JP2002095936A - Cleaning method for reverse osmosis membrane - Google Patents
Cleaning method for reverse osmosis membraneInfo
- Publication number
- JP2002095936A JP2002095936A JP2000291936A JP2000291936A JP2002095936A JP 2002095936 A JP2002095936 A JP 2002095936A JP 2000291936 A JP2000291936 A JP 2000291936A JP 2000291936 A JP2000291936 A JP 2000291936A JP 2002095936 A JP2002095936 A JP 2002095936A
- Authority
- JP
- Japan
- Prior art keywords
- reverse osmosis
- osmosis membrane
- water
- washing
- organic polymer
- 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.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、逆浸透膜の洗浄方
法に関し、詳しくは、廃水中の有機高分子物質を回収す
る工程で使用される逆浸透膜の工業的に有利な洗浄方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for cleaning a reverse osmosis membrane, and more particularly to an industrially advantageous method for cleaning a reverse osmosis membrane used in a step of recovering an organic polymer substance in wastewater.
【０００２】[0002]
【従来の技術】有機高分子物質含有廃水は各種の工程か
ら排出される。例えば、医療用透析膜製造工程や一般水
処理用途膜製造における被膜形成材工程では、その被膜
形成剤として、分子量１０，０００〜７００，０００の
ポリビニルピロリドン（ＰＶＰ）等が使用され、溶剤と
して、ジメチルアセトアミド（ＤＭＡＣ）、ジメチルホ
ルムアミド（ＤＭＦ）等が使用される。上記の各工程に
は、形成された膜表面の水洗工程が付設されており、斯
かる水洗工程から、通常０．２〜１．０重量％濃度の有
機高分子物質含有廃水が排出される。2. Description of the Related Art Wastewater containing organic polymer substances is discharged from various processes. For example, in a film forming material process in a medical dialysis membrane manufacturing process or a general water treatment membrane manufacturing process, polyvinylpyrrolidone (PVP) having a molecular weight of 10,000 to 700,000 is used as a film forming agent, and a solvent is used as a solvent. Dimethylacetamide (DMAC), dimethylformamide (DMF) and the like are used. Each of the above-mentioned steps is provided with a step of washing the surface of the formed membrane, and wastewater containing an organic polymer substance having a concentration of 0.2 to 1.0% by weight is discharged from the washing step.
【０００３】上記の様な廃水の処理方法としては、回収
再利用を目的とした場合には逆浸透膜装置を利用した濃
縮法が採用される場合が多い。ところで、有機高分子物
質含有廃水を逆浸透膜装置にて処理する場合、経時的な
膜表面への有機高分子物質の付着による閉塞現象すなわ
ち処理水量の低下現象が起こるため、逆浸透膜の定期的
な洗浄が必要となる。As a method for treating wastewater as described above, a concentration method using a reverse osmosis membrane device is often adopted for the purpose of recovery and reuse. By the way, when treating wastewater containing an organic polymer substance with a reverse osmosis membrane device, a blocking phenomenon due to the adhesion of the organic polymer substance to the membrane surface over time, that is, a decrease in the amount of treated water occurs. Cleaning is required.
【０００４】逆浸透膜の洗浄方法としては、酸、アルカ
リ、界面活性剤または溶剤による薬剤洗浄法が知られて
いる。しかしながら、薬剤洗浄法による場合は、洗浄排
水の処理として中和や溶剤処理が必要となり、しかも、
逆浸透膜に付着した薬液の洗浄のために多量の用水が必
要となる。As a method for cleaning a reverse osmosis membrane, a chemical cleaning method using an acid, an alkali, a surfactant or a solvent is known. However, in the case of using the chemical cleaning method, neutralization and solvent treatment are required as treatment of cleaning wastewater, and moreover,
A large amount of water is required for cleaning the chemical solution attached to the reverse osmosis membrane.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記実情に
鑑みなされたものであり、その目的は、有機高分子物質
含有廃水を逆浸透膜装置にて処理して廃水中の有機高分
子物質を回収する工程において採用される逆浸透膜の洗
浄方法であって、薬液洗浄液を使用する従来法の欠点を
解消した工業的に有利な逆浸透膜の洗浄方法を提供する
ことにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to treat an organic polymer substance contained in an organic polymer substance by treating the waste water containing the organic polymer substance with a reverse osmosis membrane device. An object of the present invention is to provide a reverse osmosis membrane washing method employed in the step of recovering water, which is an industrially advantageous method of cleaning a reverse osmosis membrane, which has solved the drawbacks of the conventional method using a chemical solution.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の目
的を達成すべく鋭意検討を重ねた結果、次の様な知見を
得た。すなわち、中性かつ親水性物質の代表である水
は、逆浸透膜に捕捉された有機高分子物質の洗浄除去に
効果的でないと考えられが、特定の条件下では意外にも
有機高分子物質の洗浄除去に十分な効果を発揮する。Means for Solving the Problems The present inventors have made intensive studies in order to achieve the above object, and as a result have obtained the following knowledge. In other words, water, which is a representative of neutral and hydrophilic substances, is not considered to be effective for washing and removing organic polymer substances trapped in reverse osmosis membranes. Demonstrate sufficient effect for cleaning and removing.
【０００７】本発明は、上記の知見に基づき完成された
ものであり、その要旨は、有機高分子物質含有廃水を逆
浸透膜装置にて処理して廃水中の有機高分子物質を回収
する工程において、上記の有機高分子物質によって閉塞
した逆浸透膜を洗浄するに当たり、３０〜９０℃の加圧
温水を通水することを特徴とする逆浸透膜の洗浄方法に
存する。[0007] The present invention has been completed based on the above findings, and the gist of the present invention is a process of recovering organic polymer substances in wastewater by treating an organic polymer substance-containing wastewater with a reverse osmosis membrane device. The present invention also provides a method for cleaning a reverse osmosis membrane, characterized in that, when the reverse osmosis membrane closed by the organic polymer substance is washed, pressurized hot water at 30 to 90 ° C. is passed.
【０００８】[0008]
【発明の実施の形態】以下、本発明を添付図面に基づき
詳細に説明する。図１は本発明の洗浄方法の説明図であ
る。図中、符号（１）は原液タンク、（２）はポンプ、
（３）は逆浸透膜装置、（４）は洗浄水タンク、（５）
は加温手段、（５１）〜（５３）は切り替えバルブ、
（６１）〜（６９）は配管を表し、波線の矢印は有機高
分子物質含有廃水の処理時（通水時）の流れ、実線の矢
印は逆浸透膜の洗浄時の流れを表す。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is an explanatory view of the cleaning method of the present invention. In the figure, reference numeral (1) denotes a stock solution tank, (2) denotes a pump,
(3) is a reverse osmosis membrane device, (4) is a washing water tank, (5)
Is a heating means, (51) to (53) are switching valves,
(61) to (69) indicate pipes, the wavy arrows indicate the flow during the treatment (when passing water) of the organic polymer substance-containing wastewater, and the solid arrows indicate the flow during the cleaning of the reverse osmosis membrane.
【０００９】先ず、逆浸透膜装置による有機高分子物質
含有廃水の処理工程について説明する。この工程は従来
公知の方法に従って行うことが出来る。First, a process of treating an organic polymer substance-containing wastewater by a reverse osmosis membrane device will be described. This step can be performed according to a conventionally known method.
【００１０】有機高分子物質含有廃水の具体例として
は、医療用透析膜製造工程や一般水処理用途膜製造にお
ける被膜形成材工程などに付設された水洗工程から排出
される廃液が挙げられる。廃水中に含まれる有機高分子
物質の重量平均分子量は、通常３００以上、好ましくは
１０，０００〜７００，０００であり、その具体例とし
てはＰＶＰ等が挙げられる。また、通常、廃水中の有機
高分子物質の含有量は約０．２〜１．０重量％である。[0010] Specific examples of the wastewater containing the organic polymer substance include wastewater discharged from a washing step provided in a step of producing a dialysis membrane for medical use or a film forming material step in producing a membrane for general water treatment. The weight average molecular weight of the organic polymer substance contained in the wastewater is usually 300 or more, preferably 10,000 to 700,000, and specific examples include PVP. In addition, the content of the organic polymer substance in the wastewater is usually about 0.2 to 1.0% by weight.
【００１１】逆浸透膜装置における膜のエレメント構造
としては、スパイラル型、中空糸型、チューブラー型な
どが知られているが、何れのエレメント構造であっても
よい。また、膜の素材としては、酢酸セルロース系、ポ
リアミド系、架橋ポリアミン系、架橋ポリエーテル系、
スルホン化ポリスルホン等が知られているが、何れの素
材であってもよい。本発明では、市販の逆浸透膜装置を
適宜選択して使用することが出来る。As the element structure of the membrane in the reverse osmosis membrane device, a spiral type, a hollow fiber type, a tubular type and the like are known, but any element structure may be used. Further, as the material of the membrane, cellulose acetate, polyamide, crosslinked polyamine, crosslinked polyether,
Although sulfonated polysulfone and the like are known, any material may be used. In the present invention, a commercially available reverse osmosis membrane device can be appropriately selected and used.
【００１２】原液タンク（１）中の有機高分子物質含有
廃水は、配管（６１）、切り替えバルブ（５１）及び配
管（６２）を経由し、昇圧ポンプ（２）により、逆浸透
膜装置（３）に供給される。この際、切り替えバルブ
（５１）の配管（６９）側の流路は閉止されている。The organic polymer substance-containing wastewater in the stock solution tank (1) passes through a pipe (61), a switching valve (51) and a pipe (62), and is supplied to a reverse osmosis membrane device (3) by a pressure increasing pump (2). ). At this time, the flow path on the pipe (69) side of the switching valve (51) is closed.
【００１３】有機高分子物質含有廃水は、逆浸透膜装置
（３）において処理されて透過水（処理水）と濃縮水と
に分離される。透過水は、配管（６３）及び切り替えバ
ルブ（５２）を経由して配管（６４）から取り出され
る。この際、切り替えバルブ（５２）の配管（６７）側
の流路は閉止されている。一方、濃縮水は、配管（６
５）及び切り替えバルブ（５３）を経由して配管（６
６）から取り出される。この際、切り替えバルブ（５
３）の配管（６８）側の流路は閉止されている。上記の
透過水は、排出基準値を満足していることを条件に放流
され、濃縮水は、有機高分子物質の回収のため、減圧濃
縮工程などの次工程に供給される。The wastewater containing the organic polymer substance is treated in the reverse osmosis membrane device (3) and separated into permeated water (treated water) and concentrated water. The permeated water is taken out of the pipe (64) via the pipe (63) and the switching valve (52). At this time, the flow path on the pipe (67) side of the switching valve (52) is closed. On the other hand, the concentrated water
5) and the piping (6) via the switching valve (53).
6). At this time, the switching valve (5
The flow path on the pipe (68) side of 3) is closed. The above permeated water is discharged under the condition that the discharge reference value is satisfied, and the concentrated water is supplied to the next step such as a reduced pressure concentration step in order to recover the organic polymer substance.
【００１４】逆浸透膜装置（２）の長時間の運転の結
果、膜表面への有機高分子物質の付着による閉塞現象す
なわち処理水量の低下現象が起こる。斯かる現象は昇圧
ポンプ（２）の圧力増加によって容易に把握することが
出来る。As a result of the long-term operation of the reverse osmosis membrane device (2), a clogging phenomenon due to the adhesion of the organic polymer substance to the membrane surface, that is, a reduction in the amount of treated water occurs. Such a phenomenon can be easily grasped by an increase in the pressure of the booster pump (2).
【００１５】次に、有機高分子物質によって閉塞した逆
浸透膜を洗浄する工程（洗浄工程）について説明する。
本発明においては、逆浸透膜を洗浄するに当たり、３０
〜９℃（好ましくは４０〜７０℃）の加圧温水を通水す
る。温水の圧力は、エレメント構造などを考慮して適切
な範囲から選択されるが、通常０．１〜０．５ＭＰａ、
好ましくは０．２〜０．３ＭＰａである。温度が３０℃
未満の洗浄水や常圧の洗浄水を使用した場合は逆浸透膜
の洗浄効果が不十分である。一方、温度が９０℃を超え
る洗浄水や過度に高圧の洗浄水を使用した場合は、耐熱
性および耐圧性の観点から逆浸透膜装置（２）に対する
負荷が大きくなる。Next, the step of washing the reverse osmosis membrane closed by the organic polymer substance (washing step) will be described.
In the present invention, when washing the reverse osmosis membrane, 30
加 圧 9 ° C (preferably 40 to 70 ° C) pressurized hot water is passed through. The pressure of the hot water is selected from an appropriate range in consideration of the element structure and the like, but is usually 0.1 to 0.5 MPa,
Preferably it is 0.2-0.3 MPa. Temperature is 30 ° C
When the washing water of less than or the normal pressure is used, the effect of washing the reverse osmosis membrane is insufficient. On the other hand, when washing water having a temperature exceeding 90 ° C. or washing water having an excessively high pressure is used, the load on the reverse osmosis membrane device (2) increases from the viewpoint of heat resistance and pressure resistance.
【００１６】洗浄水タンク（４）中の洗浄水は、配管
（６９）、切り替えバルブ（５１）及び配管（６２）を
経由し、昇圧ポンプ（２）により、逆浸透膜装置（３）
に供給される。この際、切り替えバルブ（５１）の配管
（６１）側の流路は閉止されている。また、洗浄水タン
ク（４）中の洗浄水は、加温手段（４１）によって３０
〜９０℃の温水とされ且つ昇圧ポンプ（２）によって加
圧温水とされて逆浸透膜装置（３）に供給される。The washing water in the washing water tank (4) passes through the pipe (69), the switching valve (51), and the pipe (62), and is supplied to the reverse osmosis membrane device (3) by the pressurizing pump (2).
Supplied to At this time, the flow path on the pipe (61) side of the switching valve (51) is closed. The washing water in the washing water tank (4) is heated by the heating means (41).
Hot water of up to 90 ° C. and pressurized hot water by a pressurizing pump (2) are supplied to a reverse osmosis membrane device (3).
【００１７】逆浸透膜装置（３）に供給された加圧温水
は、その温度と圧力の作用により、逆浸透膜に捕捉され
た有機高分子物質を逆浸透膜から剥離する。そして、逆
浸透膜を透過した温水は、配管（６３）及び切り替えバ
ルブ（５２）を経由して配管（６７）から取り出されて
洗浄水タンク（４）に循環される。この際、切り替えバ
ルブ（５２）の配管（６４）側の流路は閉止されてい
る。一方、逆浸透膜を透過しなかった温水は、配管（６
５）及び切り替えバルブ（５３）を経由して配管（６
８）から取り出されて洗浄水タンク（４）に循環され
る。この際、切り替えバルブ（５３）の配管（６６）側
の流路は閉止されている。The pressurized hot water supplied to the reverse osmosis membrane device (3) separates the organic polymer substance captured by the reverse osmosis membrane from the reverse osmosis membrane by the action of the temperature and pressure. Then, the hot water that has passed through the reverse osmosis membrane is taken out of the pipe (67) via the pipe (63) and the switching valve (52), and is circulated to the washing water tank (4). At this time, the flow path on the pipe (64) side of the switching valve (52) is closed. On the other hand, the hot water that did not pass through the reverse osmosis membrane
5) and the piping (6) via the switching valve (53).
8) and is circulated to the washing water tank (4). At this time, the flow path on the pipe (66) side of the switching valve (53) is closed.
【００１８】上記の洗浄工程による効果は、昇圧ポンプ
（２）の圧力の監視によって容易に把握することが出来
る。通常０．５〜２時間の洗浄（循環通水）により、逆
浸透膜が回生し、有機高分子物質含有廃水の処理工程に
復帰することが出来る。そして、以降、上記と同様の洗
浄工程を繰り返し行うことにより、有機高分子物質含有
廃水の処理工程を長期間に亘って行うことが出来る。そ
して、循環通水方式の洗浄工程によれば、洗浄廃水は洗
浄水タンク（４）に貯留されるため、排出液処理が不要
である。The effect of the above-mentioned cleaning step can be easily grasped by monitoring the pressure of the booster pump (2). The reverse osmosis membrane is usually regenerated by washing (circulating water) for 0.5 to 2 hours, and it is possible to return to the treatment process of the wastewater containing the organic polymer substance. Thereafter, by repeatedly performing the same washing step as above, the treatment step of the wastewater containing the organic polymer substance can be performed over a long period of time. According to the circulating water washing process, the washing wastewater is stored in the washing water tank (4), so that there is no need to treat the discharged liquid.
【００１９】[0019]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明は、その要旨を超えない限り、以下の実
施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
【００２０】実施例１ 芳香族ポリアミド系のスパイラル型逆浸透膜モジュール
備えた逆浸透膜装置を使用し、ＰＶＰ０．２重量％、Ｄ
ＭＡＣ１．５重量％を含む廃水を処理した。濃縮倍率６
倍で通水したところ、一週間の連続通水により、初期供
給圧力３．０ＭＰａであった性能が供給圧力３．９ＭＰ
ａまで上昇した。Example 1 A reverse osmosis membrane device equipped with an aromatic polyamide-based spiral reverse osmosis membrane module was used.
Wastewater containing 1.5% by weight of MAC was treated. Concentration magnification 6
When the water was passed twice, the performance was changed from the initial supply pressure of 3.0 MPa to the supply pressure of 3.9 MP by continuous water supply for one week.
a.
【００２１】そこで、上記の廃水処理を停止し、供給圧
力０．２〜０．３ＭＰａ、設定水温４０℃、循環通水時
間１Hｒの条件で洗浄処理を行った結果、供給圧力は
３．４ＭＰａまで回復した。更に、１時間洗浄処理を続
行した結果、初期供給圧力である３．０ＭＰａまでの回
復が見られた。Therefore, the above wastewater treatment was stopped, and a cleaning treatment was performed under the conditions of a supply pressure of 0.2 to 0.3 MPa, a set water temperature of 40 ° C., and a circulation water flow time of 1 hour. As a result, the supply pressure was increased to 3.4 MPa. Recovered. Further, as a result of continuing the cleaning treatment for one hour, a recovery to the initial supply pressure of 3.0 MPa was observed.
【００２２】実施例２ 実施例１において、耐熱性を特徴とするスパイラル型逆
浸透膜モジュール備えた逆浸透膜装置を使用した以外
は、実施例１と同様に廃水処理を行った。一週間の連続
通水の結果、初期供給圧力２．５ＭＰａに対し、３．５
ＭＰａの上昇が確認された。そこで、上記の廃水処理を
停止し、供給圧力０．２〜０．３ＭＰａ、設定水温７０
℃、循環通水時間１Hｒの条件で洗浄処理を行った結
果、供給圧力である２．５ＭＰａまでの回復を確認し
た。Example 2 A wastewater treatment was carried out in the same manner as in Example 1 except that a reverse osmosis membrane device provided with a spiral type reverse osmosis membrane module characterized by heat resistance was used. As a result of continuous water flow for one week, the initial supply pressure was 2.5 MPa, and the pressure was 3.5.
An increase in MPa was confirmed. Therefore, the above wastewater treatment is stopped, the supply pressure is set to 0.2 to 0.3 MPa, and the set water temperature is set to 70 MPa.
As a result of performing the washing treatment under the conditions of ° C. and a circulation water flow time of 1 hour, it was confirmed that the supply pressure was recovered to 2.5 MPa.
【００２３】[0023]
【発明の効果】以上説明した本発明によれば、洗浄排水
の処理として中和や溶剤処理が不必要で且つ逆浸透膜に
付着した薬液の洗浄のために多量の用水が不必要であ
る、工業的に有利な逆浸透膜の洗浄方法が提供される。According to the present invention described above, neutralization and solvent treatment are not required as treatment of washing wastewater, and a large amount of water is not required for washing a chemical solution attached to a reverse osmosis membrane. An industrially advantageous method for cleaning a reverse osmosis membrane is provided.
【図１】本発明の洗浄方法の説明図FIG. 1 is an explanatory view of a cleaning method of the present invention.
１：原液タンク ２：ポンプ ３：逆浸透膜装置 ４：洗浄水タンク ５：加温手段 1: stock solution tank 2: pump 3: reverse osmosis membrane device 4: washing water tank 5: heating means
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D006 GA03 HA01 HA21 HA61 KC02 KC15 MA01 MA02 MA03 MC18 MC45 MC54 MC60 MC62 PA04 PB08 PC80 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA03 HA01 HA21 HA61 KC02 KC15 MA01 MA02 MA03 MC18 MC45 MC54 MC60 MC62 PA04 PB08 PC80
Claims (1)
にて処理して廃水中の有機高分子物質を回収する工程に
おいて、上記の有機高分子物質によって閉塞した逆浸透
膜を洗浄するに当たり、３０〜９０℃の加圧温水を通水
することを特徴とする逆浸透膜の洗浄方法。In the step of treating an organic polymer substance-containing wastewater with a reverse osmosis membrane device and recovering the organic polymer substance in the wastewater, the reverse osmosis membrane clogged with the organic polymer substance is washed. A method for cleaning a reverse osmosis membrane, characterized in that pressurized hot water at 30 to 90 ° C is passed through.
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| JP2000291936A JP2002095936A (en) | 2000-09-26 | 2000-09-26 | Cleaning method for reverse osmosis membrane |
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| JP2000291936A JP2002095936A (en) | 2000-09-26 | 2000-09-26 | Cleaning method for reverse osmosis membrane |
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| JP2002095936A true JP2002095936A (en) | 2002-04-02 |
Family
ID=18774946
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| JP2006218440A (en) * | 2005-02-14 | 2006-08-24 | Nitto Denko Corp | Washing method of membrane module for ultrapure water |
| CN102020367A (en) * | 2009-09-10 | 2011-04-20 | 株式会社东芝 | Membrane filtration system |
| JP2012232311A (en) * | 2012-09-05 | 2012-11-29 | Toshiba Corp | Membrane filtration treatment system |
| CN102814123A (en) * | 2012-09-12 | 2012-12-12 | 西安兴仪启动发电试运有限公司 | Reverse osmosis membrane chemical cleaning method |
| JP2014514966A (en) * | 2011-05-16 | 2014-06-26 | アドヴァンスド ハイドロ インコーポレイテッド | Improved membrane with polydopamine coating |
| WO2016171105A1 (en) * | 2015-04-21 | 2016-10-27 | 三菱重工業株式会社 | Reverse osmosis membrane cleaning method and reverse osmosis membrane cleaning apparatus |
| US9833743B2 (en) | 2011-12-19 | 2017-12-05 | Hitachi, Ltd. | Reverse osmosis treatment device and method for cleaning reverse osmosis treatment device |
| CN107879498A (en) * | 2017-12-21 | 2018-04-06 | 深圳恒通源环保科技有限公司 | A kind of electroplating wastewater processing recycling system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006218440A (en) * | 2005-02-14 | 2006-08-24 | Nitto Denko Corp | Washing method of membrane module for ultrapure water |
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| WO2016171105A1 (en) * | 2015-04-21 | 2016-10-27 | 三菱重工業株式会社 | Reverse osmosis membrane cleaning method and reverse osmosis membrane cleaning apparatus |
| JP2016203081A (en) * | 2015-04-21 | 2016-12-08 | 三菱重工業株式会社 | Reverse osmosis membrane washing method, and reverse osmosis membrane washing device |
| CN107879498A (en) * | 2017-12-21 | 2018-04-06 | 深圳恒通源环保科技有限公司 | A kind of electroplating wastewater processing recycling system |
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