Chelating collecting agent for mineral separation flotation and preparation method of chelating collecting agent

Abstract

The invention discloses a chelating collector for mineral separation flotation and a preparation method thereof, and relates to the technical field of mineral processing, the chelating collector comprises the following raw materials by weight: 52-58 parts of plant cotton oil asphalt, 20-25 parts of liquid caustic soda, 5-8 parts of a complexing agent, 12-18 parts of a surfactant, and 5-10 parts of a solid carrier, the solid carrier is diatomite, and the particle size of the diatomite is 20-30 microns; carrying out hydroxylation reaction on the plant cotton oil asphalt and liquid caustic soda in a high-pressure reaction kettle for 1-2 hours; and cooling to 80-100 DEG C, adding the complexing agent, the surfactant and the solid carrier, and uniformly stirring and mixing to obtain the collecting agent. The diatomite can stabilize the chemical structure of the collecting agent and prevent the collecting agent from premature decomposition or failure in ore liquid; and the service life of the collecting agent is prolonged, and the overall efficiency of flotation operation is improved.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing, and in particular to a chelating collector for ore dressing and flotation and a preparation method thereof. Background Art

[0002] Flotation refers to the mineral processing process of floating solid minerals from a water suspension (slurry) based on the differences in the physical and chemical properties of the mineral surface. Flotation has been widely used in the mineral processing industry and is most suitable for sorting low-grade, fine-grained impregnated ores. During flotation, air is introduced into the pulp to form a large number of bubbles, so that particles that are not easily wetted by water, usually called hydrophobic minerals, adhere to the bubbles and float to the surface of the pulp along with the bubbles to form a mineralized foam layer. However, those particles that are easily wetted by water, usually called hydrophilic minerals, cannot adhere to the bubbles and remain in the pulp. The purpose of sorting is achieved by discharging the mineralized foam. For example, the Chinese patent, application number CN202111200585.8, is a method for preparing a ilmenite collector based on modified plant asphalt. The plant asphalt and liquid alkali are subjected to hydroxylation reaction in a high-pressure reactor for 1h-2h; after cooling to 80-100°C, a complexing agent and a surfactant are added, and the collector is obtained by stirring and mixing evenly; the raw materials used are calculated by mass percentage as follows: 52-58% plant asphalt, 25% liquid alkali, 2%-8% complexing agent, and 12%-18% surfactant; the invention uses plant cotton oil asphalt containing more double bonds, and plant bitumen cotton oil asphalt contains a certain number of hydroxyl groups, and a polyhydroxyl mixture is obtained after hydroxylation reaction. Hydroxyl groups have a certain chelation effect with titanium iron ions, and chelation adsorption occurs on the surface of minerals, so it has good selectivity for ilmenite.

[0003] However, the adsorption and chelation effects need to be improved, the stability is insufficient, and it is easy to fall off or disperse due to stirring or bubble action during the flotation process. Summary of the invention

[0004] The embodiments of the present application provide solutions to the problems of insufficient stability and insufficient adsorption effect in the prior art, and achieve better chelating adsorption effect.

[0005] The present application example provides a chelating collector for mineral processing and flotation, and the raw materials are calculated by weight as follows: 52-58 parts of plant cotton oil asphalt, 20-25 parts of liquid alkali, 5-8 parts of complexing agent, 12-18 parts of surfactant, and 5-10 parts of solid carrier.

[0006] Furthermore, the liquid alkali is a 45wt% potassium hydroxide solution.

[0007] Furthermore, the complexing agent is benzyl arsenic acid.

[0008] Furthermore, the surfactant is sodium dodecylbenzene sulfonate.

[0009] Furthermore, the solid carrier is diatomaceous earth.

[0010] Furthermore, the particle size of the diatomaceous earth is 20-30 microns.

[0011] The preparation method of the chelating collector for mineral flotation mentioned above has the following specific preparation steps: subjecting plant cotton oil asphalt and liquid alkali to hydroxylation reaction in a high-pressure reactor for 1h-2h; after cooling to 80-100°C, adding a complexing agent, a surfactant and a solid carrier, stirring and mixing evenly to obtain the collector.

[0012] Further, half of the solid carrier is subjected to hydroxylation reaction together with the plant cottonseed oil asphalt and liquid alkali, and the remaining half is mixed with the complexing agent and the surfactant.

[0013] Furthermore, the solid carrier is a combination of large particles and small particles. The large particles of diatomaceous earth have a particle size of 40-50 microns; the small particles of diatomaceous earth have a particle size of 1-10 microns, and the large particles have the same mass as the small particles.

[0014] Furthermore, the diatomaceous earth that has not been co-hydroxylated and the diatomaceous earth that has been co-hydroxylated have different mass combinations of large and small particles, specifically: The mass ratio of large particles: small particles in diatomite that has not been co-hydroxylated is (1-9):(1-9); The mass ratio of large particles to small particles in the diatomaceous earth subjected to co-hydroxylation is (1-9):(1-9).

[0015] One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages: Diatomaceous earth, due to its porosity and high specific surface area, can be used as a solid carrier and also has the function of a partial adsorbent, so that diatomaceous earth can adsorb more collector components. The surface of diatomaceous earth is rich in hydroxyl (-OH) functional groups, which interact with other components in the collector to form a stable adsorption layer, enhance the adsorption performance of the collector, improve the adsorption capacity of the collector, and enhance the adsorption capacity of the collector on the mineral surface. Under high pressure and high temperature conditions, the molecular chains of plant cottonseed oil asphalt become more flexible and penetrate into the pore structure of diatomite during the process of co-hydroxylation with diatomite; this part of diatomite and plant cottonseed oil asphalt are combined not only through chemical reaction, but also through physical spatial position relationship, so that the synergistic effect of the two is further optimized; The combined use of large and small diatomaceous earth particles improves the collection efficiency by improving the physical mixing effect, dispersibility and adsorption performance of the collector; the combined use of hydroxylation reaction and diatomaceous earth improves the chemical stability of the collector and extends its service life; The combined use of large and small particles in different mass ratios can increase the application scenarios of chelating collectors. DETAILED DESCRIPTION

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which the present invention belongs; the terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention; the term "and / or" used herein includes any and all combinations of one or more related listed items.

[0017] Example 1: The present application provides a chelating collector for mineral processing and flotation, and the raw materials are calculated by weight as follows: 52-58 parts of plant cotton oil asphalt, 20-25 parts of liquid alkali, 5-8 parts of complexing agent, 12-18 parts of surfactant, 5-10 parts of solid carrier; The liquid alkali is a 45wt% potassium hydroxide solution; the complexing agent is benzyl arsenic acid; the surfactant is sodium dodecylbenzene sulfonate; the solid carrier is diatomaceous earth, and the particle size of the diatomaceous earth is 20-30 microns; The preparation method of the chelating collector for ore dressing flotation is as follows: The plant cotton oil asphalt and liquid alkali are subjected to hydroxylation reaction in a high-pressure reactor for 1h-2h; after cooling to 80-100°C, a complexing agent, a surfactant and a solid carrier are added, and the mixture is stirred and mixed to obtain a collector.

[0018] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: Diatomaceous earth, due to its porosity and high specific surface area, can be used as a solid carrier and also has the function of a partial adsorbent, so that diatomaceous earth can adsorb more collector components. The surface of diatomaceous earth is rich in hydroxyl (-OH) functional groups, which interact with other components in the collector to form a stable adsorption layer, enhance the adsorption performance of the collector, improve the adsorption capacity of the collector, and enhance the adsorption capacity of the collector on the mineral surface. Diatomaceous earth can stabilize the chemical structure of the collector, preventing it from prematurely decomposing or failing in the mineral solution; prolonging the service life of the collector and improving the overall efficiency of the flotation operation; the porous structure of diatomaceous earth allows the physical mixing and dispersion of plant cottonseed oil asphalt and its modified products inside it; allowing the collector to cover the mineral surface more evenly; the hydroxyl groups and other active groups on the surface of diatomaceous earth undergo chemical adsorption or chelation with the hydroxyl groups, double bonds, etc. in the plant cottonseed oil asphalt, thereby enhancing the binding force between the collector and the mineral surface and producing a synergistic effect, thereby improving the collection effect; by adding diatomaceous earth, the adsorption capacity, selectivity and stability of the collector are enhanced, thereby improving the flotation efficiency.

[0019] The effectiveness of chelating collectors in mineral flotation was verified by using different experimental groups, and the experiment was conducted by flotation of titanium ore with a grade of 23.44%. The results are shown in Table 1; The specific experimental groups are as follows: Experiment 1: 58 parts of plant cotton oil asphalt, 25 parts of liquid alkali, 8 parts of complexing agent, 12 parts of surfactant, 5 parts of solid carrier; Experiment 2: 56 parts of plant cotton oil asphalt, 23 parts of liquid alkali, 5 parts of complexing agent, 15 parts of surfactant, 10 parts of solid carrier; Experiment 3: 52 parts of plant cotton oil asphalt, 20 parts of liquid alkali, 6 parts of complexing agent, 18 parts of surfactant, 8 parts of solid carrier; Experiment 4: 56 parts of plant cotton oil asphalt, 23 parts of liquid alkali, 5 parts of complexing agent, 15 parts of surfactant;

[0020] Table 1 Example 2: The above example increases the binding capacity of the chelating agent and the mineral by adding a solid carrier to the chelating collector. In order to further optimize the internal stability and binding capacity of the chelating collector, further improvements are made on the basis of Example 1.

[0021] Some solid carriers are added during the hydroxylation reaction of plant cottonseed oil asphalt, specifically: Carry out hydroxylation reaction of plant cotton oil asphalt, liquid alkali and half of solid carrier in a high-pressure reactor for 1h-2h; after cooling to 80-100°C, add complexing agent, surfactant and remaining solid carrier, stir and mix evenly to obtain collector.

[0022] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: Under high pressure and high temperature conditions, the molecular chains of plant cottonseed oil asphalt become more flexible and penetrate into the pore structure of diatomite during the process of co-hydroxylation with diatomite; this part of diatomite and plant cottonseed oil asphalt are combined not only through chemical reaction, but also through physical spatial position relationship, so that the synergistic effect of the two is further optimized; The porosity of diatomaceous earth enables it to absorb a large number of plant cottonseed oil asphalt molecules, forming a combination with strong chelating and capturing capabilities, thereby enhancing the chelating and capturing effect; the plant cottonseed oil asphalt undergoes a hydroxylation reaction with liquid alkali to generate more hydroxyl functional groups that hydrogen bond with the hydroxyl groups on the surface of the diatomaceous earth, thereby enhancing the binding force between the two; through the co-hydroxylation reaction, the plant cottonseed oil asphalt is more evenly covered on the surface and pores of the diatomaceous earth, thereby improving the dispersion and uniformity of the collector.

[0023] The co-hydroxylation reaction helps to form a more stable collector structure. The strong binding force between diatomaceous earth and plant cotton oil asphalt can prevent the collector from prematurely decomposing or failing in the mineral solution and extend its service life.

[0024] Further experiments were conducted based on Experiment 2 of Example 1. The results are shown in Table 2.

[0025] Table 2 Example 3: Example 2 is further improved on the basis of Example 2 by jointly carrying out hydroxylation reaction with part of the solid carrier so that the plant cotton oil asphalt is more evenly covered on the surface and pores of the diatomaceous earth, thereby improving the dispersibility and uniformity of the collector and improving the chelating effect.

[0026] The solid carrier is a combination of large particles and small particles, specifically a mixture of large and small diatomaceous earth particles; the large diatomaceous earth particle size is 40-50 microns; the small diatomaceous earth particle size is 1-10 microns, and the large particles and the small particles have the same mass.

[0027] The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: The use of a combination of large and small particles as solid supports has a dramatic effect on both co-hydroxylated and non-co-hydroxylated diatomaceous earths; For diatomite that has not been co-hydroxylated, the combination of large-particle diatomite and small-particle diatomite allows the small-particle diatomite to be adsorbed in the pores or on the surface of the large-particle diatomite to form a more compact stacking structure. The small-particle diatomite has a larger specific surface area and can provide more adsorption sites to enhance the adsorption performance of the collector. Although the large-particle diatomite has a smaller specific surface area, its porous structure can control the dispersion of plant cottonseed oil asphalt to form a more stable adsorption layer. The combined use of large-particle diatomaceous earth and small-particle diatomaceous earth can not only adsorb minerals, but also penetrate deep into the interior of the minerals for deep chelation capture. The small-particle diatomaceous earth can be better dispersed in the mineral solution, increasing the contact opportunity between the collector and the mineral surface; and the large particles can fix the plant cotton oil asphalt, while the small particles extend outward with the plant cotton oil asphalt to the surface and interior of the mineral, thereby improving the capture effect of the collector; For the co-hydroxylated diatomite, small-particle diatomite has a larger specific surface area, which can provide more hydroxyl reaction sites and promote the hydroxylation reaction; large-particle diatomite promotes the fixation of plant cotton oil asphalt through its porous structure to form a more stable hydroxylation product; after the hydroxylation reaction, the number of hydroxyl groups on the surface of diatomite increases, and the adsorption performance is further improved; the combination of large-particle diatomite and small-particle diatomite forms a richer hydroxyl adsorption layer, which enhances the adsorption performance of the collector; The combined use of large and small diatomaceous earth particles improves the collection efficiency by improving the physical mixing effect, dispersibility and adsorption performance of the collector; the combined use of hydroxylation reaction and diatomaceous earth improves the chemical stability of the collector and extends its service life; The chelating collector is composed of large particles that have not been hydroxylated as the "heart", large particles that have been hydroxylated as the "bones", large particles that have been hydroxylated as the "meat", and small particles that have not been hydroxylated as the "skin", thereby obtaining an efficient chelating collector with strong chelating ability.

[0028] Further experiments were conducted on the basis of Experiment 2 in Example 1, and the results are shown in Table 3;

[0029] Table 3 Embodiment 4: Embodiment 3 greatly increases the chelating capacity by combining large and small particles. In order to broaden the application scenarios, further improvements are made on the basis of Embodiment 3.

[0030] The application scenarios are increased by using different mass combinations of large and small particles in diatomaceous earth that has not been co-hydroxylated and diatomaceous earth that has been co-hydroxylated.

[0031] The mass ratio of large particles: small particles in diatomite that has not been co-hydroxylated is (1-9):(1-9); The mass ratio of large particles to small particles in the diatomaceous earth subjected to co-hydroxylation is (1-9): (1-9); The technical solutions in the above embodiments of the present application have at least the following technical effects or advantages: For diatomite that has not been co-hydroxylated, large-particle diatomite has a relatively large volume and heavy mass, which can provide a more stable support structure in the collector, reduce sedimentation and stratification. For coarse-grained minerals, large-particle diatomite can better contact with its surface, forming a thicker adsorption layer and improving the collection effect; small-particle diatomite has a larger specific surface area and can provide more adsorption sites, thereby enhancing the adsorption performance of the collector; small-particle diatomite is easier to disperse in the mineral solution, increasing the contact opportunity with the mineral surface and improving the collection efficiency; for fine-grained minerals, small-particle diatomite can penetrate deeper into the mineral particles and form a more uniform adsorption layer; For the diatomite that undergoes co-hydroxylation, during the hydroxylation reaction, large-particle diatomite can provide more surface areas to interact with plant cottonseed oil asphalt and its modified products, forming stronger chemical bonds or hydrogen bonds; the large-particle diatomite after hydroxylation is more firmly bonded to other components in the collector, improving the chemical stability of the collector; in application scenarios where the collector needs to form a strong bond with the mineral surface, hydroxylated diatomite with more large particles is more advantageous; Small-particle diatomaceous earth has a larger specific surface area, can provide more hydroxyl reaction sites, promote the hydroxylation reaction, and improve the reaction efficiency; the hydroxylated small-particle diatomaceous earth has stronger adsorption properties and better dispersibility, and can more effectively contact the mineral surface and adsorb the useful components thereon; in application scenarios where the collector needs to have high adsorption properties, hydroxylated diatomaceous earth with more small particles is more suitable.

[0032] Further experiments were conducted based on Experiment 2 in Example 3, and the results are shown in Table 4;

[0033] Table 4 The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A chelating collector for mineral flotation, characterized in that: The raw materials are calculated by weight as follows: 52-58 parts of plant cotton oil asphalt, 20-25 parts of liquid alkali, 5-8 parts of complexing agent, 12-18 parts of surfactant, and 5-10 parts of solid carrier.

2. A chelating collector for mineral processing and flotation as claimed in claim 1, characterized in that: The liquid alkali is a 45wt% potassium hydroxide solution.

3. The chelating collector for mineral processing and flotation as claimed in claim 1, characterized in that: The complexing agent is benzyl arsenic acid.

4. A chelating collector for mineral processing and flotation as claimed in claim 1, characterized in that: The surfactant is sodium dodecylbenzene sulfonate.

5. The chelating collector for mineral processing and flotation as claimed in claim 1, characterized in that: The solid carrier is diatomaceous earth.

6. A chelating collector for mineral processing and flotation as claimed in claim 5, characterized in that: The particle size of the diatomaceous earth is 20-30 microns.

7. A method for preparing a chelating collector for mineral processing and flotation as claimed in any one of claims 1 to 6, characterized in that: The specific preparation steps are: subjecting plant cotton oil asphalt and liquid alkali to hydroxylation reaction in a high-pressure reactor for 1h-2h; after cooling to 80-100°C, adding a complexing agent, a surfactant and a solid carrier, stirring and mixing evenly to obtain a collector.

8. The method for preparing a chelating collector for ore flotation as claimed in claim 7, characterized in that: Half of the solid carrier is subjected to hydroxylation reaction together with the vegetable cotton oil asphalt and liquid alkali, and the remaining half is mixed with the complexing agent and the surfactant.

9. The method for preparing a chelating collector for ore flotation as claimed in claim 8, characterized in that: The solid carrier is a combination of large particles and small particles. The large particles of diatomaceous earth have a particle size of 40-50 microns; the small particles of diatomaceous earth have a particle size of 1-10 microns, and the large particles and the small particles have the same mass.

10. The method for preparing a chelating collector for ore flotation according to claim 9, characterized in that: The diatomaceous earth without co-hydroxylation and the diatomaceous earth with co-hydroxylation have different mass combinations of large and small particles, specifically: The mass ratio of large particles: small particles in diatomite that has not been co-hydroxylated is (1-9):(1-9); The mass ratio of large particles to small particles in the diatomaceous earth subjected to co-hydroxylation is (1-9):(1-9).

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