WO2018161651A1 - Beneficiation method for mixed copper ore with low oxidation rate and high binding rate - Google Patents

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 of mixed copper mine with low oxidation rate and high combined rate Technical field

The invention relates to a beneficiation method for a mixed copper mine with low oxidation rate and high combined rate, belonging to the technical field of mineral processing.

Background technique

Copper resources mainly include two major parts of copper sulfide and copper oxide, copper sulfide ore accounts for 80%, and copper oxide ore accounts for 20%. Due to the large amount of copper sulfide ore and the relatively easy recovery of ore dressing, more than 80% of the copper is currently derived from copper sulfide ore resources. The recovery of copper oxide ore is difficult, and the recovery rate of ore dressing is low. In the current shortage of copper resources, the efficient use of copper oxide resources is imperative, so the ore recovery of copper oxide ore has also made some progress. However, in the copper resources, the surface of the copper sulfide deposit is oxidized, forming a huge amount of oxygen-sulfur mixed copper ore resources. This oxygen-sulfur mixed copper mine, mineral processing and metallurgical recovery have encountered certain difficulties.

The selectivity of copper oxide ore is worse than that of copper sulfide. The copper resources are mainly copper sulfide ore. The research on copper oxide ore is relatively rare in recent years. There is a shortage of copper resources in China. At the same time as the recovery of copper sulfide ore, the beneficiation of copper oxide ore has also received great attention. For the mixed copper ore, it is generally treated as a copper sulfide ore, that is, while recovering the copper sulfide ore in the flotation, considering the recovery of the copper oxide ore, but for the low-oxidation rate and high-combination rate of the oxygen-sulfur mixed copper ore, there is no good The way to deal with it.

The main methods of flotation of copper oxide ore are vulcanization flotation method and direct flotation method. The former is widely used. In the process of vulcanization, ammonium sulfate, D ₂ and other enhanced sulfurization reactions are added, and certain effects are obtained. Ammonium sulfate is used as a vulcanization accelerator in industrial production. Direct flotation is suitable for some copper oxide ore of simple gangue minerals. For example, when the gangue mineral is mainly quartz, the direct flotation of hydroxamic acid and fatty acid can obtain good technical indicators.

The treatment of high-calcium-magnesium-oxygen-sulfur mixed copper ore, the normal-temperature and normal-pressure ammonia-leaching-slag flotation technology of the ore has obtained good results, that is, for the copper oxide ore, the direct ore recovery of raw ore is used for the copper sulfide ore. The leaching residue after ammonia leaching is recovered by flotation. Ammonia leaching is suitable for copper oxide ore, and flotation is suitable for copper sulfide ore. This process has been applied in Dongchuan, Yunnan. However, for low-grade, high-binding oxygen-sulfur mixed copper ore, it is difficult to obtain good technical specifications because ammonia leaching cannot be leached with bound copper.

Heap leaching is an effective method for treating copper oxide ore. It is widely used in Yunnan, Jiangxi, Anhui and other provinces in Africa, America and China. However, for the oxygen-sulfur mixed copper ore, sulfuric acid is difficult to leach the primary copper sulfide therein, and the total leaching rate is low. This method is not suitable for the treatment of low-oxidation oxygen-sulfur mixed copper ore.

Application No. 94111476.7, a method for treating mixed copper ore and copper oxide ore to extract copper ore, after crushing the ore, adding ammonium carbonate, ammonium sulfate and ammonium chloride, leaching in ammonia water, copper entering the solution, using precipitation The agent precipitates copper to recover copper resources. Since ammonia leaching cannot dissolve copper in copper and copper in primary copper sulfide, this method cannot treat ore containing copper and primary copper sulfide.

A vulcanization-oxidation mixed copper ore flotation method of application number 200610136735.2 is to use a mixture of xanthate and hydroxamic acid to float copper sulfide ore and copper oxide ore to obtain a high recovery rate. However, this method cannot be recycled for the combined copper ore in the ore.

The wet leaching method of the low-grade high-alkaline mixed copper ore, nickel ore and zinc ore with the application number of 200510031356.2, firstly crushing the ore and then using the ammonium salt concentration of 0.5-5 mol/L and the ammonia concentration of 0.1-0.5 mol/ The ammonium salt of L and the ammonia hydrate are combined with a leaching agent for leaching. This method also fails to treat ores containing bound copper and native copper sulfide.

Application method of high-integration rate carbonate gangue type oxygen-sulfur mixed copper ore with application number 201010178875.2, for oxygen-sulfur mixed copper ore with high combined rate and high content of calcium-magnesium carbonate gangue minerals Flotation recovery of copper sulfide minerals and free copper oxide minerals, floatation of tailings with fatty acids, reverse flotation of calcium and magnesium carbonate minerals, to obtain calcium-magnesium carbonate minerals with low, containing copper in the middle ore Then, sulfuric acid is stirred and leached to combine copper, and the copper-containing solution after solid-liquid separation is obtained by metallurgical method. The method combines smelting and smelting, complements each other's advantages, and efficiently recycles the high-combination carbonate gangue-type oxygen-sulfur mixed copper ore resources that cannot be processed at present. However, for mixed copper ore with low oxidation rate and high binding rate, after copper sulfide and free copper oxide flotation, the copper remaining in the tailings mainly exists in the form of chrysocolla, combined copper, etc., and the grade is already low. The tailings sulfuric acid leaching, solid-liquid separation, and extraction of electrowinning are used to recover copper. Due to the complicated process, high investment and operation costs, there is no economic benefit.

Therefore, for a single copper oxide ore, flotation can obtain better technical indicators, and flotation technology is better applied. For simple oxygen-sulfur mixed copper ore, the use of copper sulfide ore-based flotation to simultaneously recover copper sulfide and copper oxide minerals can also achieve better results. For low calcium and magnesium content, a single copper oxide ore, sulfuric acid heap leaching can achieve good results. For the low binding rate, high calcium magnesium oxysulfide mixed copper ore, the normal temperature and atmospheric pressure ammonia leaching-slag flotation technology of the ore is applied. For the recycling of these copper mines, a higher technology has been achieved. The level has advanced the progress of the copper oxide ore smelting technology. For the low oxidation rate, high binding rate oxygen-sulfur mixed copper ore, the combination of mineral processing and metallurgy, to play their respective advantages, is the basic principle of dealing with this oxygen-sulfur mixed copper ore. However, the current post-election post-mineralization or post-metallurgical post-election can not simultaneously solve the problem of recycling of low-oxidation rate and high-binding oxygen-sulfur mixed copper ore, resulting in oxygen-sulfur mixed copper ore, especially low oxidation rate, The problem of high-combination rate oxygen-sulfur mixed copper ore resource selection and smelting has not been broken.

Summary of the invention

The object of the present invention is to provide a beneficiation method for a low-oxidation rate and high-combination rate mixed copper ore with low oxidation rate and high binding rate oxygen-sulfur mixed copper ore, thereby realizing efficient utilization of the refractory copper ore resource.

The invention is realized by the following technical scheme: a beneficiation method of a mixed copper mine with low oxidation rate and high binding rate, which is carried out according to the following steps:

(1) Mixing copper ore containing 0.5% to 1.2% of copper, 20% to 30% of oxidation rate, 15% to 20% of combination, and less than 4% of calcium and magnesium oxide, grinding to copper sulfide minerals and free 80% monomer of copper oxide mineral dissociates, adding 300g ~ 500g of sodium sulfide per ton of mixed copper ore to vulcanize the free copper oxide mineral, adding 300g ~ 500g xanthate as copper sulfide mineral and free oxidation after vulcanization Copper mineral collector, and add foaming agent 30g ~ 40g per ton of mixed copper ore to control flotation foam, flotation to obtain oxygen-sulfur mixed copper concentrate, leaving free copper oxide with partial hard-to-float selection and bonding Copper tailings;

(2) Desulfurization of the oxygen-sulfur mixed copper concentrate obtained in the step (1) to obtain a copper oxide concentrate as the final copper concentrate; the roasting flue gas contains sulfur dioxide gas, and the smoke produced by the industrial ozone machine is introduced into the flue gas. The equimolar ozone of sulfur dioxide in the gas is introduced into the mixing barrel of tailings slurry formed in step (1), and 200g-400g of manganese dioxide is added per ton of dry tailings, which is controlled by the amount of flue gas. The pH value of the slurry is 2~3, and a stirring reaction is carried out for 40 minutes to 60 minutes. The slurry discharged from the mixing drum No. 1 enters the mixing drum No. 2, and the second reaction is carried out for 20 minutes to 30 minutes. The pH of the reaction end point is controlled at 5~. 6; the flue gas discharged from the mixing drum No. 1 is discharged after being neutralized by lime;

(3) Introducing the slurry of the mixing drum No. 2 in the step (2) into the mixing drum No. 3, adding sodium sulfide to precipitate the copper ions therein to form a copper sulfide precipitate, and controlling the addition amount of the sodium sulfide to make the copper ion concentration in the slurry solution less than 0.001g/L;

(4) Introducing the slurry of No. 3 mixing drum in step (3) into the No. 4 mixing drum, and adding 200g to 300g of xanthate collector to float copper sulfide to obtain copper concentrate per ton of dry tailings. The copper sulfide concentrate is mixed with the oxygen-sulfur mixed copper concentrate of step (1), and after desulfurization in the roasting desulfurization furnace, the final copper oxide concentrate is obtained. Flotation tailings are the final tailings.

The No. 1 mixing drum has an aspect ratio of 3 to 4. Other mixing tanks are flotation plants and dip-factory universal mixing drums.

The xanthate collectors are butyl xanthate and isoamyl xanthate.

The foaming agent is pine oil and No. 2 oil.

The present invention has the following advantages and positive effects:

(1) For copper flotation minerals that are easy to float, they are pre-recovered by low-cost flotation method to obtain metallurgically qualified copper concentrate products, which avoids the tailings loss caused by the subsequent addition of sulfur dioxide.

(2) The first step of the oxygen-sulfur mixed copper concentrate in the wet smelting plant is roasting and desulfurization. The first step of the wet smelting plant is moved to the concentrator, and the low-concentration sulfur dioxide flue gas is used for the copper oxide in the tailings. Combined with the leaching of copper, the cost of flue gas desulfurization is saved.

(3) The use of concentrate roasting flue gas to leach copper oxide and copper in the tailings, saving sulfuric acid and reducing the cost of tailings leaching.

(4) Low oxidation rate and high binding rate Mixed copper ore tailings after flotation, the copper grade is already very low, and it is recovered by metallurgical method alone. The cost is high and there is no economic benefit. At present, this part of copper is lost in tailings. There is no recovery, so the recovery rate of this copper ore resource is low. The present invention leaches low-grade tailings by sulfur dioxide generated by sulfur in its own concentrate, recovers difficult-to-recover refractory copper oxide and combined copper, and significantly improves copper. Comprehensive recovery rate.

DRAWINGS

Figure 1 is a flow chart of the principles of the present invention.

detailed description

Those skilled in the art will appreciate that the following examples are merely illustrative of the invention and are not to be considered as limiting the scope of the invention. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained through purchase.

Embodiment 1:

Raw materials: mixed copper ore containing 1.2% copper, 30% oxidation rate, 20% binding rate and less than 4% calcium oxide and magnesium content.

(1) Grinding to where the copper sulfide mineral and the free copper oxide mineral 80% monomer dissociation, dry mix per ton Adding 500g of sodium sulfide to the free copper oxide mineral in the copper ore, adding 500g of butyl xanthate as a collector of copper sulfide mineral and free copper oxide mineral after vulcanization, adding 30g of foaming agent pine oil Flotation foam, flotation to obtain oxygen-sulfur mixed copper concentrate, leaving tailings containing partially difficult to float free copper oxide and copper.

(2) Desulfurization of oxygen-sulfur mixed copper concentrate to obtain copper oxide concentrate as final copper concentrate; roasting flue gas containing sulfur dioxide gas, introducing into the flue gas an equimolar amount of sulfur dioxide produced by industrial ozone machine and flue gas Ozone, the flue gas is introduced into the mixing drum No. 1 containing the tailings slurry formed in the step (1), the height-to-diameter ratio of the No. 1 mixing drum is 4, and 400 g of manganese dioxide is added per ton of dry-base tailings, and the smoke is passed. The gas inlet quantity controls the pH value of the slurry to 2~3, and a stirring reaction is carried out for 60 minutes. The slurry discharged from the mixing drum No. 1 enters the mixing drum No. 2, and the second reaction is carried out for 30 minutes. The pH of the reaction end point is controlled at 5-6. The flue gas discharged from the mixing drum No. 1 is discharged after being neutralized by lime.

(3) Introducing the slurry of the mixing drum No. 2 in the step (2) into the mixing drum No. 3, adding sodium sulfide to precipitate the copper ions therein to form a copper sulfide precipitate, and controlling the addition amount of the sodium sulfide to make the copper ion concentration in the slurry solution less than 0.001 g / L.

(4) Introduce the slurry of No. 3 mixing drum in step (3) into No. 4 mixing drum, and add 300g of xanthate collector to float copper sulfide to form copper concentrate, which is obtained by adding 300g of xanthate collector per ton of dry tailings. The concentrate is mixed with the oxygen-sulfur mixed copper concentrate of step (1), and after desulfurization into the roasting desulfurization furnace, the final copper oxide concentrate is obtained, and the flotation tailings is the final tailings.

The copper concentrate has a copper content of 24% and a copper recovery of 92%.

Embodiment 2:

Raw materials: mixed copper ore containing 0.8% copper, 26% oxidation rate, 18% binding rate and less than 4% calcium oxide and magnesium content.

(1) Grinding to 80% of the copper sulfide mineral and free copper oxide mineral dissociated, adding 400g of sodium sulfide per ton of mixed copper ore to vulcanize the free copper oxide mineral, adding 400g of isoamyl xanthate As a collector of copper sulfide mineral and free copper oxide mineral after vulcanization, adding 40g of foaming agent No. 2 oil to control flotation foam, flotation to obtain oxygen-sulfur mixed copper concentrate, leaving partially difficult to float free Copper oxide and tailings combined with copper.

(2) Desulfurization of the oxygen-sulfur mixed copper concentrate obtained in the step (1) to obtain a copper oxide concentrate as the final copper concentrate; the roasting flue gas contains sulfur dioxide gas, and the smoke produced by the industrial ozone machine is introduced into the flue gas. The equimolar ozone of sulfur dioxide in the gas is introduced into the mixing bucket of tailings slurry formed in step (1). The height-to-diameter ratio of the mixing drum No. 1 is 3.5, and manganese dioxide is added per ton of dry tailings. 300g, through the smoke through The amount of pulp is controlled to be 2~3, and a stirring reaction is carried out for 50 minutes. The slurry discharged from the mixing drum No. 1 enters the mixing drum No. 2, and the second reaction is carried out for 25 minutes. The pH of the reaction end point is controlled at 5-6; The flue gas discharged from the mixing drum No. 1 is discharged after being neutralized by lime.

(3) Introducing the slurry of the mixing drum No. 2 in the step (2) into the mixing drum No. 3, adding sodium sulfide to precipitate the copper ions therein to form a copper sulfide precipitate, and controlling the addition amount of the sodium sulfide to make the copper ion concentration in the slurry solution less than 0.001 g / L.

(4) Introducing the slurry of the mixing drum No. 3 in step (3) into the mixing drum No. 4, and adding 250 g of butyl xanthate collector to float copper sulfide per ton of dry tailings to obtain copper concentrate. The copper sulfide concentrate is mixed with the oxygen-sulfur mixed copper concentrate in step (1), and after desulfurization in the roasting desulfurization furnace, the final copper oxide concentrate is obtained, and the flotation tailings is the final tailings.

The copper concentrate has a copper content of 22% and a copper recovery of 88%.

Embodiment 3:

A mixed copper ore containing 0.5% copper, an oxidation rate of 20%, a bonding ratio of 15%, and a calcium oxide and magnesium content of less than 4%.

(1) Grinding to 80% of the copper sulfide mineral and free copper oxide mineral dissociated, adding 300g of sodium sulfide per ton of mixed copper ore to vulcanize the free copper oxide mineral, adding 300g of butyl yellow drug as The collector of copper sulfide mineral and free copper oxide mineral after vulcanization, adding 40g of foaming agent pine oil to control the flotation foam, flotation to obtain oxygen-sulfur mixed copper concentrate, leaving part of the difficult flotation free oxidation Copper and copper tailings.

(2) Desulfurization of the oxygen-sulfur mixed copper concentrate obtained in the step (1) to obtain a copper oxide concentrate as the final copper concentrate; the roasting flue gas contains sulfur dioxide gas, and the smoke produced by the industrial ozone machine is introduced into the flue gas. The gas is equal to the equimolar ozone of sulfur dioxide, and the flue gas is introduced into the mixing barrel of the tailings slurry formed in the step (1). The height-to-diameter ratio of the mixing drum No. 1 is 3, and manganese dioxide is added per ton of the dry tailings. 200g, control the pH value of the slurry by 2~3, and carry out a stirring reaction for 40 minutes. The slurry discharged from the mixing drum No. 1 enters the mixing drum No. 2, and the second reaction is carried out for 20 minutes. The pH value of the reaction end point is controlled. At 5-6; the flue gas discharged from the mixing drum No. 1 is neutralized by lime and discharged.

(3) Introducing the slurry of the mixing drum No. 2 in the step (2) into the mixing drum No. 3, adding sodium sulfide to precipitate the copper ions therein to form a copper sulfide precipitate, and controlling the addition amount of the sodium sulfide to make the copper ion concentration in the slurry solution less than 0.001 g / L.

(4) Introducing the slurry of No. 3 mixing drum in step (3) into the No. 4 mixing drum, and adding 200 g of butyl xanthate collector per ton of dry tailings to float and precipitate copper sulfide to obtain copper concentrate, the vulcanization Copper concentrate and steps (1) The oxygen-sulfur mixed copper concentrate is mixed and desulfurized into a roasting desulfurization furnace to obtain a final copper oxide concentrate, and the flotation tailings is the final tailings.

The copper concentrate has a copper content of 18% and a copper recovery of 84%.

The basic principles, main features, and advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the present invention is only described in the foregoing description and the description of the present invention, without departing from the spirit and scope of the invention. Various changes and modifications are intended to be included within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and their equivalents.

Claims (4)

A beneficiation method for mixing copper with low oxidation rate and high binding rate, which is characterized by the following steps: (1) Mixing copper ore containing 0.5% to 1.2% of copper, 20% to 30% of oxidation rate, 15% to 20% of combination, and less than 4% of calcium and magnesium oxide, grinding to copper sulfide minerals and free 80% monomer of copper oxide mineral dissociates, adding 300g ~ 500g of sodium sulfide per ton of mixed copper ore to vulcanize the free copper oxide mineral, adding 300g ~ 500g xanthate as copper sulfide mineral and free oxidation after vulcanization Copper mineral collector, and add foaming agent 30g ~ 40g per ton of mixed copper ore to control flotation foam, flotation to obtain oxygen-sulfur mixed copper concentrate, leaving free copper oxide with partial hard-to-float selection and bonding Copper tailings; (2) Desulfurization of the oxygen-sulfur mixed copper concentrate obtained in the step (1) to obtain a copper oxide concentrate as the final copper concentrate; the roasting flue gas contains sulfur dioxide gas, and the smoke produced by the industrial ozone machine is introduced into the flue gas. The equimolar ozone of sulfur dioxide in the gas is introduced into the mixing barrel of tailings slurry formed in step (1), and 200g-400g of manganese dioxide is added per ton of dry tailings, which is controlled by the amount of flue gas. The pH value of the slurry is 2~3, and a stirring reaction is carried out for 40 minutes to 60 minutes. The slurry discharged from the mixing drum No. 1 enters the mixing drum No. 2, and the second reaction is carried out for 20 minutes to 30 minutes. The pH of the reaction end point is controlled at 5~. 6; the flue gas discharged from the mixing drum No. 1 is discharged after being neutralized by lime; (3) Introducing the slurry of the mixing drum No. 2 in the step (2) into the mixing drum No. 3, adding sodium sulfide to precipitate the copper ions therein to form a copper sulfide precipitate, and controlling the addition amount of the sodium sulfide to make the copper ion concentration in the slurry solution less than 0.001g/L; (4) Introducing the slurry of No. 3 mixing drum in step (3) into the No. 4 mixing drum, and adding 200g to 300g of xanthate collector to float copper sulfide to obtain copper concentrate per ton of dry tailings. The copper sulfide concentrate is mixed with the oxygen-sulfur mixed copper concentrate in step (1), and after desulfurization in the roasting desulfurization furnace, the final copper oxide concentrate is obtained, and the flotation tailings is the final tailings. The beneficiation method of mixed copper with low oxidation rate and high binding rate according to claim 1, wherein the mixing drum No. 1 has an aspect ratio of 3 to 4. . The beneficiation method of mixed copper with low oxidation rate and high binding rate according to claim 1, wherein the xanthate-type collector is butyl xanthate and isoamyl xanthate. The beneficiation method of mixed copper with low oxidation rate and high binding ratio according to claim 1, wherein the foaming agent is pine oil and No. 2 oil.

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