Flotation collecting agent, preparation method of flotation collecting agent and application of flotation collecting agent in refractory copper oxide ore
By preparing flotation collectors containing carboxyl and sulfate groups, the problem of difficulty in recovering copper oxide ores such as pseudomalachite in existing technologies has been solved, achieving efficient flotation recovery and good dispersion performance.
Patent Information
- Application Number
- CN202511250242.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-03
- Publication Date
- 2025-10-31
AI Technical Summary
Existing technologies are insufficient for the effective recovery of difficult-to-process copper oxide ores, especially ores such as pseudomalachite. Sulfide flotation and commonly used collectors have low selectivity and collectivity.
A flotation collector is provided, the collector molecule containing two active functional groups, carboxyl and sulfate groups. By reacting with linoleic acid and concentrated sulfuric acid at 0°C, a collector capable of interacting with the surface of copper oxide minerals is prepared, thereby expanding the coverage area and enhancing the collection ability.
It achieves efficient flotation recovery of difficult-to-process copper oxide ores such as pseudomalachite, with high recovery rate and no need to add extra frother, and has strong dispersion performance and foaming ability.
Smart Images
Figure CN120861275A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of mineral processing technology, specifically relating to a flotation collector, its preparation method, and its application in refractory copper oxide ores. Background Technology
[0002] Copper is one of the oldest metals ever used and a crucial element in the development of civilization. Located in Group 11 of the periodic table, copper's fully filled 3d electron orbitals and half-occupied 4s orbitals give it high ductility, excellent electrical and thermal conductivity. These unique properties have made copper a major industrial metal, widely used in electrical and electronic products, wires, building materials, and medicine. As an important conductive and thermally conductive material, copper demand is experiencing explosive growth due to the widespread application of renewable energy sources such as wind power and photovoltaics, and the rise of emerging industries like electric vehicles and smart grids. However, with the gradual depletion of easily beneficiated primary sulfide copper ore resources, the development and utilization of difficult-to-beneficiate oxide copper ore resources has become particularly important.
[0003] Copper oxide ores are diverse, and currently, the main exploitable copper oxide ores include malachite (CuCO3·Cu(OH)2), azurite (2CuCO3·Cu(OH)2), cuprite (Cu2O), pseudomalachite (Cu5(PO4)2(OH)4), chalcopyrite (CuO), and siliceous malachite (CuSiO3·2H2O). These ores are characterized by easy mud formation and difficulty in separation, resulting in low overall resource utilization. Sulfide flotation is the most widely used method for processing copper oxide ores in industry, but this method is only suitable for processing easily floatable carbonate-type copper oxide ores containing malachite and azurite, and requires strict control of the sulfiding agent dosage, as excessive sulfiding agent can inhibit the formation of copper oxide ores. Commonly used collectors in direct flotation, such as fatty acids, amines, and hydroxamic acid chelating collectors, are mainly suitable for easily floatable carbonate-type copper oxide ores, such as malachite and azurite, but their collection and selectivity are relatively low. For refractory copper oxide ores such as pseudomalachite and silicomalachite, neither sulfide flotation nor direct flotation with conventional collectors can effectively recover them. Therefore, there is an urgent need to develop a highly efficient collector for copper oxide ores to achieve effective flotation recovery of refractory copper oxide ores. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a flotation collector, its preparation method, and its application in refractory copper oxide ores. This collector has strong collecting ability and good foaming ability, and can directly float copper oxide ores such as pseudomalachite, thereby achieving efficient flotation recovery of refractory copper oxide ores.
[0005] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:
[0006] In a first aspect, the present invention provides a flotation collector having a structure of Formula I.
[0007]
[0008] The flotation collector of the present invention contains two active functional groups, carboxyl and sulfate, which can both interact with the surface of copper oxide minerals, thereby expanding the coverage area of the reagent and enhancing the collection ability of difficult-to-process copper oxide ores. It can effectively recover difficult-to-process copper oxide ores such as pseudomalachite.
[0009] Secondly, the present invention provides a method for preparing a flotation collector, used to prepare the flotation collector described in the first aspect, and includes the following preparation steps:
[0010] S1. Add linoleic acid to the reactor;
[0011] S2. Slowly add concentrated sulfuric acid to linoleic acid at 0℃ with stirring;
[0012] S3. After adding the ingredients, heat the mixture.
[0013] S4. After the predetermined reaction time, add water to stop the reaction;
[0014] S5. Obtain the flotation collector.
[0015] As a preferred technical solution of the present invention, the molar ratio of linoleic acid to concentrated sulfuric acid is 1:0.9 to 1.1, for example, it can be 1:0.9, 1:1 or 1:1.1, but it is not limited to the listed values. Other unlisted values within this range are also applicable.
[0016] In S3, the reaction temperature after heating is between 0 and 15°C. For example, it can be 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, or 15°C, but it is not limited to the listed values. Other unlisted values within this range are also applicable.
[0017] In S4, the predetermined reaction time is 1 to 2 hours;
[0018] The chemical reaction formula corresponding to this preparation method is shown in Formula II.
[0019]
[0020] The preparation method of the present invention is simple and efficient, with a wide range of raw material sources, and can be applied to the flotation of different types of copper oxide ores.
[0021] Thirdly, the present invention provides the application of a flotation collector in refractory oxidized copper ores, wherein a flotation collector as described in the first aspect is used for efficient flotation recovery of refractory oxidized copper ores, comprising the following flotation steps.
[0022] S1. Weigh out the difficult-to-process copper oxide ore;
[0023] S2. Place the refractory copper oxide ore in the flotation cell and add deionized water;
[0024] S3. Stir;
[0025] S4. Adjust the pH of the solution;
[0026] S5. Add flotation collector;
[0027] S6. After stirring, begin skimming off the foam;
[0028] S7. Filter and dry the foam product and tailings; the foam product is a concentrate.
[0029] S8. Recycling.
[0030] The flotation collector provided by this invention has good dispersion performance in slurry and strong foaming ability. No foaming agent needs to be added during the flotation process. It has good application effect, high recovery rate, and can be applied to the flotation of different types of copper oxide ores.
[0031] The beneficial effects of this invention are:
[0032] 1. The flotation collector of the present invention contains two active functional groups, carboxyl and sulfate, which can both interact with the surface of copper oxide minerals, thereby expanding the coverage area of the reagent, enhancing the collection ability of difficult-to-process copper oxide minerals, and effectively recovering difficult-to-process copper oxide minerals such as pseudomalachite.
[0033] 2. The preparation method of the present invention is simple and efficient, with a wide range of raw material sources, and is applicable to the flotation of different types of copper oxide ores;
[0034] 3. The flotation collector provided by this invention has good dispersion performance in slurry and strong foaming ability. No foaming agent needs to be added during the flotation process, resulting in good application effect and high recovery rate. Attached Figure Description
[0035] The present invention can be further illustrated by the non-limiting embodiments given in the accompanying drawings;
[0036] Figure 1 The above are flotation flowcharts for embodiments 4-6 of the present invention and flotation application experiments;
[0037] Figure 2 The above diagram shows the flotation performance of the flotation collector in Example 6 of this invention on pure azurite mineral at different pH values. Detailed Implementation
[0038] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include those that make any obvious substitutions and modifications to the embodiments described herein.
[0039] Example 1 ( Preparation of flotation collectors)
[0040] Add 0.1 mol of linoleic acid to a 150 mL three-necked flask and stir for 10 min at 0 °C. Then, slowly add 0.10 mol of concentrated sulfuric acid (98% concentration, industrial grade) dropwise while stirring at 0 °C. After the addition is complete, raise the temperature to 10 °C and react for 1 h. Finally, add 10 mL of water to stop the reaction. The resulting brown viscous solution is the flotation collector for refractory copper oxide ore.
[0041] Example 2 (Preparation of flotation collector)
[0042] Add 0.1 mol of linoleic acid to a 150 mL three-necked flask and stir for 10 min at 0 °C. Then, slowly add 0.11 mol of concentrated sulfuric acid (98% concentration, industrial grade) dropwise while stirring at 0 °C. After the addition is complete, react at 0 °C for 2 h. Finally, add 10 mL of water to stop the reaction. The resulting brown viscous solution is the flotation collector for difficult-to-process copper oxide ore.
[0043] Example 3 (Preparation of flotation collector)
[0044] Add 0.1 mol of linoleic acid to a 150 mL three-necked flask and stir for 10 min at 0 °C. Then, slowly add 0.09 mol of concentrated sulfuric acid (98% concentration, industrial grade) dropwise while stirring at 0 °C. After the addition is complete, raise the temperature to 15 °C and react for 1 h. Finally, add 10 mL of water to stop the reaction. The resulting brown viscous solution is the flotation collector for refractory oxidized copper ore.
[0045] Flotation Application Experiment
[0046] The flotation collectors prepared in Examples 1 to 3 were used for the flotation of refractory copper oxide ore pseudomalachite pure mineral.
[0047] Weigh 2.0g of pure pseudomalachite mineral and place it in a 40mL flotation cell. Add 38mL of deionized water, then adjust the impeller speed to 1800r / min and stir. After stirring for 2 minutes, add a pH adjuster (0.5% NaOH solution) to adjust the pH of the solution to 11. After 1 minute, add 500g / t of the refractory oxidized copper ore flotation collector of this invention. Stir for 3 minutes, then begin skimming the foam and continue for 3 minutes. After skimming, filter the foam product (concentrate) and tailings and dry them in a vacuum drying oven. Finally, weigh the dried product and calculate the recovery rate. The flotation process is as follows: Figure 1 The flotation results are shown in Table 1.
[0048] Comparative Example 1 (Comparison of flotation recovery of pure minerals containing pseudo-malachite)
[0049] 2.0 g of pure pseudomalachite mineral was weighed and placed in a 40 mL flotation cell. 38 mL of deionized water was added, and the impeller speed was adjusted to 1800 r / min for stirring. After stirring for 2 min, 500 g / t sodium sulfide was added, and after stirring for 1 min, 500 g / t butyl xanthate was added. After stirring for 2 min, 300 g / t No. 2 oil frother was added, and after stirring for 2 min, foam scraping was started and continued for 3 min. After the foam scraping was completed, the foam product (concentrate) and tailings were filtered and dried in a vacuum drying oven. Finally, the dried product was weighed and the recovery rate was calculated. The results are shown in Table 1.
[0050] Comparative Example 2 (Comparison of flotation recovery of pure minerals containing pseudo-malachite)
[0051] 2.0 g of pure pseudomalachite mineral was weighed and placed in a 40 mL flotation cell. 38 mL of deionized water was added, and the impeller speed was adjusted to 1800 r / min for stirring. After stirring for 2 min, pH adjuster (0.5% NaOH solution) was added to adjust the pH of the solution to 11. After 1 min, 500 g / t benzoyl hydroxyxamic acid copper oxide collector was added. After stirring for 2 min, 300 g / t No. 2 oil frother was added. After stirring for 3 min, foam scraping was started and continued for 3 min. After the foam scraping was completed, the foam product (concentrate) and tailings were filtered and dried in a vacuum drying oven. Finally, the dried product was weighed and the recovery rate was calculated. The results are shown in Table 1.
[0052] Comparative Example 3 (Comparison of flotation recovery of pure minerals containing pseudo-malachite)
[0053] 2.0 g of pure pseudomalachite mineral was weighed and placed in a 40 mL flotation cell. 38 mL of deionized water was added, and the impeller speed was adjusted to 1800 r / min for stirring. After stirring for 2 min, pH adjuster (0.5% NaOH solution) was added to adjust the pH of the solution to 11. After 1 min, 500 g / t linoleic acid collector was added. After stirring for 3 min, foam scraping was started and continued for 3 min. After the foam scraping was completed, the foam product (concentrate) and tailings were filtered and dried in a vacuum drying oven. Finally, the dried product was weighed and the recovery rate was calculated. The results are shown in Table 1.
[0054] Table 1. Flotation conditions and results of pure pseudomalachite mineral.
[0055]
[0056] The experimental results in Table 1 show that, compared with sulfide flotation, benzoyl hydroxyxamic acid, and linoleic acid collectors, the flotation collectors prepared in Examples 1 to 3 of this invention achieve significantly higher flotation recovery rates when flotating refractory copper oxide ore pseudomalachite pure minerals. Furthermore, the flotation collectors in Examples 1 to 3 of this invention exhibit good dispersion performance in the pulp and strong foaming ability, eliminating the need for adding foaming agents during the flotation process.
[0057] Example 4 (Recovery of pure azurite mineral by flotation)
[0058] Weigh 2.0g of pure azurite mineral and place it in a 40mL flotation cell. Add 38mL of deionized water, then adjust the impeller speed to 1800r / min and stir. After stirring for 2 minutes, add a pH adjuster (0.5% NaOH solution) to adjust the pH of the solution to 9. After 1 minute, add 500g / t of the flotation collector of Example 2 of this invention. Stir for 3 minutes, then begin skimming the foam and continue for 3 minutes. After skimming, filter the foam product (concentrate) and tailings and dry them in a vacuum drying oven. Finally, weigh the dried product and calculate the recovery rate. The flotation process is as follows: Figure 1 The recovery rate was 92.69%.
[0059] Comparative Example 4 (Comparison of pure azurite mineral flotation recovery)
[0060] 2.0 g of pure azurite mineral was weighed and placed in a 40 mL flotation cell. 38 mL of deionized water was added, and the impeller speed was adjusted to 1800 r / min for stirring. After stirring for 2 minutes, 500 g / t sodium sulfide was added, followed by 1 minute of stirring. Then, 500 g / t butyl xanthate was added, and after another 2 minutes of stirring, 300 g / t No. 2 oil frother was added. After stirring for 2 minutes, frothing was initiated and continued for 3 minutes. After frothing, the froth product (concentrate) and tailings were filtered and dried in a vacuum drying oven. Finally, the dried product was weighed, and the recovery rate was calculated. The recovery rate was 18.87%.
[0061] Example 5 (Malachite pure mineral flotation recovery)
[0062] Weigh 2.0g of pure malachite mineral into a 40mL flotation cell, add 38mL of deionized water, then adjust the impeller speed to 1800r / min and stir. After stirring for 2 minutes, add pH adjuster (0.5% NaOH solution) to adjust the pH of the solution to 9. After 1 minute, add 500g / t of the flotation collector of Example 2 of this invention, stir for 3 minutes, then start skimming the foam and continue for 3 minutes. After skimming, filter the foam product (concentrate) and tailings and dry them in a vacuum drying oven. Finally, weigh the dried product and calculate the recovery rate. The flotation process is as follows: Figure 1 The recovery rate was 97.95%.
[0063] Comparative Example 5 (Comparison of pure malachite mineral flotation recovery)
[0064] 2.0 g of pure malachite mineral was weighed and placed in a 40 mL flotation cell. 38 mL of deionized water was added, and the impeller speed was adjusted to 1800 r / min for stirring. After stirring for 2 minutes, 500 g / t sodium sulfide was added, followed by stirring for 1 minute. Then, 500 g / t butyl xanthate was added, and after stirring for 2 minutes, 300 g / t No. 2 oil frother was added. After stirring for 2 minutes, frothing was initiated and continued for 3 minutes. After frothing, the froth product (concentrate) and tailings were filtered and dried in a vacuum drying oven. Finally, the dried product was weighed, and the recovery rate was calculated. The recovery rate was 93.01%.
[0065] Example 6 (Experiment on the effect of flotation collectors on the flotation recovery performance of pure azurite mineral at different pH levels)
[0066] Weigh 2.0g of pure azurite mineral and place it in a 40mL flotation cell. Add 38mL of deionized water, then adjust the impeller speed to 1800r / min and stir. After stirring for 2 minutes, add a pH adjuster (0.5% H2SO4 solution or 0.5% NaOH solution) to adjust the solution pH (tested at pH 5, 7, 9, and 11 respectively). After 1 minute, add 500g / t of the flotation collector of Example 2 of this invention. Stir for 3 minutes, then begin skimming the foam and continue for 3 minutes. After skimming, filter the foam product (concentrate) and tailings and dry them in a vacuum drying oven. Weigh the dried product and calculate the recovery rate. Finally, the flotation performance of the refractory copper oxide ore flotation collector on pure azurite mineral at different pH values is obtained. The flotation process is as follows: Figure 1 The flotation results are shown in the present invention patent. Figure 2 As shown.
[0067] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.
Claims
1. A flotation collector, characterized in that: This flotation collector has the structure of Formula I.
2. A method for preparing a flotation collector, characterized in that: The preparation of a flotation collector as described in claim 1 includes the following preparation steps: S1. Add linoleic acid to the reactor; S2. Slowly add concentrated sulfuric acid to linoleic acid at 0℃ with stirring; S3. After adding the ingredients, heat the mixture. S4. After the predetermined reaction time, add water to stop the reaction; S5. Obtain the flotation collector.
3. The method for preparing a flotation collector according to claim 2, characterized in that: The molar ratio of linoleic acid to concentrated sulfuric acid is 1:0.9 to 1.
1.
4. The method for preparing a flotation collector according to claim 3, characterized in that: In step S3, the reaction temperature after heating is between 0 and 15°C.
5. The method for preparing a flotation collector according to claim 4, characterized in that: In step S4, the predetermined reaction time is 1 to 2 hours.
6. The application of flotation collectors in refractory copper oxide ores, characterized in that: The flotation collector described in claim 1 is used for efficient flotation recovery of refractory oxidized copper ore.
7. The application of the flotation collector according to claim 6 in refractory copper oxide ores, characterized in that: The flotation process includes the following steps: S1. Weigh out the difficult-to-process copper oxide ore; S2. Place the refractory copper oxide ore in the flotation cell and add deionized water; S3. Stir; S4. Adjust the pH of the solution; S5. Add flotation collector; S6. After stirring, begin skimming off the foam; S7. Filter and dry the foam product and tailings; the foam product is a concentrate. S8. Recycling.