Method for producing carbon black and reaction furnace for producing carbon black

Abstract

Provided is a method for producing carbon black, which is characterized in that, in a furnace process in which a secondary starting material is used as a starting material hydrocarbon, the purpose of the present invention is to provide a method for producing carbon black having desired characteristics at a high yield while reducing the discharge amount of carbon dioxide (CO2). A reaction furnace for carbon black production is used in which a fuel combustion region, a primary starting material introduction region, a heating region, and a secondary starting material introduction region are provided in this order from the upstream to the downstream of a gas flow path, and an oxygen-containing gas and a fuel are introduced into the fuel combustion region, mixed and combusted to generate a fuel combustion gas flow. A hydrocarbon as a primary starting material is introduced into the primary starting material introduction region while the fuel combustion gas stream is introduced into the primary starting material introduction region to generate a gas containing a primary reactant, and then the gas containing the primary reactant is electrically heated in the heating region. A secondary reaction is performed by introducing a hydrocarbon as a secondary raw material while introducing the electrically heated gas containing the primary reactant into the secondary raw material introduction region.

Description

Technical Field

[0001] This invention relates to a method for manufacturing carbon black and a reaction furnace for manufacturing carbon black. Background Technology

[0002] As for carbon black manufacturing methods, furnace process, acetylene black process, and cellar process are commonly known. Among them, furnace process is known as a manufacturing method that can produce carbon black in large quantities and is economically efficient.

[0003] The furnace method described above is known as follows: using liquid feedstock oils such as heavy oils and / or natural gas as raw materials, the carbon black is produced by thermally decomposing them in an oxygen-deficient state in a refractory furnace.

[0004] Specifically, as described in Patent Documents 1 and 2, a method for manufacturing carbon black is known, which typically uses a reactor having a fuel combustion zone that generates a flow of combustion gases, a reaction zone that introduces liquid feedstock oil and / or natural gas as feedstock hydrocarbons into the flow of combustion gases obtained in the fuel combustion zone and converts them into carbon black through a thermal decomposition reaction, and a reaction stop zone that stops the reaction by rapidly cooling the reaction gases obtained in the reaction zone.

[0005] In addition, carbon black used for rubber reinforcement comes in a variety of types based on its properties. These properties are the main factors that determine the various properties of rubber. Therefore, when compounding with rubber compositions, carbon black with properties suitable for the intended use of the component should be selected.

[0006] For example, as a carbon black compounded in tire tread rubber compositions that can improve durability such as abrasion resistance and further reduce rolling resistance, a carbon black with a dibutyl phthalate (DBP) absorption of 40~180 mL / 100 g and a nitrogen adsorption specific surface area (N2SA) of 40~300 m² has been proposed. 2 Carbon black with various properties such as / g and toluene color transmittance (LT) of over 90% (Patent Document 3, etc.).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2004-43598

[0010] Patent Document 2: Japanese Patent Application Publication No. 2004-277443

[0011] Patent Document 3: Japanese Patent Application Publication No. 2011-026392 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] The carbon black compounded in the aforementioned tire tread rubber composition is required to have a dibutyl phthalate (DBP) absorption of 40-180 mL / 100 g and a nitrogen adsorption specific surface area (N2SA) of 40-190 m². 2 / g, toluene color transmittance (LT) is over 90%.

[0014] As mentioned above, furnace black manufacturing methods, acetylene black manufacturing methods, and cellar black manufacturing methods are generally known. Among them, the furnace black manufacturing method is known as a manufacturing method that can produce carbon black in large quantities and is economically efficient.

[0015] The furnace method described above is known as follows: using liquid feedstock oils such as heavy oils and / or natural gas as raw materials, the carbon black is produced by thermally decomposing them in an oxygen-deficient state in a refractory furnace.

[0016] On the other hand, with the increasing environmental awareness in recent years, various manufacturing industries require methods to reduce carbon dioxide (CO2) emissions. In the aforementioned furnace process using hydrocarbons as raw materials, there is also a requirement to reduce carbon dioxide (CO2) emissions.

[0017] However, the inventors conducted research and determined that in the above-mentioned furnace method, when it is desired to limit the amount of fuel supplied to the fuel combustion zone to reduce the emission of carbon dioxide (CO2), it is impossible to raise the obtained combustion gas flow to the desired temperature, and it is impossible to produce the target carbon black in high yield.

[0018] Under such circumstances, the object of the present invention is to provide a method for producing carbon black with desired properties in a furnace process by reducing the emission of carbon dioxide (CO2) and producing it in a high yield, as well as a reaction furnace for producing carbon black.

[0019] Solution for solving the problem

[0020] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that the above-mentioned technical problems could be solved by using the following method for manufacturing carbon black. Based on this discovery, the present invention was completed.

[0021] In the method described, a carbon black manufacturing reactor is used, which is provided with a fuel combustion zone, a primary raw material introduction zone, a heating zone, and a secondary raw material introduction zone arranged sequentially from upstream to downstream of the gas flow path.

[0022] Oxygen-containing gas and fuel are introduced into the fuel combustion zone, where they are mixed and combusted to generate a fuel combustion gas stream. Simultaneously, hydrocarbons, serving as primary feedstock, are introduced into the primary feedstock introduction zone to generate a gas containing primary reactants. The gas containing primary reactants is then electrically heated in the heating zone. Next, the electrically heated gas containing primary reactants is introduced into the secondary feedstock introduction zone, while hydrocarbons, serving as secondary feedstock, are introduced to carry out a secondary reaction.

[0023] That is, the present invention provides:

[0024] (1) A method for manufacturing carbon black, characterized in that a carbon black manufacturing reactor is used, which is provided with a fuel combustion zone, a primary raw material introduction zone, a heating zone and a secondary raw material introduction zone in sequence from upstream to downstream of the gas flow path.

[0025] Oxygen-containing gas and fuel are introduced into the fuel combustion zone, where they are mixed and combusted to generate a fuel combustion gas stream. This fuel combustion gas stream is then introduced into the primary feedstock introduction zone, along with hydrocarbons as primary feedstock, to generate a gas containing primary reactants. This gas is then electrically heated in the heating zone. Following this...

[0026] The electrically heated gas containing the primary reactants is introduced into the secondary feedstock introduction zone, along with hydrocarbons as secondary feedstock, to initiate a secondary reaction.

[0027] (2) According to the carbon black manufacturing method described in (1) above, wherein the dibutyl phthalate (DBP) absorption is 40~180mL / 100g and the nitrogen adsorption specific surface area (N2SA) is 40~190m². 2 Carbon black with a toluene color transmittance (LT) of over 90% per gram.

[0028] (3) A reactor for carbon black manufacturing, characterized in that a fuel combustion zone, a primary raw material introduction zone, a heating zone, and a secondary raw material introduction zone are sequentially arranged from upstream to downstream of the gas flow path.

[0029] The fuel combustion zone is the area where oxygen-containing gas and fuel are introduced, mixed, and combusted to generate a fuel combustion gas flow.

[0030] The primary feedstock introduction zone is the area where hydrocarbons, as primary feedstocks, are introduced simultaneously with the fuel combustion gas stream to generate a gas containing primary reactants.

[0031] The heating zone is the area where the gas containing the primary reactant is electrically heated.

[0032] The secondary raw material introduction area is a region in which a secondary reaction is carried out by introducing a gas containing the primary reactants after electric heating, along with hydrocarbons as secondary raw materials.

[0033] The effects of the invention

[0034] According to the present invention, a carbon black manufacturing reactor is proposed to be used, in which a fuel combustion zone, a primary feedstock introduction zone, a heating zone, and a secondary feedstock introduction zone are sequentially arranged from upstream to downstream of the gas flow path. Hydrocarbons, serving as primary feedstock, are introduced into the primary feedstock introduction zone, and a portion of them are thermally decomposed to generate primary reactants (carbon nuclei) that serve as precursors. Based on this, the generated gas containing the primary reactants is heated in the heating zone by electric heating. This reduces the emission of carbon dioxide (CO2) and appropriately generates a gas containing sufficient primary reactants (carbon nuclei) that are the precursors obtained from the thermal decomposition of the remaining portion of the primary feedstock. Furthermore, in the secondary feedstock introduction zone, by simultaneously introducing hydrocarbons, which are secondary feedstock, into the gas containing the primary reactants, primary particles that increase the particle size of the primary reactants (carbon nuclei) can be formed using the thermal decomposition products of the secondary feedstock. A secondary reaction then occurs, forming aggregates of these primary particles linked in a beaded chain structure. This allows for the convenient and continuous production of carbon black with desired properties in high yield.

[0035] Therefore, according to the present invention, it is possible to provide a method for producing carbon black with desired properties in a furnace process that reduces the emission of carbon dioxide (CO2) and produces carbon black with a high yield in a furnace process that uses primary and secondary raw materials together as raw hydrocarbons, and a reaction furnace for producing carbon black that can be used in the method. Attached Figure Description

[0036] Figure 1 This is a schematic diagram showing the cross-section of a reactor used for carbon black manufacturing.

[0037] Figure 2 This is a schematic diagram showing the cross-section of a conventionally used reactor for carbon black manufacturing. Detailed Implementation

[0038] First, the method for manufacturing carbon black according to the present invention will be described.

[0039] The carbon black manufacturing method of the present invention is characterized by using a carbon black manufacturing reactor that has a fuel combustion zone, a primary raw material introduction zone, a heating zone, and a secondary raw material introduction zone arranged sequentially from upstream to downstream of the gas flow path.

[0040] Oxygen-containing gas and fuel are introduced into the fuel combustion zone, where they are mixed and combusted to generate a fuel combustion gas stream. Simultaneously, hydrocarbons, serving as primary feedstock, are introduced into the primary feedstock introduction zone to generate a gas containing primary reactants. This gas is then electrically heated in the heating zone.

[0041] A secondary reaction is carried out by introducing the electrically heated gas containing the primary reactants into the secondary raw material introduction area, while simultaneously introducing hydrocarbons as secondary raw materials.

[0042] In the carbon black manufacturing method of the present invention, the reactor for carbon black manufacturing is provided with a fuel combustion zone, a primary raw material introduction zone, a heating zone and a secondary raw material introduction zone arranged sequentially from upstream to downstream of the gas flow direction (gas flow path) in the furnace.

[0043] As the aforementioned reactor for carbon black manufacturing, the gas flow path preferably has the gas flowing in a roughly unidirectional direction from upstream to downstream.

[0044] Examples of such reactors for carbon black manufacturing include, for instance... Figure 1 The figure schematically shows an example of its cross-sectional shape. In the figure, in the carbon black manufacturing reactor 1, a fuel combustion zone 3, a primary raw material introduction zone 5, a heating zone 8 and a secondary raw material introduction zone 9 are arranged sequentially from upstream to downstream of the gas flow path 20 formed in the furnace.

[0045] The following is based on Figure 1 The shown carbon black manufacturing reactor is a suitable example to illustrate the method for manufacturing carbon black according to the present invention.

[0046] In the carbon black manufacturing method of the present invention, oxygen-containing gas and fuel are introduced into the fuel combustion zone 3, and they are mixed and burned to generate a fuel combustion gas flow.

[0047] As the oxygen-containing gas mentioned above, gases composed of oxygen, air, or mixtures thereof can be cited. As the fuel mentioned above, one or more of the following can be cited: hydrogen, carbon monoxide, FCC residue oil, petroleum-based liquid fuels such as heavy oil and coal-based liquid fuels such as creosote oil, hydrocarbon gases such as methane, ethane, propane, natural gas, petroleum gas, ethylene, acetylene, mixtures thereof, and gases produced during the thermal decomposition of rubber and / or plastics.

[0048] In the carbon black manufacturing method of the present invention, when air is used as the oxygen-containing gas, the air supply amount is preferably 5 to 20 Nm relative to the total supply amount of 1 kg of primary and secondary raw materials described later. 3 More preferably 6~18 Nm 3 More preferably 7~15Nm3 .

[0049] In the fuel combustion zone 3, for example, oxygen-containing gas preheated to 400°C to 600°C can be supplied while fuel is supplied, so that the two are mixed and burned to generate a high-temperature combustion gas flow.

[0050] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the example, the fuel combustion zone 3 is provided with an oxygen gas inlet 31 for introducing oxygen-containing gas such as air and a combustion burner 32 for supplying fuel. Oxygen-containing gas and fuel are introduced into the fuel combustion zone 3 respectively, and they are mixed and burned, thereby generating a fuel combustion gas flow.

[0051] In the carbon black manufacturing method of the present invention, hydrocarbons as primary raw materials are introduced into the primary raw material introduction zone 5 at the same time as the fuel combustion gas flow generated in the fuel combustion zone 3.

[0052] In the carbon black manufacturing method of the present invention, the hydrocarbons used as primary raw materials can be gaseous fuels (gaseous hydrocarbons) or fuels with high molecular weights (hydrocarbons with high molecular weights). Here, gaseous fuels refer to fuels that are gaseous under standard conditions (25°C, 1 atm), and fuels with high molecular weights refer to fuels with a molecular weight of 70 or more as determined by GC-TOF / MS in the following measurements.

[0053] (Methods for determining molecular weight)

[0054] The molecular weight was determined using GC-TOF / MS under the following apparatus and conditions.

[0055] Measuring device

[0056] JMS-T200GC (Japanese Electronics Manufacturing)

[0057] Measurement conditions

[0058] Inlet temperature: 280℃

[0059] Carrier gas: Helium

[0060] Column: BPX-5

[0061] Ionization method: EI method

[0062] Ionization voltage: 70 eV

[0063] Ionization current: 300µA

[0064] Examples of gaseous fuels include one or more selected from hydrocarbon gases such as methane, ethane, propane, natural gas, petroleum gas, ethylene, and acetylene, mixtures thereof, and gases produced during the thermal decomposition of rubber and / or plastics.

[0065] In addition, as fuels with large molecular weights, one or more of the following can be selected: aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and anthracene; coal-based hydrocarbons such as creosote oil, tar, and carboxylic acid oil; petroleum-based heavy oils such as ethylene heavy oil and FCC residue oil; acetylene-based unsaturated hydrocarbons; ethylene-based hydrocarbons; aliphatic saturated hydrocarbons such as pentane and / or hexane; vegetable oils such as rapeseed oil and soybean oil; and oils produced from the thermal decomposition of rubber and / or plastics. From the perspective of various properties of the carbon black produced by appropriate preparation, benzene, toluene, xylene, naphthalene, anthracene, creosote oil, carboxylic acid oil, ethylene heavy oil, and FCC residue oil are preferred.

[0066] In this invention, the primary raw material can be obtained by mixing two or more of the aforementioned hydrocarbons.

[0067] In this invention, the hydrocarbon used as a primary feedstock preferably contains fuel with a large molecular weight. By including fuel with a large molecular weight in the hydrocarbon used as a primary feedstock, it is easy to generate a gas containing primary reactants (carbon nuclei) that become precursors during thermal decomposition.

[0068] In the carbon black manufacturing method of the present invention, when air is used as the oxygen-containing gas, under standard conditions (25°C, 1 atm), relative to the aforementioned air 1 Nm 3 The amount of primary raw material introduced in the primary raw material introduction area 5 is preferably 0.01~5.00 kg, more preferably 0.02~4.90 kg, and even more preferably 0.03~4.80 kg.

[0069] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the example, a primary raw material introduction zone 5 is provided in communication with the fuel combustion zone 3, and primary raw material is introduced from the primary raw material introduction nozzle 4 which supplies primary raw material along the furnace axis.

[0070] As the aforementioned primary material inlet nozzle 4, a single-fluid nozzle can be cited as an example.

[0071] Preferably, the primary raw material that is solid at room temperature is appropriately heated to make it into a liquid or gaseous state, and then the primary raw material is introduced into the primary raw material inlet nozzle 4.

[0072] In the carbon black manufacturing method of the present invention, by introducing hydrocarbons as primary raw materials into the primary raw material introduction zone 5 at the same time as introducing fuel combustion gas stream generated in the fuel combustion zone 3, a gas containing primary reactants (carbon nuclei) that have been partially thermally decomposed into precursors can be generated.

[0073] The gas containing the primary reactants generated above is electrically heated in heating zone 8.

[0074] In the carbon black manufacturing method of the present invention, electric heating can include resistance heating, induction heating, dielectric heating, etc. Specifically, one or more methods selected from heating using an electric heater, electromagnetic induction heating, microwave heating, etc., can be used.

[0075] In the carbon black manufacturing method of the present invention, the heating temperature in the heating zone 8 is preferably 1000~2000℃, more preferably 1100~1900℃, and even more preferably 1200~1800℃.

[0076] In the carbon black manufacturing method of the present invention, the heating time in the heating zone 8 can be appropriately adjusted so as to generate a gas containing primary reactants (carbon nuclei) by the primary thermal decomposition of the raw material introduced into the heating zone 8.

[0077] The heating time in heating zone 8 can be controlled by adjusting the flow path length of heating zone 8 (the length of the path for the fuel combustion gas flow and the primary raw material flow in heating zone 8) and / or the flow rate of the fuel combustion gas flow and the primary raw material in heating zone 8.

[0078] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the morphological example, the furnace wall 21 of the heating zone 8 in the furnace wall 2 is formed of a constituent material with high thermal conductivity compared with the furnace wall of other zones. Heat can be conducted to the inner surface of the furnace wall 21 by heating the outer surface of the furnace wall 21, thereby heating the furnace.

[0079] Examples of methods for heating the furnace wall 21 include electric heaters, electromagnetic induction heating, and microwave heating.

[0080] Alternatively, the primary reactants introduced into the heating region 8 can be heated by dielectric heating. Examples of dielectric heating methods include microwave heating.

[0081] In the carbon black manufacturing method of the present invention, by electrically heating in the heating zone 8 while generating a fuel combustion gas flow in the fuel combustion zone 3, the emission of carbon dioxide (CO2) can be reduced and the hydrocarbons used as primary raw materials can be appropriately thermally decomposed to generate primary reactants (carbon nuclei) with appropriate particle size. Furthermore, the structure can be controlled in the secondary reaction described later, and the target carbon black can be easily manufactured.

[0082] In the carbon black manufacturing method of the present invention, when carbon black is manufactured by heating only the fuel combustion gas flow generated in the fuel combustion zone 3 without electric heating in the heating zone 8 (using high-temperature fuel combustion gas), the resulting carbon black is micronized, making it difficult to obtain carbon black with the desired nitrogen adsorption specific surface area (N2SA).

[0083] Furthermore, in the carbon black manufacturing method of the present invention, it is difficult to generate carbon black when carbon black is manufactured only by electric heating in the heating zone 8 without generating a fuel combustion gas flow in the fuel combustion zone 3.

[0084] According to the carbon black manufacturing method of the present invention, a carbon black manufacturing reactor 1 is used, which is provided in sequence from upstream to downstream of the gas flow path as a fuel combustion zone 3, a primary raw material introduction zone 5, a heating zone 8 and a secondary raw material introduction zone 9. Based on the primary raw material being introduced into the primary raw material introduction zone 5, the generated gas containing primary reactants is heated in the heating zone 8 by electric heating, thereby reducing the emission of carbon dioxide (CO2) and appropriately generating gas containing primary reactants (carbon nuclei).

[0085] In the carbon black manufacturing method of the present invention, a hydrocarbon as a secondary raw material is introduced into the secondary raw material introduction zone 9 at the same time as the gas containing the primary reactants generated in the heating zone 8, and a secondary reaction is carried out.

[0086] In the carbon black manufacturing method of the present invention, the hydrocarbons used as secondary raw materials can be gaseous fuels (gaseous hydrocarbons) or fuels with high molecular weights (hydrocarbons with high molecular weights). Here, gaseous fuels refer to fuels that are gaseous under standard conditions (25°C, 1 atm), and fuels with high molecular weights refer to fuels with a molecular weight of 70 or more as determined by GC-TOF / MS.

[0087] Examples of gaseous fuels include one or more selected from hydrocarbon gases such as methane, ethane, propane, natural gas, petroleum gas, ethylene, and acetylene, mixtures thereof, and gases produced during the thermal decomposition of rubber and / or plastics.

[0088] In addition, as fuels with large molecular weights, one or more of the following can be cited: aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and anthracene; coal-based hydrocarbons such as creosote oil, tar, and carboxylic acid oil; petroleum-based heavy oils such as FCC residue oil and ethylene heavy oil; acetylene-based unsaturated hydrocarbons; ethylene-based hydrocarbons; aliphatic hydrocarbons such as pentane and / or hexane; vegetable oils such as rapeseed oil and soybean oil; and oils produced from the thermal decomposition of rubber and / or plastics.

[0089] In the carbon black manufacturing method of the present invention, as a secondary raw material, a gaseous fuel is preferred in terms of appropriately adjusting the various properties of the generated carbon black, and in particular, one or more hydrocarbon gases selected from methane, ethane, propane, natural gas, petroleum gas, ethylene, acetylene, etc. are preferred.

[0090] In the carbon black manufacturing method of the present invention, the amount of secondary raw material introduced into the secondary raw material introduction area 9 is preferably 0.10 to 5.00 times by mass, more preferably 0.15 to 4.95 times by mass, and even more preferably 0.20 to 4.90 times by mass, relative to the amount of primary raw material introduced into the primary raw material introduction area 5.

[0091] In the carbon black manufacturing method of the present invention, by ensuring that the amount of secondary raw material introduced into the secondary raw material introduction zone 9 is within the above-mentioned range relative to the amount of primary raw material introduced into the primary raw material introduction zone 5, carbon black with desired characteristics can be easily manufactured.

[0092] In the carbon black manufacturing method of the present invention, the secondary raw material is introduced into the secondary raw material introduction zone 9 at the same time as the gas containing the primary reactant generated in the heating zone 8, and the secondary raw material is thermally decomposed to carry out a secondary reaction while the two are circulating in the furnace.

[0093] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the example, a secondary raw material introduction area 9 is provided coaxially with the primary raw material introduction area 5. The secondary raw material introduction area 9 supplies secondary raw materials from the secondary raw material introduction nozzle 6, which supplies secondary raw materials in a direction perpendicular to the furnace axis.

[0094] As the secondary material introduction nozzle 6 mentioned above, a single-fluid nozzle can be cited as an example.

[0095] The secondary raw material, which is solid at room temperature, is appropriately heated to become liquid or gaseous and then introduced into the secondary raw material inlet nozzle 6.

[0096] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the morphological example, the secondary raw material introduced into the secondary raw material introduction area 9 undergoes a secondary reaction in the reaction area 10, which is thermally decomposed while flowing along the furnace axis.

[0097] According to the carbon black manufacturing method of the present invention, a carbon black manufacturing reactor is used, which is provided in sequence from upstream to downstream of the gas flow path as a fuel combustion zone 3, a primary raw material introduction zone 5, a heating zone 8, and a secondary raw material introduction zone 9. By introducing a gas containing primary reactants (carbon nuclei) obtained from the heating zone 8 into the secondary raw material introduction zone 9, hydrocarbons as secondary raw materials can be introduced simultaneously. This allows the primary reactant (carbon nuclei) particles to grow in size using the thermal decomposition products of the secondary raw materials to form primary particles. A secondary reaction is then carried out to form an aggregate with a chain-like structure in which multiple primary particles are linked together in a bead-like manner. This allows carbon black with desired properties to be easily manufactured with a high yield.

[0098] In the carbon black manufacturing method of the present invention, the reaction is appropriately stopped after the target carbon black is generated.

[0099] exist Figure 1 In the carbon black manufacturing reactor 1 shown in the example, a reaction stop zone 11 is also provided coaxially with the reaction zone 10. In the reaction stop zone 11, a coolant inlet nozzle 7 is provided in a direction perpendicular to the furnace axis. The reaction can be stopped by spraying coolant from the coolant inlet nozzle 7.

[0100] Water or similar liquids can be used as coolants to cool carbon black particles suspended in high-temperature combustion gases by spraying the coolant.

[0101] After cooling, the carbon black particles pass through flues and other channels, and are separated and collected by collection systems (separation and collection devices) such as cyclone separators and bag filters, thereby enabling the recovery of the target carbon black.

[0102] In the carbon black manufacturing method of the present invention, the reactor used for carbon black manufacturing is not limited to [specific type]. Figure 1 The shape shown can take various forms.

[0103] The dibutyl phthalate (DBP) absorption of the carbon black obtained by the manufacturing method of the present invention is preferably 40~180mL / 100g, more preferably 55~175mL / 100g, and even more preferably 70~170mL / 100g.

[0104] The DBP uptake mentioned above is an indicator of the degree of development of the structure, that is, the complexity of the aggregate structure.

[0105] The carbon black obtained by the manufacturing method of the present invention has a dibutyl phthalate (DBP) absorption amount within the above-mentioned range, and can appropriately exert the desired tensile stress and elongation when, for example, it is blended into a rubber composition for tire tread.

[0106] It should be noted that in this application document, the DBP absorption refers to the value determined by the method specified in JISK6217-4 "Carbon black for rubber - basic properties - Part 4, method for determining DBP absorption".

[0107] The nitrogen adsorption specific surface area (N2SA) of the carbon black obtained by the manufacturing method of the present invention is preferably 40 to 190 m². 2 / g, more preferably 55~180m 2 / g, further preferably 70~170m 2 / g.

[0108] The carbon black obtained by the manufacturing method of the present invention, when mixed with N2SA within the above-mentioned range, can appropriately exhibit the desired tensile strength and abrasion resistance when incorporated into a rubber composition for tire tread.

[0109] It should be noted that in this application document, N2SA refers to the value determined by nitrogen adsorption using the method specified in JIS K6217-2 2001 "Test methods for basic properties of carbon black for rubber".

[0110] The carbon black obtained by the manufacturing method of the present invention has a toluene color transmittance (LT) of preferably 90% or more, more preferably 93% or more, and even more preferably 95% or more.

[0111] The carbon black obtained by the manufacturing method of the present invention has a toluene color transmittance (LT) within the above-mentioned range, which can suppress the tar components, especially aromatic components, on the surface of the carbon black, and can appropriately exert the desired wear resistance when it is compounded into a rubber composition for tire tread.

[0112] It should be noted that in this application document, the toluene color transmittance (LT) refers to the value determined by JISK6218 "Test methods for incidental properties of carbon black for rubber, 8 Toluene color transmittance method A".

[0113] In the carbon black manufacturing method of the present invention, in the furnace process using secondary raw materials as raw hydrocarbons, a method can be provided to reduce carbon dioxide (CO2) emissions and produce carbon black with desired properties in high yield.

[0114] Next, the reaction furnace for manufacturing carbon black according to the present invention will be described.

[0115] The reactor for carbon black manufacturing of the present invention is characterized in that, from upstream to downstream of the gas flow path, a fuel combustion zone, a primary raw material introduction zone, a heating zone, and a secondary raw material introduction zone are sequentially arranged.

[0116] The fuel combustion zone is the area where oxygen-containing gas and fuel are introduced, mixed, and combusted to generate a fuel combustion gas flow.

[0117] The primary feedstock introduction zone is the region where hydrocarbons, serving as primary feedstock, are introduced simultaneously with the fuel combustion gas stream to generate a gas containing primary reactants.

[0118] The heating zone is the area where the gas containing the primary reactant is electrically heated.

[0119] The secondary raw material introduction area is a region where the electrically heated gas containing the primary reactants is introduced, along with hydrocarbons as secondary raw materials, to carry out a secondary reaction.

[0120] The details of the reactor for manufacturing carbon black according to the present invention are as described in the description of the method for manufacturing carbon black according to the present invention. As a specific example, the above-described reactor 1 for manufacturing carbon black can be cited.

[0121] The reactor for carbon black manufacturing of the present invention is suitable for use in the carbon black manufacturing method of the present invention.

[0122] According to the present invention, a reactor for manufacturing carbon black can be provided, which is used in a furnace process with secondary raw materials as feedstock hydrocarbons, and can reduce the emission of carbon dioxide (CO2) and produce carbon black with desired properties in high yield.

[0123] The present invention will now be described in more detail by way of examples, but these are merely illustrative and do not limit the scope of the invention.

[0124] Example

[0125] (Examples 1-9)

[0126] Use with Figure 1 Carbon black is produced in a roughly cylindrical reactor 1, as shown in the mid-section view.

[0127] exist Figure 1 The reactor shown has a fuel combustion zone 3, a primary feedstock introduction zone 5, a heating zone 8, a secondary feedstock introduction zone 9, a reaction zone 10, and a reaction stop zone 11 arranged sequentially from upstream to downstream of the gas flow path 20 formed in the furnace.

[0128] exist Figure 1 In the carbon black manufacturing reactor 1 shown, the fuel combustion zone 3 is equipped with an oxygen gas inlet 31 for introducing oxygen-containing gases such as air and a combustion burner 32 for supplying fuel.

[0129] In addition, the primary raw material introduction zone 5 is provided with a primary raw material introduction nozzle 4, i.e. a single-fluid nozzle, which supplies primary raw materials along the furnace axis and is connected to the fuel combustion zone 3.

[0130] The heating zone 8 has a furnace wall 21 made of a material with high thermal conductivity compared to the furnace wall 2 of other parts, and is configured such that heat is conducted to the inner surface of the furnace wall 21 by electrically heating the outer surface of the furnace wall 21, thereby heating the furnace interior.

[0131] The secondary raw material introduction zone 9 is provided with a secondary raw material introduction nozzle 6, i.e., a single-fluid nozzle, in a direction perpendicular to the furnace axis, and is coaxially connected to the heating zone 8. Furthermore, the reaction zone 10 is coaxially connected to the secondary raw material introduction zone 9. In addition, the reaction stopping zone 11 is provided with a coolant introduction nozzle 7 (water-cooled quenching) that supplies coolant in a direction perpendicular to the furnace axis and can be repositioned in the vertical direction shown in the figure, and is coaxially connected to the reaction zone 10.

[0132] In Examples 1 to 9, each carbon black was manufactured using a carbon black manufacturing reactor 1 as follows.

[0133] First, in the fuel combustion zone 3, air preheated to 500°C (oxygen content 21% by volume) is supplied from the oxygen-containing gas inlet 31 in the manner shown in Table 1, and city gas (gas type 13A) is injected from the combustion burner 32 in the manner shown in Table 1 as fuel, so that they are mixed and burned to form a high-temperature combustion gas flow circulating in the furnace.

[0134] While introducing the high-temperature combustion gas stream into the primary raw material introduction zone 5, naphthalene (molecular weight 128) as a primary raw material is supplied from the primary raw material introduction nozzle 4, i.e., the single-fluid nozzle, in the manner shown in Table 1. Then, the high-temperature combustion gas stream and the primary raw material are introduced into the heating zone 8.

[0135] In heating zone 8, the outer surface of furnace wall 21 is electrically heated at 1200~1400°C using an electric heater, thereby heating the furnace interior at the electric heating temperatures shown in Table 1 to fully generate gas containing primary reactants.

[0136] Next, while introducing gas containing the primary reactants into the secondary feedstock introduction zone 9, city gas (gas type 13A) is supplied from the secondary feedstock introduction nozzle 6 at the amounts shown in Table 1. After the secondary reaction is fully carried out in the reaction zone 10, the mixture is introduced into the reaction stop zone 11, where cooling water is sprayed from the coolant introduction nozzle 7. The cooled carbon black particles are then collected by a separation and collection device (not shown) through a flue, etc., to recover the target carbon black.

[0137] Based on the partial pressure of the gas in the latter part of the reaction zone 10 (the part just before reaching the reaction stop zone 11), the proportions (volume %) of H2, CO2, and CO in the furnace after the secondary reaction were calculated. The results are shown in Table 1.

[0138] In addition, the nitrogen adsorption specific surface area N2SA (m²) of each carbon black was measured. 2The absorbance of dibutyl phthalate (DBP) (mL / 100g) and the toluene color transmittance LT (%) were measured. The results are shown in Table 2.

[0139] Then, the amount of carbon black (CB) produced (kg) and the amount of CO2 produced (m³) were calculated. 3 ), calculate the CO2 production / CB production (m 3 / kg).

[0140] The results are shown in Table 2.

[0141] (Comparative Examples 1 to 10)

[0142] Use with Figure 2 Carbon black is produced in a roughly cylindrical reactor 1A, as shown in the mid-section view.

[0143] Figure 2 The carbon black manufacturing reactor 1A shown does not have a furnace wall 21 made of a highly thermally conductive material, and it does not have a heating zone 8. Apart from this, its structure, furnace dimensions, etc., are similar to... Figure 1 The shown carbon black manufacturing reactor 1 is common.

[0144] exist Figure 2 In the various parts of the carbon black manufacturing reactor 1A shown, for those related to... Figure 1 The areas or components common to the carbon black manufacturing reactor 1 shown are labeled with the same as those shown. Figure 1 The common symbol number for the carbon black manufacturing reactor 1 shown.

[0145] In Comparative Examples 1 to 10, each carbon black was manufactured using a carbon black manufacturing reactor 1A as follows.

[0146] First, in the fuel combustion zone 3, air preheated to 500°C (oxygen content 21% by volume) is supplied from the oxygen-containing gas inlet 31 in the manner shown in Table 3, and city gas (gas type 13A) is injected from the combustion burner 32 in the manner shown in Table 3 as fuel, so that they are mixed and burned to form a high-temperature combustion gas flow in the furnace.

[0147] While introducing the aforementioned high-temperature combustion gas flow into the primary raw material inlet area 5, naphthalene (molecular weight 128) as a primary raw material is supplied from the primary raw material inlet nozzle 4, i.e., the single-fluid nozzle, in the manner shown in Table 3.

[0148] It should be noted that in Comparative Example 1, the initial raw material supply was 0 kg / h (no initial raw material was supplied).

[0149] Next, while introducing gas containing the primary reactants into the secondary feedstock introduction zone 9, city gas (gas type 13A) is supplied from the secondary feedstock introduction nozzle 6 at the amounts shown in Table 3. After the secondary reaction is fully carried out in the reaction zone 10, the mixture is introduced into the reaction stop zone 11, where cooling water is sprayed from the coolant introduction nozzle 7. The cooled carbon black particles are then collected by a separation and collection device (not shown) through a flue, etc., and the target carbon black is recovered.

[0150] It should be noted that no carbon black was obtained in Comparative Example 1.

[0151] Based on the partial pressure of the gas in the latter part of the reaction zone 10 (the part just before reaching the reaction stop zone 11), the proportions (volume %) of H2, CO2, and CO in the furnace after the secondary reaction were calculated. The results are shown in Table 3.

[0152] In addition, the nitrogen adsorption specific surface area N2SA (m²) of each carbon black was measured. 2 The absorbance of dibutyl phthalate (DBP) (mL / 100g) and the toluene color transmittance LT (%) were measured. The results are shown in Table 4.

[0153] Then, the amount of carbon black (CB) produced (kg) and the amount of CO2 produced (m³) were calculated. 3 ), calculate the CO2 production / CB production (m 3 / kg).

[0154] The results are shown in Table 4.

[0155] [Table 1]

[0156]

[0157] [Table 2]

[0158]

[0159] [Table 3]

[0160]

[0161] [Table 4]

[0162]

[0163] Examples 1 to 9 use a carbon black manufacturing reactor 1, which is provided with a fuel combustion zone 3, a primary raw material introduction zone 5, a heating zone 8, and a secondary raw material introduction zone 9 in a sequential manner from upstream to downstream of the gas flow path 20. Oxygen-containing gas and fuel are introduced into the fuel combustion zone 3 and mixed and burned to generate a fuel combustion gas flow. Primary raw materials are introduced into the primary raw material introduction zone 5 at the same time as the fuel combustion gas flow to generate a gas containing primary reactants. The gas containing primary reactants is electrically heated in the heating zone 8. Then, secondary raw materials are introduced into the secondary raw material introduction zone 9 at the same time as the gas containing primary reactants to carry out a secondary reaction to produce carbon black.

[0164] Therefore, as shown in Tables 1 and 2, in the furnace process using secondary raw materials as hydrocarbon feedstocks in Examples 1 to 9, the CO2 production per unit of carbon black (CB) (CO2 production / CB production) is as low as 0.76~1.43m³. 3 / kg, which can produce carbon black while reducing carbon dioxide (CO2) emissions.

[0165] In addition, as shown in Table 1, the amount of H2 generated after the secondary reaction in Examples 1 to 9 is as high as 13.2 to 21.5 vol%, which can effectively thermally decompose the primary and secondary raw materials to produce carbon black in high yield.

[0166] Furthermore, as shown in Table 2, Examples 1 to 9 can produce nitrogen adsorption specific surface areas (N2SA) of 41 to 190 m². 2 Carbon black with excellent properties including a phthalate (DBP) absorption of 45~180mL / 100g and a toluene color transmittance (LT) of 96~99%.

[0167] On the other hand, as can be seen from Tables 3 and 4, in the relationship between Comparative Example 1 and Examples 1 to 9, no primary raw material was supplied in the primary raw material introduction zone 5 and no electric heating was performed in the heating zone 8, so carbon black could not be obtained.

[0168] Furthermore, as shown in Table 4, in the relationship between Comparative Examples 2 to 10 and Examples 1 to 9, no electric heating was performed in the heating zone. Therefore, the CO2 production per unit of carbon black (CB) (CO2 production / CB production) was high, and the amount of carbon dioxide (CO2) emitted could not be reduced during the carbon black manufacturing process.

[0169] Furthermore, as shown in Table 3, in the relationship between Comparative Examples 2 to 10 and Examples 1 to 9, no electric heating was performed in the heating zone, so the thermal decomposition of the primary and secondary raw materials was lower, the amount of H2 generated after the secondary reaction was lower, and therefore the yield of carbon black was poor.

[0170] Furthermore, as shown in Table 4, in the relationship between Comparative Examples 2 to 10 and Examples 1 to 9, no electric heating was performed in the heating zone, so only carbon black with a toluene color transmittance LT as low as 1 to 43% could be obtained.

[0171] Industrial availability

[0172] According to the present invention, it is possible to provide a method for reducing the emission of carbon dioxide (CO2) and producing carbon black with desired properties in a high yield in a furnace process using secondary raw materials as feedstock hydrocarbons, and a reaction furnace for carbon black manufacturing suitable for use in the method.

[0173] Explanation of reference numerals in the attached figures

[0174] 1.1A Reactor for Carbon Black Manufacturing

[0175] 2 Furnace wall

[0176] 21 Furnace wall in the heating zone

[0177] 3. Fuel Combustion Zone

[0178] 31 Oxygen-containing gas inlet

[0179] 32 Combustion burner

[0180] 4. Primary raw material inlet nozzle

[0181] 5. Primary raw material introduction area

[0182] 6 Secondary material inlet nozzle

[0183] 7. Coolant inlet nozzle

[0184] 8 Heating Zones

[0185] 9. Secondary raw material introduction area

[0186] 10 Reaction Zone

[0187] 11. Reaction Stoppage Region

[0188] 20 Gas Flow Path

Claims

1. A method for producing carbon black, characterized by, A carbon black manufacturing reaction furnace in which a fuel combustion region, a primary raw material introduction region, a heating region, and a secondary raw material introduction region are provided in this order from the upstream to the downstream of a gas flow path, An oxygen-containing gas and a fuel are introduced into the fuel combustion region, mixed, and combusted to generate a fuel combustion gas stream, the fuel combustion gas stream is introduced into the primary raw material introduction region, and a hydrocarbon as a primary raw material is introduced to generate a gas containing a primary reactant, the gas containing the primary reactant is electrically heated in the heating region, and then, The electrically heated gas containing the primary reactant is introduced into the secondary raw material introduction region, and a hydrocarbon as a secondary raw material is introduced to perform a secondary reaction.

2. The method for producing carbon black according to claim 1, wherein to obtain carbon black having dibutyl phthalate (DBP) absorption of 40 to 180 mL / 100 g, nitrogen adsorption specific surface area (N2SA) of 40 to 190 m 2 / g, and toluene color transmission (LT) of 90% or more.

3. A reaction furnace for manufacturing carbon black, characterized by comprising: A fuel combustion region, a primary raw material introduction region, a heating region, and a secondary raw material introduction region are provided in this order from the upstream to the downstream of a gas flow path, The fuel combustion region is a region in which an oxygen-containing gas and a fuel are introduced, mixed, and combusted to generate a fuel combustion gas stream, The primary raw material introduction region is a region in which a hydrocarbon as a primary raw material is introduced while the fuel combustion gas stream is introduced to generate a gas containing a primary reactant, The heating region is a region in which the gas containing the primary reactant is electrically heated, The secondary raw material introduction region is a region in which a hydrocarbon as a secondary raw material is introduced while the gas containing the primary reactant is introduced to perform a secondary reaction.

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