JPH0322237B2 - - Google Patents
Info
- Publication number
- JPH0322237B2 JPH0322237B2 JP22762883A JP22762883A JPH0322237B2 JP H0322237 B2 JPH0322237 B2 JP H0322237B2 JP 22762883 A JP22762883 A JP 22762883A JP 22762883 A JP22762883 A JP 22762883A JP H0322237 B2 JPH0322237 B2 JP H0322237B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- water
- gas
- decarboxylation
- acidic water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000012528 membrane Substances 0.000 claims description 55
- 230000002378 acidificating effect Effects 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006114 decarboxylation reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 238000005341 cation exchange Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 3
- 230000000911 decarboxylating effect Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 15
- 239000012510 hollow fiber Substances 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
Description
【発明の詳細な説明】 本発明は、純水製造方法に関する。[Detailed description of the invention] The present invention relates to a method for producing pure water.
従来、純水は一般に原水を陽イオン交換し、脱
炭酸した後、陰イオン交換して製造されており、
上記脱炭酸は充填塔式気液接触又は真空式脱気法
によつて行なわれている。充填塔式気液接触法
は、陽イオン交換後の酸性水を充填塔にて空気と
気液接触させて炭酸ガスを放出させるので、この
気液接触の間に処理水に空気中のバクテリヤや微
粒子が混入し、しかも、バクテリヤは脱炭酸水が
貯槽に蓄えられる間に増殖して処理水を汚染す
る。また、脱炭酸の反面、酸素等の他の気体が処
理水溶解する問題もある。一方真空脱気法によれ
ば、上記した問題は解消されるものの、真空に必
要な10ｍ以上の水頭を確保するために装置が大型
化する。 Conventionally, pure water is generally produced by cation-exchanging raw water, decarboxylating it, and then anion-exchanging it.
The above decarboxylation is carried out by packed column gas-liquid contact or vacuum degassing. In the packed tower type gas-liquid contact method, acidic water after cation exchange is brought into gas-liquid contact with air in a packed tower to release carbon dioxide, so during this gas-liquid contact, bacteria and bacteria in the air are added to the treated water. Particulate matter is introduced, and bacteria proliferate and contaminate the treated water while the decarbonated water is stored in the storage tank. Furthermore, while decarboxylation is achieved, there is also the problem that other gases such as oxygen dissolve in the treated water. On the other hand, according to the vacuum deaeration method, although the above-mentioned problems are solved, the equipment becomes larger in order to secure a water head of 10 m or more required for vacuum.
本発明は上記した問題を解決するためになされ
たものであつて、脱炭酸を密閉系で行なうために
処理水にバクテリヤや微粒子の混入がなく、しか
も、装置を小型化し得る純粋製造方法を提供する
ことを目的とする。 The present invention has been made in order to solve the above-mentioned problems, and provides a pure manufacturing method in which decarboxylation is carried out in a closed system, so that treated water is not contaminated with bacteria or particulates, and the equipment can be miniaturized. The purpose is to
本発明による純水製造方法は、原水を陽イオン
交換し、脱炭酸し、次いで陰イオン交換して純水
を製造する方法において、気体は透過させるが水
は透過させない疎水性重合体多孔質膜に陽イオン
交換後の酸性水を接触させ、炭酸ガスを膜透過さ
せて脱炭酸することを特徴とする。 The method for producing pure water according to the present invention is a method for producing pure water by subjecting raw water to cation exchange, decarboxylation, and anion exchange using a hydrophobic polymer porous membrane that allows gas to pass through but not water. The method is characterized in that it is brought into contact with acidic water after cation exchange, and carbon dioxide gas is permeated through the membrane to be decarboxylated.
本発明において用いる膜は、疎水性重合体から
なる多孔質膜であつて、通気性を有して、炭酸ガ
スは透過するが、水は透過しない膜であることが
必要である。 The membrane used in the present invention is a porous membrane made of a hydrophobic polymer, and needs to be breathable, allowing carbon dioxide to pass therethrough but not water.
好ましくは、疎水性については、膜素材からフ
イルムを形成したとき、その接触角が50°以上で
ある。また、ガス透過量は5Nm3／m2・時・Kg／
cm2以上、好ましくは10Nm3／m2・時・Kg／cm2以上
であり、バブルポイントは0.5Kg／cm2以上、好ま
しくは１Kg／cm2以上であり、0.5Kg／cm2以下の圧
力では水を透過させないことを要する。但し、上
記において、ガス透過量は、多孔質膜の乾燥膜に
対する加圧空気又は窒素の透過量で表わされ、ま
た、バブルポイントはASTM Ｄ 2499に従つて
測定される。本発明において用いる多孔質膜は疎
水性であるため、バルブポイントは、環状又は中
空糸状に成形した膜の内部の空気をアルコールで
置換し、かかる膜をアルコール又は水中に浸漬
し、膜内部に加圧空気を送入し、空気が気泡とし
て膜を透過し始めるときの空気の圧力で表わされ
る。多孔膜質のガス透過量が5Nm3／m2・時・
Kg／cm2よりも少ないときは、脱炭酸の効率が悪く
なる。一方、ガス透過量は大きいほど好ましい
が、その上限はバルブポイントより自ずから制限
される。また、バルブポイントが0.5Kg／cm2より
も小さいときは、酸性水が膜を透過するおそれが
あるので好ましくない。 Preferably, regarding hydrophobicity, when a film is formed from the membrane material, its contact angle is 50° or more. In addition, the gas permeation amount is 5Nm 3 /m 2・hour・Kg/
cm 2 or more, preferably 10 Nm 3 /m 2 · hour · Kg / cm 2 or more, the bubble point is 0.5 Kg / cm 2 or more, preferably 1 Kg / cm 2 or more, and the pressure is 0.5 Kg / cm 2 or less Therefore, it is necessary not to allow water to pass through. However, in the above, the amount of gas permeation is expressed as the amount of pressurized air or nitrogen permeated through the dry porous membrane, and the bubble point is measured according to ASTM D 2499. Since the porous membrane used in the present invention is hydrophobic, the valve point is to replace the air inside the membrane formed into an annular or hollow fiber shape with alcohol, immerse the membrane in alcohol or water, and add water to the inside of the membrane. It is expressed as the pressure of air when the air begins to pass through the membrane as bubbles when compressed air is introduced. The gas permeation rate of the porous membrane is 5Nm 3 /m 2 hr.
When it is less than Kg/ cm2 , the efficiency of decarboxylation becomes poor. On the other hand, the larger the gas permeation amount, the better, but its upper limit is naturally limited by the valve point. Further, when the valve point is smaller than 0.5 Kg/cm 2 , acidic water may permeate through the membrane, which is not preferable.
上記のような特性を有する多孔膜質として、例
えばポリエチレン、ポリプロピレン等のポリオレ
フイン、ポリスルホン、ポリエーテルスルホン、
シリコーン樹脂、フツ素樹脂等からなる多孔膜質
を挙げることができる。また、親水性樹脂からな
る膜であつても、酸性水への接触面が上記のよう
な疎水性樹脂により疎水化されていれば、本発明
において疎水性多孔膜質として用いることができ
る。 Porous membranes having the above characteristics include, for example, polyolefins such as polyethylene and polypropylene, polysulfone, polyethersulfone,
Examples include porous membranes made of silicone resins, fluorine resins, and the like. Furthermore, even a membrane made of a hydrophilic resin can be used as a hydrophobic porous membrane in the present invention if the surface in contact with acidic water is made hydrophobic by the hydrophobic resin as described above.
また、本発明において用いる多孔膜質は、大き
い通気性を有するように、精密濾過膜又は限外濾
過膜であるのが好ましいが、特に、比較的高圧に
て酸性水を膜面に接触させて、効率よく脱炭酸し
得る限外濾過膜が好ましい。構造的には、上記限
外濾過膜又は精密濾過膜は、それらが有する微孔
は比較的均一であつてもよく、或いは一方又は両
方の表面に緻密層を有し、これが多孔膜質によつ
て支持される異方性膜であつてもよい。かかる多
孔膜質の厚みは、通常、５〜500μｍであればよ
く、必要に応じて、かかる膜はその強度を高める
ために、不織布等により裏打ちされていてもよ
い。また、形状は特に制限されず、平膜、管状
膜、中空糸状膜その他任意の形状の膜を用いるこ
とができる。 In addition, the porous membrane used in the present invention is preferably a microfiltration membrane or an ultrafiltration membrane so as to have high air permeability. An ultrafiltration membrane that can efficiently decarboxylate is preferred. Structurally, the ultrafiltration membrane or microfiltration membrane described above may have relatively uniform micropores, or may have a dense layer on one or both surfaces, which is caused by the porous nature of the membrane. It may also be a supported anisotropic membrane. The thickness of such a porous membrane may normally be 5 to 500 μm, and if necessary, such a membrane may be lined with a nonwoven fabric or the like to increase its strength. Further, the shape is not particularly limited, and membranes of any shape such as flat membranes, tubular membranes, hollow fiber membranes, etc. can be used.
本発明の方法は、上記のように多孔膜質が疎水
性であるため、その一方の表面に陽イオン交換し
た後の酸性水を加圧下に膜面に接触させても、水
が膜を透過しないにもかかわらず、この酸性水中
に溶存している炭酸ガスは、膜を透過し、かくし
て、効率よく酸性水を脱炭酸することができる。
上記膜の他方の表面側は大気圧でもよいが、好ま
しくは減圧する。但し、膜を挿む圧力差は膜のバ
ルブポイント以下であることが必要である。 In the method of the present invention, since the porous membrane is hydrophobic as described above, even if acidic water after cation exchange is brought into contact with the membrane surface under pressure, water will not pass through the membrane. Nevertheless, the carbon dioxide gas dissolved in this acidic water permeates through the membrane, and thus the acidic water can be efficiently decarboxylated.
The other surface side of the membrane may be at atmospheric pressure, but preferably at reduced pressure. However, the pressure difference when inserting the membrane must be below the valve point of the membrane.
図面は本発明の方法を実施するための脱炭酸装
置の好ましい一例を示し、陽イオン交換後の酸性
水の入口１と脱炭酸水の出口２を有する円筒状の
外套３内に多数の前記したような疎水性多孔質中
空糸状膜４が集束されて収容されており、各中空
系状膜の両端はそれぞれ酸性水入口及び脱炭酸水
出口に開口するように樹脂５で外套に封止固定さ
れている。 The drawing shows a preferred example of a decarboxylation device for carrying out the method of the invention, in which a number of the above-mentioned units are housed in a cylindrical jacket 3 having an inlet 1 for acidic water after cation exchange and an outlet 2 for decarbonated water. Hydrophobic porous hollow fiber membranes 4 such as the one described above are housed in a bundle, and both ends of each hollow membrane are sealed and fixed to the jacket with resin 5 so as to open to the acidic water inlet and the decarbonated water outlet, respectively. ing.
また、外套は酸性水出口及び脱炭酸水出口の近
傍でそれぞれ排気口６及び７に接続され、これら
排気口は適宜の減圧手段に接続されて、外套内が
減圧される。従つて、酸性水入口から上記中空繊
維膜に分配された酸性水は膜を介して減圧雰囲気
と接触されるため、酸性水中の炭酸ガスは膜を透
過し、酸性水は脱炭酸去れた後、脱炭酸出口から
脱炭酸水を得る。 Further, the mantle is connected to exhaust ports 6 and 7 near the acidic water outlet and the decarbonated water outlet, respectively, and these exhaust ports are connected to appropriate pressure reducing means to reduce the pressure inside the mantle. Therefore, the acidic water distributed from the acidic water inlet to the hollow fiber membrane is brought into contact with the reduced pressure atmosphere through the membrane, so the carbon dioxide gas in the acidic water permeates through the membrane, and after the acidic water is decarboxylated, Obtain decarbonated water from the decarboxylation outlet.
尚、外套内を減圧する代わりに、上記排気口の
うち一方をパージガス入口、他方をパージガス出
口として、外套内パージガスを流通させてもよ
い。但し、この場合、膜内の水圧が外套内のパー
ジガス圧より高いことが必要である。 Note that instead of reducing the pressure inside the mantle, one of the exhaust ports may be used as a purge gas inlet and the other as a purge gas outlet, and the purge gas inside the mantle may be allowed to flow. However, in this case, it is necessary that the water pressure within the membrane be higher than the purge gas pressure within the mantle.
また、脱炭酸装置としては、逆浸透膜モジユー
ルにおいて知られるスパイラル型（特公昭44−
14216号等）やプリーツ型（実公昭56−33608号）
等であつてもよい。 In addition, as a decarboxylation device, we use a spiral type known in reverse osmosis membrane modules.
14216, etc.) and pleated type (Jikko No. 56-33608)
etc. may be used.
以上のように、本発明の方法によれば、脱炭酸
のための気液接触が膜を介して密閉系で行なわれ
るため、脱炭酸の過程で大気中のバクテリアや微
粒子が混入することがなく、また、酸素が不必要
に溶解することもないうえに、装置を小型化し得
て、効率よく純水を得ることができる。 As described above, according to the method of the present invention, the gas-liquid contact for decarboxylation is performed in a closed system through a membrane, so that bacteria and particles in the atmosphere are not mixed in during the decarboxylation process. Moreover, oxygen is not dissolved unnecessarily, the apparatus can be downsized, and pure water can be obtained efficiently.
実施例 １
TDS115ppm、PH6.4、Ｍアルカリ度51.9ppmの
原水を酸型陽イオン交換樹脂により陽イオン交換
して、PH2.9、炭酸ガス濃度63ppmの酸性水を得
た。Example 1 Raw water with TDS of 115 ppm, PH of 6.4, and M alkalinity of 51.9 ppm was cation-exchanged using an acid type cation exchange resin to obtain acidic water with PH of 2.9 and carbon dioxide concentration of 63 ppm.
バルブポイント10Kg／cm2以上、ガス透過量20
m3／m2・時・Kg／cm2のポリスルホン中空糸状膜を
多数外套内に平行に集束して図示したような膜モ
ジユールを構成し、外套内を50mmHgに減圧しつ
つ、上で得た酸性水を膜モジユールに通水して脱
炭酸し。このようにして得た脱炭酸水中の炭酸ガ
ス濃度は5ppm以下であつた。次いで、この脱炭
酸水を陰イオン交換して電気抵抗0.5MΩcmの純
水を得た。この純水に含まれる0.2μｍ以上の微粒
子は約103個／mlであり、溶存酸素は2ppmであつ
た。 Valve point 10Kg/cm2 or more, gas permeation amount 20
A membrane module as shown was constructed by converging a large number of polysulfone hollow fiber membranes of m 3 /m 2 hr.Kg/cm 2 in parallel inside the mantle, and while reducing the pressure inside the mantle to 50 mmHg, the membrane obtained above was Acidic water is decarboxylated by passing through the membrane module. The carbon dioxide concentration in the decarbonated water thus obtained was 5 ppm or less. Next, this decarbonated water was subjected to anion exchange to obtain pure water with an electrical resistance of 0.5 MΩcm. This pure water contained approximately 10 3 particles/ml of particles larger than 0.2 μm, and dissolved oxygen was 2 ppm.
一方、比較のために脱炭酸装置として従来の充
填塔式気液接触装置を用いた以外は上記と全く同
様に原水を処理した結果、得られた純水に含まれ
る微粒子数は約105個／ml、溶存酸素濃度は約
10ppmであつた。 On the other hand, for comparison, raw water was treated in exactly the same manner as above except that a conventional packed column type gas-liquid contact device was used as the decarboxylation device, and the number of fine particles contained in the obtained pure water was approximately 10 5 /ml, dissolved oxygen concentration is approx.
It was 10ppm.
実施例 ２
バルブポイント５Kg／cm2、ガス透過量500N
m3／m2・時・Kg／cm2のフツ素樹脂多孔膜質（日東
電気工業(株)製NTF−5800）を備え、透過側を減
圧に保つたスパイラル型膜モジユールを脱炭酸装
置として実施例１と同様に原水を処理し、電気抵
抗0.5MΩcm．微粒子数約103個／ml、溶存酸素
2ppm以下の純水を得た。Example 2 Valve point 5Kg/cm 2 , gas permeation amount 500N
A spiral-type membrane module equipped with a fluororesin porous membrane (NTF-5800, manufactured by Nitto Electric Industries, Ltd.) with a capacity of m 3 /m 2 hr.Kg/cm 2 and maintaining a reduced pressure on the permeate side was used as a decarboxylation device. Raw water was treated in the same manner as in Example 1, and the electrical resistance was 0.5 MΩcm. Number of fine particles: approx. 103 particles/ml, dissolved oxygen
Pure water of less than 2 ppm was obtained.
図面は本発明の方法における脱炭酸装置の好ま
しい一例を示す断面図である。
１……酸性水入口、２……脱炭酸水出口、３…
…外套、４……中空糸状膜、５……樹脂、６，７
……排気口。
The drawing is a sectional view showing a preferred example of a decarboxylation device in the method of the present invention. 1...Acidic water inlet, 2...Decarbonated water outlet, 3...
...Cloak, 4...Hollow fiber membrane, 5...Resin, 6,7
……exhaust port.
Claims (1)
イオン交換して純水を製造する方法において、気
体は透過させるが水は透過させない疎水性重合体
多孔質膜に陽イオン交換後の酸性水を接触させ、
炭酸ガスを膜透過させて脱炭酸することを特徴と
する純水製造方法。1 In a method of producing pure water by cation-exchanging raw water, decarboxylating it, and then anion-exchanging it, acidic water after cation-exchange is passed through a hydrophobic polymer porous membrane that allows gas to pass through but not water. in contact with
A method for producing pure water characterized by decarboxylation by permeating carbon dioxide gas through a membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22762883A JPS60118284A (en) | 1983-11-30 | 1983-11-30 | Pure water preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22762883A JPS60118284A (en) | 1983-11-30 | 1983-11-30 | Pure water preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60118284A JPS60118284A (en) | 1985-06-25 |
| JPH0322237B2 true JPH0322237B2 (en) | 1991-03-26 |
Family
ID=16863893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22762883A Granted JPS60118284A (en) | 1983-11-30 | 1983-11-30 | Pure water preparing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60118284A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02303587A (en) * | 1989-05-16 | 1990-12-17 | Dainippon Ink & Chem Inc | Device and method for cleaning water |
| JPH0377683A (en) * | 1989-08-18 | 1991-04-03 | Takuma Co Ltd | Pure water producing device |
| JPH0380983A (en) * | 1989-08-24 | 1991-04-05 | Dainippon Ink & Chem Inc | Gas-liquid contact type water purifying apparatus and method |
-
1983
- 1983-11-30 JP JP22762883A patent/JPS60118284A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60118284A (en) | 1985-06-25 |
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