High-efficiency fluorite collector and preparation method thereof

Abstract

The application discloses a high-efficiency fluorite collecting agent and a preparation method thereof, and comprises the following raw materials in parts by weight: 20-45 parts of oleic acid with different iodine values, 5-10 parts of amide surfactant, 3-5 parts of inorganic alkali or organic alkali, and 10-25 parts of low-carbon-chain alcohol compounds; the amide surfactant is a non-ionic surfactant, and a general structure of the amide surfactant is R1-C(O)NH(CH2) n CH2-R2, wherein R1 is a carbon-hydrogen chain with 12-18 carbon atoms, n=5-6, and R2 is a functional group with hydrogen bond effect. The fluorite collecting agent can ensure high fluorite recovery rate, improve the grade of fluorite concentrate to a certain extent, reduce the amount of the collecting agent, and solve the problem of low fluorite concentration efficiency of the fatty acid fluorite collecting agent.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of mineral flotation collector technology, and particularly relates to a high-efficiency fluorite collector and a preparation method thereof. BACKGROUND

[0002] Fluorite (CaF2) is an important non-renewable mineral, which is mainly used for the production of hydrofluoric acid, glass, cement, filler, and as a flux regulator in steelmaking, and is considered an important strategic mineral in recent years. In natural deposits, fluorite is mainly associated with other calcium-containing minerals, such as calcite and barite. As high-quality fluorite resources continue to decrease, low-grade fluorite resources containing complex gangue minerals are also being developed and utilized, which poses new challenges for fluorite beneficiation. In addition, production practice shows that when the ratio of fluorite content to calcite content in the raw ore is less than 5, the separation of fluorite and calcite is greatly increased in difficulty, and it is difficult to obtain high-quality fluorite concentrate products (CaF2> 90%, CaCO3< 1%). Therefore, it is particularly important to develop high-efficiency and environmentally friendly fluorite flotation reagents.

[0003] So far, using fatty acid collectors for flotation has been considered one of the most commonly used techniques for separating fluorite from gangue minerals. However, it is important to note that the flotation separation of fluorite from calcium-containing minerals is a very challenging task, as their surface reactivity is similar to the conventional fatty acid collector combination, and the poor solubility and dispersibility of the fatty acid-based fluorite collector can lead to a decrease in fluorite recovery, an increase in the amount of collector used, a decrease in atomic economy, and a decrease in enterprise efficiency.

[0004] In the prior art, to solve the problem of poor collecting ability of oleic acid collectors and multiple cleaning, for example, Chinese patent document CN114054213B discloses a fluorite collector and a preparation method thereof. The disclosed fluorite collector and preparation method can improve the fluorite recovery rate to some extent, but the preparation process of the fluorite collector involves complex chemical reactions, which are dangerous and polluting, so the method has certain limitations. Chinese patent document CN107138288B discloses a low-temperature fluorite collector, which specifically discloses a fluorite collector formed by mixing the product after complete saponification of oleic acid and sodium carbonate with alkyl amide and a foaming agent. The solubility and dispersibility of the fluorite collector are relatively good, but the foam is too rich and stable during the flotation process, and it is not easy to defoam, which can cause the recovery rate to decrease.

[0005] In summary, it is necessary to develop a high-efficiency fluorite collector that has strong collecting ability and selectivity, ensures high fluorite recovery rate, has low raw material cost, and produces foam of appropriate size and stability during use, under the condition of fewer cleaning times, to solve the above problems. SUMMARY

[0006] In order to overcome the problems in the prior art, the application provides a high-efficiency fluorite collector and a preparation method thereof, which can obviously reduce the concentration times, ensure the high-efficiency fluorite recovery rate, improve the fluorite concentrate grade to a certain extent, reduce the collector consumption, and solve the problem of poor fluorite concentration efficiency of the fatty acid fluorite collector.

[0007] To solve the above technical problems, the technical scheme provided by the application is:

[0008] The application provides a high-efficiency fluorite collector, which comprises the following raw materials in parts by weight:

[0009] 20-45 parts of oleic acid with different iodine values, 5-10 parts of amide surfactant, 3-5 parts of inorganic or organic alkali, and 10-25 parts of low-carbon chain alcohol compound; the amide surfactant is a non-ionic surfactant, and the structural general formula of the amide surfactant is R1-C(O)NH(CH2) n R2, wherein R1 is a carbon-hydrogen chain with 12-18 carbon atoms, n=6-7, and R2 is a functional group with hydrophilic properties.

[0010] The amide surfactant in the application is a non-ionic surfactant, which is relatively stable in acid or alkali solution, can promote the dispersibility and foaming capacity of the alkali product of oleic acid, and has good emulsifying, dispersing, foaming and non-fluorite impurity inhibiting capacity. The chemical formula of the amide surfactant has an amide bond and a hydrophilic group at the tail in the structure, and will not form a phase separation in water after being dissolved with oleic acid. Meanwhile, the low-carbon chain alcohol compound itself has one or more hydroxyl groups, which have strong polarity and can well mix oleic acid alkali, amide, and water. Meanwhile, the defoaming capacity is strong, and the foam will not be difficult to eliminate and overflow the flotation tank in the flotation process. Meanwhile, the use of oleic acid with different iodine values improves the fluorite recovery rate and grade, and utilizes the acid-base neutralization of alkali and oleic acid.

[0011] As an optional embodiment, in the collector provided by the application, R2 is selected from one of -H, -OH and -COOH.

[0012] As an optional embodiment, in the collector provided by the application, R2 in the amide surfactant is selected from -COOH.

[0013] In the application, under the condition of the same inhibition of gangue minerals, the addition of -COOH further increases the fluorite collecting capacity.

[0014] As an optional embodiment, in the collector provided by the application, the amide surfactant is R1-COOCH3 and H2N(CH2) n R2 is reacted under the catalysis of a catalyst and under alkaline conditions by heating.

[0015] The synthetic general formula is:

[0016] .

[0017] As an optional embodiment, in the collector provided by the application, the R1-COOCH3 and H2N(CH2) n The amount-of-substance ratio of R2 is 0.5-1.5.

[0018] As an optional embodiment, in the collector provided by the application, the catalyst is potassium hydroxide, and the amount of the potassium hydroxide is 0.5-5% of the total weight of the reactants.

[0019] As an optional embodiment, in the collector provided by the application, the low-carbon-chain alcohol compound is selected from one or more of methanol, ethanol, ethylene glycol, diethylene glycol, isopropyl alcohol or glycerol.

[0020] As an optional embodiment, in the collector provided by the application, the inorganic base or organic base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, diethylamine or triethylamine.

[0021] As an optional embodiment, in the collector provided by the application, the oil acid with different iodine values includes at least one high-iodine-value oil acid and at least one low-iodine-value oil acid, the iodine value of the high-iodine-value oil acid ranges from 120 to 140, and the iodine value of the low-iodine-value oil acid ranges from 90 to 105.

[0022] As an optional embodiment, in the collector provided by the application,

[0023] The structural formula of the oil acid is as follows:

[0024] .

[0025] Based on the same technical concept, the application further provides a preparation method of the high-efficiency fluorite collector.

[0026] S1, adding an alkali solution to oil acid with different iodine values to form a mixed solution with a mass concentration of 60%-80%.

[0027] S2, sequentially adding an amide surfactant and a low-carbon-chain alcohol compound to the solution of step S1 to obtain a mixture.

[0028] S3, shearing and stirring the mixture obtained in step S2 for 20-30 min to obtain a high-efficiency fluorite collector.

[0029] As an optional embodiment, in the preparation method provided by the present application, in step S1, the oil acid with different iodine values is dissolved in the lye at 70-85 DEG C to prepare the oil acid alkalization solution.

[0030] As an optional embodiment, in the preparation method provided by the present application, in step S1, the oil acid with different iodine values is dissolved in the lye at 85 DEG C to prepare the oil acid alkalization solution with a mass concentration of 60%.

[0031] As an optional embodiment, in the preparation method provided by the present application, in step S2, the low-carbon alcohol compound and the amide surfactant are added into the oil acid alkalization solution in multiple times to ensure that the amide compound will not be largely decomposed in the high-temperature alkaline solution.

[0032] The working principles of the raw materials in the present application are as follows:

[0033] The oil acid has a collecting effect on fluorite, and has a long straight chain structure. According to the hydrophilic-lipophilic balance theory, the carboxyl group thereof is a hydrophilic group, and the rear end of the alpha position is a whole hydrocarbon structure. Therefore, the hydrophobicity of the hydrocarbon chain of the oil acid is strong, and the oil acid is more easily collected on fluorite. After saponification of the oil acid, the dispersibility is stronger.

[0034] The amide surfactant is stable in nature, resistant to acid and alkali at room temperature, can promote the dispersibility and foaming capacity of the oil acid after alkalization, and has an inhibiting effect on non-fluorite minerals, further improving the selectivity and collecting effect of the oil acid. Compared with the commonly used oil acid amide (R-CONH2 disclosed in the prior art CN11369021A), the chemical formula of the amide surfactant in the present application has both an amide bond and a hydrophilic group at the tail. After being similarly compatible with the oil acid, it will not form a separate phase in water.

[0035] Compared with the prior art, the present application has the following advantages:

[0036] (1) The amide surfactant is used in the collector of the present application, and the chemical structure formula contains both an amide bond and a hydrophilic group such as -H, -OH and -COOH connected at the tail. After being similarly compatible with the oil acid, it will not form a separate phase in water.

[0037] (2) The collector of the present application is prepared by compounding oil acid, inorganic or organic base, amide surfactant and low-carbon alcohol. Except for the amide surfactant, other raw materials are common chemical products on the market. The raw materials are easy to obtain, low in cost, environmentally friendly, easy to degrade, and have great market promotion value.

[0038] (3) The collecting agent provided by the application has greatly improved collecting performance compared with general fatty acid collecting agents, can obviously reduce the number of cleaning times, greatly improve the recovery rate of the fluorite ore, reduce the amount of the collecting agent, and ensure the quality of the concentrate. BRIEF DESCRIPTION OF DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or the prior art description. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without any creative effort on the basis of these drawings.

[0040] Figure 1 The flow chart of the high-efficiency fluorite collecting agent in the present application applied to the fluorite ore flotation. DETAILED DESCRIPTION

[0041] In order to facilitate the understanding of the present application, the following will make a more comprehensive and detailed description of the present application in combination with the drawings of the specification and the preferred embodiments, but the protection scope of the present application is not limited to the following specific embodiments.

[0042] Unless otherwise defined, all the professional terms used in the following have the same meaning as generally understood by those skilled in the art. The professional terms used in the present application are only for the purpose of describing the specific embodiments and are not intended to limit the protection scope of the present application.

[0043] Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by the existing method.

[0044] Embodiment 1

[0045] The weight ratio of each raw material of the high-efficiency fluorite collecting agent in the present embodiment is as follows: iodine value = 120 oil acid 20 parts, iodine value = 90 oil acid 20 parts, amide compound surfactant 10 parts (R1 is a carbon hydrogen hydrocarbon chain with 15 carbon atoms, R2 is H, and n = 6), inorganic base sodium hydroxide 5 parts, isopropyl alcohol 10 parts.

[0046] The preparation method of the high-efficiency fluorite collecting agent is as follows:

[0047] (1) Add liquid alkali to the oil acid to prepare a mixed solution with a mass concentration of 70%.

[0048] (2) The chemical equation for synthesizing the amide compound surfactant is as follows: CH3 (CH2) 14The molar ratio of COOCH3 and H2N(CH2)5CH3 is 1:2, and the amount of potassium hydroxide added is 1% of the total weight of the reactants.

[0049] .

[0050] (3) Add the amide compound surfactant and isopropyl alcohol to the oleic acid alkaline solution of step (1) in sequence to obtain a mixture.

[0051] (4) Shear stir the mixture obtained in step (3) for 20-30 min to obtain a high-efficiency fluorite collector.

[0052] Comparison of the use effect of the high-efficiency fluorite collector of the present embodiment and the fluorite collector of the prior art.

[0053] The high-efficiency fluorite collector prepared in the present embodiment and the fluorite collector of the prior art are respectively applied to the flotation of fluorite ore with a grade of 13.18% CaF2, please refer to the flotation flow shown in Figure 1 The adjusting agent is sodium carbonate, the depressant is water glass, and the use effect comparison results are shown in Table 1.

[0054] Table 1: Flotation results

[0055]

[0056] From the comparison results, it can be seen that in the room temperature slurry, under the condition of the same amount of collector, the fluorite concentrate obtained by using the collector of the present embodiment is about 21% higher than that of the traditional sodium oleate, and the grade of the fluorite concentrate still remains above 90%. The use of a single high-iodine value and low-iodine value oleic acid complex mixture can improve the collecting ability to a certain extent, but the separation is poor, and the overall effect is not significant.

[0057] Example 2

[0058] The weight ratio of each raw material of the high-efficiency fluorite collector of the present embodiment is: iodine value = 140 oleic acid 10 parts, iodine value = 90 oleic acid 10 parts, amide compound surfactant 10 parts (R1 is a carbon-hydrogen hydrocarbon chain with 17 carbon atoms, R2 is -OH, and n = 5), organic base diethylamine 5 parts, and diethylene glycol 10 parts.

[0059] Preparation of the fluorite low-temperature collector of the present embodiment:

[0060] (1) Add liquid alkali to oleic acid to prepare a mixed solution with a mass concentration of 70%.

[0061] (2) The chemical equation for synthesizing the amide compound surfactant is as follows, wherein CH3(CH2) 16The molar ratio of COOCH3 and H2N(CH2)5OH is 1:1, and the amount of potassium hydroxide added is 1.5% of the total weight of the reactants.

[0062] .

[0063] (3) The oleic acid alkalization solution of step (1) is sequentially added with an amide compound surfactant and isopropyl alcohol to obtain a mixture.

[0064] (4) The mixture obtained in step (3) is sheared and stirred for 20-30 min to obtain a high-efficiency fluorite collector.

[0065] The use effect of the high-efficiency fluorite collector of the present embodiment is compared with that of the fluorite collector of the prior art.

[0066] The high-efficiency fluorite collector prepared in the present embodiment and the fluorite collector of the prior art are respectively applied to the flotation of a fluorite ore with a grade of 13.18% CaF2, please refer to the flotation flow shown in Figure 1 The adjusting agent is sodium carbonate, the depressant is water glass, and the use effect comparison results are shown in Table 2.

[0067] Table 2: Flotation results

[0068]

[0069] From the comparison results, it can be seen that in the room temperature slurry, under the condition of the same amount of collector, the fluorite concentrate obtained by using the collector of the present embodiment 2 is improved by about 7.5% compared with the traditional sodium oleate, and the grade of the fluorite concentrate still remains above 90%. In the comparison experiment, a single equivalent amount of amide compound surfactant is used as a collector, and it is found that its collecting ability is poor, and it needs to be combined with oleic acid and other additives to produce a positive synergistic effect, which can improve the fluorite recovery rate while ensuring the fluorite grade.

[0070] Example 3

[0071] The weight ratio of each raw material of the high-efficiency fluorite collector of the present embodiment is as follows: iodine value = 140 oleic acid 20 parts, iodine value = 100 oleic acid 10 parts, amide compound surfactant 10 parts (R1 is a carbon hydrogen hydrocarbon chain with 13 carbon atoms, R2 is -COOH, and n = 5), inorganic base potassium hydroxide 5 parts, and methanol 5 parts.

[0072] Preparation of the fluorite low-temperature collector of the present embodiment:

[0073] (1) Liquid alkali is added to oleic acid to prepare a mixed solution with a mass concentration of 70%.

[0074] (2) The chemical equation for synthesizing the amide compound surfactant is as follows, wherein CH3(CH2) 12The molar ratio of COOCH3 and H2N(CH2)5COOH is 1:1.5, and the amount of potassium hydroxide added is 5% of the total weight of the reactants.

[0075] .

[0076] (3) The amide compound surfactant and isopropyl alcohol are sequentially added to the oleic acid alkalization solution of step (1) to obtain a mixture.

[0077] (4) The mixture obtained in step (3) is sheared and stirred for 20-30 min to obtain a high-efficiency fluorite collector.

[0078] The use effect of the high-efficiency fluorite collector of the present embodiment is compared with that of the fluorite collector of the prior art.

[0079] The high-efficiency fluorite collector prepared in the present embodiment and the fluorite collector of the prior art are respectively applied to the flotation of a fluorite ore with a grade of 13.18% CaF2, please refer to the flotation process shown in Figure 1 The adjusting agent is sodium carbonate, the depressant is water glass, and the use effect comparison results are shown in Table 3.

[0080] Table 3: Flotation results

[0081]

[0082] From the comparison results, it can be seen that in the room temperature slurry, under the condition of the same amount of collector, after adding an appropriate amount of low alcohol in the collector of the present embodiment 3, although the concentrate recovery rate will decrease slightly, the concentrate grade will increase significantly. The reason is that in the comparison test without adding low alcohol, the amount of foam in the flotation process is large and not easy to dissipate, and non-fluorite mineral impurities are easily floated, and the separation efficiency is reduced.

[0083] Comparative Example 1

[0084] The weight ratio of each raw material is: iodine value = 140 oleic acid 10 parts, iodine value = 90 oleic acid 10 parts, oleic acid amide 10 parts, organic base diethylamine 5 parts, diethylene glycol 10 parts, and ordinary fluorite collector is synthesized. The preparation method is the same as that of Example 2.

[0085] The collector in Comparative Example 1 and the high-efficiency fluorite collector in Example 2 are respectively applied to the flotation of a fluorite ore with a grade of 13.18% CaF2, please refer to the flotation process shown in Figure 1 The adjusting agent is sodium carbonate, the depressant is water glass, and the use effect comparison results are shown in Table 4.

[0086] Table 4: Flotation results

[0087]

[0088] From the comparison results, in the room temperature pulp, under the condition of the same amount of collector, the concentrate recovery rate and the concentrate grade of the comparative example 1 decrease after using oleic acid amide in the collector. The reason is that the oleic acid amide in the comparative example 1 has no hydrophilic group -OH in the tail, and after mixing with oleic acid, the compatibility is poor, and the separation efficiency decreases.

[0089] The above is a further detailed description of the present application in combination with specific preferred embodiments, and the specific implementation of the present application should not be limited to these descriptions. For ordinary skilled persons in the art to which the present application belongs, without departing from the concept of the present application, a number of simple deductions or substitutions can be made, which should be considered as belonging to the protection scope of the present application.

Claims

1. A high efficiency fluorite collector characterized in that, Comprise the following weight parts of substances: Different iodine value oleic acid 20-45 parts, amide surfactant 5-10 parts, inorganic or organic base 3-5 parts, low carbon chain alcohol compound 10-25 parts;The amide surfactant is a nonionic surfactant, and the structural general formula of the amide surfactant is R1-C(O)NH(CH2) n R2, wherein, in the formula, R1 is a carbon hydrogen chain containing 12-18 carbon atoms, n=6-7, wherein R2 is a functional group with hydrophilic properties.

2. The high efficiency fluorite collector according to claim 1, characterized in that, The R2 is selected from one of -H, -OH, -COOH.

3. The high efficiency fluorite collector according to claim 1, characterized in that, The R2 is selected from -COOH.

4. The high efficiency fluorite collector of claim 1, wherein, The amide surfactant is formed from R1-COOCH3 and H2N(CH2) n R2 is formed by heating the reaction under basic conditions in the presence of a catalyst.

5. The high efficiency fluorite collector according to claim 4, characterized in that, said R1-COOCH3 and H2N(CH2) n The molar ratio of R2 is 0.5-1.

5.

6. The high efficiency fluorite collector of claim 4, wherein, The catalyst is potassium hydroxide, and the amount of potassium hydroxide is 0.5-5% of the total weight of the reactants.

7. The high efficiency fluorite collector of claim 1, wherein, The low-carbon chain alcohol compound is selected from one or more of methanol, ethanol, ethylene glycol, diethylene glycol, isopropanol or glycerol; and the inorganic base or organic base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, diethylamine or triethylamine.

8. A process for the preparation of a high efficiency fluorite collector as claimed in any one of claims 1 to 7, characterised in that, Comprise the following steps: S1, adding alkali liquor to different iodine value oleic acid to prepare a mixed solution with a mass concentration of 60-80%; S2, adding amide surfactant and low-carbon chain alcohol compound to the solution of step S1 in sequence to obtain a mixture; S3, shearing and stirring the mixture obtained in step S2 for 20-30 min to obtain a high-efficiency fluorite collector.

9. The process for the preparation of high efficiency fluorite collector as claimed in claim 8, wherein, In step S1, the different iodine value oleic acid is dissolved in 70-85℃ alkali liquor to prepare an oleic acid alkali solution.

10. The process for the preparation of high efficiency fluorite collector as claimed in claim 8 wherein, In step S2, the low-carbon chain alcohol compound and the amide surfactant are added to the oleic acid alkali solution in multiple times to ensure that the amide compound does not decompose in large quantities in the high-temperature alkaline solution.

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