Low-temperature-resistant collecting agent and preparation method thereof

Abstract

The invention provides a low-temperature-resistant collecting agent and a preparation method thereof, the low-temperature-resistant collecting agent comprises oleic acid and an auxiliary agent, and the oleic acid and the auxiliary agent are compounded according to a first preset proportion. According to the low-temperature-resistant collecting agent and the preparation method thereof, the problem that the collecting agent is poor in collecting capacity under the low-temperature condition can be solved, and the effect that the collecting agent has high selectivity and high collecting capacity at the low temperature is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of mineral flotation collector preparation, in particular to a low-temperature resistant collector and a preparation method thereof. Background Art

[0002] The market value of fluorite is constantly increasing. The raw fluorite ore for mineral processing is becoming poorer, finer and more complex, and the difficulty of mineral processing technology is becoming higher and higher. At present, fluorite is mainly floated by fatty acid collectors, among which oleic acid is the most used fatty acid. Its main mechanism of action is that oleate (R-) reacts with Ca on the surface of fluorite. 2+ The reaction produces calcium oleate (CaR 2 ) precipitates on the surface of fluorite to make it hydrophobic and float. Since ordinary industrial oleic acid is not composed of a single oleic acid, but a mixture of various unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and various saturated fatty acids such as palmitic acid and stearic acid, one of the important characteristics of these fatty acids is that the melting points are very different. Industrial oleic acid usually presents a solid-liquid mixed state below 15°C, which seriously affects the use of collectors. Therefore, fluorite beneficiation is significantly affected by seasons and ambient temperatures. In winter in northern regions, measures such as heating reagents or slurry are often required to ensure production. The artificial heating method has no technical content and the production cost increases sharply. Especially in recent years, due to the restrictions of environmental protection policies, coal-fired boilers have been forced to be banned, and the heating cost has further increased. Moreover, after heating, there is still a problem of poor collector collection ability, and the amount of collector must be greatly increased, resulting in an increase in production costs. The development of new and efficient collectors with high selectivity and high collection ability for fluorite at low temperatures is of great significance to fluorite beneficiation. Summary of the invention

[0003] In view of the above problems, the present invention is proposed to provide a low-temperature resistant collector and a preparation method thereof that overcomes the above problems or at least partially solves the above problems, which can solve the problem of poor collection ability of the collector under low temperature conditions and achieve the effect that the collector has high selectivity and high collection ability at low temperatures.

[0004] Specifically, the present invention provides a low-temperature resistant collector, comprising: target oleic acid and an auxiliary agent, wherein the target oleic acid and the auxiliary agent are compounded according to a first preset ratio.

[0005] Optionally, the composition and ratio of the target oleic acid are as follows: Saturated acids: palmitic acid 2.54%, stearic acid 3.89%; Unsaturated acids: oleic acid 33.94%, linoleic acid 53.19%, linolenic acid 3.01%, α-linolenic acid 3.43%; The ingredients and proportions of the additives are as follows: Saturated acids: palmitic acid 6.62%, stearic acid 1.24%, arachidic acid 0.11%, heneicosanoic acid 3.01%, behenic acid 0.12%; Unsaturated acids: palmitoleic acid 0.22%, oleic acid 85.48%, linoleic acid 2.86%, linolenic acid 0.12%, α-linolenic acid 0.22%.

[0006] Optionally, the first preset ratio is 2:1 to 6:1.

[0007] The present invention also provides a method for preparing the low-temperature resistant collector as described in any one of the above items, comprising: Preparation of primary oleic acid from fats and oils; screening the primary oleic acid to obtain target oleic acid; The target oleic acid is compounded with the auxiliary agent to obtain the low-temperature resistant collector.

[0008] Optionally, the preparation of primary oleic acid using oils and fats comprises: Performing saponification separation treatment on the oil to obtain a first treatment liquid; Performing acidification and separation treatment on the first treatment liquid to obtain the primary oleic acid; The screening of the primary oleic acid to obtain the target oleic acid comprises: Performing freeze crystallization treatment on the primary oleic acid, and obtaining a second treatment liquid after filtering; The second treated liquid is subjected to distillation separation treatment to obtain the target oleic acid.

[0009] Optionally, the step of performing saponification separation treatment on the oil to obtain a first treatment liquid comprises: Mixing fat, sodium hydroxide and water in a second preset ratio, performing saponification reaction while stirring at a first preset temperature, standing and stratifying after reacting for a first preset time, and discharging the clear liquid in the lower layer to obtain the first treated liquid; The step of subjecting the first treatment liquid to an acidification separation treatment to obtain the primary oleic acid comprises: The first treatment liquid is mixed with a sulfuric acid solution of a preset concentration, acidified while stirring at a second preset temperature, allowed to stand for a second preset time to separate into layers, and the clear liquid at the lower layer is discharged to obtain the primary oleic acid.

[0010] Optionally, the second preset ratio is 10:1:20, the first preset temperature is 95° C. to 100° C., and the first preset time is 1 hour to 2 hours; The preset concentration is 5% to 15%, the second preset temperature is 85° C. to 95° C., and the second preset time is 30 min to 50 min.

[0011] Optionally, the freezing and crystallization of the primary oleic acid and filtering to obtain a second treatment solution comprises: The primary oleic acid and methanol are mixed in a third preset ratio, frozen at a third preset temperature for a third preset time, and then filtered to obtain the second treatment liquid.

[0012] Optionally, the third preset ratio is 1:2 to 1:4, the third preset temperature is -20°C to 0°C, and the third preset time is 1h to 3h; The distillation temperature is 70°C to 90°C.

[0013] Optionally, the first treatment liquid is subjected to an acidification separation treatment, and in the step of obtaining the primary oleic acid, the acidification separation treatment of the first treatment liquid is repeated multiple times.

[0014] In a low-temperature resistant collector and a preparation method thereof of the present invention, the low-temperature resistant collector includes a target oleic acid and an auxiliary agent. By selectively separating and purifying oleic acid, the target oleic acid having high selectivity and collection capacity at low temperatures is screened out. When in use, the target oleic acid and the auxiliary agent are mixed in a first preset ratio and added to the fluorite slurry. The target oleic acid is used as a main agent to float fluorite, and the auxiliary agent is used as an auxiliary agent to modify the target oleic acid, thereby enhancing the selectivity and collection capacity of the target oleic acid for fluorite, thereby improving the flotation result of the low-temperature resistant collector for fluorite ore.

[0015] Furthermore, in a low-temperature resistant collector and a preparation method thereof of the present invention, oil is used as a raw material to prepare the collector. When preparing the collector, primary oleic acid is first prepared using oil. The primary oleic acid is then screened to select a target oleic acid that is still liquid at low temperatures, so that the target oleic acid has high selectivity and capture capacity. Finally, the obtained target oleic acid is compounded with an auxiliary agent, and the auxiliary agent modifies the target oleic acid to enhance the selectivity and capture capacity of the target oleic acid for fluorite, thereby further improving the selectivity and capture capacity of the collector. By screening out the target oleic acid that is liquid at low temperatures, the collector is in a liquid state at low temperatures, preventing the collector from presenting a solid-liquid mixed state in a low-temperature environment, thereby enabling the collector to still have high selectivity and capture capacity at low temperatures.

[0016] Based on the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will become more aware of the above and other objects, advantages and features of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Hereinafter, some specific embodiments of the present invention will be described in detail in an exemplary and non-limiting manner with reference to the accompanying drawings. The same reference numerals in the accompanying drawings indicate the same or similar components or parts. It should be understood by those skilled in the art that these drawings are not necessarily drawn to scale. In the accompanying drawings: Figure 1 is a schematic flow chart of preparing a low-temperature resistant collector according to one embodiment of the present invention; Figure 2 is a specific schematic flow chart of preparing a low-temperature resistant collector according to one embodiment of the present invention; Figure 3 is a schematic flow chart of an open circuit test of Luanchuan fluorite mine according to an embodiment of the present invention; Figure 4 It is a schematic flow chart of an open circuit test of Chengde fluorite mine according to an embodiment of the present invention. DETAILED DESCRIPTION

[0018] Refer to the following Figures 1 to 4 To describe a low-temperature resistant collector and a preparation method thereof according to an embodiment of the present invention. In the description of this embodiment, it should be understood that the terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features, that is, include one or more of the features. In the description of the present invention, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined. When a feature "includes or contains" one or some of the features it covers, unless otherwise specifically described, this indicates that other features are not excluded and may further include other features.

[0019] In the description of the present embodiment, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0020] The embodiment of the present invention provides a low-temperature resistant collector, comprising target oleic acid and an auxiliary agent, wherein the target oleic acid and the auxiliary agent are compounded according to a first preset ratio, wherein the auxiliary agent is a surfactant-type agent.

[0021] In this embodiment, the low temperature resistant collector includes a target oleic acid and an auxiliary agent. By selectively separating and purifying oleic acid, the target oleic acid having high selectivity and collection capacity at low temperature is screened out. When in use, the target oleic acid and the auxiliary agent are mixed in a first preset ratio and added to the fluorite slurry. The target oleic acid is used as a main agent to float fluorite, and the auxiliary agent is used as an auxiliary agent to modify the target oleic acid, thereby enhancing the selectivity and collection capacity of the target oleic acid for fluorite, thereby improving the flotation result of the low temperature resistant collector for fluorite ore.

[0022] In some embodiments of the present invention, the composition and proportion of the target oleic acid are as follows: saturated acids: palmitic acid 2.54%, stearic acid 3.89%; unsaturated acids: oleic acid 33.94%, linoleic acid 53.19%, linolenic acid 3.01%, α-linolenic acid 3.43%.

[0023] The composition and proportion of the additives are as follows: saturated acids: palmitic acid 6.62%, stearic acid 1.24%, arachidic acid 0.11%, heneicosanoic acid 3.01%, behenic acid 0.12%; unsaturated acids: palmitoleic acid 0.22%, oleic acid 85.48%, linoleic acid 2.86%, linolenic acid 0.12%, α-linolenic acid 0.22%.

[0024] In some embodiments of the present invention, the first preset ratio is 2:1 to 6:1.

[0025] In this embodiment, the first preset ratio is the weight ratio of the target oleic acid to the additive. For example, the first preset ratio is 2:1, 3:1, 4:1, 5:1 or 6:1.

[0026] Preferably, the first preset ratio is 4:1.

[0027] Figure 1 is a schematic flow chart of preparing a low-temperature resistant collector according to one embodiment of the present invention, such as Figure 1 As shown, and refer to Figure 2 The present invention also provides a method for preparing a low-temperature resistant collector as in any one of the above embodiments, comprising: Step S100, preparing primary oleic acid using oil.

[0028] Step S200, screening primary oleic acid to obtain target oleic acid.

[0029] Step S300, compounding the target oleic acid with an auxiliary agent to obtain a low-temperature resistant collector.

[0030] In the present embodiment, grease is used as a raw material to prepare a low-temperature resistant collector. When preparing the low-temperature resistant collector, primary oleic acid is first prepared using grease. Primary oleic acid is then screened to select a target oleic acid that is still liquid at low temperatures, so that the target oleic acid has a high selectivity and a collecting capacity. Finally, the obtained target oleic acid is compounded with an auxiliary agent, and the auxiliary agent modifies the target oleic acid to enhance the selectivity and the collecting capacity of the target oleic acid to fluorite, and further enhances the selectivity and the collecting capacity of the low-temperature resistant collector. By screening out the target oleic acid that is liquid at low temperatures, the low-temperature resistant collector is in a liquid state at low temperatures, preventing the low-temperature resistant collector from presenting a solid-liquid mixed state in a low-temperature environment, and then the low-temperature resistant collector still has a high selectivity and a collecting capacity at low temperatures.

[0031] In some embodiments of the present invention, the oil is a composite oil of waste oil residue of food oil.

[0032] In this embodiment, oleic acid is prepared using waste oil residue and composite oil in food oil, which recycles waste resources, reduces resource waste, prevents improper treatment of waste resources from affecting the environment, improves resource utilization, and thus reduces the preparation cost of low-temperature resistant collectors.

[0033] In some embodiments of the present invention, step S100, preparing primary oleic acid using oil, comprises: Step S110, performing saponification separation treatment on the oil and fat to obtain a first treatment liquid.

[0034] Step S120, performing acidification separation treatment on the first treatment liquid to obtain primary oleic acid.

[0035] In this embodiment, when preparing primary oleic acid, oil is subjected to saponification reaction to generate fatty acid salt and glycerol, and the first treatment liquid is a fatty acid salt solution. Then, an acid solution is added to the fatty acid salt solution for acidification treatment, and the fatty acid salt solution reacts with the acid solution to generate fatty acid and salt solution, and the generated fatty acid is primary oleic acid. The preparation method of primary oleic acid is simple in process, easy to operate, and convenient for mass production of primary oleic acid.

[0036] In some embodiments of the present invention, step S200, screening primary oleic acid to obtain target oleic acid comprises: Step S210, freeze-crystallize the primary oleic acid, and obtain a second treated liquid after filtering.

[0037] Step S220, performing distillation separation treatment on the second treated liquid to obtain target oleic acid.

[0038] In the present embodiment, when screening primary oleic acid, the primary oleic acid is frozen to crystallize some components in the primary oleic acid. After freezing, it is quickly filtered to separate the filtrate from the filter cake, and the separated filtrate is the second treatment liquid. The filtrate is distilled, and the obtained liquid is the target oleic acid. By freezing the primary oleic acid in a low temperature environment, the solid fatty acid is filtered out, and the fatty acid that is still liquid in the low temperature environment is screened out as the target oleic acid, so that the low temperature resistant collector is in a liquid state at low temperatures, so that the low temperature resistant collector still has high selectivity and collecting capacity at low temperatures.

[0039] In some embodiments of the present invention, step S110, performing saponification separation treatment on oil to obtain a first treatment liquid, comprises: Step S111, oil, sodium hydroxide and water are mixed in a second preset ratio, and saponification reaction is carried out while stirring at a first preset temperature. After the reaction lasts for a first preset time, the mixture is allowed to stand and separate into layers, and the clear liquid in the lower layer is discharged to obtain a first treated liquid.

[0040] In this embodiment, when the oil undergoes saponification reaction, the oil, sodium hydroxide and water are added to a reactor and mixed, and the oil and sodium hydroxide are heated while being stirred to undergo saponification reaction. After the reaction is completed, the mixed solution is allowed to stand, and the solution begins to separate. The upper layer solution is a fatty acid salt solution, and the lower layer solution is glycerol. The glycerol is discharged, and the fatty acid salt solution remaining in the reactor is the first treatment solution. The reaction rate of the saponification reaction is increased by heating and stirring, and the reaction time of the saponification reaction is reduced, thereby reducing the preparation time of primary oleic acid, reducing the preparation time of the low-temperature resistant collector, and saving the production cost of the low-temperature resistant collector.

[0041] In some embodiments of the present invention, the second preset ratio is 10:1:20, and the second preset ratio is the volume ratio of oil, sodium hydroxide and water.

[0042] In some embodiments of the present invention, the first preset temperature is 95° C. to 100° C. For example, the first preset temperature may be 95° C., 96° C., 97° C., 98° C., 99° C. or 100° C.

[0043] In this embodiment, oil and sodium hydroxide are subjected to saponification reaction at a temperature of 95°C to 100°C. Increasing the temperature can increase the movement speed of molecules and increase the collision probability between molecules. A higher reaction temperature can promote the saponification reaction, thereby saving the preparation time of the low-temperature resistant collector and improving the preparation efficiency of the low-temperature resistant collector. However, when the reaction temperature is too high, it is easy to cause the oil to be unable to be completely saponified, affecting the quality of the fatty acid salt. Therefore, it is necessary to select a suitable saponification reaction temperature to increase the rate of the saponification reaction and ensure the quality of the fatty acid salt.

[0044] In some embodiments of the present invention, the first preset duration is 1 hour to 2 hours. For example, the first preset duration may be 1 hour, 1.5 hours or 2 hours.

[0045] In the present embodiment, the appropriate reaction time can ensure that the reaction is fully carried out, while too long or too short a reaction time may have an adverse effect on the saponification reaction. A reaction time that is too short will result in an incomplete saponification reaction, affecting the quality of the fatty acid salt. The saponification reaction is an exothermic reaction. As time goes on, the reversibility of the reaction gradually becomes more obvious and may also lead to the generation of by-products. Therefore, it is necessary to select a suitable saponification reaction time to ensure the quality of the generated fatty acid salt, and then to ensure the quality of the low-temperature resistant collector, so that the low-temperature resistant collector has higher selectivity and capture capacity.

[0046] In some embodiments of the present invention, step S120, performing acidification separation treatment on the first treatment liquid to obtain primary oleic acid, comprises: Step S121, mixing the first treatment liquid with a sulfuric acid solution of a preset concentration, acidifying with stirring at a second preset temperature, standing to separate layers after reacting for a second preset time, and discharging the clear liquid at the lower layer to obtain primary oleic acid.

[0047] In this embodiment, when the fatty acid salt generated by the oil reacts with the sulfuric acid solution, the fatty acid salt and the sulfuric acid are heated while being stirred to undergo an acidification reaction. After the reaction is completed, the mixed solution is allowed to stand and the solution begins to separate. The upper layer solution is the fatty acid, and the lower layer solution is the sulfate solution. The sulfate solution below is discharged, and the fatty acid remaining in the reactor is the primary oleic acid. The reaction rate of the acidification reaction is increased by heating and stirring, and the reaction time of the acidification reaction is reduced, thereby reducing the preparation time of the primary oleic acid, reducing the preparation time of the low-temperature resistant collector, and saving the production cost of the low-temperature resistant collector.

[0048] In some embodiments of the present invention, the first treatment liquid is subjected to an acidification separation treatment, and in the step of obtaining primary oleic acid, the acidification separation treatment of the first treatment liquid is repeated multiple times.

[0049] In this embodiment, when preparing primary oleic acid, sulfuric acid solution is added multiple times so that fatty acid salts can fully react with sulfuric acid to be converted into fatty acids, thereby improving the quality of primary oleic acid and thus improving the quality of low-temperature resistant collectors. For example, the acidification step of the first treatment liquid is repeated three, four, five or six times until the oleic acid in the upper layer is clear and transparent.

[0050] In some embodiments of the present invention, the preset concentration is 5% to 15%. For example, the preset concentration may be 5%, 7%, 9%, 11%, 13% or 15%.

[0051] In this embodiment, the amount of sulfuric acid added is not only enough to completely convert the fatty acid salt into fatty acid, but also to neutralize the excess alkali during the saponification reaction.

[0052] Preferably, the preset concentration is 9%.

[0053] The second preset temperature is 85° C. to 95° C., for example, the second preset temperature is 85° C., 88° C., 90° C., 93° C. or 95° C. The higher the temperature, the faster the acidification reaction speed.

[0054] The second preset time length is 30 minutes to 50 minutes. For example, the second preset time length is 30 minutes, 35 minutes, 40 minutes, 45 minutes or 50 minutes.

[0055] Preferably, the second preset time length is 40 minutes.

[0056] In some embodiments of the present invention, step S210, performing freeze crystallization treatment on primary oleic acid and filtering to obtain a second treatment liquid, comprises: Step S211, mixing primary oleic acid and methanol according to a third preset ratio, freezing at a third preset temperature for a third preset time, and then filtering to obtain a second treated liquid.

[0057] In the present embodiment, when primary oleic acid is frozen, primary oleic acid is mixed with methanol so that primary oleic acid is fully dissolved in methanol, and the mixed solution of primary oleic acid and methanol is placed in a freezing device for freezing, and the fatty acid with a higher melting point is frozen into crystals, and the fatty acid with a lower melting point is still in a liquid state. The mixed solution is filtered through a filtering device to separate the liquid and solid fatty acids, and the liquid fatty acid is the second treatment solution. The fatty acid that is still liquid at low temperature is separated by freezing crystallization, and the separation cost of the fatty acid is low, and the oleic acid obtained is of high quality, and there is no environmental pollution, which is convenient for realizing large-scale industrial production.

[0058] In some embodiments of the present invention, the frozen solution is filtered using a filtering device, and the filtering device and the mixed solution are placed in a freezing device for freezing. The filtering device and the mixed solution are taken out and then quickly filtered.

[0059] In this embodiment, the filter device is placed in a freezer and frozen. During filtration, the temperature of the freezer is the same as that of the solution, which prevents the temperature of the filter device from being too high. During filtration, the crystallized fatty acid is melted into a liquid state, thereby improving the quality of the oleic acid at the separation point, and thus improving the quality of the low-temperature resistant collector. Moreover, the filter device and the mixed solution are taken out and quickly filtered to prevent the crystallized fatty acid from melting into a liquid state due to a long filtration time, thereby further improving the quality of the low-temperature resistant collector.

[0060] In some embodiments of the present invention, the third preset ratio is 1:2 to 1:4. The third preset ratio is the weight ratio of primary oleic acid to methanol. For example, the third preset ratio can be 1:2, 1:3 or 1:4.

[0061] Preferably, the third preset ratio is 1:3.

[0062] The third preset temperature is -20°C to 0°C. The third preset temperature is the temperature at which the mixed solution of primary oleic acid and methanol is frozen. The third preset temperature can be -20°C, -15°C, -10°C, -5°C or 0°C.

[0063] Preferably, the third preset temperature is -10°C.

[0064] In some embodiments of the present invention, the third preset time is 1 hour to 3 hours. The third preset time is the time for freezing the mixed solution of primary oleic acid and methanol.

[0065] Preferably, the third preset time length is 2 hours.

[0066] In some embodiments of the present invention, the distillation temperature is 70° C. to 90° C. The distillation temperature may be 70° C., 75° C., 80° C., 85° C. or 90° C.

[0067] In this embodiment, a methanol solution is used to separate fatty acids, and primary oleic acid is dissolved in a methanol solution, and a second treatment liquid is obtained after freeze filtration. The second treatment liquid includes methanol and oleic acid, and the second treatment liquid is distilled to evaporate methanol, thereby obtaining the target oleic acid. The boiling point of methanol is 64.7°C, and the distillation temperature is set at 70°C to 90°C to ensure that the methanol in the second treatment liquid is completely evaporated, thereby ensuring the quality of the target oleic acid. The preparation method of the target oleic acid is simple, the cost is low, and the quality of the target oleic acid obtained is high, thereby preparing a high-quality low-temperature resistant collector.

[0068] In some embodiments of the present invention, after step S300, compounding the target oleic acid with the auxiliary agent to obtain a low-temperature resistant collector, the step further includes: Step S400, using the prepared low-temperature resistant collector to conduct a mineral flotation test to verify the flotation effect of the low-temperature resistant collector.

[0069] In this embodiment, after the low-temperature resistant collector is prepared, the low-temperature resistant collector is used to carry out a mineral flotation test. Sodium carbonate is used as a regulator to adjust the pH of the ore pulp, control the chemical composition of the ore pulp, the surface characteristics of the ore particles, etc., thereby improving the flotation effect. Water glass is used as an inhibitor to increase the hydrophilicity of the mineral and prevent the mineral from interacting with the low-temperature resistant collector, so that the floatability of other minerals is inhibited. Example

[0070] A low-temperature resistant collector was prepared according to the preparation method, and the prepared low-temperature resistant collector was used to test the Luanchuan fluorite mine. The test flow chart is as follows: Figure 3 shown.

[0071] Step S11, add oil, sodium hydroxide and water into a reaction kettle in a ratio of 10:1:20, carry out saponification reaction at 95°C to 100°C while stirring, let stand for 1.5 hours to separate the layers, and discharge the clear liquid in the lower layer to obtain the first treated liquid.

[0072] Step S12, add 100 mL of concentrated sulfuric acid and 1000 mL of water to the first treated liquid, acidify at 85°C to 95°C while stirring, react for 40 minutes, let stand to separate, and discharge the lower layer of clear liquid. Repeat adding 100 mL of concentrated sulfuric acid and 1000 mL of water for acidification and separation several times until the upper layer of oleic acid is clear and transparent, and obtain primary oleic acid.

[0073] Step S13, primary oleic acid and methanol are mixed in a ratio of 1:3, frozen at -10°C for 2 hours, and then filtered to obtain a second treated liquid.

[0074] Step S14, pouring the second treated liquid into a rotary evaporator, distilling it at 80° C., and obtaining the target oleic acid after distilling out the methanol.

[0075] Step S15, compounding the target oleic acid and the auxiliary agent in a ratio of 4:1 to obtain a low-temperature resistant collector.

[0076] Step S16, a flotation test of fluorite ore is carried out at 9°C using a low-temperature resistant collector. The flotation test flow chart is as follows: Figure 3 shown.

[0077] The flotation results of the low-temperature resistant collector are shown in Table 1: Table 1 Results of open circuit test of Luanchuan fluorite as a low temperature resistant collector

[0078] From the data in Table 1, it is found that the low-temperature resistant collector in the present invention has a good flotation index for Luanchuan fluorite ore, and the concentrate yield is 48.75%, CaF 2 The grade is 97.49%, CaF 2 The recovery rate reached 91.91%. Example

[0079] The prepared low-temperature resistant collector was used to test the Chengde fluorite mine. The test flow chart is as follows: Figure 4 The test steps are the same as those in Example 1. The flotation results of the low temperature resistant collector are shown in Table 2: Table 2 Results of open circuit test of low temperature resistant collectors in Chengde fluorite mine

[0080] From the data in Table 2, it is found that the low-temperature resistant collector in the present invention has a good flotation index for Chengde fluorite ore, and the concentrate yield is 57.98%, CaF 2 The grade is 98.39%, CaF 2 The recovery rate reached 92.03%.

[0081] Comparative Example 1 The conventional oleic acid collector was used to test the Luanchuan fluorite mine. The test flow chart is as follows: Figure 3 The test steps are the same as those in Example 1. The flotation results of conventional oleic acid collector are shown in Table 3: Table 3 Results of Luanchuan fluorite open circuit test with conventional oleic acid collector

[0082] From the data in Table 3, it is found that the conventional oleic acid collector is used to flotate Luanchuan fluorite ore, and the concentrate yield is 45.22%, CaF 2 The grade is 96.66%, CaF 2 The recovery rate is 83.88%.

[0083] By comparing the data in Table 1 with those in Table 3, it is found that the low-temperature resistant collector prepared by the present invention has good flotation index at 9°C. 2 The grade is 0.83% higher than that of conventional oleic acid collector, and the concentrate CaF 2 The recovery rate is 8.03% higher than that of conventional oleic acid collector.

[0084] Comparative Example 2 The conventional oleic acid collector was used to test the Chengde fluorite mine. The test flow chart is as follows: Figure 4 The test steps are the same as those in Example 1. The flotation results of conventional oleic acid collector are shown in Table 4: Table 4 Results of open circuit test of conventional oleic acid collector at Chengde fluorite mine

[0085] From the data in Table 4, it is found that the conventional oleic acid collector is used to flotation Chengde fluorite ore, and the concentrate yield is 54.17%, CaF 2 The grade is 97.01%, CaF 2 The recovery rate is 83.79%.

[0086] By comparing the data in Table 2 with those in Table 4, it is found that the low-temperature resistant collector prepared by the present invention has good flotation index at 9°C. 2 The grade is 1.38% higher than that of conventional oleic acid collector, and the concentrate CaF2 The recovery rate is 8.24% higher than that of conventional oleic acid collector.

[0087] The low-temperature resistant collector of the present invention was used to carry out flotation tests on Luanchuan fluorite mine and Chengde fluorite mine, and showed excellent and stable flotation indicators in a low-temperature environment. Therefore, the low-temperature resistant collector of the present invention can solve the problem of poor collection ability of the collector under low-temperature conditions, and significantly improve the recovery rate of fluorite concentrate without heating the slurry, thereby greatly reducing the cost of fluorite ore flotation.

[0088] At this point, those skilled in the art should recognize that, although multiple exemplary embodiments of the present invention have been shown and described in detail herein, many other variations or modifications that conform to the principles of the present invention can still be directly determined or derived based on the content disclosed in the present invention without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention should be understood and recognized as covering all these other variations or modifications.

Claims

1. A low temperature resistant collector, characterized in that: include: Target oleic acid and an auxiliary agent, wherein the target oleic acid and the auxiliary agent are compounded according to a first preset ratio.

2. The low temperature resistant collector according to claim 1, characterized in that: The composition and ratio of the target oleic acid are as follows: Saturated acids: palmitic acid 2.54%, stearic acid 3.89%; Unsaturated acids: oleic acid 33.94%, linoleic acid 53.19%, linolenic acid 3.01%, α-linolenic acid 3.43%; The ingredients and proportions of the additives are as follows: Saturated acids: palmitic acid 6.62%, stearic acid 1.24%, arachidic acid 0.11%, heneicosanoic acid 3.01%, behenic acid 0.12%; Unsaturated acids: palmitoleic acid 0.22%, oleic acid 85.48%, linoleic acid 2.86%, linolenic acid 0.12%, α-linolenic acid 0.22%.

3. The low temperature resistant collector according to claim 1, characterized in that: The first preset ratio is 2:1 to 6:

1.

4. A method for preparing a low-temperature resistant collector as claimed in any one of claims 1 to 3, characterized in that: include: Preparation of primary oleic acid from fats and oils; screening the primary oleic acid to obtain target oleic acid; The target oleic acid is compounded with the auxiliary agent to obtain the low-temperature resistant collector.

5. The method for preparing a low-temperature resistant collector according to claim 4, characterized in that: The method of preparing primary oleic acid by utilizing oils and fats comprises: Performing saponification separation treatment on the oil to obtain a first treatment liquid; Performing acidification and separation treatment on the first treatment liquid to obtain the primary oleic acid; The screening of the primary oleic acid to obtain the target oleic acid comprises: Performing freeze crystallization treatment on the primary oleic acid, and obtaining a second treatment liquid after filtering; The second treated liquid is subjected to distillation separation treatment to obtain the target oleic acid.

6. The method for preparing a low-temperature resistant collector according to claim 5, characterized in that: The step of performing saponification separation treatment on the oil to obtain a first treatment liquid comprises: Mixing fat, sodium hydroxide and water in a second preset ratio, performing saponification reaction while stirring at a first preset temperature, standing and stratifying after reacting for a first preset time, and discharging the clear liquid in the lower layer to obtain the first treated liquid; The step of subjecting the first treatment liquid to an acidification separation treatment to obtain the primary oleic acid comprises: The first treatment liquid is mixed with a sulfuric acid solution of a preset concentration, acidified while stirring at a second preset temperature, allowed to stand for a second preset time to separate into layers, and the clear liquid at the lower layer is discharged to obtain the primary oleic acid.

7. The method for preparing a low-temperature resistant collector according to claim 6, characterized in that: The second preset ratio is 10:1:20, the first preset temperature is 95° C. to 100° C., and the first preset time is 1 hour to 2 hours; The preset concentration is 5% to 15%, the second preset temperature is 85° C. to 95° C., and the second preset time is 30 min to 50 min.

8. The method for preparing a low-temperature resistant collector according to claim 5, characterized in that: The freezing and crystallization treatment of the primary oleic acid and filtering to obtain a second treatment liquid comprises: The primary oleic acid and methanol are mixed in a third preset ratio, frozen at a third preset temperature for a third preset time, and then filtered to obtain the second treatment liquid.

9. The method for preparing a low-temperature resistant collector according to claim 8, characterized in that: The third preset ratio is 1:2 to 1:4, the third preset temperature is -20°C to 0°C, and the third preset time is 1h to 3h; The distillation temperature is 70°C to 90°C.

10. The method for preparing a low-temperature resistant collector according to claim 6, characterized in that: The first treatment liquid is subjected to an acidification and separation treatment to obtain the primary oleic acid step, and the acidification and separation treatment of the first treatment liquid is repeated multiple times.

Images