JP2014001379A - Method for producing carbon black, carbon black, rubber composition, and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing carbon black, for which a wide variety of non-fossil materials can be used, and to provide carbon black obtained by the method, and having physicochemical characteristics which are by no means inferior to those of carbon black originating from fossil materials, a rubber composition with the carbon black compounded therein, and a tire using the rubber composition.SOLUTION: In a method for producing carbon black, a reaction apparatus including a combustion gas generation zone, a reaction zone, and a reaction stopping zone coaxially provided in a connected row arrangement is used, and the reaction is controlled in such a way that a ratio of a reactor diameter (Dr) in the reaction stopping zone to a reactor diameter (Df) in a raw material hydrocarbon introducing section satisfies a relation 2.75≤Dr/Df≤5.00.

Description

  The present invention relates to a method for producing carbon black, carbon black obtained by this method, a rubber composition containing the carbon black, and a tire using the rubber composition.

Carbon black sprays and introduces raw material hydrocarbons into the high-temperature combustion gas generated in the furnace and / or externally generated in the furnace under strictly controlled conditions, It is an industrially useful raw material composed of almost pure carbon element produced by thermal decomposition or incomplete combustion of the raw material hydrocarbon. And since it has unique properties that can dramatically improve the mechanical properties, especially tensile strength, wear resistance, etc., with respect to the composition at the time of rubber compounding, various properties including tires It is widely used as a filler for rubber products and has been used for a long period of about 100 years, and is also used as a raw material for various paints and inks by utilizing its color characteristic, blackness.
Carbon black for rubber compounding is based on its physicochemical characteristics, that is, the unit particle diameter, the surface area per unit weight (specific surface area), the degree of particle connection (structure), the surface properties, etc. Therefore, carbon black having different properties is selectively used depending on the required performance of the rubber product, the environment in which it is used, and the like.

Carbon black is widely used in this way, but as a raw material for its production, coal / petroleum raw material oil, which is mainly a fossil raw material, is used because of its high yield. However, considering the current global situation and reserves in the future, it cannot be said that the supply of oil is stable over a long period of time, so alternative raw materials have been studied.
Although it is necessary to place importance on the alternative raw materials that can be supplied inexpensively and stably, as an example, non-fossil raw materials, that is, animal and vegetable oils or modified products thereof are currently being studied. We are studying the production of carbon black using castor oil.
However, when a non-fossil raw material is used as a carbon black raw material oil, the aggregate growth reaction tends to be extremely slow when carbon black is generated. Therefore, when the above physicochemical characteristics of carbon black are used As a result, there is a problem in that it cannot be controlled freely and is inferior to carbon black derived from fossil raw materials in physical properties at the time of rubber blending, for example, reinforcement. Therefore, normally, carbon black derived from non-fossil raw materials is rarely used alone, and often used in combination with other reinforcing materials such as silica and fossil raw material-based carbon black.

For such a problem, attempts have been made to use raw material oil having physical properties in a certain range. Patent Document 2 uses a raw material oil whose BMCI value has a constant relationship with the boiling point and specific gravity. In this case, carbon black is produced using a raw material oil having a C / H ratio in a certain range.
Although these measures provide some improvement to the problem of poor physicochemical property control compared to fossil raw material carbon black, only some specific non-fossil raw material feedstocks are used as described above. The problem of being unable to use a wide range of raw materials has not been improved.

JP 2008-56802 A JP 2009-24071 A Special table 2012-505939 gazette

  The present invention relates to a method for producing carbon black in which a wide range of non-fossil raw materials can be used, carbon black obtained by this method and having physicochemical properties comparable to those of fossil raw material-derived carbon black, An object is to provide a blended rubber composition and a tire using the rubber composition.

The above problems are solved by the following inventions 1) to 4).
1) Using a reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected on the same axis, high-temperature combustion gas is generated by combustion of fuel hydrocarbons in the combustion gas generation zone, and then the high temperature is generated in the reaction zone. Raw material hydrocarbons are sprayed and introduced into the combustion gas stream from a plurality of raw material introduction devices to form a reaction gas stream containing carbon black converted from the raw material hydrocarbon by incomplete combustion or thermal decomposition reaction, and then rapidly cooled in the reaction stop zone A method of producing carbon black in which the reaction gas flow is cooled to a reaction stop temperature by introducing a medium to terminate the reaction, and a reaction furnace diameter (Dr) in a reaction stop zone and a reaction furnace diameter in a raw material hydrocarbon introduction site A method for producing carbon black, wherein a ratio of (Df) is controlled to satisfy “2.75 ≦ Dr / Df ≦ 5.00”.
2) Carbon black obtained by the production method described in 1).
3) A rubber composition containing the carbon black described in 2).
4) A tire produced using the rubber composition described in 3).

  According to the present invention, it is possible to provide a method for producing carbon black in which a wide range of non-fossil raw materials can be used without being limited to non-fossil raw materials having specific physical properties as in the prior art. Moreover, the carbon black which has the physicochemical characteristic which is inferior compared with the carbon black derived from a fossil raw material can be provided. Furthermore, a rubber composition utilizing the characteristics of the carbon black and a tire using the rubber composition can be provided.

The longitudinal front explanatory drawing of an example of the carbon black reaction apparatus used for this invention. Sectional drawing in the AA arrow of FIG. Sectional drawing containing the thermocouple apparatus for reaction space temperature measurement in the BB arrow cross section of FIG. The relationship diagram of Dr / Df and DBP of carbon black obtained by each condition.

Hereinafter, the present invention will be described in detail.
In the conventional method for producing carbon black using non-fossil raw materials, the inventors of the present invention have a slow growth reaction of aggregates formed by collision and bonding between primary particles. Has been found to be low, i.e., exhibit low DBP.
As a result of repeated studies, we succeeded in increasing the collision frequency between primary particles and promoting the growth of aggregates by increasing the turbulent state in the reactor after the reactor reaction zone.
That is, the production method of the present invention is a carbon black production method using 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 a reaction furnace diameter (Dr) in the reaction stop zone In this method, the turbulent flow conditions in and after the reaction section are increased by controlling the ratio (Dr / Df) to the reaction furnace diameter (Df) at the raw material hydrocarbon introduction site within a certain range. And since the collision frequency between primary particles increases, carbon black having a high DBP equivalent to the carbon black derived from fossil raw materials, which could only be achieved with only a part of the non-fossil raw materials in the prior art. Can be produced using a wide range of non-fossil raw materials.

First, each band in the present invention will be described with reference to FIG. FIG. 1 is a diagram showing an example of a carbon black reactor used in the present invention.
The carbon black reactor 1 includes an oxygen-containing gas introduction pipe 3 and an oxygen-containing gas having a rectifying plate 5 for rectifying the oxygen-containing gas introduced from the outer periphery of the reactor head into the combustible fluid introduction chamber 2. A cylinder 4 for introduction and a fuel hydrocarbon spraying device introduction pipe 6 at its central axis are provided as a converging chamber 7 which is gradually converged on the downstream side of the cylinder, and an example is shown in FIG. The raw material hydrocarbon spraying apparatus 9 including the raw material hydrocarbon spraying planes (8A to 8D) forming four separate planes on which the raw material hydrocarbon spraying apparatus is installed on the same plane is provided. The apparatus is composed of a reaction continuation and cooling chamber 10 provided with rapid refrigerant pressure injection means (a to y) for stopping, and is entirely covered with a refractory.
The name of the reaction continuation / cooling chamber 10 is used because the reaction zone extends from the raw material introduction time to the operation time of the abrupt refrigerant pressure injection means, and the reaction is stopped after the operation time of the abrupt refrigerant pressure injection means on the downstream side. This is because the operating point of the sudden refrigerant pressure injection spray means may move depending on the required carbon black performance.
Moreover, water is usually used as the rapid refrigerant body.

  The combustion gas generation zone is a region where a high-temperature gas flow is generated by the reaction of fuel and air, and its downstream end is a point where raw material hydrocarbons are introduced into the reactor, for example, raw material hydrocarbons of FIG. When the raw material hydrocarbon is introduced from the spray plane, it indicates from the upstream side (left end in FIG. 1) to 8A where the raw material hydrocarbon is introduced, and the reactor diameter in 8A is Df. Further, the combustion gas generation zone when the raw material hydrocarbons are introduced from a plurality of positions is, for example, when the raw material hydrocarbons are simultaneously introduced from the raw material hydrocarbon spray planes 8A, 8B, and 8C of FIG. From the left end to the most upstream 8C where the raw material hydrocarbons are introduced, and the reactor diameter at 8C is Df.

The reaction zone refers to the space for installing the rapid refrigerant pressure injection spray means (approximately between a and z) in the reaction continuation and cooling chamber 10 from the point where the raw material hydrocarbons are introduced (in the case of introduction at a plurality of positions, the most upstream side). To the point at which the rapid refrigerant pressure injection spray means (a to y) for the reaction product in the space is operated.
The rapid refrigerant pressure injection spray means (a to y) can be freely inserted and removed, and the use position is selected according to the type and characteristics to be produced. That is, when the raw material hydrocarbon is introduced at 8B and the quenching refrigerant is introduced at the position f, the region (8B to f) in between is the reaction zone. The reaction furnace diameter in the reaction continuation and cooling chamber 10 is defined as Dr.
In addition, a reaction space temperature measuring device is installed in the space immediately upstream of the position where the rapid refrigerant pressure injection means is installed [for example, when the above-mentioned 8B to f are reaction zones, they are installed in e, and the temperature here is T ₁ (° C.)]. FIG. 3 shows a cross section taken along line BB when a temperature measuring device is provided in FIG. Tc is a thermocouple device for measuring the reaction space temperature.

The reaction stop zone refers to a zone on the downstream side (right side in FIG. 1) from the point where the rapid refrigerant pressure injection means (a to y) is operated.
Note that z is merely a meaning of the downstream end of the space for installing the rapid refrigerant pressure injection means (approximately a space between a and z), and does not limit the number or length of the installation spaces. Further, z is the last reaction stop position in the reaction stop zone. As described above, the rapid refrigerant pressure injection means (a to y) is appropriately selected so as to satisfy the conditions specified in the present invention. As a result, the reaction stop position also changes.

  In the present invention, control is performed so as to satisfy “2.75 ≦ Dr / Df ≦ 5.00”. A preferred range is “3.70 ≦ Dr / Df ≦ 5.00”. Thereby, the turbulent flow in the reaction furnace is increased, and the aggregate growth caused by the collision and bonding of the primary particles of carbon black generated in the reaction zone is promoted. When Dr / Df is smaller than 2.75, the turbulent flow in the reaction furnace that promotes the collision between the primary particles does not become sufficiently large, so that the aggregate is difficult to grow. On the other hand, even if Dr / Df is excessively increased, the effect of agglomerate growth is limited, so the upper limit is practically about 5.00 from the viewpoint of reactor manufacturing.

  The carbon black of the present invention is suitable for use in a rubber composition for tires. The rubber composition, when blended with non-fossil raw material-derived carbon black by a conventional manufacturing method, tends to be inferior in terms of reinforcement and the like as compared with the case where carbon black derived from a fossil raw material is blended. By blending the carbon black of the present invention, it is possible to obtain an excellent rubber composition having characteristics equivalent to those when blending carbon black derived from a fossil raw material. Furthermore, if this rubber composition is used, a useful tire can be produced.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.

Examples 1-8, Comparative Examples 1-3
Carbon black was manufactured by using the carbon black reactor 1 shown in FIGS. 1 to 3 so that the conditions shown in the columns of Examples and Comparative Examples in Table 1 were satisfied.
The reactor 1 includes an oxygen-containing gas introduction cylinder 4 (inner diameter 250 mmφ, length 300 mm) having a rectifying plate 5 inside a combustible fluid introduction chamber 2 (inner diameter 450 mmφ, length 400 mm), and a fuel hydrocarbon sprayer introduction pipe. 6 and the downstream side of the cylinder is the converging chamber 7 (upstream end inner diameter 370 mmφ, downstream end inner diameter 80 mmφ, convergence angle 5.3 °), and the downstream side of the converging chamber 7 is illustrated in FIG. A raw material hydrocarbon introduction chamber 9 including raw material hydrocarbon spray planes (8A to 8D) forming four separate planes on which two raw hydrocarbon spray devices (8B-1 to 4) are installed on the same plane; This downstream side is a device which is composed of a reaction continuation and cooling chamber 10 (length 6500 mm) provided with 25 rapid refrigerant pressure injection spray means at intervals of 200 mm and is entirely covered with a refractory. The inner diameter (Dr) of the reaction continuation / cooling chamber 10 was appropriately selected so as to be Dr / Df shown in the columns of Examples and Comparative Examples in Table 1.

Table 2 shows the physicochemical characteristics of the carbon blacks of Examples and Comparative Examples.

Each characteristic shown in the above Table 2 is measured by the following method.
(1) 24M4DBP absorption amount Measured by the method described in JIS K6217-4: 2008. Amount of dibutyl phthalate (DBP) absorbed per 100 g of carbon black (mL / 100 g)
(2) CTAB adsorption specific surface area Specific surface area per unit weight (m ² / g) measured by the method described in JIS K6217-3: 2001
(3) Toluene coloring transmittance The transmittance (%) of the treatment liquid measured by the method described in JIS K6218-4: 2011 when the transmittance of pure toluene is 100%. Higher numbers mean less toluene contamination, i.e. less undecomposed aromatic hydrocarbon components.

The effects and advantages of the carbon black production method of the present invention will be described from the physicochemical characteristics of each carbon black shown in Table 2 and the relationship diagram of Dr / Df and DBP shown in FIG.
Comparative Examples 1 and 2 are examples in which non-fossil raw material oil is used but the requirements of the present invention are not satisfied, and Comparative Example 3 is an example in which a general fossil raw material oil is used.
The carbon blacks of Examples 1 to 8 all showed higher DBP values than the carbon blacks of Comparative Examples 1 and 2, and the DBP values substantially the same as the carbon black of Comparative Example 3.

Examples 9-16, Comparative Examples 4-6
<Preparation and evaluation of rubber composition>
Using the carbon blacks of Examples 1 to 8 and Comparative Examples 1 to 3, the rubber compositions having the compounding formulations shown in the columns of Examples 9 to 16 and Comparative Examples 4 to 6 in Table 3 were kneaded with a Banbury mixer. Prepared. The fracture strength and abrasion resistance of each rubber composition obtained were measured by the following methods.
The results are shown in Table 3.

<Destructive strength>
Based on JIS K6301, each rubber composition was subjected to a tensile test to measure the tensile strength (Tb), and the tensile strength value of Comparative Example 6 was set to 100 and indicated as an index.
The larger the index value, the larger the tensile strength value and the higher the breaking strength.

<Abrasion resistance>
The test was conducted using a Lambone-type wear tester under the conditions of room temperature and a slip rate of 25%, and the index was displayed with the reciprocal of the wear amount of Comparative Example 6 being 100. The larger the index value, the smaller the amount of wear and the better the wear resistance.

上記表３中の＊１〜＊４の材料の詳細は次のとおりである。
＊１ 乳化重合ＳＢＲ ［ＪＳＲ社製ＳＢＲ＃１５００］
＊２ 老化防止剤６ＰＰＤ ［大内新興化学工業社製ノクラック６Ｃ］
＊３ 加硫促進剤ＤＰＧ ［大内新興化学工業社製ノクセラーＤ］
＊４ 加硫促進剤ＤＭ ［大内新興化学工業社製ノクセラーＤＭ］

The details of the materials of * 1 to * 4 in Table 3 are as follows.
* 1 Emulsion polymerization SBR [JBR SBR # 1500]
* 2 Anti-aging agent 6PPD [Nouchi 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.]
* 3 Vulcanization accelerator DPG [Okushin Seikagaku noxeller D]
* 4 Vulcanization accelerator DM [Noxeller DM manufactured by Ouchi Shinsei Chemical Co., Ltd.]

The rubber compositions of Examples 9 to 16 showed higher fracture strength and higher wear resistance than Comparative Examples 4 and 5. Moreover, it was equal to or more than the rubber composition of Comparative Example 6 using carbon black produced from a general fossil raw material oil. That is, the carbon black of the present invention exhibits a reinforcing effect equivalent to that of carbon black produced using a general fossil raw material even when blended with rubber. Therefore, a tire inferior to that of a tire made of a rubber composition using carbon black produced from a general fossil raw material oil can be obtained.
As described above, the present invention is a technology that can use a wide range of non-fossil raw materials by controlling production conditions, and not only vegetable oils shown in the examples but also other oil types such as animal oils can be used. .

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 hydrocarbon spraying apparatus introduction pipe 7 Converging chamber provided with fuel introduction means 8A Raw material hydrocarbon spray plane 8B Raw material hydrocarbon spraying plane 8C Raw material hydrocarbon spraying plane 8D Raw material hydrocarbon spraying plane 8B-1 Raw material hydrocarbon spraying device 8B-2 Raw material hydrocarbon spraying device 8B-3 Raw material hydrocarbon spraying device 8B-4 Raw material hydrocarbon spraying device 9 Raw material hydrocarbon introduction chamber 10 Reaction continuation / cooling chamber az Space for installing rapid refrigerant pressure injection spray means ay Space for installing rapid refrigerant pressure injection means or reaction space temperature measuring device z Last reaction stop in reaction stop zone Position Tc Thermocouple device for reaction space temperature measurement

Claims (4)

  Using a reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected coaxially, a high temperature combustion gas is generated by combustion of fuel hydrocarbons in the combustion gas generation zone, and then the high temperature combustion gas in the reaction zone A raw material hydrocarbon is sprayed and introduced from a plurality of raw material introduction devices into the flow to form a reaction gas flow containing carbon black converted from the raw material hydrocarbon by incomplete combustion or thermal decomposition reaction, and then in the reaction stop zone, A method of producing carbon black in which the reaction gas stream is cooled to a reaction stop temperature by introduction to terminate the reaction, and the reaction furnace diameter (Dr) in the reaction stop zone and the reaction furnace diameter (Df) in the feed hydrocarbon introduction site ) Is controlled so as to satisfy “2.75 ≦ Dr / Df ≦ 5.00”.   Carbon black obtained by the production method according to claim 1.   A rubber composition containing the carbon black according to claim 2.   A tire produced using the rubber composition according to claim 3.

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