JP4765913B2 - Reverse osmosis membrane module having nozzle with coating - Google Patents
Reverse osmosis membrane module having nozzle with coating Download PDFInfo
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- JP4765913B2 JP4765913B2 JP2006321091A JP2006321091A JP4765913B2 JP 4765913 B2 JP4765913 B2 JP 4765913B2 JP 2006321091 A JP2006321091 A JP 2006321091A JP 2006321091 A JP2006321091 A JP 2006321091A JP 4765913 B2 JP4765913 B2 JP 4765913B2
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- reverse osmosis
- osmosis membrane
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- water
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- 239000012528 membrane Substances 0.000 title claims description 99
- 238000001223 reverse osmosis Methods 0.000 title claims description 73
- 239000011248 coating agent Substances 0.000 title claims description 14
- 238000000576 coating method Methods 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 239000012510 hollow fiber Substances 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000013535 sea water Substances 0.000 claims description 19
- 239000008400 supply water Substances 0.000 claims description 17
- 238000010612 desalination reaction Methods 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 239000002184 metal Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000003761 preservation solution Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は、脱塩等に用いられる逆浸透膜モジュールに関する発明である。特に本発明は、海水を淡水化する場合や酸性水溶液を処理する場合等、逆浸透膜の供給水、濃縮水、透過水の腐食性が高い状態であっても、供給水、濃縮水、透過水ノズルが腐食しにくく耐久性に優れる逆浸透膜モジュールを提供することを目的とする。 The present invention relates to a reverse osmosis membrane module used for desalting and the like. In particular, the present invention is applicable to the case where the corrosiveness of the feed water, concentrated water, and permeate of the reverse osmosis membrane is high, such as when desalinating seawater or treating an acidic aqueous solution. An object of the present invention is to provide a reverse osmosis membrane module in which a water nozzle is hardly corroded and has excellent durability.
逆浸透法は、海水及びかん水の淡水化、半導体工業及び医薬品工業用の純水、超純水の製造、都市排水処理等の幅広い分野で利用されている。蒸発法、電気透析法と比較して省エネルギーの点で有利であり、広く普及が進んでいる。特に、中空糸型逆浸透膜は、単位容積当たりの膜面積を大きくできるため、膜分離操作に適した形状であり、例えば、逆浸透膜による海水淡水化分野では広く用いられている。以下、主に海水淡水化分野で使用される状況を例にとり、説明を行う。 The reverse osmosis method is used in a wide range of fields such as desalination of seawater and brine, production of pure water for the semiconductor industry and pharmaceutical industry, ultrapure water, and municipal wastewater treatment. Compared to the evaporation method and electrodialysis method, it is advantageous in terms of energy saving and is widely spread. In particular, since the hollow fiber type reverse osmosis membrane can increase the membrane area per unit volume, the hollow fiber type reverse osmosis membrane has a shape suitable for membrane separation operation, and is widely used, for example, in the field of seawater desalination using a reverse osmosis membrane. In the following, description will be given mainly taking the situation of use in the seawater desalination field as an example.
逆浸透法で処理される場合は逆浸透膜モジュールが用いられる。一般には、供給水ノズルから供給された供給水は逆浸透膜モジュールへ供給され、逆浸透膜を透過した水は透過水ノズルから取りだされ、透過せずに濃縮された水は濃縮水ノズルから取り出される。図１は両端開口型中空糸膜エレメント２本（１、１’）を装填した逆浸透膜モジュールの断面模式図である。海水等の供給水１２は供給水ノズル９から逆浸透膜モジュールの内部に供給され、中空糸膜エレメント１の内部を通過する間に、透過水１４、１４’と濃縮水１３に分離され、それぞれ透過水ノズル１１，１１’および濃縮水ノズル１０から逆浸透膜モジュールの外部に排出される。なお、図１においては、ノズルの詳細な形状は省略し、概略の形状を記載してある。 In the case of processing by the reverse osmosis method, a reverse osmosis membrane module is used. In general, the supply water supplied from the supply water nozzle is supplied to the reverse osmosis membrane module, the water that has permeated the reverse osmosis membrane is taken out from the permeate nozzle, and the water that has not been permeated is concentrated from the concentrate water nozzle. It is taken out. FIG. 1 is a schematic cross-sectional view of a reverse osmosis membrane module loaded with two open end hollow fiber membrane elements (1, 1 '). Supply water 12 such as seawater is supplied from the supply water nozzle 9 to the inside of the reverse osmosis membrane module and separated into permeated water 14 and 14 ′ and concentrated water 13 while passing through the inside of the hollow fiber membrane element 1. The permeated water nozzles 11 and 11 'and the concentrated water nozzle 10 are discharged to the outside of the reverse osmosis membrane module. In FIG. 1, the detailed shape of the nozzle is omitted, and a schematic shape is shown.
供給水ノズル、濃縮水ノズルは高塩濃度水と接触するために腐食により損傷しやすく、さらには、海水淡水化用逆浸透膜モジュールにおいては５〜１０MPa程度の高い内圧に耐える必要があることから、耐食性と強度を兼ね備える材料として、ＳＵＳ３０４、ＳＵＳ３０４Ｌ、ＳＵＳ３１６、ＳＵＳ３１６L、ＳＵＳ３１７、ＳＵＳ３１７L等の耐腐食性ステンレスが主として用いられている。一方、透過水ノズルについては、耐圧性の要求レベルが低い低圧仕様あるいは超低圧仕様の逆浸透膜モジュールの一部では、透過水ノズルを硬質塩化ビニル樹脂製としたものがごく一部で用いられているが、金属配管との接続において強度が不十分なため変形・破損し水もれを起こす場合があり、その使用には注意が必要であった。要求レベルこそ供給水ノズルおよび濃縮水ノズルと比較すると低いものの、透過水ノズルについてもやはり耐食性と内圧に対する耐圧性が要求されるため、一般的には耐食性ステンレス等の材料が用いられている。耐食性ステンレスは、一般鋼材と比べると高価であり、また近年は需給状況が逼迫傾向にあり調達に時間を要する傾向にあるとの問題点がある。さらに、逆浸透膜による海水淡水化において、ペルシャ湾等の高塩濃度海水の海水淡水化処理や回収率の向上による濃縮水の高塩濃度化が進展しており、それに伴って従来よりも高いレベルでの耐食性が要求されるようになっており、ＳＵＳ３１６製のノズルでさえも腐食が発生する場合があることがわかってきた。 Since the feed water nozzle and the concentrated water nozzle are in contact with the high salt concentration water, they are easily damaged by corrosion. Further, in the reverse osmosis membrane module for seawater desalination, it is necessary to withstand a high internal pressure of about 5 to 10 MPa. Corrosion-resistant stainless steels such as SUS304, SUS304L, SUS316, SUS316L, SUS317, and SUS317L are mainly used as materials having both corrosion resistance and strength. On the other hand, with regard to the permeated water nozzle, only a part of the low osmosis or ultra low pressure reverse osmosis membrane modules with low pressure resistance requirement is made of rigid polyvinyl chloride resin. However, due to insufficient strength in connection with metal piping, it may be deformed or damaged, causing water leakage, and caution must be exercised in its use. Although the required level is lower than the supply water nozzle and the concentrated water nozzle, the permeated water nozzle is also required to have a corrosion resistance and a pressure resistance against the internal pressure. Therefore, a material such as a corrosion resistant stainless steel is generally used. Corrosion-resistant stainless steel is expensive compared to general steel materials, and in recent years, there is a problem that the supply and demand situation tends to be tight and it takes time to procure. Furthermore, in the desalination of seawater using reverse osmosis membranes, the concentration of concentrated water is increasing due to seawater desalination and recovery of high-salt seawater in Persian Gulf, etc. Corrosion resistance at the level has been required, and it has been found that even a SUS316 nozzle may cause corrosion.
本発明は、このような点に鑑みてなされたもので、塩水との接触による腐食による損傷が発生せず、高い内圧に耐え、かつ金属配管との接続によって損傷を受けることの無い逆浸透膜用ノズルおよびそれを有する逆浸透膜モジュールを提供することを目的とする。また、近年の耐食性ステンレスの価格高騰および長納期化に対する対応策として、一般鋼材製であっても実用上十分な耐久性を有する逆浸透膜用ノズルおよびそれを有する逆浸透膜モジュールを提供することを目的とする。 The present invention has been made in view of the above points, and is a reverse osmosis membrane that does not cause damage due to corrosion due to contact with salt water, withstands high internal pressure, and is not damaged by connection with metal piping. It is an object to provide a nozzle for use and a reverse osmosis membrane module having the same. In addition, as a countermeasure against the recent rise in the price of corrosion-resistant stainless steel and a longer delivery time, to provide a reverse osmosis membrane nozzle and a reverse osmosis membrane module having the practically sufficient durability even if it is made of general steel. With the goal.
本発明者らは、上記課題を克服すべく鋭意検討を重ねた結果、本発明に到達した。すなわち、本願発明は下記の構成を有するものである。
（１）供給水、透過水、濃縮水の出入口となるノズルを有する逆浸透膜モジュールにおいて、該ノズルの表面にリン酸塩化成処理を施した後、その表面にフッ素系樹脂、フェノール樹脂、ポリアミドイミド樹脂から選ばれる１種以上の皮膜を形成することにより、JIS K5400（1990）規定の鉛筆硬度が５Ｈ以上の皮膜が形成されたノズルを有することを特徴とする逆浸透膜モジュール。
（２）前記ノズルが、炭素鋼またはステンレス鋼からなることを特徴とする（１）に記載の逆浸透膜モジュール。
（３）該皮膜の厚みが５μｍ以上５０μｍ以下であることを特徴とする（１）または（２）に記載の逆浸透膜モジュール。
（４）該皮膜が少なくともノズルの接液部に形成されていることを特徴とする（１）から（３）のいずれかに記載の逆浸透膜モジュール。
（５）該ノズルが逆浸透膜モジュールに装脱着可能に勘合されていることを特徴とする（１）から（４）のいずれかに記載の逆浸透膜モジュール。
（６）該逆浸透膜モジュールが海水淡水化用の逆浸透膜モジュールであることを特徴とする（１）から（５）のいずれかに記載の逆浸透膜モジュール。
（７）逆浸透膜が酢酸セルロース系高分子からなる中空糸型逆浸透膜からなることを特徴とする（１）から（６）のいずれかに記載の逆浸透膜モジュール。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to overcome the above problems. That is, the present invention has the following configuration.
(1) In a reverse osmosis membrane module having a nozzle serving as an inlet / outlet for supply water, permeated water, and concentrated water, the surface of the nozzle is subjected to a phosphate conversion treatment, and then the surface is fluorinated resin, phenol resin, polyamide A reverse osmosis membrane module comprising a nozzle having a coating with a pencil hardness of 5 H or more defined in JIS K5400 (1990) by forming at least one coating selected from imide resins .
(2) The reverse osmosis membrane module according to (1), wherein the nozzle is made of carbon steel or stainless steel.
(3) The reverse osmosis membrane module according to (1) or (2) , wherein the thickness of the coating is 5 μm or more and 50 μm or less.
(4) The reverse osmosis membrane module according to any one of (1) to ( 3), wherein the film is formed at least in a liquid contact portion of a nozzle.
(5) The reverse osmosis membrane module according to any one of (1) to ( 4), wherein the nozzle is fitted to the reverse osmosis membrane module so as to be detachable.
(6) The reverse osmosis membrane module according to any one of (1) to ( 5), wherein the reverse osmosis membrane module is a reverse osmosis membrane module for seawater desalination.
(7) The reverse osmosis membrane module according to any one of (1) to ( 6), wherein the reverse osmosis membrane is a hollow fiber type reverse osmosis membrane made of a cellulose acetate polymer.
逆浸透膜モジュールに鉛筆硬度が４H以上の皮膜で被覆されているノズルを用いることにより、塩水による腐食による損傷を防止でき、かつ、金属配管との接続に際しての機械的損傷も抑制可能で、水漏れが防止可能である。特に、海水淡水化に用いる逆浸透膜モジュールに適するほか、酸性水溶液等の腐食性の強い液体を取り扱う逆浸透プロセスで用いられる逆浸透膜モジュールへの適用が好適である。 By using a nozzle that has a pencil hardness of 4H or more on the reverse osmosis membrane module, it is possible to prevent damage caused by corrosion due to salt water, and to suppress mechanical damage when connected to metal piping. Leakage can be prevented. In particular, it is suitable for a reverse osmosis membrane module used for seawater desalination and also for a reverse osmosis membrane module used in a reverse osmosis process for handling a highly corrosive liquid such as an acidic aqueous solution.
本発明における金属部材としては、炭素鋼やステンレス鋼等、配管材料として用いられている種々の公知の材料が好適に用いられる。耐食性は皮膜によって発揮されるので、金属部材自体が耐食性であることは必ずしも必要でなく、力学的な強度があれば十分である。例えば、錆が発生するので通常は水と接触する環境では使用しにくいＳＳ４００についても、本発明においては表面に耐久性の高い耐食性の皮膜を形成させるので使用可能であり、ステンレス鋼からなるものよりもコスト面で有利となる等の利点がある。一方、耐食性に関する高度の信頼性を要求され多重安全的な設計が必要な場合や微量の金属イオンの溶出も許されない場合には、ステンレス鋼等の耐食性の金属部材でノズルを形成しさらに樹脂系の皮膜で被覆することにより要求に応えることができ、このような態様も好ましい実施態様に含まれる。 As the metal member in the present invention, various known materials used as piping materials such as carbon steel and stainless steel are suitably used. Since the corrosion resistance is exhibited by the film, it is not always necessary that the metal member itself be corrosion resistant, and it is sufficient if it has mechanical strength. For example, SS400, which is difficult to use in an environment that normally comes into contact with water because rust is generated, can be used because a highly durable and corrosion-resistant film is formed on the surface in the present invention. Has advantages such as being advantageous in terms of cost. On the other hand, when a high level of reliability regarding corrosion resistance is required and multiple safe designs are required, or when elution of a small amount of metal ions is not allowed, a nozzle is formed with a corrosion-resistant metal member such as stainless steel and a resin system It is possible to meet the requirements by coating with the above film, and such an embodiment is also included in a preferred embodiment.
本発明における樹脂系の材料は、海水等の浸透を防ぐことができるものであり、海水等の金属腐食性の溶液に対して、非腐食性で化学的に安定な樹脂系の材質であれば特に限定されない。２種類以上の異種の樹脂の混合物やポリマーアロイであってもよく、充填材を包含した複合材料であってもよい。充填材の材質は、無機物、有機物あるいはそれらの混合物等、種々のものがあるが、いずれのものであっても良い。また、充填材には繊維状、粒状、板状等の種々の形状があるが、いずれの形状であってもよい。充填材の配合量には特に制限はないが、１〜５０％とすることが好適である。 The resin-based material in the present invention can prevent penetration of seawater or the like, and is a non-corrosive and chemically stable resin-based material against a metal corrosive solution such as seawater. There is no particular limitation. It may be a mixture of two or more different kinds of resins, a polymer alloy, or a composite material including a filler. There are various kinds of filler materials such as inorganic substances, organic substances or mixtures thereof, and any of these may be used. In addition, the filler has various shapes such as a fiber shape, a granular shape, and a plate shape, and may be any shape. Although there is no restriction | limiting in particular in the compounding quantity of a filler, It is suitable to set it as 1 to 50%.
本発明における樹脂系の材料としては、フッ素系樹脂やフェノール系樹脂、ポリアミド系樹脂、ポリアミドイミド樹脂が好適な例として挙げられる。フッ素系の樹脂の例としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、四フッ化エチレン−パーフルオロアルキルビニルエーテル共重合体、四フッ化エチレン−ヘキサフルオロプロピレン共重合体、四フッ化エチレン−六フッ化プロピレン共重合体などがあげられる。腐食性の溶液に対する耐性や表面の鉛筆硬度の面から、フッ素系の樹脂が特に好ましい。 Preferred examples of the resin material in the present invention include a fluorine resin, a phenol resin, a polyamide resin, and a polyamideimide resin. Examples of fluororesins include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, four Examples thereof include a fluorinated ethylene-hexafluoropropylene copolymer. From the viewpoints of resistance to corrosive solutions and pencil hardness on the surface, fluorine-based resins are particularly preferable.
本発明における皮膜の形成方法としては、種々の公知の方法が適用できるが、例えば浸漬処理、スプレー処理、はけ塗り等の方法が例示できる。また、左記の処理に先立ち、種々の前処理を行うことができ、例えばアセトン等の有機溶剤によって皮膜が形成される金属の表面を脱脂することにより皮膜の密着性を高め皮膜の耐久性を高めることができる。また、後処理として乾燥や熱処理を施すことによって、皮膜の強度を高めることができる場合もある。さらに、皮膜を２層あるいはそれ以上の多層構造にすることによって、皮膜の強度や耐久性を向上させることも可能である。 Various known methods can be applied as the method for forming a film in the present invention, and examples thereof include immersion treatment, spray treatment, and brushing. Prior to the treatment shown on the left, various pretreatments can be performed. For example, degreasing the surface of the metal on which the film is formed with an organic solvent such as acetone increases the adhesion of the film and increases the durability of the film. be able to. In some cases, the strength of the film can be increased by performing drying or heat treatment as a post-treatment. Furthermore, it is possible to improve the strength and durability of the coating by forming the coating into a multilayer structure having two or more layers.
本発明において、皮膜の厚みは５μｍ以上５０μｍ以下であることが好ましい。このような厚みであれば、皮膜の耐久性が十分確保される上、ノズル生産に際しノズル寸法を寸法公差内に収めることも容易である。皮膜が薄すぎると、皮膜の耐久性が劣り、皮膜の破損を起こし金属部材の腐食および金属イオンの溶出を生じる恐れがあり、好ましくない。皮膜が厚すぎると、皮膜厚さの制御が難しく寸法精度の確保が困難であり、特に高い寸法精度を要求される勘合構造を持つノズルの製作において不利となる。 In the present invention, the thickness of the coating is preferably 5 μm or more and 50 μm or less. With such a thickness, the durability of the coating is sufficiently secured, and it is easy to keep the nozzle dimensions within dimensional tolerances during nozzle production. If the film is too thin, the durability of the film is inferior, and the film may be damaged, which may cause corrosion of the metal member and elution of metal ions. If the film is too thick, it is difficult to control the film thickness and it is difficult to ensure dimensional accuracy, which is disadvantageous in the manufacture of a nozzle having a fitting structure that requires particularly high dimensional accuracy.
本発明において、ノズル表面のうち、すべての接液部に皮膜が形成されていることが好ましい。逆浸透膜モジュールの使用状況を鑑みると、例えば逆浸透膜エレメントを交換する際等には通常の使用状態においては接液しない部位であっても海水等処理液体や膜エレメント保存液等が付着する可能性が有り、それによって腐食を発生する恐れがあるので、逆浸透膜モジュールの運転中には非接液部となる部位についても皮膜を形成することが、より好ましい。 In this invention, it is preferable that the film is formed in all the liquid contact parts among the nozzle surfaces. Considering the use situation of the reverse osmosis membrane module, for example, when replacing the reverse osmosis membrane element, a treatment liquid such as seawater or a membrane element preservation solution adheres even in a portion where the liquid does not come into contact in a normal use state. Since there is a possibility that corrosion may occur due to this, it is more preferable to form a film also on a portion that becomes a non-wetted part during operation of the reverse osmosis membrane module.
本発明における表面の鉛筆硬度は、ノズルの表面を構成する皮膜を、ＪＩＳ Ｋ ５４００（１９９０）手かき法により測定した値とする。但し、ノズルの形状上の制限により、上記方法による鉛筆硬度の測定が困難な場合には、ノズルと同材質の平板にノズルに皮膜を形成する場合と同じ方法で形成した皮膜に関する測定値で代用することとする。鉛筆硬度は表面硬度の指標であり、この値が大きいほど表面の硬度が大きく、接触時の損傷を受けにくい。各ノズルは、金属配管と接続して用いられ、逆浸透膜装置の運転の起動・停止時に生じる振動や、ノズルの装着・脱着の際の接触の繰り返し等により、機械的な接触にさらされるので、表面硬度が高いことが必要となる。傷つき等の損傷はノズルからの水もれの原因となる。特に、供給水、濃縮水は５ＭＰａ以上の高圧の場合があり、水漏れの発生は危険を伴い好ましくない。本発明で用いられる樹脂系の材料の表面硬度は、好ましくは４Ｈ以上であり、より好ましくは５Ｈ以上である。この値が小さいと、ノズルが傷つき等の損傷を受け易くなり、シール部に傷がつくと水漏れを生じる原因となる。また樹脂系の材料の皮膜に傷がついて金属部材が露出すると、金属部材に腐食が生じ、水漏れあるいはノズル破損の原因となるので、そのような事態を招かないために、高い表面硬度が必要である。このため、本発明における樹脂系材料の鉛筆硬度は高いほど好ましい。 The pencil hardness of the surface in the present invention is a value obtained by measuring the film constituting the surface of the nozzle by the JIS K 5400 (1990) handwriting method. However, if it is difficult to measure the pencil hardness by the above method due to restrictions on the shape of the nozzle, substitute the measured value for the film formed by the same method as when forming a film on the nozzle on a flat plate of the same material as the nozzle. I decided to. Pencil hardness is an index of surface hardness, and the larger the value, the greater the surface hardness and the less likely to be damaged during contact. Each nozzle is used in connection with a metal pipe, and is exposed to mechanical contact due to vibrations that occur when starting and stopping the operation of the reverse osmosis membrane device and repeated contact when the nozzle is installed and removed. The surface hardness is required to be high. Damage such as scratches may cause water leakage from the nozzle. In particular, supply water and concentrated water may have a high pressure of 5 MPa or more, and the occurrence of water leakage is dangerous and undesirable. The surface hardness of the resin material used in the present invention is preferably 4H or more, and more preferably 5H or more. When this value is small, the nozzle is easily damaged such as scratches, and if the seal portion is scratched, water leakage may occur. Also, if the film of the resin material is damaged and the metal member is exposed, the metal member will be corroded, causing water leakage or nozzle breakage. Therefore, high surface hardness is required to prevent such a situation. It is. For this reason, the higher the pencil hardness of the resin material in the present invention, the better.
本発明は、逆浸透膜モジュールが装脱着可能に勘合されているノズルを有する場合において、特に有効である。このタイプのノズルは、ノズルの装脱着の際に配管部材や工具との衝突を生じる機会が多く、また勘合の際に勘合相手と擦れるため、ノズル表面に傷がつきやすい。本発明によれば、ノズル表面硬度が高いため、このような使用状況にあっても傷がつかず、十分な耐久性を発揮することができる。 The present invention is particularly effective when the reverse osmosis membrane module has a nozzle fitted so as to be detachable. In this type of nozzle, there are many opportunities to collide with piping members and tools when the nozzle is mounted and removed, and the surface of the nozzle is easily scratched because it rubs against the mating partner when mating. According to the present invention, since the surface hardness of the nozzle is high, it is not damaged even in such a use situation, and sufficient durability can be exhibited.
本発明において、ノズルと外部の金属配管との接続は、ビクトリックジョイント接続、フランジ接続、クランプ接続等の接続方法により行うことができ、ノズルの先端形状は接続方法に適した形状に加工される。ノズルと配管の装脱着の際には、ノズルと配管の衝突のほか、工具と衝突を生じる機会が多く、ノズル表面に傷がつきやすい。本発明によればノズルの表面硬度が高いため、このような使用状況にあっても傷がつかず、十分な耐久性を発揮することができる。 In the present invention, the nozzle and the external metal pipe can be connected by a connection method such as a Victorian joint connection, a flange connection, a clamp connection, or the like, and the tip shape of the nozzle is processed into a shape suitable for the connection method. . When attaching and detaching the nozzle and the pipe, there are many opportunities to cause a collision with the tool in addition to the collision between the nozzle and the pipe, and the nozzle surface is easily damaged. According to the present invention, since the surface hardness of the nozzle is high, it is not damaged even in such a use situation, and sufficient durability can be exhibited.
本発明における逆浸透膜とは、数十ダルトンの分子量の分離特性を有する領域の分離膜であり、具体的には、０．５ＭＰａ以上の操作圧力で、食塩を９０％以上、除去可能であるものである。海水淡水化に使用される逆浸透膜は、操作圧力が大きく、また、食塩の除去率は９９％以上が一般的である。 The reverse osmosis membrane in the present invention is a separation membrane in a region having a molecular weight separation characteristic of several tens of daltons, and specifically, 90% or more of salt can be removed at an operating pressure of 0.5 MPa or more. Is. The reverse osmosis membrane used for seawater desalination has a large operating pressure, and the removal rate of salt is generally 99% or more.
本発明における逆浸透膜エレメントとは、圧力容器に装着し、供給水ノズル、濃縮水ノズル、透過水ノズルを設置することで、逆浸透膜モジュールとなるものである。圧力容器に装填される逆浸透膜エレメントの本数は逆浸透膜の種類により異なる。各逆浸透膜エレメントの透過水が個別の透過水ノズルから取り出される構造の場合は、逆浸透膜エレメントの劣化状況が反映された水質の透過水が透過水ノズルに接触するため、逆浸透膜エレメントの劣化が進んだ場合には透過水ノズルへ腐食が顕著となり本発明の効果が現れやすい一例となる。この場合のROモジュール内に装填される逆浸透膜エレメントの本数は２本以内が実用上好ましい。 The reverse osmosis membrane element in the present invention is a reverse osmosis membrane module that is attached to a pressure vessel and provided with a supply water nozzle, a concentrated water nozzle, and a permeated water nozzle. The number of reverse osmosis membrane elements loaded in the pressure vessel varies depending on the type of reverse osmosis membrane. In the case where the permeated water of each reverse osmosis membrane element is taken out from an individual permeated water nozzle, the permeated water of water quality reflecting the deterioration state of the reverse osmosis membrane element comes into contact with the permeated water nozzle. When the deterioration of the water progresses, the permeated water nozzle is significantly corroded, which is an example in which the effect of the present invention is likely to appear. In this case, the number of reverse osmosis membrane elements loaded in the RO module is preferably within two.
本発明における酢酸セルロース系高分子としては、酢酸セルロース、三酢酸セルロース、両者の混合物が例としてあげられる。塩除去性能および透水性能、また、性能の安定性等から三酢酸セルロースが好ましい。酢酸セルロース系高分子は耐塩素性に優れるため、供給水に殺菌剤として塩素を添加することが可能である。塩素を含む原水を逆浸透膜に供給すると、供給水、濃縮水、透過水にも塩素が混入する。塩素の混入は逆浸透膜モジュールの各ノズルの腐食性を増す傾向にあるので、本発明の効果がよく発揮される事例である。 Examples of the cellulose acetate polymer in the present invention include cellulose acetate, cellulose triacetate, and a mixture of both. Cellulose triacetate is preferred from the standpoint of salt removal performance and water permeability, and stability of performance. Since the cellulose acetate polymer is excellent in chlorine resistance, chlorine can be added to the supply water as a bactericidal agent. When raw water containing chlorine is supplied to the reverse osmosis membrane, chlorine is also mixed into the supply water, concentrated water, and permeated water. Since mixing of chlorine tends to increase the corrosivity of each nozzle of the reverse osmosis membrane module, this is an example in which the effect of the present invention is well exhibited.
本発明における中空糸膜とは中空糸状の膜であり、その寸法は限定されない。海水淡水化用の中空糸型逆浸透膜モジュールの場合には、中空糸膜外径は例えば１００μｍから３００μｍ、中空糸膜内径は中空糸膜の内径と外径とから算出される中空率も考慮して設定することが好ましく、例えば３０μｍから１５０μｍが好適な事例として挙げられる。 The hollow fiber membrane in the present invention is a hollow fiber membrane, and its dimensions are not limited. In the case of a hollow fiber type reverse osmosis membrane module for seawater desalination, the hollow fiber membrane outer diameter is, for example, 100 μm to 300 μm, and the hollow fiber membrane inner diameter takes into account the hollow ratio calculated from the inner diameter and outer diameter of the hollow fiber membrane. For example, 30 to 150 μm is a preferable example.
以下に、実施例を挙げて本発明を説明するが、本発明はこれらの実施例により何ら制限されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
（実施例１）
炭素鋼ＳＳ４００からなる逆浸透膜モジュール用の供給水ノズルをアセトンで洗浄・脱脂したのち、その表面上に浸漬処理によってリン酸塩化成処理皮膜を形成させ、さらにその表面上にスプレー塗装によって加熱硬化型フッ素系樹脂塗料を塗布し、次いで２００℃で３０分間焼付けをして、フッ素系樹脂からなる皮膜をノズルの内外表面に形成させた。皮膜の厚みは約３０ミクロンであった。また、皮膜の鉛筆硬度は５Ｈであった。
Example 1
The feed water nozzle for the reverse osmosis membrane module made of carbon steel SS400 is washed and degreased with acetone, and then a phosphate chemical conversion coating film is formed on the surface by dipping treatment, and further heat curing by spray coating on the surface A type fluorine resin coating was applied, followed by baking at 200 ° C. for 30 minutes to form a film made of fluorine resin on the inner and outer surfaces of the nozzle. The film thickness was about 30 microns. The pencil hardness of the film was 5H.
このノズルについて、以下の脱着耐久性試験を実施した。すなわち、ノズルとＳＵＳ３１６からなる金属配管をビクトリックジョイントによる締結の装着・脱着を１００回実施し、その後、ノズル内に水を充填し内圧１ＭＰａをかけ水漏れ発生の有無を観察した。脱着耐久試験後も水漏れは発生せず、また、目視観察によると皮膜に破損は認められなかった。次いで、脱着耐久性試験を終えたノズルを金属配管とビクトリックジョイントで接合した状態で食塩５重量％の食塩水に６ケ月間接触させる腐食試験を実施した。いずれのノズルにも目視観察で腐食は観察されなかった。結果を表１にまとめて示した。 The following desorption durability test was conducted on this nozzle. That is, the fitting and removal of the metal pipe composed of the nozzle and SUS316 by means of a victoic joint were performed 100 times, and then the nozzle was filled with water and an internal pressure of 1 MPa was applied to observe the occurrence of water leakage. Water leakage did not occur even after the desorption durability test, and the film was not damaged by visual observation. Next, a corrosion test was conducted in which the nozzle after completion of the desorption durability test was brought into contact with a 5% by weight salt solution for 6 months in a state where the nozzle was joined to a metal pipe with a Victoria joint. No corrosion was observed in any nozzle by visual observation. The results are summarized in Table 1.
（実施例２〜３および比較例１〜７）
種々の樹脂系の材料によって皮膜を形成した供給水ノズルを作製し、実施例１と同様の試験を実施した。結果を表１にまとめて示した。脱着耐久性試験後のノズルの皮膜には、いずれの場合にも傷が認められ、水漏れが発生した。そのうち、金属部材の露出が認められたものについては、腐食試験により腐食の発生が認められた。
(Examples 2-3 and Comparative Examples 1-7)
A feed water nozzle having a film formed of various resin-based materials was produced, and the same test as in Example 1 was performed. The results are summarized in Table 1. In any case, the film of the nozzle after the desorption durability test was scratched and water leakage occurred. Among them, the occurrence of corrosion was recognized by the corrosion test for those in which the metal member was exposed.
（実施例４〜７）
種々の金属部材で形成した供給水ノズルに、実施例１と同様にして皮膜を形成し、実施例１と同様の試験を実施した。結果を表２にまとめて示した。いずれの場合も、脱着耐久性試験後のノズルの皮膜に破損は認められず、腐食試験後のノズルに腐食は観察されなかった。
(Examples 4 to 7)
A film was formed on the feed water nozzle formed of various metal members in the same manner as in Example 1, and the same test as in Example 1 was performed. The results are summarized in Table 2. In any case, no damage was observed in the nozzle film after the desorption durability test, and no corrosion was observed in the nozzle after the corrosion test.
（実施例８）
三酢酸セルロース膜からなる中空糸型逆浸透膜を乾湿式紡糸法により作製し、外径１２０μｍ、内径４７μｍの中空糸膜を得た。この中空糸膜の脱塩性能を、３．５重量％の食塩水、中空糸膜有効長さ1m、供給水圧力５．４MPa、供給水温度２５℃、回収率２％で測定したところ、透過水量５６Ｌ／ｍ２／日、食塩除去率９９．８％であった。多孔管からなる供給流体分配管をその軸を中心に回転させ、これに中空糸膜の束をトラバースさせながら巻きつけることにより、中空糸膜を交差状に配置させ、中空糸膜の集合体を形成させた。この中空糸膜の集合体の両端部をエポキシ樹脂で封止固定した後、両端を切断して中空糸膜を開口させた。その後、供給流体分配管の内部に内部管を通し、両端部に設置される透過流体収集部材で固定して、中空糸膜エレメントを得た。この中空糸膜エレメントの中空糸膜集合体の外径は２６０ｍｍ、開口部間の軸方向の長さは１３１０ｍｍであった。
(Example 8)
A hollow fiber type reverse osmosis membrane composed of a cellulose triacetate membrane was prepared by a dry and wet spinning method to obtain a hollow fiber membrane having an outer diameter of 120 μm and an inner diameter of 47 μm. When the desalting performance of this hollow fiber membrane was measured at 3.5% by weight saline solution, the effective length of the hollow fiber membrane was 1 m, the feed water pressure was 5.4 MPa, the feed water temperature was 25 ° C., and the recovery rate was 2%. The amount of water was 56 L / m 2 / day, and the salt removal rate was 99.8%. By rotating a supply fluid distribution pipe comprising a perforated tube around its axis and winding the bundle of hollow fiber membranes while traversing them, the hollow fiber membranes are arranged in a crossing manner, and the assembly of hollow fiber membranes is formed. Formed. After sealing and fixing both ends of the hollow fiber membrane assembly with an epoxy resin, both ends were cut to open the hollow fiber membrane. Thereafter, the inner pipe was passed through the supply fluid distribution pipe and fixed with a permeating fluid collecting member installed at both ends to obtain a hollow fiber membrane element. The hollow fiber membrane assembly of this hollow fiber membrane element had an outer diameter of 260 mm and an axial length between the openings of 1310 mm.
上記のようにして製作した中空糸膜エレメント２本を圧力容器に装填し、図１に示す膜モジュールを得た。図１では供給水ノズル９、濃縮水ノズル１０、透過水ノズル１１のＯリング溝およびビクトリックジョイント接続用溝は省略して記載した。また、供給水ノズル９、濃縮水ノズル１０、透過水ノズル１１には実施例１と同様の方法で製作したものを装着した。この膜モジュールを用い、実海水を供給水として１年間にわたり海水淡水化テストを実施した。左記運転期間中、ノズル近傍からの水漏れは発生しなかった。また左記運転期間終了後、ノズルを取り外して点検したところ、供給水ノズル、濃縮水ノズルおよび透過水ノズルのいずれにも皮膜の損傷およびノズルの腐食は認められず、これらのノズルが高度な耐久性を持つことが実証された。 Two hollow fiber membrane elements produced as described above were loaded into a pressure vessel to obtain a membrane module shown in FIG. In FIG. 1, the O-ring groove and the Victoria joint connection groove of the supply water nozzle 9, the concentrated water nozzle 10 and the permeated water nozzle 11 are omitted. In addition, the supply water nozzle 9, the concentrated water nozzle 10, and the permeated water nozzle 11 were mounted by the same method as in Example 1. Using this membrane module, a seawater desalination test was conducted for one year using actual seawater as the supply water. During the operation period on the left, no water leaked from the vicinity of the nozzle. After the operation period on the left, the nozzles were removed and inspected, and no damage to the coating or corrosion of the nozzles was observed in any of the supply water nozzle, concentrated water nozzle, and permeated water nozzle. Proven to have.
本発明の逆浸透膜モジュールは、透過水の腐食性が高い場合でも腐食による損傷が発生せず、なおかつ振動や接触にも耐える機械的強度を有するため、海水淡水化や酸性水溶液の逆浸透処理等への利用が可能である。 The reverse osmosis membrane module of the present invention has a mechanical strength that does not cause damage due to corrosion even when the corrosiveness of the permeated water is high, and is resistant to vibration and contact. Etc. are possible.
１、１’：中空糸膜エレメント
２、２’：中空糸膜
３、３’：供給流体分配管
４ａ、４ｂ、４ａ’、４ｂ’：樹脂
５ａ、５ｂ、５ａ’、５ｂ’：中空糸膜開口部
６ａ、６ｂ、６ａ’、６ｂ’：透過流体収集部
７、７’：内部管
８：圧力容器
９：供給水ノズル
１０：濃縮水ノズル
１１、１１’：透過水ノズル
１２：供給水
１３：濃縮水
１４、１４’：透過水
１５：Ｏ−リング
１６：中間コネクタ
DESCRIPTION OF SYMBOLS 1, 1 ': Hollow fiber membrane element 2, 2': Hollow fiber membrane 3, 3 ': Supply fluid distribution piping 4a, 4b, 4a', 4b ': Resin 5a, 5b, 5a', 5b ': Hollow fiber membrane Openings 6a, 6b, 6a ′, 6b ′: Permeated fluid collecting units 7, 7 ′: Inner pipe 8: Pressure vessel 9: Supply water nozzle 10: Concentrated water nozzle 11, 11 ′: Permeate water nozzle 12: Supply water 13 : Concentrated water 14, 14 ': Permeated water 15: O-ring 16: Intermediate connector
Claims (7)
The reverse osmosis membrane module according to any one of claims 1 to 6, wherein the reverse osmosis membrane is a hollow fiber type reverse osmosis membrane made of a cellulose acetate polymer.
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