A novel fine molybdenite combined collector and application thereof

Abstract

The application discloses a novel fine molybdenite combined collector and application thereof. The combined collector is composed of a main collector coconut oil, a secondary collector palm oil and an emulsifier methyl naphthalene, wherein the mass ratio of the coconut oil, the palm oil and the methyl naphthalene is (9-16):(3.8-10):1. The combined collector can completely replace kerosene and diesel oil, which are molybdenum ore collectors in traditional copper-molybdenum separation flotation, and the effect is obviously better than that of kerosene. The combined collector has strong dispersion performance in ore pulp and good collecting effect, can improve the grade of molybdenum concentrate and the recovery rate of molybdenum concentrate, and has the characteristics of simple formula, environmental friendliness and no peculiar smell. The application can improve the peculiar smell of the working environment, obtain better comprehensive recovery effect of molybdenum ore in the actual production process, and create good economic benefits and social benefits.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flotation, and particularly relates to a novel combined collector for micro-fine molybdenite and application thereof. BACKGROUND

[0002] Molybdenum is an important strategic resource, and is widely used in steel, chemical, electrical and military industries due to its good properties such as high temperature resistance, corrosion resistance, heat conduction and electrical conductivity. Most of the molybdenum resources in the world come from molybdenum sulfide ore, which is often associated with copper sulfide ore. Flotation is an important method for separating chalcopyrite from molybdenite.

[0003] Molybdenite has good natural floatability, and is difficult to activate once it is inhibited, so the method of inhibiting copper and floating molybdenum is often used in the process of copper-molybdenum separation. By adding hydrocarbon oil flotation reagent, the effective recovery of molybdenite is realized. Among them, kerosene is the main collector for floating molybdenum in the industrial separation of copper and molybdenum. With the continuous development and utilization of molybdenum resources, the embedded particle size of molybdenite is getting finer and finer, and the grade is getting lower and lower. As a traditional collector for molybdenite, kerosene has been difficult to meet the current production needs. At the same time, industrial kerosene has a strong odor and can easily harm the human body and the environment, so the control of kerosene is becoming more and more strict, and the procurement will be more difficult. Diesel is a collector that can replace kerosene, but its freezing point is high, its dispersion in water is poor, and its selectivity is not high, which greatly affects the concentrate quality.

[0004] Emulsified hydrocarbon oil and magnetized hydrocarbon oil are two methods to improve the water dispersion of hydrocarbon oil. The emulsifier used in emulsified hydrocarbon oil is mostly octoxin, which is expensive. Magnetized hydrocarbon oil also has the problem of difficult long-term preservation. SUMMARY

[0005] One of the purposes of the present application is to provide a novel micro-fine molybdenite combined collector with good collecting effect and environmental friendliness.

[0006] The second purpose of the present application is to provide an application of the combined collector.

[0007] To achieve the above-mentioned purposes, the present application provides the following technical solutions:

[0008] The novel micro-fine molybdenite combined collector provided by the present application is composed of main collector coconut oil, auxiliary collector palm oil and emulsifier methyl naphthalene, and the mass ratio of the coconut oil, palm oil and methyl naphthalene is (9-16):(3.8-10):1.

[0009] Preferably, the mass ratio of the coconut oil, palm oil and methyl naphthalene is 15.2:3.8:1.

[0010] The main components of the combined collector are all environmentally friendly bio-oil, which can effectively improve the recovery rate of low-grade molybdenum minerals, and at the same time, the grade of molybdenum concentrate reaches the index requirements. The combined collector is a new type of molybdenum ore collector which can completely replace kerosene in industrial production. The combined collector has the characteristics of simple formula, easy storage, environmental friendliness, no special smell, etc.

[0011] The research of the application finds that the combined collector has excellent flotation performance in the field of mineral flotation.

[0012] The application also provides an application of the combined collector in the flotation of molybdenite in copper-molybdenum mixed concentrate.

[0013] Preferably, the flotation slurry environment suitable for the combined collector is pH 7-12.

[0014] Preferably, the molybdenum grade in the copper-molybdenum mixed concentrate is 0.3%-0.7%.

[0015] The flotation method can adopt the existing conventional method.

[0016] Preferably, the application of the combined collector in the flotation of molybdenite in copper-molybdenum mixed concentrate comprises the following steps:

[0017] a) adding the copper-molybdenum mixed concentrate prepared into a slurry into a flotation tank;

[0018] b) adding an inhibitor, water glass and the combined collector into the slurry in sequence, stirring for 2-5 min, performing roughing, and obtaining a rough concentrate and a rough tailing.

[0019] Preferably, the inhibitor can be a commonly used agent with inhibitory performance in the industry, and no special inhibitor is needed, for example, one or more of sodium sulfide, sodium hydrosulfide and sodium mercaptoacetate.

[0020] Preferably, before the combined collector is added into the slurry, the coconut oil, the palm oil, the methylnaphthalene and the water are mixed uniformly to obtain a mixture, and then the mixture is fully stirred and dispersed in a stirrer before being added into the slurry.

[0021] Preferably, the stirring and dispersing conditions are that the rotating speed is 1000-1500 r / min, and the stirring time is 10-20 min.

[0022] Specifically, the application of the combined collector in the flotation of molybdenite in copper-molybdenum mixed concentrate comprises the following steps:

[0023] a) adding the copper-molybdenum mixed concentrate prepared into a slurry into a flotation tank;

[0024] b) After adding sodium sulfide and sodium mercaptoacetate into the ore pulp, stirring for 2-5 min; then adding water glass, stirring for 2-5 min; then adding the combined collector, stirring for 2-5 min, and roughing for 1-2 min, the roughing time being 5-10 min; after the flotation ends, obtaining the rough concentrate and the rough tailings.

[0025] The application of the combined collector in the flotation of molybdenite in copper-molybdenum bulk concentrate includes the following steps:

[0026] 1) After preparing the copper-molybdenum bulk concentrate into ore pulp, adding the depressant, water glass and the combined collector into the ore pulp in sequence, roughing to obtain the rough concentrate and the tailings;

[0027] 2) Carrying out at least 4 times of cleaning on the rough concentrate to obtain the molybdenite concentrate; the cleaning process includes adding the depressant, water glass and the combined collector in sequence each time, stirring for 2-5 min to carry out the flotation.

[0028] The application will be further explained as follows:

[0029] The combined collector has good compatibility among the components under suitable ratio and dosage, can realize the accurate separation of molybdenite and chalcopyrite, and can ensure the recovery rate of the target mineral. The main principle lies in that:

[0030] 1. Molybdenite has a layered crystal structure, which is composed of a single sheet of molybdenum atoms sandwiched between two sheets of sulfur atoms. Strong covalent bonds act within the S-Mo-S layers, while only weak van der Waals forces act between adjacent S-S layers. Therefore, the molybdenite particles exhibit two types of surfaces: faces and edges. The breakage of van der Waals forces between faces makes molybdenite particles naturally floatable. However, due to the significant influence of the face / edge width-height ratio on the hydrophobicity of the molybdenite surface, its natural floatability decreases with decreasing particle size. Molybdenite coarse particles have a high face / edge length-width ratio, and have excellent natural floatability. Molybdenite fine particles have a small length-diameter ratio and small mass, so they exhibit poor floatability and flotation kinetics. The addition of neutral oils such as coconut oil and palm oil can improve the floatability of molybdenite.

[0031] 2. Increasing the molecular weight of the main components in the neutral oil is beneficial to improving the recovery rate of molybdenite, but too large molecular weight will lead to poor molecular fluidity, making it difficult to transfer to the surface of molybdenite, which is not conducive to the contact between neutral oil molecules and fine molybdenite particles. At the same time, aliphatic groups can increase the adhesion strength of oil to the surface of molybdenite more than aromatic groups, and have higher stability. The coconut oil and palm oil used in the application are common neutral oils, and the main components of both are saturated aliphatic groups with appropriate carbon chain length.

[0032] 3、Methyl naphthalene is used as an emulsifier in molybdenite flotation, and its surface energy is similar to that of molybdenite, so it can be adsorbed on the surface of molybdenite according to the principle of similar dissolves similar. Adding methyl naphthalene can improve the dispersion performance of neutral oil in water to some extent, and can also adjust the fluidity of neutral oil molecules and increase the contact ability with the surface of molybdenite.

[0033] The present application uses coconut oil as the main collector, palm oil as the auxiliary collector, and methyl naphthalene to emulsify the hydrocarbon oil, thereby further improving the contact performance of the combined collector with molybdenite molecules. The main components of the combined collector, coconut oil and palm oil, are environmentally friendly bio-oil, have no special odor, are harmless to the human body and environment, are simple and widely available, have good selection effect and dispersion effect, can completely replace kerosene in the process of high alkaline fine particle copper-molybdenum separation flotation molybdenum, can improve the grade of molybdenite concentrate obtained by selection and ensure the recovery rate, and has important significance for improving the recycling of molybdenum resources. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The process flow chart of molybdenum ore flotation for the present application comparative examples 1-5 and comparative example 7, and examples 1-4 is shown.

[0035] Figure 2 The process flow chart of molybdenum ore flotation for the present application example 5 and comparative example 6 is shown. DETAILED DESCRIPTION

[0036] In order to make the technical problems, technical solutions and advantages of the present application clearer, specific embodiments will be described in detail below, but the protection scope of the present application is not limited to the following specific embodiments.

[0037] Unless otherwise defined, all professional terms used herein have the same meaning as understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present application.

[0038] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0039] Comparative example 1

[0040] The process steps for obtaining copper concentrate and molybdenum concentrate by copper-molybdenum separation are as follows:

[0041] The depressant and the single collector are prepared respectively. The depressant is composed of the following components in mass fraction: 2 parts of sodium sulfide and 1 part of sodium mercaptoacetate. The single collectors are coconut oil, palm oil, linseed oil, liquid paraffin and kerosene respectively. Before the collector is added to the ore pulp, it is mixed with water, stirred for not less than 10 minutes, and then added to the ore pulp.

[0042] Test conditions: The test ore sample molybdenum ore is the copper-molybdenum mixed concentrate ore pulp of a certain concentrator, the grade of the raw ore is 0.3%, the grinding fineness is 85%-90% of -0.043 μm, and the pulp pH is 12. According to the process Figure 1 , the separation is carried out, the dosage of the depressant is 4.66 kg / t of sodium sulfide and 2.33 kg / t of sodium mercaptoacetate, and the flotation time is 8 minutes.

[0043] After the flotation is completed, the flotation products are filtered, dried, weighed, sampled and sent for inspection. The grade, calculated yield and recovery rate are obtained. The specific results are shown in Table 1.

[0044] Table 1: Flotation results of single collector

[0045]

[0046] From the single flotation reagent type test, it is known that when single linseed oil, liquid paraffin, coconut oil and palm oil are used as the flotation collector, the grade and recovery rate of the molybdenum rough concentrate obtained by flotation are not as high as when traditional kerosene is used as the collector. It is proved that single collectors cannot achieve ideal flotation effect. Among them, except for kerosene, the recovery rate is the highest when palm oil is used as the collector. When coconut oil is used as the collector, the flotation yield, molybdenum rough concentrate grade and recovery rate are the lowest, because the solidification point of single coconut oil is high, and it is solid at room temperature (25°C), and its dispersion performance in the ore pulp is the worst.

[0047] Example 1

[0048] The process steps for copper-molybdenum separation to obtain copper concentrate and molybdenum concentrate are as follows:

[0049] The depressant and the combined collector are prepared respectively. The depressant is composed of the following components in mass fraction: 2 parts of sodium sulfide and 1 part of sodium mercaptoacetate. The combined collector is composed of coconut oil, palm oil and methyl naphthalene in a mass ratio of 50:50:5. Before the combined collector is added to the ore pulp, coconut oil, palm oil and methyl naphthalene are mixed with water, stirred for not less than 10 minutes, and then added to the ore pulp.

[0050] Test conditions: The test ore sample molybdenum ore is the copper-molybdenum mixed concentrate ore pulp of a certain concentrator, the molybdenum content of the raw ore is 0.5-0.6%, the grinding fineness is 85%-90% of -0.043 μm, and the pulp pH is 12. According to the process Figure 1The process was selected, and the amount of inhibitor was 4.67 kg / t and 2.33 kg / t of sodium sulfide and sodium mercaptoacetate, respectively, and the flotation time was 5 min.

[0051] After the completion of the flotation, the flotation products were filtered, dried, weighed, sampled, and sent for inspection. The grade, calculated yield, and recovery rate were obtained. The specific flotation results are shown in Table 2.

[0052] Table 2 Test results of different collector combinations

[0053]

[0054] Comparative Example 2

[0055] The difference between this comparative example and Example 1 is only that the composition of the main collector and the auxiliary collector in the combined collector is different (see Table 2 for details), and the other conditions are the same. The flotation results are shown in Table 2.

[0056] Comparative Example 3

[0057] The difference between this comparative example and Example 1 is only that the collector is kerosene, and the other conditions are the same. The flotation results are shown in Table 2.

[0058] From the results in Table 2, it can be seen that when other conditions remain unchanged, changing only the types of main collector and auxiliary collector can achieve different flotation effects. In Comparative Example 2, the grade and recovery rate of the molybdenum rough concentrate obtained by flotation are lower than those of Example 1. And the grade of molybdenum rough concentrate obtained by flotation in Example 1 is increased by 0.083% compared with kerosene, the yield is increased by 0.59%, the recovery rate is increased by 3.67%, and at the same time, the grade and recovery rate of copper in the molybdenum rough concentrate are decreased to a certain extent. Therefore, not any two neutral oils can be combined to obtain excellent flotation results. Only the appropriate combination can show excellent positive synergistic effect.

[0059] Example 2

[0060] The difference between this example and Example 1 is only that the mass ratio of coconut oil and palm oil in the combined collector is 4:1, and the amount of methyl naphthalene is 5% of the amount of the combined collector, and the other conditions remain unchanged. The specific flotation results are shown in Table 3.

[0061] Example 3

[0062] The difference between this example and Example 1 is only that the mass ratio of coconut oil and palm oil in the combined collector is 2:1, and the amount of methyl naphthalene is 5% of the amount of the combined collector, and the other conditions remain unchanged. The specific flotation results are shown in Table 3.

[0063] Example 4

[0064] The embodiment differs from example 1 only in that the mass ratio of coconut oil and palm oil in the combined collector is 1:1, the amount of methylnaphthalene is 5% of the amount of the combined collector, and the rest of the conditions remain unchanged. The specific flotation results are shown in Table 3.

[0065] Comparative example 4

[0066] The embodiment differs from example 1 only in that the mass ratio of coconut oil and palm oil in the combined collector is 1:2, the amount of methylnaphthalene is 5% of the amount of the combined collector, and the rest of the conditions remain unchanged. The specific flotation results are shown in Table 3.

[0067] Comparative example 5

[0068] The comparative example differs from example 1 only in that the mass ratio of coconut oil and palm oil in the combined collector is 8:1, the amount of methylnaphthalene is 5% of the amount of the combined collector, and the rest of the conditions remain unchanged. The specific flotation results are shown in Table 3.

[0069] Table 3 Flotation test results of combined collectors with different proportions

[0070]

[0071] From the test results of examples 2-4 and Table 3, it can be seen that in the case of coconut oil as the main collector and palm oil as the auxiliary collector, adjusting the component ratio of the two can obtain different flotation effects, and the flotation effect becomes better as the proportion of coconut oil increases. When the mass ratio of coconut oil to palm oil is 4:1, the grade of molybdenum rough concentrate is 4.738%, and the recovery rate is 76.35%, which is the best flotation effect. When the mass ratio of coconut oil to palm oil is 1:2, the grade of molybdenum rough concentrate is 3.003%, and the recovery rate is 52.20%, which are slightly lower than the flotation effect when kerosene is used as the collector in comparative example 3. In addition, it is found during the experiment that when the proportion of coconut oil is too large and exceeds the control threshold of the best condition, the dispersion performance of the combined collector in water becomes poor, the stirring time required for compounding is longer, and it is easy to caking at room temperature, which is not conducive to flotation. Therefore, only under a specific ratio can the combined collector exhibit good compatibility and achieve the best flotation effect.

[0072] Example 5

[0073] The process flow of copper-molybdenum separation to obtain copper concentrate and molybdenum concentrate is as follows:

[0074] The depressant and the combined collector are configured respectively. The depressant is composed of the following components in mass fraction: sodium sulfide 2 parts, sodium mercaptoacetate 1 part. In the combined collector, the mass ratio of coconut oil to palm oil is 4:1, and the amount of methylnaphthalene is 5% of the total mass of coconut oil and palm oil.

[0075] Test conditions: The test ore sample of molybdenum raw ore is a copper-molybdenum mixed concentrate ore slurry from a certain ore dressing plant, the grade of the raw ore is 0.45%, the grinding fineness is 85% to 90% of -0.043 μm, and the slurry pH is 12. According to Figure 2 The flowsheet is selected for separation.

[0076] After the flotation is completed, the flotation products are filtered, dried, weighed, sampled, and sent for inspection. The grade, calculated yield, and recovery rate are obtained. The specific results are shown in Table 4.

[0077] Table 4 Test results of copper-molybdenum separation one roughing and four cleaning

[0078]

[0079] Comparative Example 6

[0080] The difference between this comparative example and Example 5 is only that the collector is kerosene, and other conditions are unchanged. The specific flotation results are shown in Table 4.

[0081] As can be seen from the results in Table 4, when the flotation process is one roughing and four cleaning, the combined collector is obviously superior to kerosene as a collector for the separation of molybdenite and chalcopyrite in the copper-molybdenum mixed ore slurry. The grade of the molybdenum concentrate obtained by flotation with the combined collector is 36.363%, which is 3.728% higher than that of kerosene, and the recovery rate is 73.21%, which is 12.58% higher than that of kerosene.

[0082] Comparative Example 7

[0083] The difference between this comparative example and Example 2 is only that the emulsifier is naphthalene or octylphenoxy polyethoxyethanol, and other conditions are unchanged. The specific flotation results are shown in Table 5.

[0084] Table 5 Test results of copper-molybdenum separation one roughing

[0085]

[0086] As can be seen from the results in Table 5, the grade and recovery rate of the molybdenum rough concentrate obtained by flotation in Comparative Example 7 are lower than those of Example 2. It can be seen that not any emulsifier and coconut oil, palm oil can produce good flotation effect, only the appropriate combination can show excellent positive synergistic effect.

[0087] As can be seen from the above, the interaction strength between a single neutral oil and the surface of molybdenite is poor, and it is difficult to achieve good flotation effect. Different neutral oils have different interaction strengths with the surface of molybdenite, and not all neutral oils will produce good synergistic effect, and only a certain range of ratio can achieve good effect for specific components. That is, only specific components and specific ratios can achieve the best flotation effect.

[0088] The above merely provides the preferred examples of the present application but are not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. Application of a combined collector in the flotation of molybdenite in copper-molybdenum mixed concentrate; The combined collector is composed of a main collector coconut oil, a secondary collector palm oil and an emulsifier methylnaphthalene, and the mass ratio of the coconut oil, palm oil and methylnaphthalene is (9-16):(3.8-10):

1.

2. Use according to claim 1, characterized in that, The mass ratio of the coconut oil, palm oil and methylnaphthalene is 15.2:3.8:

1.

3. Use according to claim 1, characterized in that, The combined collector is suitable for a flotation slurry environment with a pH of 7-12.

4. Use according to claim 1, characterized in that, The molybdenum grade in the copper-molybdenum mixed concentrate is 0.3%-0.7%.

5. The use according to claim 1, characterized in that, Before adding the slurry, the coconut oil, palm oil, methylnaphthalene and water are mixed uniformly to obtain a mixture, and then the mixture is fully stirred and dispersed in a stirrer before being added to the slurry.

6. Use according to claim 5, characterized in that, The stirring and dispersing conditions are: rotation speed 1000-1500 r / min, stirring time 10-20 min.

7. The application of claim 1, comprising the following steps: a) adding the copper-molybdenum mixed concentrate prepared into a slurry to a flotation tank; b) sequentially adding an inhibitor, water glass and the combined collector to the slurry, stirring for 2-5 min to adjust the pulp, and performing roughing to obtain a rough concentrate and a rough tailing.

8. The application of claim 1, comprising the following steps: 1) adding an inhibitor, water glass and the combined collector to the slurry prepared from the copper-molybdenum mixed concentrate to perform roughing and obtain a rough concentrate and a tailing; 2) performing at least 4 times of cleaning on the rough concentrate obtained in step 1) to obtain a molybdenite concentrate; the cleaning process comprises sequentially adding an inhibitor, water glass and the combined collector each time, stirring for 2-5 min to adjust the pulp and performing flotation.

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