JPS6134073A - Acetylene black and production thereof - Google Patents
Acetylene black and production thereofInfo
- Publication number
- JPS6134073A JPS6134073A JP6183184A JP6183184A JPS6134073A JP S6134073 A JPS6134073 A JP S6134073A JP 6183184 A JP6183184 A JP 6183184A JP 6183184 A JP6183184 A JP 6183184A JP S6134073 A JPS6134073 A JP S6134073A
- Authority
- JP
- Japan
- Prior art keywords
- acetylene
- oxygen
- acetylene black
- gas
- manufacturing
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明の高性能なアセチレンブラックは、乾電池の陽極
合剤中に乾電池電解液の吸液保持と合剤への導電性附与
に使用出来、乾電池に対して従来のアセチレンブラック
以上の性能を与える。[Detailed Description of the Invention] [Industrial Application Field] The high-performance acetylene black of the present invention can be used for absorbing and retaining dry battery electrolyte in the anode mixture of dry batteries and imparting conductivity to the mixture. , gives dry cell battery performance superior to that of conventional acetylene black.
又、合成樹脂に配合した場合、高性能な導電性樹脂を与
え、その様な導電性樹脂は、帯電防止用シート、静電気
除去用アース、ベルト、通信用アンテナ、面状発熱、電
磁波遮蔽用の筐体、同軸ケーブル、ビデオディスク、導
電性塗料への利用が期待出来る。In addition, when blended with synthetic resin, it provides a high-performance conductive resin, and such conductive resin can be used for antistatic sheets, static electricity removal grounds, belts, communication antennas, sheet heating, and electromagnetic wave shielding. It can be expected to be used in housings, coaxial cables, video discs, and conductive paints.
アセチレンブラックについて
本発明の高性能なアセチレンブラックに匹敵する吸液性
能と導電性附与能力の有するカーざンプランクとしては
、■副生カーボンブランクと■特開昭５３−１１０９９
２号公報記載のアセチレンブラックが知られているが、
いずれも次の様な欠点があり、乾電池業界及び導電性樹
脂業界の要望を満足するものではない。Regarding acetylene black, Karzanplanks with liquid absorption performance and conductivity imparting ability comparable to the high-performance acetylene black of the present invention include ■By-product carbon blank and ■Japanese Patent Application Laid-Open No. 53-11099.
Acetylene black described in Publication No. 2 is known, but
All of them have the following drawbacks and do not satisfy the needs of the dry battery industry and the conductive resin industry.
■ 副生カーボンブラックは炭化水素の部分燃焼反応に
よって脅威がス原料である水素ガス及び−酸化炭素ガス
を製造する際に副生物として得られるカーボンブラック
である。このカーボンブランクは、原料の炭化水素に対
して２〜６％得られ、高い吸液性能を示し、且つ導電性
も高いが、アセチレンブラックに比して鉄、ニッケル、
コバルト、バナジウム等の重金属不純物が多量に含有す
るため、乾電池用として使用した場合乾電池の貯蔵安定
性能を劣化せしめ、乾電池として使用できない。(2) By-product carbon black is carbon black obtained as a by-product when producing hydrogen gas and carbon oxide gas, which are dangerous raw materials, through a partial combustion reaction of hydrocarbons. This carbon blank has a yield of 2 to 6% based on the raw material hydrocarbon, exhibits high liquid absorption performance, and has high conductivity, but compared to acetylene black, it contains iron, nickel,
Since it contains large amounts of heavy metal impurities such as cobalt and vanadium, when used as a dry battery, the storage stability of the battery deteriorates, making it impossible to use it as a dry battery.
又、導電性樹脂に使用した場合には、副生カーボンブラ
ンク中の不純物が異物として残り、製品の外観を大幅に
損ねるため導電性ブランクとして使用できない。Furthermore, when used in a conductive resin, impurities in the by-product carbon blank remain as foreign matter, which significantly impairs the appearance of the product, so that it cannot be used as a conductive blank.
■ 特開昭５３−１１０９９２号公報記載のアセチレン
ブラックは、乾電池業界及び導電性樹脂業界の要望を充
分満足していない。このアセチレンブラックは、電気比
抵抗、比表面積、吸液性の点から見て十分にストラフチ
ャー構造が発達してにらず、乾電池業界の特殊な導電附
与剤として有用な作用を及ぼさず、又導電性樹脂に使用
した場合でも十分な導を性附与性能を有していない。(2) The acetylene black described in JP-A-53-110992 does not fully satisfy the needs of the dry battery industry and the conductive resin industry. This acetylene black does not have a sufficiently developed struttle structure in terms of electrical resistivity, specific surface area, and liquid absorption, and does not have a useful effect as a special conductive agent in the dry battery industry. Even when used in a conductive resin, it does not have sufficient conductivity imparting performance.
前述の特開昭５３−１１０９９２号公報にはアセチレン
がスの空気による部分酸化（燃焼）の記載がある。しか
し単にアセチレンガスの部分酸化では、純度のよいもの
は得られても、アセチレンブラックのストラフチャー構
造が発達していないので、導電性附与分野には使用でき
ない欠点がある。The above-mentioned Japanese Patent Application Laid-open No. 110992/1983 describes the partial oxidation (combustion) of acetylene with air. However, if acetylene black is simply partially oxidized, even if a product of high purity is obtained, the structure of acetylene black is not developed, so it has the disadvantage that it cannot be used in the field of imparting conductivity.
本発明は、従来以上、にストラフチャー構造が発達し、
吸液性能及び導電性附与能力を高めた高性能なアセチレ
ンブラック及びその製造方法を提供することを目的とす
る。The present invention has a more developed struttle structure than before,
The object of the present invention is to provide a high-performance acetylene black with improved liquid absorption performance and conductivity imparting ability, and a method for producing the same.
本発明の第１の発明は、５０〜／傭２訓圧下の電気比抵
抗値０．６０．３０Ωｃｍ未満、塩酸吸液量２０〜４０
ｗＬ１１５，９及び比表面積１００〜４００ ｍ２７１
の高性能アセチレンブラックであり、第２の発明は、ア
セチレンガスに不飽和炭化水素を存在させ又は存在させ
ずして、酸素含有気体と水蒸気の混合がス流によって連
続的に熱分解させることな特徴とする５ ０ Ｋ９／ｃ
＋ｕ２加圧下の電気比抵抗値０．３０Ω傭未満、塩酸吸
液１１２０〜ＡＱｍ１１５９及び比表面積１００〜４０
０１１２７ｉの高性能アセチレンブラックの製造方法で
ある。The first invention of the present invention has an electric specific resistance value of less than 0.60.30 Ωcm under a conditioning pressure of 50~/200 m, and a hydrochloric acid absorption amount of 20~40 Ωcm.
wL115.9 and specific surface area 100-400 m271
The second invention is a high-performance acetylene black with or without the presence of unsaturated hydrocarbons in the acetylene gas, so that the mixture of oxygen-containing gas and water vapor does not undergo continuous thermal decomposition due to the gas flow. Features 50 K9/c
+u2 Electrical resistivity under pressure less than 0.30Ω, hydrochloric acid absorption 1120~AQm1159 and specific surface area 100~40
01127i is a method for producing high performance acetylene black.
第１の発明の説明
電気比抵抗が０．５０Ωユ以上、塩酸吸液量２０ｄ１５
ｇ未満、比表面積１００ ｍ”７９未満では、乾電池作
成時に合剤中の乾電池電解液の吸液保持と合剤への導電
性附与能力において劣り又は合成樹脂に配合して導電性
樹脂を製造するときの導電性附与能力も充分でない。Description of the first invention: Electrical resistivity is 0.50Ω or more, hydrochloric acid absorption amount is 20d15
If the specific surface area is less than 100 m''79, the ability to absorb and retain the dry battery electrolyte in the mixture and impart conductivity to the mixture during dry battery production is poor, or it may be mixed with synthetic resin to produce conductive resin. The ability to impart electrical conductivity is also insufficient.
又、塩酸吸液量４０ｄ１５．？を越え、比表面積４００
ＦＩＬ”／９を越えると、乾電池作成時に合剤中の乾
電池電解液の吸液保持と合剤への導電性附与能力におい
て優れているものの合剤の充填特性が悪くなり、又、合
成樹脂に配合して導電性樹脂を製造するとき、その流動
性が悪くなり、好筐しくない。In addition, the amount of hydrochloric acid absorbed is 40d15. ? Exceeding, specific surface area 400
If FIL''/9 is exceeded, the filling characteristics of the mixture deteriorate, and the synthetic resin When a conductive resin is produced by blending it with a resin, its fluidity deteriorates and the housing is not suitable.
第２の発明の説明
本発明者は、鋭意アセチレンがスの熱分解反応について
研究したところ、次の反応式に導きかれた方法によって
得たアセチレンブラックが極めて高性能なアセチレンブ
ラックを与えることが判った。Description of the Second Invention The present inventor has conducted extensive research on the thermal decomposition reaction of acetylene gas, and has found that acetylene black obtained by a method derived from the following reaction formula provides extremely high-performance acetylene black. Ta.
つまり、アセチレンがスに対して、酸素０２、気体状の
水Ｈ２０を供給して
Ｃ２Ｈ２＋ ｃＪ、０２＋ｂ Ｈ２（）”（２−２ａ−
ｂ）ｄ＋（２ａ＋ｂ）ＣＯ＋（ｂ＋１ ）Ｈ２なる反応
を行う。In other words, by supplying oxygen 02 and gaseous water H20 to acetylene gas, C2H2+ cJ, 02+b H2()''(2-2a-
b) Carry out the reaction d+(2a+b)CO+(b+1)H2.
ここで、ａ、ｂは夫々アセチレンガス１モル当りに対す
る酸素、水のモル比を表わす。Here, a and b represent the molar ratios of oxygen and water per mole of acetylene gas, respectively.
つ筺り、アセチン／がスな熱分解するに当り、酸素と水
蒸気を存在させると、従来想像もできなかった高性能な
アセチレンブラックを得ることを見出した。We have discovered that when oxygen and water vapor are present during the thermal decomposition of acetin, acetylene black with a previously unimaginable high performance can be obtained.
ここで、アセチレンがスは、カーバイド法或いは石油化
学法で得られた高純度のガスである。また酸素含有ガス
はクロード法等で得られた高純度酸素がよいが、ガスで
あってもよい。空気でもよい。さらに両者の混合水蒸気
は、イオノ交換された又は蒸発法による高純度の水を加
熱して蒸気状とし、完全に乾燥した水蒸気のことを表わ
す。混った状態の水があると、アセチレンがス、酸素、
水の６者が充分混合された状態とはならず、従って生成
したアセチレンブラックを高倍率の透過型電子顕微鏡で
観察すると部分的に粒径の大なるアセチレンブラックが
見られ、均一に粒径のそろったアセチレンブラックが得
られない。アセチレンがスに対して、自己継続的発熱分
解を阻害しない程度のエチレン、ゾロピレン、プタジエ
／、ベンゼン、ナフタレン、アントラセン等の不飽和炭
化水素を混合することは本発明の趣旨九反しないもので
ある。つまり、アセチレンがス１００重童部電対して不
飽和炭化水素の添刀口量は４０重量部未満が好ましい。Here, acetylene gas is a highly purified gas obtained by a carbide method or a petrochemical method. Further, the oxygen-containing gas is preferably high-purity oxygen obtained by Claude's method or the like, but any gas may be used. Air may also be used. Furthermore, the mixed steam of the two refers to steam obtained by heating high-purity water that has been subjected to ion exchange or evaporation to form a steam, and then completely drying the water. When there is mixed water, acetylene, oxygen,
The six components of water are not sufficiently mixed, so when the acetylene black produced is observed with a high-magnification transmission electron microscope, acetylene black with large particle sizes can be seen in some parts, and the particles are uniformly distributed. Unable to obtain uniform acetylene black. It is not contrary to the spirit of the present invention to mix an unsaturated hydrocarbon such as ethylene, zolopyrene, putadiene, benzene, naphthalene, anthracene, etc. with the acetylene gas to an extent that does not inhibit self-sustaining exothermic decomposition. . That is, the amount of unsaturated hydrocarbon added is preferably less than 40 parts by weight per 100 parts by weight of acetylene.
不飽和炭化水素が４０重量部以上となると本発明者が目
的とする電気比抵抗がＯｌろＯΩ儂未満のものが得られ
ないので好ましくない。If the amount of unsaturated hydrocarbon is 40 parts by weight or more, it is not preferable because it is impossible to obtain the electrical resistivity of less than 0Ω or 0Ω, which is the objective of the present inventors.
アセチレンガス又はアセチレンガスに不飽和炭化水素を
添加した原料（以下アセチレンガス等と略す）に対する
酸素等と水蒸気の添加量によって得られるアセチレンブ
ラックの収率が影響を受ける。The yield of acetylene black obtained is affected by the amount of oxygen, etc. and water vapor added to acetylene gas or a raw material obtained by adding an unsaturated hydrocarbon to acetylene gas (hereinafter abbreviated as acetylene gas, etc.).
つまり（１１式よりアセチレンブラックの収率を出２−
２ａ −ｂ
すと、アセチレンブラックの収率＝ −Ｘ １００ （
（イ）の関係であり、アセチレンブラックの収率は１％
以上好ましくは１重チ以上が望まれる。In other words, (from equation 11, the yield of acetylene black is 2-
2a -b then yield of acetylene black = -X 100 (
The relationship is (a), and the yield of acetylene black is 1%.
More than 1 layer is preferable.
そのためには、０＜ａ＜１．０＜１）＜２で且つを満足
する必要がある。For this purpose, it is necessary to satisfy 0<a<1.0<1)<2.
酸素含有気体量は純酸素として、アセチレンがス等１モ
ル当り、０．０１以上１．０モル未満が好ましく、水蒸
気は０．０１以上２．０モル未満が好ましい。The amount of oxygen-containing gas, as pure oxygen, is preferably 0.01 or more and less than 1.0 mol per 1 mol of acetylene, etc., and the amount of water vapor is preferably 0.01 or more and less than 2.0 mol.
熱分解炉にアセチレンがス等と酸素及び／又は空気と水
蒸気を供給するに当り、垂直型分解炉の頂部に設けたア
セチレンがス供給ノズルを２重管構造成いは６重管構造
として、２重管中央部より酸素及び／又は空気と気体状
の水の混合がス糺を２重管の外側環状部からアセチレン
がス等を供給更に又６重管構造にあっては、３重管の中
央部と最外側環状部に酸素及び／又は空気と気体状の水
の混合がスを６重管の中外側の環状部からアセチレンが
ス等を供給することもできる。In order to supply acetylene gas, etc., oxygen and/or air, and steam to the pyrolysis furnace, the acetylene gas supply nozzle installed at the top of the vertical cracking furnace has a double-pipe structure or a six-pipe structure. A mixture of oxygen and/or air and gaseous water is supplied from the central part of the double pipe, and acetylene is supplied from the outer annular part of the double pipe. It is also possible to supply a mixture of oxygen and/or air and gaseous water to the central part and outermost annular part of the tube, and acetylene gas, etc. from the middle and outer annular parts of the sextuple pipe.
熱分解炉は８００℃以上に保持されていることが好まし
い。ｓ ｏ ｏ ’ｃ未満では失火するので好ましくな
い。It is preferable that the temperature of the pyrolysis furnace is maintained at 800°C or higher. If it is less than s o o 'c, misfire will occur, which is not preferable.
熱分解炉を８００°Ｃ以上にするには、外部加熱しても
よい。To raise the temperature of the pyrolysis furnace to 800°C or higher, external heating may be used.
又、２重管或いは６重管構造のノズルの内部でアセチレ
ンガス等、酸素及び／又は空気、気体状の水が予混合さ
れて、分解炉に供給されてもよい。Furthermore, acetylene gas, oxygen and/or air, and gaseous water may be premixed inside a nozzle having a double-pipe or six-pipe structure and then supplied to the cracking furnace.
この様にアセチレンガス等と酸素含有気体と水蒸気が熱
分解炉にて熱分解反応を受けてアセチレンブラックを生
成するとき、酸素含有気体、水蒸気の混合ガス流の界面
にてアセチレンがスの一部が燃焼及び熱分解反応によっ
て水素ガス、−酸化炭素がスを生成し乍ら、高度に発達
したアセチレンブラックを生成するものである。In this way, when acetylene gas, etc., oxygen-containing gas, and water vapor undergo a thermal decomposition reaction in a pyrolysis furnace to produce acetylene black, a portion of the acetylene gas forms at the interface of the mixed gas flow of oxygen-containing gas and water vapor. The combustion and thermal decomposition reactions produce hydrogen gas, carbon oxide, and highly developed acetylene black.
熱分解炉から排出されたアセチレンブラックは常法によ
り冷却され、次いでこれを懸濁するガス相から分解、捕
集される。Acetylene black discharged from the pyrolysis furnace is cooled by a conventional method, and then decomposed and collected from the gas phase in which it is suspended.
この様な高性能なアセチレンブラックは、乾電池の陽極
合剤中に乾電池電解液の吸液保持と合剤への導電性附与
に使用でき、乾電池に対して従来のアセチレンブラック
以上の性能を与える。This kind of high-performance acetylene black can be used in the anode mixture of dry batteries to absorb and retain the battery electrolyte and to impart conductivity to the mixture, giving dry batteries performance superior to that of conventional acetylene black. .
又、合成樹脂に配合した場合、高性能な導電性樹脂を与
え、その様な導電性樹脂は、帯電防止用シート、静電気
除去用アース、ベルト、通信用アンテナ、面状発熱、電
磁波遮蔽用の筐体、同軸ケーブル、ビデオディスク、導
電性塗料への利用が期待できる。In addition, when blended with synthetic resin, it provides a high-performance conductive resin, and such conductive resin can be used for antistatic sheets, static electricity removal grounds, belts, communication antennas, sheet heating, and electromagnetic wave shielding. It is expected to be used in housings, coaxial cables, video discs, and conductive paints.
本発明のアセチレンブラックの物性測定は次によった。 The physical properties of the acetylene black of the present invention were measured as follows.
アセチレンブラックの電気比抵抗はＪＩＳＫ−１４６９
，塩酸吸液量は、ＴＩＳ Ｋ −１”４６９によった。The electric specific resistance of acetylene black is JISK-1469
The amount of hydrochloric acid absorbed was determined according to TIS K-1''469.
比表面積については、力／タソープ法によって測定した
。The specific surface area was measured by the force/tussop method.
次に実施例にて詳しく説明する。Next, this will be explained in detail in Examples.
実施例１
使用したアセチレンがス熱分解炉は、竪型の全長２，４
ｍ、内径Ｑ、 ４ ｍ 、排出口の径０．２５ ｍ 、
炉内頂部から０．３ｍ迄の内壁が水冷ジャケントによっ
て構成され、他の内壁が耐火レンガで構築されている。Example 1 The acetylene pyrolysis furnace used was a vertical type with a total length of 2.4 mm.
m, inner diameter Q, 4 m, outlet diameter 0.25 m,
The inner wall up to 0.3 m from the top of the furnace is constructed of water-cooled jackets, and the other inner walls are constructed of refractory bricks.
熱分解炉温度を８００℃以上に保持するため、−酸化炭
素１０ Ｎｍ３／Ｈ，２気６０ Ｎ ｍ３／Ｈ供給して
燃焼させたところ８５０°Ｃとなった。In order to maintain the pyrolysis furnace temperature at 800°C or higher, 10 Nm3/H of -carbon oxide and 60 Nm3/H of 2 gas were supplied for combustion, resulting in a temperature of 850°C.
この熱分解炉によって熱分解炉頂部中央に設けた２重管
ノズル中央から、酸素８．３ Ｎｍ３／ Ｈと４．０騨
／ｃｍ２で飽和された水蒸気（温度１５０°Ｃ）８．６
Ｎｍ” ／ Ｈの混合がス１６．６ Ｎｍ” ／ Ｈを
供給し、又２重管ノズルの外側環状部からアセチレンが
スを１８Ｎｍ”／Ｈ供給し、アセチレンガス、酸素、水
蒸気を反応せしめ、次いで常法に従い虫取したアセチレ
ンブラックを冷却捕集した。With this pyrolysis furnace, steam (temperature 150°C) 8.6 saturated with oxygen 8.3 Nm3/H and 4.0 Nm/cm2 was released from the center of the double tube nozzle installed at the center of the top of the pyrolysis furnace.
A mixture of Nm''/H supplies 16.6 Nm''/H of gas, and 18 Nm''/H of acetylene gas is supplied from the outer annular part of the double tube nozzle to cause the acetylene gas, oxygen, and water vapor to react, Next, the acetylene black that had been removed by the insects was cooled and collected according to a conventional method.
アセチレンガスの熱分解炉への供給線速度は、５、９
ｍ ／ ｓｅｃであり、又酸素と水蒸気の混合ガスの供
給線速度は６９．７ ｍ／ｓｅｃである。アセチレンが
スに対する酸素、水蒸気のモル比は各々０．４６であり
、又水蒸気に対する酸素のモル比は１．０で収率は３０
％であった。得られたアセチレンブラックの品質を見る
と電気比抵抗０．２０Ωｃｍ、ＨＣＩ吸液量２４．５
ｃｃ１５ 、！ｉ’、比表面積２５０ ｍ２７ｉの高性
能なアセチレンブラックであった。第１表に各種ブラッ
クの特性を比較例と共に示す。The linear velocity of acetylene gas supplied to the pyrolysis furnace is 5,9
m/sec, and the linear velocity of the mixed gas of oxygen and water vapor is 69.7 m/sec. The molar ratio of oxygen and water vapor to acetylene gas was each 0.46, and the molar ratio of oxygen to water vapor was 1.0, and the yield was 30.
%Met. Looking at the quality of the obtained acetylene black, the electric specific resistance is 0.20 Ωcm, and the HCI absorption amount is 24.5.
cc15,! It was a high-performance acetylene black with a specific surface area of 250 m27i. Table 1 shows the characteristics of various blacks along with comparative examples.
第１表 各種ブランクの物性比較
ここで比較例は
アセチレンブラック：商品名［デンカプラツクホ危り特
開昭５３−１１０９９２ ： アセチレンがスを空気に
よって部分燃焼させて得たアセチレンブラック
副生ブランク ニー酸化炭素、水素の混合ガスを得る
プロセスとして、テキサコ法、或いは宇
部法によって副生じたカーボンブラン
ク
本発明による実施例では、電気比抵抗において優れ、ま
た、ＨＣＩ吸液量が高く、比表面積においても優れる。Table 1 Comparison of physical properties of various blanks Here, a comparative example is acetylene black: Product name [Denka Platsukuho Kori JP 53-110992: Acetylene black by-product blank obtained by partially burning acetylene gas with air, carbon oxide, The carbon blank produced by the Texaco method or the Ube method as a process for obtaining a hydrogen gas mixture is excellent in electrical resistivity, has a high HCI absorption amount, and is also excellent in specific surface area.
特開昭５３−１１０９９２は、電気比抵抗に劣り、ＨＣ
Ｉ吸液性、比表面積も小さい。JP-A-53-110992 has poor electrical resistivity and HC
I liquid absorption property and specific surface area are also small.
副生ブランクは比表面積が大きいがＨＣＩ吸液において
大きくない。Although the by-product blank has a large specific surface area, it is not large in HCI absorption.
実施例２〜１５
実施例１と同様にアセチレンガスの流量を１８Ｎｍ”／
Ｈとして酸素、水蒸気の流量を変えてその時のアセチレ
ンガスに対する酸素、水蒸気のモル比、水蒸気に対する
モル比の関係を見たのが第２表である。Examples 2 to 15 As in Example 1, the flow rate of acetylene gas was changed to 18 Nm”/
Table 2 shows the relationship between the molar ratio of oxygen and water vapor to acetylene gas and the molar ratio to water vapor when the flow rates of oxygen and water vapor were changed as H.
いずれも電気比抵抗が良く、塩酸吸液量の優ねた高比表
面株のアセチレンブラックであった。All of them were high specific surface acetylene blacks with good electrical resistivity and excellent hydrochloric acid absorption.
比較例１〜６
実施例１と同じ熱分解炉を使用してアセチレンガスの流
量を１８ Ｎｍ”／Ｈとして酸素、水蒸気を供給しない
場合、或いは各々単独の効果を見たのが比較例１〜６で
ある。Comparative Examples 1 to 6 Comparative Examples 1 to 6 used the same pyrolysis furnace as in Example 1, set the acetylene gas flow rate to 18 Nm"/H, and examined the effects of oxygen and water vapor not being supplied, or the effects of each independently. It is 6.
その条件、特性を比較したのが第３衣である。The third item is a comparison of the conditions and characteristics.
以上の様に、酸素及び水蒸気単独を供給した場合いずれ
も高性能のアセチレンブラックは得られなかった。As described above, high-performance acetylene black could not be obtained in any case where oxygen and water vapor were supplied alone.
実施例１５〜２０、比較例７〜８ 実施例１と同じ熱分解炉を使用した。Examples 15-20, Comparative Examples 7-8 The same pyrolysis furnace as in Example 1 was used.
実施例１５〜１７は不飽和炭化水素としてエチレンガス
を使用し、エチレンガスをアセチレンが７１００部に対
して１０．２０部（アセチレンがス１８ Ｎｍ”／Ｈに
対して各々１．７ Ｎｍ３／Ｈ，３，５Ｎｍ”／Ｈ）、
４［１（アセチレンガス１５ Ｎｍ３７Ｂに対して５．
７ Ｎｍ３／）ｒ ）を共存せしめた。Examples 15 to 17 used ethylene gas as the unsaturated hydrocarbon, and the ethylene gas was 10.20 parts per 7100 parts of acetylene (1.7 Nm/H per 18 Nm/H of acetylene). ,3,5Nm"/H),
4 [1 (acetylene gas 15 Nm 5 for 37B)
7 Nm3/)r) were allowed to coexist.
実施例１８〜２０は、不飽和炭化水素として、べ／ダン
をガス状態とした。その添ａｐｔは１０．２０部（アセ
チレンがス１８Ｎｍ３／Ｈに対して各々０、６ Ｎｍ３
／’Ｈ５１，’ｌ Ｎｍ３／）（）、４０部（アセチレ
ンガス１５ Ｎｍ”／’Ｈに対して２． Ｑ Ｎｍ″Ｌ
／Ｈ）であった。In Examples 18 to 20, the unsaturated hydrocarbon was veneer/dane in a gaseous state. The apt added was 10.20 parts (0 and 6 Nm3/H, respectively, for acetylene 18Nm3/H).
/'H51,'l Nm3/) (), 40 parts (acetylene gas 15 Nm"/'H to 2.Q Nm"L
/H).
又、比較例７．８は、エチレンがス、べ／ゼ／がスな各
々５０部（アセチレンガス１５ Ｎｍ’／）（に対して
エチレンガスはＺＯＮｍ３／Ｈ、ベンゼンがスは２．５
Ｎｍ３／Ｈ）をアセチレンがスと共存せしめた。In addition, in Comparative Example 7.8, 50 parts each of ethylene gas and benzene gas (acetylene gas 15 Nm'/H) (for which ethylene gas is ZONm3/H and benzene gas is 2.5
Nm3/H) was made to coexist with acetylene gas.
その不飽和炭化水素はアセチレンガスと混合して２重管
ノズルの外側環状部に供給した。The unsaturated hydrocarbon was mixed with acetylene gas and fed to the outer annulus of the double tube nozzle.
その結果を第４表に示す。The results are shown in Table 4.
実施例１５〜２０に示す様にエチレンガス、ベンゼンが
スの様な不飽和炭化水素を４０部迄共存しても高性能な
アセチレンブラックを得ることができる。As shown in Examples 15 to 20, high-performance acetylene black can be obtained even when up to 40 parts of unsaturated hydrocarbons such as ethylene gas and benzene gas are present.
５０部となると不飽和炭化水素の熱分解熱量がアセチレ
ンがスの熱分解熱に比して小さいため、炉内の温度が低
くなり、本発明の目的とする物性のアセチレンブラック
が得られなくなる。When it reaches 50 parts, the heat of thermal decomposition of the unsaturated hydrocarbon is smaller than the heat of thermal decomposition of acetylene, so the temperature in the furnace becomes low and it becomes impossible to obtain acetylene black with the physical properties targeted by the present invention.
実施例２１〜２４
実施例１と同じ熱分解炉を使用してアセチレンガスの流
量を１２Ｎｍ”／Ｈとして、酸素源として純酸素及び空
気（酸素２１％、窒素７９％）の効果を見た。Examples 21 to 24 Using the same pyrolysis furnace as in Example 1, the flow rate of acetylene gas was set to 12 Nm''/H, and the effects of pure oxygen and air (21% oxygen, 79% nitrogen) as oxygen sources were examined.
アセチレンがスを酸素と水蒸気の混合がス流で熱分解す
ることにより、高品質のアセチレンブラックを得ること
ができる。酸素だけでは、品質の向上が十分でなく、水
蒸気だけでは炉内温度が低く品質のよいアセチレンブラ
ックは得られない。High quality acetylene black can be obtained by thermally decomposing acetylene gas in a stream of a mixture of oxygen and water vapor. Oxygen alone is not enough to improve quality, and steam alone cannot produce high-quality acetylene black due to the low furnace temperature.
またエチレンガスやベンゼンガスの様な不飽和炭化水素
を共存させても高性能なアセチレンブラックを得ること
ができる。Furthermore, high-performance acetylene black can be obtained even when an unsaturated hydrocarbon such as ethylene gas or benzene gas is coexisting.
特許出願人 電気化学、工業株式会社
手続補正書
昭和５９年 ４月２３日
１、事件の表示
昭和５９年特許願第６１８３１号
２、発明の名称
アセチレンブラック及びその製造方法
３、補正をする者
事件との関係 特許出願人
〒１００
住 所 東京都千代田区有楽町１丁目４番１号よい。空
気でもよい。さらに両者の混合水蒸気は、イオン交換さ
れ」を「酸素がよいが、空気でもよい。Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment April 23, 1980 1, Case Description 1982 Patent Application No. 61831 2, Title of Invention Acetylene Black and Process for Producing the Same 3, Person Making Amendment Case Relationship with Patent applicant Address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo 1-4-1 Yoi. Air may also be used. Furthermore, the water vapor mixed with both is ion-exchanged."Oxygen is preferable, but air may also be used.
さらに両者の混合ガスであってもよい。水蒸気は、イオ
ン交換され」と訂正する。Furthermore, a mixed gas of both may be used. "Water vapor is ion-exchanged," he corrected.
２）第８頁第１〜２行の「混った状態のＪを「湿った状
態の」と訂正する。2) On page 8, lines 1 and 2, correct J for ``in a mixed state'' to ``in a wet state.''
手 続 補 正 書（方式）
％式％
１、事件の表示
昭和５９年特許願第６１８３１号
２、発明の名称
アセチレンブラック及びその製造方法
３、補正をする者
事件との関係 特許出願人
■１００
住所 東京都千代田区有楽町１丁目４番１号昭和６０
年８月２７日
５補正の対象
明細書の発明の名称の欄
６、補正の内容Procedure Amendment (Method) % Formula % 1. Indication of the case Patent Application No. 61831 of 1982 2. Name of the invention Acetylene black and its manufacturing method 3. Person making the amendment Relationship with the case Patent applicant ■ 100 Address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo 1980
August 27, 2016 5. Name of invention column 6 of the specification subject to the amendment, Contents of the amendment
Claims (8)
０Ωｃｍ未満、塩酸吸液量２０〜４０ｍｌ／５ｇ及び比
表面積１００〜４００ｍ＾２／ｇの高性能アセチレンブ
ラック。(1) Electrical specific resistance value under pressure of 50Kg/cm^2 0.3
High-performance acetylene black with a hydrochloric acid absorption capacity of less than 0 Ωcm, a hydrochloric acid absorption capacity of 20 to 40 ml/5 g, and a specific surface area of 100 to 400 m^2/g.
存在させずして、酸素含有気体と水蒸気の混合ガス流に
よつて連続的に熱分解させることを特徴とする５０Ｋｇ
／ｃｍ＾２加圧下の電気比抵抗値０．６０Ωｃｍ未満、
塩酸吸液量２０〜４０ｍｌ／５ｇ及び比表面積１００〜
４００ｍ＾２／ｇの高性能アセチレンブラックの製造方
法。(2) 50 kg characterized in that the acetylene gas is thermally decomposed continuously by a mixed gas flow of oxygen-containing gas and water vapor in the presence or absence of unsaturated hydrocarbons.
/cm^2 Electrical resistivity under pressure less than 0.60Ωcm,
Hydrochloric acid absorption amount 20-40ml/5g and specific surface area 100-
A method for producing high-performance acetylene black of 400m^2/g.
対して４０重量部未満である特許請求の範囲第２項記載
の製造方法。(3) The manufacturing method according to claim 2, wherein the amount of unsaturated hydrocarbon is less than 40 parts by weight based on 100 parts by weight of acetylene gas.
エン、ベンゼン、ナフタレン及びアントラセンから選ば
れた１種以上である特許請求の範囲第２〜３項記載の製
造方法。(4) The manufacturing method according to claims 2 to 3, wherein the unsaturated hydrocarbon is one or more selected from ethylene, propylene, butadiene, benzene, naphthalene, and anthracene.
）との間にモル単位でａ＋（ｂ／２）＜１（但し、０＜
ａ＜１、０＜ｂ＜２）なる関係にある特許請求の範囲第
２項記載の製造方法。(5) Oxygen-containing gas is pure oxygen (a), water vapor (b
) in molar units a+(b/2)<1 (however, 0<
The manufacturing method according to claim 2, which has the following relationship: a<1, 0<b<2.
気体である特許請求の範囲第２項記載の製造方法。(6) The manufacturing method according to claim 2, wherein the oxygen-containing gas is pure oxygen, air, or a mixture of both.
れた完全乾燥物である特許請求の範囲第２項記載の製造
方法。(7) The manufacturing method according to claim 2, wherein the water vapor is a completely dried product obtained from water by an ion exchange or evaporation method.
れる特許請求の範囲第２項記載の製造方法。(8) The manufacturing method according to claim 2, wherein the thermal decomposition is performed in a decomposition furnace maintained at 800° C. or higher.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6183184A JPS6134073A (en) | 1984-03-29 | 1984-03-29 | Acetylene black and production thereof |
| US06/717,063 US4664900A (en) | 1984-03-29 | 1985-03-28 | Electrically conductive compositions |
| EP85103750A EP0156390B1 (en) | 1984-03-29 | 1985-03-28 | Electrically conductive composition |
| DE8585103750T DE3570886D1 (en) | 1984-03-29 | 1985-03-28 | Electrically conductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6183184A JPS6134073A (en) | 1984-03-29 | 1984-03-29 | Acetylene black and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6134073A true JPS6134073A (en) | 1986-02-18 |
| JPH0471109B2 JPH0471109B2 (en) | 1992-11-12 |
Family
ID=13182430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6183184A Granted JPS6134073A (en) | 1984-03-29 | 1984-03-29 | Acetylene black and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6134073A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049145A (en) * | 1999-08-09 | 2001-02-20 | Tokai Carbon Co Ltd | Carbon black and ptc composition compounded therewith |
| JP2008218798A (en) * | 2007-03-06 | 2008-09-18 | Denki Kagaku Kogyo Kk | Polarizable-electrode forming material and use application of polarizable electrode |
| JP2013199641A (en) * | 2012-02-23 | 2013-10-03 | Asahi Carbon Kk | Method for producing carbon black |
| WO2022118923A1 (en) * | 2020-12-04 | 2022-06-09 | デンカ株式会社 | Carbon black, slurry, and lithium ion secondary battery |
| WO2023054377A1 (en) * | 2021-09-30 | 2023-04-06 | デンカ株式会社 | Carbon black, composition, laminate, and battery |
| WO2023054375A1 (en) * | 2021-09-30 | 2023-04-06 | デンカ株式会社 | Carbon black, composition, laminate, and battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53110992A (en) * | 1977-03-09 | 1978-09-28 | Ugine Kuhlmann | Acetylene black having high electric conductivity and high absorbing power and method of making same |
| JPS5711576A (en) * | 1980-06-24 | 1982-01-21 | Ricoh Co Ltd | Facsimile system |
-
1984
- 1984-03-29 JP JP6183184A patent/JPS6134073A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53110992A (en) * | 1977-03-09 | 1978-09-28 | Ugine Kuhlmann | Acetylene black having high electric conductivity and high absorbing power and method of making same |
| JPS5711576A (en) * | 1980-06-24 | 1982-01-21 | Ricoh Co Ltd | Facsimile system |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001049145A (en) * | 1999-08-09 | 2001-02-20 | Tokai Carbon Co Ltd | Carbon black and ptc composition compounded therewith |
| JP2008218798A (en) * | 2007-03-06 | 2008-09-18 | Denki Kagaku Kogyo Kk | Polarizable-electrode forming material and use application of polarizable electrode |
| JP2013199641A (en) * | 2012-02-23 | 2013-10-03 | Asahi Carbon Kk | Method for producing carbon black |
| WO2022118923A1 (en) * | 2020-12-04 | 2022-06-09 | デンカ株式会社 | Carbon black, slurry, and lithium ion secondary battery |
| EP4235846A1 (en) * | 2020-12-04 | 2023-08-30 | Denka Company Limited | Carbon black, slurry, and lithium ion secondary battery |
| WO2023054377A1 (en) * | 2021-09-30 | 2023-04-06 | デンカ株式会社 | Carbon black, composition, laminate, and battery |
| WO2023054375A1 (en) * | 2021-09-30 | 2023-04-06 | デンカ株式会社 | Carbon black, composition, laminate, and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0471109B2 (en) | 1992-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3053877B1 (en) | Method for manufacturing bundle-type carbon nanotubes having a large specific surface area | |
| JP5430571B2 (en) | Carbon nanotube powder, carbon nanotube and method for producing the same | |
| JP6359081B2 (en) | Boron nitride nanotube and method for producing the same | |
| KR101274492B1 (en) | Process for producing carbon nanotube | |
| Tsoufis et al. | Catalytic production of carbon nanotubes over Fe–Ni bimetallic catalysts supported on MgO | |
| US20100072430A1 (en) | Compositions of carbon nanosheets and process to make the same | |
| US20100160539A1 (en) | Carbon black, method for producing the same, and its use | |
| US4664900A (en) | Electrically conductive compositions | |
| KR20150110513A (en) | Carbon nano-tube production from carbon dioxide | |
| Awadallah et al. | Direct conversion of natural gas into COx-free hydrogen and MWCNTs over commercial Ni–Mo/Al2O3 catalyst: Effect of reaction parameters | |
| JPS6134073A (en) | Acetylene black and production thereof | |
| Cao et al. | Carbon nanotubes modified by multi-heteroatoms polymer for oxidative dehydrogenation of propane: Improvement of propene selectivity and oxidation resistance | |
| Ombaka et al. | A facile approach towards increasing the nitrogen-content in nitrogen-doped carbon nanotubes via halogenated catalysts | |
| JP5046078B2 (en) | Method for producing single-walled carbon nanotube | |
| Zhang et al. | Solid supported ruthenium catalyst for growing single-walled carbon nanotubes with narrow chirality distribution | |
| US11718525B2 (en) | System and method of producing carbon nanotubes | |
| Keller et al. | Carbon nanotube formation in situ during carbonization in shaped bulk solid cobalt nanoparticle compositions | |
| KR101241035B1 (en) | Process for preparing catalyst compositions for the synthesis of carbon nanotube having high bulk density | |
| WO2021035769A1 (en) | Catalyst for preparing phosgene and preparation method therefor, and method for preparation of phosgene and comprehensive utilization of energy thereof | |
| Du et al. | The synthesis of single-walled carbon nanotubes with controlled length and bundle size using the electric arc method | |
| JPS6295351A (en) | Production of carbon black of composite structure | |
| WO2022047600A1 (en) | Method for preparing multi-walled carbon nanotubes | |
| JPH01188568A (en) | Production of high-performance acetylene black | |
| JP2010248397A (en) | Method for producing carbon black composite | |
| WO2020157285A1 (en) | Polyethylene composition comprising carbonaceous structures and having improved mechanical properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |