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

Method for producing carbon black, carbon black, rubber composition, and tire Download PDF

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JP2014001379A
JP2014001379A JP2013109355A JP2013109355A JP2014001379A JP 2014001379 A JP2014001379 A JP 2014001379A JP 2013109355 A JP2013109355 A JP 2013109355A JP 2013109355 A JP2013109355 A JP 2013109355A JP 2014001379 A JP2014001379 A JP 2014001379A
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carbon black
reaction
raw material
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rubber composition
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Naoya Sakamoto
直也 坂本
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Asahi Carbon Co Ltd
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Asahi Carbon Co Ltd
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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

本発明は、カーボンブラックの製造方法、この方法により得られるカーボンブラック、該カーボンブラックを配合したゴム組成物、及び該ゴム組成物を用いたタイヤに関する。   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.

カーボンブラックは、厳密に制御された条件下においてファーネス炉内で発生させた高温燃焼ガス中及び／又は外部で発生させて炉内に導入された高温燃焼ガス中へ原料炭化水素を噴霧導入し、この原料炭化水素の熱分解又は不完全燃焼により生産される産業上有用でほぼ純粋な炭素元素からなる原材料である。そして、ゴム配合時の組成物に対して機械的性質、特に引張り強さ、耐摩耗性などの特性を飛躍的に向上させることができるという特異な性質を有することから、タイヤを始めとする各種ゴム製品の充填補強剤として広く、かつ約１００年もの長期間にわたって用いられてきており、その色彩的特徴である黒色度を利用して各種塗料、インキ用原材料などとしても利用されている。
ゴム配合用カーボンブラックは、その物理化学的特性、即ちカーボンブラックを構成する単位粒子径、単位重量当たりの表面積（比表面積）、粒子のつながり度合（ストラクチャー）、表面性状などにより、配合ゴム組成物の特性・性能に大きな影響を与えるので、要求されるゴム製品の性能、使用される環境等によって各種特性の異なるカーボンブラックが選択的に使用されている。 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.

このように多岐に渡って用いられているカーボンブラックであるが、その製造原料には、収率の高さから主として化石原料である石炭・石油系の原料油を用いている。しかし、この原料油は昨今の世界情勢、将来における埋蔵量を考慮すると、その供給が長期に亘って安定であるとは言えない為、代替原料の検討が行われてきた。
代替原料は、安価・安定に供給できる点を重視する必要があるが、その一例として現在、非化石原料、即ち動植物油又はその改質品に関する検討が進められており、例えば特許文献１では主にひまし油を用いたカーボンブラックの生成について検討している。
しかし、非化石原料をカーボンブラック原料油として用いた場合、カーボンブラック生成時の凝集体成長反応が著しく遅い傾向にあり、その為、上記のカーボンブラックの物理化学的特性が化石原料を用いた場合と比較して自由に制御できず、ゴム配合時の物性、例えば補強性等において化石原料由来のカーボンブラックに劣るという問題があった。したがって、通常は非化石原料由来のカーボンブラックを単独で用いることは少なく、シリカや化石原料系カーボンブラック等の他の補強性のある材料と併用する場合が多かった。 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.

このような問題に対して、物性が一定範囲にある原料油を用いる対策が試みられており、特許文献２ではＢＭＣＩ値が沸点及び比重と一定の関係にある原料油を用いて、特許文献３ではＣ／Ｈ比が一定の範囲にある原料油を用いて、カーボンブラックの製造を行っている。
これらの対策により、化石原料系カーボンブラックと比較して物理化学的特性制御に劣るという問題に対する一定の改善は見られるが、上記のとおり一部の特定の非化石原料系原料油しか用いることが出来ず、広範な原料を使用することが出来ないという問題に関しては未だに改善されていない。 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.

特開２００８−５６８０２号公報JP 2008-56802 A 特開２００９−２４０７１号公報JP 2009-24071 A 特表２０１２−５０５９３９号公報Special table 2012-505939 gazette

本発明は、広範な非化石原料を用いることができるカーボンブラックの製造方法、この方法により得られる、化石原料由来のカーボンブラックと比べて遜色の無い物理化学特性を有するカーボンブラック、該カーボンブラックを配合したゴム組成物、及び該ゴム組成物を用いたタイヤの提供を目的とする。   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.

上記課題は、次の１）〜４）の発明によって解決される。
１） 燃焼ガス生成帯域、反応帯域及び反応停止帯域を同軸上に連設した反応装置を用い、燃焼ガス生成帯域で燃料炭化水素の燃焼により高温燃焼ガスを生成させ、続いて反応帯域で前記高温燃焼ガス流中に複数の原料導入装置から原料炭化水素を噴霧導入し、不完全燃焼又は熱分解反応により前記原料炭化水素から転化したカーボンブラックを含む反応ガス流となし、次いで反応停止帯域において急冷媒体の導入により前記反応ガス流を反応停止温度まで冷却して反応を終結させるカーボンブラックの製造方法であって、反応停止帯域における反応炉径（Ｄｒ）と、原料炭化水素導入部位における反応炉径（Ｄｆ）の比が、「２．７５≦Ｄｒ／Ｄｆ≦５．００」を満たすように制御することを特徴とするカーボンブラックの製造方法。
２） １）記載の製造方法により得られるカーボンブラック。
３） ２）記載のカーボンブラックを配合したゴム組成物。
４） ３）記載のゴム組成物を用いて作製されたタイヤ。 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).

本発明によれば、従来技術のように特定物性の非化石原料に限定されず、広範な非化石原料を用いることができるカーボンブラックの製造方法を提供できる。また、化石原料由来のカーボンブラックと比べて遜色の無い物理化学特性を有するカーボンブラックを提供できる。更に、該カーボンブラックの特性を活かしたゴム組成物、及び該ゴム組成物を用いたタイヤを提供できる。   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.

本発明に用いるカーボンブラック反応装置の一例の縦断正面説明図。The longitudinal front explanatory drawing of an example of the carbon black reaction apparatus used for this invention. 図１のＡ−Ａ矢視における断面図。Sectional drawing in the AA arrow of FIG. 図１のＢ−Ｂ矢視断面における反応空間温度測定用熱電対装置を含む断面図。Sectional drawing containing the thermocouple apparatus for reaction space temperature measurement in the BB arrow cross section of FIG. Ｄｒ／Ｄｆと各条件により得られたカーボンブラックのＤＢＰとの関係図。The relationship diagram of Dr / Df and DBP of carbon black obtained by each condition.

以下、上記本発明について詳しく説明する。
本発明者らは、非化石原料を用いた従来のカーボンブラックの製造方法では、一次粒子同士の衝突や結合によって形成される凝集体の成長反応が遅いこと、その為、生成したカーボンブラックは粒子の繋がりが低いこと、即ち低位のＤＢＰを示すことを見出した。
そこで検討を重ねた結果、反応炉反応帯域以降における炉内乱流状態を高めることにより、一次粒子間の衝突頻度を向上させ、凝集体の成長を促進させることに成功した。
即ち、本発明の製造方法は、燃焼ガス生成帯域、反応帯域及び反応停止帯域を同軸上に連設した反応装置を用いたカーボンブラックの製造方法において、反応停止帯域における反応炉径（Ｄｒ）と、原料炭化水素導入部位における反応炉径（Ｄｆ）との比（Ｄｒ／Ｄｆ）を一定範囲に制御することにより、反応部以降の炉内乱流条件を高める方法である。そして、一次粒子間の衝突頻度が高まるので、従来技術では非化石原料の内、極一部の油種でしか達成できなかった、化石原料由来のカーボンブラックと同等の高位のＤＢＰを有するカーボンブラックを、広範な非化石原料を用いて製造することが出来る。 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.

まず、本発明における各帯域について図１を参照しつつ説明する。図１は本発明で用いるカーボンブラック反応装置の一例を示す図である。
このカーボンブラック反応装置１は、酸素含有ガス導入管３と、可燃性流体導入室２の内部に反応装置頭部外周から導入された酸素含有ガスを整流するための整流板５を有する酸素含有ガス導入用円筒４と、その中心軸に燃料炭化水素噴霧装置導入管６を有し、前記円筒の下流側は次第に収れんする収れん室７とし、収れん室７の下流側には図２に一例を示したような原料炭化水素噴霧装置を同一平面上に設置した４つの別個の平面を形成する原料炭化水素噴霧平面（８Ａ〜８Ｄ）を含む原料炭化水素導入室９を有し、この下流側は反応停止のための急冷媒体圧入噴霧手段（ａ〜ｙ）を備えた反応継続兼冷却室１０からなり、全体が耐火物で覆われた装置である。
なお、反応継続兼冷却室１０という名称を用いたのは、原料導入時点から前記急冷媒体圧入噴霧手段の作動時点までが反応帯域、その下流側で急冷媒体圧入噴霧手段の作動時点以降が反応停止帯域であり、この急冷媒体圧入噴霧手段の作動時点が、要求されるカーボンブラック性能により移動することがある為である。
また、通常、急冷媒体としては水を用いる。 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.

燃焼ガス生成帯域とは燃料と空気との反応により高温ガス流が生成される領域であり、この下流端は原料炭化水素が反応装置内に導入される点、例えば図１の８Ａの原料炭化水素噴霧平面から原料炭化水素が導入される場合は、それよりも上流側（図１では左端）から原料炭化水素が導入される８Ａまでを指し、８Ａにおける反応炉径をＤｆとする。また、複数位置から原料炭化水素が導入される場合の燃焼ガス生成帯域とは、例えば図１の８Ａ、８Ｂ、８Ｃの原料炭化水素噴霧平面から同時に原料炭化水素が導入される場合は、図１の左端から原料炭化水素が導入される最も上流の８Ｃまでを指し、８Ｃにおける反応炉径をＤｆとする。   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.

反応帯域とは原料炭化水素が導入された点（複数位置での導入の場合は最も上流側）から、反応継続兼冷却室１０内の急冷媒体圧入噴霧手段設置用空間（略ａとｚの間の空間）における反応生成物用の急冷媒体圧入噴霧手段（ａ〜ｙ）を作動させた点までを指す。
急冷媒体圧入噴霧手段（ａ〜ｙ）は抜き差し自在であり、生産する品種、特性により使用位置は選択される。即ち、８Ｂで原料炭化水素を導入し、急冷媒体を位置ｆで導入した場合、この間の領域（８Ｂ〜ｆ）が反応帯域となる。また、反応継続兼冷却室１０における反応炉径をＤｒとする。
また、急冷媒体圧入噴霧手段設置位置のすぐ上流側空間には、反応空間温度測定装置が設置されている〔例えば、上記８Ｂ〜ｆが反応帯域の場合にはｅに設置され、ここの温度がＴ１（℃）となる〕。図３に、図１のｂに温度測定装置を設けた場合のＢ−Ｂ矢視断面を示す。Ｔｃは反応空間温度測定用熱電対装置である。 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.

反応停止帯域とは急冷媒体圧入噴霧手段（ａ〜ｙ）を作動させた点よりも下流側（図１では右側）の帯域を指す。
なお、ｚは急冷媒体圧入噴霧手段設置用空間（略ａとｚの間の空間）の下流端という意味合いだけで、設置空間の数又は長さを限定するものではない。また、ｚは反応停止帯域の最後の反応停止位置であるが、前述のように急冷媒体圧入噴霧手段（ａ〜ｙ）は本願発明で特定した条件を満足させるように適宜選択されるから、これに伴い、反応停止位置も変化する。 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.

本発明では、「２．７５≦Ｄｒ／Ｄｆ≦５．００」を満たすように制御する。好ましい範囲は「３．７０≦Ｄｒ／Ｄｆ≦５．００」である。これにより反応炉内の乱流が大きくなり、反応帯域で発生するカーボンブラックの一次粒子同士の衝突や結合によって起こる凝集体成長が促進される。Ｄｒ／Ｄｆが２．７５より小さいと、一次粒子同士の衝突を促進させる反応炉内の乱流が十分に大きくならない為、凝集体が成長しにくい。一方、Ｄｒ／Ｄｆを過剰に大きくしても、凝集体成長の効果には限度がある為、反応炉製造上の関係からも、現実的には５．００程度が上限となる。   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.

本発明のカーボンブラックはタイヤ用のゴム組成物に用いると好適である。ゴム組成物は、従来の製造法による非化石原料由来のカーボンブラックを配合した場合には、化石原料由来のカーボンブラックを配合した場合と比較して補強性等の点で劣る傾向にあるが、本発明のカーボンブラックを配合することにより、化石原料由来のカーボンブラック配合時と同等の特性を有する優れたゴム組成物を得ることができる。更に該ゴム組成物を用いれば、有用なタイヤを作製することができる。   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.

以下、実施例及び比較例を示して本発明を更に具体的に説明するが、本発明はこれらの実施例により限定されるものではない。   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.

実施例１〜８、比較例１〜３
図１〜図３に示すカーボンブラック反応装置１を用い、表１の各実施例及び比較例の欄に示す条件となるように制御してカーボンブラックを製造した。
反応装置１は、可燃性流体導入室２（内径４５０ｍｍφ、長さ４００ｍｍ）の内部に整流板５を有する酸素含有ガス導入用円筒４（内径２５０ｍｍφ、長さ３００ｍｍ）と燃料炭化水素噴霧装置導入管６を備え、円筒の下流側が収れん室７（上流端内径３７０ｍｍφ、下流端内径８０ｍｍφ、収れん角度５．３°）となり、かつ、収れん室７の下流側には図２に８Ｂ平面で例示した４つの原料炭化水素噴霧装置（８Ｂ−１〜４）を同一平面上に設置した４つの別個の平面を形成する原料炭化水素噴霧平面（８Ａ〜８Ｄ）を含む原料炭化水素導入室９を有し、この下流側は急冷媒体圧入噴霧手段を２００ｍｍ間隔で２５ヶ所備えた反応継続兼冷却室１０（長さ６５００ｍｍ）からなる、全体が耐火物で覆われた装置である。なお、反応継続兼冷却室１０の内径（Ｄｒ）は、表１の各実施例及び比較例の欄に示すＤｒ／Ｄｆとなるように適宜選択した。 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.

Figure 2014001379
Figure 2014001379

実施例及び比較例の各カーボンブラックの物理化学的特性を表２に示す。

Figure 2014001379
Table 2 shows the physicochemical characteristics of the carbon blacks of Examples and Comparative Examples.
Figure 2014001379

上記表２に示した各特性は、下記の方法により測定したものである。
（１）２４Ｍ４ＤＢＰ吸収量
ＪＩＳ Ｋ６２１７−４：２００８に記載の方法で測定。カーボンブラック１００ｇ当たりに吸収されるジブチルフタレート（ＤＢＰ）の量（ｍＬ／１００ｇ）
（２）ＣＴＡＢ吸着比表面積
ＪＩＳ Ｋ６２１７−３：２００１に記載の方法で測定される、単位重量当たりの比表面積（ｍ２／ｇ）
（３）トルエン着色透過度
ＪＩＳ Ｋ６２１８−４：２０１１記載の方法で測定した、純粋なトルエンの透過率を１００％としたときの処理液の透過率（％）。数字が大きいほど、トルエン汚染度が小さい、即ち未分解芳香族炭化水素成分が少ないことを意味する。 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.

表２に示した各カーボンブラックの物理化学特性、及び図４に示したＤｒ／ＤｆとＤＢＰの関係図から、本発明のカーボンブラック製造方法の効果・利点を説明する。
比較例１、２は非化石原料油を用いているが本発明の要件を満たさない例であり、比較例３は一般的な化石原料油を用いた例である。
実施例１〜８のカーボンブラックは、比較例１、２のカーボンブラックと比べて何れも高いＤＢＰ値を示し、比較例３のカーボンブラックと略同等のＤＢＰ値を示している。 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.

実施例９〜１６、比較例４〜６
＜ゴム組成物の調製及び評価＞
実施例１〜８及び比較例１〜３の各カーボンブラックを使用し、表３の実施例９〜１６、比較例４〜６の各欄に示す配合処方のゴム組成物を、バンバリーミキサーにより混練して調製した。得られた各ゴム組成物の破壊強度及び耐摩耗性を下記の方法で測定した。
その結果を表３に示す。 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.

＜破壊強度＞
ＪＩＳ Ｋ６３０１に準拠して、各ゴム組成物の引張試験を行って引張り強さ（Ｔｂ）を測定し、比較例６の引張り強さの値を１００として指数表示した。
指数値が大きい程、引張り強さの値が大きく、破壊強度が高いことを示す。 <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.

＜耐摩耗性＞
ランボーン型摩耗試験機を用いて、室温、スリップ率２５％の条件で試験を行い、比較例６の摩耗量の逆数を１００として指数表示した。指数値が大きい程、摩耗量が少なく、耐摩耗性が良好であることを示す。 <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.

Figure 2014001379
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］
Figure 2014001379
 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.]

実施例９〜１６のゴム組成物は、比較例４、５に比べて高い破壊強度と高い耐摩耗性を示した。また一般的な化石原料油から製造されたカーボンブラックを用いた比較例６のゴム組成物と同等以上であった。即ち、本発明のカーボンブラックは、ゴム配合時においても一般的な化石原料を用いて製造されたカーボンブラックと同等の補強効果を示す。したがって、一般的な化石原料油から製造されたカーボンブラックを用いたゴム組成物によるタイヤと比較しても、何ら遜色のないタイヤを得ることが出来る。
上記のように、本発明は、製造条件の制御により広範な非化石原料を用いることが可能な技術であり、実施例で示した植物油だけでなく動物油等の他の油種も使用可能である。 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. .

１ カーボンブラック反応装置
２ 可燃性流体導入室
３ 酸素含有ガス導入管
４ 酸素含有ガス導入用円筒
５ 整流板
６ 燃料炭化水素噴霧装置導入管
７ 燃料導入手段を備えた収れん室
８Ａ 原料炭化水素噴霧平面
８Ｂ 原料炭化水素噴霧平面
８Ｃ 原料炭化水素噴霧平面
８Ｄ 原料炭化水素噴霧平面
８Ｂ−１ 原料炭化水素噴霧装置
８Ｂ−２ 原料炭化水素噴霧装置
８Ｂ−３ 原料炭化水素噴霧装置
８Ｂ−４ 原料炭化水素噴霧装置
９ 原料炭化水素導入室
１０ 反応継続兼冷却室
ａ〜ｚ 急冷媒体圧入噴霧手段設置用空間
ａ〜ｙ 急冷媒体圧入噴霧手段、又は反応空間温度測定装置設置用空間
ｚ 反応停止帯域の最後の反応停止位置
Ｔｃ 反応空間温度測定用熱電対装置 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)

燃焼ガス生成帯域、反応帯域及び反応停止帯域を同軸上に連設した反応装置を用い、燃焼ガス生成帯域で燃料炭化水素の燃焼により高温燃焼ガスを生成させ、続いて反応帯域で前記高温燃焼ガス流中に複数の原料導入装置から原料炭化水素を噴霧導入し、不完全燃焼又は熱分解反応により前記原料炭化水素から転化したカーボンブラックを含む反応ガス流となし、次いで反応停止帯域において急冷媒体の導入により前記反応ガス流を反応停止温度まで冷却して反応を終結させるカーボンブラックの製造方法であって、反応停止帯域における反応炉径（Ｄｒ）と、原料炭化水素導入部位における反応炉径（Ｄｆ）の比が、「２．７５≦Ｄｒ／Ｄｆ≦５．００」を満たすように制御することを特徴とするカーボンブラックの製造方法。   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”. 請求項１記載の製造方法により得られるカーボンブラック。   Carbon black obtained by the production method according to claim 1. 請求項２記載のカーボンブラックを配合したゴム組成物。   A rubber composition containing the carbon black according to claim 2. 請求項３記載のゴム組成物を用いて作製されたタイヤ。   A tire produced using the rubber composition according to claim 3.
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JP7378513B2 (en) 2015-11-21 2023-11-13 サンコール インダストリーズ ゲゼルシャフト ミット ベシュレンクテル ハフツング Particulate carbon material that can be produced from renewable raw materials and its production method

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