JPS63205369A - Production of magnetic carbon black - Google Patents
Production of magnetic carbon blackInfo
- Publication number
- JPS63205369A JPS63205369A JP3788687A JP3788687A JPS63205369A JP S63205369 A JPS63205369 A JP S63205369A JP 3788687 A JP3788687 A JP 3788687A JP 3788687 A JP3788687 A JP 3788687A JP S63205369 A JPS63205369 A JP S63205369A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- magnetic
- transition metal
- injected
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 28
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000002347 injection Methods 0.000 claims abstract description 18
- 239000007924 injection Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000567 combustion gas Substances 0.000 claims abstract description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 26
- 150000003623 transition metal compounds Chemical class 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 organic acid salt Chemical class 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003921 oil Substances 0.000 abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 239000011280 coal tar Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 235000019241 carbon black Nutrition 0.000 description 61
- 239000002245 particle Substances 0.000 description 30
- 239000010419 fine particle Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 6
- 239000007771 core particle Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 3
- 235000006173 Larrea tridentata Nutrition 0.000 description 3
- 244000073231 Larrea tridentata Species 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229960002126 creosote Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、カーボンブラックを基体として電気的特性、
とくに安定な磁気的性能を有する磁性カーボンブラック
の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention uses carbon black as a base material to improve electrical properties,
In particular, the present invention relates to a method for producing magnetic carbon black having stable magnetic performance.
カーボンブラックは、ゴム補強用充填材として、タイヤ
および各種工業用ゴム製品をはじめ、印刷インキ、塗料
等の顔料、プラスチックの着色材や機能材等の分野で広
く使用されている。Carbon black is widely used as a filler for reinforcing rubber in fields such as tires and various industrial rubber products, pigments for printing inks and paints, colorants for plastics, and functional materials.
カーボンブラックは炭素質から成り、導電性を有してい
るので、ゴムやプラスチック等の導電用充填材としても
用いられているが、磁気的性能は元来有していない。そ
こで、これらカーボンブラックに磁気的性能を付与する
ことができれば、複合化したゴムやプラスデックに、カ
ーボンブラック固有の補強性、着色性、導電性等の諸機
能に磁気的機能が加わり、磁性ゴムや磁性プラスチック
等の機能素材として、電子工業、機械工業、化学工業等
の分野において有用されることが期待される。Since carbon black is made of carbonaceous material and has electrical conductivity, it is also used as a conductive filler for rubber, plastic, etc., but it does not inherently have magnetic properties. Therefore, if magnetic performance could be imparted to these carbon blacks, magnetic functions would be added to the various functions inherent to carbon black, such as reinforcing properties, coloring properties, and conductivity, to composite rubber and Plus Deck. It is expected that it will be useful as a functional material for magnetic plastics, etc. in fields such as the electronics industry, machinery industry, and chemical industry.
また、インキ、顔料等の分野においてもカーボンブラッ
ク本来の黒色度を損なうことなく、磁性インキ、磁性顔
料、電子コピー用トナー等の用途に有用視される。Furthermore, in the field of inks, pigments, etc., carbon black is useful for magnetic inks, magnetic pigments, toners for electronic copying, etc. without impairing the original blackness of carbon black.
カーボンブラックは、粒子径に対応して多様な品種があ
り、一般的には平均粒子径がｌＯ〜２００ｎｍの球状微
粒子が融着および二次的に凝集した鎖状構造から成って
いる。また、粒子径の分布も平均粒子径に応じて夫々広
し司Ｊをもっており、更にカーボンブラックの密度は約
１８で金属の密度とは大きく異なっている。したがって
、カーボンブラックと磁性金属微粉末とを二次的に混合
する方法では、均質かつ高度にミクロ分散させることが
困難であり、またゴム、プラスチック、インキ、塗料等
のマトリックス物質にカーボンブラックと磁性金属微粉
末を加えて混合する方法も混合過程において分離等が生
じ易く、安定に均質高分散させることが難しい。更に、
単に機械的に混合分散した状態では、磁性金属微粉末は
カーボンブラックに固定化されていないために、高度の
磁気的性能を付与することができない。Carbon black has a variety of types depending on its particle size, and generally has a chain structure in which spherical fine particles with an average particle size of 10 to 200 nm are fused and secondarily agglomerated. Furthermore, the particle size distribution has a wide range depending on the average particle size, and the density of carbon black is about 18, which is significantly different from the density of metals. Therefore, with the method of secondarily mixing carbon black and magnetic metal fine powder, it is difficult to achieve homogeneous and highly micro-dispersion, and it is difficult to mix carbon black and magnetic metal fine powder into matrix materials such as rubber, plastic, ink, and paint. The method of adding and mixing fine metal powder also tends to cause separation during the mixing process, making it difficult to achieve stable, homogeneous and high dispersion. Furthermore,
If the magnetic metal fine powder is simply mixed and dispersed mechanically, it is not immobilized on the carbon black, and therefore it is not possible to impart a high degree of magnetic performance.
磁性を有するカーボンブラックを製造する方法として、
特公昭３９−２５２７７号公報には、Ｆｅ。As a method for producing magnetic carbon black,
In Japanese Patent Publication No. 39-25277, Fe.
Ｎｉ、Ｃｏを含有する添加物を炭化水素原料からカーボ
ンブラックが生成する反応帯域に導入する方法が開示さ
れている。同公報によれば、カーボンブラックへの変換
帯域に導入された添加物の金属成分は磁性核に変換し、
この磁性核がカーボンブラックとその形成の瞬間に共有
するので、カーボンブラックと均一かつ密接に結合して
永久磁性を有する生成物が形成すると推定している。ま
た、この磁性核はカーボンブラック粒子と同様の大きさ
のものであって、これと充分かつ密埠に混和または結合
されている異常な物理的形の金属であろうとしている。A method is disclosed in which additives containing Ni and Co are introduced into a reaction zone where carbon black is produced from a hydrocarbon feedstock. According to the publication, the metal component of the additive introduced into the conversion zone to carbon black is converted into magnetic nuclei,
Since this magnetic core is shared with carbon black at the moment of its formation, it is presumed that a product having permanent magnetism is formed by uniformly and closely bonding with carbon black. It is also believed that the magnetic core is of a similar size to the carbon black particles and is a metal in an unusual physical form that is fully and intimately mixed or bonded thereto.
本発明はこの先行技術を基に、カーボンブラックの生成
過程を詳細に解析した結果、磁性遷移金属化合物を特定
条件下にカーボンブラック反応炉に噴射注入することに
よって、承成した磁性微粒子がカーボンブラック粒子の
組織内部に捕捉されて、安定に固定化されるという事実
を知見して完成したものである。The present invention is based on this prior art, and as a result of detailed analysis of the carbon black production process, it has been found that by injecting a magnetic transition metal compound into a carbon black reactor under specific conditions, the produced magnetic fine particles become carbon black. This method was completed based on the discovery that particles are trapped inside the tissue and stably immobilized.
すなわち本発明は、反応炉頭部の燃焼室で、燃料を燃焼
させて高温燃焼ガス流を形成し、この高温燃焼ガス流中
に炭化水素原料を噴射導入して熱分解反応によりカーボ
ンブラックを生成させ、次いで水を噴霧して冷却した後
カーボンブラックを分離捕集するカーボンブラックの製
造方法において、磁性遷移金属化合物を炭化水素原料の
噴射導入部の下流域に噴射注入し、かつ同時に水素ガス
を供給することを特徴とする。That is, the present invention burns fuel in a combustion chamber at the head of the reactor to form a high-temperature combustion gas flow, and injects a hydrocarbon raw material into this high-temperature combustion gas flow to generate carbon black through a pyrolysis reaction. In a method for producing carbon black in which the carbon black is separated and collected after cooling by spraying water, a magnetic transition metal compound is injected into the downstream region of the injection introduction part of the hydrocarbon raw material, and at the same time hydrogen gas is injected. It is characterized by supplying.
カーボンブラックは通常、軽質炭化水素油あるいは天然
ガス等の燃料を完全燃焼させて高温燃焼ガス流を形成し
、この高温燃焼ガス流中に炭化水素原料を噴射導入して
熱分解反応を起生させて、カーボンブラックに転化する
方法で製造されている。炭化水素原料は、酸化性雰囲気
である高温燃焼ガス流中で、一部分が遊離状態にある酸
素と反４一
応して燃焼する。その結果、反応炉内は遊離酸素の存在
しない還元性高温雰囲気が形成される。炭化水素原料は
、主にこの雰囲気中で熱分解してカーボンブラックに転
化する。Carbon black is usually produced by completely burning a fuel such as light hydrocarbon oil or natural gas to form a high-temperature combustion gas stream, and then injecting a hydrocarbon raw material into this high-temperature combustion gas stream to cause a pyrolysis reaction. It is produced by converting it into carbon black. The hydrocarbon feedstock combusts in a hot combustion gas stream that is an oxidizing atmosphere, with a portion of the oxygen being in the free state. As a result, a reducing high temperature atmosphere free of free oxygen is formed in the reactor. Hydrocarbon raw materials are mainly thermally decomposed in this atmosphere and converted into carbon black.
カーボンブラックの生成機構は、一般に下記の過程を経
て生成するとして説明されている。The production mechanism of carbon black is generally explained as being produced through the following process.
炭化水素原料は、熱分解縮合によって多環芳香族物質を
生じ、分子量の増加に伴って凝縮液滴化し、固体カーボ
ン状の多結晶体となる。更に、これらは物理的作用で凝
集して核粒子となり、凝集、成長を経て一次粒子、二次
粒子（アグリゲート）が完成される。The hydrocarbon raw material produces a polycyclic aromatic substance through thermal decomposition and condensation, and as the molecular weight increases, it condenses into droplets and becomes a solid carbon-like polycrystalline substance. Further, these particles aggregate by physical action to form core particles, and through aggregation and growth, primary particles and secondary particles (aggregates) are completed.
一般的に、このカーボンブラックの生成プロセスは、反
応初期の核成長および反応後期の粒子成長の２ステージ
で説明される。Generally, this carbon black production process is explained in two stages: nucleus growth at the early stage of the reaction and particle growth at the latter stage of the reaction.
例えば、Ｋ、Ｒ，Ｄｏｈｍｅｎ ＆ Ｎ、Ｎ、Ｍｃ
Ｒｅｅ（Ｒｕｂｂｅｒ ＷｏｒｌｄＭａｙ、 １９７
４． 、Ｐ ６）等によれば、これらプロセスは、熱分
解反応の極めて初期にポリアセチレン、多環芳香族化合
物、その他店性な炭化水素が生成し、ラジカル反応を経
て４０〜５０人のカーボンブラック核粒子を形成する。For example, K, R, Dohmen & N, N, Mc
Ree (Rubber World May, 197
4. According to , P. 6), these processes produce polyacetylene, polycyclic aromatic compounds, and other store hydrocarbons at the very early stage of the thermal decomposition reaction, and after a radical reaction, 40 to 50 carbon black nuclei are produced. form particles.
これらの反応は、通常のカーボンブラック原料で１００
ＫｃａＩ２／ｍｏｌｅ以上の反応エネルギーを要し、
これ以下では核粒子の増加生成は生じないとされる。（
この段階では、系内の酸素が十分に供給され、原料の一
部燃焼による高熱エネルギーとして供給されるものであ
る）。These reactions can be carried out at 100% using ordinary carbon black raw materials.
Requires reaction energy greater than KcaI2/mole,
It is said that no increase in the production of nuclear particles occurs below this level. (
At this stage, oxygen in the system is sufficiently supplied and is supplied as high thermal energy through partial combustion of the raw materials).
核粒子が生成した後系内に残存する炭素源は、気相から
の炭素種子（５ｐｅｃｉｅｓ）として、カーボンブラッ
ク生成粒子表面に堆積成長する粒子成長の段階に入る。After the core particles are generated, the carbon source remaining in the system enters a particle growth stage in which it is deposited and grown on the surface of the carbon black generation particles as carbon seeds (5 pecies) from the gas phase.
これら反応は、３０〜５０ Ｋｃａｌ／ｍｏｌｅと核粒
子生成域に対し低い活性化エネルギーで生じ、カーボン
ブラック粒子生成後の非酸化性かつ相対的に低温域で反
応が継続する。そして、反応系内の水冷反応停止に至る
滞留時間に依存しつつ、最終的カーボンブラックの基本
粒子やアゲリケードが完成される。These reactions occur at activation energy of 30 to 50 Kcal/mole, which is low compared to the nuclear particle generation region, and the reactions continue in a non-oxidizing and relatively low temperature region after carbon black particle generation. Then, depending on the residence time in the reaction system until the water-cooled reaction stops, the final basic particles or agelicade of carbon black are completed.
本発明においては、上記カーボンブラ・ｙりの生成過程
において、磁性遷移金属化合物を遊離酸素の存在しない
雰囲気中に噴射注入して熱分解し、炭化水素原料の熱分
解とくにカーボンブラック核粒子の生成直後に磁性遷移
金属やその化合物である磁性微粒子を生成させるもので
ある。この磁性微粒子は、カーボンブラック核粒子に凝
集捕捉されて共存しつつ、次いで系内の炭素源からの気
相炭化反応による粒子成長を経て、カーボンブラック粒
子組織内にとり込まれ一体化する。このようにして磁性
微粒子は、カーボンブラックの基本粒子内部および粒子
凝集体（アゲリケード）内部にカーボン層におおわれて
、安定に固定化される。In the present invention, in the production process of carbon black, a magnetic transition metal compound is injected into an atmosphere free of free oxygen and thermally decomposed, and the hydrocarbon raw material is thermally decomposed, particularly to generate carbon black core particles. Immediately thereafter, magnetic fine particles of magnetic transition metals and their compounds are generated. These magnetic fine particles coexist while being coagulated and captured by the carbon black core particles, and then undergo particle growth due to a gas phase carbonization reaction from the carbon source in the system, and are incorporated and integrated into the carbon black particle structure. In this way, the magnetic fine particles are stably immobilized inside the basic particles of carbon black and inside the particle aggregates (agelicades), covered with a carbon layer.
したがって、磁性遷移金属化合物を遊離酸素が存在する
酸化性雰囲気中に噴射注入する場合は、分解生成物であ
る磁性微粒子はカーボンブラックと共存して、カーボン
ブラック基本粒子内部や粒子凝集体内部に固定化される
頻度は著しく減少する。Therefore, when a magnetic transition metal compound is injected into an oxidizing atmosphere where free oxygen exists, the magnetic fine particles that are decomposition products coexist with carbon black and are fixed inside carbon black basic particles or particle aggregates. The frequency with which this happens is significantly reduced.
遊離酸素の存在しない雰囲気中に、磁性遷移金属化合物
を噴射注入するためには炭化水素原料の噴射導入部の下
流域に噴射注入することが必要であり、かつ同時に水素
ガスを供給することにより残存する遊離酸素を迅速に反
応消費することができる。供給する水素ガス量は、カー
ボンブラックの生成反応条件に基づいて適宜設定する。In order to inject a magnetic transition metal compound into an atmosphere where free oxygen does not exist, it is necessary to inject it into the downstream region of the injection introduction part of the hydrocarbon raw material, and at the same time, by supplying hydrogen gas, residual Free oxygen can be rapidly consumed by reaction. The amount of hydrogen gas to be supplied is appropriately set based on the carbon black production reaction conditions.
また、炭化水素原料を反応炉の炉軸方向に設けた２ケ所
以上の導入部から噴射して、反応炉上流側第１の導入部
から供給される炭化水素原料の燃焼によって系内の遊離
酸素を反応消費し、第２の導入部以降の炭化水素原料等
ともに、または別途に磁性遷移金属化合物を噴射注入す
ることで達成することができる。In addition, the hydrocarbon raw material is injected from two or more introduction parts provided in the axial direction of the reactor, and the free oxygen in the system is released by combustion of the hydrocarbon raw material supplied from the first introduction part on the upstream side of the reactor. This can be achieved by reacting and consuming the magnetic transition metal compound and injecting the magnetic transition metal compound together with the hydrocarbon raw material etc. from the second introduction part or separately.
磁性遷移金属化合物としては、Ｆｅ、Ｃｏ、Ｎｉから選
ばれた少なくとも１種の金属の芳香族環状錯化合物であ
るメタロセンやカルボニル錯化合物等の有機化合物、あ
るいは塩化物、硝酸塩、硫酸塩等の無期塩もしくは酢酸
塩、蓚酸塩等の有機酸塩が使用される。これらの磁性遷
移金属化合物は、適宜な溶媒中に溶解あるいは分散させ
て、反応炉に噴射注入する。なお、分散させる場合は、
少量の界面活性剤を用いると安定な分散液が得られるの
で好ましい。また、炭化水素原料を２ケ所以上の導入部
から噴射導入してもよく、この場合には磁性遷移金属化
合物を第２の導入部以降の炭化水素原料中に溶解もしく
は分散させて反応炉に噴射注入することもできる。メタ
ロセンやカルボニル錯化合物を用いる場合は、気化した
状態で反応炉に噴射注入することも可能である。また、
磁性遷移金属化合物として、例えば鉄化合物とコバルト
化合物を併用すれば、Ｆｅ／Ｃｏ合金系の磁性微粒子が
固定化されたカーボンブラックが得られ、より高度の磁
気性能を付与することができる。Examples of magnetic transition metal compounds include organic compounds such as metallocenes, which are aromatic cyclic complex compounds of at least one metal selected from Fe, Co, and Ni, and carbonyl complex compounds, or non-porous compounds such as chlorides, nitrates, and sulfates. Salts or organic acid salts such as acetates and oxalates are used. These magnetic transition metal compounds are dissolved or dispersed in a suitable solvent and then injected into a reactor. In addition, when dispersing,
It is preferred to use a small amount of surfactant, as this results in a stable dispersion. Alternatively, the hydrocarbon raw material may be introduced by injection from two or more introduction ports; in this case, the magnetic transition metal compound is dissolved or dispersed in the hydrocarbon raw material from the second introduction port onwards, and then injected into the reactor. It can also be injected. When using metallocene or carbonyl complex compounds, it is also possible to inject them into the reactor in a vaporized state. Also,
If, for example, an iron compound and a cobalt compound are used together as the magnetic transition metal compound, carbon black in which Fe/Co alloy magnetic fine particles are immobilized can be obtained, and a higher degree of magnetic performance can be imparted.
炭化水素原料としては、コールタール油やエチレンボト
ム浦あるいはベンゼン、トルエン、キシレン、スチレン
モノマー等各種の芳香族炭化水素化合物が使用される。As the hydrocarbon raw material, various aromatic hydrocarbon compounds such as coal tar oil, ethylene bottom chloride, benzene, toluene, xylene, and styrene monomers are used.
この磁性微粒子が均質に固定化されたカーボンブラック
の緒特性は、通常適用する公知の技術手法により調節制
御されるとともに、カーボンブラック生成ガス流は、噴
霧された水により冷却して反応を停止した後バッグフィ
ルター等の適宜な装置を介して分離し、捕集される。The properties of this carbon black, on which magnetic fine particles are homogeneously immobilized, are adjusted and controlled by commonly applied known technical methods, and the carbon black production gas stream is cooled by sprayed water to stop the reaction. It is separated and collected through a suitable device such as a post-bag filter.
上記構成に基づき、本発明によれば磁性遷移金属化合物
の分解生成物である磁性微粒子が、カーボンブラック生
成過程の初期段階で生成するカーボンブラック核粒子に
凝集、捕捉されて共存しつつ、カーボンブラック粒子へ
と成長する。したがって、カーボンブラック基本粒子内
部や粒子凝集体内部に均質に分散するとともに安定に固
定化される。Based on the above configuration, according to the present invention, magnetic fine particles, which are decomposition products of magnetic transition metal compounds, are aggregated and captured by carbon black core particles generated in the initial stage of the carbon black generation process, and coexist with carbon black. Grows into particles. Therefore, it is homogeneously dispersed and stably immobilized inside carbon black basic particles and particle aggregates.
炉頭部に燃焼バーナーおよび原料噴射ノズル（第１の原
料噴射ノズル）を装着した燃焼室（直径２００ ａｍ、
長さ５００ｍｚ）、該燃焼室と同軸的に連結する狭径反
応室（直径８０ｍｍ、長さ１５０ｚ＊）および狭径反応
室にひき続く広径反応室（直径１２０尻尻、長さ１８０
０ｉｚ）とから構成され、広径反応室には反応停止用冷
却水噴霧孔を所定の各位置に設けた反応炉を設置した。A combustion chamber (diameter 200 am,
A narrow-diameter reaction chamber (diameter 80mm, length 150z*) coaxially connected to the combustion chamber, and a wide-diameter reaction chamber (diameter 120mm, length 180mm) following the narrow-diameter reaction chamber.
A reactor was installed in the wide-diameter reaction chamber with cooling water spray holes for stopping the reaction at predetermined positions.
狭径反応室には、その先端部から８０ｍｍの位置に、第
２の原料噴射ノズルを挿着した。また、狭径反応室先端
部から１３０ｘｘの位置に、炉軸に向って磁性遷移金属
化合物の噴射注入孔を設けた。A second raw material injection nozzle was inserted into the narrow diameter reaction chamber at a position 80 mm from the tip thereof. Further, an injection hole for a magnetic transition metal compound was provided at a position 130xx from the tip of the narrow-diameter reaction chamber toward the furnace axis.
この反応炉を用いて炭化水素原料、燃料、空気供給量、
冷却水噴霧位置および水量等を調節制御してカーボンブ
ラックを製造した。Using this reactor, hydrocarbon raw materials, fuel, air supply amount,
Carbon black was produced by adjusting and controlling the cooling water spray position, water amount, etc.
「実施例Ｉ」
炭化水素原料としてクレオソート油およびベンゼンを、
燃料にはプロパンを用いた。また、磁性遷移金属化合物
としては、フェロセン（Ｆｅ（Ｃ６１４ｓ）２）および
塩化第一鉄を使用した。"Example I" Creosote oil and benzene as hydrocarbon raw materials,
Propane was used as fuel. In addition, ferrocene (Fe(C614s)2) and ferrous chloride were used as magnetic transition metal compounds.
炭化水素原料は、全量を燃焼室に装着した第１の原料噴
射ノズルからアルゴンガスで噴射導入した。フェロセン
はエタノールを溶媒として、少量の界面活性剤を添加し
て濃度１０ｗｔ％の分散液を調製し、また塩化第一鉄は
濃度２０ｗｔ％の水溶液を調製して、夫々噴射注入孔に
挿入した注入ノズルから反応炉にアルゴンガスを用いて
噴射注入した。同時に水素ガスを注入ノズルの周囲から
所定の割合で供給した。比較例として、フェロセンをク
レオソート油に濃度１．５ｗｔ％に添加溶解した場合に
ついても実施した。The entire amount of the hydrocarbon raw material was introduced by injection using argon gas from a first raw material injection nozzle attached to the combustion chamber. For ferrocene, a dispersion liquid with a concentration of 10 wt% was prepared by using ethanol as a solvent and a small amount of surfactant was added, and for ferrous chloride, an aqueous solution with a concentration of 20 wt% was prepared, and each was inserted into the injection hole. Argon gas was injected into the reactor through a nozzle. At the same time, hydrogen gas was supplied from around the injection nozzle at a predetermined rate. As a comparative example, a case was also conducted in which ferrocene was added and dissolved in creosote oil to a concentration of 1.5 wt%.
得られた磁性カーボンブラックの緒特性を製造条件と対
比して表−１に示した。また、ＲｕｎＮｏ、１（本発明
例）およびＮｏ、３（比較例）で得られた磁性カーボン
ブラックの粒子構造を示す電子顕微鏡写真を第１図およ
び第２図に示した。Table 1 shows the properties of the obtained magnetic carbon black in comparison with the manufacturing conditions. Furthermore, electron micrographs showing the particle structures of the magnetic carbon blacks obtained in Run No. 1 (inventive example) and No. 3 (comparative example) are shown in FIGS. 1 and 2.
表−１の結果から本発明の磁性カーボンブラックは、優
れた磁気的特性を有していることが判明する。また、第
１図、第２図の比較から、本発明の磁性カーボンブラッ
クは鉄微粒子の大部分がカーボンブラック粒子内部に捕
捉固定化されているのに対して、比較例においては鉄微
粒子はカーボンブラック粒子と単に融着結合して表面に
露出している傾向が顕著であることが分かる。From the results shown in Table 1, it is clear that the magnetic carbon black of the present invention has excellent magnetic properties. Furthermore, from a comparison between FIG. 1 and FIG. 2, it is clear that in the magnetic carbon black of the present invention, most of the iron fine particles are captured and immobilized inside the carbon black particles, whereas in the comparative example, the iron fine particles are carbon It can be seen that there is a remarkable tendency for the black particles to be simply fused and bonded and exposed on the surface.
なお、鉄微粒子の組成は、Ｘ線回折による解析結果から
、ａ−Ｆｅの他にＦ ｅｏ 、Ｆｅ５０ 、等の組「実
施例２」
炭化水素原料としてクレオソート油を用い、燃料にはプ
ロパンを使用した。炭化水素原料は、第１の原料噴射ノ
ズルと第２の原料噴射ノズルに分けて、アルゴンガスを
用いて噴射導入した。また、磁性繊維金属化合物として
は実施例１で用し）たフェロセン分散液およびペンタカ
ルボニル鉄溶液（ａ度９５ｗｔ％）を噴射注入孔に挿入
した注入ノズルからアルゴンガスで噴射注入し、同時に
水素ガスを注入ノズルの周囲から供給した。得られた磁
性カーボンブラックの緒特性を製造条件と対比して表−
２に示した。The composition of the iron particles was determined from the analysis results by X-ray diffraction, including a-Fe, Feo, Fe50, etc. (Example 2) Creosote oil was used as the hydrocarbon raw material, and propane was used as the fuel. used. The hydrocarbon raw material was divided into a first raw material injection nozzle and a second raw material injection nozzle, and introduced by injection using argon gas. In addition, as a magnetic fiber metal compound, the ferrocene dispersion (used in Example 1) and pentacarbonyl iron solution (a degree 95 wt%) were injected with argon gas from an injection nozzle inserted into the injection hole, and at the same time hydrogen gas was injected. was supplied from around the injection nozzle. The properties of the obtained magnetic carbon black are compared with the manufacturing conditions.
Shown in 2.
表−２
〔発明の効果〕
」−記説明で明らかなように、本発明により製造される
磁性カーボンブラックは、磁性遷移金属化合物の熱分解
で生成する磁性微粒子が、カーボンブラック粒子の組織
内部に高度に分散して捕捉され、安定に固定化される。Table 2 [Effects of the Invention] As is clear from the description, the magnetic carbon black produced by the present invention has magnetic fine particles produced by thermal decomposition of a magnetic transition metal compound inside the structure of the carbon black particles. Highly dispersed capture and stable immobilization.
この場合、酸化性雰囲気においては、カーボンブラック
が酸素受容体として作用するために磁性微粒子の酸化に
よる磁気性能の劣化を生じるが、本発明では水素ガスの
供給作用によりこの種の現象は巧みに防止され、常に安
定した優れた磁気機能の付与が可能となる。In this case, in an oxidizing atmosphere, carbon black acts as an oxygen acceptor, causing deterioration of magnetic performance due to oxidation of magnetic fine particles, but in the present invention, this type of phenomenon can be skillfully prevented by supplying hydrogen gas. This makes it possible to always provide stable and excellent magnetic function.
第１図および第２図は、磁性微粒子が分散固定化したカ
ーボンブラックの粒子構造を示す電子顕微鏡写真である
。FIGS. 1 and 2 are electron micrographs showing the particle structure of carbon black in which magnetic fine particles are dispersed and fixed.
Claims (1)
ガス流を形成し、この高温燃焼ガス流中に炭化水素原料
を噴射導入して熱分解反応によりカーボンブラックを生
成させ、次いで水を噴霧して冷却した後カーボンブラッ
クを分離捕集するカーボンブラックの製造方法において
、磁性遷移金属化合物を炭化水素原料の噴射導入部の下
流域に噴射注入し、かっ同時に水素ガスを供給すること
を特徴とする磁性カーボンブラックの製造方法。 ２、磁性遷移金属化合物がＦｅ、Ｃｏ、Ｎｉから選ばれ
た少なくとも１種の金属のメタロセン、またはカルボニ
ル錯化合物あるいは無機塩、もしくは有機酸塩である特
許請求の範囲第１項記載の磁性カーボンブラックの製造
方法。[Claims] 1. In the combustion chamber at the head of the reactor, fuel is combusted to form a high-temperature combustion gas flow, and a hydrocarbon raw material is injected into the high-temperature combustion gas flow to generate carbon by a pyrolysis reaction. In a carbon black production method in which black is generated, then water is sprayed to cool it, and then the carbon black is separated and collected, a magnetic transition metal compound is injected into the downstream region of the injection introduction part of the hydrocarbon raw material, and at the same time A method for producing magnetic carbon black, characterized by supplying hydrogen gas. 2. The magnetic carbon black according to claim 1, wherein the magnetic transition metal compound is a metallocene, a carbonyl complex compound, an inorganic salt, or an organic acid salt of at least one metal selected from Fe, Co, and Ni. manufacturing method.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3788687A JPS63205369A (en) | 1987-02-23 | 1987-02-23 | Production of magnetic carbon black |
| DE8888301105T DE3863651D1 (en) | 1987-02-13 | 1988-02-10 | MAGNETIC CARBON, METHOD FOR THE PRODUCTION AND MODIFICATION OF MAGNETIC CARBON. |
| US07/154,259 US4900465A (en) | 1987-02-13 | 1988-02-10 | Process for preparing magnetic carbon black |
| EP88301105A EP0278743B1 (en) | 1987-02-13 | 1988-02-10 | Magnetic carbon black, process for preparing the same, and method of modifying magnetic carbon black |
| US07/527,688 US4995999A (en) | 1987-02-13 | 1990-05-21 | Method of producing magnetic carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3788687A JPS63205369A (en) | 1987-02-23 | 1987-02-23 | Production of magnetic carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63205369A true JPS63205369A (en) | 1988-08-24 |
| JPH0586986B2 JPH0586986B2 (en) | 1993-12-15 |
Family
ID=12510020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3788687A Granted JPS63205369A (en) | 1987-02-13 | 1987-02-23 | Production of magnetic carbon black |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63205369A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185295A (en) * | 1997-04-18 | 2009-08-20 | Cabot Corp | Method for producing aggregate |
-
1987
- 1987-02-23 JP JP3788687A patent/JPS63205369A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185295A (en) * | 1997-04-18 | 2009-08-20 | Cabot Corp | Method for producing aggregate |
| JP2012251164A (en) * | 1997-04-18 | 2012-12-20 | Cabot Corp | Method of making aggregate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0586986B2 (en) | 1993-12-15 |
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