JP2011106052A - Activated carbon fiber - Google Patents
Activated carbon fiber Download PDFInfo
- Publication number
- JP2011106052A JP2011106052A JP2009261973A JP2009261973A JP2011106052A JP 2011106052 A JP2011106052 A JP 2011106052A JP 2009261973 A JP2009261973 A JP 2009261973A JP 2009261973 A JP2009261973 A JP 2009261973A JP 2011106052 A JP2011106052 A JP 2011106052A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- carbon fiber
- pore volume
- adsorption
- less
- 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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
本発明は、沸点が７０〜１２０℃の範囲内である有機化合物に対し特に優れた吸着性能を有する活性炭素繊維に関するものである。 The present invention relates to an activated carbon fiber having particularly excellent adsorption performance for an organic compound having a boiling point in the range of 70 to 120 ° C.
活性炭素繊維は、粒状活性炭と比較し、外表面積が大きく、細孔が表面に存在するために吸着性能が優れ、繊維状のため紙状、織布状など多様な形態に加工できることとも併せ、様々な分野で活用されている。 Activated carbon fiber has a large outer surface area compared to granular activated carbon, and has excellent adsorption performance due to the presence of pores on the surface. In addition, it can be processed into various forms such as paper and woven cloth because of its fibrous form. It is used in various fields.
従来の活性炭素繊維として、たとえば特開２００５−１３８０３８号公報（特許文献１）には、比表面積７００〜１５００ｍ2／ｇ、全細孔容積０．３〜０．７ｃｃ／ｇ、且つ表面酸性基量が０．５ｍｅｑ／ｇ以下である有機化合物吸着用繊維状活性炭が開示されている。このような特許文献１に開示された繊維状活性炭によれば、塩化メチレン、塩化ビニルモノマーなどの活性炭に対する吸着性の低い、低分子量、低沸点化合物の吸着処理に対して効果が発揮され、たとえば排ガス処理装置に適用した場合に、コンパクトで、しかも低コストにでき、化学工場、医薬工場などの工業プロセスから排出される低分子量、低沸点化合物の排出濃度を低減でき、環境浄化、リサイクルに貢献できるものである。 As a conventional activated carbon fiber, for example, Japanese Patent Application Laid-Open No. 2005-138038 (Patent Document 1) discloses a specific surface area of 700 to 1500 m 2 / g, a total pore volume of 0.3 to 0.7 cc / g, and a surface acidic group. An organic compound-adsorbing fibrous activated carbon having an amount of 0.5 meq / g or less is disclosed. According to such a fibrous activated carbon disclosed in Patent Document 1, an effect is exerted on an adsorption treatment of a low molecular weight, low boiling point compound having low adsorptivity to activated carbon such as methylene chloride and vinyl chloride monomer. When applied to exhaust gas treatment equipment, it is compact and low-cost, and can reduce the concentration of low molecular weight and low-boiling compounds emitted from industrial processes such as chemical factories and pharmaceutical factories, contributing to environmental purification and recycling. It can be done.
またたとえば特開平７−１４５５１６号公報（特許文献２）には、２５℃、相対湿度３７％における平衡水分率が０．０５〜１．０％、ＢＥＴ比表面積が３００〜３０００ｍ2／ｇ、細孔容積が０．２５〜２．００ｃｃ／ｇで、かつ水蒸気法で測定した細孔半径が７〜１４Åの範囲または９〜２０Åの範囲である細孔の容積が、細孔半径が１００Å以下の細孔が占める容積の８０％以上である活性炭素繊維が開示されている。このような特許文献２に開示された活性炭素繊維は、水中に溶解するハロゲン化炭化水素などの水に対する溶解度の小さい疎水性有機化合物の吸着に好適に用いられるものである。 Further, for example, in JP-A-7-145516 (Patent Document 2), an equilibrium moisture content at 25 ° C. and a relative humidity of 37% is 0.05 to 1.0%, a BET specific surface area is 300 to 3000 m 2 / g, fine. The pore volume with a pore volume of 0.25 to 2.00 cc / g and a pore radius measured by the water vapor method in the range of 7 to 14 mm or 9 to 20 mm, the pore radius is 100 mm or less An activated carbon fiber that is 80% or more of the volume occupied by the pores is disclosed. Such activated carbon fibers disclosed in Patent Document 2 are suitably used for adsorption of hydrophobic organic compounds having low solubility in water such as halogenated hydrocarbons that are dissolved in water.
また、たとえば特開平６−９９０６５号公報（特許文献３）には、比表面積が８００ｍ2／ｇ以上であり、水蒸気吸着法で測定した細孔半径９Å以下の細孔の占める累積細孔容積が０．２０ｃｃ／ｇ以上であり、且つ水蒸気吸着法で測定した細孔半径９Å以下の細孔の占める累積細孔容積が細孔半径１００Å以下の細孔の占める累積細孔容積の５０％以上である繊維状活性炭からなる浄水器用充填材が開示されている。このような特許文献３に開示された浄水器用充填材（繊維状活性炭）は、水中に含まれるトリハロメタンの除去能が極めて高く、特に水道水中のトリハロメタンの大半を占めるクロロホルムを効率よく除去でき、家庭、工場、店舗、会社等の種々の場所で使用する浄水器用に有効に使用することができる。 Also, for example, in JP-A-6-99065 (Patent Document 3), the cumulative pore volume occupied by pores having a specific surface area of 800 m 2 / g or more and a pore radius of 9 mm or less measured by the water vapor adsorption method is disclosed. The cumulative pore volume occupied by pores having a pore radius of 9 mm or less as measured by the water vapor adsorption method is 0.20 cc / g or more and 50% or more of the cumulative pore volume occupied by pores having a pore radius of 100 mm or less. A filler for water purifiers made of a certain fibrous activated carbon is disclosed. Such a water purifier filler (fibrous activated carbon) disclosed in Patent Document 3 has an extremely high ability to remove trihalomethane contained in water, and can effectively remove chloroform, which occupies most of the trihalomethane in tap water. It can be effectively used for water purifiers used in various places such as factories, stores, and companies.
さらに、特開２００５−９０３号公報（特許文献４）、特開２００５−２１８５１号公報（特許文献５）には、２５℃、相対湿度３７％における平衡吸着水分率が１．０〜１５．０％、ＢＥＴ比表面積が３００〜２５００ｍ2／ｇまたは５００〜２０００ｍ2／ｇ、細孔容積が０．２５〜２．０ｃｃ／ｇまたは０．２５〜１．５ｃｃ／ｇで、かつ水蒸気法で測定した細孔半径６〜１６Åの範囲にある細孔の容積が、細孔半径１００Å以下の細孔の占める容積の８０％以上であって、Ｘ線回折強度曲線の（００２）面の回折ピークにおける黒鉛的結晶性構造パラメータＩｐ／Ｉｏが０．３５以下の繊維状活性炭を用いた、有機塩素系溶剤の回収方法が開示されている。このような特許文献４、５に記載された方法によれば、装置の腐食が少なくして、有機塩素系溶剤または混合溶剤の効率的な回収が可能となる。 Furthermore, in Japanese Patent Application Laid-Open No. 2005-903 (Patent Document 4) and Japanese Patent Application Laid-Open No. 2005-21851 (Patent Document 5), the equilibrium adsorption moisture content at 25 ° C. and a relative humidity of 37% is 1.0 to 15.0. %, BET specific surface area of 300~2500m 2 / g or 500~2000m 2 / g, pore volume of at 0.25~2.0cc / g or 0.25~1.5cc / g, and measured by a water vapor method The volume of the pores in the range of the pore radius of 6 to 16 mm is 80% or more of the volume occupied by pores having a pore radius of 100 mm or less, and in the diffraction peak on the (002) plane of the X-ray diffraction intensity curve An organic chlorine solvent recovery method using a fibrous activated carbon having a graphitic crystalline structure parameter Ip / Io of 0.35 or less is disclosed. According to the methods described in Patent Documents 4 and 5, the corrosion of the apparatus is reduced, and the organic chlorine solvent or the mixed solvent can be efficiently recovered.
沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物は、吸着される分子の容積が比較的大きく、小さな細孔には吸着せず、また大きな細孔になると吸着速度が遅くなるという性質を有するため、このような有機化合物を活性炭素繊維で吸着させようとする場合、活性炭素繊維の細孔が有効に活用できないという問題がある。したがって、このような有機化合物に対し特に優れた吸着性能を有する活性炭素繊維の開発が望まれている。 An organic compound such as toluene having a boiling point in the range of 70 to 120 ° C. has a relatively large volume of molecules to be adsorbed, and does not adsorb to small pores. Due to its nature, when trying to adsorb such an organic compound with activated carbon fibers, there is a problem that the pores of the activated carbon fibers cannot be used effectively. Therefore, development of activated carbon fibers having particularly excellent adsorption performance for such organic compounds is desired.
本発明は、上記課題を解決するためになされたものであって、その目的とするところは、沸点が７０〜１２０℃の範囲内の有機化合物に対し特に優れた吸着性能を有する活性炭素繊維を提供することである。 The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide activated carbon fibers having particularly excellent adsorption performance for organic compounds having a boiling point in the range of 70 to 120 ° C. Is to provide.
本発明の活性炭素繊維は、ＢＥＴ比表面積が１０００〜１８００ｍ2／ｇ、全細孔容積が０．４〜０．９ｃｃ／ｇ、細孔直径１ｎｍ以下のマイクロポア細孔容積が全マイクロポア細孔容積の９３〜９４％であり、かつ、温度２５℃、相対湿度５２％における水分吸着率が６％以下であることを特徴とする。 The activated carbon fiber of the present invention has a BET specific surface area of 1000 to 1800 m 2 / g, a total pore volume of 0.4 to 0.9 cc / g, and a micropore pore volume of 1 nm or less in pore diameter of all micropores. It is 93 to 94% of the pore volume, and the moisture adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% is 6% or less.
本発明の活性炭素繊維において、カルボキシル基量が０．０４ｍｅｑ／ｇ以下であることが好ましい。 In the activated carbon fiber of the present invention, the amount of carboxyl groups is preferably 0.04 meq / g or less.
本発明の活性炭素繊維は、沸点が７０〜１２０℃の範囲内の有機化合物を吸着させるために用いられるものであることが、好ましい。 The activated carbon fiber of the present invention is preferably used for adsorbing an organic compound having a boiling point in the range of 70 to 120 ° C.
本発明によれば、沸点が７０〜１２０℃の範囲内の有機化合物に対し特に優れた吸着性能を有する活性炭素繊維が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the activated carbon fiber which has the especially outstanding adsorption | suction performance with respect to the organic compound in the range whose boiling point is 70-120 degreeC is provided.
本発明の活性炭素繊維は、ＢＥＴ比表面積が１０００〜１８００ｍ2／ｇの範囲内であることを特徴の１つとする。本発明の活性炭繊維のＢＥＴ比表面積が１０００ｍ2／ｇ未満である場合には、沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着されないという不具合があり、また、１８００ｍ2／ｇを超える場合には、吸着速度が遅くなるという不具合がある。沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着できるためには、活性炭素繊維のＢＥＴ比表面積は１２００〜１７００ｍ2／ｇの範囲内であることが好ましい。なお、ＢＥＴ比表面積とは、液体窒素温度での窒素ガス吸着等温線によるＢＥＴ法により求められる比表面積を意味し、たとえば比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を用いて測定することができる。 One feature of the activated carbon fiber of the present invention is that the BET specific surface area is in the range of 1000 to 1800 m 2 / g. When the BET specific surface area of the activated carbon fiber of the present invention is less than 1000 m 2 / g, there is a problem that an organic compound such as toluene having a boiling point in the range of 70 to 120 ° C. is not sufficiently adsorbed, and 1800 m If it exceeds 2 / g, there is a problem that the adsorption speed becomes slow. In order to sufficiently adsorb an organic compound such as toluene having a boiling point in the range of 70 to 120 ° C., the BET specific surface area of the activated carbon fiber is preferably in the range of 1200 to 1700 m 2 / g. The BET specific surface area means a specific surface area determined by a BET method using a nitrogen gas adsorption isotherm at a liquid nitrogen temperature, and is measured using, for example, a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). be able to.
本発明の活性炭素繊維はまた、全細孔容積が０．４〜０．９ｃｃ／ｇの範囲内であることを特徴の１つとする。本発明の活性炭繊維の全細孔容積が０．４ｃｃ／ｇ未満である場合には、沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着されないという不具合があり、また、０．９ｃｃ／ｇを超える場合には、吸着速度が遅くなるという不具合がある。沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着できるためには、活性炭素繊維の全細孔容積は０．６〜０．７ｃｃ／ｇの範囲内であることが好ましい。なお、全細孔容積は、たとえば比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を用いて測定することができる。 The activated carbon fiber of the present invention is also characterized in that the total pore volume is in the range of 0.4 to 0.9 cc / g. When the total pore volume of the activated carbon fiber of the present invention is less than 0.4 cc / g, there is a problem that an organic compound such as toluene having a boiling point in the range of 70 to 120 ° C. is not sufficiently adsorbed, In the case of exceeding 0.9 cc / g, there is a problem that the adsorption rate becomes slow. In order to sufficiently adsorb organic compounds such as toluene having a boiling point in the range of 70 to 120 ° C., the total pore volume of the activated carbon fiber should be in the range of 0.6 to 0.7 cc / g. preferable. The total pore volume can be measured using, for example, a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics).
本発明の活性炭素繊維は、細孔直径１ｎｍ以下のマイクロポア細孔容積が全マイクロポア細孔容積の９３〜９４％以上であることを特徴の１つとする。細孔直径１ｎｍ以下のマイクロポア細孔容積が全マイクロポア細孔容積の９３％未満である場合には、細孔が大きくなりすぎて、沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着されないという不具合があり、また、９４％を超える場合には、細孔が小さくなりすぎて、沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着されないという不具合がある。沸点が７０〜１２０℃の範囲内のたとえばトルエンなどの有機化合物が十分に吸着できるためには、活性炭素繊維の細孔直径１ｎｍ以下のマイクロポア細孔容積は、全マイクロポア細孔容積の９３．３〜９３．８％の範囲内であることが好ましい。なお、細孔直径１ｎｍ以下のマイクロポア細孔容積の割合は、たとえば比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を用いて測定することができる。 The activated carbon fiber of the present invention is characterized in that the micropore pore volume having a pore diameter of 1 nm or less is 93 to 94% or more of the total micropore pore volume. When the micropore pore volume having a pore diameter of 1 nm or less is less than 93% of the total micropore pore volume, the pores become too large and the boiling point is in the range of 70 to 120 ° C. There is a problem that the organic compound is not sufficiently adsorbed, and when it exceeds 94%, the pores become too small and an organic compound such as toluene having a boiling point in the range of 70 to 120 ° C. is sufficiently adsorbed. There is a bug that is not done. In order to sufficiently adsorb organic compounds such as toluene having a boiling point in the range of 70 to 120 ° C., the micropore pore volume of the activated carbon fiber having a pore diameter of 1 nm or less is 93 of the total micropore pore volume. It is preferable to be within the range of 3 to 93.8%. The ratio of the micropore pore volume having a pore diameter of 1 nm or less can be measured using, for example, a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics).
また本発明の活性炭素繊維は、温度２５℃、相対湿度５２％における水分吸着率が６％以下であることも特徴の１つとする。温度２５℃、相対湿度５２％における水分吸着率が６％を超える場合には、細孔周辺に先に水分子が吸着されるため、その細孔には有機化合物の吸着量が吸着されず、その分低下してしまうという不具合がある。水分子の吸着の影響を受けにくくするためには、温度２５℃、相対湿度５２％における水分吸着率は５％以下であることが好ましい。温度２５℃、相対湿度５２％における水分吸着率は、たとえば恒温恒湿器ＳＨ−６６１（エスペック社製）を用いて測定することができる。 The activated carbon fiber of the present invention is also characterized in that the moisture adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% is 6% or less. When the moisture adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% exceeds 6%, water molecules are first adsorbed around the pores, so that the adsorption amount of the organic compound is not adsorbed in the pores. There is a problem that it is lowered accordingly. In order to make it less susceptible to the adsorption of water molecules, the moisture adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% is preferably 5% or less. The moisture adsorption rate at a temperature of 25 ° C. and a relative humidity of 52% can be measured using, for example, a constant temperature and humidity chamber SH-661 (manufactured by Espec Corp.).
本発明の活性炭素繊維は、上述したＢＥＴ比表面積、全細孔容積、マイクロポア細孔容積の割合および水分吸着率がそれぞれ上述した範囲内であることで、沸点が７０〜１２０℃の範囲内（より好適には１００〜１２０℃の範囲内）の有機化合物に対し特に高い吸着性能を示す。これは、沸点が７０〜１２０℃の範囲内の有機化合物を吸着するのに好適な細孔があり、それが上述したＢＥＴ比表面積、全細孔容積、マイクロポア細孔容積の割合および水分吸着率の活性炭素繊維であるという理由のためであると考えられる。 The activated carbon fiber of the present invention has a boiling point in the range of 70 to 120 ° C. because the above-mentioned BET specific surface area, total pore volume, micropore pore volume ratio and moisture adsorption rate are within the above-mentioned ranges, respectively. It exhibits particularly high adsorption performance for organic compounds (more preferably within the range of 100 to 120 ° C.). This has pores suitable for adsorbing organic compounds having a boiling point in the range of 70-120 ° C., which is the BET specific surface area, total pore volume, percentage of micropore pore volume and moisture adsorption described above. It is believed that this is because of the rate of activated carbon fiber.
ここで、本発明の活性炭素繊維による吸着させる対象として好適な有機化合物としては、たとえばトルエン（沸点：１１０．６℃）、ベンゼン（沸点：８０．１℃）、イソプロピルアルコール（沸点：８２．２℃）、ブタノール（沸点：１１７．７℃）、シクロヘキサン（沸点：８０．７℃）、トリエチルアミン（沸点：８９．６℃）、アセトニトリル（沸点：８１．６℃）、ジクロロエタン（沸点：８３．５℃）などが挙げられる。中でも、水に不溶な点から、本発明の活性炭素繊維による吸着対象としてトルエンが特に好適である。 Here, as an organic compound suitable as an object to be adsorbed by the activated carbon fiber of the present invention, for example, toluene (boiling point: 110.6 ° C.), benzene (boiling point: 80.1 ° C.), isopropyl alcohol (boiling point: 82.2 ° C.). ° C), butanol (boiling point: 117.7 ° C), cyclohexane (boiling point: 80.7 ° C), triethylamine (boiling point: 89.6 ° C), acetonitrile (boiling point: 81.6 ° C), dichloroethane (boiling point: 83.5 ° C) ° C). Among these, toluene is particularly suitable as an object to be adsorbed by the activated carbon fiber of the present invention because it is insoluble in water.
本発明の活性炭素繊維は、水分が吸着しにくくなるという理由からは、カルボキシル基量が０．０４ｍｅｑ／ｇ以下であることが好ましく、０．０２ｍｅｑ／ｇ以下であることがより好ましい。活性炭素繊維のカルボキシル基量は、塩基との中和滴定によって測定することができる。 In the activated carbon fiber of the present invention, the amount of carboxyl groups is preferably 0.04 meq / g or less, and more preferably 0.02 meq / g or less, for the reason that moisture hardly adsorbs. The amount of carboxyl groups of the activated carbon fiber can be measured by neutralization titration with a base.
なお、本発明の活性炭素繊維におけるフェノール性水酸基量、全酸性基量、全塩基性基量については特に制限されるものではないが、フェノール性水酸基量については通常０．０５〜０．１５ｍｅｑ／ｇ、全酸性基量については通常０．０５〜０．２５ｍｅｑ／ｇ、全塩基性基量については通常０．３０〜０．６０ｍｅｑ／ｇである。なお、活性炭素繊維のフェノール性水酸基量、全酸性基量は塩基との中和滴定によって測定することができ、全塩基性基量は酸との中和滴定によって測定することができる。 The amount of phenolic hydroxyl groups, the total amount of acidic groups, and the amount of total basic groups in the activated carbon fiber of the present invention are not particularly limited, but the amount of phenolic hydroxyl groups is usually 0.05 to 0.15 meq / The amount of g and total acidic groups is usually 0.05 to 0.25 meq / g, and the amount of total basic groups is usually 0.30 to 0.60 meq / g. In addition, the amount of phenolic hydroxyl groups and the total amount of acidic groups of the activated carbon fiber can be measured by neutralization titration with a base, and the amount of total basic groups can be measured by neutralization titration with an acid.
本発明の活性炭素繊維は、その原料（前駆体）としては特に制限されるものではなく、たとえばフェノール、セルロース、ポリアクリロニトリル系、ピッチ系、アラミド、ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンベンゾビスオキサゾール、ポリビニルアルコール、ポリスルホンエーテル、ポリスルホン、ポリフェニレンオキサイドなどの当分野において原料として通常用いられる繊維を用いることができる。これらの中で、セルロース系は原料中の酸素含有率が高く、活性炭の中でも比較的表面酸性基量が多い。フェノール系はセルロース系に比べて酸素含有量が少なく、灰分に由来する極性部分が少なく、セルロース系よりは極性度が小さく水分吸着の影響を受けにくい。中でも、疎水性が高く、加工性と実用的強度を併せ持つことから、フェノール繊維を原料として用いることが、好ましい。 The activated carbon fiber of the present invention is not particularly limited as a raw material (precursor), for example, phenol, cellulose, polyacrylonitrile, pitch, aramid, polyimide, polyamide, polyamideimide, polyphenylenebenzobisoxazole, Fibers commonly used as raw materials in the art such as polyvinyl alcohol, polysulfone ether, polysulfone, polyphenylene oxide, and the like can be used. Among these, the cellulose type has a high oxygen content in the raw material, and the amount of surface acidic groups is relatively large among activated carbons. The phenol type has a lower oxygen content than the cellulose type, has a small polar portion derived from ash, has a lower degree of polarity than the cellulose type, and is less susceptible to moisture adsorption. Among them, it is preferable to use phenol fiber as a raw material because it is highly hydrophobic and has both workability and practical strength.
本発明の活性炭素繊維を製造するに際しては、まず、フェノール繊維を原料とする場合には、窒素流動下で管状炉中を移動させながら８００〜９５０℃程度の温度にまで昇温し、２．０〜３．５時間保持させた状態で、純水を供給し続けるという賦活処理を施す。ここで、上述した保持時間（賦活時間）を調整することで、得られる活性炭素繊維におけるＢＥＴ比表面積、全細孔容積、マイクロポア細孔容積の割合および水分吸着率を制御することができる。 In producing the activated carbon fiber of the present invention, first, when phenol fiber is used as a raw material, the temperature is raised to a temperature of about 800 to 950 ° C. while moving in a tubular furnace under a nitrogen flow. An activation process is performed in which pure water is continuously supplied in a state of being held for 0 to 3.5 hours. Here, by adjusting the retention time (activation time) described above, the BET specific surface area, the total pore volume, the ratio of the micropore pore volume, and the moisture adsorption rate in the obtained activated carbon fiber can be controlled.
賦活処理後、酸素濃度を０．５％以下（好適には０．１％以下）とした状態で冷却する。この冷却の際の酸素濃度を０．５％以下とすることで、温度２５℃、相対湿度５２％における水分吸着率が１５％以下と従来より低い本発明の活性炭素繊維が得られる。これは、冷却工程において、活性炭素繊維の表面官能基の生成が抑制されるためであると考えられる。このように酸素濃度を０．５％以下とするためには、具体的には、冷却工程での窒素の流量を増やし、出入口の炉内圧が２Ｐａ以上を維持できるような操作を施せばよい。この点、従来は冷却工程の際の酸素濃度には着目がなく、特に上述したような操作を施さずに冷却を行っており、通常、酸素濃度は１％程度である。 After the activation treatment, cooling is performed in a state where the oxygen concentration is 0.5% or less (preferably 0.1% or less). By setting the oxygen concentration during this cooling to 0.5% or less, the activated carbon fiber of the present invention having a moisture adsorption rate of 15% or less at a temperature of 25 ° C. and a relative humidity of 52% can be obtained. This is considered to be because the generation of surface functional groups of activated carbon fibers is suppressed in the cooling step. In order to reduce the oxygen concentration to 0.5% or less as described above, specifically, an operation may be performed in which the flow rate of nitrogen in the cooling process is increased and the furnace pressure at the inlet / outlet can be maintained at 2 Pa or higher. In this regard, conventionally, there is no focus on the oxygen concentration in the cooling step, and cooling is performed without performing the above-described operation, and the oxygen concentration is usually about 1%.
本発明の活性炭素繊維は、沸点が７０〜１２０℃の範囲内の有機化合物に対し特に優れた吸着性能を示すものであるため、このような有機化合物を主な吸着対象とするフィルタに好適に適用することができる。本発明の活性炭素繊維を適用したフィルタは、吸着と水蒸気による脱着を交互に切り替え可能であり、化学工場、医薬工場などの工業プロセスから排出される有機化合物を除去、回収するための排ガス処理装置に好適に用いられる。 Since the activated carbon fiber of the present invention exhibits particularly excellent adsorption performance for organic compounds having a boiling point in the range of 70 to 120 ° C., the activated carbon fiber is suitable for a filter having such an organic compound as a main adsorption target. Can be applied. The filter to which the activated carbon fiber of the present invention is applied is capable of alternately switching between adsorption and desorption with water vapor, and an exhaust gas treatment device for removing and recovering organic compounds discharged from industrial processes such as chemical factories and pharmaceutical factories. Is preferably used.
以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
＜実施例１＞
内径７０ｍｍ、有効長３０ｃｍの管状炉を用いて、繊維径２４μｍのフェノール繊維を、５Ｌ／ｍｉｎでの窒素流動下で昇温速度５℃／ｍｉｎで９００℃まで昇温し、２．５時間（賦活時間）保持させた状態で純水を０．６ｍＬ／ｍｉｎで供給し続けて、賦活処理を行った。その後、出入口の炉内圧を２Ｐａ以上に維持し、常温になるまで冷却した。出入口の炉内圧を２Ｐａ以上に維持するために、炉内の温度が下がるにつれて窒素の流量を徐々に増やしていき、最終的には３０Ｌ／ｍｉｎの窒素を流すことで、冷却時の酸素濃度が０．０５％（東レエンジニアリング社のジルコニア酸素濃度計ＬＣ−７５０Ｌで測定）となるようにした。このようにして実施例１の活性炭素繊維を得た。
<Example 1>
Using a tubular furnace having an inner diameter of 70 mm and an effective length of 30 cm, a phenol fiber having a fiber diameter of 24 μm was heated to 900 ° C. at a heating rate of 5 ° C./min under nitrogen flow at 5 L / min for 2.5 hours ( (Activation time) Pure water was continuously supplied at 0.6 mL / min in the state of being kept, and the activation treatment was performed. Thereafter, the furnace pressure at the entrance / exit was maintained at 2 Pa or higher and cooled to room temperature. In order to maintain the furnace pressure at the inlet / outlet at 2 Pa or higher, the flow rate of nitrogen is gradually increased as the temperature in the furnace decreases, and finally, by flowing 30 L / min of nitrogen, the oxygen concentration during cooling is reduced. 0.05% (measured with a zirconia oxygen concentration meter LC-750L manufactured by Toray Engineering Co., Ltd.). Thus, the activated carbon fiber of Example 1 was obtained.
＜実施例２＞
賦活時間を３時間としたこと以外は実施例１と同様にして、実施例２の活性炭素繊維を得た。
<Example 2>
An activated carbon fiber of Example 2 was obtained in the same manner as in Example 1 except that the activation time was 3 hours.
＜比較例１＞
酸素濃度の制御をせずに冷却工程を行った（酸素濃度：１．０％）こと以外は実施例１と同様にして、比較例１の活性炭素繊維を得た。
<Comparative Example 1>
An activated carbon fiber of Comparative Example 1 was obtained in the same manner as in Example 1 except that the cooling step was performed without controlling the oxygen concentration (oxygen concentration: 1.0%).
＜比較例２＞
賦活時間を３時間としたこと以外は比較例１と同様にして、比較例２の活性炭素繊維を得た。
<Comparative example 2>
An activated carbon fiber of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the activation time was 3 hours.
得られた実施例１、２、比較例１、２の活性炭素繊維について、以下の評価試験を行った。 The following evaluation tests were performed on the activated carbon fibers obtained in Examples 1 and 2 and Comparative Examples 1 and 2.
（１）ＢＥＴ比表面積（ｍ2／ｇ）
試料を約３０ｍｇ採取し、１２０℃で１２時間真空乾燥して秤量し、比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を使用して測定した。液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で測定し、試料の吸着等温線を作成した。相対圧０．０２〜０．１５の範囲での結果をもとに、ＢＥＴ法により重量あたりのＢＥＴ比表面積（単位：ｍ2／ｇ）を求めた。
(1) BET specific surface area (m 2 / g)
About 30 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and measured using a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). The adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) was measured in the range of relative pressure of 0.02 to 0.95, and the adsorption isotherm of the sample was created. Based on the results in the relative pressure range of 0.02 to 0.15, the BET specific surface area (unit: m 2 / g) per weight was determined by the BET method.
（２）全細孔容積（ｃｃ／ｇ）
試料を約３０ｍｇ採取し、１２０℃で１２時間真空乾燥して秤量し、比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を使用して測定した。液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で測定し、試料の吸着等温線を作成した。相対圧０．９５での結果より全細孔容積（単位：ｃｃ／ｇ）を算出した。
(2) Total pore volume (cc / g)
About 30 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and measured using a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). The adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) was measured in the range of relative pressure of 0.02 to 0.95, and the adsorption isotherm of the sample was created. The total pore volume (unit: cc / g) was calculated from the result at a relative pressure of 0.95.
（３）全マイクロポア細孔容積（Ａ）（ｃｃ／ｇ）
試料を約３０ｍｇ採取し、１２０℃で１２時間真空乾燥して秤量し、比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を使用して測定した。液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で測定し、試料の吸着等温線を作成した。この結果をＭＰ法によって解析範囲０〜２０Å、ｔ決定式Ｈ．Ｊの条件で解析し、吸着時のマイクロポア細孔径分布数表の結果より全マイクロポア細孔容積（Ａ）（単位：ｃｃ／ｇ）を算出した。
(3) Total micropore pore volume (A) (cc / g)
About 30 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and measured using a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). The adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) was measured in the range of relative pressure of 0.02 to 0.95, and the adsorption isotherm of the sample was created. This result was analyzed by the MP method with an analysis range of 0 to 20 cm and a t-determining formula H.264. Analysis was performed under the conditions of J, and the total micropore pore volume (A) (unit: cc / g) was calculated from the results of the micropore pore diameter distribution number table at the time of adsorption.
（４）細孔直径１ｎｍ以下のマイクロポア細孔容積（Ｂ）（ｃｃ／ｇ）
試料を約３０ｍｇ採取し、１２０℃で１２時間真空乾燥して秤量し、比表面積・細孔分布測定装置Ｇｅｍｉｎｉ２３７５（Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製）を使用して測定した。液体窒素の沸点（−１９５．８℃）における窒素ガスの吸着量を相対圧が０．０２〜０．９５の範囲で測定し、試料の吸着等温線を作成した。この結果をＭＰ法によって解析範囲０〜２ｎｍ、ｔ決定式Ｈ．Ｊの条件で解析し、吸着時のマイクロポア細孔径分布数表の結果より全マイクロポア細孔容積（Ａ）から細孔直径１．００３ｎｍ以上のマイクロポア細孔容積を引いて、細孔直径１ｎｍ以下のマイクロポア細孔容積Ｂ（単位：ｃｃ／ｇ）を算出した。
(4) Micropore pore volume with pore diameter of 1 nm or less (B) (cc / g)
About 30 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and measured using a specific surface area / pore distribution measuring device Gemini 2375 (manufactured by Micromeritics). The adsorption amount of nitrogen gas at the boiling point of liquid nitrogen (-195.8 ° C.) was measured in the range of relative pressure of 0.02 to 0.95, and the adsorption isotherm of the sample was created. This result was analyzed by the MP method with an analysis range of 0 to 2 nm and a t-determining formula H.264. Analyzing under the conditions of J, subtracting the micropore pore volume with a pore diameter of 1.003 nm or more from the total micropore pore volume (A) from the results of the micropore pore diameter distribution number table at the time of adsorption, The micropore pore volume B (unit: cc / g) of 1 nm or less was calculated.
（５）温度２５℃、相対湿度５２％における水分吸着率（％）
試料を約０．２ｍｇ採取し、１２０℃で１２時間真空乾燥して秤量し、恒温恒湿器ＳＨ−６６１（エスペック社製）を使用し、温度２５℃、相対湿度５２％で２時間置いたときの重量変化から水分吸着率（％）を求めた。
(5) Moisture adsorption rate (%) at a temperature of 25 ° C. and a relative humidity of 52%
About 0.2 mg of a sample was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, and placed in a thermo-hygrostat SH-661 (manufactured by Espec) for 2 hours at a temperature of 25 ° C. and a relative humidity of 52%. The moisture adsorption rate (%) was determined from the change in weight.
（６）全酸性基量（ｍｅｑ／ｇ）
試料を水洗、乾燥後、約１ｇを採取し、１２０℃で１２時間真空乾燥して秤量し、１／１０ＭのＮａＯＨ水溶液５０ｍｌ中に浸漬し、２５℃で２時間振盪した。この液をガラス濾過器で濾過し、濾液２０ｍｌを正確に分取して１／１０ＭのＨＣｌ水溶液により逆滴定した。滴定の際は０．１ｗ／ｖ％のメチルオレンジ溶液（和研薬社製）を指示薬として用いた。空試験も同様に行い、空試験での滴定量を差し引いた値から全酸性基量（単位：ｍｅｑ／ｇ）を求めた。
(6) Total acidic group content (meq / g)
After washing and drying the sample, about 1 g was collected, vacuum-dried at 120 ° C. for 12 hours, weighed, immersed in 50 ml of 1/10 M NaOH aqueous solution, and shaken at 25 ° C. for 2 hours. This solution was filtered with a glass filter, and 20 ml of the filtrate was accurately collected and back-titration was performed with a 1/10 M aqueous HCl solution. For titration, a 0.1 w / v% methyl orange solution (manufactured by Wakken Yakuhin Co., Ltd.) was used as an indicator. The blank test was performed in the same manner, and the total amount of acidic groups (unit: meq / g) was determined from the value obtained by subtracting the titration value in the blank test.
（７）カルボキシル基量（ｍｅｑ／ｇ）
試料を水洗、乾燥後、約１ｇを採取し、１２０℃で１２時間真空乾燥して秤量し、１／２０ＭのＮａ2ＣＯ3水溶液５０ｍｌ中に浸漬し、２５℃で２時間振盪した。この液をガラス濾過器で濾過し、濾液２０ｍｌを正確に分取して１／１０ＭのＨＣｌ水溶液により逆滴定した。滴定の際は０．１ｗ／ｖ％のメチルオレンジ溶液（和研薬社製）を指示薬として用いた。空試験も同様に行い、空試験での滴定量を差し引いた値からカルボキシル基量（単位：ｍｅｑ／ｇ）を求めた。
(7) Carboxyl group amount (meq / g)
After the sample was washed with water and dried, about 1 g was collected, vacuum dried at 120 ° C. for 12 hours, weighed, immersed in 50 ml of 1/20 M Na 2 CO 3 aqueous solution, and shaken at 25 ° C. for 2 hours. This solution was filtered with a glass filter, and 20 ml of the filtrate was accurately collected and back-titration was performed with a 1/10 M aqueous HCl solution. For titration, a 0.1 w / v% methyl orange solution (manufactured by Wakken Yakuhin Co., Ltd.) was used as an indicator. The blank test was performed in the same manner, and the carboxyl group amount (unit: meq / g) was determined from the value obtained by subtracting the titration value in the blank test.
（８）フェノール性水酸基量（ｍｅｑ／ｇ）
全酸性基量からカルボキシル基量を引いて、フェノール性水酸基量（単位：ｍｅｑ／ｌ）を求めた。
(8) Amount of phenolic hydroxyl group (meq / g)
The amount of phenolic hydroxyl groups (unit: meq / l) was determined by subtracting the amount of carboxyl groups from the total amount of acidic groups.
（９）全塩基性基量（ｍｅｑ／ｇ）
試料を水洗、乾燥後、約１ｇを採取し、１２０℃で１２時間真空乾燥して秤量し、１／１０ＭのＨＣｌ水溶液５０ｍｌ中に浸漬し、２５℃で２時間振盪した。この液をガラス濾過器で濾過し、濾液２０ｍｌを正確に分取して１／１０ＭのＮａＯＨ水溶液により逆滴定した。滴定の際は０．１ｗ／ｖ％のメチルオレンジ溶液（和研薬社製）を指示薬として用いた。空試験も同様に行い、空試験での滴定量を差し引いた値から全塩基性基量（単位：ｍｅｑ／ｇ）を求めた。
(9) Total basic group amount (meq / g)
After the sample was washed with water and dried, about 1 g was collected, vacuum dried at 120 ° C. for 12 hours, weighed, immersed in 50 ml of 1/10 M HCl aqueous solution, and shaken at 25 ° C. for 2 hours. This liquid was filtered with a glass filter, and 20 ml of the filtrate was accurately collected and back titrated with a 1/10 M NaOH aqueous solution. For titration, a 0.1 w / v% methyl orange solution (manufactured by Wakken Yakuhin Co., Ltd.) was used as an indicator. The blank test was performed in the same manner, and the total basic group amount (unit: meq / g) was determined from the value obtained by subtracting the titration value in the blank test.
（１０）トルエンに対する吸着性能評価
試料を約３ｋｇ充填した吸着槽を２槽併設した吸着装置に、濃度１０００ｐｐｍ、温度３０℃、湿度５０％、風量１０ｍ3／ｍｉｎのトルエンのガスを流し、一定時間吸着し、吸着終了時に吸着槽に水蒸気を噴出させて脱着するサイクルを１０回繰り返して、平均の吸着破過時間（分）を求めた。
(10) Adsorption performance evaluation for toluene Toluene gas having a concentration of 1000 ppm, a temperature of 30 ° C., a humidity of 50%, and an air volume of 10 m 3 / min was passed through an adsorption apparatus equipped with two adsorption tanks filled with about 3 kg of a sample for a certain time. The cycle of adsorbing and desorbing water vapor into the adsorption tank at the end of adsorption was repeated 10 times to obtain the average adsorption breakthrough time (minutes).
実施例１、２、比較例１、２の活性炭素繊維について得られた結果を表１、２にそれぞれ示す。 The results obtained for the activated carbon fibers of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Tables 1 and 2, respectively.
今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009261973A JP5482134B2 (en) | 2009-11-17 | 2009-11-17 | Activated carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009261973A JP5482134B2 (en) | 2009-11-17 | 2009-11-17 | Activated carbon fiber |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2011106052A true JP2011106052A (en) | 2011-06-02 |
| JP2011106052A5 JP2011106052A5 (en) | 2013-07-11 |
| JP5482134B2 JP5482134B2 (en) | 2014-04-23 |
Family
ID=44229844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009261973A Active JP5482134B2 (en) | 2009-11-17 | 2009-11-17 | Activated carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5482134B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013530114A (en) * | 2010-05-17 | 2013-07-25 | エスゲーエル カーボン ソシエタス ヨーロピア | Porous carbon with high volumetric capacity for double layer capacitors |
| JP6471256B1 (en) * | 2018-05-18 | 2019-02-13 | ユニチカ株式会社 | Deodorizing material and deodorizing sheet |
| JP7282719B2 (en) | 2019-08-20 | 2023-05-29 | 国立研究開発法人産業技術総合研究所 | Activated carbon adsorbing per- and polyfluoroalkyl compounds |
-
2009
- 2009-11-17 JP JP2009261973A patent/JP5482134B2/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013530114A (en) * | 2010-05-17 | 2013-07-25 | エスゲーエル カーボン ソシエタス ヨーロピア | Porous carbon with high volumetric capacity for double layer capacitors |
| JP6471256B1 (en) * | 2018-05-18 | 2019-02-13 | ユニチカ株式会社 | Deodorizing material and deodorizing sheet |
| JP2019198542A (en) * | 2018-05-18 | 2019-11-21 | ユニチカ株式会社 | Deodorant and deodorizing sheet |
| JP7282719B2 (en) | 2019-08-20 | 2023-05-29 | 国立研究開発法人産業技術総合研究所 | Activated carbon adsorbing per- and polyfluoroalkyl compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5482134B2 (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5482133B2 (en) | Activated carbon fiber | |
| Mahar et al. | Rapid adsorption of lead ions using porous carbon nanofibers | |
| Jahangiri et al. | The adsorption of benzene, toluene and xylenes (BTX) on the carbon nanostructures: the study of different parameters | |
| JP5327009B2 (en) | Activated carbon fiber | |
| Tofighy et al. | Copper ions removal from water using functionalized carbon nanotubes–mullite composite as adsorbent | |
| Wang et al. | Comparison of chemical, ultrasonic and thermal regeneration of carbon nanotubes for acetaminophen, ibuprofen, and triclosan adsorption | |
| Chen et al. | Sustainable recovery of gaseous mercury by adsorption and electrothermal desorption using activated carbon fiber cloth | |
| WO2018116859A1 (en) | Active carbon and production method thereof | |
| JP6683968B1 (en) | Activated carbon | |
| Hassani et al. | Activated carbon fiber for environmental protection | |
| Mirzaei et al. | Plasma modification of a natural zeolite to improve its adsorption capacity of strontium ions from water samples | |
| JP5482134B2 (en) | Activated carbon fiber | |
| JP2022132348A (en) | Activated carbon and production method thereof | |
| JP2008100186A (en) | Gas adsorption apparatus | |
| ZHANG et al. | Removal of elemental mercury from coal combustion flue gas by bentonite-chitosan and their modifier | |
| JP2008188493A (en) | Water treatment apparatus | |
| JP2008149267A (en) | Organic halide based compound removal filter | |
| Nuray et al. | SO2 adsorption capability of activated carbon nanofibers produced by different activation process parameters | |
| Pourfayaz et al. | An evaluation of the adsorption potential of MWCNTs for benzene and toluene removal | |
| Pourfayaz et al. | A study of effects of different surface modifications of MWCNTs on their adsorption capacity of benzene and toluene | |
| Salawudeen et al. | Evaluation of the removal of phenol from contaminated water by graphene oxide functionalized with polydiallydimethylammonium chloride (GPDADMAC) | |
| Wang et al. | Sorption of volatile organic compounds on organic substance-modified titanate nanotubes | |
| JP4378612B2 (en) | Fibrous activated carbon for adsorbing organic compounds and exhaust gas treatment apparatus using the same | |
| Othman et al. | Adsorption of cadmium (II) ions by polyacrylonitrile-based activated carbon nanofibers/magnesium oxide as its adsorbents | |
| Moon et al. | Packaging vertically aligned carbon nanotubes into a heat-shrink tubing for efficient removal of phenolic pollutants |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121010 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130527 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140117 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140121 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140203 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5482134 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |