A flotation frother for separating sulfide minerals and clay minerals and a preparation method thereof

Abstract

A flotation frother for separating sulfide minerals from clay minerals and a preparation method thereof. The flotation frother is composed of the following components in parts by weight: 3-8 parts of polyethylene glycol, 8-22 parts of mixed hexavalent alcohol, 10-18 parts of mixed ether alcohol, C5-C 14 Mixed fatty alcohol ether ester blended with 36-66 parts diesel; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether; the C5-C 14 Mixed fatty alcohol ether ester blended diesel to produce industrial C5~C 14 A mixture of fatty alcohol ether ester and light diesel. The flotation frother provided by the present invention, by compounding the various components and utilizing the synergistic effect between the components, can effectively achieve the flotation separation of copper sulfide, nickel, and molybdenum minerals from common clay gangues such as talc, serpentine, chlorite, and mica, thereby improving the comprehensive recovery and utilization rate of copper sulfide, nickel, and molybdenum ore resources.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal ore beneficiation, and in particular relates to a flotation frother for separating sulfide minerals and clay minerals and a preparation method thereof. Background Art

[0002] Currently, copper, nickel, and molybdenum sulfides, as strategic resources, have become crucial mineral sources for their recycling. According to statistics, copper sulfide ore resources account for over 75% of proven copper resources. However, due to factors such as Earth's mineralization and geological evolution, some copper, nickel, and molybdenum sulfides often coexist closely with clay minerals such as talc, serpentine, chlorite, and mica. These clay minerals generally have low hardness, making them prone to over-grinding or over-crushing during crushing and grinding. This leads to severe clay mineralization in the flotation slurry, causing heterogeneous agglomeration (slime capping) between different minerals and foam entrainment / inclusion during flotation. This significantly reduces the flotation recovery of useful minerals and lowers the grade of the final concentrate. Furthermore, some clay minerals (such as talc, serpentine, and chlorite) are naturally hydrophobic. When conventional flotation processes are used to process copper, nickel, and molybdenum sulfide-containing mineral resources, these easily floatable gangue minerals will float up in large quantities along with the target minerals (copper, nickel, and molybdenum sulfides), seriously affecting the grade and recovery rate of the target minerals. In order to more effectively utilize copper, nickel, and molybdenum sulfide ores containing easily floatable clay minerals, frothers are usually added to pre-float and remove easily floatable clay gangue minerals such as talc, chlorite, and serpentine to reduce their impact on the flotation of copper, nickel, and molybdenum sulfides.

[0003] However, most current flotation frothers are organic heteropolar surfactants composed of polar and non-polar groups. These frothers are primarily used to generate large, stable, and suitable foams in ore pulp. However, they present several challenges, including low solubility, difficulty dispersing in the ore pulp, poor foam durability, limited secondary enrichment, uneven bubble size, and severe entrainment / inclusion during flotation. Furthermore, flotation processes containing clay minerals often require the addition of large amounts of inhibitors such as soda ash, phosphates, water glass, polysaccharides (such as gum, starch, and cellulose), and polyphenols (such as lignin derivatives, tannins, and tannin extracts) to mitigate the impact of clay minerals on the quality of the flotation concentrate. However, excessive use of these dispersants and inhibitors not only reduces the floatability of gangue minerals but also can compromise the frothing effectiveness of conventional flotation frothers, thereby affecting the flotation recovery of valuable minerals.

[0004] Therefore, to improve the comprehensive utilization efficiency of copper, nickel, and molybdenum sulfide ores containing clay minerals, and to enhance the flotation recovery rate and concentrate grade of the final copper, nickel, and molybdenum sulfide minerals, it is necessary to develop a flotation frother suitable for copper, nickel, and molybdenum sulfide minerals in systems with high dispersant and inhibitor dosages. If this frother can remove easily floatable clay minerals such as talc and serpentine during the pre-flotation stage, thereby reducing the loss of copper, nickel, and molybdenum sulfide minerals caused by entrainment or inclusion, its application will be further broadened. Summary of the Invention

[0005] The present invention aims to provide a flotation frother for separating sulfide minerals from clay minerals and a preparation method thereof. The method is simple and easy to implement, can reduce the amount of frother used in the flotation process without increasing the comprehensive use cost, improve the separation accuracy of copper sulfide, nickel, molybdenum minerals and clay minerals, thereby improving the flotation recovery rate and concentrate grade of copper sulfide, nickel, and molybdenum minerals, and realizing the conservation and efficient utilization of precious mineral resources such as copper, nickel, and molybdenum. The prepared flotation frother has the following advantages: strong stability, low usage, can effectively enhance the flotation ability during the flotation process, generate uniform and stable foam, have strong secondary enrichment ability, and at the same time, have weak entrainment / inclusion effect of gangue, and can tolerate high dosage environments of dispersants and inhibitors. The flotation frother is particularly suitable for the flotation recovery of mineral resources such as copper sulfide, nickel, and molybdenum containing clay minerals.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a flotation frother for separating sulfide minerals and clay minerals, the flotation frother is composed of the following components in parts by weight: 3 to 8 parts of polyethylene glycol, 8 to 22 parts of mixed hexavalent alcohol, 10 to 18 parts of mixed ether alcohol, C5 to C 14 Mixed fatty alcohol ether esters and diesel 36 to 66 parts, these parts can be integers or decimals between integers; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether; the C5 to C 14 Mixed fatty alcohol ether ester blended diesel is industrial C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0008] The flotation frother provided herein utilizes a rational combination of frother components, effectively leveraging the synergistic effects of these components to significantly reduce the entrainment of fine-grained clay minerals in flotation foam during the forward flotation of copper, nickel, and molybdenum sulfide ores. Furthermore, the frother effectively reduces the loss of valuable metallic minerals, such as copper sulfide, nickel, and molybdenum, during the removal of fine, easily floatable clay minerals (such as talc, chlorite, and serpentine) during pre-desludging during reverse flotation. This not only helps improve the quality of copper, nickel, and molybdenum sulfide concentrates, but also reduces the loss of fine-grained copper, nickel, and molybdenum metal during the desludging process, ensuring efficient recovery of valuable metal elements.

[0009] In the present invention, the polyethylene glycol is a liquid polymer with a relative molecular mass between 250 and 425. It has good lubricity, moisture retention, dispersibility, adhesion and water solubility, and has good compatibility with many organic components. It can be used for solubilizing inorganic salts and adjusting the viscosity of pharmaceuticals.

[0010] Preferably, the mass ratio between the cyclohexanol and methyl isobutyl carbinol is 1:1.

[0011] In the present invention, the cyclohexanol is a colorless, transparent, oily liquid with a camphor-like odor and good foaming ability. It has good miscibility with various other organic substances and can enhance the brittleness and fluidity of the foam in a mixed foaming agent system.

[0012] In this invention, methyl isobutyl carbinol (MIBC) is an industrially synthesized frother. It is a transparent, colorless liquid with a mild odor (the odor of higher alcohols). Compared to the commonly used frother, pine oil, MIBC produces bubbles with a lower reduction in foam height and liquid content. This means that the bubbles generated by MIBC have greater stability and lower liquid content, which is crucial for mineral flotation. Specifically, the liquid content of the bubbles produced by MIBC is significantly lower than that of pine oil, which helps improve the efficiency and effectiveness of the flotation process.

[0013] Preferably, in the present invention, the ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether, and tripropylene glycol butyl ether, with a weight ratio of 2:1:1. Ether alcohol foaming agents are a type of foaming agent artificially synthesized from petrochemical products. This type of foaming agent has good fluidity and viscosity, high water solubility, dense foam structure, non-stickiness, good selectivity, easy defoaming, and low usage. It can generate a large number of small bubbles less than 0.2 mm that are beneficial for flotation. The general usage is only 1 / 3 to 2 / 3 of pine oil, which can assist and enhance the comprehensive recovery of precious metals such as gold and silver. In the present invention, the weight proportion of the ether alcohol foaming agent is relatively small, and the overall agent cost is controllable.

[0014] Preferably, the C5~C 14 Mixed fatty alcohol ether ester blended diesel, C5~C 14 The mass ratio between the mixed fatty alcohol ether ester and the light diesel is 4:1, and the blending method is ordinary mechanical stirring and mixing.

[0015] In the present invention, the C5~C 14 Mixed fatty alcohol ether esters are by-products of the petrochemical industry, with advantages such as strong foaming ability, uniform foam, and low price. 12 ~C 14 Fatty alcohol ether esters also have certain collector and foam stabilizing effects. They have a certain inhibitory effect on clay minerals such as talc in high-salt environments and can be used as auxiliary collectors for non-polar minerals such as molybdenite. Proper utilization of these industrial byproducts can transform waste into valuable resources, consuming them while reducing the cost of mineral processing reagents.

[0016] In the present invention, the diesel fuel is a light petroleum product. Diesel fuel itself is a good solvent, increasing the dispersibility and fluidity of the foaming agent, while also eliminating excessive foam and promoting foam coalescence and secondary enrichment. Diesel fuel also has a certain capture effect on non-polar minerals such as talc and molybdenite.

[0017] In a second aspect, the present invention provides a method for preparing a flotation frother for separating sulfide minerals and clay minerals, the preparation method comprising: first mixing polyethylene glycol and mixed hexavalent alcohol according to a formula, then mixing the obtained material with mixed ether alcohol for a second time, and finally mixing the obtained material with C5~C 14 The fatty alcohol ether ester is mixed with diesel to perform a third mixing and stirring, thereby preparing a flotation frother.

[0018] As a preferred technical solution of the present invention, stirring should be performed during the mixing process. Specifically, the mixing can be performed in a stirrer or a reactor, with any type of stirring paddle, and the stirring method can be mechanical stirring or jet stirring.

[0019] In addition, the stirring time specified in the present invention is 30-50 minutes, and the stirring time can be an integer number of minutes or a decimal between integers.

[0020] In the present invention, the stirring speed is 80-200 rpm / min, for example, it can be 80 rpm / min, 85 rpm / min, 90 rpm / min, 95 rpm / min, 100 rpm / min, 105 rpm / min, 110 rpm / min, 115 rpm / min, 120 rpm / min, 125 rpm / min, 130 rpm / min, 135 rpm / min, 140 rpm / min, 145 rpm / min, 150 rpm / min, 155 rpm / min, 160 rpm / min, 165 rpm / min, 170 rpm / min, 175 rpm / min, 180 rpm / min, 185 rpm / min, 190 rpm / min, 195 rpm / min or 200 rpm / min, etc., but is not limited to the listed values, and other values ​​within the range not listed are equally applicable.

[0021] In a further preferred embodiment, the first mixing time is 5-10 min, the stirring speed is 80-200 rpm / min, and the mixing time and the stirring speed can be an integer or a decimal between integers. The second mixing time is 10-15 min, the stirring speed is 80-200 rpm / min, and the mixing time and the stirring speed can be an integer or a decimal between integers. The third mixing time is 10-20 min, the stirring speed is 100-200 rpm, and the mixing time and the stirring speed can be an integer or a decimal between integers.

[0022] In the preparation method provided by the present invention, the materials can be mixed directly, or some materials can be mixed first and then other materials are gradually added for mixing. The distributed mixing method helps to better reflect the performance of the foaming agent.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] (1) The present invention prepares a frother by using a specific dosage ratio, which has the following advantages: strong stability, small dosage, uniform foam size during flotation, suitable foam stability, strong secondary enrichment ability, weak gangue entrainment / inclusion effect, and the ability to tolerate high dosage of inhibitors. In the forward flotation process, when used for the flotation separation of metal minerals such as copper sulfide, nickel, and molybdenum from common clay minerals that are easily muddied and have strong hydrophilicity, the frother only needs a small dosage to achieve a good separation effect, significantly improving the flotation recovery rate of metal minerals such as copper sulfide, nickel, and molybdenum, while also effectively improving the concentrate grade.

[0025] (2) The frother prepared by the present invention can also be used for pre-desilting of copper sulfide, nickel and molybdenum ores containing clay minerals that are easily floated or easily muddied (such as talc, chlorite, serpentine, etc.). By removing the easily floatable ores, the impact on the subsequent flotation of copper sulfide, nickel and molybdenum can be effectively reduced. Compared with traditional frothers, the frother can significantly reduce the inclusion instant of copper, nickel and molybdenum in easily floatable gangue, thereby improving the utilization rate of copper sulfide, nickel and molybdenum resources containing easily floatable clay gangue.

[0026] (3) The foaming agent prepared by the present invention fully utilizes the synergistic advantages of each component, which not only maintains the foaming ability and foam stability of the traditional foaming agent, but also improves the foaming speed and foam annealing speed of the foaming agent. 12 ~C 14 Fatty alcohol ether ester) has a foam stabilizing effect. In addition, the diesel component has a defoaming effect and has a certain capture ability for non-polar minerals (such as talc and molybdenite). DETAILED DESCRIPTION

[0027] The present invention is further described in detail below with reference to Examples and Comparative Examples.

[0028] Example 1

[0029] A flotation frother for separating sulfide minerals and clay minerals, comprising 8 parts of polyethylene glycol, 20 parts of mixed hexavalent alcohol, 16 parts of mixed ether alcohol, C5~C 14 The invention relates to a mixture of fatty alcohol ether ester and diesel fuel; the relative molecular mass of the polyethylene glycol is 400; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol in a mass ratio of 1:1; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether in a mass ratio of 2:1:1; the C5~C 14 Mixed fatty alcohol ether ester blended diesel is C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0030] The preparation method of the foaming agent is as follows: under normal temperature and pressure conditions, polyethylene glycol and mixed hexavalent alcohol are mixed and stirred at 80 rpm / min for 10 minutes, then mixed ether alcohol is added and mixed and stirred at 100 rpm / min for 15 minutes, and then C5~C 14 The fatty alcohol ether ester and diesel were mixed and stirred at 120 rpm / min for 15 minutes to fully mix them, thereby obtaining the flotation frother.

[0031] Example 2

[0032] A flotation frother for separating sulfide minerals and clay minerals, comprising 5 parts of polyethylene glycol, 16 parts of mixed hexavalent alcohol, 12 parts of mixed ether alcohol, C5~C14 The invention relates to a mixture of fatty alcohol ether ester and diesel fuel of 52 parts; the relative molecular mass of the polyethylene glycol is 400; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol in a mass ratio of 1:1; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether in a mass ratio of 2:1:1; the C5~C 14 Mixed fatty alcohol ether ester blended diesel is C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0033] The preparation method of the foaming agent is as follows: under normal temperature and pressure conditions, polyethylene glycol and mixed hexavalent alcohol are mixed and stirred at 80 rpm / min for 6 minutes, then mixed ether alcohol is added and mixed and stirred at 100 rpm / min for 12 minutes, and then C5~C 14 The fatty alcohol ether ester blended with diesel was stirred at 120 rpm / min for 20 min to ensure thorough mixing.

[0034] Comparative Example 1

[0035] A flotation frother for separating sulfide minerals and clay minerals, comprising 5 parts of polyethylene glycol, 16 parts of mixed hexavalent alcohol, 12 parts of mixed ether alcohol, C5~C 14 The invention relates to a mixture of fatty alcohol ether ester and diesel fuel of 52 parts; the relative molecular mass of the polyethylene glycol is 400; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol in a mass ratio of 1:1; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether in a mass ratio of 2:1:1; the C5~C 14 Mixed fatty alcohol ether ester blended diesel is C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0036] The preparation method of the foaming agent is as follows: under normal temperature and pressure conditions, hexavalent alcohol and C5~C 14 The mixed fatty alcohol ether ester and diesel were mixed at 100 rpm / min for 15 min, and then polyethylene glycol and the mixed ether alcohol were added and stirred at 80 rpm / min for 20 min to fully mix them.

[0037] Comparative Example 2

[0038] Compared with Example 2, the foaming agent provided in this embodiment does not contain polyethylene glycol. That is, under normal temperature and pressure, the mixed hexavalent alcohol and the mixed ether alcohol are mixed at 100 rpm / min for 12 minutes, and then C5~C 14 Mix the fatty alcohol ether ester and diesel fuel and stir at 120 rpm / min for 20 min to fully mix them.

[0039] Comparative Example 3

[0040] Compared with Example 2, the foaming agent provided in this embodiment is added with polyethylene glycol having a molecular weight of 600-2000, and the other formulas and preparation methods are the same as those in Example 2.

[0041] Comparative Example 4

[0042] Compared with Example 2, the foaming agent provided in this embodiment does not contain C5~C 14 Mix the fatty alcohol ether ester and diesel. That is, under normal temperature and pressure, mix the polyethylene glycol and the mixed hexavalent alcohol at 80 rpm for 6 minutes, then add the mixed ether alcohol and stir at 120 rpm for 12 minutes to fully mix.

[0043] Comparative Example 5

[0044] Compared with Example 2, the foaming agent provided in this embodiment does not contain mixed ether alcohol and C5~C 14 Mix the fatty alcohol ether ester and diesel. That is, under normal temperature and pressure, stir the polyethylene glycol and the mixed hexavalent alcohol at 80 rpm for 6 minutes to fully mix them.

[0045] Comparative Example 6

[0046] The foaming agent provided in this embodiment is pine oil.

[0047] Comparative Example 7

[0048] The foaming agent provided in this embodiment is methyl isobutyl carbinol (MIBC).

[0049] Comparative Example 8

[0050] The foaming agent provided in this embodiment is butyl ether alcohol.

[0051] Comparative Example 9

[0052] Compared with Example 2, the foaming agent provided in this embodiment is replaced by an equal amount of MIBC in the mixed hexavalent alcohol. That is, under normal temperature and pressure, polyethylene glycol and MIBC are mixed at 80 rpm / min for 6 minutes, then the mixed ether alcohol is added and mixed at 100 rpm / min for 12 minutes, and then C5~C 14 Mix the fatty alcohol ether ester and diesel fuel and stir at 120 rpm / min for 20 min to fully mix them.

[0053] Comparative Example 10

[0054] Compared with Example 2, the foaming agent provided in this embodiment is replaced by an equal amount of butyl ether alcohol. That is, under normal temperature and pressure, polyethylene glycol and mixed hexavalent alcohol are mixed at 80 rpm / min for 6 minutes, butyl ether alcohol is added and mixed at 100 rpm / min for 12 minutes, and then C5~C 14 Mix the fatty alcohol ether ester and diesel fuel and stir at 120 rpm / min for 20 min to fully mix them.

[0055] Comparative Example 11

[0056] Compared with Example 2, the foaming agent provided in this embodiment is C5~C 14 Mixed fatty alcohol ether ester blended diesel is replaced with an equal amount of C5~C 14 Mix fatty alcohol ether ester. That is, under normal temperature and pressure, mix polyethylene glycol and mixed hexavalent alcohol at 80 rpm / min for 6 minutes, then add mixed ether alcohol and mix at 100 rpm / min for 12 minutes, then add C5~C 14 The mixed fatty alcohol ether ester was stirred at 120 rpm / min for 20 min to allow for thorough mixing.

[0057] Comparative Example 12

[0058] Compared with Example 2, the foaming agent provided in this embodiment is C5~C 14 Replace the mixed fatty alcohol ether ester blended diesel with an equal amount of diesel. That is, at room temperature and pressure, mix the polyethylene glycol and mixed hexavalent alcohol at 80 rpm / min for 6 minutes, then add the mixed ether alcohol and mix at 100 rpm / min for 12 minutes, then add diesel and stir at 120 rpm / min for 20 minutes to fully mix.

[0059] Comparative Example 13

[0060] Compared with Example 2, the foaming agent provided in this embodiment is C5~C 14 Mixed fatty alcohol ether ester blended diesel was replaced with an equal amount of pine oil. That is, at room temperature and pressure, polyethylene glycol and mixed hexavalent alcohol were mixed at 80 rpm / min for 6 minutes, then the mixed ether alcohol was added and mixed at 100 rpm / min for 12 minutes, and then pine oil was added and stirred at 100 rpm / min for 20 minutes to ensure thorough mixing.

[0061] The performance of the frothers provided in Examples 1-2 and Comparative Examples 1-13 in pre-removing easily floating clay minerals by reverse flotation was tested, specifically:

[0062] In order to process a copper-nickel ore containing easily floating clay gangue minerals in Yunnan (copper content 0.38%, nickel content 0.64%, chlorite content 38.1%, talc content 21.7%, mica content 9.7%), a frother was added to pre-remove talc, chlorite, serpentine and other easily floating gangue minerals. After grinding the copper-nickel ore containing easily floating gangue (-0.074mm accounting for 73%), a frother was added to pre-float (de-sludging) the easily floating gangue, and the easily floated gangue minerals were removed and directly discarded.

[0063] In order to treat a copper-nickel ore containing easily floating clay gangue minerals in Xinjiang Uygur Autonomous Region (copper content 0.28%, nickel content 0.66%, chlorite talc content 39.5%, tremolite actinolite content 21.4%, olivine and pyroxene content 23.1%), a frother was added to pre-remove the easily floating clay gangue minerals. After grinding the copper-nickel ore containing easily floating gangue (-0.074mm accounting for 67%), a frother was added to pre-flotate (de-sludging) the easily floating gangue, and the easily floated gangue minerals were removed and directly discarded.

[0064] The above specific results are shown in Table 1.

[0065]

[0066] According to the data in Table 1, the following conclusions can be drawn: 14 The mixture of fatty alcohol ether ester and diesel can be used to prepare a flotation frother with low cost and significant effect, which can effectively remove floatable clay minerals from metal ores such as copper sulfide, nickel, and molybdenum (see Example 2). 14 While increasing the ratio of fatty alcohol ether ester to diesel mixtures can improve flotation separation accuracy (Example 1), it also increases overall reagent costs. Furthermore, altering the reagent preparation process, including the order of addition and mixing method, can negatively impact separation performance (Comparative Example 1). Changing the ratio and type of polyethylene glycol (Comparative Examples 2 and 3) can also adversely affect reverse flotation desludging.

[0067] When the mixed foaming agent system does not contain C5~C 14 While the inclusion loss of sulfide minerals was minimized when using fatty alcohol ether esters with diesel and mixed ether alcohols (Comparative Examples 4 and 5), desludging yields were low and reagent costs were high in practice. Desludging using a single conventional flotation frother (Comparative Examples 6 to 8) was less effective than in Examples 1 and 2, and sulfide losses were significant. This was particularly true when using pine oil as the frother. This is likely because the foam formed by pine oil has a high viscosity and stability, making it less susceptible to breakage and coalescence.

[0068] When MIBC was used instead of mixed hexavalent alcohol (Comparative Example 9), the desludging index was close to that of Example 2, but this would significantly increase the reagent cost. 14 Types of reagents for fatty alcohol ether esters and diesel (Comparative Examples 10-12), or using pine oil to replace C5-C 14 Fatty alcohol ether ester and diesel (Comparative Example 13) showed no significant improvement in flotation index compared with Example 2, and the reagent cost of some systems was even higher.

[0069] In summary, the application of the frother proposed in this patent in the reverse flotation process can effectively remove floatable clay minerals from sulfide copper-nickel ore in advance. The copper and nickel content in the easily floated gangue minerals removed by this process is relatively low, and the copper-nickel recovery rate in the mud is not significantly improved. This shows that the use of the frother of this patent to pre-treat the sulfide minerals containing clay minerals for desludging can significantly reduce the copper-nickel mixed loss in the easily floated gangue, thereby improving the mining efficiency of this type of copper-nickel ore resources containing easily floated clay. In practice, in order to further improve the desludging effect, especially in reducing the grade and recovery rate of copper-nickel impurities in easily floated clay minerals, the proportion of polyethylene glycol, mixed hexavalent alcohol and mixed ether alcohol in the combined frother can be appropriately increased, while the proportion of C5~C 14 The proportion of mixed fatty alcohol ether esters blended with diesel. Furthermore, flotation frothers prepared by adding reagents in batches and stirring them together exhibit superior performance. This preparation method not only optimizes the reagent ratio but also improves the overall performance of the flotation frother, providing strong support for improving mineral resource extraction efficiency.

[0070] The performance of the frothers provided in Examples 1-2 and Comparative Examples 1-13 in the positive flotation separation of copper sulfide, nickel, molybdenum minerals and clay minerals was tested, specifically:

[0071] A copper-nickel ore containing chlorite, serpentine, amphibole, and talc from Gansu (copper content of 0.79%, nickel content of 0.74%, and clay mineral content of 34.43% calculated as magnesium oxide) was processed. The ore was ground to a particle size of less than 0.074 mm, accounting for 70%. After grinding, sodium carbonate, sodium hexametaphosphate, butyl xanthate, carboxymethyl cellulose, and the frothers provided in Examples 1-2 and Comparative Examples 1-13 were sequentially added in a roughing operation at a flotation temperature of 18-22°C, and the mixture was stirred and slurried. After slurrying, the ore was placed in a flotation tank for flotation.

[0072] A talc-type molybdenum ore in Henan Province (molybdenum content of 0.17%, clay mineral content of 18.11% calculated as magnesium oxide) was processed. The ore was ground to a particle size of less than 0.074 mm, accounting for 75%. Subsequently, at a flotation temperature of 22-26°C, modified water glass, polysaccharide inhibitor, kerosene, and the frothers provided in Examples 1-2 and Comparative Examples 1-13 were sequentially added in a roughing operation, followed by stirring and slurrying. After slurrying, the ore was placed in a flotation tank for flotation.

[0073] The above specific results are shown in Table 2.

[0074]

[0075] According to the data in Table 2, the following conclusions can be drawn: by carefully blending polyethylene glycol, mixed hexavalent alcohol, mixed ether alcohol, C5~C 14 A mixture of fatty alcohol ether ester and diesel fuel can be used to prepare a cost-effective and effective flotation frother. This frother can effectively recover valuable metals such as copper, nickel, and molybdenum from sulfide copper, nickel, and molybdenum ores containing clay gangue. 14 The ratio of fatty alcohol ether ester to diesel mixture will not only increase the cost of the reagent, but also reduce the recovery rate of copper, nickel and molybdenum metals. 14 Fatty alcohol ether ester blended with diesel plays a key role in the capture process of sulfide ores.

[0076] Changing the reagent preparation process, including adjusting the order of addition and mixing method, can adversely affect separation performance (Comparative Example 1). Changing the proportion and type of polyethylene glycol (Comparative Examples 2 and 3) can also negatively impact the final separation index of direct flotation, increasing the loss rate of copper, nickel, and molybdenum metals in the tailings.

[0077] When the mixed foaming agent lacks C5~C 14 When fatty alcohol ether esters are combined with diesel and mixed with ether alcohols (Comparative Examples 4 and 5), concentrate recovery also decreases. This is because the lack of these components reduces the stability of the frother, hindering the capture and enrichment of sulfide minerals while increasing reagent costs. When a single conventional flotation frother is used for forward flotation (Comparative Examples 6 to 8), the results are inferior to those of Examples 1 and 2, demonstrating that the mixed frother of the present invention has greater adaptability in the flotation of clay-containing copper, nickel, and molybdenum sulfide minerals.

[0078] When MIBC replaced the mixed hexavalent alcohol (Comparative Example 9), although the reagent cost increased significantly, the flotation recovery effect of the target mineral was not ideal. 14 Types of reagents for fatty alcohol ether esters and diesel (Comparative Examples 10 to 12), or using pine oil to replace C5~C 14The flotation index of diesel blended with fatty alcohol ether ester (Comparative Example 13) did not show significant improvement.

[0079] In summary, the frother provided by the present invention can achieve higher concentrate grades and higher copper, nickel, and molybdenum metal recoveries compared to conventional flotation frothers (such as pine oil, MIBC, butyl ether alcohol, etc.) when separating copper sulfide, nickel, and molybdenum minerals from clay minerals (such as chlorite, serpentine, and talc). Therefore, using the frother of the present invention to treat copper sulfide, nickel, and molybdenum metal ores containing clay gangue minerals helps improve the utilization rate of these mineral resources. Increasing C5~C 14 The ratio of mixed fatty alcohol ether ester to diesel can significantly reduce the overall reagent cost and improve the comprehensive recovery rate of copper sulfide, nickel and molybdenum ore. This is because under the conditions of high dispersant and high inhibitor dosage, C5~C 14 Mixed fatty alcohol ether esters and long hydrocarbon chain alcohol ether esters in diesel (such as C 12 ~C 14 Fatty alcohols not only effectively stabilize foam but also have a certain inhibitory effect on clay minerals, while diesel has a certain ability to capture molybdenite. Furthermore, flotation frothers prepared by timed and batch dosing and mixing exhibit superior performance.

[0080] In summary, the mixed frother described in this invention, by rationally adjusting the proportions of its components, is not only suitable for direct or reverse flotation desludging of clay-containing gangue minerals such as copper sulfide, nickel, and molybdenum, but also exhibits excellent adaptability to process and reagent systems, significantly improving the convenience of flotation operations and reducing on-site operating costs. Furthermore, this combined frother utilizes a variety of petroleum industry byproducts instead of chemically pure reagents, effectively reducing overall reagent costs and offering significant competitive advantages.

Claims

1. A method for preparing a flotation frother for separating sulfide minerals and clay minerals, characterized in that: The flotation frother is composed of the following components in parts by weight: 3-8 parts of polyethylene glycol, 8-22 parts of mixed hexavalent alcohol, 10-18 parts of mixed ether alcohol, C5-C 14 Mixed fatty alcohol ether ester blended with 36-66 parts diesel; the mixed hexavalent alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether; the C5-C 14 Mixed fatty alcohol ether ester blended diesel is industrial C5~C 14 mixtures of fatty alcohol ether esters and light diesel fuel; According to the formula, polyethylene glycol and mixed hexavalent alcohol are first mixed and stirred, the obtained material and mixed ether alcohol are second mixed and stirred, and then the obtained material is mixed with C5~C 14 The fatty alcohol ether ester is mixed with diesel fuel for a third mixing and stirring to obtain the flotation frother.

2. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 1, wherein: The relative molecular mass of the polyethylene glycol is between 250 and 425.

3. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 1, characterized in that: The mass ratio of the cyclohexanol to the methyl isobutyl carbinol is 1:

1.

4. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 1, wherein: The mass ratio of the butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether is 2:1:

1.

5. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 1, characterized in that: The C5~C 14 Mixed fatty alcohol ether ester blended diesel, C5~C 14 The mass ratio between the mixed fatty alcohol ether ester and the light diesel is 4:1, and the blending method is ordinary mechanical stirring and mixing.

6. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 1, wherein: The first mixing and stirring time is 5-10 minutes, and the stirring speed is 80-200 rpm / min; the second mixing and stirring time is 10-15 minutes, and the stirring speed is 80-200 rpm / min; the third mixing and stirring time is 10-20 minutes, and the stirring speed is 100-200 rpm / min.

Images