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JP3001608B2 - Removal method of gas or low boiling volatile organic matter - Google Patents

Removal method of gas or low boiling volatile organic matter

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Publication number
JP3001608B2
JP3001608B2 JP2109855A JP10985590A JP3001608B2 JP 3001608 B2 JP3001608 B2 JP 3001608B2 JP 2109855 A JP2109855 A JP 2109855A JP 10985590 A JP10985590 A JP 10985590A JP 3001608 B2 JP3001608 B2 JP 3001608B2
Authority
JP
Japan
Prior art keywords
water
gas
volatile organic
aqueous solution
low
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 - Lifetime
Application number
JP2109855A
Other languages
Japanese (ja)
Other versions
JPH047002A (en
Inventor
武 佐々木
修美 戸沢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
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Filing date
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Priority to JP2109855A priority Critical patent/JP3001608B2/en
Publication of JPH047002A publication Critical patent/JPH047002A/en
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Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、水溶液中に溶解した気体、もしくは低沸点
揮発性有機物の除去方法に関する。
The present invention relates to a method for removing gas or low-boiling volatile organic substances dissolved in an aqueous solution.

〔従来の技術及び発明が解決しようとする課題〕[Problems to be solved by conventional technology and invention]

水溶液の使用上、その中に溶存している気体もしくは
溶解している有機物の除去を必要とする分野は非常に多
い。
There are numerous fields in which the use of aqueous solutions requires the removal of dissolved gases or dissolved organic matter therein.

例えば分析機器関連としては液体クロマトグラフィ
ー、自動臨床化学分析、医用分光光度計等の脱気があ
る。また工業用用途としては、イオン交換水プロセス、
超純水システム、ボイラー用水、原発用水、タービン用
水等の脱気がある。
For example, related to analytical instruments are degassing such as liquid chromatography, automatic clinical chemistry analysis, and medical spectrophotometer. Industrial applications include ion exchange water processes,
Deaeration of ultrapure water systems, boiler water, nuclear power water, turbine water, etc.

例えば、液体クロマトグラフィーでは、溶媒に空気が
溶存していると、ポンプ内、弁周辺、検知器内に気泡が
生じトラブルの原因となる。また溶存酸素は溶質と化学
反応を起こす可能性もある。自動臨床化学分析では、検
体量の少量化に伴い、わずかの溶存酸素も分析精度に悪
影響を及ぼす。また分光光度計では紫外短波長領域にお
ける溶存酸素等による吸収の影響が大きい。一方、イオ
ン交換水プロセスでは液体中の溶存酸素や炭酸ガスがイ
オン交換樹脂の寿命を短くする。さらにボイラー用水、
原発用水では溶存酸素が容器、配管等の腐食を促進す
る。
For example, in liquid chromatography, when air is dissolved in a solvent, air bubbles are generated in a pump, around a valve, and in a detector, causing a trouble. Also, dissolved oxygen may cause a chemical reaction with the solute. In automated clinical chemistry analysis, small amounts of dissolved oxygen adversely affect the analysis accuracy as the sample volume is reduced. In a spectrophotometer, absorption by dissolved oxygen and the like in an ultraviolet short wavelength region has a large influence. On the other hand, in the ion exchange water process, dissolved oxygen or carbon dioxide in the liquid shortens the life of the ion exchange resin. Boiler water,
In nuclear power water, dissolved oxygen promotes corrosion of containers, piping, etc.

従来より液体中の溶存ガスを脱気するために、例えば
加熱沸騰法、減圧法、超音波法、ヘリウム法等の方法が
知られている。しかしながら加熱沸騰法は高温操作のた
め危険性が高く、減圧法および超音波法は脱気能力が低
く、ヘリウム法は運転費が高いなど決して効果的、経済
的な方法ではなかった。
Conventionally, methods for degassing a dissolved gas in a liquid, such as a heating boiling method, a decompression method, an ultrasonic method, and a helium method, are known. However, the heating and boiling method has a high danger due to high temperature operation, the decompression method and the ultrasonic method have low degassing ability, and the helium method is not an effective and economical method because the operation cost is high.

さらに詳しく述べると、例えばボイラー用水中に溶存
しているガス、主に溶存酸素は、ボイラー、プレボイラ
ー系の特に孔食の主原因になるので、それを除去する処
理が必要になる。かかる脱酸素には、脱気器を用いて加
熱沸騰法や真空法等により機械的に脱酸素する方法と、
溶存酸素を化学的に還元する例えばヒドラジンや亜硫酸
ナトリウム等の脱酸素剤を注入する方法があり、これら
の方法を併用しなければ脱酸素効率を大きくすることが
できず、特に中高圧ボイラーには不可欠の処理である。
More specifically, for example, gas dissolved in boiler water, mainly dissolved oxygen, is a major cause of pitting corrosion in boiler and pre-boiler systems, so that a treatment for removing it is necessary. For such deoxidation, a method of mechanically deoxidizing by a heating boiling method or a vacuum method using a deaerator,
There is a method of injecting an oxygen scavenger such as hydrazine or sodium sulfite to chemically reduce dissolved oxygen, and it is not possible to increase the oxygen scavenging efficiency unless these methods are used in combination. Indispensable processing.

また飲料水やビル給水中に溶存しているガス、主に溶
存酸素は、給水管の腐蝕の主原因であり、この腐蝕が赤
水の発生へとつながる。赤水は味などの感覚的問題や洗
濯物の着色などの障害を与えるため、その発生が認めら
れた場合は何らかの対策を検討する必要が生じる。現
在、かかる赤水対策として給水管の敷設替え、ライニン
グによる管更迭、給水用防錆剤の連続注入等が行われて
いる。これら赤水発生防止対策は、いずれも経済性、確
実性、安全性などの面で必ずしも十分とは言えず、各種
の制約を伴う。従って、安価で簡便かつ確実な防止方法
が望まれている。
Gases dissolved in drinking water and building supply water, mainly dissolved oxygen, are the main cause of corrosion of water supply pipes, and this corrosion leads to generation of red water. Since red water causes sensory problems such as taste and discoloration of laundry, it is necessary to consider some countermeasures when its occurrence is recognized. At present, replacement of water supply pipes, replacement of pipes by lining, continuous injection of rust preventives for water supply, and the like are being performed as measures against such red water. All of these measures for preventing the generation of red water are not necessarily sufficient in terms of economy, reliability, safety, etc., and involve various restrictions. Therefore, an inexpensive, simple and reliable prevention method is desired.

また従来、超純水システムにおける脱気の目的は大き
く分けて2種類ある。その一つはイオン交換プロセス中
の陰イオン交換樹脂の寿命を延ばすための脱溶存炭酸ガ
スであり、もう一つは超純水中での生菌の発生を抑制す
るための脱溶存酸素である。半導体の製造において、メ
モリー容量が256Kビットレベルまでは、上記の目的のた
めの溶存酸素濃度(以下、DO値という)としては、0.5p
pmレベルで十分であった。その結果、脱気方法として真
空脱気方法が用いられてきた。
Conventionally, the purpose of deaeration in an ultrapure water system is roughly divided into two types. One is de-dissolved carbon dioxide to extend the life of the anion exchange resin during the ion-exchange process, and the other is de-dissolved oxygen to suppress the generation of viable bacteria in ultrapure water. . In the manufacture of semiconductors, when the memory capacity is up to the 256 Kbit level, the dissolved oxygen concentration (hereinafter referred to as DO value) for the above purpose is 0.5p
The pm level was enough. As a result, a vacuum degassing method has been used as a degassing method.

しかし近年、メモリー容量が更に大きい4Mビット、16
Mビットの半導体が開発されつつある。
However, in recent years, the memory capacity is even larger, 4Mbit, 16Mbit.
M-bit semiconductors are being developed.

これら大容量の半導体の製造においては、脱気の目的
として上記の2点以外に、溶存酸素によるシリコンウエ
ハー上の酸化被膜形成を防止する点が加わっている。こ
の溶存酸素によるシリコンウエハーの酸化を防止するた
めには、DO値として0.01〜0.05ppmが要求される。さら
にユースポイント付近での脱気を行なう必要があるた
め、脱気装置としても比較的小型の装置が要求される。
しかしながら従来の真空脱気装置では脱溶存酸素能力が
不十分であり、また装置サイズもかなり大きくなるとい
う欠点があった。
In the production of these large-capacity semiconductors, in addition to the above two points, the point of preventing formation of an oxide film on a silicon wafer due to dissolved oxygen is added for the purpose of degassing. To prevent oxidation of the silicon wafer by the dissolved oxygen, a DO value of 0.01 to 0.05 ppm is required. Furthermore, since it is necessary to perform degassing near the use point, a relatively small degassing device is required.
However, the conventional vacuum degassing apparatus has the drawbacks that the dissolved oxygen capacity is insufficient and the size of the apparatus becomes considerably large.

また、一般にビール、ジュース、コーヒー等の飲料製
造に使用する原料水やそれらの製造工程で使用する水で
ある飲料製造用水は、製品の劣化、酸化を防止するため
に溶存酸素を除去しかつ無菌のものが望ましい。
In addition, raw water used for the production of beverages such as beer, juice and coffee and water used in the production of beverages, which is used in the production process, remove dissolved oxygen to prevent product deterioration and oxidation and remove aseptic and sterile water. Is desirable.

従来、このような目的に使用する水を造るため、加熱
沸騰法、減圧法、二酸化炭素ガス又は二酸化炭素ガスと
不活性ガスの混合ガスを被処理水に接触させる方法等で
被処理水を脱気する方法が知られている。
Conventionally, in order to produce water used for such a purpose, the water to be treated is removed by a heating boiling method, a decompression method, a method of bringing carbon dioxide gas or a mixed gas of carbon dioxide gas and an inert gas into contact with the water to be treated, or the like. There are known ways to care.

しかしながら、加熱沸騰法では、水中の溶存酸素を0.
1ppm程度にするには被処理水を104℃以上に加熱するこ
とが必要であり、この加熱によりエネルギーコストが高
くなり、さらに長時間の運転により装置の各部にスケー
ルが沈着し、その洗浄に多大な労力を必要とする。減圧
法は、水中の溶存酸素を0.2ppm程度までしか減少させる
ことができず脱気能力が低いという欠点があった。また
二酸化炭素ガスを被処理水に接触させる方法は、水中の
溶存酵素を0.1ppm程度にするには装置内にラッシヒリニ
グ等の充填材をつめ、かつ温度を70℃程度の高温にする
ことが必要であり、この充填材を洗浄するのに大変な労
力を必要とする。またコーヒー等の抽出用水に使用した
場合、水中に二酸化炭素が溶解しているため、美味で風
味豊かなコーヒーが得られない。また二酸化炭素ガスと
不活性ガスの混合ガスを被処理水に接触させる方法で
は、水中の溶存酸素を0.05ppm程度にするには、被処理
水を101℃以上に加熱することが必要であり、この場合
も加熱によるエネルギーコストが高くなるうえ、上記と
同様に美味で風味豊かなコーヒーが得られないという問
題があった。
However, in the heating boiling method, dissolved oxygen in water is reduced to 0.
It is necessary to heat the water to be treated to 104 ° C or higher to make it about 1 ppm, and this heating increases the energy cost. Requires great effort. The decompression method has a drawback that the dissolved oxygen in water can be reduced only to about 0.2 ppm and the degassing ability is low. In addition, the method of bringing carbon dioxide gas into contact with the water to be treated requires filling the equipment with a filler such as lashing nig and raising the temperature to about 70 ° C in order to reduce dissolved enzymes in the water to about 0.1 ppm. However, cleaning the filler requires great effort. In addition, when used in water for extracting coffee or the like, delicious and flavorful coffee cannot be obtained because carbon dioxide is dissolved in the water. In the method of contacting the mixed gas of the carbon dioxide gas and the inert gas with the water to be treated, it is necessary to heat the water to be treated to 101 ° C. or higher to make the dissolved oxygen in the water about 0.05 ppm, In this case, too, there is a problem that the energy cost by heating becomes high and a delicious and flavorful coffee cannot be obtained similarly to the above.

また半導体関連等において、非水中に含まれるクロロ
ホルム、トリクロロエタン、トリクロロエチレン、四塩
化炭素、カーボンテトラクロライド、テトラクロロエチ
レン等の低沸点揮発性有機物は、環境問題の点から回収
しなければならない。しかし、現在用いられている活性
炭吸着法では、排水が希薄水溶液であるため、回収コス
トが非常に高くなり経済的でない。
Further, in semiconductors and the like, low-boiling volatile organic substances such as chloroform, trichloroethane, trichloroethylene, carbon tetrachloride, carbon tetrachloride, and tetrachloroethylene contained in non-water must be recovered from the viewpoint of environmental problems. However, in the activated carbon adsorption method currently used, the wastewater is a dilute aqueous solution, so that the recovery cost is extremely high and it is not economical.

飲料水分野においても、水源の川や湖等の汚染によ
り、従来は含まれていなかった低沸点揮発性有機物が、
環境基準以上の値を示すようになったり、さらに汚染の
進行とともに塩素殺菌のため、塩素使用量が増大し、化
学反応によって塩素系有機物が生成されるようになって
いる。しかし、近年の飲料水への関心の高まりととも
に、高度処理が必要とされているにもかかわらず、コス
ト的な問題から有効な処理がなされていないのが現状で
ある。
In the field of drinking water, low-boiling volatile organic substances that had not been included before due to pollution of rivers and lakes, etc.
The amount of chlorine used has become higher than the environmental standard, and furthermore, the amount of chlorine used has increased due to chlorine sterilization with the progress of pollution, and chlorine-based organic substances have been generated by chemical reactions. However, with the growing interest in drinking water in recent years, despite the need for advanced treatment, effective treatment has not been performed due to cost issues.

以上に述べた如く、気体もしくは低沸点揮発性有機物
の除去を必要とする分野は非常に多く、いずれの分野に
おいても満足できる除去方法はなかった。
As described above, there are so many fields that require removal of gas or low-boiling volatile organic substances, and there has been no satisfactory removal method in any of the fields.

近年、シリコーン、ポリテトラフルオロエチレン等の
合成樹脂からなるチューブ(中空)状の膜を用いた脱気
方法が提案されている(特開昭60−25514号、実開昭63
−43609号等)。
In recent years, a deaeration method using a tube (hollow) membrane made of a synthetic resin such as silicone or polytetrafluoroethylene has been proposed (Japanese Patent Application Laid-Open No. Sho 60-25514, Japanese Utility Model Application Laid-Open No. 63-63).
No. 43609).

しかしながら、かかる合成樹脂からなる薄膜は機械的
強度上及び成形上限界があり、実用的に脱気用膜として
使用するには、経済効率を決定する脱気速度が小さくな
るほど膜厚を大きくしなければならないという問題があ
った。
However, a thin film made of such a synthetic resin has limitations in mechanical strength and molding, and in order to use it practically as a film for deaeration, the film thickness must be increased as the deaeration rate that determines economic efficiency decreases. There was a problem that had to be.

〔課題を解決するための手段〕[Means for solving the problem]

本発明者らは、種々の水溶液中に溶存する気体もしく
は低沸点揮発性有機物の除去における前記問題点を解決
するために鋭意研究した結果、水不透過性膜を介して、
他方を、水溶液成分の蒸気圧をゼロに近づけることによ
り、かつその際上記水溶液の液温を室温以上かつ水の沸
点以下とすることにより、効率よく上記成分を除去する
ことができることを見い出して、本発明に至ったもので
ある。
The present inventors have conducted intensive studies to solve the above-mentioned problems in removing gas or low-boiling volatile organic substances dissolved in various aqueous solutions, and as a result, through a water-impermeable membrane,
On the other hand, by making the vapor pressure of the aqueous solution component close to zero, and at that time, by setting the liquid temperature of the aqueous solution to be equal to or higher than room temperature and equal to or lower than the boiling point of water, it has been found that the component can be efficiently removed. This has led to the present invention.

即ち本発明は、水不透過性膜を介して、一方に、気体
溶解水溶液もしくは低沸点揮発性有機物溶解水溶液を、
室温以上かつ水の沸点以下に保ちながら接触させ、他方
を、該水溶液成分の蒸気圧をゼロに近づけることによ
り、透過する溶解成分を除去することを特徴とする気体
もしくは低沸点揮発性有機物の除去方法を提供する。
That is, the present invention, through a water-impermeable membrane, on the one hand, a gas-dissolved aqueous solution or a low-boiling volatile organic substance-dissolved aqueous solution,
Gas or low-boiling volatile organic substances are removed while maintaining the temperature at room temperature or higher and the boiling point of water or lower while bringing the other into contact with the vapor pressure of the aqueous solution component close to zero, thereby removing dissolved components that permeate. Provide a way.

本発明が適用される水溶液は、その中に気体が溶存し
ている水溶液もしくは低沸点揮発性有機物が溶解してい
る水溶液であれば、特に限定されない。
The aqueous solution to which the present invention is applied is not particularly limited as long as it is an aqueous solution in which gas is dissolved or an aqueous solution in which low-boiling volatile organic substances are dissolved.

例えば、液体クロマトグラフィー、自動臨床化学分
析、医用分光光度計等の分析機器関連、イオン交換水プ
ロセス、半導体製造用の超純水システム、発電用、一般
産業用、船舶用ボイラー等に用いられるボイラー用水、
原発用水、タービン用水等の工業用途関連に用いられる
液体及び排水等が挙げられる。これらの液体は通常、河
川水、井水、水道水、工業用水、局方常水等を含み、一
般にCa、Mg、Na、K等の陽イオン、塩素イオン、硫酸イ
オン、炭酸水素イオン等の陰イオン、生物が腐敗分解し
た有機物を含有している液体である。また、コロイド粒
子、懸濁粒子等の水に対して溶解性を示さない物質を含
有している液体も含まれる。
For example, boilers used for liquid chromatography, automated clinical chemistry analysis, analytical instruments such as medical spectrophotometers, ion-exchange water processes, ultrapure water systems for semiconductor manufacturing, power generation, general industry, and marine boilers Water,
Liquids and wastewaters used for industrial applications, such as water for nuclear power plants and water for turbines, may be mentioned. These liquids usually include river water, well water, tap water, industrial water, local water, etc., and generally include cations such as Ca, Mg, Na, and K, chloride ions, sulfate ions, and hydrogen carbonate ions. It is a liquid containing anions and organic substances decomposed by living organisms. Further, a liquid containing a substance that does not dissolve in water, such as colloid particles and suspended particles, is also included.

また本発明は一般家庭用水道配管、ビル給水管、クー
リングタワー、循環水配管等の内部を流れる飲料水やビ
ル給水にも適用できる。
The present invention can also be applied to drinking water and building water flowing inside general household water pipes, building water supply pipes, cooling towers, circulating water pipes, and the like.

また本発明は醤油等の製造用水、ビール、酒、ジュー
ス、コーヒー等の飲料の製造に使用する原料水や製造工
程で使用する水にも適用できる。
The present invention can also be applied to raw water used in the production of beverages such as soy sauce, beer, sake, juice, coffee and the like and water used in the production process.

上記の種々の水溶液に溶解している気体とは、酸素、
炭酸ガス、窒素、塩素、アンモニア等である。
The gases dissolved in the various aqueous solutions described above include oxygen,
Carbon dioxide, nitrogen, chlorine, ammonia and the like.

また、低沸点揮発性有機物とは、水より沸点が低い物
質であり、その蒸気圧が同温度で大きいものを指す。例
えば、メタノール、エタノール、ブタノール、プロパノ
ール等の低級アルコール、四塩化炭素、クロロホルム、
フロン等のハロゲン炭化水素、その他メチルエーテル、
エチルエーテル等のエーテル類、メチルエチルケトン、
アセトン等のケトン類等が挙げられる。
In addition, a low-boiling volatile organic substance is a substance having a boiling point lower than that of water and having a high vapor pressure at the same temperature. For example, methanol, ethanol, butanol, lower alcohols such as propanol, carbon tetrachloride, chloroform,
Halogen hydrocarbons such as Freon, other methyl ethers,
Ethers such as ethyl ether, methyl ethyl ketone,
And ketones such as acetone.

本発明においては、上記水溶液を室温以上かつ水の沸
点以下に保ちながら水不透過性膜の一方に接触させ、他
方において水溶液成分の蒸気圧をゼロに近づけることに
より、透過する溶解成分を除去する。
In the present invention, the aqueous solution is brought into contact with one of the water-impermeable membranes while maintaining the aqueous solution at room temperature or higher and the boiling point of water or lower, and the vapor component of the aqueous solution component is brought close to zero on the other side, thereby removing the permeated dissolved component. .

上記水溶液を水不透過性膜に接触させる際の水溶液の
液温は、室温(通常20℃程度)以上かつ水の沸点以下で
あれば特に限定されないが、通常20〜60℃とするのが好
ましい。上記範囲外の液温の場合、膜モジュール構成部
材、装置配管部材等が耐熱性を必要とし、設備費の増加
を招き、室温以下では液粘度の上昇等でポンプ負荷が増
加するので好ましくない。
The temperature of the aqueous solution when the aqueous solution is brought into contact with the water-impermeable membrane is not particularly limited as long as it is at least room temperature (usually about 20 ° C.) and the boiling point of water, but is preferably 20 to 60 ° C. . If the liquid temperature is out of the above range, the membrane module constituent members, the apparatus piping members, etc. need to have heat resistance, which leads to an increase in equipment costs, and below room temperature, the pump load increases due to an increase in liquid viscosity, which is not preferable.

本発明における水溶液成分の蒸気圧をゼロに近づける
方法としては、真空ポンプ等で機械的に透過成分を除去
する方法、不活性ガスを流して透過成分を除去する方
法、または透過成分が水より溶解度の高い溶媒を流して
透過成分を除去する方法が挙げられる。
The method of bringing the vapor pressure of the aqueous solution component in the present invention close to zero includes a method of mechanically removing a permeated component with a vacuum pump or the like, a method of removing the permeated component by flowing an inert gas, or a method in which the permeated component is more soluble than water And removing a permeated component by flowing a solvent having a high concentration.

ここで、真空ポンプ等で機械的に透過成分を除去する
場合、透過成分として被除去成分以外に水蒸気が透過し
て、真空ポンプの負荷が増大し運転コストが増加する場
合がある。また不活性ガスを流して透過成分を除去する
場合には、不活性ガスへ被除去成分以外の水蒸気が透過
し、目的成分の除去効率が落ちる恐れがある。よって、
真空ポンプを用いる場合は、操作温度の飽和水蒸気以上
に、真空度を上げないようにしたり、不活性ガスを用い
る場合には、あらかじめ操作温度の水蒸気を含ませた湿
った不活性ガス、すなわち操作温度における飽和水蒸気
と平衡な不活性ガスを流すことが好ましく、これによ
り、さらに効率よく透過成分を除去できる。
Here, when mechanically removing a permeated component with a vacuum pump or the like, water vapor may permeate as a permeated component other than the component to be removed, which may increase the load on the vacuum pump and increase operating costs. Further, when the permeated component is removed by flowing an inert gas, water vapor other than the component to be removed permeates the inert gas, and the efficiency of removing the target component may be reduced. Therefore,
When using a vacuum pump, do not raise the degree of vacuum above the saturated steam at the operating temperature, or when using an inert gas, wet inert gas containing steam at the operating temperature in advance, It is preferable to flow an inert gas which is in equilibrium with the saturated steam at the temperature, so that the permeated component can be more efficiently removed.

本発明において用いる不活性ガスは、特に制限されな
いが、例えば通常、窒素、アルゴン、ヘリウム等が挙げ
られ、透過成分によっては空気や炭酸ガス等も使用でき
る。
The inert gas used in the present invention is not particularly limited, but usually includes, for example, nitrogen, argon, helium and the like, and depending on the permeated component, air or carbon dioxide gas can also be used.

また本発明において用いられる、透過成分を溶かす溶
媒も、その透過成分に応じて適宜選ばれ、例えば、低沸
点揮発性有機物としてエタノールを含む水溶液に対して
は、メチルエーテル、エチルエーテル等のエーテル類が
用いられる。
The solvent used in the present invention to dissolve the permeating component is also appropriately selected according to the permeating component. For example, for an aqueous solution containing ethanol as a low-boiling volatile organic substance, ethers such as methyl ether and ethyl ether are used. Is used.

本発明において用いる水不透過性膜は、特にその構造
に限定されないが、例えば非多孔質活性薄膜からなる均
質膜や、緻密層または活性緻密層とこれを一体に支持す
る多孔質層とからなる非対称膜や、かかる非対称膜上に
非多孔質活性薄膜が形成されてなる複合膜、好ましくは
非対称膜の緻密層中に非多孔質活性薄膜が一部しみこん
で形成されてなる複合膜等である。ここで活性とは、溶
存物質と液体とを分離する性質を有するという意味であ
る。
The water-impermeable membrane used in the present invention is not particularly limited to its structure, but includes, for example, a homogeneous membrane made of a non-porous active thin film, and a dense layer or an active dense layer and a porous layer integrally supporting the same. An asymmetric membrane, a composite membrane in which a non-porous active thin film is formed on such an asymmetric membrane, preferably a composite membrane in which a non-porous active thin film is partially impregnated in a dense layer of the asymmetric membrane, and the like. . Here, the activity means having a property of separating a dissolved substance and a liquid.

上記水不透過性膜の30℃における窒素ガス透過速度
は、7×10-4〜2×102Nm3/m2・h・atm、好ましくは、
3×10-3〜5×100Nm3/m2・h・atmである。窒素ガス透
過速度が7×10-4Nm3/m2・h・atmより小さい場合、溶
存物質の透過速度が小さくなる恐れがあり、一方 2×
102Nm3/m2・h・atmより大きい場合は、水不透過性が維
持できなくなる可能性があるため好ましくない。
The nitrogen gas permeation rate at 30 ° C. of the water-impermeable membrane is 7 × 10 −4 to 2 × 10 2 Nm 3 / m 2 · h · atm, preferably
It is 3 × 10 -3 to 5 × 10 0 Nm 3 / m 2 · h · atm. If the nitrogen gas permeation rate is smaller than 7 × 10 −4 Nm 3 / m 2 · h · atm, the permeation rate of the dissolved substance may decrease, while 2 ×
If it is larger than 10 2 Nm 3 / m 2 · h · atm, it is not preferable because water impermeability may not be maintained.

上記均質膜や非多孔質活性薄膜の具体例としては、シ
リコーン、ポリ(4−メチルペンテン−1)、天然ゴ
ム、ポリ(2,6−ジメチルフェニレンオキシド、テフロ
ン、ネオプレン、ポリエチレン、ポリスチレン、ポリプ
ロピレン等が挙げられる。
Specific examples of the homogeneous film and the non-porous active thin film include silicone, poly (4-methylpentene-1), natural rubber, poly (2,6-dimethylphenylene oxide, Teflon, neoprene, polyethylene, polystyrene, polypropylene, etc. Is mentioned.

また本発明において用いる非対称膜は特に限定されな
いが、例えば芳香族ポリスルホン系、芳香族ポリアミド
系、芳香族ポリイミド系等が挙げられるが、特に耐塩素
性、耐pH性、耐熱性等の水系での耐久性を有するという
理由により、芳香族ポリスルホン系が好ましく用いられ
る。
Further, the asymmetric membrane used in the present invention is not particularly limited, for example, aromatic polysulfone-based, aromatic polyamide-based, aromatic polyimide-based and the like, but particularly chlorine-resistant, pH-resistant, and water-based such as heat resistance. For reasons of durability, aromatic polysulfones are preferably used.

前記水不透過性膜の形状は特に限定されないが、中空
糸状または平膜状が好ましく、不織布のような補強材上
に形成されていてもよい。
The shape of the water-impermeable membrane is not particularly limited, but is preferably a hollow fiber shape or a flat membrane shape, and may be formed on a reinforcing material such as a nonwoven fabric.

かかる水不透過性膜及びその膜を内蔵してなるモジュ
ールの形状は何ら限定されないが、シート状の膜を巻回
してなる所謂スパイラル型モジュールやその他の構造の
モジュールも用いることができる。
The shape of the water-impermeable membrane and the module including the membrane are not particularly limited, but a so-called spiral module formed by winding a sheet-like membrane or a module having another structure can also be used.

〔発明の効果〕〔The invention's effect〕

本発明の方法によれば、従来の合成樹脂のチューブを
用いた場合に比べて、蒸気透過速度を大きくでき、かつ
水蒸気の透過を抑えることができるため、設備費、運転
費、メンテナンス費等が低減できるという利点がある。
According to the method of the present invention, as compared with the case where a conventional synthetic resin tube is used, the vapor permeation rate can be increased and the permeation of water vapor can be suppressed, so that equipment costs, operation costs, maintenance costs, and the like are reduced. There is an advantage that it can be reduced.

〔実施例〕〔Example〕

以下に実施例により本発明を説明するが、本発明はこ
れら実施例に何ら限定されるものではない。以下におい
て部は重量部を意味する。
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following, parts mean parts by weight.

実施例1 不織布上に形成されたポリスルホン多孔質膜上に、ポ
リジメチルシロキサンを1μmの厚みで形成させて複合
膜を得た。かかる複合膜の30℃における窒素ガス透過速
度は、0.75Nm3/m2・h・atmであった。
Example 1 Polydimethylsiloxane was formed to a thickness of 1 μm on a polysulfone porous membrane formed on a nonwoven fabric to obtain a composite membrane. The nitrogen gas permeation rate at 30 ° C. of the composite membrane was 0.75 Nm 3 / m 2 · h · atm.

かかる膜を用いてスパイラル型モジュール(膜面積:
6.5m2)を成型し、室温20℃において、大気酸素と飽和
させた40℃の水道水(溶存酸素6.59ppm)を、通水量2.4
t/hで通水し、透過側を真空ポンプにより真空度−710mm
Hgに保った結果、溶存酸素濃度は0.72ppmであった。
Spiral type module (membrane area:
6.5m 2 ), and at room temperature 20 ° C, tap water (dissolved oxygen 6.59ppm) at 40 ° C saturated with atmospheric oxygen was passed through at 2.4
Water is passed at t / h, and the vacuum side of the permeate side is -710 mm
As a result of maintaining Hg, the dissolved oxygen concentration was 0.72 ppm.

実施例2 実施例1において、水道水の液温を60℃とした以外
は、実施例1と同様に処理した結果、溶存酸素濃度は0.
495ppmであった。
Example 2 The same treatment as in Example 1 was carried out except that the temperature of the tap water was changed to 60 ° C., and as a result, the dissolved oxygen concentration was 0.1%.
It was 495 ppm.

比較例 実施例1において、水道水の液温を室温以下の10℃と
した以外は、実施例1と同様に処理した結果、溶存酸素
濃度は3.42ppmであった。
Comparative Example In Example 1, the same treatment as in Example 1 was carried out except that the liquid temperature of the tap water was set to 10 ° C. or lower, and the dissolved oxygen concentration was 3.42 ppm.

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】水不透過性膜を介して、一方に、気体もし
くは低沸点揮発性有機物が溶解している水溶液を、室温
以上かつ水の沸点以下に保ちながら接触させ、他方を、
該水溶液成分の蒸気圧をゼロに近づけることにより、透
過する溶解成分を除去する気体もしくは低沸点揮発性有
機物の除去方法であって、該水溶液成分の蒸気圧をゼロ
に近づける方法として、真空ポンプ等で機械的に透過成
分を除去する方法を用いることを特徴とする気体もしく
は低沸点揮発性有機物の除去方法。
1. An aqueous solution in which a gas or a low-boiling volatile organic substance is dissolved is brought into contact with one of them via a water-impermeable membrane while maintaining the temperature above room temperature and below the boiling point of water.
A method for removing gas or low-boiling volatile organic matter that removes dissolved components that pass through by bringing the vapor pressure of the aqueous solution component close to zero. A method of removing the vapor pressure of the aqueous solution component close to zero includes a vacuum pump or the like. A method for removing gaseous or low-boiling volatile organic substances, wherein a method for mechanically removing permeated components is used.
【請求項2】水不透過性膜を介して、一方に、気体もし
くは低沸点揮発性有機物が溶解している水溶液を、室温
以上かつ水の沸点以下に保ちながら接触させ、他方を、
該水溶液成分の蒸気圧をゼロに近づけることにより、透
過する溶解成分を除去する気体もしくは低沸点揮発性有
機物の除去方法であって、該水溶液成分の蒸気圧をゼロ
に近づける方法として、不活性ガスを流して透過成分を
除去する方法を用いることを特徴とする気体もしくは低
沸点揮発性有機物の除去方法。
2. An aqueous solution in which a gas or a low-boiling volatile organic substance is dissolved is brought into contact with one of the aqueous solutions through a water-impermeable membrane while maintaining the temperature at a room temperature or higher and a boiling point of water or lower.
A method for removing a gas or a low-boiling volatile organic substance that removes dissolved components that pass through by bringing the vapor pressure of the aqueous solution component close to zero, wherein inert gas is used as a method of bringing the vapor pressure of the aqueous solution component close to zero. A method for removing gaseous or low-boiling volatile organic substances, wherein a method for removing permeated components by flowing gas is used.
【請求項3】水不透過性膜を介して、一方に、気体もし
くは低沸点揮発性有機物が溶解している水溶液を、室温
以上かつ水の沸点以下に保ちながら接触させ、他方を、
該水溶液成分の蒸気圧をゼロに近づけることにより、透
過する溶解成分を除去する気体もしくは低沸点揮発性有
機物の除去方法であって、該水溶液成分の蒸気圧をゼロ
に近づける方法として、水より溶解度の高い溶媒を流し
て透過成分を除去する方法を用いることを特徴とする気
体もしくは低沸点揮発性有機物の除去方法。
3. An aqueous solution in which a gas or a low-boiling volatile organic substance is dissolved is brought into contact with one of the aqueous solutions via a water-impermeable membrane while maintaining the temperature at or above room temperature and at or below the boiling point of water.
A method for removing gas or low-boiling volatile organic matter that removes dissolved components that permeate by bringing the vapor pressure of the aqueous solution component close to zero. Using a method of removing a permeated component by flowing a solvent having a high boiling point.
JP2109855A 1990-04-24 1990-04-24 Removal method of gas or low boiling volatile organic matter Expired - Lifetime JP3001608B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2109855A JP3001608B2 (en) 1990-04-24 1990-04-24 Removal method of gas or low boiling volatile organic matter

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2109855A JP3001608B2 (en) 1990-04-24 1990-04-24 Removal method of gas or low boiling volatile organic matter

Publications (2)

Publication Number Publication Date
JPH047002A JPH047002A (en) 1992-01-10
JP3001608B2 true JP3001608B2 (en) 2000-01-24

Family

ID=14520900

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2109855A Expired - Lifetime JP3001608B2 (en) 1990-04-24 1990-04-24 Removal method of gas or low boiling volatile organic matter

Country Status (1)

Country Link
JP (1) JP3001608B2 (en)

Also Published As

Publication number Publication date
JPH047002A (en) 1992-01-10

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