JP2017196579A - Production method of catalyst precursor for production of carbon nanotube - Google Patents
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Abstract
Description
本発明はカーボンナノチューブ製造用触媒前駆体に関する。更に詳しくは、カーボンナノチューブ製造用触媒と、それを用いて製造されるカーボンナノチューブに関する。 The present invention relates to a catalyst precursor for producing carbon nanotubes. More specifically, the present invention relates to a carbon nanotube production catalyst and a carbon nanotube produced using the catalyst.
直径が１μｍ以下のカーボンナノチューブは、例えば樹脂へ配合され、導電性や強度等の特性を付与するフィラーとして、種々の検討がなされている。そして、このようなカーボンナノチューブは、従来、主にアーク放電法、レーザー蒸着法、気相成長法などで製造されていた。 Carbon nanotubes having a diameter of 1 μm or less are variously studied as fillers that are blended into, for example, a resin and impart properties such as conductivity and strength. Such carbon nanotubes have heretofore been produced mainly by arc discharge method, laser vapor deposition method, vapor phase growth method and the like.
その中でも、気相成長法は、アーク放電法やレーザー蒸着法に比べて効率良く不純物の少ないカーボンナノチューブが得られるという利点がある。また、気体状態の原料を使用することによって、連続反応が可能であり、更には原料ガスとなる炭化水素や一酸化炭素等の炭素を含むガスが安価に入手できるので、カーボンナノチューブの量産化に適した技術といえる。 Among them, the vapor phase growth method has an advantage that carbon nanotubes with less impurities can be obtained more efficiently than the arc discharge method or the laser vapor deposition method. In addition, by using a raw material in a gaseous state, a continuous reaction is possible, and further, gas containing carbon such as hydrocarbon and carbon monoxide, which is a raw material gas, can be obtained at low cost. This is a suitable technology.
気相成長法によりカーボンナノチューブを得る際に使用される触媒（以下、カーボンナノチューブ製造用触媒と称する）は、例えばシリカ、アルミナ、マグネシア、ゼオライト等の担持成分に、鉄、コバルト、ニッケル等の活性成分の金属を担持させた触媒等が提案されている（例えば特許文献１参照）。 Catalysts used for obtaining carbon nanotubes by vapor deposition (hereinafter referred to as carbon nanotube production catalysts) are, for example, supported components such as silica, alumina, magnesia, zeolite, and the like, iron, cobalt, nickel, etc. A catalyst or the like on which a component metal is supported has been proposed (for example, see Patent Document 1).
前記触媒の製造方法としては、金属水溶液と担持体を混合した後、乾燥させて触媒を製造する含侵法（例えば特許文献２参照）や、さらに担持効率を高めるために高温含侵熟成工程を導入した方法が提示されている（例えば特許文献３参照）。しかし、この方法により得られた触媒は、触媒活性が低く、生産効率が低いことが課題である。 The catalyst production method includes an impregnation method in which a metal aqueous solution and a support are mixed and then dried to produce the catalyst (see, for example, Patent Document 2), and a high temperature impregnation maturation step to further increase the support efficiency. An introduced method is presented (see, for example, Patent Document 3). However, the catalyst obtained by this method has a problem of low catalytic activity and low production efficiency.
また、溶液からの共沈殿による触媒の製造方法が提示されている（例えば特許文献４参照）。
この方法によれば、触媒活性金属が、他の金属酸化物と共に触媒粒子内でどの場所にも均質に分配され、効率性が向上する。しかし、この方法により得られたカーボンナノチューブは、絡み合ったカーボンナノチューブとして得られ、分散が困難なことが課題である。
Moreover, the manufacturing method of the catalyst by the coprecipitation from a solution is shown (for example, refer patent document 4).
According to this method, the catalytically active metal is homogeneously distributed everywhere in the catalyst particles together with other metal oxides, and the efficiency is improved. However, the carbon nanotubes obtained by this method are obtained as entangled carbon nanotubes and are difficult to disperse.
本発明の目的は、かかる諸問題を解決する、生産効率が高く、樹脂への分散を容易にするとともに、樹脂における導電性と漆黒性が向上するカーボンナノチューブを、触媒を利用して効率よく製造するために用いる触媒前駆体の製造方法を提供することを目的とする。 The object of the present invention is to solve these problems, produce carbon nanotubes with high production efficiency, facilitate dispersion in the resin, and improve the conductivity and jetness of the resin efficiently using a catalyst. An object of the present invention is to provide a method for producing a catalyst precursor used for the purpose.
本発明の製造方法によれば、生産効率が高く、樹脂への分散を容易にするとともに、樹脂における導電性と漆黒性が向上するカーボンナノチューブを、触媒を利用して効率よく製造するために用いる触媒前駆体を得ることができる。 According to the production method of the present invention, carbon nanotubes having high production efficiency, facilitating dispersion in a resin, and improving the conductivity and jetness in the resin are used for efficiently producing a catalyst using a catalyst. A catalyst precursor can be obtained.
すなわち、本発明は、以下の工程１〜２を含むカーボンナノチューブ製造用触媒前駆体の製造方法に関する。
工程１：酸化マグネシウム、酸化アルミニウム、水酸化マグネシウムおよび水酸化アルミニウムからなる群より選ばれる少なくとも１種の担持成分を含む懸濁液と、活性成分の金属元素を含む金属塩の水溶液とを混合する工程。
工程２：工程１の混合時または混合後に、アルカリ性下で活性成分の金属元素を含む金属塩を水酸化物として析出させる工程。
That is, this invention relates to the manufacturing method of the catalyst precursor for carbon nanotube manufacture including the following processes 1-2.
Step 1: Mixing a suspension containing at least one supported component selected from the group consisting of magnesium oxide, aluminum oxide, magnesium hydroxide and aluminum hydroxide, and an aqueous solution of a metal salt containing a metal element as an active ingredient. Process.
Step 2: A step of depositing a metal salt containing a metal element as an active component as a hydroxide under alkalinity during or after mixing in
また本発明は、担持成分の平均粒径が０．５〜５μｍであることを特徴とする前記カーボンナノチューブ製造用触媒前駆体の製造方法に関する。 The present invention also relates to the above-described method for producing a catalyst precursor for producing carbon nanotubes, wherein the average particle size of the supported component is 0.5 to 5 μm.
また本発明は、担持成分の吸油量が４０〜６０ｍｌ／１００ｇであることを特徴とする前記カーボンナノチューブ製造用触媒前駆体の製造方法に関する。 The present invention also relates to the above-mentioned method for producing a catalyst precursor for producing carbon nanotubes, wherein the supported component has an oil absorption of 40 to 60 ml / 100 g.
また本発明は、担持成分が水酸化アルミニウムであることを特徴とする、前記カーボンナノチューブ製造用触媒前駆体の製造方法に関する。 The present invention also relates to the above-mentioned method for producing a catalyst precursor for producing carbon nanotubes, wherein the supported component is aluminum hydroxide.
また本発明は、カーボンナノチューブ製造用触媒前駆体中の活性成分の金属元素と、担持成分の金属元素との合計１００モル％に対する、活性成分の金属元素の含有割合が、５〜２０モル％であることを特徴とする前記カーボンナノチューブ製造用触媒前駆体の製造方法に関する。 In the present invention, the content ratio of the active element metal element to the total of 100 mol% of the active element metal element and the supported metal element in the catalyst precursor for carbon nanotube production is 5 to 20 mol%. The present invention relates to a method for producing a catalyst precursor for producing carbon nanotubes.
また本発明は、担持成分を含む懸濁液の質量パーセント濃度が５〜２０％であることを特徴とする前記カーボンナノチューブ製造用触媒前駆体の製造方法に関する。 The present invention also relates to the above-described method for producing a catalyst precursor for producing carbon nanotubes, wherein the suspension containing the supporting component has a mass percent concentration of 5 to 20%.
本発明のカーボンナノチューブ製造用触媒前駆体の製造方法によれば、担持体への活性金属の均一担持を実現し、高いカーボンナノチューブの生産効率、樹脂への分散が容易な束状構造、樹脂における高い導電性と漆黒性を有する触媒前駆体を製造することができる。 According to the method for producing a catalyst precursor for producing carbon nanotubes of the present invention, the active metal is uniformly supported on the support, high carbon nanotube production efficiency, a bundle structure that can be easily dispersed in the resin, A catalyst precursor having high conductivity and jetness can be produced.
以下に本発明のカーボンナノチューブ製造用触媒前駆体及びそれを用いたカーボンナノチューブ製造用触媒、カーボンナノチューブを製造するための実施の形態を詳細に説明する。 Hereinafter, a catalyst precursor for producing carbon nanotubes, a catalyst for producing carbon nanotubes using the same, and an embodiment for producing carbon nanotubes will be described in detail.
＜カーボンナノチューブ製造用触媒前駆体＞
まず、本発明のカーボンナノチューブ製造用触媒前駆体について説明する。
<Catalyst precursor for carbon nanotube production>
First, the catalyst precursor for producing carbon nanotubes of the present invention will be described.
以下の工程１〜２を含むことを特徴とする。
工程１：酸化マグネシウム、酸化アルミニウム、水酸化マグネシウムおよび水酸化アルミニウムからなる群より選ばれる少なくとも１種の担持成分を含む懸濁液と、活性成分の金属元素を含む金属塩の水溶液とを混合する工程。
工程２：工程１の混合時または混合後に、アルカリ性下で活性成分の金属元素を含む金属塩を水酸化物として析出させる工程。
It includes the following steps 1-2.
Step 1: Mixing a suspension containing at least one supported component selected from the group consisting of magnesium oxide, aluminum oxide, magnesium hydroxide and aluminum hydroxide, and an aqueous solution of a metal salt containing a metal element as an active ingredient. Process.
Step 2: A step of depositing a metal salt containing a metal element as an active component as a hydroxide under alkalinity during or after mixing in
担持成分としてマグネシウム、アルミニウムから選ばれる少なくともいずれか１つ以上の金属元素を含む酸化物または水酸化物の懸濁液の作製について説明する。 The production of an oxide or hydroxide suspension containing at least one metal element selected from magnesium and aluminum as the supporting component will be described.
担持成分としてマグネシウム、アルミニウムから選ばれる少なくともいずれか１つ以上の金属元素を含む酸化物または水酸化物の懸濁液は、担体成分単独で所定量を水と混合し作製する。水分散させる際に、ビーズミル分散機等を使用して、微細分散を行ってもよい。 A suspension of an oxide or hydroxide containing at least one metal element selected from magnesium and aluminum as a supporting component is prepared by mixing a predetermined amount of water with water alone. When dispersing in water, fine dispersion may be performed using a bead mill disperser or the like.
担持成分として、水酸化マグネシウム、酸化マグネシウム、水酸化アルミニウム、酸化アルミニウムから選択される一つまたは二つ以上のものを使用することができる。特に水酸化アルミニウムが最も好ましい。 As the supporting component, one or two or more selected from magnesium hydroxide, magnesium oxide, aluminum hydroxide, and aluminum oxide can be used. In particular, aluminum hydroxide is most preferable.
担持成分の平均粒径は０．５〜５μｍであることが好ましく、より好ましくは１〜３μｍである。この範囲であれば、活性成分が均一に担持し、触媒効率がもっとも高くなる。 The average particle size of the supported component is preferably 0.5 to 5 μm, more preferably 1 to 3 μm. If it is this range, an active component will carry | support uniformly and a catalyst efficiency will become the highest.
担持成分の吸油量は４０〜６０ｍｌ／１００ｇであることが好ましい。この範囲であれば、効率的に活性成分が担持成分に吸着される。 The oil absorption amount of the supported component is preferably 40 to 60 ml / 100 g. Within this range, the active component is efficiently adsorbed on the supported component.
担持成分としてマグネシウム、アルミニウムから選ばれる少なくともいずれか１つ以上の金属元素を含む酸化物または水酸化物の懸濁液の製造において、懸濁液の質量パーセント濃度が５〜２０％であることが好ましく、５〜１０％であることがより好ましい。この範囲であれば、活性成分を均一に担持することができる。 In the production of an oxide or hydroxide suspension containing at least one metal element selected from magnesium and aluminum as a supporting component, the mass percentage concentration of the suspension should be 5 to 20%. Preferably, it is more preferably 5 to 10%. If it is this range, an active ingredient can be carry | supported uniformly.
次に、活性成分としての金属元素を含む金属塩の水溶液をアルカリ性下で混合し、活性成分としての金属元素を含む金属塩を水酸化物として析出させる工程について説明する。 Next, a process of mixing an aqueous solution of a metal salt containing a metal element as an active ingredient under alkalinity and precipitating the metal salt containing the metal element as an active ingredient as a hydroxide will be described.
この工程は、担持成分の懸濁液中で、活性成分としての金属元素を含む金属塩を水酸化物化し析出させることを特徴とする。水酸化物化はアルカリ性条件で行われることにより実行される。 This step is characterized in that a metal salt containing a metal element as an active component is hydroxideized and precipitated in a suspension of a supported component. Hydroxidation is carried out by being carried out under alkaline conditions.
上記工程において、活性成分としての金属元素を含む金属塩の水酸化物として析出させるのは、活性成分としての金属元素を含む金属塩を完全に混合してから析出させてもよいし、混合しながら析出させてもよい。より好ましい方法としては、アルカリ性の担持成分の懸濁液の撹拌と、金属塩水溶液の滴下によって製造する方法である。 In the above step, the metal salt containing the metal element as the active component is precipitated as a hydroxide of the metal salt containing the metal element as the active component. However, it may be deposited. A more preferable method is a method of producing the suspension by stirring a suspension of an alkaline carrier component and dropping a metal salt aqueous solution.
活性成分の金属元素を含む金属塩としては、鉄、コバルト、ニッケルを含む金属塩であれば、特に限定されるものではないが、生産性の観点から、クエン酸塩、酢酸塩等が好ましい。 Although it will not specifically limit if it is a metal salt containing iron, cobalt, and nickel as a metal salt containing the metal element of an active ingredient, From a viewpoint of productivity, a citrate, acetate, etc. are preferable.
また、アルカリ性を維持するために、特に限定されるものではないが、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム等を用いてもよい。 Moreover, in order to maintain alkalinity, although it does not specifically limit, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, etc. may be used.
ｐＨは９〜１３が好ましく、より好ましくは９〜１１である。この範囲であれば、適度な速度で析出が起こるため、活性成分の粒子サイズをコントロールしやすい。 The pH is preferably 9-13, more preferably 9-11. Within this range, precipitation occurs at an appropriate rate, so that the particle size of the active ingredient can be easily controlled.
また、温度は６０〜８０℃が好ましい。この範囲であれば、活性成分が適度に析出し、担持成分に吸着する。 The temperature is preferably 60 to 80 ° C. If it is this range, an active component will precipitate moderately and will adsorb | suck to a support component.
カーボンナノチューブ製造用触媒前駆体中、活性成分の金属元素と、担持成分の金属元素との合計１００モル％に対する、活性成分の金属元素の含有割合は、５〜２０モル％であることが好ましく、５〜１０モル％であることがより好ましい。この範囲であれば、活性成分が有効的に機能し、触媒活性が高くなるため、生産効率が良好となる。 In the catalyst precursor for producing carbon nanotubes, the content ratio of the active component metal element to the total of 100 mol% of the active component metal element and the supported component metal element is preferably 5 to 20 mol%, More preferably, it is 5-10 mol%. Within this range, the active component functions effectively and the catalytic activity increases, so that the production efficiency is good.
次に、活性成分としての金属元素を含む水酸化物を担持成分に吸着させる工程について説明する。 Next, a process of adsorbing a hydroxide containing a metal element as an active component on a support component will be described.
活性成分としての金属元素を含む水酸化物の析出が終了した後、適切な温度及びｐＨでその混合液を静置または攪拌して維持し、担持成分に水酸化物として析出した活性成分を吸着させることを特徴とする。 After the precipitation of the hydroxide containing the metal element as the active ingredient is completed, the mixed liquid is left standing or stirred at an appropriate temperature and pH, and the active ingredient deposited as the hydroxide is adsorbed on the supported ingredient. It is characterized by making it.
前記工程の維持温度は６０〜８０℃が好ましい。 As for the maintenance temperature of the said process, 60-80 degreeC is preferable.
前記工程の維持ｐＨは９〜１３が好ましく、より好ましくは９〜１１である。 The maintenance pH of the step is preferably 9 to 13, more preferably 9 to 11.
前記工程は３０分〜１０時間維持することが好ましく、より好ましくは３０分〜１時間である。 The step is preferably maintained for 30 minutes to 10 hours, more preferably 30 minutes to 1 hour.
前記混合液の維持が終了した後、沈殿物を濾過、洗浄、乾燥、粉砕する工程を経て、粉末状のカーボンナノチューブ製造用触媒前駆体が製造される。 After the maintenance of the mixed solution is completed, a catalyst precursor for producing powdered carbon nanotubes is produced through steps of filtering, washing, drying and crushing the precipitate.
＜カーボンナノチューブ製造用触媒＞
カーボンナノチューブ製造用触媒は、本発明のカーボンナノチューブ製造用触媒前駆体を焼成、粉砕する工程を経て得られる。
<Catalyst for carbon nanotube production>
The catalyst for producing carbon nanotubes is obtained through a step of firing and pulverizing the catalyst precursor for producing carbon nanotubes of the present invention.
カーボンナノチューブ製造用触媒前駆体の焼成は、焼成雰囲気として酸素の存在下、空気中ないし空気と窒素混合雰囲気を用いる。焼成温度は４５０〜５５０℃の範囲であることが好ましい。この範囲内であれば、活性成分の酸化金属成分を適度な一時粒子サイズに制御され、さらに有機化合物部位が分解されるためカーボンナノチューブにおける異物の原因とならない。 Firing of the catalyst precursor for producing carbon nanotubes uses air or a mixed atmosphere of air and nitrogen in the presence of oxygen as the firing atmosphere. The firing temperature is preferably in the range of 450 to 550 ° C. Within this range, the metal oxide component of the active component is controlled to an appropriate temporary particle size, and further, the organic compound site is decomposed, so that no foreign matter is caused in the carbon nanotube.
得られた焼成物をさらに微細化処理を行ってもよい。微細化処理をすれば、カーボンナノチューブを合成する際に、カーボンナノチューブ製造用触媒に炭素源を十分に接触させることが可能となり、結果として生産効率を向上させることができる。 The fired product obtained may be further refined. If the micronization treatment is performed, the carbon source can be sufficiently brought into contact with the catalyst for producing carbon nanotubes when the carbon nanotubes are synthesized, and as a result, the production efficiency can be improved.
微細化手段としては特に制限はないが、少量の場合は乳鉢を用いて、一度に多量を処理する場合は、ピンミル、ハンマーミル、パルペライザー、ジェットミル等を用いることができる。 Although there is no restriction | limiting in particular as a refinement | miniaturization means, A pin mill, a hammer mill, a pulverizer, a jet mill etc. can be used when processing a large quantity at once using a mortar in the case of a small quantity.
（カーボンナノチューブ）
次に、カーボンナノチューブ製造用触媒を用いたカーボンナノチューブの製造方法について説明する。
(carbon nanotube)
Next, a method for producing carbon nanotubes using a carbon nanotube production catalyst will be described.
本発明の製造方法によってカーボンナノチューブを製造するためには、触媒として前記カーボンナノチューブ製造用触媒を用いて、炭素源としての原料ガスを加熱下、この触媒に接触させて、カーボンナノチューブの析出反応を行い製造する。 In order to produce carbon nanotubes by the production method of the present invention, the catalyst for producing carbon nanotubes is used as a catalyst, and a raw material gas as a carbon source is brought into contact with the catalyst under heating to cause a carbon nanotube precipitation reaction. To make.
カーボンナノチューブの炭素源としての原料ガスとしては、従来公知の任意のものを使用でき、例えば、炭素を含むガスとしてメタンやエチレン、プロパン、ブタン、アセチレンなどの炭化水素や、一酸化炭素、アルコールなどを用いることが出来るが、特に使い易さの理由により、炭化水素やアルコールを用いることが望ましい。 As a raw material gas as a carbon source of the carbon nanotube, any conventionally known gas can be used. For example, as a gas containing carbon, hydrocarbons such as methane, ethylene, propane, butane, acetylene, carbon monoxide, alcohol, etc. However, it is desirable to use hydrocarbons or alcohols for reasons of ease of use.
また、必要に応じて、還元雰囲気下で触媒を活性化した後、又は還元性ガスと共にカーボンナノチューブ原料ガスと接触させて製造することが好ましい。活性化時における還元性ガスは、水素、アンモニア等を用いることができるが、特に水素が好ましく、その濃度は、原料ガス濃度１００体積％に対して０．１〜１００体積％、特に１〜１００体積％であることが好ましい。この範囲であれば、還元性ガスの還元効果が期待でき、相対的に原料ガスが少なくなりすぎることなく、カーボンナノチューブの製造が可能である。 If necessary, it is preferable to produce the catalyst after activating the catalyst in a reducing atmosphere or by bringing it into contact with the carbon nanotube raw material gas together with the reducing gas. As the reducing gas at the time of activation, hydrogen, ammonia or the like can be used, but hydrogen is particularly preferable, and the concentration thereof is 0.1 to 100% by volume, particularly 1 to 100% with respect to 100% by volume of the raw material gas. It is preferable that it is volume%. If it is this range, the reduction effect of reducing gas can be anticipated, and manufacture of a carbon nanotube is possible, without raw material gas reducing too much relatively.
製造時の温度や原料ガスの供給量は、従来公知の任意の値から、適宜選択し決定すれば良いが、本発明の触媒においては、６００〜８５０℃、特に６５０〜７５０℃が好ましく、反応圧力はゲージ圧で０ｋＰａ以上３０ｋＰａ以下とすることが好ましい。反応時間は反応温度や触媒と原料ガスとの触媒比率に応じて任意に設定されるが、通常０．５〜６時間程度である。本発明での反応速度は反応開始から約２０分で最大となり、その後、徐々に失速して反応開始から５〜５．５時間で停止する。従って、反応時間は０．５〜６時間の範囲で管理することが好ましい。 The temperature at the time of production and the supply amount of the raw material gas may be appropriately selected and determined from any conventionally known values. In the catalyst of the present invention, 600 to 850 ° C., particularly 650 to 750 ° C. is preferable, The pressure is preferably a gauge pressure of 0 kPa to 30 kPa. Although reaction time is arbitrarily set according to reaction temperature and the catalyst ratio of a catalyst and raw material gas, it is about 0.5 to 6 hours normally. In the present invention, the reaction rate reaches its maximum at about 20 minutes from the start of the reaction, and then gradually slows down and stops at 5 to 5.5 hours from the start of the reaction. Therefore, the reaction time is preferably managed in the range of 0.5 to 6 hours.
反応終了後の原料ガス置換には、アルゴンガスや窒素等の不活性ガスを用いることが好ましい。 It is preferable to use an inert gas such as argon gas or nitrogen for the replacement of the raw material gas after completion of the reaction.
このような本発明のカーボンナノチューブ製造用触媒を用いるカーボンナノチューブの製造方法によれば、担持部分に均一に担持された微粒子の酸化鉄、酸化コバルトを核として、触媒カーボンナノチューブが析出、成長し配向性を有した束状カーボンナノチューブが得られる。 According to the method for producing carbon nanotubes using the catalyst for producing carbon nanotubes of the present invention, catalytic carbon nanotubes are precipitated, grown, and oriented with fine particles of iron oxide and cobalt oxide uniformly supported on the supported portion as nuclei. Thus, a bundled carbon nanotube having properties can be obtained.
以下に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。例中、特に断わりのない限り、「部」とは「質量部」、「％」とは「質量％」をそれぞれ意味する。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.
なお、以下の実施例および比較例で用いた触媒は、次のように製造した。
＜カーボンナノチューブ製造用触媒前駆体の製造＞
The catalysts used in the following examples and comparative examples were produced as follows.
<Manufacture of catalyst precursor for carbon nanotube production>
（実施例１）［触媒前駆体（Ａ）の製造］
水酸化アルミニウム（平均粒径１．２μｍ、吸油量４８ｍｌ／１００ｇ）９０ｇと精製水１４１０ｇをディスパーを用いて激しく撹拌し、水酸化アルミニウム懸濁液を作製した。次いで、クエン酸鉄（ＩＩＩ）アンモニウム３０ｇを精製水１０２ｇで溶解させ、クエン酸鉄（ＩＩＩ）アンモニウム水溶液を作製した。水酸化アルミニウム懸濁液を６０℃、水酸化ナトリウム溶液の添加でｐＨ１０を維持し、撹拌しながらクエン酸鉄（ＩＩＩ）アンモニウム水溶液を２０ｍｌ／分のペースで滴下した。すべて滴下した後、６０℃で２時間撹拌した。沈殿した固形物を、濾過により分離し、３回水洗し、１００℃で１０時間乾燥させた後、８０メッシュを通して粒径を整えて、触媒前駆体（Ａ）を得た。
(Example 1) [Production of catalyst precursor (A)]
90 g of aluminum hydroxide (average particle size 1.2 μm, oil absorption 48 ml / 100 g) and 1410 g of purified water were vigorously stirred using a disper to prepare an aluminum hydroxide suspension. Next, 30 g of iron (III) ammonium citrate was dissolved in 102 g of purified water to prepare an aqueous iron (III) ammonium citrate solution. The pH of the aluminum hydroxide suspension was maintained at 60 ° C. by addition of a sodium hydroxide solution, and an aqueous iron (III) citrate solution was added dropwise at a rate of 20 ml / min while stirring. After dripping all, it stirred at 60 degreeC for 2 hours. The precipitated solid was separated by filtration, washed with water three times, dried at 100 ° C. for 10 hours, and then adjusted in particle size through 80 mesh to obtain a catalyst precursor (A).
（実施例２〜７）［触媒前駆体（Ｂ）〜（Ｇ）の製造］
表１に掲載した、原料と仕込み量を用い、それ以外は実施例１と同様にして製造を行い、触媒前駆体（Ｂ）〜（Ｇ）を得た。
(Examples 2 to 7) [Production of catalyst precursors (B) to (G)]
Using the raw materials and preparation amounts listed in Table 1, production was carried out in the same manner as in Example 1 to obtain catalyst precursors (B) to (G).
（比較例１）［触媒前駆体（ａ）の製造］
（溶液によるカーボンナノチューブ製造用触媒前駆体の調整）
水酸化アルミニウム（平均粒径１．２μｍ、吸油量４８ｍｌ／１００ｇ）９０ｇ、クエン酸鉄（ＩＩＩ）アンモニウム３０ｇと精製水１４１０ｇをディスパーを用いて激しく撹拌し、懸濁液を作製した。次いで、オーブンで１００℃、２４時間乾燥させ、固形物を得た。得られた固形物を８０メッシュを通して粒径を整えて、触媒前駆体（ａ）を得た。
(Comparative Example 1) [Production of catalyst precursor (a)]
(Preparation of catalyst precursor for carbon nanotube production by solution)
90 g of aluminum hydroxide (average particle size 1.2 μm, oil absorption 48 ml / 100 g), 30 g of iron (III) ammonium citrate and 1410 g of purified water were vigorously stirred using a disper to prepare a suspension. Then, it was dried in an oven at 100 ° C. for 24 hours to obtain a solid. The particle size of the obtained solid was adjusted through 80 mesh to obtain a catalyst precursor (a).
（比較例２）［触媒前駆体（ｂ）の製造］
（含浸によるカーボンナノチューブ製造用触媒前駆体の調整）
水酸化アルミニウム９０ｇ、クエン酸鉄（ＩＩＩ）アンモニウム３０ｇと精製水１４１０ｇをディスパーを用いて激しく撹拌し、懸濁液を作製し、超音波洗浄機で３０分間処理した。固形物を濾過により分離し、１００℃で１０時間乾燥させた後、８０メッシュを通して粒径を整えて、触媒前駆体（ｂ）を得た。
(Comparative Example 2) [Production of catalyst precursor (b)]
(Preparation of catalyst precursor for carbon nanotube production by impregnation)
90 g of aluminum hydroxide, 30 g of iron (III) ammonium citrate and 1410 g of purified water were vigorously stirred using a disper to prepare a suspension, which was treated with an ultrasonic cleaner for 30 minutes. The solid was separated by filtration and dried at 100 ° C. for 10 hours, and then the particle size was adjusted through 80 mesh to obtain a catalyst precursor (b).
（比較例３）［触媒前駆体（ｃ）の製造］
（熟成含浸によるカーボンナノチューブ製造用触媒前駆体の調整）
水酸化アルミニウム９０ｇ、クエン酸鉄（ＩＩＩ）アンモニウム３０ｇと精製水１４１０ｇをディスパーを用いて激しく撹拌し、懸濁液を作製し、超音波洗浄機で３０分間処理した。その後、上記懸濁液を、９５℃の還流槽を含む恒温反応機で１２時間撹拌して熟成させた。固形物を濾過により分離し、１００℃で１０時間乾燥させた後、８０メッシュを通して粒径を整えて、触媒前駆体（ｃ）を得た。
(Comparative Example 3) [Production of catalyst precursor (c)]
(Adjustment of catalyst precursor for carbon nanotube production by aging impregnation)
90 g of aluminum hydroxide, 30 g of iron (III) ammonium citrate and 1410 g of purified water were vigorously stirred using a disper to prepare a suspension, which was treated with an ultrasonic cleaner for 30 minutes. Thereafter, the suspension was aged by stirring for 12 hours in a constant temperature reactor containing a 95 ° C. reflux tank. The solid was separated by filtration, dried at 100 ° C. for 10 hours, and then adjusted in particle size through 80 mesh to obtain a catalyst precursor (c).
（比較例４）［触媒前駆体（ｄ）の製造］
（溶液からの共沈殿によるカーボンナノチューブ製造用触媒前駆体の調整）
硝酸アルミニウム・９水和物４３３ｇ、クエン酸鉄（ＩＩＩ）アンモニウム３０ｇを精製水５３７ｇに溶解させ、硝酸アルミニウム、クエン酸鉄（ＩＩＩ）アンモニウムの混合水溶液を作製した。精製水１０００ｇを６０℃、水酸化ナトリウム溶液の添加でｐＨ１０を維持し、撹拌しながら混合水溶液を２０ｍｌ／分のペースで滴下した。すべて滴下した後、沈殿した固形物を、濾過により分離し、３回水洗し、１００℃で１０時間乾燥させた後、８０メッシュを通して粒径を整えて、触媒前駆体（ｄ）を得た。
(Comparative Example 4) [Production of catalyst precursor (d)]
(Preparation of catalyst precursor for carbon nanotube production by coprecipitation from solution)
433 g of aluminum nitrate nonahydrate and 30 g of iron (III) ammonium citrate were dissolved in 537 g of purified water to prepare a mixed aqueous solution of aluminum nitrate and iron (III) ammonium citrate. The pH of the purified water 1000g was maintained at 60 ° C by adding sodium hydroxide solution at 60 ° C, and the mixed aqueous solution was added dropwise at a rate of 20 ml / min with stirring. After dropping all, the precipitated solid was separated by filtration, washed with water three times, dried at 100 ° C. for 10 hours, and then adjusted in particle size through 80 mesh to obtain a catalyst precursor (d).
尚、実施例、比較例に使用する担持成分の平均粒径（μｍ）と吸油量（ｍｌ／１００ｇ）は下記の条件で測定、算出した。 The average particle size (μm) and the oil absorption (ml / 100 g) of the supported components used in Examples and Comparative Examples were measured and calculated under the following conditions.
＜担持成分の平均粒径＞
レーザー回折式粒度分布測定装置（ＳＡＬＤ―３１００、（株）島津製作所製）を使用して平均粒径（μｍ）を求めた。
<Average particle size of supported components>
The average particle size (μm) was determined using a laser diffraction particle size distribution analyzer (SALD-3100, manufactured by Shimadzu Corporation).
＜担持成分の吸油量＞
ＪＩＳ Ｋ−５１０１−１３−２に準じて、担持成分と煮アマニ油を少しずつ混ぜ、ヘラを用いてらせん状に巻くことが出来る状態になったときの、試料１００ｇあたりの煮アマニ油の使用量を求め、下記の式（１）により吸油量を算出した。
吸油量（ｍｌ／１００ｇ）＝煮アマニ油（ｍｌ）／担持成分質量（ｇ）×１００ ・・・・・式（１）
<Oil absorption amount of supported component>
Use of boiled linseed oil per 100 g of sample when it becomes ready to be spirally wound using a spatula after mixing the supported components and boiled linseed oil little by little according to JIS K-5101-13-2 The amount of oil was calculated and the amount of oil absorption was calculated by the following equation (1).
Oil absorption (ml / 100g) = boiled linseed oil (ml) / supported component mass (g) × 100 Formula (1)
実施例１〜７、および比較例１〜４の担持成分の平均粒径、担持成分の吸油量、担持成分懸濁液の濃度、活性成分の金属元素の含有割合を下記表１、表２に示す。 Tables 1 and 2 below show the average particle diameters of the supporting components of Examples 1 to 7 and Comparative Examples 1 to 4, the oil absorption amount of the supporting components, the concentration of the supporting component suspension, and the metal element content of the active components. Show.
＜カーボンナノチューブ製造用触媒の製造＞
（実施例８〜１４）
得られた触媒前駆体５０ｇを耐熱容器に秤取り、マッフル炉にて、空気中４５０℃±５℃雰囲気下で３０分間焼成した後、乳鉢で粉砕して触媒（Ａ）〜（Ｇ）をそれぞれ得た。
（比較例５〜８）
得られた触媒前駆体５０ｇを耐熱容器に秤取り、マッフル炉にて、空気中４５０℃±５℃雰囲気下で３０分間焼成した後、乳鉢で粉砕して触媒（ａ）〜（ｄ）をそれぞれ得た。
<Manufacture of catalyst for carbon nanotube production>
(Examples 8 to 14)
50 g of the obtained catalyst precursor was weighed in a heat-resistant container, calcined in a muffle furnace in an atmosphere of 450 ° C. ± 5 ° C. for 30 minutes, and then pulverized in a mortar to obtain catalysts (A) to (G), respectively. Obtained.
(Comparative Examples 5 to 8)
50 g of the obtained catalyst precursor was weighed in a heat-resistant container, calcined in a muffle furnace in an atmosphere of 450 ° C. ± 5 ° C. for 30 minutes, and then pulverized in a mortar to obtain catalysts (a) to (d), respectively. Obtained.
＜カーボンナノチューブの製造＞
（実施例１５）
加圧可能で、外部ヒーターで加熱可能な、内容積が１０リットルの横型反応管の中央部に、カーボンナノチューブ製造用触媒(Ａ)１．０ｇを散布した石英ガラス製耐熱皿を設置した。アルゴンガスを注入しながら排気を行い、反応管内の空気をアルゴンガスで置換し、横型反応管中の雰囲気を酸素濃度１体積％以下とした。次いで、外部ヒーターにて加熱し、横型反応管内の中心部温度が７００℃になるまで加熱した。７００℃に到達した後、炭素源としてエチレンを毎分１リットルの流速で反応管内に導入し、４時間接触反応させた。反応終了後、反応管内のガスをアルゴンガスで置換し、反応管内の温度を１００℃以下になるまで冷却し、得られたカーボンナノチューブを採取した。得られたカーボンナノチューブ（Ａ）は、導電性、漆黒性を比較するため、８０メッシュの金網で粉砕ろ過した。
<Manufacture of carbon nanotubes>
(Example 15)
A quartz glass heat-resistant dish in which 1.0 g of the carbon nanotube production catalyst (A) was dispersed was installed in the central part of a horizontal reaction tube capable of being pressurized and heated by an external heater and having an internal volume of 10 liters. Exhaust was performed while injecting argon gas, the air in the reaction tube was replaced with argon gas, and the atmosphere in the horizontal reaction tube was adjusted to an oxygen concentration of 1% by volume or less. Subsequently, it heated with the external heater and it heated until the center part temperature in a horizontal type reaction tube became 700 degreeC. After reaching 700 ° C., ethylene as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute, and contact reaction was performed for 4 hours. After completion of the reaction, the gas in the reaction tube was replaced with argon gas, the reaction tube was cooled to a temperature of 100 ° C. or less, and the resulting carbon nanotubes were collected. The obtained carbon nanotubes (A) were pulverized and filtered with an 80-mesh wire mesh in order to compare conductivity and jetness.
（実施例１６〜２１）
触媒（Ｂ）〜（Ｇ）を用いた以外は、実施例１５と同様な方法により、カーボンナノチューブ（Ｂ）〜（Ｇ）をそれぞれ得た。
(Examples 16 to 21)
Carbon nanotubes (B) to (G) were obtained in the same manner as in Example 15 except that the catalysts (B) to (G) were used.
（比較例９〜１２）
触媒（ａ）〜（ｄ）を用いた以外は、実施例１５と同様な方法により、カーボンナノチューブ（ａ）〜（ｄ）をそれぞれ得た。
(Comparative Examples 9-12)
Carbon nanotubes (a) to (d) were obtained in the same manner as in Example 15 except that the catalysts (a) to (d) were used.
＜物性の測定方法＞
後述の各実施例及び比較例において製造されたカーボンナノチューブ製造用触媒およびカーボンナノチューブの物性は、以下の方法により測定した。
<Method of measuring physical properties>
The physical properties of the carbon nanotube production catalyst and carbon nanotube produced in each of Examples and Comparative Examples described below were measured by the following methods.
＜走査型電子顕微鏡による観察と平均粒径＞
走査型電子顕微鏡（日本電子社製）によって、カーボンナノチューブ製造用触媒またはカーボンナノチューブの形態観察を実施した。観察は、カーボンナノチューブ製造用触媒またはカーボンナノチューブをカーボンペーパー上にそのままの状態で散布して実施した。１００個のカーボンナノチューブ製造用触媒またはカーボンナノチューブの１００本の短軸と長軸の径の長さを計測し、その数平均値をもってカーボンナノチューブ製造用触媒またはカーボンナノチューブの平均粒径（ｎｍ）とした。また束状のカーボンナノチューブについては、１００束の長さを計測し、その数平均値をもってカーボンナノチューブの束の長さ（μｍ）とした。
<Observation by scanning electron microscope and average particle size>
The morphology of the carbon nanotube production catalyst or carbon nanotube was observed with a scanning electron microscope (manufactured by JEOL Ltd.). The observation was carried out by spraying the carbon nanotube production catalyst or the carbon nanotube on the carbon paper as it is. Measure the length of 100 short axis and long axis diameters of 100 carbon nanotube production catalysts or carbon nanotubes, and use the number average value to determine the average particle diameter (nm) of the carbon nanotube production catalyst or carbon nanotubes. did. For the bundled carbon nanotubes, the length of 100 bundles was measured, and the number average value was taken as the length (μm) of the bundle of carbon nanotubes.
表３に、実施例１５〜２１、比較例９〜１２で得られたカーボンナノチューブの形状、平均粒径（ｎｍ）、束の長さ（μｍ）を示す。 Table 3 shows the shape, average particle diameter (nm), and bundle length (μm) of the carbon nanotubes obtained in Examples 15 to 21 and Comparative Examples 9 to 12.
＜カーボンナノチューブの生産効率＞
合成で得られたカーボンナノチューブは、合成時に使用した触媒と混合した形で得られるため、触媒効率の指標として、生産効率で比較した。
生産効率は、式（２）によって算出した。
生産効率＝（合成で得られたカーボンナノチューブ質量−仕込み触媒質量）÷（仕込み触媒質量）・・・・・・式（２）
<Production efficiency of carbon nanotubes>
Since the carbon nanotubes obtained by synthesis are obtained in a form mixed with the catalyst used at the time of synthesis, comparison was made by production efficiency as an index of catalyst efficiency.
The production efficiency was calculated by equation (2).
Production efficiency = (mass of carbon nanotubes obtained by synthesis−mass of charged catalyst) ÷ (mass of charged catalyst) ··· formula (2)
カーボンナノチューブの生産効率の評価基準は、生産効率が３０を超えるものをＡ（優良）、２０を超え、３０以下のものをＢ（良好）、２０以下のものをＣ（不良）とした。 The evaluation criteria for the production efficiency of carbon nanotubes were A (excellent) when the production efficiency exceeded 30, B (good) when 20 or more, and C (bad) when 30 or less.
＜カーボンナノチューブ含有塗膜の体積抵抗率とカーボンナノチューブの分散性および導電性評価＞
カーボンナノチューブの導電性を評価するために、カーボンナノチューブを分散した塗膜を作成し、その体積抵抗率を測定することにより導電性評価を行った。
三菱化学社製エポキシ樹脂グレード１２５６を、ブチルカルビトールアセテートに溶解して、固形分４０％のエポキシ樹脂溶液を作製し、エポキシ樹脂溶液の固形分１５ｇに対して、評価用のカーボンナノチューブ０．７８９ｇを混合し、フーバーマーラーで荷重１５０ｌｂ（＝６６７Ｎ）、回転速度１００ｒｐｍの条件で１〜３回練り、評価用のカーボンナノチューブ分散体を得た。その後、東洋紡績社製ＰＥＴ（ポリエチレンテレフタレート）フィルムに、アプリケーターを用いて、乾燥後の塗膜厚さが１０±１μｍとなるように塗工後、電気オーブン中で１５０±５℃にて６０分間乾燥させて、カーボンナノチューブを含有する塗膜を得た。（株）三菱化学アナリテック社製：ロレスターＧＰ粉体低効率測定システムＭＣＰ−ＰＤ−５１を用いて、上記塗膜の体積抵抗率（Ω・ｃｍ）を測定した。
<Volume resistivity of carbon nanotube-containing coating film and evaluation of dispersibility and conductivity of carbon nanotube>
In order to evaluate the electrical conductivity of the carbon nanotube, a coating film in which the carbon nanotube was dispersed was prepared, and the electrical conductivity was evaluated by measuring the volume resistivity.
An epoxy resin grade 1256 manufactured by Mitsubishi Chemical Corporation is dissolved in butyl carbitol acetate to prepare an epoxy resin solution having a solid content of 40%, and 0.789 g of carbon nanotubes for evaluation with respect to a solid content of 15 g of the epoxy resin solution. And kneaded 1 to 3 times with a Hoovermarler under the conditions of a load of 150 lb (= 667 N) and a rotation speed of 100 rpm to obtain a carbon nanotube dispersion for evaluation. Then, it applied to PET (polyethylene terephthalate) film made by Toyobo Co., Ltd. using an applicator so that the coating thickness after drying was 10 ± 1 μm, and then in an electric oven at 150 ± 5 ° C. for 60 minutes. It was made to dry and the coating film containing a carbon nanotube was obtained. (Mitsubishi Chemical Analytech Co., Ltd.) The volume resistivity (Ω · cm) of the coating film was measured using a Lorester GP powder low-efficiency measurement system MCP-PD-51.
カーボンナノチューブの導電性の評価基準は、３回練りの塗膜の体積抵抗率が１０（Ω・ｃｍ）以下の場合をＡ（優良）、１０（Ω・ｃｍ）を超え１００（Ω・ｃｍ）以下の場合をＢ（良好）、１００（Ω・ｃｍ）を超える場合をＣ（不良）とした。 The evaluation criteria for the conductivity of carbon nanotubes are A (excellent), 10 (Ω · cm), and 100 (Ω · cm) when the volume resistivity of the coating film kneaded three times is 10 (Ω · cm) or less. The following cases were defined as B (good) and those exceeding 100 (Ω · cm) as C (defective).
カーボンナノチューブの分散性の評価基準は、式（３）から求めた値で、２以下の場合をＡ（優良）、２を超え５以下の場合をＢ（良好）、５を超える場合をＣ（不良）とした。つまり、１回練りと３回練りの時の体積抵抗率の差が少ないものほど分散性良好とした。
分散性＝（樹脂分散体積抵抗率１回練り（Ω・ｃｍ）÷（樹脂分散体積抵抗率３回練り（Ω・ｃｍ）・・・・・・式（３）
＜漆黒性の評価＞
カーボンナノチューブの漆黒性を評価するために、カーボンナノチューブを分散した塗膜を作成し、そのＬ*値を測定することにより漆黒性評価を行った。
カーボンナノチューブ３．２ｇ、アクリル樹脂（ＤＩＣ社製、アクリディック４７−７１２）２５．６ｇ、溶媒（トルエン：キシレン：酢酸ブチル：東燃ゼネラル社製ソルベッソ１５０の質量比３：３：２：２の混合溶媒）６８．２ｇ、ジルコニアビーズ１５０ｇを２２５ｍｌガラス瓶に投入した。これらの原料をレッドデビル社製ペイントシェーカーにて２時間分散させた。その後、分散された原料からジルコニアビーズを分離除去することで、カーボンナノチューブの分散体を得た。この分散体１００質量部、アクリル樹脂（ＤＩＣ社製アクリディック４７−７１２）１１９．１質量部、メラミン樹脂（ＤＩＣ社製スーパーベッカミンＬ−１７７−６０）３０．３質量部を高速攪拌機にて撹拌して評価用のカーボンナノチューブ分散液を得た。 得られたカーボンナノチューブ分散液を厚さ１ｍｍの無色透明なガラス板に塗布し焼き付け、ガラス板上に塗膜を形成する。ガラス板の面側から測定したときのＪＩＳ Ｚ８７２９で規定されるＬ*a*ｂ*表色系の測定値に基づき、エックスライト社製多角度分光測色計ＭＡ６８ＩＩにて、積層された面の垂線方向に対して４５°の角度で入射した光の正反射光からのオフセット角４５°の角度で測定し、測色値を得た。
The evaluation criteria for the dispersibility of the carbon nanotubes are the values obtained from the formula (3): A (excellent) when 2 or less, B (good) when 2 or more and 5 or less, C ( Bad). That is, the smaller the difference in volume resistivity between the first kneading and the third kneading, the better the dispersibility.
Dispersibility = (resin dispersion volume resistivity kneaded once (Ω · cm) ÷ (resin dispersion volume resistivity kneaded 3 times (Ω · cm) ··· Formula (3)
<Evaluation of jetness>
In order to evaluate the jetness of carbon nanotubes, a jet film in which carbon nanotubes were dispersed was prepared, and jetness evaluation was performed by measuring the L * value.
Mixing of 3.2 g of carbon nanotubes, 25.6 g of acrylic resin (manufactured by DIC, Acridick 47-712), solvent (toluene: xylene: butyl acetate: Solvesso 150 manufactured by TonenGeneral) in a mass ratio of 3: 3: 2: 2. Solvent) 68.2 g and zirconia beads 150 g were put into a 225 ml glass bottle. These raw materials were dispersed for 2 hours using a paint shaker manufactured by Red Devil. Then, the dispersion | distribution of the carbon nanotube was obtained by isolate | separating and removing a zirconia bead from the disperse | distributed raw material. In a high-speed stirrer, 100 parts by mass of this dispersion, 119.1 parts by mass of acrylic resin (Acridic 47-712 manufactured by DIC), and 30.3 parts by mass of melamine resin (Super Becamine L-177-60 manufactured by DIC) A carbon nanotube dispersion for evaluation was obtained by stirring. The obtained carbon nanotube dispersion is applied to a colorless and transparent glass plate having a thickness of 1 mm and baked to form a coating film on the glass plate. Based on the measured value of the L * a * b * color system defined by JIS Z8729 when measured from the surface side of the glass plate, the multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd. A colorimetric value was obtained by measuring at an angle of 45 ° offset from the regular reflected light of light incident at an angle of 45 ° with respect to the normal direction.
測色器を用いて測定し、測定角度が４５°の時、Ｌ*が１．５以下のものをＡ（優良）、１．５を超え２．０以下のものをＢ（良好）、２．０を超え４．０以下のものをＣ（普通）とした。また、４．０を超えるものをＤ（不良）とした。 When measured using a colorimeter and the measurement angle is 45 °, L * is 1.5 or less when A (excellent), 1.5 to 2.0 but less than B (good), 2 A value exceeding 0.0 and not more than 4.0 was defined as C (normal). Moreover, the thing exceeding 4.0 was made into D (defect).
表４に、実施例１５〜２１、比較例９〜１２で得られたカーボンナノチューブの生産効率、カーボンナノチューブ含有塗膜の体積抵抗率、カーボンナノチューブの分散性、導電性および漆黒性の評価結果を示す。 Table 4 shows the evaluation results of the production efficiency of carbon nanotubes obtained in Examples 15 to 21 and Comparative Examples 9 to 12, the volume resistivity of the carbon nanotube-containing coating film, the dispersibility of carbon nanotubes, the conductivity and jet blackness. Show.
本発明の製造方法によって得られたカーボンナノチューブ製造用触媒前駆体を用いた場合、平均粒径が小さい束状構造を有するカーボンナノチューブが得られ、比較例で使用したカーボンナノチューブ製造用触媒前駆体を用いた場合よりも、カーボンナノチューブが高い生産効率で得られ、得られたカーボンナノチューブは樹脂への容易な分散性、樹脂における高い導電性と漆黒性を有することがわかった。 When the carbon nanotube production catalyst precursor obtained by the production method of the present invention is used, a carbon nanotube having a bundle structure with a small average particle diameter is obtained, and the carbon nanotube production catalyst precursor used in the comparative example is obtained. It was found that carbon nanotubes were obtained with higher production efficiency than when used, and the obtained carbon nanotubes had easy dispersibility in the resin, high conductivity in the resin, and jet blackness.
以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は本発明の範囲に含まれる。 As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.
Claims (6)
工程１：酸化マグネシウム、酸化アルミニウム、水酸化マグネシウムおよび水酸化アルミニウムからなる群より選ばれる少なくとも１種の担持成分を含む懸濁液と、活性成分の金属元素を含む金属塩の水溶液とを混合する工程。
工程２：工程１の混合時または混合後に、アルカリ性下で活性成分の金属元素を含む金属塩を水酸化物として析出させる工程。 The manufacturing method of the catalyst precursor for carbon nanotube manufacture including the following processes 1-2.
Step 1: Mixing a suspension containing at least one supported component selected from the group consisting of magnesium oxide, aluminum oxide, magnesium hydroxide and aluminum hydroxide, and an aqueous solution of a metal salt containing a metal element as an active ingredient. Process.
Step 2: A step of depositing a metal salt containing a metal element as an active component as a hydroxide under alkalinity during or after mixing in Step 1.
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| JP2021526121A (en) * | 2018-07-27 | 2021-09-30 | エルジー・ケム・リミテッド | Manufacturing method of carbon nanotubes |
| WO2023159700A1 (en) * | 2022-02-23 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Synthesis method for superfine catalyst powder |
| WO2023159698A1 (en) * | 2022-02-24 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Method for synthesizing highly active catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021526121A (en) * | 2018-07-27 | 2021-09-30 | エルジー・ケム・リミテッド | Manufacturing method of carbon nanotubes |
| JP7086418B2 (en) | 2018-07-27 | 2022-06-20 | エルジー・ケム・リミテッド | Manufacturing method of carbon nanotubes |
| US11964870B2 (en) | 2018-07-27 | 2024-04-23 | Lg Chem, Ltd. | Method for preparing carbon nanotubes |
| WO2023159700A1 (en) * | 2022-02-23 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Synthesis method for superfine catalyst powder |
| WO2023159698A1 (en) * | 2022-02-24 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Method for synthesizing highly active catalyst |
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