JP2017008214A - Method of producing carbon black, carbon black, rubber composition, tire - Google Patents

Abstract

A method for producing carbon black using a raw material other than a general fossil raw material, a carbon black obtained by the method and having physicochemical properties comparable to carbon black derived from a general fossil raw material, A rubber composition containing carbon black and a tire using the rubber composition. In a method for producing carbon black using a reactor in which a combustion gas generation zone, a reaction zone and a reaction stop zone are coaxially connected, as a raw material hydrocarbon introduced into the reaction zone, a pyrolysis reaction of waste tires is performed. A method for producing carbon black using the generated liquid hydrocarbon. [Selection figure] None

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 Widely used as a filler for rubber products 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 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 recent 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.
As an example of an alternative raw material, non-fossil raw materials, that is, animal and vegetable oils or modified products thereof are currently being studied. For example, Patent Document 1 mainly examines 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 There is a problem that it cannot be freely controlled as compared with the carbon black and is inferior to carbon black derived from a fossil raw material in physical properties at the time of rubber blending, for example, reinforcing properties. Therefore, carbon black derived from non-fossil raw materials is rarely used alone, and is often used in combination with other reinforcing materials such as silica and fossil raw material-based carbon black.

In response to such a problem, the present inventor obtains carbon black having physicochemical characteristics comparable to carbon black derived from fossil raw materials by controlling the diameter of a specific part of the reactor used for carbon black generation. (See Patent Document 2).
In addition to this invention, various studies on non-fossil raw materials as alternative raw materials have been conducted. However, since there are various restrictions on the production of carbon black by these techniques, studies on raw materials that can be used more easily are currently underway.

JP 2008-56802 A JP 2014-1379 A

  The present invention is a method for producing carbon black using raw materials other than general fossil raw materials, carbon black obtained by the method and having physicochemical properties comparable to carbon black derived from general fossil raw materials, An object of the present invention is to provide a rubber composition containing the carbon black 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 In the method for producing carbon black in which the reaction gas stream is cooled to a reaction stop temperature by introducing a medium to terminate the reaction, liquid hydrocarbons generated by a pyrolysis reaction of waste tires are used as the raw material hydrocarbons. A method for producing carbon black.
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).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of carbon black using raw materials other than a general fossil raw material can be provided. Further, it is possible to provide carbon black having physicochemical characteristics that are comparable to carbon black derived from general fossil raw materials. 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.

Hereinafter, the present invention will be described in detail.
In order to examine carbon black raw materials other than general fossil raw materials, the present inventors have produced carbon black using various non-fossil raw materials, and as a result, liquid hydrocarbons produced by pyrolysis reaction of waste tires. It was found that when this is used, carbon black having physical properties comparable to those obtained when a general fossil raw material is used can be obtained.
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 coaxially connected. It is a method for producing carbon black, which is a liquid hydrocarbon to be produced.
This makes it possible not only to produce carbon black using raw materials other than general fossil raw materials, but also to build a material cycle because the raw materials are hydrocarbons contained in waste tires. Thus, inexpensive and stable raw material supply is achieved.

Here, the carbon black reactor used in the present invention will be described with reference to FIG. 1 as an example.
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 up to 8A from which the raw material hydrocarbon is introduced from the upstream side (the left end in FIG. 1). 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. To the most upstream 8C where the raw material hydrocarbon is introduced.

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 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, but 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. Along with this, the reaction stop position also changes.

  The carbon black obtained by the production method of the present invention is suitable for use in a rubber composition for tires. The rubber composition blended with the carbon black has the same characteristics as the rubber composition blended with the carbon black derived from a general fossil raw material. Furthermore, if this rubber composition is used, a useful tire can be produced.

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

Examples 1-3, Reference Examples 1-3, Comparative Examples 1-3
Each carbon black was manufactured by using the carbon black reactor 1 shown in FIGS. 1 to 2 and controlling the conditions shown in the columns of Examples, Reference Examples and Comparative Examples in Tables 1 to 3.
Examples 1 to 3 are examples using liquid hydrocarbons (tire pyrolysis oil) produced by pyrolysis reaction of waste tires according to the present invention, and Reference Examples 1 to 3 are general fossil raw material oils. Examples using heavy oil and Comparative Examples 1 to 3 are examples using tall oil which is a typical non-fossil raw material.
In addition, Examples and Comparative Examples in Tables 1 to 3 are performed for the purpose of producing carbon black having physical properties as close as possible to Reference Examples 1 to 3 in each table.
The carbon black reactor 1 includes a combustible fluid introduction chamber 2 (inner diameter 450 mmφ, length 400 mm), an oxygen-containing gas introduction cylinder 4 (inner diameter 250 mmφ, length 300 mm) having a rectifying plate 5 and a fuel hydrocarbon spray. The apparatus introduction pipe 6 is provided, 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 an 8B plane in FIG. A raw material hydrocarbon introduction chamber 9 including raw material hydrocarbon spraying planes (8A to 8D) forming four separate planes in which the four raw material hydrocarbon spraying apparatuses (8B-1 to 4) illustrated in FIG. The downstream side is a device that is composed of a reaction continuation and cooling chamber 10 (length: 6500 mm) provided with 25 rapid refrigerant press-fitting spray means at intervals of 200 mm and is entirely covered with a refractory.

About each said carbon black, the physicochemical characteristic was measured by the method of following (1)-(3). The results are shown in Tables 4-6.
(1) DBP oil absorption, 24M4 DBP oil absorption The amount (mL / 100 g) of dibutyl phthalate (DBP) absorbed per 100 g of carbon black was measured by the method described in JIS K6217-4: 2008.
(2) IA (Iodine adsorption amount)
The iodine adsorption amount (mg / g) per 1 g of the sample was measured by the method described in JIS K6217-1: 2008.
(3) N2SA (nitrogen adsorption specific surface area)
The specific surface area (m ² / g) per unit weight was measured by the method described in JIS K6217-2: 2001.

As shown in Tables 1 to 3, the production conditions of Examples, Reference Examples and Comparative Examples are almost the same. However, as can be seen from the results of Tables 4 to 6, in Examples 1 to 3, the general conditions are the same. The DBP oil absorption is almost the same as in Reference Examples 1 to 3 using fossil raw materials, and carbon black comparable to the conventional manufacturing method is obtained.
On the other hand, it can be seen that Comparative Examples 1 to 3 using conventional non-fossil raw materials have a lower DBP oil absorption than other carbon blacks and tend to be inferior in aggregate growth in the carbon black production process.
Thus, in the prior art using non-fossil raw materials, it was necessary to select a limited raw material having specific oil physical properties or to select a special manufacturing method, but according to the manufacturing method of the present invention, excellent physical properties The carbon black can be easily obtained.

上記表７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］
Examples 4-6, Reference Examples 4-6, Comparative Examples 4-6
<Preparation of rubber composition>
The carbon black obtained by the production method of the present invention has physical properties equivalent to those of carbon black obtained from a general fossil raw material oil, and is therefore suitable for use in a rubber composition for tires. Accordingly, a rubber composition having the formulation shown in Table 7 below using each carbon black was prepared by kneading with a Banbury mixer.

The details of the materials of * 1 to * 4 in Table 7 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.]

<Evaluation of rubber composition>
About each said rubber composition, fracture strength and abrasion resistance were measured with the following method.
The results are shown in Tables 8-10.

<Destructive strength>
In accordance with JIS K6251: 2010, each rubber composition was subjected to a tensile test to measure the elongation at break (Eb).
The larger the index value, the better the fatigue resistance and cut resistance.

<Abrasion resistance>
Using a Lambone-type wear tester, the test was performed under conditions of room temperature and a slip rate of 25%, and the index was displayed with the reciprocal of the wear amount of each reference example being 100. The larger the index value, the smaller the amount of wear and the better the wear resistance.

  As shown in Tables 8 to 10, when a rubber composition containing conventional carbon black derived from non-fossil raw materials was used, a rubber composition containing carbon black derived from general fossil raw materials was used. Compared to the case of the conventional case, the rubber composition containing the carbon black obtained by the production method of the present invention is compounded with carbon black derived from a general fossil raw material. Compared to a tire using the rubber composition, a tire comparable to that of the tire can be obtained.

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

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, In the method for producing carbon black, in which the reaction gas stream is cooled to the reaction stop temperature by introduction to terminate the reaction, a liquid hydrocarbon produced by a pyrolysis reaction of waste tire is used as the raw material hydrocarbon Black manufacturing method.   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.

Images