JP4509523B2 - Recovery method for organic chlorinated solvents - Google Patents
Recovery method for organic chlorinated solvents Download PDFInfo
- Publication number
- JP4509523B2 JP4509523B2 JP2003345105A JP2003345105A JP4509523B2 JP 4509523 B2 JP4509523 B2 JP 4509523B2 JP 2003345105 A JP2003345105 A JP 2003345105A JP 2003345105 A JP2003345105 A JP 2003345105A JP 4509523 B2 JP4509523 B2 JP 4509523B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- solvent
- fibrous activated
- intensity
- pore
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002904 solvent Substances 0.000 title claims description 75
- 238000000034 method Methods 0.000 title claims description 32
- 238000011084 recovery Methods 0.000 title claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 166
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 90
- 239000011148 porous material Substances 0.000 claims description 81
- 238000001179 sorption measurement Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 29
- 239000000460 chlorine Substances 0.000 claims description 29
- 229910052801 chlorine Inorganic materials 0.000 claims description 29
- 238000002441 X-ray diffraction Methods 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000007789 gas Substances 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 239000000835 fiber Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000002699 waste material Substances 0.000 description 15
- 230000004913 activation Effects 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 5
- 229950005499 carbon tetrachloride Drugs 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000011295 pitch Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920001059 synthetic polymer Polymers 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920005615 natural polymer Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
本発明は有機塩素系溶剤の回収方法に関する。さらに詳しくは、平衡吸着水分率、ＢＥＴ比表面積、細孔容積、細孔容積率及び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で規定された繊維状活性炭を使用して塗装ブースや磁気テープ等の塗布工程で発生する塩化メチレン等の有機塩素系溶剤を効率よく回収する方法に関する。 The present invention relates to a method for recovering an organic chlorine solvent. More specifically, the fibrous activated carbon specified by the graphitic crystalline structure parameters at the diffraction peak of the (002) plane of the equilibrium adsorption moisture content, BET specific surface area, pore volume, pore volume fraction, and X-ray diffraction intensity curve. The present invention relates to a method for efficiently recovering an organic chlorinated solvent such as methylene chloride generated in a coating booth or a coating process such as a magnetic tape.
印刷業、電気工業、機械工業等各種産業の製造工程においては、種々の有機塩素系溶剤を含有するガスが発生する。例えば、塗装ブースや磁気テープの塗布工程においては０．１〜１０００ｐｐｍ程度の濃度の有機塩素系溶剤を含有するガスが発生する。有機塩素系溶剤は急性毒性、慢性毒性を引き起こす他、発ガン性などの毒性が強く、生分解性も低いために、近年はこのようなガスの外部放出は厳しく制限されている。 In manufacturing processes of various industries such as the printing industry, electrical industry, and machine industry, gases containing various organochlorine solvents are generated. For example, in a coating booth or a magnetic tape coating process, a gas containing an organic chlorinated solvent having a concentration of about 0.1 to 1000 ppm is generated. In addition to causing acute toxicity and chronic toxicity, organochlorine solvents have strong toxicity such as carcinogenicity and low biodegradability, and in recent years, the external release of such gases has been severely restricted.
一方、溶剤の品質が劣化した場合、劣化した溶剤は廃棄するか、品質を再生して再使用するということが行われているが、廃棄するにしても、燃焼させる場合にはダイオキシンの発生が問題になり、再生した場合には、再生する場合に発生する品質の悪い溶剤の廃棄が問題になる。このような状況下においては、排出ガスから有機塩素系溶剤を効率的に分離回収することが必須となる。 On the other hand, when the quality of the solvent deteriorates, the deteriorated solvent is discarded, or the quality is regenerated and reused. However, even when discarded, dioxins are generated when burned. In the case of recycling, there is a problem of disposal of poor quality solvents that are generated in the case of recycling. Under such circumstances, it is essential to efficiently separate and recover the organic chlorinated solvent from the exhaust gas.
従来、塩化メチレン等の有機塩素系溶剤ガスを回収するために、活性炭が使用されている。具体的には、活性炭又は活性炭素繊維（以下、これらを総称して単に活性炭ということがある）を充填した充填塔に被処理ガスを供給し、含有される有機塩素系溶剤を吸着分離した後、吸着材に吸着された有機塩素系溶剤を脱着回収する方法が採用されている（例えば、非特許文献１）。活性炭に吸着された有機塩素系溶剤は、活性炭に１１０℃〜１６０℃のスチームを吹き込むことにより有機塩素系溶剤ガスとスチームの混合ガスとして活性炭から脱着される。
この混合ガスを冷却して凝縮させ、水と有機塩素系溶剤を液状で分離することにより有機塩素系溶剤は回収され、再使用されている。スチーム加熱により再生された活性炭には再度有機塩素系溶剤を含むガスを通気し、有機塩素系溶剤を吸着させる。この操作を繰り返すことにより、有害な有機塩素系溶剤を外部に排出することなく、有機塩素系溶剤を回収再利用することができる。 The mixed gas is cooled and condensed, and the organic chlorine solvent is recovered and reused by separating water and the organic chlorine solvent in a liquid state. The activated carbon regenerated by steam heating is again vented with a gas containing an organic chlorine solvent to adsorb the organic chlorine solvent. By repeating this operation, the organic chlorine solvent can be recovered and reused without discharging the harmful organic chlorine solvent to the outside.
活性炭を溶剤回収用の素材という観点から粒状活性炭と繊維状活性炭とに大別して見た場合、繊維状活性炭を使用して有機塩素系溶剤の吸脱着を行うと、粒状活性炭に比べて、回収された溶剤の品質がよいといわれている。この理由は、繊維状活性炭の方が粒状活性炭より吸脱着速度が速く、したがって、溶剤の吸脱着を頻繁に行うことができるため、溶剤が活性炭に吸着されている時間が短く、溶剤が劣化しにくいことによる。 When activated carbon is broadly divided into granular activated carbon and fibrous activated carbon from the viewpoint of solvent recovery material, the adsorption and desorption of organic chlorinated solvent using fibrous activated carbon is recovered compared to granular activated carbon. It is said that the quality of the solvent is good. The reason for this is that fibrous activated carbon has a faster adsorption / desorption rate than granular activated carbon, and therefore the adsorption / desorption of the solvent can be carried out frequently, so the time during which the solvent is adsorbed on the activated carbon is short, and the solvent deteriorates. Because it is difficult.
ところで、上記した従来の溶剤回収方法において最も問題となるのは回収される有機塩素系溶剤の品質である。すなわち、有機塩素系溶剤は、活性炭に吸着されたとき、分解して塩酸を発生する。この点に関しては、繊維状活性炭においても同様であり、有機塩素系溶剤中に塩酸が混じり、溶剤の酸性度が徐々に高くなることは不可避である。その結果、溶剤回収装置が急速に腐食するという問題が生じており、塩酸の発生が少ない有機塩素系溶剤の回収方法が待望されているのが現状である。したがって、本発明の目的は、効率がよく、溶剤回収装置の腐食が少ない有機塩素系溶剤の回収方法を提供することにある。 By the way, what is most problematic in the conventional solvent recovery method described above is the quality of the recovered organic chlorinated solvent. That is, the organic chlorinated solvent decomposes to generate hydrochloric acid when adsorbed on the activated carbon. Regarding this point, the same applies to fibrous activated carbon, and it is inevitable that hydrochloric acid is mixed in the organic chlorine solvent and the acidity of the solvent gradually increases. As a result, there is a problem that the solvent recovery device corrodes rapidly, and there is a long-awaited situation in which a method for recovering an organic chlorine solvent that generates less hydrochloric acid is desired. Accordingly, an object of the present invention is to provide a method for recovering an organochlorine solvent that is efficient and has little corrosion of the solvent recovery device.
本発明者らは、上記目的を達成するため種々検討を行い、特定の平衡吸着水分率、ＢＥＴ比表面積、細孔容積及び細孔容積率を満足し、非晶構造よりなる繊維状活性炭を吸着材として使用した場合には、溶剤回収を繰返し実施しても、回収溶剤の酸性度が上がらず、したがって溶剤回収装置の腐食が少なく、吸脱着を繰返しても、有機塩素系溶剤の品質が殆ど劣化しないので、回収された溶剤は半永久的に使用することが可能であることを見出し、本発明に到達した。 In order to achieve the above-mentioned object, the present inventors have made various studies, satisfying specific equilibrium adsorption moisture content, BET specific surface area, pore volume and pore volume ratio, and adsorbing fibrous activated carbon having an amorphous structure. When used as a material, even if repeated solvent recovery is performed, the acidity of the recovered solvent does not increase, and therefore the corrosion of the solvent recovery device is low. Since it does not deteriorate, it has been found that the recovered solvent can be used semipermanently, and the present invention has been achieved.
すなわち、本発明は、（ａ）２５℃、相対湿度３７％における平衡吸着水分率が１．０〜１５．０％、（ｂ）ＢＥＴ比表面積が３００〜２５００ｍ２／ｇ、（ｃ）細孔容積が０．２５〜２．０ｃｃ／ｇで、かつ（ｄ）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、（ｅ）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使用することを特徴とする有機塩素系溶剤の回収方法であって、スチームにより該溶剤を繊維状活性炭から脱着させることを特徴とする有機塩素系溶剤の回収方法である。ただし、ＩｐはＸ線回折強度曲線において、（００２）面の回折ピ−クの両裾に接線を引き、その接線から上の部分の強度の最大値であり、Ｉｏは（００２）面の回折強度から空気の散乱強度を差し引いた残りの強度である。
That is, the present invention provides (a) an equilibrium adsorption moisture content of 1.0 to 15.0% at 25 ° C. and a relative humidity of 37%, (b) a BET specific surface area of 300 to 2500 m 2 / g, and (c) pores. The volume of the pores having a volume of 0.25 to 2.0 cc / g and (d) a pore radius in the range of 6 to 16 mm measured by the water vapor method is a volume occupied by pores having a pore radius of 100 mm or less. It is characterized by using a fibrous activated carbon that is 80% or more and (e) a graphitic crystalline structure parameter Ip / Io at a diffraction peak on the (002) plane of the X-ray diffraction intensity curve is 0.35 or less. A method for recovering an organic chlorine solvent , which comprises desorbing the solvent from fibrous activated carbon with steam . In the X-ray diffraction intensity curve, Ip is the maximum value of the intensity of the portion above the tangent line of the (002) plane and Io is the diffraction value of the (002) plane. This is the remaining intensity obtained by subtracting the scattering intensity of air from the intensity.
本発明により、（ａ）平衡吸着水分率１．０〜１５．０％、（ｂ）ＢＥＴ比表面積５００〜２５００ｍ２／ｇ、（ｃ）細孔容積０．２５〜２．００ｃｃ／ｇで、（ｄ）水蒸気法で測定した細孔半径が６〜１６Åの範囲である細孔の容積が、細孔半径が１００Å以下の細孔の占める容積の８０％以上であって、（ｅ）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使用して有機塩素系溶剤を回収する方法を提供することができる。本発明の方法によれば、品質を劣化させることなく、装置の腐食が少なく、効率よく有機塩素系溶剤を回収することができる。 According to the present invention, (a) Equilibrium moisture content 1.0-15.0%, (b) BET specific surface area 500-2500 m 2 / g, (c) pore volume 0.25-2.00 cc / g, (D) The volume of the pores having a pore radius measured by the water vapor method in the range of 6 to 16 mm is 80% or more of the volume occupied by the pores having a pore radius of 100 mm or less, and (e) X-ray It is possible to provide a method for recovering an organic chlorine solvent using a fibrous activated carbon having a graphite crystalline structure parameter Ip / Io of 0.35 or less at a diffraction peak of the (002) plane of the diffraction intensity curve. According to the method of the present invention, the organic chlorinated solvent can be efficiently recovered without deteriorating the quality and with little corrosion of the apparatus.
本発明において用いられる繊維状活性炭は、（ａ）２５℃、相対湿度３７％における平衡吸着水分率が１．０〜１５．０％であることが必要である。平衡吸着水分率が１．０％未満のものは細孔半径が大きくなるためか、有機塩素系溶剤の吸着性能が悪くなる。一方、平衡吸着水分率が１５．０％を超えると親水性が高くなりすぎ、有機塩素系溶剤の吸着性能が低下すると同時に、スチームを使用して繊維状活性炭を再生した場合に、繊維状活性炭に吸着された水分が抜けにくく、次の吸着に使用した場合、有機塩素系溶剤の吸着性能が低下する。２５℃、相対湿度３７％における平衡吸着水分率は１．５〜１０．０％であるのが好ましい。 The fibrous activated carbon used in the present invention (a) needs to have an equilibrium adsorption moisture content of 1.0 to 15.0% at 25 ° C. and a relative humidity of 37%. If the equilibrium adsorption moisture content is less than 1.0%, the pore radius is increased, or the adsorption performance of the organic chlorine solvent is deteriorated. On the other hand, if the equilibrium adsorption moisture content exceeds 15.0%, the hydrophilicity becomes too high and the adsorption performance of the organic chlorine solvent is lowered. At the same time, when the fibrous activated carbon is regenerated using steam, the fibrous activated carbon The moisture adsorbed on the organic solvent is difficult to escape, and when used for the next adsorption, the adsorption performance of the organic chlorine solvent is lowered. The equilibrium adsorption moisture content at 25 ° C. and relative humidity of 37% is preferably 1.5 to 10.0%.
また、本発明において用いられる繊維状活性炭は、（ｂ）ＢＥＴ比表面積が３００〜２５００ｍ２／ｇであることが必要である。本発明における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である。ＢＥＴ比表面積が３００ｍ２／ｇ未満の場合、有機塩素系溶剤の脱着性能が低くなり、一方ＢＥＴ比表面積が２５００ｍ２／ｇを越えると、有機塩素系溶剤の低濃度域での吸着性能が低くなる。 In addition, the fibrous activated carbon used in the present invention needs to have (b) a BET specific surface area of 300 to 2500 m 2 / g. The BET specific surface area in this invention is a specific surface area calculated | required by BET method by the nitrogen gas adsorption isotherm in liquid nitrogen temperature. When the BET specific surface area is less than 300 m 2 / g, the desorption performance of the organic chlorinated solvent is low. On the other hand, when the BET specific surface area exceeds 2500 m 2 / g, the adsorption performance in the low concentration region of the organic chlorinated solvent is low. Become.
本発明において用いられる繊維状活性炭は、（ｃ）細孔容積が０．２５〜２．０ｃｃ／ｇで、かつ（ｄ）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％以上である。細孔容積が０．２５ｃｃ／ｇ未満であると有機塩素系溶剤の吸着量が不足し、一方細孔容積が２．０ｃｃ／ｇを越えると、有機塩素系溶剤への吸着力が低下し、低濃度での吸着性能が悪くなる。 The fibrous activated carbon used in the present invention has (c) a pore volume in the range of 0.25 to 2.0 cc / g and (d) a pore radius in the range of 6 to 16 mm measured by the water vapor method. The volume is 80% or more of the volume occupied by pores having a pore radius of 100 mm or less. When the pore volume is less than 0.25 cc / g, the adsorption amount of the organic chlorine solvent is insufficient, while when the pore volume exceeds 2.0 cc / g, the adsorption power to the organic chlorine solvent is reduced, Adsorption performance at low concentrations is poor.
水蒸気法は、窒素ガスによるＢＥＴ法と比較して、細孔半径２０Å以下の細孔を正確に測定するのに好適な方法であるので、本発明において細孔半径の測定には水蒸気法を採用する。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、及び細孔半径１００Å以下の細孔の占める容積とは、例えば特開平６−９９０６５号公報などに詳述されているように、次の方法により作成された細孔分布曲線に基づいて求められるものである。 Since the water vapor method is a suitable method for accurately measuring pores having a pore radius of 20 mm or less as compared with the BET method using nitrogen gas, the water vapor method is employed in the measurement of the pore radius in the present invention. To do. The volume of pores having a pore radius in the range of 6 to 16 mm measured by the water vapor method and the volume occupied by pores having a pore radius of 100 mm or less are described in detail, for example, in JP-A-6-99065. Thus, it is obtained based on the pore distribution curve created by the following method.
細孔分布曲線の作成：一定濃度の硫酸水溶液の平衡水蒸気圧は一定値をとることから、硫酸水溶液の硫酸濃度と平衡水蒸気圧との間には一律の関係がある。したがって、所定濃度の硫酸水溶液を存在させた吸着室の気相部に繊維状活性炭を入れ、１気圧（絶対圧）、３０℃の条件で水蒸気と接触させた後、該繊維状活性炭における重量増加分として水の飽和吸着量（重量）を測定する。 Creation of pore distribution curve: Since the equilibrium water vapor pressure of a sulfuric acid aqueous solution having a constant concentration takes a constant value, there is a uniform relationship between the sulfuric acid concentration of the sulfuric acid aqueous solution and the equilibrium water vapor pressure. Therefore, after putting the fibrous activated carbon into the gas phase part of the adsorption chamber in which a sulfuric acid aqueous solution of a predetermined concentration is present and contacting with water vapor at 1 atm (absolute pressure) and 30 ° C., the weight increase in the fibrous activated carbon Measure the saturated adsorption amount (weight) of water as a minute.
一方、この飽和吸着量の測定試験において水の吸着に利用された繊維状活性炭の細孔は、採用した硫酸水溶液の硫酸濃度に固有の１気圧（絶対圧）、３０℃での平衡水蒸気圧の値（Ｐ）から下記式（Ｉ）で表されるＫｅｌｖｉｎの式に基づいて求められる細孔半径（ｒ）以下の細孔の細孔半径を有するものである。すなわち、該Ｋｅｌｖｉｎの式に基づいて求められる細孔半径以下の細孔の累積細孔容積が、その測定試験での飽和吸着量の相当する３０℃の水の体積となる。 On the other hand, the pores of the fibrous activated carbon used for water adsorption in this saturation adsorption amount measurement test are 1 atm (absolute pressure) inherent to the sulfuric acid concentration of the sulfuric acid aqueous solution, and the equilibrium water vapor pressure at 30 ° C. From the value (P), the pore radius of the pore is equal to or less than the pore radius (r) determined based on the Kelvin equation represented by the following formula (I). That is, the accumulated pore volume of pores having a pore radius equal to or smaller than that obtained based on the Kelvin equation is the volume of 30 ° C. water corresponding to the saturated adsorption amount in the measurement test.
数１
ｒ＝−[２ＶｍγｃｏｓΦ]／[ＲＴｌｎ（Ｐ／Ｐ０）] （Ｉ）
ｒ：細孔半径（ｃｍ）
Ｖｍ：水の分子容（ｃｍ3／ｍｏｌ）＝１８．０７９（３０℃）
γ：表面張力（ｄｙｎｅ／ｃｍ）＝７１．１５（３０℃）
Φ：毛細管壁と水との接触角（°）＝５５°
Ｒ：ガス定数（ｅｒｇ／ｄｅｇ・ｍｏｌ）＝８．３１４３×１０７
Ｔ：絶対温度（Ｋ）＝３０３．１５
Ｐ：細孔内の水の示す飽和蒸気圧（ｍｍＨｇ）
Ｐ０：水の１気圧（絶対圧）、３０℃における飽和蒸気圧（ｍｍＨｇ）＝３１．８２４
Number 1
r = − [2VmγcosΦ] / [RTln (P / P 0 )] (I)
r: pore radius (cm)
Vm: Molecular volume of water (cm 3 /mol)=18.079 ( 30 ° C.)
γ: surface tension (dyne / cm) = 71.15 (30 ° C.)
Φ: Contact angle between the capillary wall and water (°) = 55 °
R: Gas constant (erg / deg · mol) = 8.3143 × 10 7
T: Absolute temperature (K) = 303.15
P: Saturated vapor pressure of water in the pores (mmHg)
P 0 : 1 atm (absolute pressure) of water, saturated vapor pressure (mmHg) at 30 ° C. = 31.824
同様にして、同種の繊維状活性炭を用いて、硫酸濃度を変化させた１３種類の硫酸水溶液（すなわち、１．０５〜１．３０までの０．０２５間隔の比重を有する１１種類の硫酸水溶液、１．３５の比重を有する硫酸水溶液及び１．４０の比重を有する硫酸水溶液）について飽和吸着量の測定試験を行い、各測定試験において、対応する細孔半径以下の細孔の累積細孔容積を求める。このようにして求めた累積細孔容積のデータに基づいて、累積細孔容積を細孔半径に対してプロットすることにより、繊維状活性炭の細孔分布曲線を得ることができる。 Similarly, using the same type of fibrous activated carbon, 13 types of sulfuric acid aqueous solutions having different sulfuric acid concentrations (that is, 11 types of sulfuric acid aqueous solutions having a specific gravity of 0.025 intervals from 1.05 to 1.30, 1. A saturated adsorption amount measurement test was performed on a sulfuric acid aqueous solution having a specific gravity of 1.35 and a sulfuric acid aqueous solution having a specific gravity of 1.40. In each measurement test, the cumulative pore volume of pores having a corresponding pore radius or less was measured. Ask. A pore distribution curve of fibrous activated carbon can be obtained by plotting the cumulative pore volume against the pore radius based on the cumulative pore volume data thus obtained.
２５℃、相対湿度３７％における平衡吸着水分率：上記水蒸気法による細孔分布測定と同様にして、２５℃での硫酸水溶液（比重＝１．３９５）下の活性炭繊維の平衡吸着水分率から求めた。 Equilibrium adsorption moisture content at 25 ° C. and 37% relative humidity: obtained from the equilibrium adsorption moisture content of activated carbon fiber under sulfuric acid aqueous solution (specific gravity = 1.395) at 25 ° C. in the same manner as the pore distribution measurement by the water vapor method. It was.
細孔容積：相対圧０．９６における窒素ガスの気体吸着法により測定した。 Pore volume: Measured by a gas adsorption method of nitrogen gas at a relative pressure of 0.96.
細孔半径が６Å未満の場合には、有機塩素系溶剤の吸着が強すぎて脱着が困難になり、一方、細孔半径が１６Åを越えるものは、低濃度での有機塩素系溶剤の吸着性が低くなる。なお、細孔半径とは、細孔分布曲線におけるピークトップの細孔半径をいう。とくに、細孔半径が７〜１５Å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％以上である繊維状活性炭は、有機塩素系溶剤の吸着性能が優れており、好ましい。 When the pore radius is less than 6 mm, the adsorption of the organic chlorine solvent is too strong and desorption becomes difficult, while when the pore radius exceeds 16 mm, the adsorption property of the organic chlorine solvent at a low concentration is low. Becomes lower. The pore radius means the peak top pore radius in the pore distribution curve. In particular, fibrous activated carbon whose pore radius is in the range of 7 to 15 mm and whose pore volume is 80% or more of the volume occupied by pores having a pore radius of 100 mm or less has excellent adsorption performance of organochlorine solvents. It is preferable.
また、本発明において用いられる繊維状活性炭は、（ｅ）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以下である。ここで、Ｉｐとは、Ｘ線回折強度曲線において、（００２）面の回折ピ−クの両裾に接線を引き、その接線から上の部分の強度の最大値をいい、Ｉｏとは（００２）面の回折強度から空気の散乱強度を差し引いた残りの強度をいう。黒鉛的結晶性構造パラメータはＩｐ／Ｉｏで定義されるものであり、黒鉛的結晶性構造の発達度合いを示すものである。図２は、水蒸気と炭酸ガスの混合ガスで賦活を行ったピッチ系繊維状活性炭（比表面積１１００ｍ２／ｇ）のＸ線回折強度曲線である。（００２）面のＸ線回折ピークの両裾に接線ιを引き、実測曲線と接線との差をベースライン上に書き直し、曲線Ｉを得た。曲線Ｉの最大値ＩｐおよびＩｐを示す回折角２θさらにその回折角２θにおける実測曲線の強度から空気の散乱強度を差し引き、強度Ｉｏを求めた。空気の散乱強度は試料のない状態で同一条件において走査して求められる。ここでＩｐは黒鉛的な結晶性構造に起因するＸ線回折強ピークであり、（Ｉｏ−Ｉｐ）は非晶性構造に起因するＸ線散乱強度である。 In the fibrous activated carbon used in the present invention, (e) the graphitic crystalline structure parameter Ip / Io at the diffraction peak on the (002) plane of the X-ray diffraction intensity curve is 0.35 or less. Here, Ip refers to the maximum value of the intensity of the portion above the tangent line drawn from both hems of the diffraction peak of the (002) plane in the X-ray diffraction intensity curve, and Io is (002 ) The remaining intensity obtained by subtracting the scattering intensity of air from the diffraction intensity of the surface. The graphitic crystalline structure parameter is defined by Ip / Io and indicates the degree of development of the graphite crystalline structure. FIG. 2 is an X-ray diffraction intensity curve of pitch-based fibrous activated carbon (specific surface area 1100 m 2 / g) activated with a mixed gas of water vapor and carbon dioxide. A tangent line ι was drawn at both hems of the X-ray diffraction peak of the (002) plane, and the difference between the measured curve and the tangent line was rewritten on the baseline to obtain a curve I. The diffraction angle 2θ showing the maximum values Ip and Ip of the curve I, and the scattering intensity of air were subtracted from the intensity of the actually measured curve at the diffraction angle 2θ to obtain the intensity Io. The scattering intensity of air is obtained by scanning under the same conditions without a sample. Here, Ip is an X-ray diffraction strong peak attributed to a graphite-like crystalline structure, and (Io-Ip) is an X-ray scattering intensity attributed to an amorphous structure.
一般に、Ｘ線回折ピーク強度は、結晶子の結晶サイズ、結晶化度が大きい程大きくなり、結晶の発達の程度を表す。結晶サイズは回折ピークのシャープさにより定量される（非特許文献２）。結晶化度は一般に全結晶散乱強度の全散乱強度に対する割合であって、Ｘ線照射体積中の体積分率を意味する（非特許文献３）。
しかしながら、炭素材料の場合、結晶部分と非晶部分とは構造的に明確に分かれてはいない（非特許文献４）。したがって、炭素材料の場合は、通常の結晶性高分子のように、内部構造を単純に結晶部分と非晶部分からなる二相構造としてとらえることはできない。活性炭あるいは活性炭繊維の場合、非晶の海の中に極めて完成度の低い微結晶が分散し（非特許文献５）、それらの集合組織の黒鉛的結晶性領域からの干渉性散乱がＩｐであり、非晶性領域からの非干渉性散乱が（Ｉｏ−Ｉｐ）である。
本発明で用いられる黒鉛的結晶性構造パラメータＩｐ／Ｉｏは黒鉛的結晶性構造の発達度合いを示すものである。活性炭の場合、結晶部分と非晶部分とは構造的に明確に分かれていない。十分に発達した完全に近い黒鉛結晶ではＩｐ／Ｉｏは０．９６以上であるが、本発明に使用される繊維状活性炭のＩｐ／Ｉｏは０．３５以下であり、黒鉛的結晶性構造が未発達のものである。黒鉛的結晶性構造パラメータＩｐ／Ｉｏは０．３以下であるのがさらに好ましい。 The graphitic crystalline structure parameter Ip / Io used in the present invention indicates the degree of development of the graphitic crystalline structure. In the case of activated carbon, the crystalline part and the amorphous part are not clearly separated structurally. In fully developed nearly perfect graphite crystals, Ip / Io is 0.96 or more, but Ip / Io of the fibrous activated carbon used in the present invention is 0.35 or less, and the graphite-like crystalline structure is not yet present. It is a developmental one. The graphitic crystalline structure parameter Ip / Io is more preferably 0.3 or less.
本発明に用いられる繊維状活性炭の原料としては、合成高分子化合物、半合成高分子化合物、天然高分子化合物、天然及び合成ピッチなどが挙げられる。合成高分子化合物としては、ナイロンなどのポリアミド系、ビニロンなどのポリビニルアルコール（ＰＶＡ）系、ポリエステルなどのポリエステル系、アクリルなどのポリアクリロニトリル系、ポリエチレン、ポリプロピレンなどのポリオレフィン系、ポリウレタンなどのポリウレタン系、フェノール樹脂などのフェノール系などを例示することができる。 Examples of the raw material of the fibrous activated carbon used in the present invention include synthetic polymer compounds, semi-synthetic polymer compounds, natural polymer compounds, natural and synthetic pitches. Synthetic polymer compounds include polyamides such as nylon, polyvinyl alcohol (PVA) such as vinylon, polyesters such as polyester, polyacrylonitriles such as acrylic, polyolefins such as polyethylene and polypropylene, polyurethanes such as polyurethane, Examples include phenolic resins such as phenol resins.
また、半合成高分子化合物としては、アセテート、トリアセテートなどのセルロース系、プロミックスなどの蛋白質系などを例示することができる。そして、天然高分子化合物としては、レーヨンなどのセルロース系、カゼイン繊維などの蛋白質系、キチン繊維などを例示することができる。なかでも、フェノール系又はＰＶＡ系の繊維が好ましい。 Examples of semi-synthetic polymer compounds include celluloses such as acetate and triacetate, and proteins such as promix. Examples of the natural polymer compound include celluloses such as rayon, proteins such as casein fiber, and chitin fiber. Of these, phenol-based or PVA-based fibers are preferable.
本発明の活性炭素繊維は、上記原料を賦活して得ることができるが、賦活は繊維状活性炭の結晶構造が発達しないように、９５０℃以下の温度で行うのがよい。９５０℃以上の賦活温度では、結晶構造が発達するために、Ｉｐ／Ｉｏが０．３５を越えることがある。より好ましい賦活温度は９００℃以下であるが、賦活温度があまり下がると賦活反応速度が低下するので、７００℃以上で行うのがよい。 The activated carbon fiber of the present invention can be obtained by activating the above raw materials, but activation is preferably performed at a temperature of 950 ° C. or lower so that the crystalline structure of the fibrous activated carbon does not develop. At an activation temperature of 950 ° C. or higher, the crystal structure develops, so that Ip / Io may exceed 0.35. A more preferable activation temperature is 900 ° C. or lower. However, if the activation temperature is lowered too much, the activation reaction rate is lowered.
賦活に使用されるガスは、特に限定されないが、水蒸気と炭酸ガスの混合ガスを使用するのが好ましい。すなわち、本発明の繊維状活性炭は、低い温度で賦活して非晶性の炭素構造を作ることが一つのポイントであり、比較的低温で賦活を進めるためには賦活の反応速度が速い水蒸気が好ましく、一方細孔が小さい状態で賦活を進めるためには反応速度が遅い炭酸ガスが好ましい。 The gas used for activation is not particularly limited, but it is preferable to use a mixed gas of water vapor and carbon dioxide. That is, the fibrous activated carbon of the present invention is activated at a low temperature to form an amorphous carbon structure, and in order to promote activation at a relatively low temperature, steam having a high activation reaction rate is used. On the other hand, in order to advance the activation with small pores, carbon dioxide gas having a slow reaction rate is preferable.
かかる観点から、非晶性の構造を保持しながら、細孔半径を６〜１６Åの大きさにするためには、水蒸気と炭酸ガスの混合ガスを使用することが推奨される。水蒸気と炭酸ガスの混合ガスは、好ましくは、水蒸気／炭酸ガス＝１／０．５〜０．５／１の混合比率で使用される。 From this point of view, it is recommended to use a mixed gas of water vapor and carbon dioxide in order to make the pore radius 6 to 16 mm while maintaining the amorphous structure. The mixed gas of water vapor and carbon dioxide is preferably used at a mixture ratio of water vapor / carbon dioxide = 1 / 0.5 to 0.5 / 1.
繊維状活性炭に用いる原料繊維としては、１デニール〜１０デニールのものを使用するのがよい。特に好ましくは、２デニール〜８デニールである。本発明の繊維状活性炭の繊維径はあまり小さくなると、吸脱着の性能は向上するが、圧力損失が上昇し、また、繊維径があまり大きくなると、圧力損失は低下するが、吸脱着の性能は低下するので、５μｍ〜３０μｍのものが好ましい。特に好ましくは、８μｍ〜２０μｍである。 As a raw material fiber used for fibrous activated carbon, it is good to use the thing of 1 denier-10 denier. Particularly preferred is 2 denier to 8 denier. When the fiber diameter of the fibrous activated carbon of the present invention is too small, the adsorption / desorption performance is improved, but the pressure loss increases, and when the fiber diameter is too large, the pressure loss is reduced, but the adsorption / desorption performance is Since it falls, the thing of 5 micrometers-30 micrometers is preferable. Particularly preferably, it is 8 μm to 20 μm.
本発明において、吸着の対象となる有機塩素系溶剤としては、塩化メチル、塩化メチレン（ジクロロメタン）、クロロホルム（トリクロロメタン）、四塩化炭素（テトラクロロメタン）、塩化エチル（クロロエタン）、１，１−ジクロロエタン、１，２−ジクロロエタン等が挙げられる。なかでも塩化メチレンは、塩素化メタンの中で最も毒性が低く、安全上の問題から溶剤として適しており、多用されている点、及び効果の発現性が大きく、好適な有機塩素系溶剤である。 In the present invention, the organic chlorine solvent to be adsorbed includes methyl chloride, methylene chloride (dichloromethane), chloroform (trichloromethane), carbon tetrachloride (tetrachloromethane), ethyl chloride (chloroethane), 1,1- Examples include dichloroethane and 1,2-dichloroethane. Among them, methylene chloride has the lowest toxicity among chlorinated methane and is suitable as a solvent for safety reasons. It is a suitable organochlorine solvent because it is widely used and has a large effect. .
本発明の繊維状活性炭が有機塩素系溶剤の回収に優れている理由を明確に説明することはできないが、活性炭の非晶構造は有機塩素系溶剤を分解させにくく、活性炭の細孔構造は低濃度の有機塩素系溶剤の吸着性に優れ、これらの相乗効果によるものと推定している。本発明の方法によれば、有機塩素系溶剤を回収しながら半永久的に使用することができるので実用的である。以下、実施例により、本発明を更に具体的に説明する。 The reason why the fibrous activated carbon of the present invention is excellent in the recovery of the organic chlorinated solvent cannot be clearly explained, but the amorphous structure of the activated carbon is difficult to decompose the organic chlorinated solvent, and the pore structure of the activated carbon is low. It is presumed to be due to the synergistic effect of the organic chlorinated solvent at high concentration. The method of the present invention is practical because it can be used semipermanently while recovering the organic chlorine solvent. Hereinafter, the present invention will be described more specifically with reference to examples.
ポリビニルアルコール系繊維を出発原料とする繊維状活性炭の製造：
出発原料として平均重合度１７００のポリビニルアルコールを溶解した水溶液を、凝固浴としてホウ酸水溶液を使用して湿式紡糸し、１８００デニールのポリビニルアルコール繊維を得た。該ポリビニルアルコール繊維をカード機で処理し、さらに、ニードルパンチを施すことにより不織布を作製した。
Production of fibrous activated carbon starting from polyvinyl alcohol fiber:
An aqueous solution in which polyvinyl alcohol having an average polymerization degree of 1700 was dissolved as a starting material was wet-spun using an aqueous boric acid solution as a coagulation bath to obtain 1800 denier polyvinyl alcohol fibers. The polyvinyl alcohol fiber was treated with a card machine and further subjected to needle punching to produce a nonwoven fabric.
脱水・炭化剤として、硫酸アンモニウムと燐酸アンモニウムの各５０ｇを１０００ｇの水に溶解し、６０℃に加温したものを使用し、不織布を５分間浸漬し、その後マングルで絞液し、１０５℃で３分間乾燥させた。脱水剤の付着率は重量法で１０％であった。脱水剤が付着した不織布を、２００℃で３０分加熱し、その後、３００℃で１０分間、４００℃で２０分間加熱し、さらに５００℃で１０分間加熱することにより、炭化糸を得た。この炭化した不織布を、水蒸気と二酸化炭素の混合ガス（混合比率１：１）で、８５０℃で４５分間賦活を行って繊維状活性炭とした。 As a dehydrating / carbonizing agent, 50 g each of ammonium sulfate and ammonium phosphate dissolved in 1000 g of water and heated to 60 ° C. were used. The non-woven fabric was immersed for 5 minutes, then squeezed with mangle, Let dry for minutes. The adhesion rate of the dehydrating agent was 10% by weight method. The nonwoven fabric to which the dehydrating agent was attached was heated at 200 ° C. for 30 minutes, then heated at 300 ° C. for 10 minutes, 400 ° C. for 20 minutes, and further heated at 500 ° C. for 10 minutes to obtain carbonized yarn. This carbonized nonwoven fabric was activated with a mixed gas of water vapor and carbon dioxide (mixing ratio 1: 1) at 850 ° C. for 45 minutes to obtain fibrous activated carbon.
得られた繊維状活性炭は２５℃、相対湿度３７％における平衡水分率が５．１％、窒素ガスによるＢＥＴ法の比表面積は１１００ｍ２／ｇ、細孔容積０．３４ｃｃ／ｇ、水蒸気法で測定した細孔半径７〜１５Åの範囲にある細孔容積は、細孔半径１００Å以下の細孔の占める容積の９５％であった。 The obtained fibrous activated carbon has an equilibrium moisture content of 5.1% at 25 ° C. and a relative humidity of 37%, a specific surface area of the BET method using nitrogen gas of 1100 m 2 / g, a pore volume of 0.34 cc / g, and a water vapor method. The pore volume in the range of the measured pore radius of 7 to 15% was 95% of the volume occupied by pores having a pore radius of 100 mm or less.
この繊維状活性炭のＸ線回折強度曲線を、理学電機（株）製回転対陰極型Ｘ線回折装置ＲＩＮＴ−２４００を用いて測定した。電圧は４０ｋＶ、電流は１００ｍＡ、ターゲットは銅、Ｘ線波長はＣｕＫα１線（λ＝１．５４０５Å）、検出器はシンチレーションカウンターで測定を行った。走査速度は１°／ｍｉｎ、Ｆｉｘ Ｔｉｍｅは０ｓｅｃ、ＳＴＥＰは０．０２°とした。スリット条件は、発散が１／２°、散乱が１／２°、受光が０．１５ｍｍで行い、測定範囲（２θ）は５〜４０°とした。 The X-ray diffraction intensity curve of the fibrous activated carbon was measured using a rotating counter cathode type X-ray diffraction apparatus RINT-2400 manufactured by Rigaku Corporation. The voltage was 40 kV, the current was 100 mA, the target was copper, the X-ray wavelength was CuKα1 line (λ = 1.5405Å), and the detector was measured with a scintillation counter. The scanning speed was 1 ° / min, Fix Time was 0 sec, and STEP was 0.02 °. The slit conditions were as follows: divergence was 1/2 °, scattering was 1/2 °, received light was 0.15 mm, and the measurement range (2θ) was 5 to 40 °.
以上のようにして求めたＸ線回折強度曲線を図１に示した。２θが２５°付近には（００２）に基づくピークがほとんど観察されず、Ｉｐ／Ｉｏ＝０．１０であり、得られた繊維状活性炭は主として非晶構造よりなる繊維状活性炭であることは明らかである。 The X-ray diffraction intensity curve obtained as described above is shown in FIG. When 2θ is around 25 °, a peak based on (002) is hardly observed and Ip / Io = 0.10, and it is clear that the obtained fibrous activated carbon is a fibrous activated carbon mainly composed of an amorphous structure. It is.
実施例１で得られた繊維状活性炭５００ｇをカラムに充填し、相対湿度３０〜４０％の状態で塩化メチレンを１０００ｐｐｍの濃度で２５ｇ通気した。カラムの入口及び出口の塩化メチレンの濃度を測定したところ、塩化メチレンの除去率は９９％以上であり、吸着性能は良好であった。 The column was packed with 500 g of fibrous activated carbon obtained in Example 1, and 25 g of methylene chloride was aerated at a concentration of 1000 ppm at a relative humidity of 30 to 40%. When the concentration of methylene chloride at the inlet and outlet of the column was measured, the methylene chloride removal rate was 99% or more, and the adsorption performance was good.
繊維状活性炭に塩化メチレンを吸着させた後、カラムに１２０℃のスチームを通気して塩化メチレンを脱着させた。脱着させた塩化メチレンは、冷却して液化させ、セパレーターで、水層（分離廃液）と塩化メチレン層に分離した。分離した塩化メチレンは、再度通気用として使用し、分離廃液は、繊維状活性炭再生のためのスチーム用として使用した。分離廃液は、少量ではあるが塩化メチレンを溶解してしまうため、そのまま廃棄することは避けるべきであって、再利用するのが望ましい。したがって、塩化メチレンの回収実験においては、この点を考慮し、塩化メチレンについてクローズドシステムになるように構成した。 After adsorbing methylene chloride on the fibrous activated carbon, 120 ° C. steam was passed through the column to desorb the methylene chloride. The desorbed methylene chloride was cooled and liquefied, and was separated into an aqueous layer (separation waste liquid) and a methylene chloride layer by a separator. The separated methylene chloride was used again for aeration, and the separated waste liquid was used for steam for regenerating fibrous activated carbon. Since the separation waste liquid dissolves methylene chloride, although it is a small amount, it should be avoided to discard it as it is, and it is desirable to reuse it. Therefore, in the methylene chloride recovery experiment, in consideration of this point, the methylene chloride was configured to be a closed system.
塩化メチレンなどの有機塩素系溶剤が活性炭繊維と接触して塩酸を発生する場合、塩酸は水層側（分離廃液側）の方に多く移るので、分離廃液のｐＨを測定することにより塩酸の発生度合いの指標とすることができる。吸脱着を１００回繰返した時点の分離廃液のｐＨは６．５であって、ｐＨの上昇は観察されず、塩化メチレンの塩酸への分解は殆ど起こっていないことがわかる。結果を表１に示す。 When an organic chlorinated solvent such as methylene chloride comes into contact with the activated carbon fiber to generate hydrochloric acid, hydrochloric acid is transferred more to the aqueous layer side (separated waste liquid side), so the hydrochloric acid is generated by measuring the pH of the separated waste liquid. It can be a measure of degree. The pH of the separation waste liquid after the adsorption / desorption was repeated 100 times was 6.5, and no increase in pH was observed, indicating that methylene chloride was hardly decomposed into hydrochloric acid. The results are shown in Table 1.
フェノール樹脂系繊維を出発原料とする繊維状活性炭の製造：
フェノール樹脂繊維（株式会社製日本カイノール製フェノール樹脂繊維、商品名カイノール繊維）を用い、実施例１と同様にして不織布を製造し、４００℃及び６５０℃で２段階の昇温を行い、繊維を炭化した。この炭化繊維を、水蒸気と炭酸ガスからなる混合ガス（混合比率水蒸気／炭酸ガス＝１／１）の存在下、８５０℃で賦活した。得られたフェノール樹脂系繊維状活性炭の２５℃、相対湿度３７％における平衡水分率は３．３％、窒素ガスによるＢＥＴ比表面積は１３００ｍ２／ｇ、細孔容積は０．４２ｃｃ／ｇであり、水蒸気法で測定した細孔半径７〜１５Åの範囲にある細孔容積は、細孔半径１００Å以下の細孔の占める容積の９６％であった。
Production of fibrous activated carbon starting from phenolic fiber:
A non-woven fabric was produced in the same manner as in Example 1 using phenol resin fibers (Phenol resin fibers manufactured by Nihon Kynol Co., Ltd., trade name Kynol fibers), and the temperature was increased in two stages at 400 ° C and 650 ° C. Carbonized. This carbonized fiber was activated at 850 ° C. in the presence of a mixed gas composed of water vapor and carbon dioxide (mixing ratio water vapor / carbon dioxide = 1/1). The obtained phenol resin fibrous activated carbon has an equilibrium moisture content of 3.3% at 25 ° C. and a relative humidity of 37%, a BET specific surface area of 1300 m 2 / g by nitrogen gas, and a pore volume of 0.42 cc / g. The pore volume in the range of pore radius of 7 to 15 mm measured by the water vapor method was 96% of the volume occupied by pores having a pore radius of 100 mm or less.
実施例１と同様にしてＩｐ／Ｉｏを測定したところ、Ｉｐ／Ｉｏは０．２７であった。また、この繊維状活性炭の溶剤回収性能を実施例１と同様にして測定した。吸脱着を１００回繰返した後の分離廃液のｐＨは６．３であって、吸脱着の繰返しによる塩酸の発生は認められなかった。結果を表１に示す。塩化メチレン除去率は９９％以上であり良好であった。 When Ip / Io was measured in the same manner as in Example 1, Ip / Io was 0.27. Further, the solvent recovery performance of this fibrous activated carbon was measured in the same manner as in Example 1. The pH of the separated waste liquid after repeating adsorption and desorption 100 times was 6.3, and generation of hydrochloric acid due to repeated adsorption and desorption was not observed. The results are shown in Table 1. The methylene chloride removal rate was 99% or more, which was good.
ＰＶＡ繊維を原料とし、表１に示す条件でＢＥＴ表面積が１６００ｍ２／ｇの繊維状活性炭を得た。この繊維状活性炭の平衡吸着水分率は１．５％であった。実施例１と同様にして塩化メチレンの吸着性能を測定したところ、塩化メチレン除去率は９６％であった。 Fibrous activated carbon having a BET surface area of 1600 m 2 / g was obtained using PVA fibers as raw materials under the conditions shown in Table 1. The equilibrium adsorption moisture content of this fibrous activated carbon was 1.5%. When the adsorption performance of methylene chloride was measured in the same manner as in Example 1, the methylene chloride removal rate was 96%.
フェノール樹脂繊維の賦活条件を変えることにより、平衡吸着水分率１４．３％、ＢＥＴ比表面積９００ｍ２／ｇ、水蒸気法で測定した細孔半径７〜１５Åの範囲にある細孔容積が、細孔半径１００Å以下の細孔の占める容積の８３％の繊維状活性炭を得た。実施例１と同様にして塩化メチレンの回収を行ったところ、分離廃液のｐＨは６．１、塩化メチレン除去率は９５％であり、良好な結果であった。 By changing the activation conditions of the phenol resin fiber, the pore volume in the range of equilibrium adsorbed moisture content 14.3%, BET specific surface area 900 m 2 / g, pore radius 7-15 mm measured by the water vapor method is A fibrous activated carbon having 83% of the volume occupied by pores having a radius of 100 mm or less was obtained. When methylene chloride was recovered in the same manner as in Example 1, the separation waste liquid had a pH of 6.1 and a methylene chloride removal rate of 95%.
実施例２のフェノール系繊維状活性炭を使用し、有機塩素系溶剤としてトリクロロエチレンを用いて実施例２と同様にトリクロロエチレンの回収を行った。結果を表１に示す。分離廃液のｐＨは６．５、トリクロロエチレン除去率は９８％であった。 Trichloroethylene was recovered in the same manner as in Example 2 using the phenol-based fibrous activated carbon of Example 2 and using trichlorethylene as the organic chlorine-based solvent. The results are shown in Table 1. The pH of the separated waste liquid was 6.5, and the trichlorethylene removal rate was 98%.
実施例１のＰＶＡ繊維状活性炭を使用し、有機塩素系溶剤として四塩化炭素を用いて実施例１と同様に四塩化炭素の回収を行った。結果を表１に示す。分離廃液のｐＨは６．３であり、四塩化炭素除去率は９９％以上であり良好であった。 The carbon tetrachloride was recovered in the same manner as in Example 1 using the PVA fibrous activated carbon of Example 1 and using carbon tetrachloride as the organic chlorine solvent. The results are shown in Table 1. The pH of the separation waste liquid was 6.3, and the carbon tetrachloride removal rate was 99% or more, which was good.
比較例１
ピッチ系繊維を使用し、賦活温度８５０℃で賦活を行った。得られた繊維状活性炭のＸ線回折強度曲線を図２に示すが、Ｉｐ／Ｉｏは０．５３であり、高い結晶性を有していた。この繊維状活性炭を使用し、実施例１と同様にして塩化メチレンの吸脱着試験を１００回行い、分離廃液のｐＨを測定したところ３．１であり、強い酸性を示した。
Comparative Example 1
Activation was performed at an activation temperature of 850 ° C. using pitch fibers. The X-ray diffraction intensity curve of the obtained fibrous activated carbon is shown in FIG. 2, and Ip / Io was 0.53 and had high crystallinity. Using this fibrous activated carbon, the adsorption / desorption test of methylene chloride was carried out 100 times in the same manner as in Example 1, and the pH of the separated waste liquid was measured to be 3.1, indicating strong acidity.
比較例２
アクリル系繊維を使用した以外は実施例１と同様にして繊維状活性炭を製造した。この繊維状活性炭のＩｐ／Ｉｏは０．４８であり、結晶性の高い繊維状活性炭であった。実施例１と同様にして塩化メチレンの回収を行ったところ、分離廃液のｐＨは３．５であり、強い酸性を示した。
Comparative Example 2
A fibrous activated carbon was produced in the same manner as in Example 1 except that acrylic fiber was used. This fibrous activated carbon had an Ip / Io of 0.48 and was a fibrous activated carbon with high crystallinity. When methylene chloride was recovered in the same manner as in Example 1, the pH of the separated waste liquid was 3.5, indicating strong acidity.
比較例３
フェノール系繊維の賦活条件を変更することにより、水分吸着率が０．８％、ＢＥＴ比表面積２６００ｍ２／ｇ、細孔容積率７３％、Ｉｐ／Ｉｏ０．２の繊維状活性炭を得た。実施例１と同様にして塩化メチレンの回収を行ったところ、分離廃液のｐＨは６．５であったが、塩化メチレン除去率は８２％と低かった。
Comparative Example 3
By changing the activation conditions of the phenol fiber, fibrous activated carbon having a moisture adsorption rate of 0.8%, a BET specific surface area of 2600 m 2 / g, a pore volume ratio of 73%, and Ip / Io of 0.2 was obtained. When methylene chloride was recovered in the same manner as in Example 1, the pH of the separated waste liquid was 6.5, but the methylene chloride removal rate was as low as 82%.
比較例４
フェノール系繊維の賦活条件を変更することにより、水分吸着率１６．８％の繊維状活性炭を得た。この繊維状活性炭のＢＥＴ比表面積は８００ｍ２／ｇ、細孔容積は０．２２ｃｃ／ｇ、細孔割合は７２％、Ｉｐ／Ｉｏは０．３７であった。実施例１と同様にして塩化メチレンの回収を行ったところ、分離廃液のｐＨは６．２であったが、塩化メチレン除去率は７８％と低かった。
Comparative Example 4
By changing the activation conditions of the phenol fiber, a fibrous activated carbon having a moisture adsorption rate of 16.8% was obtained. The fibrous activated carbon had a BET specific surface area of 800 m 2 / g, a pore volume of 0.22 cc / g, a pore ratio of 72%, and Ip / Io of 0.37. When methylene chloride was recovered in the same manner as in Example 1, the pH of the separated waste liquid was 6.2, but the methylene chloride removal rate was as low as 78%.
比較例５
比較例１で製造したピッチ系の繊維状活性炭を使用し、有機塩素系溶剤としてトリクロロエチレンを使用し、トリクロロエチレンの回収を行った。分離廃液のｐＨは２．９で極めて強い酸性を示した。
Comparative Example 5
The pitch-based fibrous activated carbon produced in Comparative Example 1 was used, and trichlorethylene was recovered using trichlorethylene as the organic chlorine solvent. The pH of the separated waste liquid was 2.9, indicating extremely strong acidity.
本発明により、有害な有機塩素系溶剤を外部に排出することなく、回収再利用することができ、印刷業、電気工業、機械工業など各種産業の製造工程など種々の有機塩素系溶剤ガスが発生する工程に適用することができる。 According to the present invention, harmful organic chlorinated solvents can be recovered and reused without being discharged to the outside, and various organic chlorinated solvent gases are generated in various industries such as the printing industry, electrical industry, and machine industry. It can be applied to the process.
Ｉ・・・Ｘ線回折強度の実測曲線と接線の差をベースライン上に書き直した曲線
ι・・・（００２）面のＸ線回折ピークの両裾に引いた接線
Ｉｐ・・・（００２）面のＸ線回折ピークの両裾に引いた接線から上の部分の強度の最大値
Ｉｏ・・・（００２）面の回折強度から空気の散乱強度を差し引いた残りの強度
I: Curve obtained by rewriting the difference between the measured curve and the tangent of the X-ray diffraction intensity on the baseline ι ... Tangent drawn on both hems of the X-ray diffraction peak of the (002) plane Ip ... (002) Maximum value of the intensity of the upper part from the tangent drawn at the bottom of the X-ray diffraction peak of the surface Io ... (002) Remaining intensity obtained by subtracting the scattering intensity of air from the diffraction intensity of the surface
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003345105A JP4509523B2 (en) | 2003-05-19 | 2003-10-03 | Recovery method for organic chlorinated solvents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003140595 | 2003-05-19 | ||
| JP2003345105A JP4509523B2 (en) | 2003-05-19 | 2003-10-03 | Recovery method for organic chlorinated solvents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005000903A JP2005000903A (en) | 2005-01-06 |
| JP4509523B2 true JP4509523B2 (en) | 2010-07-21 |
Family
ID=34106373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003345105A Expired - Lifetime JP4509523B2 (en) | 2003-05-19 | 2003-10-03 | Recovery method for organic chlorinated solvents |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4509523B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4509502B2 (en) * | 2003-07-01 | 2010-07-21 | クラレケミカル株式会社 | Recovery method of mixed solvent |
| EP2073569B1 (en) | 2007-07-20 | 2014-05-07 | Kuraray Chemical Co., Ltd. | Material for speaker device and speaker device using it |
| JP5327009B2 (en) * | 2009-11-17 | 2013-10-30 | 東洋紡株式会社 | Activated carbon fiber |
| JP6542559B2 (en) * | 2015-03-30 | 2019-07-10 | 株式会社クラレ | Activated carbon for gas phase adsorption |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63100009A (en) * | 1986-10-14 | 1988-05-02 | Kuraray Co Ltd | Activated carbon |
| JPH11276840A (en) * | 1998-03-27 | 1999-10-12 | Toho Kako Kensetsu Kk | Method and device for recovering organic solvent |
| JP2001240407A (en) * | 1999-12-24 | 2001-09-04 | Kuraray Chem Corp | Activated carbon and its manufacturing method |
| JP2001293329A (en) * | 2000-04-17 | 2001-10-23 | Toho Kako Kensetsu Kk | Device and method for recovering organic solvent |
-
2003
- 2003-10-03 JP JP2003345105A patent/JP4509523B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63100009A (en) * | 1986-10-14 | 1988-05-02 | Kuraray Co Ltd | Activated carbon |
| JPH11276840A (en) * | 1998-03-27 | 1999-10-12 | Toho Kako Kensetsu Kk | Method and device for recovering organic solvent |
| JP2001240407A (en) * | 1999-12-24 | 2001-09-04 | Kuraray Chem Corp | Activated carbon and its manufacturing method |
| JP2001293329A (en) * | 2000-04-17 | 2001-10-23 | Toho Kako Kensetsu Kk | Device and method for recovering organic solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005000903A (en) | 2005-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105329976B (en) | The method for adsorbing perfluorochemical in simultaneously degradation water | |
| KR20010086268A (en) | Activated carbon and method for producing it | |
| WO2021106364A1 (en) | Molecular polar substance-adsorbing charcoal | |
| GB2125388A (en) | Fibrous activated carbon and process of producing it | |
| WO2018116858A1 (en) | Active carbon and production method thereof | |
| JP5482133B2 (en) | Activated carbon fiber | |
| JP4509523B2 (en) | Recovery method for organic chlorinated solvents | |
| Hassani et al. | Activated carbon fiber for environmental protection | |
| JP3997745B2 (en) | Regeneration method of ozonolysis type gas adsorbent | |
| Yue et al. | Elucidating the porous and chemical structures of ZnCl 2-activated polyacrylonitrile on a fiberglass substrate | |
| KR20120132873A (en) | Recycle method of spent carbons by chemical impregnation and heating treatments in vacuum | |
| JP4509502B2 (en) | Recovery method of mixed solvent | |
| JPS6331253B2 (en) | ||
| CN102824901A (en) | Preparation method of alveolate multilayer pore structure activated carbon film | |
| JP2008149267A (en) | Organic halide based compound removal filter | |
| JP2967389B2 (en) | Activated carbon fiber, method for producing the same, and water purifier using the activated carbon fiber as an adsorbent | |
| JPS62149917A (en) | Production of active carbon yarn | |
| JPWO2019244904A1 (en) | Activated carbon | |
| JP4378612B2 (en) | Fibrous activated carbon for adsorbing organic compounds and exhaust gas treatment apparatus using the same | |
| JPH11240707A (en) | Activated carbon | |
| JP5929130B2 (en) | Water treatment equipment | |
| JPH0268140A (en) | Adsorbent for removal of iodine in gas | |
| JP2022116822A (en) | Adsorbent and method for producing the same | |
| JP2011106052A (en) | Activated carbon fiber | |
| KR20060036866A (en) | Adsorbent for aldehydes and making method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A625 | Written request for application examination (by other person) |
Free format text: JAPANESE INTERMEDIATE CODE: A625 Effective date: 20060605 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080411 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081014 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20091201 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100219 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20100308 |
|
| 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: 20100406 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100428 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130514 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4509523 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140514 Year of fee payment: 4 |
|
| 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 |
|
| EXPY | Cancellation because of completion of term |