JP4384310B2 - Membrane cleaning method - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、精密膜ろ過装置または限外膜ろ過装置等の膜ろ過装置に用いられている膜の洗浄方法に関するものである。
【０００２】
【従来の技術】
上記のような膜ろ過装置においては、運転に伴い膜面に付着する物質により膜が次第に閉塞してくる。もちろん運転期間中は逆圧洗浄を行ったり、膜面に高流束の水を流したりして膜面に付着した物質を除去しているが、長期的に見ると膜のろ過能力の低下を避けることはできない。したがって長期間にわたり安定した運転を行うためには、薬品を用いた洗浄を行うことにより、定期的に膜能力を回復させることが必要である。
【０００３】
図３は従来の膜の洗浄方法を概念的に示す図である。図中、１は精密ろ過膜、限外ろ過膜等の膜であり、２は薬品洗浄水槽、３は薬品洗浄ポンプである。図示のように、膜１の原水側に薬品洗浄ポンプ３により洗浄用の薬液を供給して循環させることにより、この薬液が膜１を透過してろ過水側にまで達するようにし、ろ過水側配管４により薬液を薬品洗浄水槽２に回収している。このようにして洗浄を行った後、加圧空気によりろ過水側の薬液を原水側に押し戻して排水したうえ、希釈洗浄用の水で膜ろ過装置の全体を満たし、薬液を希釈洗浄する。このように従来法の洗浄法によれば、膜ろ過装置の全体を薬液で満たした状態で洗浄を行うため、優れた洗浄効果を得ることができる。
【０００４】
しかしこの従来法には次のような問題があった。
▲１▼ 膜ろ過装置の全体を薬液で満たした状態で洗浄を行うため、大量の薬液を必要とし、経済的ではない。
▲２▼ 薬液を希釈洗浄するためにも大量の水（希釈洗浄水）を必要とし、結果として大量の洗浄廃液が発生する。そのためその処理コストがかかる。
▲３▼ 原水側からろ過水側へ薬液が流れるため、洗浄時に汚れた薬液が膜の内部を汚染する可能性がある。
【０００５】
【発明が解決しようとする課題】
本発明は上記した従来の問題点を解決し、薬液及び希釈洗浄水の使用量を大幅に削減することができ、洗浄時の汚れた薬液による膜全体の汚損もなく、しかも従来と同様に膜のろ過能力を回復させることができる膜の洗浄方法を提供するためになされたものである。
【０００６】
【課題を解決するための手段】
上記の課題を解決するためになされた本発明の膜の洗浄方法は、精密膜ろ過装置または限外膜ろ過装置の膜を洗浄する方法であって、膜のろ過水側を０．１〜５．０×１０５Ｐａの気体で加圧して膜の洗浄範囲を制御しながら、原水側に大気圧下で洗浄用薬液を循環させる第１工程と、膜のろ過水側を０．１〜５．０×１０５Ｐａの気体で加圧して膜の洗浄範囲を制御しながら、原水側に大気圧下で薬液希釈洗浄水を循環させる第２工程とからなり、前記第２工程において、ろ過水側の気体の圧力を前記加圧の範囲内で上昇させ、膜内部へ浸出した薬液希釈洗浄水の一部を膜外に排出し、次にろ過水側の気体の圧力を前記加圧の範囲内で低下させ、再び薬液希釈洗浄水を膜内に浸出させる操作を繰り返し加えることを特徴とするものである。
【０００７】
本発明によれば、膜のろ過水側を気体で加圧しながら原水側に洗浄用の薬液を循環させることにより、ろ過性能を低下させる原因となる物質が付着している膜の表層部分だけに薬液を接触させて洗浄を行うことができる。このため、薬液及び希釈洗浄水の使用量を大幅に削減することができ、薬液は原水側からろ過水側へ流れないので洗浄時の汚れた薬液による膜全体の汚損もない。
【０００８】
【発明の実施の形態】
以下に、本発明の好ましい実施形態を示す。
図１は本発明の実施形態を示す図であるが、従来と同様に、１は精密ろ過膜、限外ろ過膜等のセラミック質の膜、２は薬品洗浄水槽、３は薬品洗浄ポンプである。しかし本発明においては従来とは異なり、膜１のろ過水側を加圧空気等の気体で加圧しながら、膜１の原水側に薬品洗浄ポンプ３により洗浄用の薬液を循環させる。( 第１工程)
【０００９】
図２に拡大して示したように精密ろ過膜、限外ろ過膜等のセラミック質の膜１は層状構造を有した非対称膜であり、孔径が最も小さい表層部５においてろ過が行われ、その背後は孔径の大きい多孔質の支持層６を構成している。通常運転中は膜１の支持層６は（Ａ）のようにろ液で満たされているが、膜１のろ過水側を空気等の気体で加圧すると、（Ｂ）のように多孔質の支持層６内のろ液は表層部５に向かって押し戻される。この状態で膜１の原水側に薬液を循環させると、薬液はろ過性能を低下させる原因となる物質７が付着している膜１の表層部分だけに接触し、この付着している物質７を溶解させ、原水側の循環流に乗せて膜外に排出させる。なお、本発明は層状構造を有しない対称膜にも適用可能である。
【００１０】
薬液としては、次亜塩素酸、クエン酸、蓚酸、水酸化ナトリウム、硫酸等が使用される。その濃度は膜１の汚れの程度、除去対象物によって、１ppm から3 ％程度までの範囲内で適宜決定すればよい。また循環方向は上向流でも下向流でもよく、流速は0.01〜3m/sec程度が好ましい。気体の圧力は、0.1 〜5.0 ×105Pa 程度の範囲が適当であり、その圧力によって膜１の洗浄範囲を制御することができる。すなわち、気体の圧力が高いと薬液は表層部５のみにしか浸入できないために膜１の表層部５のみが洗浄され、逆に圧力が低いと薬液は表層部５から多孔質の支持層６の内部にまで浸入し、洗浄範囲が多くなる。なお、孔径が0.1 μm の膜１の表層部５を洗浄したい場合には、1.0 〜1.7 ×105Pa が適当である。また、膜の汚れの度合いによっては、ろ過水側を加圧した状態で、薬液の循環を停止し、膜の表層部５を薬液に接触させ放置する工程を加えることも有効である。このときも、循環時と同様に、加圧する圧力によって薬液と膜１の接触範囲を制御することができる。
【００１１】
また、薬液循環中、薬液接触放置中、ろ過水側圧力を上げ、膜内部へ浸出した薬液の一部を膜外に排出し、次に圧力を下げ、再び膜内に薬液を浸出させる操作を繰り返し加えることにより、膜内における薬液移動速度を上げることができ、さらに洗浄の効率を高めることが可能である。本操作はろ過水側の圧力の調整によっても行うことが可能である。
【００１２】
上記した第１工程の終了後、原水側の薬液を排出し、薬液希釈洗浄工程（第２工程）に入る。第１工程で使用した薬液は膜１の表層部分にのみ残留しているために、その部分のみを希釈洗浄すればよい。従ってこの第２工程でも、膜１のろ過水側を同様に気体で加圧しながら原水側に薬液希釈洗浄用の水を循環させる。この第２工程は循環水を交換しながら複数回繰り返し、残留薬液濃度が十分に低くなるまで実施する。この第２工程でも膜１のろ過水側は加圧されているため、薬液希釈洗浄用の水を膜１の表層部分だけに接触させることができ、水の使用量を削減することができる。
【００１３】
また、希釈洗浄水循環中、ろ過圧力を上げ、膜内部へ浸出した希釈洗浄水の一部を膜外に排出し、次に圧力を下げ、再び希釈洗浄水を膜内に浸出させる操作を繰り返し加えることにより、膜内における希釈洗浄水の移動速度を上げることができ、希釈洗浄の効率を高めることが可能である。本操作はろ過水側の圧力の調整によっても行うことが可能である。なお、第２工程開始前にろ過水側の圧力を、第１工程、第２工程で加えるよりも高い圧力にすることで膜表層部に含まれる液体を押し出し排水し、薬液の残留量を減らし、第２工程の希釈洗浄効率を上げることができる。
【００１４】
このように、本発明によれば薬液および薬液希釈洗浄用の水の使用量を従来よりも大幅に削減することができ、薬液のコストのみならず洗浄廃液の処理コストも削減することができる。しかも膜１の表層部５に付着している物質７は確実に除去することができるため、従来と同様に膜１のろ過能力を回復させることが可能である。
【００１５】
【実施例】
次に本発明の実施例を示す。
直径180mm 、長さ1000mm、孔径が0.1 μm のセラミックス質の内圧式モノリス膜を河川水を原水として３ヵ月使用したところ、使用開始時は27m3/(m2・日・98.1kPa)(at 25℃) であった補正流束が、4.8 m3/(m2・日・98.1kPa)にまで低下した。そこでこのろ過能力の低下した膜を図１に示す装置にて下記の手順で洗浄した。なおこの実施例では、膜面に付着した有機成分を溶解させるための次亜塩素酸による洗浄と、膜面に付着した金属成分を溶解させるためのクエン酸による洗浄とを実施した。
【００１６】
（次亜塩素酸による洗浄）
まず通常の逆洗、ブロー工程の終了後、膜のろ過水側を１×105Pa の加圧空気で満たし、ろ過水側を完全に排水した。そしてこの加圧状態を維持したまま、原水側に3000ppm の次亜塩素酸を膜面流速５cm/secで３時間循環させ、膜面の付着物を洗浄した。その後、循環を停止させ、ろ過水側の圧力を2.0 ×105Pa に高めながら原水側を排水した。次にろ過水側の圧力を再び１×105Pa に下げ、原水側に純水を循環させて残留している次亜塩素酸を希釈洗浄し、希釈洗浄に使用した水を排水した。この希釈洗浄工程を２回繰り返して、次亜塩素酸の濃度を１ppm 以下とした。
【００１７】
（クエン酸による洗浄）
次に、膜のろ過水側を１×105Pa の加圧空気で満たし、原水側に１％のクエン酸を膜面流速５cm/secで３時間循環させた。その後、循環を停止させ、ろ過水側の圧力を2.0 ×105Pa に高めながら原水側を排水した。次に、ろ過水側の圧力を再び１×105Pa に下げ、原水側に純水を循環させて残留しているクエン酸を希釈洗浄し、希釈洗浄に使用した水を排水した。この希釈洗浄工程を２回繰り返してpHが６以上になるまで希釈洗浄した。
【００１８】
上記の洗浄の結果、洗浄前に4.8m3/(m2 ・日・98.1kPa)であった膜の補正流束は27m3/(m2・日・98.1kPa) にまで回復した。このとき使用した薬液量は次亜塩素酸、クエン酸あわせて50リットル、希釈洗浄水量は150 リットルであった。一方、従来の洗浄法により次亜塩素酸による洗浄とクエン酸による洗浄とを行ったところ、洗浄前に３m3/(m2・日・98.1kPa)であった膜の流束を25m3/(m2・日・98.1kPa)にまで回復させることができたが、使用した薬液量は次亜塩素酸、クエン酸あわせて100 リットル、希釈洗浄水量は300 リットルであった。このように、本発明の方法により使用した薬液量を半分にできた。
【００１９】
【発明の効果】
以上に説明したように、本発明の膜の洗浄法によれば、膜のろ過水側を気体で加圧しながら原水側に洗浄用の薬液や薬液希釈洗浄用の水を循環させるようにしたので、必要部分のみを効率よく洗浄することができ、洗浄効果を低下させることなく、薬液および薬液希釈洗浄用の水の使用量を従来よりも大幅に削減することができる。従って、薬液のコストのみならず希釈洗浄廃液の処理コストも削減することができる。また薬液および薬液希釈洗浄用の水は膜の表層部分に浸入するのみであるから、ろ過水中に薬液が混入するおそれがなくなり、汚れた薬液と接触することにより膜全体が汚染されるおそれもない。
【図面の簡単な説明】
【図１】本発明の実施形態を示す概念的な断面図である。
【図２】本発明の作用を説明する膜の拡大断面図である。
【図３】従来法を示す概念的な断面図である。
【符号の説明】
１ 膜、２ 薬品洗浄水槽、３ 薬品洗浄ポンプ、４ ろ過水側配管、５ 表層部、６ 支持層、７ ろ過性能を低下させる原因となる物質[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for cleaning a membrane used in a membrane filtration device such as a precision membrane filtration device or an ultramembrane filtration device.
[0002]
[Prior art]
In the membrane filtration apparatus as described above, the membrane is gradually clogged with substances adhering to the membrane surface during operation. Of course, during the operation period, backwashing is performed or high flux water is flowed on the membrane surface to remove substances adhering to the membrane surface. It cannot be avoided. Therefore, in order to perform a stable operation over a long period of time, it is necessary to periodically restore the membrane capacity by performing cleaning with chemicals.
[0003]
FIG. 3 conceptually shows a conventional film cleaning method. In the figure, 1 is a membrane such as a microfiltration membrane or an ultrafiltration membrane, 2 is a chemical cleaning water tank, and 3 is a chemical cleaning pump. As shown in the figure, a chemical solution for cleaning is supplied to the raw water side of the membrane 1 by the
[0004]
However, this conventional method has the following problems.
(1) Cleaning is performed in a state where the entire membrane filtration apparatus is filled with a chemical solution, which requires a large amount of chemical solution and is not economical.
(2) A large amount of water (diluted cleaning water) is required to dilute and wash the chemical solution, and as a result, a large amount of washing waste liquid is generated. Therefore, the processing cost is high.
(3) Since the chemical solution flows from the raw water side to the filtered water side, there is a possibility that the chemical solution contaminated during cleaning may contaminate the inside of the membrane.
[0005]
[Problems to be solved by the invention]
The present invention solves the above-described conventional problems, can greatly reduce the amount of chemical solution and diluted cleaning water used, and does not cause contamination of the entire membrane due to a dirty chemical solution during cleaning. The present invention has been made in order to provide a membrane cleaning method that can restore the filtration ability of the membrane.
[0006]
[Means for Solving the Problems]
The membrane cleaning method of the present invention made to solve the above-mentioned problems is a method for cleaning a membrane of a precision membrane filtration device or an ultrafiltration membrane filtration device, wherein the filtration water side of the membrane is 0.1-5. A first step of circulating a cleaning chemical solution under atmospheric pressure to the raw water side while controlling the membrane cleaning range by pressurizing with a gas of 0.0 × 10 5 Pa, and 0.1 to 5 for the filtered water side of the membrane A second step of circulating the chemical-diluted cleaning water under atmospheric pressure to the raw water side while controlling the membrane cleaning range by pressurizing with a gas of 0.0 × 10 5 Pa . In the second step, filtered water The pressure of the gas on the side is increased within the range of pressurization, and a part of the chemical-diluted washing water leached into the membrane is discharged out of the membrane, and then the pressure of the gas on the filtered water side is within the range of pressurization. lowering the inner, it is characterized in adding Repeat to leach again chemical dilution wash water in the membrane
[0007]
According to the present invention, by circulating a chemical solution for cleaning on the raw water side while pressurizing the filtered water side of the membrane with gas, only on the surface layer portion of the membrane to which a substance causing a reduction in filtration performance is adhered. Cleaning can be performed by contacting the chemical solution. For this reason, the usage-amount of a chemical | medical solution and dilution washing | cleaning water can be reduced significantly, and since a chemical | medical solution does not flow from the raw | natural water side to the filtrate water side, there is no contamination of the whole film | membrane by the chemical | medical solution which became dirty at the time of washing | cleaning.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiments of the present invention are shown below.
FIG. 1 is a diagram showing an embodiment of the present invention. As in the prior art, 1 is a ceramic membrane such as a microfiltration membrane and an ultrafiltration membrane, 2 is a chemical cleaning water tank, and 3 is a chemical cleaning pump. . However, in the present invention, unlike the prior art, a chemical solution for cleaning is circulated by the
[0009]
As shown in FIG. 2, the ceramic membrane 1 such as a microfiltration membrane and an ultrafiltration membrane is an asymmetric membrane having a layered structure, and filtration is performed in the
[0010]
As the chemical solution, hypochlorous acid, citric acid, oxalic acid, sodium hydroxide, sulfuric acid and the like are used. The concentration may be appropriately determined within the range of 1 ppm to 3% depending on the degree of contamination of the film 1 and the object to be removed. The direction of circulation may be upward or downward, and the flow rate is preferably about 0.01 to 3 m / sec. The gas pressure is suitably in the range of about 0.1 to 5.0 × 10 5 Pa, and the cleaning range of the membrane 1 can be controlled by the pressure. That is, when the gas pressure is high, the chemical solution can only enter the
[0011]
In addition, while the chemical solution is circulating or left in contact with the chemical solution, raise the pressure on the filtered water side, discharge part of the chemical solution that has leached into the membrane, then lower the pressure, and leaching the chemical solution into the membrane again. By repeatedly adding, the moving speed of the chemical solution in the membrane can be increased, and the cleaning efficiency can be further increased. This operation can also be performed by adjusting the pressure on the filtered water side.
[0012]
After the completion of the first step, the chemical solution on the raw water side is discharged, and the chemical solution dilution cleaning step (second step) is started. Since the chemical solution used in the first step remains only in the surface layer portion of the membrane 1, only that portion needs to be diluted and cleaned. Accordingly, also in the second step, the chemical solution dilution cleaning water is circulated to the raw water side while the filtered water side of the membrane 1 is similarly pressurized with gas. This second step is repeated a plurality of times while exchanging the circulating water, and is carried out until the residual chemical concentration becomes sufficiently low. Even in this second step, the filtered water side of the membrane 1 is pressurized, so that the water for chemical dilution cleaning can be brought into contact with only the surface layer portion of the membrane 1 and the amount of water used can be reduced.
[0013]
Also, during the circulation of the diluted cleaning water, increase the filtration pressure, discharge a part of the diluted cleaning water leached out of the membrane to the outside of the membrane, then lower the pressure and repeat the operation of leaching the diluted cleaning water into the membrane again. As a result, the moving speed of the diluted cleaning water in the membrane can be increased, and the efficiency of the diluted cleaning can be increased. This operation can also be performed by adjusting the pressure on the filtered water side. Before starting the second step, the pressure on the filtered water side is set to a pressure higher than that applied in the first step and the second step, thereby pushing out and draining the liquid contained in the membrane surface layer, thereby reducing the residual amount of the chemical solution. The efficiency of dilution cleaning in the second step can be increased.
[0014]
As described above, according to the present invention, the amount of the chemical solution and the water used for diluting and cleaning the chemical solution can be greatly reduced as compared with the conventional case, and not only the cost of the chemical solution but also the processing cost of the cleaning waste liquid can be reduced. Moreover, since the
[0015]
【Example】
Next, examples of the present invention will be described.
A ceramic internal pressure monolithic membrane with a diameter of 180 mm, a length of 1000 mm, and a pore diameter of 0.1 μm was used for 3 months using river water as raw water. At the beginning of use, 27 m 3 / (m 2 · day · 98.1 kPa) (at 25 ° C) was reduced to 4.8 m 3 / (m 2 · day · 98.1 kPa). Therefore, the membrane having the reduced filtration ability was washed by the following procedure using the apparatus shown in FIG. In this example, cleaning with hypochlorous acid for dissolving the organic component adhering to the film surface and cleaning with citric acid for dissolving the metal component adhering to the film surface were performed.
[0016]
(Cleaning with hypochlorous acid)
First, after the normal backwashing and blowing processes were completed, the filtered water side of the membrane was filled with 1 × 10 5 Pa of pressurized air, and the filtered water side was completely drained. While maintaining this pressurized state, 3000 ppm of hypochlorous acid was circulated on the raw water side at a membrane surface flow rate of 5 cm / sec for 3 hours to wash the deposits on the membrane surface. Thereafter, the circulation was stopped, and the raw water side was drained while increasing the pressure on the filtrate side to 2.0 × 10 5 Pa. Next, the pressure on the filtrate side was again lowered to 1 × 10 5 Pa, pure water was circulated on the raw water side to dilute and wash remaining hypochlorous acid, and the water used for the dilution washing was drained. This dilution washing step was repeated twice to make the concentration of hypochlorous acid 1 ppm or less.
[0017]
(Washing with citric acid)
Next, the filtered water side of the membrane was filled with 1 × 10 5 Pa of pressurized air, and 1% citric acid was circulated on the raw water side at a membrane surface flow rate of 5 cm / sec for 3 hours. Thereafter, the circulation was stopped, and the raw water side was drained while increasing the pressure on the filtrate side to 2.0 × 10 5 Pa. Next, the pressure on the filtrate water side was lowered to 1 × 10 5 Pa again, pure water was circulated to the raw water side to dilute and wash the remaining citric acid, and the water used for the dilution washing was drained. This dilution washing step was repeated twice and diluted and washed until the pH reached 6 or more.
[0018]
As a result of the above washing, the corrected flux of the film, which was 4.8 m 3 / (m 2 · day · 98.1 kPa) before washing, was restored to 27 m 3 / (m 2 · day · 98.1 kPa). The amount of the chemical solution used at this time was 50 liters including hypochlorous acid and citric acid, and the amount of diluted washing water was 150 liters. On the other hand, when cleaning with hypochlorous acid and citric acid was performed by the conventional cleaning method, the membrane flux that was 3 m 3 / (m 2 · day · 98.1 kPa) before cleaning was reduced to 25 m 3 / (m 2 · day · 98.1 kPa), the amount of chemicals used was 100 liters including hypochlorous acid and citric acid, and the diluted washing water amount was 300 liters. Thus, the amount of the chemical used by the method of the present invention was halved.
[0019]
【The invention's effect】
As explained above, according to the membrane cleaning method of the present invention, the chemical solution for cleaning and the water for chemical solution dilution cleaning are circulated to the raw water side while pressurizing the filtered water side of the membrane with gas. Only the necessary part can be efficiently cleaned, and the amount of water used for the chemical solution and the chemical solution diluted cleaning can be greatly reduced as compared with the prior art without deteriorating the cleaning effect. Therefore, not only the cost of the chemical solution but also the processing cost of the diluted cleaning waste liquid can be reduced. In addition, since the chemical solution and water for chemical solution cleaning only enter the surface layer of the membrane, there is no risk of the chemical solution entering the filtered water, and there is no risk of contamination of the entire membrane by contact with the contaminated chemical solution. .
[Brief description of the drawings]
FIG. 1 is a conceptual cross-sectional view showing an embodiment of the present invention.
FIG. 2 is an enlarged cross-sectional view of a film for explaining the operation of the present invention.
FIG. 3 is a conceptual cross-sectional view showing a conventional method.
[Explanation of symbols]
1 Membrane, 2 Chemical Washing Water Tank, 3 Chemical Washing Pump, 4 Filtration Water Side Piping, 5 Surface Layer, 6 Support Layer, 7 Substances that Cause Filtration Performance to be Reduced
Claims (2)
膜のろ過水側を０．１〜５．０×１０５Ｐａの気体で加圧して膜の洗浄範囲を制御しながら、原水側に大気圧下で洗浄用薬液を循環させる第１工程と、
膜のろ過水側を０．１〜５．０×１０５Ｐａの気体で加圧して膜の洗浄範囲を制御しながら、原水側に大気圧下で薬液希釈洗浄水を循環させる第２工程とからなり、
前記第２工程において、ろ過水側の気体の圧力を前記加圧の範囲内で上昇させ、膜内部へ浸出した薬液希釈洗浄水の一部を膜外に排出し、次にろ過水側の気体の圧力を前記加圧の範囲内で低下させ、再び薬液希釈洗浄水を膜内に浸出させる操作を繰り返し加えることを特徴とする膜の洗浄方法。A method of cleaning a membrane of a precision membrane filtration device or an ultramembrane filtration device,
A first step of circulating a cleaning chemical at atmospheric pressure to the raw water side while pressurizing the filtered water side of the membrane with a gas of 0.1 to 5.0 × 10 5 Pa and controlling the cleaning range of the membrane;
A second step of circulating the chemical-diluted cleaning water under atmospheric pressure to the raw water side while pressurizing the filtered water side of the membrane with a gas of 0.1 to 5.0 × 10 5 Pa and controlling the cleaning range of the membrane; Consists of
In the second step, the pressure of the filtered water side gas is raised within the range of the pressurization, and a part of the chemical-diluted washing water leached into the membrane is discharged out of the membrane, and then the filtered water side gas The membrane cleaning method is characterized in that an operation of lowering the pressure in the range of the pressurization and repeatedly leaching the chemical diluted cleaning water into the membrane is repeated .
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| JP30033299A JP4384310B2 (en) | 1999-10-22 | 1999-10-22 | Membrane cleaning method |
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