JPH0751568A - Carbon black composite and manufacture thereof - Google Patents
Carbon black composite and manufacture thereofInfo
- Publication number
- JPH0751568A JPH0751568A JP5226435A JP22643593A JPH0751568A JP H0751568 A JPH0751568 A JP H0751568A JP 5226435 A JP5226435 A JP 5226435A JP 22643593 A JP22643593 A JP 22643593A JP H0751568 A JPH0751568 A JP H0751568A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- carbon black
- average particle
- fine particles
- particle size
- 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.)
- Pending
Links
- 239000006229 carbon black Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002245 particle Substances 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000010419 fine particle Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000011882 ultra-fine particle Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000696 magnetic material Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 235000019241 carbon black Nutrition 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- -1 nickel formate-carbon Chemical compound 0.000 description 1
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- UMTMDKJVZSXFNJ-UHFFFAOYSA-N nickel;trihydrate Chemical compound O.O.O.[Ni] UMTMDKJVZSXFNJ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高性能触媒を初めとし
て電極材料や磁性材料などの用途に優れた機能性を有す
るカーボンブラック複合体に関するものであり、より詳
しくはカーボンブラック表面にニッケル微粒子を担持さ
せた複合体ならびにその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon black composite having excellent functionality for applications such as high performance catalysts, electrode materials and magnetic materials. The present invention relates to a composite supporting γ and a method for producing the same.
【０００２】[0002]
【従来の技術】カーボンブラックに金属を複合させた材
料は、カーボンブラックが本来持つ導電性や着色性など
の機能とともに、その大きな表面積を利用して、更に高
度な触媒機能や電気特性、磁気特性などの特殊な機能を
も付与できるため、有用な機能性材料として着目されて
いる。例えば、特開昭６３−１９９２７２号公報や特開
昭６４−４３５６９号公報（出願人：いずれも東海カー
ボン株式会社）などに見られるカーボンブラック中に磁
性金属微粒子を複合させた材料はその例であり、またも
う一つの例は、特開平３−１７７４６２号公報（出願
人：旭カーボン株式会社）にみられる、カーボンブラッ
クを金属の超薄膜で被覆し、高度な導電性を付与したも
のなどがある。ところで、金属に対する微粒子化の技術
の進展の結果、金属微粒子は粒子径が小さくなるにつれ
従来の物質では見られなかった優れた現象を示すように
なることが最近知られてきている。例えば、一酸化炭素
と水素からの炭化水素の合成や含酸素化合物の合成反応
では金属超微粒子が触媒として有効であることが知られ
ている（伊藤ら、表面、Vol．28，ｐ79，1990）。また
鉄やニッケル、コバルトなどの強磁性金属微粒子の磁気
特性は、その粒子径に依存し超微粒子では超常磁性を示
すといわれている（尾崎ら、表面、Vol．22，ｐ684，19
84）。どの程度の粒子径でこの様な特異な現象を示すか
についてみると、金属により異なるが、概ね１０〜２０
ｎｍより小さい粒子径と考えられている。したがって、
カーボンブラックに複合する金属微粒子の粒子径も、こ
れより小さい方が、従来とは異なった新たな用途に適用
できると期待される。ところが従来の技術では１５ｎｍ
以下の微細な金属粒子をカーボンブラックに複合した例
は見られない。例えば、特開昭６３−２０５３６９公報
や特開昭６４−４３５６９号公報に見られる磁性金属微
粒子をカーボンブラックに複合した例においては最も微
細な粒子径でも１６．０ｎｍであり、概ね２０ｎｍ前後
か、あるいはそれ以上の粒子径である。また、特公平３
−５６５９６公報（出願人：電気化学工業株式会社）に
は、気相法による炭素繊維と複合構造にあるカーボンブ
ラックについて記載されており、その前駆体となる金属
微粒子をシーディングしたカーボンブラックについても
述べられている。実施例には、金属微粒子の粒子径につ
いての具体的な記載はないが、成長してきた炭素繊維の
太さが２０〜５０ｎｍであることおよび、気相成長炭素
繊維の成長メカニズムから見て、これとほぼ同等の粒子
径であると推定される。2. Description of the Related Art A material in which a metal is combined with carbon black has a function such as conductivity and coloring property which carbon black originally has, and further utilizes its large surface area to further enhance the catalytic function, electric property and magnetic property. Since it can also be given special functions such as, it is attracting attention as a useful functional material. For example, a material obtained by compounding magnetic metal fine particles in carbon black found in JP-A-63-199272 and JP-A-64-43569 (applicant: Tokai Carbon Co., Ltd.) is an example. There is another example, which is disclosed in JP-A-3-177462 (Applicant: Asahi Carbon Co., Ltd.), in which carbon black is coated with an ultrathin metal film to impart a high degree of conductivity. is there. By the way, it has been recently known that, as a result of the progress of the technology for making fine particles for metals, the fine particles of metal exhibit an excellent phenomenon that has not been observed in conventional substances as the particle diameter becomes smaller. For example, it is known that ultrafine metal particles are effective as a catalyst in the synthesis reaction of hydrocarbons from carbon monoxide and hydrogen and the synthesis reaction of oxygen-containing compounds (Ito et al., Surface, Vol. 28, p79, 1990). . The magnetic properties of ferromagnetic metal particles such as iron, nickel, and cobalt depend on their particle size, and it is said that ultrafine particles exhibit superparamagnetism (Ozaki et al., Surface, Vol. 22, p684, 19).
84). Looking at what particle size shows such a peculiar phenomenon, it depends on the metal, but it is about 10 to 20.
It is considered to have a particle size smaller than nm. Therefore,
It is expected that if the particle size of the metal fine particles complexed with carbon black is smaller than this, it can be applied to a new application different from the conventional one. However, with conventional technology, 15 nm
No example is found in which the following fine metal particles are compounded with carbon black. For example, in the examples in which the magnetic metal fine particles disclosed in JP-A-63-205369 and JP-A-64-43569 are combined with carbon black, the finest particle diameter is 16.0 nm, which is about 20 nm. Alternatively, the particle size is larger than that. In addition, special fair 3
JP-A-56596 (Applicant: Denki Kagaku Kogyo Co., Ltd.) describes carbon black having a composite structure with carbon fibers by a vapor phase method, and also about carbon black seeded with metal fine particles as a precursor thereof. Stated. Although there is no specific description about the particle size of the metal fine particles in the examples, the thickness of the grown carbon fiber is 20 to 50 nm and the growth mechanism of the vapor grown carbon fiber shows that It is estimated that the particle size is almost the same as
【０００３】[0003]
【目的】本発明の目的は、従来にない超微細なＮｉ粒子
を担持させたカーボンブラック複合体を提供する点にあ
る。[Purpose] An object of the present invention is to provide a carbon black composite supporting unprecedented ultrafine Ni particles.
【０００４】[0004]
【発明の構成】本発明の一つは、カーボンブラック表面
上に数平均粒子径が１５ｎｍ以下のニッケル微粒子を担
持させたカーボンブラック複合体に関する。本発明の他
の一つは、カーボンブラックとニッケル塩の混合物を１
８０℃以上３００℃以下の温度に加熱処理してニッケル
微粒子をカーボンブラック表面に担持させることを特徴
とするニッケル微粒子を担持させたカーボンブラック複
合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION One of the present invention relates to a carbon black composite in which nickel fine particles having a number average particle diameter of 15 nm or less are carried on the surface of carbon black. According to another aspect of the present invention, a mixture of carbon black and nickel salt is used.
The present invention relates to a method for producing a carbon black composite supporting nickel fine particles, which comprises heat-treating the particles at a temperature of 80 ° C. or higher and 300 ° C. or lower to support the nickel fine particles on the carbon black surface.
【０００５】前記ニッケル塩としては、有機塩のニッケ
ル塩などの比較的低い温度で熱分解し、金属ニッケルを
放出するようなものが好ましく、例えば、酢酸ニッケ
ル、シュウ酸ニッケル、蟻酸ニッケルなどが挙げられる
が、とりわけ蟻酸ニッケルが好ましい。本発明に用られ
る蟻酸ニッケル〔Ｎｉ（ＨＣＯＯ）2〕は、２００℃前
後で下記に示す熱分解反応を起こして金属ニッケルを放
出する。The nickel salt is preferably an organic salt such as a nickel salt that thermally decomposes at a relatively low temperature to release metallic nickel. Examples thereof include nickel acetate, nickel oxalate, and nickel formate. However, nickel formate is particularly preferable. The nickel formate [Ni (HCOO) 2 ] used in the present invention causes the following thermal decomposition reaction at about 200 ° C. to release metallic nickel.
【化１】 この反応で生じた金属ニッケルは、空気に直接触れない
限り、極めて反応性、還元性が高く触媒活性が高い。本
発明では、とくに蟻酸ニッケル水溶液にカーボンブラッ
クを添加分散させた懸濁液を噴霧乾燥し、カーボンブラ
ック表面に蟻酸ニッケルを均一に析出させ、さらにそれ
を１８０〜３００℃で熱処理すると、超微粒でかつ粒子
径の揃ったニッケル粒子を均一にカーボンブラック表面
に担持複合することができる。このニッケル微粒子の数
平均粒子径（Ｄ1）は１５ｎｍ以下、体積平均粒子径
（Ｄ2）は２３ｎｍ以下、好ましくは７〜１６ｎｍであ
り、Ｄ1／Ｄ2の比は１．５３以下、好ましくは１．３５
〜１．５０である。[Chemical 1] The metallic nickel produced by this reaction has extremely high reactivity and reducibility and high catalytic activity unless directly exposed to air. In the present invention, in particular, a suspension in which carbon black is added and dispersed in a nickel formate aqueous solution is spray-dried to uniformly deposit nickel formate on the surface of carbon black, which is further heat treated at 180 to 300 ° C. to obtain ultrafine particles. In addition, nickel particles having a uniform particle size can be uniformly supported and composited on the surface of carbon black. The number average particle diameter (D 1 ) of the nickel fine particles is 15 nm or less, the volume average particle diameter (D 2 ) is 23 nm or less, preferably 7 to 16 nm, and the D 1 / D 2 ratio is 1.53 or less, preferably Is 1.35
˜1.50.
【０００６】カーボンブラック懸濁液を調製する場合、
カーボンブラックができるだけ均一に分散されるように
少量のアルコールや界面活性剤などを添加することが好
ましい。分散手段としては、機械的撹拌や超音波処理な
ど通常の分散手段を用いて分散させることができる。When preparing a carbon black suspension,
It is preferable to add a small amount of alcohol or a surfactant so that the carbon black is dispersed as uniformly as possible. As a dispersing means, a usual dispersing means such as mechanical stirring or ultrasonic treatment can be used for dispersion.
【０００７】噴霧乾燥に用いられる装置としては、通常
使用されているもので十分であり、例えば、噴霧装置が
回転ディスク式で熱風との接触が並流方式のものなどを
用いることができる。噴霧乾燥条件としては特殊なもの
はないが、ニッケル塩が蟻酸ニッケルの場合は、噴霧乾
燥品の温度が１８０℃を超えないようにすることが重要
である。なぜなら、この温度を超えると蟻酸ニッケルが
熱分解する可能性が高まるからであり、このため噴霧乾
燥品の温度は１００〜１１０℃とするのが好ましい。As a device used for spray drying, a commonly used device is sufficient. For example, a spraying device of a rotating disk type and a co-current system of contacting with hot air can be used. There are no special conditions for spray drying, but when the nickel salt is nickel formate, it is important that the temperature of the spray dried product does not exceed 180 ° C. This is because if this temperature is exceeded, the possibility that nickel formate will be thermally decomposed increases, and therefore the temperature of the spray-dried product is preferably 100 to 110 ° C.
【０００８】加熱処理の方法としては、種々の方法が適
用できるが、空気、特に酸素に直接触れない状態で行な
う必要がある。加熱処理時の雰囲気としては、不活性ガ
スであるＨｅ、Ｎｅ、Ａｒ、ＸｅやＮ2、Ｈ2、ＣＯ2、
ＣＯ、Ｈ2Ｏなどの非酸化性ガスもしくは、これらの混
合ガス中で熱処理することができるが、より望ましく
は、加熱処理温度以上の沸点をもつ有機溶剤中で熱処理
することが挙げられる。有機溶剤としてはジエチレング
リコール、ブチルカルビトール、ジフェニルエーテル、
ビフェニールなどが本発明での熱処理媒体として好適で
ある。これにより加熱処理後も溶剤中に浸しておくこと
で空気に直接、触れることを避けることができる。熱処
理は１８０〜３００℃で行なわれるがニッケル粒子同士
の焼結を避けるためには１８０〜２５０℃の条件がさら
に好ましい。また熱処理時間では、あまり長すぎるとニ
ッケル粒子同士の焼結が起きるので３０分以内の条件が
望ましい。しかし、加熱温度が低く、加熱時間があまり
に短いと蟻酸ニッケルから金属ニッケルへの分解反応が
終了しないこともあるので、熱処理条件は２００〜２５
０℃の温度で１５〜３０分の熱処理が最も望ましい。Although various methods can be applied to the heat treatment, it is necessary to perform the heat treatment without directly contacting air, particularly oxygen. The atmosphere during the heat treatment includes He, Ne, Ar, Xe and N 2 , H 2 , CO 2 which are inert gases,
The heat treatment can be carried out in a non-oxidizing gas such as CO or H 2 O or a mixed gas thereof, but more preferably, the heat treatment can be carried out in an organic solvent having a boiling point higher than the heat treatment temperature. Organic solvents include diethylene glycol, butyl carbitol, diphenyl ether,
Biphenyl and the like are suitable as the heat treatment medium in the present invention. As a result, it is possible to avoid direct contact with air by immersing it in the solvent even after the heat treatment. The heat treatment is performed at 180 to 300 ° C., but the condition of 180 to 250 ° C. is more preferable in order to avoid sintering of nickel particles. If the heat treatment time is too long, sintering of the nickel particles will occur, so a condition of 30 minutes or less is desirable. However, if the heating temperature is low and the heating time is too short, the decomposition reaction of nickel formate into metallic nickel may not be completed.
A heat treatment of 15 to 30 minutes at a temperature of 0 ° C. is most desirable.
【０００９】[0009]
【実施例】蟻酸ニッケル２水和塩〔Ｎｉ（ＨＣＯＯ）2
・２Ｈ2Ｏ；和光純薬（株）製〕６３．０ｇを２．０リ
ッットルの脱イオン水に溶解し、その液にカーボンブラ
ック３０ｇを添加した。またカーボンブラックの分散剤
としてエチルアルコール２０ｍｌを添加した後、市販の
プロペラ型撹拌装置で１昼夜撹拌し、よく分散させて噴
霧乾燥用懸濁液を調製した。懸濁液は表１にその理化学
性状を示した４種類のカーボンブラックを用いて調製し
た。カーボンブラック懸濁液は、スプレードライヤー
〔大川原化工機(株)製Ｌ−８型〕により製品粒径２０〜
３０μｍ、製品温度１００±５℃という条件で噴霧乾燥
した。得られた噴霧乾燥品１ｇに対し１０ｍｌのジフェ
ニルエーテル〔Ｃ6Ｈ5ＯＣ6Ｈ5 沸点２５０℃、関東化
学（株）製〕を添加し、２５０℃で１５分間、加熱処理
し、超微粒ニッケル複合カーボンブラックを得た。EXAMPLE Nickel formate dihydrate [Ni (HCOO) 2
2H 2 O; manufactured by Wako Pure Chemical Industries, Ltd.] 63.0 g was dissolved in 2.0 liters of deionized water, and 30 g of carbon black was added to the solution. After adding 20 ml of ethyl alcohol as a dispersant for carbon black, the mixture was stirred for one day with a commercially available propeller-type stirrer and well dispersed to prepare a suspension for spray drying. The suspension was prepared using four kinds of carbon blacks whose physical and chemical properties are shown in Table 1. The carbon black suspension was produced with a spray dryer [L-8 type manufactured by Okawara Kakoki Co., Ltd.] with a product particle size of 20-
Spray drying was carried out under the conditions of 30 μm and product temperature 100 ± 5 ° C. To 1 g of the obtained spray-dried product, 10 ml of diphenyl ether [C 6 H 5 OC 6 H 5 boiling point 250 ° C., manufactured by Kanto Chemical Co., Inc.] was added, and heat treatment was performed at 250 ° C. for 15 minutes to obtain an ultrafine nickel composite. Carbon black was obtained.
【表１】 [Table 1]
【００１０】本発明のカーボンブラックに複合されたニ
ッケル粒子の電子顕微鏡による粒子径の測定結果を表２
〜３に示した。比較例として、噴霧乾燥方法を用いずに
減圧乾燥法によって得られたニッケル複合カーボンブラ
ックの測定結果を比較例１に示した。さらに、カーボン
ブラックを添加せず、蟻酸ニッケル単独をジフェニルエ
ーテル中で実施例と同一条件で加熱処理して得られたニ
ッケル粒子の測定結果を比較例２に示した。この結果か
ら明らかなように、同じ蟻酸ニッケル・カーボンブラッ
ク懸濁液を用いても乾燥方法によりニッケル粒子の粒子
径が異なり、噴霧乾燥を用いた実施例１〜４は減圧乾燥
を用いた比較例１に比較して数平均粒子径が著しく小さ
くなっており、かつ粒子径のバラツキの目安となる体積
平均径との比Ｄ1／Ｄ2も小さくなっていて、均一に微粒
化されていることが理解される。Table 2 shows the measurement results of the particle size of the nickel particles composited with the carbon black of the present invention by an electron microscope.
~ 3. As a comparative example, Comparative Example 1 shows the measurement results of the nickel composite carbon black obtained by the vacuum drying method without using the spray drying method. Further, Comparative Example 2 shows the measurement results of nickel particles obtained by heat-treating nickel formate alone in diphenyl ether under the same conditions as in Example without adding carbon black. As is clear from this result, even if the same nickel formate-carbon black suspension is used, the particle size of nickel particles varies depending on the drying method, and Examples 1 to 4 using spray drying are comparative examples using vacuum drying. Compared with No. 1, the number average particle size is remarkably small, and the ratio D 1 / D 2 to the volume average size, which is a measure of variation in particle size, is also small, and the particles are uniformly atomized. Is understood.
【表２】 [Table 2]
【表３】 [Table 3]
【００１１】＜水素添加触媒性能＞実施例と比較例で調
製した各サンプルについて、図１に示す装置を用い、フ
ェニルアセチレンに対する水素添加触媒活性を測定し
た。スターラーに置かれた反応フラスコに、アセチレン
１ｇ、特級エタノール４０ｍｌおよび触媒（実施例、比
較例に示したそれぞれの触媒をＮｉとして０．５ｇ）よ
りなる組成物を加え、系を２０℃に保ちつつ、高純度水
素ガスを供給して、下記の反応式<Hydrogenation Catalytic Performance> The hydrogenation catalytic activity for phenylacetylene was measured for each of the samples prepared in Examples and Comparative Examples using the apparatus shown in FIG. To a reaction flask placed on a stirrer, a composition consisting of 1 g of acetylene, 40 ml of special grade ethanol and a catalyst (0.5 g of each catalyst shown in Examples and Comparative Examples as Ni) was added, while maintaining the system at 20 ° C. , Supplying high-purity hydrogen gas, the following reaction formula
【化２】 に従ってフェニルアセチレンをスチレンを経てエチルベ
ンゼンに変換した。この反応において反応開始後４０分
間で吸収される水素量をガスビレットにより測定し、こ
れを標準状態（２５℃、１気圧）での量に換算した。そ
の結果を表４に示す。なお、市販のラネーニッケル触媒
を用いた結果を比較例３として示した。表４の結果から
明らかなように、本発明のニッケル超微粒子担持カーボ
ンブラック複合体は水素添加触媒として用いられ、かつ
同じニッケルが原料であるラネーニッケルよりも優れた
性能を有していることは表中の水素吸収量の差から明ら
かである。[Chemical 2] Following conversion of phenylacetylene to ethylbenzene via styrene. In this reaction, the amount of hydrogen absorbed 40 minutes after the start of the reaction was measured with a gas billet, and this was converted into the amount in the standard state (25 ° C, 1 atm). The results are shown in Table 4. The result using a commercially available Raney nickel catalyst is shown as Comparative Example 3. As is clear from the results in Table 4, it is shown that the nickel black ultrafine particle-supporting carbon black composite of the present invention is used as a hydrogenation catalyst and has superior performance to Raney nickel which is the same nickel as a raw material. It is clear from the difference in the amount of absorbed hydrogen.
【表４】 [Table 4]
【００１２】[0012]
【効果】本発明の超微粒子ニッケルを担持させたカーボ
ンブラック複合体は、複合されたニッケル微粒子が超微
粒でかつ均一なため、触媒材料として優れ、触媒機能を
要求される電極材料、例えばガス拡散電極材料などに有
用である。また、カーボンブラックに複合してあるた
め、トナー現像用着色材料、磁性塗料用材料などの用途
にも使用できる。[Effect] The carbon black composite supporting ultrafine nickel particles of the present invention is excellent as a catalyst material because the composite nickel fine particles are ultrafine particles and are uniform, for example, gas diffusion. It is useful as an electrode material. In addition, since it is compounded with carbon black, it can be used for applications such as coloring materials for toner development and materials for magnetic paints.
【図１】フェニルアセチレンに対する水素添加触媒活性
測定装置の説明図である。FIG. 1 is an explanatory diagram of a hydrogenation catalytic activity measuring device for phenylacetylene.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 15/073 15/46 Ｃ０８Ｌ 21/00 Ｃ２３Ｃ 18/08 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07C 15/073 15/46 C08L 21/00 C23C 18/08
Claims (7)
が１５ｎｍ以下のニッケル微粒子を担持させたカーボン
ブラック複合体。1. A carbon black composite in which nickel fine particles having a number average particle diameter of 15 nm or less are carried on the surface of carbon black.
２３ｎｍ以下である請求項１記載のカーボンブラック複
合体。2. The carbon black composite according to claim 1, wherein the volume average particle diameter of the nickel fine particles is 23 nm or less.
1）と体積平均粒子径（Ｄ2）の比が１．５３以下である
請求項１または２記載のカーボンブラック複合体。3. The number average particle diameter (D
The carbon black composite according to claim 1 or 2, wherein the ratio of 1 ) to the volume average particle diameter (D 2 ) is 1.53 or less.
を１８０℃以上３００℃以下の温度に加熱処理してニッ
ケル微粒子をカーボンブラック表面に担持させることを
特徴とするニッケル微粒子を担持させたカーボンブラッ
ク複合体の製造方法。4. A carbon black composite supporting nickel fine particles, characterized in that nickel fine particles are carried on the surface of carbon black by heat-treating a mixture of carbon black and a nickel salt at a temperature of 180 ° C. or higher and 300 ° C. or lower. Manufacturing method.
点をもつ有機溶剤中で行われる請求項４記載の製造方
法。5. The method according to claim 4, wherein the heat treatment is carried out in an organic solvent having a boiling point higher than the heat treatment temperature.
４または５記載の製造方法。6. The method according to claim 4, wherein the nickel salt is nickel formate.
を分散させた懸濁液を噴霧乾燥させて前記カーボンブラ
ックとニッケル塩の混合物を調製する請求項４、５また
は６記載のニッケル微粒子を担持させたカーボンブラッ
ク複合体の製造方法。7. The nickel-loaded carbon according to claim 4, 5 or 6, wherein a suspension of carbon black dispersed in an aqueous nickel formate solution is spray-dried to prepare a mixture of the carbon black and a nickel salt. Method for producing black composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5226435A JPH0751568A (en) | 1993-08-19 | 1993-08-19 | Carbon black composite and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5226435A JPH0751568A (en) | 1993-08-19 | 1993-08-19 | Carbon black composite and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0751568A true JPH0751568A (en) | 1995-02-28 |
Family
ID=16845072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5226435A Pending JPH0751568A (en) | 1993-08-19 | 1993-08-19 | Carbon black composite and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0751568A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007083831A1 (en) * | 2006-01-20 | 2007-07-26 | Showa Denko K.K. | Platelet-type slit vapor-grown carbon fiber and process for production thereof |
| JP4775664B2 (en) * | 2005-06-17 | 2011-09-21 | 住友金属鉱山株式会社 | Nickel film forming coating solution, nickel film and method for producing the same |
| JP2012512188A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene in the presence of styrene |
| CN103817323A (en) * | 2014-03-17 | 2014-05-28 | 杨福河 | Nickel-coated graphite electric conduction powder used for electric conduction rubber and manufacturing method thereof |
-
1993
- 1993-08-19 JP JP5226435A patent/JPH0751568A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4775664B2 (en) * | 2005-06-17 | 2011-09-21 | 住友金属鉱山株式会社 | Nickel film forming coating solution, nickel film and method for producing the same |
| WO2007083831A1 (en) * | 2006-01-20 | 2007-07-26 | Showa Denko K.K. | Platelet-type slit vapor-grown carbon fiber and process for production thereof |
| JP5036564B2 (en) * | 2006-01-20 | 2012-09-26 | 昭和電工株式会社 | Method for producing platelet-type slit vapor-grown carbon fiber |
| JP2012512188A (en) * | 2008-12-18 | 2012-05-31 | 中国石油化工股▲ふん▼有限公司 | Method for selectively adding hydrogen to phenylacetylene in the presence of styrene |
| CN103817323A (en) * | 2014-03-17 | 2014-05-28 | 杨福河 | Nickel-coated graphite electric conduction powder used for electric conduction rubber and manufacturing method thereof |
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