High-efficiency flotation separation and water purification method for copper-molybdenum ores in high-altitude organic-rich areas

Abstract

The present invention discloses a method for efficient flotation separation and water purification of copper-molybdenum ores in high-altitude, organic-rich areas, comprising crushing and grinding operations; copper-molybdenum mixed flotation operations; mixed concentrate pretreatment operations; copper-molybdenum separation operations; return water diversion operations; tailings concentration and water treatment operations. The present invention utilizes the characteristics of high sodium sulfide in flotation return water and combines it with a water treatment agent to circulate and self-purify the flotation return water, thereby reducing the negative impact of organic water on copper-molybdenum separation from the source. The present invention uses ferrous sulfate, ferric chloride, and sodium hexametaphosphate as mixed copper inhibitors to enhance the inhibitory effect of copper sulfide minerals and improve the copper-molybdenum separation efficiency. The present invention is simple to operate and low in cost, and can provide a reference for the comprehensive recovery of this ore resource.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to a method for efficient flotation separation and water purification of copper-molybdenum ores in high-altitude, organic-rich areas. Background Art

[0002] Porphyry copper-molybdenum deposits are the primary source of copper and molybdenum concentrates. Porphyry copper mines produce over 60% of global copper production and over 50% of global molybdenum production annually. Obtaining copper and molybdenum concentrates from porphyry copper-molybdenum deposits typically requires crushing and grinding, mixed copper-molybdenum flotation, and separation to ultimately produce copper sulfide and molybdenite concentrates. Because copper sulfide and molybdenite have similar floatabilities, and the flotation stage often utilizes highly captive collectors such as polycarbonate xanthate and butylammonium nitrosulfate, or even copper sulfate for activation, separation of copper and molybdenum is difficult or impossible to achieve, severely hindering the efficient development and utilization of copper-molybdenum resources.

[0003] To improve the efficiency of copper-molybdenum separation, current research directions, both domestically and internationally, focus on de-doping copper-molybdenum mixed concentrates, such as through concentration, grinding, and heating; developing highly effective copper mineral inhibitors, such as sodium sulfide, sodium bisulfide, sodium thioglycolate, sodium cyanide, and Knox compounds; and employing new processes and equipment, such as flotation columns and potential control technologies. Furthermore, water quality significantly impacts copper-molybdenum separation. For example, due to soil characteristics in Northeast my country, the organic matter content in the water is high, making conventional flotation methods difficult to effectively separate the copper-molybdenum mixed concentrate produced there. This is especially true during the summer snowmelt, when the elevated organic matter content renders copper sulfide minerals unrestricted. Efficient copper-molybdenum separation in this region remains a challenge, resulting in a waste of copper and molybdenum resources. Currently, most production still utilizes a sodium sulfide + kerosene copper-molybdenum separation process. Flotation return water is often fed into a tailings pond along with the mixed flotation tailings and then directly recycled. This can lead to the accumulation of recalcitrant organic matter in the return water system, impacting copper-molybdenum separation and even the flotation performance of the mixed copper-molybdenum concentrate.

[0004] Therefore, developing an efficient copper-molybdenum separation technology for high-altitude, organic-rich areas to solve the negative impact of organic water on copper-molybdenum flotation will help improve the copper and molybdenum recovery rate of porphyry copper-molybdenum ore resources, improve the quality of copper and molybdenum concentrates, reduce inter-containment, and improve the utilization level of this type of ore resources. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the present invention aims to provide a method for efficient flotation separation and water purification of copper-molybdenum ores in high-altitude, organic-rich areas.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The method for efficient flotation separation and water purification of copper-molybdenum ores in high-altitude organic-rich areas comprises the following steps:

[0008] S1. Crushing and grinding: Crushing the copper-molybdenum ore, mixing the crushed product with one or both of organic-rich fresh water or purified water, and then feeding it into the mill for grinding to obtain the floating product with qualified particle size;

[0009] S2, copper-molybdenum mixed flotation operation: feeding the flotation product obtained in step S1 into a flotation machine, sequentially adding a collector butyl xanthate and a frother pine oil to carry out copper-molybdenum mixed flotation to obtain a copper-molybdenum mixed concentrate and a copper-molybdenum mixed flotation tailings;

[0010] S3, mixed concentrate pretreatment operation: the copper-molybdenum mixed concentrate obtained in step S2 is fed into a thickener for concentration and drug removal, and a water treatment agent is added for water purification. The resulting underflow is the concentrated mixed concentrate, and the overflow is the purified water. The concentrated mixed concentrate enters the copper-molybdenum separation operation, and the purified water enters the tailings pond; the water treatment agent is ferric chloride;

[0011] S4, copper-molybdenum separation: The concentrated mixed concentrate obtained in step S3 is mixed with purified water and fed into a flotation machine for copper-molybdenum separation and flotation. A copper inhibitor ZJDB-1, sodium sulfide, and kerosene are sequentially added to ultimately obtain copper concentrate and molybdenum concentrate. The copper concentrate and molybdenum concentrate are each fed into a concentration filter press system for dehydration to recover flotation return water. The copper inhibitor ZJDB-1 is a mixture of ferrous sulfate, ferric chloride, and sodium hexametaphosphate in a mass ratio of 5:5:1.

[0012] S5, backwater diversion operation: the flotation return water obtained in step S4 is sent to the sedimentation tank to further recover fine metal particles, and the overflow water is divided, part of which enters step S6 and part enters the tailings pond;

[0013] S6, tailings concentration and water treatment: The copper-molybdenum mixed flotation tailings obtained in step S2 and the overflow water diverted in step S5 are fed into a tailings thickener, and flocculants and water treatment agents are added for concentration and water purification. The purified water obtained is directly returned to step S1 for use. The concentrated tailings enter the tailings pond and are mixed and stored with the purified water and overflow water returned to the tailings pond. The flocculant is polyphenylene amide and the water treatment agent is ferric chloride.

[0014] Furthermore, in step S2, the copper-molybdenum mixed flotation includes one roughing selection, multiple scavenging selections and multiple concentrating selections. Based on the weight of dry ore per ton of copper-molybdenum ore, 50-100 g / t of butyl xanthate as a collector and 20-50 g / t of pine oil as a foaming agent are added in the roughing selection, 10 g / t of butyl xanthate as a collector is added in the scavenging selection, and no reagent is added in the concentrating selection.

[0015] Furthermore, in step S3, the amount of water treatment agent used is 500-2000 g / t based on the weight of dry ore per ton of copper-molybdenum mixed concentrate.

[0016] Furthermore, in step S4, the copper-molybdenum separation flotation includes one roughing, multiple scavenging and multiple concentrating. Based on the dry ore weight of each ton of copper-molybdenum mixed concentrate, 3000-6000 g / t of copper inhibitor ZJDB-1, 6000-12000 g / t of sodium sulfide and 500-1500 g / t of kerosene are added in the roughing, 1000 g / t of sodium sulfide and 100-200 g / t of kerosene are added in the scavenging, and no reagent is added in the concentrating. The copper inhibitor ZJDB-1 is a mixture of ferrous sulfate, ferric chloride and sodium hexametaphosphate in a mass ratio of 5:5:1.

[0017] Furthermore, in step S6, based on the weight of dry ore per ton of copper-molybdenum ore, the amount of flocculant used is 10-30 g / t, and the amount of water treatment agent used is 500-1000 g / t.

[0018] Furthermore, in step S5, the mass of the overflow water entering step S6 is 1 / 30 of the total mass of the overflow water.

[0019] The beneficial effects of the present invention are:

[0020] (1) The present invention utilizes the characteristic of high sodium sulfide in flotation return water, combines it with water treatment agent, circulates and self-purifies the flotation return water, and then reuses it as grinding water, thereby reducing the negative impact of organic-rich water on copper-molybdenum separation from the source.

[0021] (2) The present invention uses ferrous sulfate, ferric chloride and sodium hexametaphosphate as a mixed copper inhibitor to form a hydrophilic film on the surface of the copper mineral, thereby strengthening the inhibitory effect of the copper sulfide mineral and improving the copper-molybdenum separation efficiency.

[0022] (3) The present invention is simple to operate and low in cost, and can provide a reference for the comprehensive recovery of the ore resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a flow chart of the method of Example 1 of the present invention. DETAILED DESCRIPTION

[0024] The present invention will be further described below in conjunction with the accompanying drawings. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to this embodiment.

[0025] A porphyry copper-molybdenum mine in Heilongjiang Province contains 0.40% copper and 0.017% molybdenum. The copper minerals are mainly chalcopyrite and bornite, the molybdenum minerals are mainly molybdenite, and the gangue is mainly quartz, feldspar, etc. The soil in this area is black soil and the external water is rich in organic matter, which makes it difficult to separate copper and molybdenum. The molybdenum recovery rate using conventional copper-molybdenum flotation separation process is less than 30%. This embodiment provides a method for the efficient flotation separation and water purification of copper-molybdenum ores in high-altitude and organic-rich areas to treat the above-mentioned porphyry copper-molybdenum mine in Heilongjiang Province. The specific process is as follows: Figure 1 As shown:

[0026] The raw ore is crushed to -12mm, accounting for 95%, and then ground and classified with purified water or organic-rich new water from nearby rivers (initially, only organic-rich new water is used, and then it is mixed with purified water after the operation is stable). The grinding concentration is 75%, and the classified products with a fineness of -0.074mm, accounting for 65%, enter the copper-molybdenum mixed flotation operation. After one roughing, two scavenging and three concentrating processes (the dosage of reagents in each stage is as follows: 80g / t of butyl xanthate and 20g / t of pine oil are added in the roughing, 10g / t of butyl xanthate is added in the first scavenging, 10g / t of butyl xanthate is added in the second scavenging, and no reagents are added in the concentrating), copper-molybdenum mixed concentrate and copper-molybdenum mixed flotation tailings are obtained.

[0027] The copper-molybdenum mixed concentrate is concentrated using a 60m thickener and 500g / t of ferric chloride is added. The overflow (purified water) from the 60m thickener enters a tailings pond. The underflow (concentrated mixed concentrate) undergoes a first roughing, second scavenging, and sixth concentrating process for copper-molybdenum separation. (The reagent dosages for each stage are as follows: 5000g / t of ZJDB-1, 10,000g / t of sodium sulfide, and 500g / t of kerosene are added in the roughing process; 1000g / t of sodium sulfide and 200g / t of kerosene are added in the first scavenging process; 1000g / t of sodium sulfide and 100g / t of kerosene are added in the second scavenging process; and no reagents are added in the concentrating process.) This yields copper concentrate (slurry) and molybdenum concentrate (foam). The molybdenum and copper concentrates are further concentrated and dewatered by filter press, and the flotation return water is recovered. The copper depressant, ZJDB-1, is a mixture of ferrous sulfate, ferric chloride, and sodium hexametaphosphate in a mass ratio of 5:5:1.

[0028] Flotation return water adopts 3000m 3 The sedimentation tank further recovers useful metals. 3 One-third of the overflow water from the sedimentation tank is diverted to a 62-meter thickener, where copper-molybdenum mixed flotation tailings are added. A flocculant, polyphenylene amide (10g / t) and ferric chloride (500g / t), calculated per ton of dry copper-molybdenum ore, are then added for concentration. The flotation return water and ferric chloride synergistically purify the water. The overflow from the 62-meter thickener (purified water, pH ≈ 10) is returned to the grinding operation, and the underflow enters the tailings pond.

[0029] The 3000m3 The remaining overflow water from the sedimentation tank enters the tailings pond.

[0030] The backwater from the tailings pond can also be returned for use in grinding operations and copper-molybdenum separation operations.

[0031] The specific process experimental indicators of this embodiment are shown in Table 1.

[0032] Table 1

[0033]

[0034] As can be seen from Table 1, after the method of this embodiment is implemented, the comprehensive recovery rate of molybdenum in the concentrator is increased by more than 40 percentage points, with significant economic benefits, and the efficient comprehensive recovery of the copper-molybdenum resources is achieved.

[0035] Those skilled in the art can make various corresponding changes and modifications based on the above technical solutions and concepts, and all of these changes and modifications should be included in the scope of protection of the claims of the present invention.

Claims

1. A method for efficient flotation separation and water purification of copper-molybdenum ores in high-altitude, organic-rich areas, characterized by: The following steps are involved: S1. Crushing and grinding: Crushing the copper-molybdenum ore, feeding the crushed product and one or both of organic-rich fresh water or purified water into the mill for grinding to obtain the floating product of qualified particle size; S2, copper-molybdenum mixed flotation operation: feeding the flotation product obtained in step S1 into a flotation machine for copper-molybdenum mixed flotation to obtain copper-molybdenum mixed concentrate and copper-molybdenum mixed flotation tailings; S3, mixed concentrate pretreatment operation: the copper-molybdenum mixed concentrate obtained in step S2 is fed into a thickener for concentration and drug removal, and a water treatment agent is added for water purification. The resulting underflow is the concentrated mixed concentrate, and the overflow is the purified water. The concentrated mixed concentrate enters the copper-molybdenum separation operation, and the purified water enters the tailings pond; the water treatment agent is ferric chloride; S4, copper-molybdenum separation operation: the concentrated mixed concentrate obtained in step S3 is mixed with purified water and fed into a flotation machine for copper-molybdenum separation and flotation to obtain copper concentrate and molybdenum concentrate. The copper concentrate and molybdenum concentrate are respectively fed into a concentration filter press system for dehydration to recover flotation return water; S5, backwater diversion operation: the flotation return water obtained in step S4 is sent to the sedimentation tank to further recover fine metal particles, and the overflow water is divided, part of which enters step S6 and part enters the tailings pond; S6, tailings concentration and water treatment: The copper-molybdenum mixed flotation tailings obtained in step S2 and the overflow water diverted in step S5 are fed into a tailings thickener, and flocculants and water treatment agents are added for concentration and water purification. The purified water obtained is directly returned to step S1 for use. The concentrated tailings enter the tailings pond and are mixed and stored with the purified water and overflow water returned to the tailings pond. The flocculant is polyphenylene amide and the water treatment agent is ferric chloride.

2. The method according to claim 1, characterized in that In step S2, the copper-molybdenum mixed flotation includes one roughing selection, multiple scavenging selections and multiple concentrating selections. Based on the weight of dry ore per ton of copper-molybdenum ore, 50-100 g / t of butyl xanthate as a collector and 20-50 g / t of pine oil as a foaming agent are added in the roughing selection, 10 g / t of butyl xanthate as a collector is added in the scavenging selection, and no reagent is added in the concentrating selection.

3. The method according to claim 1, characterized in that In step S3, the amount of water treatment agent used is 500-2000 g / t based on the weight of dry ore per ton of copper-molybdenum mixed concentrate.

4. The method according to claim 1, wherein In step S4, the copper-molybdenum separation flotation includes one roughing process, multiple scavenging processes, and multiple concentrating processes. Based on the dry ore weight of each ton of copper-molybdenum mixed concentrate, 3000-6000 g / t of copper inhibitor ZJDB-1, 6000-12000 g / t of sodium sulfide, and 500-1500 g / t of kerosene are added in the roughing process, 1000 g / t of sodium sulfide and 100-200 g / t of kerosene are added in the scavenging process, and no reagent is added in the concentrating process. The copper inhibitor ZJDB-1 is a mixture of ferrous sulfate, ferric chloride, and sodium hexametaphosphate in a mass ratio of 5:5:

1.

5. The method according to claim 1, wherein In step S6, based on the weight of dry ore per ton of copper-molybdenum ore, the amount of flocculant used is 10-30 g / t, and the amount of water treatment agent used is 500-1000 g / t.

6. The method according to claim 1, wherein In step S5, the mass of the overflow water entering step S6 is 1 / 30 of the total mass of the overflow water.

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