Nanoparticle copper sulfide inhibitor and preparation and application thereof
By preparing copper sulfide inhibitors using nanoparticles under an oxygen-free magnetic field, the problems of high toxicity and high cost of existing inhibitors in copper-molybdenum separation have been solved, achieving efficient separation of copper and molybdenum and environmentally friendly resource recycling.
Patent Information
- Application Number
- CN202511320986.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-16
- Publication Date
- 2025-11-11
AI Technical Summary
Existing inorganic inhibitors have problems such as toxicity, high cost, and difficult wastewater treatment in the flotation of chalcopyrite and molybdenite, while organic inhibitors have high synthesis costs, limited applicability, and are difficult to effectively separate copper-molybdenum mixed concentrates.
A method for preparing copper sulfide nanoparticle inhibitors under anaerobic and magnetic field conditions was adopted. Using starch solution as a medium, FeS nanoparticles were rapidly generated by the reaction of ferrous sulfate and sodium sulfide for copper-molybdenum flotation separation. A multi-stage flotation operation was carried out in combination with kerosene and sodium sulfide.
It achieves efficient separation of copper and molybdenum, reduces costs, minimizes the loss of copper sulfide in molybdenum concentrate, improves resource utilization, and is environmentally friendly and pollution-free.
Smart Images
Figure CN120920205A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of mineral processing technology, specifically to a nanoparticle copper sulfide inhibitor and its preparation and application. Background Technology
[0002] When separating chalcopyrite and molybdenite by flotation, suppressing the flotation of chalcopyrite to remove molybdenite is one of the most common processes in mineral processing. Chalcopyrite suppressants are classified into inorganic and organic types. Commonly used inorganic suppressants include sulfides (Na₂S, NaHS), cyanides (NaCN, KCN), sulfates (Na₂S₂O₃, Na₂SO₅), and noxes (phosphorus noxes P₂S₅ + NaOH, arsenic noxes As₂O₃ + Na₂S). Due to their good inhibitory effect on chalcopyrite, inorganic suppressants are widely used in industrial production; however, their inherent toxicity, high cost, and difficulty in wastewater treatment limit their application. In the context of vigorously developing green mines, environmentally friendly reagents are receiving more attention. Organic suppressants, with their low toxicity and high efficiency, have been extensively researched and applied.
[0003] Common organic inhibitors include sulfhydryl groups, thioureas, and polysaccharides. Sulfhydryl groups are small-molecule organic compounds, such as sulfhydryl acetic acid and thiolactic acid, with the structural formula HS—R—COOH. In mineral pulp, the -HS group exhibits strong adsorption activity, desorbing xanthate from the surface of chalcopyrite and contacting it, exposing the hydrophilic -COOH group and increasing the hydrophilicity of the chalcopyrite. Inorganic inhibitors are most widely used in mineral processing, showing significant inhibitory effects on chalcopyrite, but most are environmentally unfriendly and require large reagent quantities. In contrast, organic inhibitors are more environmentally friendly and have greater application potential; however, the synthesis cost of novel organic inhibitors is high, and their versatility is generally limited.
[0004] Therefore, developing an efficient and economical copper inhibitor is of great significance for the recovery of copper and molybdenum from copper-molybdenum mixed concentrates. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention aims to provide a nanoparticle copper sulfide inhibitor, its preparation, and its application.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] A method for preparing a copper sulfide nanoparticle inhibitor includes the following steps:
[0008] S1. Prepare a starch aqueous solution by mixing starch with water;
[0009] S2. Nitrogen gas is continuously introduced into the starch aqueous solution obtained in step S1 to obtain an oxygen-free starch aqueous solution.
[0010] S3. Insert a permanent magnet into the oxygen-free starch aqueous solution obtained in step S2, and then add ferrous sulfate and sodium sulfide solid in sequence. After rapid reaction, a black suspension is obtained. Nitrogen gas is continuously introduced during the reaction.
[0011] S4. Place the black suspension obtained in step S3 into a sealed brown bottle for storage, thus obtaining the nanoparticle copper sulfide inhibitor.
[0012] Further, in step S1, the mass concentration of the starch aqueous solution is 0.5%.
[0013] Furthermore, in step S2, the nitrogen filling time is greater than 30 minutes.
[0014] Furthermore, in step S3, the rapid reaction time is 1 minute.
[0015] Furthermore, in step S3, the surface magnetic field strength of the permanent magnet rod is 1.0-1.5T.
[0016] Furthermore, in step S3, the amount of ferrous sulfate added is 1 / 5 of the weight of starch, and the amount of sodium sulfide added is 2 / 5 of the weight of starch.
[0017] The present invention also provides a nanoparticle copper sulfide inhibitor prepared by any one of the preparation methods described in claims 1-6.
[0018] The present invention also provides an application of the nanoparticle copper sulfide inhibitor prepared by the above preparation method in copper-molybdenum flotation separation.
[0019] Further, the specific process is as follows: Nanoparticle inhibitors and kerosene are added sequentially to the copper-molybdenum mixed concentrate slurry for copper-molybdenum separation roughing to obtain molybdenum rough concentrate and roughing tailings; sodium sulfide and kerosene are added sequentially to the obtained roughing tailings for copper-molybdenum separation scavenging, and the scavenged concentrate is returned to the copper-molybdenum separation roughing, while the scavenged tailings are the copper concentrate; sodium sulfide and kerosene are added sequentially to the molybdenum rough concentrate for copper-molybdenum separation fine cleaning, and the fine cleaning tailings are returned to the copper-molybdenum separation roughing, while the fine cleaning concentrate is the molybdenum concentrate.
[0020] Furthermore, in the roughing process of copper-molybdenum separation, the dosage of nanoparticle inhibitor is 10,000-30,000 g / t and the dosage of kerosene is 500-1,000 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate; in the scavenging process of copper-molybdenum separation, the dosage of sodium sulfide is 2,000-5,000 g / t and the dosage of kerosene is 100-300 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate; in the beneficiation process of copper-molybdenum separation, the dosage of sodium sulfide is 2,000-5,000 g / t and the dosage of kerosene is 100-300 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate.
[0021] The beneficial effects of this invention are as follows:
[0022] (1) In this invention, ferrous sulfate and sodium sulfide react rapidly under anaerobic and magnetic field conditions to generate FeS nanoparticles, and starch is used to maintain the stability of the reagent.
[0023] (2) The nano-ion inhibitor of the present invention is applied to copper-molybdenum flotation separation. It has a strong inhibitory effect on copper sulfide ore, but no effect on molybdenite. It can realize efficient copper-molybdenum flotation separation. It has the characteristics of simple operation, low cost, green and pollution-free, and significantly improves the copper-molybdenum separation efficiency.
[0024] In summary, under background magnetic field and nitrogen purging conditions, this invention prepares stable nanoparticle copper sulfide inhibitors using starch solution as a medium and ferrous sulfate and sodium sulfide as raw materials. These inhibitors are then applied to copper-molybdenum flotation separation operations. As a copper sulfide ore inhibitor, it features simple operation, low cost, and environmental friendliness, significantly improving copper-molybdenum flotation separation efficiency, reducing copper sulfide loss in molybdenum concentrate, and increasing the utilization rate of copper-molybdenum resources. Attached Figure Description
[0025] Figure 1 The particle size analysis results are for the copper sulfide nanoparticle inhibitor prepared in Example 1 of this invention. Detailed Implementation
[0026] The present invention will be further described below with reference to the accompanying drawings. It should be noted that this embodiment is based on the present technical solution and provides detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to this embodiment.
[0027] Example 1
[0028] This embodiment provides a method for preparing a copper sulfide inhibitor using nanoparticles, the specific process of which is as follows:
[0029] Prepare a 0.5% starch aqueous solution by mixing 5g of starch with nitrogen. Place the starch aqueous solution in a three-necked flask and aerate it with nitrogen for 30 minutes. Then, insert a permanent magnet rod with a surface magnetic field strength of 1.0T and continue to aerate it with nitrogen. Add 1g of ferrous sulfate and 2g of sodium sulfide in sequence and react for 1 minute. The resulting black reaction suspension is the nanoparticle copper sulfide inhibitor. Transfer it to a sealed brown bottle for storage.
[0030] The particle size analysis results of the nano-copper sulfide inhibitor prepared in this embodiment are as follows: Figure 1 As shown.
[0031] like Figure 1 It can be seen that the particle size range of the prepared nanoparticle inhibitor is between 200-1000 nm, with an average particle size of 568 nm, and the particle size is relatively concentrated.
[0032] Example 2
[0033] A copper-molybdenum mixed concentrate from Heilongjiang Province contains 18.78% copper and 0.79% molybdenum. The copper mineral is primarily chalcopyrite, while the molybdenum is mainly molybdenite. Other minerals include pyrite and quartz. The original process used sodium sulfide and kerosene as depressants and collectors for copper-molybdenum flotation separation to obtain molybdenum and copper concentrates. However, the production process suffered from high reagent consumption, poor copper-molybdenum separation, and severe cross-contamination of copper and molybdenum concentrates. The molybdenum concentrate contained more than 10% copper, and the copper concentrate contained more than 0.2% molybdenum, hindering the efficient utilization of copper and molybdenum resources.
[0034] In this embodiment, the nanoparticle copper sulfide inhibitor prepared in Example 1 is used in the copper-molybdenum flotation separation operation of a copper-molybdenum mixed concentrate in Heilongjiang Province.
[0035] A copper-molybdenum mixed concentrate was mixed with water to prepare a 30% mass concentration slurry, which was then placed in a flotation machine and stirred. Based on the dry weight of each ton of copper-molybdenum mixed concentrate, 10,000 g / t of the nanoparticle inhibitor prepared in Example 1 and 500 g / t of kerosene were added sequentially. After stirring for 3 minutes, copper-molybdenum separation roughing was performed to obtain molybdenum rough concentrate (foam) and roughing tailings. Based on the dry weight of each ton of copper-molybdenum mixed concentrate, 3,000 g / t of sodium sulfide and 200 g / t of kerosene were added sequentially to the roughing tailings. After stirring for 3 minutes, copper-molybdenum separation scavenging was performed to obtain scavenged concentrate (foam) and scavenged tailings (copper concentrate product). The molybdenum rough concentrate (foam) was placed in a flotation cell to prepare a 30% mass concentration slurry. Based on the dry weight of each ton of copper-molybdenum mixed concentrate, 3,000 g / t of sodium sulfide and 200 g / t of kerosene were added sequentially. After stirring for 3 minutes, copper-molybdenum separation cleaning was performed to obtain molybdenum concentrate and cleaned tailings. The selected tailings and scavenged concentrate are returned to the copper-molybdenum separation roughing process, and the above operation is repeated until the weights of the molybdenum concentrate and copper concentrate are balanced.
[0036] The process parameters obtained in this embodiment are shown in Table 1.
[0037] Table 1
[0038]
[0039] As shown in Table 1, after the implementation of the method in this embodiment, compared with the original process, the molybdenum recovery rate in the molybdenum concentrate increased by 18.00 percentage points, the copper loss rate decreased by 1.21 percentage points, and the grade of the molybdenum concentrate increased by 15.10 percentage points, thus achieving efficient and comprehensive recovery of the copper and molybdenum resources.
[0040] Example 3
[0041] A copper-molybdenum mixed concentrate from Tibet contains 17.53% copper and 1.25% molybdenum. The copper mineral is primarily chalcopyrite, while the molybdenum is mainly molybdenite. Other minerals include pyrite and quartz. The original process used sodium sulfide and kerosene as depressants and collectors for copper-molybdenum flotation separation to obtain molybdenum and copper concentrates. However, the production process suffered from high reagent consumption, poor copper-molybdenum separation, and severe cross-contamination of copper and molybdenum concentrates. The molybdenum concentrate contained more than 7% copper, and the copper concentrate contained more than 0.15% molybdenum, hindering the efficient utilization of copper and molybdenum resources.
[0042] In this embodiment, the nanoparticle copper sulfide inhibitor prepared in Example 1 is used in the copper-molybdenum flotation separation operation of a copper-molybdenum mixed concentrate in Heilongjiang Province.
[0043] A copper-molybdenum mixed concentrate was mixed with water to prepare a 30% (w / w) slurry, which was then stirred in a flotation machine. Based on the dry weight of each ton of copper-molybdenum mixed concentrate, 30,000 g / t of nanoparticle inhibitor and 1,000 g / t of kerosene were added sequentially. After stirring for 3 minutes, copper-molybdenum separation roughing was performed to obtain molybdenum rough concentrate (foam) and roughing tailings. Based on the dry weight of each ton of copper-molybdenum mixed concentrate, 3,000 g / t of sodium sulfide and 200 g / t of kerosene were added sequentially to the roughing tailings. After stirring for 3 minutes, copper-molybdenum separation scavenging was performed to obtain scavenged concentrate (foam) and scavenged tailings (copper concentrate product). The molybdenum rough concentrate (foam) was placed in a flotation cell to prepare a 30% (w / w) slurry. 3,000 g / t of sodium sulfide and 200 g / t of kerosene were added sequentially. After stirring for 3 minutes, copper-molybdenum separation cleaning was performed to obtain molybdenum concentrate product and cleaned tailings. The selected tailings and scavenged concentrate are returned to the copper-molybdenum separation roughing process, and the above operation is repeated until the weights of the molybdenum concentrate and copper concentrate are balanced.
[0044] The process experimental parameters of the method in this embodiment are shown in Table 2.
[0045] Table 2
[0046]
[0047]
[0048] As shown in Table 2, after implementing the method in this embodiment, compared with the original process, the molybdenum recovery rate in the molybdenum concentrate increased by 5.54 percentage points, the copper loss rate decreased by 0.77 percentage points, and the grade of the molybdenum concentrate increased by 8.73 percentage points, achieving efficient and comprehensive recovery of the copper and molybdenum resources.
[0049] For those skilled in the art, various corresponding changes and modifications can be made based on the above technical solutions and concepts, and all such changes and modifications should be included within the protection scope of the claims of this invention.
Claims
1. A method for preparing a nanoparticle copper sulfide inhibitor, characterized in that, Includes the following steps: S1. Prepare a starch aqueous solution by mixing starch with water; S2. Nitrogen gas is continuously introduced into the starch aqueous solution obtained in step S1 to obtain an oxygen-free starch aqueous solution. S3. Insert a permanent magnet into the oxygen-free starch aqueous solution obtained in step S2, and then add ferrous sulfate and sodium sulfide solid in sequence. After rapid reaction, a black suspension is obtained. Nitrogen gas is continuously introduced during the reaction. S4. Place the black suspension obtained in step S3 into a sealed brown bottle for storage, thus obtaining the nanoparticle copper sulfide inhibitor.
2. The preparation method according to claim 1, characterized in that, In step S1, the mass concentration of the starch aqueous solution is 0.5%.
3. The preparation method according to claim 1, characterized in that, In step S2, the nitrogen filling time is greater than 30 minutes.
4. The preparation method according to claim 1, characterized in that, In step S3, the rapid reaction time is 1 minute.
5. The preparation method according to claim 1, characterized in that, In step S3, the surface magnetic field strength of the permanent magnet rod is 1.0-1.5T.
6. The preparation method according to claim 1, characterized in that, In step S3, the amount of ferrous sulfate added is 1 / 5 of the weight of starch, and the amount of sodium sulfide added is 2 / 5 of the weight of starch.
7. A nanoparticle copper sulfide inhibitor prepared by any one of the preparation methods described in claims 1-6.
8. The application of a nanoparticle copper sulfide inhibitor prepared by any one of claims 1-6 in copper-molybdenum flotation separation.
9. The application according to claim 8, characterized in that, The specific process is as follows: Nanoparticle inhibitors and kerosene are added sequentially to the copper-molybdenum mixed concentrate slurry for copper-molybdenum separation roughing to obtain molybdenum rough concentrate and roughing tailings; sodium sulfide and kerosene are added sequentially to the obtained roughing tailings for copper-molybdenum separation scavenging, and the scavenged concentrate is returned to the copper-molybdenum separation roughing, while the scavenged tailings are the copper concentrate; sodium sulfide and kerosene are added sequentially to the molybdenum rough concentrate for copper-molybdenum separation fine cleaning, and the fine cleaning tailings are returned to the copper-molybdenum separation roughing, while the fine cleaning concentrate is the molybdenum concentrate.
10. The application according to claim 9, characterized in that, In the roughing process of copper-molybdenum separation, the dosage of nanoparticle inhibitor is 10,000-30,000 g / t and the dosage of kerosene is 500-1,000 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate. In the scavenging process of copper-molybdenum separation, the dosage of sodium sulfide is 2,000-5,000 g / t and the dosage of kerosene is 100-300 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate. In the beneficiation process of copper-molybdenum separation, the dosage of sodium sulfide is 2,000-5,000 g / t and the dosage of kerosene is 100-300 g / t, based on the dry weight of each ton of copper-molybdenum mixed concentrate.