JP6230944B2 - Vertical graphitization furnace and method for producing graphite - Google Patents
Vertical graphitization furnace and method for producing graphite Download PDFInfo
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本発明は、連続式の縦型黒鉛化炉に関する。 The present invention relates to a continuous vertical graphitization furnace.
黒鉛は、潤滑性、導電性、耐熱性、耐酸耐アルカリ性に優れており、電極用ペースト、鋳物塗料剤、乾電池、鉛筆、耐火物、製綱用保温材、ゴム樹脂用、固体潤滑剤、ルツボ、パッキング、耐熱、耐熱品、導電塗料、鉛筆、電気ブラシ、グリース、粉末治金、ブレーキパッド、ライニング、クラッチ、メカニカルシール、ゴム樹脂の添加剤等、様々な用途に使用されている。近年では、黒鉛の結晶の積層構造部分にＬｉイオンが入り込む現象を利用してリチウムイオン電池の電極材として使用されることもある。このように、黒鉛は様々な分野で使用されており、効率的な製造方法の確立は極めて重要といえる。 Graphite is excellent in lubricity, conductivity, heat resistance, acid resistance and alkali resistance, and is used for electrode pastes, casting paints, dry batteries, pencils, refractories, heat insulating materials for steel ropes, rubber resins, solid lubricants, crucibles. , Packing, heat-resistant, heat-resistant products, conductive paint, pencil, electric brush, grease, powder metallurgy, brake pads, linings, clutches, mechanical seals, rubber resin additives, etc. In recent years, it is sometimes used as an electrode material of a lithium ion battery by utilizing a phenomenon that Li ions enter a laminated structure portion of graphite crystals. Thus, graphite is used in various fields, and it can be said that establishment of an efficient manufacturing method is extremely important.
人造黒鉛を製造する際には、一般に、コークス等の炭素物質からなる原料材料を粉末化させて、おおむね２２００℃以上で長時間加熱しなくてはならない。こうした２２００℃以上の加熱に耐えられる材料として、炭素材（黒鉛材等）を用いることが一般的であり、炉およびその内壁、またはその他の炉を構成する各種部材（シャフト、ヒーター、断熱材）等に使用されている。 When producing artificial graphite, generally, a raw material made of a carbon material such as coke must be pulverized and heated at about 2200 ° C. or more for a long time. As a material that can withstand such heating at 2200 ° C. or higher, it is common to use a carbon material (graphite material or the like), and various members (shaft, heater, heat insulating material) constituting the furnace and its inner wall or other furnaces. Etc. are used.
工業的には、アチソン炉（例えば、特許文献１）を使用し、バッチ式で黒鉛化することが多いが、効率的に製造するために連続式で行うことも取り組まれている。連続式で黒鉛化を行うには、炉を横方向に設置し、黒鉛材製の炉の中で黒鉛化の原料を載せたトレーをコンベアーで横方向に移動して加熱する方法などがある。この方法は高温での作業を要するため、設備の部品材料の選択が必要であり、また、排ガスの対策や入口と出口の熱の管理が困難な場合がある。このため、構造が複雑となり、設置や運用に手間がかかる。 Industrially, an Atchison furnace (for example, Patent Document 1) is used to perform graphitization in batch mode, but it is also attempted to perform it continuously in order to produce it efficiently. In order to perform graphitization in a continuous manner, there is a method in which a furnace is installed in a horizontal direction, and a tray on which a raw material for graphitization is placed is moved in a horizontal direction by a conveyor in a furnace made of graphite. Since this method requires work at a high temperature, it is necessary to select material materials for the equipment, and it may be difficult to take measures against exhaust gas and to manage the heat at the inlet and outlet. For this reason, the structure becomes complicated, and it takes time to install and operate.
近年、炉を縦におき、上部から原料を投入して内部で加熱し、下部から黒鉛を取り出す連続式の縦型黒鉛化炉が試みられている（特許文献２，３）。連続式の縦型黒鉛化炉は、炉の内部において、原料を下部から上部にかけて積み上げて加熱し、下方口から黒鉛を取り出しながら取り出した分に相当する原料を上部口から投入することによって、常に一定量の原料が炉の中に存在し、かつ、黒鉛化するものである。この方法は、加熱される部分が炉の内部のみであり、加熱に耐えるトレーやコンベアーが必要でないので、構造が比較的単純であり、かつ、移動のための設備や動力も必要がないため、余分な配線も必要なく、操作も簡単である。 In recent years, a continuous vertical graphitization furnace in which a furnace is placed vertically, a raw material is charged from the upper part and heated inside, and graphite is taken out from the lower part has been tried (Patent Documents 2 and 3). In a continuous vertical graphitization furnace, the raw materials are stacked and heated from the bottom to the top inside the furnace, and the raw material corresponding to the amount taken out while taking out the graphite from the lower port is always charged from the upper port. A certain amount of raw material is present in the furnace and graphitizes. In this method, the part to be heated is only inside the furnace, and no tray or conveyor that can withstand heating is required. Therefore, the structure is relatively simple, and no equipment or power for movement is required. No extra wiring is required and operation is simple.
しかしながら、本発明者は、特許文献２に記載される連続式黒鉛化炉では、原料の炭素材料が徐々に加熱されていくため、炭素材料の中に存在する不純物が不適切な化合物となって蒸発していく場合があることを見出した。特に、炭素材料が石油に由来する石油コークスや石油コークスのカルサイン品（カルサインコークス）である場合、不純物として含む硫黄分が１５００〜２２００℃において、硫化水素または硫黄として脱離する。つまり、黒鉛化炉の内壁が炭素材（黒鉛材）である場合に、脱離した硫化水素等の硫黄分が、黒鉛化炉の内壁を構成する炭素と反応して、内壁を損耗させることを見出した。さらに、内壁を透過した硫化水素等の硫黄分が、炉を構成する各種部材（断熱材、ヒーター）の炭素とも反応して劣化損耗させることを見出した。 However, in the continuous graphitization furnace described in Patent Document 2, the present inventor gradually heats the carbon material as a raw material, so that impurities present in the carbon material become an inappropriate compound. We found that it may evaporate. In particular, when the carbon material is petroleum coke derived from petroleum or a calcine product (calcine coke) of petroleum coke, sulfur contained as impurities is desorbed as hydrogen sulfide or sulfur at 1500 to 2200 ° C. In other words, when the inner wall of the graphitization furnace is a carbon material (graphite material), the desorbed sulfur content such as hydrogen sulfide reacts with the carbon constituting the inner wall of the graphitization furnace and wears the inner wall. I found it. Furthermore, it discovered that sulfur content, such as hydrogen sulfide which permeate | transmitted the inner wall, also reacts with the carbon of the various members (heat insulating material, heater) which comprise a furnace, and carries out deterioration wear.
他方、特許文献３に記載される連続式黒鉛化炉は、通電加熱によって急速に加熱することが可能である。通電加熱では原料の炭素材料自体が発熱するため、先に記述した硫化水素等の硫黄分は原料の炭素材料と反応するので、炉の内壁、ヒーターおよび断熱材等を損耗劣化させることがない。しかしながら、本発明者は、通電加熱は、原料が５〜３０μｍの微粉末である場合、均一に加熱するには不十分であるため、得られる製品が不均一となることを見出した。また、特許文献１には、通電加熱による焼成体の黒鉛化する方法が記載されている。この方法は、炭化物をピッチ等のバインダーで混錬し、円筒状の固体にして黒鉛化材料を製造するものである。つまり、焼成体の黒鉛化を目的とした手法であって、粉末の黒鉛化には適してはいない。 On the other hand, the continuous graphitization furnace described in Patent Document 3 can be rapidly heated by energization heating. Since the raw material carbon material itself generates heat in the current heating, the sulfur content such as hydrogen sulfide described above reacts with the raw material carbon material, so that the inner wall of the furnace, the heater, the heat insulating material and the like are not worn out and deteriorated. However, the present inventor has found that when the raw material is a fine powder of 5 to 30 μm, the product obtained is not uniform because it is insufficient for uniform heating. Patent Document 1 describes a method of graphitizing a fired body by electric heating. In this method, a graphitized material is produced by kneading carbide with a binder such as pitch to form a cylindrical solid. In other words, it is a method aimed at graphitization of the fired body and is not suitable for graphitization of powder.
以上のことから、本発明の目的は、炉およびその内壁、各種部材（シャフト、ヒーター、断熱材）等を炭素材（黒鉛材）で構成した場合でも、これら部材の硫黄分を含むガスによる損耗および劣化が極めて少なく、また、原料である炭素材料に均一に熱を加えることができ、均質な黒鉛が得られる縦型黒鉛化炉を提供する。 From the above, the object of the present invention is to wear the furnace and its inner wall, various members (shaft, heater, heat insulating material), etc., with carbon materials (graphite materials), etc., due to gas containing sulfur content of these members. Further, the present invention provides a vertical graphitization furnace that is extremely little deteriorated and that can uniformly apply heat to a carbon material that is a raw material, thereby obtaining homogeneous graphite.
本発明は、一つの態様によれば、上部から投入された炭素材料を加熱して黒鉛化し、得られた黒鉛を下部から取り出す連続式の縦型黒鉛化炉であって、
前記炭素材料を投入するために前記炉の上部に設けられた投入口と、
前記投入口の下に設けられ、前記炉の内部および／または内壁に設けられた対向する少なくとも２つの電極であって、前記電極に通電して前記炭素材料を加熱する通電領域を形成する少なくとも２つの電極と、
前記通電領域の下で前記炉の外周部に設けられた熱源であって、前記炉の外側から前記炭素材料を加熱する外部熱源領域を形成する熱源と、
前記外部熱源領域の下で前記炉の外周部に設けられ、生成された黒鉛を冷却する冷却領域を形成する冷却用ジャケットと、
前記冷却領域の下に設けられた前記黒鉛を取り出す取り出し口と
を備える縦型黒鉛化炉を提供することができる。
また、本発明の別の態様によると、炭素材料を、縦型黒鉛化炉に投入する工程と、前記投入された炭素材料を、前記炉の内部および／または内壁に設けられた対向する少なくとも２つの電極で通電して１７００〜２３００℃に加熱する通電領域を通過させる工程と、さらに、前記炉の外周部に設けられた熱源で、２３００〜３０００℃に加熱する外部熱源領域を通過させて黒鉛に変換する工程と、前記黒鉛を冷却する工程と、前記冷却された黒鉛を前記炉の下部から取り出す工程とを少なくとも含む黒鉛の製造方法を提供することができる。
The present invention, according to one aspect, is a continuous vertical graphitization furnace in which a carbon material charged from the upper part is heated and graphitized, and the obtained graphite is taken out from the lower part.
A charging port provided at the top of the furnace for charging the carbon material;
At least two opposing electrodes provided under the charging port and provided on the interior and / or inner wall of the furnace to form an energized region that energizes the electrodes to heat the carbon material. Two electrodes,
A heat source provided on the outer periphery of the furnace under the energized region, the heat source forming an external heat source region for heating the carbon material from the outside of the furnace;
A cooling jacket provided on the outer periphery of the furnace under the external heat source region and forming a cooling region for cooling the generated graphite;
It is possible to provide a vertical graphitization furnace including a take-out port for taking out the graphite provided under the cooling region.
According to another aspect of the present invention, the step of introducing a carbon material into a vertical graphitization furnace, and the at least two opposing carbon materials provided on the inside and / or inner wall of the furnace are provided. A step of passing through an energized region that is energized with one electrode and heated to 1700-2300 ° C., and further, a heat source provided at the outer periphery of the furnace is passed through an external heat source region heated to 2300-3000 ° C. It is possible to provide a method for producing graphite, which includes at least a step of converting to graphite, a step of cooling the graphite, and a step of taking out the cooled graphite from the lower part of the furnace.
本発明の縦型黒鉛化炉によれば、炉内に、少なくとも２つの電極に通電して炭素材料を加熱する通電領域と、炉の外側から炭素材料を加熱する外部熱源領域を備えることで、炭素材料に粉末を用いた場合でも、均一に熱を加えることができるため、均質な黒鉛を得ることが可能となる。具体的には、炉の上部に少なくとも２つの電極を設置して炭素材料を直接通電することによって、炭素材料の温度を急速に上昇させ、炭素材料中にわずかに残存する不純物を脱離させる。このことによって、炉内に不純物由来の硫黄分を含むガスが、炉の内壁および炉を構成する各種部材、例えばシャフト、ヒーター、断熱材等の炭素材（等方性黒鉛）とではなく、原料の炭素材料と反応する。このため、炉およびその内壁、各種部材（シャフト、ヒーター、断熱材）等を等方性黒鉛で構成した場合でも、これら部材が硫黄分を含むガスによって損耗および劣化することが極めて少なく、炉を傷めにくい。さらに、通電領域の後に外部熱源領域を設けることにより、微粉末である炭素材料中に反応の不十分な箇所が生じず、炭素材料の加熱ムラが極めて少なくなることから、所望の黒鉛を得ることができる。 According to the vertical graphitization furnace of the present invention, the furnace includes an energized area for heating the carbon material by energizing at least two electrodes, and an external heat source area for heating the carbon material from the outside of the furnace. Even when powder is used for the carbon material, heat can be applied uniformly, so that homogeneous graphite can be obtained. Specifically, at least two electrodes are installed in the upper part of the furnace, and the carbon material is directly energized, thereby rapidly increasing the temperature of the carbon material and desorbing impurities slightly remaining in the carbon material. As a result, the gas containing sulfur derived from impurities in the furnace is not a raw material, but a carbon material (isotropic graphite) such as a shaft, a heater, a heat insulating material, etc. Reacts with other carbon materials. For this reason, even when the furnace, its inner wall, various members (shaft, heater, heat insulating material), etc. are made of isotropic graphite, these members are very unlikely to be worn and deteriorated by the gas containing sulfur. Hard to hurt. Furthermore, by providing an external heat source region after the energized region, there is no insufficient reaction in the fine carbon material, and the heating unevenness of the carbon material is extremely reduced. Can do.
以下、本発明を実施するための一例である最良の形態を詳細に説明するが、本発明の範囲はこの形態に限定するものではない。 Hereinafter, the best mode which is an example for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to this mode.
本発明は、一実施の形態によれば、連続式の縦型黒鉛化炉に関する。本発明の縦型黒鉛化炉は、上部から投入された炭素材料を加熱して黒鉛化し、得られた黒鉛を下部から取り出す連続式の縦型黒鉛化炉であって、炭素材料を投入するために炉の上部に設けられた投入口と、投入口の下に設けられ、炉の内部および／または内壁に設けられた対向する少なくとも２つの電極であって、電極に通電して炭素材料を加熱する通電領域を形成する少なくとも２つの電極と、通電領域の下で炉の外周部に設けられた熱源であって、炉の外側から炭素材料を加熱する外部熱源領域を形成する熱源と、外部熱源領域の下で炉の外周部に設けられ、生成された黒鉛を冷却する冷却領域を形成する冷却用ジャケットと、冷却領域の下に設けられた黒鉛を取り出す取り出し口とを備えている。 The present invention, according to one embodiment, relates to a continuous vertical graphitization furnace. The vertical graphitization furnace of the present invention is a continuous vertical graphitization furnace in which a carbon material charged from the upper part is heated to be graphitized, and the obtained graphite is taken out from the lower part. And at least two opposing electrodes provided on the inside and / or inner wall of the furnace, and heating the carbon material by energizing the electrodes. At least two electrodes that form an energized region, a heat source provided on the outer periphery of the furnace under the energized region, and forming an external heat source region that heats the carbon material from the outside of the furnace, and an external heat source A cooling jacket provided on the outer periphery of the furnace under the region and forming a cooling region for cooling the generated graphite, and a take-out port for taking out the graphite provided under the cooling region are provided.
図１に、一実施形態の縦型黒鉛化炉２ａを用いる黒鉛製造システム１ａの一例を示す。炭素材料Ｍは、計量フィーダー６から炉２ａの上部に設けられた、ホッパー７を備えた投入口２ａ−１を経て、炉２ａ内に一定量ずつ投入される。炉２ａにおいて、炉２ａの内部および／または内壁に少なくとも２つの電極３ａ−１、３ａ−２を、炭素材料Ｍを介して対向して備え、これらの電極３ａ−１、３ａ−２に通電することにより、炭素材料Ｍを加熱する通電領域を形成する。また、通電領域の下の炉２ａの外周部に、熱源として加熱装置８を備え、炉２ａの外側から炭素材料Ｍを加熱する外部熱源領域を形成する。炭素材料Ｍは、通電領域と外部熱源領域を通過されることにより、黒鉛Ｇに変換される。さらに、外部熱源領域の下の炉２ａの外周部に、冷却用ジャケット１１を備え、生成された黒鉛Ｇを冷却する冷却領域を形成する。冷却された黒鉛Ｇは、冷却領域の下に設けられた取り出し口１２を経て、回収部１３で回収される。 FIG. 1 shows an example of a graphite production system 1a that uses a vertical graphitization furnace 2a according to an embodiment. The carbon material M is charged into the furnace 2a by a certain amount from the weighing feeder 6 through the charging port 2a-1 provided with the hopper 7 provided in the upper part of the furnace 2a. In the furnace 2a, at least two electrodes 3a-1, 3a-2 are provided on the inside and / or inner wall of the furnace 2a so as to face each other through the carbon material M, and the electrodes 3a-1, 3a-2 are energized. Thus, an energization region for heating the carbon material M is formed. In addition, a heating device 8 is provided as a heat source on the outer periphery of the furnace 2a below the energized region, and an external heat source region for heating the carbon material M from the outside of the furnace 2a is formed. The carbon material M is converted into graphite G by passing through the energization region and the external heat source region. Furthermore, a cooling jacket 11 is provided on the outer periphery of the furnace 2a below the external heat source region, and a cooling region for cooling the generated graphite G is formed. The cooled graphite G is recovered by the recovery unit 13 through the takeout port 12 provided below the cooling region.
炉を構成する材料としては、炭素材（好ましくは黒鉛、さらに好ましくは等方性黒鉛）、アルミナ等のセラミックス材、タングステンおよびタンタル等の高融点金属材等が挙げられる。特に、耐熱性が求められることから炭素材（好ましくは黒鉛、さらに好ましくは等方性黒鉛）が好ましく、少なくとも炉の内壁（シャフト炉のシャフトを含む）は、好ましくは等方性黒鉛材料で構成される。
投入口は、炉の上部に設けられており、その上部にテーバー形状のホッパーを設置してもよい。さらに、ホッパーの上に計量フィーダーを設置し、炭素材料を一定量ずつ炉に投入してもよい。投入口から投入された炭素材料は、炉内に十分に充填された状態で加熱され黒鉛に変換される。
Examples of the material constituting the furnace include a carbon material (preferably graphite, more preferably isotropic graphite), a ceramic material such as alumina, and a refractory metal material such as tungsten and tantalum. In particular, a carbon material (preferably graphite, more preferably isotropic graphite) is preferable because heat resistance is required, and at least the inner wall of the furnace (including the shaft of the shaft furnace) is preferably made of an isotropic graphite material. Is done.
The charging port is provided in the upper part of the furnace, and a Taber-shaped hopper may be installed on the upper part. Furthermore, a weighing feeder may be installed on the hopper, and a certain amount of carbon material may be put into the furnace. The carbon material charged from the charging port is heated and converted into graphite while being sufficiently filled in the furnace.
炉は、円筒状の形状、例えば高さ４．５ｍ、内径２０ｃｍの円筒状の形状であってもよく、好ましくは、上方から下方に向けて加熱ゾーンと冷却ゾーンに分かれる。必要に応じて、加熱ゾーンの上に予熱ゾーンを設けることもある。加熱ゾーンは、炉の内部および／または内壁に少なくとも２つの電極を対向させて備え、これらの電極に通電することにより炭素材料を加熱する通電領域と、炉の外周部に熱源を備え、炉の外側から炭素材料を加熱する外部熱源領域を含んでいる。さらに、この２つの領域の後に、１９００〜２１００℃となる中間領域を含んでいてもよい。加熱ゾーンで炭素材料を黒鉛に変換した後に、得られた黒鉛を例えば３０〜２００℃に冷却する冷却領域を冷却ゾーンとして設ける。加熱ゾーンと冷却ゾーンの長さの割合は、好ましくは加熱ゾーンを１とすると、冷却ゾーンは０．２〜０．５である。通電領域と外部熱源領域の長さの割合は、好ましくは通電領域を１とすると、外部熱源領域は２〜１０である。また、この２つの領域の後に、中間領域を含む場合、好ましくは通電領域の長さを１とすると、外部熱源領域は２〜１０であり、中間領域は１〜５である。 The furnace may have a cylindrical shape, for example, a cylindrical shape having a height of 4.5 m and an inner diameter of 20 cm, and is preferably divided into a heating zone and a cooling zone from the top to the bottom. If necessary, a preheating zone may be provided above the heating zone. The heating zone includes at least two electrodes opposed to the interior and / or inner wall of the furnace, and includes an energized region for heating the carbon material by energizing these electrodes, a heat source on the outer periphery of the furnace, An external heat source region for heating the carbon material from the outside is included. Furthermore, you may include the intermediate area | region which becomes 1900-2100 degreeC after these two area | regions. After converting the carbon material to graphite in the heating zone, a cooling region for cooling the obtained graphite to, for example, 30 to 200 ° C. is provided as a cooling zone. The ratio of the length of the heating zone and the cooling zone is preferably 0.2 to 0.5, assuming that the heating zone is 1. The ratio of the length of the energized region and the external heat source region is preferably 2 to 10 for the external heat source region, where the energized region is preferably 1. In addition, when an intermediate region is included after these two regions, preferably the length of the energizing region is 1, the external heat source region is 2 to 10, and the intermediate region is 1 to 5.
炉は、また、炉の上部と下部に、シールガスとして不活性ガス（例えば、窒素、アルゴンまたはヘリウムなど）を流す。不活性ガスの流量は、例えば、上部では２０〜３０Ｌ／分、下部では１〜５Ｌ／分である。 The furnace also allows an inert gas (for example, nitrogen, argon or helium) to flow as a sealing gas through the upper and lower parts of the furnace. The flow rate of the inert gas is, for example, 20 to 30 L / min at the upper part and 1 to 5 L / min at the lower part.
通電領域は、炉の内部および／または内壁に少なくとも２つの電極を備え、これらの電極に通電することによって形成し、炭素材料を加熱する。通電によって、電極間の炭素材料において、炭素材料の持つ固有抵抗に応じたジュール熱が発生し、これにより加熱が行われる。電極への通電は、直流もしくは交流を用いて行ってよい。炭素材料が粉末の場合、一般に熱伝導率が小さく、炭素材料自体が断熱材の機能を果たすため、炭素材料から熱が逃げにくく、その結果、高温に保持することが可能である。 The energization region includes at least two electrodes inside and / or the inner wall of the furnace, and is formed by energizing these electrodes to heat the carbon material. By energization, Joule heat corresponding to the specific resistance of the carbon material is generated in the carbon material between the electrodes, thereby heating the carbon material. The electrodes may be energized using direct current or alternating current. When the carbon material is a powder, the heat conductivity is generally small and the carbon material itself functions as a heat insulating material, so that heat is difficult to escape from the carbon material, and as a result, it can be kept at a high temperature.
通電領域において、炭素材料が１７００〜２３００℃となるように加熱することが好ましい。１７００℃より低いと、硫黄等の不純物が原料の炭素材料から十分には脱離しない。２３００℃より高いと、原料の炭素材料が粉末である場合、加熱するための電力量が多くなりコストが高くなる。また、２３００℃より高いと、温度制御が困難となり、所望の均一な黒鉛を得られない。通電による加熱は、電極間の中央部が最も高温となる。このため、炭素材料を効率的に加熱し得るように、炉内の電極配置を考慮することが好ましい。通電することにより電極間に発現する炭素材料の高温部は、通電に投入する電力を調節することによって、温度および範囲を設定することが可能である。高温部は、２３００℃の最高温度とすることが好ましい。具体的には、電圧を３０〜３０００Ｖ、電流を３０〜３０００Ａで調節することで達成される。この範囲とすることにより、短時間、例えば５分以内、好ましくは３分以内に、高温部を所望の温度まで上昇させることが可能となる。 In the energized region, it is preferable to heat the carbon material so that the temperature becomes 1700 to 2300 ° C. When the temperature is lower than 1700 ° C., impurities such as sulfur are not sufficiently desorbed from the raw carbon material. When the temperature is higher than 2300 ° C., when the raw carbon material is powder, the amount of electric power for heating increases and the cost increases. On the other hand, when the temperature is higher than 2300 ° C., temperature control becomes difficult, and desired uniform graphite cannot be obtained. In the heating by energization, the center part between the electrodes becomes the highest temperature. For this reason, it is preferable to consider the electrode arrangement in the furnace so that the carbon material can be efficiently heated. The temperature and range of the high temperature portion of the carbon material that appears between the electrodes when energized can be set by adjusting the power supplied to the energization. The high temperature part is preferably a maximum temperature of 2300 ° C. Specifically, it is achieved by adjusting the voltage at 30 to 3000 V and the current at 30 to 3000 A. By setting it as this range, it becomes possible to raise a high temperature part to a desired temperature within a short time, for example, within 5 minutes, preferably within 3 minutes.
電極は、少なくとも１対を形成するために、少なくとも２つ用いるものであり、一方は正極、もう一方は負極として使用される。電極の材料としては、炭素材等が挙げられる。電極の形状は、特に限定されるものではなく、円柱状、直方体、板状、若しくは円筒状としてもよく、２つとも同じ形状であっても異なる形状であってもよい。例えば、一方に円柱形状の電極を用いて、他方に板状形状の電極を用いてもよい。電極の大きさは、所望の高温部の範囲を得るのに適した大きさを使用することが好ましく、２つとも同じ大きさでも異なる大きさでもよいが、正極若しくは負極として作用をもたらす電極の面積が同等であることが好ましい。また、電極は、炉内において、炭素材料をより均一に加熱させると同時に、炭素材料を一定量ずつ通過させることが可能となるように、電極の大きさおよび配置を選択することが好ましい。 In order to form at least one pair, at least two electrodes are used, one being used as a positive electrode and the other as a negative electrode. A carbon material etc. are mentioned as a material of an electrode. The shape of the electrode is not particularly limited, and may be a columnar shape, a rectangular parallelepiped shape, a plate shape, or a cylindrical shape, and both may be the same shape or different shapes. For example, a cylindrical electrode may be used on one side and a plate-shaped electrode on the other side. The size of the electrode is preferably a size suitable for obtaining a desired high temperature range, and both of them may be the same size or different sizes. The areas are preferably equal. Moreover, it is preferable that the size and arrangement of the electrodes be selected so that the carbon material can be heated more uniformly in the furnace and at the same time, the carbon material can be passed through a certain amount.
電極の配置の一つの態様としては、炉の内部に少なくとも１対の電極、例えば少なくとも１つの正極と少なくとも１つの負極を対向させて配置する。例えば、外部から電気を伝達させる配線を付した１対の各電極を、炉の内部で、炉に充填した炭素材料を介して、互いに対向させるようにして配置する。この場合、１対の各電極は、炉の内部を上下に延び炉の横断面の中心を通る中心軸から同等の距離を隔てて配置されることが好ましい。この態様において、各電極は、他方の電極および炉と直接接触せず、炭素材料を介している。 As one aspect of the arrangement of the electrodes, at least one pair of electrodes, for example, at least one positive electrode and at least one negative electrode are arranged to face each other inside the furnace. For example, a pair of electrodes provided with wiring for transmitting electricity from the outside are arranged inside the furnace so as to face each other through a carbon material filled in the furnace. In this case, it is preferable that each pair of electrodes is arranged at an equal distance from a central axis that extends vertically inside the furnace and passes through the center of the cross section of the furnace. In this embodiment, each electrode is not in direct contact with the other electrode and the furnace, but via a carbon material.
図２（ａ）、（ｂ）は、外部から電気を伝達させる配線５を付した２つの円柱状の電極、すなわち１対の円柱状電極３ａ−１、３ａ−２を、炉２ａ内に充填した炭素材料Ｍを介して、互いに対向させる配置の例を示す。この場合、２つの電極３ａ−１、３ａ−２は、炉２ａの内部の中心軸から同じ距離を隔てて配置される。図３は、２対（４つ）の円柱状電極３ａ−１、３ａ−２、３ａ−３、３ａ−４を用いる例を示す。また、図４は、２つの楕円断面の円柱状電極３ａ−５、３ａ−６を用いる例を示す。 2 (a) and 2 (b) show that the furnace 2a is filled with two cylindrical electrodes with wiring 5 for transmitting electricity from the outside, that is, a pair of cylindrical electrodes 3a-1, 3a-2. The example of arrangement | positioning which mutually opposes through the carbon material M which did is shown. In this case, the two electrodes 3a-1, 3a-2 are arranged at the same distance from the central axis inside the furnace 2a. FIG. 3 shows an example using two pairs (four) of cylindrical electrodes 3a-1, 3a-2, 3a-3, 3a-4. FIG. 4 shows an example using two elliptical cylindrical electrodes 3a-5 and 3a-6.
別の一態様としては、炉の内壁に少なくとも１対の電極を対向させて配置する。例えば、１対の各電極を、炉内に充填した炭素材料を介して、炉の壁面に予め電極の大きさに合わせてくり貫かれた部分にはめ込み、互いに対向させるようにして配置する。この場合、１対の各電極を結ぶ線の中心が、炉の内部の中心軸に合致または並ぶように、炉を設計することが好ましい。この例において、電極は炉にはめ込まれて用いられるため、炉を通電させないように、炉と電極の間を耐熱性の絶縁物質、例えばセラミック等で覆うことが好ましい。絶縁物質としてセラミックを用いることが好ましく、特に炭化ケイ素が好ましい。セラミックは、一般に、耐熱温度として２０００℃位が限界であるが、この手法による加熱は電極間の中央部が最も高温に加熱される。このため、電極近傍においては放熱がある程度行われればよく、セラミックでも十分に耐熱性を有する。また、静電気を避けるために、必要に応じてアースをとるなどの静電気対策をしてもよい。 As another aspect, at least one pair of electrodes are arranged opposite to the inner wall of the furnace. For example, a pair of electrodes are placed so as to face each other through a carbon material filled in the furnace into a portion of the furnace wall that has been cut in advance according to the size of the electrode. In this case, it is preferable to design the furnace so that the center of the line connecting each pair of electrodes matches or is aligned with the central axis inside the furnace. In this example, since the electrode is inserted into the furnace and used, it is preferable to cover the furnace and the electrode with a heat-resistant insulating material such as ceramic so as not to energize the furnace. Ceramic is preferably used as the insulating material, and silicon carbide is particularly preferable. Ceramics generally have a limit of about 2000 ° C. as a heat-resistant temperature, but heating by this method heats the central part between electrodes to the highest temperature. For this reason, heat should be dissipated to some extent in the vicinity of the electrodes, and even ceramics have sufficient heat resistance. In order to avoid static electricity, countermeasures against static electricity such as grounding may be taken as necessary.
図５（ａ）、（ｂ）は、２つの直方形状の電極３ｂ−１、３ｂ−２を、炉２ｂ内に充填した炭素材料Ｍを介して、炉２ｂの壁面の予め電極の大きさに合わせてくり貫かれた部分にはめ込む配置の例を示す。この場合、電極３ｂ−１と３ｂ−２を結ぶ線の中心は、炉２ｂの内部の中心軸と合致する配置をしている。図６は、２対（４つ）の電極３ｂ−１、３ｂ−２、３ｂ−３、３ｂ−４を、炉２ｃ内に充填した炭素材料Ｍを介して、炉２ｃの壁面の予め電極の大きさに合わせてくり貫かれた部分にはめ込む配置を示す。電極３ｂ−１、３ｂ−２、３ｂ−３、３ｂ−４の１対ごとに結ぶ線の中心が、炉２ｃの内部の中心軸と合致する配置をしている。なお、電極３ｂ−１、３ｂ−２、３ｂ−３、３ｂ−４は、例えば電極３ｂ−１、３ｂ−３が正極の場合、電極３ｂ−２、３ｂ−４は負極である。 5 (a) and 5 (b) show the size of the electrodes in advance on the wall surface of the furnace 2b through the carbon material M in which the two rectangular electrodes 3b-1, 3b-2 are filled in the furnace 2b. The example of arrangement | positioning inserted in the part penetrated together is shown. In this case, the center of the line connecting the electrodes 3b-1 and 3b-2 is arranged to coincide with the central axis inside the furnace 2b. FIG. 6 shows that two pairs (four) of electrodes 3b-1, 3b-2, 3b-3, 3b-4 are preliminarily formed on the wall surface of the furnace 2c via the carbon material M filled in the furnace 2c. An arrangement is shown that fits into the cut-out portion to fit the size. The center of the line connecting each pair of the electrodes 3b-1, 3b-2, 3b-3, 3b-4 is arranged to coincide with the central axis inside the furnace 2c. For example, when the electrodes 3b-1, 3b-2, 3b-3, and 3b-4 are positive electrodes, the electrodes 3b-2 and 3b-4 are negative electrodes.
さらに、別の一態様としては、少なくとも１対の電極の一方が、炉の内壁の一部または全部に配置され、少なくとも１対の電極の他方が、炉の内部の中心軸上に配置される。例えば、外部から電気を伝達させる配線を付した１つの電極を炉の内部の中心軸上に配置し、炉内に充填した炭素材料を介して、対極である他の電極を炉の壁面に予め電極の大きさに合わせてくり貫かれた部分にはめ込むように配置する。この場合、電極は炉の壁面にはめ込んで用いられるため、炉を通電させないように、炉と電極の間を耐熱性の絶縁物質、例えばセラミック等で覆うことが好ましい。別の例としては、外部から電気を伝達させる配線を付した１つの電極を炉の内部の中心軸上に配置し、炉内に充填した炭素材料を介して、炉の内壁に沿って、炉の内壁と接して、若しくは、炉の内壁から内側方向へ一定の距離をおいて配置する。電極が炉の内壁と接する場合、炉を通電させないように、炉と接する電極の面を耐熱性の絶縁物質、例えばセラミック等で覆うことが好ましい。炉の内部の中心軸上に配置される電極は、例えば、炉の内径の１／５〜１／１０の厚さが好ましく、例えば炉の内径の１／５〜１／１０の直径を有する、炉と同心円の円柱状としてもよい。 Furthermore, as another aspect, one of the at least one pair of electrodes is disposed on a part or all of the inner wall of the furnace, and the other of the at least one pair of electrodes is disposed on a central axis inside the furnace. . For example, one electrode with wiring for transmitting electricity from the outside is arranged on the central axis inside the furnace, and the other electrode as a counter electrode is placed on the wall surface of the furnace in advance through a carbon material filled in the furnace. It arrange | positions so that it may fit in the part penetrated according to the magnitude | size of an electrode. In this case, since the electrode is used by being fitted on the wall surface of the furnace, it is preferable to cover the space between the furnace and the electrode with a heat-resistant insulating material such as ceramic so as not to energize the furnace. As another example, one electrode with wiring for transmitting electricity from the outside is arranged on the central axis inside the furnace, and along the inner wall of the furnace through the carbon material filled in the furnace, It is arranged in contact with the inner wall of the furnace or at a certain distance inward from the inner wall of the furnace. When the electrode is in contact with the inner wall of the furnace, the surface of the electrode in contact with the furnace is preferably covered with a heat-resistant insulating material such as ceramic so that the furnace is not energized. The electrode disposed on the central axis inside the furnace preferably has a thickness of 1/5 to 1/10 of the inner diameter of the furnace, for example, has a diameter of 1/5 to 1/10 of the inner diameter of the furnace. A cylindrical shape concentric with the furnace may be used.
さらに、図７（ａ）、（ｂ）は、外部から電気を伝達させる配線５を付した、１対の電極の一方である、１つの電極３ｃ−１を炉２ｂの内部の中心軸上に配置し、炉２ｂ内に充填した炭素材料Ｍを介して、１対の電極の他方である、他の電極３ｂ−１、３ｂ−２を炉２ｂの壁面の予め電極の大きさに合わせてくり貫かれた部分にはめ込む配置の例を示す。図８は、電極３ｃ−１の対極の電極として、炉２ｃの壁面に４つ電極３ｂ−１、３ｂ−２、３ｂ−３、３ｂ−４をはめ込む配置の例を示す。図９は、外部から電気を伝達させる配線５を付した１つの電極３ｃ−１を炉２ａの内部の中心軸上に配置し、炉２ａ内に充填した炭素材料Ｍを介して、炉２ａの内壁に沿って、炉２ａの内径より一回り小さい同心円の円筒形状とした電極３ｃ−２を、炉２ａの内壁から一定の距離をおいて配置する例を示す。電極３ｃ−２は、電極３ｃ−１と対極である。電極３ｃ−２が炉２ａの内壁と接する場合、炉２ａを通電させないように、炉２ａと電極３ｃ−２の間を耐熱性の絶縁物質４、例えばセラミック等で覆うことが好ましい。 Further, FIGS. 7A and 7B show one electrode 3c-1 which is one of a pair of electrodes provided with wiring 5 for transmitting electricity from the outside on the central axis inside the furnace 2b. The other electrode 3b-1, 3b-2, which is the other of the pair of electrodes, is arranged in accordance with the size of the electrode on the wall surface of the furnace 2b through the carbon material M arranged and filled in the furnace 2b. The example of arrangement | positioning inserted in the penetrated part is shown. FIG. 8 shows an example of an arrangement in which four electrodes 3b-1, 3b-2, 3b-3, 3b-4 are fitted to the wall surface of the furnace 2c as counter electrodes of the electrode 3c-1. In FIG. 9, one electrode 3c-1 provided with wiring 5 for transmitting electricity from the outside is arranged on the central axis inside the furnace 2a, and the carbon material M filled in the furnace 2a is used for the furnace 2a. An example in which a concentric cylindrical electrode 3c-2 that is slightly smaller than the inner diameter of the furnace 2a is arranged along the inner wall at a certain distance from the inner wall of the furnace 2a. The electrode 3c-2 is a counter electrode with the electrode 3c-1. When the electrode 3c-2 is in contact with the inner wall of the furnace 2a, it is preferable to cover the space between the furnace 2a and the electrode 3c-2 with a heat-resistant insulating material 4, such as ceramic, so that the furnace 2a is not energized.
外部熱源領域は、炉の外周部に熱源を備え、炉の外側から加熱することによって形成し、炭素材料を加熱する。熱源としては、炭素材（等方性黒鉛）製のヒーター等が挙げられる。これらの熱源によって、炉の外周部から高温に加熱して、炭素材料を加熱することが可能である。また、別の熱源としては、炉の外周部にコイル備え、交流電流をかけて炭素材料を誘導加熱させる。この場合、印加する交流電流は、高周波であってもよい。必要に応じて、コイルである電熱線の外部を、断熱材等によって断熱される。この領域において、炭素材料を２３００〜３０００℃で加熱することが好ましい。２３００℃より低いと、原料の炭素材料の黒鉛化が進まず、リチウムイオン電池の電極材として容量が小さくなる。３０００℃より高いと、リチウムイオン電池の電極材としての特性（初期効率）が低くなってしまう。 The external heat source region includes a heat source on the outer peripheral portion of the furnace and is formed by heating from the outside of the furnace to heat the carbon material. Examples of the heat source include a heater made of carbon material (isotropic graphite). With these heat sources, it is possible to heat the carbon material by heating from the outer periphery of the furnace to a high temperature. As another heat source, a coil is provided on the outer periphery of the furnace, and an alternating current is applied to induce induction heating of the carbon material. In this case, the applied alternating current may be a high frequency. If necessary, the outside of the heating wire that is a coil is insulated by a heat insulating material or the like. In this region, the carbon material is preferably heated at 2300 to 3000 ° C. When the temperature is lower than 2300 ° C., graphitization of the raw material carbon material does not proceed, and the capacity as the electrode material of the lithium ion battery becomes small. When it is higher than 3000 ° C., the characteristics (initial efficiency) as an electrode material of the lithium ion battery are lowered.
炉の加熱ゾーンは、通電領域と外部熱源領域の後に、さらに、炭素材料を１９００〜２１００℃となる中間領域を含んでいてもよい。この領域は、特に加熱されることなく、それまでの工程での加熱による熱量を保持させる。このため、炉の外周部に保温材を取り付けることが好ましい。外部熱源領域で加熱された後の炭素材料を、中間領域を経ずに冷却ゾーンに投入すると、温度勾配が大きくなり炉内でブリッジングを生じ、次の工程へ進まなくなる場合がある。このため、中間領域を設けることにより、炭素材料が粉末の場合でも、外部熱源領域との温度勾配を緩やかにして原料の流れをスムーズとすることができ、より均質な黒鉛を得ることが可能となる。 The heating zone of the furnace may further include an intermediate region where the carbon material is 1900 to 2100 ° C. after the energized region and the external heat source region. This region is not particularly heated, and retains the amount of heat generated by heating in the previous steps. For this reason, it is preferable to attach a heat insulating material to the outer peripheral part of a furnace. When the carbon material heated in the external heat source region is put into the cooling zone without passing through the intermediate region, the temperature gradient becomes large and bridging occurs in the furnace, and it may not proceed to the next step. For this reason, by providing the intermediate region, even when the carbon material is powder, the temperature gradient with the external heat source region can be moderated, the flow of the raw material can be made smooth, and more homogeneous graphite can be obtained. Become.
炉の加熱ゾーンで炭素材料を黒鉛に変換した後に、冷却ゾーンの冷却領域で、得られた黒鉛を例えば３０〜２００℃に冷却する。冷却するために、炉の外周部に冷却ジャケットを取り付ける。また、冷却領域となる炉の部分は、加熱ゾーンと異なり、高温とならないため、加熱ゾーンとなる炉の部分とは別の材料で構成してもよい。 After converting the carbon material into graphite in the heating zone of the furnace, the obtained graphite is cooled to, for example, 30 to 200 ° C. in the cooling region of the cooling zone. A cooling jacket is attached to the outer periphery of the furnace for cooling. In addition, unlike the heating zone, the portion of the furnace that becomes the cooling region does not reach a high temperature, and therefore may be made of a material different from the portion of the furnace that becomes the heating zone.
このようにして得られた黒鉛は、冷却領域の下に設けられた取り出し口を経て、回収部で回収される。回収された黒鉛の取り出し方法は、区切りなく取り出してもよいし、一定の量ずつ取り出してもよい。 The graphite obtained in this way is recovered by the recovery unit through the take-out port provided under the cooling region. The recovered graphite may be taken out without any separation or may be taken out by a certain amount.
図１０に、本発明の一実施態様の縦型黒鉛化炉２ｄを用いる黒鉛製造システム１ｂの一例を示す。炭素材料Ｍは、計量フィーダー６から炉２ｄの上部に設けられた、ホッパー７を備えた投入口２ｄ−１を経て、炉２ｄ内に一定量ずつ投入される。炉２ｄにおいて、炉２ｄの内部および／または内壁に少なくとも２つの電極３ｄ−１、３ｄ−２を、炭素材料Ｍを介して対向するように備え、これらの電極３ｄ−１、３ｄ−２に通電することにより、炭素材料Ｍを加熱する通電領域を形成する。また、通電領域の下の炉２ｄの外周部に熱源として加熱装置８を備え、炉２ｄの外側から炭素材料Ｍを加熱する外部熱源領域を形成する。加えて、外部熱源領域の下の炉２ｄの外周部に保温材１０を備え、１９００〜２１００℃となる中間領域を形成する。炭素材料Ｍは、通電領域、外部熱源領域および中間領域を通過されることにより、黒鉛Ｇに変換される。さらに、この中間領域の下の炉２ｄの外周部に冷却用ジャケット１１を備え、生成された黒鉛Ｇを冷却する冷却領域を形成する。冷却された黒鉛Ｇは、冷却領域の下に設けられた取り出し口１２を経て、回収部１３で回収される。 FIG. 10 shows an example of a graphite production system 1b using the vertical graphitization furnace 2d of one embodiment of the present invention. The carbon material M is charged into the furnace 2d by a certain amount from the weighing feeder 6 through the charging port 2d-1 provided with the hopper 7 provided in the upper part of the furnace 2d. In the furnace 2d, at least two electrodes 3d-1, 3d-2 are provided on the inside and / or inner wall of the furnace 2d so as to face each other through the carbon material M, and the electrodes 3d-1, 3d-2 are energized. By doing so, an energization region for heating the carbon material M is formed. In addition, a heating device 8 is provided as a heat source on the outer periphery of the furnace 2d below the energized region, and an external heat source region for heating the carbon material M from the outside of the furnace 2d is formed. In addition, the heat insulating material 10 is provided on the outer peripheral portion of the furnace 2d below the external heat source region, and an intermediate region of 1900 to 2100 ° C. is formed. The carbon material M is converted into graphite G by passing through the energization region, the external heat source region, and the intermediate region. Furthermore, a cooling jacket 11 is provided on the outer peripheral portion of the furnace 2d below the intermediate region to form a cooling region for cooling the generated graphite G. The cooled graphite G is recovered by the recovery unit 13 through the takeout port 12 provided below the cooling region.
炉２ｄは、また、炉２ｄの加熱ゾーンに、炉２ｄと一定の距離を隔てて断熱材１４を備え、さらに断熱材１４の外周部に冷却ジャケットのシェル１５を設ける構造としてもよい。断熱材は、炭素材（カーボンファイバーの成形材）で構成してもよい。従来の炉においては、原料である炭素材料の加熱時に発生する硫黄を含むガスが、炉の内壁（シャフト）を透過して炉の外周部のヒーターおよび断熱材側に抜け出て、ヒーターおよび断熱材を損耗するため、保温効果および断熱効果が悪くなる場合があった。本発明の炉は、炉の上部で炭素材料を直接通電することにより、硫黄を含むガスが原料の炭素材料と反応するので、炉の内壁を透過することが極めて少なくなる。このため、ヒーターおよび断熱材が損耗されることなく、安定した保温効果および断熱効果を得ることが可能となる。 The furnace 2d may have a structure in which a heat insulating material 14 is provided in a heating zone of the furnace 2d at a certain distance from the furnace 2d, and a shell 15 of a cooling jacket is provided on the outer periphery of the heat insulating material 14. You may comprise a heat insulating material with a carbon material (molding material of carbon fiber). In a conventional furnace, a gas containing sulfur generated when heating a carbon material as a raw material passes through the inner wall (shaft) of the furnace and escapes to the heater and heat insulating material side of the outer periphery of the furnace. In some cases, the heat retaining effect and the heat insulating effect may deteriorate. In the furnace of the present invention, since the gas containing sulfur reacts with the carbon material of the raw material by directly energizing the carbon material at the upper part of the furnace, the permeation of the inner wall of the furnace is extremely reduced. For this reason, it is possible to obtain a stable heat retaining effect and heat insulating effect without damaging the heater and the heat insulating material.
本発明の縦型黒鉛化炉によれば、炉の上部に少なくとも２つの電極を設置して炭素材料を直接通電することによって、炭素材料の温度を急速に上昇させ、炭素材料中にわずかに残存する不純物を脱離させる。さらには、炉内に不純物由来の硫黄分を含むガスがより高温である原料の炭素材料と反応するため、炉およびその内壁、各種部材（シャフト、ヒーター、断熱材）等を等方性黒鉛で構成した場合でも、これら部材が硫黄分を含むガスによって損耗および劣化することが極めて少なく、炉を傷めにくい。さらに、通電領域の後に外部熱源領域を設けることにより、炭素材料中に反応の不十分な箇所が生じず、炭素材料の加熱ムラが極めて少なくなることから、所望の黒鉛を得ることができる。 According to the vertical graphitization furnace of the present invention, the temperature of the carbon material is rapidly increased by placing at least two electrodes on the upper part of the furnace and directly energizing the carbon material, and slightly remains in the carbon material. To remove impurities. Furthermore, since the gas containing sulfur derived from impurities in the furnace reacts with the higher-temperature raw material carbon material, the furnace, its inner wall, various members (shaft, heater, heat insulating material), etc. are made of isotropic graphite. Even when configured, these members are very unlikely to be worn and deteriorated by the gas containing sulfur, and the furnace is hardly damaged. Furthermore, by providing the external heat source region after the energized region, an insufficiently reactive portion does not occur in the carbon material, and the heating unevenness of the carbon material is extremely reduced, so that desired graphite can be obtained.
原料材料である炭素材料は、炭化水素を主とする物質であり、加熱すれば黒鉛化する。具体的には、石油コークス、石油コークスのカルサイン品（カルサインコークス）、石炭コークスおよびピッチなどが挙げられる。好ましくは、原油の処理の際の減圧蒸留油または残油流動接触装置（ＲＦＣＣ）のボトム油などから得た原料油で、特に初留点３００℃以上、アスファルテン成分およびレジン成分の合計含量が２５質量％以下、飽和成分の含量が４０質量％以上の重油と芳香族指数ｆａ０．３以上かつ初留点が１５０℃以上の重油を混合したものをディレードコーキングさせた石油コークスであり、これらは、鱗片状の黒鉛粉を得ることができる。また、この石油コークスのカルサイン品であるカルサインコークス（か焼コークス）も好ましい。このような石油コークスは、石炭コークスや他の炭素源に比べ多くの硫黄が含まれるが、均質で、結晶化に優れ、また、簡単に手に入るなどの点から、リチウムイオン蓄電池の負極材に用いる黒鉛とするのに大変好ましいものである。 The carbon material that is a raw material is a substance mainly composed of hydrocarbons, and graphitizes when heated. Specific examples include petroleum coke, petroleum coke calcine (calcine coke), coal coke and pitch. Preferably, it is a raw material oil obtained from a vacuum distilled oil or a bottom oil of a residual fluidized fluid contact device (RFCC) in the processing of crude oil. It is petroleum coke obtained by delay coking a mixture of heavy oil having a mass content of 40% by mass or less and a heavy oil having an aromatic index fa of 0.3 or more and an initial boiling point of 150 ° C. or more. Scale-like graphite powder can be obtained. Further, calcine coke (calcined coke) which is a calcine product of this petroleum coke is also preferred. Such petroleum coke contains more sulfur than coal coke and other carbon sources, but it is homogeneous, excellent in crystallization, and easily available. It is very preferable for use in graphite.
減圧蒸留油は、原油を常圧蒸留装置にかけて、ガス・軽質油・常圧残油を得た後、この常圧残油を、例えば、１０〜３０Ｔｏｒｒの減圧下、加熱炉出口温度３２０〜３６０℃の範囲で変化させて得られる減圧蒸留装置の蒸留油である。残油流動接触分解装置（ＲＦＣＣ）は、原料油として残油（常圧残油等）を使用し、触媒を使用して分解反応を選択的に行わせ、高オクタン価のＦＣＣガソリンを得る流動床式の流動接触分解する装置である。残油流動接触分解装置のボトム油としては、例えば、常圧残油等の残油をリアクター反応温度（ＲＯＴ）５１０〜５４０℃の範囲で、触媒／油質量比率を６〜８の範囲で変化させて製造したボトム油が挙げられる。ここで、残油流動接触装置（ＲＦＣＣ）の運転条件としては、１例を挙げれば、密度０．９２９３ｇ／ｃｍ３、残留炭素５．５質量％の常圧蒸留残油を反応温度５３０℃、全圧０．２１ＭＰａ、触媒／油比６で流動接触分解し得られる。初留点は、ＪＩＳ Ｋ ２２５４に従って、凝縮管の下端から留出油の最初の１滴が落下したときの温度計の読み（℃）である。 The vacuum distilled oil is obtained by subjecting crude oil to an atmospheric distillation apparatus to obtain gas, light oil, and atmospheric residual oil. Then, the atmospheric residual oil is heated at a furnace outlet temperature of 320 to 360 under a reduced pressure of 10 to 30 Torr, for example. It is a distilled oil of a vacuum distillation apparatus obtained by changing in the range of ° C. The residual oil fluid catalytic cracking unit (RFCC) uses residual oil (normal pressure residual oil, etc.) as a raw material oil and selectively performs a cracking reaction using a catalyst to obtain a high-octane FCC gasoline. Is a fluid catalytic cracking device of the type. As the bottom oil of the residual oil fluid catalytic cracker, for example, the residual oil such as atmospheric residual oil is changed in the reactor reaction temperature (ROT) range of 510 to 540 ° C., and the catalyst / oil mass ratio is changed in the range of 6 to 8. The bottom oil manufactured by letting it be mentioned is mentioned. Here, as an operating condition of the residual oil fluid contact device (RFCC), for example, an atmospheric distillation residual oil having a density of 0.9293 g / cm 3 and a residual carbon of 5.5% by mass is reacted at 530 ° C., Fluid catalytic cracking can be achieved at a total pressure of 0.21 MPa and a catalyst / oil ratio of 6. The initial boiling point is a thermometer reading (° C.) when the first drop of distilled oil falls from the lower end of the condensing tube according to JIS K 2254.
飽和成分、レジン成分およびアスファルテン成分の含有率は、ＴＬＣ−ＦＩＤ法により測定できる。ＴＬＣ−ＦＩＤ法とは、薄層クロマトグラフィー（ＴＬＣ）により試料を飽和成分、アロマ成分、レジン成分およびアスファルテン成分に４分割し、その後、水素炎イオン化検出器（Ｆｌａｍｅ Ｉｏｎｉｚａｔｉｏｎ Ｄｅｔｅｃｔｏｒ：ＦＩＤ）にて各成分を検出し、各成分量の全成分量に対する百分率をもって組成成分値としたものである。まず、試料０．２ｇ±０．０１ｇをトルエン１０ｍｌに溶解して、試料溶液を調整する。予め空焼きしたシリカゲル棒状薄層（クロマロッド）の下端（ロッドホルダーの０．５ｃｍの位置）にマイクロシリンジを用いて１μｌスポットし、ドライヤー等により乾燥させる。次に、このマイクロロッド１０本を１セットとして、展開溶媒にて試料の展開を行う。展開溶媒としては、第１展開槽にヘキサン、第２展開槽にヘキサン／トルエン（体積比２０：８０）、第３展開槽にジクロロメタン／メタノール（体積比９５：５）を使用する。飽和成分については、ヘキサンを溶媒とする第１展開槽にて溶出して展開する。アロマ成分については、第１展開の後、第２展開槽にて溶出して展開する。アスファルテン成分については、第１展開、第２展開の後、ジクロロメタン／メタノールを溶媒とする第３展開槽にて溶出して展開する。展開後のクロマロッドを測定器（例えば、ダイアヤトロン社（現三菱化学ヤトロン社）製の「イアトロスキャンＭＫ−５」(商品名)）にセットし、水素炎イオン化検出器（ＦＩＤ）で各成分量を測定する。各成分量を合計すると全成分量が得られる。 The content rates of the saturated component, the resin component, and the asphaltene component can be measured by the TLC-FID method. In the TLC-FID method, a sample is divided into four components by a thin layer chromatography (TLC) into a saturated component, an aroma component, a resin component, and an asphaltene component. The component is detected, and the percentage of each component amount with respect to the total component amount is used as the composition component value. First, a sample solution is prepared by dissolving 0.2 g ± 0.01 g of a sample in 10 ml of toluene. Use a microsyringe to spot 1 μl at the lower end (0.5 cm position of the rod holder) of a silica gel rod-like thin layer (chroma rod) that has been baked in advance, and dry it with a dryer or the like. Next, 10 microrods are taken as one set, and the sample is developed with a developing solvent. As the developing solvent, hexane is used for the first developing tank, hexane / toluene (volume ratio 20:80) is used for the second developing tank, and dichloromethane / methanol (volume ratio 95: 5) is used for the third developing tank. The saturated component is eluted and developed in the first developing tank using hexane as a solvent. About an aroma component, it elutes and develops in the 2nd development tank after the 1st development. Asphaltene components are developed by elution in a third development tank using dichloromethane / methanol as a solvent after the first development and the second development. The developed chroma rod is set in a measuring instrument (for example, “Iatroscan MK-5” (trade name) manufactured by Diatron (currently Mitsubishi Chemical Yatron)), and each flame ionization detector (FID). Measure the amount of ingredients. The total amount of each component is obtained by summing the amounts of each component.
芳香指数ｆａは、Ｋｎｉｇｈｔ法により求めることができる。Ｋｎｉｇｈｔ法では、炭素の分布を１３Ｃ−ＮＭＲ法による芳香族炭素のスペクトルとして３つの成分（Ａ１，Ａ２，Ａ３）に分割する。ここで、Ａ１は芳香族環内部炭素数、置換されている芳香族炭素と置換されていない芳香族炭素の半分（１３Ｃ−ＮＭＲの約４０〜６０ｐｐｍのピークに相当）、Ａ２は置換していない残りの半分の芳香族炭素（１３Ｃ−ＮＭＲの約６０〜８０ｐｐｍのピークに相当）Ａ３は脂肪族炭素数（１３Ｃ−ＮＭＲの約１３０〜１９０ｐｐｍのピークに相当）であり、これらから、ｆａは
ｆａ＝（Ａ１＋Ａ２）／（Ａ１＋Ａ２＋Ａ３）
により求められる。１３Ｃ−ＮＭＲ法が、ピッチ類の化学構造パラメータの最も基本的な量であるｆａを定量的に求められる最良の方法であることは、文献（「ピッチのキャラクタリゼーション ＩＩ． 化学構造」横野、真田、（炭素、１９８１（Ｎｏ．１０５）、ｐ７３〜８１）に示されている。
The fragrance index fa can be determined by the Knight method. In the Knight method, the distribution of carbon is divided into three components (A1, A2, A3) as an aromatic carbon spectrum by the 13C-NMR method. Here, A1 is the aromatic ring internal carbon number, half of the aromatic carbon that is not substituted with the substituted aromatic carbon (corresponding to a peak of about 40-60 ppm of 13C-NMR), and A2 is not substituted. The remaining half of the aromatic carbon (corresponding to a peak of about 60 to 80 ppm of 13C-NMR) A3 is the number of aliphatic carbon (corresponding to a peak of about 130 to 190 ppm of 13C-NMR), from which fa is expressed as fa = (A1 + A2) / (A1 + A2 + A3)
Is required. The 13C-NMR method is the best method for quantitatively determining fa, which is the most basic amount of chemical structural parameters of pitches, as described in the literature ("Pitch Characterization II. Chemical Structure" Yokono, Sanada (Carbon, 1981 (No. 105), p73-81).
ディレードコーキング法は、加圧条件下、ディレードコーカーによって重質油を熱処理して生コークスを得る方法である。ディレードコーカーの条件として、圧力が０．５〜０．７ＭＰａ、温度が５００〜５３０℃の範囲が好ましい。このディレードコーカープロセスの生コークスは、水分を多量に含むため、乾燥した後、粉砕、分級に供する。 The delayed coking method is a method of obtaining raw coke by heat-treating heavy oil with a delayed coker under pressurized conditions. As conditions for the delayed coker, a pressure is preferably in a range of 0.5 to 0.7 MPa and a temperature in a range of 500 to 530 ° C. The raw coke of this delayed coker process contains a large amount of moisture, so it is dried and then crushed and classified.
原料材料である炭素材料は、黒鉛化炉に導入される前に必要に応じて粉末化される。炭素材料の粉末の平均径は、好ましくは５〜５０μｍとする。５μｍより小さいと、流動性が悪くなり、炉内をスムーズに流れなくなり連続処理が困難となる場合がある。５０μｍより大きいと、リチウムイオン電池電極材としてシートとしたとき十分な薄さが得られなくなる場合がある。平均粒径は、レーザ回折・散乱法を用いて測定できる。粉末化の方法は任意であるが、石油コークスを使用する場合、好ましくは、石油コークスを振動篩等で１ｍｍ〜５ｍｍ程度にし、その後、乾燥させる。一般的には、石油コークスは回収に揮発性の油成分と使用した際の水分とを含むので乾燥が必要であり、水分を好ましくは１質量％以下まで乾燥させるとよい。必要に応じ、好ましくは６００℃程度の温度で１〜２時間加熱し、揮発性の油成分を除去させてもよい。この後、ジェットミル、ボールミル、ハンマーミルなどを使用して粉末にされる。炭素材料が石油コークス、石炭コークス等であれば、このまま黒鉛化することもよいが、そのあとの処理や出来上がる黒鉛粉の性状が良くなるため、一度好ましくは９００〜１５００℃程度の温度でか焼することがよい。かかるか焼はローターリーキルンを用いて行うことが一般的である。 The carbon material as the raw material is pulverized as necessary before being introduced into the graphitization furnace. The average diameter of the carbon material powder is preferably 5 to 50 μm. If it is smaller than 5 μm, the fluidity is deteriorated, and the continuous processing may be difficult because the fluid does not flow smoothly in the furnace. If it is larger than 50 μm, there may be a case where sufficient thickness cannot be obtained when a sheet is used as a lithium ion battery electrode material. The average particle diameter can be measured using a laser diffraction / scattering method. The method of pulverization is arbitrary, but when petroleum coke is used, the petroleum coke is preferably made to about 1 mm to 5 mm with a vibrating sieve or the like and then dried. In general, petroleum coke contains volatile oil components for recovery and moisture when used, and therefore needs to be dried, and the moisture is preferably dried to 1% by mass or less. If necessary, the volatile oil component may be removed by heating at a temperature of preferably about 600 ° C. for 1 to 2 hours. Thereafter, it is made into powder using a jet mill, a ball mill, a hammer mill or the like. If the carbon material is petroleum coke, coal coke, etc., it may be graphitized as it is. However, since the properties of the subsequent processing and the resulting graphite powder are improved, it is preferably calcined at a temperature of about 900 to 1500 ° C. once. It is good to do. Such calcination is generally performed using a rotary kiln.
本発明の別の一実施形態によれば、上記の縦型黒鉛化炉を用いた黒鉛の製造方法である。つまり、炭素材料を、縦型黒鉛化炉に投入する工程と、前記投入された炭素材料を、前記炉の内部および／または内壁に設けられた対向する少なくとも２つの電極で通電して１７００〜２３００℃に加熱する通電領域を通過させる工程と、さらに、前記炉の外周部に設けられた熱源で、２３００〜３０００℃に加熱する外部熱源領域を通過させて黒鉛に変換する工程と、前記黒鉛を冷却する工程と、前記冷却された黒鉛を前記炉の下部から取り出す工程とを少なくとも含む黒鉛の製造方法である。 According to another embodiment of the present invention, a method for producing graphite using the above vertical graphitization furnace. That is, a step of charging the carbon material into the vertical graphitization furnace, and the charged carbon material are energized through at least two opposing electrodes provided on the inside and / or the inner wall of the furnace, 1700 to 2300. A step of passing an energized region heated to ° C., a step of passing through an external heat source region heated to 2300 to 3000 ° C. with a heat source provided at the outer periphery of the furnace, and converting the graphite into a graphite A method for producing graphite, comprising at least a step of cooling and a step of taking out the cooled graphite from the lower part of the furnace.
この方法により、炭素材料に粉末を用いた場合でも、均一に熱を加えることができるため、均質な黒鉛を得ることが可能となる。 By this method, even when powder is used for the carbon material, heat can be applied uniformly, so that homogeneous graphite can be obtained.
以下、実施例および比較例によって本発明を説明するが、本発明は実施例に限定するものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to an Example.
[実施例１〜２および比較例１]
（１）炭素材料の準備
使用した原料である炭素材料は、以下のとおりである。
＜生コークスＡ＞
初留点３３５℃、アスファルテン＋レジン分の含量が２７質量％、飽和分の含量が４３質量％の重油と芳香族指数０．４以上かつ初留点が１６８℃の重油の混合物を平均温度４５０℃でディレードコーキングした生コークスを、振動篩で３ｍｍ以下に篩ったのち、１５０〜２００℃で熱風循環炉を用いて水分が１質量％以下になるまで乾燥させたのち、ローターミルで平均粒径１２μｍの粉末とした。
＜か焼コークスＡ＞（実施例１で使用）
ローターリーキルンを用いて生コークスＡを約１５００℃でか焼して得られたか焼コークスを振動篩等で３ｍｍ以下に篩ったのち、ローターミルで平均粒径１２μｍの粉末とした。
＜生コークスＢ＞
市販の生コークスを、振動篩で３ｍｍ以下に篩ったのち、１５０〜２００℃で熱風循環炉を用いて水分が１質量％以下になるまで乾燥させたのち、ローターミルで平均粒径１２μｍの粉末とした。
＜か焼コークスＢ＞（実施例２、比較例１で使用）
ローターリーキルンを用いて生コークスＢを約１５００℃でか焼して得られたか焼コークスを振動篩等で３ｍｍ以下に篩ったのち、ローターミルで平均粒径１２μｍの粉末とした。
[Examples 1 and 2 and Comparative Example 1]
(1) Preparation of carbon material The carbon material which is the used raw material is as follows.
<Raw coke A>
A mixture of heavy oil having an initial boiling point of 335 ° C., an asphaltene + resin content of 27% by mass and a saturated content of 43% by mass and a heavy oil having an aromatic index of 0.4 or more and an initial boiling point of 168 ° C. has an average temperature of 450 The raw coke that was delayed coked at ℃ was sieved to 3 mm or less with a vibrating sieve, dried at 150 to 200 ℃ using a hot air circulating furnace until the water content became 1 mass% or less, and then averaged with a rotor mill. The powder was 12 μm in diameter.
<Calcined coke A> (used in Example 1)
After calcining coke A obtained by calcining raw coke A at about 1500 ° C. using a rotor kiln to a size of 3 mm or less with a vibrating sieve or the like, it was made into a powder having an average particle size of 12 μm with a rotor mill.
<Raw coke B>
After sieving commercially available coke to 3 mm or less with a vibrating sieve, it was dried at 150 to 200 ° C. using a hot air circulating furnace until the water content became 1% by mass or less, and then an average particle size of 12 μm was obtained with a rotor mill. Powdered.
<Calcined coke B> (used in Example 2 and Comparative Example 1)
After calcining coke B obtained by calcining raw coke B at about 1500 ° C. using a rotary kiln to a size of 3 mm or less with a vibrating sieve or the like, a powder having an average particle size of 12 μm was obtained with a rotor mill.
（２）黒鉛化
得られた炭素材料を、縦型黒鉛化炉を用いて黒鉛に変換させた。黒鉛化炉は、等方性黒鉛製の内壁を備えた高さ６．５ｍ、内径２０ｃｍの円筒形状の炉であり、炉の上部に投入口、炉の下部に取り出し口が設置されている。投入口から炉に投入した炭素材料を、加熱して黒鉛に変換させた。また、加熱ゾーンとなる炉の外周部に一定の距離を隔てて、炭素材（カーボンファイバーの成形材）製の断熱材を備え、さらに断熱材の外周部に水冷ジャケットを設置した。炉の底部から上方１．０ｍの間に冷却ジャケットを設置して、黒鉛に変換した材料を冷却させ、取り出し口を経て回収部で回収した。実質上の黒鉛化時間が７〜１０時間となるようにした。
(2) Graphitization The obtained carbon material was converted into graphite using a vertical graphitization furnace. The graphitization furnace is a cylindrical furnace having an inner wall made of isotropic graphite and having a height of 6.5 m and an inner diameter of 20 cm. An inlet is provided at the upper part of the furnace and an outlet is provided at the lower part of the furnace. The carbon material charged into the furnace from the charging port was heated and converted to graphite. In addition, a heat insulating material made of carbon material (carbon fiber molding material) was provided at a certain distance on the outer peripheral portion of the furnace serving as a heating zone, and a water cooling jacket was installed on the outer peripheral portion of the heat insulating material. A cooling jacket was installed between 1.0 m upward from the bottom of the furnace to cool the material converted to graphite, and the material was recovered at the recovery part via the outlet. The substantial graphitization time was 7-10 hours.
実施例１〜２においては、図１０の縦型黒鉛化炉２ｄのように、加熱ゾーンが３領域に区分された炉を用いる。１つ目の領域は通電領域であり、０．８ｍ長である。炉内に、表面積１００ｃｍ２、厚さ３０ｃｍの板状の２つの電極を対向させて設置した。電極に２７００Ａの電流、３０Ｖの電圧を印加して、炉に充填した炭素材料を介して通電させ、高温部が２２００〜２３００℃となるように加熱した（焼成部）。２つ目の領域は外部熱源領域であり、２．４ｍ長である。通電領域の下の炉（シャフト）の外周部にカーボンヒーターを設置し、これによって炭素材料を２５００〜２６００℃に加熱した（焼成部）。３つ目の領域は中間領域であり、１．６ｍ長となる。外部熱源領域の下の炉の外周部に保温材を設置し、上記の２つの領域で炭素材料に与えた熱を用いて、１９００〜２１００℃とした（焼鈍部もしくは第1冷却部）。なお、通電領域での炉と電極の間は、セラミックで絶縁されており、炉を加熱しないように熱を逃がす構造とした。 In Examples 1 and 2, a furnace in which the heating zone is divided into three regions is used like the vertical graphitization furnace 2d of FIG. The first region is a current-carrying region and is 0.8 m long. In the furnace, two plate-like electrodes having a surface area of 100 cm 2 and a thickness of 30 cm were placed facing each other. A current of 2700 A and a voltage of 30 V were applied to the electrode, and the current was passed through the carbon material filled in the furnace, and the high temperature part was heated to 2200 to 2300 ° C. (baking part). The second area is an external heat source area, which is 2.4 m long. A carbon heater was installed on the outer periphery of the furnace (shaft) under the energized region, and the carbon material was heated to 2500 to 2600 ° C. (baking part). The third area is an intermediate area, which is 1.6 m long. A heat insulating material was installed on the outer peripheral portion of the furnace below the external heat source region, and the heat applied to the carbon material in the above two regions was set to 1900 to 2100 ° C. (annealing portion or first cooling portion). In addition, between the furnace and the electrode in the energized region is insulated with ceramics, and the heat is released so as not to heat the furnace.
比較例１においては、実施例１で用いた炉の通電領域が設置されていない代わりに、外部熱源領域が２．４ｍとなる炉を用いた。外部熱源領域での条件は、実施例と同様にして実施した。この炉は、従来用いられるものと同様の使用である。 In Comparative Example 1, a furnace having an external heat source area of 2.4 m was used in place of the energization area of the furnace used in Example 1 being not installed. The conditions in the external heat source region were the same as in the example. This furnace is used in the same manner as conventionally used.
（３）黒鉛および黒鉛化炉の評価
得られた黒鉛粉末の性状を観察し、その硫黄分を蛍光Ｘ線分析装置を用いて測定した。また、使用した黒鉛化炉の内部を観察して損傷の有無を評価し、および排ガス中の二硫化炭素濃度を、ガスクロマトグラムを用いて測定した。
(3) Evaluation of graphite and graphitization furnace The properties of the obtained graphite powder were observed, and the sulfur content was measured using a fluorescent X-ray analyzer. Further, the inside of the used graphitization furnace was observed to evaluate the presence or absence of damage, and the concentration of carbon disulfide in the exhaust gas was measured using a gas chromatogram.
実施例１〜２で得られた黒鉛粉末は、硫黄分を測定すると、２．０ｐｐｍ以下であった。また、実施例１〜２ともに、炉の排ガス中の二硫化炭素濃度は４６００ｐｐｍであり、黒鉛化炉の内部を確認したところ、損傷は見られず、問題は見いだされなかった。さらに、炉の通電領域の外周部の断熱材の温度上昇は１０℃以下であり、炉上部の損傷は軽微であり、問題は見いだされなかった。 The graphite powder obtained in Examples 1-2 was 2.0 ppm or less when the sulfur content was measured. In both Examples 1 and 2, the concentration of carbon disulfide in the exhaust gas from the furnace was 4600 ppm. When the inside of the graphitization furnace was confirmed, no damage was found and no problem was found. Furthermore, the temperature rise of the heat insulating material at the outer peripheral portion of the energized region of the furnace was 10 ° C. or less, the damage on the upper part of the furnace was slight, and no problem was found.
比較例１で得られた黒鉛粉末は、硫黄分を測定すると、３．０ｐｐｍであった。炉排ガス中の二硫化炭素濃度は４６００ｐｐｍであり、黒鉛化炉の内部を確認したところ、損傷が見られ、実施例で用いた炉の１つ目の領域（通電領域）に相当する位置でえぐれていた。また、実施例で用いた炉の通電領域に相当する位置における炉の外周部の断熱材の温度上昇は＋１００℃以上となった。これは、原料である炭素材料の加熱時に発生する硫黄を含むガスが、炉の内壁（シャフト）を透過して炉の外周部のヒーターおよび断熱材側に抜け出て、ヒーターおよび断熱材を損耗したため、断熱効果が悪くなったと推定する。 The graphite powder obtained in Comparative Example 1 was 3.0 ppm when the sulfur content was measured. The concentration of carbon disulfide in the furnace exhaust gas is 4600 ppm, and when the inside of the graphitization furnace was confirmed, damage was seen and it was removed at a position corresponding to the first area (energized area) of the furnace used in the examples. It was. Moreover, the temperature rise of the heat insulating material of the outer peripheral part of the furnace in the position corresponded to the energization area | region of the furnace used in the Example became +100 degreeC or more. This is because the sulfur-containing gas generated during heating of the carbon material, which is the raw material, permeates the inner wall (shaft) of the furnace and escapes to the heater and heat insulating material on the outer periphery of the furnace, damaging the heater and heat insulating material. It is estimated that the heat insulation effect has deteriorated.
上記結果が示すように、炭素製の従来の黒鉛化炉を用いて、粉末、もしくは微粉末に近い状態で石油コークス等を黒鉛に変換した結果、黒鉛化炉内の壁面（等方性黒鉛製）がえぐれているという状況が発生していた。比較例においては、実施例で用いた黒鉛化炉と異なり、直接通電による加熱を用いないため、脱離した硫黄による損耗が生じ、炉およびその部材（シャフト、ヒーター、断熱材）の損傷が大きくなったと推定する。 As shown in the above results, as a result of converting petroleum coke etc. to graphite in a state close to powder or fine powder using a conventional graphitization furnace made of carbon, the wall surface in the graphitization furnace (made of isotropic graphite) ) Was out of order. In the comparative example, unlike the graphitization furnace used in the examples, since direct heating is not used, wear due to desorbed sulfur occurs, and the furnace and its members (shaft, heater, heat insulating material) are greatly damaged. It is estimated that it became.
１ａ、１ｂ：縦型黒鉛化炉を用いた黒鉛製造システム
２ａ、２ｂ、２ｃ、２ｄ：炉
２ａ−１、２ｄ−１：投入口
３ａ−１、３ａ−２、３ａ−３、３ａ−４、３ａ−５、３ａ−６、３ｂ−１、３ｂ−２、３ｂ−３、３ｂ−４、３ｃ−１、３ｃ−２、３ｄ−１、３ｄ−２：電極
４：絶縁性物質
５：配線
６：計量フィーダー
７：ホッパー
８：加熱装置
１０：保温材
１１：冷却ジャケット
１２：取り出し口
１３：回収部
１４：断熱材
１５：冷却ジャケットシェル
Ｍ：炭素材料
Ｇ：黒鉛
1a, 1b: Graphite production system using a vertical graphitization furnace 2a, 2b, 2c, 2d: Furnace 2a-1, 2d-1: Input port 3a-1, 3a-2, 3a-3, 3a-4, 3a-5, 3a-6, 3b-1, 3b-2, 3b-3, 3b-4, 3c-1, 3c-2, 3d-1, 3d-2: electrode 4: insulating material 5: wiring 6 : Weighing feeder 7: Hopper 8: Heating device 10: Insulating material 11: Cooling jacket 12: Extraction port 13: Collection part 14: Heat insulating material 15: Cooling jacket shell M: Carbon material G: Graphite
Claims (6)
前記炭素材料を投入するために前記炉の上部に設けられた投入口と、
前記投入口の下に設けられ、前記炉の内部および／または内壁に設けられた対向する少なくとも２つの電極であって、前記電極に通電して前記炭素材料を加熱する通電領域を形成する少なくとも２つの電極と、
前記通電領域の下で前記炉の外周部に設けられた熱源であって、前記炉の外側から前記炭素材料を加熱する外部熱源領域を形成する熱源と、
前記外部熱源領域の下で前記炉の外周部に設けられ、生成された黒鉛を冷却する冷却領域を形成する冷却用ジャケットと、
前記冷却領域の下に設けられた前記黒鉛を取り出す取り出し口と
を備える縦型黒鉛化炉。 A continuous vertical graphitization furnace in which a carbon material charged from the upper part is heated and graphitized, and the obtained graphite is taken out from the lower part,
A charging port provided at the top of the furnace for charging the carbon material;
At least two opposing electrodes provided under the charging port and provided on the interior and / or inner wall of the furnace to form an energized region that energizes the electrodes to heat the carbon material. Two electrodes,
A heat source provided on the outer periphery of the furnace under the energized region, the heat source forming an external heat source region for heating the carbon material from the outside of the furnace;
A cooling jacket provided on the outer periphery of the furnace under the external heat source region and forming a cooling region for cooling the generated graphite;
A vertical graphitization furnace comprising a take-out port for taking out the graphite provided under the cooling region.
前記配線を付した１つの電極が、前記炉の内部の中心軸上に設けられ、
前記少なくとも２つの電極が、前記炉の内壁の一部または全部に設けられる請求項１に記載の縦型黒鉛化炉。 As a counter electrode of the at least two electrodes, further comprising one electrode with wiring for transmitting electricity from the outside,
One electrode with the wiring is provided on the central axis inside the furnace,
Wherein said at least two power poles, vertical graphitization furnace according to claim 1 in providing et be part or all of an inner wall of the furnace.
前記投入された炭素材料を、前記炉の内部および／または内壁に設けられた対向する少なくとも２つの電極で通電して１７００〜２３００℃に加熱する通電領域を通過させる工程と、
さらに、前記炉の外周部に設けられた熱源で、２３００〜３０００℃に加熱する外部熱源領域を通過させて黒鉛に変換する工程と、
前記黒鉛を冷却する工程と、
前記冷却された黒鉛を前記炉の下部から取り出す工程と
を少なくとも含む黒鉛の製造方法。 A step of introducing a carbon material into a vertical graphitization furnace;
Passing the charged carbon material through an energized region that is energized and heated to 1700 to 2300 ° C. by energizing at least two opposing electrodes provided on the inside and / or inner wall of the furnace;
Furthermore, with a heat source provided at the outer periphery of the furnace, passing through an external heat source region heated to 2300 to 3000 ° C. and converting to graphite,
Cooling the graphite;
Removing the cooled graphite from the lower part of the furnace.
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| CN108101048A (en) * | 2018-02-09 | 2018-06-01 | 李娟� | High temperature graphitization equipment |
| CN110436451A (en) * | 2018-05-02 | 2019-11-12 | 天津尚能巨源能源科技有限公司 | A kind of synthetic graphite production equipment |
| CN111285364B (en) * | 2018-12-06 | 2022-09-13 | 株洲弗拉德科技有限公司 | Three-dimensional high-temperature continuous heat treatment production system |
| CN110371966A (en) * | 2019-05-09 | 2019-10-25 | 贵阳铝镁设计研究院有限公司 | A kind of carbon raw materials continuous graphitizing furnace construction and method for graphitizing |
| DE102019126394A1 (en) * | 2019-09-30 | 2021-04-01 | Onejoon Gmbh | Process for the production of graphite and vertical graphitization furnace |
| JP2021105493A (en) * | 2019-12-26 | 2021-07-26 | 日本電極株式会社 | Heat treatment device for carbonaceous grain and method therefor |
| CN111675214A (en) * | 2020-06-29 | 2020-09-18 | 中合天成科技发展(北京)有限公司 | Preparation system of palm-based artificial graphite |
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