JPH03197589A - Manufacture of needle coke - Google Patents
Manufacture of needle cokeInfo
- Publication number
- JPH03197589A JPH03197589A JP33723189A JP33723189A JPH03197589A JP H03197589 A JPH03197589 A JP H03197589A JP 33723189 A JP33723189 A JP 33723189A JP 33723189 A JP33723189 A JP 33723189A JP H03197589 A JPH03197589 A JP H03197589A
- Authority
- JP
- Japan
- Prior art keywords
- coal tar
- tar pitch
- solvent
- pitch
- petroleum
- 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.)
- Granted
Links
- 239000011331 needle coke Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 40
- 239000011280 coal tar Substances 0.000 claims abstract description 36
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000295 fuel oil Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 239000003208 petroleum Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 2
- 208000006558 Dental Calculus Diseases 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 claims 1
- 239000011271 tar pitch Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000001007 puffing effect Effects 0.000 abstract 1
- 239000000571 coke Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000010692 aromatic oil Substances 0.000 description 4
- 239000011295 pitch Substances 0.000 description 4
- 239000011305 binder pitch Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241001385733 Aesculus indica Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Landscapes
- Coke Industry (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ニードルコークスの製造方法に関するもので
ある。さらに詳しくは黒鉛化時の膨張挙動（バッフィン
グ）が低いニードルコークスの製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing needle coke. More specifically, the present invention relates to a method for producing needle coke with low expansion behavior (buffing) during graphitization.
従来ニードルコークスはコールタールもしくはコールタ
ールピッチ又は石油系重質油を原料として製造され、黒
鉛電極の骨材として使用される。Conventionally, needle coke is produced from coal tar, coal tar pitch, or petroleum-based heavy oil, and is used as an aggregate for graphite electrodes.
一般に黒鉛電極は所定の割合に粒度配合したコークス粒
と粉を加熱混合しながらバインダーピッチを適当量添加
ねつ今後押出成形して製造される。In general, graphite electrodes are manufactured by heating and mixing coke grains and powder with particle sizes in a predetermined ratio, adding an appropriate amount of binder pitch, and then extruding the mixture.
この生電極を焼成、黒鉛化後加工して製品である黒鉛電
極を製造している。This raw electrode is fired, graphitized, and then processed to produce a graphite electrode product.
近年電力費の高騰のために原単位の低い電極、すなわち
電力使用量の多い黒鉛化時の電力費を低くする努力がな
されている。Due to the rise in electricity costs in recent years, efforts are being made to create electrodes with low unit consumption, that is, to reduce electricity costs during graphitization, which consumes a large amount of electricity.
その方法として黒鉛化時の昇温速度を早くして黒鉛化時
間を短くする方法がとられているが二ドルコークスは黒
鉛化時に非可逆膨張（バッフィング）をおこし製品が割
れる、嵩密度が低くなる等の３−
問題があるために昇温速度を早くできないのが現状であ
りバッフィングの低いニードルコークスの出現が望まれ
ている。The method used is to shorten the graphitization time by increasing the temperature rise rate during graphitization, but two-dollar coke causes irreversible expansion (buffing) during graphitization, causing the product to crack, and has a low bulk density. At present, it is not possible to increase the temperature increase rate due to 3- problems such as Naru, etc., and the emergence of needle coke with low buffing is desired.
又黒鉛電極の熱膨張係数（ＣＴＥ）の高いものがバッフ
ィングが低いことが知られているが、黒鉛電極は苛酷な
条件（高温雰囲気）で使用されるために耐熱衝撃性のよ
いものすなわち低ＣＴＥのものが望まれている。It is also known that graphite electrodes with a high coefficient of thermal expansion (CTE) have low buffing, but since graphite electrodes are used under harsh conditions (high temperature atmosphere), it is preferable to use graphite electrodes with good thermal shock resistance, that is, low CTE. is desired.
前述のように従来ニードルコークスはコールタール、コ
ールタールピッチ、又は石油系重質油を原料として製造
されていた力飄コールタールもしくはコールタールピッ
チを原料としたものはバッフィングが高いと言われてお
り上記目的を達成するために種々の方法が検討されてい
るが必ずしも十分な成果が得られているとはいい難い。As mentioned above, conventional needle coke was produced using coal tar, coal tar pitch, or petroleum-based heavy oil as a raw material.It is said that buffing is high in needle coke made from coal tar or coal tar pitch. Various methods have been studied to achieve the above objective, but it cannot be said that sufficient results have always been achieved.
黒鉛化時のバッフィングはコークス中に含まれる硫黄、
窒素に起因すると考えられておりそのバッフィングを低
減するためにコークス中の硫黄、窒素を低減する努力が
なされている。Buffing during graphitization consists of sulfur contained in coke,
It is thought that this is caused by nitrogen, and efforts are being made to reduce sulfur and nitrogen in coke in order to reduce buffing.
たとえば特公昭６３−２８４７７号公報には水素化した
コールタール系原料を使用するとバッフィングが減少す
るニードルコークスかえられることが記載されている。For example, Japanese Patent Publication No. 63-28477 describes that the use of hydrogenated coal tar-based raw materials can be used to convert needle coke to reduce buffing.
又特開昭６０−３３２０８、特開昭６０−２０８３９２
号公報では１５００℃以上の高温で石炭系生コークスを
加熱処理して、脱窒素することでバッフィングを低減す
る方法が提案されている。Also, JP-A-60-33208, JP-A-60-208392
The publication proposes a method of reducing buffing by heat treating coal-based raw coke at a high temperature of 1500° C. or higher to denitrify it.
しかしコールタール系原料を水素化したものではコーク
ス歩留が低下するという問題があり水素化したものを熱
処理することによりコークス歩留を向上する努力がなさ
れている。（特開昭６３−１５６８８５号公報）。However, there is a problem in that the coke yield decreases when coal tar-based raw materials are hydrogenated, and efforts are being made to improve the coke yield by heat-treating the hydrogenated raw material. (Japanese Patent Application Laid-open No. 156885/1985).
又特開昭６０−３３２０８号公報や特開昭６０−２０８
３９２号公報の如＜ １５００℃以上の高温で石炭系生
コークスを加熱処理して、脱窒素する方法は高温加熱に
伴うエネルギー原単位が大きくなると共に加熱炉の耐火
物の損耗も大きいという難点があり生コークスを予め酸
化処理等の前処理をした後に通常の 焼温度で 焼する
等の努力がなされている。（特開平１−１１３４８９５
号公報、特公昭６３−１３５４８６号公報）。Also, JP-A No. 60-33208 and JP-A No. 60-208
The method of denitrifying coal-based raw coke by heat treating it at a high temperature of 1500°C or higher, as described in Publication No. 392, has the disadvantage that the energy consumption increases due to high-temperature heating, and the refractories of the heating furnace are subject to large wear and tear. Efforts are being made to pre-treat raw coke, such as oxidation treatment, before baking it at normal baking temperatures. (Unexamined Japanese Patent Publication No. 1-1134895
(Japanese Patent Publication No. 63-135486).
しかし上記方法はいずれも従来方法に比ベニ程が複雑で
あリコストも高くもっと安価にバッフィングを低減する
ことが求められている。However, all of the above methods are much more complex and costly than conventional methods, and there is a need to reduce buffing at a lower cost.
一方、石油系重質油を原料としたものはコークス歩留り
が低く、低ＣＴＥ、低バッフィングのコークスを収率よ
く安価に製造することが望まれていた。On the other hand, those made from petroleum-based heavy oil have a low coke yield, and it has been desired to produce coke with low CTE and low buffing in a high yield and at low cost.
（発明が解決しようとする課題）
そこで本発明者らは上記実情に鑑み低ＣＴＥで低バッフ
ィングとなるコークスを収率よく安価に製造すべく鋭意
努力を重ねた結果特定処理によすＱｉを除去したコール
タールもしくはコールタールピッチと石油系重質油を混
合してニードルコークス原料として使用すると低ＣＴＥ
、低バッフィングとなるニードルコークスが高収率で得
られることを見い出し本発明の完成に至った。(Problems to be Solved by the Invention) In view of the above circumstances, the inventors of the present invention have made extensive efforts to produce coke with low CTE and low buffing at a high yield and at low cost.As a result, the Qi due to specific treatment has been removed. When mixed with coal tar or coal tar pitch and petroleum-based heavy oil and used as a raw material for needle coke, it has a low CTE.
They discovered that needle coke with low buffing can be obtained in high yield, leading to the completion of the present invention.
（課題を解決するための手段）
すなわち、本発明の要旨は、
（１）コールタールもしくはコールタールピッチを原料
としてニードルコークスを製造するに際し、コールター
ル又はキノリン不溶分を含治し、軟化点１００℃以下の
コールタールピッチを、下記に示される溶解度指数が２
０〜８０である溶剤と混合し、得られる混合物を静置分
離し、キノリン不溶分が実質的に除去されたコールター
ルもしくはコールタールピッチを得、このコールタール
もしくはコールタールピッチ９５〜３０重量％と石油系
重質油５〜７０重量％を混合し、この混合物を炭化する
ことを特徴とするニードルコークスの製造方法にある。(Means for Solving the Problems) That is, the gist of the present invention is as follows: (1) When producing needle coke using coal tar or coal tar pitch as a raw material, the coal tar or quinoline insoluble matter is cured, and the softening point is 100°C. The following coal tar pitch has a solubility index of 2 as shown below.
0 to 80, and the resulting mixture is separated by standing to obtain coal tar or coal tar pitch from which quinoline insoluble matter has been substantially removed, and this coal tar or coal tar pitch is 95 to 30% by weight. and 5 to 70% by weight of petroleum-based heavy oil, and the mixture is carbonized.
溶解度指数： 溶剤の沸点（ただし、沸点が８０℃以上
の溶剤では８０℃）におけるコールタールもしくはコー
ルタールピッチ２ｇの溶剤１００ｍｔ’に約する不溶分
量（重量％）。Solubility Index: The amount of insoluble matter (% by weight) in approximately 2 g of coal tar or coal tar pitch per 100 mt' of solvent at the boiling point of the solvent (80°C for solvents with a boiling point of 80°C or higher).
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
まず、本発明において出発原料として用いられるコール
タールとしては、コークス製造時に副生ずる通常のコー
ルタールが挙げられ、一方コールタールピッチとしては
、キノリン不溶分（以下ｒＱｉＪという）を含有し、軟
化点が１００℃以下、好ましくは２０〜１００℃の軟ピ
ツチ又は中ピッチと称されるピッチが挙げられる。First, the coal tar used as a starting material in the present invention includes ordinary coal tar that is produced as a by-product during coke production.On the other hand, coal tar pitch contains quinoline insoluble matter (hereinafter referred to as rQiJ) and has a softening point. Examples include pitches called soft pitches or medium pitches having a temperature of 100°C or less, preferably 20 to 100°C.
−
軟化点が１００℃を超える場合には、アントラセン油等
の芳香族系油の添加等により軟化点を１００℃以下とし
て用いることができる。- When the softening point exceeds 100°C, the softening point can be lowered to 100°C or less by adding an aromatic oil such as anthracene oil.
本発明方法においては、このようなコールタールもしく
はコールタールピッチを下記の溶解度指数が２０〜８０
である溶剤と混合する。In the method of the present invention, such coal tar or coal tar pitch has a solubility index of 20 to 80.
Mix with a solvent.
溶解度指数は、溶剤の沸点（ただし、沸点が８０℃以上
の溶剤では８００Ｃ）におけるコールタールもしくはコ
ールタールピッチ２ｇの溶剤１００ｍｌに対する不溶分
量（重量％）である。The solubility index is the amount of insoluble matter (% by weight) of 2 g of coal tar or coal tar pitch in 100 ml of the solvent at the boiling point of the solvent (800 C for solvents with a boiling point of 80° C. or higher).
上記の溶解度指数が２０〜８０である溶剤としてはシク
ロヘキサン、シクロペンタン等の環状化合物、アセトン
、エーテル等のカルボニル基をもつ化合物、灯油、軽油
等の脂肪族化合物等が利用できる。又これらの化合物と
及びその混合物とナフタリン油等の芳香族系油を混合し
ても可能である。As the above-mentioned solvent having a solubility index of 20 to 80, cyclic compounds such as cyclohexane and cyclopentane, compounds having a carbonyl group such as acetone and ether, and aliphatic compounds such as kerosene and light oil can be used. It is also possible to mix these compounds or mixtures thereof with aromatic oil such as naphthalene oil.
ピッチ：溶剤の重量比として１：２〜１： ０．３、好
適には１：１〜１： ０．４になるように加え混合され
る。The pitch:solvent is added and mixed in a weight ratio of 1:2 to 1:0.3, preferably 1:1 to 1:0.4.
又混合される温度は室温から３５０℃まで可能である８
−
が混合効率から１５０〜３００℃が望ましい。Also, the mixing temperature can range from room temperature to 350°C8.
- is preferably 150 to 300°C in terms of mixing efficiency.
次いで得られる混合物を静置分離しＱｉが実質的に除去
される。The resulting mixture is then separated by standing to substantially remove Qi.
ここでＱｉ含有量は通常０．８ｗｔ％以下、好ましくは
０．３％以下最適には０．１ｗｔ％以下に除去される。Here, the Qi content is usually removed to 0.8 wt% or less, preferably 0.3% or less, and optimally 0.1 wt% or less.
静置分離は室温から３５０℃までの温度が可能であるが
分離効率から１５０〜３００℃が望ましく、又静置時間
は通常数１０分から１０時間程度であるが好ましいのは
３０分〜５時間が望ましい。Static separation can be carried out at temperatures from room temperature to 350°C, but from the standpoint of separation efficiency, a temperature of 150 to 300°C is desirable, and the standing time is usually several tens of minutes to 10 hours, but preferably 30 minutes to 5 hours. desirable.
本発明方法においては、Ｑｉが実質的に除去された上記
の上澄液（改質コールタールもしくはコールタールピッ
チと溶剤よりなる）を得、これを石油系重質油と混合し
て、ニードルコークス製造の原料として用いることがで
きるが、通常上記上澄液を蒸留して、溶剤を除去した後
に、石油系重質油として混合して用いられる。In the method of the present invention, the above supernatant liquid (consisting of modified coal tar or coal tar pitch and solvent) from which Qi has been substantially removed is obtained, and this is mixed with petroleum heavy oil to create needle coke. Although it can be used as a raw material for manufacturing, it is usually used by distilling the supernatant liquid to remove the solvent and then mixing it as petroleum-based heavy oil.
蒸留は、溶剤の沸点、９５容量％の留出温度等で行なわ
れ、留出分は回収され、必要に応じ溶剤として再使用さ
れる。Distillation is carried out at the boiling point of the solvent, a distillation temperature of 95% by volume, etc., and the distillate is recovered and reused as a solvent if necessary.
コールタールもしくはコールタールピッチと混合する石
油系重質油としては、接触分解油、常在もしくは減在残
油、等が挙げられるが、低ＣＴＥを維持し、高コークス
歩留りを達成するために、下記■、■及びｌ又は■の条
件を満たずものから選択するのが好適である。Examples of petroleum-based heavy oil to be mixed with coal tar or coal tar pitch include catalytic cracking oil, existing or reduced residual oil, etc. In order to maintain low CTE and achieve high coke yield, It is preferable to select from those that do not satisfy the following conditions (1), (2), and (1) or (2).
■昇温速度１０℃Ｉ分での球晶発生温度がコールタール
もしくはコールタールピッチより低い。■The spherulite generation temperature at a heating rate of 10°C/min is lower than that of coal tar or coal tar pitch.
■昇温速度１０８Ｃ／分での流動停止温度がコールター
ルもしくはコールタールピッチより高い。■The flow stop temperature at a heating rate of 108C/min is higher than coal tar or coal tar pitch.
■下記キノリン不溶分増加率が１０ｗｔ％以下である。(2) The rate of increase in quinoline insoluble content shown below is 10 wt% or less.
キノリン不溶分増加率；
原料コールタールもしくはコールタールピッチ中のキノ
リン可溶分（ＱＳ）が全還流下４００’Ｃで２時間の熱
処理によりキノリン不溶分（Ｑｉ）に変化した割合を示
し、下記の式で表される。Rate of increase in quinoline insoluble content; Indicates the rate at which the quinoline soluble content (QS) in the raw material coal tar or coal tar pitch was changed to the quinoline insoluble content (Qi) by heat treatment at 400'C for 2 hours under total reflux, and is as follows: Expressed by the formula.
［（熱処理生成物と留出油混合物中のＱｉＸ熱処理生成
物と留出油混合物の歩留り）−原料コールタールもしく
はコールタールピッチ中のＱｉ Ｘ １００（％月ｌ原
料コールター９−
１〇−
ルもしくはコールタールピッチ中のＱＳ混合比率はコー
ルタールピッチ：石油系重質油が９５〜３０ｗｔ％：５
〜７０ｗｔ％、好適には９０〜５０ｗｔ％：１０〜５０
ｗｔ％である。[(Yield of heat treated product and distillate oil mixture) - Qi X 100 (%/month l raw material coal tar or The QS mixing ratio in coal tar pitch is coal tar pitch:petroleum heavy oil is 95-30wt%:5
~70wt%, preferably 90-50wt%: 10-50
It is wt%.
得られる混合原料油は、コークス化挿入原料として、通
常のニードルコークスの製造法によりコークス化される
。すなわち、デイレードコーカーにより生コークスを得
、ついで仮焼して二ドルコークスを得る。The resulting mixed feedstock oil is used as a coking feedstock and is coked by a normal needle coke manufacturing method. That is, raw coke is obtained by a delayed coker, and then calcined to obtain two-dollar coke.
得られるニードルコークスは所定の割合に粒度配合され
加熱混合しながらバインダーピッチを適当量添加ねつ今
後、押出成形して生電極が製造される。The obtained needle coke is blended with particle sizes in a predetermined ratio, and an appropriate amount of binder pitch is added while heating and mixing.Then, a raw electrode is manufactured by extrusion molding.
なお、必要に応じてねつ金時にバッフィングインヒビタ
ーとして酸化鉄を添加することができる。In addition, iron oxide can be added as a buffing inhibitor at the time of bonding, if necessary.
この生電極を焼成、黒鉛化した後、加工して製品である
黒鉛電極を製造することができる。After firing and graphitizing this raw electrode, it can be processed to produce a graphite electrode product.
［実施例］ 以下実施例によりさらに本発明の詳細な説明する。[Example] The present invention will be further explained in detail with reference to Examples below.
実施例１
軟化点４０℃のコールタールピッチと溶解度指数７０の
溶剤（灯油と芳香族系油の混合物）を混合後（混合比１
：０．６）静置分離（温度２５０℃）によりＱｉを除
去した後Ｏ：１を蒸留したコールタールピッチ（Ｑｉ＜
０．１％）と石油系重質油（接触分解油、球晶発生温度
３８０℃１流動停止温度５８０℃，Ｑｉ増加率２％）を
表１に示す割合で混合しデイレードコーカーに導入しコ
ーキングした。（コーキング温度は５００℃１時間は２
４Ｈｒであり圧力は３Ｋｇ／ｃｍ２Ｇ）なお該コールタ
ールピッチの球晶発生温度は４７２Ｃ１流動停止温度は
５５０℃であった。Example 1 After mixing coal tar pitch with a softening point of 40°C and a solvent (mixture of kerosene and aromatic oil) with a solubility index of 70 (mixture ratio 1
:0.6) Coal tar pitch (Qi <
0.1%) and petroleum heavy oil (catalytic cracking oil, spherulite generation temperature 380°C, flow stop temperature 580°C, Qi increase rate 2%) were mixed in the proportions shown in Table 1 and introduced into a delayed coker. I caulked it. (The caulking temperature is 500℃ for 1 hour.
4 hours and the pressure was 3 kg/cm2G) The spherulite generation temperature of the coal tar pitch was 472C1, and the flow stop temperature was 550°C.
コークス歩留りを表１に示す。Table 1 shows the coke yield.
このコークスを１３００℃まで仮焼後、粒度配合してニ
ーダ−で加熱混合しながら酸化鉄をインヒビターとして
添加後バインダーピッチを添加し１時間ねつ今後押出成
形して成形体を製造した。This coke was calcined to 1300° C., the particle size was mixed, iron oxide was added as an inhibitor while heating and mixing in a kneader, binder pitch was added, and the coke was extruded for 1 hour to produce a molded product.
その成形体をコークスゲリーズ中１０００℃まで焼成後
２０００’Ｃまで黒鉛化して製品を得た。The molded body was fired in a coke gully to 1000°C and then graphitized to 2000'C to obtain a product.
そのＣＴＥは表１の通りであった。The CTE was as shown in Table 1.
又１７００〜２０００℃間及び１７００〜２６００’Ｃ
間のノ（・ノフィングは、それぞれ表１に示した。Also between 1700~2000℃ and 1700~2600'C
The ノ(・noffing) in between are shown in Table 1.
比較例としてＱｉを実質的に含まないコールタールピッ
チ１００％又は石油系重質油１００％の場合を示した。As a comparative example, a case using 100% coal tar pitch or 100% petroleum heavy oil, which does not substantially contain Qi, was shown.
なおバッフィングは押出方向に垂直方向の焼成体の１７
００〜２１００℃間の寸法の伸び又は１７００〜２６０
０℃の寸法の伸びを示した。Note that buffing is carried out in the direction perpendicular to the extrusion direction.
Dimensional elongation between 00 and 2100℃ or 1700 and 260
It showed dimensional elongation at 0°C.
表１
１３
１４−
実施例２
軟化点４０℃のコールタールピッチと溶解度指数７０の
溶剤（灯油と芳香族系油の混合物）を混合後（混合比１
：０．６）実施例１に用いたＱｉを除去したコールタ
ールピッチ（Ｑ ｉ ＜ ０．１％）と表２に示す石油
系重質油（接触分解油）を混合（５０： ５０） Ｌオ
ートクレーブで５００°０１２時間圧力３Ｋｇ／Ｃｍ２
Ｇでコーキングした。Table 1 13 14- Example 2 After mixing coal tar pitch with a softening point of 40°C and a solvent (mixture of kerosene and aromatic oil) with a solubility index of 70 (mixture ratio 1
:0.6) Coal tar pitch from which Qi was removed (Qi < 0.1%) used in Example 1 and petroleum heavy oil (catalytic cracking oil) shown in Table 2 were mixed (50:50) L 500°012 hours pressure 3Kg/Cm2 in autoclave
I caulked it with G.
コークス歩留りを表２に示す。Table 2 shows the coke yield.
成形体評価は実施例１と同一方法によった。The molded product was evaluated using the same method as in Example 1.
［発明の効果］
本発明にれば、コールタールもしくはコールタールピッ
チから低ＣＴＥで、かつバッフィングが低いニードルコ
ークスを、歩留りよく得ることができる。[Effects of the Invention] According to the present invention, needle coke with low CTE and low buffing can be obtained from coal tar or coal tar pitch with a high yield.
Claims (4)
としてニードルコークスを製造するに際し、コールター
ル又はキノリン不溶分を含有し、軟化点１００℃以下の
コールタールピッチを、下記に示される溶解度指数が２
０〜８０である溶剤と混合し、得られる混合物を静置分
離し、キノリン不溶分が実質的に除去されたコールター
ルもしくはコールタールピッチを得、このコールタール
もしくはコールタールピッチ９５〜３０重量％と石油系
重質油５〜７０重量％を混合し、この混合物を炭化する
ことを特徴とするニードルコークスの製造方法。 溶解度指数： 溶剤の沸点（ただし、沸点が８０℃以上の溶剤では８０
℃）におけるコールタールもしくはコールタールピッチ
２ｇの溶剤１００ｍｌに対する不溶分量（重量％）。(1) When producing needle coke using coal tar or coal tar pitch as a raw material, coal tar pitch containing coal tar or quinoline insoluble matter and having a softening point of 100°C or less is used as a solubility index of 2 as shown below.
0 to 80, and the resulting mixture is separated by standing to obtain coal tar or coal tar pitch from which quinoline insoluble matter has been substantially removed, and this coal tar or coal tar pitch is 95 to 30% by weight. A method for producing needle coke, which comprises mixing 5 to 70% by weight of petroleum-based heavy oil and carbonizing the mixture. Solubility index: boiling point of the solvent (however, 80°C for solvents with a boiling point of 80°C or higher)
Amount (% by weight) of insoluble matter in 100 ml of solvent of 2 g of coal tar or coal tar pitch at 100 ml of solvent.
生温度がコールタールもしくはコールタールピッチより
低いものから選ばれる請求項１記載の方法。(2) The method according to claim 1, wherein the petroleum-based heavy oil is selected from those whose spherulite generation temperature at a heating rate of 10° C./min is lower than that of coal tar or coal tar pitch.
止温度がコールタールもしくはコールタールピッチより
高いものから選ばれる請求項１記載の方法。(3) The method according to claim 1, wherein the petroleum-based heavy oil is selected from those having a flow stop temperature higher than coal tar or coal tar pitch at a heating rate of 10° C./min.
１０重量％以下であるものから選ばれる請求項１記載の
方法。 キノリン不溶分増加率： 原料コールタールもしくはコールタールピッチ中のキノ
リン可溶分（ＱＳ）が全還流下４００℃で２時間の熱処
理によりキノリン不溶分（Ｑｉ）に変化した割合を示し
、下記の式で表わされる。 ［（熱処理生成物と留出油混合物中のＱｉ×熱処理生成
物と留出油混合物の歩留り）− 原料コールタールもしくはコールタール ピッチ中のＱｉ×１００（％）］／原料コールタールタ
ールピッチ中のＱＳ(4) The method according to claim 1, wherein the petroleum-based heavy oil is selected from the following oils having a quinoline insoluble content increase rate of 10% by weight or less. Rate of increase in quinoline insoluble content: Indicates the rate at which the quinoline soluble content (QS) in the raw material coal tar or coal tar pitch was changed to the quinoline insoluble content (Qi) by heat treatment at 400°C for 2 hours under total reflux, and is expressed by the following formula: It is expressed as [(Qi in heat-treated product and distillate mixture x yield of heat-treated product and distillate mixture) - Qi in raw coal tar or coal tar pitch x 100 (%)]/Qi in raw coal tar tar pitch QS
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33723189A JP2920974B2 (en) | 1989-12-26 | 1989-12-26 | Needle coke manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33723189A JP2920974B2 (en) | 1989-12-26 | 1989-12-26 | Needle coke manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03197589A true JPH03197589A (en) | 1991-08-28 |
| JP2920974B2 JP2920974B2 (en) | 1999-07-19 |
Family
ID=18306679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33723189A Expired - Lifetime JP2920974B2 (en) | 1989-12-26 | 1989-12-26 | Needle coke manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920974B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006269494A (en) * | 2005-03-22 | 2006-10-05 | Nippon Steel Chem Co Ltd | Carbonaceous material for polarized electrode for electric double-layer capacitor, and manufacturing method of polarized electrode |
| CN109370631A (en) * | 2018-10-16 | 2019-02-22 | 陕西煤业化工集团神木天元化工有限公司 | A kind of production method maximally utilizing coal tar production coal-based needle coke |
| JP2020164641A (en) * | 2019-03-29 | 2020-10-08 | 三菱ケミカル株式会社 | Method for producing raw coke |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101757168B1 (en) | 2016-05-18 | 2017-07-13 | 한국화학연구원 | Method of manufacturing cokes for producing carbon molding body from petroleum by-product |
-
1989
- 1989-12-26 JP JP33723189A patent/JP2920974B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006269494A (en) * | 2005-03-22 | 2006-10-05 | Nippon Steel Chem Co Ltd | Carbonaceous material for polarized electrode for electric double-layer capacitor, and manufacturing method of polarized electrode |
| CN109370631A (en) * | 2018-10-16 | 2019-02-22 | 陕西煤业化工集团神木天元化工有限公司 | A kind of production method maximally utilizing coal tar production coal-based needle coke |
| JP2020164641A (en) * | 2019-03-29 | 2020-10-08 | 三菱ケミカル株式会社 | Method for producing raw coke |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2920974B2 (en) | 1999-07-19 |
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