JPH0375212A - Preparation of elastic graphite - Google Patents
Preparation of elastic graphiteInfo
- Publication number
- JPH0375212A JPH0375212A JP1210283A JP21028389A JPH0375212A JP H0375212 A JPH0375212 A JP H0375212A JP 1210283 A JP1210283 A JP 1210283A JP 21028389 A JP21028389 A JP 21028389A JP H0375212 A JPH0375212 A JP H0375212A
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen dioxide
- dioxide gas
- carbonaceous material
- treatment
- carbonaceous
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 13
- 239000010439 graphite Substances 0.000 title claims abstract description 13
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 28
- 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 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 238000005087 graphitization Methods 0.000 claims abstract description 10
- 230000006835 compression Effects 0.000 claims abstract description 9
- 238000007906 compression Methods 0.000 claims abstract description 9
- 238000012856 packing Methods 0.000 claims abstract description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 229910021469 graphitizable carbon Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- 239000000571 coke Substances 0.000 description 12
- 238000005187 foaming Methods 0.000 description 9
- 239000011295 pitch Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011316 heat-treated pitch Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960002126 creosote Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は炭素材料に関し、特に軽量、耐熱性であり、か
つ、弾性にすぐれた粒状の弾性黒鉛体の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to carbon materials, and particularly to a method for producing granular elastic graphite bodies that are lightweight, heat resistant, and have excellent elasticity.
一般に炭素材料は、軽量、耐熱性、高弾性率１の他の材
料に見られない特性を持っているが、ブロック体では多
孔質なものでも剛性であり、一方、繊維、シート、フィ
ルムのように、細いかあるいは薄いものでは変形可能な
ものになる。しかし、これら炭素材料はそれ自体弾性体
としての性質は有していない。従来、弾性を持つ炭素材
料としては膨張黒鉛から製造されるシートが知られてい
る。In general, carbon materials have properties not found in other materials, such as light weight, heat resistance, and high modulus of elasticity. In addition, thin or thin objects can be deformed. However, these carbon materials themselves do not have elastic properties. Conventionally, sheets made of expanded graphite have been known as elastic carbon materials.
それでも、このシートに圧縮荷重を加えた後に荷重を除
いて求められる回復率は小さいものである（斉藤、工業
材料、２９巻３４ページ）。Still, the recovery rate determined by applying a compressive load to this sheet and then removing the load is small (Saito, Industrial Materials, Vol. 29, p. 34).
本発明者らは先に、圧縮荷重を加えた後、荷重を除いて
求められる回復率の大きい粒状弾性黒鉛体の製造方法を
提供している（特開昭６３−１３９０８０号、特開昭６
４−９８０８号および特願昭６３−２３７９２１号）。The present inventors have previously provided a method for manufacturing a granular elastic graphite body that has a high recovery rate after applying a compressive load and then removing the load (Japanese Patent Application Laid-Open No. 139080/1983,
No. 4-9808 and Japanese Patent Application No. 63-237921).
これらの発明の要旨は、特開昭６３−１３９０８０号明
細書において、硝酸もしくは硝酸と硫酸との混酸で処理
した炭素質メソフェースまたは生コークスを、また、特
開昭６４−９８０８号においては、硝酸もしくは硝酸と
硫酸との混酸で処理した炭素質メソフェースまた生コー
クスをアルカリ水溶液中で溶解させ、次いで、酸水溶液
で析出させて得られるアクアメソフェースを、約３００
℃で加熱処理して膨張・発泡させ、さらに、特願昭６３
−２３７９２１号においては炭素質メソフェースまたは
生コークスを硝酸と接触させて急速に加熱することで膨
張・発泡させて、これを２４００℃以上（特願昭６３−
２３７９２１号については２０００℃以上）の温度で黒
鉛化処理するものであった。確かに、上記の第１ないし
第２の方法によって得られる黒鉛化は優れた回復率を有
するものであるが、硝酸もしくは硝酸と硫酸との混酸で
の処理が、第２法のそれでは硝酸もしくは硝酸と硫酸と
の混酸で処理後、更に溶解、析出処理が工捏上必要であ
っｊコ。The gist of these inventions is that, in JP-A No. 63-139080, carbonaceous mesophase or raw coke treated with nitric acid or a mixed acid of nitric acid and sulfuric acid, and in JP-A No. 64-9808, carbonaceous mesophase or raw coke treated with nitric acid Alternatively, carbonaceous mesophase treated with a mixed acid of nitric acid and sulfuric acid or aqua mesophase obtained by dissolving raw coke in an alkaline aqueous solution and then precipitating it with an acid aqueous solution,
℃ heat treatment to expand and foam.
In No.-237921, carbonaceous mesophase or raw coke is brought into contact with nitric acid and rapidly heated to expand and foam, and the mixture is heated to a temperature of 2400°C or higher (Japanese Patent Application No. 63-
Regarding No. 237921, the graphitization treatment was carried out at a temperature of 2000° C. or higher. It is true that the graphitization obtained by the first or second method above has an excellent recovery rate, but the treatment with nitric acid or a mixed acid of nitric acid and sulfuric acid is After treatment with a mixed acid of sulfuric acid and sulfuric acid, further dissolution and precipitation treatments are required for fabrication.
そのとき、両者に共通な操作である硝酸もしくは硝酸と
硫酸との混酸での処理は、原料にニトロ基の導入と副反
応である酸化反応によるカルボキシル基、水酸基が同時
に導入されるというものである。このことから、約３０
０℃の熱処理間に生じる膨張・発泡現象は、ニトロ基に
よる原料の溶融とカルボン酸基と水酸基の分解で発生す
るガスによると推察された。すなわち、これらの方法に
おいては、弾性黒鉛体を製造するためにはニトロＵ、カ
ルボキシル基等の存在が必要な用件であると４゜えられ
ていた。 いずれにしても、上述した従来の製造方法は
、工程が比較的繁雑であり、時間的にも長時間を要する
ものであった。そこで、第３法では、酸による処理、可
溶化・析出処理ならびに膨張発泡処理という一連の繁雑
な工程を簡略化し、時間の短縮化を図るため、炭素質材
料に硝酸を接触させて急速加熱することにより膨張・発
泡処理を行う方法を提案している。At that time, treatment with nitric acid or a mixed acid of nitric acid and sulfuric acid, which is a common operation for both, simultaneously introduces nitro groups into the raw material and carboxyl groups and hydroxyl groups through the side reaction of oxidation reaction. . From this, approximately 30
The expansion/foaming phenomenon that occurs during the heat treatment at 0° C. is presumed to be due to the gas generated by the melting of the raw material by the nitro group and the decomposition of the carboxylic acid group and hydroxyl group. That is, in these methods, the presence of nitro U, carboxyl groups, etc. was considered to be a necessary requirement in order to produce elastic graphite bodies. In any case, the conventional manufacturing method described above has relatively complicated steps and takes a long time. Therefore, in the third method, in order to simplify a series of complicated steps such as acid treatment, solubilization/precipitation treatment, and expansion foaming treatment, and to shorten the time, the carbonaceous material is brought into contact with nitric acid and rapidly heated. We are proposing a method for performing expansion/foaming treatment.
しかしながら、この方法は、それにより製造−１−程の
簡略化は図れたものの、急速加熱処理において発生する
多量の分解ガスや蒸気の処理に手間がかかることや、接
触させる硝酸の回収が困難であることなどの問題があり
、工業化への適用は必ずしも容易ではないと考えられて
いる。However, although this method simplifies the production step (1), it takes time and effort to process the large amount of decomposed gas and steam generated during rapid heating treatment, and it is difficult to recover the nitric acid that is brought into contact. However, it is thought that it is not necessarily easy to apply it to industrialization due to certain problems.
〔発明のｗ１要〕
本発明は、上記事情により鑑みてなされたものであり、
従来法で採用されている工程を、より合理的かつ迅速な
工程にし、これにより製造工程の簡略化と製造コストの
低減化が図られ、工業化への応用が容易であり、しかも
すぐれた弾性特性を有する黒鉛体を得るための方法を提
供することを目的としている。[W1 essential points of the invention] The present invention has been made in view of the above circumstances,
The process used in conventional methods has been made more rational and faster, simplifying the manufacturing process and reducing manufacturing costs, making it easy to apply to industrialization, and providing excellent elastic properties. The object of the present invention is to provide a method for obtaining a graphite body having the following properties.
上述したように、従来の製造方法においては、その工程
は、硝酸もしくは硝酸と硫酸との混酸での処理、可溶化
ならびに析出処理、膨張・発泡処理、もしくは硝酸との
接触による加熱処理および黒鉛化処理という一連の操作
からなるが、本発明者らは、さらに鋭意研究の結果、原
料となる炭素質材料に二酸化窒素ガスを接触させるとい
う比較的簡単な工程によって、次の工程における炭素質
材料の膨張・発泡を引き起こすに十分な童のニトロ基や
カルボキシル基等の官能基を導入することができ、これ
を膨張・発泡処理した後に黒鉛化処理することによって
良好な特性の弾性黒鉛体を得ることができることを見出
した。As mentioned above, in the conventional manufacturing method, the steps include treatment with nitric acid or a mixed acid of nitric acid and sulfuric acid, solubilization and precipitation treatment, expansion/foaming treatment, or heat treatment and graphitization by contact with nitric acid. It consists of a series of operations called processing, but as a result of further intensive research, the present inventors discovered that the carbonaceous material in the next step can be processed by a relatively simple process of bringing nitrogen dioxide gas into contact with the carbonaceous material that will serve as the raw material. Functional groups such as nitro groups and carboxyl groups sufficient to cause expansion and foaming can be introduced, and elastic graphite with good properties can be obtained by graphitizing the material after expansion and foaming. I discovered that it can be done.
本発明の弾性黒鉛体の製造方法は、上記知見に基づいて
完成されたものであり、より詳しくは、炭素質材料を二
酸化窒素ガスと接触させた後、２０００℃以上の温度で
黒鉛化処理することを特徴としている。The method for producing an elastic graphite body of the present invention has been completed based on the above findings, and more specifically, after bringing a carbonaceous material into contact with nitrogen dioxide gas, it is graphitized at a temperature of 2000°C or higher. It is characterized by
以下、本発明の方法について詳細に説明する。 The method of the present invention will be explained in detail below.
炭素質材料
原料である炭素質材料としては重質瀝青物であるピッチ
類の熱処理によって製造されるピッチ、メソフェースピ
ッチ、炭素質メソフェースおよび生コークスコークスな
どであるが、炭素質メソフェースおよび（または）コー
クスが好ましく用いられる。Examples of carbonaceous materials that are raw materials include pitch produced by heat treatment of pitch, which is a heavy bituminous substance, mesoface pitch, carbonaceous mesoface, and raw coke coke, but carbonaceous mesoface and/or Coke is preferably used.
炭素質メソフェースは重質瀝青物を約３５０〜５００℃
で熱処理した時に生成する光学的異方性体である。これ
ら炭素質メソフェースの原料として用いられる重質瀝青
物はコールタールピッチ、石炭液化物の石炭系ピッチ、
６浦の蒸留残さ浦、ナフサの熱分解時に副生ずるナフサ
タールピッチ、ナフサ等の流動接触分解法（ＦＣＣ法）
で副生ずるＦＣＣデカントオイル等の石油系ピッチ、Ｐ
ＶＣ等の合成高分子の熱分解で得られるピッチ等であり
、炭素化処理によって易黒鉛化性炭素を与えるものであ
れば特に種類は問わない。これらのピッチ類は約３５０
〜５００℃で熱処理する。この熱処理によって、炭素質
メソフェースを生成させる。炭素質メソフェースの生成
は熱処理物を偏光顕微鏡下で観察することによって容易
に知ることができる。すなわち、炭素質メソフェースは
光学的等方性相であるピッチ中に光学的異方性相として
識別される。Carbonaceous mesoface heats heavy bituminous materials at approximately 350 to 500℃.
It is an optically anisotropic substance that is produced when heat-treated. The heavy bituminous materials used as raw materials for these carbonaceous mesophases include coal tar pitch, coal-based pitch from liquefied coal,
Fluid catalytic cracking method (FCC method) of 6 pores of distillation residue, naphtha tar pitch produced by-product during thermal decomposition of naphtha, naphtha, etc.
Petroleum-based pitch such as FCC decant oil, which is a by-product of P
It is pitch etc. obtained by thermal decomposition of synthetic polymers such as VC, and the type is not particularly limited as long as it can provide graphitizable carbon through carbonization treatment. These pitches are about 350
Heat treatment at ~500°C. This heat treatment produces carbonaceous mesophase. The formation of carbonaceous mesophase can be easily detected by observing the heat-treated product under a polarizing microscope. That is, the carbonaceous mesophase is identified as an optically anisotropic phase within the optically isotropic phase, pitch.
炭素質メソフェースを生成させる熱処理条件は、熱処理
したピッチから分離される炭素質メソフェースの元素組
成によって決められる。元素のうち、特に水素の含有量
が２重量％以上になるようにすることが好ましい。The heat treatment conditions for producing carbonaceous mesofaces are determined by the elemental composition of the carbonaceous mesofaces separated from the heat-treated pitch. Among the elements, it is particularly preferable that the content of hydrogen be 2% by weight or more.
従って、熱処理条件を厳しくしてピッチ類を全量固化さ
せたセミコークスでは、水素量が２％以下とならないよ
うに過度の熱処理は避ける必要がある。Therefore, in semi-coke in which pitches are completely solidified under strict heat treatment conditions, excessive heat treatment must be avoided so that the hydrogen content does not fall below 2%.
熱処理したピッチから炭素質メソフェースの分離は沈降
法または（および）溶剤分別法で行う。Separation of carbonaceous mesophase from heat-treated pitch is carried out by sedimentation method and/or solvent fractionation method.
すなわち、熱処理したピッチを、このピッチが溶融状態
において、静置すると炭素質メソフェースが下方に沈降
するので、この部分のみを採取する。That is, if the heat-treated pitch is allowed to stand in a molten state, the carbonaceous mesophase will settle downward, and only this portion will be collected.
また、溶剤としてキノリン、ピリジン等の白°機溶剤、
アントラセンやクレオソート油等の芳香族化合物を多量
に含有する芳香族系油に熱処理したピッチを溶解、分散
させ、これらの溶剤の不溶性成分として得ることができ
る。In addition, white solvents such as quinoline and pyridine can be used as solvents,
It can be obtained as an insoluble component in these solvents by dissolving and dispersing heat-treated pitch in an aromatic oil containing a large amount of aromatic compounds such as anthracene or creosote oil.
二酸化窒素ガス処理
上記炭素質材料を、二酸化窒素ガスと接触させて処理す
る。二酸化窒素ガスの濃度は必ずしも高濃度のものであ
る必要はなく、すなわち１０％以上でよいが、反応時間
を短くするためには高濃度の方が好ましく、５０％以上
のものが好ましく使用される。Nitrogen dioxide gas treatment The carbonaceous material described above is treated by contacting it with nitrogen dioxide gas. The concentration of nitrogen dioxide gas does not necessarily have to be high, that is, it can be 10% or more, but in order to shorten the reaction time, a high concentration is preferable, and 50% or more is preferably used. .
炭素質メソフェースと二酸化窒素ガスとの接触は気−固
相であるため、粒度が数關以上と大きい場合は反応が不
十分となり、膨張、発泡の程度が小さくなる恐れがある
ため、分離して得られた塊状の炭素質メソフェースをそ
のまま用いることは好ましくない。一方、粒度が約１０
μｍ以下になると、膨張、発泡の程度が好ましくなく、
得られる黒鉛体の性能が低下する。従って、好ましい粒
度範囲としては約１〜２＋ａｍから１０μｍの範囲であ
る。Since the contact between carbonaceous mesophase and nitrogen dioxide gas is in the gas-solid phase, if the particle size is several orders of magnitude larger, the reaction may be insufficient and the degree of expansion and foaming may be reduced, so separate the mesophase and nitrogen dioxide gas. It is not preferable to use the obtained massive carbonaceous mesophase as it is. On the other hand, the particle size is about 10
If it is less than μm, the degree of expansion and foaming will be unfavorable.
The performance of the graphite body obtained deteriorates. Accordingly, a preferred particle size range is from about 1-2+am to 10 micrometers.
二酸化窒素ガスの反応性を高めるために、二酸化窒素ガ
ス中への水蒸気の吹き込み、二酸化窒素ガスの酸性溶液
中の通過などの操作が有効であり、さらに、副反応であ
る酸化反応を進めるために空気、酸素、オゾン等を二酸
化窒素ガスに混合して反応させても良い。In order to increase the reactivity of nitrogen dioxide gas, operations such as blowing water vapor into nitrogen dioxide gas and passing nitrogen dioxide gas through an acidic solution are effective.Furthermore, in order to advance the oxidation reaction, which is a side reaction, Air, oxygen, ozone, etc. may be mixed with nitrogen dioxide gas and reacted.
熱処理
上記処理した炭素質材料を２５０〜５００℃の温度で熱
処理する。この処理によって、炭素質材料は数倍から数
十倍に体積が増加する。このときの体積増加率は二酸化
窒素ガス処理条件に関与すると考えられる。上記温度範
囲の加熱条件のうち昇温速度は速くても遅くても体積増
加率にほとんど影響しないが、６０℃／ｈｒ以下のよう
に極端に遅い速度は好ましくない。それは処理した炭素
質材料の分解が約２５０℃附近の狭い温度域で起こるた
めであり、極端に遅い場合は、膨張・発泡の反応がスム
ースに進まないためである。この処理は必ずしも別個の
工程として行う必要はなく、体積増加が生じるため取り
扱い上に問題がなければ熱処理にひき続いて連続的に黒
鉛化処理してもよい。Heat Treatment The carbonaceous material treated above is heat treated at a temperature of 250 to 500°C. Through this treatment, the volume of the carbonaceous material increases from several times to several tens of times. The volume increase rate at this time is considered to be related to the nitrogen dioxide gas treatment conditions. Among the heating conditions in the above temperature range, whether the heating rate is fast or slow has little effect on the volume increase rate, but an extremely slow rate of 60° C./hr or less is not preferred. This is because the treated carbonaceous material decomposes in a narrow temperature range around 250°C, and if it is extremely slow, the expansion/foaming reaction will not proceed smoothly. This treatment does not necessarily need to be carried out as a separate step, and if there is no problem in handling since an increase in volume occurs, the graphitization treatment may be carried out continuously following the heat treatment.
黒鉛化
上記熱処理を行った炭素質材料または二酸化窒素ガス処
理した炭素質材料を、２０ｏＯ℃以上に加熱し、黒鉛化
する。黒鉛化温度がこれ以ドの温度では後述する圧縮後
の回復率が低下する。Graphitization The carbonaceous material subjected to the above heat treatment or the carbonaceous material treated with nitrogen dioxide gas is heated to 20oO°C or higher to graphitize it. If the graphitization temperature is lower than this temperature, the recovery rate after compression, which will be described later, decreases.
このようにして得られたものが弾性体であるかどうかに
ついては次のような試験により確認することができる。Whether the product thus obtained is an elastic body can be confirmed by the following test.
内径１０＋＋＊の炭素鋼（Ｓ −４５Ｃ）製シリンダー
状金型に、得られた試料約０゜５ｇを入れ、周囲からた
たいて最密充填になるようにした後、上部から押し棒を
挿入し、１ｋｇ／ｃｄの荷重を加え、このときの試料の
高さを測定し、−旦Ｑ重を取り除いた後再び同じ荷重を
加えても変わらない値を示すようになったとき、この値
をｈｏとする。ついで、所定の荷重を加え、試料の高さ
を測定し、その値をｈｌとする。そして荷重を除き、そ
のときの試料の高さを測定し、その値をｈ２とする。Approximately 0.5 g of the obtained sample was placed in a cylindrical mold made of carbon steel (S-45C) with an inner diameter of 10++*, and after pounding from the periphery to form the closest packing, a push rod was inserted from the top. Then, apply a load of 1 kg/cd, measure the height of the sample at this time, and if it shows the same value even if the same load is applied again after removing the Q weight, this value is Ho. Then, a predetermined load is applied, the height of the sample is measured, and the value is set as hl. Then, the load is removed, the height of the sample at that time is measured, and the value is set as h2.
これらの値から、次式によって、充填密度、圧縮率およ
び回復率を求めることができる〇充填密度（ｇ ／ａｎ
”） −（試料型Ｈｋ （ｇ））／ （ｈＯπｒ２）
−（＋）圧縮率（％） −（（ｈＯ−ｈｌ）／ｈ
Ｏ）Ｘ１００ 、、、（２）回復率（％）
−（（ｈ２−ｈｌ）／（ｈＯ−ｈｌ）） Ｘ１
００ −（３）本発明の方法によれば、式（１）か
ら求められる充填密度が１．ｏｇ／ｃｄ以下であり、式
（２）における圧縮率が１０〜９０％のときの、式（３
）における回復率が５０％以上である弾性黒鉛体を得る
ことができる。From these values, the packing density, compression ratio, and recovery rate can be determined using the following formula.〇Filling density (g/an
”) −(sample type Hk (g))/ (hOπr2)
-(+) Compression rate (%) -((hO-hl)/h
O) X100, (2) Recovery rate (%)
-((h2-hl)/(hO-hl)) X1
00 - (3) According to the method of the present invention, the packing density determined from equation (1) is 1. og/cd or less and when the compression ratio in equation (2) is 10 to 90%, equation (3
) It is possible to obtain an elastic graphite body having a recovery rate of 50% or more.
以下、実施例を挙げて本発明の方法を更に詳細に説明す
る。Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
コールタールピッチ５００ｇに対してキノリンを約１５
００ｍｌ加え、約９０℃に加熱し、溶解させた。これを
遠心沈降機によって不溶成分を沈降させ、上澄みを定性
ろ紙によって、減圧濾過した。Example 1 Approximately 15% of quinoline is added to 500g of coal tar pitch.
00ml was added and heated to about 90°C to dissolve it. Insoluble components were precipitated using a centrifugal sedimentation machine, and the supernatant was filtered under reduced pressure using qualitative filter paper.
ろ液を減圧蒸留してキノリンを除き、フリーカーボンを
含有しないピッチを得た。このピッチ３００ｇを５００
ｍ１のガラス製円筒状容器に入れ、窒素ガス気流中、攪
拌しながら、４５０’Ｃまで加熱し、この温度で４５分
間保持した。時間経過後、直ちに室温まで冷却して熱処
理ピッチ２７３ｇを得た。熱処理ピッチ２００ｇに対し
てキノリン６００ｍ１加え、約９０℃に加熱して、溶解
、分散させた。これを遠心沈降機により、不溶成分を沈
降させ、上澄みを除き、不溶成分に新たなキノリンを加
え、約９０℃に加熱した後、遠心沈降機で不溶成分を沈
降させた。この操作を５回繰り返した後、不溶成分はベ
ンゼン、次いでアセトンで十分に洗浄してキノリンを除
き、約７０℃で乾燥して、炭素質メソフェース９８ｇを
得た。ついで、この炭素質メソフェース５０ｇを２００
ｍ１のキノリンに入れ、約２５０℃に加熱して、キノリ
ンを還流させながら３時間保持した後、遠心機で不溶成
分を沈降させ、上澄みを除いた。この操作を８回繰り返
した後、不溶成分にベンゼン、次いでアセトンで十分洗
浄してキノリンを除き、約７０℃で乾燥して、炭素質メ
ソフェース４４ｇを得た＠このようにして調製した炭素
質メンフェースの元素組成を表１に示す。The filtrate was distilled under reduced pressure to remove quinoline, yielding pitch free of free carbon. This pitch of 300g is 500g
The mixture was placed in a 1 ml glass cylindrical container, heated to 450'C while stirring in a nitrogen gas flow, and held at this temperature for 45 minutes. After the elapse of time, the mixture was immediately cooled to room temperature to obtain 273 g of heat-treated pitch. 600 ml of quinoline was added to 200 g of heat-treated pitch and heated to about 90° C. to dissolve and disperse. The insoluble components were precipitated using a centrifugal sedimentation machine, the supernatant was removed, fresh quinoline was added to the insoluble components, and after heating to about 90°C, the insoluble components were sedimented using a centrifugal sedimentation machine. After repeating this operation five times, the insoluble components were thoroughly washed with benzene and then with acetone to remove quinoline, and the mixture was dried at about 70° C. to obtain 98 g of carbonaceous mesophase. Next, 50 g of this carbonaceous mesophase was
ml of quinoline, heated to about 250° C., held for 3 hours while refluxing the quinoline, and then centrifuged to precipitate insoluble components and remove the supernatant. After repeating this operation 8 times, the insoluble components were thoroughly washed with benzene and then with acetone to remove the quinoline and dried at about 70°C to obtain 44 g of carbonaceous mesophase. Table 1 shows the elemental composition of the face.
この０．３５ｍｍ以下の粒度の５ｇを内径１０ｍｍのス
テンレス製パイプに充填し、２０ｍ１／ｌ１ｉｎの流量
で二酸化窒素ガス（製鉄化学（株）製、９９．９％）を
２５℃で１時間通し、次いで乾燥した。このときの収率
は炭素質メソフェースに対して１４０重量％であった。5 g of this particle size of 0.35 mm or less was filled into a stainless steel pipe with an inner diameter of 10 mm, and nitrogen dioxide gas (manufactured by Steel Chemical Co., Ltd., 99.9%) was passed through it at a flow rate of 20 m1/1 inch at 25 ° C. for 1 hour. It was then dried. The yield at this time was 140% by weight based on the carbonaceous mesophase.
これを５００ｍ１の円筒状ガラス容器に入れ、予め４５
０℃に加熱した塩浴中に投入し、３０分間保持した。収
率は炭素質メソフェースに対して８９．６重量％であっ
た。次いで、アルゴン気流中で２８００℃まで加熱し、
３０分間保持して黒鉛化処理した。収率は炭素質メソフ
ェースに対して６１．８ｆｒｊ１％であった。Place this in a 500m1 cylindrical glass container, and
It was placed in a salt bath heated to 0°C and held for 30 minutes. The yield was 89.6% by weight based on carbonaceous mesophase. Then, heated to 2800°C in an argon stream,
It was held for 30 minutes and graphitized. The yield was 61.8frj1% based on carbonaceous mesophase.
黒鉛化処理物０．５ｇを内径１０關のシリンダー状容器
に入れ、容器をたたいて十分に充填した後、１ ｋｇ
／ ｃｄの荷重を加え、そのときの高さを計測し、−旦
荷重を取り除いた後４４び荷重を加えても変わらない値
を示すようになったとき、その値を計測した（ｈ Ｏ）
。これから式（１）に従って充填密度を計算したところ
、０．６７ｇ／ｃｉであった。ついで、荷重を５０００
ｋｇ／ｃｄ加え、そのときの高さを計則した（ｈｌ）。Put 0.5 g of the graphitized product into a cylindrical container with an inner diameter of 10 mm, tap the container to fully fill it, and then add 1 kg.
/ cd was applied, the height at that time was measured, and after the load was removed, the value was measured when the value remained the same even after the load was applied (h O).
. The packing density was calculated from this according to formula (1) and was found to be 0.67 g/ci. Then, increase the load to 5000
kg/cd was added, and the height at that time was measured (hl).
そして、このｔ１重を除いて、再び高さを計測した（ｈ
２）。得られたｈｌ、ｈ２から式（２）および（３）に
よって、圧縮率、回復率を求めたところ、圧縮率は７２
％であり、回復率は７２％であった。反応温度を変えた
場合、二酸化窒素ガスに水蒸気を加えた場合等の収率を
表２に、充填密度、圧縮率および回復率を表３に示す。Then, excluding this t1 weight, the height was measured again (h
2). The compression ratio and recovery ratio were calculated from the obtained hl and h2 using equations (2) and (3), and the compression ratio was 72.
%, and the recovery rate was 72%. Table 2 shows the yield when the reaction temperature was changed, water vapor was added to nitrogen dioxide gas, etc., and Table 3 shows the packing density, compressibility, and recovery rate.
表１
よび黒鉛化処理を行った。そのときの収率を表４に、充
填密度、圧縮率および回復率を表５に示す。Table 1 and graphitization treatment were performed. The yield at that time is shown in Table 4, and the packing density, compression rate and recovery rate are shown in Table 5.
二酸化窒素ガス処理 表２ ガス混含 的・勉 元素組成（ｗｔ％） 炭素 水素 窒素 ９９．９ ０ ９９．９ ９９．９ ９９．９ ｔ ＮＯ２／ １ｍ＝’ｔｏ７ａ。Nitrogen dioxide gas treatment Table 2 Contains gas target/study Elemental composition (wt%) Carbon Hydrogen Nitrogen 99.9 0 99.9 99.9 99.9 t NO2/1m='to7a.
１ＮＯ２／ Ｉｌ！−７０／３０
８９．６
８３．８
７７．７
８４．７
７３．４
６１．８
Ｂｏ、３
５１．３
５５．０
４７．７
炭素質メソフェース ９２．３ ３．４ １．４生
コークス ９２．３ ３．１ ０．６態！
！ 龍（５００ｋｇ／ｃｊ）
（ｇ ／ｃｄ）腸（％） 塀（％）
龍（５０００ｋｒ ／ｄ）
ｕｓ（％）目障（％）
実施例２
デイレードコーカー法で得られた坐コークスを粉砕し、
０．３５！Ｉ１１以下に調製した。このコークスの元素
組成を表１に示す。このコークス５ｇを実施例１に示し
たと同様の方法で反応、熱処理お０．６７
０．７２
０．８６
６６３
０．６２1NO2/Il! -70/30 89.6 83.8 77.7 84.7 73.4 61.8 Bo, 3 51.3 55.0 47.7 Carbonaceous mesoface 92.3 3.4 1.4 Raw coke 92. 3 3.1 0.6 state!
! Dragon (500kg/cj) (g/cd) Intestine (%) Wall (%) Dragon (5000kr/d) us (%) Eyesight (%) Example 2 The sitting coke obtained by the delayed coker method was crushed. ,
0.35! It was adjusted to below I11. Table 1 shows the elemental composition of this coke. 5 g of this coke was reacted and heat treated in the same manner as shown in Example 1.0.67 0.72 0.86 663 0.62
Claims (1)
００℃以上の温度で黒鉛化処理することを特徴とする、
充填密度が１．０ｇ／ｃｍ＾３以下であり、かつ圧縮率
１０〜９０％における回復率が５０％以上である弾性黒
鉛体の製造方法。 ２、炭素質材料が、その水素含有量が２％以上であり、
通常の炭素化処理により易黒鉛化性炭素を与えるもので
あることを特徴とする、請求項１の方法。 ３、炭素質材料と接触させる二酸化窒素ガスの濃度が１
０％以上であり、流速が炭素質材料１ｇに対して０．１
ｃｃ／ｍｉｎ以上で、０〜２００℃の温度で５分ないし
５時間処理することを特徴とする、請求項１の方法。 ４、炭素質材料に接触させる二酸化窒素ガスに、水蒸気
、酸ミスト、空気、酸素、オゾン等を共存させることを
特徴とする、請求項１の方法。[Claims] 1. After bringing the carbonaceous material into contact with nitrogen dioxide gas, 20
Characterized by graphitization treatment at a temperature of 00°C or higher,
A method for producing an elastic graphite body having a packing density of 1.0 g/cm^3 or less and a recovery rate of 50% or more at a compression ratio of 10 to 90%. 2. The carbonaceous material has a hydrogen content of 2% or more,
2. The method according to claim 1, wherein the graphitizable carbon is obtained by a conventional carbonization treatment. 3. The concentration of nitrogen dioxide gas brought into contact with the carbonaceous material is 1
0% or more, and the flow rate is 0.1 per 1 g of carbonaceous material.
The method according to claim 1, characterized in that the treatment is carried out at a rate of cc/min or more at a temperature of 0 to 200°C for 5 minutes to 5 hours. 4. The method according to claim 1, wherein water vapor, acid mist, air, oxygen, ozone, etc. are allowed to coexist in the nitrogen dioxide gas that is brought into contact with the carbonaceous material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1210283A JPH0624967B2 (en) | 1989-08-15 | 1989-08-15 | Method for producing elastic graphite body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1210283A JPH0624967B2 (en) | 1989-08-15 | 1989-08-15 | Method for producing elastic graphite body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0375212A true JPH0375212A (en) | 1991-03-29 |
| JPH0624967B2 JPH0624967B2 (en) | 1994-04-06 |
Family
ID=16586834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1210283A Expired - Lifetime JPH0624967B2 (en) | 1989-08-15 | 1989-08-15 | Method for producing elastic graphite body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0624967B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013518034A (en) | 2010-01-21 | 2013-05-20 | アンスティチュ ナショナル ドゥ ラ サンテ エ ドゥ ラ ルシェルシュ メディカル | Special composition for use as a drug |
| FR3068886B1 (en) | 2017-07-17 | 2019-08-30 | L'oreal | AQUEOUS COSMETIC COMPOSITION COMPRISING A PYRIDINE-DICARBOXYLIC ACID DERIVATIVE AND A HYDROXYSTILBENE |
-
1989
- 1989-08-15 JP JP1210283A patent/JPH0624967B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH0624967B2 (en) | 1994-04-06 |
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