KR101547550B1 - Co-precipitation reactor comprising Couette-Taylor vortex reactor performing reaction, washing, filtration and drying by one-step process - Google Patents

Abstract

The present invention relates to a coprecipitated reactor comprising a vertical KuT-Taylor reactor in which a reaction, washing, filtration and drying are carried out in a single process. According to the present invention, the synthesis, And filtration and drying processes are performed. Therefore, it is possible to greatly reduce the size of the equipment, simplify the control, and prevent the reaction material from being exposed to the air to be contaminated, thereby greatly improving the productivity.

Description

[0001] The present invention relates to a co-precipitation reactor comprising Couette-Taylor vortex reactor performing performing reaction, washing, filtration and drying in a single process }

The present invention relates to a coprecipitated reactor, and more particularly to a coprecipitated reactor with a Kuett-Taylor reactor in which seed synthesis, reaction, washing, filtration and drying processes can be carried out in a single apparatus.

The manufacturing process of various chemical substances is generally accompanied by a crystallization process, a growth process, a cleaning process, a filtration process, and a drying process, depending on the manufacturing method.

For example, there are a solid phase reaction method and a wet process method for producing a cathode active material for a secondary battery, and a solid phase reaction method is a process of mixing and pulverizing several constituent raw powders several times. The wet process can be divided into spray pyrolysis and coprecipitation. In the spray pyrolysis process, metal oxides are obtained by dissolving a constituent material in a solvent, generating droplets of a predetermined size, and then firing instantaneously. , Synthesizing and growing a metal hydroxide precursor through PH adjustment, filtering and drying the solution containing the grown precursor, and subjecting to a predetermined firing process to obtain a cathode active material for a secondary battery.

However, in the conventional chemical manufacturing method, the reaction process, the cleaning process, the filtering process, and the filtration process of the material are performed in a separate device capable of carrying out individual processes.

Therefore, the control of the individual devices is complicated, and there is a possibility that the reaction materials are exposed to the air during the process of transferring the reactants to another device, and thus contaminated.

Korean Patent Laid-Open No. 10-2010-0059601 discloses a technique for a coprecipitation reactor. However, only a process of reacting a substance using an impeller is mentioned, and thus, a method of producing a seed, cleaning, The above-mentioned problem that the process must be performed in a separate apparatus is present.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems of the prior art as described above, and it is an object of the present invention to provide a method for producing a seed through a quattro-tail vortex, a reaction of a substance through agitation, The present invention is directed to a coprecipitated reactor which is capable of performing the above-described process.

In order to accomplish the above object, a coprecipitation reactor in which a reaction, washing, filtration, and drying are performed in a single step according to the present invention is characterized in that a reaction space is formed therein, and a drain part and a product A body provided with a discharge portion; An inner cylinder extending from the inside of the main body to the upper outer side and rotated by the first motor; An outer tube mounted around the inner tube so as to form a synthetic space between the inner passages and provided with a stirring blade around the outer tube and rotatable by a second motor; A seed discharge portion for providing a passage for discharging a seed generated in a synthetic space between the inner passage and the outer passage to the reaction space; A raw material input unit capable of inputting a raw material into the synthesis space; An additive input part capable of injecting an additive into the synthesis space or the reaction space; A filter unit for filtering the seeds discharged into the reaction space; And a heating means for adjusting the temperature of the reaction space, wherein a Kuett-Taylor vortex is formed in the synthesis space in accordance with the rotation of the inner cylinder, and a seed generated by the Kuett- The reaction seeds are separated and filtered from the filter unit, and are dried according to the operation of the heating unit, and then are discharged to the product discharge unit Can be discharged.

Here, the seed discharge unit may be mounted on the lower portion of the outer tube and be rotatable together with the outer tube, and the seed settled in the reaction space may float as the seed discharge unit rotates.

The drain portion of the main body may be located below the product discharge portion, the filter portion may be provided between the product discharge portion and the drain portion, and the seed discharge portion may be installed in a state close to the upper surface of the filter portion .

The present invention has the following effects.

First, since all the processes are performed in one apparatus, the size of the whole apparatus is reduced, and the cleaning is also simple. That is, in the prior art, there has been separately provided a device for a Kuett-Taylor reaction, a device for stirring reaction, a device for cleaning, a device for filtration, and a drying device, Since it is cleaned, the maintenance is very easy and the working time can be saved.

In addition, there is no fear of contamination of the reactant. That is, conventionally, there is a great possibility that the reaction material is contaminated with air in the process of transferring the process to the next device after completion of the process in each device. However, in the present invention, it is not necessary to take out the reaction material from the device until the drying process is completed There is no risk of exposure to air. Of course, in the conventional apparatus, in order to prevent exposure of reactants to air, each device may be connected through a transfer pipe so that the reactant can be safely transferred along the transfer pipe. In this case, however, And must be cleaned to the inside of the transfer pipe. However, in the present invention, since there is no need to transport the reaction material between the apparatus and the apparatus, there is no difficulty in the sealing work or the cleaning of the transfer tube as in the prior art.

1 is a schematic cross-sectional view for explaining a configuration of a coprecipitation reactor according to an embodiment of the present invention;
FIG. 2 is a flow chart for explaining a process through the coprecipitation reactor shown in FIG. 1. FIG.
3 is a conceptual diagram for explaining a Kuett-Taylor vortex;
FIGS. 4 to 6 are conceptual diagrams for explaining a step-by-step process performed through the coprecipitation reactor shown in FIG. 1. FIG.
FIGS. 7 to 10 are views showing examples of catalysts prepared in different shapes according to a process when a catalyst for synthesizing carbon nanotubes is manufactured through the coprecipitation reactor shown in FIG. 1; FIG.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, some configurations which are not related to the gist of the present invention may be omitted or compressed, but the configurations omitted are not necessarily those not necessary in the present invention, and they may be combined by a person having ordinary skill in the art to which the present invention belongs. .

1 is a schematic view for explaining a coprecipitation reactor (hereinafter referred to as a 'coprecipitating reactor') accompanied by a vertical KuT-Taylor reaction apparatus in which a reaction, washing, filtration and drying are performed in a single step according to an embodiment of the present invention Respectively.

1, the coprecipitation reactor 10 according to an embodiment of the present invention includes a main body 11, an inner cylinder 21, an outer cylinder 22, a first motor 26, a second motor 27, Filter portion 28 and heating means 29 (or cooling means).

The main body 11 is formed in a substantially cylindrical shape and has a reaction space 12 therein. A drain portion 14 for discharging the reaction water in the dehydrating process and a product discharging portion 15 for discharging the product after the drying process are provided in the lower portion of the main body 11. More specifically, the drain portion 14 is located below the filter portion 28, and the product outlet portion 15 is located higher than the filter portion 28. The drain portion 14 is located below the drain portion 14, Location. The upper part of the side surface of the main body 11 is provided with a puddle water discharging part 13 for discharging excessively overflowed reaction water.

The inner cylinder 21 and the outer cylinder 22 are provided concentrically with respect to the center of the main body 11. That is, the inner cylinder 21 is installed in the center of the main body 11 and extends from a predetermined height of the bottom of the main body 11 (specifically, the upper height of the filter portion 28) Lt; / RTI > The outer tube 22 is installed so as to extend to a predetermined height above the main body 11 in the form of surrounding the inner tube 21. [ At this time, between the inner cylinder 21 and the outer cylinder 22, a quart-tailor vortex is formed at a predetermined interval. This space is hereinafter referred to as a synthesis space 25.

The inner cylinder 21 is rotatable in association with the first motor 26, and the outer cylinder 22 is rotatable in association with the second motor 27.

A plurality of agitating blades 23 are provided around the outer cylinder 22 and a seed is provided at a lower portion of the outer cylinder 22 to provide a passage for allowing the seed generated in the synthesis space 25 to be discharged into the reaction space 12. [ A discharge portion 24 is provided. Here, the seed discharge portion 24 may be mounted on the lower portion of the outer cylinder 22 and rotate together with the outer cylinder 22. [

Meanwhile, raw materials and additives necessary for the process must be introduced into the synthetic space 25 between the inner cylinder 21 and the outer cylinder 22. To this end, a raw material input portion 16 and a plurality of additive input portions 17 and 18 are provided on the upper portion of the body 11 so as to be connected to the synthesis space 25 from the outside. In this embodiment, one raw material input portion 16 and two additive input portions 17 and 18 are provided so as to be connected to the outside of the synthesis space 25.

Of course, the additive must also be added to the reaction space 12 when necessary. Therefore, the third additive input unit 19 and the fourth additive input unit 20, which connect the reaction space 12 and the outside of the body 11, are separately provided.

A filter unit 28 is provided between the drain 14 of the lower part of the main body 11 and the product discharge unit 15. The filter unit 28 is provided for filtering the reaction material when the reaction water exits through the drain unit 14 in the dehydration process. Although FIG. 1 shows the filter unit 28 having a flat shape, it may be provided with a hemispherical or conical filter unit 28 whose center is downward.

The heating means 29 is provided for regulating the temperature in the reaction space 12. The heating means 29 may be manufactured in the form of a hot wire coil surrounding the main body 11 or a pipe in which hot water or hot wind passes through the main body 11 or a space into which the hot water flows is connected to the main body 11 It can also be made in the form of an enclosure. As a matter of course, cooling water may be introduced to cool the reaction space 12 according to the practice.

The coprecipitation reactor 10 shown in FIG. 1 will be further described below with reference to the stepwise process description to be described with reference to FIG. 2 to FIG.

Hereinafter, the process of the coprecipitation reactor 10 shown in FIG. 1 will be described with reference to FIGS. 2 to 6. FIG. The coprecipitation reactor 10 shown in FIG. 1 performs reaction, cleaning, filtration, and drying of various chemical substances through a single device by controlling the input raw materials and additives, controlling the reaction temperature, and changing the process sequence . However, for convenience of explanation, a process for producing a precursor for manufacturing a cathode active material for a secondary battery will be described below as an example.

The temperature of the reaction space 12 inside the main body 11 and the temperature of the synthesis space 25 inside the outer cylinder 22 is first heated to a predetermined level through the heating means 29. [ The operation of the heating means 29 is controlled by a separate control means (not shown) based on the temperature measured in the temperature measuring portion (not shown).

Thereafter, the raw material solution is introduced through the raw material input part 16 and the additive is introduced at a predetermined ratio through the first additive introduction part 17 and the second additive introduction part 18, ) To form a CuEt-Taylor vortex. The Kuett-Taylor vortex is generated by the rotation of the inner tube 21 in accordance with the operation of the first motor 26.

A brief description of the Kuett-Taylor vortex follows.

Couette-Taylor vortex means that when the fluid flows between two cylinders, the inner tube (21) or the outer tube (22) rotates to exhibit a particular flow characteristic. As shown in FIG. 3, when the inner cylinder 21 rotates, the fluids present near the inner cylinder 21 due to the centrifugal force tend to go out in the direction of the fixed outer cylinder 22. As a result, the fluid becomes unstable, The vortex (v) of the high-pitched array that is regular and rotates in opposite directions is formed according to the direction, and this is called a "Taylor vortex" or "Kuett-Taylor vortex".

The vortex cells generated in the radial direction between the two concentric cylinders are each a batch reaction process, and when these vortices are uniformly generated in the axial direction, the batch reaction process of several stages is continuously performed . This Taylor vortex occurs when the rotation speed of the inner tube (21) is above a threshold value, and when the Taylor number is 640 or more, Taylor turbulence occurs and very ideal stirring is performed at this time.

Quet-Taylor vortices are also used in place of stirred tank reactor rolls to provide a special reaction environment for mixing, extraction, precipitation (crystallization), separation and culture in the fields of biology, physics and chemistry, It is advantageous in the process of crystallizing a specific component. It is also possible to control particle size and produce products with uniform particle size distribution.

On the other hand, in the crystallization method using a Cuet-Taylor vortex, a third solvent is added to the mother liquor to induce the supersaturation of the solute, thereby performing a Drowning-out crystallization. In the mother liquor, Salting-out crystallization, in which the solubility of a substance is changed by cooling the solution when the solubility of the substance is sensitive to temperature, thereby increasing the degree of saturation of the mother liquor in which the substance is dissolved. Melting crystallization, which dissolves into pure components by lowering the temperature after melting, and Reaction crystallization, which precipitates solids through chemical reaction.

The crystallization process using the Kuett-Taylor vortex facilitates the automation and operation of the production process and can continuously produce products with uniform physical properties. In addition, it has relatively small space, low production cost and energy consumption, and it is possible to control the particle size, produce a uniform particle size distribution, and shorten the working time.

Meanwhile, the raw material input through the raw material input portion 16 is controlled according to the characteristics of the precursor to be produced. A raw material metal selected from nickel sulfate [NiSO ₄ ], cobalt sulfate [CoSO ₄ ], manganese sulfate [MnSO ₄ ] or aluminum nitrate [Al (NO ₃ ) ₃ ] is dissolved in ultrapure water.

In addition, the additive introduced through the first additive introduction portion 17 and the second additive introduction portion 18 can be sodium hydroxide [NaOH] solution and ammonia [NH ₄ OH].

The sodium hydroxide [NaOH] solution is added as a co-precipitant for the synthesis of the precursor, and the ammonia [NH ₄ OH] solution is added to control the hydrogen ion concentration in the synthesis space 25. The injection timing and amount of the ammonia solution are made under the control of the control means according to the hydrogen ion concentration measured by the PH measurement unit (not shown).

When the raw material solution and the additive are charged into the synthesis space 25 according to a predetermined ratio in a predetermined temperature and PH atmosphere and the inner cylinder 21 is rotated by the operation of the first motor 26, the inner cylinder 21 and the outer cylinder 22 ), A precursor seed is synthesized by reacting violently with the raw material solution and the additive.

The synthesized precursor seed must undergo a growth process by continuously adding and stirring additives such as sodium hydroxide at a suitable temperature and a PH atmosphere. The seed generated in the synthesis space 25 is discharged to the reaction space 12 inside the main body 11 along the seed discharge portion 24 connected to the lower portion of the outer cylinder 22. [ The movement of the seed is performed by pushing along the seed discharge portion 24 the seeds generated earlier by further adding the raw materials and the additives through the raw material input portion 16 or the additive input portions 17 and 18.

Thereafter, when the second motor 27 is operated after adjusting the reaction space 12 to a predetermined temperature and a PH atmosphere, the stirring wing 23 around the outer cylinder 22 is rotated so that the precursor seed is mixed with the sodium hydroxide solution and the ammonia solution Gt; S220 < / RTI > The sodium hydroxide solution and the ammonia solution can be continuously supplied through the third additive inlet portion 19 and the fourth additive inlet portion 20 connected to the reaction space 12 for the growth of the precursor seed.

Meanwhile, the precursor seeds generated in the synthesis space 25 are discharged through the seed discharge portion 24, and are thus caused to sink to the bottom due to their weight. The seed discharge portion 24 is provided around the lower portion of the outer cylinder 22 And the seed discharging portion 24 also rotates together with the rotation of the outer cylinder 22. The precursor seed accumulated on the filter portion 28 is forced to float as the seed discharging portion 24 rotates. As shown in FIG. 5, the precursor seeds floated throughout the reaction space 12 grow while reacting violently with the sodium hydroxide solution and the ammonia solution. The stirring time may be several hours to several tens of hours depending on the application. On the other hand, when the solution is filled in the reaction space 12 due to the addition of the additive, the over-supplied reaction water is discharged through the filled-in water discharge part 13 provided on the side of the upper part of the main body 11. Therefore, a constant water level can always be maintained in the reaction space 12.

When the growth of the precursor seed is completed according to the predefined reaction time, the operation of the second motor 27 is stopped and the drain portion 14 is opened to perform the dewatering process. When the drain 14 is opened, the grown seed (reaction material) remains on the upper surface of the filter unit 28 as shown in FIG. 6, and only the reaction water such as sodium hydroxide solution and ammonia solution passes through the filter, (14). &Lt; / RTI >

Thereafter, the washing water is injected into the reaction space 12 through the third additive input unit 19 or the fourth additive input unit 20, and the reaction material (seed) is neutralized while stirring, and impurities adhered to the seed surface (NaOH, NH4OH, and the like) is removed. When the drain portion 14 is opened again, the washing water and the impurities contained therein are discharged through the drain portion 14, and the grown precursor seed (reactive material) is filtered at the filter portion 28 and remains.

Thereafter, the reaction space 12 is heated to a high temperature through the heating means 29 and the outer cylinder 22 is rotated, whereby the precursor seed (reaction material) is exposed to a high temperature evenly, thereby drying it.

When the drying is completed, the product discharging portion 15 is opened to obtain the product (precursor seed), and subsequent treatment such as firing can proceed.

As described above, according to the coprecipitation reactor 10 of the present invention, since the whole process is performed in one apparatus, the size of the entire facility is reduced and the cleaning is also simple. That is, conventionally, each of the devices has to be cleaned by separately providing a device for a Kuett-Taylor reaction, a device for stirring reaction, a device for cleaning, a device for filtration, and a drying device, 10) Since only one cleaning is required, the maintenance is very easy and the working time can be saved.

In addition, there is no fear of contamination of the reactant. That is, conventionally, there is a great possibility that the reaction material is contaminated with air in the process of transferring the process to the next device after completion of the process in each device. However, in the present invention, it is not necessary to take out the reaction material from the device until the drying process is completed There is no risk of exposure to air. Of course, in the conventional apparatus, in order to prevent exposure of reactants to air, each device may be connected through a transfer pipe so that the reactant can be safely transferred along the transfer pipe. In this case, however, And must be cleaned to the inside of the transfer pipe. However, in the present invention, since there is no need to transport the reaction material between the apparatus and the apparatus, there is no difficulty in the sealing work or the cleaning of the transfer tube as in the prior art.

Although the process for producing a precursor for producing a cathode active material for a secondary battery has been described above, the coprecipitation reactor 10 according to the present invention can be used for controlling a raw material or an additive, controlling the reaction temperature, The reaction, cleaning, filtration and drying of various chemicals can be carried out through a single apparatus.

For example, the coprecipitation reactor 10 may be applied to a process for preparing a catalyst for synthesizing carbon nanotubes.

Typical processes for the preparation of carbon nanotube catalysts include the supported method, the probe method (coprecipitation method), the combustion method, the sol-gel method, and the liquid phase mixing and the reaction process in the above-described method of support, probe method, sol- It is possible.

For example, when a catalyst is produced by a probe method, metallic raw materials such as Fe, Co, Ni, Al, and Mg are supplied as raw materials, and ammonia water may be used as an additive.

In the combustion method, the supporting method and the sol-gel method, the seed can be produced by supplying only the metal raw material without the additive. Of course, nitric acid and a continuous accelerator may be added as an additive in the combustion method, the supporting method and the sol-gel method.

When the sol-gel method is applied using the Cuat-Taylor vortex, the A-type catalyst as shown in FIG. 7 can be produced by performing the drying process after the reaction, and the spraying process or the pyrolysis process A catalyst for synthesis of carbon nanotubes of B type, C type and D type as shown in FIGS. 8 to 10 can be prepared.

The foregoing description of the preferred embodiments of the present invention has been presented for the purpose of illustration and it will be apparent to those skilled in the art that various modifications, additions and substitutions are possible within the spirit and scope of the invention, And additions should be considered as falling within the scope of the claims of the present invention.

10: coprecipitation reactor
11: Body
12: reaction space
13:
14:
15: Product discharge section
16: Raw material input part
17: First additive introduction part
18: Second additive introduction part
19: Third additive input part
20: the fourth additive introduction part
21: My heart
22: outer tube
23: stirring blade
24:
25: Composite space
26: First motor
27: Second motor
28:
29: Heating means

Claims (3)

A body having a reaction space formed therein and a drain part and a product discharge part provided below;
An inner cylinder extending from the inside of the main body to the upper outer side and rotated by the first motor;
An outer tube mounted around the inner tube so as to form a synthetic space between the inner passages and provided with a stirring blade around the outer tube and rotatable by a second motor;
A seed discharge portion for providing a passage for discharging a seed generated in a synthetic space between the inner passage and the outer passage to the reaction space;
A raw material input unit capable of inputting a raw material into the synthesis space;
An additive input part capable of injecting an additive into the synthesis space or the reaction space;
A filter unit for filtering the seeds discharged into the reaction space; And
And heating means for controlling the temperature of the reaction space,
The quart-tail vortex is formed in the synthetic space according to the rotation of the inner cylinder. When the seed generated by the Kuett-Taylor vortex is discharged to the reaction space through the seed discharge part, Reacting and growing while agitating, and the grown seeds are separated and filtered from the filter part, dried according to the operation of the heating means, and then discharged to the product discharge part. A coprecipitation reactor involving a vertical Quattro-Taylor reaction device carried out in a single process.
The method according to claim 1,
Wherein the seed discharging portion is mounted on a lower portion of the outer tube and is rotatable together with the outer tube, and a seed settled in the reaction space floats in accordance with rotation of the seed discharging portion, wherein reaction, washing, filtration, Lt; RTI ID = 0.0 &gt; Quet-Taylor &lt; / RTI &gt;
The method according to claim 1,
The drain portion provided in the main body is located below the product discharge portion,
Wherein the filter portion is provided between the product discharge portion and the drain portion,
Wherein the seed discharging unit is installed in a state of being close to the upper surface of the filter unit. The coprecipitation reactor according to claim 1, wherein the seed discharging unit is installed near the top surface of the filter unit.

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