Silicate mineral flotation collector and preparation method thereof

Abstract

The invention provides a silicate mineral flotation collector and a preparation method thereof.The preparation method comprises the steps that N, N-dimethyl octadecylamine, oleic acid and a stirring medium are mixed and stirred, and an initial solution is obtained; adding a glutaraldehyde solution into the initial solution, heating, and treating by adopting a reflux device to obtain a reaction solution; and adjusting the pH value of the reaction liquid, carrying out standing treatment, distillation treatment and precipitation treatment, and drying the obtained precipitate to obtain the silicate mineral flotation collecting agent. By combining the advantages of anion and cation collectors, the defect that the anion and cation collectors are inactivated due to charge entanglement precipitation is overcome, the collector which can exist in a stable ionic state is prepared, the agent is added in the preparation process of super iron fine powder, anion and cation existing in ore pulp can react with silicate minerals such as quartz at the same time, and the super iron fine powder is obtained. The synergistic effect of the anion collecting agent and the cation collecting agent is exerted, and the purpose of good mineral separation is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of iron ore flotation, relates to deep separation and desiliconization of iron ore concentrate and product utilization, and in particular to a silicate mineral flotation collector and a preparation method thereof. Background Art

[0002] Super iron ore concentrate is generally made from ordinary iron ore concentrate through reprocessing. Using ordinary iron ore concentrate to produce super iron ore concentrate is not only one of the directions of scientific and technological progress in iron ore mines, but also an effective way to improve the economic benefits of iron ore mines. At present, the commonly used purification methods are flotation, magnetic separation and shaking table gravity separation, and the magnetic-flotation and magnetic-gravity combined mineral separation process is the most common.

[0003] The impurities in iron ore concentrate are mainly quartz, feldspar, etc., and the reverse flotation desiliconization method is usually used to remove quartz, feldspar and other impurity minerals in iron ore concentrate, so as to prepare qualified super iron concentrate. The collectors commonly used in reverse flotation desiliconization are mainly cationic collectors and anionic collectors. Cationic collectors are mainly amines, and amine cationic collectors are not very selective in iron ore reverse flotation desiliconization; at the same time, because grinding causes fine particles to contain many broken bonds, the cationic collectors are consumed in large quantities, and the foam formed is not easy to eliminate, and the flotation effect is relatively poor; anionic collectors are more selective than cationic collectors, but the collection effect is limited when the pulp temperature is low.

[0004] At present, the method of adding anions and cations mixedly has achieved relatively good flotation effects, but anions and cations will react, and some collectors will form insoluble salts, which will weaken the effect of the collector and seriously affect the flotation cost. The existing collectors composed of anions and cations have different surface arrangements and opposite charges. In addition, most anions are alkaline, such as various sodium salts and polymers, and most cations are acidic, such as various ammonium salts. Their direct mutual dissolution will physically cause charge entanglement to cause precipitation or flocculation, and chemically may also react directly to cause inactivation. The effect of anion and cation collectors on minerals is generally that anions or cations ionize alkaline metal ions or H+ ions in the solution to carry positive or negative charges, and anions and cations form ionic bonds with minerals through their own positive or negative charges, thereby separating useful minerals from gangue minerals. If anion and cation charge entanglement or flocculation inactivation occurs, some reagents will lose their collection ability, and the flotation effect will be greatly reduced.

[0005] Therefore, it is necessary to modify the anionic and cationic mixed collectors to eliminate the negative impact between them and improve the selectivity and flotation effect of the collectors. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a silicate mineral flotation collector and a preparation method thereof, and in particular to a collector for preparing super iron concentrate by reverse flotation of iron concentrate. Compared with the existing anionic and cationic collectors, the present invention combines the advantages of anionic and cationic collectors to overcome the disadvantage of anionic and cationic collectors being inactivated due to charge entanglement precipitation, and prepares a collector that can exist in a stable ionic state. When this agent is added during the preparation process of super iron concentrate, the anions and cations present in the slurry can react with silicate minerals such as quartz at the same time, exerting the synergistic effect of anionic collectors and cationic collectors, thereby achieving the purpose of good mineral separation.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a silicate mineral flotation collector, the preparation method comprising:

[0009] (1) mixing N,N-dimethyloctadecylamine, oleic acid and a stirring medium and stirring to obtain an initial solution;

[0010] (2) adding glutaraldehyde solution to the initial solution described in step (1), heating and refluxing to obtain a reaction solution;

[0011] (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain the silicate mineral flotation collector.

[0012] In the present invention, by combining the advantages of anionic and cationic collectors, the disadvantage of inactivation of anionic and cationic collectors due to charge entanglement precipitation is overcome, and a collector that can exist in a stable ionic state is prepared. This agent is added during the preparation process of super iron concentrate. Anions and cations present in the slurry can react with silicate minerals such as quartz at the same time, exerting the synergistic effect of anionic collectors and cationic collectors, thereby achieving the purpose of good mineral separation.

[0013] It should be noted that the present invention prepares a new type of efficient collector, so that the collection ability of gangue minerals such as quartz in the reverse flotation process is stronger. The collector contains both anions and cations. The negatively charged collector and the negatively charged ore mud in the ore pulp form a like-charge repulsion force, reducing the interaction between the cation and the ore mud; the presence of the anionic collector can react with the Fe on the surface of the iron oxide and iron sulfide in the ore. + It forms a stable chemical adsorption and can complex various ions in the solution, reduce the interference of ions on the flotation reagent, and make the reagent more selective; and the collector in the present invention can make anions and cations coexist under normal temperature conditions, avoiding the phenomenon of anion and cation reaction to form insoluble salts, while exerting the effects of the anion and cation collectors.

[0014] It should be noted that, in the present invention, before using the collector, the raw ore can be pre-classified and then the coarse particles can be re-ground to solve the problem of low mineral monomer dissociation, improve the monomer dissociation degree of gangue minerals and magnetite minerals, and improve the flotation sorting efficiency to increase the grade and recovery rate of the concentrate.

[0015] As a preferred technical solution of the present invention, the molar ratio of the N,N-dimethyloctadecylamine to the oleic acid is 1:(6-9), for example, it can be 1:6, 1:7, 1:8, 1:9, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0016] In the present invention, the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:(6-9), so that the amino group in N,N-dimethyloctadecylamine and the carboxylic acid group in oleic acid react in a fixed ratio to generate a new amphiphilic substance; if it is not within this range, it may cause one of N,N-dimethyloctadecylamine and oleic acid to react incompletely or excessively, resulting in direct reaction of N,N-dimethyloctadecylamine and oleic acid, and no new amphiphilic substance can be generated.

[0017] Preferably, in step (1), N,N-dimethyloctadecylamine, oleic acid and a stirring medium are mixed and stirred in the following manner:

[0018] N,N-dimethyloctadecylamine and oleic acid are mixed and then mixed with a stirring medium.

[0019] In the present invention, N,N-dimethyloctadecylamine and oleic acid are first mixed, and then a stirring medium is added, so that the two substances can react in advance to achieve the purpose of uniform mixing; if this mixing condition is not met, N,N-dimethyloctadecylamine and oleic acid may not react fully in the stirring medium.

[0020] As a preferred technical solution of the present invention, the stirring medium is an ethanol solution.

[0021] Preferably, the mass concentration of the ethanol solution is 90% to 99%, for example, it can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0022] Preferably, the ratio of the amount of the mixed N,N-dimethyloctadecylamine and oleic acid to the amount of the ethanol solution is 1g:1mL~20mL, for example, it can be 1g:1mL, 1g:5mL, 1g:10mL, 1g:15mL, 1g:20mL, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0023] It should be noted that the ethanol solution is used as the stirring medium in the present invention, so that the two substances N,N-dimethyloctadecylamine and oleic acid can be fully dissolved and dispersed. The mass concentration is limited to 90% to 99%, so that the purity of the product after the reaction of N,N-dimethyloctadecylamine and oleic acid is relatively high. If it is not within this range, the product after the reaction of N,N-dimethyloctadecylamine and oleic acid may be easy to agglomerate, resulting in low purity.

[0024] In the present invention, the ratio of the amount of N,N-dimethyloctadecylamine and oleic acid mixed to the amount of the ethanol solution is 1g:1mL-20mL, because within this range, N,N-dimethyloctadecylamine and oleic acid can be fully dissolved in the stirring medium, while ensuring that the purity of the product is high. If it is not within this range, N,N-dimethyloctadecylamine and oleic acid may not be fully dissolved, resulting in a low purity of the product.

[0025] Preferably, in step (1), the stirring speed is 200 r / min to 800 r / min, for example, it can be 200 r / min, 300 r / min, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0026] The stirring speed in the present invention is 200 r / min to 800 r / min, which can make the reaction product fully dispersed, not agglomerate, and have a high purity; if it is not within this range, the product may agglomerate, affecting the purity of the product.

[0027] Preferably, in step (1), the stirring time is 2 h to 10 h, for example, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] As a preferred technical solution of the present invention, in step (2), before adding the glutaraldehyde solution to the initial solution, the temperature needs to be controlled at 60°C to 70°C, for example, it can be 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, etc., but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0029] In the present invention, the temperature is controlled to be 60°C to 70°C, so that the reaction can fully react according to the target product; if it is not within this range, such as the temperature is too low, the reaction cannot continue; if the temperature is too high, the reaction will cause side reactions and the reaction cannot proceed according to the designed product.

[0030] Preferably, the terminal temperature of the heating is 75°C to 85°C, for example, it can be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] The terminal temperature of the heating in the present invention is 75° C. to 85° C., which can make the reaction complete and react according to the designed product; if it is not within this range, it may cause incomplete reaction or produce by-products, affecting the purity of the product.

[0032] As a preferred technical solution of the present invention, in step (2), the mass concentration of the glutaraldehyde solution is 25% to 50%, for example, it can be 25%, 28%, 30%, 33%, 36%, 40%, 42%, 45%, 48%, 50%, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] The mass concentration of the glutaraldehyde solution in the present invention is 25% to 50%, which can make glutaraldehyde, N, N-dimethyloctadecylamine and oleic acid connect with each other; if it is not within this range, it may cause a polymerization reaction between N, N-dimethyloctadecylamine and oleic acid, and it cannot be connected with glutaraldehyde respectively, and finally the product is a non-target product.

[0034] Preferably, the amount of the glutaraldehyde solution is 50 mL to 100 mL, for example, 50 mL, 60 mL, 70 mL, 80 mL, 90 mL, 100 mL, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] As a preferred technical solution of the present invention, in step (2), the reflux time is 2h to 8h, for example, it can be 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] The reflux time in the present invention is 2 hours to 8 hours, which can make the reactants and products fully dissolved in the medium; if it is not within this range, the reactants or products may affect the purity of the product due to crystallization.

[0037] Preferably, the reflux is carried out using a reduced pressure distillation apparatus.

[0038] It should be noted that the specific structure and model of the vacuum distillation apparatus are not particularly limited in the present invention, and those skilled in the art can make adaptive adjustments according to actual conditions. Among them, all reflux devices fall within the protection scope of the present invention.

[0039] Preferably, the reflux medium of the reflux device is deionized water.

[0040] It should be noted that the specific properties of deionized water are not particularly limited in the present invention. Deionized water is well known to those skilled in the art, and they can make adaptive adjustments according to actual conditions. The reflux medium can be a low-temperature medium flowing in a pipe arranged circumferentially on the outer wall of the reflux pipe. When the gas encounters a colder inner wall pipe, it will liquefy into liquid and flow back into the device.

[0041] As a preferred technical solution of the present invention, in step (3), the pH value of the reaction solution is adjusted using sodium hydroxide solution.

[0042] Preferably, the concentration of the sodium hydroxide solution is 2mol / L to 3mol / L, for example, it can be 2mol / L, 2.1mol / L, 2.2mol / L, 2.3mol / L, 2.4mol / L, 2.5mol / L, 2.6mol / L, 2.7mol / L, 2.8mol / L, 2.9mol / L, 3mol / L, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] The concentration of the sodium hydroxide solution in the present invention is 2 mol / L to 3 mol / L, which can make the reaction proceed completely and the product yield is high; if it is not within this range, the final reaction may be incomplete, affecting the product yield.

[0044] Preferably, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:(0.1-0.5), for example, it can be 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] In the present invention, the volume ratio of the amount of sodium hydroxide solution to the amount of stirring medium is 1:(0.1-0.5), which can make the product completely precipitate; if it is not within this range, it may cause incomplete precipitation of the product, affecting the product yield or excessive sodium hydroxide dosage, resulting in low product purity.

[0046] As a preferred technical solution of the present invention, in step (3), the standing treatment time is 0.5h to 12h, for example, it can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] It should be noted that the static treatment in the present invention can be natural static treatment to allow solid-liquid stratification, and those skilled in the art can make adaptive adjustments to the specific method.

[0048] Preferably, the temperature of the distillation treatment is 150°C to 160°C, for example, it can be 150°C, 151°C, 152°C, 153°C, 154°C, 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] The distillation temperature of the present invention is 150°C to 160°C, which can make the reaction impurities reach the required temperature for volatilization; if it is not within this range, the impurities may not volatilize completely or the temperature may be too high to affect the product.

[0050] Preferably, the distillation treatment time is 4 h to 4.5 h, for example, it can be 4 h, 4.1 h, 4.2 h, 4.3 h, 4.4 h, 4.5 h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] It should be noted that the present invention does not specifically limit the specific steps of the distillation process and the containers used, and those skilled in the art can make adaptive adjustments according to actual conditions.

[0052] Preferably, the precipitation process is natural precipitation.

[0053] Preferably, the precipitation treatment time is 6 h to 7 h, for example, it can be 6 h, 6.1 h, 6.2 h, 6.3 h, 6.4 h, 6.5 h, 6.6 h, 6.7 h, 6.8 h, 6.9 h, 7 h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0054] The precipitation treatment in the present invention is natural precipitation, which can ensure a high purity of the product. The precipitation treatment time is 6h to 7h, which can make the precipitation complete. If it is not within this range, incomplete precipitation may result in product waste.

[0055] As a preferred technical solution of the present invention, in step (3), the drying treatment is vacuum drying.

[0056] Preferably, the vacuum drying time is 6 h to 12 h, for example, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0057] Preferably, the vacuum drying temperature is 80°C to 90°C, for example, it can be 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0058] It should be noted that the present invention does not specifically limit the specific steps and devices used in the vacuum drying process, and those skilled in the art can make adaptive adjustments according to actual conditions.

[0059] Vacuum drying is used in the present invention to prevent the product from being oxidized and becoming ineffective. The vacuum drying time is limited to 6 hours to 12 hours, which can make the product completely dry. If it is not within this range, it may lead to incomplete drying or excessive drying and difficulty in dissolution.

[0060] As a preferred technical solution of the present invention, the preparation method specifically comprises:

[0061] (1) mixing N,N-dimethyloctadecylamine, oleic acid and a stirring medium and stirring to obtain an initial solution;

[0062] (2) adding glutaraldehyde solution to the initial solution described in step (1), heating and refluxing to obtain a reaction solution;

[0063] (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain the silicate mineral flotation collector.

[0064] in:

[0065] In step (1), the molar ratio of the N,N-dimethyloctadecylamine to the oleic acid is 1:(6-9), and the N,N-dimethyloctadecylamine, oleic acid and a stirring medium are mixed and stirred in the following manner: N,N-dimethyloctadecylamine and oleic acid are mixed, and then mixed with a stirring medium, wherein the stirring medium is an ethanol solution, the mass concentration of the ethanol solution is 90%-99%, the ratio of the amount of the N,N-dimethyloctadecylamine mixed with the oleic acid to the amount of the ethanol solution is 1g:1mL-20mL, the stirring speed is 200r / min-800r / min, and the stirring time is 2h-10h.

[0066] In step (2), before adding the glutaraldehyde solution to the initial solution, the temperature needs to be controlled at 60°C to 70°C, the terminal temperature of the heating is 75°C to 85°C, the mass concentration of the glutaraldehyde solution is 25% to 50%, the reflux time is 2h to 8h, and the reflux is carried out using a vacuum distillation device.

[0067] In step (3), the pH value of the reaction solution is adjusted by sodium hydroxide solution, the concentration of the sodium hydroxide solution is 2mol / L to 3mol / L, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:(0.1 to 0.5), the standing treatment time is 0.5h to 12h, the distillation treatment temperature is 150°C to 160°C, the distillation treatment time is 4h to 4.5h, the precipitation treatment is natural precipitation, the precipitation treatment time is 6h to 7h, the drying treatment is vacuum drying, the vacuum drying time is 6h to 12h, and the vacuum drying temperature is 80°C to 90°C.

[0068] In a second aspect, the present invention provides a silicate mineral flotation collector, which is prepared by the preparation method described in the first aspect.

[0069] It should be noted that the silicate mineral flotation collector in the present invention is easy to dissolve at low temperature and has the properties of both anionic collectors and cationic collectors. It can well capture silicate minerals such as quartz and has a better technical effect of mineral separation.

[0070] Exemplarily, the method for cascade utilization of iron ore concentrate using the silicate mineral flotation collector of the present invention comprises:

[0071] Grinding and classification: ordinary iron ore concentrate containing 65% iron is divided into coarse and fine grades according to the monomer dissociation degree of gangue minerals. The coarse grade is re-grinded until the fineness meets the fine grade and enters the magnetic separation and desludging system together with the fine grade.

[0072] Magnetic separation and desliming: after magnetic separation and desliming, deslimed tailings and high-grade iron concentrate are obtained. The high-grade iron concentrate enters the flotation system after slurry adjustment;

[0073] Flotation, add activator, regulator and silicate mineral flotation collector to the ore pulp in sequence for roughing, obtain the first foam product and the first flotation tank product, continue to add collector to the tank product, the amount of collector is half of the roughing, obtain the second foam product and the second tank product, continue to add collector to the tank product, the amount of collector is half of the previous process, obtain the third foam product C and the third tank product.

[0074] Among them: the dosage of roughing collector in the flotation step is 200g / t~600g / t, the desludging tailings obtained by flotation and the first foam product are combined into ordinary iron concentrate with an iron grade of 60%~65%, which is used for steel smelting; the iron grade of the second foam product is high-purity iron concentrate with an iron grade of 69%~71%, which is used for direct reduction of iron; the iron grade of the third product in the tank is super iron concentrate with an iron grade of 71.5%~72%, which is used in powder metallurgy, magnetic materials and other fields.

[0075] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0076] Compared with the prior art, the present invention has the following beneficial effects:

[0077] In the present invention, by combining the advantages of anionic and cationic collectors, the disadvantage of inactivation of anionic and cationic collectors due to charge entanglement precipitation is overcome, and a collector that can exist in a stable ionic state is prepared. This agent is added during the preparation process of super iron concentrate. Anions and cations present in the slurry can react with silicate minerals such as quartz at the same time, exerting the synergistic effect of anionic collectors and cationic collectors, thereby achieving the purpose of good mineral separation. DETAILED DESCRIPTION

[0078] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0079] Example 1

[0080] This embodiment provides a method for preparing a silicate mineral flotation collector, wherein:

[0081] (1) N,N-dimethyloctadecylamine and oleic acid are mixed and added into a reaction kettle, and then an ethanol solution is added and stirred to obtain an initial solution;

[0082] (2) When the temperature is controlled to a certain level, adding glutaraldehyde solution to the initial solution of step (1), heating and refluxing to obtain a reaction solution;

[0083] (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain a silicate mineral flotation collector.

[0084] In step (1), the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:6, the mass concentration of the ethanol solution is 90%, the amount of the ethanol solution is 30 mL, the stirring speed is 300 r / min, and the stirring time is 8 h.

[0085] In step (2), the certain temperature is 60° C., the terminal temperature of the heating is 75° C., the mass concentration of the glutaraldehyde solution is 25%, the amount of the glutaraldehyde solution is 50 mL, the reflux time is 8 h, the reflux is carried out using a vacuum distillation apparatus, and the reflux medium is deionized water.

[0086] In step (3), the pH value of the reaction solution is adjusted by sodium hydroxide solution, the concentration of the sodium hydroxide solution is 2 mol / L, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:0.1, the standing time is 2 h, the distillation temperature is 150 ° C, the distillation time is 4.5 h, the precipitation treatment is natural precipitation, the precipitation time is 6 h, the drying treatment is vacuum drying, the vacuum drying time is 6 h, and the vacuum drying temperature is 90 ° C.

[0087] The application of the silicate mineral flotation collector obtained in Example 1 may include:

[0088] The raw material is iron ore concentrate with an iron grade of 65%, the SiO2 content is 8.59%, and the main gangue minerals are quartz and actinolite.

[0089] The raw materials are graded into two particle sizes, -0.038mm and +0.038mm. The +0.038mm material is regrinded, and the +0.038mm material is ground to -0.038mm, accounting for 70-90%, and combined with the -0.038mm material to enter the magnetic separation and desliming operation. After magnetic separation and desliming, the slurry is deslimed tailings and high-grade iron ore concentrate. The high-grade iron ore concentrate enters the flotation system after slurry adjustment.

[0090] The ore pulp concentration is adjusted to 30%, the flotation temperature is 20°C, an activator, a regulator and a silicate mineral flotation collector are sequentially added to the ore pulp for roughing, to obtain a first foam product and a first flotation tank product, and silicate mineral flotation collector is continuously added to the first tank product, the amount of silicate mineral flotation collector is 1 / 2 of the roughing, to obtain a second foam product and a second tank product, and silicate mineral flotation collector is continuously added to the second tank product, the amount of silicate mineral flotation collector is 1 / 2 of the previous step, to obtain a third foam product and a third tank product, and the third tank product is a super iron concentrate, the iron content of which can reach 71.08%, and the content of hydrochloric acid insoluble matter is 0.18%.

[0091] Example 2

[0092] This embodiment provides a method for preparing a silicate mineral flotation collector, wherein:

[0093] (1) N,N-dimethyloctadecylamine and oleic acid are mixed and added into a reaction kettle, and then an ethanol solution is added and stirred to obtain an initial solution;

[0094] (2) When the temperature is controlled to a certain level, adding glutaraldehyde solution to the initial solution of step (1), heating and refluxing to obtain a reaction solution;

[0095] (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain a silicate mineral flotation collector.

[0096] In step (1), the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:8, the mass concentration of the ethanol solution is 95%, the amount of the ethanol solution is 60 mL, the stirring speed is 500 r / min, and the stirring time is 5 h.

[0097] In step (2), the certain temperature is 65° C., the terminal temperature of the heating is 80° C., the mass concentration of the glutaraldehyde solution is 40%, the amount of the glutaraldehyde solution is 70 mL, the reflux time is 5 h, the reflux is carried out using a vacuum distillation apparatus, and the reflux medium is deionized water.

[0098] In step (3), the pH value of the reaction solution is adjusted by sodium hydroxide solution, the concentration of the sodium hydroxide solution is 2.4 mol / L, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:0.35, the standing time is 5 h, the distillation temperature is 155 ° C, the distillation time is 4.2 h, the precipitation treatment is natural precipitation, the precipitation time is 6.4 h, the drying treatment is vacuum drying, the vacuum drying time is 8 h, and the vacuum drying temperature is 84 ° C.

[0099] Example 3

[0100] This embodiment provides a method for preparing a silicate mineral flotation collector, wherein:

[0101] (1) N,N-dimethyloctadecylamine and oleic acid are mixed and added into a reaction kettle, and then an ethanol solution is added and stirred to obtain an initial solution;

[0102] (2) When the temperature is controlled to a certain level, adding glutaraldehyde solution to the initial solution of step (1), heating and refluxing to obtain a reaction solution;

[0103] (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain a silicate mineral flotation collector.

[0104] In step (1), the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:9, the mass concentration of the ethanol solution is 99%, the amount of the ethanol solution is 30 mL, the stirring speed is 600 r / min, and the stirring time is 9 h.

[0105] In step (2), the constant temperature is 70° C., the terminal temperature of the heating is 85° C., the mass concentration of the glutaraldehyde solution is 50%, the amount of the glutaraldehyde solution is 50 mL, the reflux time is 3 h, the reflux is carried out using a vacuum distillation apparatus, and the reflux medium is deionized water.

[0106] In step (3), the pH value of the reaction solution is adjusted by sodium hydroxide solution, the concentration of the sodium hydroxide solution is 3 mol / L, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:0.4, the standing time is 10 h, the temperature of the distillation treatment is 160° C., the distillation time is 4 h, the precipitation treatment is natural precipitation, the precipitation treatment time is 7 h, the drying treatment is vacuum drying, the vacuum drying time is 9, and the vacuum drying temperature is 80° C.

[0107] It should be noted that the purity of N,N-dimethyloctadecylamine in the present invention is greater than 95%, and the molecular weight is 297.56.

[0108] Example 4

[0109] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:5, and other parameters and experimental conditions are the same as those in Example 1.

[0110] Example 5

[0111] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the molar ratio of N,N-dimethyloctadecylamine to oleic acid is 1:10, and other parameters and experimental conditions are the same as those in Example 1.

[0112] Example 6

[0113] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the mass concentration of the ethanol solution is 88%, and the other parameters and test conditions are the same as those in Example 1.

[0114] Example 7

[0115] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the mass concentration of the ethanol solution is 99.9%, and the other parameters and test conditions are the same as those in Example 1.

[0116] Example 8

[0117] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the certain temperature is 55° C., and other parameters and test conditions are the same as those in Example 1.

[0118] Example 9

[0119] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the certain temperature is 75° C., and other parameters and test conditions are the same as those in Example 1.

[0120] Example 10

[0121] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the mass concentration of the glutaraldehyde solution is 20%, and the other parameters and test conditions are the same as those in Example 1.

[0122] Embodiment 11

[0123] This embodiment provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that the mass concentration of the glutaraldehyde solution is 60%, and the other parameters and test conditions are the same as those in Example 1.

[0124] Example 12

[0125] This embodiment provides a method for preparing a silicate mineral flotation collector, wherein the difference from Example 1 is that the volume ratio of the sodium hydroxide solution to the stirring medium is 1:0.05, and the other parameters and experimental conditions are the same as those in Example 1.

[0126] Example 13

[0127] This embodiment provides a method for preparing a silicate mineral flotation collector, wherein the difference from Example 1 is that the volume ratio of the sodium hydroxide solution to the stirring medium is 1:6, and the other parameters and experimental conditions are the same as those in Example 1.

[0128] Comparative Example 1

[0129] This comparative example provides a method for preparing a silicate mineral flotation collector, which is different from Example 1 in that N,N-dimethyloctadecylamine, oleic acid and ethanol solution are mixed simultaneously, and other parameters and test conditions are the same as those in Example 1.

[0130] Comparative Example 2

[0131] This comparative example provides a method for preparing a silicate mineral flotation collector, which differs from Example 1 in that no glutaraldehyde solution is added, and other parameters and test conditions are the same as those of Example 1.

[0132] The silicate mineral flotation collectors in the above embodiments and comparative examples were used to flotate the super iron concentrate obtained by using ICP test and iron titration test, and the results are shown in Table 1 below.

[0133] Table 1 Test results of silicate mineral flotation collectors in Examples and Comparative Examples

[0134]

[0135]

[0136] In summary, the present invention combines the advantages of anionic and cationic collectors to overcome the disadvantages of inactivation of anionic and cationic collectors due to charge entanglement precipitation, prepares a collector that can exist in a stable ionic state, and adds this agent in the process of preparing super iron concentrate. The anions and cations present in the slurry can react with silicate minerals such as quartz at the same time, exerting the synergistic effect of anionic collectors and cationic collectors, thereby achieving the purpose of good mineral separation.

[0137] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

[0138] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a silicate mineral flotation collector, characterized in that: The preparation method comprises: (1) mixing N,N-dimethyloctadecylamine, oleic acid and a stirring medium and stirring to obtain an initial solution; (2) adding glutaraldehyde solution to the initial solution described in step (1), heating and refluxing to obtain a reaction solution; (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain the silicate mineral flotation collector.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the N,N-dimethyloctadecylamine to the oleic acid is 1:(6-9); Preferably, in step (1), N,N-dimethyloctadecylamine, oleic acid and a stirring medium are mixed and stirred in the following manner: N,N-dimethyloctadecylamine and oleic acid are mixed and then mixed with a stirring medium.

3. The preparation method according to claim 2, characterized in that: The stirring medium is an ethanol solution; Preferably, the mass concentration of the ethanol solution is 90% to 99%; Preferably, the ratio of the amount of the N,N-dimethyloctadecylamine mixed with oleic acid to the amount of the ethanol solution is 1g:1mL-20mL; Preferably, in step (1), the stirring speed is 200 r / min to 800 r / min; Preferably, in step (1), the stirring time is 2 h to 10 h.

4. The preparation method according to any one of claims 1 to 3, characterized in that: In step (2), before adding the glutaraldehyde solution to the initial solution, the temperature needs to be controlled at 60° C. to 70° C.; Preferably, the terminal temperature of the heating is 75°C to 85°C.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In step (2), the mass concentration of the glutaraldehyde solution is 25% to 50%.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In step (2), the reflux is carried out using a vacuum distillation apparatus; Preferably, the reflux time is 2 h to 8 h.

7. The preparation method according to any one of claims 1 to 6, characterized in that: In step (3), the pH value of the reaction solution is adjusted by using a sodium hydroxide solution; Preferably, the concentration of the sodium hydroxide solution is 2 mol / L to 3 mol / L; Preferably, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:(0.1-0.5).

8. The preparation method according to any one of claims 1 to 7, characterized in that: In step (3), the standing treatment time is 0.5h to 12h; Preferably, the temperature of the distillation treatment is 150°C to 160°C; Preferably, the distillation treatment time is 4h to 4.5h; Preferably, the precipitation process is natural precipitation; Preferably, the precipitation treatment time is 6h to 7h; Preferably, the drying process is vacuum drying; Preferably, the vacuum drying time is 6h to 12h; Preferably, the vacuum drying temperature is 80°C to 90°C.

9. The preparation method according to claim 1, characterized in that: The preparation method specifically comprises: (1) mixing N,N-dimethyloctadecylamine, oleic acid and a stirring medium and stirring to obtain an initial solution; (2) adding glutaraldehyde solution to the initial solution described in step (1), heating and refluxing to obtain a reaction solution; (3) adjusting the pH value of the reaction solution in step (2), and drying the obtained precipitate after standing, distilling and precipitation to obtain the silicate mineral flotation collector; in: In step (1), the molar ratio of the N,N-dimethyloctadecylamine to the oleic acid is 1:(6-9), and the N,N-dimethyloctadecylamine, oleic acid and a stirring medium are mixed and stirred in the following manner: N,N-dimethyloctadecylamine and oleic acid are mixed, and then mixed with a stirring medium, wherein the stirring medium is an ethanol solution, the mass concentration of the ethanol solution is 90%-99%, the ratio of the amount of the N,N-dimethyloctadecylamine mixed with the oleic acid to the amount of the ethanol solution is 1g:1mL-20mL, the stirring speed is 200r / min-800r / min, and the stirring time is 2h-10h; In step (2), before adding the glutaraldehyde solution to the initial solution, the temperature is controlled to be 60°C to 70°C, the terminal temperature of the heating is 75°C to 85°C, the mass concentration of the glutaraldehyde solution is 25% to 50%, the reflux time is 2h to 8h, and the reflux is carried out using a vacuum distillation apparatus; In step (3), the pH value of the reaction solution is adjusted by sodium hydroxide solution, the concentration of the sodium hydroxide solution is 2mol / L to 3mol / L, the volume ratio of the sodium hydroxide solution to the stirring medium is 1:(0.1 to 0.5), the standing treatment time is 0.5h to 12h, the distillation treatment temperature is 150°C to 160°C, the distillation treatment time is 4h to 4.5h, the precipitation treatment is natural precipitation, the precipitation treatment time is 6h to 7h, the drying treatment is vacuum drying, the vacuum drying time is 6h to 12h, and the vacuum drying temperature is 80°C to 90°C.

10. A silicate mineral flotation collector, characterized in that: The silicate mineral flotation collector is prepared by the preparation method according to any one of claims 1 to 9.

Images