A system and method for enhancing the process of flotation separation of a refractory fine-grained mineral

Abstract

The application discloses a kind of refractory fine-grained mineral flotation separation process intensification system and intensification method, belong to flotation technical field;Solve the technical problem that entrainment is serious when using existing flotation equipment and flotation reagent to the flotation of refractory fine-grained mineral;The refractory fine-grained mineral flotation separation process intensification system of the present application includes flotation device and mechanical vibration device;Flotation device includes the cleaning zone in upper and the collection zone in lower;Close to the top position of collection zone, slurry feeding port is equipped, close to the bottom position of collection zone, gas generator connecting port is equipped;Mechanical vibration device is used to make the liquid level at the interface of cleaning zone and collection zone produce up and down vibration.The present application can effectively reduce gangue entrainment and intensify intergrowth desorption by setting mechanical vibration device, finally realize intensification flotation process.

Description

Technical Field

[0001] This invention relates to the field of flotation technology for refractory fine-grained minerals, and in particular to an enhancement system and method for the flotation separation process of refractory fine-grained minerals. Background Technology

[0002] Mineral resources are the material foundation for developing the national economy and ensuring national security. Currently, my country is in a stage of high-quality development, and the demand for mineral resources remains high. The dependence on foreign sources for major strategic mineral resources continues to rise, and mineral resource security is playing an increasingly prominent role in national comprehensive security and resource security. Flotation is one of the effective methods for mineral separation, characterized by high separation efficiency and significant effect on fine-grained minerals. With the development and utilization of mineral resources, these resources are becoming increasingly characterized by being "poor, fine-grained, and complex," making the flotation of difficult-to-separate fine-grained minerals an important aspect of mineral resource development.

[0003] Flotation is a method of separating target minerals from gangue minerals based on the difference in hydrophobicity of their surfaces. Currently, for the separation of refractory fine-grained minerals, fine grinding is often required to achieve effective mineral liberation in order to recover the minerals effectively. However, during fine grinding, some easily mud-forming gangue minerals are easily reduced to extremely small particles, which are readily carried into the concentrate by the water flow, causing concentrate contamination. The entrainment problem has become a significant challenge restricting the flotation separation and utilization of refractory fine-grained minerals.

[0004] Current research on the flotation of refractory fine-grained minerals mainly focuses on three aspects: flotation processes, flotation equipment, and flotation reagents. Flotation processes typically enhance flotation by increasing the apparent diameter of fine particles, such as carrier flotation. Flotation equipment research usually involves developing new equipment or improving existing equipment to increase the probability of adhesion and collision between bubbles and the target mineral or to reduce the entrainment of fine-grained gangue minerals. Flotation reagents research typically involves developing new reagents to alter the hydrophobicity of the target mineral or gangue mineral surface, enabling selective separation. However, significant breakthroughs have not been achieved in entrainment control. Currently, the most effective and industrially applied method is column flotation technology, which has a history of over a century, but this technology is mostly used in the refining process and has limitations. Summary of the Invention

[0005] Based on the above analysis, the present invention aims to provide a method for enhancing the flotation separation process of refractory fine-grained minerals, in order to solve the technical problem of severe entrainment when using existing flotation equipment and flotation reagents to float refractory fine-grained minerals.

[0006] The objective of this invention is mainly achieved through the following technical solutions:

[0007] On the one hand, the present invention provides an enhanced system for the flotation separation process of refractory fine-grained minerals, including a flotation device and a mechanical vibration device;

[0008] The flotation device includes an upper cleaning zone and a lower collecting zone; a slurry feed port is located near the top of the collecting zone, and a gas generator connection port is located near the bottom of the collecting zone; a mechanical vibration device is used to cause the liquid surface at the interface between the cleaning zone and the collecting zone to vibrate up and down, thereby reducing gangue entrainment and enhancing the desorption of intergrowths.

[0009] In one possible design, the mechanical vibration device includes a vibrator and a perforated screen plate; the perforated screen plate is located at the interface between the cleaning zone and the collecting zone; the vibrator is fixedly connected to the perforated screen plate via a transmission rod at its bottom, and the vibrator can drive the perforated screen plate to vibrate up and down within the flotation device.

[0010] In one possible design, the perforated sieve vibrator is a circular vibrator with multiple sieve holes; the outer diameter of the perforated sieve vibrator is less than or equal to the inner diameter of the flotation device.

[0011] On the other hand, the present invention also provides a method for enhancing the flotation separation process of refractory fine-grained minerals, employing the above-mentioned enhancement system, and the enhancement method includes the following steps:

[0012] S1. Pre-treat the sample to be floated to obtain the mineral to be floated;

[0013] S2. The mineral to be floated is fed into the flotation device through the mineral feed port;

[0014] S3. Turn on the bubble generator;

[0015] S4. Start the mechanical vibration device and simultaneously turn on the flushing water at the top of the flotation device to obtain the first flotation concentrate and tailings.

[0016] Furthermore, it also includes step S5;

[0017] S5. According to the process requirements, the first flotation concentrate is subjected to a second and third flotation to obtain a flotation concentrate.

[0018] Furthermore, in step S1, the preprocessing includes:

[0019] S11. Prepare the slurry and adjust its pH value;

[0020] S12. Add the regulating agent to the slurry and stir.

[0021] S13. Add the collector to the slurry and stir.

[0022] S14. Add a frother to the slurry and stir to obtain the mineral to be floated.

[0023] Furthermore, in step S11, the pH value of the slurry is adjusted using a pH adjuster.

[0024] Furthermore, the pH adjuster is limestone.

[0025] Furthermore, in step S11, after adjusting the pH value using limestone, the pH value of the slurry is 9.0-9.5.

[0026] Furthermore, in step S13, the collector is a fatty acid collector.

[0027] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0028] (1) The present invention combines a flotation device with a mechanical vibration device, so that the mechanical vibration device generates a certain vibration amplitude at the interface between the selection zone and the collection zone of the flotation device, which can reduce the entry of gangue particles into the selection zone, thereby reducing the entrainment of gangue particles.

[0029] (2) The present invention controls the diameter of the sieve holes on the sieve vibrator within the range of 2-3 mm, which can ensure that bubbles with excessively large particle size cannot pass through the sieve holes and be broken, thereby ensuring the formation of a bubble layer with uniform bubble size, reducing the possibility of bubble merging and breaking, which is beneficial to flotation.

[0030] (3) The refractory fine-grained minerals of the present invention are usually accompanied by the presence of intergrowths. During the up-and-down vibration of the perforated sieve plate, some intergrowth minerals can be separated from the target mineral, thereby strengthening the desorption of intergrowths and thus strengthening the flotation process of refractory fine-grained minerals.

[0031] In this invention, the above-described technical solutions can be combined with each other to achieve more preferred combinations. Other features and advantages of this invention will be set forth in the following description, and some advantages may become apparent from the description or be learned by practicing the invention. The objects and other advantages of this invention can be realized and obtained through the embodiments described and the accompanying drawings, which are particularly pointed out. Attached Figure Description

[0032] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.

[0033] Figure 1 This is a schematic diagram of the structure of the flotation separation system for refractory fine-grained minerals provided by the present invention;

[0034] Figure 2 This is a schematic diagram of the structure of a perforated sieve vibrator;

[0035] Figure 3This is a schematic flowchart of the method for enhancing the flotation separation process of refractory fine-grained minerals provided in Embodiment 1 of the present invention;

[0036] Figure 4 This is a schematic flowchart of the method for enhancing the flotation separation process of refractory fine-grained minerals provided in Embodiment 2 of the present invention.

[0037] Figure label:

[0038] 1-Flotation device; 2-Vibration device; 3-Cleaning zone; 4-Collection zone; 5-Vibrator; 6-Drive rod; 7-Porcelain screen vibrator; 8-Slurry feed port; 9-Gas generator; 10-Foam layer. Detailed Implementation

[0039] The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not intended to limit the scope of the present invention.

[0040] On the one hand, the present invention provides an enhanced system for the flotation separation process of refractory fine-grained minerals, such as... Figure 1 As shown, the enhanced system includes a flotation device 1 and a mechanical vibration device 2; wherein, the flotation device 1 includes a cleaning zone 3 located at the top and a collecting zone 4 located at the bottom; a slurry feed port 8 is provided near the top of the collecting zone 4, and a gas generator 9 connection port is provided near the bottom of the collecting zone 4; the mechanical vibration device 2 is used to cause the liquid surface at the interface between the cleaning zone 3 and the collecting zone 4 to vibrate up and down, thereby reducing gangue entrainment and enhancing the desorption of intergrowths.

[0041] Specifically, the flotation apparatus 1 of the present invention includes a cleaning zone 3 and a collecting zone 4, wherein the cleaning zone 3 is located above the collecting zone 4, and the interface between the two is the bubble-slurry interface. The mechanical vibration device 2 is used to generate a certain amplitude of up-and-down vibration at the bubble-slurry interface. The slurry feed port 8 is located in the collecting zone 4 and near the top of the collecting zone 4, and is located above the connection port of the gas generator 9. When it is necessary to introduce bubbles into the collecting zone 4, the bubble generator is turned on. The bubbles generated by the bubble generator enter the bottom of the collecting zone 4 through the connection port of the gas generator 9 and move from bottom to top, while the bubbles from the slurry feed port... 8. The slurry flows downwards. At this time, the gangue particles in the slurry collide with the bubbles and adhere to them. The bubbles rise freely under the action of buoyancy, while the mineral particles either sink or rise with the water flow under the action of their own gravity and the drag force of the water flow. When the gangue particles adhering to the bubbles rise to the bubble-slurry interface, the bubbles will break due to the vibration of the mechanical vibration device 2. The gangue particles adhering to the bubbles will settle down due to their own gravity. In this way, the gangue particles are prevented from entering the foam layer 10 in the beneficiation zone 3, thereby effectively reducing gangue entrainment and ultimately enhancing the flotation process.

[0042] Compared with the prior art, the present invention combines the flotation device 1 with the mechanical vibration device 2, so that the mechanical vibration device 2 generates a certain vibration amplitude at the interface between the selection zone 3 and the collection zone 4 of the flotation device 1, which can reduce the entry of gangue particles into the selection zone 3, thereby reducing the entrainment of gangue particles.

[0043] It should be noted that the above-mentioned entrainment refers to the phenomenon that gangue particles uniformly dispersed in the slurry are entrained by the liquid film between bubbles and enter the froth layer 10 during the flotation process.

[0044] To further improve the flotation effect of refractory fine-grained minerals, such as Figure 1 As shown, the mechanical vibration device 2 of the present invention includes a vibrator 5 and a perforated screen 7; the vibrator 5 is fixedly connected to the perforated screen 7 through a transmission rod 6 provided at its bottom, and the vibrator 5 can drive the perforated screen 7 to vibrate up and down in the flotation device 1.

[0045] Specifically, the above-mentioned perforated screen vibrator is a circular vibrator with a mounting hole at its center; one end of the transmission rod 6 is fixedly connected to the vibrator 5, and the other end is detachably connected to the mounting hole of the perforated screen vibrator 7. The vibrator 5 is located above the flotation device 1. The vibrator 5 can drive the perforated screen vibrator 7 to vibrate up and down at the boundary between the selection zone 3 and the collection zone 4 through the transmission rod 6. The perforated screen vibrator has multiple screen holes.

[0046] It should be noted that during flotation, gangue particles in the slurry are affected by both their own gravity and fluid drag (the fluid drag generated when gangue particles move relative to the rising water flow caused by rising air bubbles). When the gangue particles are large, and the gravity they experience is greater than the fluid drag, the gangue particles will settle to the bottom of the flotation cell, becoming tailings. When the gangue particles are small, and the gravity they experience is less than the fluid drag, the gangue particles will be carried into the concentrate by the water flow, thereby reducing the concentrate grade and worsening the flotation performance. When the gangue particles are small enough, they can be considered uniformly dispersed in the water, and the gangue particles will not settle relative to the water. In this case, the water recovery rate is equal to the gangue recovery rate.

[0047] It should be explained that the water recovery rate mentioned above refers to the ratio of the water mass in the concentrate to the water mass in the raw ore, while the gangue recovery rate refers to the ratio of the gangue mass in the concentrate to the gangue mass in the raw ore.

[0048] The prior art does not include the mechanical vibration device 2 of the present invention. Therefore, the bubbles in the slurry foam phase interface area are not prone to merging and breaking. The gangue particles pass through the bubble-slurry phase interface (referring to the interface between the beneficiation zone 3 and the collection zone 4) with the water flow and enter the gaps between the bubbles. That is, the bubbles are evenly distributed in the foam layer 10 and are scraped up with the bubbles into the concentrate. Therefore, the entrainment phenomenon of gangue particles is relatively serious in the prior art.

[0049] Compared with the prior art, the present invention can select bubbles of appropriate particle size by setting a sieve hole vibrating plate, so that the bubbles are evenly distributed and the possibility of bubble breakage and merger is reduced.

[0050] In the prior art, when the mechanical vibration device 2 is not installed, according to the fluid dynamics continuity equation, after the gangue particles enter the foam layer 10 from the slurry foam phase interface region with the water flow, the contact surface of the gangue particles changes from the slurry foam phase interface to the gap between bubbles. That is, the contact surface of the gangue particles becomes smaller, and the water flow velocity increases. In other words, the water flow carrying gangue particles has the lowest velocity at the phase interface, and the velocity increases after entering the foam layer 10.

[0051] The above fluid dynamics continuity equation is: ρAU = constant, where ρ is the fluid density. In this flotation environment, the mineral sample can be considered to be uniformly distributed in the water flow, that is, the slurry is a liquid with uniform density, meaning that ρ remains constant during the flotation process; A is the area through which the fluid flows. When gangue particles enter the foam layer 10 with the water flow through the phase interface, the contact surface changes from the phase interface to the gaps between bubbles, meaning the contact area decreases; U is the fluid flow velocity. According to ρAU = constant, the area through which the fluid flows, A, decreases after passing the phase interface, while the fluid flow velocity U increases after passing the slurry foam phase interface.

[0052] Since the drag force on gangue particles is proportional to the water flow velocity, the drag force on gangue particles is minimal at the slurry-foam phase interface. After entering the foam layer 10, the drag force increases, making it even more difficult for them to settle. Therefore, this invention sets up a mechanical vibration device 2 at the slurry-foam phase interface. The perforated screen 7 of the mechanical vibration device 2 generates a certain amplitude of up-and-down vibration at the slurry-foam phase interface. The up-and-down vibration exerts a force on the bubbles, making them easy to break. After the bubbles break, the water trapped between the liquid films is also impacted, hindering the water flow from continuing upward. Therefore, setting up the perforated screen 7 can reduce the water flow velocity, thereby reducing the drag force on the gangue particles. When the drag force on the gangue particles is less than the weight of the gangue particles themselves, the gangue particles will settle down, thus preventing the gangue particles from entering the foam layer 10 and effectively reducing gangue entrainment.

[0053] It should be noted that the flotation device 1 includes a cylindrical flotation column. When the flotation device uses a cylindrical flotation column, the perforated sieve 7 corresponding to the flotation column is a circular sieve 7, which has multiple sieve holes of equal size. The outer diameter of the perforated sieve 7 is less than or equal to the inner diameter of the flotation device 1. For example, if a 0.5L flotation device 1 is selected, the inner diameter of the flotation device 1 is 45mm, and the outer diameter of the perforated sieve 7 is 43mm.

[0054] It needs to be emphasized that, such as Figure 2 As shown, the multiple sieve holes on the perforated sieve vibrator 7 of the present invention are a group of regular hexagonal honeycomb holes.

[0055] Compared with the prior art, the present invention sets the sieve holes on the perforated sieve vibrator in a distribution pattern of regular hexagonal honeycomb holes. The purpose is to ensure that when the perforated sieve vibrator 7 vibrates up and down at the slurry-foam layer phase interface, it generates a uniform foam oscillation force on the bubbles and avoids the generation of local bubble buoyancy deviation.

[0056] It should be noted that the flotation device 1 also includes a rectangular flotation cell. When the flotation device 1 uses a flotation cell, the shape of the perforated screen 7 corresponding to the flotation cell is rectangular. The screen holes on the perforated screen 7 are uniformly arranged in a rectangular shape, and the size of the screen holes is the same as the size of the screen holes on the circular perforated screen 7. It should be noted that in order for bubbles carrying the target mineral to pass through the perforated screen 7 and enter the foam layer 10, the screen holes on the perforated screen 7 should not be too small; at the same time, in order to play the role of oscillating the foam layer 10, the screen holes on the perforated screen 7 should not be too large. Therefore, the present invention controls the diameter of the screen holes on the perforated screen 7 within the range of 2-3 mm to ensure that bubbles with excessively large particle sizes cannot pass through the screen holes and are broken, thereby forming a bubble layer with uniform bubble size, reducing the possibility of bubble merging and breaking, and facilitating flotation.

[0057] It is important to note that the minimum spacing between adjacent sieve holes on the perforated sieve vibrator 7 is 1 / 3 to 1 / 4 of the sieve hole diameter. If this spacing is too large, most air bubbles will be blocked, significantly reducing the separation yield. If the spacing is too small, the effect of blocking air bubbles will be weak, reducing the separation efficiency. This invention controls the minimum spacing between adjacent sieve holes on the perforated sieve vibrator 7 to 1 / 3 to 1 / 4 of the sieve hole diameter, which is beneficial for flotation.

[0058] It should be emphasized that the refractory fine-grained minerals of the present invention are usually accompanied by the presence of intergrowths. During the up-and-down vibration of the perforated sieve 7, some intergrowth minerals can also be separated from the target minerals. That is, mechanical vibration can enhance the desorption of intergrowths, thereby enhancing the flotation process of refractory fine-grained minerals.

[0059] On the other hand, the present invention also provides a method for enhancing the flotation separation process of refractory fine-grained minerals, employing the above-mentioned enhancement system, and the enhancement method includes the following steps:

[0060] S1. Pre-treat the sample to be floated to obtain the mineral to be floated;

[0061] In step S1, the preprocessing includes the following steps:

[0062] S11. Prepare the slurry and adjust its pH value;

[0063] In step S11 above, limestone is used to adjust the pH value of the slurry. After adding limestone, the mixture is stirred for 1 minute until the pH value of the slurry is 9.0-9.5.

[0064] The purpose of adjusting the pH of the pulp to a slightly alkaline state is twofold: firstly, to facilitate the interaction between the silanoxy-modified hyperbranched polymer and silicate gangue minerals added later; and secondly, to facilitate the interaction between the collector added later and the target minerals, thereby providing a favorable flotation environment for subsequent flotation.

[0065] S12. Add the regulating agent to the slurry and stir.

[0066] In step S12 above, the added regulating agent is a silaneoxy-modified hyperbranched polymer. The amount of silaneoxy-modified hyperbranched polymer added is 50-200 g / t slurry, and the mixture is stirred for 2 minutes after addition.

[0067] It should be noted that the silanoxy-modified hyperbranched polymer can interact with silicate gangue minerals in the slurry to form polymer-silicate gangue mineral flocs; and these polymer-silicate gangue mineral flocs not only have a larger particle size than the original fine-grained gangue minerals, but also have better hydrophilicity and are easier to settle.

[0068] S13. Add the collector to the slurry and stir.

[0069] In step S13 above, the collector is a fatty acid collector. The purpose of adding a fatty acid collector is to change the physicochemical properties of the target mineral particles surface in order to improve the floatability of the target mineral particles.

[0070] S14. Add a frother to the slurry and stir to obtain the mineral to be floated.

[0071] In step S14 above, the purpose of adding a foaming agent is to reduce the surface tension of water in order to form foam.

[0072] S2. The mineral to be floated is fed into the flotation device 1 through the mineral feed port;

[0073] S3. Turn on the bubble generator;

[0074] In step S3 above, the slurry entering through the slurry feed port 8 and the bubbles generated by the bubble generator flow counter-currently in the collecting zone 4 of the flotation device 1. The bubbles collide with and adhere to the mineral particles. The bubbles rise freely under the action of buoyancy, while the mineral particles either descend or are carried upward by the water flow under the combined action of their own gravity and the drag force of the water flow. At this time, the larger and denser mineral particles will descend. The descending mineral particles will collide with the rising bubbles in the collecting zone 4. The hydrophobic target mineral particles will collide with and adhere to the bubbles due to their surface characteristics, forming mineralized bubbles on the bubble surface. The hydrophilic large gangue mineral particles will continue to settle to the bottom of the slurry and become tailings. The smaller and less dense gangue mineral particles are easily carried upward by the water flow. The mineralized bubbles continue to rise into the cleaning zone 3 and gather in the cleaning zone 3 of the flotation device 1 to form a mineralized foam layer 10. The fine gangue minerals carried by the water flow will also rise to the mineralized foam layer 10.

[0075] S4. Start the mechanical vibration device 2 and simultaneously turn on the flushing water at the top of the flotation device 1 to obtain the first flotation concentrate and tailings;

[0076] In step S4 above, the vibrator 5 is started. The vibrator 5 drives the perforated screen 7 to vibrate in the up and down direction through the transmission rod 6. The vibration frequency of the perforated screen 7 is 15-25Hz and the amplitude is 0.02-0.08mm. The vibrator 5 excites the perforated screen 7 to vibrate, thereby inducing foam oscillation at the pulp-foam phase interface in the flotation device 1. At the same time, the flushing water is turned on. Under the action of the flushing water, the gangue particles entrained in the foam layer 10 fall off from the foam layer 10. The two work together to effectively reduce the entrainment of fine gangue particles.

[0077] It should be noted that the obtained first flotation concentrate and tailings can be analyzed and processed according to the index requirements, which also includes step S5. In step S5, the first flotation concentrate is subjected to a second and a third flotation to obtain the flotation concentrate.

[0078] Compared with the prior art, the present invention uses a mechanical vibration device 2 to generate vibration at the bubble-slurry interface, reducing the possibility of gangue particles entering the foam layer 10. The added silanoxy modified hyperbranched polymer can react with gangue minerals physically and chemically to form polymer-gangue mineral flocs, which settle in the slurry and become tailings, effectively reducing gangue entrainment.

[0079] It should also be emphasized that the vibrator 5 of the present invention drives the perforated screen 7 to vibrate, which can separate the target mineral from the intergrowth mineral, enhance the desorption of the intergrowth, and further improve the grade of the concentrate.

[0080] It should be emphasized that the aforementioned silanoxy-modified hyperbranched polymer is a macromolecule synthesized under certain chemical conditions using hydrophilic organic macromolecules and silane coupling agents. The preparation process of the silanoxy-modified hyperbranched polymer includes:

[0081] S1. Weigh 0.1g of hydrophilic organic macromolecule and 0.1g of silane coupling agent, and transfer them to a 250ml beaker;

[0082] S2. Add 100ml of methanol to the beaker, and add pH adjuster NaHCO3 to adjust the pH to 7.5;

[0083] S3. Turn on the thermostatic magnetic stirrer and set the temperature to 70°C. Place the beaker on the thermostatic magnetic stirrer and stir for at least 3.5 hours to allow the hydrophilic organic macromolecules to fully react with the silane coupling agent. After the reaction is complete, the silaneoxy-modified hyperbranched polymer is obtained.

[0084] Compared with traditional organic macromolecular flotation control agents, the silanoxy-modified hyperbranched polymer provided by this invention can selectively and efficiently react with the silanol groups on the surface of silicate gangue minerals (i.e., difficult-to-select fine-grained minerals) to form a stable flocculent structure. While promoting the sedimentation of fine-grained gangue minerals, it also enhances the hydrophilicity of gangue mineral particles, thus achieving targeted control of the entrainment behavior of silicate gangue minerals.

[0085] The aforementioned hydrophilic organic macromolecule is one of vinyl polymers, polyamides, and polyesters. This hydrophilic organic macromolecule is used to improve the hydrophilicity of the surface of silicate gangue minerals, prevent the silicate gangue minerals from undergoing hydrophobic modification under the action of collectors and foaming agents, ensure that the silicate gangue does not adhere to the air bubbles, and thus allow it to remain in the slurry and become tailings for discharge.

[0086] The aforementioned silane coupling agent is an organosilicon compound with a special structure containing two groups with different chemical properties, and its structural formula is: YR-SiX3. Wherein: YR is a non-hydrolyzable group, and X3 consists of three hydrolyzable groups; Y is a group capable of reacting with organic macromolecules, for example, Y is one of vinyl, amino, epoxy, or azide groups; R is a short-chain alkane group with the structural formula (CH2)n, where n = 0-3, and R is used to connect Y to Si atoms; X can undergo hydrolysis to generate Si-OH groups. This silane coupling agent contains three hydrolyzable groups.

[0087] It should be noted that the aforementioned chemical auxiliaries, such as methanol, are used as solvents to create an anhydrous environment. When the hydrophilic organic macromolecules react chemically with the silane coupling agents, the non-hydrolyzable groups on the silane coupling agents undergo a synthetic reaction with the hydrophilic organic macromolecules. Different hydrophilic silane coupling agents are used to end-cap and modify the active groups of the hydrophilic organic macromolecules, forming silanoxy-modified hyperbranched polymers.

[0088] The formation process of silanoxy-modified hyperbranched polymers is as follows:

[0089]

[0090] Wherein, Y is one of vinyl, amino, epoxy, or azide groups; R is a short-chain alkane group, such as -CH2, -CH2-CH2, or -(CH2)3, used to connect Y to Si atoms; X is a hydrolyzable group, which hydrolyzes to generate Si-OH, and this silane coupling agent contains three hydrolyzable groups; -A- is a hydrophilic macromolecule, and n in (-A-)n represents the number of hydrophilic macromolecules, indicating that there are many -A- groups, and n is uncountable.

[0091] The branching hydrolysis process of silanoxy-modified hyperbranched polymers is as follows:

[0092]

[0093] Wherein, Y is one of vinyl, amino, epoxy, or azide groups; R is a short-chain alkane group, such as -CH2, -CH2-CH2, or -(CH2)3, used to connect Y to Si atoms; X is a hydrolyzable group, which hydrolyzes to generate Si-OH; n is uncountable.

[0094] Under alkaline conditions, the hydrolyzable groups on the silanoxy modified hyperbranched polymer undergo hydrolysis. After hydrolysis, they can undergo hydroxyl dehydration condensation reaction with the hydroxyl groups of Si-OH and Al-OH on the surface of silicate gangue minerals and generate hydrogen bonds to form polymer-silicate gangue mineral flocs. The polymer-silicate gangue mineral flocs remain at the bottom of the coal slurry and become tailings.

[0095] It should be noted that the specific reaction process of the above-mentioned hydroxyl dehydration condensation reaction is as follows:

[0096]

[0097] The specific reaction process for generating hydrogen bonds described above is as follows:

[0098]

[0099] It should be noted that the aforementioned hydrophilic organic macromolecules can enhance the hydrophilicity of silicate gangue minerals, thereby strengthening the hydrophilicity of the polymer-silicate gangue mineral flocs formed by the silicate gangue minerals and silane coupling agents. Furthermore, the particle size of the formed polymer-silicate gangue mineral flocs is much larger than the original particle size of the silicate gangue minerals. Both the increased hydrophilicity of the silicate gangue minerals and the increased particle size of the polymer-silicate gangue mineral flocs promote the sedimentation of silicate gangue mineral particles in the slurry, thus effectively reducing the entrainment of silicate gangue.

[0100] It should be noted that, in order to avoid structural instability of polymer-silicate gangue mineral flocs under stirring, the present invention selects a suitable flow field environment during the flotation process. A suitable process environment can both disperse the target mineral particles in the water and avoid structural breakage and dispersion of the aforementioned polymer-silicate gangue mineral flocs.

[0101] Example 1

[0102] This embodiment provides a method for enhancing the flotation of hematite from Anshan, the specific flotation process as follows: Figure 3 As shown, the process includes the following:

[0103] S1. Pre-treat the sample to be floated to obtain the mineral to be floated;

[0104] S11. Add limestone and stir for 1 minute to adjust the pH of the slurry to 9.0;

[0105] S12. Add the silanoxy-modified hyperbranched polymer as a regulating agent to the slurry and stir for 2 minutes;

[0106] S13. Add sodium oleate (NZ), a fatty acid collector, to the slurry and stir for 2 minutes;

[0107] S14. Add frother pine oil (2# oil) to the slurry and stir to obtain the mineral to be floated;

[0108] It should be noted that before adding limestone, the crushed ore sample is first put into a ball mill. Under the condition that the slurry concentration is 70%, the ore sample is ground until the grinding fineness reaches -45μm accounts for 85% to meet the requirements of mineral particle size in the subsequent flotation process.

[0109] S2. The mineral to be floated, i.e., the slurry, after being treated with flotation reagents, is fed into the slurry feed port 8 at the top of the flotation device 1.

[0110] S3. Turn on the bubble generator. The bubbles generated by the bubble generator are introduced from the lower part of the collection zone 4 of the flotation device 1.

[0111] S4. Start the vibrator 5. The vibrator 5 drives the perforated screen 7 to vibrate through the transmission rod 6. The vibration frequency of the perforated screen 7 is 20Hz and the amplitude is 0.06mm. At the same time, turn on the flushing water at the top of the flotation device 1 to obtain the first flotation concentrate and tailings.

[0112] After obtaining the first flotation concentrate and tailings, they were processed and analyzed separately. The yield and grade of the concentrate and tailings are shown in Table 1 below.

[0113] Table 1. Flotation results of Example 1

[0114]

[0115]

[0116] As shown in Table 1 above, under the condition of using mechanical vibration device 2, when the dosage of silaneoxy hyperbranched polymer is increased from 0 to 200 g / t, that is, from no silaneoxy hyperbranched polymer to 200 g / t of silaneoxy hyperbranched polymer, the concentrate grade increases from 54.03% to 65.18%, and the metal recovery rate increases from 88.03% to 90.58%, indicating a significant improvement in concentrate grade.

[0117] Example 2

[0118] The difference between this embodiment and embodiment 1 is that the refractory fine-grained mineral used is the Xinjulong coal sample, and the types of collectors and frothers added are also different: the collector used in this embodiment is kerosene, and the frother used is methyl isobutyl methanol (MIBC); in addition, the vibration frequency of the perforated sieve 7 is 22Hz, and the amplitude is 0.04mm.

[0119] The process flow diagram for sorting the new Julong coal sample in this embodiment is as follows: Figure 4 As shown, the specific flotation process is as follows:

[0120] S1. Pre-treat the sample to be floated to obtain the mineral to be floated;

[0121] S11. Add limestone and stir for 1 minute to adjust the pH of the slurry to 9.3;

[0122] S12. Add the silanoxy-modified hyperbranched polymer as a regulating agent to the slurry and stir for 2 minutes;

[0123] S13. Add fatty acid collector kerosene to the slurry and stir for 2 minutes;

[0124] S14. Add the frother methyl isobutyl methanol (MIBC) to the slurry and stir to obtain the mineral to be floated.

[0125] S2. The mineral to be floated, i.e., the slurry, after being treated with flotation reagents, is fed into the slurry feed port 8 at the top of the flotation device 1.

[0126] S3. Turn on the bubble generator. The bubbles generated by the bubble generator are introduced from the lower part of the collection zone 4 of the flotation device 1.

[0127] S4. Start the vibrator 5. The vibrator 5 drives the perforated screen 7 to vibrate through the transmission rod 6. The vibration frequency of the perforated screen 7 is 22Hz and the amplitude is 0.04mm. At the same time, turn on the flushing water at the top of the flotation device 1 to obtain the first flotation concentrate and tailings.

[0128] After obtaining the first flotation concentrate and tailings, they were processed and analyzed separately. The yield and grade of the concentrate and tailings are shown in Table 2 below.

[0129] Table 2. Flotation results of Example 2

[0130]

[0131] As shown in Table 2 above, under the condition of using mechanical vibration device 2, when the amount of silaneoxy hyperbranched polymer is increased from 0 to 200 g / t, that is, from no addition of silaneoxy hyperbranched polymer to the addition of 200 g / t of silaneoxy hyperbranched polymer, the ash content of clean coal decreases from 11.85% to 7.94%, and the ash content of clean coal is significantly reduced.

[0132] Compare with Example 1

[0133] The only difference between this embodiment and Embodiment 1 is that the mechanical vibration device 2 is not used for vibration.

[0134] Table 3 shows the flotation results compared to Example 1.

[0135]

[0136]

[0137] Comparing the flotation results obtained in this comparative example with those in Example 1 reveals that: In this comparative example, flotation under conventional conditions occurs when mechanical vibration device 2 is not used and the amount of silanoxy hyperbranched polymer is 0. Compared to the results in Example 1, which used mechanical vibration device 2, the concentrate grade decreased from 54.03% to 52.37%, and the metal recovery rate decreased from 88.03% to 87.88%, indicating a certain degree of decline in both concentrate grade and metal recovery rate. While increasing the amount of silanoxy hyperbranched polymer improves both concentrate grade and recovery rate, under the same reagent regime, the concentrate grade and metal recovery rate obtained in Example 1 are higher than those in Comparative Example 1. This demonstrates that the use of mechanical vibration device 2 can improve concentrate grade.

[0138] Compare with Example 2

[0139] The difference between this comparative example and Example 2 is that the mechanical vibration device 2 was not used, and the flotation results are shown in Table 4 below.

[0140] Table 4. Flotation results compared to Example 2

[0141]

[0142]

[0143] In this comparative example, when mechanical vibration device 2 was not used and the amount of silaneoxy hyperbranching polymer was 0, i.e., under conventional flotation conditions, the flotation results of this comparative example, compared with the results of Example 2 using mechanical vibration device 2, showed that the ash content of the clean coal increased from 11.85% to 13.09%. Furthermore, as the amount of silaneoxy hyperbranching polymer increased to 200 g / t, the ash content of the clean coal in Example 1 decreased from 11.85% to 7.94%, while the ash content of the clean coal in Comparative Example 2 decreased from 13.09% to 11.36%, indicating a certain degree of reduction in ash content. Therefore, the addition of silaneoxy hyperbranching polymer can reduce the ash content of clean coal. However, under the same reagent regime, the ash content of the clean coal obtained in Example 2 was lower than that in Comparative Example 2, indicating that the use of mechanical vibration device 2 can improve the quality of clean coal.

[0144] In summary, by setting up a mechanical stirring device and adding silanoxy hyperbranched polymer flotation reagent, this invention can effectively reduce the entrainment of fine gangue minerals during the flotation process, while also enhancing the desorption of the target mineral from the intergrowth. This invention can strengthen the flotation process from multiple aspects, thereby improving the quality of the concentrate.

[0145] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for intensifying the process of flotation separation of a fine-grained mineral that is difficult to float, characterized in that, Adopt the flotation device and mechanical vibration device; The flotation device includes a cleaning zone at the top and a collecting zone at the bottom; a slurry feeding port is arranged near the top of the collecting zone, and a gas generator connecting port is arranged near the bottom of the collecting zone; the interface between the cleaning zone and the collecting zone is a bubble-sliming phase interface, and the mechanical vibration device is used to make the liquid surface at the bubble-sliming phase interface of the cleaning zone and the collecting zone vibrate up and down, thereby reducing the gangue entrainment and strengthening the intergrowth detachment; The mechanical vibration device includes an exciter and a hole screen vibration piece, and the exciter is used to drive the hole screen vibration piece to vibrate at the interface between the cleaning zone and the collecting zone; The exciter is fixedly connected with the hole screen vibration piece through a transmission rod arranged at the bottom of the exciter, and the exciter can drive the hole screen vibration piece to vibrate up and down in the flotation device; The diameter of the screen hole on the hole screen vibration piece is controlled within the range of 2-3 mm; and the minimum spacing between adjacent screen holes on the hole screen vibration piece is 1 / 3-1 / 4 of the diameter of the screen hole. The strengthening method includes the following steps: S1, pretreating a sample to be floated to obtain a mineral to be floated; In the S1 step, the pretreatment includes: S11, preparing a slurry and adjusting the pH value of the slurry; S12, adding a control agent to the slurry and stirring; The control agent is a siloxyl-modified hyperbranched polymer, and the addition amount of the siloxyl-modified hyperbranched polymer is 50-200 g / t of the slurry; after addition, stirring for 2 minutes; The siloxyl-modified hyperbranched polymer is synthesized from a hydrophilic organic macromolecule, a silane coupling agent and a chemical additive; the hydrophilic organic macromolecule is one of a vinyl polymer, a polyamide and a polyester; the chemical additive is methanol as a solvent for creating an anhydrous environment; The silane coupling agent is an organosilicon compound containing two different chemical groups, and its structural formula is Y-R-SiX3; wherein Y-R is a non-hydrolysable group, X3 is three hydrolysable groups; Y is one of vinyl, amino, epoxy, azido; R is (CH2) n n = 0-3, R is used to connect Y with Si atom; X is a group that can undergo hydrolysis reaction and generate Si-OH, the silane coupling agent contains three hydrolysable groups; S13, adding a collector to the slurry and stirring; S14, adding a foaming agent to the slurry and stirring to obtain a mineral to be floated; S2, feeding the mineral to be floated into the flotation device through the slurry feeding port; S3, starting the gas bubble generator; S4, starting the mechanical vibration device, and at the same time, opening the shower water at the top of the flotation device to obtain a first flotation concentrate and tailings.

2. The process for the enhancement of the flotation separation of a refractory fine-grained mineral according to claim 1, characterized in that, The shape of the hole screen vibration piece is circular; the shape of the flotation device is cylindrical; and the outer diameter of the hole screen vibration piece is smaller than the inner diameter of the flotation device.

3. The method for process intensification of the flotation separation of a refractory fine-grained mineral according to claim 2, characterised by the fact that, A plurality of screen holes are arranged on the circular hole screen vibration piece.

Images