JP3195963B2 - Method for producing metal-containing activated carbon - Google Patents
Method for producing metal-containing activated carbonInfo
- Publication number
- JP3195963B2 JP3195963B2 JP09411892A JP9411892A JP3195963B2 JP 3195963 B2 JP3195963 B2 JP 3195963B2 JP 09411892 A JP09411892 A JP 09411892A JP 9411892 A JP9411892 A JP 9411892A JP 3195963 B2 JP3195963 B2 JP 3195963B2
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- softening point
- activated carbon
- metal
- pitch
- compound
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、金属含有活性炭の製造
方法に関する。The present invention relates to a method for producing a metal-containing activated carbon.
【０００２】[0002]
【従来の技術及びその課題】従来の活性炭は、主として
炭素を水蒸気存在下に焼成（賦活）して製造される。こ
のような方法によれば、主としてミクロポア（口径：
０．８〜２ｎｍ）及びサブミクロポア（口径：０．８ｎ
ｍ未満）の発達した活性炭が製造され、メソポア（口
径：２〜５０ｎｍ）及びマクロポア（口径：５０ｎｍ以
上）の比率は合計でも１０％に満たないものであった。
そのような活性炭は、比表面積が非常に大きく吸着能力
に優れている半面、活性炭に吸着される物質の大きさは
活性炭のポアの大きさによって制限されるので、従来の
活性炭は、２ｎｍ以下の口径内に入り得る小分子の吸着
には適していたが、より大きな分子を効率的に吸着する
ことはできなかった（図１参照）。2. Description of the Related Art Conventional activated carbon is mainly produced by firing (activating) carbon in the presence of steam. According to such a method, micropores (diameter:
0.8 to 2 nm) and sub-micropore (diameter: 0.8 n)
m), and the ratio of mesopores (diameter: 2 to 50 nm) and macropores (diameter: 50 nm or more) was less than 10% in total.
Although such activated carbon has a very large specific surface area and excellent adsorption capacity, the size of the substance adsorbed on the activated carbon is limited by the size of the pores of the activated carbon. Although suitable for the adsorption of small molecules that could enter the aperture, larger molecules could not be adsorbed efficiently (see FIG. 1).
【０００３】活性炭のポアの口径を大きくし、中分子以
上の物質を吸着する試みは従来から成されていたが、未
だ満足のいく結果は得られていない。Attempts to increase the pore size of activated carbon pores and to adsorb substances of medium or higher molecular weight have been made, but no satisfactory results have yet been obtained.
【０００４】本発明の目的は、活性炭のポアの大きさを
コントロールし、従来品では吸着することが難しかった
中分子及び大分子を選択的に吸着し得る活性炭の製造方
法を提供することにある。An object of the present invention is to provide a method for producing activated carbon in which the size of the pores of activated carbon can be controlled and medium and large molecules, which are difficult to adsorb with conventional products, can be selectively adsorbed. .
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記目的を
達成するため鋭意検討を重ねた結果、低軟化点ピッチと
金属化合物を混合してなる低軟化点焼成原料を炭素化処
理及び賦活処理すること或いは低軟化点ピッチとイッテ
ルビウム化合物及び／又はイットリウム化合物を混合し
てなる焼成原料を紡糸ピッチと混合し、得られた高軟化
点焼成原料を不融化処理、炭素化処理及び水蒸気賦活処
理することによりメソポア（口径：２〜５０ｎｍ）ある
いはマクロポア（口径：５０ｎｍ以上）を有する活性炭
が得られることを見出した。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a low softening point calcined raw material obtained by mixing a low softening point pitch and a metal compound is subjected to carbonization treatment and activation. Processing or mixing a baking raw material obtained by mixing a low softening point pitch with an ytterbium compound and / or a yttrium compound with a spinning pitch, and subjecting the obtained high softening point baking material to infusibilization, carbonization, and steam activation. By doing so, it was found that activated carbon having mesopores (diameter: 2 to 50 nm) or macropores (diameter: 50 nm or more) can be obtained.
【０００６】即ち、本発明は、低軟化点ピッチと金属化
合物を混合してなる低軟化点焼成原料を炭素化処理及び
賦活処理することを特徴とする金属含有活性炭の製造方
法（以下、第１方法という）を提供するものである。That is, the present invention provides a method for producing a metal-containing activated carbon, which comprises a step of carbonizing and activating a raw material having a low softening point obtained by mixing a low softening point pitch and a metal compound. Method).
【０００７】本発明はまた、低軟化点ピッチとイッテル
ビウム化合物、サマリウム化合物、ネオジウム化合物及
びイットリウム化合物からなる群の少なくとも１種を混
合してなる焼成原料を紡糸ピッチと混合し、得られた高
軟化点焼成原料を不融化処理又は炭素化処理、及び水蒸
気賦活処理することを特徴とする金属含有活性炭の製造
方法（以下、第２方法という）を提供するものである。[0007] The present invention also relates to a high softening point obtained by mixing a firing material obtained by mixing a low softening point pitch with at least one of the group consisting of a ytterbium compound, a samarium compound, a neodymium compound and an yttrium compound with a spinning pitch. An object of the present invention is to provide a method for producing a metal-containing activated carbon (hereinafter, referred to as a second method), which comprises subjecting a point firing raw material to an infusibilization treatment or a carbonization treatment and a steam activation treatment.
【０００８】本発明の第１方法で得られる金属含有活性
炭は、賦活収率が２０％以上で、メソポアの比率が１０
〜９９％、好ましくは賦活収率が４０〜７０％でメソポ
アの比率が３０〜９０％のものである。[0008] The activated carbon containing metal obtained by the first method of the present invention has an activation yield of 20% or more and a mesopore ratio of 10%.
９９99%, preferably an activation yield of 40-70% and a mesopore ratio of 30-90%.
【０００９】本発明の第２方法で得られる金属含有活性
炭は、賦活収率が２５％以上で、メソポアの比率が１５
〜９９％、好ましくは賦活収率が２５〜６０％でメソポ
アの比率が２０〜９０％のものである。The activated carbon containing metal obtained by the second method of the present invention has an activation yield of 25% or more and a mesopore ratio of 15%.
９９99%, preferably an activation yield of 25-60% and a mesopore ratio of 20-90%.
【００１０】本発明において低軟化点ピッチとは、軟化
点が６０〜１５０℃程度、好ましくは７０〜１２０℃程
度のピッチであり、その炭素源としては石炭ピッチ、石
油ピッチ及びこれらピッチの有機溶媒可溶分を使用する
ことができる。In the present invention, the low softening point pitch is a pitch having a softening point of about 60 to 150 ° C., preferably about 70 to 120 ° C. As the carbon source, coal pitch, petroleum pitch and organic solvents for these pitches are used. Soluble components can be used.
【００１１】本発明において紡糸ピッチとは、軟化点が
２３０℃以上、好ましくは２７０〜２９０℃程度のピッ
チであり、光学的に等方性及び異方性の両方のピッチを
含み、好ましくは石油系及び石炭系のいずれかのピッチ
をニトロ化合物の存在下に重合化処理したものを用い
る。In the present invention, the spinning pitch is a pitch having a softening point of 230 ° C. or higher, preferably about 270 to 290 ° C., and includes both optically isotropic and anisotropic pitches. Use is made of any one of a pitch of a coal type and a coal type which has been polymerized in the presence of a nitro compound.
【００１２】低軟化点ピッチに混合される金属化合物中
の金属成分としては、例えばマグネシウム、カルシウム
などのアルカリ土類金属、アルミニウムなどのＩＩＩＡ
族の元素、その他亜鉛、リン、ゲルマニウム、スズ、セ
レンなどの典型金属、スカンジウム、イットリウム及び
ランタン系列元素（イッテルビウム、ランタン、セリウ
ム等）などの希土類金属、アクチニウム、トリウムなど
のアクチニウム系列元素等が挙げられ、該金属化合物は
これら金属の有機金属塩及び無機金属塩のいずれも使用
できる。好ましい金属としてはスカンジウム、イットリ
ウム及びランタン系列元素（イッテルビウム、ランタ
ン、セリウム等）などの希土類元素が挙げられる。ピッ
チに含有される金属成分としての割合は、ピッチに対し
０．１〜１０重量％程度、好ましくは１〜５重量％程度
である。Examples of the metal component in the metal compound mixed with the low softening point pitch include alkaline earth metals such as magnesium and calcium, and IIIA such as aluminum.
Group metals, other typical metals such as zinc, phosphorus, germanium, tin, and selenium; rare earth metals such as scandium, yttrium, and lanthanum-based elements (such as ytterbium, lanthanum, and cerium); and actinium-based elements such as actinium and thorium. As the metal compound, any of organic metal salts and inorganic metal salts of these metals can be used. Preferred metals include rare earth elements such as scandium, yttrium, and lanthanum series elements (such as ytterbium, lanthanum, and cerium). The ratio of the metal component contained in the pitch is about 0.1 to 10% by weight, preferably about 1 to 5% by weight, based on the pitch.
【００１３】紡糸ピッチに含有される金属としては、イ
ッテルビウムの有機金属塩及び無機金属塩であるイッテ
ルビウム化合物、イットリウムの有機金属塩及び無機金
属塩であるイットリウム化合物、サマリウムの有機金属
塩及び無機金属塩であるサマリウム化合物、ネオジウム
の有機金属塩及び無機金属塩であるネオジウム化合物、
及びこれらの混合物が挙げられる。高軟化点焼成原料に
含有される金属成分の割合は、高軟化点焼成原料に対し
０．１〜１０重量％程度、好ましくは０．５〜５重量％
程度である。紡糸ピッチと焼成原料の混合比率は、紡糸
ピッチ１００重量部に対し焼成原料を０．１〜１０重量
％程度、好ましくは０．５〜５重量％程度である。高軟
化点焼成原料の軟化点は２３０℃以上、好ましくは２７
０〜２９０℃程度である。The metal contained in the spinning pitch includes an ytterbium compound which is an organic metal salt and an inorganic metal salt of ytterbium, an yttrium compound which is an organic metal salt and an inorganic metal salt of yttrium, and an organic metal salt and an inorganic metal salt of samarium. A samarium compound, a neodymium compound which is an organometallic salt and an inorganic metal salt of neodymium,
And mixtures thereof. The ratio of the metal component contained in the raw material having a high softening point is about 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the raw material having a high softening point.
It is about. The mixing ratio of the spinning pitch and the firing material is about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, based on 100 parts by weight of the spinning pitch. The softening point of the raw material having a high softening point is 230 ° C. or higher, preferably 27 ° C.
It is about 0 to 290 ° C.
【００１４】本発明の第１方法においては、上記の低軟
化点ピッチと金属化合物を均一に混合する。均一に混合
するためには、例えば低軟化点ピッチと金属化合物をテ
トラヒドロフラン、ジクロロメタン、ベンゼン、キノリ
ンなどの有機溶媒中に溶解し、溶媒を留去すれば良い。
得られた均一混合物は、好ましくは２００〜３６０℃程
度の条件下、１〜２時間程度、不活性ガス雰囲気下で溶
融し、冷却する。この操作を２〜３回繰り返すことによ
り、本第１方法に適した焼成原料が得られる。In the first method of the present invention, the low softening point pitch and the metal compound are uniformly mixed. For uniform mixing, for example, the low softening point pitch and the metal compound may be dissolved in an organic solvent such as tetrahydrofuran, dichloromethane, benzene, quinoline, and the solvent may be distilled off.
The obtained homogeneous mixture is preferably melted under an inert gas atmosphere at about 200 to 360 ° C. for about 1 to 2 hours, and cooled. By repeating this operation two or three times, a firing raw material suitable for the first method is obtained.
【００１５】得られた低軟化点焼成原料は、次いで炭素
化処理及び賦活処理を行う。炭素化処理は、アルゴン、
窒素などの不活性ガス雰囲気下に、１分あたり５〜１０
℃程度の割合で８００℃程度の温度から１２００℃程度
まで温度を上昇させ、最高温度を最大限１０分間程度保
持して行う。また、賦活処理は、水蒸気、二酸化炭素、
酸素及びこれらの混合物ならびにこれらのガスを窒素な
どの不活性ガスで希釈したガスなどの雰囲気中８００〜
１２００℃程度で５〜１２０分間程度保持することによ
り行う。The obtained raw material having a low softening point is then subjected to a carbonization treatment and an activation treatment. Carbonization treatment is argon,
5 to 10 per minute under an atmosphere of inert gas such as nitrogen
The temperature is raised from a temperature of about 800 ° C. to a temperature of about 1200 ° C. at a rate of about ° C., and the maximum temperature is maintained for a maximum of about 10 minutes. In addition, the activation treatment includes steam, carbon dioxide,
In an atmosphere such as oxygen and a mixture thereof and a gas obtained by diluting these gases with an inert gas such as nitrogen,
It is carried out by holding at about 1200 ° C. for about 5 to 120 minutes.
【００１６】本発明の第２方法において、イッテルビウ
ム化合物及び／又はイットリウム化合物を混合してなる
低軟化点焼成原料と紡糸ピッチとの混合は、例えば３０
０℃程度の温度で２０〜３０分間加熱処理することによ
り行う。In the second method of the present invention, the mixing of the low softening point firing raw material obtained by mixing the ytterbium compound and / or the yttrium compound with the spinning pitch is, for example, 30 minutes.
The heat treatment is performed at a temperature of about 0 ° C. for 20 to 30 minutes.
【００１７】得られた高軟化点焼成原料は、次いで不融
化処理、炭素化処理及び水蒸気賦活処理される。不融化
処理は、常法に従い不活性ガス雰囲気下または酸素含有
雰囲気下に、１分あたり０．１〜５℃程度の割合で３３
０℃程度の温度から４００℃程度まで昇温して行う。ま
た炭素化処理は、アルゴン、窒素などの不活性ガス雰囲
気下に、１分あたり５〜１０℃程度の割合で８００℃程
度の温度から１２００℃程度まで温度を上昇させて行
う。さらに、上記水蒸気賦活処理は、不活性ガス雰囲気
下に８００〜１２００℃程度の温度で５〜１２０分間程
度処理することにより行う。The obtained raw material having a high softening point is then subjected to infusibilization treatment, carbonization treatment and steam activation treatment. The infusibilization treatment is carried out in an inert gas atmosphere or an oxygen-containing atmosphere at a rate of about 0.1 to 5 ° C. per minute according to a conventional method.
The temperature is raised from about 0 ° C. to about 400 ° C. In addition, the carbonization treatment is performed in an atmosphere of an inert gas such as argon or nitrogen at a rate of about 5 to 10 ° C. per minute by raising the temperature from about 800 ° C. to about 1200 ° C. Further, the steam activation treatment is performed by performing the treatment at a temperature of about 800 to 1200 ° C. for about 5 to 120 minutes in an inert gas atmosphere.
【００１８】[0018]
【発明の効果】本発明の第１方法によれば、低軟化点ピ
ッチを使用し、従来の方法に比較してメソポア率が１０
％以上という高い活性炭を得ることができる。特に、ピ
ッチに混合する金属の種類を選択することにより、メソ
ポアをほぼ選択的に有する活性炭を得ることができる。According to the first method of the present invention, a low softening point pitch is used, and the mesopore ratio is reduced by 10 compared to the conventional method.
% Of activated carbon can be obtained. In particular, by selecting the type of metal to be mixed with the pitch, activated carbon having mesopores almost selectively can be obtained.
【００１９】本発明の第２方法によれば、イッテルビウ
ム化合物及び／又はイットリウム化合物を含有している
ため、特に高いメソポア比率を有する活性炭を得ること
ができる。According to the second method of the present invention, an activated carbon having a particularly high mesopore ratio can be obtained because it contains the ytterbium compound and / or the yttrium compound.
【００２０】[0020]
【実施例】以下、本発明を実施例を用いてより詳しく説
明するが、本発明はこれら実施例に限定されるものでは
ない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
【００２１】なお、以下の実施例において、比表面積は
ＢＥＴ一点法、メソポア比表面積は窒素の吸着等温線か
らＢＪＨ法により求めた。In the following examples, the specific surface area was determined by the BET one-point method, and the mesopore specific surface area was determined by the BJH method from a nitrogen adsorption isotherm.
【００２２】[0022]
【実施例１】 ＊第１方法による金属含有活性炭の調製 常法に従って精製及び熱処理を行った軟化点８５℃のピ
ッチに、金属成分としてｔ−ブチルマグネシウムクロリ
ドをマグネシウム含量が２重量％になるように加えた。
テトラヒドロフランを加えて均一に溶解し、溶媒を留去
して低軟化点焼成原料を得た。Example 1 * Preparation of Metal-Containing Activated Carbon by First Method T-butylmagnesium chloride was used as a metal component in a pitch having a softening point of 85.degree. Added.
Tetrahydrofuran was added to dissolve uniformly, and the solvent was distilled off to obtain a raw material having a low softening point.
【００２３】得られた低軟化点焼成原料を窒素雰囲気
下、２００℃から１分間に１０℃の割合で９００℃まで
昇温させて炭素化処理を行った。次いで、水蒸気飽和窒
素を３リットル／分の割合で流しながら９００℃で３０
分間賦活処理を行い、金属含有活性炭を得た。The obtained raw material having a low softening point was carbonized by raising the temperature from 200 ° C. to 900 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere. Then, at 900 ° C. for 30 while flowing steam-saturated nitrogen at a rate of 3 L / min.
Activation treatment was performed for minutes to obtain a metal-containing activated carbon.
【００２４】[0024]
【実施例２〜５】金属成分及びその含有量並びに賦活条
件を以下の表１に示すように変更した他は実施例１と同
様にして金属含有活性炭を得た。Examples 2 to 5 Metal-containing activated carbon was obtained in the same manner as in Example 1 except that the metal components, their contents and the activation conditions were changed as shown in Table 1 below.
【００２５】[0025]
【比較例１】金属成分を加えなかった他は実施例１と同
様にして、活性炭を得た。Comparative Example 1 Activated carbon was obtained in the same manner as in Example 1 except that no metal component was added.
【００２６】[0026]
【比較例２】金属成分としてのｔ−ブチルマグネシウム
クロリドの代わりに９−ＢＢＮをホウ素含量が２重量％
になるように加えた他は実施例１と同様にして、金属含
有活性炭を得た。Comparative Example 2 9-BBN was used in place of t-butylmagnesium chloride as a metal component, and the boron content was 2% by weight.
Activated carbon containing metal was obtained in the same manner as in Example 1 except that the addition was performed so that
【００２７】実施例１〜５、比較例１及び２で得られた
金属含有活性炭の各種物性値を合わせて以下の表１−１
及び表１−２に示す。The various physical properties of the metal-containing activated carbons obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were combined to obtain the following Table 1-1.
And Table 1-2.
【００２８】 表１−１ 実施例又は比較例 添加した金属成分 金属含有率（％） 実施例１ ｔ−ＢｕＭｇＣｌ Ｍｇ＝５ 実施例２ ｔ−ＢｕＭｇＣｌ Ｍｇ＝２ 実施例３ （Ｃ3 Ｈ7 Ｏ）3 Ａｌ Ａｌ＝２ 実施例４ （Ｃ5 Ｈ4 ＳｉＭｅ2 ）2 Ｙｂ Ｙｂ＝２ 実施例５ ＹｂＩ2 （ＴＨＦ） Ｙｂ＝２ 比較例１ 添加せず 比較例２ ９−ＢＢＮ Ｂ＝２ 表１−２ 実施例 賦活収率 ＢＥＴ メソポア メソポア率 細孔半径 又は （％） 比表面積 比表面積 （％） （ｎｍ）比較例 (m 2 /g) (m 2 /g) 実施例１ ３６．９５ ２５３ ９５．０ ３７．５ ４．６２ 実施例２ ６１．７０ ２３３ ４３．４ １８．６ ２．３９ 実施例３ ６４．６４ ２２０ １１１．８ ５０．８ １．９２ 実施例４ ２２．４３ ３２．７ ３２．２ ９８．５ ５．７８ 実施例５ ４４．３８ ６５．６ ４８．２ ７３．６ ７．３６ 比較例１ ７８．６７ ８０．９ １４．０ １７．３ １．５１比較例２ ５２．０２ ６０．３ １２．７ ２１．１ １．７３ Table 1-1 Example or Comparative Example Added Metal Component Metal Content (%) Example 1 t-BuMgCl Mg = 5 Example 2 t-BuMgCl Mg = 2 Example 3 (C 3 H 7 O) 3 Al Al = 2 Example 4 (C 5 H 4 SiMe 2 ) 2 Yb Yb = 2 Example 5 YbI 2 (THF) Yb = 2 Comparative Example 1 Comparative Example 2 without Addition 9-BBBN B = 2 2 Example Activation yield BET mesopore Mesopore ratio Pore radius or (%) Specific surface area Specific surface area (%) (nm) Comparative example (m 2 / g) (m 2 / g) Example 1 36.95 253 95. 0 37.5 4.62 Example 2 61.70 233 43.4 18.6 2.39 Example 3 64.64 220 111.8 50.8 1.92 Example 4 22.43 32.7 32. 298.5.78 Example 5 44.38 65.6 48. 73.6 7.36 Comparative Example 1 78.67 80.9 14.0 17.3 1.51 Comparative Example 2 52.02 60.3 12.7 21.1 1.73
【００２９】[0029]
【実施例６】 ＊第２方法による金属含有活性炭の調製 常法に従って精製及び熱処理を行った軟化点８５℃のピ
ッチに、金属成分としてＣｐ3 ＹｂをＹｂ含量が５重量
％になるように加えた。テトラヒドロフランを加え均一
に溶解し、溶媒を留去して低軟化点焼成原料を得た。な
お、Ｃｐはシクロペンタジエンを表す。Example 6 Preparation of Metal-Containing Activated Carbon by Second Method Cp 3 Yb was added as a metal component to a pitch having a softening point of 85 ° C., which had been purified and heat-treated according to a conventional method, so that the Yb content was 5% by weight. Was. Tetrahydrofuran was added and uniformly dissolved, and the solvent was distilled off to obtain a raw material having a low softening point. Cp represents cyclopentadiene.
【００３０】得られた低軟化点焼成原料に軟化点２７０
℃の紡糸ピッチを１：１の割合になるように加えて粉砕
・混合し、窒素ガス雰囲気下、３００℃で１０分間加熱
し、次いで冷却した。この操作を３回繰り返し、均一な
高軟化点焼成原料を得た。この混合物をアルゴンガス雰
囲気下に１００℃から１分間に３℃の割合で３６０℃ま
で昇温する不融化処理を行い、そのままアルゴンガス雰
囲気下に９００℃で１時間炭素化処理した。次いで水蒸
気飽和窒素を３リットル／分の割合で流しながら９００
℃で３０分間賦活処理を行い、金属含有活性炭を得た。The obtained raw material having a low softening point has a softening point of 270.
A spinning pitch of 1 ° C. was added at a ratio of 1: 1 and pulverized and mixed, heated under a nitrogen gas atmosphere at 300 ° C. for 10 minutes, and then cooled. This operation was repeated three times to obtain a uniform raw material having a high softening point. This mixture was subjected to an infusibilization treatment in which the temperature was raised from 100 ° C. to 360 ° C. at a rate of 3 ° C. per minute in an argon gas atmosphere, and then carbonized at 900 ° C. for 1 hour in an argon gas atmosphere. Then, while flowing steam-saturated nitrogen at a rate of 3 L / min, 900
Activation treatment was performed at 30 ° C. for 30 minutes to obtain a metal-containing activated carbon.
【００３１】[0031]
【実施例７】金属成分として、Ｃｐ3 ＹをＹ含量が５重
量％になるように加えた他は実施例６と同様にして金属
含有活性炭を得た。Example 7 A metal-containing activated carbon was obtained in the same manner as in Example 6, except that Cp 3 Y was added as a metal component so that the Y content was 5% by weight.
【００３２】[0032]
【比較例３】金属成分を加えなかった他は実施例６と同
様にして金属含有活性炭を得た。Comparative Example 3 A metal-containing activated carbon was obtained in the same manner as in Example 6, except that no metal component was added.
【００３３】実施例６、実施例７及び比較例３で得られ
た活性炭の各種物性値を合わせて以下の表２に示す。The physical properties of the activated carbons obtained in Examples 6, 7 and Comparative Example 3 are shown together in Table 2 below.
【００３４】 表 ２ 実施例 賦活収率 ＢＥＴ メソポア メソポア率 細孔半径 又は （％） 比表面積 比表面積 （％） （ｎｍ）比較例 (m 2 /g) (m 2 /g) 実施例６ ３０．６６ ２１５ ２０９．３ ９７．３ ２．８１ 実施例７ ６１．７０ ２３３ ２０１．０ ９０．１ ２．５７比較例３ ５０．００ ４０．０ ５．０ １２．５ − 表２の結果から、イッテルビウム及び／又はイットリウ
ム含有活性炭は、金属を含まない比較例３の活性炭に比
べ非常に大きな比表面積を有し、メソポア率も十分大き
く中分子以上の大きさの分子を吸着するのに好ましいこ
とが明らかとなった。Table 2 Example Activation Yield BET Mesopore Mesopore Ratio Pore Radius or (%) Specific Surface Area Specific Surface Area (%) (nm) Comparative Example (m 2 / g) (m 2 / g) Example 6 66 215 209.3 97.3 2.81 Example 7 61.70 233 201.0 90.1 2.57 Comparative Example 3 50.00 40.0 5.0 12.5-From the results in Table 2, ytterbium And / or the yttrium-containing activated carbon has a very large specific surface area as compared with the activated carbon of Comparative Example 3 containing no metal, and has a sufficiently large mesopore ratio, which is preferable for adsorbing a medium or larger molecule. It became.
【００３５】なお、実施例では示さないが、本発明者
は、イッテルビウム、イットリウムの代わりにサマリウ
ム化合物、ネオジウム化合物を用いた場合にも同様に高
いＢＥＴ比表面積、メソポア比表面積、メソポア率を有
し且つ賦活収率も十分実用化可能な範囲である金属含有
活性炭が得られることを確認した。Although not shown in the examples, the present inventor similarly has a high BET specific surface area, a mesopore specific surface area, and a mesopore ratio when a samarium compound or a neodymium compound is used instead of ytterbium or yttrium. In addition, it was confirmed that a metal-containing activated carbon having an activation yield in a sufficiently practical range was obtained.
【図１】活性炭のポアのサイズ（マクロポア、メソポ
ア、マイクロポア、サブ−マイクロポア）を模式的に示
す図である。FIG. 1 is a diagram schematically showing pore sizes (macropores, mesopores, micropores, sub-micropores) of activated carbon.
【図２】水蒸気による賦活処理の方法を示す概略図であ
る。FIG. 2 is a schematic diagram showing a method of activation treatment with steam.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 玉井 久司 広島県広島市中区船入南５−５−15 (56)参考文献 特開 平３−265510（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/08 C01B 31/10 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hisashi Tamai 5-5-15, Funariminami, Naka-ku, Hiroshima City, Hiroshima Prefecture (56) References JP-A-3-265510 (JP, A) (58) Fields surveyed (Int.Cl. 7 , DB name) C01B 31/08 C01B 31/10
Claims (2)
ッチと金属化合物との均一混合物を、２００〜３６０℃
の条件下、１〜２時間不活性ガス雰囲気下で溶融して得
られる低軟化点焼成原料を炭素化処理及び賦活処理する
ことを特徴とする、メソポアの比率が３０〜９０％であ
る金属含有活性炭の製造方法。A low softening point pigment having a softening point of 60 to 150 ° C.
A uniform mixture of the switch and the metal compound at 200 to 360 ° C.
Under an inert gas atmosphere for 1-2 hours
Characterized in that the low softening point firing raw material for processing and activation treatment carbonization to be the ratio of the mesopores 30% to 90% der
For producing a metal-containing activated carbon.
ッチと、イッテルビウム化合物及びイットリウム化合物
からなる群の少なくとも１種を混合してなる焼成原料
を、軟化点が２３０〜２９０℃である紡糸ピッチと混合
し、得られた高軟化点焼成原料を不融化処理又は炭素化
処理、及び水蒸気賦活処理することを特徴とする、メソ
ポアの比率が１５〜９９％である金属含有活性炭の製造
方法。2. A low softening point pitch having a softening point of 60 to 150 ° C., an ytterbium compound and an yttrium compound.
The raw material obtained by mixing at least one of the group consisting of the following is mixed with a spinning pitch having a softening point of 230 to 290 ° C., and the obtained high softening point raw material is infusibilized or carbonized, and steamed. Meso , characterized by activation treatment
A method for producing a metal-containing activated carbon having a pore ratio of 15 to 99% .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09411892A JP3195963B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing metal-containing activated carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09411892A JP3195963B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing metal-containing activated carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05294607A JPH05294607A (en) | 1993-11-09 |
| JP3195963B2 true JP3195963B2 (en) | 2001-08-06 |
Family
ID=14101517
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|---|---|---|---|
| JP09411892A Expired - Lifetime JP3195963B2 (en) | 1992-04-14 | 1992-04-14 | Method for producing metal-containing activated carbon |
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| Country | Link |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3960397B2 (en) * | 1997-06-05 | 2007-08-15 | 古河機械金属株式会社 | Electric double layer capacitor |
| KR100417688B1 (en) * | 2001-07-20 | 2004-02-11 | 재단법인 포항산업과학연구원 | Mesoporous activated carbon fiber and preparation method of the same |
| JPWO2003033135A1 (en) * | 2001-09-21 | 2005-02-03 | 株式会社アドール | Activated carbon fiber for removing organochlorine compounds |
| KR100426125B1 (en) * | 2001-11-12 | 2004-04-08 | 재단법인 포항산업과학연구원 | Mesoporous activated carbon fiber and preparation method of the same |
| CN1302987C (en) * | 2004-12-28 | 2007-03-07 | 华南理工大学 | Surface-activated carbon fiber and its preparation method |
| JP4968766B2 (en) * | 2005-09-30 | 2012-07-04 | Ｊｆｅケミカル株式会社 | Carbon material for negative electrode of lithium ion secondary battery and method for producing the same |
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1992
- 1992-04-14 JP JP09411892A patent/JP3195963B2/en not_active Expired - Lifetime
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| JPH05294607A (en) | 1993-11-09 |
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