WO2022092433A1

WO2022092433A1 - Apparatus for producing acetylene black using combination of plasma treatment and thermal decomposition

Info

Publication number: WO2022092433A1
Application number: PCT/KR2020/018824
Authority: WO
Inventors: 이승규; 이경석; 방윤혁; 박규순; 강승범
Original assignee: 재단법인 한국탄소융합기술원
Priority date: 2020-11-02
Filing date: 2020-12-21
Publication date: 2022-05-05
Also published as: KR20220060041A; KR102508756B1

Abstract

An apparatus for producing acetylene black according to one embodiment of the present invention comprises: an inflow unit through which acetylene is added; a plasma unit for forming plasma, the acetylene supplied via the inflow unit reacting with the plasma; and a thermal decomposition unit for receiving and thermally decomposing the acetylene reacted with plasma in the plasma unit, wherein the thermal decomposition unit is provided in series with the plasma unit but is positioned to follow same.

Description

Acetylene black manufacturing apparatus using plasma treatment and pyrolysis complex

The present invention relates to an acetylene black manufacturing apparatus, and more particularly, to an acetylene black manufacturing apparatus configured by combining a plasma treatment process and a thermal decomposition process.

Acetylene black is a kind of carbon black, and the raw material is acetylene gas. In Japan, only Denka Company Limited has been manufacturing and selling for over 60 years, so it is commonly called Denka Black. Denka Black is an acetylene black produced by thermal decomposition of acetylene as a kind of carbon black. It has excellent high-purity conductivity, and its properties are used to prevent conduction and static electricity in the fields of battery raw materials, silicon products including power cables, and IC packaging materials. is becoming

Denka black, that is, acetylene black, has greatly improved its properties as it is used in manganese batteries, and then it was used as a conductive material mainly for battery applications. Recently, the use of lithium ion secondary batteries and fuel cells as a conductive agent is increasing.

Acetylene black is produced by the continuous thermal decomposition reaction of acetylene gas (2600 degrees Celsius; in fact, reaction is possible at around 1800 degrees Celsius due to heat dissipation or furnace protection, etc.), and more than 99% of the raw material is acetylene gas, and heavy oil is used. It does not contain impurities such as sulfur like furnace black.

Acetylene is generated from the by-product gas of naphtha cracking by adding water to calcium carbide or cracking, and its quality is determined by the type of cracking furnace, temperature distribution in the furnace, residence time in the furnace, and cooling method.

Acetylene black is composed of particles of colloidal size of carbon black, and has properties such as electrical conductivity, high water absorption, good thermal conductivity, and each particle of acetylene black is composed of large crystallites, forming a long chain structure. and has very few impurities compared to other carbon blacks. In addition, since acetylene black is produced by self-heating pyrolysis of acetylene gas and does not contain oxygen, it is highly purified and has a very low amount of hydrogen among non-decomposed residues. Moreover, since oxygen does not exist even in the functional group, it has excellent conductivity properties.

Acetylene black has long been used as a basic material for batteries, and is a conductive rubber or plastic material with elasticity in industrial fields such as wires, cables, tires, belts, hoses, heaters, paints, adhesives, conductive agents, and many electronic fields. used as an antistatic additive in

Recently, it has been spotlighted as an electrode for electric vehicle lithium ion batteries and hydrogen electric vehicle fuel cells. In Korea, research on acetylene black content, volume resistance and thermal conductivity, and forming acetylene black as a composite material in HDPE is being conducted.

Low value-added special carbon black used in plastics and ink fields is mass-produced and exported in Korea, but high value-added special carbon black such as acetylene black used in conductive materials and paints is largely dependent on imports as domestic production is insignificant. .

While major global carbon black companies have recently closed their facilities in the US and Western Europe, they are continuing to invest in facilities in Asia, Central America, and Eastern Europe, centering on China. Accordingly, in Korea, there is an increasing need to develop high value-added special carbon black used in conductive materials and paints to replace imports in the relevant market and increase the degree of technological independence.

General-purpose carbon black can be produced in all countries, and there are contact black, furnace black, thermal black, lamp black, etc., depending on the manufacturing method of carbon black. Most companies produce furnace black, and only a few companies such as Denka, Mitsubishi Chemical, and Carbot are producing high-purity acetylene black using the acetylene method.

That is, since the production of acetylene black has to improve properties, it is very difficult to develop a technology for the manufacturing process, and most of the research is limited to the level of applying the manufactured carbon black.

On the other hand, the manufacturing apparatus of acetylene black usually includes an injection unit for injecting an injection gas, a preheating unit for preheating the injection gas, a decomposition unit for processing and decomposing the preheated injection gas, a cooling unit for cooling the decomposed gas, and a cooling unit. It consists of a collecting unit that collects acetylene black that is cooled and finally produced.

With respect to the configurations of the acetylene black manufacturing apparatus, various research and development are being actively conducted in the industry to obtain optimization, cost reduction, efficiency, and the like.

The present invention was created to solve the problems of the prior art as described above, and an object of the present invention is to provide an acetylene black manufacturing apparatus capable of efficiently producing acetylene black of high purity.

Acetylene black manufacturing apparatus according to an embodiment of the present invention, an injection unit for injecting acetylene; a plasma unit configured to form a plasma so that acetylene supplied through the injection unit reacts with the plasma; and a thermal decomposition unit for receiving and thermally decomposing acetylene reacted with plasma from the plasma unit, wherein the thermal decomposition unit is configured in series with the plasma unit and disposed subsequent to the plasma unit.

Specifically, the thermal decomposition unit may be disposed below the plasma unit, and may receive acetylene treated in the plasma unit through gravity to manufacture the acetylene as acetylene black.

Specifically, the plasma unit may be configured to supply the acetylene to the thermal decomposition unit after the plasma plasma-treats the acetylene only with a first preset reactivity.

Specifically, the first preset reactivity is the intensity generated when the intensity of the plasma is 10 Kw to 50 Kw of power and 60 Hz of frequency at an applied pressure of 0.05 to 50 torr, and the plasma temperature is 1,000 degrees Celsius to 3,000 degrees Celsius This may be the case reaction.

Specifically, the thermal decomposition unit may receive the acetylene reacted with the plasma from the plasma unit and thermally decompose it at a second preset reactivity to produce the acetylene as acetylene black.

Specifically, the second preset reactivity may be a reactivity when the temperature of thermal decomposition is 1,500 degrees Celsius to 2,200 degrees Celsius.

Specifically, the volume of the plasma unit may have a preset ratio to the volume of the thermal decomposition unit.

Specifically, the injection unit includes an acetylene supply for supplying the acetylene to the plasma unit, the plasma unit, three plasma torches for generating a plasma stream; a plasma reaction chamber providing temperature and pressure to react the plasma with the acetylene; and an inert gas supplier for supplying an inert gas, wherein the thermal decomposition unit includes: a reactive acetylene injector for supplying acetylene reacted with plasma from the plasma unit; a reaction raw material injector for supplying a material for generating an exothermic reaction; and a pyrolysis reaction chamber providing pressure so that acetylene is thermally decomposed through heat generated by the reaction raw material, wherein the plasma reaction chamber has an inner diameter of 50 mm to 180 mm, and a length of 500 mm to 1800 mm, the pyrolysis reaction The chamber may have an inner diameter of 50 mm to 100 mm, and a length of 500 mm to 1,000 mm.

The acetylene black manufacturing apparatus according to an embodiment of the present invention has the effect of maximizing productivity as the decomposition efficiency of acetylene gas is improved by configuring the plasma treatment process and the thermal decomposition process in two stages in series.

In addition, in the acetylene black manufacturing apparatus according to an embodiment of the present invention, high-temperature heat generated after decomposition of acetylene gas through the plasma treatment process at the top can be used in the pyrolysis process at the bottom, so that maintaining high temperature in the pyrolysis process is efficient As this is possible, there is an effect of remarkably reducing power consumption, and also it is not necessary to construct a separate preheating unit, thereby minimizing the size of the facility, thereby reducing the construction cost.

1 is a conceptual diagram of an acetylene black manufacturing apparatus using a conventional plasma decomposition method.

2 is a conceptual diagram of an acetylene black manufacturing apparatus using a conventional thermal decomposition method.

3 is a conceptual diagram of an acetylene black manufacturing apparatus according to an embodiment of the present invention.

The objects, specific advantages and novel features of the present invention will become more apparent from the following detailed description and preferred embodiments taken in conjunction with the accompanying drawings. In the present specification, in adding reference numbers to the components of each drawing, it should be noted that only the same components are given the same number as possible even though they are indicated on different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a conceptual diagram of an acetylene black manufacturing apparatus using a conventional plasma decomposition method, FIG. 2 is a conceptual diagram of an acetylene black manufacturing apparatus using a conventional thermal decomposition method, and FIG. 3 is a conceptual diagram of an acetylene black manufacturing apparatus according to an embodiment of the present invention am.

As shown in FIG. 3 , the acetylene black manufacturing apparatus 1 according to an embodiment of the present invention includes an injection unit 10 , a plasma unit 20 , a thermal decomposition unit 30 , a cooling unit 40 and a collecting unit. (50).

Prior to describing the acetylene black manufacturing apparatus 1 according to the embodiment of the present invention, the conventional acetylene black manufacturing apparatus 1a and 1b will be described.

1 is a conceptual diagram of an acetylene black manufacturing apparatus 1a using a conventional plasma decomposition method. The acetylene black manufacturing apparatus 1a using the plasma decomposition method generates plasma P through the plasma torch 12a with the inert gas supplied from the inert gas supply 10a, and injects the generated plasma P The acetylene supplied in step 10a and the plasma react with each other in the plasma chamber 13a to decompose the acetylene, and then cool by the cooling unit 14a to manufacture acetylene black.

However, the acetylene black manufacturing apparatus 1a using this plasma decomposition method has a disadvantage in that the yield is low due to a large amount of undecomposed acetylene gas, and the power consumption for plasma generation is very large, so that economic efficiency is lowered.

2 is a conceptual diagram of an acetylene black manufacturing apparatus 1b using a conventional thermal decomposition method. The acetylene black manufacturing apparatus 1b using the pyrolysis method receives acetylene from the acetylene supply unit 10a, receives the high-temperature combustion gas from the burner 11b, pyrolyzes it in the pyrolysis chamber 12b, and then the cooling unit 13b ) through cooling to produce acetylene as acetylene black.

However, the acetylene black manufacturing apparatus 1b using this pyrolysis method has a disadvantage in that the length of the pyrolysis chamber 12b is long to control the residence time for gas decomposition, so that the size of the equipment increases, and the high temperature of the pyrolysis chamber 12b There is a disadvantage that high power is required for maintenance.

Therefore, in order to solve the disadvantages occurring in each of the acetylene black manufacturing apparatus 1a using the plasma decomposition method and the acetylene black manufacturing apparatus 1b using the thermal decomposition method, the present applicant developed the acetylene black manufacturing apparatus 1 of the present invention did

Hereinafter, an acetylene black manufacturing apparatus 1 according to an embodiment of the present invention will be described in detail with reference to FIG. 3 .

The injection unit 10 injects acetylene. Specifically, the injection unit 10 may be disposed above the plasma unit 20 to supply acetylene gas to the plasma unit 20 .

The injection unit 10 may include an acetylene supplier 11 for supplying acetylene to the plasma unit 20 . A plurality of acetylene feeders 11 may be formed on the upper surface of the plasma unit 20 in parallel.

The plasma unit 20 is configured to form a plasma P, and acetylene supplied through the injection unit 10 reacts with the plasma P, and is configured in series with the thermal decomposition unit 30 .

The plasma unit 20 includes a plasma torch 21 generating a plasma (P) stream, a plasma reaction chamber 22 providing temperature and pressure so that the plasma P and acetylene react, and an inert gas supplying an inert gas. A feeder 23 may be included.

The plasma torch 21 may be formed to pass through the upper portion of the plasma reaction chamber 22, and form a plasma stream of at least 1,000 degrees Celsius or more (preferably 1,000 degrees Celsius to 3,000 degrees Celsius) by direct current arc discharge. can do. Here, the DC arc discharge may be generated by a power of 10 kw to 50 kw and a frequency of 60 Hz.

The plasma torch 21 may be configured in three phases, which has the advantage of improving the plasma generation effect compared to the plasma torch consisting of a single phase (one), thereby increasing the decomposition efficiency of acetylene gas there is

The plasma reaction chamber 22 is used in connection with the plasma torch 21 and the inert gas supply 23, and has a structure in which the stream of plasma P generated in the plasma torch 21 and acetylene can be mixed well. It may have the form of a chamber.

In the plasma reaction chamber 22 , when acetylene is thermally decomposed by the plasma reaction, a shield gas outlet may be configured to prevent carbon black from being deposited on the top and inner walls of the plasma reaction chamber 22 .

The plasma reaction chamber 22 may be used as a heat-resistant and heat insulating material capable of increasing energy efficiency while being able to withstand the high temperature of plasma.

The plasma reaction chamber 22 is formed to withstand a pressure of 0.05 torr to 50 torr to generate a pressure of 0.05 to 50 torr, and through this pressure, plasma generation can be optimized. At a pressure greater than the pressure of 50 torr, the plasma generation rate is lowered and the plasma production rate is lowered, and in the present invention, in order to prevent such a decrease in the plasma production rate, the plasma reaction chamber 22 has a pressure of 0.05 to 50 torr as described above. It can be supplied so that plasma can be easily formed.

The plasma reaction chamber 22 may have, for example, a cylindrical shape, and may have an inner diameter of 50 mm to 180 mm and a length of 500 mm to 1800 mm. Plasma reaction chamber 22, by having the optimal dimensions of such an inner diameter and length, there is an effect that can minimize the generation of undecomposed acetylene gas.

The inert gas supply 23 may be formed to pass through the upper portion of the plasma reaction chamber 22 , and nitrogen, argon, or the like may be used as the inert gas.

The plasma unit 20 generates a plasma P through the plasma torch 21 using an inert gas supplied from the inert gas supplier 23 , and acetylene supplied from the injection unit 10 by applying the generated plasma P to the injection unit 10 . react with each other to cause the plasma to pyrolyze at least a portion of the acetylene.

When the plasma generated by the plasma torch 21 in the plasma unit 20 reacts with acetylene for thermal decomposition, at least a part of carbon black may be generated. In this case, the thermal decomposition reaction may mainly occur at the lower end of the plasma torch 21 and inside the plasma reaction chamber 22 .

The plasma unit 20 may be configured to supply acetylene to the thermal decomposition unit 30 after plasma-treating the acetylene with only a first preset reactivity. Here, the first preset reactivity may be a reactivity when the plasma intensity is the preset intensity. That is, the intensity of the plasma is the intensity generated when the applied pressure is 0.05 to 50 torr, the electric power is 10 Kw to 50Kw, and the frequency is 60 Hz, and the plasma temperature may be the reactivity in the case of 1,000 degrees Celsius to 3,000 degrees Celsius.

The volume of the plasma unit 20 may have a predetermined ratio to the volume of the pyrolysis unit 30 . This ratio may be a ratio in which the plasma reaction chamber 22 is formed to have an inner diameter of 50 mm to 180 mm and a length of 500 mm to 1800 mm, as described above.

The thermal decomposition unit 30 pyrolyzes acetylene and is configured in series with the plasma unit 20 .

The thermal decomposition unit 30 is disposed following the plasma unit 20, is disposed below the plasma unit 20, and receives acetylene that has been at least partially processed in the plasma unit 20 through gravity to supply acetylene to acetylene black. can be manufactured with Through this, in the present invention, it is not necessary to install a separate preheating unit upstream of the thermal decomposition unit 30 (acetylene generates an exothermic reaction during decomposition due to plasma and emits heat) and at the same time, it is possible to avoid building a separate pump, There is an effect that the construction cost is reduced and the manufacturing cost is reduced.

The thermal decomposition unit 30 includes a reactive acetylene injector 31 for supplying acetylene reacted with plasma from the plasma unit 20, a reactive raw material injector 32 for supplying a material that generates an exothermic reaction, and a reaction raw material generated by It may include a pyrolysis reaction chamber 33 that provides pressure to pyrolyze acetylene through heat.

The reactive acetylene injector 31 is formed between the plasma unit 20 and the thermal decomposition unit 30 and may have a tube shape, for example. Specifically, the reactive acetylene injector 31 may have a tube shape formed between the pyrolysis reaction chamber 33 and the plasma reaction chamber 22 .

At this time, the reactive acetylene injector 31 may have a separate opening/closing valve therein, and the supply amount of acetylene reacted with the plasma supplied from the plasma unit 20 to the pyrolysis unit 30 through this opening/closing valve can be adjusted. there is.

The reaction raw material injector 32 may be, for example, a high-temperature combustion gas, a burner, or the like, and may be formed on a sidewall of the pyrolysis reaction chamber 33 .

The reaction raw material injector 32, for example, may be supplied with a high-temperature combustion gas having a temperature of 1,400 degrees Celsius to 2,200 degrees Celsius (preferably 1,500 degrees Celsius to 2,200 degrees Celsius), and the supplied combustion gas is a reaction acetylene injector ( 31) can pyrolyze acetylene supplied from. At this time, acetylene supplied from the reactive acetylene injector 31 may be completely decomposed by a high-temperature combustion gas having a heat of 1,500 to 2,200 degrees Celsius.

The pyrolysis reaction chamber 33 is used in connection with the reaction acetylene injector 31 and the reaction raw material injector 32, and has a structure in which the high temperature heat supplied from the reaction raw material injector 32 and acetylene can be mixed well. may have the form of a chamber).

The pyrolysis reaction chamber 33 may be used as a heat-resistant and heat-insulating material whose material can withstand high temperatures and increase energy efficiency.

The pyrolysis reaction chamber 33 may have, for example, a cylindrical shape, and may have an inner diameter of 50 mm to 100 mm and a length of 500 mm to 1000 mm. The thermal decomposition reaction chamber 33 has an advantage in that it is possible to maintain a uniform temperature in the chamber by having such optimal dimensions of the inner diameter and length, so that acetylene black having the same characteristics can be produced.

The thermal decomposition unit 30 may receive acetylene reacted with the plasma from the plasma unit 20 and thermally decompose it in a second preset reactivity to manufacture acetylene into acetylene black. Here, the second preset reactivity may be a reactivity when the temperature of thermal decomposition is a preset temperature, and may be, for example, 1,500 to 2,200 degrees Celsius. That is, it may be a reactivity when the temperature of the thermal decomposition is 1,500 degrees Celsius to 2,200 degrees Celsius.

On the other hand, partial decomposition of acetylene starts at approximately 1,400 to 1,500 degrees Celsius to generate nuclei (step 1), and the nuclei generated in this way collide with each other to form a chain structure (step 2), and finally form a crystal layer (Step 3) to produce acetylene black. Considering the production process of acetylene black, the length of the reactor is an important variable for the growth process time of acetylene black, and the inner diameter of the reactor is an important variable for the decomposition efficiency according to the amount of acetylene gas.

Therefore, in the present invention, the first plasma unit 20 and the second thermal decomposition unit 30 are configured in series connection, the plasma reaction chamber 22, the inner diameter is 50mm to 180mm, the length is 500mm to 1800mm, the pyrolysis reaction The chamber 33 is formed to have an inner diameter of 50 mm to 100 mm and a length of 500 mm to 1000 mm, thereby minimizing the generation of undecomposed acetylene gas and maintaining a uniform temperature in the chamber, resulting in the generation of acetylene black having the same characteristics. generate

The cooling unit 40 may be disposed below the thermal decomposition unit 30 , and may cool the acetylene black produced by thermal decomposition in the thermal decomposition unit 30 .

The cooling unit 40 may receive vacuum, for example, to cool the acetylene black produced by thermal decomposition in the pyrolysis unit 30, and a vacuum unit (not shown) for forming a vacuum may be connected to the side. .

The collecting unit 50 may be disposed below the cooling unit 40 , and may collect the acetylene black cooled by the cooling unit 40 .

The collecting unit 50 may finally collect the acetylene black produced in the plasma unit 20 and the thermal decomposition unit 30, and the collected acetylene black is supplied to and stored in a separate storage (not shown). It can be processed into the final product.

As such, in the acetylene black manufacturing apparatus 1 according to an embodiment of the present invention, the plasma treatment process and the thermal decomposition process are configured in two stages in series, and as the decomposition efficiency of acetylene gas is improved, productivity is maximized.

In addition, in the acetylene black manufacturing apparatus 1 according to an embodiment of the present invention, high-temperature heat generated after decomposition of acetylene gas through the plasma treatment process at the top can be used in the pyrolysis process at the bottom, so that the high temperature in the pyrolysis process Since maintenance is efficiently possible, there is an effect of remarkably reducing power consumption, and also, it is not necessary to construct a separate preheating unit, so the size of the facility can be minimized, thereby reducing the construction cost.

Although the present invention has been described in detail through specific examples, this is for the purpose of describing the present invention in detail, and the present invention is not limited thereto. It will be clear that the transformation or improvement is possible.

All simple modifications or changes of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

Claims

an injection unit for injecting acetylene;

a plasma unit configured to form a plasma so that acetylene supplied through the injection unit reacts with the plasma; and

and a thermal decomposition unit receiving acetylene reacted with plasma from the plasma unit and thermally decomposing it,

The thermal decomposition unit,

Doedoe configured in series with the plasma unit, acetylene black manufacturing apparatus characterized in that it is disposed following the plasma unit .
According to claim 1, wherein the thermal decomposition unit,

An acetylene black manufacturing apparatus, which is disposed below the plasma unit, receives acetylene processed in the plasma unit through gravity, and manufactures the acetylene as acetylene black .
According to claim 2, wherein the plasma unit,

Acetylene black manufacturing apparatus, characterized in that the plasma is configured to supply the acetylene to the thermal decomposition unit after plasma-treating the acetylene only with a first preset reaction rate .
According to claim 3, The first preset reactivity,

The intensity of the plasma is the intensity generated when the applied pressure is 0.05 to 50 torr, the power is 10 Kw to 50Kw, and the frequency is 60 Hz, and the plasma temperature is 1,000 degrees Celsius to 3,000 degrees Celsius. Acetylene black production, characterized in that Device.
According to claim 3, The thermal decomposition unit,

Acetylene black manufacturing apparatus, characterized in that by receiving the acetylene reacted with the plasma from the plasma unit and thermally decomposing it to a second preset reactivity to produce the acetylene as acetylene black.
According to claim 5, The second preset reactivity,

Acetylene black manufacturing apparatus, characterized in that the reactivity when the temperature of the thermal decomposition is 1,500 degrees Celsius to 2,200 degrees Celsius.
According to claim 1, wherein the plasma unit,

Acetylene black manufacturing apparatus, characterized in that the volume has a predetermined ratio to the volume of the pyrolysis unit.
The method of claim 1,

The injection unit includes an acetylene supplier for supplying the acetylene to the plasma unit,

The plasma unit,

three plasma torches generating a plasma stream; a plasma reaction chamber providing temperature and pressure to react the plasma with the acetylene; and an inert gas supply for supplying an inert gas,

The thermal decomposition unit,

a reactive acetylene injector for supplying acetylene reacted with plasma from the plasma unit; a reaction raw material injector for supplying a material for generating an exothermic reaction; and a pyrolysis reaction chamber that provides pressure to pyrolyze acetylene through heat generated by the reaction raw material,

The plasma reaction chamber,

The inner diameter is 50mm to 180mm, the length is 500mm to 1800mm,

The pyrolysis reaction chamber,

Acetylene black manufacturing apparatus, characterized in that the inner diameter is 50mm to 100mm, and the length is 500mm to 1,000mm.