CN104988528B - Method for producing electrolytic manganese dioxide by using nanocrystalline microsphere modified electrode - Google Patents
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Abstract
The invention discloses a method for producing electrolytic manganese dioxide by a nanocrystalline microsphere modified electrode, which comprises the following steps: (1) One or more manganese oxides and a dispersant are put into a nano bead mill for milling to prepare an additive mother solution with the particle size reaching the nano level; (2) Diluting the additive mother liquor to 5-10 g/l of additive solution by using water; (3) Adding the additive solution into a manganese sulfate electrolyte through a flow control system, and uniformly mixing to obtain a mixed solution containing 20-40 g/l of the nanocrystalline microsphere additive; (4) Adding the mixed solution into an electrolytic tank through a flow control system, adjusting electrolysis parameters, modifying a titanium anode, increasing the current intensity, and producing electrolytic manganese dioxide; adding the prepared manganese dioxide nanocrystalline microsphere additive with a certain particle size into the new electrolytic solution, enabling the additive to be uniformly and stably dispersed in a high-temperature and high-acid electrolyte environment, modifying the anode titanium plate under the action of an electric field, improving the apparent sectional area of the anode titanium plate, and reducing the apparent current density of the anode; thereby improving the yield of electrolytic manganese dioxide products.
Description
Technical Field
The invention relates to a method for producing electrolytic manganese dioxide, in particular to a method for producing electrolytic manganese dioxide by modifying an electrode with a nanocrystalline microsphere.
Background
With the continuous development of the battery industry, especially the popularization of electric bicycles and power automobiles, manganese dioxide special for novel battery anode materials such as zinc-manganese batteries, alkaline batteries, lithium manganate batteries and the like is rapidly developed. It is expected that with the gradual promotion of the market, lead-acid batteries will gradually quit, electrolytic manganese dioxide for novel batteries will be rapidly developed, the development of the whole electrolytic manganese dioxide product market is driven, and the demand of electrolytic manganese dioxide products will increase year by year.
However, to increase the production, it is common practice to (1) invest a large amount of capital to increase the production line, and a 1-million-ton production line per year needs to invest about 1.6 billion dollars of capital, which is large in investment; (2) the current production line adopts a method for improving the intensity of the electrolytic current to improve the unit yield without increasing the production line, but the current technical level is limited, the electrolytic electrifying current is improved, the electrolytic anode titanium plate is required to be passivated quickly, the direct current power consumption is increased, and even the anode titanium plate is scrapped, and the electrolysis cannot be carried out. The invention creatively develops the technology for producing the electrolytic manganese dioxide by modifying the electrode with the nanocrystalline microspheres, well solves the defects of the two methods, does not need to increase the production line, improves the yield of the electrolytic manganese dioxide product with minimum investment, realizes the aim of increasing the yield, and has controllable indexes such as various costs, quality and the like.
The electrolytic manganese dioxide or natural manganese dioxide is finely ground into a suspending agent to be used as an electrolytic additive in Japan JMC company and domestic enterprises, the effect of the electrolytic manganese dioxide is not ideal in practice, the main reason is that manganese dioxide particles can only reach micron level and are often mutually aggregated to reach a stable state to form an agglomeration phenomenon, or the manganese dioxide particles are easily precipitated due to self weight so as to be unevenly distributed in a solution system, the effect cannot be achieved, the current efficiency is low, the power consumption is large, and the product quality is unstable.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for producing electrolytic manganese dioxide by modifying an electrode with nanocrystalline microspheres, so that a titanium anode can normally run under higher current without passivation, the current efficiency is not reduced, and the yield of electrolytic manganese dioxide products is improved.
The technical scheme adopted by the invention for solving the technical problems is to provide a method for producing electrolytic manganese dioxide by modifying an electrode with nanocrystalline microspheres, which comprises the following steps: (1) One or more manganese oxides and a dispersant are put into a nano bead mill for milling to prepare an additive mother solution with the particle size reaching the nano level; (2) Diluting the additive mother liquor to 5-10 g/l of additive solution by using water; (3) Adding the additive solution into a manganese sulfate electrolyte through a flow control system, and uniformly mixing to obtain a mixed solution containing 20-40 g/l of the nanocrystalline microsphere additive; (4) And adding the mixed solution into an electrolytic tank through a flow control system, setting electrolysis parameters, and electrolyzing to obtain electrolytic manganese dioxide.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the following steps of (1): (11) Putting one or more manganese oxides, industrial water and a dispersant in a predetermined weight percentage into a stirring barrel, and stirring for 30-60 minutes to form a uniform slurry dispersoid; (12) Conveying the slurry dispersion to a bead mill for milling through a first pump; (13) The slurry dispersion milled by the bead mill is conveyed to enter the bead mill again through a pipeline and the first pump for circular milling; (14) Repeating the step (13) until the particle size of the slurry dispersoid reaches a preset range, and stopping milling; the slurry dispersoid reaching the preset grain diameter is nanocrystalline microsphere additive mother liquor.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the step (11), wherein the weight percentage content of the slurry dispersoid prepared in the step (11) is 10-30%, and the concentration of the dispersant is 0.1-1.0mg/l.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the following steps of (1) grinding media of a bead mill, wherein the grain size of corundum beads or zirconium beads is 0.5-2.0 mm, and the duty ratio is 60-80%; the electrolytic bath is MnSO 4 -H 2 SO 4 A system; the anode of the electrolytic cell is a pure titanium plate, and the cathode of the electrolytic cell is a copper plate or copper tube manganese; the electrolysis parameters comprise: the bath acid is 36g-40g/l, the bath pressure is 1.8v-3.0v, and the bath temperature is 99-101 ℃.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the following steps of (13): and pumping the ground slurry dispersion of the bead mill back to the stirring tank through a second pump, and then entering the bead mill through the first pump for circular grinding.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the following steps of (13): separating by a centrifugal separation disc in the grinding cylinder, leaving grinding beads in the grinding cylinder for continuous grinding, sending the slurry to a five-stage centrifugal separator for step-by-step separation of light liquid and heavy liquid due to centrifugal throwing force, wherein the light liquid is slurry with a small particle size, the heavy liquid is slurry with a large particle size, the light liquid of each stage of separation flows to the next stage of centrifugal separator, the heavy liquid returns to the bead grinding machine through the first pump for circular grinding, and the light liquid separated by the last stage of centrifugal separator is the mother liquid of the nanocrystalline microsphere additive.
In the method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode, in the step (13), in the circulating milling process, the preset reflux ratio of the whole bead milling system is kept by controlling the opening degrees of a bottom valve of the stirring barrel, a feeding valve and a discharging valve of the bead mill and a cooling water valve of a first pump.
In the method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode, in the step (13), in the process of continuously grinding for 16-20 hours, sampling every 4 hours to test the particle size of the nanocrystalline microsphere additive, so that the particle size of the nanocrystalline microsphere additive is 50-150 nanometers and reaches more than 50%.
In the method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode, the flow rate of the slurry and the rotating speed of the bead mill are controlled by a central controller, so that the fineness of the grinding material is ensured; the central controller ensures the separation of grinding beads and slurry by controlling the flow rate of materials and the rotating speed of a centrifugal separation disc of the bead mill; the central controller ensures the separation of light liquid and heavy liquid of each stage by controlling the flow rate of materials and the rotating speed of the centrifugal separator, and finally ensures that the fineness of discharged slurry is qualified; by adjusting the feeding amount and the discharging amount of each material in the system, the material balance of the system is ensured, and the whole system can normally run.
The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode comprises the following steps that the bead mill comprises a milling barrel, a main shaft is arranged in the milling barrel, and a centrifugal separation disc and a stirring impeller are arranged on the main shaft; the number of the stirring impellers is 10-15, the stirring impellers and the centrifugal separation discs are sequentially sleeved on the main shaft, the centrifugal separation discs are located at the tail part of the main shaft, the stirring impellers are sequentially fixed on the main shaft at equal intervals, the connection inclination angle of the stirring impellers and the main shaft is 1-15 degrees, and a discharge cavity connected with an outlet of the bead mill is formed between the outer side of each centrifugal separation disc and the inner side of the milling cylinder; the main shaft is provided with a through open slot along the axial direction, round holes with different apertures are formed in the stirring impeller along the circumferential direction, the apertures of the round holes are sequentially reduced from inside to outside along the radial direction, and the diameter of the centrifugal separation disc is larger than that of the main shaft and smaller than that of the stirring impeller.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a method for producing electrolytic manganese dioxide by a nanocrystalline microsphere modified electrode, which is characterized in that a prepared manganese dioxide nanocrystalline microsphere additive with a certain particle size is added into an electrolytic new liquid, so that the manganese dioxide nanocrystalline microsphere additive can be uniformly and stably dispersed in a high-temperature and high-acid electrolyte environment, an anode titanium plate is modified under the action of an electric field, the apparent sectional area of the anode titanium plate is increased, and the apparent current density of an anode is reduced. Therefore, when the electrolytic current is increased, the current density calculated according to the area of the titanium plate is improved, but the actual apparent current density is not improved due to the function of the nanocrystalline microsphere additive, the current efficiency is not less than 98 percent, and the apparent surface area of the titanium anode plate can be effectively improved in the electrolytic process. The production line is not required to be increased, the yield of the electrolytic manganese dioxide product is improved with less investment, the yield increase aim is realized, and various indexes such as cost, quality and the like are controllable.
Drawings
FIG. 1 (a) is an electrolytic schematic diagram of the production of electrolytic manganese dioxide by a nanocrystalline microsphere-modified electrode according to the present invention; FIG. 1 (b) is an enlarged partial schematic view at A in FIG. 1 (a); FIG. 1 (c) shows MnO in the electrolysis process 2 Schematic diagram of the surface state of the deposition layer;
FIG. 2 is a schematic diagram of a nano-bead milling system according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a nano-bead milling system according to another embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a bead mill in an embodiment of the present invention.
In the figure:
1. first pump of stirring tank 51 of central controller 4 of centrifugal separator 3 of bead mill 2
52. Second pump 6 slurry 7 water and dispersant 8 qualified slurry 9 pipeline
21. First stage centrifugal separator 22, second stage centrifugal separator 23, and third stage centrifugal separator
24. Four-stage centrifugal separator 25 five-stage centrifugal separator
41. Mixer
10. Belt pulley with 14 centrifugal separation discs 13 and stirring impellers of main shaft 12 of grinding cylinder 11
15. Bearing housing 16 seal 17 bead mill inlet 18 bead mill outlet
31. Electrolytic bath 32 cathode 33 anode 34 nanocrystalline microsphere
35. Nanocrystalline microsphere adsorption layer 36 MnO 2 Deposit layer
Detailed Description
The invention is further described below with reference to the figures and examples.
The invention provides a method for producing electrolytic manganese dioxide by modifying an electrode with nanocrystalline microspheres, which comprises the following steps:
step S1, one or more manganese oxides and a dispersing agent are put into a nano bead mill for milling to prepare an additive mother solution with the particle size reaching the nano level; the specific process is as follows: (11) One or more manganese oxides, industrial water and a dispersant in a predetermined weight percentage are put into a stirring barrel to be stirred for 30 to 60 minutes to form a uniform slurry dispersoid; the weight percentage content of the prepared slurry dispersoid is 10-30 percent, and the concentration of the dispersant is 0.1-1.0mg/l; the slurry is too thin, the bead milling efficiency is low, even the required fineness can not be achieved, the slurry is too thick, the material particles are not easy to disperse in equipment load and can not easily achieve the required fineness, and therefore, the proper slurry concentration is 20-30% of the solid content; the principle of the dispersant selection is to achieve the dispersion effect, to be stable in the electrolytic bath environment, and not to bring impurities into the product. The proportion of dispersant is determined in the minimum amount necessary to enable the additive to be effectively dispersed in the electrolytic solution system. (12) Conveying the slurry dispersion to a bead mill through a first pump for milling, wherein milling media of the bead mill are corundum beads or zirconium beads, the particle size of the corundum beads or the zirconium beads is 0.5-2.0 mm, and the duty ratio is 75-85%; preferably, the particle size is selected from 1.0mm-1.2mm to 40% (volume ratio), 1.8mm-2.0mm to 30% (volume ratio), 2.5mm-3.0mm to 30% (volume ratio); the proportion of the grinding balls in the effective volume of the grinding machine is called duty ratio, and the duty ratio is 60-80%; (13) The slurry dispersion milled by the bead mill is conveyed to enter the bead mill again through a pipeline and the first pump for circular milling; the slurry flows from the proportioning barrel through a circulating pump, one part of the slurry enters the bead mill, the other part of the slurry circulates back to the proportioning barrel, and the flow ratio of the two parts is called the circulation ratio. A recycle ratio of 1:4 is suitable; (14) Repeating the step (13) until the particle size of the slurry dispersoid reaches a preset range, and stopping milling; the slurry dispersoid reaching the preset grain diameter is nanocrystalline microsphere additive mother liquor.
And S2, putting the additive mother liquor into an additive preparation barrel, and diluting the additive mother liquor to 5-10 g/l of additive solution by using water.
And S3, in order to ensure that the concentration of the additive in the mixed solution is controlled in a required range, the feeding flow of the additive is integrally controlled and monitored according to the new liquid flow and the concentration of the additive. And adding the additive solution into a manganese sulfate electrolyte through a flow control system, and uniformly mixing to obtain a mixed solution containing 20-40 g/l of the nanocrystalline microsphere additive. Solutions with different additive contents need different stirring strengths to ensure that the nanocrystalline microsphere additive is uniformly dispersed and has uniform concentration.
S4, adding the mixed solution into an electrolytic tank through a flow control system, adjusting electrolysis parameters, modifying a titanium anode, increasing the current intensity, and producing to obtain a crude product of electrolytic manganese dioxide; and rinsing, grinding and mixing the electrolytic manganese dioxide crude product to obtain the electrolytic manganese dioxide finished product. Referring to FIG. 1 (a), the electrolytic bath 31 is MnSO 4 -H 2 SO 4 A system; the anode 33 of the electrolytic cell is a pure titanium plate, and the cathode 32 of the electrolytic cell is a copper plate or copper tube manganese. The process control of the electrolytic bath surface is as follows: the temperature of the tank is controlled to be 100 +/-1 ℃ by measures of linearly adding a foaming agent, automatically alarming at low temperature, automatically discharging steam condensate water and the like; the shaping and repairing of the titanium anode plate and the repairing of the copper cathode are enhanced through the enhanced groove discharging operation, and the groove pressure is controlled by adjusting the groove discharging period, wherein the preferable range of the groove pressure is 1.8-3.0 v; the bath acid is 36g-40g/l and is controlled within the fluctuation range of +/-2 g/l; the concentration of the electrolyte (bath solution) additive is controlled within the fluctuation range of +/-2 mg/l. Referring to FIG. 1 (b), the initial state of electrolysis is shown in which the nanocrystals are microcrystallineThe balls 34 are adsorbed on the titanium plate 33 to form a nanocrystalline microsphere adsorption layer 35, as shown in FIG. 1 (c), and MnO is sequentially formed on the titanium plate (anode 33) 2 Depositing a layer 36 and a nanocrystalline microsphere adsorption layer 35, mnO after the electrolysis is finished 2 The deposition layer is the crude product of the electrolytic manganese dioxide.
In the actual production process, the dispersion uniformity degree (mainly controlled by grinding the particle size and adding a dispersing agent) and the concentration of the nanocrystalline microspheres have great influence on the electrolysis process.
TABLE 1 Current efficiency of electrolytic systems of different crystallite microsphere fineness
From the above example data, it can be seen that it is good for the optimum fineness of the microspheres to be below 0.5 microns, and the current efficiency at high current intensity has reached 98% of the normal level.
Table 2 current efficiency of electrolysis system with different concentrations of crystalline microsphere additive
From the above example data, it can be seen that it is good that the concentration of the microsphere additive reaches more than 20mg/l, the current efficiency reaches 98% of the normal level under high current intensity, and the current efficiency is not obviously improved after the concentration exceeds 40 mg/l.
The structure of the nano bead mill system adopted in the preparation process of the nanocrystalline microsphere additive is different, and various different embodiments are provided, which are specifically referred to as the following embodiments:
example 1
FIG. 2 is a schematic diagram of a nano-bead milling system according to an embodiment of the present invention; FIG. 4 is a schematic structural diagram of a bead mill in an embodiment of the present invention.
Referring to fig. 2 and 4, the nano-bead mill system adopted in the present embodiment is composed of a nano-bead mill 1, a high-speed centrifugal separator 2, a central controller 3, a pipeline 9, a first pump 51 and a stirring tank 4.
The nano bead mill 1 adopts a screen-free design and comprises a milling cylinder 10, wherein a main shaft 11, a centrifugal separation disc 12 and 10-15 stirring impellers 13 which are connected with the main shaft 11 in a certain inclination way and are provided with circular holes with different apertures are arranged in the milling cylinder 10; the centrifugal separation disc 12 is sleeved on the main shaft 11 at the tail part in the milling cylinder 10, and replaces a screen mesh of the existing bead mill to play a role in separating milling media and milling materials. Between the outside of the centrifugal separation discs 12 and the inside of the grinding drum 10, a discharge chamber is formed which is connected to the outlet 18, into which centrifugal separation discs 12 the mixture of grinding pulp and grinding medium is fed in a high-speed circular motion as a result of the external pumping force. Due to the difference in density, the grinding media pass through the centrifugal separation discs 12 and return to the vortex of the grinding cylinder 10 through the open grooves on the main shaft 11 to continue to be ground with the new material entering the grinding cylinder 10; the grinding material paddle is also separated by centrifugal force and is discharged out of the bead mill 1 through another open slot on the main shaft 11, and enters the gradient centrifugal separator 2 for light-heavy liquid separation.
The number of the centrifugal separators 2 is plural, preferably 5 in the present embodiment, and five stages (21, 22, 23, 24, 25) are arranged in a gradient manner. The centrifugal separators 2 are connected in sequence, the inlet of the first-stage centrifugal separator 21 is connected with the outlet of the bead mill 1, the heavy liquid outlets of the first-stage centrifugal separator 21, the second-stage centrifugal separator 22, the third-stage centrifugal separator 23, the fourth-stage centrifugal separator 24 and the fifth-stage centrifugal separator 25 are connected with the inlet of a first pump 51, and heavy liquid returns to the bead mill 1 through a first pump 5 for circular milling; the light liquid outlets of the first-stage centrifugal separator 21, the second-stage centrifugal separator 22, the third-stage centrifugal separator 23 and the fourth-stage centrifugal separator 24 are respectively connected with the inlet of the next-stage centrifugal separator; the light liquid separated by each stage of the high-speed centrifugal separator 2 flows to the next stage, and the light liquid outlet of the last stage, namely the five-stage centrifugal separator 25, is qualified slurry.
The stirring tank 4 is used for containing slurry, and an outlet of a valve at the bottom of the stirring tank 4 is connected with an inlet of the first pump 5; the outlet of the first pump 5 is connected with the bead mill 1; forming a circulating milling system.
The central controller 3 is connected with valves, motors and the like of each process control point, and is used for linkage and intelligent control of slurry flow rate, mill rotation speed and the like. Specifically, the central controller 3 is connected to an outlet valve (not shown) of the agitation tank 1, for controlling the flow rate of the slurry. The central controller 3 is connected with a motor of the bead mill 1 and is used for controlling the rotating speed of the bead mill; the central controller 3 is connected with the centrifugal separator 2 and is used for controlling the rotating speed of the centrifugal separator 2; the central controller 3 is connected with the stirring tank 1, the first pump 5 and the inlet and outlet valves of the bead mill 1 and is used for controlling the inlet and outlet amount of materials.
The nano bead milling system can be used for preparing an electrolytic additive, namely a nanocrystalline microsphere additive, the grain diameter of the nanocrystalline microsphere can reach 50-150 nm, the grain diameter distribution range is narrow, the nanocrystalline microsphere additive is uniformly dispersed in electrolyte, and the technical requirement of producing titanium anode modification by electrolytic manganese dioxide is met. The method comprises the following specific steps:
the method comprises the steps of preparing slurry 6 with a preset concentration by using a material to be ground and water, adding the slurry 6, the water and a dispersing agent 7 into a stirring tank 4 according to a preset proportion, uniformly stirring and dispersing, conveying the slurry into a bead mill 1 by using a first pump 51 for milling, separating the slurry by using a high-speed centrifugal separation disc 12 in a milling cavity 10, keeping milling beads in the milling cavity 10 for further milling, conveying the slurry to a five-stage high-speed centrifugal separator 2 for separating light liquid (slurry with a small particle size) and heavy liquid (slurry with a large particle size) step by step due to centrifugal throwing force, allowing the light liquid separated in each stage to flow to the next stage, returning the heavy liquid to the bead mill 1 by the pump for circular milling, and obtaining qualified liquid as the light liquid separated in the fifth stage. The central controller 3 is connected with valves, motors and the like of all process control points, and is used for linkage and intelligent control of slurry flow rate, mill rotation speed and the like. The fineness of the grinding material is ensured by controlling the flow rate of the material and the rotating speed of the bead mill; the separation of grinding beads and slurry is ensured by controlling the flow rate of the materials and the rotating speed of the centrifugal separation disc; by controlling the flow rate of the materials and the rotating speed of the centrifugal separator, the separation of light liquid and heavy liquid at each stage is ensured, and finally the fineness of the discharged slurry is ensured to be qualified; by adjusting the feeding amount and the discharging amount of each material in the system, the material balance of the system is ensured, and the whole system is enabled to normally operate.
Example 2
FIG. 3 is a schematic diagram of a nano-bead milling system according to another embodiment of the present invention; FIG. 4 is a schematic structural diagram of a nano bead mill in an embodiment of the present invention.
Referring to fig. 3 and 4, the nano-bead mill system provided by the present invention comprises a stirring tank 4, a bead mill 1, a first pump 51 and a second pump 52, wherein an outlet of the stirring tank 4 is connected with an inlet of the first pump 51 through a pipeline 9, an outlet of the first pump 51 is connected with an inlet 17 of the bead mill 1 through a pipeline 9, an outlet 18 of the bead mill 1 is connected with an inlet of the second pump 52 through a pipeline 9, and an outlet of the second pump 52 is connected with an inlet of the stirring tank 4 through a pipeline 9.
The nano bead mill 1 is designed without a screen, and in the embodiment, preferably comprises a milling drum 10, wherein a main shaft 11, a centrifugal separation disc 12 and 10-15 stirring impellers 13 which are connected with the main shaft 11 in a certain inclination manner and are provided with circular holes with different apertures are arranged in the milling drum 10; the centrifugal separation disc 12 is sleeved on the tail part of the main shaft 11 in the milling cylinder 10, and replaces a screen mesh of the existing bead mill to play a role in separating milling media and milling materials. Between the outside of the centrifugal separation discs 12 and the inside of the grinding drum 10, a discharge chamber is formed which is connected to the outlet 18, into which centrifugal separation discs 12 the mixture of grinding pulp and grinding medium is fed in a high-speed circular motion as a result of the external pumping force. Due to the difference in density, the grinding media pass through the centrifugal separation discs 12 and return to the vortex of the grinding cylinder 10 through the open grooves on the main shaft 11 to continue grinding with new materials entering the grinding cylinder 10; the grinding material paddle is also separated by centrifugal force and is discharged out of the bead mill 1 through another open slot on the main shaft 11, and is pumped into the stirring tank 4 through the second pump 52 and then enters the bead mill 1 for circular grinding separation.
The power of the motor of the bead mill 1 provided by the embodiment is 55KW, and the power of the first pump 51 and the second pump 52 is 4KW. The agitation tank 4 and the piping 9 are made of stainless steel.
The nano bead milling system is used for preparing an electrolytic additive, namely a nanocrystalline microsphere additive, the grain diameter of the nanocrystalline microsphere can reach 50-150 nm, the grain diameter distribution range is narrow, the nanocrystalline microsphere additive is uniformly dispersed in an electrolyte, and the technical requirement of producing titanium anode modification by electrolytic manganese dioxide is met. The method comprises the following specific steps:
400kg of bagged manganese dioxide secondary product, 2000L of clean water, a stirring tank, a pump, a bead mill and a stainless steel pipeline are used for realizing the method.
And (3) manually putting the 400kg bagged manganese dioxide secondary product into a stirring tank 1 filled with 2000L of clear water at one time, simultaneously opening a stirrer 41, and stirring for 30-60 minutes after the materials are put. Opening first pump 21, second pump 22, the cooling water valve of pearl mill 3 in proper order, closing first pump 22 and pearl mill 3's floodgate again, opening the bottom valve switch of stirred tank 1 after the check out test set operation is normal, let nanocrystalline microballon additive coarse grade article beat into pearl mill 3 through first pump 21 and carry out the pearl mill, the nanocrystalline microballon additive that passes through pearl mill 3 is beaten back stirred tank 1, the cyclic milling of rethread pearl mill. In the process, the temperature of cooling water of the bead mill 3 and the pressure in the bead mill 3 are required to be checked, the water temperature and the pressure cannot exceed the specified range of the bead mill 3, so that equipment is prevented from being damaged, whether the whole volume is increased or decreased is also required to be checked in the grinding process, and the situation that liquid inlet and liquid leakage cause inaccurate volume and influence the used proportioning dosage is prevented.
Continuously grinding for 16-20 hours by a bead grinding machine, sampling every 4 hours, and testing the grain diameter of the nanocrystalline microsphere additive, wherein the grain diameter of the nanocrystalline microsphere additive is required to be more than 50% when the grain diameter of 50-500 nanometers reaches.
The qualified nanocrystalline microsphere additive must be stirred by a stirrer immediately before being put into a workshop, so that the coarse material is prevented from precipitating and blocking a pipeline.
The nanocrystalline microsphere additive prepared in the embodiment is applied to the electrolysis process of a manganese dioxide production line, the nanocrystalline microsphere additive with a certain particle size range and a certain concentration is added into a manganese sulfate solution, a titanium anode plate is modified under a certain condition, the apparent surface area of the titanium anode plate is increased, the current efficiency is improved, the product quality is improved, the yield can be improved by 50%, and the unit consumption of product production is not increased. The method has the advantages of realizing less investment and more output, really realizing yield increase and consumption reduction and improving economic benefits.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A method for producing electrolytic manganese dioxide by modifying an electrode with nanocrystalline microspheres is characterized by comprising the following steps:
(1) One or more manganese oxides and a dispersing agent are put into a nano bead mill for milling to prepare an additive mother solution with the particle size reaching the nano level;
(2) Diluting the additive mother liquor to 5g/L-10g/L of additive solution by using water;
(3) Adding the additive solution into a manganese sulfate electrolyte through a flow control system, and uniformly mixing to obtain a mixed solution containing the nanocrystalline microsphere additive and the manganese sulfate concentration of 20-40 g/L;
(4) Adding the mixed solution into an electrolytic tank through a flow control system, setting electrolysis parameters, and electrolyzing to obtain electrolytic manganese dioxide;
the step (1) comprises the following steps:
(11) One or more manganese oxides, industrial water and a dispersant in a predetermined weight percentage are put into a stirring barrel to be stirred for 30 to 60 minutes to form a uniform slurry dispersoid;
(12) Conveying the slurry dispersion to a bead mill for milling through a first pump;
(13) The slurry dispersion milled by the bead mill is conveyed to enter the bead mill again through a pipeline and the first pump for circular milling;
(14) Repeating the step (13) until the particle size of the slurry dispersoid reaches a preset range, and stopping milling; the slurry dispersoid reaching the preset particle size is a nanocrystalline microsphere additive mother solution;
the bead mill comprises a milling barrel, a main shaft is arranged in the milling barrel, and a centrifugal separation disc and a stirring impeller are mounted on the main shaft; the number of the stirring impellers is 10-15, the stirring impellers and the centrifugal separation discs are sequentially sleeved on the main shaft, the centrifugal separation discs are located at the tail part of the main shaft, the stirring impellers are sequentially fixed on the main shaft at equal intervals, the connection inclination angle of the stirring impellers and the main shaft is 1-15 degrees, and a discharge cavity connected with an outlet of the bead mill is formed between the outer side of each centrifugal separation disc and the inner side of the milling cylinder; the main shaft is provided with a through open slot along the axial direction, round holes with different apertures are formed in the stirring impeller along the circumferential direction, the apertures of the round holes are sequentially reduced from inside to outside along the radial direction, and the diameter of the centrifugal separation disc is larger than that of the main shaft and smaller than that of the stirring impeller;
the step (13) comprises the following steps: separating by a centrifugal separation disc in the grinding cylinder, leaving grinding beads in the grinding cylinder for continuous grinding, sending the slurry to a five-stage centrifugal separator for step-by-step separation of light liquid and heavy liquid due to centrifugal throwing force, wherein the light liquid is slurry with a small particle size, the heavy liquid is slurry with a large particle size, the light liquid of each stage of separation flows to the next stage of centrifugal separator, the heavy liquid returns to the bead grinding machine through the first pump for circular grinding, and the light liquid separated by the last stage of centrifugal separator is the mother liquid of the nanocrystalline microsphere additive.
2. The method for producing electrolytic manganese dioxide by using the electrode modified by the nano-crystalline microspheres of claim 1, wherein the slurry dispersion prepared in the step (11) has a weight percentage content of 10-30% and a dispersant concentration of 0.1-1.0mg/L.
3. The method for producing electrolytic manganese dioxide by using the electrode modified by the nano-crystalline microspheres of claim 1, wherein the grinding medium of the bead mill is corundum beads or zirconiumThe particle size of the corundum beads or the zirconium beads is 0.5mm-2.0mm, and the duty ratio is 60% -80%; the electrolytic bath is MnSO 4 -H 2 SO 4 A system; the anode of the electrolytic cell is a pure titanium plate, and the cathode of the electrolytic cell is a copper plate or copper tube manganese; the electrolysis parameters comprise: the bath acid is 36g-40g/L, the bath pressure is 1.8v-3.0v, and the bath temperature is 99-101 ℃.
4. The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode according to claim 1, wherein the step (13) is as follows: and the slurry dispersion ground by the bead mill is pumped back to the stirring tank through a second pump and then enters the bead mill through the first pump for circular grinding.
5. The method for producing electrolytic manganese dioxide by using the electrode modified by the nano-crystalline microspheres of claim 4, wherein the circulating milling process in the step (13) is implemented by controlling the opening degrees of a bottom valve of the stirring barrel, an inlet valve and an outlet valve of the bead mill and a cooling water valve of the first pump, so that the whole bead milling system is kept at a preset reflux ratio.
6. The method for producing electrolytic manganese dioxide by using the electrode modified by the nano-crystalline microspheres of claim 4, wherein during the continuous milling for 16-20 hours in the step (13), the nano-crystalline microsphere additive is sampled every 4 hours and assayed to have a particle size of 50-150 nm of 50% or more.
7. The method for producing electrolytic manganese dioxide by using the nanocrystalline microsphere modified electrode as claimed in claim 5, wherein the flow rate of the slurry and the rotating speed of the bead mill are controlled by a central controller to ensure the fineness of the grinding material; the central controller ensures the separation of grinding beads and slurry by controlling the flow rate of materials and the rotating speed of a centrifugal separation disc of the bead mill; the central controller ensures the separation of light liquid and heavy liquid of each stage by controlling the flow rate of materials and the rotating speed of the centrifugal separator, and finally ensures the fineness of discharged slurry to be qualified; by adjusting the feeding amount and the discharging amount of each material in the system, the material balance of the system is ensured, and the whole system can normally run.
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