JPH07155589A - Production of carbon material having large specific surface area - Google Patents
Production of carbon material having large specific surface areaInfo
- Publication number
- JPH07155589A JPH07155589A JP5309386A JP30938693A JPH07155589A JP H07155589 A JPH07155589 A JP H07155589A JP 5309386 A JP5309386 A JP 5309386A JP 30938693 A JP30938693 A JP 30938693A JP H07155589 A JPH07155589 A JP H07155589A
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- surface area
- specific surface
- acid
- pores
- 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
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011148 porous material Substances 0.000 claims abstract description 61
- 238000010306 acid treatment Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 230000004913 activation Effects 0.000 abstract description 27
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 9
- 238000012937 correction Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910005965 SO 2 Inorganic materials 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、均一な微細細孔を有す
る高比表面積炭素材料の製造方法に関する。本発明の炭
素材料は高比表面積を有し、均一な微細細孔の占める割
合が多く、常圧および加圧下において、優れた吸着性能
を有するので、例えば高分子物質などの特定成分の吸着
分離の分野に広く利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high specific surface area carbon material having uniform fine pores. The carbon material of the present invention has a high specific surface area, a large proportion of uniform fine pores, and has excellent adsorption performance under normal pressure and pressure. It can be widely used in various fields.
【０００２】[0002]
【従来技術】微細細孔を有する炭素材料としては、一般
的に活性炭が知られており、炭化水素の分別、工業ガス
の精製、公害発生源の除去、食品工業、化学工業におけ
る液相精製、水処理剤等の他に、空気分子ふるい材、貴
金属塩溶液からの貴金属回収、メタンの吸蔵、ガソリン
吸着用キャニスタ−、電気二重層コンデンサ−、および
解毒剤等の吸着剤として各種用途に広範囲で使用され
ている。2. Description of the Related Art Activated carbon is generally known as a carbon material having fine pores, and is used to separate hydrocarbons, purify industrial gas, remove sources of pollution, liquid phase purification in the food industry and chemical industry, In addition to water treatment agents, it has a wide range of applications as an adsorbent for air molecule sieving materials, precious metal recovery from precious metal salt solutions, methane storage, gasoline adsorption canisters, electric double layer capacitors, and detoxifying agents. It is used.
【０００３】一般に、活性炭はヤシガラ、木材、石炭、
石炭および石油コク−ス、有機性樹脂等を原料にして炭
化後、酸化性ガス雰囲気中で賦活して製造されている。
あるいは、セルロ−ス系物質等を原料として塩化亜鉛の
存在下で賦活する薬品賦活法が行われている。これらの
活性炭は、比表面積は５００〜１５００ｍ2 ／ｇと比較
的大きいが、高比表面積を有しているとはいい難い。ま
たその細孔径分布は広く均一な細孔径の占める割合は小
さい。Generally, activated carbon is coconut husk, wood, coal,
It is manufactured by using coal, petroleum coke, organic resin and the like as raw materials, carbonizing them, and then activating them in an oxidizing gas atmosphere.
Alternatively, a chemical activation method in which a cellulosic substance or the like is used as a raw material and activation is performed in the presence of zinc chloride is performed. These activated carbons have a relatively large specific surface area of 500 to 1500 m 2 / g, but it cannot be said that they have a high specific surface area. Further, the pore size distribution is wide, and the ratio of uniform pore size is small.
【０００４】従来、均一な細孔径を有する炭素材料とし
て、例えばポリ塩化ビニリデンを原料とした細孔径５〜
７オングストロームを有するものがカーボンシーブとし
て市販されている。また、ポリビニルアルコールをスル
ホン化し、不活性ガス中で焼成する方法が知られてい
る。（石橋ら、燃料協会誌第62巻、70頁、1983年）これ
らは、いずれも燃焼によって炭素が特殊な骨格構造を形
成させたものである。Conventionally, as a carbon material having a uniform pore diameter, for example, polyvinylidene chloride is used as a raw material and the pore diameter is 5 to 5.
Those having 7 Å are commercially available as carbon sieves. Further, a method is known in which polyvinyl alcohol is sulfonated and baked in an inert gas. (Ishihashi et al., Journal of Fuel Society Vol. 62, p. 70, 1983) All of these are formed by carbon to form a special skeletal structure.
【０００５】また、メソカーボン・マイクロビーズ、炭
素質メソフェーズ（生コークス含む）の原料を酸処理も
しくは酸化処理して原料中の可溶成分を溶出させた後、
不活性ガス雰囲気で加熱処理し均一な微細細孔を有する
炭素材料の製造方法が知られている（特開昭−６０−１
５０８３１号公報、特開平３−１６９３３９号公報
等）。しかしながら、これらは均一な微細細孔を有する
割合が小さく、比表面積が６００ｍ2 ／ｇ程度であり全
細孔容積も小さい。Further, after the raw material of mesocarbon microbeads and carbonaceous mesophase (including raw coke) is subjected to an acid treatment or an oxidation treatment to dissolve soluble components in the raw material,
A method for producing a carbon material having uniform fine pores by heat treatment in an inert gas atmosphere is known (JP-A-60-1).
No. 50831, JP-A-3-169339, etc.). However, these have a small proportion of uniform fine pores, a specific surface area of about 600 m 2 / g, and a small total pore volume.
【０００６】また、均一な微細細孔を有し比表面積が大
きい炭素材料として、活性炭素繊維が知られている。
これらは、ミクロポアの微細細孔が主であるが、均一な
細孔の全体に対して占める割合は、小さく十分とは言え
ない。Activated carbon fiber is known as a carbon material having uniform fine pores and a large specific surface area.
These are mainly fine pores of micropores, but the ratio of uniform pores to the whole is small and cannot be said to be sufficient.
【０００７】従来の一般的な活性炭の製造方法では、原
料を炭化、水蒸気賦活して活性炭を製造しようとした場
合、賦活度を進めても比表面積は２１００ｍ2 ／ｇ程度
が限度で、それ以上の比表面積を有する炭素材料を製造
することは困難であり、また、均一な微細細孔を多く占
めるものも得ることができない。In the conventional general method for producing activated carbon, when an activated carbon is produced by carbonizing a raw material and activating steam, the specific surface area is limited to about 2100 m 2 / g even if the activation is advanced, and more than that. It is difficult to produce a carbon material having a specific surface area of 1, and it is also impossible to obtain a carbon material having many uniform fine pores.
【０００８】近年、活性炭を製造する方法として、次に
記載する水酸化カリウム等によるアルカリ蒸気賦活法が
提案されている。例えば、特公昭６２−６１５２９号、
米国特許第３６２４００４号、米国特許第３６４２６５
７号、米国特許第３８３３５１４号、特開平１−２３０
４１４号、特開平２−９７４１４号などが知られてい
る。しかしながら、これらは、一般的な活性炭の製造方
法における炭化、賦活する方法に比べて、微細細孔の占
める割合の多い高比表面積炭素材料が得られるものの均
一な細孔半径の占める割合は小さい。In recent years, as a method for producing activated carbon, an alkali vapor activation method using potassium hydroxide or the like has been proposed as described below. For example, Japanese Patent Publication No. 62-61529,
US Pat. No. 3,624,004, US Pat. No. 3,642,265
7, U.S. Pat. No. 3,833,514, JP-A 1-230.
No. 414 and Japanese Patent Laid-Open No. 2-97414 are known. However, as compared with the carbonization and activation methods in a general activated carbon production method, although a high specific surface area carbon material having a large proportion of fine pores can be obtained, the proportion of uniform pore radius is small.
【０００９】また、いずれの方法もアルカリ蒸気を使用
する方法であり、炭素質材料に対して水酸化カリウム等
のアルカリ金属化合物を、好適には２倍以上の大過剰を
添加する必要があるため焼成工程での装置の腐食をまね
き、かつ炭素質材料とアルカリ金属化合物との混合物が
焼成中に粘着し流動性がわるく装置を詰まらせる等の問
題があり取扱が困難である。Further, both methods are methods using alkali vapor, and it is necessary to add an alkali metal compound such as potassium hydroxide to the carbonaceous material, preferably in a large excess of 2 times or more. It is difficult to handle because there is a problem that it causes corrosion of the equipment in the firing step, and the mixture of the carbonaceous material and the alkali metal compound sticks during firing and the fluidity is poor and the equipment is clogged.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、このような
状況に鑑み、高比表面積を有する炭素材料ならびに高比
表面積を有しかつ微細細孔分布がシャープで均一な微細
細孔の占める割合の多い炭素材料を、安価で広範囲の原
料から容易に製造する方法を提供するものである。In view of such a situation, the present invention is directed to a carbon material having a high specific surface area and a proportion of fine pores having a high specific surface area and a sharp fine pore distribution and uniform. A method of easily producing a carbon material containing a large amount of carbon from a wide range of raw materials at low cost.
【００１１】[0011]
【課題を解決するための手段】本発明者は、上記のよう
な欠点を解決するため鋭意研究を重ねた結果、比較的廉
価に生産されている炭素質材料を原料とし、該原料炭素
質材料中の無機成分を除去した後、加熱し賦活すること
により、高比表面積を有する炭素材料ならびに高比表面
積を有しかつ均一な微細細孔の占める割合の多い炭素材
料が製造できることを見い出し本発明を完成した。As a result of intensive studies to solve the above-mentioned drawbacks, the present inventor uses a carbonaceous material produced at a relatively low cost as a raw material, and the raw material carbonaceous material is used. It was found that a carbon material having a high specific surface area as well as a carbon material having a high specific surface area and having a large proportion of uniform fine pores can be produced by removing the inorganic components therein and then activating it by heating. Was completed.
【００１２】すなわち、本発明は、無機成分の含有量が
４ｗｔ％未満である炭素質材料を、酸化性ガス雰囲気下
で加熱処理することを特徴とする均一な微細細孔を有す
る高比表面積炭素材料およびその製造方法に係る。That is, according to the present invention, a carbonaceous material having an inorganic component content of less than 4 wt% is heat-treated in an oxidizing gas atmosphere, and a high specific surface area carbon having uniform fine pores. The present invention relates to a material and a manufacturing method thereof.
【００１３】本発明における無機成分の含有量が４ｗｔ
％未満である炭素質材料は、後述するように細孔を有す
る炭素質材料を酸、煮沸または超音波による処理を行う
ことにより得られる。The content of the inorganic component in the present invention is 4 wt.
The carbonaceous material having a content of less than 10% can be obtained by treating a carbonaceous material having pores with an acid, boiling or ultrasonic waves as described later.
【００１４】本発明の方法により得られる高比表面積炭
素材料は、５．５〜６．５オングストロームの細孔が全
容積当り少なくとも１０容積％を占め、好適には６５容
積％以上占め、しかも微細細孔分布がシャープな高性能
な炭素材料である。The high specific surface area carbonaceous material obtained by the method of the present invention has 5.5 to 6.5 angstrom pores occupying at least 10% by volume, preferably 65% by volume or more, based on the total volume, and fine It is a high performance carbon material with a sharp pore distribution.
【００１５】以下に本発明について詳細に説明する。本
発明において原料として用いられる細孔を有する炭素質
材料としては、ヤシガラ、麦ガラ、もみがら、のこく
ず、木材、及び、パルプ廃液などの植物系、および 石
炭、石油、それらのコ−クス、並びにピッチなどの重質
歴青物系の活性炭が使用できる。この炭素質材料の形状
は、特に制限がなく、粉末状、破砕状、顆粒状、およ
び、円柱状のいずれでも使用できる。粒度は、１〜３０
０メッシュの範囲で粗粒または細粒のいずれも使用でき
るが粒径が小さいほど賦活時間を短くするこができ好ま
しい。しかしながら、粒径が大きくても賦活時間を充分
長くすれば均一な微細細孔を有する炭素材料を得ること
ができる。本発明の方法は、原料の形状を維持したまま
で目的とする炭素材料を得ることができるため必ずしも
成型する必要がなく、バインダ−等で成型する必要がな
いため工業的に有利な製造方法である。The present invention will be described in detail below. Examples of the carbonaceous material having fine pores used as a raw material in the present invention include coconut husk, wheat husk, chaff, sawdust, wood, and plant systems such as pulp waste liquor, and coal, petroleum, and cokes thereof. , And heavy bituminous activated carbon such as pitch can be used. The shape of the carbonaceous material is not particularly limited, and any of powdery, crushed, granular, and cylindrical shapes can be used. Particle size is 1-30
Either coarse particles or fine particles can be used within the range of 0 mesh, but a smaller particle diameter is preferable because the activation time can be shortened. However, even if the particle size is large, a carbon material having uniform fine pores can be obtained if the activation time is sufficiently long. The method of the present invention is an industrially advantageous manufacturing method because it is not always necessary to mold the target carbon material while maintaining the shape of the raw material, and it is not necessary to mold it with a binder or the like. is there.
【００１６】通常、炭質質材料中には多種の無機成分が
含まれており、これらの無機成分を多量に含む場合には
均一な微細細孔の形成を阻害し高比表面積化が困難とな
る。炭素質材料に通常含まれている無機成分、例えばＭ
ｇ、Ａｌ、Ｂ、Ｔｉ、Ｓｉ、Ｐ、Ｃｕなどは、その含有
量が４ｗｔ％未満であれば均一な微細細孔の形成、高比
表面積化に特に問題ない。しかし、特にカリウム、ナト
リウム、カルシウム、鉄などを多量に含む場合はその影
響が大であり、これらの成分は２ｗｔ％以下の量までに
除去することが好ましい。Usually, carbonaceous materials contain various kinds of inorganic components, and when a large amount of these inorganic components is contained, formation of uniform fine pores is hindered and it becomes difficult to increase the specific surface area. . Inorganic components usually contained in carbonaceous materials, eg M
If the content of g, Al, B, Ti, Si, P, Cu, etc. is less than 4 wt%, there is no particular problem in forming uniform fine pores and increasing the specific surface area. However, particularly when a large amount of potassium, sodium, calcium, iron, etc. is contained, the effect is great, and it is preferable to remove these components up to 2 wt% or less.
【００１７】従って、本発明において使用される炭素質
材料は、無機成分の含有量が４ｗｔ％未満であることが
必要である。無機成分の含有量が４ｗｔ％未満の炭素質
材料であればそのまま使用することができるが、通常、
炭素質材料は種々の無機成分を含んでいるので、無機成
分を除去することが必要である。これら無機成分の除去
方法としては、酸による処理、水による煮沸処理、溶液
中での超音波処理等が有効であるが、通常は酸による処
理が好適である。Therefore, the carbonaceous material used in the present invention must have an inorganic component content of less than 4 wt%. A carbonaceous material having an inorganic component content of less than 4 wt% can be used as it is.
Since the carbonaceous material contains various inorganic components, it is necessary to remove the inorganic components. As a method for removing these inorganic components, treatment with acid, boiling treatment with water, ultrasonic treatment in a solution and the like are effective, but treatment with acid is usually preferable.
【００１８】酸処理に使用される酸の種類としては、一
般に塩酸、硫酸、硝酸、リン酸、炭酸及びフッ酸などの
無機酸、ギ酸、酢酸およびシュウ酸などの有機酸が好適
に使用される。これらの酸類は、通常水溶液で使用さ
れ、一般には０．００１〜１００ｗｔ％、好ましくは
０．１ｗｔ％〜５０ｗｔ％の濃度範囲で使用される。ま
た、使用量は、原料炭素質材料に対し水溶液の重量比
で、1 〜４０倍、好ましくは２〜２０倍の範囲である。Generally, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid and hydrofluoric acid, and organic acids such as formic acid, acetic acid and oxalic acid are preferably used as the kind of acid used for the acid treatment. . These acids are usually used in an aqueous solution and generally used in a concentration range of 0.001 to 100 wt%, preferably 0.1 wt% to 50 wt%. The amount used is in the range of 1 to 40 times, preferably 2 to 20 times the weight ratio of the aqueous solution to the raw carbonaceous material.
【００１９】処理温度は、特に加温する必要はなく常温
で十分であるが、所望により加温してもよい。また処理
時間は、１０分〜１０時間、好ましくは３０分〜５時間
の範囲である。本発明において処理液濃度、処理液量、
温度、及び時間の関係は、濃度、液量、温度が高いほど
短時間の処理で行うことができる。The treatment temperature is not particularly required to be warmed, and room temperature is sufficient, but it may be warmed if desired. The treatment time is in the range of 10 minutes to 10 hours, preferably 30 minutes to 5 hours. In the present invention, the treatment liquid concentration, the treatment liquid amount,
Regarding the relationship between the temperature and the time, the higher the concentration, the liquid amount, and the temperature, the shorter the treatment time.
【００２０】本発明においては、一般には無機成分の除
去処理を行った後、ろ過、水洗を行い乾燥して加熱し賦
活を行うが、場合によってはろ過後必ずしも水洗、乾燥
工程を経ることなく、ろ過後直接賦活工程に供するこも
できる。In the present invention, generally, after removal of inorganic components, filtration, washing with water, drying and heating for activation are carried out. However, in some cases, after washing, the washing and drying steps are not always required. It can also be directly subjected to the activation step after filtration.
【００２１】本発明において賦活工程は酸性ガス雰囲気
下に実施される。ここで酸化性ガス雰囲気としては、水
蒸気、二酸化炭素、酸素、オゾン、および二酸化窒素な
どが使用できる。さらにこれらのガスは燃焼ガスあるい
は不活性ガスと混合して用いることもできる。特に水蒸
気、二酸化炭素、及びこれらのガスと燃焼ガスあるいは
不活性ガスとの混合ガスの使用が好ましい。なお、本発
明の方法においては、窒素、アルゴン、ヘリウム等の不
活性ガスのみの雰囲気下で加熱処理しても賦活効果は殆
どなく好ましくない。In the present invention, the activation step is carried out under an acidic gas atmosphere. Here, water vapor, carbon dioxide, oxygen, ozone, nitrogen dioxide and the like can be used as the oxidizing gas atmosphere. Further, these gases can be used as a mixture with a combustion gas or an inert gas. It is particularly preferable to use steam, carbon dioxide, or a mixed gas of these gases with a combustion gas or an inert gas. In the method of the present invention, even if the heat treatment is carried out in an atmosphere of only an inert gas such as nitrogen, argon or helium, there is almost no activation effect, which is not preferable.
【００２２】本発明の賦活温度は、通常５００゜Ｃ〜１
２００゜Ｃ、好ましくは７００゜Ｃ〜１１００゜Ｃの範
囲である。また賦活温度での保持時間は、３０分〜６時
間、好ましくは１〜４時間の範囲である。一般には賦活
温度が高く保持時間が長いほど均一な微細細孔の炭素材
料が得られる傾向にあるが、上記温度以上に高くしても
賦活収量が低下するため上記範囲が好適である。The activation temperature of the present invention is usually 500 ° C to 1 ° C.
It is in the range of 200 ° C, preferably 700 ° C to 1100 ° C. The holding time at the activation temperature is in the range of 30 minutes to 6 hours, preferably 1 to 4 hours. Generally, the higher the activation temperature and the longer the holding time, the more uniform the carbon material with fine pores tends to be obtained. However, the activation yield is lowered even if the activation temperature is higher than the above temperature, so that the above range is preferable.
【００２３】賦活工程は、特に攪拌を行う必要はなく静
置式でもよいが、被処理炭素質材料が均一に加熱される
ことが望ましく、好ましくは移動式、回転式、および流
動式で実施するのがよい。 また、賦活方式について
は、バッチ式でもよいが、特に被処理炭素質材料が流動
性に優れている場合は、操作性が容易なことから連続式
で実施することが工業的には実用的である。The activation step does not need to be particularly stirred and may be a stationary type, but it is desirable that the carbonaceous material to be treated is uniformly heated, and it is preferably carried out by a mobile type, a rotary type or a flow type. Is good. The activation method may be a batch method, but particularly when the carbonaceous material to be treated is excellent in fluidity, it is industrially practical to carry out the continuous method because it is easy to operate. is there.
【００２４】本発明の方法において、均一な微細細孔
は、賦活工程における加熱によって炭素質の酸化が局部
的に進み、炭素骨格の拡大化と収縮により細孔が均一化
されるものと推察される。賦活終了後は、特に洗浄等を
行うことなくそのまま高品質の炭素材料として使用する
ことができるが、賦活後酸先浄、又は水洗、乾燥を行う
ことによりさらに無機成分の少ない高品質の高比表面積
を有する活性炭素材料とすることができる。In the method of the present invention, it is presumed that the uniform fine pores are such that the carbonaceous oxidation is locally promoted by the heating in the activation step, and the pores are made uniform by the expansion and contraction of the carbon skeleton. It After completion of activation, it can be used as a high-quality carbon material as it is without performing washing or the like, but after activation, acid pre-cleaning, or washing with water, and high ratio of high quality with less inorganic components by performing drying. It can be an activated carbon material having a surface area.
【００２５】本発明により得られる高比表面積炭素材料
の物性は、全細孔容積のうち５．５〜６．５Åの大きさ
の細孔の占める割合が６５％（容積）以上で、細孔分布
幅がシャープで均一な微細細孔を有しており、比表面積
２１００〜３６００ｍ2 ／ｇ、細孔容積１．０〜２．４
ｍｌ／ｇ、平均細孔半径１０〜２０Åのものである。The physical properties of the high specific surface area carbon material obtained by the present invention are such that the proportion of the pores having a size of 5.5 to 6.5Å in the total pore volume is 65% (volume) or more. It has fine fine pores with a uniform distribution width and a specific surface area of 2100 to 3600 m 2 / g and a pore volume of 1.0 to 2.4.
ml / g, average pore radius 10-20Å.
【００２６】本発明の高比表面積炭素材料は、上記のよ
うに均一でシャ−プな微細細孔を有しているため分子サ
イズの小さい物質を吸着分離するのに好適な材料であ
る。また、高比表面積を有するため着色成分、無機物
質、有機物物、ＳＯ2 、ＣＯ、ＣＯ2 等有害物質の吸着
除去、オゾンおよびＮＯX の分解、溶存金属の吸着回
収、メタンの吸蔵、ガソリン吸着用キャニスタ−、電気
二重層型コンデンサ−、電池の電極用、および、医薬用
などに用いることができる。Since the high specific surface area carbon material of the present invention has uniform and sharp fine pores as described above, it is suitable for adsorbing and separating a substance having a small molecular size. Also, since it has a high specific surface area, it adsorbs and removes coloring components, inorganic substances, organic substances, harmful substances such as SO 2 , CO, and CO 2 , decomposes ozone and NO x , adsorbs and recovers dissolved metals, adsorbs methane, and adsorbs gasoline. It can be used for a canister, an electric double layer capacitor, an electrode of a battery, a medicine, and the like.
【００２７】[0027]
【実施例】次に本発明の方法を実施例によりさらに具体
的に説明する。各炭素材料の物性は、Ｎ2 ガス吸着法に
よる吸着脱離等温線を求め、ＢＥＴ比表面積は、Ｐ／Ｐ
O ＝０．０２〜０．３の範囲でＢＥＴプロット（多点
法）により求めた。 （湯浅アイオニクス社製のオ−ト
ソ−ブ−６により測定） ミクロポアは半径１０Å以下の細孔、メソポアは、半径
１０〜２５０Åの細孔である。また、全細孔容積に占め
る約６Åの細孔容積の割合とは、脱離側の細孔分布（細
孔半径に対する細孔容積の分布）５．５〜６．５Åの容
積をＶｏｌ％で表した。EXAMPLES Next, the method of the present invention will be described more specifically by way of examples. For the physical properties of each carbon material, the adsorption / desorption isotherm obtained by the N 2 gas adsorption method was determined, and the BET specific surface area was P / P.
It was determined by BET plot (multipoint method) in the range of O = 0.02 to 0.3. (Measurement using Autosorb-6 manufactured by Yuasa Ionics) Micropores are pores with a radius of 10 Å or less, and mesopores are pores with a radius of 10 to 250 Å. Further, the ratio of the pore volume of about 6 Å to the total pore volume means the volume distribution of the pores on the desorption side (distribution of the pore volume with respect to the pore radius) of 5.5 to 6.5 Å in Vol%. expressed.
【００２８】実施例１ ２００ｍｌ容積三角フラスコに１ｗｔ％Ｈ2 ＳＯ4 水溶
液５０ｇ仕込み、その中に１２〜３２メッシュ通過の大
きさの市販の炭素質材料（無機成分５ｗｔ％）１０ｇを
投入し室温下で２．５時間攪拌処理した。次に、ろ過
し、処理した炭素質材料をイオン交換水２００ｍｌ／１
回で３回洗浄した後、真空乾燥器で１ｍｍＨｇ下、１２
０゜Ｃ、２時間乾燥した。得られた炭素質材料中の無機
成分含量は、０．７ ｗｔ％である。この炭素質材料３
ｇを石英反応管に仕込み二酸化炭素気流中で昇温速度２
５゜Ｃ／分で１０００゜Ｃまで昇温し、同温度で６０分
間保持して賦活を行い均一な微細細孔を有する炭素材料
を得た。得られた炭素材料の物性の測定結果を下記に示
す。Example 1 A 200 ml Erlenmeyer flask was charged with 50 g of a 1 wt% H 2 SO 4 aqueous solution, and 10 g of a commercially available carbonaceous material (inorganic component 5 wt%) having a size of 12 to 32 mesh was charged therein. And stirred for 2.5 hours. Next, the filtered and treated carbonaceous material is deionized water 200 ml / 1
After washing three times, use a vacuum dryer under 1 mmHg for 12
It was dried at 0 ° C for 2 hours. The inorganic component content in the obtained carbonaceous material is 0.7 wt%. This carbonaceous material 3
Charge g into a quartz reaction tube and raise the temperature in a carbon dioxide stream 2
The temperature was raised to 1000 ° C. at 5 ° C./min, and the temperature was maintained for 60 minutes for activation to obtain a carbon material having uniform fine pores. The measurement results of the physical properties of the obtained carbon material are shown below.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例２ １ｗｔ％Ｈ2 ＳＯ4 水溶液に代えて６１ｗｔ％Ｈ3 ＰＯ
4 水溶液で処理すること以外は実施例１と同様にして行
い均一な微細細孔を有する炭素材料を得た。酸処理後の
無機成分含量、および得られた炭素材料の物性を下記に
示す。Example 2 61 wt% H 3 PO in place of 1 wt% H 2 SO 4 aqueous solution
4 A carbon material having uniform fine pores was obtained in the same manner as in Example 1 except that the carbon material was treated with an aqueous solution. The content of inorganic components after the acid treatment and the physical properties of the obtained carbon material are shown below.
【００３１】[0031]
【表２】 [Table 2]
【００３２】実施例３ １ｗｔ％Ｈ2 ＳＯ4 水溶液に代えて６１ｗｔ％ＨＣＯＯ
Ｈ水溶液により処理する以外は実施例１と同様に実施す
る。酸処理後の無機成分の含有量および得られた高比表
面積炭素材料の物性を以下に示す。Example 3 61 wt% HCOO instead of 1 wt% H 2 SO 4 aqueous solution
The same procedure as in Example 1 is performed except that the treatment is performed with the H 2 aqueous solution. The content of the inorganic component after the acid treatment and the physical properties of the obtained high specific surface area carbon material are shown below.
【００３３】[0033]
【表３】 [Table 3]
【００３４】実施例４ １ｗｔ％Ｈ2 ＳＯ4 水溶液処理に代えて、水による煮沸
処理および超音波処理を実施すること及び賦活時間８０
分で行うこと以外は実施例１と同様にして行い均一な微
細細孔を有する炭素材料を得た。処理後の無機成分含
量、および得られた炭素材料の物性を下記に示す。Example 4 Instead of treatment with 1 wt% H 2 SO 4 aqueous solution, boiling treatment with water and ultrasonic treatment were carried out, and activation time was 80.
A carbon material having uniform fine pores was obtained in the same manner as in Example 1 except that the carbon material was used for a minute. The content of the inorganic components after the treatment and the physical properties of the obtained carbon material are shown below.
【００３５】[0035]
【表４】 [Table 4]
【００３６】比較例 １ 実施例１に使用した炭素質材料を何らの処理も行うこと
なく実施例１と同様にして賦活を行い炭素材料を得た。
得られた炭素材料の物性を示す。Comparative Example 1 The carbonaceous material used in Example 1 was activated in the same manner as in Example 1 without any treatment to obtain a carbon material.
The physical properties of the obtained carbon material are shown below.
【００３７】[0037]
【表５】 [Table 5]
【００３８】上記から分かるように原料中に無機成分の
含有量が５ｗｔ％の場合は比表面積は小さく約６Åの細
孔容積の割合が低く、均一な微細細孔を有する高比表面
積炭素材料を得ることができない。As can be seen from the above, when the content of the inorganic component in the raw material is 5 wt%, the specific surface area is small and the ratio of the pore volume of about 6Å is low, and a high specific surface area carbon material having uniform fine pores is obtained. Can't get
【００３９】実施例１および比較例１で得られた炭素材
料を用いて、９kg/cm2および３０kg/cm2の加圧下におけ
るメタンの吸蔵試験を行った。その結果を下記に示すUsing the carbon materials obtained in Example 1 and Comparative Example 1, a methane occlusion test was performed under a pressure of 9 kg / cm 2 and 30 kg / cm 2 . The results are shown below
【００４０】[0040]
【表６】 [Table 6]
【００４１】比較例 ２ 酸化性ガス雰囲気に代えて不活性ガス雰囲気下で行うこ
と以外は実施例１と同様にして行い炭素材料を得た。得
られた炭素材料の物性を示す。Comparative Example 2 A carbon material was obtained in the same manner as in Example 1 except that the inert gas atmosphere was used instead of the oxidizing gas atmosphere. The physical properties of the obtained carbon material are shown below.
【００４２】[0042]
【表７】 [Table 7]
【００４３】[0043]
【発明の効果】本発明方法によれば細孔を有する炭素質
材料から無機成分を除去後、賦活することにより、高比
表面積炭素を有し均一な微細細孔が全体に対して占める
割合が極めて高い炭素材料を得ることができる。本発明
の炭素材料は、常圧および加圧下において、優れた吸着
性能を有し、特に特定の均一な微細細孔の占める割合が
極めて多いため、混合ガス中の特定成分の吸着分離など
広範囲の分野で利用できる。According to the method of the present invention, the inorganic components are removed from the carbonaceous material having pores and then activated so that the ratio of uniform fine pores having a high specific surface area carbon to the whole is increased. An extremely high carbon material can be obtained. The carbon material of the present invention has excellent adsorption performance under normal pressure and pressure, and in particular, because the proportion of specific uniform fine pores is extremely large, it can be used in a wide range such as adsorption separation of specific components in a mixed gas. Available in the field.
【手続補正書】[Procedure amendment]
【提出日】平成６年８月１６日[Submission date] August 16, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００１[Correction target item name] 0001
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００１】[0001]
【産業上の利用分野】本発明は、均一な微細細孔を有す
る高比表面積炭素材料の製造方法に関する。本発明の炭
素材料は高比表面積を有し、均一な微細細孔の占める割
合が多く、常圧および加圧において、優れた吸着性能を
有するので、例えば低分子物質などの特定成分の吸着分
離の分野に広く利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high specific surface area carbon material having uniform fine pores. Since the carbon material of the present invention has a high specific surface area, a large proportion of uniform fine pores occupy, and has excellent adsorption performance under normal pressure and pressure, it can be adsorbed and separated from a specific component such as a low molecular weight substance. It can be widely used in various fields.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１６】通常、炭素質材料中には多種の目基成分が
含まれており、これらの無機成分を多量に含む場合には
均一な微細細孔の形成を阻害し高比表面積化が困難とな
る。炭素質材料に通常含まれている無機成分、例えばＭ
ｇ、Ａｌ、Ｂ、Ｔｉ、Ｓｉ、Ｐ、Ｃｕなどは、その含有
量が４ｗｔ％未満であれば均一な微細細孔の形成、高比
表面積化に特に問題ない。Generally, carbonaceous materials contain various kinds of base components, and when a large amount of these inorganic components is contained, formation of uniform fine pores is hindered and it is difficult to increase the specific surface area. Become. Inorganic components usually contained in carbonaceous materials, eg M
If the content of g, Al, B, Ti, Si, P, Cu, etc. is less than 4 wt%, there is no particular problem in forming uniform fine pores and increasing the specific surface area.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Name of item to be corrected] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】本発明の方法において、均一な微細細孔
は、賦活工程における加熱によって炭素質の酸化が局部
的に進み、炭素骨格の拡大化と収縮により細孔が均一化
されるものと推察される。賦活終了後は、特に洗浄等を
行うことなくそのまま高品質の炭素材料として使用する
ことができるが、賦活後酸洗浄、又は水洗、乾燥を行う
ことによりさらに無機成分の少ない高品質の高比表面積
を有する活性炭素材料とすることができる。In the method of the present invention, it is presumed that the uniform fine pores are such that the carbonaceous oxidation is locally promoted by the heating in the activation step, and the pores are made uniform by the expansion and contraction of the carbon skeleton. It After activation, it can be used as it is as a high-quality carbon material without any particular washing, but after activation it is subjected to acid washing , or water washing, and drying, and high quality high specific surface area with less inorganic components. Can be an activated carbon material.
Claims (3)
は超音波による処理を行い炭素質材料中の無機成分の含
有量を４ｗｔ％未満とし、次いで、酸化性ガス雰囲気中
において賦活することを特徴とする均一微細細孔を有す
る高比表面積炭素材料の製造方法。1. A carbonaceous material having pores is treated with acid, boiling or ultrasonic waves to reduce the content of inorganic components in the carbonaceous material to less than 4 wt%, and then activated in an oxidizing gas atmosphere. A method for producing a high specific surface area carbon material having uniform fine pores, characterized by:
の細孔を有する活性炭であることを特徴とする請求項１
記載の製造方法。2. The carbonaceous material is a plant-based or heavy bituminous-based activated carbon having pores.
The manufacturing method described.
ら選ばれる無機酸または有機酸の水溶液により酸処理を
行うことを特徴とする請求項１記載の製造方法。3. The method according to claim 1, wherein the acid treatment is performed with an aqueous solution of an inorganic acid or an organic acid selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or formic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30938693A JP3446771B2 (en) | 1993-12-09 | 1993-12-09 | Method for producing high specific surface area carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30938693A JP3446771B2 (en) | 1993-12-09 | 1993-12-09 | Method for producing high specific surface area carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07155589A true JPH07155589A (en) | 1995-06-20 |
| JP3446771B2 JP3446771B2 (en) | 2003-09-16 |
Family
ID=17992390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30938693A Expired - Fee Related JP3446771B2 (en) | 1993-12-09 | 1993-12-09 | Method for producing high specific surface area carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3446771B2 (en) |
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