KR102317637B1 - APPARATUS FOR MANUFACTURING manganese OXIDE OF A HIGH degree of purity - Google Patents

Abstract

A high-purity manganese oxide manufacturing apparatus is provided. According to the present invention, a reactor in which a raw material solution for manufacturing manganese oxide is stored, a plurality of pipes connected to the reactor to divide and flow the raw material solution in the reactor in small portions, and a plurality of pipes are respectively connected to the pipe, the pipe It includes a precipitant input pipe into which a precipitant is introduced for producing high-purity manganese oxide with few impurities by meeting with the raw material solution flowing down through the furnace and causing a precipitation reaction to occur.

Description

Apparatus for manufacturing high-purity manganese oxide

The present invention relates to an apparatus for producing high-purity manganese oxide, and more particularly, by improving the structure of the precipitation reactor in the precipitation process to obtain manganese oxide, thereby facilitating the precipitation reaction, thereby reducing the precipitation process time and lowering the impurity co-precipitation to facilitate high-purity manganese It relates to a high-purity manganese oxide production apparatus for producing an oxide.

Recently, with the spread of electronic devices, portable computers, mobile phones, etc., the demand for secondary batteries is increasing, and the demand for materials required for manufacturing such secondary batteries is also increasing rapidly with the rapid increase in demand for secondary batteries.

As an example of such a secondary battery, a lithium ion secondary battery is divided into a cathode material, an anode material, and an electrolyte. LCO (LiCoO ₂ ) was widely used as the cathode material, but cobalt (Co) among the raw materials of the cathode material is expensive. Low-cost raw materials became necessary.

_{Recently, a cathode material called LMO (LiMn 2} O ₄ ) without cobalt (Co) has been developed as a raw material for cathode materials. In order to manufacture such an LMO (LiMn ₂ O ₄ ), a manganese compound in the form of an oxide is required, _{and MnO 2} and Mn ₃ O ₄ are mainly employed as the manganese compound.

In order to manufacture a low-cost cathode material, the use of low-cost raw materials is absolutely necessary, and dust (dust) is generated during the manufacture of ferromanganese ferroalloy. It is mainly composed of manganese oxide and is in the form of manganese oxide containing various impurities.

The final product, manganese oxide, is obtained by precipitation in the form of hydroxide or oxide through a precipitation reaction. As disclosed in Korean Patent Application Laid-Open No. 10-2013-0122244, the pH of the manganese leachate is preferably 7 to 9. When the pH of the manganese leachate is lower than the pH of the substrate, the recovery rate of manganese decreases and If the pH is higher than that, impurities are also precipitated to lower the purity of the final product.

1 is a schematic configuration diagram of a reactor used in a precipitation process for manufacturing manganese oxide according to the prior art.

Referring to FIG 1, because it becomes a precipitate by stirring the precipitating agent injection pipe (5) while the precipitation agent was flown in small portions via a stirrer (7) made in the MnSO ₄ solution (3) stored in the reactor (1) a precipitating agent, and The _{space where the MnSO 4} solution (3) meets is inevitably narrowed, and the fished sediments are accumulated on the bottom and mixed with the unreacted solutions by the stirrer (7) so that the pH rises from the appropriate value, and the amount of precipitation The process takes a lot of time, and at this time, there were many cases where the viciousness in which other impurities were precipitated together continued.

Accordingly, an object of the present invention is to improve the precipitation process to provide an apparatus capable of reducing the precipitation process time and reducing the impurity co-precipitation.

The present invention is to improve the structure of the precipitation reactor in the precipitation process to obtain manganese oxide to facilitate the precipitation reaction, thereby reducing the precipitation process time and lowering the impurity co-precipitation to provide a high-purity manganese oxide manufacturing apparatus for easily manufacturing high-purity manganese oxide. .

According to an embodiment of the present invention, a reactor in which a raw material solution for manufacturing manganese oxide is input and stored;

A plurality of pipes connected to the reactor to divide and flow the raw material solution in the reactor in small portions, and

A high-purity manganese oxide manufacturing apparatus is provided, which includes a precipitant input pipe connected to a plurality of pipes, respectively, and into which a precipitant input pipe for producing high-purity manganese oxide with less impurities by meeting with a raw material solution flowing down through the pipe and causing a precipitation reaction can be

It is provided in the lower part of the reactor, and may include a filter for filtering the precipitate by separating the precipitate and unreacted solution generated by the precipitation reaction of the raw material solution flowing down in the pipe and the precipitating agent.

It is provided under the filter, and may include a storage tank for storing some unreacted solutions flowing down through the filter during the precipitation reaction of the raw material solution flowing down in the pipe and the precipitating agent.

It may include a reintroduction pipe for connecting the storage tank and the reactor, and for reintroducing the unreacted solution stored in the storage tank back into the reactor.

The raw material solution may be a manganese sulfate (MnSO ₄ ) solution as a raw material for manufacturing manganese oxide.

The pipe may be respectively installed at regular intervals or at arbitrary intervals at the lower end of the reactor so that the raw material solution in the reactor can be easily divided into small portions and flowed down.

A control valve for controlling the discharge of the raw material solution through the pipe may be installed in the pipe.

The precipitant input pipe may be respectively connected to the side surfaces of a plurality of pipes to facilitate a precipitation reaction with the precipitant input into the pipe and the raw material solution flowing down through the pipe.

The reintroduction pipe may connect the lower end of the storage tank and the upper portion of the reactor so that the unreacted solution stored in the storage tank can be easily reintroduced into the reactor.

A pump for pumping the unreacted solution stored in the storage tank into the reactor may be installed in the reintroduction pipe.

According to an embodiment of the present invention, when manufacturing manganese oxide, a small amount of precipitating agents _{met MnSO 4} and a precipitation reaction occurred in the reactor _{through mixing, but as in the present invention, MnSO 4} solutions are divided into small portions and meet with the precipitant As the reaction surface area increases, the reaction rate is increased, and since the precipitate is generated as it flows along the pipe without being accumulated inside the reactor, it does not meet the unreacted solution, thereby preventing the pH increase and suppressing the phenomenon of impurities being precipitated together.

1 is a schematic configuration diagram of a reactor used in a precipitation process for manufacturing manganese oxide according to the prior art.
2 is a schematic configuration diagram of a high-purity manganese oxide manufacturing apparatus according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention. As will be readily understood by those of ordinary skill in the art to which the present invention pertains, the embodiments described below may be modified in various forms without departing from the concept and scope of the present invention. Wherever possible, identical or similar parts are denoted by the same reference numerals in the drawings.

The terminology used below is for the purpose of referring only to specific embodiments and is not intended to limit the invention. As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite. As used herein, the meaning of “comprising” specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

All terms including technical terms and scientific terms used below have the same meaning as those commonly understood by those of ordinary skill in the art to which the present invention belongs. Terms defined in the dictionary are further interpreted as having a meaning consistent with the related art literature and the presently disclosed content, and unless defined, are not interpreted in an ideal or very formal meaning.

[Solution principle of the present invention]

In the present invention, after dissolving manganese dust in acid, various impurities removing agents are added to the solution to prepare a solution composed of manganese and acid. This process is called a purification process. Solution made in this purification process is the MnSO ₄ form incorporating a precipitating agent here Mn (OH) ₂ or Mn ₃ O ₄ there is obtained in the form of a precipitate MnSO ₄ solution and the precipitating agent is expanded to precipitate the meeting space hydroxide or This is to reduce the concentration of impurities by preventing the oxide from easily separating from the solution and raising the pH.

2 is a schematic configuration diagram of a high-purity manganese oxide manufacturing apparatus according to an embodiment of the present invention.

2, the high-purity manganese oxide manufacturing apparatus according to an embodiment of the present invention includes a reactor 100 in which a raw material solution 110 for manufacturing manganese oxide is input and stored;

A plurality of pipes 200 connected to the reactor 100 to put the raw material solution 110 into the reactor, and divide the raw material solution in the reactor 100 in small portions to flow down, and

A precipitant input pipe 300 connected to each of a plurality of pipes 200 and into which a precipitant for producing high-purity manganese oxide with little impurities is introduced by meeting with the raw material solution flowing down through the pipe 200 to cause a precipitation reaction may include

In addition, the precipitate 120 is filtered by separating the precipitate and unreacted solution provided in the lower part of the reactor 100 and generated by the precipitation reaction of the raw material solution 110 and the precipitating agent flowing down in the pipe 200 . It may include a filter 400 for

A storage tank provided under the filter 400 and for storing some unreacted solutions flowing down through the filter 400 during a precipitation reaction between the raw material solution 110 flowing down in the pipe 200 and the precipitating agent (500).

The storage tank 500 and the reactor 100 may be connected, and a reintroduction pipe 600 for reintroducing the unreacted solution stored in the storage tank 500 back into the reactor 100 may be included. .

The raw material solution 110 may be a manganese sulfate (MnSO ₄ ) solution as a raw material for manufacturing manganese oxide.

The manganese sulfate solution is a solution composed of manganese and acid by dissolving manganese dust in acid and then adding various impurity removers to the solution. This process is called a purification process, and the manganese sulfate (MnSO ₄ ) solution made in this purification process can be

The lower end of the reactor 100 is centered from the outer part of the reactor 100 to the center so that the raw material solution stored in the reactor 100 can easily flow down to the lower part of the reactor 100 through the pipe 200 . It may be formed to taper downward as it faces.

The pipe 200 may be respectively installed at regular intervals or at arbitrary intervals at the lower end of the reactor 100 so that the raw material solution in the reactor 100 can be easily divided into small portions and flowed down.

The plurality of pipes 200 may be provided in an appropriate number so as to maximize the area where the raw material solution 110 and the precipitant input through the precipitant input pipe 300 meet.

The length 210 of the pipe 200 may be changed according to the input amount of the raw material solution, for example, manganese sulfate (MnSO _{4 ) solution,}

In addition, the plurality of pipes 200 may be formed to have the same length or different lengths, respectively, and the size (diameter) and shape of the plurality of pipes 200 may be the same or different from each other. is of course

A control valve (not shown) for controlling the input and discharge of the raw material solution 100 through the pipe 200 may be installed in the pipe 200 .

The precipitant input pipe 300 meets the precipitant input to the pipe 200 and the raw material solution 110 flowing down through the pipe 200 to facilitate the precipitation reaction. It can be connected to each side.

In addition, the precipitant input pipe 300 may be installed in a direction perpendicular to the pipe 200 so that the precipitant can meet the raw material solution for easy precipitation reaction, and inclined at a predetermined angle with the pipe 200 . can be installed.

The reintroduction pipe 600 is a lower end of the storage tank 500 and an upper portion of the reactor 100 so that the unreacted solution stored in the storage tank 500 can be easily reintroduced back into the reactor 100 . can be connected

In addition, a pump (not shown) for pumping the unreacted solution stored in the storage tank 500 back into the reactor 100 may be installed in the reintroduction pipe 600 .

Hereinafter, with reference to FIG. 2, the operation of the high-purity manganese oxide manufacturing apparatus according to an embodiment of the present invention will be described.

An apparatus for manufacturing high-purity manganese oxide according to an embodiment of the present invention is to provide a means for preventing co-precipitation of impurities.

_{First, a MnSO 4} solution is prepared as a raw material solution 110 through a leaching-neutralization-refining process using manganese dust. The raw material solution 110 prepared in this way is stored in the reactor 100 .

Then, after inputting the raw material solution through the plurality of pipes 200 in an open state with the control valve (not shown) installed in the plurality of pipes 200 , the raw material solution flows through the pipes 200 . let it flow

At the same time, the precipitation agent is introduced into the plurality of pipes 200 to cause a precipitation reaction to occur while the raw material solution and the precipitant meet, and the raw material solution 110 flows down the pipe 200 through the pipe 200 . As it descends, the precipitation reaction continues.

Therefore, the length of the pipe 200 _{should be formed differently depending on the input amount of the raw material solution (MnSO 4} solution). In this way, the precipitation agent and the precipitation reaction occur while flowing down the pipe 200 through the pipe 200. As a result, a precipitate 120 of high-purity manganese oxide with few impurities is generated.

The precipitate 120 generated by the precipitation reaction is separated from the unreacted solution by the filter 400 and accumulated on the filter 400 , and the unreacted solution is the precipitate 120 by the filter 400 . It is separated from and passed through the filter 400 and then stored in the storage tank 500 .

The unreacted solution stored in the storage tank 500 undergoes a process of being reintroduced into the reactor 100 again through the reintroduction pipe 600 .

Therefore, since the precipitate 120 and the unreacted solution can be quickly separated, the pH of the unreacted solution can be suppressed from rising above the limit value, and also the precipitation process time can be reduced and the impurity co-precipitation can be lowered.

[Example]

The effects of the present invention will be described according to examples.

_{First, as in the solution principle of the present invention, a MnSO 4} solution is prepared as a raw material solution 110 through a leaching-neutralization-refining process using manganese dust and stored in the reactor 100,

Then, the MnSO ₄ raw material solution in the pipe 200 and the precipitating agent in the pipe 300 were differently introduced as follows to conduct a precipitation experiment.

Precipitation test result number input rate Impurity measurement result (%) raw material solution precipitant Mg Ca One One 0.1 0.092 0.100 2 One 0.5 0.200 0.230 3 One 1.0 0.220 0.240

As can be seen from Table 1, it can be seen that the amount of impurities decreases as the precipitant input ratio decreases, and in particular, it can be seen that the amount of impurities decreases to 50% or less at the precipitant input ratio of 0.1 or less. In this way, when the input pipe is separated and the input ratio of the raw material solution and the precipitant is different, high-purity precipitate can be obtained. It can be seen that there is an achievable effect.

100: reactor 110: raw material solution
200: pipe 300: precipitant input pipe
400: filter 500: storage tank
600: reintroduction tube

Claims (11)

A reactor in which a raw material solution for manufacturing manganese oxide is input and stored;
A plurality of pipes connected to the reactor to divide and flow the raw material solution in the reactor in small portions;
A precipitant input pipe connected to a plurality of pipes, each of which meets a raw material solution flowing down through the pipe and causes a precipitation reaction to occur to produce a high-purity manganese oxide with few impurities; and
A filter provided in the lower part of the reactor and filtering the precipitate by separating the precipitate and the unreacted solution generated by the precipitation reaction of the raw material solution and the precipitating agent flowing down in the pipe
A high-purity manganese oxide manufacturing apparatus comprising a. delete According to claim 1,
A high-purity manganese oxide manufacturing apparatus provided under the filter and comprising a storage tank for storing some unreacted solutions flowing down through the filter during a precipitation reaction between the raw material solution flowing down in the pipe and the precipitating agent. 4. The method of claim 3,
A high-purity manganese oxide manufacturing apparatus connecting the storage tank and the reactor, and including a re-introduction tube for re-injecting the unreacted solution stored in the storage tank back into the reactor. According to claim 1,
The raw material solution is a high-purity manganese oxide manufacturing apparatus made of a _{manganese sulfate (MnSO 4 ) solution as a raw material for manufacturing manganese oxide.} A reactor in which a raw material solution for manufacturing manganese oxide is input and stored;
A plurality of pipes connected to the reactor to divide and flow the raw material solution in the reactor in small portions, and
A precipitant input pipe connected to a plurality of pipes, each of which meets a raw material solution flowing down through the pipes and causes a precipitation reaction to occur, and a precipitant input pipe for producing high-purity manganese oxide with few impurities
including,
The pipe is a high-purity manganese oxide manufacturing apparatus that is respectively installed at regular intervals or at random intervals at the lower end of the reactor so that the raw material solution in the reactor can be easily divided into small portions to flow down. 7. The method of claim 1 or 6,
A high-purity manganese oxide manufacturing apparatus in which a control valve for controlling the discharge of the raw material solution through the pipe is installed in the pipe. 7. The method of claim 1 or 6,
The precipitant input pipe is each connected to the side of the plurality of pipes to facilitate the precipitation reaction with the precipitating agent fed into the pipe and the raw material solution flowing down through the pipe. 5. The method of claim 4,
The reintroduction pipe is a high purity manganese oxide manufacturing apparatus connecting the lower end of the storage tank and the upper portion of the reactor so that the unreacted solution stored in the storage tank can be easily reintroduced into the reactor. 10. The method of claim 9,
A high-purity manganese oxide manufacturing apparatus is installed in the re-introduction pipe for pumping the unreacted solution stored in the storage tank to be re-injected into the reactor. 9. The method of claim 8,
The precipitant input pipe is installed in a direction perpendicular to the pipe, or is installed at an angle to the pipe at an angle.

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