JP2559517C

JP2559517C -

Info

Publication number: JP2559517C
Authority: JP
Original assignee: Nippon Steel Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Publication date: 1998-09-03

Description

【発明の詳細な説明】〔産業上の利用分野〕本発明は、カーボンブラックの粒子径分布ならびに凝集体径分布を任意にコン
トロールできるカーボンブラックの製造方法及びその装置に関する。〔従来の技術〕カーボンブラックの粒子径分布に影響を及ぼす因子、また具体的な粒子径分布
の制御方法などを明記した公知文献として、例えば特公昭５４−１３２３２号公
報があり、これには、反応室に冷却した脱水排ガスを導入すると、粒子径が小さ
くなると同時に、粒子径分布が狭くなると記載されている。カーボンブラックの凝集体径分布の制御に関する公知文献としては、特開昭５
７−４２７７３号公報、特開昭６０−２２３８６５号公報などに見られる様に、
燃焼ガス充填室に軸方向から原料を噴霧して、燃焼ガスと混合させて引続き、先絞り部や拡大部等炉内での流動状態を変化させることにより、凝集体径分布を制
御する内容のものが記載されている。又高温の燃焼ガス中に熱分解性原料炭化水素を注入することに関する公知文献
として、特公昭４７−１００５号公報では、燃焼ガスの高速度流れ中に原料炭化
水素を直接注入する。即ち燃焼室から絞った所に原料炭化水素を注入すると同時
に、その位置から後がそのまま反応帯域となっており、該反応帯域は全体として
僅かに末広の円錘形テーパーはついているが、整流効果を持たせた筒状絞り部及
び拡大テーパー部は設けられていない。特開昭４７−５６３号公報では、燃焼ガス流が十分な質量速度を有している点
に原料を注入するとされ、実際には円筒状絞り部（最狭部）に注入されている。特開昭６１−１８３，３６４号公報では、ベンチュリー部の最狭部である側壁
を貫通する原料導入管より中心軸に対して９０±２０°の角度で原料油を噴霧し
ている。特開昭５２−１３３，０９９号公報では、ベンチュリー部の拡大テーパー部よ
り下流の円筒形状の反応室の最初の部分に、軸方向については１ケ所から原料が
導入されている。米国特許４，３９１，７８９号公報では、燃焼室から絞り部に到る縮小テーパ
ー部に軸方向に複数個所から原料を注入している。米国特許４，２９４，８１４号公報では、反応域での圧力損失を減少させる目
的で一部の原料油を燃焼室の軸方向から供給し、スパイラルフローの燃焼ガスと
共にベンチュリー部を通過する際、ベンチュリー部の拡大テーパー部に残りの原
料油を供給している。上記の如く、公知文献では、原料供給位置としては、縮小テーパー部又は絞り
部に設けたものは見うけられるが、整流効果を備えた筒状絞り部を設け且つ該絞
り部から拡大テーパー部および反応室にかけて原料噴霧口を軸方向に２ヶ所以上
配置して、原料油をこれら噴霧口の１ヶ所又は２ヶ所以上を選択した原料噴霧口
より噴霧し、製品カーボンブラックの粒子径分布や凝集体径分布を任意に制御す
る技術思想は見当らない。特開平１−２３０６７７号公報には、多数のかつ別々に制御されるカーボンブラック原料油流を反応器の別々の部分の中へ供給する方法が記載されており、具
体的には、燃焼室から絞り部にかけての注入帯域へ供給するものであるが、この
部分では燃焼ガス流が十分には整流されておらず、カーボンブラックの粒子径分
布や凝集体径分布を任意に制御するまでにはいたらない。〔発明が解決しようとする課題〕本発明の目的は、カーボンブラックの粒子径分布および凝集体径分布を任意に
制御することのできるカーボンブラックの製造方法及び装置を提供することであ
る。〔課題を解決するための手段〕本発明者らは、カーボンブラックの粒子径分布、凝集体径分布に影響を及ぼす
因子を解明するために、鋭意研究を行った。その結果、燃焼ガス流が筒状絞り部で整流され、整流状に流れる拡大テーパー
部で反応器の軸方向に沿って１ヶ所あるいは２ヶ所以上の分割位置に設けた噴霧
口から原料を噴霧することにより、粒子径分布、凝集体径分布を任意に制御でき
ることを見い出し本発明を完成した。また、筒状絞り部並びに燃焼ガス流が該絞り部で整流され、整流状に流れる拡
大テーパー部および反応室の側壁で反応器の軸方向に沿って２ヶ所以上の分割位
置に設けた噴霧口から原料を併用して噴霧する際に、原料噴霧口の位置、特に各
原料噴霧口間の反応器内容積を選択することにより凝集体径分布が規則的に変化
すること並びにその選択した各原料噴霧口からの原料導入比率を調節することに
より、粒子径分布及び凝集体径分布を任意に制御できることを見い出し本発明を
完成した。本発明は、下記（１）〜（６）に記載したカーボンブラック製造方法
および装置である。（１）燃焼室と、該室に比して狭められた筒状絞り部と、該絞り部から拡大テ
ーパー部を介して連続する、該絞り部に比して拡大された反応室を有するカーボ
ンブラック反応器により、少なくとも該燃焼室でカーボンブラック生成反応に必
要な燃焼ガスの熱風を作り、その下流において、筒状絞り部により該熱風を整流
状態とし、該整流熱風流中に原料炭化水素を装入して、反応室でカーボンブラッ
クを生成させた後、急冷するカーボンブラックの製造方法において、該燃焼室と該筒状絞り部と該拡大テーパー部の構成により、少なくとも拡大テーパー部にお
いて整流状態の熱風を形成させることと、原料炭化水素を、該拡大テーパー部の
軸方向２ヶ所以上の分割位置に設けた噴霧口から、個別に又は併用して熱風中へ
周方向から均一に噴霧することの組合わせを含むカーボンブラックの製造方法。（２）燃焼室と、該室に比して狭められた筒状絞り部と、該絞り部から拡大テ
ーパー部を介して、連続する該絞り部に比して拡大された反応室とを有するカー
ボンブラック反応器により、少なくとも該燃焼室でカーボンブラック生成反応に
必要な燃焼ガスの熱風を作り、これに原料炭化水素を装入し、反応室でカーボン
ブラックを生成させた後、急冷するカーボンブラックの製造方法において、該燃
焼室と該筒状絞り部と該拡大テーパー部の構成により少なくとも筒状絞り部と拡
大テーパー部において整流状態の熱風を形成させることと、原料炭化水素を、該
筒状絞り部と該拡大テーパー部および該反応室にかけて軸方向２ヶ所以上の分割
位置に設けた原料噴霧口とから選択した少なくとも２ヶ所の原料噴霧口を併用し
て熱風中へ周方向から均一に噴霧することとの組合わせを含むカーボンブラック
の製造方法。（３）前記（２）のカーボンブラックの製造方法において、原料炭化水素を、
筒状絞り部と拡大テーパー部および反応室にかけて軸方向２ヶ所以上の分割位置
に設けた原料噴霧口から選択した少なくとも２ヶ所の原料噴霧口を併用して熱風
中へ噴霧し、その際、併用する各原料噴霧口からの原料導入量比率を調節するこ
との組合わせを含むカーボンブラックの製造方法。（４）カーボンブラック生成反応に必要な熱風を発生させる燃焼室と、該燃焼
室に連結され、熱風に整流効果を持たせる燃焼室に比して狭められた筒状絞り部
の長さＬと直径Ｄの比、Ｌ／Ｄが１〜５である筒状絞り部と、該絞り部から該絞
り部に比して拡大された反応室に連通する全角度が５°〜１２°の範囲である拡
大テーパー部と、該拡大テーパー部に連通するカーボンブラック生成反応室と、
反応室末端部に連結された急速冷却室と煙道と、前記拡大テーパー部に、軸方向
に２ヶ所以上、配置された周方向から均一に原料炭化水素を導入する原料噴霧口
との組合わせを含むカーボンブラック製造装置。（５）カーボンブラック生成反応に必要な熱風を発生させる燃焼室と、該燃焼室に連結され、熱風に整流効果を持たせる燃焼室に比して狭められた筒状絞り部
の長さＬと直径Ｄの比、Ｌ／Ｄが１〜５である円筒絞り部と、該絞り部から該絞
り部に比して拡大された反応室に連通する全角度が５°〜１２°の範囲である拡
大テーパー部と該拡大テーパー部に連通するカーボンブラック生成反応室と、反
応室末端部に連結された急速冷却室と煙道と、前記筒状絞り部から拡大テーパー
部および反応室にかけて軸方向２ヶ所以上に配置された周方向から均一に原料炭
化水素を導入する原料噴霧口との組合わせを含むカーボンブラック製造装置。以下本発明を詳細に説明する。先ず本発明で使用し得る原料炭化水素としては
、特に限定するものではないが、アントラセン油及びクレオソート油等のコール
タール系重質油、石油ガス油、又は留出油並びに石油熱分解からの副生残留物等
を用いることができる。又燃料としては、石炭系ガスや石油系ガス、軽質油、重
質油等を利用できる。本発明の製造装置自体は横型方式が一般的であるが、縦型方式であってもよい
。又、燃焼室や反応室の断面は円筒形状が一般的であるが、これに限定されるも
のではない。本発明において、「少なくとも該燃焼室でカーボンブラック生成反応に必要な
燃焼ガスの熱風を作り」の少なくともの意味は、燃焼室においては燃料炭化水素
と空気を装入して燃焼させて燃焼ガスを作ったり、又外部のバーナーにより、１
次空気で燃料を予備燃焼させ、燃焼室には２次空気のみを装入して完全燃焼させ
てもよく、又全く外部の燃焼バーナーで燃焼を行い、燃焼室では燃焼ガスの充填
だけを行ってもよい事を表わす。しかし、本発明の拡大テーパー部において、燃焼ガスを可及的に整流状態を保
たしめるためには、本発明においては、特に限定するものではないが燃焼室の手
前上流端壁の中央に外部バーナー等を備えた予備燃焼室の先端を共軸的に連結す
ることにより、予備燃焼ガスにスパイラルフローを出来るだけ生じさせないで絞
り部方向へ平行して流入せしめ、燃焼室において、適宜周壁から２次空気を供給
して完全燃焼させるような方式が好ましい。この場合には特に、燃焼室において、予備燃焼室から流入してくる予備燃焼ガ
スのスパイラルフローと逆向きの接線方向に２次空気を導入して、２次空気の流れにより予備燃焼ガスのスパイラルフローを弱めながら完全燃焼させる方式が好
ましい。本発明でいう空気とは、大気の他、窒素やアルゴン等の不活性ガスと酸素とを
又は大気と酸素とを任意の割合で混合した混合ガス等の酸素含有ガスを含む。かかる燃焼室に連結された狭められた筒状絞り部では、熱風ガスを整流状態を
保たせるために、一定の長さの平行区間を設ける。又絞り部から反応室に到る拡
大テーパー部でも、熱風ガスの整流状態を保持させる必要がある。この絞り部の平行区間の長さと、後続する拡大テーパー部の角度との組合わせ
を種々変化させて実験した結果、熱風ガスの整流状態を保持させてカーボンブラ
ックの粒子径分布、および凝集体径分布を任意に制御するためには、一定の条件
が存在することを見出した。即ち、前記円筒状絞り部の長さＬと直径Ｄの比Ｌ／
Ｄが１以上、好ましくは１〜５の範囲内とし、拡大テーパー部の全角度が５°〜
１２°、好ましくは６°〜１０°である範囲が特に効果がある。なお、絞り部の入口側の角度については、絞り部の長さと、拡大テーパー角度
が上記範囲内であるかぎり、特に限定するものではないが、後続での整流効果を
考慮すると、縮小テーパーの全角度は１００°以下、好ましくは５０〜９０°の
範囲内が望ましい。又、拡大テーパー部の軸方向２ヶ所以上の分割位置に設ける
原料炭化水素噴霧口、筒状絞り部から拡大テーパー部および反応室の軸方向２ヶ
所以上の分割位置に設ける原料炭化水素噴霧口はこれら各部の壁面にほぼ垂直方
向に周壁上に複数箇所設置して、各噴霧口から均一に噴霧するのが望ましい。本発明の第１の発明においては、これらテーパー部の分割位置に設けた原料炭
化水素噴霧口からの注入は、個別又は併用して行う。目的とする粒子径分布、凝
集体径分布により１つ或は２つ以上の噴霧口よりその噴霧口を選択し原料を噴霧
する。本発明の第１の発明で重要なことは、拡大テーパー部に複数の原料噴霧口を設
け、それを個別に選択して使用するか、組み合わせて併用して、使用することで
ある。拡大テーパー部とは絞り部の後端から後続の円筒状反応室に至る区間をいう。本発明の第２の発明において、筒状絞り部、拡大テーパー部及び反応室の２ヶ所以上の分割位置に設けた原料噴霧口からの注入は、少なくとも２ヶ所を併用し
て行う。目的とする粒子径分布、凝集体径分布により２つ以上の噴霧口より周方
向について均一に少なくとも２ヶ所の噴霧口を選択し原料を噴霧する。本発明の第２の発明で重要なことは、筒状絞り部、拡大テーパー部及び反応室
の２ヶ所以上の分割位置に複数の原料噴霧口を設け、それから少なくとも２ヶ所
を選択し、組み合わせて併用して、使用することである。また、筒状絞り部に設
ける原料噴霧口は、整流状態が形成された後端部に設置するものである。筒状絞り部後端部１ヶ所と、拡大テーパー部、反応室から１ヶ所を選択した２
ヶ所から原料を噴霧することが、粒子径分布、凝集体径分布の制御を容易にでき
る点で最も好ましい。拡大テーパー部とは絞り部の後端から後続の円筒状反応室に至る区間をいう。本発明においては、燃焼ガスを整流にする点より、絞り部の長さＬと直径Ｄの
比で示せばＬ／Ｄは１以上、好ましくは１〜５の範囲内が望ましい。５より大き
いと熱風による圧力損失が大きくなり好ましくない。一方１未満では整流効果が
十分でなく好ましくない。又絞り部の直径Ｄは燃焼室の直径をＤ₁とすればＤ／Ｄ₁＝０．２〜０．５程度
が好ましい。拡大テーパー部の角度は、全角で５°〜１２°、好ましくは６°〜１０°が最
も効果がある。反応室は、拡大テーパー部に引き続いた円筒形状からなり、通常は燃焼室の直
径と同等か、小さくなるようにする。なお、反応室の一部の直径を大きくするこ
とにより、ガスの滞留時間を長くすることができる。反応室の後部には、通常通り、水噴霧口が軸方向に多段階に設けられており、
冷却室を形成している。これに続いて拡大した煙道が設けられる。これらは同軸
上に配置される。本発明の第１の発明においては拡大テーパー部において、液体炭化水素を導入
する原料噴霧口が、軸方向に沿って多段階に設けられている。各段階における原料噴霧口は、熱風中へ均一分散させるために、円周上で複数
個づつ設ける。第１図に本発明の第１の発明に利用するカーボンブラック製造装置の反応器の
概略縦断面図を示す。第１図で１はカーボンブラック反応器、２は予備燃焼室か
らの予備燃焼ガス導入口、３は２次空気導入口、４は先細りテーパー部を有する
燃焼室、５は絞り部、６は拡大テーパー部、７は反応室、８は原料導入口、９は
冷却水噴霧口である。後記、実施例との関連で、便宜上、前方から後方へ、No.１〜No.３の噴霧口と
する。図では上部より噴霧するように画いたが、軸方向の各位置について同一円
周上で複数個づつ噴霧口が設けられている。燃焼室は、上流端壁部の中心部に予備燃焼室からの予備燃焼ガス導入口を設け
、周壁部の３，３′より２次空気を導入する例を示した。冷却水噴霧口９は、反応室後部に軸方向に複数個設けてある。本発明の第２の発明においては筒状絞り部から拡大テーパー部および反応室に
かけて、液体炭化水素を導入する原料噴霧口が、軸方向に沿って多段階に設けら
れている。各段階における原料噴霧口は、熱風中へ均一分散させるために、円周上で複数
個づつ設ける。これら各原料噴霧口からの注入は、少なくとも２ヶ所の噴霧口を併用して行う
。目的とする粒子径分布、凝集体分布より少なくとも２ヶ所の噴霧口を選択し、
各原料噴霧口からの原料導入比率を調節しながら原料を導入する。このとき、一
段目の原料噴霧口としては、筒状絞り部又は拡大テーパー部に設けられた原料噴
霧口を選択し、二段目の原料噴霧口としては一段目の噴霧口よりも下流側に設け
られた原料噴霧口を選択するのがよい。この際、選択した噴霧口の位置、特には上流側に設けた原料噴霧口と下流側に
設けた原料噴霧口との間の反応器内容積即ち各原料噴霧口間でのガスの滞留時間
により、得られるカーボンブラックの凝集体径分布が異なる。すなわち、この内
容積が大きくなる程、生成するカーボンブラックの凝集体径分布が広くなる傾向
がある。特に、下流側の原料噴霧口として反応室側壁に周方向に均等に設けた原
料噴霧口を用いた場合は、凝集体径分布の広いカーボンブラックを製造できる。また、各原料噴霧口からの原料導入比率を調節することにより、カーボンブラ
ックの粒子径分布を制御できる。一般に、上流側の原料噴霧口からの原料導入量が
下流側の原料噴霧口からの原料導入量より大きいとき、粒子径分布が狭くなる傾
向があり、小さいとき、広くなる傾向がある。ただし、上流側の原料噴霧口と下
流側の原料噴霧口とからの原料導入比率により、上流側の原料噴霧口から単独で
導入する場合よりも粒子径分布が狭くなる場合がある一方で、下流側の原料噴霧
口から単独で導入する場合よりも広くなる場合があるので、各原料噴霧口からの
原料導入比率を調節することにより、１ヶ所の原料噴霧口から単独で原料を導入
する場合よりも広い範囲にわたってカーボンブラックの粒子径分布の広さを制御
できる。第６図に本発明の第２の発明に利用するカーボンブラック製造装置の反応器の
概略縦断面図を示す。第６図で１０は予備燃焼室、１１は燃料噴霧口、１２は１
次空気導入口、１３は先細りテーパー部を有する燃焼室、１４−１及び１４−２
は２次空気導入口、１５は筒状絞り部、１６は拡大テーパー部、１７は反応室、
１８−１、１８−２、１８−３、１８−４、１８−５、１８−６、１８−７は原
料導入口、１９は冷却水噴霧口である。第６図では、原料を上部より噴霧するように画いたが、軸方向の各位置につい
て同一円周上で複数個づつ噴霧口が設けられている。燃焼室は、上流端壁の中心部に予備燃焼室からの予備燃焼ガス導入口を設け、
周壁部の１４−１、１４−２より２次空気を導入する例を示した。なお２次空気
導入口１４−１、１４−２は、予備燃焼室の１次空気導入口１２とは、逆向きの
接線方向に設けられている。冷却水噴霧口１９は、反応室後部に軸方向に複数個設けてある。〔実施例〕以下に実施例によって、本発明を更に詳細に説明するが、本発明は、この実施
例によって、何等限定されるものではない。なお、下記実施例で用いた原料油分析値、カーボンブラック（ＣＢ）の粒子径
分布測定法、沈降分析法によるカーボンブラック凝集体サイズ分析法及びＤ_stと
ΔＤ₅₀の定義は下記の通りである。（１）原料油原料油としては、コールタール系重質油を用い、その性状及び組成を以下の表
に示した。％は重量％である。（２）カーボンブラックの粒子径分布測定法カーボンブラックの電子顕微鏡写真を撮影し、この写真をZeiss 社（西独）製
粒度分布測定器ＴＧＡ１０にかけて個数基準の平均粒子径Ｘ［nm］及び粒子径分
布の標準偏差σ［nm］を求めた。（３）カーボンブラック凝集体サイズ（アグリゲートサイズ）測定法沈降分析法による。その使用機器としては Disk Centrifuge（DCF）（英，Jo
yce Loebl 社製）を使用し、下記の方法で測定した。乾燥カーボンブラック試料をエタノール水溶液と混合し、超音波で十分分散さ
せて分散液を作成する。あらかじめ設定したディスク回転数で回転するディスクに沈降液（適当な濃度
のグリセリン液）を注入し、緩衝ラインスタート法による緩衝液（沈降液より比
重の小さい液）を少量注入し、「カット」及び「ブースト」コントロールの使用
により、緩衝液を拡散せしめ、回転が安定した時点で、前述の分散液を０．２ml
ディスクに注入する。ディスクの定点（フォトマル）を通過するまでの時間と濃度の関係をストーク
スの式に準じた計算式から求め、カーボンブラック凝集体のストークス相当径と
その頻度のヒストグラムが得られる。このヒストグラムにおいて、最多頻度のストークス相当径をＤ_stと呼び、カーボンブラック凝集体の平均的大きさの目安とする。またＤ_stの半値巾をΔＤ₅₀と定義し、これは凝集体径の分布広さを表わす。（実施例１）第１図における、燃焼室の直径３９０mmφ、絞り部の直径Ｄ₁が１３０mmφ、
絞り部入口の縮小テーパー角度（全角）７８°、絞り部の長さＬ₁が２６０mm、
拡大テーパー部のテーパー角度（全角）６°、テーパー部の長さ３８１mm、反応
室の直径１７０mmφとした試験装置（第１図）を使用し原料油としては上記（１
）の原料油を使用した。拡大テーパーの軸方向について、原料の導入位置を変化させて、導入位置とカを調べた。No.１原料の導入位置は、拡大テーパー部の入り口から２１mmの位置
に、No.２原料の導入位置は第１より１８０mm離れた位置に、No.３原料の導入位
置は第２より１８０mm離れた位置にそれぞれ設けた。実験条件及び結果を第１表に、粒子径分布σ／ｘと噴霧口位置の関係を第２図
に示した。この結果から原料導入位置を拡大テーパー部の下流側へずらすことに
よって、カーボンブラックの粒子径平均は大きくなり、粒子径分布はブロードに
なった。（実施例２）実施例１と同一の装置（第１図）を用いて、原料の１段噴霧と２段噴霧とがカ
ーボンブラックの凝集体径分布に与える影響について調べた。実験条件及び結果を第２表に示した。凝集体のストークス相当径ヒストグラム
において、最多頻度を与えるストークス相当径をＤ_st（nm）、Ｄ_stの半値巾をΔ
Ｄ₅₀（nm）で表わす。凝集体径分布ΔＤ₅₀／Ｄ_stと噴霧口位置との関係を第３図
に示した。この結果、１段噴霧の場合よりも、２段噴霧の方が凝集体径分布をブロードに
することができることが判る。（実施例３）燃焼ガスが拡大テーパー部で整流になっている効果を調べる。実施例１で用いた装置において絞り部の軸方向長さＬと直径Ｄについて、Ｌ／
Ｄの影響を見るために拡大部の角度を一定にして、４種のＬ／Ｄの絞り部を用い
て実験を行なった。絞り部のＬ／Ｄの関係を第４図に示す。Ｌ／Ｄの値が０．５の時、粒子径分布はシャープにできなかった。（実施例４）実施例３と同様に、拡大テーパー部で燃焼ガスが整流になっている効果を調べ
る。実施例１で用いた装置において拡大テーパー部の全角度（円錐角）が粒子径分
布に及ぼす影響を調べるために、筒状絞りのＬ／Ｄの値を一定にして、拡大テー
パー部だけを取り替えて実験を行った。実験条件とその結果を第４表に示し、製果、拡大テーパー部の全角度（円錐角）が６°〜１０°より小さいか、または大
きい場合には、粒子径分布はシャープにならない。（実施例５）第６図における、燃焼室の直径３９０mmφ、絞り部の直径Ｄ₁は１３０mmφ、
絞り部入口の縮小テーパー角度（全角）７８°、絞り部の長さＬ₁が２６０mm、
拡大テーパー部のテーパー角度（全角）６°、拡大テーパー部の長さは３８１mm
、反応室の直径は１７０mmφとした試験装置（第６図）を使用し原料油としては
上記（１）の原料油を使用した。筒状絞り部１５下流側側壁に設けた原料噴霧口１８−１及び反応室上流側側壁
に設けた原料噴霧口１８−４を併用し、各原料噴霧口からの原料導入比率を変化
させて、原料導入比率とカーボンブラックの粒子径分布との関係を調べた。原料
噴霧口１８−１の位置は、筒状絞り部の入り口から１９１mmの位置に、原料噴霧
口１８−２の位置は拡大テーパー部の入り口から１９１mmの位置に、原料噴霧口
１８−３の位置は原料噴霧口１８−２より２００mm離れた位置に、原料噴霧口１
８−４の位置は反応室入り口から３９７mmの位置にそれぞれ設けた。実験条件及び結果を第５表に、原料噴霧口１８−１からの原料導入量（一段目
導入量）と原料噴霧口１８−４からの原料導入量（二段目導入量）との比率と粒０％に対して二段目導入量を８０％としたときに粒子径分布が最もブロードになり、逆に、一段目導入量８４％に対して二段目導入量を１６％としたときに、粒
子径分布が最も狭くなった。（実施例６）実施例５と同一の装置（第６図）を用いて、筒状絞り部１５下流側側壁に設け
た原料噴霧口１８−１（一段目噴霧口）と、拡大テーパー部１６中央側壁に設け
た原料噴霧口１８−２又は拡大テーパー部１６下流側側壁に設けた原料噴霧口１
８−３又は反応室上流側側壁に分割して設けた原料噴霧口１８−４若しくは１８
−５若しくは１８−６（二段目噴霧口）とを併用した場合の、一段目噴霧口と二
段目噴霧口との間での、反応器の内容積がカーボンブラックの凝集体径分布に与
える影響について調べた。なお、原料噴霧口１８−５の位置は原料噴霧口１８−
４から４８８mm離れた位置に、原料噴霧口１８−６の位置は原料噴霧口１８−５
から７４０mm離れた位置に、原料噴霧口１８−７の位置は原料噴霧口１８−６の
位置から３７０mm離れた位置にそれぞれ設けた。実験条件及び結果を第６表に示した。凝集体のストークス相当径ヒストグラムにおいて、最多頻度を与えるストークス
相当径をＤ_st（nm）、Ｄ_stの半値巾をΔＤ₅₀（nm）で表わす。凝集体径分布ΔＤ
₅₀／Ｄ_stと噴霧口との関係を第８図に示した。この結果、二段目噴霧口の位置を下流側にするほど即ち一段目噴霧口と二段目
噴霧口との間の反応器内容積を大きくするほど、凝集体径分布をブロードにでき
ることが判る。そして、二段目噴霧口として反応室側壁に設けた原料噴霧口を用
いた場合は、拡大テーパー部に設けたものよりも、得られるカーボンブラックの
凝集体径分布がブロードになることがわかる。〔発明の効果〕本発明は、カーボンブラック原料炭化水素の噴霧に当って、反応器に整流効果
を持たせる絞り部と拡大テーパー部を構成し、それを通過する燃焼ガスを整流状
態にすると共に、拡大テーパー部の軸方向に沿って、２ヶ所以上の分割位置に複
数個の噴霧口を形成し、このうち軸方向の１個又は複数個の噴霧口を使用してこ
れを個別選択するか、２個以上を併用して、この噴霧口から原料を噴霧させるこ
とにより、また、筒状絞り部から拡大テーパー部および反応室の軸方向に沿って
、２ヶ所以上の分割位置に複数個の噴霧口を形成し、このうち軸方向の少なくと
も２ヶ所の噴霧口を選択して併用することにより、また各原料噴霧口からの原料
導入比率を調節することにより、製品カーボンブラックの粒子径分布及び凝集体
径分布を任意に制御する系統的な道を拓いたものである。従ってカーボンブラッ
ク製造工業において、製品品位の制御に寄与する所非常に大である。 DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for arbitrarily controlling the particle size distribution and the aggregate size distribution of carbon black.
The present invention relates to a method and an apparatus for producing carbon black that can be trolled. [Prior art] Factors affecting the particle size distribution of carbon black, and specific particle size distribution
For example, Japanese Patent Publication No. 54-13232 discloses a well-known document specifying the control method of
According to the report, when cooled dewatered exhaust gas was introduced into the reaction chamber, the particle size became smaller.
At the same time, the particle size distribution is narrowed. As a publicly known document relating to control of the size distribution of aggregates of carbon black, see
As seen in JP-A-7-42773 and JP-A-60-223865,
The raw material is sprayed from the axial direction into the combustion gas filling chamber, mixed with the combustion gas, and subsequently, the flow state in the furnace such as the tapered part and the enlarged part is changed to control the aggregate diameter distribution.
The ones that you control are described. Also, a known document relating to injecting a pyrolytic raw material hydrocarbon into a high-temperature combustion gas.
In Japanese Patent Publication No. 47-1005, the raw material carbonization is performed during the high-speed flow of the combustion gas.
Inject hydrogen directly. In other words, at the same time that the raw material
In addition, the reaction zone immediately after that position is a reaction zone, and the reaction zone is
It has a slightly divergent conical taper, but it has a rectifying cylindrical aperture and
No expansion taper is provided. JP-A-47-563 discloses that the combustion gas stream has a sufficient mass velocity.
The raw material is actually injected into the cylindrical narrowed portion (the narrowest portion). In Japanese Patent Application Laid-Open No. 61-183,364, the side wall which is the narrowest portion of the venturi portion is disclosed.
Spray the feed oil at an angle of 90 ± 20 ° with respect to the central axis from the feed inlet pipe passing through
ing. In Japanese Patent Application Laid-Open No. 52-133,099, an enlarged tapered portion of a venturi portion is referred to.
In the first part of the cylindrical reaction chamber downstream of the
Has been introduced. U.S. Pat. No. 4,391,789 discloses a reduced taper from a combustion chamber to a throttle.
The raw material is injected into the part from a plurality of locations in the axial direction. U.S. Pat. No. 4,294,814 discloses a technique for reducing pressure loss in a reaction zone.
And supply some raw material oil from the axial direction of the combustion chamber,
When both pass through the venturi section, the remaining tapes
Supplying oil. As described above, in the known literature, the material supply position is a reduced taper portion or a throttle.
Although it is possible to see what is provided in the portion, a cylindrical throttle portion having a rectifying effect is provided and the throttle is provided.
Two or more raw material spray ports in the axial direction from the tapered part to the enlarged taper part and the reaction chamber
A raw material spray port where one or two or more of these spray ports are selected
Spray, and arbitrarily control the particle size distribution and aggregate size distribution of the product carbon black.
There is no technical idea. JP 1-230677 describes a method for feeding a large number of separately controlled streams of carbon black feedstock into separate parts of a reactor.
Physically, it is supplied to the injection zone from the combustion chamber to the throttle.
In this part, the combustion gas flow is not sufficiently rectified, and
It is not possible to arbitrarily control the size distribution of cloth and aggregates. [Problems to be Solved by the Invention] An object of the present invention is to arbitrarily adjust the particle size distribution and the aggregate size distribution of carbon black.
To provide a controllable method and apparatus for producing carbon black.
You. [Means for Solving the Problems] The present inventors affect the particle size distribution of carbon black and the aggregate size distribution.
To elucidate the factors, intensive research was conducted. As a result, the combustion gas flow is rectified by the cylindrical throttle, and the diverging taper flows.
Spray at one or two or more split positions along the axial direction of the reactor
By spraying the raw material from the mouth, the particle size distribution and aggregate size distribution can be controlled arbitrarily.
The present invention has been completed. In addition, the cylindrical throttle portion and the combustion gas flow are rectified by the throttle portion, and the rectified expansion flows.
Two or more split positions along the axial direction of the reactor at the large taper and the side wall of the reaction chamber
When spraying the raw materials together from the spray ports provided in the equipment, the position of the raw material
Aggregate size distribution changes regularly by selecting the reactor internal volume between raw material spray ports
And adjusting the rate of introduction of raw materials from each selected raw material spray port.
The present invention has been found that the particle size distribution and the aggregate size distribution can be arbitrarily controlled.
completed. The present invention provides a method for producing carbon black described in (1) to (6) below.
And equipment. (1) A combustion chamber, a cylindrical throttle portion narrowed as compared with the combustion chamber, and an enlarged tape from the throttle portion.
A carburetor having a reaction chamber that is continuous through a
The black-black reactor is necessary for the carbon black formation reaction at least in the combustion chamber.
The hot air of the necessary combustion gas is generated, and the hot air is rectified downstream of the hot air by a cylindrical throttle.
The raw material hydrocarbon is charged into the rectified hot air flow, and the carbon black is blown in the reaction chamber.
In the method for producing carbon black, which is quenched after the generation of cracks, at least the enlarged taper portion is formed by the configuration of the combustion chamber, the cylindrical throttle portion, and the enlarged taper portion.
To form hot air in a rectified state, and feed the raw hydrocarbon to the expanded tapered portion.
From the spray ports provided at two or more split positions in the axial direction, individually or in combination, into hot air
A method for producing carbon black, comprising a combination of spraying uniformly from the circumferential direction. (2) a combustion chamber, a tubular throttle narrowed relative to the chamber, and an enlarged te
A car having a reaction chamber enlarged through the taper section as compared with the continuous constriction section.
The Bon Black reactor is used to generate carbon black in at least the combustion chamber.
Hot air of necessary combustion gas is created, raw material hydrocarbon is charged into it, and carbon is
In a method for producing carbon black, which is quenched after black is formed, the method comprises the steps of:
Due to the configuration of the firing chamber, the cylindrical narrowed portion, and the enlarged taper portion, at least the cylindrical narrowed portion is expanded.
A rectified hot air is formed in the large taper portion, and the raw hydrocarbon is
At least two divisions in the axial direction between the cylindrical throttle part, the enlarged taper part and the reaction chamber
At least two raw material spray ports selected from the raw material spray ports
Black including a combination of spraying uniformly into the hot air from the circumferential direction
Manufacturing method. (3) In the method for producing carbon black of the above (2), the raw material hydrocarbon is
Two or more split positions in the axial direction from the cylindrical throttle, the enlarged taper, and the reaction chamber
At least two raw material spray ports selected from the raw material spray ports provided in
And adjust the ratio of the amount of raw material introduced from each raw material spray port used together.
A method for producing carbon black, comprising a combination of (4) a combustion chamber for generating hot air required for a carbon black production reaction, and the combustion
A tubular throttle connected to the combustion chamber and narrowed compared to the combustion chamber, which has a rectifying effect on hot air
And a ratio of the length L to the diameter D, L / D is 1 to 5;
The total angle communicating with the reaction chamber enlarged in comparison with the angled portion is in the range of 5 ° to 12 °.
A large taper portion, a carbon black production reaction chamber communicating with the enlarged taper portion,
The rapid cooling chamber and the flue connected to the end of the reaction chamber, and the enlarged taper section,
Raw material spray port for uniformly introducing raw hydrocarbons from two or more locations in the circumferential direction
Carbon black production equipment including a combination of (5) A combustion chamber for generating hot air required for a carbon black generation reaction, and a cylindrical throttle portion connected to the combustion chamber and narrowed as compared with the combustion chamber for providing a rectifying effect to the hot air.
A cylindrical restricting portion having a ratio of length L to diameter D, L / D of 1 to 5;
The total angle communicating with the reaction chamber enlarged in comparison with the angled portion is in the range of 5 ° to 12 °.
A large taper portion and a carbon black generation reaction chamber communicating with the enlarged taper portion;
A rapid cooling chamber and a flue connected to the end of the reaction chamber, and an enlarged taper from the cylindrical throttle.
Coal is uniformly distributed from the circumferential direction at two or more locations in the axial direction between the
A carbon black production apparatus including a combination with a raw material spray port for introducing hydrogen hydride. Hereinafter, the present invention will be described in detail. First, as a raw material hydrocarbon that can be used in the present invention,
, But not limited to, coal such as anthracene oil and creosote oil
Tar-based heavy oil, petroleum gas oil, or distillate oil, and by-product residues from petroleum pyrolysis
Can be used. Fuels include coal-based gas, petroleum-based gas, light oil, and heavy oil.
High quality oil can be used. The manufacturing apparatus itself of the present invention is generally of a horizontal type, but may be of a vertical type.
. The cross section of the combustion chamber or the reaction chamber is generally cylindrical, but is not limited to this.
Not. In the present invention, "necessary for carbon black production reaction at least in the combustion chamber"
At least the meaning of "make hot air of combustion gas" means that in combustion chamber fuel hydrocarbons
And air to burn and produce combustion gas.
Preliminary combustion of fuel with secondary air, complete combustion by charging only secondary air into the combustion chamber
The combustion may be performed by a completely external combustion burner, and the combustion chamber may be filled with combustion gas.
Indicates that you may do just that. However, in the enlarged tapered portion of the present invention, the rectified state of the combustion gas is maintained as much as possible.
For the purpose of the present invention, in the present invention, although not particularly limited, the hand of the combustion chamber is used.
The front end of the pre-combustion chamber equipped with an external burner etc. in the center of the front upstream end wall is coaxially connected.
By reducing the preliminary combustion gas as much as possible
And in parallel to the direction of the air flow, to supply secondary air from the peripheral wall as appropriate in the combustion chamber.
And complete combustion is preferred. In this case, in particular, in the combustion chamber, the preliminary combustion gas flowing from the preliminary combustion chamber is supplied.
A preferred method is to introduce secondary air in a tangential direction opposite to the spiral flow of the gas, and complete combustion while weakening the spiral flow of the pre-combustion gas by the flow of the secondary air.
Good. The air referred to in the present invention means not only air but also an inert gas such as nitrogen or argon and oxygen.
Or an oxygen-containing gas such as a mixed gas in which air and oxygen are mixed at an arbitrary ratio. In the narrowed cylindrical throttle connected to the combustion chamber, the hot air gas is rectified.
In order to keep it, a parallel section of a fixed length is provided. The expansion from the throttle to the reaction chamber
It is necessary to maintain the rectification state of the hot air gas even in the large taper portion. Combination of the length of the parallel section of the throttle and the angle of the subsequent enlarged taper
As a result of experiments with various changes in
In order to arbitrarily control the particle size distribution and aggregate size distribution of
Was found to exist. That is, the ratio L / L of the length L and the diameter D of the cylindrical throttle portion is
D is 1 or more, preferably in the range of 1 to 5, and the entire angle of the enlarged tapered portion is 5 ° to
A range of 12 °, preferably 6 ° to 10 ° is particularly effective. As for the angle on the inlet side of the throttle, the length of the throttle and the enlarged taper angle
Is not particularly limited as long as it is within the above range.
In consideration, the total angle of the reduced taper is 100 ° or less, preferably 50 to 90 °.
Within the range is desirable. Also provided at two or more split positions in the axial direction of the enlarged taper portion
Raw material hydrocarbon spray port, cylindrical tapered part to enlarged tapered part and two axial parts of reaction chamber
The raw material hydrocarbon spray port provided at more than one division position should be almost perpendicular to the wall of each part.
It is desirable to install a plurality of locations on the peripheral wall in the direction and spray uniformly from each spray port. In the first invention of the present invention, the raw coal provided at the dividing position of these tapered portions
The injection from the hydrogen hydride spray port is performed individually or in combination. Target particle size distribution,
Spray the material by selecting one or two or more spray ports according to the aggregate diameter distribution
I do. What is important in the first invention of the present invention is that a plurality of raw material spray ports are provided in the enlarged tapered portion.
And use them individually or in combination with each other.
is there. The enlarged taper portion is a section extending from the rear end of the throttle portion to the subsequent cylindrical reaction chamber. In the second invention of the present invention, the injection from the raw material spray ports provided at two or more divided positions in the cylindrical constricted portion, the enlarged tapered portion, and the reaction chamber uses at least two positions in combination.
Do it. Peripheral from two or more spray ports depending on the target particle size distribution and aggregate size distribution
The raw material is sprayed by selecting at least two spray ports uniformly in the direction. What is important in the second invention of the present invention is that the cylindrical throttle portion, the enlarged taper portion and the reaction chamber
A plurality of material spray ports are provided at two or more division positions, and at least two
Are used in combination with each other. It is also installed in the cylindrical throttle
The raw material spray port is provided at the rear end where the rectification state is formed. One selected from the rear end of the cylindrical throttle part, one part from the enlarged tapered part, and the reaction chamber 2
Spraying the raw material from different locations makes it easier to control the particle size distribution and aggregate size distribution.
This is the most preferable point. The enlarged taper portion is a section extending from the rear end of the throttle portion to the subsequent cylindrical reaction chamber. In the present invention, from the viewpoint of rectifying the combustion gas, the length L and the diameter D of the throttle portion are determined.
In terms of the ratio, L / D is 1 or more, and preferably in the range of 1 to 5. Greater than 5
If this is the case, the pressure loss due to hot air increases, which is not preferable. On the other hand, if it is less than 1, the rectification effect
Not good enough. The diameter D of the throttle portion is the diameter of the combustion chamber. ₁ D / D ₁ = About 0.2 to 0.5
Is preferred. The angle of the enlarged tapered portion is 5 ° to 12 °, preferably 6 ° to 10 ° in all angles.
Is also effective. The reaction chamber has a cylindrical shape following the enlarged taper, and is
Make it equal to or smaller than the diameter. In addition, increase the diameter of a part of the reaction chamber.
Thus, the residence time of the gas can be lengthened. At the rear of the reaction chamber, as usual, water spray ports are provided in multiple stages in the axial direction,
A cooling chamber is formed. This is followed by an enlarged flue. These are coaxial
Placed on top. In the first aspect of the present invention, a liquid hydrocarbon is introduced into the enlarged tapered portion.
Are provided in multiple stages along the axial direction. In order to disperse uniformly in hot air, multiple
Provide one by one. FIG. 1 shows a reactor of a carbon black producing apparatus used in the first invention of the present invention.
1 shows a schematic longitudinal section. In FIG. 1, 1 is a carbon black reactor and 2 is a pre-combustion chamber.
These preliminary combustion gas inlets, 3 has a secondary air inlet, and 4 has a tapered portion.
Combustion chamber, 5 is a throttle section, 6 is an enlarged taper section, 7 is a reaction chamber, 8 is a material inlet, 9 is
Cooling water spray port. In the following, in connection with the embodiment, for convenience, from the front to the back, No. 1 to No. 3 spray ports
I do. In the figure, the spray is drawn from the top, but the same circle is used for each position in the axial direction.
A plurality of spray ports are provided on the circumference. The combustion chamber has a pre-combustion gas inlet from the pre-combustion chamber at the center of the upstream end wall.
The example in which the secondary air is introduced from the peripheral wall 3, 3 'is shown. A plurality of cooling water spray ports 9 are provided in the rear part of the reaction chamber in the axial direction. In the second invention of the present invention, the cylindrical narrowed portion is expanded to the enlarged tapered portion and the reaction chamber.
The raw material spray ports for introducing liquid hydrocarbons are provided in multiple stages along the axial direction.
Have been. In order to disperse uniformly in hot air, multiple
Provide one by one. The injection from each of these raw material spray ports is performed by using at least two spray ports in combination.
. Select at least two spray ports from the target particle size distribution and aggregate distribution,
Raw materials are introduced while adjusting the raw material introduction ratio from each raw material spray port. At this time,
As the raw material spray port of the stage, the raw material spray provided in the cylindrical throttle part or the enlarged taper part
Select the fog port and set the second-stage raw material spray port downstream of the first-stage spray port.
It is good to select the raw material spray port which was set. At this time, the position of the selected spray port, especially the raw material spray port provided on the upstream side and the downstream
Reactor internal volume between the provided raw material spray ports, that is, the residence time of gas between each raw material spray ports
, The aggregate size distribution of the obtained carbon black differs. That is,
The larger the volume, the wider the aggregate size distribution of the generated carbon black
There is. In particular, a raw material spray port provided on the side wall of the reaction chamber evenly in the circumferential direction as a raw material spray port on the downstream side
When a material spray port is used, carbon black having a wide aggregate size distribution can be produced. Also, by adjusting the raw material introduction ratio from each raw material spray port, the carbon
The particle size distribution of the material can be controlled. Generally, the amount of raw material introduced from the upstream material spray port is
When the amount of raw material introduced from the raw material spray port on the downstream side is larger, the particle size distribution tends to narrow.
It tends to be wide when it is small and small. However, the raw material spray port on the upstream side
Depending on the raw material introduction ratio from the upstream raw material spray port, the upstream raw material spray port alone
While the particle size distribution may be narrower than when introducing, the raw material spray on the downstream side
Because it may be wider than when introduced from the mouth alone,
Raw material is introduced independently from one raw material spray port by adjusting the raw material introduction ratio
Control the size distribution of carbon black over a wider range than
it can. FIG. 6 shows the reactor of the carbon black producing apparatus used in the second invention of the present invention.
1 shows a schematic longitudinal section. In FIG. 6, 10 is a preliminary combustion chamber, 11 is a fuel spray port, and 12 is 1
The secondary air inlet 13 is a combustion chamber having a tapered portion, and 14-1 and 14-2.
Is a secondary air inlet, 15 is a cylindrical throttle, 16 is an enlarged taper, 17 is a reaction chamber,
18-1, 18-2, 18-3, 18-4, 18-5, 18-6, 18-7
Reference numeral 19 denotes a cooling water spray port. In FIG. 6, the raw material is depicted as being sprayed from above, but each position in the axial direction is described.
And a plurality of spray ports are provided on the same circumference. The combustion chamber is provided with a preliminary combustion gas inlet from the preliminary combustion chamber at the center of the upstream end wall,
The example in which the secondary air is introduced from the peripheral wall parts 14-1 and 14-2 is shown. Secondary air
The inlets 14-1 and 14-2 are opposite to the primary air inlet 12 of the preliminary combustion chamber.
It is provided in the tangential direction. A plurality of cooling water spray ports 19 are provided in the rear part of the reaction chamber in the axial direction. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
By way of example, there is no limitation. In addition, the raw material oil analysis value used in the following Examples, the particle diameter of carbon black (CB)
Carbon black aggregate size analysis method by distribution measurement method, sedimentation analysis method and D _st When
ΔD ₅₀ Is as follows. (1) Feedstock oil Coal-tar heavy oil is used as the feedstock, and its properties and composition are shown in the following table.
It was shown to. % Is% by weight. (2) Particle size distribution measurement method of carbon black An electron micrograph of carbon black was taken, and this photograph was manufactured by Zeiss (West Germany).
The average particle diameter X [nm] and the particle diameter based on the number were measured by using a particle size distribution analyzer TGA10.
The standard deviation σ [nm] of the cloth was determined. (3) Carbon black aggregate size (aggregate size) measurement method It is based on sedimentation analysis. The equipment used is Disk Centrifuge (DCF) (English, Jo
yce Loebl) using the following method. Mix the dried carbon black sample with the aqueous ethanol solution and disperse
To make a dispersion. Settle the sediment (appropriate concentration
Glycerin solution), and inject buffer solution by buffer line start method.
Inject a small amount of light solution and use the “cut” and “boost” controls
Then, the buffer solution was diffused, and when the rotation was stabilized, 0.2 ml of the above-mentioned dispersion was added.
Inject into disc. Stokes the relationship between the time required to pass a fixed point (photomulti) on the disc and the density
The Stokes-equivalent diameter of the carbon black aggregates
A histogram of the frequency is obtained. In this histogram, the most frequent Stokes equivalent diameter is D _st , Which is a measure of the average size of the carbon black aggregates. Also D _st ΔD ₅₀ Which represents the distribution width of the aggregate diameter. (Example 1) In FIG. 1, the diameter of the combustion chamber is 390 mmφ and the diameter of the throttle portion is D. ₁ Is 130mmφ,
Reduction taper angle (full-width) at the entrance of the converging section 78 °, length L of the converging section ₁ Is 260mm,
6 ° taper angle (full angle) of the enlarged taper part, 381 mm length of the taper part, reaction
Using a test device (Fig. 1) with a chamber diameter of 170 mmφ,
) Was used. In the axial direction of the enlarged taper, change the material introduction position to Was examined. No.1 raw material is introduced 21mm from the entrance of the enlarged taper
In addition, the introduction position of No. 2 raw material is 180 mm away from the first, and the introduction position of No. 3 raw material.
The positions were provided at positions 180 mm apart from the second. Table 1 shows the experimental conditions and results, and Fig. 2 shows the relationship between the particle size distribution σ / x and the position of the spray port.
It was shown to. From this result, the raw material introduction position was shifted to the downstream side of the enlarged taper part.
Therefore, the average particle size of carbon black is large, and the particle size distribution is broad.
became. (Example 2) Using the same apparatus as in Example 1 (FIG. 1), the first-stage spraying and the two-stage spraying of the raw materials were performed.
The effect of carbon black on the aggregate size distribution was investigated. Table 2 shows the experimental conditions and results. Stokes equivalent diameter histogram of aggregates
The Stokes equivalent diameter giving the most frequent _st (Nm), D _st Δ
D ₅₀ (Nm). Aggregate size distribution ΔD ₅₀ / D _st Fig. 3 shows the relationship between spray position and spray position
It was shown to. As a result, the two-stage spray has a broader aggregate diameter distribution than the one-stage spray.
You can see that it can be done. (Example 3) The effect that the combustion gas is rectified at the enlarged taper portion is examined. In the apparatus used in the first embodiment, the axial length L and the diameter D of the narrowed portion are expressed by L /
In order to see the effect of D, the angle of the enlargement section was kept constant and four types of L / D aperture sections were used.
The experiment was performed. FIG. 4 shows the relationship between the L / D of the aperture section. When the value of L / D was 0.5, the particle size distribution could not be sharpened. (Example 4) Similar to Example 3, the effect of the combustion gas being rectified at the enlarged tapered portion was examined.
You. In the apparatus used in Example 1, the entire angle (cone angle) of the enlarged tapered portion is equal to the particle diameter.
In order to investigate the effect on the cloth, the L / D value of the cylindrical aperture was kept constant, and
The experiment was performed with only the par part replaced. Table 4 shows the experimental conditions and the results. As a result, the total angle (cone angle) of the enlarged tapered portion is smaller than 6 ° to 10 ° or larger.
In the case where the particle size is large, the particle size distribution is not sharp. (Example 5) In FIG. 6, the diameter of the combustion chamber is 390 mmφ, and the diameter of the throttle portion is D. ₁ Is 130mmφ,
Reduction taper angle (full-width) at the entrance of the converging section 78 °, length L of the converging section ₁ Is 260mm,
The taper angle (full angle) of the enlarged taper is 6 °, and the length of the enlarged taper is 381 mm
Using a test device with a diameter of the reaction chamber of 170 mmφ (Fig. 6),
The raw material oil of the above (1) was used. Raw material spray port 18-1 provided on the downstream side wall of the cylindrical throttle portion 15 and the upstream side wall of the reaction chamber
The raw material spraying port 18-4 provided at the same time is used together to change the raw material introduction ratio from each raw material spraying port.
The relationship between the raw material introduction ratio and the particle size distribution of carbon black was examined. material
The spray port 18-1 is located at a position 191 mm from the entrance of the cylindrical throttle section.
The position of the port 18-2 is 191 mm from the entrance of the enlarged tapered part, and the material spray port
The position of the material spray port 18-3 is 200 mm away from the material spray port 18-2.
The position 8-4 was provided at a position 397 mm from the entrance of the reaction chamber. Table 5 shows the experimental conditions and results, and shows the raw material introduction amount from the raw material spray port 18-1 (first stage).
Ratio between the amount of the raw material introduced from the raw material spray port 18-4 and the amount of the raw material introduced from the raw material spray port 18-4 (the amount of the second stage) When the second stage introduction amount is set to 80% with respect to 0%, the particle size distribution becomes the broadest. Conversely, when the second stage introduction amount is set to 16% with respect to the first stage introduction amount of 84%. ,grain
The diameter distribution became the narrowest. (Embodiment 6) Using the same device as that of Embodiment 5 (Fig. 6), provided on the downstream side wall of the cylindrical throttle portion 15.
Raw material spray port 18-1 (first-stage spray port) and provided on the central side wall of the enlarged tapered portion 16
Raw material spray port 18-2 or the raw material spray port 1 provided on the downstream side wall of the enlarged taper portion 16
8-3 or the raw material spray port 18-4 or 18 provided separately on the upstream side wall of the reaction chamber
-5 or 18-6 (second stage spray port) when used together with the first stage spray port
The internal volume of the reactor between the stage and the spray port affects the aggregate size distribution of carbon black.
Effects were examined. In addition, the position of the raw material spray port 18-5 is
The position of the raw material spray port 18-6 is located at a position 488 mm away from the raw material spray port 18-5.
The position of the raw material spray port 18-7 is 740 mm away from the raw material spray port 18-6.
It was provided at a position 370 mm away from the position. Table 6 shows the experimental conditions and results. Stokes that gives the highest frequency in the Stokes equivalent diameter histogram of aggregates
The equivalent diameter is D _st (Nm), D _st ΔD ₅₀ (Nm). Aggregate size distribution ΔD
₅₀ / D _st FIG. 8 shows the relationship between the nozzle and the spray port. As a result, as the position of the second-stage spray port becomes more downstream, the first-stage spray port and the second-stage spray port
The larger the volume inside the reactor between the atomizer and the spray port, the broader the aggregate size distribution can be.
You can see that Then, the raw material spray port provided on the side wall of the reaction chamber is used as the second-stage spray port.
If there is, than the carbon black obtained than the one provided in the enlarged taper part
It can be seen that the aggregate size distribution becomes broad. [Effect of the Invention] The present invention provides a rectifying effect on a reactor in spraying a carbon black raw material hydrocarbon.
And a converging section to expand the combustion gas passing through it.
Along with the enlarged taper section in the axial direction at two or more split positions.
Several spray ports are formed, of which one or more are used in the axial direction.
Select the materials individually or use two or more of them to spray the raw material from this spray port.
And, along the axial direction of the enlarged taper portion and the reaction chamber from the cylindrical throttle portion.
A plurality of spray ports are formed at two or more division positions, at least in the axial direction.
By selecting two spray ports and using them together, the raw material from each raw material spray port can be used.
By adjusting the introduction ratio, the particle size distribution and aggregate of the product carbon black
It pioneered a systematic way to arbitrarily control the diameter distribution. Therefore, carbon black
In the manufacturing industry, it is very important to contribute to the control of product quality.

【図面の簡単な説明】第１図は本発明の第１の発明に利用するカーボンブラック製造装置の反応器の
縦断面立面図を示したものである。第２図は、拡大テーパー部の原料噴霧位置とカーボンブラックの粒子径分布と
の関係を示したグラフである。第３図は、拡大テーパー部の原料噴霧位置（特に併用の時）とカーボンブラッ
クの凝集体径分布との関係を示したグラフである。第４図は絞り部のＬ／Ｄとカーボンブラックの粒子径分布との関係を示したグ
ラフである。第５図は拡大テーパー部の角度とカーボンブラックの粒子径分布との関係を示
したグラフである。第６図は本発明の第２の発明に利用するカーボンブラック製造装置の反応器の
縦断面立面図を示したものである。第７図は、一段目と二段目との原料導入比率とカーボンブラックの粒子径分布
との関係を示したグラフである。第８図は、原料噴霧位置とカーボンブラックの凝集体径分布との関係を示した
グラフである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a vertical sectional elevation view of a reactor of a carbon black producing apparatus used in the first invention of the present invention. FIG. 2 is a graph showing the relationship between the raw material spray position of the enlarged tapered portion and the particle size distribution of carbon black. FIG. 3 is a graph showing the relationship between the raw material spray position of the enlarged tapered portion (particularly when used together) and the aggregate size distribution of carbon black. FIG. 4 is a graph showing the relationship between the L / D of the narrowed portion and the particle size distribution of carbon black. FIG. 5 is a graph showing the relationship between the angle of the enlarged tapered portion and the particle size distribution of carbon black. FIG. 6 is a vertical sectional elevation view of a reactor of a carbon black producing apparatus used in the second invention of the present invention. FIG. 7 is a graph showing the relationship between the raw material introduction ratio of the first stage and the second stage and the particle size distribution of carbon black. FIG. 8 is a graph showing the relationship between the raw material spray position and the carbon black aggregate size distribution.

Claims

[Claims] 1. A carbon black reaction having a combustion chamber, a cylindrical throttle portion narrowed as compared with the chamber, and a reaction chamber expanded from the throttle portion through a tapered portion that is continuous with the throttle portion. The hot air of the combustion gas required for the carbon black production reaction is generated at least in the combustion chamber by the steam generator, and the hot air is rectified by the cylindrical throttle portion downstream thereof, and the raw material hydrocarbon is charged into the rectified hot air flow. Then, after producing carbon black, in the method of producing carbon black to be quenched, the raw material hydrocarbons,
A method for producing carbon black, comprising a combination of spraying, individually or in combination, into hot air in a circumferential direction uniformly from spray ports provided at two or more division positions in the axial direction of the enlarged tapered portion. 2. A carbon black reactor having a combustion chamber, a cylindrical throttle portion narrowed as compared with the chamber, and a reaction chamber expanded from the throttle portion through a tapered portion that is larger than the continuous throttle portion. The hot air of the combustion gas required for the carbon black production reaction is generated at least in the combustion chamber, and the hot air is rectified by a tubular throttle portion downstream thereof, and the raw material hydrocarbon is charged into the rectified hot air flow. Then, after producing carbon black, in the method of producing carbon black to be quenched, the raw material hydrocarbons,
At least two raw material spray ports selected from two or more raw material spray ports axially provided at two or more divided positions in the axial direction from the cylindrical narrowed portion, the enlarged tapered portion, and the reaction chamber are used. A method for producing carbon black, comprising a combination with spraying. 3. Feed the raw hydrocarbons through the cylindrical throttle, enlarged taper and reaction chamber,
At least two raw material spray ports selected from two or more raw material spray ports in the axial direction are sprayed into the hot air in combination, and at this time, the raw material introduction ratio from each of the raw material spray ports used in combination is determined. 3. The method for producing carbon black according to claim 2, comprising a combination with adjusting. 4. A combustion chamber for generating hot air required for the carbon black generation reaction, and a length L of a cylindrical throttle portion connected to the combustion chamber and narrowed compared to the combustion chamber for rectifying the hot air.
And a ratio of the diameter D and L / D of 1 to 5; and a total angle of 5 ° to 12 ° communicating from the throttle to the reaction chamber enlarged from the throttle. An enlarged taper portion which is a range, a carbon black producing reaction chamber communicating with the enlarged taper portion, a rapid cooling chamber and a flue connected to an end portion of the reaction chamber, and two or more axially arranged in the enlarged taper portion. A carbon black production apparatus including a combination with a raw material spray port for uniformly introducing a raw material hydrocarbon from a circumferential direction. 5. A combustion chamber for generating hot air required for the carbon black generation reaction, and a length L of a cylindrical throttle portion connected to the combustion chamber and narrowed compared to the combustion chamber for rectifying the hot air.
And a cylindrical throttle portion having a ratio L / D of 1 to 5 and a total angle communicating from the throttle portion to a reaction chamber enlarged from the throttle portion in a range of 5 ° to 12 °. An expansion taper portion, a carbon black generation reaction chamber communicating with the expansion taper portion, a rapid cooling chamber and a flue connected to the end of the reaction chamber, and a shaft extending from the cylindrical throttle portion to the expansion taper portion and the reaction chamber. A carbon black production apparatus including a combination with a raw material spray port for uniformly introducing a raw hydrocarbon from two or more circumferential directions arranged in two or more directions.