CN106902974A - A kind of beneficiation method of low oxidation ratio high-combination rate mixed copper ore - Google Patents
A kind of beneficiation method of low oxidation ratio high-combination rate mixed copper ore Download PDFInfo
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- CN106902974A CN106902974A CN201710139089.3A CN201710139089A CN106902974A CN 106902974 A CN106902974 A CN 106902974A CN 201710139089 A CN201710139089 A CN 201710139089A CN 106902974 A CN106902974 A CN 106902974A
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- copper
- ore
- concentrate
- flotation
- flue gas
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 140
- 239000010949 copper Substances 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 35
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000012141 concentrate Substances 0.000 claims abstract description 53
- 238000005188 flotation Methods 0.000 claims abstract description 48
- 229960004643 cupric oxide Drugs 0.000 claims abstract description 46
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003546 flue gas Substances 0.000 claims abstract description 34
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 23
- 239000011707 mineral Substances 0.000 claims abstract description 23
- 239000005751 Copper oxide Substances 0.000 claims abstract description 19
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 19
- 230000023556 desulfurization Effects 0.000 claims abstract description 19
- 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 abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 229910052569 sulfide mineral Inorganic materials 0.000 claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 11
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006213 oxygenation reaction Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000010494 dissociation reaction Methods 0.000 claims description 5
- 230000005593 dissociations Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 claims description 2
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical group CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims 1
- 238000001802 infusion Methods 0.000 claims 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 abstract description 17
- 238000002386 leaching Methods 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000012991 xanthate Substances 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005864 Sulphur Substances 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 10
- 235000010269 sulphur dioxide Nutrition 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052951 chalcopyrite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WTLOFSYWSLRYIR-UHFFFAOYSA-N [Mg].[O].[S] Chemical compound [Mg].[O].[S] WTLOFSYWSLRYIR-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- -1 hydroxyl Oxime Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
Abstract
The present invention is a kind of beneficiation method of low oxidation ratio high-bonding-ratio mixed copper, it is relatively low for oxygenation efficiency, Percentage bound oxygen-sulfur mixed copper ore high, first pass through flotation and reclaim copper sulfide mineral therein and free copper oxide mineral thing, flotation concentrate desulfurization with roasting technique obtains oxidation copper concentrate, baking flue gas are used to leach the refractory copper oxide in flotation tailing and combine copper simultaneously, the copper ion precipitated with vulcanized sodium again in tailing leaching ore pulp obtains copper sulfide precipitation, addition xanthate flotation precipitation copper sulfide obtains copper sulfide concentrate, copper sulfide concentrate mix with oxysulphied copper concentrate after desulfurization with roasting technique, obtain final oxidation copper concentrate.The method leaches low-grade tailings by the sulfur dioxide that the sulphur in itself concentrate is generated, and has reclaimed the hardly possible for being difficult to reclaim in flotation tailing and has selected free cupric oxide and combine copper, and low cost significantly improves the comprehensive recovery of copper.
Description
Technical field
The present invention relates to a kind of beneficiation method of low oxidation ratio high-combination rate mixed copper ore, belong to technical field of beneficiation.
Background technology
Copper ore resource mainly includes copper sulfide and cupric oxide two large divisions, and copper-sulphide ores occupy 80% ratio, cupric oxide ore
Account for 20% ratio.Because copper-sulphide ores stock number is big, ore dressing reclaims relatively easy, so current more than 80% copper is derived from
Copper-sulphide ores resource.Cupric oxide ore dressing recovery difficult is big, and recovery rate in ore-dressing is low, in today of copper ore resource shortage, efficiently utilizes
Oxidation copper resource is imperative, so the ore dressing of cupric oxide ore is reclaimed also making some progress.But in copper ore resource, sulphur
Change the surface oxidation of copper deposit, form the oxygen-sulfur mixed copper ore resource of enormous amount.This oxygen-sulfur mixed copper ore, ore dressing and smelting
Gold is reclaimed and all encounters certain difficulty.
The washability of cupric oxide ore is poorer than copper sulfide, copper resource based on copper-sulphide ores, to the research of cupric oxide ore in recent years
Come fewer.COPPER IN CHINA shortage of resources, while copper sulfide ore dressing recovery is carried out, the ore dressing of cupric oxide ore has also obtained height
Degree is paid attention to.For mixed copper ore, typically processed as copper-sulphide ores, i.e., while copper-sulphide ores are reclaimed in flotation, it is considered to oxygen
Change the recovery of copper mine, but for low oxidation ratio, the oxygen-sulfur mixed copper ore of high-bonding-ratio, so far not good method treatment.
The flotation of cupric oxide ore, main method has two kinds of sulfide flotation method, direct flotation method, and the former is used widely,
During vulcanization, addition ammonium sulfate, D2Deng reinforcing vulcanization reaction, certain effect is achieved, ammonium sulfate in industrial production
It is applied as vulcanization accelerator.Direct flotation is suitable for the simple cupric oxide ore of some gangue minerals, such as gangue mineral
When predominantly quartzy, the technical indicator that hydroximic acid and aliphatic acid direct flotation can be obtained.
The treatment of high contents of calcium and magnesium oxygen-sulfur mixed copper ore, raw ore NPT ammonia leached-slag flotation technology obtains preferably effect
Really, i.e., reclaimed using the direct ammonia leaching of raw ore, for copper-sulphide ores therein, the leaching after ammonia leaching for cupric oxide ore therein
Slag is reclaimed with method for floating again.Ammonia leaching adapts to cupric oxide ore, and flotation adapts to copper-sulphide ores, and the technique was obtained in Dongchuan District, Yunnan Province should
With.But for low-grade, high-bonding-ratio oxygen-sulfur mixed copper ore, because ammonia leaching with reference to copper to that can not leach, therefore this method is difficult
With the technical indicator for having obtained.
Dump leaching is the effective ways for processing cupric oxide ore, in Africa, Yunnan, Jiangxi, Anhui of America and China etc. so that
To extensive use.But for oxygen-sulfur mixed copper ore, sulfuric acid is difficult to leach chalcopyrite therein, and total leaching rate is low, this
Method is not suitable for the treatment of low oxidation ratio oxygen-sulfur mixed copper ore.
A kind of method of the treatment mixed copper ore and cupric oxide ore of Application No. 94111476.7 to extract copper mine, is by ore deposit
After stone is broken, ammonium carbonate, ammonium sulfate and ammonium chloride are added, leached in ammoniacal liquor, copper enters solution, is settled out copper with precipitating reagent
Come, so as to reclaim copper resource.Due to the copper in ammonia the leaching copper and chalcopyrite that are unable in dissolution combination copper, in this way not
Can process containing the ore for combining copper and chalcopyrite.
A kind of vulcanization-oxidization mixing copper ore floatation method of Application No. 200610136735.2, is using xanthate and hydroxyl
Oxime acid bulk flotation copper-sulphide ores and cupric oxide ore, obtain the rate of recovery higher.But for the combination copper mine in ore, the method
Can not reclaim.
The wet-leaching side of the low-grade high-alkali mixed copper ore, nickel minerals and zinc ore of Application No. 200510031356.2
Method, it is 0.5 ~ 5mol/L that ammonium salt concentration first will be again used after ore reduction, and ammonia density is matched somebody with somebody for the ammonium salt and ammoniacal liquor of 0.1 ~ 0.5mol/L
The cooperation leaching agent of system is leached.The method can not be processed containing the ore for combining copper and chalcopyrite.
A kind of high-bonding-ratio carbonate gangue-type oxygen-sulfur mixed copper ore of Application No. 201010178875.2 selects smelting side
Method, for the oxygen-sulfur mixed copper ore that Percentage bound is high, calcium carbonate and magnesium carbonate gangue mineral content is high, first passes through flotation and reclaims sulphur therein
Change copper mineral and free copper oxide mineral thing, flotation tailing aliphatic acid reverse flotation calcium carbonate and magnesium carbonate mineral therein obtain calcic
Magnesium carbonate mineral are low, the chats containing combination copper, then add sulfuric acid leaching combination copper, and the copper-containing solution after separation of solid and liquid leads to
Cross metallurgical method and obtain copper products.The method selects smelting to combine, and has complementary advantages, and high efficiente callback is using the combination high that cannot be processed at present
Rate carbonate gangue-type oxygen-sulfur mixed copper ore resource.But for low oxidation ratio, the mixed copper ore of high-bonding-ratio, in copper sulfide and trip
After cupric oxide flotation, retain in that copper in mine tailing is main to be existed with chrysocolla, with reference to forms such as copper, and grade is very
It is low, then using mine tailing sulfuric acid leaching, separation of solid and liquid, the method for extraction electrodeposition reclaims copper, because process is complicated, invests and running cost
Height, without economic benefit.
So, for single cupric oxide ore, flotation can obtain preferable technical indicator, and flotation technology is obtained preferably
Using.For simple oxygen-sulfur mixed copper ore, the flotation based on copper-sulphide ores is used to reclaim copper sulfide and cupric oxide ore simultaneously
Thing, can also obtain comparatively ideal effect.Cupric oxide ore low for calcium-magnesium content, single, sulfuric acid dump leaching is obtained in that good
Effect.Low for Percentage bound, high contents of calcium and magnesium oxygen-sulfur mixed copper ore, raw ore NPT ammonia leached-slag flotation technology is applied.It is right
In the recycling of these copper mines, technical merit higher is reached, advanced the progress of cupric oxide ore selecting and smelting technology.For low
Oxygenation efficiency, high-bonding-ratio oxygen-sulfur mixed copper ore, ore dressing are combined with metallurgy, play respective advantage, are that this oxygen sulphur for the treatment of is mixed
Close the basic principle of copper mine.But, metallurgical after currently used first ore dressing or first ore dressing after metallurgy can not be solved simultaneously
The recycling problem of low oxidation ratio, high-bonding-ratio oxygen-sulfur mixed copper ore, cause oxygen-sulfur mixed copper ore, particularly low oxidation ratio,
High-bonding-ratio oxygen-sulfur mixed copper ore resource selects smelting problem to never have to be broken through.
The content of the invention
The purpose of the present invention is directed to this low oxidation ratio high-bonding-ratio oxygen-sulfur mixed copper ore, there is provided a kind of low oxidation ratio is high
The beneficiation method of combination rate mixed copper ore, realizes the efficient utilization of the difficult copper ore resource.
The present invention is achieved through the following technical solutions：A kind of beneficiation method of low oxidation ratio high-combination rate mixed copper ore,
Carry out according to the following steps：
（1）By cupric 0.5%~1.2%, oxygenation efficiency 20%~30%, Percentage bound 15%~20%, oxidation calcium-magnesium content is mixed less than 4%
Copper mine, ore grinding to wherein copper sulfide mineral and the monomer dissociation of free copper oxide mineral thing 80% are closed, 300g is added by mixed copper ore per ton
~500g vulcanized sodium vulcanizes free copper oxide mineral thing therein, and addition 300g~500g xanthate class is used as copper sulfide mineral and vulcanization
The collecting agent of free copper oxide mineral thing afterwards, and by mixed copper ore per ton addition foaming agent 30g~40g control flotation froths, float
Choosing obtains oxysulphied copper concentrate, leaves the free cupric oxide containing the difficult flotation in part and combines the mine tailing of copper；
（2）By step（1）The oxysulphied copper concentrate desulfurization with roasting technique of acquisition, it is final copper concentrate to obtain oxidation copper concentrate；Roasting
Flue gas contains sulfur dioxide gas, and produced by industrial ozone machine equimolar with sulfur dioxide in flue gas smelly is introduced in flue gas
Oxygen, step is introduced by flue gas（1）In No. 1 agitator of mine tailing ore pulp of formation, while adding manganese dioxide by butt mine tailing per ton
200g~400g, slurry pH 2~3 is controlled by flue gas intake, carries out one section of stirring reaction 40 minutes~60 minutes, from 1
The ore pulp of number agitator discharge enters No. 2 agitators, carries out second segment and reacts 20 minutes~30 minutes, the control of reaction end pH value
5~6；The flue gas discharged from No. 1 agitator qualified discharge with after in lime；
（3）By step（2）In the ore pulps of No. 2 agitators introduce No. 3 agitators, addition vulcanized sodium precipitates copper ion therein and is formed
Copper sulfide precipitation, controls the addition of vulcanized sodium, the copper ion concentration in ore pulp solution is less than 0.001g/L；
（4）By step（3）In the ore pulps of No. 3 agitators introduce No. 4 agitators, it is yellow by butt mine tailing per ton addition 200g~300g
The flotation of medicine class collecting agent precipitates copper sulfide, obtains copper concentrate, the copper sulfide concentrate and step（1）Oxysulphied copper concentrate mix
Close, into after desulfurization with roasting technique stove desulfurization, obtain final oxidation copper concentrate, flotation tailing is true tailings.
No. 1 described ratio of height to diameter of agitator is 3~4.Other agitators are flotation mill and leach the general agitator of factory.
Described xanthate collectors are butyl xanthate and isoamyl xanthate.
Described foaming agent is terpenic oil and No. 2 oil.
The present invention has the advantages that：
（1）For the copper sulfide mineral of easy flotation, reclaimed in advance using the method for floating of low cost, obtain metallurgical qualified copper
Concentrate product, it is to avoid the sulfur dioxide for being added later suppresses and turns into mine tailing and lose.
（2）Oxysulphied copper concentrate is exactly desulfurization with roasting technique in the first step of hydrometallurgy factory, by the first of hydrometallurgy factory
Step moves on to ore dressing plant to be carried out, and low concentration sulphur dioxide flue gas are used for the leaching of cupric oxide and combination copper in mine tailing, save flue gas
The expense of desulfurization.
（3）The flue gas being calcined using concentrate is leached the cupric oxide in mine tailing and combines copper, saves sulfuric acid, reduces mine tailing
The cost of leaching.
（4）Low oxidation ratio high-combination rate mixed copper ore is very low containing copper grade by the mine tailing after flotation, individually uses
Metallurgical method is reclaimed, and high cost does not have economic benefit, and current this part copper is all lost in no recovery in mine tailing, so this
The rate of recovery for planting copper ore resource is low, and the present invention leaches low-grade tailings by the sulfur dioxide that the sulphur in itself concentrate is generated, time
Receive the refractory copper oxide that is difficult to reclaim and combined copper, significantly improve the comprehensive recovery of copper.
Brief description of the drawings
Fig. 1 is principle flow chart of the invention.
Specific embodiment
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and should not be regarded as limiting this hair
Bright scope.In the examples where no specific technique or condition is specified, according to the technology or condition described by document in the art
Or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can be by buying what is obtained
Conventional products.
Embodiment one：
Raw material：Cupric 1.2%, oxygenation efficiency 30%, Percentage bound 20%, mixed copper ore of the oxidation calcium-magnesium content less than 4%.
（1）Ore grinding is added to wherein copper sulfide mineral and the monomer dissociation of free copper oxide mineral thing 80% by dry-mixing copper mine per ton
Plus 500g vulcanized sodium vulcanizes free copper oxide mineral thing therein, after addition 500g butyl xanthates are as copper sulfide mineral and vulcanization
The collecting agent of free copper oxide mineral thing, addition foaming agent terpenic oil 30g control flotation froths, flotation obtains oxysulphied copper essence
Ore deposit, leaves containing the free cupric oxide of the difficult flotation in part and combines the mine tailing of copper.
（2）By oxysulphied copper concentrate desulfurization with roasting technique, it is final copper concentrate to obtain oxidation copper concentrate；Baking flue gas contain dioxy
Change sulphur gas, introduced in flue gas produced by industrial ozone machine with the equimolar ozone of sulfur dioxide in flue gas, flue gas is drawn
Enter containing step（1）In No. 1 agitator of the mine tailing ore pulp of formation, No. 1 ratio of height to diameter of agitator is 4, while pressing butt tail per ton
Ore deposit adds manganese dioxide 400g, and slurry pH 2~3 is controlled by flue gas intake, carries out one section of stirring reaction 60 minutes, from 1
The ore pulp of number agitator discharge enters No. 2 agitators, carries out second segment and reacts 30 minutes, and reaction end pH value is controlled 5~6；
The flue gas discharged from No. 1 agitator qualified discharge with after in lime.
（3）By step（2）In the ore pulps of No. 2 agitators introduce No. 3 agitators, addition vulcanized sodium precipitates copper ion therein
Copper sulfide precipitation is formed, the addition of vulcanized sodium is controlled, the copper ion concentration in ore pulp solution is less than 0.001g/L.
（4）By step（3）In the ore pulps of No. 3 agitators introduce No. 4 agitators, add 300g xanthate by butt mine tailing per ton
The flotation of class collecting agent precipitates copper sulfide, obtains copper concentrate, the copper sulfide concentrate and step（1）Oxysulphied copper concentrate mixing,
Into after desulfurization with roasting technique stove desulfurization, final oxidation copper concentrate is obtained, flotation tailing is true tailings.
Copper concentrate containing copper grade 24%, the rate of recovery 92% of copper.
Embodiment two：
Raw material：Cupric 0.8%, oxygenation efficiency 26%, Percentage bound 18%, mixed copper ore of the oxidation calcium-magnesium content less than 4%.
（1）Ore grinding is added to wherein copper sulfide mineral and the monomer dissociation of free copper oxide mineral thing 80% by mixed copper ore per ton
400g vulcanized sodium vulcanizes free copper oxide mineral thing therein, after addition 400g isoamyl xanthates are as copper sulfide mineral and vulcanization
The collecting agent of free copper oxide mineral thing, No. 2 oil 40g control flotation froths of addition foaming agent, flotation obtains oxysulphied copper concentrate,
Leave containing the free cupric oxide of the difficult flotation in part and combine the mine tailing of copper.
（2）By step（1）The oxysulphied copper concentrate desulfurization with roasting technique of acquisition, it is final copper concentrate to obtain oxidation copper concentrate；
Baking flue gas contain sulfur dioxide gas, and produced by industrial ozone machine equimolar with sulfur dioxide in flue gas is introduced in flue gas
Ozone, step is introduced by flue gas（1）In No. 1 agitator of mine tailing ore pulp of formation, No. 1 ratio of height to diameter of agitator is 3.5, while pressing
Butt mine tailing per ton adds manganese dioxide 300g, and slurry pH 2~3 is controlled by flue gas intake, carries out one section of stirring reaction
50 minutes, No. 2 agitators are entered from the ore pulp of No. 1 agitator discharge, carry out second segment and react 25 minutes, reaction end pH value control
System is 5~6；The flue gas discharged from No. 1 agitator qualified discharge with after in lime.
（3）By step（2）In the ore pulps of No. 2 agitators introduce No. 3 agitators, addition vulcanized sodium precipitates copper ion therein
Copper sulfide precipitation is formed, the addition of vulcanized sodium is controlled, the copper ion concentration in ore pulp solution is less than 0.001g/L.
（4）By step（3）In the ore pulps of No. 3 agitators introduce No. 4 agitators, the fourth of 250g is added by butt mine tailing per ton
The flotation of base xanthate collector precipitates copper sulfide, obtains copper concentrate, the copper sulfide concentrate and step（1）Oxysulphied copper concentrate mix
Close, into after desulfurization with roasting technique stove desulfurization, obtain final oxidation copper concentrate, flotation tailing is true tailings.
Copper concentrate containing copper grade 22%, the rate of recovery 88% of copper.
Embodiment three：
Cupric 0.5%, oxygenation efficiency 20%, Percentage bound 15%, mixed copper ore of the oxidation calcium-magnesium content less than 4%.
（1）Ore grinding is added to wherein copper sulfide mineral and the monomer dissociation of free copper oxide mineral thing 80% by mixed copper ore per ton
300g vulcanized sodium vulcanizes free copper oxide mineral thing therein, and addition 300g butyl xanthates are used as the trip after copper sulfide mineral and vulcanization
From the collecting agent of copper oxide mineral, addition foaming agent terpenic oil 40g control flotation froths, flotation obtains oxysulphied copper concentrate,
Leave containing the free cupric oxide of the difficult flotation in part and combine the mine tailing of copper.
（2）By step（1）The oxysulphied copper concentrate desulfurization with roasting technique of acquisition, it is final copper concentrate to obtain oxidation copper concentrate；
Baking flue gas contain sulfur dioxide gas, and produced by industrial ozone machine equimolar with sulfur dioxide in flue gas is introduced in flue gas
Ozone, step is introduced by flue gas（1）In No. 1 agitator of mine tailing ore pulp of formation, No. 1 ratio of height to diameter of agitator is 3, while by every
Ton butt mine tailing addition manganese dioxide 200g, slurry pH 2~3 is controlled by flue gas intake, carries out one section of stirring reaction 40
Minute, enter No. 2 agitators from the ore pulp of No. 1 agitator discharge, carry out second segment and react 20 minutes, the control of reaction end pH value
5~6；The flue gas discharged from No. 1 agitator qualified discharge with after in lime.
（3）By step（2）In the ore pulps of No. 2 agitators introduce No. 3 agitators, addition vulcanized sodium precipitates copper ion therein
Copper sulfide precipitation is formed, the addition of vulcanized sodium is controlled, the copper ion concentration in ore pulp solution is less than 0.001g/L.
（4）By step（3）In the ore pulps of No. 3 agitators introduce No. 4 agitators, add 200g butyl by butt mine tailing per ton
Xanthate collector flotation precipitates copper sulfide, obtains copper concentrate, the copper sulfide concentrate and step（1）Oxysulphied copper concentrate mix
Close, into after desulfurization with roasting technique stove desulfurization, obtain final oxidation copper concentrate, flotation tailing is true tailings.
Copper concentrate containing copper grade 18%, the rate of recovery 84% of copper.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (4)
1. a kind of beneficiation method of low oxidation ratio high-bonding-ratio mixed copper, it is characterised in that carry out according to the following steps：
（1）By cupric 0.5%~1.2%, oxygenation efficiency 20%~30%, Percentage bound 15%~20%, oxidation calcium-magnesium content is mixed less than 4%
Copper mine, ore grinding to wherein copper sulfide mineral and the monomer dissociation of free copper oxide mineral thing 80% are closed, 300g is added by mixed copper ore per ton
~500g vulcanized sodium vulcanizes free copper oxide mineral thing therein, and addition 300g~500g xanthate class is used as copper sulfide mineral and vulcanization
The collecting agent of free copper oxide mineral thing afterwards, and by mixed copper ore per ton addition foaming agent 30g~40g control flotation froths, float
Choosing obtains oxysulphied copper concentrate, leaves the free cupric oxide containing the difficult flotation in part and combines the mine tailing of copper；
（2）By step（1）The oxysulphied copper concentrate desulfurization with roasting technique of acquisition, it is final copper concentrate to obtain oxidation copper concentrate；Roasting
Flue gas contains sulfur dioxide gas, and produced by industrial ozone machine equimolar with sulfur dioxide in flue gas smelly is introduced in flue gas
Oxygen, step is introduced by flue gas（1）In No. 1 agitator of mine tailing ore pulp of formation, while adding manganese dioxide by butt mine tailing per ton
200g~400g, slurry pH 2~3 is controlled by flue gas intake, carries out one section of stirring reaction 40 minutes~60 minutes, from 1
The ore pulp of number agitator discharge enters No. 2 agitators, carries out second segment and reacts 20 minutes~30 minutes, the control of reaction end pH value
5~6；The flue gas discharged from No. 1 agitator qualified discharge with after in lime；
（3）By step（2）In the ore pulps of No. 2 agitators introduce No. 3 agitators, addition vulcanized sodium precipitates copper ion therein and is formed
Copper sulfide precipitation, controls the addition of vulcanized sodium, the copper ion concentration in ore pulp solution is less than 0.001g/L；
（4）By step（3）In the ore pulps of No. 3 agitators introduce No. 4 agitators, it is yellow by butt mine tailing per ton addition 200g~300g
The flotation of medicine class collecting agent precipitates copper sulfide, obtains copper concentrate, the copper sulfide concentrate and step（1）Oxysulphied copper concentrate mix
Close, into after desulfurization with roasting technique stove desulfurization, obtain final oxidation copper concentrate, flotation tailing is true tailings.
2. the beneficiation method of low oxidation ratio high-bonding-ratio mixed copper according to claim 1, it is characterised in that described 1
The ratio of height to diameter of number agitator is 3~4.
3. the beneficiation method of low oxidation ratio high-bonding-ratio mixed copper according to claim 1, it is characterised in that described Huang
Medicine class collecting agent is butyl xanthate and isoamyl xanthate.
4. the beneficiation method of low oxidation ratio high-bonding-ratio mixed copper according to claim 1, it is characterised in that described rises
Infusion is terpenic oil and No. 2 oil.
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| CN201710139089.3A CN106902974B (en) | 2017-03-09 | 2017-03-09 | A kind of beneficiation method of low oxidation ratio high-combination rate mixed copper ore |
| AU2017402487A AU2017402487B2 (en) | 2017-03-09 | 2017-12-01 | Beneficiation method for mixed copper ore with low oxidation rate and high binding rate |
| PCT/CN2017/114275 WO2018161651A1 (en) | 2017-03-09 | 2017-12-01 | Beneficiation method for mixed copper ore with low oxidation rate and high binding rate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018161651A1 (en) * | 2017-03-09 | 2018-09-13 | 昆明理工大学 | Beneficiation method for mixed copper ore with low oxidation rate and high binding rate |
| CN110681477A (en) * | 2018-07-06 | 2020-01-14 | 厦门紫金矿冶技术有限公司 | Dressing and smelting combined treatment method for recovering complex copper oxide ore |
| CN113731643A (en) * | 2021-09-13 | 2021-12-03 | 西安建筑科技大学 | Method for recovering fine-grained copper sulfide minerals after oxidation through selective agglomeration flotation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112221695B (en) * | 2020-09-28 | 2022-09-30 | 穆索诺伊矿业简易股份有限公司 | Copper separation and smelting combined copper extraction method for copper oxide ores with different oxidation rates |
| CN114950712B (en) * | 2022-05-27 | 2023-10-13 | 华刚矿业股份有限公司 | Combined treatment process for comprehensively recovering copper and cobalt |
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| AU2017402487B2 (en) | 2019-08-01 |
| AU2017402487A1 (en) | 2019-01-31 |
| WO2018161651A1 (en) | 2018-09-13 |
| CN106902974B (en) | 2018-01-12 |
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