JPH0696102B2 - Condensate treatment method - Google Patents
Condensate treatment methodInfo
- Publication number
- JPH0696102B2 JPH0696102B2 JP2055076A JP5507690A JPH0696102B2 JP H0696102 B2 JPH0696102 B2 JP H0696102B2 JP 2055076 A JP2055076 A JP 2055076A JP 5507690 A JP5507690 A JP 5507690A JP H0696102 B2 JPH0696102 B2 JP H0696102B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl alcohol
- ethylene vinyl
- hollow fiber
- alcohol copolymer
- condensate
- 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 - Fee Related
Links
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、原子力発電所、火力発電所等の復水の処理方
法に関する。Description: TECHNICAL FIELD The present invention relates to a method for treating condensate of a nuclear power plant, a thermal power plant, and the like.
（従来技術） 原子力発電所、火力発電所等では、復水の浄化のため
に、イオン交換樹脂製のプレコートフィルターが従来使
用されていた。しかし、イオン交換樹脂製のプレコート
フィルターは寿命が短く、しかも原子力発電所の場合は
放射能を帯びているために使用後はドラム缶に詰めて保
存しなければならない等のため、最近では寿命が長く、
焼却可能なポリオレフィン製中空糸膜が使われるように
なってきた。(Prior art) In a nuclear power plant, a thermal power plant, etc., the precoat filter made from an ion exchange resin was conventionally used for purification of condensate. However, the pre-coated filter made of ion-exchange resin has a short life, and in the case of a nuclear power plant, since it has radioactivity, it has to be packed in a drum and stored after use. ,
Incinerators made of polyolefin hollow fiber membranes have come into use.
（発明が解決しようとする問題点） しかし、ポリオレフィン製中空糸膜は表面がやわらかい
ために、長期間使用していると、濾過される鉄酸化物
（以下、クラッドと称する）によるとみられる膜外表面
のポアのつぶれ現象が発生し、透水量が徐々に低下し、
やがて濾過がほとんどできなくなるという欠点がある。
本発明は上記事情に鑑みてなされたものであって、ポリ
オレフィン製中空糸膜のポアのつぶれが殆ど発生せず、
復水の処理を簡単にしかも確実に長期間にわたってでき
る方法を提供することを目的とする。(Problems to be solved by the invention) However, since the surface of the polyolefin hollow fiber membrane is soft, it is thought that the outside of the membrane caused by the iron oxide (hereinafter referred to as "clad") that is filtered after long-term use. The crushing phenomenon of the pores on the surface occurs, the water permeability gradually decreases,
There is a drawback that filtration is almost impossible in the end.
The present invention has been made in view of the above circumstances, the collapse of the pores of the polyolefin hollow fiber membrane hardly occurs,
It is an object of the present invention to provide a method capable of simply and reliably treating condensate for a long period of time.
（問題点を解決するための手段） 本発明者等は上記問題点を解決するために鋭意検討した
結果、ポリオレフィン製中空糸膜の原液側の表面をエチ
レンビニルアルコール共重合体で被覆するか、ポリオレ
フィンにエチレンビニルアルコール共重合体をブレンド
した膜を用いることによって、膜表面の孔のつぶれが著
しく改良されることを見い出し本発明を完成させた。(Means for Solving Problems) The inventors of the present invention have made extensive studies in order to solve the above problems. As a result, whether the surface of the polyolefin hollow fiber membrane on the side of the undiluted solution is coated with an ethylene vinyl alcohol copolymer, The inventors have found that the collapse of pores on the surface of a film is remarkably improved by using a film obtained by blending an ethylene vinyl alcohol copolymer with a polyolefin, and completed the present invention.
即ち、本発明の要旨は下記のとおりのものである。That is, the gist of the present invention is as follows.
ポリオレフィン製中空糸状微多孔膜で復水を処理する
に当って、該ポリオレフィン製中空糸状微多孔膜にエチ
レンビニルアルコー共重合体が0.1〜10重量％被覆され
ていることを特徴とする復水の処理方法。In treating the condensate with the polyolefin hollow fiber microporous membrane, the condensate is characterized in that the polyolefin hollow fiber microporous membrane is coated with ethylene vinyl alcohol copolymer in an amount of 0.1 to 10% by weight. Processing method.
ポリオレフィン製中空糸状微多孔膜で復水を処理する
に当って、該ポリオレフィン製中空糸状微多孔膜がポリ
オレフィン樹脂に対してエチレンビニルアルコール共重
合体が１〜50重量％ブレンドされた樹脂からなることを
特徴とする復水の処理方法。In treating condensate with a polyolefin hollow fiber microporous membrane, the polyolefin hollow fiber microporous membrane is made of a resin obtained by blending 1 to 50% by weight of an ethylene vinyl alcohol copolymer with a polyolefin resin. Condensate treatment method characterized by
（作用） 復水を濾過した時の膜表面の孔のつぶれは、電子顕微鏡
で観察するとポリマーがたたかれて、流動したような表
面になっており、このような孔のつぶれは復水を濾過す
るだけでは発生しないことから、逆洗時に膜に付着した
クラッドを空気で振り落す時に、クラッドが膜にぶつか
って発生するものと考えられ、砂又はクラッドを水に懸
濁させて吹きつける液体ホーニングで同じような膜表面
の孔のつぶれが再現される。理由は明らかではないが、
エチレンビニルアルコール共重合体を含む膜は液体ホー
ニングに対して著しく効果があり、復水処理の空気によ
る逆洗に対しても効果がある。(Function) When the condensate is filtered, the pores on the surface of the membrane are crushed by observation with an electron microscope, and the polymer is struck to give a fluidized surface. Since it does not occur just by filtering, it is considered that the clad bumps against the film when it is shaken off with air during backwashing, and the liquid that sprays sand or clad in water is suspended. The same crushing of holes on the membrane surface is reproduced by honing. The reason is not clear,
Membranes containing ethylene vinyl alcohol copolymers are highly effective for liquid honing and also effective for backwashing with air during condensate treatment.
エチレンビニルアルコール共重合体をポリオレフィン製
中空糸状微多孔膜に被覆するには、エチレン含量20〜50
mol％のエチレンビニルアルコール共重合体を水とイソ
プロピルアルコールの50重量部ずつの混合溶液にとか
し、該エチレンビニルアルコール共重合体溶液にポリオ
レフィン製中空糸状膜を数分間浸漬した後、乾燥すれば
よく、該エチレンビニルアルコール共重合体の濃度を変
えることによって、種々の被覆量の膜をつくることがで
きる。被覆量は0.1〜10重量％が好ましい。0.1重量％未
満では耐液体ホーニング効果が少なく、10重量％を超え
ると透水量が低下して好ましくない。To coat an ethylene vinyl alcohol copolymer on a polyolefin hollow fiber microporous membrane, an ethylene content of 20-50
Mol% ethylene vinyl alcohol copolymer is dissolved in a mixed solution of 50 parts by weight each of water and isopropyl alcohol, the polyolefin hollow fiber membrane is immersed in the ethylene vinyl alcohol copolymer solution for several minutes, and then dried. By changing the concentration of the ethylene vinyl alcohol copolymer, it is possible to form a film having various coating amounts. The coating amount is preferably 0.1 to 10% by weight. If it is less than 0.1% by weight, the liquid honing resistance is small, and if it exceeds 10% by weight, the amount of water permeation decreases, which is not preferable.
エチレンビニルアルコール共重合体をポリオレフィン樹
脂にブレンドして使用する場合は、ポリオレフィン樹脂
にエチレンビニルアルコール共重合体を１〜50重量％ブ
レンドして、溶融紡糸して製膜すればよい。When the ethylene vinyl alcohol copolymer is used by blending it with a polyolefin resin, the polyolefin resin may be blended with 1 to 50% by weight of the ethylene vinyl alcohol copolymer, and melt spinning may be performed to form a film.
製膜は、シリカ等のフィラーを入れて、製膜後フィラー
を抽出したり、延伸して孔を形成させてもよい。エチレ
ンビニルアルコール共重合体のブレンド量は１〜50重量
％が好ましい。１重量％未満では改良の効果が少なく、
50重量％を超えると製膜が難しくなるだけでなく、中空
糸の伸度が低下し、モロクなるため好ましくない。In the film formation, a filler such as silica may be put in to extract the filler after film formation, or the film may be stretched to form pores. The blending amount of the ethylene vinyl alcohol copolymer is preferably 1 to 50% by weight. If it is less than 1% by weight, the effect of improvement is small,
If it exceeds 50% by weight, not only is it difficult to form a film, but also the elongation of the hollow fiber is lowered, and it becomes unfavorable.
以下本発明について実施例で具体的に説明する。Hereinafter, the present invention will be specifically described with reference to examples.
（実施例１、比較例１） 日本合成化学（株）製のエチレンビニルアルコール共重
合体樹脂、ソアノールD2908（エチレン含量29mol％）を
イソプロピルアルコールと水の50重量％ずつの混合溶液
にとかし、表に示す各種の濃度（％）のエチレンビニル
アルコール共重合体溶液を作成し、これらの溶液に、内
径0.68mm、外径1.25mm、空孔率70％、平均孔径0.1μｍ
のポリエチレン製中空糸状微多孔膜を60℃で10分間浸漬
し、乾燥して、表に示すような各種の付着量（％）でエ
チレンビニルアルコール共重合体を被覆した膜（No.1〜
No.5）を製作した。(Example 1, Comparative Example 1) Ethanol-vinyl alcohol copolymer resin, Soarnol D2908 (ethylene content 29 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was dissolved in a mixed solution of 50 wt% each of isopropyl alcohol and water. Ethylene vinyl alcohol copolymer solutions of various concentrations (%) shown in Fig. 1 were prepared, and these solutions were used to have an inner diameter of 0.68 mm, an outer diameter of 1.25 mm, a porosity of 70%, and an average pore diameter of 0.1 μm
The polyethylene hollow-fiber microporous membrane of 1 is immersed at 60 ° C for 10 minutes, dried, and coated with ethylene vinyl alcohol copolymer at various adhesion amounts (%) as shown in the table (No. 1 to
No.5) was produced.
これらの膜に（株）不二精機製造所製の液体ホーニング
装置を用い、＃120の砂20vol％含む36℃の液を、0.7kg/
cm2の圧力で70cmの距離から一定時間吹きつけ、さらに
膜の反対側をも同様に吹きつけた後、水洗して透水性能
を測定したところ添付図面に示すような結果が得られ
た。また、比較例として、エチレンビニルアルコール共
重合体を被覆しなかった基材膜についても同様の実験を
行ったところ、図に示す結果が得られた。 A liquid honing device manufactured by Fuji Seiki Co., Ltd. was used for these membranes, and 0.7 kg / 36 kg of a liquid at 36 ° C containing 20 vol% sand # 120 was used.
After spraying with a pressure of cm 2 from a distance of 70 cm for a certain period of time and further spraying on the opposite side of the membrane in the same manner, washing with water and measuring the water permeation performance gave the results shown in the attached drawings. In addition, as a comparative example, the same experiment was conducted on the base film not coated with the ethylene vinyl alcohol copolymer, and the results shown in the figure were obtained.
図に示すように、エチレンビニルアルコール共重合体が
0.1〜10重量％の範囲内で被覆されているNo.1〜No.5の
中空糸状膜では、液体ホーニングによる透水性能の低下
は少く、特にNo.3〜No.5の各膜では液体ホーニング時間
による低下は見られなかったが、比較例の基材膜では透
水性能が急激に低下した。As shown in the figure, the ethylene vinyl alcohol copolymer
In the No. 1 to No. 5 hollow fiber membranes coated within the range of 0.1 to 10% by weight, the decrease in water permeability due to liquid honing is small, and especially in the No. 3 to No. 5 membranes, liquid honing is performed. Although no decrease due to time was observed, the water permeability of the base material film of the Comparative Example deteriorated sharply.
（実施例２、比較例２） 実施例１で使用した基材膜とエチレンビニルアルコール
共重合体を1.6％被覆したNo.3膜でそれぞれ別個のモジ
ュールを組み立てた。これら２種のモジュールについ
て、下記の条件で試験した。即ち、導電率0.1μs/cm、
クラッド濃度100ppbの復水模擬液を、40℃、0.55m3/m2H
rで外圧の全濾過を行ない、１週間毎に濾過を停止し、
モジュールの下部から中空糸の外側に空気を入れて、空
気を中空糸に沿って上昇させるエアースクラビングを行
って、付着したクラッドを除去しながら、３ケ月濾過し
た後、モジュールを解体し、膜を6N−Hclで洗浄してク
ラッドを除去して透水保持率を測定したところ、比較例
２の基材膜は初期値の70％に低下していたが、実施例２
のエチレンビニルアルコール共重合体を1.6％被覆した
膜は96％の保持率であった。また電子顕微鏡で膜外表面
の観察を行ったところ、比較例２の基材膜は孔が大部分
つぶれてなくなっていたが、実施例２のエチレンビニル
アルコール共重合体被覆膜はほとんどの孔が残ってい
た。(Example 2 and Comparative Example 2) Separate modules were assembled with the base film used in Example 1 and the No. 3 film coated with 1.6% of ethylene vinyl alcohol copolymer. These two types of modules were tested under the following conditions. That is, the conductivity 0.1 μs / cm,
A condensate simulation solution with a clad concentration of 100 ppb was applied at 40 ° C and 0.55 m 3 / m 2 H.
At r, complete external pressure filtration, stop filtration every week,
Air is injected from the bottom of the module to the outside of the hollow fiber, and air scrubbing is performed to raise the air along the hollow fiber to remove adhering clad, and after filtering for 3 months, disassemble the module and remove the membrane. When the water retention rate was measured after removing the clad by washing with 6N-Hcl, the base material film of Comparative Example 2 was reduced to 70% of the initial value.
The film coated with 1.6% ethylene vinyl alcohol copolymer had a retention of 96%. When the outer surface of the film was observed with an electron microscope, most of the pores were not crushed in the base material film of Comparative Example 2, but most of the pores were observed in the ethylene vinyl alcohol copolymer-coated film of Example 2. Was left.
（実施例３） 旭化成工業（株）製高密度ポリエチレン；サンテックＳ
−360 18部、日本合成化学（株）製エチレンビニルア
ルコール共重合体樹脂；ソアノールD2908（エチレン含
量29mol％）２部、日本シリカ工業（株）製のシリカ;Ni
psilLP 24部、ジオクチルフタレート 56部からなる混
合物を中空糸状に押出した後、ジオクチルフタレートを
１、１、１トリクロルエタンで抽出し、次いで、シリカ
を15％NaOHで抽出して、糸外径1.25mm、糸内径0.67mm、
空孔率70％、透水量1800/m2Hrkg/cm2at25℃の膜を得
た。(Example 3) High-density polyethylene manufactured by Asahi Kasei Kogyo KK; Suntech S
−360 18 parts, Nippon Synthetic Chemical Co., Ltd. ethylene vinyl alcohol copolymer resin; Soarnol D2908 (ethylene content 29 mol%) 2 parts, Nihon Silica Industry Co., Ltd. silica; Ni
After extruding a mixture of 24 parts of psilLP and 56 parts of dioctyl phthalate into hollow fibers, dioctyl phthalate was extracted with 1,1,1 trichloroethane, and then silica was extracted with 15% NaOH to obtain a yarn outer diameter of 1.25 mm. , Thread inner diameter 0.67mm,
A membrane having a porosity of 70% and a water permeability of 1800 / m 2 Hrkg / cm 2 at 25 ° C was obtained.
この膜に、（実施例１）で用いた液体ホーニング装置を
用い、＃120の砂20vol％含む36℃の液を0.7kg/cm2の圧
力で70cmの距離から60秒間（実施例１）と同様な方法で
吹きつけて、水洗後、透水量を測定したところ、1720
/m2Hrkg/cm2at25℃であった。Using the liquid honing device used in (Example 1), a liquid at 36 ° C. containing 20 vol% of # 120 sand was applied to this membrane at a pressure of 0.7 kg / cm 2 from a distance of 70 cm for 60 seconds (Example 1). After spraying in the same manner, washing with water and measuring the amount of water permeation, it was 1720.
It was / m 2 Hrkg / cm 2 at 25 ° C.
（比較例３） サンテックＳ−360;20部で、エチレンビニルアルコール
共重合体を含まない他は（実施例３）と同じ組成、同じ
方法で膜を作り、糸外径1.24mm、糸内径0.65mm、空孔率
70％、透水量1560/m2Hrkg/cm2at25℃の膜を得た。(Comparative Example 3) A film was made by the same composition and the same method as in (Example 3) except that 20 parts of Suntec S-360 and no ethylene vinyl alcohol copolymer were included, and the yarn outer diameter was 1.24 mm and the yarn inner diameter was 0.65. mm, porosity
A membrane having 70% and a water permeability of 1560 / m 2 Hrkg / cm 2 at 25 ° C was obtained.
この膜を（実施例３）と同様に液体ホーニングを行って
透水量を測定したところ、330/m2Hrkg/cm2at25℃であ
り、実施例３に比較して著しく低い値であった。When this membrane was subjected to liquid honing in the same manner as in (Example 3) and the water permeation rate was measured, it was 330 / m 2 Hrkg / cm 2 at 25 ° C, which was a remarkably low value as compared with Example 3.
（発明の効果） 本発明によれば、中空糸膜表面の孔のつぶれが殆ど発生
しないので、長期間にわたって簡単にしかも確実に復水
の濾過に使用できる。(Effect of the Invention) According to the present invention, since the pores on the surface of the hollow fiber membrane are hardly crushed, the hollow fiber membrane can be easily and reliably used for condensate filtration for a long period of time.
添付図面は、実施例１と比較例１の試験結果を示す図で
ある。The accompanying drawings show the test results of Example 1 and Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ２１Ｃ 19/307 Ｇ２１Ｆ 9/06 ５１１ Ｇ 9216−2Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location G21C 19/307 G21F 9/06 511 G 9216-2G
Claims (2)
を処理するに当って、該ポリオレフィン製中空糸状微多
孔膜にエチレンビニルアルコール共重合体が0.1〜10重
量％被覆されていることを特徴とする復水の処理方法。1. When treating condensate with a polyolefin hollow fiber microporous membrane, the polyolefin hollow fiber microporous membrane is coated with 0.1 to 10% by weight of an ethylene vinyl alcohol copolymer. And the condensate treatment method.
を処理するに当って、該ポリオレフィン製中空糸状微多
孔膜がポリオレフィン樹脂に対してエチレンビニルアル
コール共重合体が１〜50重量％ブレンドされた樹脂から
なることを特徴とする復水の処理方法。2. In treating condensate with a polyolefin hollow fiber microporous membrane, the polyolefin hollow fiber microporous membrane is blended with 1 to 50% by weight of ethylene vinyl alcohol copolymer with respect to a polyolefin resin. A method for treating condensate, which comprises a resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055076A JPH0696102B2 (en) | 1990-03-08 | 1990-03-08 | Condensate treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2055076A JPH0696102B2 (en) | 1990-03-08 | 1990-03-08 | Condensate treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258331A JPH03258331A (en) | 1991-11-18 |
| JPH0696102B2 true JPH0696102B2 (en) | 1994-11-30 |
Family
ID=12988614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2055076A Expired - Fee Related JPH0696102B2 (en) | 1990-03-08 | 1990-03-08 | Condensate treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696102B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013147187A1 (en) | 2012-03-30 | 2013-10-03 | 三菱レイヨン株式会社 | Composite hollow fiber membrane and hollow fiber membrane module |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61125408A (en) * | 1984-11-20 | 1986-06-13 | Mitsubishi Rayon Co Ltd | Method for making porous polyolefin hollow yarn hydrophilic |
| JPS6328406A (en) * | 1986-07-21 | 1988-02-06 | Asahi Medical Co Ltd | Network porous hollow yarn membrane |
| JPS63310602A (en) * | 1987-06-12 | 1988-12-19 | Asahi Chem Ind Co Ltd | Novel method for purifying condensate |
-
1990
- 1990-03-08 JP JP2055076A patent/JPH0696102B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013147187A1 (en) | 2012-03-30 | 2013-10-03 | 三菱レイヨン株式会社 | Composite hollow fiber membrane and hollow fiber membrane module |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03258331A (en) | 1991-11-18 |
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