AU2017402487B2 - Beneficiation method for mixed copper ore with low oxidation rate and high binding rate - Google Patents
Beneficiation method for mixed copper ore with low oxidation rate and high binding rate Download PDFInfo
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- AU2017402487B2 AU2017402487B2 AU2017402487A AU2017402487A AU2017402487B2 AU 2017402487 B2 AU2017402487 B2 AU 2017402487B2 AU 2017402487 A AU2017402487 A AU 2017402487A AU 2017402487 A AU2017402487 A AU 2017402487A AU 2017402487 B2 AU2017402487 B2 AU 2017402487B2
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- copper
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- oxide
- concentrate
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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 139
- 239000010949 copper Substances 0.000 title claims abstract description 139
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000005751 Copper oxide Substances 0.000 claims abstract description 61
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 61
- 238000005188 flotation Methods 0.000 claims abstract description 58
- 239000012141 concentrate Substances 0.000 claims abstract description 54
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003546 flue gas Substances 0.000 claims abstract description 44
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 16
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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
- 239000012991 xanthate Substances 0.000 claims abstract description 9
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000006477 desulfuration reaction Methods 0.000 claims description 12
- 230000023556 desulfurization Effects 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical group CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 238000010517 secondary reaction Methods 0.000 claims description 5
- CONMNFZLRNYHIQ-UHFFFAOYSA-N 3-methylbutoxymethanedithioic acid Chemical compound CC(C)CCOC(S)=S CONMNFZLRNYHIQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 2
- 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 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000005272 metallurgy Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 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
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- 238000003723 Smelting Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
A beneficiation method for a mixed copper ore with a low oxidation rate and a high binding rate. For an oxide-sulfide mixed copper ore with a low oxidation rate and a high binding rate, in the method, a copper sulfide ore and a free copper oxide ore therein are recovered by means of floatation, a floated ore concentrate is desulfurized by roasting to obtain a copper oxide concentrate, flue gas produced after the roasting is used for leaching out difficult-to-float copper oxide and bound copper in flotation tailings, then the tailings are precipitated by sodium sulfide to leach copper ions in ore pulp so as to obtain a copper sulfide sediment, a xanthate is added for floating the copper sulfide sediment to obtain a copper sulfide concentrate, the copper sulfide concentrate and an oxide-sulfide mixed copper concentrate are mixed, then a mixture is desulfurized by roasting, and a final copper oxide concentrate is obtained. According to the method, low-grade tailings are leached out by sulfur dioxide generated by sulfur in an ore concentrate, difficult-to-float free copper oxide and bound copper which are difficult to recover in flotation tailings are recovered, costs are low, and the comprehensive recovery rate of copper is improved significantly.
Description
BENEFICIATION METHOD FOR MIXED COPPER ORE WITH LOW
OXIDATION RATE AND HIGH BINDING RATE
Technical Field
The present invention relates to a beneficiation method for mixed copper ore with low oxidation rate and high binding rate, and belongs to the technical field of beneficiation.
Prior Art Discussion
Copper ore resources mainly include copper sulfide ore and copper oxide ore, wherein, copper sulfide ore accounts for 80%, and copper oxide ore accounts for 20%. Owing to the fact that the copper sulfide ore resources are in a larger amount and relatively easy for beneficiation and recovery, more than 80% of copper comes from the copper sulfide ore resources presently. Though copper oxide ore is difficult for beneficiation and recovery and the beneficiation and recovery ratio is low, it is necessary to utilize copper oxide resources efficiently in the current shortage of copper ore resource shortage. Therefore, some achievements have been made in the beneficiation and recovery of copper oxide ore. However, in copper ore resources, a huge amount of oxide-sulfide mixed copper ore resources are formed owing to surface oxidation of copper sulfide ore deposits. There are some difficulties in beneficiation and metallurgical recovery of such oxide-sulfide mixed copper ore.
In view that the selectivity of copper oxide ore is worse than that of copper sulfide ore and copper resource is mainly copper sulfide ore, research on copper oxide ore is seldom made in recent years. Since the copper ore resources are in shortage in China, while high attention is paid to the beneficiation and recovery of copper oxide ore, beneficiation and recovery of copper sulfide ore is also valued. Mixed copper ore is usually treated as copper sulfide ore, i.e., recovery of copper oxide ore is taken into consideration while flotation and recovery of copper sulfide ore is carried out. However, there is no effective method for treating oxide-sulfide mixed copper ore with a low oxidation ratio and high binding ratio yet at present.
Available methods for flotation of copper oxide ore mainly includes sulfurization flotation method and direct flotation method, wherein, the former is widely applied. Some effects have been attained by adding ammonium sulfate, D2 and the like in the sulfurization process to enhance the sulfurization reaction. Ammonium sulfate is applied as a sulfurization accelerant in industrial production. Direct flotation method is suitable for some copper oxide ore having simple gangue minerals (e.g., the gangue minerals are mainly quartz). For such copper oxide ore, direct flotation method with hydroximic acid and aliphatic acid can attain good technical effect.
In the processing of high calcium-magnesium-oxide-sulfide mixed copper ore, a good effect is attained with a technique of ammonia leaching and residue flotation of raw ore at normal temperature and normal pressure, i.e., the copper oxide ore in the mixed copper ore is recovered by direct ammonia leaching of the raw ore, while the copper sulfide ore in the mixed copper ore is recovered by flotation of the leached residue from the ammonia leaching. Ammonia leaching is suitable for copper oxide ore, while flotation is suitable for copper sulfide ore. That process was applied in Dongchuan, Yunnan. However, for oxide-sulfide mixed copper ore with low grade and high binding rate, such a method cannot attain good technical indexes because bound copper cannot be leached out by ammonia leaching.
Dump leaching is an efficient method for treating copper oxide ore, and has been widely applied in Africa, America, and China (in Yunnan, Jiangxi and Anhui, etc.). However, for oxide-sulfide mixed copper ore, it is difficult to leach out the primary copper sulfide in the oxide-sulfide mixed copper ore, and the overall leaching ratio is very low. Therefore, that method is inapplicable to the treatment of oxide-sulfide mixed copper ore with low oxidation rate.
The Patent Application with Application No. 94111476.7 has disclosed a method for processing mixed copper ore and copper oxide ore to extract copper ore, in which the ore is crushed, ammonium carbonate, ammonium sulfate and ammonium chloride are added to the ore, the ore is leached in ammonium hydroxide so that copper enters into the solution, and then a precipitant is added so that the copper precipitates and thereby the copper resource is recovered. However, owing to a fact that the copper in the bound copper and primary copper sulfide can't be leached out by ammonia leaching, that method can't be used to process ore which contain bound copper and primary copper sulfide.
The Patent Application with Application No. 200610136735.2 has disclosed a flotation method for sulfurization-oxidation mixed copper ore, which employs mixed xanthate and hydroximic acid for flotation of copper sulfide ore and copper oxide ore, and can attain high recovery ratio. However, this method cannot recover bound copper ore in the ore.
The Patent Application with Application No. 200510031356.2 has disclosed a wet leaching method for mixed copper ore, nickel ore and zinc ore with low grade and high alkalinity, in which the ore is crushed, and then are leached with a co-leaching agent prepared from ammonium salt with a concentration of 0.5~5mol/L and ammonia with a concentration of 0.1-0.5mol/L. That method also cannot process ore that contain bound copper and primary copper sulfide.
The Patent Application with Application No.201010178875.2 has disclosed a flotation and metallurgy method for high-binding-ratio carbonate gangue-type oxide-sulfide mixed copper ore, which is oriented to high-binding-ratio oxide-sulfide mixed copper ore with high content of calcium-magnesium carbonate gangue ores. In the method, first, the copper sulfide ore and free copper oxide ore are recovered by flotation, and the calcium-magnesium carbonate ores in the flotation tailing are processed by reverse flotation with aliphatic acid to obtain middling that contains bound copper with low content of calcium-magnesium carbonate ores; then, sulfuric acid is added to the middling and the mixture is agitated to leach out the bound copper, and then a copper product is obtained through a metallurgical process from the copper-containing solution after solid-liquid separation. The method incorporates beneficiation and metallurgy to obtain an advantage complementation effect, and can efficiently recycle high-bindingratio carbonate gangue-type oxide-sulfide mixed copper ore resources which cannot be processed at present. However, for mixed copper ore with low oxidation rate and high binding rate, the copper that remains in the tailing after flotation of copper sulfide and free copper oxide mainly exists in the form of chrysocolla and bound copper, and its grade is already very low; therefore, there is no economic benefit to recover the copper in the tailing with a method of sulfuric acid leaching, solid-liquid separation and extraction-electro-depositing, in view of the complex process and high investment and operation cost.
Hence, for simplex copper oxide ore, flotation techniques can attain good technical indexes and can be applied well. For simple oxide-sulfide mixed copper ore, an ideal effect can also be attained by main flotation of copper sulfide ore and recovering copper sulfide and copper oxide ores at the same time. For simplex copper oxide ore with low calcium-magnesium content, a good effect can be attained by dump leaching with sulfuric acid. For oxide-sulfide mixed copper ore with low binding ratio and high calcium magnesium, a technique of ammonia leaching and residue flotation of raw ore at normal temperature and normal pressure can be applied. A high technical level has attained for recycling of those copper ore, and advancements in the beneficiation and metallurgy of copper oxide ore have been made. For oxide-sulfide mixed copper ore with low oxidation rate and high binding rate, a basic principle for processing such oxide-sulfide mixed copper ore is to combine beneficiation and metallurgy to give full play to respective advantages of them. However, at present, existing techniques of flotation followed by metallurgy or metallurgy followed by flotation cannot solve the problem of recycling of oxide-sulfide mixed copper ore with low oxidation rate and high binding rate at the same time. As a result, up to now, no breakthrough has been made in beneficiation and metallurgy of oxide-sulfide mixed copper ore resources, especially oxide-sulfide mixed copper ore resources with low oxidation rate and high binding rate.
Summary of the Invention
For oxide-sulfide mixed copper ore with low oxidation rate and high binding rate, the present invention provides a beneficiation method for mixed copper ore with low oxidation rate and high binding rate, to realize efficient utilization of the copper ore resources which are hard to process.
The object of the present invention is attained with the following technical scheme: a beneficiation method for mixed copper ore with low oxidation rate and high binding rate, comprising the following steps:
(1) grinding mixed copper ore that contains 0.5%~1.2% of copper, 20%~30% of oxidation ratio, 15%~20% of binding ratio and less than 4% of calcium oxide and magnesium oxide such that 80% of monomers of copper sulfide ore and free copper oxide ore in the mixed copper ore is dissociated, sulfurizing the free copper oxide ore by adding 300g~500g of sodium sulfide per ton of mixed copper ore, adding 300g~500g of xanthate as a collecting agent for the copper sulfide ore and the sulfurized free copper oxide ore, adding 30g~40g frothing agent per ton of mixed copper ore to control flotation froth, and proceeding flotation to obtain oxide-sulfide mixed copper concentrate, while leaving tailing containing free copper oxide and bound copper that are hard to recover by flotation;
(2) roasting the oxide-sulfide mixed copper concentrate obtained in the step (1) to desulfurize, so as to obtain copper oxide concentrate which is the final copper concentrate; the flue gas produced in the roasting contains sulfur dioxide gas, introducing ozone produced by an industrial ozone generator in the same molar quantity as the sulfur dioxide in the flue gas into the flue gas, introducing the flue gas to an agitating vessel #1 that contains the tailing pulp formed in the step (1), and adding 200g to 400g manganese dioxide per ton of dry tailing to the agitating vessel #1 at the same time, controlling the pH of the pulp at 2-3 by the charging amount of the flue gas, proceeding primary agitating reaction for 40-60 min, transferring the pulp discharged from the agitating vessel #1 to an agitating vessel 2#, proceeding secondary reaction for 20 to 30 min., and controlling the pH value at 5-6 at the end of the reaction; neutralizing the flue gas discharged from the agitating vessel 1# with lime so that the flue gas meets the emission standard, and then discharging the flue gas;
(3) introducing the pulp in the agitating vessel #2 in the step (2) to an agitating vessel 3#, adding sodium sulfide to precipitate the copper ions therein and therefore to form copper sulfide deposit, and controlling the amount of added sodium sulfide so that the concentration of copper ions in the pulp solution is less than 0.001 g/L;
(4) introducing the pulp in the agitating vessel 3# in the step (3) to an agitating vessel #4, adding 200g to 300g of xanthate collecting agent per ton of dry tailing for flotation and deposition of the copper sulfide so as to obtain copper concentrate, mixing the copper sulfide concentrate with the oxide-sulfide mixed copper concentrate in the step (1), and introducing the mixture into a roasting desulfurization furnace for desulfurization, so as to obtain copper oxide concentrate finally, wherein, the flotation tailing is final tailing.
The height-diameter ratio of the agitating vessel #1 is 3 to 4. The other agitating vessels are general-purpose agitating vessels commonly used in flotation plants and leaching plants.
The xanthate collecting agent is butyl xanthate or isopentyl xanthate.
The frothing agent is terpenic oil or Oil 2#.
The present invention has the following advantages and beneficial effects:
(1) The copper sulfide ore that is easy to recover by flotation is recovered in advance with a low-cost flotation method to obtain a copper concentrate product that is acceptable in metallurgy, to prevent from inhibition by the sulfur dioxide added subsequently and lost in the tailing consequently.
(2) The first step of proceeding oxide-sulfide mixed copper concentrate in the wet smelting plant is roasting desulfurization. The first step in the wet smelting plant is moved to the flotation plant, and low-concentration sulfur dioxide flue gas is used to leach out the copper oxide and bound copper in the tailing, and thereby the cost of flue gas desulfurization is saved.
(3) Since the flue gas produced in the roasting of the concentrate is utilized to leach out the copper oxide and bound copper, sulfuric acid is saved, and tailing leaching cost is reduced.
(4) The copper grade in the tailing after flotation of the mixed copper ore with low oxidation rate and high binding rate is already very low, and there is no economic benefit owing to the high cost if the copper in the tailing is recovered separately with a metallurgical method. Since this part of copper is lost in the tailing and is not recovered at present, the recovery ratio of such copper ore resources is very low. In the present invention, by utilizing sulfur dioxide generated by the sulfur in the concentrate to leach the low-grade tailing, the copper oxide and bound copper that are hard to recover by flotation are recovered, and thereby the overall recovery ratio of copper is improved remarkably.
Brief Description of Drawing
Fig. 1 is a flow chart of the principle of the present invention.
Detailed Description of Drawing
Those skilled in the art should appreciate that the following embodiments are provided only to explain the present invention and shall not be deemed as limiting the scope of the present invention. The specific technique or condition which is not indicated in the embodiments is carried out according to the techniques or conditions described in available literature in the art or the product specification. Any reagent or instrument which is not indicated by the manufacturer is a conventional product that is commercially available.
Embodiment 1:
Raw materials: mixed copper ore that contains 1.2% of copper, 30% of oxidation ratio, 20% of binding ratio, and lower than 4% of calcium oxide and magnesium oxide.
(1) The mixed copper ore is ground such that 80% of monomers of copper sulfide ore and free copper oxide ore in the mixed copper ore is dissociated, the free copper oxide ore is sulfurized by adding 500g of sodium sulfide per ton of dry mixed copper ore, 500g of butyl xanthate is added as a collecting agent for the copper sulfide ore and the sulfurized free copper oxide ore, 30g of frothing agent (terpenic oil) is added to control flotation froth, and flotation is proceeded to obtain oxide-sulfide mixed copper concentrate, while tailing containing free copper oxide and bound copper that are hard to recover by flotation is left.
(2) The oxide-sulfide mixed copper concentrate is roasted to desulfurize, so as to obtain copper oxide concentrate which is the final copper concentrate; the flue gas produced in the roasting contains sulfur dioxide gas, ozone produced by an industrial ozone generator is introduced in the same molar quantity as the sulfur dioxide in the flue gas into the flue gas, the flue gas is led to an agitating vessel #1 which the height-diameter ratio thereof is 4 and contains the tailing pulp formed in the step (1), and 400g of manganese dioxide is added per ton of dry tailing to the agitating vessel #1 at the same time, the pH of the pulp is controlled at 2 to 3 by the charging amount of the flue gas, primary agitating reaction is proceeded for 60 min, the pulp discharged from the agitating vessel #1 is transferred to an agitating vessel 2#, secondary reaction is proceeded for 30 min, and the pH value is controlled at 5 to 6 at the end of the reaction; the flue gas discharged from the agitating vessel 1# is neutralized with lime so that the flue gas meets the emission standard, and then the flue gas is dischared.
(3) The pulp in the agitating vessel #2 in the step (2) is introduced to an agitating vessel 3#, sodium sulfide is added to precipitate the copper ions therein and therefore to form copper sulfide deposit, and the amount of added sodium sulfide is controlled so that the concentration of copper ions in the pulp solution is less than 0.00 lg/L.
(4) The pulp in the agitating vessel 3# in the step (3) is introduced to an agitating vessel #4, 300g of xanthate collecting agent is added per ton of dry tailing for flotation and deposition of the copper sulfide so as to obtain copper concentrate, the copper sulfide concentrate is mixed with the oxide-sulfide mixed copper concentrate in the step (1), and the mixture is introduced into a roasting desulfurization furnace for desulfurization, so as to obtain copper oxide concentrate finally, wherein, the flotation tailing is final tailing.
The copper grade in the copper concentrate is 24%, and the recovery ratio of copper is 92%.
Embodiment 2:
Raw materials: mixed copper ore that contains 0.8% of copper, 26% of oxidation ratio, 18% of binding ratio, and lower than 4% of calcium oxide and magnesium oxide.
(1) The mixed copper ore is ground such that 80% of monomers of copper sulfide ore and free copper oxide ore in the mixed copper ore is dissociated, the free copper oxide ore is sulfurized by adding 400g of sodium sulfide per ton of mixed copper ore, 400g of isopentyl xanthate is added as a collecting agent for the copper sulfide ore and the sulfurized free copper oxide ore, 40g of frothing agent (Oil 2#) is added to control flotation froth, and flotation is proceeded to obtain oxide-sulfide mixed copper concentrate, while tailing containing free copper oxide and combined copper that are hard to recover by flotation is left.
(2) The oxide-sulfide mixed copper concentrate obtained in the step (1) to desulfurize is roasted, so as to obtain copper oxide concentrate which is the final copper concentrate; the flue gas produced in the roasting contains sulfur dioxide gas, ozone produced by an industrial ozone generator is introduced in the same molar quantity as the sulfur dioxide in the flue gas into the flue gas, the flue gas is led to an agitating vessel #1 with heightdiameter ratio thereof is 3.5 and contains the tailing pulp formed in the step (1), and 300g of manganese dioxide is added per ton of dry tailing to the agitating vessel #1 at the same time, the pH of the pulp is controlled at 2 to 3 by the charging amount of the flue gas, primary agitating reaction is proceeded for 50 min, the pulp discharged from the agitating vessel #1 is transferred to an agitating vessel 2#, secondary reaction is proceeded for 25 min, and the pH value is controlled at 5 to 6 at the end of the reaction; the flue gas discharged from the agitating vessel 1# is neutralized with lime so that the flue gas meets the emission standard, and then the flue gas is discharged.
(3) The pulp in the agitating vessel #2 in the step (2) is introduced to an agitating vessel 3#, sodium sulfide is added to precipitate the copper ions therein and therefore to form copper sulfide deposit, and the amount of added sodium sulfide is controlled so that the concentration of copper ions in the pulp solution is less than 0.00 lg/L.
(4) The pulp in the agitating vessel 3# in the step (3) is introduced to an agitating vessel #4, 250g of butyl xanthate collecting agent is added per ton of dry tailing for flotation and deposition of the copper sulfide so as to obtain copper concentrate, the copper sulfide concentrate is mixed with the oxide-sulfide mixed copper concentrate in the step (1), and the mixture is introduced into a roasting desulfurization furnace for desulfurization, so as to obtain copper oxide concentrate finally, wherein, the flotation tailing is final tailing.
The copper grade in the copper concentrate is 22%, and the recovery ratio of copper is 88%.
Embodiment 3:
Raw materials: mixed copper ore that contains 0.5% of copper, 20% of oxidation ratio, 15% of binding ratio, and lower than 4% of calcium oxide and magnesium oxide.
(1) The mixed copper ore is ground such that 80% of monomers of copper sulfide ore and free copper oxide ore in the mixed copper ore is dissociated, the free copper oxide ore is sulfurized by adding 300g of sodium sulfide per ton of dry mixed copper ore, 300g of butyl xanthate is added as a collecting agent for the copper sulfide ore and the sulfurized free copper oxide ore, 40g of frothing agent (terpenic oil) is added to control flotation froth, and flotation is proceeded to obtain oxide-sulfide mixed copper concentrate, while tailing that containing free copper oxide and bound copper that are hard to recover by flotation is left.
(2) The oxide-sulfide mixed copper concentrate obtained in the step (1) to desulfurize is roasted, so as to obtain copper oxide concentrate which is the final copper concentrate; the flue gas produced in the roasting contains sulfur dioxide gas, ozone produced by an industrial ozone generator is introduced in the same molar quantity as the sulfur dioxide in the flue gas into the flue gas, the flue gas is led to an agitating vessel #1 with heightdiameter ratio thereof is 3 and contains the tailing pulp formed in the step (1), and 200g of manganese dioxide is added per ton of dry tailing to the agitating vessel #1 at the same time, the pH of the pulp is controlled at 2 to 3 by the charging amount of the flue gas, primary agitating reaction is proceeded for 40 min, the pulp discharged from the agitating vessel #1 is transferred to an agitating vessel 2#, secondary reaction is proceeded for 20 min, and the pH value is controlled at 5 to 6 at the end of the reaction;
the flue gas discharged from the agitating vessel 1# is neutralized with lime so that the flue gas meets the emission standard, and then the flue gas is discharged.
(3) The pulp in the agitating vessel #2 in the step (2) is introduced to an agitating vessel 3#, sodium sulfide is added to precipitate the copper ions therein and therefore to form copper sulfide deposit, and the amount of added sodium sulfide is controlled so that the concentration of copper ions in the pulp solution is less than 0.00 lg/L.
(4) The pulp in the agitating vessel 3# in the step (3) is introduced to an agitating vessel #4, 200g of butyl xanthate collecting agent is added per ton of dry tailing for flotation and deposition of the copper sulfide so as to obtain copper concentrate, the copper sulfide concentrate is mixed with the oxide-sulfide mixed copper concentrate in the step (1), and the mixture is introduced into a roasting desulfurization furnace for desulfurization, so as to obtain copper oxide concentrate finally, wherein, the flotation tailing is final tailing.
The copper grade in the copper concentrate is 18%, and the recovery ratio of copper is 84%.
The basic principle, main features and advantages of the present invention are illustrated and described above. The person skilled in the art should appreciate that the present invention is not limited to above embodiments. The embodiments and description are provided only to explain the principle of the present invention. Various modifications and improvements can be made to the present invention without departing from the spirit and scope of the present invention, and all of such modifications and improvements shall be deemed as falling into the scope of protection of the present invention. The scope of protection of the present invention is only defined by the attached claims and their equivalents.
Claims (4)
- Claims1. A flotation method for mixed copper ore with low oxidation rate and high binding rate, comprising the following steps:(1) grinding mixed copper ore that contains 0.5% to 1.2% of copper, 20% to 30% of oxidation ratio, 15% to 20% of binding ratio and less than 4% of calcium oxide and magnesium oxide such that 80% of monomers of copper sulfide ore and free copper oxide ore in the mixed copper ore is dissociated, sulfurizing the free copper oxide ore by adding 300g to 500g sodium sulfide per ton of mixed copper ore, adding 300g to 500g of xanthates as a collecting agent for collecting the copper sulfide ore and the sulfurized free copper oxide ore, adding 30g to 40g of frothing agent per ton of mixed copper ore to control flotation froth, and proceeding flotation to obtain oxide-sulfide mixed copper concentrate, while leaving tailing containing free copper oxide and bound copper that are hard to recover by flotation;
- (2) roasting the oxide-sulfide mixed copper concentrate obtained in the step (1) to desulfurize, so as to obtain copper oxide concentrate which is the final copper concentrate; the flue gas produced in the roasting contains sulfur dioxide gas, introducing ozone produced by an industrial ozone generator in the same molar quantity as the sulfur dioxide in the flue gas into the flue gas, leading the flue gas to an agitating vessel #1 that contains the tailing pulp formed in the step (1), and adding 200g to 400g of manganese dioxide per ton of dry tailing to the agitating vessel #1 at the same time, controlling the pH of the pulp at 2 to 3 by the charging amount of the flue gas, proceeding primary agitating reaction for 40 to 60 min, transferring the pulp discharged from the agitating vessel #1 to an agitating vessel 2#, proceeding secondary reaction for 20 to 30min., and controlling the pH value at 5 to 6 at the end of the reaction; neutralizing the flue gas discharged from the agitating vessel 1# with lime so that the flue gas meets the emission standard, and then discharging the flue gas;
- (3) introducing the pulp in the agitating vessel #2 in the step (2) to an agitating vessel 3#, adding sodium sulfide to precipitate the copper ions therein and therefore to form copper sulfide deposit, and controlling the amount of added sodium sulfide so that the concentration of copper ions in the pulp solution is less than 0.00lg/L;
- (4) introducing the pulp in the agitating vessel 3# in the step (3) to an agitating vessel #4, adding 200g to 300g of xanthate collecting agent per ton of dry tailing for flotation and deposition of the copper sulfide so as to obtain copper concentrate, mixing the copper sulfide concentrate with the oxide-sulfide mixed copper concentrate in the step (1), and introducing the mixture into a roasting desulfurization furnace for desulfurization, so as to obtain copper oxide concentrate finally, wherein, the flotation tailing is final tailing.2. The flotation method for mixed copper ore with low oxidation rate and high binding rate according to claim 1, wherein, the height-diameter ratio of the agitating vessel #1 is 3 to 4.3. The flotation method for mixed copper ore with low oxidation rate and high binding rate according to claim 1, wherein, the xanthate collecting agent is butyl xanthate or isopentyl xanthate.4. The flotation method for mixed copper ore with low oxidation rate and high binding rate according to claim 1, wherein, the frothing agent is terpenic oil or Oil 2#.
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| CN201710139089.3 | 2017-03-09 | ||
| 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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| CN110681477B (en) * | 2018-07-06 | 2021-08-10 | 厦门紫金矿冶技术有限公司 | Dressing and smelting combined treatment method for recovering complex copper oxide ore |
| 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 |
| CN113731643B (en) * | 2021-09-13 | 2023-02-28 | 西安建筑科技大学 | Method for recovering fine-grained copper sulfide minerals after oxidation through selective agglomeration flotation |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3220551A (en) * | 1962-12-06 | 1965-11-30 | American Cyanamid Co | Flotation of sulfide ores |
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| CN102688809B (en) * | 2012-06-19 | 2013-04-03 | 昆明理工大学 | Ammonium-amine coupling activation method based on copper mineral sulfurization floatation system |
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