JP5908185B2 - Organic film modification method, modified organic film, and reformer - Google Patents
Organic film modification method, modified organic film, and reformer Download PDFInfo
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- JP5908185B2 JP5908185B2 JP2015542092A JP2015542092A JP5908185B2 JP 5908185 B2 JP5908185 B2 JP 5908185B2 JP 2015542092 A JP2015542092 A JP 2015542092A JP 2015542092 A JP2015542092 A JP 2015542092A JP 5908185 B2 JP5908185 B2 JP 5908185B2
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- 238000002715 modification method Methods 0.000 title claims description 12
- 239000012528 membrane Substances 0.000 claims description 111
- 230000001590 oxidative effect Effects 0.000 claims description 81
- 239000007800 oxidant agent Substances 0.000 claims description 63
- 238000002407 reforming Methods 0.000 claims description 60
- 239000007864 aqueous solution Substances 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 53
- 230000033116 oxidation-reduction process Effects 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 25
- 238000011033 desalting Methods 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 230000004907 flux Effects 0.000 claims description 13
- 238000006057 reforming reaction Methods 0.000 claims description 12
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- 230000010354 integration Effects 0.000 claims description 10
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010979 pH adjustment Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940077239 chlorous acid Drugs 0.000 claims description 3
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 claims description 3
- GEOVEUCEIQCBKH-UHFFFAOYSA-N hypoiodous acid Chemical compound IO GEOVEUCEIQCBKH-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000003637 basic solution Substances 0.000 claims description 2
- DKSMCEUSSQTGBK-UHFFFAOYSA-N bromous acid Chemical compound OBr=O DKSMCEUSSQTGBK-UHFFFAOYSA-N 0.000 claims description 2
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 description 40
- 239000010410 layer Substances 0.000 description 31
- 238000001223 reverse osmosis Methods 0.000 description 27
- 239000000126 substance Substances 0.000 description 23
- 239000013535 sea water Substances 0.000 description 21
- 238000000926 separation method Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000013505 freshwater Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 230000002328 demineralizing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- -1 but recently Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009292 forward osmosis Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000025508 response to water Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Description
本発明は、各種の造水設備や超純水、用水の製造に用いられる有機膜の改質処理方法、改質膜、及び改質処理装置に関する。 The present invention relates to a method for reforming an organic film, a reforming film, and a reforming apparatus used for manufacturing various types of water production equipment, ultrapure water, and water.
海水の淡水化や廃水の浄化処理において、原水からイオン、懸濁物質等の不純物を分離する様々な分離膜が用いられている。分離膜は、断面構造によって、対称膜と非対称膜に分類される。海水淡水化や超純水製造・電力用の用水設備などに用いられる脱塩用逆浸透膜は非対称膜に属する。逆浸透膜の表面はスキン層と呼ばれる緻密な薄い層（機能層）で、その他の大部分はこのスキン層を支える支持層で構成されている。スキン層には孔径０．１〜１ｎｍの通路が存在し、水分子は通過できるが、孔径よりも大きいイオンや分子は阻止される。海水淡水化では、この原理を利用して海水から真水を得ている。 Various separation membranes for separating impurities such as ions and suspended substances from raw water are used in seawater desalination and wastewater purification. Separation membranes are classified into symmetric membranes and asymmetric membranes according to the cross-sectional structure. Desalination reverse osmosis membranes used in seawater desalination, ultrapure water production, and water supply facilities for electric power belong to asymmetric membranes. The surface of the reverse osmosis membrane is a dense thin layer (functional layer) called a skin layer, and most of the other is composed of a support layer that supports the skin layer. The skin layer has a passage having a pore diameter of 0.1 to 1 nm, and water molecules can pass through, but ions and molecules larger than the pore diameter are blocked. In seawater desalination, fresh water is obtained from seawater using this principle.
海水淡水化では塩濃度の高い海水側を加圧する必要がある。海水側と真水側が等圧の場合、拡散の原理に従って、海水側から真水側に移動する水分子の数よりも、真水側から海水側に移動する水分子の数が多くなるためである。また、水分子がスキン層の微細な通路を通過する際に流体力学的な抵抗も受けるため、より多くの真水を得ようとすれば、海水側により高い圧力をかける必要がある。 In seawater desalination, it is necessary to pressurize the seawater side with a high salt concentration. This is because when the seawater side and the fresh water side are isobaric, according to the principle of diffusion, the number of water molecules moving from the fresh water side to the seawater side is larger than the number of water molecules moving from the seawater side to the fresh water side. Further, since water molecules are also subjected to hydrodynamic resistance when passing through fine skin passages, it is necessary to apply higher pressure to the seawater side in order to obtain more fresh water.
逆浸透膜の素材として、酢酸セルロース、芳香族ポリアミド、ポリビニルアルコール、ポリスルホンなどが、単独でもしくは複合材として用いられている。酢酸セルロースは、最初に逆浸透膜用に開発された素材であるが、最近では操作圧の低い芳香族ポリアミドが海水淡水化や超純水製造・電力用の用水設備など、多様な分野で使用されている。 As a material for the reverse osmosis membrane, cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone and the like are used alone or as a composite material. Cellulose acetate was first developed for reverse osmosis membranes, but recently, aromatic polyamides with low operating pressure have been used in various fields such as seawater desalination, ultrapure water production, and water facilities for electric power. Has been.
逆浸透膜を長時間使用すると、微生物や有機物、難溶性無機物の付着によってスキン層が目詰まりし、膜を透過する水の量（透過流束）が減少する。操作圧を高めることによって透過流束は維持できるが、動力コストが増えてしまう。このため、逆浸透膜に有機物が付着しないよう液中に極少量の次亜塩素酸ナトリウムを混入しておくか、定期的に次亜塩素酸ナトリウム水溶液で洗浄する必要がある。しかしながら、次亜塩素酸ナトリウムには芳香族ポリアミドを分解する性質があり、逆浸透膜の洗浄を繰り返すと、スキン層の微小流路が拡がり、脱塩性能が低下してしまう。 When the reverse osmosis membrane is used for a long time, the skin layer is clogged due to adhesion of microorganisms, organic substances, and hardly soluble inorganic substances, and the amount of water permeating through the membrane (permeation flux) is reduced. Although the permeation flux can be maintained by increasing the operating pressure, the power cost increases. For this reason, it is necessary to mix a very small amount of sodium hypochlorite in the liquid so that organic substances do not adhere to the reverse osmosis membrane or to periodically wash with a sodium hypochlorite aqueous solution. However, sodium hypochlorite has the property of decomposing aromatic polyamide, and repeated washing of the reverse osmosis membrane expands the fine flow path of the skin layer and lowers the desalting performance.
海水淡水化では、海水に含まれる約３．５％の塩分濃度を少なくとも０．０５％以下まで落とす必要があり、また溶解性蒸発残留物の基準値も達成するなど高い性能が求められ、このレベルより低くなると海水淡水化用の逆浸透膜として利用できなくなり、定期的な交換は避けられない。気候変動の目に見える影響で深刻化する水不足に対応し、飲料水を確保する方法として、海水淡水化設備は世界中で増加傾向にあり、逆浸透膜は世界中で大量に使われているため、ランニングコストや廃棄物の問題は深刻化している。 In seawater desalination, it is necessary to reduce the salt concentration of about 3.5% contained in seawater to at least 0.05% or less, and high performance is required such as achieving the standard value of soluble evaporation residue. If it becomes lower than the level, it cannot be used as a reverse osmosis membrane for seawater desalination, and regular replacement is inevitable. Seawater desalination facilities are on the rise worldwide, and reverse osmosis membranes are being used in large quantities around the world as a way to secure drinking water in response to water shortages caused by the visible impact of climate change. Therefore, the problem of running cost and waste is getting worse.
海水淡水化に利用できなくなった逆浸透膜は、その利用を海水淡水化用に限定すると、濾過性能が低下し、用水の基準値を満たさないが、適正な再生処理を施せば、他の用途へ転用することができる場合がある。例えば、ナノフィルターと呼ばれる利用法では、分子量数百〜数千までの分子を分離できればよい。ウルトラフィルターと呼ばれる利用法では、分子量数千〜数万までの分子や固形物を分離できればよい。さらに、マイクロフィルターと呼ばれる利用法では直径数ミリまでの固形物を分離できればよい。 Reverse osmosis membranes that can no longer be used for seawater desalination will have reduced filtration performance if they are limited to seawater desalination, and will not meet the standard values for water. May be diverted. For example, in a utilization method called a nanofilter, it is sufficient that molecules having a molecular weight of several hundred to several thousand can be separated. In an application method called an ultra filter, it is only necessary to separate molecules and solids having molecular weights of several thousand to several tens of thousands. Furthermore, the utilization method called a microfilter should just be able to isolate | separate the solid substance to a diameter of several millimeters.
特許文献１では、ボイラー供給水の脱塩用として耐用期間が切れた逆浸透膜をアルカリ溶液、もしくはｐＨの高い海水に接触させることにより部分的に加水分解して多孔質の膜を作製し、油分離装置として利用する技術が記載されている。 In Patent Document 1, a reverse osmosis membrane expired for desalination of boiler feed water is partially hydrolyzed by contacting it with an alkaline solution or seawater having a high pH to produce a porous membrane, The technology used as an oil separator is described.
特許文献２では、スキン層を酸化剤（塩素、又は次亜塩素、オゾン、第４級アンモニア塩等）で酸化処理する事により、分離膜のスキン層を除去する逆浸透膜の改質処理技術が提案されている。 In Patent Document 2, a reverse osmosis membrane modification technique for removing a skin layer of a separation membrane by oxidizing the skin layer with an oxidizing agent (chlorine, hypochlorous acid, ozone, quaternary ammonia salt, etc.). Has been proposed.
特許文献３では、酸化剤の性状を２５０〜５００ｍＶの酸化還元電位を示すもので規定し、９０％以上の脱塩率を保持するように酸化・親水化処理することで透水性と耐汚染性を向上するとの方法が記載されている。 In Patent Document 3, the nature of the oxidizing agent is defined by a redox potential of 250 to 500 mV, and water permeability and contamination resistance are obtained by oxidizing and hydrophilizing so as to maintain a desalination rate of 90% or more. The method of improving is described.
特許文献４、５では、有機膜のうち、酢酸セルロース膜において、アルカリ水溶液・アルコールに接触させることにより、分離膜のＮａＣｌの脱塩率（阻止率）を低下させて、中水生成用分離膜を得る事が記載されている。 In Patent Documents 4 and 5, among the organic membranes, the cellulose acetate membrane is brought into contact with an alkaline aqueous solution / alcohol to reduce the NaCl salt rejection (rejection rate) of the separation membrane. It is described that you get.
ある目的で使用されていた有機分離膜を他用途で再利用する場合、新しい利用目的に合わせて、脱塩率や透過流束などの特性を再調整することになる。例えば、逆浸透膜をナノフィルターとして利用する場合、改質処理によって孔径を数ｎｍ程度拡げることになるが、平均孔径が目標値から外れると用を成さないうえ、孔径分布の幅の拡がりも分別能力の低下と見做される場合がある。また、一般的に逆浸透膜のスキン層の厚みは数百ｎｍ程度で、化学的に削る量には上限があり、過剰に改質処理するとスキン層が消失して支持層が露出してしまう。スキン層と支持層とでは孔径が桁で違うので、支持層が露出すると脱塩率は一気に下がってしまう。また、逆浸透膜の製造法にも依存するが、スキン層内の孔径や孔密度に関して深さ方向に傾斜分布（外表面は非常に緻密だが、支持層に近づくにつれて粗大化していく分布）していると、スキン層を削るほど脱塩率が増えていくが、分離サイズの目標が非常に厳格に定められている場合は、スキン層削り量の許容誤差も厳密に設定されている。 When an organic separation membrane that has been used for a certain purpose is reused for other purposes, characteristics such as desalination rate and permeation flux are readjusted according to the new purpose of use. For example, when a reverse osmosis membrane is used as a nanofilter, the pore size is expanded by several nanometers by the modification treatment. However, if the average pore size deviates from the target value, it will not be used, and the width of the pore size distribution may be expanded. It may be regarded as a decrease in sorting ability. In general, the thickness of the skin layer of the reverse osmosis membrane is about several hundreds of nanometers, and there is an upper limit to the amount of chemical scraping, and if it is excessively modified, the skin layer disappears and the support layer is exposed. . Since the skin layer and the support layer have different pore sizes on the order of magnitude, when the support layer is exposed, the desalination rate drops at a stretch. Although it depends on the manufacturing method of the reverse osmosis membrane, the pore size and density in the skin layer are inclined in the depth direction (the outer surface is very dense, but becomes coarser as it approaches the support layer). In this case, the desalination rate increases as the skin layer is shaved, but when the target of the separation size is set very strictly, the tolerance of the skin layer shaving amount is also strictly set.
ここで、従来技術として知られている逆浸透膜の次亜塩素酸ナトリウム洗浄は脱塩率を低下させずに有機物汚染を除去することを目標としているので、処理条件も要求される制御性も大きく異なっている。この場合は、スキン層を削らないことが理想になっている。ただし、改質対象になっている分離膜は、何処かで使用され汚れが付着していることを前提にしているので、前処理として上記の汚染除去を実施する場合もある。しかし、これは脱塩率そのものを調整する改質工程とは別物である。 Here, sodium hypochlorite cleaning of a reverse osmosis membrane known as a prior art is aimed at removing organic contaminants without lowering the desalination rate, so that the processing conditions and the controllability required are also required. It is very different. In this case, it is ideal not to cut the skin layer. However, since the separation membrane to be reformed is premised on being used somewhere and having dirt attached thereto, the above-described decontamination may be performed as a pretreatment. However, this is different from the reforming step for adjusting the desalination rate itself.
一方、有機分離膜を他用途で再利用するために改質処理を行う場合、分離サイズが目標値に達するように、スキン層の削り量が一定の範囲になるようにする必要がある。しかしながら、有機分離膜の改質処理は、その条件を設定し難く、目標とする分離サイズの有機膜を製造することが難しいという問題があった。 On the other hand, when the reforming process is performed in order to reuse the organic separation membrane for other purposes, it is necessary to make the amount of cut of the skin layer within a certain range so that the separation size reaches the target value. However, the modification process of the organic separation membrane has a problem that it is difficult to set the conditions, and it is difficult to produce an organic membrane having a target separation size.
したがって、本発明の目的は、有機分離膜を他用途で再利用するために再生する際、目標とする脱塩率等を達成するように改質処理液の管理項目を定め、この管理項目を測定するための手段を設けて、測定値から改質反応の進行度を算出し改質処理終了の時機を決めることができるようにした有機膜の改質方法、該方法によって得られる改質膜、及び該方法を実施するための改質処理装置を提供することにある。 Therefore, the object of the present invention is to define the management items of the reforming treatment liquid so as to achieve the target desalination rate, etc. when regenerating the organic separation membrane for reuse in other applications. A method for modifying an organic film, provided with a means for measuring, so that the progress of the reforming reaction can be calculated from the measured value to determine the timing of the end of the reforming process, and the reformed film obtained by the method And a reforming apparatus for carrying out the method.
上記目的を達成するため、本発明の有機膜の改質方法は、脱塩機能を有する有機膜を酸化性水溶液に接触させることにより有機膜の脱塩性能、又は/及び、透過性能を変更する改質処理方法において、前記酸化性水溶液の酸化還元電位（Ｖ）を測定し、酸化還元電位と酸化剤濃度の乗算値（Ｖ・ｍｏｌ／L）を時間積分して積算乗算値（Ｖ・ｍｏｌ・ｈｒ／L）を算出し、積算乗算値が所定値に達したことを検知して、改質処理を終了させることを特徴とする。 In order to achieve the above object, the organic membrane modification method of the present invention changes the desalination performance and / or permeation performance of an organic membrane by bringing the organic membrane having a desalting function into contact with an oxidizing aqueous solution. In the reforming treatment method, the oxidation-reduction potential (V) of the oxidizing aqueous solution is measured, and the multiplication value (V · mol / L) of the oxidation-reduction potential and the oxidant concentration is integrated over time to obtain an integrated multiplication value (V · mol). Hr / L) is calculated, and it is detected that the integrated multiplication value has reached a predetermined value, and the reforming process is terminated.
本発明の有機膜の改質方法においては、酸化還元電位（Ｖ）と酸化剤濃度（ｍｏｌ／L）の時間積分値が０．０３〜３Ｖ・ｍｏｌ・ｈｒ／Lの範囲から選ばれる値に達した時に前記改質処理を終了させることが好ましい。 In the organic film modification method of the present invention, the time integration value of the oxidation-reduction potential (V) and the oxidant concentration (mol / L) is selected from the range of 0.03 to 3 V · mol · hr / L. Preferably, the reforming process is terminated when it reaches.
本発明の有機膜の改質方法によれば、前記酸化性水溶液の酸化還元電位を一定に保ち、下記の式（１）によって求められる処理時間から、改質処理の終了時刻を決定することが好ましい。 According to the organic film modification method of the present invention, the oxidation-reduction potential of the oxidizing aqueous solution is kept constant, and the end time of the modification treatment can be determined from the treatment time obtained by the following equation (1). preferable.
本発明の有機膜の改質方法によれば、有機膜をアミド系樹脂とし、水素イオン濃度をｐＨ６〜１３とし、液温を１０〜４０℃とし、前記酸化剤を次亜塩素酸として、改質処理する場合、前記反応速度定数として２０〜１５０％・L／Ｖ・ｍｏｌ・ｈｒを前記の式（１）に代入して、改質処理の終了時刻を決定することが好ましい。 According to the method for modifying an organic film of the present invention, the organic film is an amide resin, the hydrogen ion concentration is pH 6 to 13, the liquid temperature is 10 to 40 ° C., and the oxidizing agent is hypochlorous acid. In the case of quality treatment, it is preferable to determine the end time of the reforming treatment by substituting 20 to 150% · L / V · mol · hr as the reaction rate constant into the formula (1).
本発明の有機膜の改質方法においては、前記有機膜を、オゾン、過酸化水素、塩素、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸、臭素、次亜臭素酸、亜臭素酸、臭素酸、過臭素酸、ヨウ素、次亜ヨウ素酸、亜ヨウ素酸、ヨウ素酸、過ヨウ素酸、過マンガン酸、重クロム酸から選ばれた酸化剤もしくは界面活性剤のうちから１つ、又は２つ以上を含む水溶液に接触させることが好ましい。 In the organic film modification method of the present invention, the organic film is made of ozone, hydrogen peroxide, chlorine, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, bromine, hypochlorous acid, bromine. One of an oxidizing agent or surfactant selected from acids, bromic acid, perbromic acid, iodine, hypoiodous acid, iodic acid, iodic acid, periodic acid, permanganic acid, dichromic acid, Or it is preferable to contact the aqueous solution containing 2 or more.
本発明の有機膜の改質方法においては、塩基性水溶液、酸性水溶液、５０ｐｐｍ以下の低濃度次亜塩素酸水溶液のうちいずれか一つ、又は二種以上の組み合わせで洗浄した後、前記改質処理を行い、最後に水洗することが好ましい。 In the method for modifying an organic film of the present invention, after the washing with any one of a basic aqueous solution, an acidic aqueous solution, a low concentration hypochlorous acid aqueous solution of 50 ppm or less, or a combination of two or more, the modification is performed. It is preferable to perform the treatment and finally wash with water.
本発明の有機膜の１つは、前記改質方法によって得られ、透過流束が５〜７０ｍ/ｄａｙであることを特徴とする。 One of the organic membranes of the present invention is obtained by the above-described modification method, and has a permeation flux of 5 to 70 m / day.
本発明の有機膜のもう１つは、前記改質方法によって得られ、中心線平均粗さが１０〜２００ｎｍであることを特徴とする。 Another organic film of the present invention is obtained by the above-described modification method, and has a center line average roughness of 10 to 200 nm.
本発明の有機膜の改質装置は、脱塩機能を有する有機膜を酸化性水溶液に接触させて脱塩性能、又は/及び、透過性能を変更するための改質処理装置において、前記酸化性水溶液の酸化還元電位を測定するための酸化還元電位計を備え、酸化還元電位（Ｖ）と酸化剤濃度（ｍｏｌ／L）の乗算値（Ｖ・ｍｏｌ／L）を算出し、該乗算値を時間積分した積算乗算値（Ｖ・ｍｏｌ・ｈｒ／L）によって改質反応の進行度を解析し、改質処理を終了させる制御手段を有することを特徴とする。 The organic membrane reforming device of the present invention is the reforming treatment device for changing the desalting performance and / or permeation performance by bringing an organic membrane having a desalting function into contact with an oxidizing aqueous solution, An oxidation-reduction potentiometer for measuring the oxidation-reduction potential of an aqueous solution is calculated, a multiplication value (V · mol / L) of the oxidation-reduction potential (V) and the oxidant concentration (mol / L) is calculated, and the multiplication value is calculated. It has a control means for analyzing the progress of the reforming reaction based on the integrated multiplication value (V · mol · hr / L) integrated over time and terminating the reforming process.
本発明の有機膜改質装置は、更に、水素イオン濃度計と、温度計と、前記酸化剤の添加装置と、ｐＨ調整装置と、温度調整装置とを備え、前記酸化還元電位計によって求められる酸化還元電位が一定になるように、ｐＨ調整装置及び温度調整装置によって水素イオン濃度及び前記温度を調整し、前記の式（１）から求められる処理時間によって、改質処理の終了時刻を決定する手段を有することが好ましい。 The organic membrane reforming apparatus of the present invention further includes a hydrogen ion concentration meter, a thermometer, the oxidant addition device, a pH adjustment device, and a temperature adjustment device, and is obtained by the oxidation-reduction potentiometer. The hydrogen ion concentration and the temperature are adjusted by the pH adjusting device and the temperature adjusting device so that the oxidation-reduction potential becomes constant, and the end time of the reforming process is determined by the processing time obtained from the above equation (1). It is preferable to have a means.
本発明の有機膜改質装置の１つにおいては、有機膜に酸化性水溶液を接触させる手段が、液相撹拌式かつ回分式の装置とすることが好ましい。 In one of the organic film reforming apparatuses of the present invention, it is preferable that the means for bringing the oxidizing aqueous solution into contact with the organic film is a liquid phase agitation type and batch type apparatus.
あるいは、本発明の有機膜改質装置のもう１つにおいては、有機膜に酸化性水溶液を接触させる手段が、液循環式かつ流通式の装置とすることが好ましい。 Alternatively, in another organic film reforming apparatus of the present invention, it is preferable that the means for bringing the oxidizing aqueous solution into contact with the organic film is a liquid circulation type and circulation type apparatus.
本発明の有機膜の改質方法によれば、有機膜の脱塩性能、又は/及び、透過性能を変更する改質処理方法において、前記酸化性水溶液の酸化還元電位（Ｖ）を測定し、酸化還元電位と酸化剤濃度の乗算値（Ｖ・ｍｏｌ／L）を時間積分して積算乗算値（Ｖ・ｍｏｌ・ｈｒ／L）を算出し、積算乗算値が所定値に達したことを検知して、改質処理を終了させることにより、スキン層等の削り量を一定にして、所望の特性を有する有機膜を安定して製造することが可能となる。 According to the organic membrane modification method of the present invention, in the modification treatment method for changing the desalting performance or / and permeation performance of the organic membrane, the oxidation-reduction potential (V) of the oxidizing aqueous solution is measured, The integrated value (V · mol · hr / L) is calculated by time integration of the product (V · mol / L) of the oxidation-reduction potential and the oxidant concentration, and it is detected that the integrated product has reached the specified value. Then, by finishing the reforming process, it becomes possible to stably manufacture an organic film having desired characteristics while keeping the amount of shaving of the skin layer or the like constant.
本発明の有機膜の１つは、上記改質方法によって、透過流束が５〜７０ｍ/ｄａｙに調整されているので、膜ろ過のランニングコスト低減が可能な有機膜を提供することができる。 Since one of the organic membranes of the present invention has a permeation flux adjusted to 5 to 70 m / day by the above modification method, an organic membrane capable of reducing the running cost of membrane filtration can be provided.
本発明の有機膜のもう一つは、上記改質方法によって、中心線平均粗さが１０〜２００ｎｍになるように調整されているので、原水に含まれる難溶性成分や高分子の溶質、コロイド、微小固形物などが膜に沈着し難いという効果をもたらすことができる。 Another of the organic films of the present invention is adjusted by the above modification method so that the center line average roughness is 10 to 200 nm. Therefore, the hardly soluble component contained in the raw water, the solute of the polymer, the colloid In addition, it is possible to bring about an effect that minute solids are hardly deposited on the film.
本発明の有機膜の改質装置によれば、酸化性水溶液の酸化還元電位を測定するための酸化還元電位計を備え、前記酸化還元電位計によって測定された酸化還元電位（Ｖ）と、酸化剤濃度（ｍｏｌ／L）の乗算値（Ｖ・ｍｏｌ／L）を算出し、該乗算値を時間積分した積算乗算値（Ｖ・ｍｏｌ・ｈｒ／L）によって改質反応の進行度を解析し、改質処理を終了させる制御手段を有するので、スキン層等の削り量を一定にして、所望の特性を有する有機膜を安定して製造することが可能となる。 According to the organic membrane reforming apparatus of the present invention, a redox potential meter for measuring the redox potential of the oxidizing aqueous solution is provided, and the redox potential (V) measured by the redox potential meter and the oxidation potential are measured. Multiplying agent concentration (mol / L) (V · mol / L) is calculated, and the progress of the reforming reaction is analyzed by the integrated multiplication value (V · mol · hr / L) obtained by time integration of the multiplication value. Since the control means for terminating the reforming process is provided, it becomes possible to stably produce an organic film having desired characteristics by keeping the amount of shaving such as a skin layer constant.
本発明は、脱塩機能を有する有機膜を酸化性水溶液に接触させることにより該有機膜の脱塩性能、又は/及び、透過性能を変更する改質処理方法において、前記酸化性水溶液の酸化還元電位（Ｖ）を測定し、該酸化還元電位と該酸化剤濃度の乗算値（Ｖ・ｍｏｌ／L）を時間積分して積算乗算値（Ｖ・ｍｏｌ・ｈｒ／L）を算出し、該積算乗算値が所定値に達したことを検知して、改質処理を終了させる有機膜の改質方法と、この改質方法を実施するための装置を提供する。 The present invention provides an oxidation-reduction of the oxidizing aqueous solution in a modification treatment method for changing the desalting performance or / and permeation performance of the organic membrane by bringing the organic membrane having a desalting function into contact with the oxidizing aqueous solution. The potential (V) is measured, and the multiplication value (V · mol / L) of the oxidation-reduction potential and the oxidant concentration is integrated over time to calculate an integration multiplication value (V · mol · hr / L). Provided are an organic film reforming method for detecting that a multiplication value has reached a predetermined value and terminating the reforming process, and an apparatus for performing the reforming method.
ここで、脱塩機能を有する有機膜とは、例えば、酢酸セルロース、又は芳香族ポリアミド、ポリビニルアルコール、ポリスルホンなどの材料からなり、スキン層と呼ばれる緻密な薄い層とこれを支える支持層から構成され、水分子は通過するが、孔径よりも大きいイオンや分子は透過を阻止する機能を備えた有機膜のことを意味する。このような有機膜は、例えば、海水淡水化や浄水器などに用いられている。また、その分離機能に注目して、一般には逆浸透膜、正浸透膜あるいはナノフィルター膜などと呼ばれている。本発明では、これらの有機膜のいずれにも適用することができる。 Here, the organic membrane having a desalting function is made of, for example, a material such as cellulose acetate, aromatic polyamide, polyvinyl alcohol, or polysulfone, and is composed of a dense thin layer called a skin layer and a supporting layer that supports the layer. This means an organic film having a function of blocking water permeation of ions and molecules larger than the pore diameter, though water molecules pass through. Such organic membranes are used, for example, for seawater desalination and water purifiers. Further, paying attention to the separation function, it is generally called a reverse osmosis membrane, a forward osmosis membrane or a nanofilter membrane. The present invention can be applied to any of these organic films.
上記有機膜の形態は、特に限定されないが、例えば、中空糸膜形状、又はスパイラル膜形状、チューブラー膜形状に成型されたものが好ましく使用される。中空糸膜とは、直径３〜７ｍｍ程度の太さで中が空胴の糸状に成型された膜のことである。また、スパイラル膜とは、１枚のろ過膜を、強度を保つための不織布などと重ね合わせ、２つ折りにして袋状に接着した後、縦一直線に切れ目を入れた集水管で袋の口を挟み、これを芯にしてロールケーキ状に巻いた膜のことである。また、チューブラー膜とは、中空円筒状で中空糸膜より太い、直径が最大数センチメートルの膜のことである。 The form of the organic membrane is not particularly limited, but, for example, one formed into a hollow fiber membrane shape, a spiral membrane shape, or a tubular membrane shape is preferably used. The hollow fiber membrane is a membrane having a diameter of about 3 to 7 mm and molded into a hollow thread. A spiral membrane is a sheet of filtration membrane that is laminated with a nonwoven fabric to maintain strength, folded in two, glued in a bag shape, and then the mouth of the bag is opened with a water collecting pipe that has a vertical cut. It is a film that is sandwiched and rolled into a roll cake around this core. The tubular membrane is a hollow cylindrical membrane that is thicker than the hollow fiber membrane and has a maximum diameter of several centimeters.
本発明において、有機膜の性能は、例えば、脱塩率と透過流束によって評価することができる。 In the present invention, the performance of the organic membrane can be evaluated by, for example, the desalting rate and the permeation flux.
ここで、脱塩率は、有機膜による塩の分離機能に関わる指標のことで、下記式（２）で定義される。 Here, the desalting rate is an index related to the function of separating a salt by an organic membrane, and is defined by the following formula (2).
また、透過流束は、有機膜を透過する単位面積あたりの流量のことで、下記式（３）で定義される。 The permeation flux is a flow rate per unit area that permeates the organic film, and is defined by the following formula (3).
本発明で用いる酸化性水溶液としては、上記有機膜を化学反応によって削ることが可能な酸化剤を含有する水溶液が用いられる。該酸化剤としては、例えば、オゾン、過酸化水素、塩素、次亜塩素酸、亜塩素酸、塩素酸、過塩素酸、臭素、次亜臭素酸、亜臭素酸、臭素酸、過臭素酸、ヨウ素、次亜ヨウ素酸、亜ヨウ素酸、ヨウ素酸、過ヨウ素酸、過マンガン酸、重クロム酸から選ばれた酸化剤、もしくは界面活性剤のうちから１つ、又は２つ以上が好ましく用いられる。 As the oxidizing aqueous solution used in the present invention, an aqueous solution containing an oxidizing agent capable of shaving the organic film by a chemical reaction is used. Examples of the oxidizing agent include ozone, hydrogen peroxide, chlorine, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, bromine, hypobromous acid, bromous acid, bromic acid, perbromic acid, One or two or more of oxidizing agents or surfactants selected from iodine, hypoiodous acid, iodic acid, iodic acid, periodic acid, permanganic acid, and dichromic acid are preferably used. .
本発明では、酸化還元電位を測定し、酸化性水溶液の酸化力を表す指標として用いる。酸化還元電位は、酸化反応に関わる３要素（酸化剤の種類、水素イオン濃度、温度）を、１つに纏めた指標になっており、後述する改質処理時間の計算が容易になる。通常、酸化還元電位は、作用電極と参照電極が複合した１体型のセンサと電位差計からなる、市販の酸化還元電位測定器によって測定でき、水素の標準電極電位０Ｖとする絶対値がデジタルで表示される。本発明の実施例では、東亜ＤＫＫ製ＨＭ−３１Ｐを使用した。 In the present invention, the oxidation-reduction potential is measured and used as an index representing the oxidizing power of the oxidizing aqueous solution. The oxidation-reduction potential is an index in which three elements (kind of oxidant, hydrogen ion concentration, temperature) related to the oxidation reaction are combined into one, and the calculation of the reforming treatment time described later becomes easy. Usually, the oxidation-reduction potential can be measured with a commercially available oxidation-reduction potential measuring device consisting of a single sensor with a composite working electrode and reference electrode and a potentiometer, and the absolute value of hydrogen as a standard electrode potential is displayed digitally. Is done. In the examples of the present invention, HM-31P manufactured by Toa DKK was used.
本発明における酸化剤濃度（ｍｏｌ／Ｌ）とは、溶液１Ｌ当たりの酸化剤の原子、分子、イオンのモル数から求められるモル濃度のことである。 The oxidizing agent concentration (mol / L) in the present invention is a molar concentration determined from the number of moles of atoms, molecules, and ions of the oxidizing agent per 1 L of the solution.
本発明では、酸化剤の濃度として、改質処理を始める前の、当初の調整した濃度を適用することができる。また、改質処理中に、定期的に処理槽から酸化性水溶液をサンプリングし、例えば、滴定装置、高速液体クロマトグラフ、ＩＣＰ発光分析等によって酸化剤の濃度を測定して、経時的に測定された濃度を適用することもできる。 In the present invention, the initially adjusted concentration before the reforming treatment can be applied as the concentration of the oxidizing agent. In addition, during the reforming treatment, the oxidizing aqueous solution is periodically sampled from the treatment tank, and the concentration of the oxidizing agent is measured over time by, for example, titration device, high performance liquid chromatograph, ICP emission analysis, etc. Different concentrations can also be applied.
本発明では、改質処理の終了時刻を正確に求めるため、酸化還元電位の測定を自動化し、高頻度で測定することが好ましい。測定した酸化還元電位と、酸化剤濃度の乗算値を時間積分し、積算乗算値が所定値に達した時に、酸化性水溶液を純水に置換することで改質処理を終了させる。ここで、所定の積算乗算値とは、有機膜が改質処理によって目標とする脱塩率になるまでに要する積算乗算値のことを意味し、予備試験によってその値を決めておく必要がある。酸化還元電位と酸化剤濃度の積算乗算値は改質反応の進行度に比例する。改質処理中に酸化剤が消費されることにより、酸化還元電位や酸化剤濃度が低下し、改質反応が遅くなったとしても、その影響が酸化還元電位と酸化剤濃度の積算乗算値に反映されるため、処理時間決定において問題は生じない。 In the present invention, in order to accurately determine the end time of the reforming treatment, it is preferable to automate the measurement of the oxidation-reduction potential and measure it at high frequency. The measured oxidation-reduction potential and the multiplied value of the oxidant concentration are integrated over time, and when the integrated multiplied value reaches a predetermined value, the reforming process is terminated by replacing the oxidizing aqueous solution with pure water. Here, the predetermined integration multiplication value means an integration multiplication value required until the organic membrane reaches a target desalination rate by the reforming treatment, and it is necessary to determine the value by a preliminary test. . The integrated multiplication value of the oxidation-reduction potential and the oxidant concentration is proportional to the progress of the reforming reaction. Even if the oxidant is consumed during the reforming process, the oxidation-reduction potential and the oxidant concentration are lowered and the reforming reaction is slowed down. Therefore, there is no problem in determining the processing time.
本発明においては、酸化還元電位（Ｖ）と酸化剤濃度（ｍｏｌ／L）の時間積分値が、０．０３〜３Ｖ・ｍｏｌ・ｈｒ／Lの範囲から選ばれる値に達した時に改質処理を終了させることが好ましい。上記時間積分値が０．０３Ｖ・ｍｏｌ・ｈｒ／L未満では、改質が不十分となり、所望の特性が得にくくなる。一方、上記時間積分値が３Ｖ・ｍｏｌ・ｈｒ／Lを超えると、一般に厚さ数百ｎｍ程度であるスキン層が、急速に消失して支持層が露出しやすくなり、脱塩率が一気に低下してしまうので、脱塩率や透過率を制御しにくくなる。 In the present invention, when the time integration value of the oxidation-reduction potential (V) and the oxidant concentration (mol / L) reaches a value selected from the range of 0.03 to 3 V · mol · hr / L, the reforming treatment is performed. Is preferably terminated. If the time integral value is less than 0.03 V · mol · hr / L, the modification becomes insufficient and it becomes difficult to obtain desired characteristics. On the other hand, when the time integration value exceeds 3 V · mol · hr / L, the skin layer, which is generally about several hundreds of nanometers thick, disappears rapidly and the support layer is easily exposed, and the desalination rate decreases rapidly. Therefore, it becomes difficult to control the desalting rate and the transmittance.
本発明では、定期的に酸化還元電位を測定することにより、フィードバック制御により、酸化還元電位を一定に保つこともできる。この場合、目標脱塩率を達成するために要する処理時間は、前記式（１）で算出できる。前記式（１）の反応速度定数は予備試験で求めておく。脱塩率の低下量は、酸化還元電位×酸化剤濃度×処理時間に比例するので、直線プロットの傾きが反応速度定数になる。 In the present invention, the redox potential can be kept constant by feedback control by periodically measuring the redox potential. In this case, the processing time required to achieve the target desalination rate can be calculated by the equation (1). The reaction rate constant of the formula (1) is obtained in a preliminary test. The amount of decrease in the desalting rate is proportional to redox potential × oxidant concentration × treatment time, so the slope of the linear plot becomes the reaction rate constant.
この場合、酸化還元電位は、水素イオン濃度及び温度によって変動するため、水素イオン濃度計と、温度計と、ｐＨ調整装置と、温度調整装置とを設け、酸化還元電位が一定になるように、ｐＨ調整装置及び温度調整装置によって水素イオン濃度及び前記温度を調整することが好ましい。 In this case, since the oxidation-reduction potential varies depending on the hydrogen ion concentration and temperature, a hydrogen ion concentration meter, a thermometer, a pH adjustment device, and a temperature adjustment device are provided so that the oxidation-reduction potential becomes constant. It is preferable to adjust the hydrogen ion concentration and the temperature with a pH adjusting device and a temperature adjusting device.
また、本発明の好ましい態様においては、改質処理中に、定期的に処理槽から酸化性水溶液をサンプリングし、例えば、滴定装置、高速液体クロマトグラフ、ＩＣＰ発光分析等によって酸化剤の濃度を測定すると共に、酸化剤の添加装置を設け、前記酸化剤濃度が一定になるように酸化剤を添加するようにしてもよい。この態様によれば、酸化還元電位だけでなく、酸化剤濃度も正確に一定に保つことが可能となるので、より正確な改質処理を行うことができる。 In a preferred embodiment of the present invention, an oxidizing aqueous solution is periodically sampled from the treatment tank during the reforming treatment, and the concentration of the oxidizing agent is measured by, for example, a titration apparatus, a high performance liquid chromatograph, an ICP emission analysis or the like. In addition, an oxidant addition device may be provided to add the oxidant so that the oxidant concentration becomes constant. According to this aspect, since not only the oxidation-reduction potential but also the oxidant concentration can be kept accurately constant, a more accurate reforming process can be performed.
本発明では、改質処理に先立ち、有機物などの汚染を除去するために、前洗浄を行うことが望ましい。前洗浄液には、塩酸などの酸性溶液や、水酸化ナトリウムなどの塩基性溶液、濃度５０ｐｐｍ以下の次亜塩素酸ナトリウム水溶液が適する。前洗浄の段階で有機膜が削れると、改質処理時間を正確に決定できなくなるので、脱塩率を変化させない前洗浄条件を選択する。また、改質処理の後は、有機膜表面に酸化剤が残留しないように、水洗する必要がある。水洗が足りないと、酸化反応が止まらず、目標よりも低い脱塩率の有機膜になってしまう。 In the present invention, it is desirable to perform pre-cleaning prior to the reforming treatment in order to remove contamination such as organic matter. As the pre-cleaning solution, an acidic solution such as hydrochloric acid, a basic solution such as sodium hydroxide, or a sodium hypochlorite aqueous solution having a concentration of 50 ppm or less is suitable. If the organic film is scraped off at the pre-cleaning stage, the modification treatment time cannot be determined accurately. Therefore, pre-cleaning conditions that do not change the desalting rate are selected. Further, after the modification treatment, it is necessary to wash with water so that no oxidizing agent remains on the surface of the organic film. Insufficient water washing will not stop the oxidation reaction, resulting in an organic membrane with a lower desalination rate than the target.
本発明は、有機膜に存在する分子通路の径を拡げ、透過流束を増大させることができる。一般に逆浸透膜の透過流束は２ｍ／ｄａｙ以下であるが、０．０３〜３Ｖ・ｍｏｌ・ｈｒ／Lの範囲で改質処理して、透過流束５〜７０ｍ／ｄａｙの改質有機膜を得ることができる。この改質処理によって、海水淡水化で使用された逆浸透膜を、中水処理膜として再利用することができる。 The present invention can increase the permeation flux by expanding the diameter of the molecular passage existing in the organic film. Generally, the permeation flux of a reverse osmosis membrane is 2 m / day or less, but a modified organic membrane having a permeation flux of 5 to 70 m / day is modified in the range of 0.03 to 3 V · mol · hr / L. Can be obtained. By this reforming treatment, the reverse osmosis membrane used in seawater desalination can be reused as a middle water treatment membrane.
本発明の改質処理によって有機膜の表面が削れ、中心線平均粗さ１０〜２００ｎｍの改質有機膜を得ることができる。ここで、中心線平均粗さは、原子間力顕微鏡等の装置で測定した粗さ曲線を中心線から折り返し、その粗さ曲線と中心線によって得られた面積を測定区間の長さで割った値として定義する。 The surface of the organic film is shaved by the modification treatment of the present invention, and a modified organic film having a center line average roughness of 10 to 200 nm can be obtained. Here, the centerline average roughness is the roughness curve measured with an apparatus such as an atomic force microscope folded from the centerline, and the area obtained by the roughness curve and the centerline is divided by the length of the measurement section. Define as a value.
前記の有機膜の改質方法によれば、改質処理による逆浸透膜の孔径増加を精密に制御することができるので、イオン種によって水和イオン半径が異なることを利用して、イオン種の分別又は組成比の制御が可能になる。例えば、海水淡水化膜を改質して、マグネシウムやカルシウムなどの２価イオンを透過させない分離膜として再利用することができる。更に、逆浸透膜の孔径を拡げれば、分子量数百〜数千までの分子を分離するナノフィルター、又は分子量数千〜数万までの分子や固形物を分離するウルトラフィルターとして再利用することができる。 According to the organic membrane modification method described above, the increase in the pore size of the reverse osmosis membrane due to the modification treatment can be precisely controlled. The fractionation or the composition ratio can be controlled. For example, a seawater desalination membrane can be modified and reused as a separation membrane that does not allow permeation of divalent ions such as magnesium and calcium. Furthermore, if the pore size of the reverse osmosis membrane is expanded, it can be reused as a nanofilter that separates molecules with molecular weights of several hundred to several thousand, or an ultrafilter that separates molecules and solids with molecular weights of several thousand to several tens of thousands. Can do.
次に、本発明の改質処理装置について説明する。 Next, the reforming apparatus of the present invention will be described.
図１に、液相撹拌式かつ回分式の改質処理装置の概略を示す。酸化性水溶液を満たした薬液槽１０１に、有機膜モジュール１０２を浸漬し、改質処理を行う。薬液槽１０１には温度調節器１０３が取り付けられており、液温を所定の温度に保つことができる。また、薬液槽１０１には攪拌機１０４が取り付けられており、槽内の温度、酸化剤の濃度が均一になるように十分撹拌することができる。 FIG. 1 shows an outline of a liquid phase stirring type and batch type reforming apparatus. The organic membrane module 102 is immersed in a chemical bath 101 filled with an oxidizing aqueous solution to perform a modification process. A temperature controller 103 is attached to the chemical tank 101, and the liquid temperature can be maintained at a predetermined temperature. In addition, a stirrer 104 is attached to the chemical solution tank 101 and can be sufficiently stirred so that the temperature in the tank and the concentration of the oxidizing agent are uniform.
薬液槽１０１には、酸化還元電位測定器１０５と、温度計１０６と、ｐＨ測定器１０７が取り付けられており、これらの測定データは、制御器１０８に送られる。 The chemical solution tank 101 is provided with an oxidation-reduction potential measuring device 105, a thermometer 106, and a pH measuring device 107, and these measurement data are sent to the controller 108.
また、バルブ１１４を介して、酸化性水溶液をサンプリングするポンプ１２０が接続されており、制御器１０８の指示によってバルブ１１４が定期的に開き、サンプリングした液が、酸化剤濃度測定器１０９に送られるようになっている。この酸化剤濃度測定器１０９は、酸化剤濃度を測定し、その情報を制御器１０８に伝送する。酸化剤濃度測定器としては、例えば自動滴定装置、高速液体クロマトグラフ、ＩＣＰ発光分析等を用いることができる。 Further, a pump 120 for sampling the oxidizing aqueous solution is connected via the valve 114, and the valve 114 is periodically opened by an instruction from the controller 108, and the sampled liquid is sent to the oxidant concentration measuring device 109. It is like that. The oxidant concentration measuring device 109 measures the oxidant concentration and transmits the information to the controller 108. As the oxidant concentration measuring instrument, for example, an automatic titrator, a high performance liquid chromatograph, an ICP emission analysis, or the like can be used.
また、薬液槽１０１には、ｐＨ調整剤の供給タンク１２１が、ポンプ１１６、バルブ１１０を介して接続されている。また、酸化剤の供給タンク１２２が、ポンプ１１７、バルブ１１１を介して接続されている。また、酸化性水溶液の供給タンク１２３が、ポンプ１１８、バルブ１１２を介して接続されている。更に、純水の供給タンク１２４が、ポンプ１１９、バルブ１１３を介して接続されている。 In addition, a pH adjusting agent supply tank 121 is connected to the chemical solution tank 101 via a pump 116 and a valve 110. An oxidant supply tank 122 is connected via a pump 117 and a valve 111. An oxidizing aqueous solution supply tank 123 is connected via a pump 118 and a valve 112. Further, a pure water supply tank 124 is connected via a pump 119 and a valve 113.
ポンプ１１６〜１１９及びバルブ１１０〜１１３は、いずれも制御器１０８に接続されており、制御器１０８によって動作が制御されるようになっている。 The pumps 116 to 119 and the valves 110 to 113 are all connected to the controller 108, and the operation is controlled by the controller 108.
また、薬液槽１０１には、ドレインバルブ１１５が設けられており、ドレインバルブ１１５を開くことによって酸化性水溶液を排水することができる。 In addition, the chemical tank 101 is provided with a drain valve 115, and the oxidizing aqueous solution can be drained by opening the drain valve 115.
この装置では、改質処理を次の手順で実施する。酸化性水溶液の供給タンク１２３から酸化性水溶液を供給し、薬液槽１０１を酸化性水溶液で満たす。薬液の酸化還元電位及び温度、ｐＨが安定して改質準備が整うと、有機膜モジュール１０２を薬液槽１０１に浸漬して、改質処理を開始する。制御器１０８は、酸化還元電位測定器１０５で測定された酸化還元電位と、酸化剤濃度測定器１０９で測定された酸化剤濃度を乗算し、浸漬開始時刻を始点とする積算乗算値を算出する。積算乗算値が、所定の値に達すると、（目標脱塩率に到達すると）、制御器１０８の指令によって、薬液槽１０１から有機膜モジュール１０２が取り出され、図示しない水洗槽に移される。有機膜モジュール１０２を水洗することによって、改質反応が停止する。また、改質反応が停止は、ドレインバルブ１１５から酸化性水溶液を全量抜き取り、供給タンク１２４から純水を供給して、有機膜モジュール１０２を洗浄する方法であってもよい。 In this apparatus, the reforming process is performed in the following procedure. The oxidizing aqueous solution is supplied from the oxidizing aqueous solution supply tank 123 to fill the chemical tank 101 with the oxidizing aqueous solution. When the oxidation-reduction potential, temperature, and pH of the chemical solution are stabilized and preparation for modification is completed, the organic membrane module 102 is immersed in the chemical solution tank 101 and the modification process is started. The controller 108 multiplies the oxidation-reduction potential measured by the oxidation-reduction potential measurement device 105 by the oxidant concentration measured by the oxidant concentration measurement unit 109, and calculates an integrated multiplication value starting from the immersion start time. . When the integrated multiplication value reaches a predetermined value (when the target desalination rate is reached), the organic membrane module 102 is taken out from the chemical solution tank 101 and transferred to a water washing tank (not shown) according to a command from the controller 108. The reforming reaction is stopped by washing the organic membrane module 102 with water. Alternatively, the reforming reaction may be stopped by a method in which the entire amount of the oxidizing aqueous solution is extracted from the drain valve 115 and pure water is supplied from the supply tank 124 to clean the organic membrane module 102.
また、改質反応の進行に伴い、酸化還元電位や、酸化剤濃度が変動するが、この装置では、それらを一定に保ちながら、改質反応を進めることもできる。その場合には、酸化還元電位測定器１０５で測定された酸化還元電位と、温度計１０６によって測定された温度と、ｐＨ測定器１０７によって測定されたｐＨとに基づいて、酸化還元電位が所定の値に保たれるように、ｐＨ調整剤の供給タンク１２１から、ポンプ１１６、バルブ１１０を介して、ｐＨ調整剤が添加される。また、酸化剤濃度測定器１０９で測定された酸化剤濃度に基づいて、酸化剤の供給タンク１２２から、ポンプ１１７、バルブ１１１を介して、酸化剤が添加される。 Further, as the reforming reaction proceeds, the oxidation-reduction potential and the oxidant concentration fluctuate. With this apparatus, the reforming reaction can be advanced while keeping them constant. In that case, based on the oxidation-reduction potential measured by the oxidation-reduction potential measurement device 105, the temperature measured by the thermometer 106, and the pH measured by the pH measurement device 107, the oxidation-reduction potential is a predetermined value. The pH adjusting agent is added from the supply tank 121 of the pH adjusting agent via the pump 116 and the valve 110 so that the value is maintained. Further, based on the oxidant concentration measured by the oxidant concentration measuring device 109, the oxidant is added from the oxidant supply tank 122 through the pump 117 and the valve 111.
こうして、酸化還元電位及び酸化剤濃度を一定に保った場合には、前記式（１）によって求められる処理時間によって、改質処理の終了時刻を決定することができる。 In this way, when the oxidation-reduction potential and the oxidant concentration are kept constant, the end time of the reforming process can be determined based on the processing time obtained by the equation (1).
なお、上記実施形態では、酸化剤濃度測定器１０９を設けて、酸化還元電位測定器１０５で測定された酸化還元電位と、酸化剤濃度測定器１０９で測定された酸化剤濃度を乗算するようにしているが、酸化剤濃度測定器１０９を設けず、改質処理の開始時の酸化剤濃度を適用して、酸化還元電位測定器１０５で測定された酸化還元電位と、酸化剤濃度とを乗算してもよい。 In the above embodiment, the oxidant concentration measuring device 109 is provided, and the oxidation / reduction potential measured by the oxidation / reduction potential measuring device 105 is multiplied by the oxidant concentration measured by the oxidant concentration measuring device 109. However, the oxidizing agent concentration measuring device 109 is not provided, and the oxidizing agent concentration at the start of the reforming process is applied, and the oxidation / reduction potential measured by the oxidation / reduction potential measuring device 105 is multiplied by the oxidizing agent concentration. May be.
図２に、液循環式かつ流通式の改質処理装置の概略を示す。図中、図１と実質的に同一部分には同符号を付して、その説明を省略することにする。 FIG. 2 shows an outline of a liquid circulation type and distribution type reforming apparatus. In the figure, parts that are substantially the same as those in FIG.
この改質装置では、薬液槽１０１から、ポンプ２２５を介して、酸化性水溶液が汲み上げられ、通水容器に収容された有機膜モジュール１０２に通水されて、改質処理がなされるようになっている。有機膜モジュール１０２に通水された酸化性水溶液は、薬液槽１０１に戻され、再びポンプ２２５で汲み上げられて、循環するようになっている。 In this reformer, the oxidizing aqueous solution is pumped from the chemical solution tank 101 via the pump 225, and is passed through the organic membrane module 102 accommodated in the water flow container, so that the reforming process is performed. ing. The oxidizing aqueous solution passed through the organic membrane module 102 is returned to the chemical tank 101, and is pumped up again by the pump 225 and circulated.
なお、図２中の２２６、２２７、２２８は流量計であり、２２９、２３０は圧力計である。流量計２２６は、酸化性水溶液の供給ラインの流量を測定し、圧力計２２９は、同供給ラインの圧力を測定する。流量計２２７は、透過水ラインの流量を測定し、流量計２２８は、濃縮水ラインの流量を測定し、圧力計２３０は、膜出口の圧力を測定する。 In FIG. 2, 226, 227 and 228 are flow meters, and 229 and 230 are pressure gauges. The flow meter 226 measures the flow rate of the oxidizing aqueous solution supply line, and the pressure gauge 229 measures the pressure of the supply line. The flow meter 227 measures the flow rate of the permeate line, the flow meter 228 measures the flow rate of the concentrated water line, and the pressure gauge 230 measures the pressure at the membrane outlet.
この改質装置においては、上記流量計２２６、２２７、２２８や、圧力計２２９、２３０によって、有機膜モジュール１０２に通水される酸化性水溶液の表面線速度を制御しつつ、改質反応を行うことができる。 In this reformer, the reforming reaction is performed while controlling the surface linear velocity of the oxidizing aqueous solution passed through the organic membrane module 102 by the flow meters 226, 227, 228 and the pressure gauges 229, 230. be able to.
なお、改質反応の停止は、前記図１の改質装置と同様にして行うことができる。 The reforming reaction can be stopped in the same manner as in the reforming apparatus shown in FIG.
（試験１）
図２の装置によって、淡水化処理に用いられたポリアミド系のスキン層を有する脱塩率９０％の逆浸透膜（ＤＯＷ社製：ＳＷ３０−２５４０）を、次亜塩素酸ナトリウムを酸化剤とする０．０５質量％の酸化性水溶液に液温２５℃で接触させて改質した。(Test 1)
A reverse osmosis membrane (DOW: SW30-2540) having a desalination rate of 90% having a polyamide-based skin layer used in the desalination treatment using the apparatus of FIG. 2 and sodium hypochlorite as an oxidizing agent is used. Modification was carried out by contacting 0.05% by mass of an oxidizing aqueous solution at a liquid temperature of 25 ° C.
逆浸透膜を改質した後、３．５％塩化ナトリウム水溶液を原水とする逆浸透圧法による脱塩試験によって脱塩率を測定した。原水に６ＭＰａの圧力を加えて得られる透過水の塩濃度を東亜ＤＫＫ社製のＣＭ−１１Ｐ装置によって測定した電気伝導度から求め、原水の塩濃度と透過水の塩濃度を式（２）に代入して脱塩率を算出し、結果を表1に示した。 After modifying the reverse osmosis membrane, the desalting rate was measured by a desalting test by a reverse osmotic pressure method using a 3.5% sodium chloride aqueous solution as raw water. The salt concentration of the permeated water obtained by applying a pressure of 6 MPa to the raw water is determined from the electrical conductivity measured by a CM-11P device manufactured by Toa DKK, and the salt concentration of the raw water and the salt concentration of the permeated water are expressed by Equation (2). The desalination rate was calculated by substitution, and the results are shown in Table 1.
表1のデータを用い、酸化還元電位×酸化剤濃度×処理時間に対して、脱塩率をプロットすると、図３が得られる。図３に示される直線関係は式（１）が成立することを示している。この改質処理の反応速度定数は８２％・L／Ｖ・ｍｏｌ・ｈｒである。 When the desalination rate is plotted against the oxidation-reduction potential × oxidant concentration × treatment time using the data in Table 1, FIG. 3 is obtained. The linear relationship shown in FIG. 3 indicates that equation (1) holds. The reaction rate constant of this reforming treatment is 82% · L / V · mol · hr.
（試験２）
淡水化処理用いられたポリアミド系のスキン層を有する脱塩率９０％の逆浸透膜（ＤＯＷ社製：ＳＷ３０−２５４０）を、次亜塩素酸ナトリウムを酸化剤とする０．０５質量％の酸化性水溶液をｐＨ９に調整して酸化還元電位を７３６ｍＶとし、液温２５℃で６０ｈｒ改質処理した。(Test 2)
A desalination rate 90% reverse osmosis membrane (DOW: SW30-2540) having a polyamide-based skin layer used for desalination was oxidized to 0.05% by mass using sodium hypochlorite as an oxidizing agent. The aqueous solution was adjusted to pH 9, the oxidation-reduction potential was 736 mV, and the reforming treatment was performed at a liquid temperature of 25 ° C. for 60 hours.
この改質処理後に、実施例１と同じ逆浸透圧法による脱塩試験を実施して、脱塩率を求めた。透過流束は、改質膜の透過水量を計測し、式（３）から算出した。また、改質膜の中心線平均粗さをアサイラムテクノロジー社製の原子間力顕微鏡ＭＦＰ−３Ｄ−ＳＡによって測定した。 After this reforming treatment, a desalting test by the same reverse osmotic pressure method as in Example 1 was performed to obtain a desalting rate. The permeation flux was calculated from the equation (3) by measuring the permeated water amount of the modified membrane. Further, the center line average roughness of the modified film was measured by an atomic force microscope MFP-3D-SA manufactured by Asylum Technology.
また、この改質膜の耐薬品性を評価するため、５０ｐｐｍの次亜塩素酸ナトリウム水溶液で２４ｈｒ洗浄した後、脱塩率を再度評価して、その変化率を調べた。 Further, in order to evaluate the chemical resistance of the modified membrane, after washing for 24 hours with a 50 ppm aqueous sodium hypochlorite solution, the desalination rate was evaluated again to examine the rate of change.
さらに、この改質膜で下水濾過処理を３０日間行った後、純水の透過係数（１０−９・ｍ３／ｍ２・ｓ・Ｐａ）を評価した。ここで、透過係数とは透過流束を濾過時の操作圧力で割った値のことである。Furthermore, after performing a sewage filtration treatment with this modified membrane for 30 days, the permeability coefficient (10 −9 · m 3 / m 2 · s · Pa) of pure water was evaluated. Here, the permeation coefficient is a value obtained by dividing the permeation flux by the operating pressure during filtration.
（比較例）
市販のナノフィルター(ＮＦ)膜から、試験２の改質膜とほぼ同じ脱塩率と透過流量を有する有機膜を選択し、試験２と同じ方法によって、中心線平均粗さ、耐薬品性の評価、下水濾過処理３０日後の透過係数を測定した。(Comparative example)
An organic membrane having almost the same desalination rate and permeation flow rate as the modified membrane of Test 2 is selected from commercially available nanofilter (NF) membranes, and the centerline average roughness and chemical resistance are the same as in Test 2. Evaluation and permeability coefficient after 30 days of sewage filtration treatment were measured.
表２に、試験２で得られた脱塩率６５．２％の改質膜と、比較例で選択した初期脱塩率６４．９％の低圧逆浸透膜（≒ＮＦ膜）の性能比較を示す。改質膜の中心線平均粗さは１５ｎｍであり、低圧逆浸透膜の６ｎｍと比べて、表面は粗い。耐薬品性を比較すると、５０ｐｐｍの次亜塩素酸ナトリウム水溶液の２４ｈｒ洗浄によって、改質膜の脱塩率は０．３％減少に留まるが、低圧逆浸透膜の脱塩率は１．８％減少する。脱塩率変化率の小さい改質膜の方が、薬品耐性が高いと言える。 Table 2 compares the performance of the modified membrane with a desalination rate of 65.2% obtained in Test 2 and the low pressure reverse osmosis membrane (≈NF membrane) with an initial desalination rate of 64.9% selected in the comparative example. Show. The centerline average roughness of the modified membrane is 15 nm, and the surface is rough compared to 6 nm of the low pressure reverse osmosis membrane. Comparing the chemical resistance, the demineralization rate of the modified membrane is only reduced by 0.3% by washing with 50 ppm of sodium hypochlorite aqueous solution for 24 hours, but the demineralization rate of the low-pressure reverse osmosis membrane is 1.8%. Decrease. It can be said that the modified membrane having a smaller rate of change in desalination rate has higher chemical resistance.
一方、下水濾過処理を３０日後の透過係数の測定から、改質膜の方が透過性能の低下が少なく、堆積物（ファウリング）付着に耐性が見られる。 On the other hand, from the measurement of the permeability coefficient after 30 days of the sewage filtration treatment, the modified membrane shows less deterioration in permeation performance, and resistance to deposits (fouling) is observed.
１０１：薬液槽
１０２：有機膜モジュール
１０３：温度調節器
１０４：攪拌機
１０５：酸化還元電位測定器
１０６：温度計
１０７：ｐＨ測定器
１０８：制御器
１０９：酸化剤濃度測定器
１１０〜１１５：バルブ
１１６〜１２０、２２５：ポンプ
１２１：ｐＨ調整剤の供給タンク
１２２：酸化剤の供給タンク
１２３：酸化性水溶液の供給タンク
１２４：純水の供給タンク
２２６、２２７、２２８：流量計
２２９、２３０：圧力計
101: Chemical bath 102: Organic membrane module 103: Temperature controller 104: Stirrer 105: Redox potential measuring device 106: Thermometer 107: pH measuring device 108: Controller 109: Oxidant concentration measuring devices 110 to 115: Valve 116 ˜120, 225: Pump 121: pH adjusting agent supply tank 122: Oxidizing agent supply tank 123: Oxidizing aqueous solution supply tank 124: Pure water supply tank 226, 227, 228: Flow meters 229, 230: Pressure gauge
Claims (12)
前記酸化還元電位計によって、前記有機膜と前記酸化性水溶液とを接触させる処理時間にわたって測定された酸化還元電位（Ｖ）と、酸化剤濃度（ｍｏｌ／Ｌ）の乗算値（Ｖ・ｍｏｌ／Ｌ）を算出し、該乗算値を時間積分した積算乗算値（Ｖ・ｍｏｌ・ｈｒ／Ｌ）によって改質反応の進行度を解析し、改質処理を終了させる制御手段を有することを特徴とする有機膜の改質装置。 In the reforming apparatus for changing the desalting performance and / or permeation performance of the organic membrane by bringing the organic membrane having a desalting function into contact with an oxidizing aqueous solution containing an oxidizing agent, the oxidizing property Equipped with an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of an aqueous solution,
A product (V · mol / L) of the oxidation-reduction potential (V) and the oxidant concentration (mol / L) measured over the treatment time for bringing the organic film and the oxidizing aqueous solution into contact with the oxidation-reduction potentiometer. ), The progress of the reforming reaction is analyzed by an integrated multiplication value (V · mol · hr / L) obtained by time-integrating the multiplication value, and a control means for terminating the reforming process is provided. Organic membrane reformer.
The apparatus for reforming an organic film according to claim 9 or 10, wherein the means for bringing the oxidizing aqueous solution into contact with the organic film is a liquid circulation type and a circulation type.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230599A (en) * | 1985-07-31 | 1987-02-09 | Mitsubishi Heavy Ind Ltd | Pretreatment in pure water making apparatus |
| JPH0957076A (en) * | 1995-08-28 | 1997-03-04 | Toray Ind Inc | Operation of reverse osmosis membrane device |
| JP2005034723A (en) * | 2003-07-18 | 2005-02-10 | Mtc:Kk | Method for modifying reverse osmosis membrane and regenerated separation membrane |
| JP2005270794A (en) * | 2004-03-24 | 2005-10-06 | Kurita Water Ind Ltd | Recycling method of reverse osmosis membrane |
| JP2008296188A (en) * | 2007-06-04 | 2008-12-11 | Toray Ind Inc | Membrane separation apparatus and membrane separation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230599A (en) * | 1985-07-31 | 1987-02-09 | Mitsubishi Heavy Ind Ltd | Pretreatment in pure water making apparatus |
| JPH0957076A (en) * | 1995-08-28 | 1997-03-04 | Toray Ind Inc | Operation of reverse osmosis membrane device |
| JP2005034723A (en) * | 2003-07-18 | 2005-02-10 | Mtc:Kk | Method for modifying reverse osmosis membrane and regenerated separation membrane |
| JP2005270794A (en) * | 2004-03-24 | 2005-10-06 | Kurita Water Ind Ltd | Recycling method of reverse osmosis membrane |
| JP2008296188A (en) * | 2007-06-04 | 2008-12-11 | Toray Ind Inc | Membrane separation apparatus and membrane separation method |
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