JP4975418B2 - Cleaning solution for anion exchange membrane regeneration of electrodialysis machine - Google Patents
Cleaning solution for anion exchange membrane regeneration of electrodialysis machine Download PDFInfo
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- JP4975418B2 JP4975418B2 JP2006318495A JP2006318495A JP4975418B2 JP 4975418 B2 JP4975418 B2 JP 4975418B2 JP 2006318495 A JP2006318495 A JP 2006318495A JP 2006318495 A JP2006318495 A JP 2006318495A JP 4975418 B2 JP4975418 B2 JP 4975418B2
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- 239000003011 anion exchange membrane Substances 0.000 title claims description 80
- 238000004140 cleaning Methods 0.000 title claims description 45
- 238000011069 regeneration method Methods 0.000 title claims description 26
- 238000000909 electrodialysis Methods 0.000 title claims description 23
- 230000008929 regeneration Effects 0.000 title claims description 20
- 239000007788 liquid Substances 0.000 claims description 43
- 239000003945 anionic surfactant Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- FHSWKZUNNVWBSG-UHFFFAOYSA-M 2-[3-[(4-amino-2-methylpyrimidin-5-yl)methyl]-4-methyl-1,3-thiazol-3-ium-5-yl]ethanol;dodecyl hydrogen sulfate;dodecyl sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O.CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N FHSWKZUNNVWBSG-UHFFFAOYSA-M 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- -1 polyoxyethylene lauryl sulfate Polymers 0.000 claims description 2
- 229940083542 sodium Drugs 0.000 claims description 2
- QGVQVNIIRBPOAM-UHFFFAOYSA-N dodecyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCCCCCCCCCC)=CC=CC2=C1 QGVQVNIIRBPOAM-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 25
- 238000011033 desalting Methods 0.000 description 21
- 239000012528 membrane Substances 0.000 description 19
- 238000005406 washing Methods 0.000 description 18
- 235000011194 food seasoning agent Nutrition 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 11
- 238000005341 cation exchange Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000011109 contamination Methods 0.000 description 6
- 239000003014 ion exchange membrane Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000021018 plums Nutrition 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003531 protein hydrolysate Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 235000013555 soy sauce Nutrition 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- WDRZVZVXHZNSFG-UHFFFAOYSA-N 1-ethenylpyridin-1-ium Chemical compound C=C[N+]1=CC=CC=C1 WDRZVZVXHZNSFG-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical group C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
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- Detergent Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は、電気透析装置に使用されて汚染されたアニオン交換膜を再生するための新規なアニオン交換膜再生用洗浄液（以下、単に洗浄液ともいう。）及び該洗浄液を使用したアニオン交換膜の再生方法に関する。詳しくは、アニオン性界面活性剤の吸着によって汚染されて性能が低下したアニオン交換膜の性能を大幅に回復することが可能な、洗浄液及び再生方法を提供するものである。 The present invention relates to a novel anion exchange membrane regeneration cleaning liquid (hereinafter also simply referred to as a cleaning liquid) for regenerating a contaminated anion exchange membrane used in an electrodialysis apparatus, and regeneration of an anion exchange membrane using the cleaning liquid. Regarding the method. Specifically, the present invention provides a cleaning solution and a regeneration method that can significantly recover the performance of an anion exchange membrane that has been contaminated by the adsorption of an anionic surfactant and whose performance has been reduced.
電気透析装置は、図１に、脱塩における一般的な構造を示すように、透析槽１内に陽極２と陰極３とを備え、その陽極と陰極との間に複数枚のカチオン交換膜Ｃと複数枚のアニオン交換膜Ａとを交互に配列して、濃縮室４と脱塩室５とを形成したものであり、濃縮室では、イオン交換膜を透過してイオンが流入して濃縮され、脱塩室では、イオン交換膜を透過してイオンが流出して脱塩される。
As shown in FIG. 1, the electrodialysis apparatus includes an
上記特性を利用して、電気透析装置は、海水から食塩を製造したり、海水から飲料水を製造したりする分野に実用化されている。 Utilizing the above characteristics, electrodialyzers have been put to practical use in the field of producing salt from seawater or producing drinking water from seawater.
また、近年、健康に対する関心が高まる中、醤油、タンパク質加水分解液、漬物の調味液などの塩分を減少させるために、電気透析装置が用いられるようにもなっている（特許文献１）。 In recent years, as the interest in health has increased, electrodialyzers have also been used to reduce the salt content of soy sauce, protein hydrolysates, pickled seasonings, and the like (Patent Document 1).
ところが、漬物の調味液などには、塩分以外に種々の調味成分が含有されており、本発明者らの確認によれば、日保ち向上剤などとして含まれているアニオン性界面活性剤は、アニオン交換膜を通過せず、イオン交換膜に吸着し、電気透析装置の脱塩性能を低下させる。この場合、アニオン界面活性剤は、アニオン交換膜表面への付着のみならず、アニオン交換膜のアニオン交換基とアニオン性界面活性剤のカチオン交換基がイオンコンプレックスを形成する。 However, the seasoning liquid of pickles contains various seasoning components in addition to the salt content, and according to the present inventors' confirmation, the anionic surfactant contained as a sun protection agent is an anionic surfactant. It does not pass through the exchange membrane and is adsorbed on the ion exchange membrane, thereby reducing the desalting performance of the electrodialyzer. In this case, the anionic surfactant not only adheres to the surface of the anion exchange membrane, but an anion exchange group of the anion exchange membrane and a cation exchange group of the anionic surfactant form an ion complex.
従来、有機物によって性能が低下したイオン交換膜の性能を回復させる方法としては、幾つか提案されており、例えば、イオン交換膜の一方の面に酸溶液を他方の面にアルカリ溶液を同時に接触させる方法が提案されている（特許文献２）。 Conventionally, several methods for recovering the performance of an ion exchange membrane whose performance has been degraded by organic substances have been proposed. For example, an acid solution is simultaneously brought into contact with one surface of an ion exchange membrane and an alkaline solution is brought into contact with the other surface. A method has been proposed (Patent Document 2).
この方法は、アニオン膜表面の酸やアルカリに可溶な付着物の洗浄除去には、有効だが、アニオン界面活性剤の様にアルコールに可溶な付着物の洗浄除去には適していない。又、エタノール濃度が４０〜７０％の水溶液で、イオン交換膜を洗浄する方法も提案されている。（特許文献３）。 This method is effective for washing and removing the deposits soluble in acid and alkali on the surface of the anion membrane, but is not suitable for washing and removing deposits soluble in alcohol like an anionic surfactant. Also proposed is a method of washing the ion exchange membrane with an aqueous solution having an ethanol concentration of 40 to 70%. (Patent Document 3).
この方法は、アニオン膜表面に付着したアニオン界面活性剤には有効であるが、アニオン交換膜とイオンコンプレックスを形成しているアニオン性界面活性剤については、該イオンコンプレックスを解除し、アニオン交換膜からアニオン界面活性剤を除去する事が出来ず、洗浄回復性は、不十分であった。
従って、本発明の目的は、アニオン性界面活性剤の吸着によって汚染されて性能が低下したアニオン交換膜を、効果的に性能を回復することが可能な洗浄液及び再生方法を提供することにある。 Accordingly, an object of the present invention is to provide a cleaning solution and a regeneration method capable of effectively recovering the performance of an anion exchange membrane that has been contaminated by the adsorption of an anionic surfactant and whose performance has been reduced.
本発明者らは、上記目的を達成するために研究を重ねた結果、特定の溶媒成分と溶質成分とを含む液組成により、アニオン交換膜を接触させた場合においても、良好な洗浄効果を発揮し、アニオン性界面活性剤の吸着によって低下した性能を大幅に回復し得ることを見出し、本発明を完成するに至った。 As a result of repeated studies to achieve the above object, the present inventors have demonstrated a good cleaning effect even when an anion exchange membrane is brought into contact with a liquid composition containing a specific solvent component and a solute component. As a result, it was found that the performance deteriorated by the adsorption of the anionic surfactant can be greatly recovered, and the present invention has been completed.
即ち、本発明は、脂肪族アルコール２０〜８０体積％及び水８０〜２０体積％からなる溶媒成分、及び該溶媒成分に対し１〜３０重量％の量の無機塩からなる溶質成分を含有することを特徴とする電気透析装置のアニオン交換膜再生用洗浄液である。 That is, the present invention contains a solvent component composed of 20 to 80% by volume of an aliphatic alcohol and 80 to 20% by volume of water, and a solute component composed of an inorganic salt in an amount of 1 to 30% by weight based on the solvent component. An anion exchange membrane regeneration cleaning solution for an electrodialysis apparatus characterized by the above.
また、本発明は、上記洗浄液を使用した性能回復方法をも提供する。即ち、本発明によれば、アニオン性界面活性剤の吸着によって汚染されて性能が低下したアニオン交換膜に、脂肪族アルコール２０〜８０体積％及び水８０〜２０体積％からなる溶媒成分、及び該溶媒成分に対し１〜３０重量％の量の無機塩からなる溶質成分を含有するアニオン交換膜再生用洗浄液を接触させるアニオン交換膜の再生方法が提供される。 The present invention also provides a performance recovery method using the cleaning liquid. That is, according to the present invention, an anion exchange membrane that has been contaminated by the adsorption of an anionic surfactant and has reduced performance, a solvent component composed of 20 to 80% by volume of an aliphatic alcohol and 80 to 20% by volume of water, Provided is a method for regenerating an anion exchange membrane in which an anion exchange membrane regenerating cleaning solution containing a solute component composed of an inorganic salt in an amount of 1 to 30% by weight with respect to the solvent component is brought into contact.
また、本発明は、上記再生方法を、電気透析装置を解体すること無く実施する方法として、アニオン性界面活性剤の吸着によって汚染されて性能が低下したアニオン交換膜が存在する電気透析装置に、前記アニオン交換膜再生用洗浄液を通液することによって、上記アニオン交換膜にアニオン交換膜再生用洗浄液を接触させる操作を行う、アニオン交換膜の再生方法をも提供する。 In addition, the present invention provides an electrodialysis apparatus having an anion exchange membrane that is contaminated by adsorption of an anionic surfactant and has a reduced performance as a method for performing the regeneration method without disassembling the electrodialysis apparatus. There is also provided a method for regenerating an anion exchange membrane, wherein an operation for bringing the anion exchange membrane into contact with the cleaning liquid for anion exchange membrane regeneration is performed by passing the cleaning liquid for anion exchange membrane regeneration.
（アニオン交換膜再生用洗浄液）
本発明のアニオン交換膜再生用洗浄液は、前記成分を含有することによって、アニオン性界面活性剤の如き有機物によって汚染され、膜の電気抵抗が上昇する等の性能低下を来したアニオン交換膜に、簡易な操作で、膜の性能を大幅に回復することが可能である。
(Cleaning solution for anion exchange membrane regeneration)
The cleaning liquid for anion exchange membrane regeneration of the present invention is contaminated with organic substances such as anionic surfactants by containing the above-mentioned components, and the anion exchange membrane that has deteriorated performance such as an increase in electrical resistance of the membrane, With a simple operation, the membrane performance can be significantly recovered.
従って、前記用途において、陰イオン交換膜を長期間にわたって使用することが可能であり、工業的に極めて有用である。 Therefore, it is possible to use an anion exchange membrane for a long period of time in the above application, which is extremely useful industrially.
本発明において、アニオン交換膜は、公知のものが特に限定されない。例えば、スチレン／ジビニルベンゼン共重合体等の公知の樹脂を骨格とし、アニオン交換基を１．０〜３．０ｍｅｑ／ｇ−樹脂含むアニオン交換膜が挙げられる。好ましくは、イオン交換基として、４級アンモニウム型、４級化ビニルピリジニウム型、４級化ビニルイミダゾール型等の基を有するアニオン交換膜である。 In the present invention, known anion exchange membranes are not particularly limited. For example, an anion exchange membrane containing a known resin such as a styrene / divinylbenzene copolymer as a skeleton and an anion exchange group of 1.0 to 3.0 meq / g-resin can be used. An anion exchange membrane having a group such as a quaternary ammonium type, a quaternized vinyl pyridinium type, or a quaternized vinyl imidazole type as an ion exchange group is preferable.
また、本発明において、洗浄、再生の対象となるアニオン交換膜は、前記用途、即ち、醤油、タンパク質加水分解液、漬物の調味液などの塩分を減少させる用途等の電気透析に使用し、アニオン性界面活性剤を吸着することによって性能が低下した膜である。 Further, in the present invention, the anion exchange membrane to be washed and regenerated is used for electrodialysis in the above-mentioned use, that is, for reducing the salt content of soy sauce, protein hydrolyzate, pickled seasoning, etc. It is a film whose performance has been reduced by adsorbing the surfactant.
かかるアニオン性界面活性剤は、アニオン性の高分子量物であり、具体的にはチアミンラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンラウリル硫酸ナトリウム、ドデシルナフタレンスルホン酸ナトリウムなどが挙げられる。 Such anionic surfactants are anionic high molecular weight substances, and specific examples include sodium thiamine lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene lauryl sulfate, sodium dodecyl naphthalene sulfonate, and the like.
一般に、前記漬物の調味液などには、アニオン性界面活性剤として、例えば、チアミンラウリル硫酸ナトリウムを１０００ｐｐｍ程度を上限として含有されている。 Generally, the seasoning liquid of the pickles contains, for example, sodium thiamine lauryl sulfate as an anionic surfactant with an upper limit of about 1000 ppm.
本発明の最大の特徴は、前記アニオン性界面活性剤を吸着することによって性能が低下したアニオン交換膜に接触させる洗浄液組成として、脂肪族アルコール及び水からなる溶媒成分、及無機塩からなる溶質成分を含有したことにある。 The greatest feature of the present invention is that the cleaning liquid composition that is brought into contact with the anion exchange membrane whose performance has been reduced by adsorbing the anionic surfactant is a solvent component composed of an aliphatic alcohol and water, and a solute component composed of an inorganic salt. It is in containing.
上記脂肪族アルコールとしては、水と相溶性があるものであれば特に制限されず、例えば、炭素数１０以下、特に５以下のものが好ましい。好ましいアルコールは具体的には、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノールなどである。中でも好ましいアルコールは、エタノール、プロパノール、イソプロパノールである。これらは再生効果に優れ安全性も高いからである。 The aliphatic alcohol is not particularly limited as long as it is compatible with water. For example, an aliphatic alcohol having 10 or less carbon atoms, particularly 5 or less carbon atoms is preferable. Specific preferred alcohols are methanol, ethanol, propanol, isopropanol, butanol, pentanol and the like. Among them, preferred alcohols are ethanol, propanol and isopropanol. This is because these are excellent in regenerative effect and high in safety.
また、無機塩は、前記溶媒成分に対して溶解度が高く、また、アルカリ域でのスケールを生成し難いものが特に制限なく使用される。代表的な無機塩としては、食塩（塩化ナトリウム）、塩化カリウム、硝酸ナトリウム、硝酸カリウム、塩化アンモニウム、硝酸アンモニウム等が挙げられる。特に好ましい無機塩は食塩である。また、これらの無機塩は単独で用いてもよいし、複数種を混合して用いてもよい。 In addition, inorganic salts that are highly soluble in the solvent component and that are difficult to produce a scale in an alkaline region are used without particular limitation. Typical inorganic salts include sodium chloride (sodium chloride), potassium chloride, sodium nitrate, potassium nitrate, ammonium chloride, ammonium nitrate and the like. A particularly preferred inorganic salt is sodium chloride. Moreover, these inorganic salts may be used alone or in combination of two or more.
本発明の洗浄液において、上記溶媒成分を構成する脂肪族アルコールと水との割合は、脂肪族アルコール２０〜８０体積％及び水８０〜２０体積％、好ましくは、脂肪族アルコール５０〜７５体積％及び水５０〜２５体積％であることが重要である。 In the cleaning liquid of the present invention, the proportion of the aliphatic alcohol and water constituting the solvent component is 20 to 80 vol% aliphatic alcohol and 80 to 20 vol% water, preferably 50 to 75 vol% aliphatic alcohol and It is important that the water be 50-25% by volume.
即ち、溶媒成分中の脂肪族アルコールが２０体積％未満の場合は、アニオン交換膜の性能を十分に回復させることができない。一方、脂肪族アルコールが８０体積％を超える場合は、アニオン交換膜の性能を十分に回復させることができないばかりか、膜の膨潤が激しくなり、接触後に他の性能、例えば、膜のイオン選択性の低下等を招く。 That is, when the aliphatic alcohol in the solvent component is less than 20% by volume, the performance of the anion exchange membrane cannot be sufficiently recovered. On the other hand, when the aliphatic alcohol exceeds 80% by volume, not only the performance of the anion exchange membrane cannot be sufficiently recovered, but also the swelling of the membrane becomes severe, and other performance after contact, for example, ion selectivity of the membrane. Decrease.
上記洗浄力が発揮される理由として、本発明者らは次のように推定している。即ち、溶媒成分の脂肪族アルコールによって、該アニオン交換膜を膨潤させ、汚染物質であるアニオン性界面活性剤をアニオン交換膜から離脱し易くすると共に、離脱したアニオン性界面活性剤を溶解し易くする。次に、アニオン交換膜のアニオン交換基とアニオン性界面活性剤のカチオン交換基が形成しているイオンコンプレックスを添加されている無機塩により、アニオン性界面活性剤のカチオン交換基と無機塩中のアニオンとがイオン交換作用により入れ替わり、アニオン交換膜からアニオン性界面活性剤が離脱し、従来に無い高い洗浄効果が得られていると推定している。 The present inventors presume that the above cleaning power is exerted as follows. That is, the anion exchange membrane is swollen by the aliphatic alcohol as the solvent component, and the anionic surfactant that is a contaminant is easily released from the anion exchange membrane, and the released anionic surfactant is easily dissolved. . Next, the inorganic salt added with the ion complex formed by the anion exchange group of the anion exchange membrane and the cation exchange group of the anionic surfactant is added to the cation exchange group and the inorganic salt of the anionic surfactant. It is presumed that the anion is replaced by an anion exchange action, the anionic surfactant is detached from the anion exchange membrane, and an unprecedented high cleaning effect is obtained.
従って、前記脂肪族アルコールが不足した場合は、アニオン交換膜をアニオン性界面活性剤が離脱するほどに十分膨潤できず、また、離脱したアニオン性界面活性剤を溶解する能力が低下し、膜への再付着が生じるものと予想される。又、塩が不足した場合は、アニオン性界面活性剤のカチオン交換基と塩中のカチオンとのイオン交換が進まず、アニオン交換膜からアニオン性界面活性剤が離脱しにくくなる。 Therefore, when the aliphatic alcohol is insufficient, the anion exchange membrane cannot be sufficiently swollen so that the anionic surfactant is released, and the ability to dissolve the released anionic surfactant is reduced, leading to the membrane. It is expected that redeposition will occur. In addition, when the salt is insufficient, ion exchange between the cation exchange group of the anionic surfactant and the cation in the salt does not proceed, and the anionic surfactant becomes difficult to leave from the anion exchange membrane.
本発明の洗浄液の溶質成分である前記無機塩の割合は、該溶媒成分に対し１〜３０重量％、好ましくは、２〜６重量％である。 The proportion of the inorganic salt that is the solute component of the cleaning liquid of the present invention is 1 to 30% by weight, preferably 2 to 6% by weight, based on the solvent component.
そして、本発明のアニオン交換膜再生用洗浄液は、上記により、優れた性能回復性能を発揮するものと推定される。 And it is estimated that the washing | cleaning liquid for anion exchange membrane reproduction | regeneration of this invention exhibits the outstanding performance recovery performance by the above.
本発明の洗浄液は、本発明の効果を著しく阻害しない範囲で、前記以外の添加剤を配合してもよい。 The cleaning liquid of the present invention may contain additives other than those described above as long as the effects of the present invention are not significantly impaired.
そのうち、特に、好適に配合される添加剤として、洗浄液のｐＨを７〜９に調整するｐＨ調整剤を添加することが好ましい。即ち、かかるｐＨ調整剤の添加により、アニオン性界面活性剤の溶解性の向上を図ることができる。例えば、リン酸３ナトリウムを加えることにより、洗浄液のｐＨを８程度に調節することができる。 Among them, it is particularly preferable to add a pH adjuster that adjusts the pH of the cleaning liquid to 7 to 9 as an additive that is suitably blended. That is, the solubility of the anionic surfactant can be improved by adding such a pH adjuster. For example, the pH of the cleaning liquid can be adjusted to about 8 by adding trisodium phosphate.
本発明の洗浄液を調製する方法は特に制限されない。例えば、アルコールと水とを混合した後、この混合液に無機塩を溶解させる方法、水に無機塩を溶解した後、脂肪族アルコールと混合する方法などが一般的である。 The method for preparing the cleaning liquid of the present invention is not particularly limited. For example, after mixing alcohol and water, a method of dissolving an inorganic salt in this mixed solution, a method of dissolving an inorganic salt in water, and then mixing with an aliphatic alcohol are common.
（アニオン交換膜の再生方法）
本発明のアニオン交換膜再生用洗浄液によるアニオン交換膜の再生方法は、アニオン性界面活性剤の吸着によって汚染されて性能が低下した、電気透析装置のアニオン交換膜に該洗浄液を接触させることによって実施することができる。
(Regeneration method of anion exchange membrane)
The method of regenerating an anion exchange membrane with the washing solution for anion exchange membrane regeneration of the present invention is carried out by bringing the washing solution into contact with the anion exchange membrane of an electrodialysis apparatus, which has been contaminated by the adsorption of an anionic surfactant and has deteriorated performance can do.
通常、アニオン性界面活性剤を含有する液、例えば、アニオン性界面活性剤の濃度が５０〜１００ｐｐｍである調味液を電気透析装置で脱塩すると、脱塩効率は徐々に低下し、８０〜２００時間位で、初期の脱塩効率に対し４０％程度となる。 Usually, when a liquid containing an anionic surfactant, for example, a seasoning liquid having an anionic surfactant concentration of 50 to 100 ppm is desalted with an electrodialyzer, the desalting efficiency gradually decreases, and 80 to 200 In terms of time, it is about 40% of the initial desalting efficiency.
このように、性能が低下したアニオン交換膜に対して、本発明の洗浄液による洗浄による再生を実施することが好ましい。 Thus, it is preferable to carry out the regeneration by washing with the washing liquid of the present invention on the anion exchange membrane having lowered performance.
本発明の再生方法において、アニオン交換膜と洗浄液との接触方法は、特に制限されない。代表的な方法を例示すれば、シャワー、浸漬などの方法が好ましい。 In the regeneration method of the present invention, the method for contacting the anion exchange membrane and the cleaning liquid is not particularly limited. If a typical method is illustrated, methods, such as a shower and immersion, are preferable.
また、アニオン交換膜と洗浄液との接触時間は特に制限されないが、例えば、５〜４８０分、好ましくは、１０〜１２０分、特に好ましくは、１５〜６０分程度行われる。
更に、前記接触温度は、電気透析での使用温度範囲であり、１０〜４０℃が好ましい。
The contact time between the anion exchange membrane and the cleaning liquid is not particularly limited, and is, for example, 5 to 480 minutes, preferably 10 to 120 minutes, and particularly preferably about 15 to 60 minutes.
Furthermore, the said contact temperature is the use temperature range in electrodialysis, and 10-40 degreeC is preferable.
また、本発明の上記再生方法は、アニオン交換膜を電気透析装置から取り出すこと無く、即ち、電気透析装置を分解すること無く実施することも可能である。具体的には、脱塩効率が、電気透析装置の実使用に支障が生じるまで低下したところで電気透析装置を停止する。そして、電気透析槽から被処理液、例えば、前記調味液を排出し、透析槽を水で洗浄した後、本発明の洗浄液を導入する。導入の方法は、液供給用タンクを用意し、該タンクより、アニオン交換膜の汚染面が面する透析室に洗浄液を供給し、これを前記タンクに排出することによって、アニオン交換膜と洗浄液とを循環接触させる方法が好ましい。 In addition, the regeneration method of the present invention can be carried out without removing the anion exchange membrane from the electrodialyzer, that is, without disassembling the electrodialyzer. Specifically, the electrodialyzer is stopped when the desalting efficiency is lowered until the actual use of the electrodialyzer is hindered. And after draining a to-be-processed liquid, for example, the said seasoning liquid from an electrodialysis tank, and wash | cleaning a dialysis tank with water, the washing | cleaning liquid of this invention is introduce | transduced. The method of introduction is to prepare a liquid supply tank, supply a cleaning liquid from the tank to the dialysis chamber facing the contaminated surface of the anion exchange membrane, and discharge it to the tank, thereby allowing the anion exchange membrane, the cleaning liquid and A method of circulating contact with each other is preferred.
この場合、電気透析装置の通電を止めて行うのが一般的であるが、適度な通電を行いながら洗浄を行うこともできる。又、逆通電を行うことにより、アニオン性界面活性剤の膜からの離脱を補助することも可能である。 In this case, it is common to stop the electrodialysis apparatus from being energized, but it is also possible to carry out washing while applying an appropriate amount of electricity. Moreover, it is also possible to assist the detachment of the anionic surfactant from the membrane by applying reverse current.
以下、実施例により、本発明を更に具体的に説明するが、本発明は、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
実施例１
（アニオン交換膜の汚染）
アストム社製電気透析装置「マイクロ・アシライザーＳ３型」に、カチオン交換膜としてアストム社製「ネオセプタＣＭＸ−ＳＢ」、アニオン交換膜としてアストム社製「ネオセプタＡＭＸ−ＳＢ」を取り付けた。アニオン交換膜は、骨格としてスチレン／ジビニルベンゼン共重合体、イオン交換基として４級アンモニウム塩基を有している。
Example 1
(Anion exchange membrane contamination)
An Astom electrodialyzer “Micro Acylizer S3 type” was equipped with “Neoceptor CMX-SB” manufactured by Astom as a cation exchange membrane and “Neocepta AMX-SB” manufactured by Astom as an anion exchange membrane. The anion exchange membrane has a styrene / divinylbenzene copolymer as a skeleton and a quaternary ammonium base as an ion exchange group.
０．５モル／リットルの食塩水中で、２５℃、交流１ｋＨｚでアニオン交換膜の膜抵抗を測定したところ２．０１Ω・ｃｍ２であった。 The membrane resistance of the anion exchange membrane was measured at 25 ° C. and alternating current of 1 kHz in a 0.5 mol / liter saline solution and found to be 2.01 Ω · cm 2 .
次いで、日保ち向上剤を含有する調味梅干用の調味液２．４リットルを準備した。この液は食塩を９重量％、チアミンラウリル硫酸ナトリウムを６６７ｐｐｍ含有している。 Next, 2.4 liters of seasoning liquid for seasoning plums containing a sun-keeping improver was prepared. This solution contains 9% by weight of sodium chloride and 667 ppm of sodium thiamine lauryl sulfate.
この調味液を電気透析装置の脱塩液タンクより、電気透析装置の脱塩室に循環供給し、印加電圧１０Ｖ一定で、最大電流密度が５０ｍＡ／ｃｍ２の条件で、塩濃度３重量％まで脱塩運転をした。運転に要した平均電流はアシライザー２０型換算で３９．３Ａであった。 This seasoning liquid is circulated and supplied from the desalting solution tank of the electrodialysis device to the desalting chamber of the electrodialysis device, up to a salt concentration of 3% by weight under the condition of a constant applied voltage of 10 V and a maximum current density of 50 mA / cm 2. A desalting operation was performed. The average current required for operation was 39.3 A in terms of the type 20 acylator.
その後、電気透析装置から処理液を排出し、上記と同様にしてアニオン交換膜の膜抵抗を測定したところ１３．４Ω・ｃｍ２であった。汚染前の電流値９６．４Ａを１００として上記の脱塩時平均電流３９．３Ａを換算すると４０．７であり、また、脱塩効率は約４１％にまで低下した。 Thereafter, the treatment liquid was discharged from the electrodialyzer, and the membrane resistance of the anion exchange membrane was measured in the same manner as described above, and found to be 13.4 Ω · cm 2 . When the current value before contamination of 96.4A is taken as 100 and the above average current during desalting of 39.3A is converted to 40.7, the desalting efficiency is reduced to about 41%.
（アニオン交換膜再生用洗浄液の調製）
食塩水と９５体積％エタノールとを適量混合して、エタノール７０体積％及び水３０体積％を含有する溶媒成分中に食塩４重量／体積％を含有する洗浄液を得た。
(Preparation of cleaning solution for anion exchange membrane regeneration)
An appropriate amount of saline and 95% by volume ethanol was mixed to obtain a cleaning solution containing 4% by weight / volume of sodium chloride in a solvent component containing 70% by volume of ethanol and 30% by volume of water.
この洗浄液を電気透析装置の脱塩液タンクに２００ｃｃ、濃縮液タンクに２００ｃｃ仕込み、該洗浄液をもこのタンクを介して電気透析装置の脱塩室、濃縮質にそれぞれ循環供給した。
３０分経過後、洗浄液の循環を止め、洗浄液を排出した。その後、純水を循環させて
膜を洗浄した後、上記と同様にしてアニオン交換膜の膜抵抗を測定したところ２．２Ω・ｃｍ２であった。
This washing solution was charged into a desalting solution tank of the electrodialyzer at 200 cc and a concentrated solution tank at 200 cc, and the washing solution was also circulated and supplied to the desalting chamber and concentrate of the electrodialyzer through this tank.
After 30 minutes, the circulation of the cleaning liquid was stopped and the cleaning liquid was discharged. Thereafter, pure water was circulated to wash the membrane, and the membrane resistance of the anion exchange membrane was measured in the same manner as described above. The result was 2.2 Ω · cm 2 .
上記洗浄後の電気透析装置において、前記調味梅干用の調味液の電気透析を、前記と同様にして実施した結果、通電初期での電流はアシライザー２０型換算で９１．６Ａでありであった。これらの結果から、本発明による洗浄運転を行うことで、脱塩効率は約９５％にまで回復したといえる。 In the electrodialysis apparatus after washing, electrodialysis of the seasoning liquid for seasoning plums was carried out in the same manner as described above. As a result, the current at the initial stage of energization was 91.6 A in terms of the acylizer 20 type. From these results, it can be said that the desalting efficiency recovered to about 95% by performing the washing operation according to the present invention.
実施例２、参考例及び比較例１〜４
洗浄液の組成を表１に示すように変更すること以外は実施例１と同様にして、前記性能が低下したアニオン交換膜を再生する操作を行った。結果を表１に示す。
Example 2, Reference Example and Comparative Examples 1-4
Except for changing the composition of the cleaning solution as shown in Table 1, the same procedure as in Example 1 was carried out to regenerate the anion exchange membrane having the lowered performance. The results are shown in Table 1.
［表１］
[Table 1]
実施例３
（アニオン交換膜の汚染）
アストム社製電気透析装置「マイクロ・アシライザーＳ３型」に、カチオン交換膜としてアストム社製「ネオセプタＣＭＸ−ＳＢ」、アニオン交換膜としてアストム社製「アシプレックスＡ−１９１」を取り付けた。アニオン交換膜は、骨格としてスチレン／ジビニルベンゼン共重合体、イオン交換基として４級ピリジニウム塩基を有している。
Example 3
(Anion exchange membrane contamination)
An Astom electrodialyzer “Micro Acylizer S3 type” was equipped with “Neocepta CMX-SB” manufactured by Astom as a cation exchange membrane and “Aciplex A-191” manufactured by Astom as an anion exchange membrane. The anion exchange membrane has a styrene / divinylbenzene copolymer as a skeleton and a quaternary pyridinium base as an ion exchange group.
この運転に用いたアニオン交換膜を０．５モル／リットルの食塩水に入れ、２５℃、交流１ｋＨｚで膜抵抗を測定したところ１．８６Ω・ｃｍ２であった。 The anion exchange membrane used in this operation was placed in 0.5 mol / liter of saline and the membrane resistance was measured at 25 ° C. and alternating current of 1 kHz to find 1.86 Ω · cm 2 .
この電気透析装置の脱塩液タンクに５００ｐｐｍのドデシルベンゼンスルホン酸ナトリウムを含有する調味梅干用の調味液２．４リットルを仕込んだ。そして、印加電圧１０Ｖ一定で、電流密度５０ｍＡ／ｃｍ２の条件で、塩濃度３重量％まで２４時間脱塩運転をした。運転に要した平均電流はアシライザー２０型換算で２５．１Ａであった。
電気透析装置から処理液を排出し、上記と同様にしてアニオン交換膜の膜抵抗を測定したところ２３．２Ω・ｃｍ２であった。汚染前の電流値９６．４Ａを１００として上記の脱塩時平均電流２５．１Ａを換算すると２６．０であり、また、脱塩効率は２６％にまで低下した。
The desalting solution tank of this electrodialysis apparatus was charged with 2.4 liters of seasoning solution for seasoning plums containing 500 ppm of sodium dodecylbenzenesulfonate. Then, the desalting operation was performed for 24 hours up to a salt concentration of 3% by weight under the condition of a constant applied voltage of 10 V and a current density of 50 mA / cm 2 . The average current required for the operation was 25.1 A in terms of the acylator 20 type.
The treatment solution was discharged from the electrodialyzer, and the membrane resistance of the anion exchange membrane was measured in the same manner as described above, and found to be 23.2 Ω · cm 2 . When the above-mentioned average current 25.1A at the time of desalting was converted with the current value 96.4A before contamination as 100, it was 26.0, and the desalting efficiency was reduced to 26%.
（アニオン交換膜再生用洗浄液の調製）
食塩水と９５体積％エタノールとを適量混合して、エタノール７０体積％及び水３０体積％を含有する溶媒成分中に食塩４重量／体積％、を含有する洗浄液を得た。
(Preparation of cleaning solution for anion exchange membrane regeneration)
An appropriate amount of saline and 95% by volume ethanol was mixed to obtain a cleaning solution containing 4% by weight / volume of sodium chloride in a solvent component containing 70% by volume of ethanol and 30% by volume of water.
この洗浄液を電気透析装置の脱塩液タンクに２００ｃｃ、濃縮液タンクに２００ｃｃ仕込んで装置の洗浄運転を開始した。
３０分経過後装置を止め、洗浄液を排出した。上記と同様にしてアニオン交換膜の膜抵抗を測定したところ２．８Ω・ｃｍ２であった。
200 cc of this washing solution was charged in the desalting solution tank of the electrodialysis apparatus and 200 cc in the concentrated solution tank, and the washing operation of the apparatus was started.
After 30 minutes, the apparatus was stopped and the cleaning liquid was discharged. When the membrane resistance of the anion exchange membrane was measured in the same manner as described above, it was 2.8 Ω · cm 2 .
上記洗浄後の電気透析装置において、前記調味梅干用の調味液の電気透析を、前記と同様にして実施した結果、平均電流はアシライザー２０型換算で７９．３Ａでああった。これらの結果から、本発明による洗浄運転を行うことで、脱塩効率は約８２％にまで回復したといえる。 In the electrodialysis apparatus after washing, electrodialysis of the seasoning liquid for seasoning plum was carried out in the same manner as described above. As a result, the average current was 79.3 A in terms of the Acylizer 20 type. From these results, it can be said that the desalting efficiency recovered to about 82% by performing the washing operation according to the present invention.
１…透析槽、
２…陽極、
３…陰極、
４…濃縮食塩水、
５…希薄食塩水。
1 ... dialysis tank,
2 ... Anode,
3 ... cathode,
4 ... Concentrated saline,
5 ... Dilated saline.
Claims (6)
該脂肪族アルコールが、エタノールであり、
該無機塩が食塩であり、そして
該アニオン交換膜が、チアミンラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ポリオキシエチレンラウリル硫酸ナトリウム及びドデシルナフタレンスルホン酸ナトリウムから成る群から選択される少なくとも一種のアニオン性界面活性剤が吸着して汚染されたものである、アニオン交換膜再生用洗浄液。 Electrodialysis characterized by containing a solvent component composed of 60 to 80% by volume of an aliphatic alcohol and 40 to 20% by volume of water, and a solute component composed of an inorganic salt in a ratio of 2 to 6% by weight with respect to the solvent component. A cleaning liquid for anion exchange membrane regeneration of the apparatus ,
The aliphatic alcohol is ethanol;
The inorganic salt is sodium chloride, and
The anion exchange membrane is contaminated by adsorption of at least one anionic surfactant selected from the group consisting of sodium thiamine lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene lauryl sulfate and sodium dodecyl naphthalene sulfonate. An anion exchange membrane regeneration cleaning liquid.
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