JPS62275010A - Production of impermeable carbon molded body - Google Patents
Production of impermeable carbon molded bodyInfo
- Publication number
- JPS62275010A JPS62275010A JP61116829A JP11682986A JPS62275010A JP S62275010 A JPS62275010 A JP S62275010A JP 61116829 A JP61116829 A JP 61116829A JP 11682986 A JP11682986 A JP 11682986A JP S62275010 A JPS62275010 A JP S62275010A
- Authority
- JP
- Japan
- Prior art keywords
- molded body
- pitch
- mesophase
- molding
- carbon molded
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000465 moulding Methods 0.000 claims abstract description 16
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000000295 fuel oil Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000011280 coal tar Substances 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000003245 coal Substances 0.000 abstract 1
- -1 e.g. Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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、メソフェーズ含有ピッチからなる不透過性炭
素成形体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 an impermeable carbon molded body made of mesophase-containing pitch.
詳しくは、メソフェーズ含有ピッチを原料として、一般
の成形・焼成で不透過性炭素成形体の製造方法に関する
ものである。Specifically, the present invention relates to a method for producing an impermeable carbon molded body by general molding and firing using mesophase-containing pitch as a raw material.
気体及び液体の不透過性にすぐれる炭素材料は、リン酸
型燃料電池のセパレーターをはじめ、電子工業及び化学
工業で巾広い利用が期待されており、その安価な製法が
望まれている。Carbon materials with excellent gas and liquid impermeability are expected to be widely used in electronic and chemical industries, including separators for phosphoric acid fuel cells, and an inexpensive manufacturing method is desired.
従来、不透過性炭素材料としてはガラス状炭素がよく知
られているが、このものはフェノール樹脂等をきわめて
長時間熱処理して製造されるため、非常に高価なものと
なっている。Conventionally, glassy carbon has been well known as an impermeable carbon material, but this material is extremely expensive because it is manufactured by heat-treating phenol resin or the like for an extremely long period of time.
一方、コークス及びピッチ等を成形焼成して得られた成
形体に、ピンチ等を含浸したのち再度焼成して不透過性
の炭素成形体を得る方法も知られている。On the other hand, a method is also known in which a molded body obtained by molding and firing coke, pitch, etc. is impregnated with pinch, etc., and then fired again to obtain an impermeable carbon molded body.
〔発明が解決しようとする問題点］
しかし、この方法では含浸・再焼成の頻繁な工程を要す
ること及び成形体と含浸材の熱収縮率の相違により割れ
が生じる等の欠点を有する。[Problems to be Solved by the Invention] However, this method has drawbacks such as requiring frequent steps of impregnation and re-firing, and cracking due to the difference in thermal shrinkage rate between the compact and the impregnated material.
形・焼成で不透過性炭素成形体を製造する方法を提供す
ることを目的とする。The object of the present invention is to provide a method for producing an impermeable carbon molded body by shaping and firing.
（発明の構成）
即ち、本発明は、キノリン不溶分が８０〜９９％のメソ
フェーズ含有ピンチを粉砕した後、３７０〜４８０℃で
加圧成形し、焼成することを特徴とする不透過性炭素成
形体の製造方法である。(Structure of the Invention) That is, the present invention provides an impermeable carbon molding characterized in that a mesophase-containing pinch having a quinoline insoluble content of 80 to 99% is pulverized, then pressure molded at 370 to 480°C, and fired. It is a method of manufacturing the body.
（発明の詳細な説明）
本発明の方法において、成形原料として用いるのは、キ
ノリン不溶分８０〜９９％のメソフェーズ含有ピッチで
ある。ここに％は重量％を意味する。キノリン不溶分が
８０％に満たない場合は、成形時にピッチの流れ出しが
みられ、満足すべき成形体が得られない。一方、キノリ
ン不溶分が９９％を超える場合は不透過性が不十分とな
る。(Detailed Description of the Invention) In the method of the present invention, pitch containing mesophase with a quinoline insoluble content of 80 to 99% is used as a forming raw material. Here, % means weight %. If the quinoline insoluble content is less than 80%, pitch will flow out during molding, and a satisfactory molded product will not be obtained. On the other hand, if the quinoline insoluble content exceeds 99%, the impermeability will be insufficient.
これらのメソフェーズ含有ピッチは、常法にしたがい、
コールタール、接触分解残渣、ナフサ分解残渣等の石灰
系又は石油系重質油を窒素ガス、炭酸ガス、アルゴン等
の不活性ガス雰囲気下、３５０〜５５０℃で熱処理して
得ることができる。ナフサ分解残渣は、他の重質油に比
して重金属や硫黄などの不純物が少ないので高純度の成
形体を製造するのに適している。その場合、特開昭５８
−１５７４９２号及び１５４７９３号に開示されたよう
に水素処理改質した後熱処理する方法が高強度・高緻密
度の成形体を得るのに適しているが、改質しないものも
勿論用いることができる。These mesophase-containing pitches are prepared according to conventional methods.
It can be obtained by heat-treating lime-based or petroleum-based heavy oils such as coal tar, catalytic cracking residues, and naphtha cracking residues at 350 to 550°C in an atmosphere of an inert gas such as nitrogen gas, carbon dioxide gas, or argon. Naphtha decomposition residue contains fewer impurities such as heavy metals and sulfur than other heavy oils, so it is suitable for producing high-purity molded bodies. In that case, JP-A-58
The method of hydrogen treatment modification followed by heat treatment as disclosed in No. 157492 and No. 154793 is suitable for obtaining a molded article with high strength and high density, but it is of course possible to use a method without modification. .
このようにして得られたメソフェーズ含有ピンチは粉砕
して成形原料とする。粉砕はボールミル等の常法にした
がい、通常２００メツシユ以下に調製される。The mesophase-containing pinches thus obtained are crushed and used as a molding raw material. The powder is pulverized according to a conventional method such as a ball mill, and is usually prepared to a size of 200 mesh or less.
成形は、加熱装置を備えたプレス材を用いて行われる。Molding is performed using a press material equipped with a heating device.
黒鉛型を用いて窒素ガス、炭酸ガス、アルゴン等の不活
性ガス雰囲気で行なうこともできるが、金属金型を用い
て大気中で行っても支障はない。成形原料を型に充填し
たのち、加圧することなく、３７０〜４８０℃好ましく
は４００〜４５０℃の所望の温度に加熱し、その温度で
１０秒ないし１０分間加圧して成形される。３７０℃よ
り低い温度、或いは４８０℃より高い温度で成形した場
合には、不透過性は不十分である。成形圧力は０．２〜
２ｔ／ ｃ＋ａ ”が適当である。Although it is possible to carry out the process using a graphite mold in an atmosphere of an inert gas such as nitrogen gas, carbon dioxide gas, or argon, there is no problem even if the process is performed in the atmosphere using a metal mold. After the molding raw material is filled into a mold, it is heated to a desired temperature of 370 to 480°C, preferably 400 to 450°C, without applying pressure, and molded by applying pressure at that temperature for 10 seconds to 10 minutes. When molded at temperatures lower than 370°C or higher than 480°C, the impermeability is insufficient. Molding pressure is 0.2~
2t/c+a'' is appropriate.
得られた成形体を引続き不活性ガ囲気下約１０００℃ま
で昇温加熱することによって、炭素成形体が得られる。A carbon molded body is obtained by subsequently heating the obtained molded body to about 1000° C. under an inert gas atmosphere.
昇温速度は１０〜ｂ
ある。得られた炭素成形体のガス透過率（室温、窒素、
１気圧差）はｌ Ｑ−’ｃｍ２／３６（未満であり、曲
げ強度は約６００ ｋｇ ／ ｃｍ ”以上である。ま
た、必要に応じて、さらに２０００〜３０００℃まで加
熱し黒鉛質成形体とすることもできる。The temperature increase rate is 10-b. Gas permeability of the obtained carbon compact (room temperature, nitrogen,
1 atmospheric pressure difference) is less than lQ-'cm2/36 (and the bending strength is about 600 kg/cm" or more. If necessary, the graphite molded body is further heated to 2000 to 3000°C. You can also.
本発明によれば、特定の性状のメソフェーズ含有ピッチ
を原料とし、特定の条件で成形することにより、一段の
成形・焼成で不透過性炭素成形体を製造することができ
る。According to the present invention, by using mesophase-containing pitch with specific properties as a raw material and molding it under specific conditions, an impermeable carbon molded body can be produced in one step of molding and firing.
以下、実施例、比較例により本発明の内容を更に具体的
に説明する。Hereinafter, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１
ナフサの熱分解によるエチレン製造時に副生ずる重質油
（エチレンボトム、常圧換算沸点２７０ ’Ｃ以上）
３９７．９ ｇを熱処理反応器に仕込み、反応器底部よ
りアルゴンを毎時７．ＯＲ吹込みながら４８７℃で１５
分熱処理し、メソフェーズ含有ピッチ４２、２ ｇを得
た。本ピッチのキノリン不溶分（ＪＩＳ Ｋ ２４２５
（遠心法））は８６．５％であった。Example 1 Heavy oil (ethylene bottom, normal pressure equivalent boiling point 270'C or more) produced as a by-product during ethylene production by thermal decomposition of naphtha
397.9 g was charged into a heat treatment reactor, and argon was introduced from the bottom of the reactor at 7.5 g per hour. 15 at 487℃ while blowing with OR
A heat treatment was performed to obtain 42.2 g of mesophase-containing pitch. Quinoline insoluble content of this pitch (JIS K 2425
(centrifugation method)) was 86.5%.
本ピッチを平工製作所製ヴアイブレイティングサンプル
ミ／ｌ／ （ＶＩＢＲＡＴＩＮＧ ＳＡＭＰＬＥ Ｍ
ＩＬＬ ） Ｔｌ−１００を用いて５分間粉砕し、成形
原料を得た。This pitch is made by VIBRATING SAMPLE M
It was ground for 5 minutes using ILL) Tl-100 to obtain a molding raw material.
得られた成形原料約１．４ｇを直径３５鶴の黒鉛モール
ドに充填し、不活性雰囲気下に４５０℃まで加熱し、同
温度で０．６５ ｔ ／ ｃｖａ ！の圧力を１分間加
えたのち冷却し、成形体を得た。該成形体を不活性雰囲
気下１５℃／時の昇温速度で１０００℃まで加熱し、直
径３０．０ｍｍ、厚さ１．１鶴の炭素成形体を得た。得
られた炭素成形体のガス透過率（室温、窒素、１気圧差
）は１０−’ｃｍ２／ｓｅｃ未満、曲げ強度は１０６１
ｋｇ／ ｃｍ”であった。Approximately 1.4 g of the obtained molding raw material was filled into a graphite mold with a diameter of 35 mm and heated to 450°C under an inert atmosphere, and at the same temperature it was 0.65 t/cva! After applying pressure for 1 minute, the mixture was cooled to obtain a molded body. The molded body was heated to 1000°C at a temperature increase rate of 15°C/hour under an inert atmosphere to obtain a carbon molded body with a diameter of 30.0 mm and a thickness of 1.1 mm. The gas permeability (room temperature, nitrogen, 1 atm difference) of the obtained carbon molded body was less than 10 cm2/sec, and the bending strength was 1061
kg/cm”.
実施例２
実施例１と同様のピッチ約１．４ｇを直径３５１１のＳ
ＵＳ製モールドに充填し、大気中４５０℃まで加熱し、
同温度で１．３ｔ／ａｍ”の圧力を１分間加えたのち冷
却し、引続き同様に炭化して、直径３０．７龍、厚さｌ
、 Ｑ ＊ｍの炭素成形体を得た。得られた炭素成形体
のガス透過率は１０−’Ｃｌ１１” ／ｓｅｃ未満、曲
げ強度は１２６３ ｋｇ ／ ｃｍ ２であった。Example 2 The same pitch as in Example 1, approximately 1.4 g, was
Filled into a US mold and heated to 450℃ in the atmosphere.
After applying a pressure of 1.3 t/am for 1 minute at the same temperature, it was cooled and then carbonized in the same way.
, Q*m carbon molded body was obtained. The gas permeability of the obtained carbon molded body was less than 10-'Cl11''/sec, and the bending strength was 1263 kg/cm2.
実施例３
実施例１の実験において、エチレンボトムの熱処理温度
を４９７°Ｃとし、他は同様にして炭素成形体を得た。Example 3 In the experiment of Example 1, the heat treatment temperature of the ethylene bottom was changed to 497°C, and a carbon molded body was obtained in the same manner as above.
得られたピンチのキノリン不溶分は９８．５％、炭素成
形体のガス透過率は１０−７０ｍ２／ｓｅｃ未満、曲げ
強度は９６２ ｋｒ／ ｃｍ”であった。The quinoline insoluble content of the obtained pinch was 98.5%, the gas permeability of the carbon molded body was less than 10-70 m2/sec, and the bending strength was 962 kr/cm''.
比較例１
実施例１の実験において、エチレンボトムの熱処理温度
を４６７°Ｃとし、キノリン不溶分７８．４％のピッチ
を得た。本ピッチを同様に粉砕、成形したが、ピンチの
流れ出しのため満足すべき成形体は得られなかった。Comparative Example 1 In the experiment of Example 1, the heat treatment temperature of the ethylene bottom was set to 467°C, and pitch with a quinoline insoluble content of 78.4% was obtained. This pitch was crushed and molded in the same manner, but a satisfactory molded product could not be obtained due to the pinch flowing out.
比較例２
実施例１の実験において、エチレンボトムの熱処理温度
を５０７℃とし、キノリン不溶分９９．９％のピッチを
得た。本ピンチを同様に粉砕、成形、炭化して炭素成形
体を得た。該成形体のガス透過率は５．９ Ｘ １０−
２ｃ＋＋＋”／ｓｅｃ 、曲げ強度は１９５ｋｇ／Ｌ：
ｍ”であった。Comparative Example 2 In the experiment of Example 1, the heat treatment temperature of the ethylene bottom was set at 507° C. to obtain pitch with a quinoline insoluble content of 99.9%. This pinch was similarly crushed, molded, and carbonized to obtain a carbon molded body. The gas permeability of the molded body is 5.9 x 10-
2c+++”/sec, bending strength is 195kg/L:
It was "m".
実施例４〜６、比較例３〜４
実施例１の実験において、成形温度を変化させ、他は同
様にして、炭素成形体を得た。得られた成形体の性状は
第１表の通りであった。Examples 4 to 6, Comparative Examples 3 to 4 Carbon molded bodies were obtained in the same manner as in the experiment of Example 1 except that the molding temperature was changed. The properties of the obtained molded product were as shown in Table 1.
第１表Table 1
Claims (1)
ッチを粉砕した後、３７０〜４８０℃で加圧成形し、焼
成することを特徴とする不透過性炭素成形体の製造方法
。A method for producing an impermeable carbon molded body, which comprises pulverizing mesophase-containing pitch having a quinoline insoluble content of 80 to 99%, followed by pressure molding and firing at 370 to 480°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116829A JPS62275010A (en) | 1986-05-21 | 1986-05-21 | Production of impermeable carbon molded body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116829A JPS62275010A (en) | 1986-05-21 | 1986-05-21 | Production of impermeable carbon molded body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62275010A true JPS62275010A (en) | 1987-11-30 |
Family
ID=14696653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61116829A Pending JPS62275010A (en) | 1986-05-21 | 1986-05-21 | Production of impermeable carbon molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62275010A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2440492A1 (en) * | 2009-06-12 | 2012-04-18 | Graftech International Holdings Inc. | Highly oriented graphite product |
-
1986
- 1986-05-21 JP JP61116829A patent/JPS62275010A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2440492A1 (en) * | 2009-06-12 | 2012-04-18 | Graftech International Holdings Inc. | Highly oriented graphite product |
| EP2440492A4 (en) * | 2009-06-12 | 2013-03-20 | Graftech Int Holdings Inc | Highly oriented graphite product |
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