JP6922327B2 - Graphite and its manufacturing method, and mixtures - Google Patents
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本発明は、黒鉛及びその製造方法、並びに該黒鉛を製造する際に用いられる混合物に関する。 The present invention relates to graphite, a method for producing the same, and a mixture used in producing the graphite.
黒鉛製品は低熱膨張高熱伝導熱膨張が小さく、また、熱伝導性が高いことによる優れた耐熱性、良好な電気伝導性、軽量で高強度などの優れた特性から冶金、電気、機械、化学、原子力などの幅広い分野で利用される。このような幅広い用途に合わせて黒鉛製品の物性を作り分ける必要があり、具体的には複数の炭素材をブレンドすることや原料オイルの重質化による改質処理などが広く行われてきた。 Graphite products have low thermal expansion and high thermal conductivity. Due to their high thermal conductivity, they have excellent heat resistance, good electrical conductivity, light weight and high strength. It is used in a wide range of fields such as nuclear power. It is necessary to make different physical characteristics of graphite products according to such a wide range of applications. Specifically, blending of a plurality of carbon materials and reforming treatment by making the raw material oil heavier have been widely performed.
その際に重要視される物性として、成形体硬度、熱膨張率、電気伝導性、熱拡散率、ヤング率などがあるが、我々の検討から、これらの物性値は基本的には黒鉛の密度、細孔構造、結晶構造、異方性、配向性などが互いに影響しあうため、切り分けることが難しく、一物性の改善が他物性の低下に繋がる、所謂、トレードオフになることを見出した。 At that time, the physical characteristics that are emphasized include the hardness of the molded body, the coefficient of thermal expansion, the electrical conductivity, the coefficient of thermal diffusion, and the Young's modulus. From our examination, these physical characteristics are basically the density of graphite. , Pore structure, crystal structure, anisotropy, orientation, etc. affect each other, so it is difficult to separate them, and it has been found that improvement of one physical characteristic leads to deterioration of other physical characteristics, which is a so-called trade-off.
熱膨張を低減することができる有孔率を向上した例として、文献１にコールタールピッチの熱処理物に添加剤として硫黄、ニッケル、硫化銅、塩化アルミニウムを加えて成形し焼成を行った検討がある。この論文において各添加剤を加えることで焼成後の有効率が数％増加することを見出しているが、一方でショア硬度は５から１０程度低下する結果が報告されている。細孔を導入することは熱膨張を緩和する上で有効な手段であるが、既存の手法では硬度物性をも低減されてしまうことが報告されている（例えば、非特許文献１）。 As an example of improving the coefficient of thermal expansion capable of reducing thermal expansion, a study in which sulfur, nickel, copper sulfide, and aluminum chloride were added as additives to a heat-treated product of coal tar pitch and molded and fired. be. In this paper, it is found that the effective rate after firing is increased by several percent by adding each additive, but on the other hand, it is reported that the shore hardness is reduced by about 5 to 10. Introducing pores is an effective means for alleviating thermal expansion, but it has been reported that existing methods also reduce hardness physical properties (for example, Non-Patent Document 1).
主要物性である成形体硬度と熱膨張率は、成形体及び炭素質の空孔に強く影響を受けることが知られている。硬度を高める上で空孔率を低減することが重要だとされているが、炭素質中の空孔は熱膨張を抑制する空間として働くために、これらの物性はトレードオフの関係となっている。上記非特許文献１においても成形体硬度と低熱膨張率の両立はなされてはいない。本発明の課題は、十分な硬度を維持しつつ、熱膨張が抑制された黒鉛を提供することにある。また、本発明の課題は、この黒鉛の製造方法及びこの黒鉛を得るために調整される混合物を提供することにある。 It is known that the hardness and coefficient of thermal expansion of a molded body, which are the main physical properties, are strongly influenced by the pores of the molded body and carbonaceous material. It is said that it is important to reduce the porosity in order to increase the hardness, but since the porosity in the carbonaceous material acts as a space that suppresses thermal expansion, these physical properties are in a trade-off relationship. There is. Even in the above-mentioned Non-Patent Document 1, the hardness of the molded product and the low coefficient of thermal expansion are not compatible with each other. An object of the present invention is to provide graphite in which thermal expansion is suppressed while maintaining sufficient hardness. Another object of the present invention is to provide a method for producing this graphite and a mixture prepared to obtain the graphite.
本発明者等は上記課題を解決するために鋭意検討した結果、特定の細孔分布を有する黒鉛により上記課題を解決し得ることを見出した。即ち、本発明の要旨は以下の通りである。 As a result of diligent studies to solve the above problems, the present inventors have found that graphite having a specific pore distribution can solve the above problems. That is, the gist of the present invention is as follows.
［１］水銀圧入法により測定した細孔分布のピークトップが０．０１〜１０μｍ、細孔分布が０．００５〜２０μｍであり、かつ窒素ガス吸着量測定の相対圧に対するプロットでＰ／Ｐ０が０．３〜０．７となる範囲でガス脱離曲線とガス吸着曲線にヒステリシスを生
じる黒鉛。
［２］インクボトル型の細孔を有する、［１］に記載の黒鉛。
[1] The peak top of the pore distribution measured by the mercury intrusion method is 0.01 to 10 μm, the pore distribution is 0.005 to 20 μm, and P / P 0 is plotted against the relative pressure of the nitrogen gas adsorption amount measurement. Graphite that causes hysteresis in the gas desorption curve and the gas adsorption curve in the range of 0.3 to 0.7.
[2] The graphite according to [1], which has ink bottle-shaped pores.
［３］キノリン不溶分が７０〜９９重量％である生コークスとマンガン及びマンガン化合物のうちの少なくとも一方とを含む混合物。
［４］前記生コークスと前記マンガン及びマンガン化合物との合計量に対し、マンガン及びマンガン化合物の少なくとも一方を０．０１〜３０重量％含む、請求項３に記載の混合物。
[3] A mixture containing raw coke having a quinoline insoluble content of 70 to 99% by weight and at least one of manganese and a manganese compound.
[4] The mixture according to claim 3, wherein at least one of the manganese and the manganese compound is contained in an amount of 0.01 to 30% by weight based on the total amount of the raw coke and the manganese and the manganese compound.
［５］キノリン不溶分が７０〜９９重量％である生コークスとマンガン及びマンガン化合物の少なくとも一方とを混合し、６００〜１７００℃でのか焼、２０００〜３５００℃での黒鉛化を経る黒鉛の製造方法。
［６］前記混合の後、か焼する前に加圧成型を行う、請求項５に記載の黒鉛の製造方法。
[5] Production of graphite by mixing raw coke having a quinoline insoluble content of 70 to 99% by weight and at least one of manganese and a manganese compound, baking at 600 to 1700 ° C., and graphitizing at 2000 to 3500 ° C. Method.
[6] The method for producing graphite according to claim 5, wherein pressure molding is performed after the mixing and before calcination.
本発明によれば、成形体硬度と低熱膨張率のいずれにも優れた黒鉛及びその製造方法、並びに該黒鉛を得るための混合物が提供される。 According to the present invention, graphite having excellent hardness of molded article and low coefficient of thermal expansion, a method for producing the same, and a mixture for obtaining the graphite are provided.
以下、本発明を詳細に説明するが、本発明は以下の説明に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。なお、本発明において、「〜」を用いてその前後に数値又は物性値を挟んで表現する場合、その前後の値を含むものとして用いることとする。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention. In addition, in this invention, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that.
〔黒鉛〕
本発明の黒鉛は、水銀圧入法により測定した細孔分布のピークトップが０．０１〜１０μｍ、細孔分布が０．００５〜２０μｍであり、かつ窒素ガス吸着量測定の相対圧に対するプロットでＰ／Ｐ０が０．３〜０．７となる範囲でガス脱離曲線とガス吸着曲線にヒステリシスを生じるものである。前述の通り、成形体の硬度と低熱膨張率は通常、両立することが困難であったが、本発明の黒鉛は、これらの物性がいずれも優れるという効果を奏する。
〔graphite〕
In the graphite of the present invention, the peak top of the pore distribution measured by the mercury intrusion method is 0.01 to 10 μm, the pore distribution is 0.005 to 20 μm, and the plot with respect to the relative pressure of the nitrogen gas adsorption amount measurement is P. Hysteresis occurs in the gas desorption curve and the gas adsorption curve in the range where / P 0 is 0.3 to 0.7. As described above, it is usually difficult to achieve both the hardness of the molded product and the low coefficient of thermal expansion, but the graphite of the present invention has the effect of being excellent in all of these physical properties.
［細孔の構造］
水銀圧入法により測定した細孔分布のピークトップが０．０１〜１０μｍ、０．０５ｍＬ／ｇ以上の対数微分細孔容積を有する細孔分布が０．００５〜２０μｍである。この細孔分布のピークトップは、０．０１μｍ以上であり、一方、１０μｍ以下であることにより黒鉛中の広範囲に空孔が分布することで硬度を高めることとなり、この観点から、細孔分布のピークトップは好ましくは８μｍ以下である。また、０．０５ｍＬ／ｇ以上の対数微分細孔容積を有する細孔分布は、０．００５μｍ以上であり、また、２０μｍ以下であることにより強度低下の原因となる粗大な細孔が減少することとなり、この観点から、細孔分布は好ましくは１５μｍ以下である。
[Pore structure]
The peak top of the pore distribution measured by the mercury intrusion method is 0.01 to 10 μm, and the pore distribution having a logarithmic differential pore volume of 0.05 mL / g or more is 0.005 to 20 μm. The peak top of this pore distribution is 0.01 μm or more, while when it is 10 μm or less, the pores are distributed over a wide range in graphite, which increases the hardness. The peak top is preferably 8 μm or less. Further, the pore distribution having a logarithmic differential pore volume of 0.05 mL / g or more is 0.005 μm or more, and 20 μm or less reduces the coarse pores that cause a decrease in strength. From this viewpoint, the pore distribution is preferably 15 μm or less.
本発明の黒鉛は上記の細孔分布を満たし、更に、窒素ガス吸着量測定において相対圧に対してガスの吸着量及び脱離量をプロットした際に相対圧Ｐ／Ｐ０が０．３〜０．７となる範囲でガス脱離曲線とガス吸着曲線に差が生じ、２曲線にヒステリシスが確認される。この現象が見られる場合、本発明の黒鉛において、細孔の構造が単純な球状や円柱状ではなく、インクボトル型と呼ばれる細孔構造を有することを示しており、吸着ガスが流入す
る入り口がその先の細孔より狭まった構造をとる場合に確認される。上記の相対圧Ｐ／Ｐ０が上記範囲であると、本発明における特定の細孔構造を有することを示すものであり、特に、この値は好ましくは０．４〜０．６である。
The graphite of the present invention satisfies the above pore distribution, and further, when the gas adsorption amount and desorption amount are plotted against the relative pressure in the nitrogen gas adsorption amount measurement, the relative pressure P / P 0 is 0.3 to 0.3 to There is a difference between the gas desorption curve and the gas adsorption curve in the range of 0.7, and hysteresis is confirmed in the two curves. When this phenomenon is observed, it is indicated that the graphite of the present invention has a pore structure called an ink bottle type instead of a simple spherical or columnar structure, and the inlet where the adsorbed gas flows in is indicated. This is confirmed when the structure is narrower than the pores beyond it. When the relative pressure P / P 0 is in the above range, it indicates that the pore structure has a specific pore structure in the present invention, and in particular, this value is preferably 0.4 to 0.6.
〔混合物〕
本発明の混合物はキノリン不溶分が７０〜９９重量％である生コークスとマンガン及びマンガン化合物の少なくとも一方とを含むものである。この混合物は前述した本発明の黒鉛を得るために有用である。
〔mixture〕
The mixture of the present invention contains raw coke having a quinoline insoluble content of 70 to 99% by weight and at least one of manganese and a manganese compound. This mixture is useful for obtaining the graphite of the present invention described above.
［生コークス］
本発明において、「生コークス」とは、キノリン不溶分が０〜３０重量％、トルエン不溶キノリン可溶分を０〜２０重量％である重質油を３００〜５００℃で熱処理することで得られる炭素前駆体を意味する。生コークスとしては、例えば、石炭由来の石炭生コークス、石油由来の石油生コークス等が挙げられる。
[Raw coke]
In the present invention, "raw coke" is obtained by heat-treating heavy oil having a quinoline-insoluble content of 0 to 30% by weight and a toluene-insoluble quinoline-soluble content of 0 to 20% by weight at 300 to 500 ° C. Means carbon precursor. Examples of the raw coke include coal raw coke derived from coal, petroleum raw coke derived from petroleum, and the like.
本発明の混合物において、生コークスはキノリン不溶分が７０〜９９重量％であるものを用いる。キノリン不溶分が、７０重量％未満であると、本発明における成形体焼成時に膨張による低密度化や融解が生じるために、良好な黒鉛が得られない。また、９９重量％超過であると自己融着性がなく低密度化や割れ、硬度低下が確認される。これらの観点から、このキノリン含有量は、好ましくは８５重量％以上であり、一方、好ましくは９８重量％以下である。生コークスにおけるキノリン不溶分含有量は、生コークス粉末を粉砕後、溶剤キノリンと共に混合し、不溶分重量を測定するＪＩＳ Ｋ ２４２５の方法により測定することができる。 In the mixture of the present invention, raw coke having a quinoline insoluble content of 70 to 99% by weight is used. If the quinoline insoluble content is less than 70% by weight, good graphite cannot be obtained because the density is lowered or melted due to expansion during firing of the molded product in the present invention. On the other hand, if it exceeds 99% by weight, there is no self-bonding property, and low density, cracking, and hardness reduction are confirmed. From these viewpoints, the quinoline content is preferably 85% by weight or more, while preferably 98% by weight or less. The quinoline insoluble content in raw coke can be measured by the method of JIS K 2425, in which raw coke powder is pulverized, mixed with solvent quinoline, and the insoluble content is measured.
［マンガン及びマンガン化合物］
本発明の混合物にはマンガン及びマンガン化合物のうちの少なくとも一方が用いられるが、マンガン化合物の種類は特に制限されない。マンガン化合物としては、例えば、酸化マンガン、硫化マンガン、炭化マンガン、硝酸マンガン、過マンガン酸カリウム等が挙げられる。これらの中でも好ましくは、酸化マンガン、炭化マンガン等である。以上に挙げたマンガン化合物は、１種のみで用いても２種以上を組み合わせて用いてもよい。
[Manganese and manganese compounds]
At least one of manganese and a manganese compound is used in the mixture of the present invention, but the type of the manganese compound is not particularly limited. Examples of the manganese compound include manganese oxide, manganese sulfide, manganese carbide, manganese nitrate, potassium permanganate and the like. Among these, manganese oxide, manganese carbide and the like are preferable. The manganese compounds listed above may be used alone or in combination of two or more.
［混合物の調整方法］
本発明の混合物は、前記生コークスと前記マンガン及びマンガン化合物との合計量に対し、マンガン化合物及びマンガン化合物の少なくとも一方の含有量が、０．０１重量％以上であることが好ましく、１重量％以上であることがより好ましく、一方、３０重量％以下であることが好ましく、２０重量％以下であることがより好ましい。本発明の混合物におけるマンガン化合物の含有量が上記下限値以上であると熱膨張が明確に低減されるために好ましく、一方、上記上限値以下であると成形体の自己結着性を保持する観点で好ましい。なお、混合した前記マンガン及びマンガン化合物は加熱処理後に酸処理などにより使用用途に合わせ調整してもよい。
[How to adjust the mixture]
In the mixture of the present invention, the content of at least one of the manganese compound and the manganese compound is preferably 0.01% by weight or more, and 1% by weight, based on the total amount of the raw coke and the manganese and the manganese compound. The above is more preferable, while it is preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the manganese compound in the mixture of the present invention is at least the above lower limit value, thermal expansion is clearly reduced, while when it is at least the above upper limit value, the self-bonding property of the molded product is maintained. Is preferable. The mixed manganese and the manganese compound may be adjusted according to the intended use by heat treatment and then acid treatment.
本発明の混合物において、生コークスは次のような大きさに調整した上で用いることが高密度で高硬度の黒鉛が得られる観点で好ましい。即ち、生コークスの大きさは、好ましくは１０００μｍ以下、より好ましくは１００μｍ以下である。下限値は特に制限されないが、通常、０．１μｍ以上である。 In the mixture of the present invention, it is preferable to use the raw coke after adjusting it to the following size from the viewpoint of obtaining high-density and high-hardness graphite. That is, the size of raw coke is preferably 1000 μm or less, more preferably 100 μm or less. The lower limit is not particularly limited, but is usually 0.1 μm or more.
また、本発明の混合物において、マンガン及びマンガン化合物は次のような大きさに調整した上で用いることが骨格となる炭素との反応を促進する観点で好ましい。即ち、マンガン及びマンガン化合物の大きさは、好ましくは１０００μｍ以下、より好ましくは１００μｍ以下である。下限値は特に制限されないが、通常、０．１μｍ以上である。 Further, in the mixture of the present invention, it is preferable to use manganese and the manganese compound after adjusting them to the following sizes from the viewpoint of promoting the reaction with carbon as a skeleton. That is, the size of manganese and the manganese compound is preferably 1000 μm or less, more preferably 100 μm or less. The lower limit is not particularly limited, but is usually 0.1 μm or more.
本発明の混合物には、前述の生コークスとマンガン及びマンガン化合物以外の成分として、バインダーピッチやホウ素系化合物、マンガン以外の金属粉及び金属化合物粉等が含まれていてもよい。 The mixture of the present invention may contain a binder pitch, a boron-based compound, a metal powder other than manganese, a metal compound powder, and the like as components other than the above-mentioned raw coke and manganese and manganese compounds.
本発明の混合物の調整方法は特に制限されないが、手動混合、ボールミルなどによる機械混合、生コークス粉末をマンガン化合物分散溶液に含浸した後、溶剤を飛ばすなどの湿式混合等の方法の他、原料油にマンガン及びマンガン化合物の少なくとも一方を混ぜ込み、マンガンを含有する生コークスを作製する方法を用いることができる。 The method for preparing the mixture of the present invention is not particularly limited. A method of producing raw coke containing manganese by mixing at least one of manganese and a manganese compound with manganese can be used.
〔黒鉛の製造方法〕
本発明の黒鉛の製造方法（以下、「本発明の製造方法」と称することがある。）は、キノリン不溶分が７０〜９９重量％である生コークスとマンガン及びマンガン化合物の少なくとも一方とを混合し、６００〜１７００℃でのか焼、２０００〜３５００℃での黒鉛化を経るものである。即ち、本発明の製造方法は、前述の本発明の混合物を用い、これを特定の温度範囲でのか焼及び黒鉛化を経るものである。
[Graphite manufacturing method]
The method for producing graphite of the present invention (hereinafter, may be referred to as "the method for producing the present invention") is a mixture of raw coke having a quinoline insoluble content of 70 to 99% by weight and at least one of manganese and a manganese compound. Then, it undergoes coking at 600 to 1700 ° C. and graphitization at 2000 to 3500 ° C. That is, the production method of the present invention uses the above-mentioned mixture of the present invention, and undergoes baking and graphitization in a specific temperature range.
［か焼］
本発明の製造方法において、か焼は６００〜１７００℃で行われる。か焼の温度範囲が、６００℃未満であると成形体の収縮や揮発分散逸が不十分となり、一方、１７００℃超過であると、黒鉛化前にピッチ含浸などの高密度化処理を行う際にピッチの浸透が困難となる。これらの観点から、か焼の温度範囲は、好ましくは８００℃以上、より好ましくは９００℃以上であり、一方、好ましくは１５００℃以下、より好ましくは１４００℃以下である。
[Calcination]
In the production method of the present invention, calcination is performed at 600 to 1700 ° C. If the temperature range of calcination is less than 600 ° C, shrinkage and volatilization and dispersion loss of the molded product will be insufficient, while if it exceeds 1700 ° C, high density treatment such as pitch impregnation before graphitization will be performed. It becomes difficult to penetrate the pitch. From these viewpoints, the temperature range of calcination is preferably 800 ° C. or higher, more preferably 900 ° C. or higher, while preferably 1500 ° C. or lower, more preferably 1400 ° C. or lower.
［黒鉛化］
本発明の製造方法において、黒鉛化は２０００〜３５００℃で行われる。黒鉛化の温度範囲が、２０００℃未満であると本発明における添加物や原料由来の不純物が残存し黒鉛純度が低下し、一方、３５００℃超過であると、黒鉛化の進行は停止しているものの余剰なエネルギーを費やすこととなる。これらの観点から、黒鉛化の温度範囲は、好ましくは２２００℃以上、より好ましくは２５００℃以上であり、一方、好ましくは３３００℃以下、より好ましくは３０００℃以下である。
[Graphitization]
In the production method of the present invention, graphitization is performed at 2000 to 3500 ° C. If the temperature range of graphitization is less than 2000 ° C, impurities derived from additives and raw materials in the present invention remain and the graphite purity decreases, while if it exceeds 3500 ° C, the progress of graphitization is stopped. It will consume surplus energy of things. From these viewpoints, the temperature range of graphitization is preferably 2200 ° C. or higher, more preferably 2500 ° C. or higher, while preferably 3300 ° C. or lower, more preferably 3000 ° C. or lower.
［加圧成型］
本発明の製造方法は、特に、前記混合の後、か焼する前に加圧成型を行うことが好ましい。加圧成型を行うことにより黒鉛を高密度化しかつ添加剤の効果を高めることができるために好ましい。加圧成型の方法としては金型成型、押出成型、冷間静水等方圧加圧成型等が挙げられる。
[Pressure molding]
In the production method of the present invention, it is particularly preferable to perform pressure molding after the mixing and before calcination. It is preferable to perform pressure molding because the density of graphite can be increased and the effect of the additive can be enhanced. Examples of the pressure molding method include mold molding, extrusion molding, cold hydrostatic isotropic pressure pressure molding, and the like.
加圧成型の条件として、温度は通常、８０〜２００℃、好ましくは１００〜１７０℃である。また、圧力は通常、１〜１００ＭＰａ、好ましくは１０〜５０ＭＰａである。 As a condition of pressure molding, the temperature is usually 80 to 200 ° C., preferably 100 to 170 ° C. The pressure is usually 1 to 100 MPa, preferably 10 to 50 MPa.
［コークス粉の乾燥］
成形体作製に用いるコークス及び生コークスは８０〜３００℃程度で乾燥を行うことで、水分量、揮発分量などを任意に調整することが出来る。この工程はコークス及び生コークスの粉砕前及び粉砕後、ブレンド後、バインダーピッチ添加及び混練後のいずれにおいても可能であるが、より厳密な物性調整とバインダー親和性の観点からコークス及び生コークス粉砕前及び粉砕後に行うことが望ましい。
[Drying coke powder]
The amount of water, the amount of volatile matter, etc. can be arbitrarily adjusted by drying the coke and raw coke used for producing the molded product at about 80 to 300 ° C. This step can be performed before and after crushing the coke and raw coke, after blending, after adding the binder pitch and after kneading, but before crushing the coke and raw coke from the viewpoint of stricter physical property adjustment and binder affinity. And it is desirable to do it after crushing.
［混合］
成形体を作製する上で主要材料であるか焼コークスは、性状の異なる２種類以上のか焼コークスを混合することで物性を微調整可能である。本発明における成形体の主材料である生コークスについても同様で、性状の異なる２種類以上の生コークスをブレンドして使用することで物性を微調整することができる。なお、上記の物性微調整はあくまで前述のとおり、物性トレードオフの関係にある点を注意する必要がある。
[mixture]
The physical properties of calcinated coke, which is the main material for producing a molded product, can be finely adjusted by mixing two or more types of calcinated coke having different properties. The same applies to the raw coke which is the main material of the molded product in the present invention, and the physical properties can be finely adjusted by using a blend of two or more kinds of raw coke having different properties. It should be noted that the above fine adjustment of physical properties has a trade-off relationship with physical properties as described above.
［結着成分の添加・混練］
通常の黒鉛材料製造では、主要材料であるか焼コークス自身は融着性を有しないため、バインダーピッチなどの結着成分を添加して成形を行う。この際、か焼コークスと結着成分を十分に馴染ませる目的で、通常、結着成分の軟化点以上で加温をしつつか焼コークスと結着成分を混合する。この工程は混練と呼ばれ、黒鉛成形体の密度、硬度、電気抵抗などの諸物性に大きく影響する。本発明における生コークスは基本的に自身が融着性を有するため、結着成分の添加は不要であるが、か焼コークス同様に結着成分を加え、混練操作を行った上で成形体とすることも可能である。以上の結着成分の添加及び混練の工程はか焼コークス及び生コークスの粉砕前、粉砕後のどちらでも行うことが出来るが、結着成分との十分な馴染みを達成する上で、粉砕後に行うことが望ましい。また、混練後に得られる混合物は再粉砕し、粒度を調節することもできる。
[Addition and kneading of binding ingredients]
In ordinary graphite material production, since the main material, calcinated coke itself, does not have cohesiveness, molding is performed by adding a binder component such as a binder pitch. At this time, for the purpose of fully blending the calcination coke and the binding component, usually, the calcination coke and the binding component are mixed while being heated above the softening point of the binding component. This process is called kneading and greatly affects various physical properties such as density, hardness, and electrical resistance of the graphite compact. Since the raw coke in the present invention basically has a cohesive property by itself, it is not necessary to add a cohesive component. It is also possible to do. The above steps of adding and kneading the binding component can be performed either before or after crushing the calcinated coke and raw coke, but they are performed after crushing in order to achieve sufficient compatibility with the binding component. Is desirable. The mixture obtained after kneading can also be reground to adjust the particle size.
［含浸・再か焼］
か焼によって生成した空隙にさらに含浸ピッチを浸漬する工程をピッチ含浸という。その後、再度か焼により結着成分を焼結するが、この含浸・再か焼を繰り返すことでより高密度化された黒鉛を得ることができる。この工程は成形体か焼後及び黒鉛化後に行うことができるが、含浸ピッチの浸透し易さから成形体か焼後に行うことが望ましい。
[Immersion / recalcination]
The process of further immersing the impregnation pitch in the voids created by calcination is called pitch impregnation. After that, the binding component is sintered again by calcination, and by repeating this impregnation and calcination, higher density graphite can be obtained. This step can be performed after the molded product is baked and after graphitization, but it is desirable to perform this step after the molded product or baked because of the ease of penetration of the impregnation pitch.
［その他の処理］
一部の高純度が求められる用途では、ハロゲンガスなどと反応させることで黒鉛中に含まれる不純物元素が除去することができる。また、薬品耐性や表面硬さが求められる用途には表面にガラス状炭素などによるコーティング処理を行ってもよい。
[Other processing]
In some applications where high purity is required, impurity elements contained in graphite can be removed by reacting with halogen gas or the like. Further, for applications where chemical resistance and surface hardness are required, the surface may be coated with glassy carbon or the like.
以下、実施例により本発明の内容を更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、以下の実施例によって限定されるものではない。なお、以下の実施例における各種の製造条件や評価結果の値は、本発明の実施態様における上限又は下限の好ましい値としての意味を持つものであり、好ましい範囲は前記した上限又は下限の値と、下記実施例の値又は実施例同士の値との組み合わせで規定される範囲であってもよい。 Hereinafter, the content of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.
（成形体の作製）
以下の実施例及び比較例において、金型成型により加圧成型を行った。生コークス粉単味又は生コークス粉と各添加剤（二酸化マンガン、鉄化合物又は硫黄）との混合粉１．３ｇをφ２０ｍｍのコイン状の金型に封入し、１２０℃まで加温したのち３０ＭＰａまで加圧し、１０分間維持した後、取出しを行うことでφ２０ｍｍ×厚み２〜３ｍｍのコイン型成形体を得た。また、以下の物性測定に用いるためにコイン型成形体から２ｍｍ×２ｍｍ×１４ｍｍの直方体サンプル３本を切り出し、以降の物性測定に使用した。
(Making a molded product)
In the following examples and comparative examples, pressure molding was performed by mold molding. Raw coke powder Single or mixed powder of raw coke powder and each additive (manganese dioxide, iron compound or sulfur) is sealed in a coin-shaped mold of φ20 mm, heated to 120 ° C, and then up to 30 MPa. After pressurizing and maintaining for 10 minutes, it was taken out to obtain a coin-shaped molded body having a diameter of 20 mm and a thickness of 2 to 3 mm. In addition, three 2 mm × 2 mm × 14 mm rectangular parallelepiped samples were cut out from the coin-shaped molded body for use in the following physical property measurement, and used for the subsequent physical property measurement.
（熱膨張率の測定）
熱膨張率測定にはＲｉｇａｋｕ社製の熱機械分析装置（Ｔｈｅｒｍｏ ｐｌｕｓ ＥＶＯ２ ／ ＴＭＡ）を利用し、ＳｉＯ２標準を使用した２００℃〜１０００℃における示唆膨張方式により測定を行った。本測定において１８０℃〜２０１℃及び９８０℃〜１００１℃の範囲では１℃／分の速度で昇温を行い、上記以外の範囲では１００℃／分で昇温を行った。
(Measurement of coefficient of thermal expansion)
The coefficient of thermal expansion was measured by a thermomechanical analyzer (Thermo plus EVO2 / TMA) manufactured by Rigaku Co., Ltd. by a suggested expansion method at 200 ° C. to 1000 ° C. using the SiO 2 standard. In this measurement, the temperature was raised at a rate of 1 ° C./min in the range of 180 ° C. to 201 ° C. and 980 ° C. to 1001 ° C., and the temperature was raised at 100 ° C./min in the range other than the above.
（成形体ショア硬度の測定）
ショア硬度測定には今井精機社製のカタサ試験機（ショア式Ｄ型）を用いて、直方体サンプルの２面（成形時圧力をかけた面と断面）を３カ所ずつ測定し、計６カ所の平均値をサンプルのショア硬度として採用した。
(Measurement of molded shore hardness)
For the shore hardness measurement, Imai Seiki Co., Ltd.'s Katasa testing machine (shore type D type) was used to measure two sides (the side to which pressure was applied during molding and the cross section) of the rectangular parallelepiped sample at three locations, for a total of six locations. The average value was used as the shore hardness of the sample.
（電気抵抗率の測定）
電気抵抗率測定は四探針法により行いＪＩＳ Ｋ ７１９４に準ずる測定を計５回実施し、平均値をサンプルの電気抵抗率として採用した。
(Measurement of electrical resistivity)
The electrical resistivity was measured by the four-probe method, and the measurement according to JIS K 7194 was carried out a total of five times, and the average value was adopted as the electrical resistivity of the sample.
（黒鉛の細孔分析）
細孔測定には上記の物性測定に用いた直方体サンプルを粉砕せず、そのまま使用した。０．０１〜５０μｍの範囲における細孔測定には、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製のＡｕｔｏＰｏｒｅ ＩＶ ９５２０を利用し、５０μｍＨｇまで室温で１０分間減圧した上で水銀圧入法による細孔容積測定を実施した。０．００１〜０．１μｍの範囲における細孔測定には、Ｑｕａｎｔａｃｈｒｏｍｅ社製のＡｕｔｏｓｏｒｂ−ｉＱ３を利用し、減圧下、２５０℃で５時間保持した後、窒素吸着法による細孔容積測定を行った。
(Graphite pore analysis)
For the pore measurement, the rectangular parallelepiped sample used for the above physical property measurement was used as it was without being pulverized. For the pore measurement in the range of 0.01 to 50 μm, AutoPore IV 9520 manufactured by Micromeritics was used, and the pore volume was measured by the mercury intrusion method after reducing the pressure to 50 μmHg at room temperature for 10 minutes. For the pore measurement in the range of 0.001 to 0.1 μm, Autosorb-iQ3 manufactured by Quantachrome was used, and the pore volume was measured by the nitrogen adsorption method after holding at 250 ° C. for 5 hours under reduced pressure. ..
（実施例１）
キノリン不溶分が９６重量％である生コークス（以下、「炭素材Ａ」と称することがある。）を粉砕し５３〜１００μｍとした生コークス粉を使用し、この生コークス粉に対して添加剤として５３〜１００μｍに粉砕した二酸化マンガン粉末を、添加量が１０重量％となるよう混合した。この混合粉を金型成型して炭素成形体を１３００℃まで昇温し２時間熱処理したのち常温まで冷却し、黒鉛化炉にて２８００℃まで昇温し３０分間熱処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Example 1)
Raw coke powder having a quinoline insoluble content of 96% by weight (hereinafter, may be referred to as "carbon material A") is crushed to make 53 to 100 μm, and raw coke powder is used, and an additive is added to this raw coke powder. The manganese dioxide powder pulverized to 53 to 100 μm was mixed so that the addition amount was 10% by weight. The mixed powder was molded into a mold, the temperature of the carbon molded product was raised to 1300 ° C., heat treatment was performed for 2 hours, the mixture was cooled to room temperature, and the temperature was raised to 2800 ° C. in a graphite furnace and heat treatment was performed for 30 minutes. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（実施例２）
実施例１において生コークスをキノリン不溶分が９３重量％である生コークス（「炭素材Ｂ」と称することがある。）を粉砕し５３〜１００μｍとした生コークス粉とした以外、実施例１と同様の処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Example 2)
In Example 1, raw coke was obtained by crushing raw coke having a quinoline insoluble content of 93% by weight (sometimes referred to as "carbon material B") to obtain raw coke powder having a thickness of 53 to 100 μm. The same process was performed. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（実施例３）
実施例１において二酸化マンガン粉末の添加量が５重量％となるようにした以外、実施例１と同様の処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Example 3)
The same treatment as in Example 1 was carried out except that the amount of manganese dioxide powder added was 5% by weight in Example 1. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（比較例１）
炭素材Ａを粉砕し５３〜１００μｍとした生コークス粉を使用した。この生コークス粉を金型成型して得られた炭素成形体を１３００℃まで昇温し２時間熱処理したのち常温まで冷却し、黒鉛化炉にて２８００℃まで昇温し３０分間熱処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Comparative Example 1)
Raw coke powder obtained by crushing carbon material A to a thickness of 53 to 100 μm was used. The carbon molded product obtained by molding this raw coke powder was heated to 1300 ° C. and heat-treated for 2 hours, then cooled to room temperature, heated to 2800 ° C. in a graphite furnace, and heat-treated for 30 minutes. .. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（比較例２）
実施例１において生コークス粉に対する添加剤を二酸化マンガンの代わりに５３〜１００μに粉砕した酸化鉄（Ｆｅ２Ｏ３）粉末を用いた以外、実施例１と同様の処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Comparative Example 2)
In Example 1, the same treatment as in Example 1 was carried out except that iron oxide (Fe 2 O 3 ) powder obtained by crushing the additive to the raw coke powder to 53 to 100 μm was used instead of manganese dioxide. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（比較例３）
実施例１において生コークス粉に対する添加剤を二酸化マンガンの代わりに５３μｍ以
下に粉砕した硫黄粉末とした以外、実施例１と同様の処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Comparative Example 3)
In Example 1, the same treatment as in Example 1 was carried out except that the additive to the raw coke powder was sulfur powder pulverized to 53 μm or less instead of manganese dioxide. Table 1 shows the results of each of the above evaluations of the obtained graphite.
（比較例４）
比較例１において生コークスをキノリン不溶分が９３重量％である生コークス（炭素材Ｂ）を粉砕して５３〜１００μｍの生コークス粉とした以外、比較例１と同様の処理を行った。得られた黒鉛について、上記の各評価を行った結果を表−１に示す。
(Comparative Example 4)
In Comparative Example 1, the same treatment as in Comparative Example 1 was carried out except that the raw coke was pulverized with raw coke (carbon material B) having a quinoline insoluble content of 93% by weight to obtain 53 to 100 μm raw coke powder. Table 1 shows the results of each of the above evaluations of the obtained graphite.
表−１に実施例１〜４及び比較例１〜４の熱膨張率、ショア硬度、電気抵抗及びサンプルの詳細をまとめて示した。 Table 1 summarizes the thermal expansion coefficient, shore hardness, electrical resistance, and sample details of Examples 1 to 4 and Comparative Examples 1 to 4.
図−１に実施例１及び比較例１〜４の熱膨張率、ショア硬度をそれぞれ比較した。比較
例１、４は原料の生コークスのみを変更したもので、前述のように熱膨張が大きいものではショア硬度が高く、逆に熱膨張が小さいものではショア硬度が低いことが確認された。更に酸化鉄Ｆｅ２Ｏ３を１０重量％添加した比較例２及び前記非特許文献１においても用いられている硫黄を１０重量％添加した比較例３でも、比較例１と比較すると熱膨張率が低減されているものの、ショア硬度も同様に低下していることが確認された。この様に炭素質の変更や先行技術では熱膨張を抑制するためにはショア硬度が低くなり、これらはトレードオフの関係にあることがわかる。
FIG. 1 compares the coefficient of thermal expansion and the shore hardness of Example 1 and Comparative Examples 1 to 4, respectively. In Comparative Examples 1 and 4, only the raw coke as a raw material was changed, and it was confirmed that the shore hardness was high when the thermal expansion was large and the shore hardness was low when the thermal expansion was small as described above. Further, in Comparative Example 2 in which 10% by weight of iron oxide Fe 2 O 3 was added and in Comparative Example 3 in which 10% by weight of sulfur was added, which is also used in Non-Patent Document 1, the coefficient of thermal expansion was higher than that of Comparative Example 1. Although it was reduced, it was confirmed that the shore hardness was also reduced. In this way, it can be seen that there is a trade-off relationship between the change in carbon quality and the prior art, which lowers the shore hardness in order to suppress thermal expansion.
一方、図−１において、実施例１では比較例１に対して熱膨張率の低減とショア硬度の向上が両立していることが確認できる。この傾向は表−１に示す実施例２及び実施例３と比較例４の比較においても確認され、使用する生コークスが炭素質Ａから炭素質Ｂに変更され、単味としての物性が大きく変わっても（比較例１と比較例４の差異に相当する。）、熱膨張率の低減とショア硬度向上に効果があることがわかる。 On the other hand, in FIG. 1, it can be confirmed that in Example 1, both the reduction of the coefficient of thermal expansion and the improvement of the shore hardness are compatible with those of Comparative Example 1. This tendency was also confirmed in the comparison between Example 2 and Example 3 and Comparative Example 4 shown in Table 1, and the raw coke used was changed from carbonaceous A to carbonaceous B, and the physical characteristics as a simple taste changed significantly. However (corresponding to the difference between Comparative Example 1 and Comparative Example 4), it can be seen that it is effective in reducing the coefficient of thermal expansion and improving the shore hardness.
実施例１〜３及び比較例１、４を水銀圧入法により細孔測定した結果、ピークトップ径が実施例１、２、３ではそれぞれ０．１４μｍ、０．２７μｍ及び１．１２μｍとなり、同じ生コークスから得られる黒鉛と比較してＭｎ酸化物を添加しない比較例１、４での０．３７μｍ及び１．４５μｍに対し、ピークトップ径が小さくなることが確認された。更に０．０５ｍｌ／ｇ以上の対数微分細孔容積を有する細孔径の分布が実施例１、２、３ではそれぞれ０．００５〜０．９μｍ、０．０８〜１μｍ及び０．１〜２μｍとなり、Ｍｎ酸化物を添加しない比較例１、４の０．１３〜０．６６μｍ及び０．９〜３μｍに対し、細孔径分布が小細孔径側にシフトする傾向が確認された。一方で比較例２、３の試料では上記の様な特異的な細孔は確認されず、ピークトップ径も１μｍ以上と比較的大きな細孔が得られている。この微小サイズの細孔が熱膨張を抑制しつつも硬度を維持した構造の要因であると推定される。 As a result of pore measurement of Examples 1 to 3 and Comparative Examples 1 and 4 by the mercury intrusion method, the peak top diameters were 0.14 μm, 0.27 μm and 1.12 μm in Examples 1, 2 and 3, respectively. It was confirmed that the peak top diameter was smaller than that of 0.37 μm and 1.45 μm in Comparative Examples 1 and 4 in which Mn oxide was not added as compared with graphite obtained from coke. Further, in Examples 1, 2 and 3, the distribution of the pore diameter having a logarithmic differential pore volume of 0.05 ml / g or more is 0.005 to 0.9 μm, 0.08 to 1 μm and 0.1 to 2 μm, respectively. It was confirmed that the pore size distribution tended to shift toward the small pore size side with respect to 0.13 to 0.66 μm and 0.9 to 3 μm of Comparative Examples 1 and 4 to which Mn oxide was not added. On the other hand, in the samples of Comparative Examples 2 and 3, the specific pores as described above were not confirmed, and relatively large pores with a peak top diameter of 1 μm or more were obtained. It is presumed that these minute-sized pores are a factor in the structure that maintains the hardness while suppressing thermal expansion.
また、窒素吸着法による細孔解析結果から、実施例１〜３では特異的なガス脱吸着挙動を示しており、窒素ガス吸着量測定の相対圧に対するプロットで相対圧Ｐ／Ｐ０が０．３以上０．７以下となる範囲でガス脱吸着ヒステリシスを生じている。脱吸着ヒステリシスは細孔構造に依存しており、今回の挙動は一般的にはインクボトル型細孔と呼ばれる細孔構造で観察され、細孔内部で一部の孔が狭まった構造をとることがわかる。 In addition, from the results of pore analysis by the nitrogen adsorption method, Examples 1 to 3 showed specific gas desorption behavior, and the relative pressure P / P 0 was 0 in the plot against the relative pressure of the nitrogen gas adsorption amount measurement. Gas desorption hysteresis occurs in the range of 3 or more and 0.7 or less. Deadsorption hysteresis depends on the pore structure, and this behavior is generally observed in the pore structure called ink bottle type pores, and some pores are narrowed inside the pores. I understand.
本発明の黒鉛は、熱膨張率が低く、かつ成形体硬度が高いことから、特に、冶金、電気、機械、化学、原子力用途等に利用される人造黒鉛として有用である。より具体的には、本発明の黒鉛は、発熱材・坩堝・断熱材、集電体、減摩材、熱交材、原子炉の減速材・遮蔽物等として好ましく用いることができる。 Since the graphite of the present invention has a low coefficient of thermal expansion and a high hardness of the molded body, it is particularly useful as artificial graphite used for metallurgy, electricity, machinery, chemistry, nuclear power applications, and the like. More specifically, the graphite of the present invention can be preferably used as an exothermic material, a crucible, a heat insulating material, a current collector, an antifriction material, a heat mixing material, a moderator / shield of a nuclear reactor, and the like.
Claims (3)
うちの少なくとも一方とを含み、
前記生コークスと前記マンガン及びマンガン化合物との合計量に対し、マンガン及びマン
ガン化合物の少なくとも一方を０．０１〜３０重量％含む混合物。 See containing and at least one of quinoline insolubles raw coke and manganese and manganese compounds is 70 to 99 wt%,
Manganese and manganese with respect to the total amount of the raw coke and the manganese and the manganese compound
At least one of 0.01 to 30 wt% including a mixture of cancer compound.
少なくとも一方とを混合し、
前記生コークスと前記マンガン及びマンガン化合物との合計量に対し、マンガン及びマン
ガン化合物の少なくとも一方を０．０１〜３０重量％とし、
６００〜１７００℃でのか焼、２０００〜３５００℃での黒鉛化を経る黒鉛の製造方法。 A mixture of raw coke having a quinoline insoluble content of 70 to 99% by weight and at least one of manganese and a manganese compound is used.
Manganese and manganese with respect to the total amount of the raw coke and the manganese and the manganese compound
At least one of the cancer compounds is 0.01 to 30% by weight.
A method for producing graphite through smoldering at 600 to 1700 ° C. and graphitization at 2000 to 3500 ° C.
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