Flotation foaming agent for separating sulfide minerals and clay minerals and preparation method of flotation foaming agent

Abstract

The invention discloses a flotation foaming agent for separating sulfide minerals and clay minerals and a preparation method of the flotation foaming agent. The flotation foaming agent consists of the following components in parts by weight: 3-8 parts of polyethylene glycol, 8-22 parts of mixed hexahydric alcohol, 10-18 parts of mixed ether alcohol and 36-66 parts of C5-C14 mixed fatty alcohol ether ester blended diesel oil, the mixed hexahydric alcohol is a mixture of cyclohexanol and methyl isobutyl carbinol; the mixed ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol monomethyl ether and tripropylene glycol butyl ether; the C5-C14 mixed fatty alcohol ether ester blended diesel oil is a mixture of industrial C5-C14 mixed fatty alcohol ether ester and light diesel oil. According to the flotation foaming agent provided by the invention, by compounding all the components and utilizing the synergistic effect among the components, flotation separation of copper sulfide, nickel sulfide and molybdenum minerals and common clay gangue such as talc, serpentine, chlorite and mica can be effectively realized, so that the comprehensive recycling rate of copper sulfide, nickel sulfide and molybdenum ore resources is improved.

Description

Technical Field

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

[0002] At present, copper sulfide, nickel, molybdenum, etc., as important strategic resources, have become important mineral sources for the recycling of copper, nickel and molybdenum metals. According to statistics, copper sulfide ore resources account for more than 75% of the proven copper resources. However, due to the influence of factors such as the earth's mineralization and geological environment evolution, some copper sulfide, nickel and molybdenum ores are often closely associated with clay minerals such as talc, serpentine, chlorite and mica. These clay minerals generally have low hardness, and the minerals are easily over-grinded or over-crushed during the crushing and grinding process, resulting in severe mudification of clay minerals in the flotation slurry, thereby causing heterogeneous coagulation (slime cover) between different minerals and foam entrainment / inclusion problems during the flotation process, which significantly deteriorates the flotation recovery of useful minerals or reduces the grade of the final concentrate. At the same time, some clay minerals (such as talc, serpentine, and chlorite) have good natural hydrophobicity. When conventional flotation processes are used to treat such mineral resources containing copper sulfide, nickel, and molybdenum, these easily floatable gangue minerals will float up in large quantities along with the target minerals (copper sulfide, nickel, and molybdenum), thus seriously affecting the grade and recovery rate of the target minerals. In order to more effectively utilize copper sulfide, nickel, and molybdenum ore resources containing easily floatable clay minerals, talc, chlorite, serpentine, and other easily floatable clay gangue minerals can usually be removed by adding frothers to reduce their impact on the flotation of copper sulfide, nickel, and molybdenum ores.

[0003] However, most of the current flotation frothers are organic heteropolar molecular surfactants composed of polar and non-polar groups. Such frothers are mainly used to form a large amount of stable and suitable foam in the pulp. However, they have some problems, such as low solubility, difficulty in dispersion in the pulp, poor foam persistence, insignificant secondary enrichment effect, uneven bubble size, and serious entrainment / inclusion during flotation. In addition, a large amount of soda ash, phosphate, water glass, polysaccharides (such as gum, starch, cellulose, etc.) and polyphenols (such as lignin derivatives, tannins, tannins, etc.) inhibitors are usually added in the flotation process containing clay minerals to reduce the impact of clay minerals on the quality of flotation concentrates. However, excessive use of these dispersants and inhibitors will not only reduce the floatability of gangue minerals, but may also affect the foaming effect of conventional flotation frothers, thereby affecting the flotation recovery of useful minerals.

[0004] Therefore, in order to improve the comprehensive utilization efficiency of copper, nickel and molybdenum sulfide ore resources containing clay minerals, and to improve the final flotation recovery rate of copper, nickel and molybdenum sulfide minerals and the grade of concentrate products, it is necessary to develop a flotation frother suitable for copper, nickel and molybdenum sulfide minerals in a high-dosage system of dispersants and inhibitors. If the frother can reduce the loss caused by the entrainment or inclusion of copper, nickel and molybdenum sulfide minerals when removing talc, serpentine and other easy-floating clay minerals in the pre-flotation stage, its scope of application will be further broadened. Summary of the invention

[0005] The object of the present invention is to provide a flotation frother for separating sulfide minerals from clay minerals and a preparation method thereof. The method is simple and easy to operate, and can reduce the dosage of the frother in the flotation process without increasing the comprehensive use cost, thereby improving 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, molybdenum minerals, and realizing the saving and efficient utilization of precious copper, nickel, molybdenum and other mineral resources; the prepared flotation frother has the following advantages: strong stability, small dosage, can effectively enhance the frothing ability in the flotation process, generate uniform and stable foam, have strong secondary enrichment ability, and at the same time, the entrainment / inclusion effect of gangue is weak, and can tolerate the high dosage environment of dispersant and inhibitor, and is particularly suitable for the flotation recovery of copper sulfide, nickel, molybdenum and other mineral resources containing clay minerals.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: In a first aspect, the present invention provides a flotation frother for separating sulfide minerals from clay minerals, 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 The mixed fatty alcohol ether ester is blended with 36 to 66 parts of diesel, and the parts can be either integer parts or decimal parts between integer parts; 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.

[0007] In the present invention, the flotation frother provided by the present invention is through the reasonable compounding of the frother components. The present invention effectively utilizes the synergistic effect between the components, and can significantly reduce the entrainment of fine-grained clay minerals by flotation foam during the positive flotation of copper sulfide, nickel and molybdenum ores. In addition, the frother can also effectively reduce the inclusion loss of useful metal minerals such as copper sulfide, nickel, and molybdenum when removing fine-grained easy-floating clay minerals (such as talc, chlorite, and serpentine) during the reverse flotation pre-desludging process. This not only helps to improve the quality of copper sulfide, nickel, and molybdenum mineral concentrate products, but also reduces the loss of fine-grained copper sulfide, nickel, and molybdenum metals during the desludging process, ensuring the efficient recovery and utilization of valuable metal elements.

[0008] In the present invention, the polyethylene glycol is a liquid polymer with a relative molecular mass between 250 and 425, good lubricity, moisture retention, dispersibility, adhesion and water solubility, and good compatibility with many organic components, and can be used for inorganic salt solubilization, drug viscosity adjustment, etc.

[0009] Preferably, the mass ratio between the cyclohexanol and methyl isobutyl carbinol is 1:1.

[0010] 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 other organic substances and can enhance the brittleness and fluidity of the foam in a mixed foaming agent system.

[0011] In the present invention, the methyl isobutyl carbinol (MIBC) is an industrial synthetic foaming agent, which is a transparent colorless liquid with a mild odor (higher alcohol odor). Compared with the commonly used foaming agent pine oil, the bubbles generated by MIBC show a lower amplitude reduction in foam height and liquid content, which means that the bubbles generated by MIBC have better stability and lower liquid content, which is very important for the mineral flotation process. Specifically, the liquid content of the bubbles generated by MIBC is significantly lower than that of pine oil, which helps to improve the efficiency and effect of the flotation process.

[0012] Preferably, in the present invention, the ether alcohol is a mixture of butyl ether alcohol, tripropylene glycol methyl ether, and tripropylene glycol butyl ether, and the weight ratio of the three is 2:1:1. Ether alcohol foaming agents are a type of foaming agent artificially synthesized using petrochemical products as raw materials. This type of foaming agent has good fluidity and viscosity, high water solubility, dense foam structure, non-stickiness, good selectivity, easy defoaming, and small dosage. It can generate a large number of small bubbles less than 0.2 mm that are beneficial to flotation. The general dosage is only 1 / 3 to 2 / 3 of pine oil, which can assist and strengthen the comprehensive recovery of precious metals such as gold and silver. In the present invention, the weight of ether alcohol foaming agents accounts for a small proportion, and the comprehensive agent cost is controllable.

[0013] Preferably, the C5~C 14 In the blending of diesel fuel with mixed fatty alcohol ether ester, 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.

[0014] In the present invention, the C5~C 14 Mixed fatty alcohol ether esters are byproducts of the petrochemical industry. They have the advantages of strong foaming ability, uniform foam, and low price. Long-chain fatty alcohol ether esters (such as C 12 ~C 14 Fatty alcohol ether esters) also have certain collection and foam stabilization effects. The high-salt environment system has certain inhibition on clay minerals such as talc, and can be used as an auxiliary collector for non-polar minerals (such as molybdenite). Reasonable use of this part of industrial by-products can turn waste into treasure, which not only consumes industrial by-products but also reduces the cost of mineral processing reagents.

[0015] In the present invention, the diesel is a light petroleum product. Diesel itself is a good solvent, which can increase the dispersibility and fluidity of the foaming agent, eliminate excessive foam, and promote the annealing and secondary enrichment of foam. Diesel also has a certain capture effect on non-polar minerals such as talc and molybdenite.

[0016] In a second aspect, the present invention provides a method for preparing a flotation frother for separating sulfide minerals from clay minerals, the method comprising first mixing and stirring polyethylene glycol and mixed hexahydric 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 process, thereby preparing a flotation frother.

[0017] 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, the type of the stirring paddle is not limited, and the stirring method can be mechanical stirring or jet stirring.

[0018] 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 number between integers.

[0019] In the present invention, the stirring speed is 80-200rpm / min, for example, it can be 80rpm / min, 85rpm / min, 90rpm / min, 95rpm / min, 100rpm / min, 105rpm / min, 110rpm / min, 115rpm / min, 120rpm / min, 125rpm / min, 130rpm / min, 135rpm / min, 140rpm / min, 145rpm / min, 150rpm / min, 155rpm / min, 160rpm / min, 165rpm / min, 170rpm / min, 175rpm / min, 180rpm / min, 185rpm / min, 190rpm / min, 195rpm / min or 200rpm / min, but is not limited to the listed values, and other values ​​within the range not listed are equally applicable.

[0020] In a further preferred embodiment, the first mixing time is 5-10 min, the speed is 80-200 rpm / min, and the mixing time and the stirring speed can be integers or decimals between integers. The second mixing time is 10-15 min, the speed is 80-200 rpm / min, and the mixing time and the stirring speed can be integers or decimals 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 integers or decimals between integers.

[0021] In the preparation method provided by the present invention, the materials can be directly mixed, or some materials can be mixed first and then other materials are gradually added for mixing, wherein the distributed mixing method helps to better reflect the performance of the foaming agent.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention prepares a frother through a specific dosage ratio, and 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 ability to tolerate high dosage of inhibitors. In the positive flotation process, when used for flotation separation of metal minerals such as copper sulfide, nickel, and molybdenum from common clay minerals that are easy to mud 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, and at the same time effectively improving the concentrate grade.

[0023] (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 easy to float and easy to mud (such as talc, chlorite, serpentine, etc.). By removing the easy-floating ore, 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 the easy-floating gangue, thereby improving the utilization rate of copper sulfide, nickel and molybdenum resources containing easy-floating clay gangue.

[0024] (3) The foaming agent prepared by the present invention fully utilizes the synergistic advantages of each component, not only maintaining the foaming ability and foam stability of the traditional foaming agent, but also improving the foaming speed and foam annealing speed of the foaming agent. 12 ~C 14 Fatty alcohol ether esters) have 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

[0025] The present invention is further described in detail below with reference to Examples and Comparative Examples. Example 1

[0026] 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 mixed fatty alcohol ether ester is blended with 38 parts of diesel; the relative molecular mass of the polyethylene glycol is 400; the mixed hexahydric 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 The mixed fatty alcohol ether ester and diesel are C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0027] The preparation method of the foaming agent is as follows: at room temperature and pressure, polyethylene glycol and mixed hexavalent alcohol are mixed and stirred at 80 rpm / min for 10 min according to the formula, then mixed ether alcohol is added and mixed and stirred at 100 rpm / min for 15 min, and then C5~C 14 The mixed fatty alcohol ether ester and diesel were stirred at 120 rpm / min for 15 minutes to fully mix them, thereby obtaining the flotation frother. Example 2

[0028] 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 14The invention relates to a mixed fatty alcohol ether ester blended with 52 parts of diesel; the relative molecular mass of the polyethylene glycol is 400; the mixed hexahydric 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 The mixed fatty alcohol ether ester and diesel are C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0029] The preparation method of the foaming agent is as follows: at room temperature and pressure, polyethylene glycol and mixed hexavalent alcohol are mixed and stirred at 80 rpm / min for 6 minutes according to the formula, and then mixed ether alcohol is added and mixed and stirred at 100 rpm / min for 12 minutes, and then C5~C 14 The mixed fatty alcohol ether ester and diesel were stirred at 120 rpm / min for 20 min to make them fully mixed.

[0030] Comparative Example 1 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 mixed fatty alcohol ether ester blended with 52 parts of diesel; the relative molecular mass of the polyethylene glycol is 400; the mixed hexahydric 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 The mixed fatty alcohol ether ester and diesel are C5~C 14 A mixture of fatty alcohol ether esters and light diesel.

[0031] The preparation method of the foaming agent is as follows: under normal temperature and pressure conditions, a 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 mixed ether alcohol were added and stirred at 80 rpm / min for 20 min to fully mix them.

[0032] Comparative Example 2 Compared with Example 2, the foaming agent provided in this embodiment does not contain polyethylene glycol. That is, under normal temperature and pressure conditions, the mixed hexavalent alcohol and the mixed ether alcohol are mixed 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 make them fully mixed.

[0033] Comparative Example 3 Compared with Example 2, the foaming agent provided in this embodiment adds polyethylene glycol with a molecular weight of 600-2000, and the other formulas and preparation methods are consistent with Example 2.

[0034] Comparative Example 4 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, at normal temperature and pressure, mix the polyethylene glycol and the mixed hexavalent alcohol at 80 rpm / min for 6 minutes, then add the mixed ether alcohol and stir at 120 rpm / min for 12 minutes to fully mix them.

[0035] Comparative Example 5 Compared with Example 2, the foaming agent provided in this embodiment does not add 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 / min for 6 minutes to fully mix them.

[0036] Comparative Example 6 The foaming agent provided in this embodiment is pine oil.

[0037] Comparative Example 7 The foaming agent provided in this embodiment is methyl isobutyl carbinol (MIBC).

[0038] Comparative Example 8 The foaming agent provided in this embodiment is butyl ether alcohol.

[0039] Comparative Example 9 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, at room 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 The fatty alcohol ether ester blended with diesel was stirred at 120 rpm / min for 20 min to make them fully mixed.

[0040] Comparative Example 10 Compared with Example 2, the foaming agent provided in this embodiment is replaced by an equal amount of butyl ether alcohol. That is, at room temperature and pressure, polyethylene glycol and mixed hexavalent alcohol are mixed at 80 rpm / min for 6 min, butyl ether alcohol is added and mixed at 100 rpm / min for 12 min, and then C5~C 14 The fatty alcohol ether ester blended with diesel was stirred at 120 rpm / min for 20 min to make them fully mixed.

[0041] Comparative Example 11 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 Mixed fatty alcohol ether ester. That is, at room temperature and pressure, polyethylene glycol and mixed hexavalent alcohol are mixed at 80 rpm / min for 6 minutes, then mixed ether alcohol is added and mixed at 100 rpm / min for 12 minutes, and then C5~C 14 The mixed fatty alcohol ether ester was stirred at 120 rpm / min for 20 min to allow for thorough mixing.

[0042] Comparative Example 12 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 diesel. That is, at normal temperature and pressure, polyethylene glycol and mixed hexahydric alcohol are mixed at 80 rpm / min for 6 minutes, then mixed ether alcohol is added and mixed at 100 rpm / min for 12 minutes, and then diesel is added and stirred at 120 rpm / min for 20 minutes to fully mix.

[0043] Comparative Example 13 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 normal temperature and pressure, polyethylene glycol and mixed hexahydric alcohol were mixed at 80 rpm / min for 6 minutes, then 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 fully mix.

[0044] The performance of the frothers provided in Examples 1-2 and Comparative Examples 1-13 in pre-removing the easily floating clay minerals by reverse flotation was tested, specifically: In order to treat a copper-nickel ore containing 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 remove talc, chlorite, serpentine and other floating gangue minerals in advance. After grinding the copper-nickel ore containing floating gangue (-0.074mm accounting for 73%), a frother was added to pre-float (de-sludging) the floating gangue, and the floating gangue minerals were removed and directly discarded.

[0045] In order to treat a copper-nickel ore containing floating clay gangue minerals in Xinjiang (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 remove the floating clay gangue minerals in advance. After grinding the copper-nickel ore containing floating gangue (-0.074mm accounting for 67%), a frother was added to pre-float (de-sludging) the floating gangue, and the floating gangue minerals were removed and directly discarded.

[0046] The above specific results are shown in Table 1

[0047] 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 Although the ratio of fatty alcohol ether ester to diesel mixture can improve the accuracy of flotation separation (Example 1), it will lead to an increase in the overall reagent cost. In addition, changing the preparation process of the reagent, including the order of addition and the mixing method, will have a negative impact on the separation effect (Comparative Example 1). Changes in the ratio and type of polyethylene glycol (Comparative Examples 2 and 3) will also have an adverse effect on the reverse flotation desludging process.

[0048] When the mixed foaming agent system does not contain C5~C 14 When fatty alcohol ether ester and diesel and mixed ether alcohol (Comparative Examples 4 and 5), although the inclusion loss of sulfide minerals is minimal, it is found in actual application that the desludging yield is not high and the reagent cost is high. When a single conventional flotation frother is used for desludging (Comparative Examples 6 to 8), the desludging effect is not as good as that of Examples 1 and 2, and the loss of sulfide is relatively large, especially when pine oil is used as a frother, which may be because the foam formed by pine oil has high viscosity and stability and is not easy to break and merge.

[0049] When MIBC was used to replace the mixed hexavalent alcohol (Comparative Example 9), the desludging index was close to that of Example 2, but this would significantly increase the cost of the reagent. 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), the flotation index is not significantly improved compared with Example 2, and the reagent cost of some systems is even higher.

[0050] In summary, the application of the frother proposed in this patent in the reverse flotation process can effectively remove the floatable clay minerals from the sulfide copper-nickel ore in advance. The copper and nickel contents in the floating gangue minerals removed by this process are relatively low, and the copper-nickel recovery rate in the mud has not been 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 losses in the floating gangue, thereby improving the mining efficiency of this type of copper-nickel ore resources containing floating clay. In practice, in order to further improve the desludging effect, especially in reducing the grade and recovery rate of copper-nickel impurities in the removal of floating 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 ester blended with diesel. In addition, the flotation frother prepared by adding reagents in batches and stirring and mixing has better performance. This preparation method not only optimizes the combination ratio of reagents, but also improves the overall performance of the flotation frother, providing strong support for improving the mining efficiency of mineral resources.

[0051] 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: A copper-nickel ore containing chlorite, serpentine, amphibole and talc in Gansu (copper content of 0.79%, nickel content of 0.74%, 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%, and after grinding, sodium carbonate, sodium hexametaphosphate, butyl xanthate, carboxymethyl cellulose and the frother provided in Example 1-12 were added in sequence in the roughing operation under the condition of flotation temperature of 18-22°C, and then stirred and slurried. After slurrying, the ore was put into the flotation tank for flotation.

[0052] A talc-type molybdenum ore in Henan (molybdenum content is 0.17%, clay mineral content is 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%, and then, under the flotation temperature of 22-26°C, modified water glass, polysaccharide inhibitor, kerosene and the frother provided in Example 1-15 were added in sequence in the roughing operation, and then stirred and slurried. After slurrying, the ore was put into the flotation tank for flotation.

[0053] The above specific results are shown in Table 2

[0054] 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 14The mixture of fatty alcohol ether ester and diesel can be used to prepare a cost-effective and effective flotation frother. This frother can effectively recover precious 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 lead to a decrease in the recovery rate of copper, nickel and molybdenum metals. 14 Fatty alcohol ether ester blended diesel plays a key role in the capture process of sulfide ores.

[0055] Changing the preparation process of the reagents, including adjusting the order of addition and the mixing method, will have an adverse effect on the separation effect (Comparative Example 1). Changes in the proportion and type of polyethylene glycol (Comparative Examples 2 and 3) will also have a negative impact on the final separation index of direct flotation and increase the loss rate of copper, nickel and molybdenum metals in the tailings.

[0056] When the mixed foaming agent lacks C5~C 14 When fatty alcohol ether ester and diesel and mixed ether alcohol (Comparative Examples 4 and 5), the recovery rate of concentrate will also decrease. This is because the lack of these components will lead to a decrease in the stability of the frother, which is not conducive to the capture and enrichment of sulfide minerals, and at the same time increase the cost of the reagent. When a single conventional flotation frother is used for positive flotation (Comparative Examples 6 to 8), the effect is not as good as that of Examples 1 and 2, which shows that the mixed frother of the present invention has better adaptability in the flotation of clay-containing copper sulfide, nickel, and molybdenum minerals.

[0057] 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 use pine oil to replace C5~C 14 The flotation index of diesel blended with fatty alcohol ether ester (Comparative Example 13) did not show significant improvement.

[0058] In summary, the frother provided by the present invention can obtain a higher concentrate grade and a higher copper, nickel and molybdenum metal recovery rate when separating copper sulfide, nickel and molybdenum minerals from clay minerals (such as chlorite, serpentine, talc, etc.) by positive flotation compared with conventional flotation frothers (such as pine oil, MIBC, butyl ether alcohol, etc.). Therefore, using the frother of the present invention to treat copper sulfide, nickel and molybdenum metal ores containing clay gangue minerals is helpful to 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 14Long hydrocarbon chain alcohol ether ester substances (such as C 12 ~C 14 Fatty alcohols can not only effectively stabilize foam, but also have a certain inhibitory effect on clay minerals, while diesel has a certain collection ability for molybdenite. In addition, the flotation frother prepared by adding drugs in batches and stirring and mixing has a more superior performance.

[0059] In summary, the mixed frother of the present invention is not only suitable for the direct flotation or reverse flotation desludging of clay gangue minerals such as copper sulfide, nickel, molybdenum, etc., by reasonably adjusting the proportion of each component, but also has good adaptability to the process and reagent system, significantly improving the convenience of flotation operation and reducing the on-site operation cost. At the same time, the combined frother uses a variety of petroleum industry by-products instead of chemically pure reagents, effectively reducing the comprehensive reagent cost, and has obvious competitive advantages.

Claims

1. A flotation frother for separating sulfide minerals from 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 esters and diesel 36-66 parts; the mixed hexahydric 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 A mixture of fatty alcohol ether esters and light diesel.

2. A flotation frother for separating sulfide minerals and clay minerals according to claim 1, characterized in that: The relative molecular weight of the polyethylene glycol is between 250 and 425.

3. 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. A flotation frother for separating sulfide minerals and clay minerals according to claim 1, characterized in that: The mass ratio of the butyl ether alcohol, tripropylene glycol methyl ether and tripropylene glycol butyl ether is 2:1:

1.

5. The flotation frother for separating sulfide minerals and clay minerals according to claim 1, characterized in that: C5~C 14 In the blending of diesel fuel with mixed fatty alcohol ether ester, 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. A method for preparing a flotation frother for separating sulfide minerals and clay minerals as claimed in claims 1 to 5, characterized in that: 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 to perform a third mixing and stirring to obtain the flotation frother.

7. The method for preparing a flotation frother for separating sulfide minerals and clay minerals according to claim 6, characterized in that: The mixing and stirring is mechanical stirring, the stirring time is 30-50 minutes, and the stirring speed is 80-200 rpm / min.

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

Images