JPH068164B2 - Method for preparing magnetic porous carbon material - Google Patents
Method for preparing magnetic porous carbon materialInfo
- Publication number
- JPH068164B2 JPH068164B2 JP63126325A JP12632588A JPH068164B2 JP H068164 B2 JPH068164 B2 JP H068164B2 JP 63126325 A JP63126325 A JP 63126325A JP 12632588 A JP12632588 A JP 12632588A JP H068164 B2 JPH068164 B2 JP H068164B2
- Authority
- JP
- Japan
- Prior art keywords
- porous carbon
- asphalts
- heat treatment
- carbon material
- preparing magnetic
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 ［技術分野］ 本発明は、多孔性炭素材料の調製に関するものである。TECHNICAL FIELD The present invention relates to the preparation of a porous carbon material.
［従来技術］ アスファルト類から活性炭を製造する方法として、次の
ような技術開発が進められている。その一部は実用化も
なされている。[Prior Art] The following technical development is under way as a method for producing activated carbon from asphalt. Some of them have been put to practical use.
（１）アスファルト類を酸素、硫黄あるいは硫酸で酸化
処理して出来たカーボンを賦活して活性炭とする技術。(1) A technology for activating carbon produced by oxidizing asphalts with oxygen, sulfur or sulfuric acid to produce activated carbon.
（２）可性ソーダ、塩化亜鉛等のような軽金属化合物を
添加して熱処理を行い活性炭とする技術。(2) A technology of adding light metal compounds such as caustic soda and zinc chloride and performing heat treatment to make activated carbon.
しかしながら、アスファルト類にはバナジウムなどの重
金属及び硫黄が多量に含まれているため、製造された活
性炭は質的に劣ることになる。従って、特殊な利点を有
しない限り、一般の活性炭に対して不利になるものと考
えられる。However, since the asphalts contain a large amount of heavy metals such as vanadium and sulfur, the quality of the activated carbon produced is inferior. Therefore, it is considered to be disadvantageous to general activated carbon unless it has a special advantage.
［目的］ 本発明は、アスファルト類から磁性を有する多孔性炭素
材料を調製することを目的とする。[Purpose] The present invention aims to prepare a porous carbon material having magnetism from asphalts.
［構成］ 本発明者らは、前記目的を達成すべく種々検討を重ねた
結果、アスファルト類に可溶な磁性金属の化合物をアス
ファルト類に添加し、所定の条件で熱処理を行うことに
よって、磁性を有する多孔性炭素材料が得られることを
見いだした。[Structure] As a result of various studies to achieve the above-mentioned object, the present inventors added a compound of a magnetic metal soluble in asphalts to asphalts, and heat-treated them under predetermined conditions to obtain magnetic properties. It was found that a porous carbon material having
ここで、アスファルト類とは石油の蒸溜残さ、アスファ
ルテン、天然アスファルト、タール及びピッチ等を意味
する。Here, the asphalts mean the distillation residue of petroleum, asphaltene, natural asphalt, tar, pitch and the like.
アスファルト類に可溶な磁性金属の化合物としては、例
えば ナフテン酸ニッケル Ni(RCOO)2 ナフテン酸鉄 Fe(RCOO)3 アセチルアセトンニッケル Ni(Acac)2 アセチルアセトン鉄 Fe(Acac)3 等が挙げられる。Ｒは炭化水素基である。Examples of magnetic metal compounds soluble in asphalts include nickel naphthenate Ni (RCOO) 2 iron naphthenate Fe (RCOO) 3 acetylacetone nickel Ni (Acac) 2 acetylacetone iron Fe (Acac) 3 . R is a hydrocarbon group.
熱処理の条件としては、後に詳述するが、大きく次の２
段階に分けられる。The heat treatment conditions will be described in detail later, but the following 2
It is divided into stages.
(1) 酸素を含む雰囲気下で熱処理し、熱軟化溶融しな
い炭化物を得る段階。(1) A step of heat-treating in an atmosphere containing oxygen to obtain a carbide that is not softened by heat.
(2) 生成した炭化物を不活性ガス雰囲気下で熱処理
し、細孔を形成させる段階。(2) A step of heat treating the generated carbide in an inert gas atmosphere to form pores.
本発明の特徴は、油溶性の磁性金属の化合物をアスファ
ルト類に添加し、上記の２段階の熱処理を行うことによ
って磁性を有した多孔性炭化材料が調製されることであ
る。即ち、アスファルト類に可溶な金属化合物は、第１
段の熱処理でアスファルト類の炭化反応に触媒作用をす
ると共に、自ら分解し、炭化物内に磁区が形成できる程
度に高分散する。この炭化物に、第２段の熱処理で細孔
を生成させるものである。A feature of the present invention is that a magnetic porous carbonized material is prepared by adding an oil-soluble magnetic metal compound to asphalts and performing the above-described two-step heat treatment. That is, the metal compound soluble in asphalt is
The step heat treatment catalyzes the carbonization reaction of asphalts, and decomposes by itself and disperses to a high degree to the extent that magnetic domains can be formed in the carbide. Pores are generated in this carbide by the second stage heat treatment.
上記の化合物をアスファルト類に添加する量について
は、一般に、アスファルト１重量部に対して金属として
0.02重量部以上、好ましくは0.05から0.6重量部であ
る。金属量が少ないと炭化反応に対して触媒作用が発揮
されず、熱軟化溶融しない炭素質物質は得られないこと
があると共に、例え炭化物が生成したにしても、その磁
化の値が著しく小さく、本目的には合致しない。また、
金属量が多いと、細孔を構成する炭素分が少なくなるた
め表面積の観点からは好ましくない。Regarding the amount of the above compound added to asphalt, the amount of metal is generally 1 part by weight of asphalt.
The amount is 0.02 part by weight or more, preferably 0.05 to 0.6 part by weight. When the amount of metal is small, no catalytic action is exhibited for the carbonization reaction, and a carbonaceous material that does not soften and melt in some cases may not be obtained, and even if a carbide is formed, its magnetization value is extremely small, It does not meet this purpose. Also,
When the amount of metal is large, the carbon content of the pores is small, which is not preferable from the viewpoint of surface area.
以上のように混合した試料に対して以下の処理を行う。
第１段階として、酸素を含む気流中で、250〜380℃まで
を５℃／min以下、好ましくは３℃／min以下の速度で昇
温し、380〜410℃で２時間以内、好ましくは内部温度を
観察して発熱が生ずる直前まで保持する。続いて、第２
段階として、450〜750℃、好ましくは500〜700℃で、２
時間以内、好ましくは１時間以内で不活性ガス雰囲気で
熱処理を行う。第２段階の温度が低すぎると細孔を生成
するための揮発分の脱離が少なく、逆に高すぎると、構
成物質の収縮が生じ細孔が減少すると共に、磁化低下の
現象も生じ、本目的には好ましくないことが分かってい
る。また、時間も余り長いと収縮が進み細孔が減少す
る。The following processing is performed on the sample mixed as described above.
As the first step, in an air flow containing oxygen, the temperature is raised from 250 to 380 ° C at a rate of 5 ° C / min or less, preferably 3 ° C / min or less, and at 380 to 410 ° C within 2 hours, preferably inside. Observe the temperature and hold until just before the exotherm occurs. Then, the second
As a step, at 450 to 750 ° C, preferably 500 to 700 ° C, 2
The heat treatment is performed in an inert gas atmosphere for less than one hour, preferably less than one hour. If the temperature in the second step is too low, the desorption of volatile components for forming pores is small, and if it is too high, the contraction of the constituent substance occurs and the number of pores decreases, and the phenomenon of magnetization decrease also occurs. It turns out to be unfavorable for this purpose. Further, if the time is too long, the shrinkage proceeds and the number of pores decreases.
［実施例］ 次に本発明を実施例によりさらに詳細に説明する。な
お、以下の実施例に用いた原料アスファルトはカフジ原
油のプロパン不溶分である。その性状は表１に示した通
りである。また、第１段の熱処理に用いた反応器は、内
容積100mlのガス流通攪拌式オートクレーブである。EXAMPLES Next, the present invention will be described in more detail with reference to examples. In addition, the raw material asphalt used in the following examples is a propane-insoluble component of cafji crude oil. The properties are as shown in Table 1. The reactor used for the first stage heat treatment was a gas flow stirring autoclave with an internal volume of 100 ml.
実施例１ まず、オートクレーブに原料アスファルトとナフテン酸
ニッケルを下記の割合で入れ、空気を約70ml／minで吹
きこみながら、約５℃／minで昇温し、380から400℃で
約１時間第１段の熱処理を行った。続いて、オートクレ
ーブを急冷後生成した炭化物をかきだし、粉砕混合し
た。この粉末を錠剤成型器にてペレット状にし、窒素を
流通させな がら、所定の温度で第２段の熱処理を行った。アスファ
ルトとナフテン酸ニッケルの混合割合は、１：２、
１：１および２：１である。使用したナフテン酸ニッ
ケルのニッケル分は５％である。この結果を図１及び２
に示した。Example 1 First, raw material asphalt and nickel naphthenate were placed in an autoclave at the following ratios, the temperature was raised at about 5 ° C./min while blowing air at about 70 ml / min, and the temperature was raised from 380 to 400 ° C. for about 1 hour. A one-step heat treatment was performed. Then, the carbide produced after rapid cooling of the autoclave was scraped out and pulverized and mixed. This powder is pelletized with a tablet molding machine and nitrogen is not passed through. However, the second stage heat treatment was performed at a predetermined temperature. The mixing ratio of asphalt and nickel naphthenate is 1: 2,
1: 1 and 2: 1. The nickel content of the nickel naphthenate used is 5%. This result is shown in FIGS.
It was shown to.
図２から分かるように、比表面積の最高値が320cm2／ｇ
に達し、第２段階の熱処理は600℃が一番良い。磁性は
ニッケル含有量が多いほど高いが、第２段階の熱処理温
度を高めて行くと山型を描く傾向がみられる。なお、こ
の場合の最高磁化は約４で金属ニッケルの１／５であ
る。As can be seen from Fig. 2, the maximum specific surface area is 320 cm 2 / g.
And the second stage heat treatment is best done at 600 ° C. The higher the nickel content, the higher the magnetism, but there is a tendency to draw a chevron when the second stage heat treatment temperature is increased. The maximum magnetization in this case is about 4, which is 1/5 of that of metallic nickel.
図１は、第２段階の熱処理温度と比表面積の関係を見た
ものである。アスファルトとナフテン酸ニッケルの混合
割合が異なるが、他の条件は皆同じである。記号は以下
の通りである。■、●、▲はそれぞれ実施例１の、
及びに対応する。図２は、同じく第２段階の熱処理温
度と磁化の関係を見たものである。FIG. 1 shows the relationship between the second stage heat treatment temperature and the specific surface area. The mixing ratios of asphalt and nickel naphthenate are different, but all other conditions are the same. The symbols are as follows. ■, ●, and ▲ are from Example 1, respectively.
Corresponds to and. FIG. 2 also shows the relationship between the second stage heat treatment temperature and the magnetization.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 肥沼 豊 茨城県つくば市小野川16番３ 工業技術院 公害資源研究所内 (72)発明者 水野 光一 茨城県つくば市小野川16番３ 工業技術院 公害資源研究所内 (72)発明者 大内 日出夫 茨城県つくば市小野川16番３ 工業技術院 公害資源研究所内 (72)発明者 北川 浩 茨城県つくば市小野川16番３ 工業技術院 公害資源研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yutaka Konuma 16-3 Onogawa, Tsukuba-shi, Ibaraki Institute of Industrial Science and Technology Pollution Resource Research Institute (72) Koichi Mizuno 16-3 Onogawa, Tsukuba-shi, Ibaraki Industrial Technology Institute In-house (72) Hideo Ouchi, 16-3 Onogawa, Tsukuba-shi, Ibaraki Institute of Industrial Technology, Institute of Pollution Resources (72) Inventor Hiroshi Kitagawa 16-3, Onogawa, Tsukuba-shi, Ibaraki, Institute of Pollution Resources
Claims (1)
をアスファルト類に添加し、酸素を含む気流中で熱処理
をし、その後、不活性ガス中で熱処理を行うことにより
磁性を有する多孔性炭素材料を調製する方法。1. A porous carbon having magnetism by adding a compound of a magnetic metal soluble in asphalts to asphalts, heat-treating the mixture in an air stream containing oxygen, and then heat-treating it in an inert gas. How to prepare materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63126325A JPH068164B2 (en) | 1988-05-24 | 1988-05-24 | Method for preparing magnetic porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63126325A JPH068164B2 (en) | 1988-05-24 | 1988-05-24 | Method for preparing magnetic porous carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01294508A JPH01294508A (en) | 1989-11-28 |
| JPH068164B2 true JPH068164B2 (en) | 1994-02-02 |
Family
ID=14932392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63126325A Expired - Lifetime JPH068164B2 (en) | 1988-05-24 | 1988-05-24 | Method for preparing magnetic porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH068164B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06100308A (en) * | 1991-08-22 | 1994-04-12 | Agency Of Ind Science & Technol | Ferromagnetic carbon material and its production |
-
1988
- 1988-05-24 JP JP63126325A patent/JPH068164B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01294508A (en) | 1989-11-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |