Composite collecting agent and method for flotation of argillized molybdenite with high oxidation rate

Abstract

The invention belongs to the field of molybdenum ore flotation, and particularly relates to a composite collecting agent and method for flotation of high-oxidation-rate argillization molybdenite, and the composite collecting agent comprises a component A and a component B; the component A is at least one of silicone oil, paraffin oil, solvent oil, mineral oil, naphthenic oil, white oil and switch oil; the component B is at least one of a formula 1 (# imgabs 0 #) and a formula 2 (# imgabs 1 #). Innovative research shows that the composition A and the composition B are combined, so that the composition A and the composition B can be synergistically matched with the mineral characteristics of high-oxidation-rate argillization molybdenite, the flotation effect of refractory minerals can be effectively improved, and in addition, the composition of the composite collecting agent has 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 high-oxidation-rate, highly-mudified refractory molybdenite. Background Art

[0002] Molybdenum minerals are often embedded in fine particles, 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, and the main components of the collector are light diesel, kerosene, and condensed aromatic hydrocarbons. The Chinese patent document with publication number CN115569738A discloses a new type of molybdenum ore collector and its preparation and application, and 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 unmagnetized 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. Mechanism and application of composite hydrocarbon oil in flotation enhancement of molybdenite of different particle sizes [J]. The Chinese Journal of Nonferrous Metals, 2023, 33(3): 912-921.) used a composite hydrocarbon oil mainly composed of kerosene to enhance the flotation of molybdenite of different particle sizes. The study found that the composite hydrocarbon oil can increase the hydrophobicity of coarse and fine minerals and enhance the flotation effect of molybdenite.

[0003] With the increasing demand for molybdenum resources, the scale of mining has gradually increased, and molybdenum resources have gradually shown a trend of "poor, fine, and mixed". The slurry environment has become more complex, and the difficulty of mineral processing and recovery has increased. The most commonly used collectors for molybdenite are kerosene and diesel, both of which are fuel oils with low flash points. They are both flammable and dangerous chemicals, and there are great safety hazards in transportation and use. Therefore, it is of great significance to find green, safe and environmentally friendly molybdenum collectors to replace kerosene and diesel, which is also the development trend of molybdenum flotation collectors in the future.

[0004] In addition, the main mineral configuration of molybdenite is MoS 2 Its oxidation rate and mudification degree greatly affect the capture and recovery efficiency of minerals. For molybdenite with high oxidation rate, the current flotation technology lacks effective treatment methods. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides a composite collector for flotation of highly oxidized and slime molybdenite, aiming to improve the flotation effect of highly oxidized and slime molybdenite based on the said flotation collector.

[0006] The second object of the present invention is to provide a method for flotation of highly oxidized and slime molybdenite using the composite collector of the present invention.

[0007] The oxidation rate and slime degree of molybdenite will greatly affect its flotation effect. In view of this problem, through in-depth research, the present invention provides the following solutions:

[0008] A composite collector for flotation of highly oxidized and slime molybdenite, comprising component A and component B;

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

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

[0011] Formula 1;

[0012] Formula 2;

[0013] In formula 1, the said R 1 is an alkyl group of C 1 ~C 6 ; the said R 2 is H, Na, K, NH 4 , an alkyl group of C 1 ~C 6 , a substituted alkyl group, an alkene of C 2 ~C 6 or a substituted alkene; In formula 2, the said R 3 , R 4 are each independently an alkyl group of C 1 ~C 6 , a substituted alkyl group or a substituted alkene; The said substituted alkyl group is a substituent with substituent a on an alkyl group of C 1 ~C 6 ; the said substituted alkene is a substituent with substituent b on a vinyl group; the said substituent a and substituent b each include at least one of an alkoxy group of C 1 ~C 6 , an alkylthio group of C 1 ~C 6 , phenyl, vinyl, halogen, and cyano.

[0014] The innovative research of the present invention shows that the combination of the described Component A and Component B can achieve synergy, adapt to the mineral characteristics of highly oxidized and slime molybdenite ores, and can effectively improve the flotation effect of refractory minerals. For example, good collection effects can be obtained under low reagent dosages and mild conditions. In addition, the components of the present invention have excellent safety.

[0015] Preferably, the described Component A includes one or a combination of silicone oil, paraffin oil, white oil, and switch oil; more preferably paraffin oil. Research shows that the combination of the preferred Component A and Component B helps to further synergistically improve the collection effect of the reagent on oxidized molybdenite ores.

[0016] In the described Component B, R in Formula 1 1 is an alkyl group of C 2 ~C 6 ; the R 2 is a substituted alkyl group; among them, the substituent a in the substituted alkyl group includes at least one of vinyl, phenyl, and alkylthio groups.

[0017] In Formula 2, R 3 is an alkyl group of C 1 ~C 6 , R 4 is cyano vinyl or allyl.

[0018] In the present invention, the weight ratio of the described Component A to Component B is 1:0.15 to 0.5.

[0019] In the present invention, the described 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, aryl ether alcohol, and α-phenylethyl alcohol.

[0020] Research shows that the combination of Component A, Component B, and Component C can further strengthen the synergy between the components and help to further solve the refractory problems caused by high oxidation and slime.

[0021] In the present invention, the content of the described Component C in the composite collector is below 10 wt.%, and further can be 5 to 10 wt.%.

[0022] The present invention also provides a method for flotation of highly oxidized and slime molybdenite ores. The to-be-selected highly oxidized and slime molybdenite ores are subjected to flotation treatment in flotation reagents to obtain flotation molybdenum concentrate; among them, the flotation reagents contain the composite collector described in the present invention.

[0023] The research of the present invention shows that the described composite collector can adapt to the mineral characteristics of highly oxidized and slime molybdenite ores and can improve the flotation effect of such refractory minerals.

[0024] In the present invention, in the highly oxidized argillized molybdenite, the oxidation rate is above 10%; further, it can be above 30%, and more preferably 35 - 65%. The flotation method of the present invention can be applied to molybdenite with different oxidation rates, especially for highly oxidized argillized molybdenite, and can exhibit better low - reagent, mild, and short - process high - flotation effects.

[0025] In the present invention, the Mo grade in the highly oxidized argillized molybdenite is 0.04% - 0.20%.

[0026] 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.

[0027] In the present invention, the pH of the pulp in the flotation stage can be 5 - 11, and further can be 7 - 9.

[0028] Beneficial Effects

[0029] (1) Innovative research in the present invention shows that the combination of Component A and Component B can achieve synergy, adapt to the mineral characteristics of highly oxidized argillized molybdenite, and can effectively improve the flotation effect of refractory minerals. On this basis, further combining Component A, Component B, and Component C can further strengthen the component synergy, which helps to further improve the flotation effect of highly oxidized argillized molybdenite.

[0030] (2) Compared with conventional fuel - oil collectors such as kerosene and diesel, the composite collector of the present invention, due to the combined synergy between components, can not only simplify the flotation process, reduce the dosage of reagents, but also improve the flotation effect. Brief Description of the Drawings

[0031] Figure 1 The flotation flow chart of a molybdenum mine in Inner Mongolia provided for Example 1.

[0032] Figure 2 The flotation flow chart of a molybdenum mine in Shaanxi provided for Example 2.

[0033] Figure 3 The flotation flow chart of a molybdenum mine in Jiangxi provided for Example 4.

[0034] Figure 4 The flotation flow chart of a molybdenum mine in Hebei provided for Example 5. Detailed Embodiments

[0035] In the present invention, the dosage parts of the reagents all refer to weight parts. The specific dosage can be adjusted according to the application scale. For example, as an optional scheme, 1 weight part below can be understood as 1 g.

[0036] Example 1

[0037] Pharmaceutical preparation:

[0038] Add 150 parts of 100# white oil (Component A) to a 500 mL reaction flask, and then add 40 parts of Component B ( ), and 10 parts of sec-octanol (Component C) under stirring. Stir 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, with the code FM-11.

[0039] Flotation:

[0040] A large molybdenum mine in Inner Mongolia is an ore with a high oxidation rate, up to 60%. The main valuable metal mineral is molybdenite, and the gangue minerals mainly include quartz, chlorite, mica, etc. The content of Mo metal 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 SiO 2 content is as high as 66.93%.

[0041] At a grinding fineness of -0.075 mm accounting for 85%, the effects of various different types of collectors on the indexes of molybdenum flotation rough concentrate were investigated and compared. The types of collectors, test conditions, processes and results are shown in Appendix Figure 1 and Table 1 respectively.

[0042]

[0043] It can be seen from the test results that for ultra-low-grade molybdenite with an ultra-high oxidation rate, when using traditional kerosene, diesel, and a mixture of kerosene + diesel (mass ratio 1:1) as collectors, good flotation indexes cannot be obtained, and the metal recovery rate of molybdenum roughing is lower than 36%; while when using FM-11 of the present invention as the collector, molybdenum rough concentrate with a Mo recovery rate of 42.12% can be obtained. The flotation recovery rate is 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 the mixed collector of kerosene and diesel. If the middlings are added, the Mo recovery rate can reach 50.76%, and the Mo grade in the tailings can be reduced to 0.04%, which is significantly better than traditional kerosene or diesel collectors. Thus, it can be seen that the composite collector FM-11 of the present invention has a strong collecting ability for molybdenum ore with a high oxidation rate, and can obtain good flotation effects even at a lower dosage, while conventional collectors have a weak collecting ability for such ores.

[0044] Example 2

[0045] Pharmaceutical preparation:

[0046] Add 48 parts of Component A (light paraffin oil) to a 150 mL reaction flask, and then add 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 collector for molybdenum ore flotation, with the code FM-22.

[0047] In a large molybdenum mine in Shaanxi, the main metal minerals are molybdenite, chalcopyrite, pyrite, etc. The molybdenite is severely oxidized, with an oxidation rate of 45.3%. Molybdenite is distributed in the form of sheet-like and scaly aggregates similar to graphite, occurring as veins and scattered dots in other gangues, and a small amount passes through pyrite. The disseminated particle size of molybdenite is generally medium-fine grained, which is a complex molybdenum polymetallic ore, and the Mo grade of the raw ore is 0.13%.

[0048] Under the condition that the grinding fineness is about 60% passing -0.074mm, the effects of the traditional diesel oil and the composite collector FM-22 of the present invention on the molybdenum flotation rougher concentrate indexes were investigated and compared. The test conditions, processes and results of the collector types are shown in Appendix Figure 2 and Table 2.

[0049] Comparative Example 1

[0050] Compared with Example 2, the difference is only that in Components A and B, Component A is missing, and the missing Component A is replaced by an equal amount of Component B, and other operations and parameters are the same as in Example 2.

[0051] Comparative Example 2

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

[0053] Comparative Example 3 Compared with Example 2, the difference is only that an equal amount of diesel oil is used to replace Components A and B, and other operations and parameters are the same as in Example 2.

[0054]

[0055] In the flotation operation, one roughing is adopted to obtain molybdenum rougher concentrate and tailings. The test results show that when the traditional diesel oil is used, the Mo grade in the rougher concentrate after roughing is only 8.27%, and the Mo recovery rate is only 42.55%; while when the composite collector FM-22 of the present invention is used to replace diesel oil, the final rougher concentrate can obtain excellent indexes of Mo grade of 19.28% and Mo recovery rate of 67.54%; compared with the traditional diesel oil collector, the Mo grade in the rougher concentrate after roughing is increased by 11.01 percentage points, and the Mo recovery rate is increased by 24.99 percentage points, and both the Mo grade and recovery rate in the rougher concentrate are greatly improved.

[0056] In addition, it can also be known from Example 2 and Comparative Examples 1-2 that by combining Component A and Component B described in the present invention, synergy can be achieved to further enhance the flotation ability of oxidized molybdenite.

[0057] It can be seen from this that the collector of the present invention has excellent flotation selectivity for this complex polymetallic molybdenum ore, while the conventional diesel oil has weak collecting ability for such ores.

[0058] Example 3

[0059] Compared with Example 2, the difference is only that Component A is changed. The experimental groups are as follows:

[0060] Group A: Component A is silicone oil.

[0061] Group B: Component A is solvent oil.

[0062] Other operations and parameters are the same as those in Example 2.

[0063] The results are as follows: The flotation recovery rate of the rough concentrate in Group A is 50.78%.

[0064] The flotation recovery rate of the rough concentrate in Group B is 47.75%.

[0065] By comparing Example 2 and Example 3, when the paraffin oil component is used as Component A and combined with Component B, better synergy can be obtained, and good collecting effect of molybdenite can be achieved.

[0066] Example 4

[0067] Agent preparation: Add 60 parts of mineral oil to a 250 mL reaction flask, and add 30 parts of Component B ( ) and 10 parts of propylene glycol monobutyl ether under stirring. Stir at room temperature for 15 minutes to obtain a light yellow oily liquid. The product can be directly used as a collector for molybdenum ore flotation, coded as FM-33.

[0068] For a large molybdenum mine in Jiangxi, the Mo grade in the ore is 0.06% and the S grade is 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 minerals such as chlorite and sericite. The oxidation rate of molybdenite is 15%.

[0069] Under the condition that the grinding fineness is about 70% of -0.074 mm, the effects of the traditional kerosene and the composite collector FM-33 of the present invention on the indexes of molybdenum flotation rough concentrate were investigated and compared. The test process and results of the collector types are shown in the appendix respectively Figure 3As shown in Table 3, in the flotation operation, two-stage roughing was combined to obtain molybdenum rougher concentrate and tailings. The results showed that after roughing with traditional kerosene (200 + 100 g / t), the Mo grade in the rougher concentrate was 5.51% and the Mo recovery rate was 82.86%. After replacing kerosene with the composite collector FM-22 (150 + 75 g / t) of the present invention, the rougher concentrate finally obtained excellent indexes of Mo grade of 6.05% and Mo recovery rate of 88.78%. Compared with the traditional kerosene collector, the Mo grade in the rougher concentrate after roughing increased by 0.54 percentage points, and the Mo recovery rate increased by 5.92 percentage points. The molybdenum recovery rate in the rougher concentrate increased significantly, and the total dosage of the composite collector of the present invention was significantly lower than that of traditional kerosene, which was beneficial to reducing production costs.

[0070]

[0071] Example 5

[0072] Agent preparation: Add 420 parts of low-temperature switch oil to a 1000 mL reaction flask, and add 150 parts of Component B (with the structure of ) and 50 parts of α-phenylethyl alcohol under stirring at room temperature. Stir for 10 minutes to obtain a light yellow oily liquid. The product can be directly used as a collector for molybdenum ore flotation, with the code FM-44.

[0073] For a certain molybdenum ore in Hebei, the molybdenum oxidation rate is 25%. Molybdenum mainly exists in the form of molybdenite. The Mo grade in the raw 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.

[0074] Under the condition that the grinding fineness is about 84% passing -0.074 mm, the effects of traditional diesel oil, kerosene and the composite collector FM-44 of the present invention on the indexes of molybdenum flotation rougher concentrate were investigated and compared. The test conditions, process and results of the collector types are shown in Appendix Figure 4 and Table 4. In the flotation operation, one-stage roughing was carried out to obtain molybdenum rougher concentrate and tailings.

[0075]

[0076] The test results show that when using traditional diesel oil, the Mo grade in the rougher concentrate after rough selection is only 8.27%, and the Mo recovery rate is only 42.55%; while after using the composite collector FM-44 of the present invention to replace kerosene and diesel oil, the rougher concentrate in rough selection can finally obtain excellent indexes of Mo grade of 1.94% and Mo recovery rate of 91.51%; compared with traditional kerosene, the Mo recovery rate in the rougher concentrate after rough selection has increased by 13.81 percentage points, and compared with traditional diesel oil, the Mo recovery rate in the rougher concentrate has increased by 11.16 percentage points. The Mo recovery rate in the rougher concentrate has increased significantly, and the Mo grade has also increased slightly; and after using the collector of the present invention, the dosage of the foaming agent No. 2 oil has been reduced, which is beneficial to reducing the reagent cost.

Claims

1. A composite collector for flotation of high oxidation rate muddy molybdenite, characterized in that: comprising component A and component B; The component A is at least one of silicone oil, paraffin oil, solvent oil, mineral oil, naphthenic oil, white 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 substituted alkyl group, a C2-C6 olefin group, or a substituted olefin group; 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 having 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.

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, white 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 substituted alkyl group; wherein the substituent a in the substituted alkyl group includes at least one of vinyl, phenyl, and alkylthio; 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 weight ratio of component A to component B is 1:0.15-0.

5.

5. The composite collector for flotation of high oxidation rate muddy molybdenite according to any one of claims 1 to 4, characterized in that: The invention also comprises component C, wherein the component C is at least one of octanol, cyclohexanol, benzyl alcohol, polyethylene glycol, polypropylene glycol, propylene glycol butyl ether, ethylene glycol butyl ether, triethoxybutane, aromatic ether alcohol and α-phenylethanol.

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

7. 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 6.

8. The method for flotation of high oxidation rate muddy molybdenite according to claim 7, characterized in that: The oxidation rate of the high-oxidation-rate muddy molybdenite is above 10%.

9. The method for flotation of high oxidation rate muddy molybdenite according to claim 8, characterized in that: The Mo grade in the high oxidation rate muddy molybdenite is 0.04%-0.20%.

10. The method for flotation of high oxidation rate muddy molybdenite according to any one of claims 7 to 9, characterized in that: In the flotation stage, the dosage of the composite collector is 50~500g / t.

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