JPH0269308A - Production of crude pitch coke and isotropic high density carbon material - Google Patents
Production of crude pitch coke and isotropic high density carbon materialInfo
- Publication number
- JPH0269308A JPH0269308A JP63218281A JP21828188A JPH0269308A JP H0269308 A JPH0269308 A JP H0269308A JP 63218281 A JP63218281 A JP 63218281A JP 21828188 A JP21828188 A JP 21828188A JP H0269308 A JPH0269308 A JP H0269308A
- Authority
- JP
- Japan
- Prior art keywords
- coke
- pitch coke
- pitch
- fine
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006253 pitch coke Substances 0.000 title claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 12
- 230000003111 delayed effect Effects 0.000 claims abstract description 11
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 9
- 239000000571 coke Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000006229 carbon black Substances 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000007770 graphite material Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000004898 kneading Methods 0.000 abstract description 4
- 238000005087 graphitization Methods 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011305 binder pitch Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 Na or Ca Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、原子炉用黒鉛材、放電加工用電極材、機械用
軸受は材、治具材等に利用される等方性炭素材料及びそ
れに適した生ピッチコークスの製造法に関するものであ
る０本発明によって製造される生ピッチコークスは組織
が微細であるため高強度の等方性炭素材料を製造する際
の原料として用いることができる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to isotropic carbon materials used in graphite materials for nuclear reactors, electrode materials for electric discharge machining, bearing materials for machinery, jig materials, etc. Since the raw pitch coke produced by the present invention has a fine structure, it can be used as a raw material for producing a high-strength isotropic carbon material.
従来の技術
等方性炭素材料の原料の製造方法は、従来石炭系、石油
系ピッチを室炉或はデイレードコーカーによって生コー
クスとし、更にロータリーキルンによって１４００℃で
焼成して囃焼ピッチコークスとしていた。Conventional technology The method for producing raw materials for isotropic carbon materials has traditionally been to convert coal-based or petroleum-based pitch into green coke in a room furnace or delayed coker, and then to burn it in a rotary kiln at 1,400°C to produce baked pitch coke. .
等方性高密度黒鉛材の製造は、この増焼ピッチコークス
を微粉細した物を骨材として、これにバインダーピッチ
などのバインダーを添加し、混線、再粉砕したのち、成
型、焼成しさらに必要に応じて含浸、再焼成を行い、そ
の後黒鉛化する方法が一般的である（特開昭５１−５０
３１４号、特開昭５２−１０８４１２号）。The production of isotropic high-density graphite material involves using the finely pulverized material of this reheated pitch coke as an aggregate, adding a binder such as binder pitch to it, mixing it, re-pulverizing it, molding it, and firing it. A common method is to impregnate and re-fire according to the conditions, and then graphitize it (Japanese Patent Application Laid-Open No. 51-50
No. 314, JP-A-52-108412).
こめ様に、デイレードコーカーによる連続フィ−ド方式
でピッチを熱処理して得られた生コークスを清規した場
合、得られるピッチコークスは光学的異方性組織が強い
ため、この物を粉砕した場合には針状に破砕されやすい
、このためこれを用いて成型、焼成しても高密度でしか
も強度の強い等方性の炭素材料は得られにくかった。そ
こで、組織を微細化するために、これまでにも種々の方
法が行われている。Similarly, when raw coke obtained by heat-treating pitch using a continuous feeding method using a delayed coker is clarified, the resulting pitch coke has a strong optically anisotropic structure. It is easy to fracture into needle-like shapes, so even if it is used and molded and fired, it is difficult to obtain a high-density, strong, and isotropic carbon material. Therefore, various methods have been used to refine the structure.
例えば、■ピッチにＮｉ、 Ｇｏ、 Ｎｏ等の金属また
はその醜化物を添加して加熱する方法（特開昭５４−９
２５９０号）あるいはＮａ、 Ｃａなどのアルカリ金属
を添加する方法、■ピッチを空気酸化する方法（特開昭
４９−１９３号）等がある。For example, ■ a method of adding metals such as Ni, Go, and No or their ugliness to pitch and heating it (Japanese Patent Laid-Open No. 54-9
2590), a method of adding an alkali metal such as Na or Ca, and (2) a method of air oxidation of pitch (Japanese Patent Application Laid-Open No. 1987-193).
■の方法では、得られたコークス中に添加物が金属不純
物として残るため、さらに高純度化処理する必要がある
ばかりでなく、高純度化時に大気中に飛散するため環境
上好ましくない、■の方法では、高温で長時間空気を吹
き込む必要があるが、このときローカルヒートを起こす
恐れがある等の問題点がある。In method (2), additives remain as metal impurities in the coke obtained, which not only requires further purification treatment, but also scatters into the atmosphere during purification, which is environmentally undesirable. This method requires blowing air at high temperatures for a long period of time, but there are problems such as local heat generation.
また、バインダーを用いないでｒ＆型炭素材料を製造す
る方法も知られている０例えば、ピッチを熱処理する際
に析出してくるメソフェース球晶を抽出して用いるメン
カーボンマイクロビーズ法（特公昭５０−３９６３３号
、特公昭６０−２５３６４号）であるが、この方法では
ピッチを加熱し過ぎるとメンフェース球体が合体するた
め、１０ ｇ ｍ程度のビーズの揃った球晶を得るため
には一回の熱処理で約２０％程度の収率しか挙げること
ができない、さらにこの球晶を分離するため溶剤抽出を
繰り返さなくてはならないため工程が煩雑になり、この
ものを得ようとするとコストも高いものとなる。In addition, there are also known methods for producing R& type carbon materials without using a binder. -39633, Japanese Patent Publication No. 60-25364), but in this method, if the pitch is heated too much, the memphis spheres will coalesce, so in order to obtain spherulites with aligned beads of about 10 gm, it is necessary to heat the pitch once. Only about 20% yield can be achieved by heat treatment.Furthermore, the process is complicated as solvent extraction must be repeated to separate the spherulites, and the cost is high when trying to obtain this product. becomes.
また、炭素微粉を加える従来法（特開昭８２−７２５０
８号、特開昭６２− ＩＥｉ２Ｂ１３号）は、パッチ方
式であったため、熱処理時に添加剤である炭素微粉の分
散状態が悪くなることがあった。このため、コークス組
織を均一にするためには、添加剤の量を１０〜７０重量
部と多くする必要があった。In addition, the conventional method of adding carbon fine powder (Japanese Patent Application Laid-Open No. 82-7250
No. 8, JP-A No. 62-IEi2B13) was a patch method, so the dispersion state of carbon fine powder as an additive sometimes deteriorated during heat treatment. Therefore, in order to make the coke structure uniform, it was necessary to increase the amount of additive to 10 to 70 parts by weight.
発明が解決しようとする課題
上記の問題点に鑑み１本発明は、簡便かつ安価な方法で
不純物の少ない微細組織を有する等方性高密度炭素材料
の原料に適した生ピッチコークスと、前記生ピッチコー
クスを用いた等方性高密度炭素材料の製造方法を提供す
るものである。Problems to be Solved by the Invention In view of the above-mentioned problems, the present invention provides raw pitch coke suitable as a raw material for an isotropic high-density carbon material having a microstructure with few impurities, and The present invention provides a method for producing an isotropic high-density carbon material using pitch coke.
本発明の方法によって製造された炭素材料は、黒鉛化性
が高く、電気比抵抗が低く、切削性のよい黒鉛材料から
硬くて強い黒鉛材料まで各種用途に応じた炭素材料をつ
くり分けることができる。The carbon material produced by the method of the present invention has high graphitizability, low electrical resistivity, and can be used to create carbon materials suitable for various uses, from graphite materials with good machinability to hard and strong graphite materials. .
課題を解決するための手段
本発明は、実質的にキノリン不溶分を含まないコールタ
ールピッチ１００重量部に対し、カーボンブラック、壇
焼ピッチコークス微粉、生ピッチコークス微粉などの炭
素質微粉を１０重量部を越えない範囲で添加して混練し
た後、これを管炉にて４２０〜５００℃に加熱して、デ
ィレードコーカー方式によって等方性炭素材に適した微
細組織を有す゛る生ピッチコークスを製造する事を特徴
とするものである。Means for Solving the Problems The present invention provides 10 parts by weight of carbonaceous fine powder such as carbon black, Danyaki pitch coke fine powder, raw pitch coke fine powder, etc. to 100 parts by weight of coal tar pitch which does not substantially contain quinoline insoluble matter. After adding and kneading the mixture in an amount not exceeding 50%, the mixture is heated in a tube furnace to 420-500°C to produce raw pitch coke with a microstructure suitable for isotropic carbon materials using a delayed coker method. It is characterized by the fact that
また、この生ピッチコークスは揮発分が５〜２５％に制
御されているため、この物を微粉細して成形、焼成して
黒鉛化する場合にはバインダーピッチを必要としない。Moreover, since the volatile content of this raw pitch coke is controlled to 5 to 25%, binder pitch is not required when this material is pulverized, molded, fired, and graphitized.
以下に本発明について詳細に説明する。The present invention will be explained in detail below.
コールタールピッチには、通常キノリン不溶分が２〜３
ｗｔ％含まれているので、これを濾過、遠心分離などの
方法で０．１ｗｔ％以下にし実質的にキノリン不溶分を
含まないコールタールピッチを準備する。Coal tar pitch usually contains 2 to 3 quinoline insolubles.
Since it contains quinoline by weight%, this is reduced to 0.1wt% or less by methods such as filtration and centrifugation to prepare coal tar pitch that does not substantially contain quinoline insoluble matter.
このキノリン不溶分を実質的に含まないピッチをそのま
まデイレードコーカー設備へ連続的に装入し炭素化する
と、この炭素化物は光学的異方性組織の発達した針状コ
ークスが出来る。When this pitch containing substantially no quinoline-insoluble matter is continuously charged as it is into a delayed coker facility and carbonized, the carbonized product forms needle-shaped coke with a developed optically anisotropic structure.
針状コークスは粉砕時に針状に破砕されるため、これを
原料として等方性炭素材料を製造しても高密度の材料は
得られにくい、そこで、この原料となるコールタールピ
ッチ１００重量部に対し、炭素微粉末を１０重量部を越
えない範囲で添加した後、このピッチを４２０℃〜５０
０’Ｃ！に加熱した状態でデイレードコーカーへ連続的
に装入することで微細組織を有する生ピッチコークスを
得ることができる。Since needle coke is crushed into needles during crushing, it is difficult to obtain a high-density material even if an isotropic carbon material is produced using it as a raw material. On the other hand, after adding fine carbon powder in an amount not exceeding 10 parts by weight, the pitch was heated at 420°C to 50°C.
0'C! By continuously charging pitch coke into a delayed coker in a heated state, raw pitch coke having a fine structure can be obtained.
ディレードコーカー方式とは遅延式コークス化のことで
、上述のコールタールピッチをまず蒸留塔に装入して、
ピッチコークスに成り得ないナフタリン成分等の軽質油
分を除去した後、管炉にて４２０〜５００℃に加熱する
。この加熱されたピッチをコークドラムへ２４時間かけ
て連続装入し、コークドラム圧５ｋｇ／ｃｍ２以下の圧
力下で生ピッチコークスとする方式である。本発明によ
る生ピッチコークスは、更にロータリーキルンで１４０
０℃に焼成すると微細組織の嘔焼ピッチコークスとする
事もできる。The delayed coker system refers to delayed coking, in which the coal tar pitch mentioned above is first charged into a distillation column.
After removing light oil components such as naphthalene components that cannot be turned into pitch coke, it is heated to 420 to 500°C in a tube furnace. This heated pitch is continuously charged into a coke drum over a period of 24 hours to produce raw pitch coke under a coke drum pressure of 5 kg/cm2 or less. The raw pitch coke according to the present invention is further produced in a rotary kiln for 140 min.
When calcined at 0°C, it can also be made into sintered pitch coke with a fine structure.
本発明でコールタールピッチに添加する炭素質微す末と
しては、カーボンブラック、黒鉛微粉、生ピッチコーク
ス微粉、壇焼ピッチコークス微粉等の炭素質の物が使用
できる。微粉のサイズとしては、３０ＩＬｍ以下でもモ
ザイク組織となるが組織サイズがやや大きくなるため、
微細組織とするためには望ましくはＩＯＪＬｍ以下がよ
い。As the carbonaceous powder added to the coal tar pitch in the present invention, carbonaceous substances such as carbon black, graphite powder, raw pitch coke powder, and tanyaki pitch coke powder can be used. As for the size of the fine powder, even if it is less than 30 ILm, a mosaic structure will be formed, but the structure size will be slightly larger, so
In order to obtain a fine structure, the thickness is preferably IOJLm or less.
カーボンブラックは、ＨＡＦ 、ＦＥＦ 、 ＧＰＦ
、工ＳＡＦ等のゴム用カーボンブラックや、ＭＣＣ、Ｍ
ＣＦ、ＬＦＦ 、 ＲＣＦ等のカラー用カーボンブラッ
クなどが使用できる。Carbon black is HAF, FEF, GPF
, carbon black for rubber such as SAF, MCC, M
Color carbon blacks such as CF, LFF, and RCF can be used.
コールタールピッチへ添加する炭素質微粉の添加量は、
添加量が増加するにつれてピッチの粘度が増加するため
、連続的にピッチを装入するディレードコーカー方式で
は上限が１０重量部未満、下限については得られるコー
クスの組織制御の面から３重量部が必要である。The amount of carbonaceous fine powder added to coal tar pitch is
The viscosity of pitch increases as the amount added increases, so in a delayed coker system where pitch is continuously charged, the upper limit is less than 10 parts by weight, and the lower limit is 3 parts by weight in order to control the structure of the resulting coke. It is.
また、本発明のディレードコーカー方式に於ける熱処理
温度を、 ４２０℃〜５００℃にコントロールすること
によって得られた生ピッチコークスの揮発分を、５〜２
５ｗｔ％と成るように調製し、バインダーを用いること
なく成型、焼成できるバインダーレス原料の調製が可能
である。なお、生ピッチコークスの揮発分とは、熱天秤
により測定し、室温より１０００℃まで加熱した際の重
量減少で表す。In addition, the volatile content of the raw pitch coke obtained by controlling the heat treatment temperature in the delayed coker system of the present invention at 420°C to 500°C is 5 to 2.
It is possible to prepare a binder-less raw material that can be adjusted to 5 wt% and molded and fired without using a binder. Note that the volatile content of raw pitch coke is measured using a thermobalance and is expressed as the weight loss when heated from room temperature to 1000°C.
この生ピッチコークスを用いて等方性高密度炭素材料を
製造する場合には、生ピッチコークスを所望のサイズに
粉砕した後、成型、焼成、黒鉛化して製品を得ることが
出来る。前述の熱処理温度が４２０℃未満の場合には、
ピッチの炭化が不十分でこの材料粉を用いて成型、焼成
しても発泡変形を起こす、また、熱処理温度が５００℃
を越えたときには得られるコークス中のバインダー成分
が不足するため強度の強い成型体を得ることは困難であ
る。When producing an isotropic high-density carbon material using this raw pitch coke, the product can be obtained by pulverizing the raw pitch coke to a desired size, then molding, firing, and graphitizing. When the aforementioned heat treatment temperature is less than 420°C,
The pitch is not sufficiently carbonized and foaming deformation occurs even when molding and firing using this material powder, and the heat treatment temperature is 500℃.
When it exceeds 20%, it is difficult to obtain a strong molded body because the binder component in the resulting coke is insufficient.
実施例 以下本発明の実施例を示す。Example Examples of the present invention will be shown below.
実施例１
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ３５重量部に対して、カーボンブラック（ＦＥ
Ｆ） ５重量部を加え、アルミ鋳込みヒーター付き二軸
混線装置にて５０℃で、回転速度は３０回転／分で１時
間混練した。この様にして得られた試料１ｋｇを、容量
２ｋｇのミニデイレードコーカー設備にプランジャーポ
ンプを用いて一定量ずつ１０時間かけて連続装入し、
４８０℃で熱処理して揮発分を９％とした生ピッチコー
クスを得た。前記生ピッチコークスを振動ボールミルに
てモ均粒径１３弘ｍに粉砕した。Example 1 Carbon black (FE
F) 5 parts by weight were added and kneaded for 1 hour at 50° C. and a rotational speed of 30 revolutions/minute using a twin-screw mixer equipped with an aluminum casting heater. 1 kg of the sample obtained in this way was continuously charged in fixed amounts over 10 hours into a mini-delayed coker equipment with a capacity of 2 kg using a plunger pump.
A raw pitch coke with a volatile content of 9% was obtained by heat treatment at 480°C. The raw pitch coke was pulverized in a vibrating ball mill to an average particle size of 13 hm.
この試料３０ｇを３０ｍ５φの金型にいれ、５０ｋｇ／
ａｍ２の圧力で仮成型した後、ラバープレスにて２ｊａ
ｎ／ｃ■２の圧力で成型した。これをコークスプリーズ
中に入れ、窒素雰囲気下で、０．０５℃／■ｉｎで１１
００℃まで昇温して焼成した。この後、タンマン炉にて
、！０℃Ｉｓ ｉｎの昇温速度にて２７００℃まで昇温
し、１時間保持して黒鉛化した。この黒鉛化量の物性を
、表−１に示した。30g of this sample was put into a 30m5φ mold, and 50kg/
After temporarily molding with a pressure of am2, 2ja with a rubber press
It was molded at a pressure of n/c 2. This was placed in a coke spray and heated at 0.05℃/■in for 11 hours under a nitrogen atmosphere.
The temperature was raised to 00°C and fired. After this, at the Tanman furnace! The temperature was raised to 2700° C. at a temperature increase rate of 0° C. Is in, and maintained for 1 hour to graphitize. The physical properties of this amount of graphitization are shown in Table-1.
実施例？
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ８５重量部に対して、平均３ｐｍに粉砕した増
焼コークス粉を５重量部加え、アルミ鋳込みヒーター付
き二軸混線装置にて５０℃で、回転速度は３０回転／分
で１時間混練した。この様にして得られた試料１ｋｇを
、容量２ｋｇのミニデイレードコーカー設備に、プラン
ジャーポンプを用いて一定量ずつ１０時間かけて連続装
入し、４８０℃で熱処理して揮発分を９％とした生ピッ
チコークスを得た。前記生ピッチコークスを振動ボール
ミルにて平均粒径１３μｍに粉砕した。Example? To 85 parts by weight of coal tar-based pitch that does not contain quinoline insolubles and has a softening point of 35°C, 5 parts by weight of increased coke powder pulverized to an average particle size of 3 pm was added, and the mixture was heated at 50°C in a twin-shaft mixer equipped with an aluminum casting heater. The mixture was kneaded for 1 hour at a rotational speed of 30 rpm. 1 kg of the sample thus obtained was continuously charged into a mini-delayed coker with a capacity of 2 kg using a plunger pump in fixed amounts over 10 hours, and heat-treated at 480°C to reduce the volatile content to 9%. I got raw pitch coke. The raw pitch coke was pulverized to an average particle size of 13 μm using a vibrating ball mill.
この試料３０ｇを３０■菖φの金型にいれ、５０ｋｇ／
ｃ！１２の圧力で仮載型した後、ラバープレスにて２ｔ
ｏｎ／Ｃｍ２の圧力で成型した。これをコークスプリー
ズ中に入れ、窒素雰囲気下で、０．０５℃／ｓｉｎで１
１００℃まで昇温して焼成した。この後、タンマン類に
て、ｌＯ℃／ｗｉｎの昇温速度にて２７００℃まで昇温
し、１時間保持して黒鉛化した。この黒鉛化品の物性を
表−１に示した。Put 30g of this sample into a mold with a diameter of 30mm and weigh 50kg/
c! After temporary molding with 12 pressure, 2t with rubber press
Molding was carried out at a pressure of on/Cm2. This was placed in a coke spray and heated at 0.05°C/sin for 1 hour under a nitrogen atmosphere.
The temperature was raised to 100°C and fired. Thereafter, the temperature was raised to 2700° C. at a temperature increase rate of 10° C./win using a Tamman, and the temperature was maintained for 1 hour to graphitize. The physical properties of this graphitized product are shown in Table 1.
実施例３
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ９５重量部に対して、カーボンブラック（ＦＥ
Ｆ） ５１ｉ部加え、アルミ鋳込みヒーター付き二軸混
練装置にて５０℃で、回転速度は３０回転／分で１時間
混練した。この様にして得られた試料１ ｋｇを、容量
２ｋｇのミニデイレードコーカー設備にプランジャーポ
ンプを用いて一定量ずつ１０時間かけて連続装入し、４
７０℃で熱処理して揮発分を１０％とした生ピッチコー
クスを得た。前記生ピッチコークスを振動ボールミルに
て平均粒径１１ＪＬｍに粉砕した。Example 3 Carbon black (FE
F) 51i parts were added and kneaded for 1 hour at 50° C. and a rotational speed of 30 rpm in a twin-screw kneading device equipped with an aluminum casting heater. 1 kg of the sample obtained in this way was continuously charged in fixed amounts over 10 hours into a mini-delayed coker equipment with a capacity of 2 kg using a plunger pump.
A raw pitch coke with a volatile content of 10% was obtained by heat treatment at 70°C. The raw pitch coke was pulverized to an average particle size of 11 JLm using a vibrating ball mill.
この試料３０ｇを３０＋ｕ＋φの金型にいれ、５０ｋｇ
／ｃ１１２の圧力で仮載型した後、ラバープレスにて２
ＥＯｎ／Ｃ１１２の圧力で成型した。これをコークスプ
リーズ中に入れ、窒素雰囲気下で、０．０５℃／ｗｉｎ
で１１００℃まで昇温して焼成した。この後、タンマン
類にて、１０℃／ｗｉｎの昇温速度にて２７００℃まで
昇温し、１時間保持して黒鉛化した。この黒鉛化品の物
性を表−１に示した。Put 30g of this sample into a mold of 30+u+φ and weigh 50kg.
After temporarily mounting with a pressure of /c112, press 2 with a rubber press.
It was molded under the pressure of EOn/C112. This was placed in a coke spray and heated at 0.05℃/win under a nitrogen atmosphere.
The temperature was raised to 1100°C and fired. Thereafter, the temperature was raised to 2700° C. at a temperature increase rate of 10° C./win using a Tamman, and the temperature was maintained for 1 hour to graphitize. The physical properties of this graphitized product are shown in Table 1.
実施例４
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ８５重量部に対して、平均３ＪＬｍに粉砕した
令焼コークス粉を５重量部加え、アルミ鋳込みヒーター
付き二軸混線装置にて５０℃で、回転速度は３０回転／
分１時間混練した。この様にして得られた試料１ｋｇを
、容３１２ｋｇのミニデイレードコーカー設備にプラン
ジャーポンプを用いて一定値ずつ１０時間かけて連続装
入し、 ４７０℃で熱処理して揮発分を１０％とした生
ピッチコークスを得た。前記生ピッチコークスを振動ボ
ールミルにて平均粒径１１用ｍに粉砕した。Example 4 To 85 parts by weight of a coal tar-based pitch that does not contain quinoline insolubles and has a softening point of 35°C, 5 parts by weight of freshly baked coke powder crushed to an average of 3 JLm was added, and the mixture was heated in a two-shaft crosstalk device equipped with an aluminum casting heater. At 50℃, the rotation speed is 30 rotations/
The mixture was kneaded for 1 hour. 1 kg of the sample obtained in this way was continuously charged into a 312 kg mini-delayed coker equipment using a plunger pump in constant increments over 10 hours, and heat-treated at 470°C to reduce the volatile content to 10%. Got raw pitch coke. The raw pitch coke was pulverized to an average particle size of 11 m in a vibrating ball mill.
この試料３０ｇを３０■φの金型にいれ、５０ｋｇ／Ｃ
履２の圧力で仮載型した後、ラバープレスにて２ｔｏｎ
／ｃｍ２の圧力で成型した。これをコークスプリーズ中
に入れ、窒素雰囲気下で０．０５℃／ｓｉｎで１１００
°Ｃまで昇温しで焼成した。この後、タンマン類にて１
０℃／ｌｌ１ｎの昇温速度にて２７００℃まで昇温し、
１時間保持して黒鉛化した。この黒鉛化品の物性を表−
１に示した。Put 30g of this sample into a 30mm diameter mold, and 50kg/C
After temporarily mounting with pressure of 2, press 2 tons with rubber press.
It was molded at a pressure of /cm2. This was placed in a coke spray and heated at 1100°C at 0.05°C/sin under a nitrogen atmosphere.
The temperature was raised to °C and fired. After this, 1 in Tamman class
The temperature was raised to 2700°C at a temperature increase rate of 0°C/ll1n,
It was held for 1 hour and graphitized. The physical properties of this graphitized product are shown below.
Shown in 1.
比較例工
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ１ｋｇを、容量２ｋｇのミニデイレードコーカ
ー設備にプランジャーポンプを用いて一定着ずつ１０時
間かけて連続装入し、４８０℃で熱処理して生コークス
を得た。前記生ピッチコークスをマツフル炉に入れてＮ
気流下１１００℃まで焼成し清規コークスを得た。これ
を振動ボールミルにて平均粒径１３μｍに粉砕した。こ
の粉砕コークス１００重量部に対しへインダーピッチ９
０重量部加えニーダ−にて１時間混練した後この混練物
を振動ボールミルにて再粉砕して平均粒径１３ｐｍにし
た。Comparative Example: 1 kg of coal tar-based pitch containing no quinoline-insoluble matter with a softening point of 35°C was continuously charged into a mini-delayed coker with a capacity of 2 kg using a plunger pump in constant portions over 10 hours, and heated to 480°C. Raw coke was obtained by heat treatment. Put the raw pitch coke into the Matsufuru furnace and press N.
Seiki coke was obtained by firing to 1100° C. under an air flow. This was ground to an average particle size of 13 μm using a vibrating ball mill. Inner pitch 9 for 100 parts by weight of this pulverized coke
After adding 0 parts by weight and kneading in a kneader for 1 hour, the kneaded product was re-pulverized in a vibrating ball mill to give an average particle size of 13 pm.
この試料３０ｇを３０ｍｍφの金型にいれ、５０ｋｇ／
ｃ１１２の圧力で仮載型した後、ラバープレスにて２ｔ
ｏｎ／ｃ濡２の圧力で成型した。これをコークスプリー
ズ中に入れ、窒素雰囲気下で０．０５℃／ｗｉｎで１１
００℃まで昇温しで焼成した。この後、タンマン類にて
１０℃／ｗｉｎの昇温速度にて２７００℃まで昇温し、
１時間保持して黒鉛化した。この黒鉛化品の物性を表−
１に併せて示した。Put 30g of this sample into a 30mmφ mold and weigh 50kg/
After temporarily mounting with a pressure of c112, 2t is pressed with a rubber press.
It was molded at a pressure of on/c wet 2. This was placed in a coke spray and heated at 0.05℃/win for 11 hours under a nitrogen atmosphere.
The temperature was raised to 00°C and fired. After this, the temperature was raised to 2700°C at a temperature increase rate of 10°C/win in a Tamman type,
It was held for 1 hour and graphitized. The physical properties of this graphitized product are shown below.
It is also shown in 1.
比較例２
軟化点３５℃のキノリン不溶分を含まないコールタール
系ピッチ１ｋｇを、容量２ｋｇのミニデイレードコーカ
ー設備にプランジャーポンプを用いて一定量ずつ１０時
間かけて連続装入し、４７０℃で熱処理して揮発分を１
０％とした生ピッチコークスを得た。前記生ピッチコー
クスを振動ボールミルにて平均粒径１１鉢ｍに粉砕した
。Comparative Example 2 1 kg of coal tar-based pitch containing no quinoline-insoluble matter with a softening point of 35°C was continuously charged in fixed amounts over 10 hours into a 2 kg capacity mini-delayed coker equipment using a plunger pump, and heated at 470°C. Heat treated to reduce volatile content to 1
Raw pitch coke with a concentration of 0% was obtained. The raw pitch coke was pulverized in a vibrating ball mill to an average particle size of 11 m.
この試料３０ｇを３０■φの金型にいれ、５０ｋｇ／Ｃ
１１２の圧力で仮載型した後、ラバープレスにて２ｔｏ
ｎ／ｃ＋ｓ２の圧力で成型した。これをコークスプリー
ズ中に入れ、窒素雰囲気下で０．０５℃／＋ｓｉｎで１
１００℃まで昇温しで焼成した。この後、タンマン炉に
て１０℃／ｖａ ｉｎの昇温速度にて２７００℃まで昇
温し、１時間保持して黒鉛化した。この黒鉛化量の物性
を表−１に併せて示した。Put 30g of this sample into a 30mm diameter mold, and 50kg/C
After temporarily mounting with a pressure of 112, press 2to with a rubber press.
It was molded at a pressure of n/c+s2. This was placed in a coke drizzle at 0.05°C/+sin under a nitrogen atmosphere.
The temperature was raised to 100°C and fired. Thereafter, the temperature was raised to 2700° C. at a temperature increase rate of 10° C./va in in a Tammann furnace and maintained for 1 hour to graphitize. The physical properties of this amount of graphitization are also shown in Table-1.
表＝１ じであるため、製造工程が簡単である。Table=1 Since they are the same, the manufacturing process is simple.
（２）連続製造設備であるため、微細組織を有するピッ
チコークスを大量で安価に製造できる。(2) Since it is a continuous production facility, pitch coke with a fine structure can be produced in large quantities at low cost.
（３）原料に不純物を含まず、しかも添加するものも炭
素質微粉を使用するため、得られるピッチコークス中に
は不純物が極めて少ないため高純度化処理をしないで済
むか、その処理時間が短くてよい。(3) The raw material does not contain any impurities, and the added material is carbonaceous fine powder, so the resulting pitch coke has very few impurities, so there is no need for high purity treatment, or the treatment time is short. It's fine.
（０木発明の生ピッチコークスを用いて得られる等方性
高密度黒鉛材料は、従来の炭素材料より異方比が小さい
。(The isotropic high-density graphite material obtained using Oki's raw pitch coke has a smaller anisotropic ratio than conventional carbon materials.
Claims (2)
ピッチ１００重量部に対し、炭素質微粉を１０重量部を
越えない範囲で添加して混練した後、これを管炉にて加
熱してコークドラムに連続フィードするディレードコー
カー方式により４２０〜５００℃の温度で生ピッチコー
クスとし、この生ピッチコークスの揮発分が５〜２５％
である事を特徴とする生ピッチコークスの製造方法。(1) Carbonaceous fine powder is added to 100 parts by weight of coal tar pitch, which does not substantially contain quinoline insoluble matter, in an amount not exceeding 10 parts by weight, kneaded, and then heated in a tube furnace to form coke. A delayed coker system that continuously feeds the drum produces raw pitch coke at a temperature of 420 to 500°C, and the volatile content of this raw pitch coke is 5 to 25%.
A method for producing raw pitch coke characterized by the following.
コークスを使いバインダーを用いることなく成形、焼成
して炭化もしくは黒鉛化することを特徴とする等方性高
密度炭素材料の製造方法。(2) A method for producing an isotropic high-density carbon material, characterized in that the raw pitch coke produced by the method according to claim 1 is molded and fired to carbonize or graphitize without using a binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63218281A JPH0269308A (en) | 1988-09-02 | 1988-09-02 | Production of crude pitch coke and isotropic high density carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63218281A JPH0269308A (en) | 1988-09-02 | 1988-09-02 | Production of crude pitch coke and isotropic high density carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0269308A true JPH0269308A (en) | 1990-03-08 |
Family
ID=16717393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63218281A Pending JPH0269308A (en) | 1988-09-02 | 1988-09-02 | Production of crude pitch coke and isotropic high density carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0269308A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7008573B2 (en) | 2000-11-16 | 2006-03-07 | Nippon Steel Chemical Co., Ltd. | Amorphous coke for special carbon material and production process for the same |
| JP2019157073A (en) * | 2018-03-16 | 2019-09-19 | 三菱ケミカル株式会社 | Manufacturing method of caking additive for producing coke |
| US11434428B2 (en) | 2016-01-29 | 2022-09-06 | Tokai Cobex Gmbh | Coke with additives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53142394A (en) * | 1977-05-18 | 1978-12-12 | Nittetsu Kagaku Kogyo Kk | Method of making isotropic carbon material |
| JPS62162613A (en) * | 1986-01-10 | 1987-07-18 | Nippon Steel Corp | Production of isotropic, high-density carbon material |
-
1988
- 1988-09-02 JP JP63218281A patent/JPH0269308A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53142394A (en) * | 1977-05-18 | 1978-12-12 | Nittetsu Kagaku Kogyo Kk | Method of making isotropic carbon material |
| JPS62162613A (en) * | 1986-01-10 | 1987-07-18 | Nippon Steel Corp | Production of isotropic, high-density carbon material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7008573B2 (en) | 2000-11-16 | 2006-03-07 | Nippon Steel Chemical Co., Ltd. | Amorphous coke for special carbon material and production process for the same |
| US11434428B2 (en) | 2016-01-29 | 2022-09-06 | Tokai Cobex Gmbh | Coke with additives |
| JP2019157073A (en) * | 2018-03-16 | 2019-09-19 | 三菱ケミカル株式会社 | Manufacturing method of caking additive for producing coke |
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