An apparatus and method for degrading a potassium salt flotation reagent

Abstract

The application provides a device for degrading potassium salt flotation reagent, which comprises a gas-phase reactor, an anode, a reactor, a cathode pressing plate, the anode is connected with a discharge gas storage device, the bottom of the reactor is fixedly connected with the cathode pressing plate, mixed gas generated by ionization of reaction gas in the gas-phase reactor forms bubbles through bubbling holes and then enters into an electrolyte solution, when the anode is electrified, a first alternating electric field is formed between the anode and the cathode pressing plate, and the mixed gas and plasma synergistically act to degrade the potassium salt flotation reagent in the electrolyte solution. The application further provides a method for degrading potassium salt flotation reagent. The mixed gas generated by the gas-phase reactor forms bubbles in the electrolyte solution in the reactor, plasma is prepared between the anode and the cathode pressing plate, and the mixed gas and the plasma synergistically act to degrade the potassium salt flotation reagent in the electrolyte solution.

Description

Technical Field

[0001] This invention belongs to the field of flotation collector degradation technology in potassium salt flotation process, and particularly relates to an apparatus and method for degrading potassium salt flotation reagents. Background Technology

[0002] Currently, over 80% of the world's potash fertilizer is produced via flotation, with octadecylamine (ODA) and dodecylmorpholine (DMP) being the two most common flotation reagents. With global population growth, agricultural output needs to increase significantly, leading to a corresponding increase in demand for potash fertilizer. Over the long term, the residue of flotation reagents in potash fertilizer production can directly affect its quality and pose a potential threat to the ecological environment of salt lakes.

[0003] Currently, common pollutant treatment technologies include adsorption, filtration, gravity separation, sedimentation, ozone oxidation, ultrasonic decomposition, Fenton technology, electrocatalysis, and photocatalysis. While these methods are widely used in removing pollutants from aqueous solutions, most have several drawbacks. For example, filtration can only treat pollutants insoluble in aqueous solutions; it has no effect on pollutants dissolved in the solution. Adsorption and sedimentation only move pollutants from the liquid phase to the solid phase, without completely degrading them, thus failing to achieve the goal of degradation. Membrane processes require high-quality feed water and are often subject to secondary pollution from residual concentrate. Ozone oxidation and ultrasonic methods have low energy efficiency, high operating costs, and high energy consumption. In Fenton reagent and Fenton-type treatment processes, large amounts of residual sludge often cause secondary pollution. Photocatalysis and electrocatalysis require different catalysts for different pollutants and suffer from issues related to solid-liquid separation and cycle stability / lifespan. The aforementioned common pollutant treatment technologies have certain technical limitations in the degradation of flotation reagents. Therefore, designing a more environmentally friendly pollutant treatment method is of great significance for potash fertilizer production. Summary of the Invention

[0004] To address the various shortcomings of existing pollutant treatment technologies described in the background art when treating potassium salt flotation reagents, the present invention proposes the following technical solution:

[0005] An apparatus for degrading potassium salt flotation reagents includes: a gas phase reactor, an anode, a reactor, and a cathode pressure plate; the gas phase reactor includes: an insulating plate and conductive plates and a grounding plate respectively disposed on both sides of the insulating plate; one side of the insulating plate is recessed to form a gas storage tank, and the other side of the insulating plate is fixedly connected to the grounding plate; one side of the conductive plate is connected to a power source, and one side of the grounding plate is grounded, thereby forming a second alternating electric field for ionizing the reaction gas in the gas storage tank; the surface of the conductive plate is provided with a gas guiding channel connecting the reaction gas storage device and the gas storage tank, and an exhaust channel connecting the gas storage tank and the reactor; one end of the anode is connected to the discharge gas storage device, and the other end of the anode extends into the reactor; the bottom of the reactor is connected to the cathode pressure plate. The cathode plate is fixedly connected; the surface of the cathode plate is provided with bubbling holes, and the mixed gas generated by the ionization of the reaction gas by the gas phase reactor forms bubbles through the bubbling holes and enters the electrolyte solution; when the anode is energized, a first alternating electric field for generating plasma is formed between the anode and the cathode plate; when the reaction gas storage device supplies reaction gas to the gas phase reactor 1, the reaction gas is ionized in the second alternating electric field and forms a mixed gas composed of ozone, oxygen, high-energy electrons, and oxygen free radicals; wherein, the proportion of ozone in the mixed gas is greater than the proportion of oxygen, high-energy electrons, and oxygen free radicals; the mixed gas and the plasma work together to degrade the potassium salt flotation reagent in the electrolyte solution.

[0006] Furthermore, the anode is tubular, with one end connected to the discharge gas storage device and the other end located above the surface of the electrolyte solution.

[0007] Furthermore, the air guide channel and the exhaust channel are symmetrically distributed about the insulating plate.

[0008] Furthermore, the gap between the anode and the electrolyte solution is between 3 mm and 12 mm.

[0009] Furthermore, the anode is energized after bubbling occurs in the electrolyte solution.

[0010] Furthermore, the surface of the reactor is provided with an outlet for discharging exhaust gas and a sampling port for discharging electrolyte solution, with the outlet located above the sampling port.

[0011] Another object of the present invention is to provide a method for degrading potassium salt flotation reagents, wherein the above-mentioned apparatus for degrading potassium salt flotation reagents comprises:

[0012] Prepare a mixed gas and continuously pass it into the reactor;

[0013] Bubbling is created in an electrolyte solution;

[0014] Plasma is prepared and introduced into the electrolyte solution;

[0015] Once the anode has been energized for a preset time, the anode will be de-energized and the electrolyte solution in the reactor will be discharged.

[0016] Furthermore, when preparing the mixed gas, the output flow rate of the gas phase reactor is 50 mL / min to 300 mL / min; when preparing plasma, the gas output flow rate of the anode is 100 mL / min to 800 mL / min.

[0017] Beneficial effects: The present invention generates a mixed gas in a gas phase reactor to form bubbles in the electrolyte solution within the reactor, and plasma is generated between the anode and cathode pressure plates. The potassium salt flotation reagent in the electrolyte solution is degraded by the synergistic effect of the mixed gas and the plasma. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of an apparatus for degrading potassium salt flotation reagents according to an embodiment of the present invention;

[0019] Figure 2 This is a flowchart of a method for degrading potassium salt flotation reagent according to an embodiment of the present invention;

[0020] Figure 3 This is a schematic diagram illustrating the degradation effect of a 30 mg / L ODA solution using different discharge gases at a power discharge rate of 25 W.

[0021] Figure 4 A schematic diagram showing the degradation effect of a 30 mg / L DMP solution using different discharge gases at a power discharge of 25 W.

[0022] Figure 5 This is a schematic diagram illustrating the degradation effect of a 30 mg / L ODA solution using different discharge gases at a power discharge of 15 W.

[0023] Figure 6 This is a schematic diagram showing the degradation effect of a 30 mg / L DMP solution using different discharge gases at a power discharge of 15 W. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of this application clearer, the present invention will be described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention.

[0025] It should be understood that the terms “center,” “upper,” “lower,” “front,” “back,” “left,” “right,” “vertical,” “horizontal,” “top,” “bottom,” “inner,” and “outer,” etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this patent and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this patent.

[0026] Figure 1 This is a schematic diagram of an apparatus for degrading potassium salt flotation reagents according to an embodiment of the present invention.

[0027] Reference Figure 1 An apparatus for degrading potassium salt flotation reagents according to an embodiment of the present invention includes: a gas phase reactor 1, an anode 2, a reactor 3, and a cathode plate 134. One side of the gas phase reactor 1 is connected to a reaction gas storage device 5, and the other side of the gas phase reactor 1 is connected to the reactor 3. One end of the anode 2 is connected to a discharge gas storage device 6, and the other end of the anode 2 extends into the reactor 3. The reactor 3 is provided with a reaction chamber for containing an electrolyte solution, and the bottom of the reactor 3 is fixedly connected to the cathode plate 134. The surface of the cathode plate 134 is provided with bubbling holes 41. The mixed gas generated after the gas phase reactor 1 ionizes the reaction gas passes through the bubbling holes 41 and forms bubbles, thus entering the electrolyte solution. When the anode 2 is energized, a first alternating electric field for forming a mixed gas is formed between the anode 2 and the cathode plate 134. The plasma and the mixed gas work together to degrade the potassium salt flotation reagents in the electrolyte solution.

[0028] In the degradation of potassium salt flotation reagents, a mixed gas is first generated using a gas-phase reactor 1, and then an electrolyte solution is introduced to create bubbles. This mixed gas contains ozone, oxygen, and high-energy electrons formed after ionization. Upon introduction into the electrolyte solution, the ozone rapidly reacts with the potassium salt flotation reagent, thereby degrading it. After energization, anode 2 simultaneously ionizes the gas and liquid between anode 2 and the electrolyte solution surface to form plasma. The active species in the plasma then enter the electrolyte solution. During this process, the movement of the bubbles alters the solute distribution within the electrolyte solution, and after the bubbles burst, the gas within the bubbles is ionized by the electric field between anode 2 and cathode plate 134.

[0029] Specifically, the gas phase reactor 1 includes an insulating plate 11, conductive plates 12 disposed on both sides of the insulating plate 11, and a grounding plate. One side of the insulating plate 11 is recessed to form a gas storage tank 111, and the other side of the insulating plate 11 is fixedly connected to the grounding plate. One side of the conductive plate 12 is connected to a power supply 7, and one side of the grounding plate is grounded, forming a second alternating electric field for ionizing the reaction gas between the conductive plate 12 and the grounding plate. The surface of the conductive plate 12 is provided with a gas guiding channel 121 connecting the reaction gas storage device 5 and the gas storage tank 111, and an exhaust channel 122 connecting the gas storage tank 111 and the reactor 3. The reaction gas is output from the reaction gas storage device 5, enters the gas storage tank 111 through the gas guiding channel 121, is ionized to form a mixed gas, and enters the reactor 3 through the exhaust channel 122. Under the action of the gas guiding holes on the surface of the cathode pressure plate 134 in the reactor 3, the plasma introduced into the reactor 3 forms bubbles. The insulating plate 11 is an insulator. In this embodiment, the insulating plate 11 is glass; in other embodiments, the insulating plate 11 may also be an insulator such as rubber.

[0030] Furthermore, the anode 2 is generally cylindrical. The discharge gas output from the discharge gas storage device 6 is discharged along the anode 2 and then ionized into plasma between the anode 2 and the cathode plate 134. The gap between the anode 2 and the liquid surface of the electrolyte solution is between 3mm and 12mm. The surface of the reactor 3 is provided with an outlet 31 for discharging exhaust gas and a sampling port 32 for discharging electrolyte solution. The outlet 31 is located above the sampling port 32, and the sampling port 32 is located on the side closer to the cathode plate 134.

[0031] Preferably, in this embodiment, the gap between the anode 2 and the electrolyte solution surface is 12 mm. In other embodiments, the gap between the anode 2 and the electrolyte solution surface can also be 3 mm, 4 mm, 5 mm, etc. As the gap between the anode 2 and the electrolyte solution surface increases, the channel generated between the anode 2 and the electrolyte solution surface after the anode 2 is energized becomes longer, resulting in more active species generated after electrolysis and a higher degradation reaction rate within the electrolyte solution. When the gap between the anode 2 and the electrolyte solution surface exceeds 12 mm or falls below 3 mm, electrolysis no longer occurs.

[0032] Figure 2 This is a flowchart of a method for degrading potassium salt flotation reagent according to an embodiment of the present invention.

[0033] Reference Figure 2 Another object of the present invention is to provide a method for degrading potassium salt flotation reagents, using the above-described apparatus for degrading potassium salt flotation reagents, comprising:

[0034] S000, Prepare a mixed gas and continuously pass it into reactor 3.

[0035] Specifically, in this step, a second alternating electric field is formed in the gas storage tank 111 between the conductive plate 12 and the ground plate by electrically connecting the conductive plate 12 to the power supply 7. When the reaction gas storage device 5 supplies reaction gas to the gas phase reactor 1, the reaction gas is ionized in the second alternating electric field and forms a mixed gas composed of ozone, oxygen, high-energy electrons, oxygen free radicals, etc. Among them, the ozone content in the mixed gas is relatively high.

[0036] S100, Bubbling is produced in an electrolyte solution.

[0037] Specifically, in this step, the mixed gas formed after the ionization of the reactant gas forms bubbles as it passes through the bubbling holes 41 on the cathode plate 134, thus entering the electrolyte solution. During this process, substances with high-energy electrons and oxygen atoms undergo redox reactions with the potassium salt flotation reagent in the electrolyte solution, thereby degrading the potassium salt flotation reagent. Furthermore, as the bubbles formed by the mixed gas move within the electrolyte solution, they agitate the surrounding solution, causing convection. This convection promotes the diffusion and mixing of ions and solutes in the electrolyte solution, thereby altering the uniformity of solute distribution. Through convective mixing, the solute concentration gradient can be reduced, resulting in a more uniform distribution of solute in the solution.

[0038] Furthermore, in this embodiment, the reactant gas is oxygen, and the discharge gas is oxygen or other gases commonly used in plasma preparation, including but not limited to argon and nitrogen. The movement of the bubbles can also affect the mass transfer process of the solute. When the bubbles pass through the solution, they can carry away or introduce solute molecules, which alters the concentration distribution of the solute in the solution and affects the diffusion and transfer of the solute. During the bubble formation process, only ozone and the reactant gas form bubbles, while high-energy electrons and oxygen atoms react directly with the solute in the electrolyte solution. The ozone in the bubbles is also gradually consumed during the bubble's movement due to reactions with the solute. Unconsumed reactant gases within the bubbles are further ionized in the first alternating electric field.

[0039] S200, prepare plasma and input it into the electrolyte solution.

[0040] Specifically, when bubbles appear in the electrolyte solution, the anode 2 is connected to the power supply 7, thereby forming a first alternating electric field between the anode 2 and the cathode plate 134. When the discharge gas is output from the anode 2 port, it is ionized by the first electric field. At this time, the gas released after the bubbles break is also ionized by the first alternating electric field.

[0041] Furthermore, the electric field strength of the first alternating electric field is different from that of the second alternating electric field. In this embodiment, the discharge AC frequency of the power supply 7 connected to the conductive plate 12 is 3kHz-6kHz, and the input power is 1W-15W. The discharge AC frequency of the power supply 7 connected to the anode 2 is 9kHz-12kHz, and the input power is 15W-40W.

[0042] S300. When the energization time of anode 2 reaches the preset time, the energization of anode 2 is turned off and the electrolyte solution in reactor 3 is discharged.

[0043] Specifically, before degrading the potassium salt flotation reagent in the electrolyte solution, the energizing time of anode 2 needs to be preset. Generally, the degradation time of potassium salt flotation reagents of different concentrations can be calculated through repeated experiments. When the energizing time of anode 2 reaches the preset time, the connection between anode 2 and power supply 7 is first disconnected, and then the operation of gas phase reactor 1 is stopped, thereby interrupting the formation of plasma and mixed gas.

[0044] Before discharging the electrolyte solution from reactor 3, to ensure that the potassium salt flotation reagent in the electrolyte solution is fully degraded, it is generally necessary to quantitatively extract the electrolyte solution after the reaction from sampling port 32 and test its potassium salt flotation reagent concentration. If the concentration test result of the potassium salt flotation reagent is not zero after the reaction is completed, degradation needs to continue according to the test result.

[0045] The following examples demonstrate the degradation effect of potassium salt flotation reagents under different concentration conditions, wherein the reaction gas is oxygen.

[0046] Example 1:

[0047] Figure 3 This is a schematic diagram showing the degradation effect of a 30 mg / L ODA solution using different discharge gases at a power discharge of 25 W.

[0048] An ODA solution with a concentration of 30 mg / L was introduced into reactor 3 through outlet 31. The input power of gas phase reactor 1 was 10 W, and the gas flow rate of the reaction gas was 200 mL / min. The gas flow rate of the discharge gas was 500 mL / min, and nitrogen, oxygen, and argon were used for the experiment. Power supply 7 discharged at an AC frequency of 10 kHz, with a discharge power of 25 W and a discharge gap of 8 mm. Samples were taken at regular intervals. The ODA degradation rate is shown in the figure. Figure 3 It can be seen that the ODA solution is basically completely degraded in about ten minutes, and the degradation efficiency is the highest when both the reaction gas and the discharge gas are oxygen.

[0049] Example 2:

[0050] Figure 4This is a schematic diagram showing the degradation effect of a 30 mg / L DMP solution using different discharge gases at a power discharge of 25 W.

[0051] A 30 mg / L DMP solution was introduced into reactor 3 through outlet 31. The input power of gas-phase reactor 1 was 10 W, and the gas flow rate of the reaction gas was 200 mL / min. The gas flow rate of the discharge gas was 500 mL / min, and nitrogen, oxygen, and argon were used for the experiment. Power supply 7 had an AC discharge frequency of 10 kHz, a discharge power of 25 W, and a discharge gap of 8 mm. Samples were taken at regular intervals. The ODA degradation rate is shown in the figure. Figure 4 It can be seen that the ODA solution is basically completely degraded in about 30 minutes, and the degradation efficiency is the highest when both the reaction gas and the discharge gas are oxygen.

[0052] Example 3:

[0053] Figure 5 This is a schematic diagram showing the degradation effect of a 30 mg / L ODA solution using different discharge gases at a power discharge of 15 W.

[0054] An ODA solution with a concentration of 30 mg / L was introduced into reactor 3 through outlet 31. The input power of gas-phase reactor 1 was 5 W, and the reaction gas flow rate was 200 mL / min. The discharge gas flow rate was 500 mL / min, and nitrogen, reaction gas, and argon were used in the experiment. The discharge AC frequency was 10 kHz, and the discharge power was 15 W. The discharge gap was 8 mm, and samples were taken at regular intervals. The degradation rate of ODA is shown in the figure. (Refer to...) Figure 5 It can be seen that ODA can be basically completely degraded in about 30 minutes. Among them, the degradation efficiency is the highest when both the reaction gas and the discharge gas are oxygen.

[0055] Example 4:

[0056] Figure 6 This is a schematic diagram showing the degradation effect of a 30 mg / L DMP solution using different discharge gases at a power discharge of 15 W.

[0057] A 30 mg / L DMP reaction solution was introduced into reactor 3 through outlet 31. The input power of gas-phase reactor 1 was 5 W, and the reaction gas flow rate was 200 mL / min. The discharge gas flow rate was 500 mL / min, and nitrogen, reaction gas, and argon were used for the experiments. The AC discharge frequency of power supply 7 was 10 kHz, the discharge power was 15 W, and the discharge gap was 8 mm. Samples were taken at regular intervals. The degradation rate of DMP is shown in the figure. (Refer to...) Figure 6It can be seen that DMP is basically completely degraded in about 70 minutes. Among them, the degradation efficiency is the highest when both the reaction gas and the discharge gas are oxygen.

[0058] In summary, this invention utilizes a gas-phase reactor to generate a mixed gas that forms bubbles in the electrolyte solution within the reactor, while plasma is generated between the anode and cathode plates. The synergistic effect of the mixed gas and plasma degrades the potassium salt flotation reagent in the electrolyte solution. Furthermore, this invention improves the solute distribution within the electrolyte solution by ionizing the reactant gas and allowing it to enter the electrolyte solution in a bubbling manner.

[0059] The foregoing has described specific embodiments of the invention. Other embodiments are within the scope of the appended claims.

[0060] The terms “exemplary,” “example,” etc., used throughout this specification mean “serving as an example, instance, or illustration” and do not imply “preferred” or “advantageous” than other embodiments. Detailed descriptions are included for the purpose of providing an understanding of the described techniques. However, these techniques can be practiced without these detailed descriptions. In some instances, well-known structures and apparatuses are shown in block diagram form to avoid obscuring the concepts of the described embodiments.

[0061] The optional embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the embodiments of the present invention are not limited to the specific details in the above embodiments. Within the scope of the technical concept of the embodiments of the present invention, various simple modifications can be made to the technical solutions of the embodiments of the present invention, and these simple modifications all fall within the protection scope of the embodiments of the present invention.

[0062] The foregoing description of this specification is provided to enable any person skilled in the art to implement or use the content of this specification. Various modifications to the content of this specification will be apparent to those skilled in the art, and the general principles defined herein can be applied to other variations without departing from the scope of protection of this specification. Therefore, this specification is not limited to the examples and designs described herein, but is consistent with the widest scope of the principles and novel features disclosed herein.

Claims

1. An apparatus for degrading potassium salt flotation reagents, characterized in that, include: The reactor comprises a gas phase reactor (1), an anode (2), a reactor (3), and a cathode pressure plate (4). The gas phase reactor (1) includes an insulating plate (11) and conductive plates (12) and a grounding plate (13) respectively disposed on both sides of the insulating plate (11). One side of the insulating plate (11) is recessed to form a gas storage tank (111), and the other side of the insulating plate (11) is fixedly connected to the grounding plate (13). One side of the conductive plate (12) is connected to a power supply (7), and one side of the grounding plate (13) is grounded, thereby allowing gas storage tanks to be stored in the gas phase reactor (111). A second alternating electric field for ionizing the reaction gas is formed in the gas tank (111); the surface of the conductive plate (12) is provided with a gas guiding channel (121) connecting the reaction gas storage device (5) and the gas storage tank (111), and an exhaust channel (122) connecting the gas storage tank (111) and the reactor (3); one end of the anode (2) is connected to the discharge gas storage device (6), and the other end of the anode (2) extends into the reactor (3); the anode (2) is tubular, and the anode (2) One end of the anode (2) is connected to the discharge gas storage device (6), and the other end of the anode (2) is located above the surface of the electrolyte solution; the bottom of the reactor (3) is fixedly connected to the cathode plate (4); the surface of the cathode plate (4) is provided with bubbling holes (41), and the mixed gas generated by the ionization of the reaction gas by the gas phase reactor (1) forms bubbles through the bubbling holes (41) and enters the electrolyte solution; when the anode (2) is energized, a first alternating electric field for generating plasma is formed between the anode (2) and the cathode plate (4); when the reaction gas storage device (5) supplies the reaction gas to the gas phase reactor 1, the reaction gas is ionized in the second alternating electric field and forms a mixed gas composed of ozone, oxygen, high-energy electrons, and oxygen free radicals; wherein, the proportion of ozone in the mixed gas is greater than the proportion of oxygen, high-energy electrons, and oxygen free radicals; the mixed gas and the plasma work together to degrade the potassium salt flotation reagent in the electrolyte solution.

2. The apparatus for degrading potassium salt flotation reagents according to claim 1, characterized in that, The air guide channel and the exhaust channel are symmetrically distributed about the insulating plate (11).

3. The apparatus for degrading potassium salt flotation reagents according to claim 2, characterized in that, The gap between the anode (2) and the electrolyte solution is between 3 mm and 12 mm.

4. The apparatus for degrading potassium salt flotation reagents according to claim 2, characterized in that, The anode (2) is energized after bubbling occurs in the electrolyte solution.

5. The apparatus for degrading potassium salt flotation reagents according to claim 2, characterized in that, The surface of the reactor (3) is provided with an outlet (31) for discharging exhaust gas and a sampling port (32) for discharging electrolyte solution, with the outlet (31) located above the sampling port (32).

6. A method for degrading potassium salt flotation reagents, characterized in that, The apparatus for degrading potassium salt flotation reagents according to any one of claims 1 to 5 comprises: Prepare a mixed gas and continuously pass it into the reactor (3); Bubbling is created in an electrolyte solution; Plasma is prepared and introduced into the electrolyte solution; When the anode (2) is energized for a preset time, the anode (2) is de-energized and the electrolyte solution in the reactor (3) is discharged.

7. A method for degrading potassium salt flotation reagents according to claim 6, characterized in that, When preparing a mixed gas, the output flow rate of the gas phase reactor (1) is 50 mL / min ~ 300 mL / min; when preparing plasma, the gas output flow rate of the anode (2) is 100 mL / min ~ 800 mL / min.

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