JP5929130B2 - Water treatment equipment - Google Patents
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- JP5929130B2 JP5929130B2 JP2011261782A JP2011261782A JP5929130B2 JP 5929130 B2 JP5929130 B2 JP 5929130B2 JP 2011261782 A JP2011261782 A JP 2011261782A JP 2011261782 A JP2011261782 A JP 2011261782A JP 5929130 B2 JP5929130 B2 JP 5929130B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 79
- 238000001179 sorption measurement Methods 0.000 claims description 80
- 238000003795 desorption Methods 0.000 claims description 31
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 13
- 238000006297 dehydration reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
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- 150000004665 fatty acids Chemical class 0.000 claims description 10
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- 229920001568 phenolic resin Polymers 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 description 27
- 239000011148 porous material Substances 0.000 description 22
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 239000004745 nonwoven fabric Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- -1 Orthophosphoric acid ester Chemical class 0.000 description 5
- 229920006282 Phenolic fiber Polymers 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 229920003986 novolac Polymers 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000003140 primary amides Chemical class 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 150000002989 phenols Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 229920003987 resole Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003334 secondary amides Chemical class 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 230000007062 hydrolysis Effects 0.000 description 1
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003511 tertiary amides Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明は、有機化合物を含有する水から有機化合物を除去して浄化する装置に関し、特に各種工場、研究施設等から排出される有機溶剤等の有機化合物を含有した産業排水の浄化に用いられる装置に関するものである。 The present invention relates to an apparatus for removing and purifying organic compounds from water containing organic compounds, and in particular, an apparatus used for purifying industrial wastewater containing organic compounds such as organic solvents discharged from various factories and research facilities. It is about.
従来、有機化合物など被吸着物を含有する水を浄化する装置として、活性炭などの吸着材からなる交換可能な吸着素子を用いた交換式吸着装置が広く用いられている。交換式吸着装置においては、被吸着物を含有する水が吸着材を充填された槽に流入されて、吸着材が被吸着物を吸着することにより、水中に含まれる被吸着物が除去される。 Conventionally, as an apparatus for purifying water containing an adsorbent such as an organic compound, an exchangeable adsorption apparatus using a replaceable adsorption element made of an adsorbent such as activated carbon has been widely used. In the exchangeable adsorption device, water containing an adsorbent is introduced into a tank filled with an adsorbent, and the adsorbent adsorbs the adsorbent to remove the adsorbate contained in the water. .
しかしながら、交換式吸着装置は被吸着物を一定時間吸着し続け、吸着材の吸着能力が飽和に達すれば、新品への交換、もしくは一度装置から吸着材を取り出して再生が必要となって連続浄化ができず、更に、水の浄化は、空気の浄化と異なり、微生物の繁殖が不可避であり、吸着材の寿命を縮めることもあって、交換および再生への労力、コスト増大が問題であった。
また、従来の浄化装置では、吸着材使用開始時と使用終了前では吸着性能が変化しており、安定に浄化処理することができないという問題点も有していた。
However, the exchangeable adsorption device continues to adsorb the adsorbed material for a certain period of time, and if the adsorption capacity of the adsorbent reaches saturation, it is necessary to replace it with a new one, or to remove the adsorbent from the device once and regenerate it for continuous purification. Furthermore, unlike the purification of air, the purification of water is unavoidable for the growth of microorganisms, and the life of the adsorbent may be shortened. .
Further, the conventional purification apparatus has a problem that the adsorption performance changes between the start of use of the adsorbent and before the end of use, and the purification process cannot be stably performed.
特許文献１には、有機化合物など被吸着物を含有する水を連続浄化可能で、基本的に吸着材の交換の必要がない水処理装置が記載されている。この水処理装置においては、活性炭素繊維を含む吸着素子に被吸着物を含有する水を通流させて被吸着物を吸着させる吸着工程、その後被吸着物を吸着した吸着素子に高速のガスを通風させて吸着素子に付着する付着水を除去するパージ（脱水）工程、高温の加熱ガスを通気させることにより、吸着素子に吸着された被吸着物を脱離させて吸着素子を再生する脱着工程を連続的に行なっている。 Patent Document 1 describes a water treatment apparatus that can continuously purify water containing an adsorbed substance such as an organic compound and basically does not require replacement of an adsorbent. In this water treatment apparatus, an adsorption process in which water containing an adsorbed substance is caused to flow through an adsorbing element containing activated carbon fibers to adsorb the adsorbing object, and then a high-speed gas is applied to the adsorbing element that adsorbs the adsorbing object. A purge (dehydration) process for removing adhering water adhering to the adsorbing element by ventilating, and a desorption process for regenerating the adsorbing element by desorbing the adsorbed material adsorbed on the adsorbing element by ventilating high-temperature heated gas Is performed continuously.
特許文献１の水処理装置において、吸着素子の再生エネルギーとしては、吸着素子に吸着された被吸着物の脱離のほかに、吸着素子に吸着した水の脱離および吸着素子表面に残存した付着水の乾燥に使用される加熱ガスの供給に必要なエネルギーが必要となる。そのため、付着水を高効率に脱水除去させることができれば、吸着素子の再生エネルギーの削減が可能となる。 In the water treatment apparatus of Patent Document 1, as the regeneration energy of the adsorption element, in addition to the desorption of the adsorbed object adsorbed on the adsorption element, the desorption of water adsorbed on the adsorption element and the adhesion remaining on the surface of the adsorption element The energy required to supply the heated gas used for water drying is required. Therefore, if the adhering water can be dehydrated and removed with high efficiency, the regeneration energy of the adsorption element can be reduced.
また、特許文献１の水処理装置において、吸着素子の再生エネルギーとしては、加熱ガスの給気手段である送風機やブロワーなどに使用される電気エネルギーがかかるが、吸着素子に含まれる吸着材の圧力損失が高い場合、給気に使用する電気エネルギーが多くかかる。そのため、低圧力損失な吸着材を吸着素子として使用することができれば、吸着素子の再生エネルギーの削減が可能となる。 Further, in the water treatment apparatus of Patent Document 1, as the regeneration energy of the adsorption element, electric energy used for a blower or a blower that is a heating gas supply means is applied, but the pressure of the adsorbent contained in the adsorption element When the loss is high, a lot of electric energy is used for supplying air. Therefore, if an adsorbent with a low pressure loss can be used as the adsorbing element, the regeneration energy of the adsorbing element can be reduced.
本発明は、吸着素子の再生エネルギーの削減を課題としてなされたものであって、吸着性能を維持しながら、吸着素子の再生エネルギー量を低減することができる、水処理装置を提供することを課題とする。 The present invention has been made with the object of reducing the regeneration energy of the adsorption element, and it is an object to provide a water treatment apparatus capable of reducing the amount of regeneration energy of the adsorption element while maintaining adsorption performance. And
本発明者らは鋭意検討した結果、以下に示す手段により、上記課題を解決できることを見出し、本発明に到達した。すなわち本発明は以下の構成からなる。 As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have reached the present invention. That is, the present invention has the following configuration.
１．有機化合物を含有する水を、繊維径２１〜４０μｍ以、トルエン吸着容量２００〜７５０ｍｇ／ｇの活性炭素繊維を含む吸着素子に通流させて該吸着素子に有機化合物を吸着させる吸着工程と、該吸着素子に高温の加熱ガスを通気させて該吸着素子に吸着された有機化合物を脱着する脱着工程とを、交互に行うことを特徴とする水処理装置。
２．前記脱着工程の前に高速ガスを前記吸着素子に通風させて、該吸着素子表面に付着する水分を除去する脱水工程を含む上記１に記載の水処理装置。
３．前記付着水を前記吸着素子の前に返送させて、再度、該吸着素子に吸着させる上記２に記載の水処理装置。
４．前記活性炭素繊維が、フェノール樹脂に、脂肪酸アミド類、リン酸エステル類、セルロース類よりなる群から選択される少なくとも１種の化合物を混合した混合物を紡糸し、硬化して得たフェノール系繊維を炭化・賦活して得られる活性炭素繊維である上記１〜３のいずれかに記載の水処理装置。
1. An adsorption step in which water containing an organic compound is passed through an adsorption element containing activated carbon fibers having a fiber diameter of 21 to 40 μm or less and a toluene adsorption capacity of 200 to 750 mg / g to adsorb the organic compound to the adsorption element; A water treatment apparatus characterized by alternately performing a desorption step of desorbing an organic compound adsorbed on the adsorption element by passing a high-temperature heating gas through the adsorption element.
2. 2. The water treatment apparatus according to 1 above, comprising a dehydration step in which a high-speed gas is passed through the adsorption element before the desorption step to remove water adhering to the surface of the adsorption element.
3. 3. The water treatment apparatus according to 2 above, wherein the adhering water is returned before the adsorbing element and is adsorbed by the adsorbing element again.
4). A phenolic fiber obtained by spinning and curing a mixture in which the activated carbon fiber is a phenol resin mixed with at least one compound selected from the group consisting of fatty acid amides, phosphate esters, and celluloses. 4. The water treatment apparatus according to any one of 1 to 3, which is an activated carbon fiber obtained by carbonization / activation.
本発明の水処理装置によれば、吸着素子の再生エネルギー量を低減することができる。 According to the water treatment apparatus of the present invention, the amount of regeneration energy of the adsorption element can be reduced.
本発明にかかる水処理装置は、有機化合物を含有する水を吸着素子に通流させて該吸着素子に有機化合物を吸着させる吸着工程と、該吸着素子に高温の加熱ガスを通流させて該吸着素子に吸着された有機化合物を脱着する脱着工程を備え、かかる工程を交互に行う水処理装置である。かかる構造を採用することにより、処理を連続的に行うことができるからである。 The water treatment apparatus according to the present invention includes an adsorption step of allowing water containing an organic compound to flow through an adsorption element and adsorbing the organic compound to the adsorption element, and passing a high-temperature heating gas through the adsorption element. A water treatment apparatus includes a desorption process for desorbing an organic compound adsorbed on an adsorption element, and alternately performs the process. This is because the processing can be continuously performed by adopting such a structure.
より好ましい装置の構造としては、吸着素子が幾つかに分割されており、それらの吸着工程と脱着工程をダンパー等にて切替操作を行い、吸着と脱着を連続的に行う水処理装置である。また、吸着素子が回転することができ、吸着工程で有機化合物を吸着した吸着素子の部位が、吸着素子の回転により、脱着工程へ移動する構造を有する水処理装置も好ましい装置の構造である。 A more preferable apparatus structure is a water treatment apparatus in which the adsorption element is divided into several parts, and the adsorption process and the desorption process are switched by a damper or the like, and the adsorption and desorption are continuously performed. A water treatment apparatus having a structure in which the adsorbing element can rotate and the part of the adsorbing element that adsorbs the organic compound in the adsorption process moves to the desorption process by the rotation of the adsorbing element is also a preferable apparatus structure.
本発明の水処理装置は、有機化合物の吸着工程後に吸着素子表面に残存する付着水を、ガスの通流により除去する脱水工程を有することが好ましい。付着水を気流で除去することにより、加熱による有機化合物の脱着が容易になるからである。除去した水滴は、戻りラインより装置入口の有機化合物を含有する原水に戻すことが好ましい。かかる方法によれば、工程数を省略でき、効率的だからである。 The water treatment apparatus of the present invention preferably has a dehydration step of removing adhering water remaining on the surface of the adsorption element after the organic compound adsorption step by gas flow. This is because the organic compound can be easily desorbed by heating by removing the adhering water with an air stream. The removed water droplets are preferably returned to the raw water containing the organic compound at the inlet of the apparatus from the return line. This is because the number of steps can be omitted and this method is efficient.
本発明の吸着素子は回転し、脱水工程の後工程で脱着領域にて加熱ガスにより吸着素子を加熱することで吸着した有害物質を脱着して再度吸着が行える状態に再生される脱着工程を有することが好ましい。加熱により有機化合物を脱着した後、連続的に吸着工程に移動することができるからである。脱着工程により発生した有機化合物を含有したガスは、直接燃焼装置や触媒燃焼装置、蓄熱式燃焼装置等の燃焼装置や活性炭素繊維を使用した溶剤回収装置等の一般的に用いられるガス処理装置にて処理することができる。 The adsorbing element of the present invention has a desorption step that rotates and is regenerated to a state in which the adsorbed harmful substance is desorbed and heated again by heating the adsorbing element with a heated gas in the desorption region after the dehydration step. It is preferable. This is because the organic compound can be desorbed by heating and then moved to the adsorption step continuously. Gas containing organic compounds generated in the desorption process is used in gas processing devices such as direct combustion devices, catalytic combustion devices, regenerative combustion devices, and other commonly used gas processing devices such as solvent recovery devices using activated carbon fibers. Can be processed.
本発明の吸着素子は、性能面から活性炭素繊維を用いたものである。つまり、活性炭素繊維は表面にミクロ孔を有することと繊維状構造であることで、水との接触効率が高く、特に水中の有機化合物の吸着速度が速くなり、他の吸着材に比べて、極めて高い除去効率を発現できるからである。 The adsorbing element of the present invention uses activated carbon fibers from the viewpoint of performance. In other words, the activated carbon fiber has micropores on the surface and a fibrous structure, so the contact efficiency with water is high, especially the adsorption rate of organic compounds in water is faster, compared to other adsorbents, This is because extremely high removal efficiency can be expressed.
本発明で用いる活性炭素繊維は、繊維径が２１〜４０μｍである。繊維径が２２μｍ未満では、繊維表面に付着する水分量が多くなることで、脱着効率が低下する。繊維径が４０μｍを超えると、繊維径が大きくなることにより、水中の被吸着物質と吸着素子との接触効率が低下するために、吸着速度が低下する。 The activated carbon fiber used in the present invention has a fiber diameter of 21 to 40 μm. If the fiber diameter is less than 22 μm, the amount of moisture adhering to the fiber surface increases, and the desorption efficiency decreases. When the fiber diameter exceeds 40 μm, the fiber diameter increases, and the contact efficiency between the substance to be adsorbed in water and the adsorbing element decreases, so the adsorption rate decreases.
本発明で用いる活性炭素繊維の前駆体であるフェノール繊維としては、フェノール樹脂に、脂肪酸アミド類、リン酸エステル類、セルロース類よりなる群から選択される少なくとも１種の化合物を混合した混合物を紡糸し、硬化して得られるフェノール系繊維であることが好ましい。前記化合物を混合させることで、化合物を混合させていない太繊維径のフェノール繊維では、引張伸度が低く、不織布の製造が困難であったり、例え不織布が製造できても炭化・賦活後の活性炭素繊維不織布の引張強度が低いという問題を、解決でき、引張強度の高い活性炭素繊維不織布を得ることができる。 As the phenol fiber which is a precursor of the activated carbon fiber used in the present invention, a mixture obtained by mixing a phenol resin with at least one compound selected from the group consisting of fatty acid amides, phosphate esters and celluloses is spun. And phenolic fibers obtained by curing. By mixing the compound, the phenol fiber having a thick fiber diameter not mixed with the compound has low tensile elongation and it is difficult to produce a nonwoven fabric. The problem that the tensile strength of the carbon fiber nonwoven fabric is low can be solved, and an activated carbon fiber nonwoven fabric having a high tensile strength can be obtained.
本発明で用いるフェノール系繊維としては、フェノール樹脂に脂肪酸アミド類、リン酸エステル類、セルロース類よりなる群から選択される少なくとも１種の化合物（配合物）を混合した混合物を紡糸して得られるフェノール系繊維が好適に用いられる。 The phenol fiber used in the present invention is obtained by spinning a mixture obtained by mixing a phenol resin with at least one compound (compound) selected from the group consisting of fatty acid amides, phosphate esters, and celluloses. Phenol fiber is preferably used.
フェノール樹脂としては、酸性触媒の存在下でフェノール類とアルデヒド類とを反応させて得られるノボラック型フェノール樹脂、塩基性触媒の存在下でフェノール類とアルデヒド類とを反応させて得られるレゾール型フェノール樹脂、各種変性フェノール樹脂又はこれらの混合物等が挙げられる。 As the phenol resin, a novolac type phenol resin obtained by reacting phenols and aldehydes in the presence of an acidic catalyst, or a resol type phenol obtained by reacting phenols and aldehydes in the presence of a basic catalyst Examples thereof include resins, various modified phenolic resins, and mixtures thereof.
本発明では、ノボラック型フェノール樹脂、レゾール型フェノール樹脂を用いることが好ましい。フェノール樹脂は、一種を単独で用いてもよく、二種以上を併用してもよい。 In the present invention, it is preferable to use a novolac type phenol resin or a resol type phenol resin. A phenol resin may be used individually by 1 type, and may use 2 or more types together.
本発明において配合物として用いられる脂肪酸アミド類とは、アンモニア又はアミンの窒素原子に結合する水素原子の１以上がアシル基によって置換された構造をもつ非重合体を意味し、該窒素原子に水素原子が２つ結合する第１級アミド、該窒素原子に水素原子が１つ結合する第２級アミド、該窒素原子に水素原子が結合していない第３級アミド、ラクタム、及び１分子中にアミンの窒素原子を２個以上有するものを包含する。したがって、本発明における「脂肪酸アミド類」は、ナイロン−６、ナイロン−６，６に代表される所謂、脂肪族ポリアミドのような重合体とは異なる。なお、「脂肪酸アミド類」は脂肪酸アマイド類とも称される。 The fatty acid amides used as a blend in the present invention means a non-polymer having a structure in which one or more hydrogen atoms bonded to the nitrogen atom of ammonia or amine are substituted with an acyl group. A primary amide in which two atoms are bonded, a secondary amide in which one hydrogen atom is bonded to the nitrogen atom, a tertiary amide in which no hydrogen atom is bonded to the nitrogen atom, a lactam, and one molecule Includes those having two or more amine nitrogen atoms. Therefore, the “fatty acid amides” in the present invention are different from polymers such as so-called aliphatic polyamides typified by nylon-6 and nylon-6,6. “Fatty acid amides” are also referred to as fatty acid amides.
上脂肪酸アミド類のなかでも、原料混合物の取扱い性、安定性又は紡糸性等の点から、第１級アミド、第２級アミドが好ましく、第１級アミドがより好ましく、飽和脂肪酸モノアミド、不飽和脂肪酸モノアミドが特に好ましい。 Among the above fatty acid amides, primary amides and secondary amides are preferred, primary amides are more preferred, saturated fatty acid monoamides, unsaturated, from the viewpoints of handleability, stability or spinnability of the raw material mixture. Fatty acid monoamides are particularly preferred.
本発明において配合物として用いられるリン酸エステル類の「リン酸」とは、十酸化四リン（Ｐ4Ｏ10）が加水分解を受けて生ずる種々のオキソ酸の総称であり、オルトリン酸、ピロリン酸（二リン酸）、三リン酸、四リン酸、メタリン酸等を包含する。 “Phosphoric acid” of the phosphoric acid esters used as a compound in the present invention is a general term for various oxo acids generated by hydrolysis of tetraphosphorus decaoxide (P 4 O 10 ). Including acid (diphosphoric acid), triphosphoric acid, tetraphosphoric acid, metaphosphoric acid and the like.
本発明において「リン酸エステル類」とは、リン酸における−ＯＨの一つ以上が下記一般式（１）で表される基に置換されたもの（リン酸エステル）又はその塩を意味する。 In the present invention, the “phosphate esters” mean those in which one or more of —OH in phosphoric acid is substituted with a group represented by the following general formula (1) (phosphate esters) or salts thereof.
リン酸エステル類としては、特に太径のフェノール系繊維とした際に機械的強度が高まりやすいことから、オルトリン酸における−ＯＨの一つ以上が前記式（１）で表される基に置換されたもの（オルトリン酸エステル）又はその塩が好ましい。 As phosphate esters, since mechanical strength is likely to increase particularly when a large-diameter phenolic fiber is used, at least one of —OH in orthophosphoric acid is substituted with the group represented by the above formula (1). (Orthophosphoric acid ester) or a salt thereof is preferred.
リン酸エステルの塩としては、リン酸エステルのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩等が挙げられる。リン酸エステル類は、単独で用いても、二種以上を併用してもよい。 Examples of the phosphate ester salt include alkali metal salts, alkaline earth metal salts, ammonium salts and amine salts of phosphate esters. Phosphate esters may be used alone or in combination of two or more.
本発明において配合物として用いられるセルロース類としては、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、カルボキシメチルセルロース等が挙げられる。セルロース類は、単独で用いても、二種以上を併用してもよい。 Examples of celluloses used as a blend in the present invention include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Cellulose may be used independently or may use 2 or more types together.
本発明で用いる活性炭素繊維は、前記フェノール繊維を前駆体とし、炭化・賦活処理することで得られる。 The activated carbon fiber used in the present invention is obtained by carbonizing and activating the phenol fiber as a precursor.
本発明で用いる活性炭素繊維の上記以外の物性は特に限定されるものではないが、ＢＥＴ比表面積が９００〜２０００ｍ２／ｇで、細孔容積が０．４〜０．９ｃｍ３／ｇで平均細孔経が１４〜１８Åのものが好ましい。ＢＥＴ比表面積が９００ｍ２／ｇ未満、細孔容積が０．４ｃｍ３／ｇ未満、細孔径が１４Å未満では、有機化合物の吸着量が低くなり、ＢＥＴ比表面積が２０００ｍ２／ｇを超え、細孔容積が０．９ｃｍ３／ｇを超え、細孔径が１８Åを超えると、細孔径が大きくなることで、有機化合物の吸着能力が低下したり、吸着素子の強度が弱くなり、また素材のコストが高くなり経済的では無くなる。 The physical properties other than those described above of the activated carbon fiber used in the present invention are not particularly limited, but the BET specific surface area is 900 to 2000 m 2 / g, and the pore volume is 0.4 to 0.9 cm 3 / g on average. Those having a pore diameter of 14 to 18 mm are preferred. When the BET specific surface area is less than 900 m 2 / g, the pore volume is less than 0.4 cm 3 / g, and the pore diameter is less than 14 mm, the amount of adsorption of the organic compound is low, and the BET specific surface area exceeds 2000 m 2 / g. When the pore volume exceeds 0.9 cm 3 / g and the pore diameter exceeds 18 mm, the pore diameter increases, so that the adsorption capacity of the organic compound decreases, the strength of the adsorption element decreases, and the cost of the material Becomes expensive and not economical.
以下に実施例を示し、本発明をより具体的に説明する。実施例中に示した特性は以下の方法で測定した。 Hereinafter, the present invention will be described in more detail with reference to examples. The characteristics shown in the examples were measured by the following methods.
（ＢＥＴ比表面積）
ＢＥＴ比表面積は、液体窒素の沸点（−１９５．８℃）雰囲気下、相対圧力０．０〜０．１５の範囲で上昇させたときの試料への窒素吸着量を数点測定し、ＢＥＴプロットにより試料単位質量あたりの表面積（ｍ２／ｇ）を求めた。
(BET specific surface area)
The BET specific surface area was measured by measuring the amount of nitrogen adsorbed on the sample when the relative pressure was raised in the range of 0.0 to 0.15 in the atmosphere of the boiling point of liquid nitrogen (-195.8 ° C), and a BET plot. Was used to determine the surface area (m 2 / g) per unit mass of the sample.
（細孔容積）
細孔容積は、相対圧０．９５における窒素ガスの気体吸着法により測定した。
(Pore volume)
The pore volume was measured by a nitrogen gas adsorption method at a relative pressure of 0.95.
（平均細孔径）
平均細孔径は、以下の式で求めた。
ｄｐ＝４００００Ｖｐ／Ｓ（ただし、ｄｐ：平均細孔径（Å））
Ｖｐ：細孔容積（ｃｃ／ｇ）
Ｓ：ＢＥＴ比表面積（ｍ２／ｇ）
(Average pore diameter)
The average pore diameter was determined by the following formula.
dp = 40000 Vp / S (where dp: average pore diameter (径))
Vp: pore volume (cc / g)
S: BET specific surface area (m 2 / g)
（トルエン吸着容量）
トルエン吸着容量は、ＪＩＳ Ｋ１４７７に定める方法で測定した。
(Toluene adsorption capacity)
The toluene adsorption capacity was measured by the method defined in JIS K1477.
（有機化合物濃度）
装置入口・出口の水中の有機化合物濃度は、ガスクロマトグラフ法により分析し測定した。
(Organic compound concentration)
The concentration of organic compounds in the water at the inlet / outlet of the apparatus was analyzed and measured by gas chromatography.
（平衡吸着量）
平衡吸着量（ｑ＊）は、５０％破過時間を測定し、以下の式で求めた。
ｑ＊（ｍｇ／ｇ）＝有機化合物供給量×５０％破過時間／吸着材重量
(Equilibrium adsorption amount)
The equilibrium adsorption amount (q * ) was determined by measuring the 50% breakthrough time and using the following equation.
q * (mg / g) = organic compound supply amount × 50% breakthrough time / adsorbent weight
（吸着帯厚み）
吸着帯厚み（１０％Ｚａ）は、１０％破過する破過時間を測定し、以下の式で求めた。
１０％Ｚａ＝（５０％破過時間−１０％破過時間）×２／（５０％破過時間）
(Adsorption band thickness)
The adsorption band thickness (10% Za) was determined by the following formula by measuring the breakthrough time for breakthrough by 10%.
10% Za = (50% breakthrough time−10% breakthrough time) × 2 / (50% breakthrough time)
（付着水分量）
付着水分量は、脱水操作後の吸着材の重量を測定し、以下の式で求めた。
付着水分量（ｇ／ｇ）＝脱水操作後の吸着材重量（ｇ）／絶乾時の吸着材重量（ｇ）
(Moisture content)
The amount of adhering moisture was determined by the following equation by measuring the weight of the adsorbent after the dehydration operation.
Adhesive water content (g / g) = Adsorbent weight after dehydration operation (g) / Adsorbent weight in absolute dryness (g)
（吸着材の平均圧力損失）
吸着材の平均圧力損失は、脱水及び脱着操作中の装置入口・出口の圧力をマノスターケージにて測定し、装置入口・出口の圧力の平均値より以下の式で求めた。
吸着材の平均圧力損失（ｋＰａ）＝装置入口の圧力（ｋＰａ）−装置出口の圧力（ｋＰａ）
(Average pressure loss of adsorbent)
The average pressure loss of the adsorbent was determined by measuring the pressure at the inlet / outlet of the apparatus during the dehydration and desorption operations with a manostar cage and calculating the average value of the pressure at the inlet / outlet of the apparatus by the following formula.
Average pressure loss of adsorbent (kPa) = apparatus inlet pressure (kPa) −apparatus outlet pressure (kPa)
（ブロワー動力）
ブロワー動力は、以下の式で求めた。
ブロワー動力（Ｗ）＝風量（ｍ３／ｍｉｎ）×装置入口の圧力（ｋＰａ）／６１２０／９．８１／０．７×１０６
(Blower power)
The blower power was obtained by the following formula.
Blower power (W) = air volume (m 3 / min) × inlet pressure (kPa) /6120/9.81/0.7×10 6
（脱着熱量）
脱着熱量は、以下の式で求めた。
脱着熱量（ｋＪ）＝付着水の加温熱量（ｋＪ）＋付着水の蒸発熱量（ｋＪ）
(Desorption heat amount)
The desorption heat amount was determined by the following equation.
Desorption heat amount (kJ) = Heating heat amount (kJ) of adhering water + Evaporation heat amount (kJ) of adhering water
[実施例１ ]
フェノール１０００質量部と３７質量％ホルマリン７３３質量部とシュウ酸５質量部を、還流冷却器を備えた反応容器に仕込み、４０分間で常温から１００℃に昇温させ、さらに１００℃で４時間反応させた後、２００℃まで加熱して脱水濃縮した後、冷却してノボラック型フェノール樹脂を得た。
[Example 1]
1000 parts by weight of phenol, 733 parts by weight of formalin 733 parts by weight and 5 parts by weight of oxalic acid were charged into a reaction vessel equipped with a reflux condenser, heated from room temperature to 100 ° C. over 40 minutes, and further reacted at 100 ° C. for 4 hours. Then, the mixture was heated to 200 ° C., dehydrated and concentrated, and then cooled to obtain a novolac type phenol resin.
上記ノボラック型フェノール樹脂４７５ｋｇとベヘン酸アミド２５ｋｇとを、二軸混練機（高速二軸連続ミキサー）に投入して、１５０℃で混練（溶融混合）を行い、室温まで冷却して、淡黄色透明なブロック状物を得た。なお、ベヘン酸アミドは日本精化社製のベヘニン酸アミド（ＢＮＴ−２２Ｈ）を用いた。 475 kg of the above-mentioned novolak type phenol resin and 25 kg of behenamide are charged into a biaxial kneader (high-speed biaxial continuous mixer), kneaded (melted and mixed) at 150 ° C., cooled to room temperature, and light yellow transparent A block-like product was obtained. In addition, behenic acid amide (BNT-22H) manufactured by Nippon Seika Co., Ltd. was used as the behenic acid amide.
次に、このブロック状物を粗粉砕し、溶融紡糸装置（グリッドメルター式）を用いて２００℃で溶融し、該溶融により得られた溶融物を、１７０℃に保たれた孔径０．１ｍｍ、Ｌ／Ｄ＝３、ホール数１０個の紡糸口金から一定吐出量を保ちながら紡糸速度７５ｍ／分で紡糸（溶融紡糸）して糸条を得た。 Next, this block-like product is coarsely pulverized and melted at 200 ° C. using a melt spinning apparatus (grid melter type), and the melt obtained by the melting has a pore diameter of 0.1 mm maintained at 170 ° C., A yarn was obtained by spinning (melt spinning) at a spinning speed of 75 m / min while maintaining a constant discharge rate from a spinneret with L / D = 3 and 10 holes.
得られた糸条を、長さ７０ｍｍにカットして容器に入れ、塩酸１４質量％かつホルムアルデヒド８質量％の水溶液に常温で３０分間浸漬した後、２時間で９８℃まで昇温し、さらに９８℃で２時間保持することにより硬化を行った。 The obtained yarn was cut into a length of 70 mm, placed in a container, immersed in an aqueous solution of 14% by mass hydrochloric acid and 8% by mass formaldehyde for 30 minutes at room temperature, heated to 98 ° C. in 2 hours, and further 98 Curing was performed by holding at 2 ° C. for 2 hours.
次いで、得られた硬化物を、前記容器から取出して十分に水洗した後、３質量％アンモニア水溶液で６０℃、３０分間の中和を行った。その後、再度十分に水洗し、９０℃、３０分間乾燥することにより、単繊維繊度１１ｄｔｅｘ、繊維長７０ｍｍ、繊維クリンプなしのフェノール系繊維を得た。 Subsequently, after taking out the hardened | cured material obtained from the said container and fully washing with water, neutralization was performed for 30 minutes at 60 degreeC with 3 mass% ammonia aqueous solution. Thereafter, it was thoroughly washed with water again and dried at 90 ° C. for 30 minutes to obtain a phenolic fiber having a single fiber fineness of 11 dtex, a fiber length of 70 mm, and no fiber crimp.
得られたフェノール系繊維を使用し、ニードルパンチ機により、針密度５００本／ｉｎｃｈ2、針深度１２ｍｍ（裏）、７ｍｍ（表）の条件で裏表処理を行い、ＡＣＦ不織布前駆体を得、その前駆体を不活性雰囲気（窒素雰囲気）中３０分かけて、常温から８９０℃まで加熱して炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で１００分間賦活して、繊維径が２４μｍ、平均細孔径１４Å、ＢＥＴ比表面積１６５０ｍ２／ｇ、全細孔容積０．７ｃｍ３／ｇ、トルエン吸着容量４９０ｍｇ／ｇの活性炭素繊維からなる不織布を得た。 Using the obtained phenol-based fiber, a back and front treatment was performed with a needle punch machine under the conditions of a needle density of 500 / inch 2 , a needle depth of 12 mm (back) and 7 mm (front) to obtain an ACF nonwoven fabric precursor, The precursor is heated from normal temperature to 890 ° C. for 30 minutes in an inert atmosphere (nitrogen atmosphere) and carbonized, and then activated for 100 minutes at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor. A nonwoven fabric composed of activated carbon fibers having a diameter of 24 μm, an average pore diameter of 14 mm, a BET specific surface area of 1650 m 2 / g, a total pore volume of 0.7 cm 3 / g, and a toluene adsorption capacity of 490 mg / g was obtained.
得られた活性炭素繊維不織布を使用した１３０ｍｍφで、厚み１５０ｍｍの絶乾重量２００ｇの吸着素子を２個作成し、図１のダンパー切替方式の水処理装置に設置して１０００ｍｇ／lの１,４−ジオキサンを含む原水を通水線速３．６ｃｍ／ｍｉｎで導入した。その際の出口濃度の経時変化を確認した結果、表１に示すように吸着帯厚み（Ｚａ１０％）が３９ｍｍであり、平衡吸着量（ｑ＊）が１７７ｍｇ／ｇと良好な吸着性能であった。 Two adsorbing elements with a dry weight of 200 g having a thickness of 150 mm and a thickness of 150 mm using the obtained activated carbon fiber nonwoven fabric were prepared and installed in the damper-switching water treatment apparatus of FIG. -Raw water containing dioxane was introduced at a water linear velocity of 3.6 cm / min. As a result of confirming the change with time of the outlet concentration at that time, as shown in Table 1, the adsorption band thickness (Za 10%) was 39 mm and the equilibrium adsorption amount (q * ) was 177 mg / g, which was a good adsorption performance. .
次に、水処理装置の脱水工程のガスとして３０℃の空気を風速５０ｃｍ／ｓで５ｍｉｎ通風し、吸着素子に付着する水分を脱水除去した。その際の付着水分量は１．９ｇ／ｇであった。 Next, 30 ° C. air was passed for 5 minutes at a wind speed of 50 cm / s as a gas for the dehydration process of the water treatment apparatus, and water adhering to the adsorption element was dehydrated and removed. The amount of moisture adhering at that time was 1.9 g / g.
次に、脱着工程における加熱ガスとして１２０℃の空気を風速５０ｃｍ／ｓで通風した。その際の吸着材の平均圧力損失は４．８ｋＰａであった。また、ブロワー動力は４６Ｗ、脱着熱量は９６９ｋＪと試算された。 Next, air at 120 ° C. was blown at a wind speed of 50 cm / s as a heating gas in the desorption process. At that time, the average pressure loss of the adsorbent was 4.8 kPa. The blower power was 46 W, and the heat of desorption was 969 kJ.
[実施例２ ]
実施例１で製造したフェノール系繊維を使用し、実施例１と同様のＡＣＦ不織布前駆体を得、その前駆体を、不活性雰囲気中１８分かけて、常温から８７０℃まで加熱して炭化させ、次に水蒸気１２質量％を含有する雰囲気中８７０℃の温度で１２０分間賦活して、繊維径が２４μｍ、平均細孔径１４Å、ＢＥＴ比表面積１１００ｍ２／ｇ、全細孔容積０．５ｃｍ３／ｇ、トルエン吸着容量３２０ｍｇ／ｇの活性炭素繊維からなる不織布を得た。
[Example 2]
Using the phenol-based fiber produced in Example 1, an ACF nonwoven fabric precursor similar to that in Example 1 was obtained, and the precursor was heated from normal temperature to 870 ° C. for 18 minutes in an inert atmosphere to be carbonized. Next, activation was performed at 870 ° C. for 120 minutes in an atmosphere containing 12% by mass of water vapor, the fiber diameter was 24 μm, the average pore diameter was 14 mm, the BET specific surface area was 1100 m 2 / g, and the total pore volume was 0.5 cm 3 /. g, A nonwoven fabric made of activated carbon fibers having a toluene adsorption capacity of 320 mg / g was obtained.
得られた活性炭素繊維不織布を使用した１３０ｍｍφで、厚み１５０ｍｍの絶乾重量２００ｇの吸着素子を２個作成し、図１のダンパー切替方式の水処理装置に設置して１０００ｍｇ／lのイソプロピルアルコールを含む原水を通水線速３．６ｃｍ／ｍｉｎで導入した。その際の出口濃度の経時変化を確認した結果、表１に示すように吸着帯厚み（Ｚａ１０％）が４２ｍｍであり、平衡吸着量（ｑ＊）が１３０ｍｇ／ｇと良好な吸着性能であった。 Two adsorbing elements with an absolute dry weight of 200 g with a thickness of 150 mm and a thickness of 150 mm using the obtained activated carbon fiber nonwoven fabric were prepared, and installed in the damper-switching water treatment apparatus of FIG. 1 to supply 1000 mg / l isopropyl alcohol. The raw water containing was introduced at a water linear velocity of 3.6 cm / min. As a result of confirming the change with time of the outlet concentration at that time, as shown in Table 1, the adsorption band thickness (Za 10%) was 42 mm and the equilibrium adsorption amount (q * ) was 130 mg / g, which was a good adsorption performance. .
次に、水処理装置の脱水工程のガスとして３０℃の空気を風速５０ｃｍ／ｓで５ｍｉｎ通風し、吸着素子に付着する水分を脱水除去した。その際の付着水分量は１．８ｇ／ｇであった。 Next, 30 ° C. air was passed for 5 minutes at a wind speed of 50 cm / s as a gas for the dehydration process of the water treatment apparatus, and water adhering to the adsorption element was dehydrated and removed. The amount of moisture attached was 1.8 g / g.
次に、脱着工程における加熱ガスとして１２０℃の空気を風速５０ｃｍ／ｓで通風した。その際の吸着材の平均圧力損失は３．８ｋＰａであった。また、ブロワー動力は３６Ｗ、脱着熱量は９１８ｋＪと試算された。 Next, air at 120 ° C. was blown at a wind speed of 50 cm / s as a heating gas in the desorption process. At that time, the average pressure loss of the adsorbent was 3.8 kPa. The blower power was estimated to be 36 W, and the heat of desorption was estimated to be 918 kJ.
[比較例１ ]
単繊維繊度５．６ｄｔｅｘ、繊維長７０ｍｍ、繊維クリンプなしのフェノール系繊維（群栄化学工業（株）社製、カイノールＫＦ−０５７０）を使用し、ニードルパンチ機により、針密度５００本／ｉｎｃｈ2、針深度１２ｍｍ（裏）、７ｍｍ（表）の条件で裏表処理を行いＡＣＦ不織布前駆体を得、その前駆体を不活性雰囲気中１８分かけて、常温から８９０℃まで加熱して炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で６０分間賦活して、繊維径１７μｍ、平均細孔径１４Å、ＢＥＴ比表面積１６５０ｍ２／ｇ、全細孔容積０．７ｃｍ３／ｇ、トルエン吸着容量４９０ｍｇ／ｇの活性炭素繊維からなる不織布を得た。
[Comparative Example 1]
A monofilament fineness of 5.6 dtex, a fiber length of 70 mm, a phenolic fiber (Kinei Chemical Industry Co., Ltd., Kynol KF-0570) without fiber crimp is used, and a needle density of 500 / inch 2 is obtained by a needle punch machine. The ACF nonwoven fabric precursor was obtained by performing backside treatment under conditions of needle depth 12 mm (back) and 7 mm (front), and the precursor was heated from normal temperature to 890 ° C. over 18 minutes in an inert atmosphere, and carbonized. Next, activation was performed for 60 minutes at a temperature of 890 ° C. in an atmosphere containing 12% by mass of water vapor, a fiber diameter of 17 μm, an average pore diameter of 14 mm, a BET specific surface area of 1650 m 2 / g, a total pore volume of 0.7 cm 3 / g, A nonwoven fabric made of activated carbon fibers having a toluene adsorption capacity of 490 mg / g was obtained.
得られた活性炭素繊維不織布を使用した１３０ｍｍφで、厚み１５０ｍｍの絶乾重量２００ｇの吸着素子を２個作成し、図１のダンパー切替方式の水処理装置に設置して１０００ｍｇ／lの１,４−ジオキサンを含む原水を通水線速３．６ｃｍ／ｍｉｎで導入した。その際の出口濃度の経時変化を確認した結果、表１に示すように吸着帯厚み（Ｚａ１０％）が４０ｍｍであり、平衡吸着量（ｑ＊）が１７５ｍｇ／ｇと良好な吸着性能であった。 Two adsorbing elements with a dry weight of 200 g having a thickness of 150 mm and a thickness of 150 mm using the obtained activated carbon fiber nonwoven fabric were prepared and installed in the damper-switching water treatment apparatus of FIG. -Raw water containing dioxane was introduced at a water linear velocity of 3.6 cm / min. As a result of confirming the change with time in the outlet concentration at that time, as shown in Table 1, the adsorption band thickness (Za 10%) was 40 mm, and the equilibrium adsorption amount (q * ) was 175 mg / g, which was a good adsorption performance. .
次に、水処理装置の脱水工程のガスとして３０℃の空気を風速５０ｃｍ／ｓで５ｍｉｎ通風し、吸着素子に付着する水分を脱水除去した。その際の付着水分量は２．６ｇ／ｇであった。 Next, 30 ° C. air was passed for 5 minutes at a wind speed of 50 cm / s as a gas for the dehydration process of the water treatment apparatus, and water adhering to the adsorption element was dehydrated and removed. The amount of moisture adhering at that time was 2.6 g / g.
次に、脱着工程における加熱ガスとして１２０℃の空気を風速を風速５０ｃｍ／ｓで通風した。その際の吸着材の平均圧力損失は８．５ｋＰａであった。ブロワー動力は８１Ｗ、脱着熱量は１３２６ｋＪと試算され、実施例１と比較して１．７倍以上のブロワー動力、１．４倍以上の脱着熱量が必要であった。 Next, air at 120 ° C. was blown at a wind speed of 50 cm / s as a heating gas in the desorption process. The average pressure loss of the adsorbent at that time was 8.5 kPa. The blower power was 81 W and the heat of desorption was estimated to be 1326 kJ. Compared with Example 1, the blower power was 1.7 times or more and the heat of desorption was 1.4 times or more.
[比較例２ ]
比較例１で製造したフェノール繊維を使用し、比較例１と同様のＡＣＦ不織布前駆体を得、その前駆体を、不活性雰囲気中１８分かけて、常温から８７０℃まで加熱して炭化させ、次に水蒸気１２質量％を含有する雰囲気中８７０℃の温度で６０分間賦活して、繊維径１７μｍ、平均細孔径１３Å、ＢＥＴ比表面積１１００ｍ２／ｇ、全細孔容積０．５ｃｍ３／ｇ、トルエン吸着容量３２０ｍｇ／ｇの活性炭素繊維からなる不織布を得た。
[Comparative Example 2]
Using the phenol fiber produced in Comparative Example 1, the same ACF nonwoven fabric precursor as in Comparative Example 1 was obtained, and the precursor was carbonized by heating from room temperature to 870 ° C. over 18 minutes in an inert atmosphere. Next, activation was performed for 60 minutes at a temperature of 870 ° C. in an atmosphere containing 12% by mass of water vapor, a fiber diameter of 17 μm, an average pore diameter of 13 mm, a BET specific surface area of 1100 m 2 / g, a total pore volume of 0.5 cm 3 / g, A nonwoven fabric made of activated carbon fibers having a toluene adsorption capacity of 320 mg / g was obtained.
得られた活性炭素繊維不織布を使用した１３０ｍｍφで、厚み１５０ｍｍの絶乾重量２００ｇの吸着素子を２個作成し、図１のダンパー切替方式の水処理装置に設置して１０００ｍｇ／lのイソプロピルアルコールを含む原水を通水線速３．６ｃｍ／ｍｉｎで導入した。その際の出口濃度の経時変化を確認した結果、表１に示すように吸着帯厚み（Ｚａ１０％）が４２ｍｍであり、平衡吸着量（ｑ＊）が１３０ｍｇ／ｇと良好な吸着速度と破過時間であった。 Two adsorbing elements with an absolute dry weight of 200 g with a thickness of 150 mm and a thickness of 150 mm using the obtained activated carbon fiber nonwoven fabric were prepared, and installed in the damper-switching water treatment apparatus of FIG. 1 to supply 1000 mg / l isopropyl alcohol. The raw water containing was introduced at a water linear velocity of 3.6 cm / min. As a result of confirming the change over time in the outlet concentration at that time, as shown in Table 1, the adsorption band thickness (Za 10%) is 42 mm, and the equilibrium adsorption amount (q * ) is 130 mg / g. It was time.
次に、水処理装置の脱水工程のガスとして３０℃の空気を風速５０ｃｍ／ｓで５ｍｉｎ通風し、吸着素子に付着する水分を脱水除去した。その際の付着水分量は２．５ｇ／ｇであった。 Next, 30 ° C. air was passed for 5 minutes at a wind speed of 50 cm / s as a gas for the dehydration process of the water treatment apparatus, and water adhering to the adsorption element was dehydrated and removed. The amount of moisture attached was 2.5 g / g.
次に、脱着工程における加熱ガスとして１２０℃の空気を風速を風速５０ｃｍ／ｓで通風した。その際の吸着材の平均圧力損失は７．０ｋＰａであった。ブロワー動力は６６Ｗ、脱着熱量は１２７５ｋＪと試算され、実施例２と比較して１．８倍以上のブロワー動力、１．４倍以上の脱着熱量が必要であった。 Next, air at 120 ° C. was blown at a wind speed of 50 cm / s as a heating gas in the desorption process. The average pressure loss of the adsorbent at that time was 7.0 kPa. The blower power was 66 W and the heat of desorption was estimated to be 1275 kJ. Compared with Example 2, the blower power was 1.8 times or more and the heat of desorption was 1.4 times or more.
本発明の水処理装置は、有機化合物を含む水の連続浄化を実現し、基本的に吸着材の交換が必要なく、多量の有機化合物を高効率かつ安定に除去することができる処理装置であるため、設備増大を必要とせずに、吸着材交換作業を省略でき、コスト低減、有害物質を安定除去でき、特に研究所や工場等の幅広い分野に利用することができ、産業界に寄与することが大である。 The water treatment apparatus of the present invention is a treatment apparatus that realizes continuous purification of water containing an organic compound, basically eliminates the need for replacement of an adsorbent, and can remove a large amount of organic compounds with high efficiency and stability. Therefore, the adsorbent replacement work can be omitted without the need for additional equipment, cost reduction, toxic substances can be removed stably, and it can be used in a wide range of fields such as laboratories and factories, contributing to the industry. Is big.
１１ 原水導入ライン
１２ 吸着素子
１３ 吸着領域
１４ 脱水領域
１５ 戻りライン
１６ 脱着領域
２１ 原水
２２ 処理出口水
２３ 脱着空気
２４ 濃縮ガス
２５ 吸着素子
DESCRIPTION OF SYMBOLS 11 Raw water introduction line 12 Adsorption element 13 Adsorption area 14 Dehydration area 15 Return line 16 Desorption area 21 Raw water 22 Treatment outlet water 23 Desorption air 24 Concentrated gas 25 Adsorption element
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