Collector and preparation method thereof, and method for flotation of fluorite using the collector

Abstract

The present application relates to the technical field of ore flotation, and specifically discloses a collector and a preparation method thereof, and a method for flotation of fluorite using the collector. The collector is prepared from the following raw materials: oleic acid and triethanolamine; the volume ratio of oleic acid and triethanolamine is (1.7-2.3): 1; the concentration of oleic acid is 7-12%; the concentration of triethanolamine is 8-13%. The preparation method of the collector is: under stirring, triethanolamine is slowly poured into oleic acid, reacted at room temperature, and a modified oleic acid solution is obtained, which is the collector. The collector prepared in the present application has fine foam after foaming, strong collecting ability, and still has a good collecting effect at low temperature (0-5°C). The collector or the collector prepared by the preparation method is applied to fluorite flotation, and the flotation effect of fine-grained fluorite is good.

Description

[0001] The priority basis of the present invention includes: an invention application with an application date of September 30, 2021, application number 2021111612834, and patent name "A method and equipment for preparing quartz purified from secondary tungsten tailings". Technical Field

[0002] The present application relates to the technical field of ore flotation, and more specifically, to a collector and a preparation method thereof, and a method for flotating fluorite using the collector. Background Art

[0003] Fluorite, also known as fluorspar, is mainly composed of calcium fluoride (CaF2). It crystallizes in octahedrons and cubes. The crystals have a glassy luster, bright and varied colors, and are brittle. It has a Mohs hardness of 4 and a melting point of 1360°C. It has the property of complete cleavage and is a common mineral in nature, often coexisting with multiple other minerals.

[0004] Oleic acid is a fatty acid collector with the molecular formula C 17 H 33 COOH, which belongs to fatty acid (RCOOH), R is hydroxyl, can be used for fluorite flotation. However, oleic acid has poor flotation effect on fluorite, which is specifically manifested in the following two aspects: First, oleic acid is insoluble in water and has poor dispersibility. It cannot fully contact with fluorite in water, and has poor collection (flotation) effect on fluorite at room temperature; Second, oleic acid has a high freezing point, low solubility in low-temperature slurry, slow dispersion speed, low activity, and poor flotation effect. Especially at low temperatures (0-5℃), the flotation slurry has a very poor collection effect on fluorite. In winter, the slurry solution needs to be heated before flotation, which increases production costs.

[0005] In order to solve the above technical problems, the commonly used method in the prior art is to add emulsifiers and surfactants to oleic acid to emulsify and disperse the oleic acid. The oleic acid changes from large particles to fine oil particles and is dispersed in water to achieve the purpose of full contact with fluorite. However, the flotation effect of the flotation pulp on fluorite is still not very ideal at low temperatures. In addition, there are strict requirements on the amount of emulsifiers and surfactants added. If the amount of emulsifiers and surfactants added is too little, the emulsification and dispersion effects of oleic acid are not ideal; if the amount of emulsifiers and surfactants added is too much, the flotation effect of fluorite is affected. In addition, some emulsifiers and surfactants are harmful and have an impact on the environment and people. Since the foaming effect of oleic acid is not ideal, a small amount of foaming agent is often required to be added during the flotation of fluorite. If the foam produced by the foaming agent is not fine, it will also affect the capture of fine particles of fluorite by oleic acid. Summary of the invention

[0006] The present application provides a collector and a preparation method thereof, and a method for flotation of fluorite using the collector. The collector prepared in the present application has fine foam after foaming, strong collecting ability, and still has a good collecting effect at low temperature (0-5°C).

[0007] In the first aspect, the present application provides a collector, which adopts the following technical solution:

[0008] A collector is prepared from the following raw materials:

[0009] Oleic acid and triethanolamine;

[0010] The volume ratio of oleic acid to triethanolamine is (1.7-2.3):1;

[0011] The oleic acid concentration is 7-12%;

[0012] The concentration of triethanolamine is 8-13%.

[0013] By adopting the above technical scheme, oleic acid and triethanolamine react to generate a modified oleic acid solution (oleic acid triethanolamine), which has excellent emulsification and dispersibility in water, strong foaming ability, fine foam, strong stability in acidic and alkaline media, and good flotation effect on fluorite. The modified oleic acid solution also has excellent emulsification and dispersibility for oleic acid. Even if the collector contains oleic acid, under the influence of the modified oleic acid solution, the oleic acid can be changed from large particles to fine particles and dispersed in water, so as to achieve the purpose of full contact with fluorite, enhance the collection ability of oleic acid, and help to increase the content of fluorite (CaF2) in fluorite concentrate and improve product quality. In addition, the modified oleic acid solution does not need to add emulsifiers, surfactants or foaming agents when used for collecting (floating) fluorite, and has strong collection ability, can reduce costs, and does not pollute the environment. More importantly, the modified oleic acid solution still has a good collection ability for fluorite at low temperature (0-5) °C, and the fluorite can be well floated without heating the fluorite ore pulp, which greatly saves energy and costs.

[0014] In the present application, oleic acid with a concentration of 7-12% and triethanolamine with a concentration of 8-13% are selected, and oleic acid with a concentration of 10% and triethanolamine with a concentration of 10% are further preferred. The concentrations of oleic acid and triethanolamine are relatively low, which can reduce the resistance to stirring and is conducive to the complete reaction of the two, thereby improving the yield of the modified oleic acid solution, thereby improving the collector's ability to collect fluorite. In addition, it is also conducive to the preparation of the collector in the later fluorite flotation process, saving time and cost.

[0015] Preferably, the volume ratio of oleic acid to triethanolamine is 2:1.

[0016] By adopting the above technical scheme, oleic acid and triethanolamine react in a volume ratio of 2:1, so that the reaction is as complete as possible, the content of modified oleic acid solution in the collector can be increased, which is beneficial to improve the collector's ability to collect fluorite and increase the yield of fluorite.

[0017] In a second aspect, the present application provides a method for preparing a collector, using the following technical solution: A method for preparing the collector as described above, comprising the following steps:

[0018] Under stirring, triethanolamine is slowly poured into oleic acid, and reacted at room temperature to obtain a modified oleic acid solution, which is the collector.

[0019] In the present application, the yield of the modified oleic acid solution can be greatly improved by reacting triethanolamine and oleic acid at relatively low concentrations at room temperature. In the present application, the synthesis rate of the modified oleic acid solution in the collector is greater than 90%. In addition, the present application reacts at room temperature, and the reaction does not need to be heated to 130-160°C, which can reduce the preparation cost and save time. The inventors also found that the modified oleic acid solution will reduce the fluorite collection ability after being placed for a long time, affecting the use effect, so in the actual production process, it is best to prepare it for immediate use. The synthesis method of the present application is simple and fast, with low synthesis technology requirements, and no special requirements for synthesis equipment, a simple container is sufficient, and the modified oleic acid solution can be prepared at room temperature, so it can be prepared for immediate use. In short, the modified oleic acid solution prepared by the preparation method of the present application is used to float fluorite, and the flotation effect of the modified oleic acid solution can be best exerted.

[0020] In a third aspect, the present application provides a method for flotation of fluorite using the above collector or the collector prepared by the above preparation method.

[0021] A method for flotation of fluorite using a collector comprises the following steps:

[0022] S1. preparing fluorite ore slurry: crushing and grinding the fluorite ore, and then mixing it with water to prepare a fluorite ore slurry with a mass concentration of 30-40%;

[0023] S2, flotation I process: adding sodium carbonate to the fluorite ore pulp to adjust the pH to 7.5-8.5, then adding 1500-2000g / t of water glass and 100-300g / t of collector in sequence, stirring, and flotation operation is performed. After the flotation operation, the flotation tank bottom mineral I and foam I are obtained;

[0024] S3, flotation II process: add 300-500g / t of water glass and 50-100g / t of collector to the foam I in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral II and foam II are obtained;

[0025] S4, scavenging process; mixing the flotation tank bottom mineral I with the flotation tank bottom mineral II, and performing scavenging operation. After the scavenging operation, the scavenged foam mineral is returned to the flotation process II and mixed with the foam I, and flotation is performed again;

[0026] S5, flotation III process: add 700-1000 g / t of acidified water glass and 50-100 g / t of collector to the foam II in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral III and foam III are obtained;

[0027] S6, flotation process IV: add 500-800 g / t of acidified water glass and 20-50 g / t of collector to the foam III in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral IV and foam IV are obtained;

[0028] S7, flotation step V: add 500-800 g / t of acidified water glass and 10-30 g / t of collector to the foam IV in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral V and foam V are obtained;

[0029] S8, flotation process VI: add 100-300g / t of acidified water glass to the foam V, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral VI and foam VI are obtained; the foam VI is fluorite concentrate.

[0030] Fluorite ore refers to a mineral containing fluorite. The content of fluorite in the mineral is uncertain. The fluorite content can be high or low. The fluorite content cannot meet the requirements of the required industry and needs to be processed and purified. Fluorite refers to a fluorite mineral with a high CaF2 content, which basically does not need to be processed and purified.

[0031] In this application, "t" in "100-300g / t of collector" refers to the mass of fluorite ore, that is, when 1 ton of fluorite ore is crushed, ground and mixed with water to form a fluorite ore slurry with a mass concentration of 30-40%, 100-300g of collector needs to be added to the fluorite ore slurry. Similarly, "t" in the units of the addition amount of water glass, sodium carbonate and acidified water glass also refers to the mass of fluorite ore.

[0032] Fluorite ore contains fluorite, mica and other substances. The method of the present application is used to float fluorite. The flotation tank bottom minerals I and II are mixed ores (quartz, mica); the flotation tank bottom minerals III, IV, V and VI are mostly conjoined minerals (quartz, mica and fluorite).

[0033] In the flotation production process, flotation I-flotation II process is the rough selection of fluorite (obtaining fluorite rough concentrate), and flotation III-flotation VI process is the fine selection of fluorite (obtaining fluorite concentrate). By adopting the method of the present application, during the roughing of fluorite, sodium carbonate is first used to adjust the pH value of the flotation to 7.5-8.5 (the amount of sodium carbonate added is 1600-2000 g / t), then a water glass inhibitor is added, and finally a collector is added. At this time, the fluorite is made to enter the fluorite rough concentrate as much as possible, thereby improving the recovery rate of the fluorite; and during the fine selection, the pH value of the flotation is weakly acidic (the pH value is approximately equal to 5.0-6.0), an acidified water glass inhibitor is first added, and then a collector is added. Under weakly acidic conditions, silicon dioxide, aluminosilicates, and carbonates are well inhibited (that is, they are not floated out, and silicon dioxide, aluminosilicates, and carbonates are prevented from entering the fluorite concentrate), thereby improving the floatability of the fluorite, obtaining a fluorite concentrate with high quality and high recovery rate, and reducing the amount of the collector. The use of the collector and method of the present application for flotation of fluorite can greatly improve the recovery rate and yield of fluorite, increase the content of CaF2 in fluorite concentrate, and break through the technical difficulty that the recovery rate of fluorite concentrate and the fluorite content in fluorite concentrate cannot be taken into account at the same time.

[0034] The scavenging process also greatly enhances the recovery rate of fluorite concentrate. In each flotation process of the present application, reagents are added in sequence, which can provide better flotation conditions for fluorite flotation and improve flotation efficiency.

[0035] Preferably, in step S1, the fluorite ore is crushed and ground to a particle size of -0.1 mm.

[0036] “+” represents the material on the sieve, “-” represents the material under the sieve, and -0.1mm refers to the material under the sieve after screening with a 150-mesh sieve.

[0037] The collector (modified oleic acid solution) has a good foaming effect and very fine foam, which is conducive to the collection (flotation) of fine particles of fluorite. In the present application, the fluorite raw material is crushed to -0.1mm and then prepared with water to prepare fluorite ore slurry. The particle size of the crushed fluorite raw material is: -0.1mm accounts for 100%, -0.074mm accounts for 99.89%, -0.038mm accounts for 71.45%, and -0.019mm accounts for 40.17%. It belongs to fine particle minerals and is a difficult-to-select mineral in the field of mineral processing. However, the use of the collector (modified oleic acid solution) for flotation can still improve the yield and recovery rate of fluorite concentrate and the content of CaF2 in the fluorite concentrate.

[0038] Preferably, the flotation temperature of the fluorite ore slurry is 0-25°C.

[0039] Preferably, the flotation temperature of the fluorite ore slurry is 0-5°C.

[0040] When the fluorite content in the fluorite ore is 20.13%, the particle size of -0.074 mm accounts for 99.89%, -0.038 mm accounts for 71.45%, and -0.019 mm accounts for 40.17%, by adopting the above technical scheme, at 0-5°C, using a collector (modified oleic acid solution) to float fluorite, the yield of fluorite concentrate is greater than 52%, the recovery rate is greater than 89.5%, and the fluorite (CaF2) content in the fluorite concentrate is greater than 96.0%; at 25°C, using a collector (modified oleic acid solution) to float fluorite, the yield of fluorite concentrate is greater than 52.5%, the recovery rate is greater than 91.5%, and the fluorite (CaF2) content in the fluorite concentrate is greater than 97.0%.

[0041] The fluorite (CaF2) content in the fluorite concentrate (96%-97%) is 76%-77% higher than that in the fluorite ore (20.13%), indicating that the flotation effect of fluorite by the modified oleic acid flotation method in the present application is good when the fluorite content in the fluorite ore is low, especially at low temperature (0-5°C).

[0042] After the fluorite raw materials are crushed and ground, the particle size of -0.074mm accounts for 99.89%, -0.038mm accounts for 71.45%, and -0.019mm accounts for 40.17%. Fluorite ore powder is a fine-grained mineral and is difficult to select. However, by using modified oleic acid solution flotation, fluorite concentrate with high yield, high recovery rate and high fluorite (CaF2) content can still be obtained.

[0043] With the increase of fluorite (CaF2) content in fluorite ore, the flotation effect of collector (modified oleic acid solution) on fluorite is better at 0-25℃.

[0044] The flotation tank bottom mineral III obtained in step S5 is returned to the flotation process III, mixed with the foam II, and then floated again;

[0045] Similarly, the flotation tank bottom mineral IV, the flotation tank bottom mineral V and the flotation tank bottom mineral VI obtained in step S6-8 are refluxed, respectively mixed with the foam III, the foam IV and the foam V, and floated again.

[0046] By adopting the above technical scheme, the yield and recovery rate of fluorite concentrate and the content of fluorite (CaF2) in the fluorite concentrate can be better improved, and the content of fluorite (CaF2) in the tailings can be reduced.

[0047] In summary, this application has the following beneficial effects:

[0048] 1. The collector (modified oleic acid solution) prepared in this application has good emulsification and dispersibility, strong foaming ability and fine foam;

[0049] 2. The modified oleic acid solution also has excellent emulsification and dispersibility of oleic acid;

[0050] 3. When the modified oleic acid solution is used for flotation of fluorite, no emulsifier, surfactant or foaming agent is needed, which can reduce costs and does not pollute the environment;

[0051] 4. The modified oleic acid solution still has a good capture ability for fluorite at 0-5℃;

[0052] 5. The present application prepares the modified oleic acid solution at room temperature, and the reaction does not need to be heated to 130-160°C, so the preparation cost is low, and the synthesis method is simple and fast, the synthesis technology requirements are low, and there are no special requirements for the synthesis equipment. A simple container is sufficient, and it can be prepared and used immediately, which can best exert the capture effect of the modified oleic acid solution;

[0053] 6. The use of the collector (modified oleic acid solution) and method of the present application for flotation of fluorite can better improve the yield and recovery rate of fluorite concentrate and the content of fluorite (CaF2) in the fluorite concentrate, and reduce the content of fluorite (CaF2) in the tailings. DETAILED DESCRIPTION

[0054] In the prior art, oleic acid and triethanolamine are used to synthesize oleic acid triethanolamine soap at high temperature. Because the concentration is too high, and the oleic acid triethanolamine soap synthesized at room temperature is in the form of an oil paste due to its high viscosity and cannot be stirred, oleic acid and triethanolamine cannot fully react at this time, and the purity of the synthesized oleic acid triethanolamine soap is low. Therefore, the synthesis temperature needs to be greater than 130°C to ensure that the synthesized oleic acid triethanolamine soap has high purity. However, when synthesizing oleic acid triethanolamine soap at high temperature, the synthesis equipment needs to be closed, a heating source is required, and the equipment materials need to be resistant to high temperature and corrosion. The reaction instruments are generally resistant to high temperature and corrosion, such as chemical oil pumps, etc., which increases the production cost and the investment in production equipment.

[0055] The viscosity of triethanolamine oleate soap is inversely proportional to the temperature, that is, the higher the synthesis temperature, the lower the viscosity of the synthesized triethanolamine oleate soap. However, after the synthesized triethanolamine oleate soap is cooled from 130°C to room temperature, it becomes an ointment due to its high viscosity. Therefore, when flotating fluorite, the ointment-like triethanolamine oleate soap needs to be made into a triethanolamine oleate soap of a certain dilute concentration (5-15%), and then used for flotation of fluorite. The usual practice is to first heat the ointment-like triethanolamine oleate soap to prepare a triethanolamine oleate soap of a certain dilute concentration (5-15%), and then accurately measure and calculate the required volume or mass number. In this process, the triethanolamine oleate soap needs to be heated first to melt it, and then measured and calculated, with many steps and cumbersome operation. However, the paste-like triethanolamine oleate soap is not conducive to accurately measuring and calculating the required volume or mass number. Moreover, when the paste-like triethanolamine oleate soap is directly added to the flotation pulp during flotation, it cannot be quickly dissolved in the pulp, but will stick to a small part of the solid minerals in the pulp, lose the collection ability, and the flotation effect of fluorite is poor. Moreover, if the triethanolamine oleate soap is left for a long time, it will affect the collection ability of fluorite and affect the use effect.

[0056] Therefore, in order to overcome the above defects, the inventors mixed oleic acid with a concentration of 7-12% and triethanolamine with a concentration of 8-13% in a volume ratio of (1.7-2.3):1, and then reacted at room temperature to obtain oleic acid triethanolamine, i.e., modified oleic acid solution, and the synthesis rate of the modified oleic acid solution was greater than 90%. The synthesis method is simple and fast, with low requirements for synthesis technology, and no special requirements for synthesis equipment, and a simple container is sufficient. The modified oleic acid solution can be prepared and used immediately. The modified oleic acid solution can be directly measured with a measuring tool, which is convenient to measure and conducive to accurate calculation. When the modified oleic acid solution prepared and used is added to the flotation pulp, it can be quickly dissolved in the pulp, and the capture effect is good.

[0057] The present application is further described in detail below in conjunction with the embodiments and application examples. It is particularly noted that if no specific conditions are specified in the following embodiments and application examples, the conventional conditions or the conditions recommended by the manufacturer shall be followed; the raw materials used in the following embodiments and application examples can all be sourced from common commercial sources unless otherwise specified.

[0058] 10% oleic acid: concentrated oleic acid (solution): water = 10:90 (volume ratio);

[0059] 10% triethanolamine: commercially available triethanolamine (solution): water = 10:90 (volume ratio);

[0060] Acidified water glass: sulfuric acid 5%: water glass 5% = 1:1 (volume ratio);

[0061] Sulfuric acid 5%: commercial concentrated sulfuric acid: water = 1:19 (volume ratio);

[0062] Water glass 5%: Commercially available concentrated water glass: water = 1:19 (volume ratio).

[0063] Example

[0064] Example 1

[0065] The preparation of the collector is as follows:

[0066] Under stirring, 10% triethanolamine is slowly poured into 10% oleic acid, the mass ratio of oleic acid to triethanolamine is 2:1, and the reaction is carried out at room temperature to obtain a modified oleic acid solution (oleic acid triethanolamine), i.e., a collector, and the synthesis rate of the modified oleic acid solution is 95.2%.

[0067] Example 2

[0068] The preparation of the collector is as follows:

[0069] Under stirring, 7% triethanolamine is slowly poured into 13% oleic acid, the mass ratio of oleic acid to triethanolamine is 2:1, and the reaction is carried out at room temperature to obtain a modified oleic acid solution (oleic acid triethanolamine), i.e., a collector, and the synthesis rate of the modified oleic acid solution is 93.3%.

[0070] Example 3

[0071] The preparation of the collector is as follows:

[0072] Under stirring, triethanolamine with a concentration of 12% is slowly poured into oleic acid with a concentration of 8%. The mass ratio of oleic acid to triethanolamine is 2:1. The reaction is carried out at room temperature to obtain a modified oleic acid solution (oleic acid triethanolamine), i.e., a collector. The synthesis rate of the modified oleic acid solution is 93.7%.

[0073] Example 4

[0074] The preparation of the collector is as follows:

[0075] Under stirring, 10% triethanolamine is slowly poured into 10% oleic acid, the mass ratio of oleic acid to triethanolamine is 1.5:1, and the mixture is reacted at room temperature to obtain a modified oleic acid solution (oleic acid triethanolamine), i.e., a collector. The synthesis rate of the modified oleic acid solution in the collector is 75.5%.

[0076] By comparing the modified oleic acid solutions prepared in Examples 1-4, it can be seen that the synthesis rate of the modified oleic acid solution in the prepared collector by the preparation method of the present application is 92.7-95.2%, and the content of the modified oleic acid solution is high. Most preferably, at room temperature, when oleic acid with a concentration of 10% and triethanolamine with a concentration of 10% react in a volume ratio of 2:1, the synthesis rate of the modified oleic acid solution in the prepared collector is the highest, which is 95.2%.

[0077] In summary, the collector is prepared by adopting the formula and preparation method of the present application. The preparation method is simple, fast, low-cost and the content of modified oleic acid solution in the prepared collector is high.

[0078] Application Examples

[0079] A method for flotation of fluorite using a collector comprises the following steps:

[0080] S1. preparing fluorite ore slurry: crushing and grinding the fluorite ore, and then mixing it with water to prepare a fluorite ore slurry with a mass concentration of 30-40%;

[0081] S2, flotation I process: add 1600-2000g / t sodium carbonate to the fluorite ore pulp (adjust the pH to 7.5-8.5), then add 1500-2000g / t water glass and 100-300g / t collector in sequence, stir, and perform flotation operation. After the flotation operation, obtain the flotation tank bottom mineral I and foam I;

[0082] S3, flotation II process: add 300-500g / t of water glass and 50-100g / t of collector to the foam I in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral II and foam II are obtained;

[0083] S4, scavenging process: mixing the flotation tank bottom mineral I with the flotation tank bottom mineral II, and performing scavenging operation, and then returning the scavenged foam mineral to the flotation process II and mixing it with the foam I, and flotation again;

[0084] S5, flotation III process: add 700-1000 g / t of acidified water glass and 50-100 g / t of collector to the foam II in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral III and foam III are obtained;

[0085] S6, flotation process IV: add 500-800 g / t of acidified water glass and 20-50 g / t of collector to the foam III in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral IV and foam IV are obtained;

[0086] S7, flotation step V: add 500-800 g / t of acidified water glass and 10-30 g / t of collector to the foam IV in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral V and foam V are obtained;

[0087] S8, flotation process VI: add 100-300g / t of acidified water glass to the foam V, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral VI and foam VI are obtained; the foam VI is fluorite concentrate.

[0088] Fluorite ore contains fluorite, mica and other substances. The method of the present application is used to float fluorite. The flotation tank bottom minerals I and II are mixed ores (quartz, mica); the flotation tank bottom minerals III, IV, V and VI are mostly conjoined minerals (quartz, mica and fluorite).

[0089] The collector is the modified oleic acid solution prepared in Example 1 of the present application.

[0090] Table 1 Mineral composition and particle size distribution of ground fluorite ore

[0091]

[0092] Selection of dosage of modified oleic acid solution

[0093] A method for flotation of fluorite using a modified oleic acid solution comprises the following steps:

[0094] The collector is the modified oleic acid solution prepared in Example 1 of the present application.

[0095] S1. preparing fluorite ore slurry: crushing and grinding the fluorite ore raw material, and then mixing it with water to prepare a fluorite ore slurry with a mass concentration of 35%;

[0096] S2, flotation I process: add 1600g / t of sodium carbonate, 2000g / t of water glass and 300g / t of collector to the fluorite ore pulp in sequence, stir and carry out flotation operation. After the flotation operation, mineral I and foam I at the bottom of the flotation tank are obtained, and foam I is the rough fluorite concentrate.

[0097] The mineral components and particle size distribution of the ground fluorite raw material are shown in Table 1. The flotation temperature of the fluorite ore slurry is 25°C.

[0098] Fluorite was floated using the above method. While other conditions remained unchanged, the amount of modified oleic acid solution in flotation step I was changed, and the flotation of fluorite was calculated. The specific data are shown in Table 2 below.

[0099] Table 2 Effect of dosage of modified oleic acid solution on fluorite flotation effect

[0100]

[0101] It can be seen from the data in Table 2 that with the increase in the amount of modified oleic acid solution, the fluorite (CaF2) content in the fluorite rough concentrate is gradually decreasing, while the recovery rate of the fluorite rough concentrate is gradually increasing. That is, the fluorite (CaF2) content in the fluorite rough concentrate is inversely proportional to the recovery rate. The higher the fluorite (CaF2) content, the lower the recovery rate of the fluorite rough concentrate. When the amount of modified oleic acid solution is 100g / t-300g / t, the fluorite (CaF2) content and recovery rate in the fluorite rough concentrate are both ideal, and a higher fluorite (CaF2) content and recovery rate can be taken into account at the same time. Therefore, when using modified oleic acid solution to float fluorite, the optimal amount of modified oleic acid solution is 100-300g / t.

[0102] In the process of fluorite flotation with collector (modified oleic acid solution), the influence of the amount of each reagent added in each flotation process on the flotation effect of fluorite.

[0103] The fluorite raw material is the fluorite in Table 1, and the CaF2 content in the fluorite raw material is 20.13%. The flotation temperature of the fluorite ore slurry is 25°C.

[0104] The difference between Application Example 1-2 and Comparative Application Example 1-2 is that the amount of reagent added in each flotation process is different, as shown in Table 3 below.

[0105] The recovery rate of the fluorite concentrate obtained in Application Example 1-2 and Comparative Example 1-2 and the fluorite (CaF2) content in the fluorite concentrate are shown in Table 4 below.

[0106] Table 3 Dosage of each agent in Application Example 1-2 and Comparative Application Example 1-2

[0107]

[0108]

[0109] Table 4

[0110]

[0111] From the data in Table 4, it can be seen that by adopting the method of the present application to flotate fluorite, a fluorite concentrate with high recovery rate and high fluorite (CaF2) can be obtained.

[0112] Comparison of the effect of fluorite flotation with collector and fluorite flotation with oleic acid

[0113] The collector (modified oleic acid solution) prepared in Example 1 of the present application was used to float fluorite ores 1#, 2# and 3# at 25°C and 0-5°C, respectively.

[0114] The specific process conditions are as follows:

[0115] A method for flotation of fluorite using a modified oleic acid solution comprises the following steps:

[0116] S1. preparing fluorite ore slurry: crushing and grinding the fluorite ore raw material, and then mixing it with water to prepare a fluorite ore slurry with a mass concentration of 35%;

[0117] S2, flotation I process: add 1600g / t of sodium carbonate, 2000g / t of water glass, and 300g / t of collector to the fluorite ore pulp in sequence, stir, and perform flotation operation. After the flotation operation, flotation tank bottom mineral I and foam I are obtained;

[0118] S3, flotation II process: add 500g / t of water glass and 80g / t of collector to the foam I in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral II and foam II are obtained;

[0119] S4, scavenging process: after mixing the flotation tank bottom mineral I with the flotation tank bottom mineral II, after scavenging operation, the scavenged foam mineral is returned to the flotation process II and mixed with the foam I, and flotation is performed again;

[0120] S5, flotation process III: add 800g / t of acidified water glass and 100g / t of collector to the foam II in sequence, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral III and foam III are obtained; the flotation tank bottom mineral III flows back to the flotation process III and is mixed with the foam II, and the flotation process III is performed again; the foam III flows to the next flotation process IV;

[0121] S6, flotation process IV: add 650g / t of acidified water glass and 50g / t of collector to foam III in sequence, stir, and perform flotation operation. After flotation operation, mineral IV and foam IV at the bottom of flotation tank are obtained; mineral IV at the bottom of flotation tank flows back to flotation process IV and is mixed with foam III, and flotation process III is performed again; foam IV flows to the next flotation process V; S7, flotation process V: add 500g / t of acidified water glass and 30g / t of collector to foam IV in sequence, stir, and perform flotation operation. After flotation operation, mineral V and foam V are obtained; mineral V at the bottom of flotation tank flows back to flotation process V and is mixed with foam IV, and flotation process V is performed again; foam V flows to the next flotation process VI;

[0122] S8, flotation process VI: add 200g / t of acidified water glass into the foam V, stir, and perform flotation operation. After the flotation operation, the flotation tank bottom mineral VI and foam VI are obtained; the flotation tank bottom mineral VI is returned to the flotation process VI and mixed with the foam V, and the flotation process VI is performed again; the foam VI is fluorite concentrate.

[0123] Fluorite ores 1#, 2# and 3# were floated with oleic acid at 25°C and 0-5°C respectively.

[0124] The process parameters for flotation of fluorite ore using oleic acid are consistent with the process parameters in the method for flotation of fluorite using the collector (modified oleic acid solution) prepared in Example 1 of the present application.

[0125] The mineral compositions of fluorite ores 1#, 2# and 3# are shown in Table 5 below.

[0126] Table 5 Multi-element analysis and particle size distribution of fluorite ores 1#, 2# and 3#

[0127]

[0128]

[0129] From Table 5, we can see the particle size and yield of the minerals in fluorite mines 1#, 2# and 3#; among the mineral particle sizes of the three minerals, -0.10mm accounts for almost 100%, -0.038mm accounts for 67.32-73.15%, and -0.019mm accounts for 37.34-4.17%. Most of the minerals are fine particles, which are difficult to select minerals.

[0130] The process conditions for flotation of fluorite are the same. At the same temperature (25°C and 0-5°C), the flotation effects of fluorite ores 1#, 2# and 3# using the collector (modified oleic acid solution) prepared in Example 1 of the present application and oleic acid are compared, as shown in Table 6.

[0131] Table 6 Comparison of flotation effects of modified oleic acid solution and oleic acid at the same temperature

[0132]

[0133]

[0134] From the data in Table 6, it can be seen that when the flotation pulp temperature is 25℃ and 0-5℃ respectively and other flotation conditions are the same, the effect of flotation of fluorite with modified oleic acid solution (fluorite concentrate content and recovery rate) is better than that of flotation of fluorite with oleic acid (fluorite concentrate content and recovery rate); the difference between the two is small when flotation is performed at 25℃; while the difference between the two is large when flotation is performed at 0-5℃. The lower the flotation pulp temperature, the greater the difference in the flotation effect of oleic acid flotation of fluorite, while the difference in the flotation effect of modified oleic acid solution is small, especially in terms of fluorite (CaF2) content in fluorite concentrate and fluorite concentrate recovery rate. The effect of flotation of fluorite with modified oleic acid solution is particularly good. It can be seen that at 0-5℃, modified oleic acid solution is more suitable for flotation of fluorite.

[0135] From the data in Table 6, it can be seen that when the flotation slurry temperature is 25℃ and 0-5℃ respectively and other flotation conditions are the same, the modified oleic acid solution and oleic acid are used to float fluorite respectively. With the increase of the fluorite (CaF2) content in the fluorite ore, when oleic acid is used to float fluorite, the difference between the recovery rate when the flotation slurry temperature is 0-5℃ and the recovery rate when the flotation slurry temperature is 25℃ is large, and the fluorite (CaF2) content in the fluorite concentrate is also different. When the modified oleic acid solution is used to float fluorite, the difference between the recovery rate when the flotation slurry temperature is 0-5℃ and the recovery rate when the flotation slurry temperature is 25℃ is small, and the fluorite (CaF2) content in the fluorite concentrate is also small.

[0136] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed. However, as long as it is within the scope of the claims of the present application, it shall be protected by the patent law.

Claims

1. A method for preparing a collector, Features: The steps include: Under stirring, triethanolamine is slowly poured into oleic acid, and reacted at room temperature to obtain a modified oleic acid solution, which is the collector; The volume ratio of oleic acid to triethanolamine is (1.7-2.3):1; The oleic acid concentration is 7-12%; The triethanolamine concentration is 8-13%.

2. A method for preparing a collector according to claim 1, Features: The volume ratio of oleic acid to triethanolamine is 2:

1.

3. The preparation method of the collector according to claim 1, Features: The synthesis rate of modified oleic acid solution in the collector is greater than 90%.

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