JP5697304B2 - Production method of carbon black - Google Patents

Description

  The present invention relates to a method for producing carbon black, which can simultaneously satisfy high abrasion resistance and excellent low heat buildup, which are preferable as a rubber composition for tire treads when blended with a rubber component.

  Carbon black is produced by spraying raw material hydrocarbons into a high-temperature combustion gas generated in a furnace and / or externally generated and introduced into the furnace under strictly controlled conditions. It is a raw material composed of industrially useful almost pure carbon elements produced by thermal decomposition or incomplete combustion of the material, and mechanical properties, especially tensile strength, wear resistance, etc. for the composition when rubber is compounded Because it has a unique property that can dramatically improve the characteristics of, it is not only widely used as a filling reinforcing agent for various rubber products including tires, and has been used for a long period of about 100 years, It is also used as a raw material for various paints and inks by utilizing the blackness that is its color feature.

  Carbon black for rubber compounding depends on its physicochemical properties, that is, the unit particle diameter, the surface area per unit weight (specific surface area), the degree of particle connection (structure), surface properties, etc. Carbon black with different characteristics is selectively used depending on the required performance of the rubber product, the environment in which it is used, etc., since it has a great influence on the specific and performance.

  The rubber composition used for the ground contact surface (tread portion) of the tire is excellent in resistance to abrasion (abrasion resistance) because it contacts the road surface while rotating at a high speed. Hysteresis characteristics that have a large effect on the heat generation characteristics of the rubber composition due to repeated deformation caused by the contact are also important factors. In addition, elongation characteristics that greatly affect the fatigue resistance and cut resistance of the rubber composition due to repeated deformation from the road surface to the tire are also important factors. It is known that these three characteristics are contradictory to each other, that is, when one characteristic is improved, the other characteristic is degraded, and this resolution or high-level compromise is a major issue.

  When carbon black with a tire tread compound is used to improve the abrasion resistance of the rubber composition, for example, when a carbon black having a larger specific surface area or a higher structure is adopted, heat is generated in addition to improving the abrasion resistance as described above. These characteristics are contradictory to each other such that the characteristics and the elongation characteristics decrease, and carbon black having various characteristics has been proposed to solve this problem.

  For example, inventions (Patent Documents 1 and 2, etc.) have been proposed that focus on constituent elements other than carbon and surface activity contained in carbon black and specify the sum or ratio of the amount of hydrogen and the amount of oxygen on the surface of carbon black. .

  In addition, by reducing the solvent extraction component (heavy tar component: polycyclic aromatic hydrocarbon component, etc.) with pyridine or toluene contained in carbon black, reinforcement of compounded rubber composition by improving dispersion in rubber, etc. Inventions (such as Patent Documents 2 and 3) that improve the properties and wear resistance have been proposed.

The reaction process in which carbon black composed of 10 ⁵ to 10 ⁹ carbon atoms is produced in just a few milliseconds by pyrolysis or incomplete combustion of the raw hydrocarbon introduced into the hot gas stream is extremely complex. However, it has not been elucidated in detail, but in general, if the carbon black generation conditions are constant, the rapid refrigerant body introduction position for stopping the carbon black formation reaction is moved away from the throttling position and / or the reaction stop water amount is lowered. It is disclosed that a carbon black containing a low aromatic hydrocarbon amount having a UV absorbance of 0.15 or less is obtained (Patent Document 4).
However, these inventions relate to a method for producing carbon black for coloring, and since generally long-term exposure to carbon black after being produced in a high temperature atmosphere reduces surface activity, rubber This is a manufacturing method in which the influence on the characteristics important in the performance characteristics at the time of rubber compounding, such as abrasion resistance or low heat build-up at the time of compounding, is not considered at all.

An invention specifying the reaction residence time from the introduction of the raw material oil into the high-temperature gas stream to the introduction of the rapid refrigerant is disclosed in Patent Document 5, and the reaction is stopped within 0.002 seconds after the introduction of the raw material oil. A process for producing carbon black is described in which the first rapid cooling is performed and then the reaction is stopped further downstream by lowering the temperature.
However, the values of toluene discoloration shown in the table in the present invention (in the present invention, indicated as toluene color transmission) are low values of 41 to 78%, which is a polycyclic aromatic contained in carbon black. This means that the amount of hydrocarbons is large, and this component has little or no interaction with rubber, so improvement in characteristics such as wear resistance or low heat build-up at the time of rubber blending can not be expected, There is also a drawback that surface contamination occurs in the compounded rubber. In addition, many polycyclic aromatic hydrocarbons are known to have carcinogenicity, and the lower the health, the better.

The present applicant newly created a manufacturing method for solving these problems, and applied for this as Patent Document 6.
The gist of the invention of the prior application is as follows.
The invention of claim 1 of the prior application uses a carbon black reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are coaxially connected, and high temperature combustion gas is produced by combustion of fuel hydrocarbons in the combustion gas generation zone. Followed by spraying feed hydrocarbons into the hot combustion gas stream in the reaction zone to form a reaction gas stream comprising carbon black converted from the feed hydrocarbon by incomplete combustion or thermal cracking reaction; In the carbon black production method comprising quenching the reaction gas stream in the reaction stop zone to terminate the reaction, the residence time from when the raw material hydrocarbon is introduced into the high temperature gas stream until the rapid refrigerant is introduced T ₁ (second), the average reaction temperature in this space is T ₁ (° C.), and the car from the introduction of the sudden refrigerant to the passage of the reaction stop zone The residence time of the reaction gas flow containing bon black is t ₂ (seconds), the average reaction temperature in this space is T ₂ (° C.), and controlled under the conditions satisfying the following formulas (1) and (2). It is related with the manufacturing method of carbon black characterized by this.
(1) 2.00 ≦ α ≦ 9.00
(2) -2.5α + 85.0 ≦ β ≦ 90.0
(Wherein, α = t ₁ × T ₁ , β = t ₂ × T ₂ is represented)
In the invention of claim 2 of the prior application, the α and β are (1) 3.00 ≦ α ≦ 8.00.
(2) −2.5 × α + 85.0 ≦ β ≦ 86.0
It is more preferable that the above range is satisfied.
In the invention of claim 3 of the prior application, air or a mixture of oxygen and hydrocarbons or a mixture of these in the space from the raw material hydrocarbon introduction position to the cooling medium introduction position and / or the space from the cooling medium introduction position to the passage of the reaction stop zone. The present invention relates to a method for producing carbon black according to claim 1 or 2, wherein a gas body containing a combustion gas by the combustion reaction is introduced and added.

That is, in the technique of Patent Document 6 (hereinafter referred to as the prior application technique) disclosed by the present applicant, the high-temperature combustion gas and the raw material hydrocarbon from the raw material hydrocarbon introduction position to the rapid refrigerant introduction position have passed since the initial contact. The residence time is t ₁ (second), the average reaction temperature in this space is T ₁ (° C.), and the residence time of the reaction gas flow from the introduction of the rapid refrigerant to the passage of the reaction stop zone is t ₂ (second). ), And the average reaction temperature T ₂ (° C.) in this space, these parameters indicate at what temperature and for how long the carbon black being produced and / or subjected to thermal exposure in each step Product (an index indicating the degree of heat history as a product of strength and length) and these values are 2.00 ≦ α ≦ 9.00
And −2.5 × α + 85.0 ≦ β ≦ 90.0
(Wherein, α = t ₁ × T ₁ , β = t ₂ × T ₂ is represented)
By reducing the mechanical properties of the rubber composition, in particular the wear resistance, by optimizing the heat history during and / or the carbon black produced, Thus, the present invention relates to a manufacturing method that has been completed by finding out that carbon black for blending tire tread rubber can be highly compatible with wear resistance and low heat generation.

As a result of studying carbon black that can achieve both high wear resistance, low heat build-up, and high elongation characteristics with respect to the carbon black obtained by the prior application, the present applicant mainly exists on the surface of carbon black. It was concluded that it is effective to increase the amount of active hydrogen. However, when the amount of active hydrogen is increased using the prior application technique, the problem that the solvent extraction component (polycyclic aromatic hydrocarbon component) due to monochlorobenzene contained in carbon black increases cannot be avoided. found.
In this monochlorobenzene extract, the raw material hydrocarbons remain in the carbon black without being completely pyrolyzed, and there is almost no reinforcement to the rubber component due to the nature of its origin. There is also a negative health aspect of carcinogenicity that many polycyclic aromatic hydrocarbons have.

Japanese Patent Laid-Open No. 4-108837 JP 10-36703 A JP-A-9-40883 JP-A-8-269360 Japanese Patent Laid-Open No. 3-62858 JP 2005-272729 A

  An object of the present invention is to focus attention on the hydrogen release rate (%) as a surface property of carbon black suitable for high compatibility of wear resistance, low heat build-up and elongation characteristics for use in tire tread rubber compounding. The object is to provide a method for producing carbon black.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have made contact after the initial contact between the high-temperature combustion gas and the raw material hydrocarbons from the raw material hydrocarbon introduction position to the rapid refrigerant body introduction position defined in the prior application technique. The value of α representing the product of the residence time t ₁ (seconds) elapsed in this period and the average reaction temperature T ₁ (° C.) in this space is further subdivided into α ₁ and α ₂ , and the heat history condition is more strictly determined. By controlling the system, we succeeded in solving this problem.

The carbon black production method of the present invention uses a reaction apparatus in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected on the same axis, and high temperature combustion gas is produced by combustion of fuel hydrocarbons in the combustion gas generation zone. And subsequently spraying feed hydrocarbons into the hot combustion gas stream in the reaction zone to form a reaction gas stream containing carbon black converted from the feed hydrocarbon by incomplete combustion or pyrolysis reaction, and then reacting In the method for producing carbon black, comprising cooling the reaction gas stream to a reaction stop temperature in the stop zone to terminate the reaction, the first quenching body after the raw material hydrocarbon is introduced into the high-temperature combustion gas stream The first quenching time is defined as t ₁ (second), the residence time until the first quenching medium is introduced, and T ₁ (° C.) as the reaction temperature immediately before the first quenching medium is introduced. The residence time from the introduction of the medium to the introduction of the next second quenching medium is t ₂ (seconds), the reaction temperature immediately before the second quenching medium is introduced is T ₂ (° C.), and The residence time t ₃ (second) of the reaction gas flow from the introduction of the second quenching medium to the passage of the reaction stop zone, and the reaction temperature (reaction immediately before the reaction is terminated by quenching the reaction gas flow in the reaction stop zone) The temperature in the vicinity of the downstream end space of the continuation / cooling chamber) is T ₃ (° C.) and is controlled under the conditions satisfying the following formulas (1), (2) and (3): It is a manufacturing method.
(1) 3.00 ≦ α ₁ ≦ 5.00
(2) 6.00 ≦ α ₂ ≦ 8.00
(3) −2.5 × (α ₁ + α ₂ ) + 85.0 ≦ β ≦ 86.0
However, β ≧ 59.3
(Where α ₁ = t ₁ × T ₁ , α ₂ = t ₂ × T ₂ , β = t ₃ × T ₃ )

Here, each band in the present invention will be described.
The combustion gas generation zone is a region where a high-temperature gas flow is generated by the reaction of fuel and air, and the downstream end is the point where the raw material oil is introduced into the reactor, for example, the raw material oil from 8B in FIG. In the case of being introduced, it means from the upstream side (the left end in FIG. 1) to 8B where the feedstock is introduced. Further, the combustion gas generation zone when the raw material oil is introduced from a plurality of positions, for example, when the raw material oil is simultaneously introduced from 8A, 8B and 8C in FIG. Up to (the left end in FIG. 1).
Reaction zone 1 is a space for installing a thermometer or quenching water spray device (a in the reaction continuation / cooling chamber 10 from the point where raw material hydrocarbons are introduced (in the case of introduction at a plurality of positions, the most upstream side). To z) First quench water spray means (b to v) for cooling the reaction product, which can be freely inserted and removed in the reaction continuation / cooling chamber 10, depending on the type and characteristics to be produced. The point of use is selected) up to the point of operation (introducing water). That is, when the feedstock oil is introduced at 8B and water is introduced at the first cooling medium introduction position at c, the region (8B to c) therebetween is the reaction zone 1.
The reaction zone 2 is for the reaction continuation and cooling of the reaction product in the space (az) for installing the thermometer or the quenching water spray device in the cooling chamber 10 from the point where the first cooling medium is introduced. The second quenching water spraying means (denoted by d to x, these means can be inserted and removed in the reaction continuation / cooling chamber 10 and the use position is selected depending on the type and characteristics to be produced) (water Point to the point). That is, when water is introduced at the first cooling medium introduction position at c and water is introduced at the second cooling medium introduction position at h, the region (c to h) therebetween becomes the reaction zone 2. In addition, a reaction space temperature measuring device is installed in the space immediately upstream of the first cooling medium and second cooling medium spraying means installation positions [for example, in the above case, installed in b and g, these The temperature becomes T ₁ (° C.) and T ₂ (° C.)].
The reaction stop zone refers to a zone below (on the right side in the drawing) below the point at which the second quench water injection spraying means is operated.
In addition, the reaction temperature immediately before the reaction gas flow is rapidly cooled in the reaction stop zone to terminate the reaction (reaction continuation and temperature in the downstream end space of the cooling chamber) indicates y on the right end of FIG. This is to install a cooling water introduction device that lowers the ambient temperature introduced into the reaction product separation device at the point, and the temperature at this point y is regarded as the reaction temperature immediately before the end, but the multi-alpha thermometer is installed. Or, in the display of the space for installing the quenching water spray device, it is merely the meaning of the vicinity of the downstream end, and does not limit the number or length of the installation space, but appropriately under the conditions satisfying the temperature and residence time specified in the present invention. Selected.

In the carbon black production method of the present invention, the exposure of the carbon black to the heat in the reaction zone and the reaction stop zone, in other words, α ₁ , α ₂ and β values representing the magnitude of thermal history satisfy the above range. In order to adjust the reaction temperature, air and oxygen or hydrocarbon combustion gas, etc. are required in the range from the raw material hydrocarbon introduction position to the rapid refrigerant body introduction position and / or the range from the rapid refrigerant body introduction position to the final reaction step. A gas body can be introduced and added.

Each residence time is calculated by calculating the volume of the combustion gas fluid by a known thermodynamic calculation method using a combustion reaction product of fuel and air introduced into the combustion zone, and then calculating the residence time by the following equation.
It should be noted that the decomposition reaction of the raw material oil and the volume change due to the rapid refrigerant are ignored.

The present invention is described in detail below.
In the method for producing carbon black of the present invention, the residence time from the raw material hydrocarbon introduction position until the first quenching medium is introduced is t ₁ (seconds), and the reaction temperature just before the first quenching medium is introduced is T ₁ (° C.), the residence time from the introduction of the first sudden refrigerant body to the introduction of the next second sudden refrigerant body is t ₂ (seconds), and immediately before the second sudden refrigerant body is introduced. The reaction temperature is set to T ₂ (° C.), and the residence time t ₃ (second) of the reaction gas flow from the introduction of the second quenching medium to the passage of the reaction stop zone is rapidly cooled in the reaction stop zone. Assuming that the reaction temperature immediately before the reaction is terminated (temperature in the vicinity of the downstream end space of the reaction continuation and cooling chamber) is T ₃ (° C.), what is the temperature at what temperature in each zone after the combustion gas production zone Time, generating and / or generated carbon black These products indicating which receives heat (the index indicating the degree of thermal history) newly defined, and these values
In reaction zone 1, 3.00 ≦ α ₁ ≦ 5.00,
In reaction zone 2, 6.00 ≦ α ₂ ≦ 8.00,
In the reaction stop zone, −2.5 × (α ₁ + α ₂ ) + 85.0 ≦ β ≦ 86.0
However, β ≧ 59.3
(Wherein, α ₁ = t ₁ × T ₁ , α ₂ = t ₂ × T ₂ , β = t ₃ × T ₃ is represented)
By optimizing the thermal history of the carbon black being generated and / or generated, the hydrogen release rate (%) is increased over the prior application technology, thereby increasing the tire tread. The present invention has been completed by finding out that carbon black for rubber compounding is highly compatible with wear resistance, low heat build-up and elongation characteristics.

In the method for producing carbon black of the present invention, the residence time from the raw material hydrocarbon introduction position until the first quenching medium is introduced is t ₁ (seconds), and the reaction temperature just before the first quenching medium is introduced is T ₁ (° C.), the product thereof is α ₁ , the residence time from the introduction of the first sudden refrigerant body to the introduction of the next second sudden refrigerant body is t ₂ (seconds), the second quenching medium T ₂ (° C.) immediately before the introduction of the reaction gas, the product thereof is α _2, and the residence time t ₃ of the reaction gas flow from the introduction of the second quenching medium to the passage of the reaction stop zone ( Second), the reaction temperature immediately before the reaction gas flow is rapidly cooled in the reaction stop zone and the reaction is terminated (temperature in the vicinity of the downstream end space of the reaction continuation and cooling chamber) is T ₃ (° C.), and the product thereof is β And when
3.00 ≦ α ₁ ≦ 5.00, 6.00 ≦ α ₂ ≦ 8.00
And −2.5 × (α ₁ + α ₂ ) + 85.0 ≦ β ≦ 86.0
However, β ≧ 59.3
This is a necessary condition for obtaining the target carbon black.
The carbon black product alpha ₁ of t ₁ and _{T 1} is obtained by the manufacturing conditions of less than 3.00, light transmittance of toluene is less than 90%, or monochlorobenzene extraction amount exceeds 0.15%, in the carbon black Many polycyclic aromatic hydrocarbon components are present, and this component is not preferable because it does not give sufficient reinforcement to rubber and wear resistance is reduced.
Further, under the production conditions where α ₁ exceeds 5.00, the polycyclic aromatic hydrocarbon component contained in the carbon black is reduced, but the hydrogen release rate of the prior invention cannot be exceeded, and the rubber composition The effect of increasing the wear resistance of the object is not seen.
be exceeded light transmittance of toluene is less than 90%, or 0.15% of toluene extract quantity for the carbon black product alpha ₂ of t ₂ and T ₂ is obtained by the manufacturing conditions of less than 6.00, contained in the carbon black Since many polycyclic aromatic hydrocarbon components are present and sufficient reinforcing properties are not given to rubber, an increase in wear resistance cannot be expected. On the other hand, carbon black obtained under production conditions in which α ₂ exceeds 8.00, that is, under the condition of receiving an excessive thermal history in the carbon black reaction zone has a significantly reduced hydrogen release rate, and the rubber composition This is not preferable because the wear resistance of the rubber composition decreases and the heat generation of the rubber composition increases.

Even if the α ₁ value and the α ₂ value satisfy the above-mentioned range, the product β of t ₃ and T ₃ is [−2.5 × (α ₁ + α ₂ ) + 85.0 ≦ β ≦ 86.0 However, β ≧ 59.3 ]
The carbon black obtained under the production conditions less than the relational expression value, that is, when the heat history from the introduction of the rapid refrigerant to the reaction stop zone is small, has a toluene coloring permeability of 90% or less, or a monochlorobenzene extraction amount of 0.15. The carbon black obtained under the production conditions where the β value exceeds 86.0 and the excess heat history is conversely reduced in the hydrogen release rate, the wear resistance of the rubber composition, and the rubber Since the heat generation of the composition increases, it is not preferable.

Further, the method for producing carbon black of the present invention includes a range from the raw material hydrocarbon introduction position to the rapid refrigerant introduction position in order to adjust the reaction temperature T ₁ or T ₂ or T ₃ in the reaction zone or the reaction stop zone. In addition, a gas body such as air, a mixture of oxygen and hydrocarbons, or a combustion gas resulting from these combustion reactions may be introduced and added into a space ranging from the position where the quenching medium is introduced to the downstream end of the reaction stop zone. for ₂ and T ₃ adjusted, quench medium in the quench medium introduced position, for example, the introduction of water or the like may be appropriately controlled.

According to the present invention, in the method for producing carbon black, by producing it under a specific range of reaction conditions, it is possible to achieve both high wear resistance and low heat buildup for use in tire tread rubber blending. Therefore, it is possible to provide an industrially useful carbon black that achieves both a low content and a low content of polycyclic aromatic hydrocarbons.
The carbon black for blending tire tread rubber of the present invention has the following physical properties.
(1) DBP absorption (DBP) is 40 to 250 ml / 100 g
(2) DBP absorption after compression operation (24M4DBP) is 35 to 220 ml / 100 g
(3) CTAB adsorption specific surface area (CTAB) is 70 to 200 m ² / g.
(4) Hydrogen release rate (%)> 0.350-0.000625 × (CTAB)
(5) Toluene coloring transmittance of 90% or more The carbon black of the present invention needs to have a DBP absorption of 40 to 250 ml / 100 g and a 24M4DBP absorption of 35 to 220 ml / 100 g. More preferably, the DBP absorption is in the range of 95 to 220 ml / 100 g, and the 24M4 DBP absorption is 90 to 200 ml / 100 g.
When the DBP absorption amount is less than 40 ml / 100 g or the 24M4 DBP absorption amount is less than 35 ml / 100 g, it is not preferable because the minimum tensile stress required for a tire tread rubber composition cannot be exhibited.
Further, if the DBP absorption exceeds 250 ml / 100 g, or if the 24M4 DBP absorption exceeds 220 ml / 100 g, the minimum required elongation cannot be ensured, which is not preferable.
In addition, the upper limits of the DBP absorption amount and the 24M4 DBP absorption amount of 250 ml / 100 g and 220 ml / 100 g exceed this upper limit when there is no addition of other components (such as water vapor) in the reaction zone. This range is set because there is almost no possibility (if the additive is added into the furnace, it is generally not preferable because the wear resistance imparted by the carbon black is lowered).
The carbon black of the present invention is required to have a CTAB adsorption specific surface area of 70 to 200 m ² / g.
If it is less than 70 m ² / g, the minimum tensile strength required as a rubber composition for a tire tread cannot be expressed, and if it exceeds 200 m ² / g, dispersibility in the rubber composition can be sufficiently secured. On the contrary, it is not preferable because the wear resistance of the rubber composition deteriorates.
The carbon black of the present invention needs to have a toluene coloring transmittance of 90% or more. When the toluene coloring transmittance is less than 90%, undecomposed components contained in the carbon black (polycyclic aromatic hydrocarbons). Etc.), and this component is not preferable because it does not give sufficient reinforcement to the rubber and the wear resistance is lowered and the rubber composition itself is contaminated.
The amount of monochlorobenzene extracted is preferably 0.15% or less, and when this exceeds 0.15%, undecomposed components (polycyclic aromatic hydrocarbons, etc.) contained in the carbon black tend to increase. In some cases, the reinforcing effect on rubber and the wear resistance may be reduced.
That is, the carbon black of the present invention has a DBP absorption of 40 to 250 ml / 100 g, more preferably 95 to 220 ml / 100 g, a 24M4 DBP absorption of 35 to 220 ml / 100 g, preferably 70 to 220 ml / 100 g, more preferably 90. ~ 200 mL / 100 g, CTAB adsorption specific surface area of 70~200m ² / g, greater than the hydrogen release rate equation value [0.350-0.000625 × (CTAB)], those light transmittance of toluene is 90% or more Alternatively, it is preferable that the amount of monochlorobenzene extracted is 0.15% or less.
When the hydrogen release rate is equal to or less than the relational value, the wear resistance of the tire tread rubber composition is lowered and the hysteresis characteristics are lowered, which is not preferable.

  Examples of the present invention will be described in detail below in comparison with comparative examples, but the scope of the present invention is not limited thereby.

Examples and Comparative Examples Using the carbon black reactor shown in FIGS. 1 to 12 carbon blacks were produced as follows.

An oxygen-containing gas introduction cylinder (inner diameter 250 mmφ, long) having a rectifying plate 5 for rectifying the oxygen-containing gas introduced from the outer periphery of the reactor head inside the combustible fluid introduction chamber (inner diameter 450 mmφ, length 400 mm) 2 300 mm) 4 and a fuel spray introducing means 6 at the central axis thereof, and the downstream side of the cylinder becomes a converging chamber (upstream end inner diameter 370 mmφ, downstream end inner diameter 80 mmφ, convergence angle 5.3 °) 7 which gradually converges, and Four feed oil spray ports (8B-1, 8B-2, 8B-3, 8B-4) as illustrated on the 8B plane in FIG. It has a feed oil introduction chamber 9 including a feed oil spray plane (8A to 8D) that forms a separate plane, and this downstream side is equipped with 26 quenching water injection spray means (az; 200 mm intervals) for stopping the reaction. Continued reaction and cold A reactor 1 consisting of a rejection chamber (inner diameter 160 mmφ, length 7500 mm) 10 and entirely covered with a refractory was used.
Here, the name of the reaction continuation / cooling chamber 10 is used because the reaction zone 1 extends from the raw material introduction time to the operation time of the quenching water injection spray means for stopping the reaction, and the second rapid refrigerant introduction point downstream thereof. This is because the reaction zone 2 and the point after the second quenching medium introduction point are the reaction stop zone, and this quenching water introduction position may move depending on the required carbon black performance.
For example, in FIG. 1, when the feed oil introduction position is 8B, the first rapid refrigerant introduction position is c, and the second rapid refrigerant introduction position is h, the reaction zone 1 is between 8B and c. From here on, the reaction zone 2 extends to the second quenching medium water introduction point h, and the downstream side thereof becomes the reaction stop zone.

  In the present invention, the temperature in each reaction zone is an important factor, but the “reaction temperature immediately before the rapid refrigerant is introduced” is explained in the above example when the cooling water introduction position is c. One of the temperatures, that is, the temperature in the reaction chamber at b at the cooling water introduction position, is shown in FIGS. 3 and 4 as cross sections. Similarly, when the introduction position of the second quenching medium is h, the temperature measured at the previous g position is the immediately preceding temperature. In addition, when the water spray device installation position for terminating the reaction in the reaction stop zone (for adjusting the introduction temperature to the separation device downstream) is z, the temperature measured at the previous y position is the immediately preceding temperature. It becomes temperature.

A heavy oil having a specific gravity of 0.8622 (15 ° C / 4 ° C) was used as the fuel, and a heavy oil having the properties shown in Table 1 was used as the feedstock oil.
In addition, 0.8622 (15 ° C / 4 ° C) indicates that the ratio of the mass of heavy oil A at 15 ° C to the mass of water at 4 ° C is 0.8622.

  Using the carbon black reactor, carbon black was produced under the operating conditions that satisfy the requirements of the invention shown in Tables 2 to 3 and the operating conditions that were removed.

  The carbon black production conditions were as follows: the total amount of air introduced, the amount of raw material oil introduced and temperature, the amount of fuel introduced, and the position of introduction of the raw material hydrocarbon from the carbon black of the example carbon black and the comparative example carbon black using the reactor described above. Residence time until the sudden refrigerant body introduction position, reaction temperature immediately before the introduction of the first rapid refrigerant body, further residence time from the introduction of the first sudden refrigerant body to the introduction of the second sudden refrigerant body, second quenching medium The reaction temperature immediately before the introduction of the second quenching medium, the residence time from the introduction of the second quenching medium to the passage of the reaction stop zone, the reaction temperature immediately before the reaction is terminated by quenching the reaction gas flow in the reaction stop zone, etc. It manufactured by adjusting conditions as described in Tables 2-3.

  Tables 4 to 5 show the physicochemical characteristics of the carbon blacks produced under the operating conditions shown in Tables 2 to 3.

  Each characteristic of the carbon black described in the present invention is measured by the following method.

(1) DBP absorption amount, 24M4 DBP absorption amount It is measured by the method described in JIS K6217-4: 2001, and is expressed in ml of dibutyl phthalate (DBP) absorbed per 100 g of carbon black.

(2) CTAB adsorption specific surface area It is measured by the method described in JIS K6217-3: 2001, and is expressed as a specific surface area m ² / g per unit weight.

(3) Toluene coloring transmittance Measured by the method described in Item B method of JIS K6218: 1997, and displayed as the transmittance (%) of the treatment liquid when the transmittance of pure toluene is 100%. .
A larger number means a lower degree of toluene contamination, that is, less undecomposed aromatic hydrocarbon components.

(4) Hydrogen release rate (a) A carbon black sample is dried in a constant temperature dryer at 105 ° C. for 1 hour and cooled to room temperature in a desiccator.
(B) About 10 mg of a sample is precisely weighed in a tubular tube sample container made of tin, and is crimped and sealed.
(C) A hydrogen analyzer (Horiba Seisakusho EMGA621W) is used to measure the amount of hydrogen gas generated when heated at 2000 ° C. for 15 minutes under an argon stream, and the mass fraction (%) is obtained.

(5) Monochlorobenzene extraction amount In accordance with JIS K6218-5: 2005 “Carbon black for rubber-incidental characteristics-determination of solvent extraction amount”, extraction amount was obtained by using monochlorobenzene as a solvent and extraction time for 16 hours. (%) Was measured.

Run No. having the physicochemical properties shown in Tables 4 and 5. In order to evaluate the performance of 1 to 12 carbon blacks, rubber compositions were prepared at the blending ratios shown in Table 6 and their characteristic tests were performed.
The results are shown in Tables 7-8. In addition, the performance evaluation of each rubber characteristic was performed in Comparative Example Run No. 8 was expressed as an index with a control standard (this characteristic value was 100).

Rubber properties were measured as follows.
(1) Rubber compounding method The rubber composition of the compounding ratio shown in Table 6 was kneaded using a Banbury mixer, and further vulcanized at 145 ° C. for 30 minutes with a pressure vulcanizer to obtain a vulcanized rubber.
(2) Evaluation of Lambourn Wear Resistance Index The wear loss was measured using a Lambourn abrasion tester, and the wear resistance index was calculated from the following equation.
In addition, it is excellent in abrasion resistance, so that a numerical value is large.
Wear resistance index = (S / T) x 100
Here, S: comparison reference (comparative example Run No. 8) test piece wear loss amount
T: Abrasion loss amount of each rubber specimen (3) Evaluation of impact resilience index The impact resilience was measured by the method described in JIS K6255: 1996.
In addition, the measured value was displayed by the index | exponent with the impact resilience of the test piece of the comparative example (Run No. 8) as 100.
The larger the index value, the higher the impact resilience and the lower the heat buildup.
(4) Tensile test (Eb)
It was carried out by the method described in JIS K6251: 2004 "Vulcanized rubber and thermoplastic rubber-Determination of tensile properties". The test piece was dumbbell-shaped No. 3 and measured at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min, and the elongation at break (Eb) was calculated.
In addition, the measured value was displayed as an index with the elongation (Eb) of the test piece of the comparative example (Run No. 8) as 100.
The larger the index value, the higher the elongation and the better the fatigue resistance and cut resistance.

The effects and advantages of the carbon black production process according to the present invention will be described based on the physicochemical characteristics shown in Tables 4 and 5 and the rubber characteristics shown in Tables 7 and 8.
RunNo. The carbon blacks 1 to 4 are for the production process of the present invention. Carbon blacks of 5-12 are comparative examples that deviate from one or more of the specific requirements of the present invention.

RunNo. 5 is an example in which the value of α ₁ , which is one of the essential requirements of the production conditions of the present invention, exceeds the upper limit of 5.0. 1 but with a decrease in performance in the lambone wear resistance. 6 is an example in which alpha ₂ exceeds the upper limit of the calculated value, rebound, elongation Run No.. Although it approximates to 2, it is inferior in Lambourn abrasion resistance. In addition, RunNo. No. 7 does not satisfy −2.5 × (α ₁ + α ₂ ) + 85 ≦ β in which the value of β, which is one of the essential requirements of the production conditions of the present invention, is within the range of the present invention. The toluene color permeability is 90% or less, and the resilience and elongation are Run No. Although it is close to 3, there is a decrease in the lambone wear resistance. RunNo. 8 is an example in which the values of α ₂ and β, which are one of the essential requirements of the production conditions of the present invention, exceed the upper limit of the range of the present invention. 4 is inferior in Lambourne wear resistance.
Furthermore, RunNo. No. 9 is an example in which the values of α ₁ and α ₂ , which are one of the essential requirements of the production conditions of the present invention, exceeded the upper limit of the range of the present invention. 3 but is inferior in Lambourn abrasion resistance and elongation. No. 10 is an example in which the values of α ₁ and β, which are one of the essential requirements of the production conditions of the present invention, exceed the upper limit of the range of the present invention. Approximate to 3, but decreased in Lambone wear resistance and elongation.
RunNo. 11 and RunNo. 12 is an example of not introducing a second quench medium in the present invention, i.e. alpha Patent Document 6 (JP 2005-272729) is a manufacturing example based on the description of (Patent Document 6 alpha ₁ As the display of the table And α ₂ is displayed as −). RunNo. 11 and RunNo. No. 12 has a high thermal history, so the amount of toluene extracted is small, but the hydrogen release rate is lower than that of carbon black obtained by the production conditions of the present invention, so that no effect is seen in Lambourne wear and impact resilience.

  From the rubber compounding characteristics shown in Tables 7 and 8, the carbon black satisfying the manufacturing conditions disclosed in the examples is very good in wear resistance and low heat build-up (rebound resilience) as compared with the corresponding comparative examples. It can be seen that a high level is maintained even if it is evaluated as above.

It is longitudinal section explanatory drawing of an example of the carbon black reaction apparatus used for this invention. It is sectional drawing in the AA arrow of FIG. It is sectional drawing containing the apparatus for reactor temperature measurement in the BB arrow cross section of FIG. It is sectional drawing of the 1st rapid refrigerant body introduction in CC arrow of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Carbon black reaction apparatus 2 Flammable fluid introduction chamber 3 Oxygen-containing gas introduction pipe 4 Oxygen-containing gas introduction cylinder 5 Rectifier plate 6 Fuel oil spraying apparatus introduction pipe 7 Converging chamber 8A Raw material oil spraying plane 8B Raw material oil spraying plane 8C Raw material oil Spray plane 8D Raw material oil spray plane 9 Raw material oil introduction chamber 10 Reaction continuation and quenching chamber ay Space for installing thermometer or quenching water spray device z Cooling water spraying space for adjusting downstream ambient temperature Tc Thermocouple for measuring furnace temperature Equipment Qa1, Qa2 Quenched water injection spray nozzles installed in the installation space of the quenching water injection spray means in 10 spaces

Claims (2)

Using a reaction device in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected coaxially, high-temperature combustion gas is generated by combustion of hydrocarbons for fuel in the combustion gas generation zone, and then the high-temperature combustion in the reaction zone A raw material hydrocarbon is sprayed into the gas stream to form a reaction gas stream containing carbon black converted from the raw material hydrocarbon by incomplete combustion or thermal decomposition reaction, and then the reaction gas stream is stopped in the reaction stop zone In the carbon black production method comprising cooling to a temperature and terminating the reaction, the residence time from when the raw material hydrocarbon is introduced into the high-temperature combustion gas stream to when the first quenching medium is introduced is t ₁ (second), T ₁ (° C.) is the reaction temperature immediately before the first quenching medium is introduced, and the second quenching medium is introduced after the first quenching medium is introduced. The residence time until the second quenching medium is introduced is t ₂ (seconds), the reaction temperature immediately before the second quenching medium is introduced is T ₂ (° C.), and the reaction stop zone after the second quenching medium is introduced. Retention time t ₃ (seconds) of reaction gas flow until passing, reaction temperature immediately before quenching reaction gas flow in reaction stop zone and terminating reaction (temperature in the vicinity of downstream end space of reaction continuation and cooling chamber) A method for producing carbon black, comprising controlling T ₃ (° C.) under conditions satisfying the following formulas (1), (2) and (3):
(1) 3.00 ≦ α ₁ ≦ 5.00
(2) 6.00 ≦ α ₂ ≦ 8.00
(3) −2.5 × (α ₁ + α ₂ ) + 85.0 ≦ β ≦ 86.0
However, β ≧ 59.3
(Where α ₁ = t ₁ × T ₁ , α ₂ = t ₂ × T ₂ , β = t ₃ × T ₃ )   Combustion by air, a mixture of oxygen and hydrocarbons, or a combustion reaction thereof in the zone from the feed hydrocarbon introduction position to the quenching medium introduction position and / or in the zone from the quenching refrigerant introduction position to the reaction stop zone passing The method for producing carbon black according to claim 1, wherein a gas body containing a gas is introduced and added.