Composite collector and method for flotation of high oxidation rate muddy molybdenite

Abstract

This invention belongs to the field of molybdenum ore flotation, specifically relating to a composite collector and method for flotating highly oxidized argillized molybdenite. The composite collector comprises components A and B; component A is at least one of silicone oil, paraffin oil, solvent oil, mineral oil, naphthenic oil, white oil, and switch oil; and component B is at least one of Formula 1 ( ) and Formula 2 ( ). Innovative research in this invention demonstrates that the combination of components A and B achieves synergistic results, adapting to the mineral characteristics of highly oxidized argillized molybdenite and effectively improving the flotation efficiency of this difficult-to-separate mineral. Furthermore, the composite collector components of this invention exhibit excellent safety.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation, and in particular relates to a flotation method for refractory molybdenite with high oxidation rate and high mudification. Background Art

[0002] Molybdenum minerals are often embedded in fine particle size, with low metal grade, and most of them coexist with metal minerals such as copper, tungsten, iron, and tin, making comprehensive recovery difficult. Molybdenite is the main form of existence of molybdenum metal. Currently, 99% of the molybdenum in the world is extracted from molybdenite. For low-grade, fine-grained molybdenite, flotation is the most important way to recover it. For example, the Chinese patent document with publication number CN102069037A discloses a composite hydrocarbon oil molybdenum collector and a preparation method thereof, wherein the main components of the collector are light diesel, kerosene, and condensed ring aromatics. The Chinese patent document with publication number CN115569738A discloses a novel molybdenum ore collector and its preparation and application, wherein the main components of the collector are diesel and pine oil. He Tingshu et al. (He Tingshu, Shi Xu, Li Hui, et al. Effect of magnetized modified kerosene on low-temperature flotation index of a molybdenum ore in Luoyang [J]. Metal Mines, 2017, (6): 99-103.) used magnetized modified kerosene to recover a molybdenum ore in Luoyang under low-temperature conditions. The comparison results showed that the molybdenum grade of the concentrate obtained when magnetized kerosene was used as a collector was 0.5 percentage points higher than that when the non-magnetized collector was used, and the molybdenum recovery rate was 2.53 percentage points higher. Liu Runqing et al. (Liu Runqing, Li Jie, Song Xin, et al. Flotation enhancement mechanism and application of composite hydrocarbon oil on molybdenite of different particle sizes [J]. Journal of the Chinese Society of Nonferrous Metals, 2023, 33(3): 912-921.) used composite hydrocarbon oil mainly based on kerosene to enhance the flotation of molybdenite of different particle sizes. The study found that composite hydrocarbon oil can increase the hydrophobicity of coarse and fine minerals, thereby enhancing the flotation effect of molybdenite.

[0003] With the increasing demand for molybdenum resources and the gradual expansion of mining scale, molybdenum resources are becoming increasingly "poor, fine, and mixed," resulting in a more complex slurry environment and increasing the difficulty of mineral processing and recovery. The most commonly used collectors for molybdenite are kerosene and diesel. Both are fuel oils with low flash points and are flammable and hazardous chemicals, posing significant safety risks in transportation and use. Therefore, finding green, safe, and environmentally friendly molybdenum collectors to replace kerosene and diesel is of great significance and is also a future trend in the development of molybdenum flotation collectors.

[0004] In addition, the main mineral structure of molybdenite is MoS2, and its oxidation rate and mudification degree greatly affect the capture and recovery efficiency of the mineral. For molybdenite with high oxidation rate, current flotation technology lacks an effective treatment method. Summary of the Invention

[0005] In view of the problems existing in the prior art, the present invention proposes a composite collector for flotation of high-oxidation-rate muddy molybdenite, aiming to improve the collection effect of high-oxidation-rate and muddy molybdenite based on the flotation collector.

[0006] The second object of the present invention is to provide a method for flotation of high-oxidation-rate muddy molybdenite using the composite collector of the present invention.

[0007] The oxidation rate and mudification degree of molybdenite will greatly affect its flotation collection effect. To address this problem, the present invention has conducted in-depth research and provides the following solutions:

[0008] A composite collector for flotation of high-oxidation-rate muddy molybdenite, comprising component A and component B;

[0009] The component A is at least one of silicone oil, paraffin oil, solvent oil, mineral oil, naphthenic oil, white oil, and switch oil;

[0010] The component B is at least one of Formula 1 and Formula 2;

[0011] Formula 1;

[0012] Formula 2;

[0013] In formula 1, R1 is a C1-C6 alkyl group; R2 is H, Na, K, NH4, a C1-C6 alkyl group, a substituted alkyl group, a C2-C6 olefin group, or a substituted olefin group;

[0014] In Formula 2, R3 and R4 are independently C1-C6 alkyl, substituted alkyl or substituted olefin;

[0015] The substituted alkyl group is a substituent with a substituent a on a C1~C6 alkyl group; the substituted olefin is a substituent with a substituent b on a vinyl group; the substituent a and the substituent b respectively include at least one of a C1~C6 alkoxy group, a C1~C6 alkylthio group, a phenyl group, a vinyl group, a halogen group, and a cyano group.

[0016] The innovative research of the present invention shows that the combination of component A and component B can achieve synergy, can adapt to the mineral characteristics of high-oxidation rate muddy molybdenite, and can effectively improve the flotation effect of difficult-to-select minerals. For example, a good capture effect can be obtained with low reagent dosage and mild conditions. In addition, the components of the present invention have excellent safety.

[0017] Preferably, Component A comprises one or a combination of silicone oil, paraffin oil, white oil, and switch oil; more preferably, paraffin oil. Studies have shown that the preferred combination of Component A and Component B further synergistically improves the agent's capture efficiency for oxidized molybdenite.

[0018] In the component B, R1 in the formula 1 is a C2-C6 alkyl group; R2 is a substituted alkyl group; wherein the substituent a in the substituted alkyl group includes at least one of a vinyl group, a phenyl group, and an alkylthio group.

[0019] In the formula 2, R3 is a C1-C6 alkyl group, and R4 is a cyanovinyl group or an allyl group.

[0020] In the present invention, the weight ratio of component A to component B is 1:0.15~0.5.

[0021] In the present invention, the component C is at least one of sec-octanol, cyclohexanol, benzyl alcohol, polyethylene glycol, polypropylene glycol, propylene glycol butyl ether, ethylene glycol butyl ether, triethoxybutane, aromatic ether alcohol, and α-phenylethanol.

[0022] Studies have shown that the combination of components A, B, and C can further enhance the synergy between the components and help further solve the difficult selection problems caused by high oxidation and mud.

[0023] In the present invention, the content of component C in the composite collector is below 10 wt.%, and can further be 5-10 wt.%.

[0024] The present invention also provides a method for flotation of high-oxidation-rate muddy molybdenite, wherein the high-oxidation-rate muddy molybdenite to be selected is subjected to flotation treatment in a flotation reagent to obtain a flotation molybdenum concentrate; wherein the flotation reagent contains the composite collector of the present invention.

[0025] The present invention studies show that the composite collector can adapt to the mineral characteristics of high oxidation rate and muddy molybdenite, and can improve the flotation effect of this type of refractory minerals.

[0026] In the present invention, the oxidation rate of the highly oxidized argillized molybdenite is above 10%, further above 30%, and even further between 35% and 65%. The flotation method of the present invention can be used for molybdenites of different oxidation rates, especially for highly oxidized molybdenites, achieving a more optimal low-reagent, mild, short-process, and high-performance flotation.

[0027] In the present invention, the Mo grade in the high-oxidation-rate muddy molybdenite is 0.04% to 0.20%.

[0028] In the present invention, in the flotation stage (referring to the roughing stage), the dosage of the composite collector is 50-500 g / t, preferably 70-150 g / t.

[0029] In the present invention, the pH of the pulp in the flotation stage may be 5-11, and further may be 7-9.

[0030] Beneficial effects

[0031] (1) The innovative research of the present invention shows that the combination of the components A and B can achieve synergy, can adapt to the mineral characteristics of high-oxidation-rate muddy molybdenite, and can effectively improve the flotation effect of difficult-to-separate minerals. On this basis, further combining the components A, B and C can further enhance the synergy of the components, which helps to further improve the flotation effect of high-oxidation-rate muddy molybdenite.

[0032] (2) Compared with conventional fuel oil collectors such as kerosene and diesel, the composite collector of the present invention can not only simplify the flotation process and reduce the amount of reagents used, but also improve the flotation effect due to the combined synergy between the components. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 The flotation flow chart of a molybdenum mine in Inner Mongolia provided in Example 1.

[0034] Figure 2 The flotation flow chart of a molybdenum mine in Shaanxi provided in Example 2.

[0035] Figure 3 The flotation flow chart of a molybdenum mine in Jiangxi provided in Example 4.

[0036] Figure 4 This is a flotation flow chart of a molybdenum mine in Hebei provided in Example 5. DETAILED DESCRIPTION

[0037] In the present invention, the dosage of the pharmaceutical agent refers to parts by weight. The specific dosage can be adjusted according to the application scale. For example, as an optional solution, 1 part by weight below can be understood as 1 g.

[0038] Example 1

[0039] Preparation of medicine:

[0040] Add 150 parts of 100# white oil (component A) to a 500mL reaction bottle, and add 40 parts of component B ( ) and 10 parts of 2-octanol (ingredient C), stirred at room temperature for 10 minutes to obtain a light yellow oily liquid. The product can be directly used as a composite collector for molybdenum ore flotation, code-named FM-11.

[0041] Flotation:

[0042] A large molybdenum mine in Inner Mongolia has a high oxidation rate of 60%. The main valuable metal mineral is molybdenite, and the main gangue minerals include quartz, chlorite, and mica. The Mo metal content in the raw ore is only 0.076%, the Fe content is 2.68%, the Cu content is 0.025%, the S content is 0.17%, and the SiO2 content is as high as 66.93%.

[0043] When the grinding fineness is -0.075 mm, accounting for 85%, the effects of various types of collectors on the indicators of molybdenum flotation coarse concentrate were investigated and compared. The test conditions, process and results of the collector types are shown in the attached Figure 1 and Table 1.

[0044]

[0045] The test results show that for ultra-low-grade molybdenite with ultra-high oxidation rate, when using traditional kerosene, diesel, and kerosene + diesel (mass ratio 1:1) mixed reagents as collectors, no good flotation index was achieved, and the molybdenum roughing metal recovery rate was less than 36%. However, when using FM-11 of the present invention as a collector, a molybdenum rough concentrate with a Mo recovery rate of 42.12% was obtained. The flotation recovery rate was 7.59 percentage points higher than that of conventional diesel, 11.51 percentage points higher than that of conventional kerosene, and 6.48 percentage points higher than that of a mixed collector of kerosene and diesel. If middlings were added, the Mo recovery rate could reach 50.76%, and the Mo grade in the tailings could be reduced to 0.04%, which is significantly better than traditional kerosene or diesel collectors. It can be seen that the composite collector FM-11 of the present invention has a strong collection ability for molybdenum ores with high oxidation rate, and can achieve good flotation effect at a lower dosage, while conventional collectors have weak collection ability for such ores.

[0046] Example 2

[0047] Preparation of medicine:

[0048] In a 150 mL reaction flask, 48 parts of component A (light paraffin oil) were added, and 9 parts of component B ( ) and 3 parts of component C (polyethylene glycol), stirred at room temperature for 15 minutes to obtain a yellow oily liquid. The product can be directly used as a molybdenum ore flotation collector, code-named FM-22.

[0049] A large molybdenum mine in Shaanxi Province has molybdenite, chalcopyrite, and pyrite as its main metal minerals. Molybdenite is severely oxidized, with an oxidation rate of 45.3%. Molybdenite is distributed as graphite-like flake and scale-like aggregates, impregnated in other gangues in the form of veins and scattered points, with a small amount passing through pyrite. The embedded particle size of molybdenite is generally medium-fine, making it a complex molybdenum polymetallic ore with an original Mo grade of 0.13%.

[0050] Under the condition that the grinding fineness is -0.074mm, accounting for about 60%, the effects of traditional diesel and the composite collector FM-22 of the present invention on the indicators of molybdenum flotation coarse concentrate were investigated and compared. The collector types, test conditions, process and results are shown in the attached Figure 2 and Table 2.

[0051] Comparative Example 1

[0052] Compared with Example 2, the only difference is that, in Component A and Component B, Component A is missing, and the missing Component A is replaced by an equal amount of Component B. Other operations and parameters are the same as in Example 2.

[0053] Comparative Example 2

[0054] Compared with Example 2, the only difference is that, in component A and component B, component B is missing, and the missing component B is replaced by an equal amount of component A. Other operations and parameters are the same as in Example 2.

[0055] Comparative Example 3

[0056] Compared with Example 2, the only difference is that equal amounts of diesel are used to replace component A and component B, and other operations and parameters are the same as those in Example 2.

[0057]

[0058] Flotation operation uses a single roughing process to obtain molybdenum rough concentrate and tailings. Test results show that when conventional diesel is used for roughing, the Mo grade in the rough concentrate is only 8.27%, and the Mo recovery rate is only 42.55%. However, when the composite collector FM-22 of the present invention is used instead of diesel, the rough concentrate can finally obtain excellent Mo grade of 19.28% and Mo recovery rate of 67.54%. Compared with the conventional diesel collector, the Mo grade in the rough concentrate after roughing is increased by 11.01 percentage points, and the Mo recovery rate is increased by 24.99 percentage points. Both the Mo grade and the Mo recovery rate in the rough concentrate are greatly improved.

[0059] In addition, it can be seen from Example 2 and Comparative Examples 1-2 that the combination of component A and component B described in the present invention can achieve synergy and further enhance the flotation ability of oxidized molybdenite.

[0060] It can be seen that the collector of the present invention has excellent flotation selectivity for this complex polymetallic molybdenum ore, while conventional diesel has weak collection ability for this type of ore.

[0061] Example 3

[0062] Compared with Example 2, the only difference is that component A is changed. The experimental groups are:

[0063] Group A: Component A is silicone oil.

[0064] Group B: Component A is solvent oil.

[0065] Other operations and parameters are the same as in Example 2.

[0066] The results were as follows: The flotation recovery rate of the coarse concentrate in group A was 50.78%.

[0067] The flotation recovery rate of the rough concentrate in Group B was 47.75%.

[0068] By comparing Examples 2 and 3, the paraffin oil component as component A, combined with component B, can obtain better synergy and achieve a good molybdenite collection effect.

[0069] Example 4

[0070] Preparation of the drug: Add 60 parts of mineral oil to a 250 mL reaction bottle, and add 30 parts of component B ( ) and 10 parts of propylene glycol butyl ether, stirred at room temperature for 15 minutes to obtain a light yellow oily liquid. The product can be directly used as a flotation collector for molybdenum ore, code-named FM-33.

[0071] A large molybdenum mine in Jiangxi Province has an ore Mo grade of 0.06% and an S grade of 1.52%. The main metal minerals in the ore are molybdenite and pyrite, and the main gangue minerals are quartz, feldspar, biotite, muscovite, etc., followed by chlorite, sericite and other minerals. The oxidation rate of molybdenite is 15%.

[0072] Under the condition that the grinding fineness is -0.074mm, accounting for about 70%, the effects of traditional kerosene and the composite collector FM-33 of the present invention on the indicators of molybdenum flotation coarse concentrate were investigated and compared. The test process and results of the collector types are shown in the attached Figure 3 As shown in Table 3, the flotation operation adopts secondary roughing to obtain molybdenum rough concentrate and tailings. The results show that the Mo grade in the rough concentrate after roughing with traditional kerosene (200+100g / t) is 5.51%, and the Mo recovery rate is 82.86%. However, after using the composite collector FM-22 (150+75g / t) of the present invention instead of kerosene, the rough concentrate can finally obtain excellent indicators of Mo grade of 6.05% and Mo recovery rate of 88.78%. Compared with the traditional kerosene collector, the Mo grade in the rough concentrate after roughing is increased by 0.54 percentage points, and the Mo recovery rate is increased by 5.92 percentage points. The molybdenum recovery rate in the rough concentrate is greatly improved. In addition, the total dosage of the composite collector of the present invention is significantly lower than that of traditional kerosene, which is conducive to reducing production costs.

[0073]

[0074] Example 5

[0075] Preparation of reagent: Add 420 parts of low temperature switch oil to a 1000mL reaction bottle, add 150 parts of component B (structure ) and 50 parts of α-phenylethanol, stirred at room temperature for 10 minutes to obtain a light yellow oily liquid. The product can be directly used as a flotation collector for molybdenum ore, code-named FM-44.

[0076] A molybdenum ore in Hebei has a molybdenum oxidation rate of 25%. Molybdenum mainly exists in the form of molybdenite. The Mo grade in the original ore is 0.14%, the S grade is 0.63%, and the Cu grade is 0.016%. The most recoverable mineral is single molybdenite, and the main gangue minerals are quartz, feldspar, mica and chlorite.

[0077] Under the condition of grinding fineness of -0.074mm accounting for about 84%, the effects of traditional diesel, kerosene and the composite collector FM-44 of the present invention on the indicators of molybdenum flotation coarse concentrate were investigated and compared. The test conditions, process and results of the collector types are shown in the attached Figure 4 As shown in Table 4, the flotation operation uses a primary roughing process to obtain molybdenum rough concentrate and tailings.

[0078]

[0079] Test results show that when conventional diesel is used for roughing, the Mo grade in the rough concentrate after roughing is only 8.27%, and the Mo recovery rate is only 42.55%. However, when the composite collector FM-44 of the present invention is used instead of kerosene and diesel, the rough concentrate can be roughed to obtain excellent indicators of a Mo grade of 1.94% and a Mo recovery rate of 91.51%. Compared with conventional kerosene, the Mo recovery rate in the rough concentrate after roughing is increased by 13.81 percentage points, and compared with conventional diesel, the Mo recovery rate in the rough concentrate is increased by 11.16 percentage points. The Mo recovery rate in the rough concentrate is greatly improved, and the molybdenum grade is also slightly improved. Moreover, after using the collector of the present invention, the amount of the foaming agent 2# oil used is reduced, which is beneficial to reducing the cost of the reagent.

Claims

1. A composite collector for flotation of high oxidation rate muddy molybdenite, characterized in that: including component A, component B and component C; The component A is at least one of silicone oil, paraffin oil, solvent oil, naphthenic oil, and switch oil; The component B is at least one of Formula 1 and Formula 2; Formula 1 Formula 2 In formula 1, R1 is a C1-C6 alkyl group; R2 is H, Na, K, NH4, a C1-C6 alkyl group, a C1-C6 substituted alkyl group, a C2-C6 olefin, or a C2-C6 substituted olefin; In Formula 2, R3 and R4 are independently C1-C6 alkyl, substituted alkyl or substituted olefin; The substituted alkyl group is a substituent with a substituent a on a C1~C6 alkyl group; The substituted olefin is a substituent with a substituent b on the vinyl group; The substituent a and the substituent b respectively include at least one of a C1-C6 alkoxy group, a C1-C6 alkylthio group, a phenyl group, a vinyl group, a halogen group, and a cyano group; The component C is at least one of octanol, cyclohexanol, benzyl alcohol, polyethylene glycol, polypropylene glycol, propylene glycol butyl ether, ethylene glycol butyl ether, aromatic ether alcohol, and α-phenylethanol; The weight ratio of component A to component B is 1:0.15~0.5; The content of component C in the composite collector is below 10 wt.%; The oxidation rate of high-oxidation-rate muddy molybdenite is above 10%.

2. The composite collector for flotation of high oxidation rate muddy molybdenite according to claim 1, characterized in that: The component A includes one of silicone oil, paraffin oil, switch oil, or a combination thereof.

3. The composite collector for flotation of high oxidation rate muddy molybdenite according to claim 1, characterized in that: In the component B, R1 in the formula 1 is a C2-C6 alkyl group; R2 is a C1-C6 substituted alkyl group; wherein the substituent a in the substituted alkyl group includes at least one of a vinyl group, a phenyl group, and an alkylthio group; In the formula 2, R3 is a C1-C6 alkyl group, and R4 is a cyanovinyl group or an allyl group.

4. The composite collector for flotation of high oxidation rate muddy molybdenite according to claim 1, characterized in that: The content of component C in the composite collector is 5-10 wt.%.

5. A method for flotation of high oxidation rate muddy molybdenite, characterized in that: The high-oxidation-rate muddy molybdenite to be selected is subjected to flotation treatment in a flotation agent to obtain a flotation molybdenum concentrate; wherein the flotation agent contains the composite collector according to any one of claims 1 to 4.

6. The method for flotation of high oxidation rate muddy molybdenite according to claim 5, characterized in that: The oxidation rate of the high-oxidation-rate muddy molybdenite is above 30%.

7. The method for flotation of high oxidation rate muddy molybdenite according to claim 5, characterized in that: The Mo grade in the high-oxidation-rate muddy molybdenite is 0.04%-0.20%.

8. The method for flotation of high oxidation rate muddy molybdenite according to any one of claims 5 to 7, characterized in that: During the flotation stage, the dosage of the composite collector is 50~500g / t.

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