) placing the magnetic separation residue into a heating furnace for melting, wherein the melting temperature is 1250 ℃, and obtaining copper ingot products and calcium sulfate, and the recovery rate of copper is 97%.
Claims (7)
1. The method for comprehensively utilizing the copper sulfide ore base hydrogen reduction short process is characterized by comprising the following steps of:
(1) The method comprises the steps of (1) taking copper sulfide-containing minerals and base oxides as raw materials, and taking hydrogen as a reducing agent to carry out base hydrogen reduction reaction in a continuous packed bed;
(2) The base sulfide in the solid product generated by the continuous packed bed reactor is oxidized by utilizing self waste heat to obtain base sulfate; or alternatively
The base sulfide and water in the solid product generated by the continuous packed bed reactor are converted into hydrogen sulfide and water conversion solution, the hydrogen sulfide is catalyzed and electrolyzed to obtain sulfur and hydrogen, the hydrogen is recycled for the first stage reduction reaction, and the sulfur is used as a product;
(3) Magnetically separating the reaction product to obtain elemental iron powder;
(4) And smelting and separating the magnetic separation residue to obtain copper ingots and base sulfate.
2. The method for short-process comprehensive utilization of base hydrogen reduction of copper sulfide ore according to claim 1, wherein in the step (1), the mineral containing copper sulfide is one or more of chalcopyrite, chalcocite, chalcopyrite and matte; the base oxide is one or more of a calcium-based compound, a sodium-based compound and a potassium-based compound.
3. The method for short-process comprehensive utilization of base hydrogen reduction of copper sulphide ore according to claim 1, wherein in the step (1), the addition amount of the base oxide is calculated according to 1-3 times of stoichiometric number of the alkali metal and sulfur in the copper sulphide ore in the base hydrogen reduction reaction, and the base oxide is added in a reduced amount.
4. The method for short-process comprehensive utilization of base hydrogen reduction of copper sulfide ore according to claim 1, wherein in the step (1), the reaction temperature of the base hydrogen reduction reaction is 500-1200 ℃ and the reaction time is 10-120 min.
5. The method for comprehensively utilizing the base hydrogen reduction short process of the copper sulphide ore according to claim 1, wherein the base sulphide in the solid slag generated after the base hydrogen reduction reaction is oxidized by self waste heat to obtain the base sulphate, the temperature of the solid slag is kept between 50 and 300 ℃, the oxidation time is between 10 and 120 minutes, and S in the solid slag 2- The content is less than or equal to 0.1 percent.
6. The method for short-process comprehensive utilization of base hydrogen reduction of copper sulfide ore according to claim 1, wherein in the step (3), elemental iron powder is recovered through magnetic separation, the magnetic separation strength is 0.1-1T, and the recovery rate of iron is more than 95%.
7. The method for comprehensively utilizing the base hydrogen reduction short process of the copper sulfide ore according to claim 1, wherein in the step (4), the magnetic separation residual material is placed into a heating furnace for melting, the melting temperature is 1000-1250 ℃, the copper ingot product and the base sulfate are obtained, and the recovery rate of copper is more than 95%.
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