JPH01133915A - Production of starting material for carbon material - Google Patents
Production of starting material for carbon materialInfo
- Publication number
- JPH01133915A JPH01133915A JP62291626A JP29162687A JPH01133915A JP H01133915 A JPH01133915 A JP H01133915A JP 62291626 A JP62291626 A JP 62291626A JP 29162687 A JP29162687 A JP 29162687A JP H01133915 A JPH01133915 A JP H01133915A
- Authority
- JP
- Japan
- Prior art keywords
- heavy oil
- powder
- mixture
- carbon
- pressure
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 title claims description 29
- 239000007858 starting material Substances 0.000 title abstract 2
- 239000000295 fuel oil Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 230000000802 nitrating effect Effects 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 239000002994 raw material Substances 0.000 claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
- 239000011280 coal tar Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 abstract description 9
- 239000002641 tar oil Substances 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 abstract description 3
- 235000006173 Larrea tridentata Nutrition 0.000 abstract description 3
- 244000073231 Larrea tridentata Species 0.000 abstract description 3
- 229960002126 creosote Drugs 0.000 abstract description 3
- 230000035939 shock Effects 0.000 abstract description 2
- 238000009489 vacuum treatment Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011295 pitch Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000011294 coal tar pitch Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 101150114515 CTBS gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、低電気抵抗性の要求される放電加工用電極や
耐熱衝撃性に優れた高温用黒鉛ルツボ、あるいはＳｉＣ
等の耐酸化性被膜を形成するための炭素基板等種々の品
質の異なる炭素材用途に適応し、かつ、炭素材製造にお
いて、従来のようにバインダーピッチを加えることなく
成形・炭化できる原料を、コールタール等の重質油の主
原料として製造する方法に関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention is applicable to electrical discharge machining electrodes that require low electrical resistance, high-temperature graphite crucibles that have excellent thermal shock resistance, or SiC
We have developed a raw material that is suitable for use in carbon materials of various quality, such as carbon substrates for forming oxidation-resistant films such as This relates to a method for producing heavy oil such as coal tar as a main raw material.
従来、炭素材料の製造は、コークスや黒鉛等の骨材とピ
ンチやフェノール樹脂等のバインダーとを混練したもの
を原料とし、これを成形・炭化した後、さらにピッチ類
の含浸・再炭化をくり返し黒鉛化して品質の向上を図っ
ている。この従来法に対して、バインダーの混練、ピッ
チ含浸、再炭化工程を省略できる原料粉の製造が種々状
みられている。Conventionally, the production of carbon materials uses a mixture of aggregates such as coke and graphite and binders such as pinch and phenol resin as raw materials, which is shaped and carbonized, and then impregnated with pitch and recarbonized repeatedly. We are trying to improve the quality by graphitizing it. In contrast to this conventional method, there are various methods of producing raw material powder that can omit the binder kneading, pitch impregnation, and recarbonization steps.
例えば、（１）特開昭６１−１３６９０６号公報におい
ては、炭素質炭素、黒鉛質炭素、金属化合物等の粉末と
、メソフェーズ含有ピッチに由来する炭素質または黒鉛
質炭素からなる炭素系複合成形体の製造方法が提案され
ており、また、（２）本発明者らも特願昭６２−７６９
８１号において、重質油に炭素質または黒鉛質粉末とニ
トロ化剤を混合した後、３００〜５００℃で減圧下で熱
処理を行い炭素材原料を製造する方法を提案している。For example, (1) JP-A-61-136906 discloses a carbon-based composite molded body made of powders such as carbonaceous carbon, graphitic carbon, and metal compounds, and carbonaceous or graphitic carbon derived from mesophase-containing pitch. (2) The present inventors also filed Japanese Patent Application No. 62-769.
No. 81 proposes a method for producing a carbon material raw material by mixing heavy oil with carbonaceous or graphite powder and a nitrating agent, and then heat-treating the mixture at 300 to 500° C. under reduced pressure.
上記方法（１）、 （２１で得られる炭素材原料は、い
ずれもバインダーを加えずに成形・炭化・黒鉛化を行い
炭素材料を製造できる点では優れているが、炭素質炭素
、黒鉛質炭素等の炭素粉末をメソフェーズ含有ピッチあ
るいはコールタールピッチ等の重質油に混合する際、特
に数１０μｍ以下の微粉の炭素粉末を用いた場合に炭素
粉末が凝集してしまい、均一に分散し難く、均質な炭素
材原料が得られないという問題点がある。The carbon material raw materials obtained by the above methods (1) and (21) are excellent in that they can be molded, carbonized, and graphitized without adding a binder to produce carbon materials, but carbonaceous carbon and graphitic carbon When mixing carbon powder such as mesophase-containing pitch or coal tar pitch with heavy oil, especially when fine carbon powder of several tens of micrometers or less is used, the carbon powder aggregates and is difficult to disperse uniformly. There is a problem that a homogeneous carbon material raw material cannot be obtained.
さらに、上記炭素粉末が凝集するということは、炭素粉
末の持つ気孔・隙間にコールタールピンチ等の重質油の
浸透が充分に行われないことになりこの点でも問題であ
る。Furthermore, when the carbon powder agglomerates, heavy oil such as coal tar pinch cannot sufficiently penetrate into the pores and gaps of the carbon powder, which is also a problem.
そこで、本発明では、これらの問題点を解決するため、
品質が安定で、かつ高強度で電気比抵抗、熱膨張係数（
以下ＣＴＥと略記する）の異なる炭素材が得られ、広い
範囲の用途に適用できる原料を提供することを主目的と
する。Therefore, in the present invention, in order to solve these problems,
Stable quality, high strength, electrical resistivity, thermal expansion coefficient (
The main objective is to provide a raw material that can obtain carbon materials with different CTE (hereinafter abbreviated as CTE) and that can be applied to a wide range of applications.
本発明者らは、炭素材品質の制御幅を拡大するため、コ
ールタールに対しニトロ化剤の添加率の増加により炭素
材の電気抵抗、ＣＴＥが高くなることに対処するために
、低電気抵抗、低ＣＴ Ｅをもつ人造黒鉛または天然黒
鉛の混合について検討したところ、単にこれらの黒鉛粉
を添加しても、物性の改善が充分でないことが判明した
。In order to expand the control range of carbon material quality, the present inventors developed a method to reduce the electrical resistance in order to cope with the fact that the electrical resistance and CTE of the carbon material increase due to an increase in the addition rate of a nitrating agent to coal tar. , a study on mixing artificial graphite or natural graphite with low CTE revealed that simply adding these graphite powders did not sufficiently improve the physical properties.
この原因は、前述したように、コールタールピッチ等の
重質油に混合する炭素質または黒鉛質の粉末が凝集し、
均一分散せず、均質な炭素材原料が得られないためであ
る。また、炭素粉末の凝集により炭素粉末の持つ気孔・
隙間にコールタールピッチ等の重質油の浸透が充分行わ
れないという問題もある。As mentioned above, the cause of this is the agglomeration of carbonaceous or graphite powder mixed with heavy oil such as coal tar pitch.
This is because it is not uniformly dispersed and a homogeneous carbon material raw material cannot be obtained. In addition, due to the agglomeration of carbon powder, the pores and
There is also the problem that heavy oil such as coal tar pitch does not penetrate sufficiently into the gaps.
しかし、コールタールピッチ等の重質油に炭素粉末を混
合する際、重質油をよく溶かす溶剤、例えばコールター
ルのタール油分（クレオソート油ともいう）で炭素質粉
末を事前に分散しペースト状にしたものを重質油に混合
する方法を用い、また、減圧蒸留の際に減圧から常圧に
戻す操作を１回以上繰り返すことにより、混合する炭素
質粉末の凝集が完全になくなり、均質な炭素材原料が得
られ、炭素材物性を改善できることが判った。However, when mixing carbon powder with heavy oil such as coal tar pitch, the carbonaceous powder is dispersed in advance in a solvent that dissolves the heavy oil well, such as the tar oil component of coal tar (also called creosote oil). By mixing the carbonaceous powder with heavy oil, and by repeating the operation from reduced pressure to normal pressure at least once during vacuum distillation, the agglomeration of the carbonaceous powder to be mixed is completely eliminated, resulting in a homogeneous product. It was found that a carbon material raw material was obtained and the physical properties of the carbon material could be improved.
すなわち、本第１発明は、重質油と炭素質または黒鉛質
粉末とニトロ化剤とを混合し、加熱および減圧処理する
ことにより炭素材用原料を製造する方法であって、上記
混合物を非酸化性雰囲気下で撹拌しなから３００１ｎＨ
ｇ以下の減圧下で最高４００℃まで加熱した後、常圧ま
で戻し再び減圧する操作を１回以上行い、最後に３００
ｍｍＨｇ以下の減圧下で５００℃まで加熱することを特
徴とするものであり、また本第２発明は、重質油を溶か
す溶剤と炭素質または黒鉛質粉末と、重質油と、ニトロ
化剤とを混合し、加熱および減圧処理することにより炭
素材用原料を製造する方法であって、上記混合物を非酸
化性雰囲気下で撹拌しながら３００ ｍＨｇ以下の減圧
下で最高４００℃まで加熱した後、常圧まで戻し再び減
圧する操作を１回以上行い、最後に３００ ｍＨｇ以下
の減圧下で５００℃まで加熱することを特徴とするもの
である。That is, the first invention is a method for producing a raw material for carbon materials by mixing heavy oil, carbonaceous or graphite powder, and a nitrating agent, and subjecting the mixture to heating and reduced pressure treatment, the method comprising: 3001nH without stirring in an oxidizing atmosphere
After heating to a maximum of 400℃ under reduced pressure of less than
The second invention is characterized by heating up to 500°C under a reduced pressure of not more than mmHg, and the second invention is characterized by a solvent that dissolves heavy oil, carbonaceous or graphite powder, heavy oil, and a nitrating agent. A method for producing a raw material for carbon materials by mixing and heating and depressurizing the mixture, wherein the mixture is heated to a maximum of 400°C under a reduced pressure of 300 mHg or less while stirring in a non-oxidizing atmosphere. It is characterized by performing the operation of returning to normal pressure and reducing the pressure again once or more, and finally heating to 500° C. under reduced pressure of 300 mHg or less.
〔発明の具体的構成〕 以下に本発明をさらに詳述する。[Specific structure of the invention] The present invention will be described in further detail below.
本発明における重質油とは石炭乾留時に産出するコール
タールやアスファルト、原油熱分解で生成する重質油、
エチレンボトム油、あるいはこれらを分解重合処理した
重質油等を用いることができる。Heavy oil in the present invention refers to coal tar and asphalt produced during coal carbonization, heavy oil produced during crude oil pyrolysis,
Ethylene bottom oil or heavy oil obtained by decomposing and polymerizing these oils can be used.
次に混合する炭素質または黒鉛質の粉末（本発明におい
ては両者を併用する場合も含む）としては、１０００℃
程度で仮焼したピッチコークス、人造黒鉛粉末、天然黒
鉛粉末等を挙げることができ、それらの混合物であって
もよく、その粒度は用途に応じ任意に変えることができ
るが、高密度・高強度品を得るには微粉化した方が好ま
しい。Next, the carbonaceous or graphite powder to be mixed (including the case where both are used together in the present invention) is heated to 1000°C.
Examples include pitch coke, artificial graphite powder, natural graphite powder, etc., which have been calcined to a certain degree, and may also be a mixture of these, and the particle size can be changed arbitrarily depending on the application, but high density and high strength can be used. In order to obtain a product, it is preferable to micronize it.
また、重質油に対する炭素粉または黒鉛粉の混合率は、
重質油１００重量部に対し２〜４０重量部が好ましく、
２重量部未満では添加効果が少ない。一方、４０重量部
を超えると、重質油との混合の際に見掛は上の粘度が高
くなり、混合した炭素粉または黒鉛粉の均一分散が難し
く不均一な製品となるため好ましくない。In addition, the mixing ratio of carbon powder or graphite powder to heavy oil is
Preferably 2 to 40 parts by weight per 100 parts by weight of heavy oil,
If the amount is less than 2 parts by weight, the effect of addition is small. On the other hand, if it exceeds 40 parts by weight, the apparent viscosity increases when mixed with heavy oil, making it difficult to uniformly disperse the mixed carbon powder or graphite powder, resulting in a non-uniform product, which is not preferable.
次に炭素粉または黒鉛粉を重質油に混合する方法は、タ
レオソート油またはナフタレン油等の重質油に容易に混
合するタール油分と炭素粉または黒鉛粉を混合し、事前
にペースト状としてから重質油と混合・混練する。この
事前ペースト化処理によって、そのペーストを重質油あ
るいはさらにニトロ化剤を加えたものと混合したとき、
炭素粉または黒鉛粉の凝集を防止でき、良好に分散でき
る。ペースト状にするためのタール油分の混合比は炭素
粉または黒鉛粉に対し、１〜２倍程度がよい。Next, the method of mixing carbon powder or graphite powder with heavy oil is to mix carbon powder or graphite powder with tar oil, which is easily mixed with heavy oil such as taleosote oil or naphthalene oil, and make it into a paste in advance. Mix and knead with heavy oil. This pre-pasting process ensures that when the paste is mixed with heavy oil or with the addition of a nitrating agent,
Agglomeration of carbon powder or graphite powder can be prevented and it can be dispersed well. The mixing ratio of tar oil to form a paste is preferably about 1 to 2 times that of carbon powder or graphite powder.
次に重合による収率の増加を促進するためのニトロ化剤
としては、希硝酸や濃硝酸、硝酸アセチル、二酸化窒素
等が用いられる。ニトロ化剤の混合率は、重質油１００
重量部に対し多くとも２０重量部が望ましい。ニトロ化
剤の混合率が、１０重量部を超えると収率は著しく増加
するが、反面、メソフエーズの生成が進みにくく接着性
の低下する傾向にあるけれども、次工程の加熱温度を低
下し重合の進行を緩和すれば、ニトロ剤の混合率は２０
重量部まで可能である。混合率が２０重量部を超えると
接着性の低下が著しくなり成形工程における密度の上昇
が少なくなり、炭化中も接着不足による微細亀裂の発生
を起こし、好ましくない。Next, dilute nitric acid, concentrated nitric acid, acetyl nitrate, nitrogen dioxide, etc. are used as a nitrating agent to promote an increase in yield through polymerization. The mixing ratio of the nitrating agent is heavy oil 100
Preferably at most 20 parts by weight. When the mixing ratio of the nitrating agent exceeds 10 parts by weight, the yield increases significantly, but on the other hand, the formation of mesophase tends to be slow and the adhesiveness tends to decrease. If the progress is moderated, the mixing ratio of nitro agent is 20
Up to parts by weight are possible. If the mixing ratio exceeds 20 parts by weight, the adhesion will drop significantly, the increase in density during the molding process will be less, and even during carbonization, microcracks will occur due to insufficient adhesion, which is not preferable.
なお、これら重質油、ニトロ化剤、炭素・黒鉛粉末の混
合は常圧下で行う。減圧下ではニトロ化剤が蒸発してし
まうからである。The heavy oil, nitrating agent, and carbon/graphite powder are mixed under normal pressure. This is because the nitrating agent evaporates under reduced pressure.
次に、上記混合物は３００ｗｍＨｇ以下の減圧下で４０
０℃まで加熱される。減圧下で加熱する目的は、炭素粉
または黒鉛の持つ気孔・隙間にある空気を脱気し、常圧
に戻したときの重質油の浸透を促進することと、炭素粉
をペースト状にするために用いたタール油分の回収能率
を上げるためである。また、加熱温度を４００℃までと
したのは、４００℃を超えると重質油が重合反応を始め
粘度の上昇が起こるため、次に行う減圧と常圧のくり返
しによる重質油の炭素粉または黒鉛粉への浸透効果が低
下し好ましくないからである。Next, the above mixture was heated at 40 wmHg or less under reduced pressure.
Heated to 0°C. The purpose of heating under reduced pressure is to deaerate the air in the pores and gaps of the carbon powder or graphite, to promote penetration of heavy oil when the pressure is returned to normal, and to turn the carbon powder into a paste. This is to increase the recovery efficiency of the tar oil used for this purpose. In addition, the heating temperature was set to 400℃ because if the temperature exceeds 400℃, heavy oil will start a polymerization reaction and its viscosity will increase. This is because the effect of penetrating into graphite powder decreases, which is undesirable.
タール油分の除去を終った混合液は、チッ素ガス、アル
ゴンガス等の非酸化性ガスを用いて常圧に戻し、再び減
圧する操作を１回以上くり返し、炭素粉または黒鉛粉の
気孔・隙間への重質油の浸透を促進し、分散性を向上す
る。次いで再び３００ｍｍＨｇ以下まで減圧し、少なく
とも５００℃まで加熱する。ここで、加熱温度が５００
℃を超える場合は、炭素質または黒鉛質の粉末を混合し
た炭素材原料の接着性が低下し、炭素材の品質低下を招
く。加熱中の減圧が、３００ｗＨｇを超えると、加熱中
の油分の除去が不充分となるばかりでなく、混合した炭
素質または黒鉛質の粒子の気孔・隙間への重質油の侵入
が不充分で、かつ粒子の分散性も劣り品質上不適当であ
る。After the tar oil content has been removed, the mixed liquid is returned to normal pressure using a non-oxidizing gas such as nitrogen gas or argon gas, and the pressure is reduced again once or more. promotes the penetration of heavy oil into the oil and improves its dispersibility. Then, the pressure is again reduced to 300 mmHg or less and heated to at least 500°C. Here, the heating temperature is 500
If the temperature exceeds .degree. C., the adhesion of the carbon material raw material mixed with carbonaceous or graphite powder decreases, leading to a deterioration in the quality of the carbon material. If the reduced pressure during heating exceeds 300 wHg, not only will oil be insufficiently removed during heating, but also the heavy oil will not be able to penetrate into the pores and gaps of the mixed carbonaceous or graphite particles. Moreover, the dispersibility of the particles is also poor and the quality is inappropriate.
本発明に係る炭素材用原料は、ピッチ類やフェノールレ
ジン等のバインダー成分を使用することなく成形が可能
であり、また成形手段も通常の型込めプレスあるいはラ
バープレス等の何れをも採用でき、炭化および黒鉛化前
の成形体はハンドリングに充分耐える強度を有している
。The raw material for carbon materials according to the present invention can be molded without using binder components such as pitch or phenol resin, and the molding means can be any of ordinary mold presses, rubber presses, etc. The compact before carbonization and graphitization has sufficient strength to withstand handling.
そして、成形体は常法通りに不活性ガスあるいは粉コー
クス中で千数百℃で炭化し、さらに、二千数百℃で黒鉛
化して炭素材を製造することがモきる。Then, the compact can be carbonized in an inert gas or coke powder at a temperature of 1,000-odd hundred degrees Celsius in a conventional manner, and then graphitized at a temperature of 2,000-odd degrees Celsius to produce a carbon material.
次いで、本発明を実施例により比較例と対比しながら具
体的に説明する。Next, the present invention will be specifically explained using Examples and in comparison with Comparative Examples.
コールタールに平均粒径１５μｍの人造黒鉛粉末と、ニ
トロ化剤として濃硝酸を種々の比率で混合し、得られる
混合物を第１表に示す条件で熱処理し、残渣ピッチを得
た。Coal tar was mixed with artificial graphite powder having an average particle size of 15 μm and concentrated nitric acid as a nitration agent in various ratios, and the resulting mixture was heat-treated under the conditions shown in Table 1 to obtain residual pitch.
上記人造黒鉛粉末の混合方法は、実施例−１〜３では人
造黒鉛粉末を粉状のままコールタールに混合し、実施例
−４〜９では、人造黒鉛粉末とクレオソート油を１対２
の比率で充分混合し、事前にペースト状としたものをコ
ールタールに混合し、また減圧加熱の際に３５０℃で減
圧からチッ素ガスにより常圧に戻す操作を２回くり返し
た。実施例−３，４はこの操作を１回だけ行なった。一
方、比較例では、黒鉛粉末を粉状のままコールタールに
混合し、また減圧から常圧に戻す操作は行わなかった。In Examples 1 to 3, the artificial graphite powder was mixed with coal tar in powder form, and in Examples 4 to 9, the artificial graphite powder and creosote oil were mixed in a ratio of 1:2.
The mixture was thoroughly mixed at a ratio of 1, and the mixture was prepared into a paste in advance and mixed with coal tar, and during heating under reduced pressure, the operation of returning from reduced pressure to normal pressure using nitrogen gas at 350° C. was repeated twice. In Examples 3 and 4, this operation was performed only once. On the other hand, in the comparative example, graphite powder was mixed with coal tar in powder form, and the operation of returning the pressure from reduced pressure to normal pressure was not performed.
次に、上記残渣ピッチを平均粒径１５μｍに粉砕し直径
２００ ＋ｖｓで高さ２００ 鶴の円筒形ゴム形に充填
し、１．５ｔ／ａ＋１の圧力で水圧等方加圧成形を行っ
た後、この成形体を粉コークスを詰めた容器内で窒素雰
囲気中で１０００℃まで炭化し、さらに黒鉛化炉でアル
ゴン気流中２５００℃で黒鉛化を行った。得られた物性
を同じく第１表に示す。Next, the above-mentioned residual pitch was pulverized to an average particle size of 15 μm, filled into a cylindrical rubber shape with a diameter of 200+vs and a height of 200 mm, and was subjected to hydrostatic isostatic pressing at a pressure of 1.5t/a+1. This compact was carbonized to 1000° C. in a nitrogen atmosphere in a container filled with coke powder, and further graphitized at 2500° C. in an argon stream in a graphitization furnace. The obtained physical properties are also shown in Table 1.
第１表において、実施例Ｉ〜９のものは、炭素材強度の
バラツキが非常に小さく品質が安定していることが比較
例１〜４のものとの対比から明らかとなった。また、炭
素材の密度・強度がほぼ同等で、硬度・電気抵抗・ＣＴ
Ｅの異なる炭素材が得られた。In Table 1, it is clear from comparison with Comparative Examples 1 to 4 that Examples I to 9 have very small variations in carbon material strength and stable quality. In addition, the density and strength of carbon materials are almost the same, and the hardness, electrical resistance, and CT
Carbon materials with different E values were obtained.
他方、比較例５はニトロ化剤の多い例、比較例６は黒鉛
粉の多い例であり、いずれも粒子間の接着が悪く高強度
の炭素材が得られなかった。On the other hand, Comparative Example 5 was an example in which a large amount of nitrating agent was used, and Comparative Example 6 was an example in which a large amount of graphite powder was used, and in both cases, adhesion between particles was poor and a high-strength carbon material could not be obtained.
以上の通り、本発明によればコールタール等の重質油を
主原料とし、品質が安定で、かつ高強度で電気比抵抗、
ＣＴＢの異なる炭素材が得られ、広い範囲の用途に適用
しうる炭素材の原料を提供することができる。As described above, according to the present invention, heavy oil such as coal tar is used as the main raw material, the quality is stable, the strength is high, the electric specific resistance is
Carbon materials with different CTBs can be obtained, and raw materials for carbon materials that can be used in a wide range of applications can be provided.
手続令甫正書１発）
昭和６３年２月１日
１、事件の表示
昭和６２年 特許願 第２９１６２６号２、発明の名称
炭素材用原料の製造方法
３、補正をする者
事件との関係 特許出願人
住所
名称 （２１））住友金属工業株式会社４、代理人■
１０１
氏名 （８２６４） 弁理士 永 井 義 久５、
補正命令の日付 自発補正
６、補正の対象
明細書、発明の詳細な説明の欄
７、補正の内容
（１）明細書、発明の詳細な説明の欄を下記の通り訂正
する。Procedural Ordinance (Procedural Ordinance 1) February 1, 1988 1, Indication of the case 1988 Patent Application No. 291626 2, Name of the invention Method for producing raw materials for carbon materials 3, Person making the amendment Relationship with the case Patent Applicant Address Name (21)) Sumitomo Metal Industries Co., Ltd. 4, Agent■
101 Name (8264) Patent attorney Yoshihisa Nagai5,
Date of amendment order Voluntary amendment 6, Specification to be amended, Detailed explanation of the invention column 7, Contents of amendment (1) The specification and Detailed explanation of the invention column are corrected as follows.
■第２頁、１）行「重質油の主原料」とあるのを「重質
油を主原料」とする。■Page 2, line 1) "Main raw material of heavy oil" should be changed to "Main raw material of heavy oil".
■第１２頁、第１表を別紙の通り訂正する。■Page 12, Table 1 is corrected as shown in the attached sheet.
Claims (2)
を混合し、加熱および減圧処理することにより炭素材用
原料を製造する方法であって、上記混合物を非酸化性雰
囲気下で撹拌しながら３００ｍｍＨｇ以下の減圧下で最
高４００℃まで加熱した後、常圧まで戻し再び減圧する
操作を１回以上行い、最後に３００ｍｍＨｇ以下の減圧
下で５００℃まで加熱することを特徴とする炭素材用原
料の製造方法。(1) A method for producing a raw material for carbon materials by mixing heavy oil, carbonaceous powder or graphite powder, and a nitrating agent, and subjecting the mixture to heating and reduced pressure treatment, wherein the mixture is mixed in a non-oxidizing atmosphere. Charcoal characterized by heating to a maximum of 400°C under a reduced pressure of 300 mmHg or less while stirring, then returning to normal pressure and reducing the pressure again once or more, and finally heating to 500°C under a reduced pressure of 300 mmHg or less. A method for producing raw materials for materials.
を混合してペースト状としたものと、重質油と、ニトロ
化剤とを混合し、加熱および減圧処理することにより炭
素材用原料を製造する方法であって、上記混合物を非酸
化性雰囲気下で撹拌しながら３００ｍｍＨｇ以下の減圧
下で最高４００℃まで加熱した後、常圧まで戻し再び減
圧する操作を１回以上行い、最後に３００ｍｍＨｇ以下
の減圧下で５００℃まで加熱することを特徴とする炭素
材用原料の製造方法。(2) Carbon material is produced by mixing a paste-like mixture of a solvent that dissolves heavy oil and carbonaceous or graphite powder, heavy oil, and a nitration agent, and then heating and depressurizing the mixture. A method for producing a raw material for use, which comprises heating the above mixture to a maximum of 400°C under reduced pressure of 300 mmHg or less while stirring in a non-oxidizing atmosphere, and then returning to normal pressure and reducing the pressure again at least once. A method for producing a raw material for a carbon material, which is finally heated to 500° C. under a reduced pressure of 300 mmHg or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291626A JPH01133915A (en) | 1987-11-18 | 1987-11-18 | Production of starting material for carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62291626A JPH01133915A (en) | 1987-11-18 | 1987-11-18 | Production of starting material for carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01133915A true JPH01133915A (en) | 1989-05-26 |
Family
ID=17771392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62291626A Pending JPH01133915A (en) | 1987-11-18 | 1987-11-18 | Production of starting material for carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01133915A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008206933A (en) * | 2007-02-23 | 2008-09-11 | Asami Taniguchi | Sanitary product package bag |
-
1987
- 1987-11-18 JP JP62291626A patent/JPH01133915A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008206933A (en) * | 2007-02-23 | 2008-09-11 | Asami Taniguchi | Sanitary product package bag |
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