JP2010036183A - Separating membrane module for treating wastewater containing oil, and method and device for treating wastewater containing oil - Google Patents

Separating membrane module for treating wastewater containing oil, and method and device for treating wastewater containing oil Download PDF

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JP2010036183A
JP2010036183A JP2009100379A JP2009100379A JP2010036183A JP 2010036183 A JP2010036183 A JP 2010036183A JP 2009100379 A JP2009100379 A JP 2009100379A JP 2009100379 A JP2009100379 A JP 2009100379A JP 2010036183 A JP2010036183 A JP 2010036183A
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oil
hollow fiber
wastewater
water
fiber membrane
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JP5446416B2 (en
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Kiyoshi Ida
Toru Morita
清志 井田
徹 森田
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Sumitomo Electric Fine Polymer Inc
住友電工ファインポリマー株式会社
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a separating membrane module suitable for filtration of wastewater containing oil. <P>SOLUTION: The separating membrane module for treating wastewater containing oil which separates water-insoluble oil contents from highly turbid and/or high-temperature wastewater containing oil is composed of an alkali resistant porous membrane selected from among PTFE (polytetrafluoroethylene), PSF (polysulfone) and PES (polyethersulfone), and uses a hollow fiber membrane of a tensile strength of 30 N or larger. A heat distortion temperature of the hollow fiber membrane and an end sealing material for the hollow fiber membrane is 100°C or higher. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、含油排水処理用の分離膜モジュール、これを用いた含油排水処理方法および分離膜モジュールの洗浄装置を付設した含油排水処理装置に関し、長期に渡り、含油排水から非水溶性油分を効率良く分離するものである。   The present invention relates to a separation membrane module for oil-containing wastewater treatment, an oil-containing wastewater treatment method using the same, and an oil-containing wastewater treatment device provided with a cleaning device for the separation membrane module. It separates well.
従来より、非水溶性油分を含む含油排水から非水溶性油分を除去する処理装置および処理方法が提供されている。
含油排水の一種として油田随伴水があり、この油田随伴水から非水溶性油分を除去する必要がある。すなわち、原油採掘の際、海水を地層の油層に注入して、非水溶性油分の圧力を高め、生産量を確保することが一般的に行われている。このような原油採掘に使用された排水である「油田随伴水」は非水溶性油分を多く含むため、非水溶性油分の除去処理がなされた後に廃棄されている。
しかしながら、近年、海洋・湖沼等の汚染を引き起こす要因となることから、排水中の非水溶性油分含有量の規制が強化されてきており、最も厳格な国や地域では5mg/L未満の非水溶性油分含有量とすることが要求されている。
Conventionally, a treatment apparatus and a treatment method for removing water-insoluble oil from oil-containing wastewater containing water-insoluble oil are provided.
One type of oil-containing wastewater is oilfield associated water, and it is necessary to remove water-insoluble oil from the oilfield associated water. That is, when crude oil is mined, it is generally performed to inject seawater into the oil layer of the formation to increase the pressure of the water-insoluble oil and to secure the production amount. Since “oil field associated water”, which is wastewater used for crude oil mining, contains a large amount of water-insoluble oil, it is discarded after the water-insoluble oil is removed.
However, in recent years, regulations on water-insoluble oil content in wastewater have been tightened because it causes pollution of oceans, lakes and marshes, and in the most stringent countries and regions, water-insoluble water of less than 5 mg / L It is required to have the content of the essential oil.
通常、油田随伴水は、重力差分離、固/液ハイドロサイクロン等による固体分離の後、板フィルター、液/液ハイドロサイクロン等による一次処理、凝集沈殿・加圧浮上等による二次処理を経たのち、濾過や活性炭処理等の三次処理が行われるが、一次、二次、三次処理と高次処理になればなる程、処理水量が低下するため、大量に排出される油田随伴水の処理に追いつかなくなる問題がある。その結果、大量排出される油田随伴水の処理においては、精密な分離手段は、その処理速度の点から適用できず、結果的に、実用上は非水溶性油分含有量20mg/Lまでの処理が限界と言われている。また、処理コストも問題である。   Usually, oilfield-associated water is subjected to gravity separation, solid separation with solid / liquid hydrocyclone, etc., followed by primary treatment with plate filters, liquid / liquid hydrocyclone, etc., and secondary treatment with coagulation sedimentation, pressurized flotation, etc. The tertiary treatment such as filtration and activated carbon treatment is performed, but the higher the primary, secondary, and tertiary treatment, the lower the treated water volume. There is a problem that disappears. As a result, in the treatment of oilfield-associated water discharged in large quantities, precise separation means cannot be applied in terms of the treatment speed, and as a result, practically treatment up to a water-insoluble oil content of 20 mg / L. Is said to be the limit. Also, processing costs are a problem.
そこで、含油排水の処理に分離膜モジュールを利用することが有望とされている。分離膜モジュールは高い処理水量を確保でき、高度な水処理を行うことができるという利点がある。例えば、特開平5−245472号公報(特許文献1)では、図9に示すように、含油排水100を油粒子よりも小さな平均細孔径のセラミック分離膜101を備えた濾過装置102の一次側S1に供給し、セラミック分離膜101の二次側S2から処理水を取り出すと共に一次側の濃縮水が所定濃度になるまで濾過装置の一次側に濃縮水を循環供給するようにする処理方法を提供している。   Therefore, it is considered promising to use a separation membrane module for the treatment of oil-containing wastewater. The separation membrane module has an advantage that a high amount of treated water can be secured and advanced water treatment can be performed. For example, in Japanese Patent Laid-Open No. 5-245472 (Patent Document 1), as shown in FIG. 9, the primary side S1 of a filtration device 102 provided with a ceramic separation membrane 101 having an oil-containing wastewater 100 having an average pore diameter smaller than oil particles. And a processing method for removing the treated water from the secondary side S2 of the ceramic separation membrane 101 and circulatingly supplying the concentrated water to the primary side of the filtration device until the concentrated water on the primary side reaches a predetermined concentration. ing.
特開平5−245472号公報JP-A-5-245472
しかし、含油排水の継続的な処理においては、分離膜の膜面への非水溶性油分付着により流量の低下が起こる。そのため、通常、非水溶性油分を分解除去し、継続的に濾過を行うために水酸化ナトリウム等の強アルカリ性薬剤を用いた化学洗浄が必須である。しかし、分離膜にセラミック膜を用いている特許文献1では、非水溶性油分の洗浄に有効な高濃度のアルカリ性水溶液に対する耐久性が十分でないため膜面の化学洗浄が十分に行えない問題がある。また、オリジナルの物理的強度は強いものの、前記アルカリ等による薬液洗浄の累積頻度が上がってくると徐々に強度劣化がはじまり、逆洗、散気などの物理洗浄実施時の微量とはいえ負荷される衝撃などの影響を受け、その衝撃によりクラック等のトラブルも発生しやすくなる。さらに、特許文献1では分離膜を平膜としているため、処理水量も制限され、大量に排出される含油排水の継続的処理には適さない。   However, in the continuous treatment of oil-containing wastewater, the flow rate decreases due to the non-water-soluble oil adhering to the membrane surface of the separation membrane. Therefore, in order to decompose and remove the water-insoluble oil and continuously perform filtration, chemical cleaning using a strong alkaline agent such as sodium hydroxide is essential. However, in Patent Document 1 using a ceramic membrane as a separation membrane, there is a problem that chemical cleaning of the membrane surface cannot be sufficiently performed because durability to a high-concentration alkaline aqueous solution effective for cleaning a water-insoluble oil is not sufficient. . In addition, although the original physical strength is strong, as the cumulative frequency of chemical cleaning with alkali increases, the strength gradually begins to deteriorate, and even though it is a trace amount during physical cleaning such as backwashing and aeration, it is loaded. It is easy to generate troubles such as cracks. Furthermore, in patent document 1, since the separation membrane is made into a flat membrane, the amount of treated water is also limited and it is not suitable for continuous treatment of oil-containing wastewater discharged in large quantities.
また、現在、耐薬品性に優れるとして市販されているポリフッ化ビニリデン(PVDF)からなる分離膜も前記のセラミック膜同様、高濃度のアルカリ性水溶液に対する耐久性がなく、ポリエチレン、ポリプロピレンからなる分離膜は物理的強度が不足する問題がある。   In addition, separation membranes made of polyvinylidene fluoride (PVDF), which are currently marketed as having excellent chemical resistance, are not durable against high-concentration alkaline aqueous solutions, like the above-mentioned ceramic membranes. There is a problem of insufficient physical strength.
また、加温された含油排水を温度を低下させずに分離処理する装置では、耐熱性および、停止時の低温と加熱時の高温とが周期的に繰り返され、含油排水処理装置の設置場所が例えば寒冷地で低温と高温の差が100℃以上であるヒートサイクルに対しても耐性を有することが要求される。
しかしながら、従来、油水分離処理用として汎用されている樹脂製の濾過膜は耐熱性が十分ではない。
例えば、PP、PE、PVDEでは、常時60℃以上の加熱含油排水が供給されると、軟化して孔径が変化し、PEでは破断が発生しやすい。
さらに、従来用いられている高温の油水分離装置として、セラミック粉末焼結体で形成している場合もあるが、この場合は耐熱性を有するが重量が増加する等の問題があり、かつ、前記ヒートサイクルでの温度変化時に熱的障害を受けてクラック等が発生しやすい。
かつ、セラミック製の分離装置を備えた従来装置は、膜面積あたりの膜エレメント容積が大きいため、設置面積が多く必要である一方それが故に膜装置を多段にする場合があるが、装置全体の重量が大きく大型の装置となり、洗浄時や調査の為に、濾過装置を取り外しにくい問題がある。
In addition, in a device that separates heated oil-containing wastewater without lowering the temperature, the heat resistance and the low temperature when stopped and the high temperature when heated are repeated periodically, and the installation location of the oil-containing wastewater treatment device is For example, it is required to have resistance to a heat cycle in which a difference between a low temperature and a high temperature is 100 ° C. or more in a cold region.
However, resin filtration membranes that have been widely used for oil-water separation treatment have not been sufficiently heat resistant.
For example, in PP, PE, and PVDE, when heated oil-impregnated wastewater at 60 ° C. or higher is always supplied, the pore size changes due to softening, and PE tends to break.
Furthermore, as a conventionally used high-temperature oil-water separator, there is a case where it is formed of a ceramic powder sintered body, but in this case, there is a problem such as having heat resistance but an increase in weight, and Cracks are likely to occur due to thermal failure during temperature changes in the heat cycle.
In addition, a conventional apparatus having a ceramic separator has a large membrane element volume per membrane area, and thus requires a large installation area. There is a problem that the apparatus becomes heavy and large, and it is difficult to remove the filtration device for cleaning or investigation.
本発明は前記問題に鑑みてなされたものであり、含油排水に対する高性能な濾過性能を有し、かつ、非水溶性油分除去に効果的なアルカリに対する耐久性を有して繰り返しの再生を可能とし、さらに耐熱性に優れ、長期に渡り高性能濾過を持続させることを課題としている。   The present invention has been made in view of the above problems, has high-performance filtration performance for oil-containing wastewater, and has durability against alkali that is effective for removing water-insoluble oil, and can be repeatedly regenerated. Furthermore, it is excellent in heat resistance and has a problem of maintaining high-performance filtration over a long period of time.
前記課題を解決するため、第一の発明として、高濁度あるいは/および高温の含油排水から非水溶性油分を分離する含油排水処理用の分離膜モジュールであって、
PTFE(ポリテトラフルオロエチレン)、PSF(ポリスルホン)およびPES(ポリエーテルスルホン)から選択される耐アルカリ性を備えた多孔質膜からなり、抗張力が30N以上である中空糸膜を用い、
前記中空糸膜の熱変形温度は100℃以上であり、
前記該中空糸膜の端末封止材は、熱変形温度が100℃以上の熱硬化性樹脂、または融点が使用温度の1.5倍以上である熱溶融性樹脂からなることを特徴とする含油排水処理用の分離膜モジュールを提供している。
In order to solve the above-mentioned problem, as a first invention, a separation membrane module for oil-containing wastewater treatment that separates water-insoluble oil from high-turbidity or / and high-temperature oil-containing wastewater,
Using a hollow membrane having an alkali resistance selected from PTFE (polytetrafluoroethylene), PSF (polysulfone) and PES (polyethersulfone), and having a tensile strength of 30 N or more,
The hollow fiber membrane has a heat deformation temperature of 100 ° C. or higher,
The hollow fiber membrane end-sealing material is composed of a thermosetting resin having a heat deformation temperature of 100 ° C. or higher, or a heat-melting resin having a melting point of 1.5 times or more of the use temperature. Separation membrane module for wastewater treatment is provided.
本発明者らは、高濁度、高温の含油排水から非水溶性油分を分離する場合において、PTFE(ポリテトラフルオロエチレン)、PSF(ポリスルホン)、PES(ポリエーテルスルホン)から選択される多孔質分離膜の中空糸または平膜を用いた分離膜モジュールは、極めて優れた非水溶性油分除去性能と耐薬品性、特に、耐アルカリ性を備え、かつ耐久(正常な濾過性能を発揮する使用可能期間)とを兼ね備えることを知見した。その結果、5mg/L未満、さらには1mg/L未満の低濃度にまで非水溶性油分含有量を低減できる高性能濾過を実現しながら、膜面に付着した非水溶性油分はアルカリ性水溶液による化学洗浄により溶解除去して繰り返し再生が可能であるので、高性能濾過を長期に渡り持続させることができる。   In the case of separating a water-insoluble oil component from high-turbidity, high-temperature oil-containing wastewater, the present inventors have selected a porous material selected from PTFE (polytetrafluoroethylene), PSF (polysulfone), and PES (polyethersulfone). Separation membrane modules using separation membrane hollow fibers or flat membranes have excellent water-insoluble oil removal performance and chemical resistance, especially alkali resistance and durability (usable period of normal filtration performance) ). As a result, while realizing high-performance filtration that can reduce the water-insoluble oil content to a low concentration of less than 5 mg / L and even less than 1 mg / L, the water-insoluble oil adhering to the membrane surface is chemically treated with an alkaline aqueous solution High performance filtration can be maintained for a long time because it can be repeatedly removed by dissolving and removing by washing.
前記濾過膜を構成するPTFE(ポリテトラフルオロエチレン)、PSF(ポリスルホン)、PES(ポリエーテルスルホン)は抗張力が30N以上の強度を備えている。そのため、高濃度のアルカリ性洗浄液で繰り返し濾過しても、濾過性能及び強度が低下することがなく、かつ、長期に渡り、高性能濾過を持続することができる。抗張力は、好ましくは50N以上であり、上限は150N程度である。
なお、抗張力はJIS K 7161に準拠し、試験体としては中空糸膜そのものを用いた。試験時の引張速度は100mm/分、標線間距離は50mmとして測定した。
PTFE (polytetrafluoroethylene), PSF (polysulfone), and PES (polyethersulfone) constituting the filtration membrane have a tensile strength of 30 N or more. Therefore, even if it repeatedly filters with a high concentration alkaline cleaning liquid, filtration performance and intensity | strength do not fall, and high performance filtration can be maintained over a long period of time. The tensile strength is preferably 50 N or more, and the upper limit is about 150 N.
The tensile strength was based on JIS K 7161, and the hollow fiber membrane itself was used as a test body. The tensile speed during the test was 100 mm / min, and the distance between the marked lines was 50 mm.
また、前記濾過膜を構成するPTFE(ポリテトラフルオロエチレン)、PSF(ポリスルホン)、PES(ポリエーテルスルホン)は熱変形温度が100℃以上である。具体的には、PTFEは121℃、PSFは181℃、PESは210℃である。該熱変形温度は、処理する含油排水温度に応じて、上記膜を選択することができる。
また、濾過膜の端末封止材も前記濾過膜の形成材と同様な熱変形温度が100℃以上の樹脂、あるいは熱溶融性樹脂では耐熱温度が高いフッ素系樹脂を用いて形成している。
このように、濾過膜および端末封止材を耐熱性としているため、加熱含油排水の濾過膜として経年使用しても熱劣化が発生しにくいものとすることができる。
Further, PTFE (polytetrafluoroethylene), PSF (polysulfone), and PES (polyethersulfone) constituting the filtration membrane have a heat distortion temperature of 100 ° C. or higher. Specifically, PTFE is 121 ° C., PSF is 181 ° C., and PES is 210 ° C. The heat distortion temperature can be selected from the above membrane according to the temperature of the oil-containing wastewater to be treated.
Further, the end sealing material of the filtration membrane is also formed by using a resin having a heat deformation temperature of 100 ° C. or more similar to the formation material of the filtration membrane, or a fluororesin having a high heat resistance temperature in the case of a thermomeltable resin.
Thus, since the filtration membrane and the terminal sealing material are heat resistant, even when used as a filtration membrane for heated oil-containing wastewater, thermal deterioration can hardly occur.
前記濾過膜で濾過される前記含油排水は、20℃における粘度0.1〜5.0mPa・sの非水溶性油分を含有する含油排水に好適に用いられ、前記濾過膜による濾過処理済み水の油分含有量を10mg/L〜0.1mg/Lとしている。一方、排水の温度が100℃等の高温の場合は粘度が下がるため常温ベースでの粘度がさらに大きいものでも濾過可能となる。   The oil-containing wastewater filtered by the filtration membrane is preferably used for oil-containing wastewater containing a water-insoluble oil component having a viscosity of 0.1 to 5.0 mPa · s at 20 ° C. The oil content is set to 10 mg / L to 0.1 mg / L. On the other hand, when the temperature of the waste water is a high temperature such as 100 ° C., the viscosity decreases, so that even a higher viscosity on a normal temperature basis can be filtered.
本発明の含油排水処理用分離膜モジュールにより処理される含油排水の20℃における粘度を0.1〜5.0mPa・sとしているのは、含有非水溶性油分の粘度が5.0mPa・sを超えると多孔質材料への付着力が大きくなり、不可逆的な膜の目詰まりが生じて十分な処理水量を確保しにくいことによる。一方、粘度0.1mPa・s未満であると微小な非水溶性油分同士が結合して粗大化、粒子化しにくいことによる。
含油排水に含有される非水溶性油分としては前記粘度範囲で、かつ、水中で水と分離して粒子を形成する非水溶性物質であれば問わないが、ナフサ等の主に石油系の炭化水素系溶剤が挙げられる。
前記含油排水は後述するように重量分離等で分離できる浮上油等は予め除去しておき、非水溶性油分含有量が10〜2000mg/Lに調整され、前記非水溶性油分はミクロンからサブミクロンオーダーの粒径の微粒子として分散油の状態で水中に存在しているものであることが好ましい。
なお、前記非水溶性油分の粘度は、20℃において英弘精機製レオメーターを用いて測定したものである。
The viscosity at 20 ° C. of the oil-containing wastewater treated by the separation membrane module for oil-containing wastewater treatment of the present invention is 0.1 to 5.0 mPa · s because the viscosity of the contained water-insoluble oil is 5.0 mPa · s. If it exceeds, adhesion to the porous material will increase, irreversible membrane clogging will occur, and it will be difficult to ensure a sufficient amount of treated water. On the other hand, when the viscosity is less than 0.1 mPa · s, minute water-insoluble oil components are bonded to each other, and are not easily coarsened and formed into particles.
The water-insoluble oil contained in the oil-containing wastewater is not limited as long as it is in the above-mentioned viscosity range and is a water-insoluble substance that separates from water in water to form particles, but mainly petroleum-based carbonization such as naphtha. A hydrogen solvent is mentioned.
As described later, the oil-containing wastewater is separated from floating oil that can be separated by weight separation or the like, the water-insoluble oil content is adjusted to 10 to 2000 mg / L, and the water-insoluble oil content is from micron to submicron. It is preferable that the fine particles having an order particle diameter exist in water in the state of dispersed oil.
The viscosity of the water-insoluble oil is measured at 20 ° C. using a Hidehiro Seiki rheometer.
また、前記濾過膜で濾過される前記含油排水は、懸濁物質の濃度が5〜20000mg/L、特に、100mmg/L以上の高濁度の含油排水に好適に用いられる。   Moreover, the oil-containing wastewater filtered by the filtration membrane is suitably used for oily wastewater having a high turbidity with a suspended substance concentration of 5 to 20000 mg / L, particularly 100 mmg / L or more.
また、前記濾過膜で濾過される前記含油排水の温度が60〜200℃の加熱された高温含油排水である場合にも好適に用いられる。前記のように、含油排水の温度に応じて濾過膜および端末封止材は含油排水温度で熱変形が発生しない耐熱温度を有するものとしている。   Moreover, it is used suitably also when the temperature of the said oil-containing wastewater filtered with the said filter membrane is 60-200 degreeC heated high temperature oil-containing wastewater. As described above, according to the temperature of the oil-containing wastewater, the filtration membrane and the terminal sealing material have a heat resistant temperature at which thermal deformation does not occur at the oil-containing wastewater temperature.
前記中空糸膜は、単層、または支持層と該支持層の少なくとも外側に積層する濾過層を備えた多孔質複層あるいは非対称濾過膜のいずれでもよい。
前記濾過膜の平均空孔径は0.01〜1μmとしていることが好ましい
The hollow fiber membrane may be a single layer, or a porous multilayer or an asymmetric filtration membrane provided with a support layer and a filtration layer laminated on at least the outside of the support layer.
The average pore diameter of the filtration membrane is preferably 0.01-1 μm.
前記中空糸膜は、中空糸膜全体で内径0.3〜12mm、外径0.8〜14mm、バブルポイント50〜400kPa、膜厚0.2〜1mm、気孔率30〜90%、最大許容膜間差圧は0.1〜1.0MPaの耐圧性を備えたものとすることが好ましい。   The hollow fiber membrane has an inner diameter of 0.3 to 12 mm, an outer diameter of 0.8 to 14 mm, a bubble point of 50 to 400 kPa, a film thickness of 0.2 to 1 mm, a porosity of 30 to 90%, and a maximum allowable membrane. It is preferable that the differential pressure has a pressure resistance of 0.1 to 1.0 MPa.
バブルポイントは前述同様、イソプロピルアルコール(IPA)を用いて、JIS K 3832に記載の方法に準拠し、試験体としては中空糸膜そのものを用いた。
中空糸膜の気孔率はアルキメデス法により求めた。算出の際、PTFEの比重は2.17とした。
最大許容膜間差圧の測定は、内圧濾過式の場合は、中空糸膜面にシリコングリス等を塗布し加圧面を非多孔化したあと、1500mg/lの水酸化鉄粒子が分散された水を媒体として内圧を負荷した。負荷前後での膜の寸法が実質的に変化しない範囲での膜の1次側/2次側の圧力差を10kPaごとに測定した。
外圧濾過式の場合は、所定の長さで中空糸膜の両端を拘束状態で固定し、チューブ内側に透過した水が両端から抜き出せる状態において、チューブ外面に同じくシリコングリスを塗布した状態で、これを密閉されたハウジング内におさめ水圧をかけた。そのとき、チューブが負荷圧力を開放したあと、加圧前の外径に復帰するときの最大圧力を10kPaごとに測定した。
As described above, isopropyl alcohol (IPA) was used as the bubble point in accordance with the method described in JIS K3832, and the hollow fiber membrane itself was used as a test specimen.
The porosity of the hollow fiber membrane was determined by the Archimedes method. At the time of calculation, the specific gravity of PTFE was 2.17.
In the case of the internal pressure filtration type, the maximum allowable transmembrane pressure is measured by applying water to the hollow fiber membrane surface to make the pressure surface non-porous, and then water in which 1500 mg / l iron hydroxide particles are dispersed. The internal pressure was loaded using as a medium. The pressure difference between the primary side and the secondary side of the membrane in a range where the size of the membrane before and after loading did not substantially change was measured every 10 kPa.
In the case of the external pressure filtration type, both ends of the hollow fiber membrane are fixed in a fixed state with a predetermined length, and in a state where the water permeated to the inside of the tube can be extracted from both ends, the same condition is applied to the outer surface of the tube with silicon grease. This was put in a sealed housing and water pressure was applied. At that time, after the tube released the load pressure, the maximum pressure when returning to the outer diameter before pressurization was measured every 10 kPa.
前記中空糸膜は耐アルカリ性を備えると共に、前記したバブルポイント、気孔率、最大許容膜間差圧を有するものであれば、前記のように単層、複層のいずれの中空糸膜でも良い。該中空糸膜は、特に、耐アルカリ性があり、かつ、強度、耐久性に優れた点で、多孔質延伸PTFE製であることが好ましい。   As long as the hollow fiber membrane has alkali resistance and has the above-described bubble point, porosity, and maximum allowable inter-membrane differential pressure, it may be a single-layer or multi-layer hollow fiber membrane as described above. The hollow fiber membrane is particularly preferably made of porous expanded PTFE in terms of alkali resistance and excellent strength and durability.
前記中空糸膜は抗張力が30N以上150N以下、IPAバブルポイントを50kPa以上400kPa以下としていることが好ましい。
前記中空糸膜のIPAバブルポイントを50kPa以上400kPa以下としているのは、50kPaを下回ると孔径が大き過ぎて液状の非水溶性油分が前記多孔質膜の孔を通過してしまい非水溶性油分含有量が5mg/L未満の処理済み水を得ることができないことによる。一方、400kPaを超えると、孔径が小さすぎて処理水量の確保が困難になること、および膜の化学洗浄に使用する洗浄液の浸透性が悪いため洗浄回復性が悪いからである。
IPAバブルポイントの下限値は好ましくは80kPa以上、さらに好ましくは100kPa以上であり、上限値は好ましくは380kPa以下、さらに好ましくは350kPa以下である。
なお、IPAバブルポイントは、イソプロピルアルコール(IPA)を用いて、JIS K 3832に記載の方法に準拠し、試験体としては中空糸膜そのものを用いた。
The hollow fiber membrane preferably has a tensile strength of 30 N to 150 N and an IPA bubble point of 50 kPa to 400 kPa.
The IPA bubble point of the hollow fiber membrane is set to 50 kPa or more and 400 kPa or less. When the pressure is below 50 kPa, the pore diameter is too large and the liquid water-insoluble oil component passes through the pores of the porous membrane and contains a water-insoluble oil component. This is because it is impossible to obtain treated water whose amount is less than 5 mg / L. On the other hand, if it exceeds 400 kPa, it is difficult to ensure the amount of treated water because the pore size is too small, and the cleaning recoverability is poor because the permeability of the cleaning liquid used for chemical cleaning of the membrane is poor.
The lower limit value of the IPA bubble point is preferably 80 kPa or more, more preferably 100 kPa or more, and the upper limit value is preferably 380 kPa or less, more preferably 350 kPa or less.
In addition, the IPA bubble point was based on the method of JISK3832 using isopropyl alcohol (IPA), and used the hollow fiber membrane itself as a test body.
前記中空糸膜とし、支持層とする多孔質延伸PTFEチューブに、濾過層とする多孔質延伸PTFEシートを巻き付けた多孔質複層中空糸膜が好適に用いられる。
前記PTFE多孔質複層中空糸膜において、外層である濾過層をシートの巻き付け構造としているのは、多孔質シートは1軸延伸、2軸延伸共に行いやすく、表面の空孔の形状や大きさ等の調整が容易である上に、薄膜での積層が容易であるためである。内層の支持層は押出成形されたチューブとすることで、成形性も良く、ある程度の厚みを有し十分な強度を持たせやすく、空孔率も大きくしやすくなる。
As the hollow fiber membrane, a porous multilayer hollow fiber membrane in which a porous expanded PTFE sheet as a filtration layer is wound around a porous expanded PTFE tube as a support layer is suitably used.
In the PTFE porous multilayer hollow fiber membrane, the filtration layer, which is the outer layer, has a sheet winding structure. The porous sheet is easy to perform both uniaxial stretching and biaxial stretching, and the shape and size of the pores on the surface. This is because such adjustments are easy and lamination with a thin film is easy. By using an extruded tube as the inner support layer, the moldability is good, the thickness is certain, the strength is sufficient, and the porosity is easily increased.
支持層、濾過層共に、少なくとも1軸方向に延伸されていれば良く、チューブの軸方向や周方向、径方向等に延伸することができ、軸方向等の1軸、又は軸方向と周方向の2軸等とすることができる。延伸倍率は、適宜設定することができるが、押出成形チューブの場合、軸方向には50%〜700%、周方向には5%〜100%、多孔質シートの場合、長手方向には50%〜1000%、横方向には50%〜2500%とすることができる。特に、多孔質延伸PTFEシートを用いると、横方向の延伸が容易であるため、チューブ状に巻きつけたときに、周方向の強度を向上することができ、散気等による膜の揺れや逆洗浄による圧力負荷に対する耐久性を向上することができる。
さらに、多孔質延伸PTFE製のチューブからなる支持層と濾過層は一体化され、互いの空孔が三次元的に連通しているため、良好な透過性を得ることができる。
Both the support layer and the filtration layer may be extended in at least one axial direction, and can be extended in the axial direction, circumferential direction, radial direction, etc. of the tube, uniaxial in the axial direction, or axial direction and circumferential direction. 2 axes or the like. The draw ratio can be set as appropriate. In the case of an extruded tube, it is 50% to 700% in the axial direction, 5% to 100% in the circumferential direction, and 50% in the longitudinal direction in the case of a porous sheet. ˜1000%, and in the lateral direction 50% ˜2500%. In particular, when a porous stretched PTFE sheet is used, it is easy to stretch in the lateral direction. Therefore, when wound in a tube shape, the strength in the circumferential direction can be improved. Durability against pressure load due to cleaning can be improved.
Furthermore, since the support layer and the filtration layer made of a porous expanded PTFE tube are integrated and the respective pores communicate with each other in three dimensions, good permeability can be obtained.
濾過層の外周面に多数存在する各空孔の平均最大長さは、支持層中に多数存在する繊維状骨格により囲まれた各空孔の平均最大長さより小さくしている。具体的には、濾過層の空孔の平均長さを、前記支持層の空孔の平均長さの1%〜30%としているのが良く、できるだけ小さくしている方が良い。これにより、外周面側から内周面側への透過性を高めることができる。   The average maximum length of each hole present in large numbers on the outer peripheral surface of the filtration layer is set to be smaller than the average maximum length of each hole surrounded by the fibrous skeleton present in large numbers in the support layer. Specifically, the average length of the pores in the filtration layer is preferably 1% to 30% of the average length of the pores in the support layer, and is preferably as small as possible. Thereby, the permeability | transmittance from the outer peripheral surface side to an inner peripheral surface side can be improved.
濾過層の外表面において、該外表面の全表面積に対する前記空孔の面積占有率が、画像処理で測定して、30%〜90%であることが好ましい。空孔の最大長さが小さくても、空孔の面積占有率がある程度大きいと、流量を減らすこともなく、効率良く、濾過性能を向上することができる。   In the outer surface of the filtration layer, the area occupation ratio of the pores with respect to the total surface area of the outer surface is preferably 30% to 90% as measured by image processing. Even if the maximum length of the holes is small, if the area occupation ratio of the holes is large to some extent, the flow rate is not reduced and the filtration performance can be improved efficiently.
具体的には、濾過層の空孔率は30%〜80%、支持層の空孔率は50%〜85%であることが好ましい。これにより、強度とのバランスを保ちながら、中空糸膜の外周面側から内周面側への透過性をさらに高めることができる。空孔率が小さすぎると流量が低下しやすく、空孔率が大きすぎると強度が低下しやすい。   Specifically, the porosity of the filtration layer is preferably 30% to 80%, and the porosity of the support layer is preferably 50% to 85%. Thereby, the permeability | transmittance from the outer peripheral surface side of a hollow fiber membrane to an inner peripheral surface side can further be improved, maintaining a balance with intensity | strength. If the porosity is too small, the flow rate tends to decrease, and if the porosity is too large, the strength tends to decrease.
濾過層の厚みは5μm〜100μmであることが好ましい。これは、前記範囲より小さいと濾過層の形成が困難であり、前記範囲より大きくしても濾過性能向上への影響は望み難いためである。支持層の厚みは0.1mm〜5mmであることが好ましい。これにより、軸方向、径方向、周方向のいずれにおいても良好な強度を得ることができ、内外圧や屈曲等に対する耐久性を向上することができる。なお、支持層の内径は0.3mm〜12mmであることが好ましい。   The thickness of the filtration layer is preferably 5 μm to 100 μm. This is because if it is smaller than the above range, it is difficult to form a filtration layer, and if it is larger than the above range, it is difficult to expect an effect on the improvement of the filtration performance. The thickness of the support layer is preferably 0.1 mm to 5 mm. As a result, good strength can be obtained in any of the axial direction, radial direction, and circumferential direction, and durability against internal / external pressure, bending, and the like can be improved. In addition, it is preferable that the internal diameter of a support layer is 0.3 mm-12 mm.
本発明の含油排水処理用の分離膜モジュールは、外圧式、外圧循環式、内圧式、内圧循環式、浸漬式のいずれでもよい。
具体的には、前記中空糸膜を複数本備えた集束体とし、該集束体を外筒内に収容し、
前記中空糸膜は一端開口、他端閉鎖とし、前記外筒内に前記含油排水を導入する導入部と、前記中空糸膜の一端開口と連通した濾過済み処理液の導出部と、濾過されなかった非濾過液の排出部を前記外筒に連通して備えた外圧濾過式または外圧循環濾過式としている。
または、前記中空糸膜を両端開口とし、該中空糸膜の一端開口に前記含油排水を導入する導入部と、他端開口から濾過されなかった非濾過液を排出する排出部と、前記外筒内と連通した濾過済み処理液の導出部を備えた内圧濾過式または内圧循環濾過式としている。
浸漬濾過式とする場合は、前記中空糸膜を複数本備えた集束体とし、該集束体を前記含油排水の浸漬槽中に配置し、前記中空糸膜は一端開口、他端閉鎖とし、前記中空糸膜の一端開口と連通した濾過済み処理液の導出部を備えたものとしている。
The separation membrane module for oil-containing wastewater treatment of the present invention may be any of an external pressure type, an external pressure circulation type, an internal pressure type, an internal pressure circulation type, and an immersion type.
Specifically, it is a converging body provided with a plurality of the hollow fiber membranes, the converging body is accommodated in an outer cylinder,
The hollow fiber membrane is open at one end and closed at the other end, an introduction portion for introducing the oil-containing drainage into the outer cylinder, a filtered treatment liquid outlet portion communicating with the one end opening of the hollow fiber membrane, and not filtered In addition, an external pressure filtration type or an external pressure circulation filtration type in which a non-filtrate discharge portion is provided in communication with the outer cylinder.
Alternatively, the hollow fiber membrane is open at both ends, the introduction portion that introduces the oil-containing drainage into one end opening of the hollow fiber membrane, the discharge portion that discharges the non-filtrate that has not been filtered from the other end opening, and the outer cylinder It is an internal pressure filtration type or an internal pressure circulation filtration type equipped with a filtered treatment liquid lead-out portion communicating with the inside.
In the case of the immersion filtration type, a converging body provided with a plurality of the hollow fiber membranes, the converging body is disposed in the immersion tank of the oil-containing drainage, the hollow fiber membrane is open at one end, closed at the other end, It is assumed that a filtered treatment liquid outlet portion communicated with one end opening of the hollow fiber membrane is provided.
前記外圧濾過式または外圧循環濾過式として用いる前記中空糸膜は、外径1〜5mm、内径0.5〜4mm、気孔率30〜90%であることが好ましい。
前記内圧濾過式または内圧循環式として用いる前記中空糸膜は、外径1.3〜20mm、内径1〜10mm、気孔率30〜90%であることが好ましい。
The hollow fiber membrane used as the external pressure filtration type or the external pressure circulation filtration type preferably has an outer diameter of 1 to 5 mm, an inner diameter of 0.5 to 4 mm, and a porosity of 30 to 90%.
The hollow fiber membrane used as the internal pressure filtration type or internal pressure circulation type preferably has an outer diameter of 1.3 to 20 mm, an inner diameter of 1 to 10 mm, and a porosity of 30 to 90%.
前記中空糸膜の集束体は、耐薬品性と非水溶性油分の濾過性能に優れる中空糸膜を500〜8000程度の多数本備えたものとしている。
該集束体における中空糸膜充填率は20〜60%程度とし、隣接する中空糸の寸法を広げ、含油排水の流通路を確保できるようにしていることが好ましい。
分離膜モジュールを、中空糸膜の外側から内側に向けて含油排水を通過させる外圧濾過式、濾過されなかった含油排水を再度分離膜モジュールに循環させる外圧循環式とした場合、被処理液の流れで中空糸膜の膜面の汚れを剥ぎ取ることができる。よって、被処理液の非水溶性油分含有量や懸濁物質の濃度が高くても膜面の汚れや目詰まりを抑制しながら濾過を継続させることができる。液の濾過が容易で目詰まりしにくい場合は、被処理液を循環させない全濾過の外圧式としてもよい
一方、原水中の粒子が支持層の孔径に比べ十分大きい場合などは、中空糸膜の内側から外側に向けて処理済み水を透過させる内圧濾過、あるいは内圧循環濾過式としてもよい。
The bundle of hollow fiber membranes is provided with a large number of hollow fiber membranes of about 500 to 8000, which are excellent in chemical resistance and water-insoluble oil content filtration performance.
It is preferable that the hollow fiber membrane filling rate in the bundling body is about 20 to 60%, and the dimensions of the adjacent hollow fibers are widened so as to ensure a flow path for the oil-containing drainage.
When the separation membrane module is an external pressure filtration type that allows oil-containing wastewater to pass from the outside to the inside of the hollow fiber membrane, and an external pressure circulation type that recirculates unfiltered oil-containing wastewater to the separation membrane module, the flow of the liquid to be treated Thus, the dirt on the membrane surface of the hollow fiber membrane can be removed. Therefore, even if the water-insoluble oil content of the liquid to be treated and the concentration of suspended substances are high, filtration can be continued while suppressing contamination and clogging of the membrane surface. If filtration of the liquid is easy and clogging is difficult, it may be an external pressure type of total filtration that does not circulate the liquid to be treated.On the other hand, if the particles in the raw water are sufficiently larger than the pore size of the support layer, the hollow fiber membrane An internal pressure filtration that allows the treated water to permeate from the inside toward the outside, or an internal pressure circulation filtration type may be employed.
処理対象の含油排水が高濁度で且つ高温である場合には、前記集束体における中空糸膜間の寸法平均値が0.5mm〜5mmと比較的広くすることが好ましい。
また、前記集束体の断面積に対する前記中空糸膜の充填率が20%〜60%とすることが好ましい。
このように中空糸膜間の離間寸法を比較的大きくとることで、高濁度の含油排水を中空糸膜間に詰まりの発生を抑制しながら流すことができる。
When the oil-containing wastewater to be treated has high turbidity and high temperature, it is preferable that the dimensional average value between the hollow fiber membranes in the convergent body is relatively wide as 0.5 mm to 5 mm.
Moreover, it is preferable that the filling rate of the said hollow fiber membrane with respect to the cross-sectional area of the said focusing body shall be 20%-60%.
Thus, by taking the separation dimension between the hollow fiber membranes relatively large, highly turbid oil-containing wastewater can be allowed to flow while suppressing the occurrence of clogging between the hollow fiber membranes.
本発明では、後述するように、中空糸膜をアルカリ性水溶液で洗浄するため、中空糸膜以外の固定材、集水ヘッダー、封止用樹脂、被処理液導入管および外筒等の他部材も耐アルカリ性樹脂で形成することが望ましい。
具体的には、中空糸膜の一端開口を閉鎖すると共に集束体として固定する封止材、中空糸膜の他端開口を開口状態として固定する固定材については、エポキシ樹脂、ポリウレタン樹脂、シリコン樹脂(ゴム)、不飽和ポリエステル樹脂などの熱硬化性樹脂、あるいはポリオレフィン樹脂、フッ素樹脂などの熱可塑性樹脂が用いられる。
前記外筒については、ステンレスなどの金属材料やABS樹脂、PVC、FRP、PTFE、PSF、PES及びPEEKなどのエンジニアリングプラスチックで成形していることが好ましい。
配管やその付属部品などは同じくステンレス、PVCなどで構成される。
前記中空糸膜モジュールを構成する部材は、熱硬化性樹脂の場合は熱変形温度が100℃以上の耐熱性を有するものとし、または、熱溶融性樹脂の場合は、その融点が使用温度の1.5倍を有するものとしている。
In the present invention, since the hollow fiber membrane is washed with an alkaline aqueous solution as described later, other members such as a fixing material other than the hollow fiber membrane, a water collection header, a sealing resin, a liquid to be treated introduction pipe, and an outer cylinder are also included. It is desirable to form with an alkali resistant resin.
Specifically, for a sealing material that closes one end opening of the hollow fiber membrane and fixes it as a converging body, and a fixing material that fixes the other end opening of the hollow fiber membrane in an open state, epoxy resin, polyurethane resin, silicon resin (Rubber), thermosetting resins such as unsaturated polyester resins, or thermoplastic resins such as polyolefin resins and fluororesins are used.
The outer cylinder is preferably formed of a metal material such as stainless steel or an engineering plastic such as ABS resin, PVC, FRP, PTFE, PSF, PES, or PEEK.
The piping and its accessory parts are also made of stainless steel, PVC or the like.
In the case of a thermosetting resin, the member constituting the hollow fiber membrane module has a heat distortion temperature of 100 ° C. or higher, or in the case of a thermomeltable resin, the melting point is 1 of the use temperature. .5 times.
また、本発明の分離膜モジュールは、垂直方向に配置した中空糸膜の集束体の下部に散気用空気配管を配置し、かつ、前記処理済み液の導出部より中空糸膜の内部に該処理済み液を逆洗浄液を加圧送液する逆洗浄手段を備えていることが好ましい。
上記散気用空気配管を備えることで、通常の濾過運転時に、分離膜モジュールの下部またはモジュール下部に接続される配管から散気用のエアーのバブリングを発生させ、中空糸膜を揺動させることで中空糸膜の外面に付着する微粒子をふるい落とすことができる。
また、定期的に分離膜モジュールの中空糸膜の内部に処理済み液を逆洗浄水として加圧送液し、逆洗浄することにより、濾過性能の持続を図ることができる。
In the separation membrane module of the present invention, an air pipe for aeration is disposed below the converging body of the hollow fiber membranes arranged in the vertical direction, and the inside of the hollow fiber membrane is disposed from the treated liquid outlet. It is preferable to provide a reverse cleaning means for feeding the treated liquid with a reverse cleaning liquid under pressure.
By providing the air pipe for air diffusion, during normal filtration operation, bubbling of air for air diffusion is generated from the lower part of the separation membrane module or the pipe connected to the lower part of the module, and the hollow fiber membrane is swung. The fine particles adhering to the outer surface of the hollow fiber membrane can be screened off.
Further, the filtration performance can be maintained by periodically feeding the treated liquid as backwash water into the hollow fiber membrane of the separation membrane module and backwashing.
第二の発明として、前記含油排水処理用分離膜モジュールを用いた含油排水処理方法を提供している。該含油排水処理方法は、
非水溶性油分含有量(n−ヘキサン値)が3〜5000mg/Lである含油排水を、前記中空糸膜のIPAバブルポイントが50kPa以上100kPa未満で膜間差圧50kPa以下、前記IPAバブルポイントが100kPa以上150kPa未満で膜間差圧100kPa以下、前記IPAバブルポイントが150kPa以上400kPa以下で膜間差圧200kPa以下の濾過条件とし、含油排水の非水溶性油分含油量が10mg/L以上2000mg/L以下の場合は濾過処理済み水の非水溶性油分含有量を5mg/L未満、含油排水の非水溶性油分含油量が3mg/L以上10mg/L未満の場合は濾過処理済み水の非水溶性油分含有量を1mg/L未満としていることを特徴とする。
As a second invention, there is provided an oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment. The oil-containing wastewater treatment method is:
An oil-containing wastewater having a water-insoluble oil content (n-hexane value) of 3 to 5000 mg / L, the IPA bubble point of the hollow fiber membrane is 50 kPa or more and less than 100 kPa, the transmembrane pressure difference is 50 kPa or less, and the IPA bubble point is The filtration conditions are 100 kPa or more and less than 150 kPa and the transmembrane differential pressure is 100 kPa or less, the IPA bubble point is 150 kPa or more and 400 kPa or less and the transmembrane differential pressure is 200 kPa or less. In the following cases, the water-insoluble oil content of the filtered water is less than 5 mg / L, and the water-insoluble oil content of the oil-containing wastewater is 3 mg / L or more and less than 10 mg / L, water-insoluble in the filtered water The oil content is less than 1 mg / L.
本処理方法では、中空糸膜のIPAバブルポイントと膜間差圧のバランスを取ることにより、中空糸膜の多孔質膜の孔に非水溶性油分が透過せず、効率的に含油排水から非水溶性油分を除去することができるよう調整している。
前記中空糸膜のIPAバブルポイントの各条件において、規定の膜間差圧の上限値を超えると多孔質膜の孔に非水溶性油分が透過しやすくなり、5mg/L未満または1mg/L未満の非水溶性油分含有量が得られにくくなるため好ましくない。
前記中空糸膜のIPAバブルポイントが50kPa以上100kPa未満の場合の膜間差圧は、50kPa以下とすることが好ましい。
前記IPAバブルポイントが100kPa以上150kPa未満の場合の膜間差圧は、100kPa以下とすることが好ましい。
前記IPAバブルポイントが150kPa以上400kPa以下の場合の膜間差圧は、200kPa以下とすることが好ましい。
下限値についてはより低圧を維持するのが望ましいが、濾過の継続とともに徐々に差圧があがってくる。前記記載の圧力まで上昇した時点でアルカリ性水溶液等の薬品洗浄を実施するのが望ましい。
なお、膜間差圧は、運転中の分離膜モジュール直近の原水入口圧力P1およびモジュール透過水出口直近の圧力P2を測定し、これらの値から(P1−P2)を算出している。
In this treatment method, by balancing the IPA bubble point of the hollow fiber membrane and the inter-membrane differential pressure, the water-insoluble oil component does not permeate through the pores of the porous membrane of the hollow fiber membrane, and it is efficiently removed from the oil-containing wastewater. The water-soluble oil is adjusted so that it can be removed.
In each condition of the IPA bubble point of the hollow fiber membrane, when the specified upper limit value of the transmembrane pressure difference is exceeded, water-insoluble oil easily penetrates into the pores of the porous membrane, and less than 5 mg / L or less than 1 mg / L This is not preferable because the water-insoluble oil content is difficult to obtain.
When the IPA bubble point of the hollow fiber membrane is 50 kPa or more and less than 100 kPa, the transmembrane pressure difference is preferably 50 kPa or less.
When the IPA bubble point is 100 kPa or more and less than 150 kPa, the transmembrane pressure difference is preferably 100 kPa or less.
When the IPA bubble point is 150 kPa or more and 400 kPa or less, the transmembrane pressure difference is preferably 200 kPa or less.
As for the lower limit value, it is desirable to maintain a lower pressure, but the differential pressure gradually increases as filtration continues. It is desirable to perform chemical cleaning of an alkaline aqueous solution or the like when the pressure reaches the above-described pressure.
For the transmembrane pressure difference, the raw water inlet pressure P1 closest to the separation membrane module in operation and the pressure P2 closest to the module permeated water outlet are measured, and (P1-P2) is calculated from these values.
本処理方法において、濾過膜で処理する含油排水を非水溶性油分含有量(n−ヘキサン値)を3〜2000mg/Lとしているのは、2000mg/Lを超えると含有非水溶性油分量が多過ぎて、中空糸膜が目詰まり等を起こし易くなり、処理水量の確保が困難となるからである。
一方、3mg/L未満であると非水溶性油分が極めて小さい粒子として分散する場合、膜内部で微小な粒子が会合し粗大化しにくいため、膜内部での安定的な補足ができず、確実に除去できないからである。
本処理方法の処理する含油排水の非水溶性油分含有量は、10〜2000mg/Lが好ましく、特に、20〜1000mg/Lであることが好ましい。
本発明の含油排水処理用分離膜モジュールは、非水溶性油分含有量が希薄な、具体的には30mg/L未満の含油排水であれば、5mg/L以下は当然のこと、1mg/L未満に処理することができる。
非水溶性油分含有量は、JIS K 0102 24.2に準拠した測定方法によるn−ヘキサン値により得られたものである。
In this treatment method, the oil-containing wastewater treated with the filtration membrane has a water-insoluble oil content (n-hexane value) of 3 to 2000 mg / L. If it exceeds 2000 mg / L, the content of water-insoluble oil is large. This is because the hollow fiber membrane is likely to be clogged, and it becomes difficult to secure the amount of treated water.
On the other hand, when it is less than 3 mg / L, when the water-insoluble oil component is dispersed as extremely small particles, minute particles are aggregated inside the membrane and are difficult to coarsen. This is because it cannot be removed.
The water-insoluble oil content of the oil-containing wastewater treated by this treatment method is preferably 10 to 2000 mg / L, particularly preferably 20 to 1000 mg / L.
The separation membrane module for oil-containing wastewater treatment according to the present invention has a low water-insoluble oil content, specifically, if it is an oil-containing wastewater of less than 30 mg / L, naturally 5 mg / L or less is less than 1 mg / L. Can be processed.
Water-insoluble oil content is obtained by the n-hexane value by the measuring method based on JISK0102 24.2.
前記含油排水のJIS K 0102 14.1で測定される懸濁物質(SS)の濃度は5〜2000mg/Lであると、通常、含油排水は懸濁物質を含み、不均一系分散状態となっている。なお、処理する含油排水の温度は、通常、25〜90℃程度である。   When the concentration of suspended solids (SS) measured in JIS K 0102 14.1 in the oil-containing wastewater is 5 to 2000 mg / L, the oil-containing wastewater usually contains suspended solids and is in a heterogeneous dispersion state. ing. In addition, the temperature of the oil-containing waste water to process is about 25-90 degreeC normally.
また、本発明の含油排水の処理方法では、含油排水の非水溶性油分含有量が3〜200mg/Lで、かつ懸濁物質(SS)の濃度が100mg/L以下の場合は、被処理液の全量を中空糸膜を通過させる外圧式の全濾過で行うことが好ましい。
非水溶性油分含有量が200mg/Lを超えて2000mg/L以下、懸濁物質(SS)が100〜20000mg/Lの場合は、被処理液を循環して流す外圧循環式または内圧循環式のクロスフロー方式で行うことが好ましい。
特に、非水溶性油分が1000mg/L以上もしくは懸濁物質が500mg/L以上の場合は循環濾過で濾過することが好ましい。
このように非水溶性油分や懸濁物質の濃度に応じて、処理方法を変更することで効率的に処理を行うことができ、処理水量を確保することができる。
In the method for treating oil-containing wastewater of the present invention, when the water-insoluble oil content of the oil-containing wastewater is 3 to 200 mg / L and the concentration of suspended solids (SS) is 100 mg / L or less, the liquid to be treated It is preferable to carry out the total amount of the above by external pressure-type total filtration through a hollow fiber membrane.
When the water-insoluble oil content is more than 200 mg / L and not more than 2000 mg / L and the suspended solid (SS) is 100 to 20000 mg / L, the external pressure circulation type or the internal pressure circulation type is used. The cross flow method is preferable.
In particular, when the water-insoluble oil content is 1000 mg / L or more or the suspended substance is 500 mg / L or more, it is preferable to filter by circulation filtration.
As described above, the treatment can be efficiently performed by changing the treatment method according to the concentration of the water-insoluble oil and the suspended substance, and the amount of treated water can be ensured.
前記した含油排水処理方法は、油田随伴水を前処理して非水溶性油分含有量(n−ヘキサン値)を低減した後の含油排水を前記分離膜モジュールで精密濾過する場合に用いられる。   The oil-containing wastewater treatment method described above is used when oil-containing wastewater after pretreatment of oilfield-associated water and reducing the water-insoluble oil content (n-hexane value) is subjected to microfiltration with the separation membrane module.
また、前記含油排水処理用の分離膜モジュールを用いた含油排水処理方法であって、
含油排水が、油含有量が20〜2000mg/L、懸濁成分の含有量が100〜10000mg/L、60〜200℃の高温である場合、この高温の含油排水を前記分離膜モジュールで濾過処理して、処理水中の非水溶性油分含有量を5mg/L以下、懸濁成分含有量0〜1mg/Lとしている含油排水処理方法を提供している。
In addition, an oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment,
When the oil-containing wastewater has a high oil content of 20 to 2000 mg / L, a suspended component content of 100 to 10,000 mg / L, and a high temperature of 60 to 200 ° C., the high-temperature oil-containing wastewater is filtered by the separation membrane module. In addition, an oil-containing wastewater treatment method in which the water-insoluble oil content in the treated water is 5 mg / L or less and the suspended component content is 0 to 1 mg / L is provided.
さらに、第三の発明として、前記含油排水処理用の分離膜モジュールを備えた含油排水処理装置を提供している。
該含油排水処理装置は、前記分離膜モジュールの中空糸膜の表面に付着した非水溶性油分除去用として、アルカリ性水溶液からなる洗浄液を前記中空糸膜の表面に送液する洗浄手段を備えていることを特徴とする。
Furthermore, as a third invention, an oil-containing wastewater treatment apparatus provided with the separation membrane module for oil-containing wastewater treatment is provided.
The oil-containing wastewater treatment apparatus is equipped with a cleaning means for sending a cleaning liquid made of an alkaline aqueous solution to the surface of the hollow fiber membrane for removing the water-insoluble oil adhering to the surface of the hollow fiber membrane of the separation membrane module. It is characterized by that.
本発明で用いる含油排水処理用の分離膜モジュールはPTFE等で中空糸膜を形成し、極めて優れた耐アルカリ性を有するものとしているため、4質量%水酸化ナトリウム水溶液(1mol/L)のような高濃度アルカリ溶液の洗浄液を送液しても、中空糸膜は損傷されず、高性能な濾過性能を維持することができる。そのため、表面に付着した捕捉非水溶性油分を十分に溶解・除去し、繰り返し多孔質膜を再生利用することができる。   The separation membrane module for oil-containing wastewater treatment used in the present invention forms a hollow fiber membrane with PTFE or the like and has extremely excellent alkali resistance, so that it is like 4% by mass sodium hydroxide aqueous solution (1 mol / L) Even if a cleaning solution of a high-concentration alkaline solution is fed, the hollow fiber membrane is not damaged and high-performance filtration performance can be maintained. Therefore, the captured water-insoluble oil adhering to the surface can be sufficiently dissolved and removed, and the porous membrane can be reused repeatedly.
本発明の含油排水処理装置は、含油排水貯留槽と、前記洗浄手段の洗浄液貯留槽と、前記含油排水貯留槽および洗浄液貯留槽と前記分離膜モジュールの導入部とを連通すると共にポンプを介設した導入用配管と、前記含油排水貯留槽および洗浄液貯留槽と前記分離膜モジュールの非処理液の排出部とを連通する循環用配管とを備え、
前記導入用配管の分岐管および循環用配管の分岐管を、それぞれ前記含油排水貯留槽と洗浄液貯留槽と連通した構成としていることが好ましい。
The oil-containing wastewater treatment apparatus of the present invention communicates the oil-containing wastewater storage tank, the cleaning liquid storage tank of the cleaning means, the oil-containing wastewater storage tank and the cleaning liquid storage tank, and the introduction portion of the separation membrane module and is provided with a pump. An introduction pipe, and a circulation pipe that communicates the oil-containing drainage storage tank and the cleaning liquid storage tank with the non-treatment liquid discharge part of the separation membrane module,
The branch pipe of the introduction pipe and the branch pipe of the circulation pipe are preferably configured to communicate with the oil-containing drainage storage tank and the cleaning liquid storage tank, respectively.
前記のように、含油排水を含油排水貯留槽と分離膜モジュールとの間に循環用配管を設けて、循環式に被処理液の含油排水を分離膜モジュールに供給して濾過している。また、アルカリ性水溶液からなる洗浄液を貯留する洗浄液貯留槽と分離膜モジュールとの間にも循環用配管を設けて、洗浄液を分離膜モジュールに循環して供給している。
前記被処理液の循環と洗浄液の循環とは交互に行い、分離膜モジュールの濾過性能の低下を防止している。
As described above, the oil-containing wastewater is provided with a circulation pipe between the oil-containing wastewater storage tank and the separation membrane module, and the oil-containing wastewater of the liquid to be treated is supplied to the separation membrane module and filtered in a circulating manner. A circulation pipe is also provided between the cleaning liquid storage tank for storing the cleaning liquid made of the alkaline aqueous solution and the separation membrane module, and the cleaning liquid is circulated and supplied to the separation membrane module.
The circulation of the liquid to be treated and the circulation of the cleaning liquid are alternately performed to prevent a decrease in the filtration performance of the separation membrane module.
前記導入用配管に介設した前記ポンプの吐出圧力は50〜300kPaとすることが好ましい。かつ、前記分岐管の分岐位置に切替弁を介設し、被処理液と洗浄液とを分離膜モジュールに切り替えて送液している。   The discharge pressure of the pump interposed in the introduction pipe is preferably 50 to 300 kPa. In addition, a switching valve is provided at the branch position of the branch pipe, and the liquid to be treated and the cleaning liquid are switched to the separation membrane module and fed.
前記のように、含油排水を分離膜モジュールに循環するクロスフロー方式とすることにより、非水溶性油分含有量が200mg/Lを超えて2000mg/L以下、懸濁物質(SS)が100〜20000mg/Lである被処理液でも5mg/L未満まで、懸濁物質(SS)、非水溶性油分が少ない場合には1mg/L未満まで処理することができる。
また、前記含油排水をポンプの吐出圧力を50〜300kPaとして供給することにより、前述したIPAバブルポイントを有する中空糸膜の膜間差圧を前述した範囲とすることができる。
さらに、前記洗浄手段を備えることにより、含油排水の導入用配管をアルカリ性水溶液の洗浄液の導入用配管に切替を行うことができ、中空糸膜の膜面の捕捉非水溶性油分の除去を定期的に行うため、濾過膜の再生を容易に行うことができる。
As described above, the water-insoluble oil content exceeds 200 mg / L and is 2000 mg / L or less, and the suspended solid (SS) is 100 to 20000 mg by using a cross-flow method in which oil-containing wastewater is circulated to the separation membrane module. Even if the liquid to be treated is / L, it can be processed to less than 5 mg / L and less than 1 mg / L when the suspended solid (SS) and water-insoluble oil content are small.
Moreover, the transmembrane differential pressure of the hollow fiber membrane which has an IPA bubble point mentioned above can be made into the range mentioned above by supplying the discharge pressure of a pump with the said oil-containing waste water as 50-300 kPa.
Furthermore, by providing the washing means, the oil-containing drainage introduction pipe can be switched to the alkaline aqueous washing liquid introduction pipe, and the removal of the trapped water-insoluble oil on the membrane surface of the hollow fiber membrane can be performed periodically. Therefore, it is possible to easily regenerate the filtration membrane.
本発明の含油排水処理装置は、油田随伴水を前処理して、非水溶性油分含有量を低減し、例えば、非水溶性油分含油量(n−ヘキサン値)を10〜2000mg/Lとした後に、該含油排水を精密濾過する装置として好適に用いることができる。
具体的には、油田随伴水を既存の油水分離処理手段で粗大な非水溶性油分と含油水分とに分離し、分離された含油水分を電気凝集・浮上手段で非水溶性油分と金属分を凝集させて粗く除いた後の含油排水を被処理液として精密濾過する含油排水処理装置として用いている。
The oil-containing wastewater treatment apparatus of the present invention pretreats oil field-associated water to reduce the water-insoluble oil content, for example, the water-insoluble oil content (n-hexane value) is 10 to 2000 mg / L. Later, the oil-containing wastewater can be suitably used as a device for microfiltration.
Specifically, oil field-associated water is separated into coarse water-insoluble oil and oil-containing moisture by existing oil-water separation treatment means, and the separated oil-containing water is separated into water-insoluble oil and metal by means of electrocoagulation / levitation. It is used as an oil-containing wastewater treatment device that finely filters oil-containing wastewater that has been agglomerated and roughly removed as a liquid to be treated.
油田随伴水の原水は、通常、浮上油等の大量の油が存在すると共に汚泥を含むため、予め油水分離処理手段及び電気凝集・浮上手段で非水溶性油分を粗く除いた後の含油排水を精密濾過する本発明の装置に用いている。このときの含油量は10〜100mg/Lである。
本構成とすれば、浮上油等の大部分の非水溶性油分を予め除去しているので、処理水量を確保しながら、清澄な処理済み水を得ることができ、得られた処理済み水は、例えば、灌漑用水として利用することができる。
Since the raw water of the oilfield-associated water usually contains a large amount of oil such as floating oil and contains sludge, oil-containing wastewater after roughly removing water-insoluble oil by oil-water separation treatment means and electrocoagulation / flotation means in advance Used in the apparatus of the present invention for microfiltration. The oil content at this time is 10 to 100 mg / L.
With this configuration, since most of the water-insoluble oil such as floating oil has been removed in advance, clear treated water can be obtained while ensuring the amount of treated water. For example, it can be used as irrigation water.
前記高温の含油排水処理用として用いる中空糸膜型の分離膜モジュールでは、集束体における中空糸膜間の寸法平均値が0.5mm〜5mmと比較的広くし、かつ、集束体の断面積に対する前記中空糸膜の充填率が20%〜60%とすることが好ましい。
このように、中空糸膜間の寸法を広くとると端末封止材にクラックもしくはひずみによるリークが発生しやすくなる。これに対して、本発明は、多数本の中空糸膜と、その少なくとも一端を連結固定する端末封止材とを固定する製造方法として、下記の方法を用いて、端末封止材にクラックが発生しないようにしている。
In the hollow fiber membrane type separation membrane module used for the high-temperature oil-containing wastewater treatment, the dimensional average value between the hollow fiber membranes in the converging body is relatively wide as 0.5 mm to 5 mm, and the cross-sectional area of the converging body The filling rate of the hollow fiber membrane is preferably 20% to 60%.
Thus, when the dimension between the hollow fiber membranes is wide, leakage due to cracks or strain is likely to occur in the terminal sealing material. On the other hand, the present invention uses the following method as a manufacturing method for fixing a large number of hollow fiber membranes and a terminal sealing material for connecting and fixing at least one end thereof, and the terminal sealing material is cracked. It does not occur.
(熱硬化性樹脂を封止材として用いる場合)
例えば容器内に熱変形温度が120℃以の耐熱エポキシ樹脂(芳香族アミン系硬化剤)を注入、充填し、50℃〜60℃で予備加熱した後、常温で少なくとも3時間以上、好ましくは6時間以上保持して予備硬化する。
ついで、使用温度以上で熱変形温度である120℃以下の温度(100℃で使用する場合100℃以上120℃以下)で1時間以上加熱する。
その後、少なくとも6時間以上かつ1℃/分の温度勾配で持って除冷する。
(熱溶融性樹脂を封止材として用いる場合)
予め端末形状に成型されたロッドの所定位置に中空糸膜のサイズにあわせて穴をあけ、そこへ中空糸膜を挿入し所定間隔をあけて配列した状態で、加熱し端末封止材の実体温度が樹脂の融点以上の温度になるまで予備加熱し、さらにその溶融温度で1時間以上加熱し、その後、少なくとも6時間以上かつ1℃/分の温度勾配で持って除冷する。
(When using thermosetting resin as sealing material)
For example, a heat-resistant epoxy resin (aromatic amine-based curing agent) having a heat deformation temperature of 120 ° C. or less is injected and filled in a container, preheated at 50 ° C. to 60 ° C., and then at room temperature for at least 3 hours, preferably 6 Pre-harden for more than an hour.
Next, heating is performed for 1 hour or more at a temperature not lower than the use temperature and not higher than 120 ° C. which is a heat distortion temperature (when used at 100 ° C., not lower than 100 ° C. and not higher than 120 ° C.).
Then, it is cooled for at least 6 hours with a temperature gradient of 1 ° C./min.
(When using a hot-melt resin as a sealing material)
The body of the terminal sealing material is heated in a state in which holes are made in advance according to the size of the hollow fiber membrane at a predetermined position of a rod molded into a terminal shape in advance, the hollow fiber membranes are inserted therein and arranged at predetermined intervals. Preheating is carried out until the temperature is equal to or higher than the melting point of the resin, followed by heating for 1 hour or more at the melting temperature, and then cooling is carried out with a temperature gradient of at least 6 hours and 1 ° C./min.
このように、予備加熱した後に所定時間保持し、その後に加熱成形し、かつ、加熱後に所要時間をかけて除冷している。この方法で製造した中空糸膜分離モジュールでは、100℃程度の温度差でヒートサイクルが繰り返されても、端末封止材自体および端末封止材と中空糸との間にクラックが生じるのを防止できることを、本発明者は実験により知見している。   Thus, after preheating, it hold | maintains for a predetermined time, after that, it heat-molds, and it takes the required time after heating and is cooled. In the hollow fiber membrane separation module manufactured by this method, even if the heat cycle is repeated at a temperature difference of about 100 ° C., the terminal sealing material itself and the cracking between the terminal sealing material and the hollow fiber are prevented. The present inventor has found through experiments that this can be done.
前述したように、本発明の分離膜モジュールを用いると、含油排水を、5mg/L未満、さらには1mg/L未満の低濃度にまで非水溶性油分含有量を低減できる高性能濾過を実現できる。   As described above, when the separation membrane module of the present invention is used, it is possible to realize high performance filtration that can reduce the water-insoluble oil content of oil-containing wastewater to a low concentration of less than 5 mg / L and even less than 1 mg / L. .
また、本発明の含油排水処理方法によれば、油田随伴水の含油排水や加温された高温の含油排水を前記分離膜モジュールを用いて処理すると、非水溶性油分が透過せず、効率的に含油排水から非水溶性油分を除去し、処理水量を低下させずに清浄な処理済み液を得ることができる。   Moreover, according to the oil-containing wastewater treatment method of the present invention, when the oil-containing wastewater from the oil field or the heated high-temperature oil-containing wastewater is treated using the separation membrane module, the water-insoluble oil component does not permeate and is efficient. In addition, water-insoluble oil can be removed from the oil-containing wastewater, and a clean treated liquid can be obtained without reducing the amount of treated water.
また、本発明の含油排水処理装置によれば、定期的に分離膜モジュールを洗浄する洗浄手段を備え、中空糸膜の膜面に付着した非水溶性油分をアルカリ性水溶液による化学洗浄により溶解除去して繰り返し再生しているため、含油排水の高性能濾過を長期に渡り持続させることができる。   In addition, the oil-containing wastewater treatment apparatus of the present invention is equipped with a cleaning means for periodically cleaning the separation membrane module, and dissolves and removes the water-insoluble oil adhering to the membrane surface of the hollow fiber membrane by chemical cleaning with an alkaline aqueous solution. Therefore, high-performance filtration of oil-containing wastewater can be sustained over a long period of time.
油田随伴水の含油排水処理に用いた場合、浮上油等の大部分の非水溶性油分を予め除去した後に分離膜モジュールで精密濾過しているため、高い処理水量を確保しながら、5mg/L未満、さらに非水溶性油分含有量が少ない場合には1mg/L未満の清澄な処理済み液を得ることができる。   When used for oil-bearing wastewater treatment of oilfield-associated water, since most water-insoluble oils such as floating oil are removed in advance and then subjected to microfiltration with a separation membrane module, 5 mg / L while securing a high amount of treated water If the content of water-insoluble oil is less, a clear treated liquid of less than 1 mg / L can be obtained.
第1実施形態の含油排水処理用の分離膜モジュールの断面図である。It is sectional drawing of the separation membrane module for oil-containing wastewater treatment of 1st Embodiment. 第1実施形態の分離膜モジュールを備えた含油排水処理装置を示す全体図である。It is a general view which shows the oil-containing wastewater treatment equipment provided with the separation membrane module of 1st Embodiment. (A)(B)は、多孔質複層中空糸膜の概略構成図である。(A) (B) is a schematic block diagram of a porous multilayer hollow fiber membrane. 第2実施形態の含油排水処理用の分離膜モジュールの断面図である。It is sectional drawing of the separation membrane module for oil-containing wastewater treatment of 2nd Embodiment. 第2実施形態の分離膜モジュールを備えた含油排水処理装置を示す全体図である。It is a general view which shows the oil-containing wastewater treatment equipment provided with the separation membrane module of 2nd Embodiment. 第3実施形態の含油排水処理用の分離膜モジュールの断面図である。It is sectional drawing of the separation membrane module for oil-containing wastewater treatment of 3rd Embodiment. 第3実施形態の分離膜モジュールを備えた含油排水処理装置を示す全体図である。It is a general view which shows the oil-containing wastewater treatment equipment provided with the separation membrane module of 3rd Embodiment. (A)(B)は第4実施形態の分離膜モジュールの断面図である。(A) (B) is sectional drawing of the separation membrane module of 4th Embodiment. 従来例を示す図である。It is a figure which shows a prior art example.
本発明の実施形態を図面を参照して説明する。
図1乃至図3に本発明の第1実施形態の含油排水処理用の分離膜モジュール1を示す。
該第1実施形態の分離膜モジュール1は、油田随伴水を予め粗分離処理してなる含油排水を精密に分離処理するものとして用いている、なお、該油田随伴水に限定されず、工場排水や生活排水を含め、粘度0.1〜5.0mPa・sの非水溶性油分を含有する含油排水から非水溶性油分を分離するために用いることができるものである。
前記分離膜モジュール1は、非水溶性油分含有量が3〜2000mg/Lの含有排水から、非水溶性油分含有量1mg/L未満の処理済み水を得るものとしている。
Embodiments of the present invention will be described with reference to the drawings.
1 to 3 show a separation membrane module 1 for oil-containing wastewater treatment according to a first embodiment of the present invention.
The separation membrane module 1 of the first embodiment is used to precisely separate oil-containing wastewater obtained by subjecting oilfield-associated water to rough separation treatment in advance, and is not limited to the oilfield-associated water. It can be used for separating water-insoluble oil from oil-containing wastewater containing water-insoluble oil having a viscosity of 0.1 to 5.0 mPa · s, including domestic wastewater.
The separation membrane module 1 is configured to obtain treated water having a water-insoluble oil content of less than 1 mg / L from wastewater having a water-insoluble oil content of 3 to 2000 mg / L.
分離膜モジュール1は、前記含油排水を循環して流す外圧循環濾過方式(外圧クロスフロー方式)に用いるものとしている。
中空糸膜2を複数本(本実施形態では3500本)束ねた集束体3を備え、該集束体3の下端を封止材4で封止し、各中空糸膜2の下端開口を閉鎖している。集束体3の上端は中空糸膜2の上端開口2aは開口状態として、固定材5で固定している。
前記集束体3を外筒6内に収容している。外筒6の上端に上部キャップ7を接着して取り付け、該上部キャップ7の内部を各中空糸膜2の中空部と連通させた導出口7aを設け、該導出口7aを処理液取出用の導出用配管8と接続している。
前記外筒6の下端に下部キャップ9を接着固定し、該下部キャップ9に含油排水からなる被処理液の導入口9aを設け、該導入口9aを被処理液を導入する導入用配管10と接続している。
集束体3の下端の封止材4と外筒6の内壁との間には空間Sを確保し、前記導入口9aから導入される含油排水を外筒6内において集束体3へすみやかに流れるようにしている。
また、外筒6の上端近傍の周壁に、濾過されなかった非処理液の排出口11を設け、該排出口11を循環用配管12と連通している。
The separation membrane module 1 is used for an external pressure circulation filtration method (external pressure cross flow method) for circulating the oil-containing wastewater.
A converging body 3 in which a plurality of hollow fiber membranes 2 (3500 in this embodiment) are bundled is provided, the lower end of the converging body 3 is sealed with a sealing material 4, and the lower end opening of each hollow fiber membrane 2 is closed. ing. The upper end of the converging body 3 is fixed by a fixing material 5 with the upper end opening 2a of the hollow fiber membrane 2 being opened.
The converging body 3 is accommodated in the outer cylinder 6. An upper cap 7 is bonded and attached to the upper end of the outer cylinder 6, and a lead-out port 7 a that connects the inside of the top cap 7 with the hollow portion of each hollow fiber membrane 2 is provided. It is connected to the lead-out pipe 8.
A lower cap 9 is bonded and fixed to the lower end of the outer cylinder 6, an inlet 9a for the liquid to be treated is formed in the lower cap 9, and the inlet 9a for introducing the liquid to be processed is provided in the inlet 9a. Connected.
A space S is secured between the sealing material 4 at the lower end of the converging body 3 and the inner wall of the outer cylinder 6, and the oil-containing drainage introduced from the introduction port 9 a immediately flows into the converging body 3 in the outer cylinder 6. I am doing so.
Further, a non-processed liquid discharge port 11 is provided on the peripheral wall near the upper end of the outer cylinder 6, and the discharge port 11 communicates with the circulation pipe 12.
さらに、外筒6の下部周壁から散気用空気導入管14を挿入し、集束体3の内部に通している。図2に示すように、散気用空気導入管14はブロア15と接続している。該散気用空気導入管14に必要時にブロア15より所定量の空気を導入し、集束体3の各中空糸膜2に向けて散気している。これにより、中空糸膜2を振動させて、その外周面に付着した含油排水中に含まれる固形分等をふるい落としている。   Further, the air introduction pipe 14 for aeration is inserted from the lower peripheral wall of the outer cylinder 6 and is passed through the inside of the focusing body 3. As shown in FIG. 2, the air diffusion introduction pipe 14 is connected to the blower 15. A predetermined amount of air is introduced from the blower 15 to the aeration air introduction pipe 14 when necessary, and is diffused toward the hollow fiber membranes 2 of the focusing body 3. Thereby, the hollow fiber membrane 2 is vibrated and the solid content etc. which are contained in the oil-containing waste water adhering to the outer peripheral surface are screened off.
さらに、上部の固定材5と下部の封止材4との中央部を補強棒16で連結している。該補強棒16は剛性のない中空糸膜2が下部からの含油排水の水流の力で持ち上げられてしまうのを防ぎ、鉛直性を確保するためである。
なお、外筒6、上部キャップ7、下部キャップ9はABS樹脂、固定材5、封止材4はエポキシ樹脂、連通棒16はステンレスまたは耐熱樹脂としモジュール全体として耐アルカリ性に優れたものとしている。
Further, the central portion of the upper fixing member 5 and the lower sealing member 4 is connected by a reinforcing rod 16. The reinforcing rod 16 is used to prevent the non-rigid hollow fiber membrane 2 from being lifted by the force of the water flow of the oil-containing drainage from the lower portion and to ensure verticality.
The outer cylinder 6, the upper cap 7, and the lower cap 9 are made of ABS resin, the fixing material 5 and the sealing material 4 are made of epoxy resin, and the connecting rod 16 is made of stainless steel or heat-resistant resin.
中空糸膜2は、図3に示すように、多孔質延伸PTFE製のチューブ2bからなる支持層と、該支持層の外表面に多孔質膜延伸PTFEシート2cからなる濾過層を備えた多孔質複層中空糸膜からなる。
中空糸膜2は、中空糸膜全体で内径0.3〜12mm、外径0.8〜14mm、IPAバブルポイント50kPa以上400kPa以下、膜厚0.2〜1mm、気孔率50〜90%、最大許容膜間差圧0.1〜1.0MPaの耐圧性を備えたものとしており、抗張力は30〜150Nとしている。なお、これら物性は前記した方法と同様の方法で測定している。
As shown in FIG. 3, the hollow fiber membrane 2 is a porous layer comprising a support layer made of a porous expanded PTFE tube 2b, and a filtration layer made of a porous membrane extended PTFE sheet 2c on the outer surface of the support layer. It consists of a multilayer hollow fiber membrane.
The hollow fiber membrane 2 has an inner diameter of 0.3 to 12 mm, an outer diameter of 0.8 to 14 mm, an IPA bubble point of 50 kPa to 400 kPa, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum. The pressure resistance of the allowable transmembrane pressure is 0.1 to 1.0 MPa, and the tensile strength is 30 to 150 N. These physical properties are measured by the same method as described above.
前記多孔質複層中空糸膜からなる中空糸膜2は、押出成形により得られた多孔質延伸PTFEチューブ2bの外周面に多孔質延伸PTFEシート2cを巻き付けて形成している。
具体的には、多孔質延伸PTFEチューブ2bの外周面を火炎処理等により凹凸を設けた後に多孔質延伸PTFEシート2cを位置ずれなく全周に巻き付けた後にダイス等を通して荷重を付加して密着させ、その後、PTFEの融点以上の温度で加熱焼結して、両者を融着一体化している。
The hollow fiber membrane 2 composed of the porous multilayer hollow fiber membrane is formed by winding a porous expanded PTFE sheet 2c around the outer peripheral surface of a porous expanded PTFE tube 2b obtained by extrusion molding.
Specifically, after the outer peripheral surface of the porous expanded PTFE tube 2b is provided with irregularities by flame treatment or the like, the porous expanded PTFE sheet 2c is wound around the entire circumference without being displaced, and then a load is applied through a die or the like to be brought into close contact therewith. Thereafter, heat sintering is performed at a temperature equal to or higher than the melting point of PTFE, and both are fused and integrated.
前記分離膜モジュール1を備えた含油排水処理装置20は、図2に示す構成としている。
含油排水OLが配管19から連続投入される含油排水貯留槽21と、アルカリ性水溶液の洗浄液(以下、アルカリ洗浄液と略す)ALを貯留する洗浄液貯留槽22と、含油排水貯留槽21および洗浄液貯留槽22と分離膜モジュール1の被処理液の導入口9aとを連通すると共に、ポンプ23と切替弁24を介設した前記導入用配管10と、含油排水貯留槽21および洗浄液貯留槽22と分離膜モジュール1の濾過されなかった非処理液の排出口11とを連通する前記循環用配管12とを備えている。
The oil-containing wastewater treatment apparatus 20 provided with the separation membrane module 1 is configured as shown in FIG.
An oil-containing wastewater storage tank 21 into which oil-containing wastewater OL is continuously supplied from the pipe 19, a cleaning liquid storage tank 22 that stores a cleaning liquid of an alkaline aqueous solution (hereinafter abbreviated as an alkali cleaning liquid) AL, an oil-containing drainage storage tank 21, and a cleaning liquid storage tank 22. And the inlet 9a of the liquid to be treated of the separation membrane module 1, and the introduction pipe 10 provided with the pump 23 and the switching valve 24, the oil-containing drainage storage tank 21, the cleaning liquid storage tank 22, and the separation membrane module 1 and the circulation pipe 12 communicating with the discharge port 11 of the non-processed untreated liquid.
前記導入用配管10はポンプ23の上流に切替弁24を備え、該切替弁24で配管を分岐し、分岐管10Aを含油排水貯留槽21と接続し、分岐管10Bを洗浄液貯留槽22と接続している。また、導入用配管10にはポンプ23の下流で切替弁25を介して逆洗浄水の排出管10Cと接続している。
前記洗浄液経路となる循環用配管12も分岐し、分岐管12Aを含油排水貯留槽21と接続し、分岐管12Bを洗浄液貯留槽22と接続している。かつ、該分岐位置に切替弁29を介設して、濾過されなかった非処理液を含油排水貯留槽21へ戻し、アルカリ洗浄時にはアルカリ洗浄液を洗浄液貯留槽22に戻して循環している。
The introduction pipe 10 includes a switching valve 24 upstream of the pump 23, the pipe is branched by the switching valve 24, the branch pipe 10 </ b> A is connected to the oil-containing drainage storage tank 21, and the branch pipe 10 </ b> B is connected to the cleaning liquid storage tank 22. is doing. The introduction pipe 10 is connected to the backwash water discharge pipe 10 </ b> C via the switching valve 25 downstream of the pump 23.
The circulation pipe 12 serving as the cleaning liquid path is also branched, the branch pipe 12A is connected to the oil-containing drainage storage tank 21, and the branch pipe 12B is connected to the cleaning liquid storage tank 22. Further, a non-processed liquid that has not been filtered is returned to the oil-containing drainage storage tank 21 via the switching valve 29 at the branch position, and the alkali cleaning liquid is returned to the cleaning liquid storage tank 22 and circulated during alkali cleaning.
前記ポンプ23の吐出圧力は50〜300kPaとし、含油排水OLとアルカリ洗浄液ALとを加圧して分離膜モジュール1へ送液している。
ポンプ23の吐出圧力は50〜300kPaとして、中空糸膜2のIPAバブルポイントの膜間差圧に調整している。
このように、本装置では、分離膜モジュール1に、アルカリ洗浄液ALと含油排水OLとは定期的に交互に供給し、定期的にアルカリ洗浄液ALで中空糸膜2を洗浄している。
アルカリ洗浄液ALとしては、0.5〜20質量%の水酸化ナトリウム水溶液を用いている。
The discharge pressure of the pump 23 is 50 to 300 kPa, and the oil-containing wastewater OL and the alkaline cleaning liquid AL are pressurized and fed to the separation membrane module 1.
The discharge pressure of the pump 23 is 50 to 300 kPa, and is adjusted to the transmembrane differential pressure at the IPA bubble point of the hollow fiber membrane 2.
Thus, in this apparatus, the alkaline cleaning liquid AL and the oil-containing wastewater OL are periodically and alternately supplied to the separation membrane module 1, and the hollow fiber membrane 2 is periodically cleaned with the alkaline cleaning liquid AL.
As the alkaline cleaning liquid AL, a 0.5 to 20% by mass sodium hydroxide aqueous solution is used.
濾過済みの処理液の導出口7aと接続して処理液を取り出す導出用配管8は処理液貯留槽26と接続している。かつ、該処理液貯留槽26に貯留された処理液を逆洗浄水として利用するため、逆洗用ポンプ27を介設した逆洗水の配管28を処理液貯留槽26と前記導出用配管8との間に接続している。   A derivation pipe 8 for connecting the filtered treatment liquid outlet 7 a to take out the treatment liquid is connected to the treatment liquid storage tank 26. In addition, in order to use the processing liquid stored in the processing liquid storage tank 26 as backwashing water, a backwashing water pipe 28 provided with a backwashing pump 27 is connected to the processing liquid storage tank 26 and the outlet piping 8. Connected between.
次に、前記分離膜モジュール1を備えた含油排水処理装置の作用について説明する。
前記含油排水貯留槽21に連続的に供給される含油排水OLは、油田随伴水の油水分離処理手段で非水溶性油分と含油水分とに分離し、分離された含油水分を電気凝集・浮上手段で非水溶性油分と金属分を凝集させて粗く除いた後の非水溶性油分含有量(n−ヘキサン値)が約1000mg/L以下の含油排水からなる。
Next, the operation of the oil-containing wastewater treatment apparatus provided with the separation membrane module 1 will be described.
The oil-containing wastewater OL continuously supplied to the oil-containing wastewater storage tank 21 is separated into water-insoluble oil and oil-containing water by the oil-water separation processing means of the oil field-associated water, and the separated oil-containing water is electrocoagulated / floating means. The water-insoluble oil content and the water content of the water-insoluble oil content (n-hexane value) after roughly removing the water and the metal content are about 1000 mg / L or less.
含油排水貯留槽21から含油排水OLがポンプ23で加圧されて導入用配管10から分離膜モジュール1の下端の導入口9aに導入される。導入された含油排水OLは外筒6内で上向きに流れ、その間に集束体3内の中空糸膜2の外周へと流入していく。中空糸膜2の外周から中空糸膜2の中空部へと外圧濾過される。   The oil-containing wastewater OL is pressurized by the pump 23 from the oil-containing wastewater storage tank 21 and is introduced from the introduction pipe 10 into the inlet 9a at the lower end of the separation membrane module 1. The introduced oil-containing wastewater OL flows upward in the outer cylinder 6 and flows into the outer periphery of the hollow fiber membrane 2 in the focusing body 3 in the meantime. External pressure filtration is performed from the outer periphery of the hollow fiber membrane 2 to the hollow portion of the hollow fiber membrane 2.
濾過された処理液SLは中空糸膜2の中空部から上端の導出口7aを通って導出用配管8を通り、処理液貯留槽26に貯留される。
一方、濾過されてなかった非処理液は排出口11から循環用配管12へと排出され、分岐管12Aを経て含油排水貯留槽21または洗浄液貯留槽22へと戻している。
The filtered processing liquid SL is stored in the processing liquid storage tank 26 from the hollow portion of the hollow fiber membrane 2 through the outlet outlet port 7a through the outlet pipe 8.
On the other hand, the non-treated liquid that has not been filtered is discharged from the discharge port 11 to the circulation pipe 12 and returned to the oil-containing drainage storage tank 21 or the cleaning liquid storage tank 22 via the branch pipe 12A.
前記のように、含油排水OLを中空糸膜2で濾過する際、中空糸膜2としてIPAバブルポイントが50kPa以上100kPa未満のものを用いた場合は、膜間差圧を50kPa以下に調整している。
IPAバブルポイントが100kPa以上150kPa未満のものを用いた場合は、膜間差圧を100kPa以下に調整している。
IPAバブルポイントが150kPa以上200kPa以下の場合は膜間差圧を超えて200kPa以下の濾過条件としている。
As described above, when the oil-containing wastewater OL is filtered through the hollow fiber membrane 2, when the IPA bubble point is 50 kPa or more and less than 100 kPa as the hollow fiber membrane 2, the transmembrane pressure difference is adjusted to 50 kPa or less. Yes.
When an IPA bubble point of 100 kPa or more and less than 150 kPa is used, the transmembrane pressure difference is adjusted to 100 kPa or less.
When the IPA bubble point is 150 kPa or more and 200 kPa or less, the filtration condition is set to 200 kPa or less exceeding the transmembrane pressure difference.
このように中空糸膜2のIPAバブルポイントと膜間差圧のバランスを取ることにより、中空糸膜2の孔に非水溶性油分が透過することがなく、効率的に含油排水OLから非水溶性油分を除去し、非水溶性油分含有量1mg/L未満の処理済み水を得ることができる。   Thus, by balancing the IPA bubble point of the hollow fiber membrane 2 and the transmembrane pressure difference, the water-insoluble oil component does not permeate through the pores of the hollow fiber membrane 2, and the water-impervious drainage OL is effectively made water-insoluble. The treated water having a water-insoluble oil content of less than 1 mg / L can be obtained.
なお、含油排水貯留槽21に含油排水OLを連続供給する代わりに、間歇的に供給してもよい。その場合、含油排水OLは循環濾過を複数回繰り返すことで、濾過が進行して濃縮されていく。含油排水OLの濃度が、例えば2000mg/L付近になったところで、含油排水貯留槽21内の残存する被処理液を排出して、新たに含油排水OLを入れ変えてもよい。
また、別の運転方法として、新たに投入される非水溶性油分、固形分の量の総量と等しい量を含む濃縮排水を系外に排出する等して一定の非水溶性油分、固形分を維持しながら継続して濾過してもよい。
Instead of continuously supplying the oil-containing wastewater OL to the oil-containing wastewater storage tank 21, it may be supplied intermittently. In this case, the oil-containing wastewater OL is concentrated by repeating the circulation filtration a plurality of times, so that the filtration proceeds. When the concentration of the oil-containing wastewater OL reaches, for example, around 2000 mg / L, the liquid to be treated remaining in the oil-containing wastewater storage tank 21 may be discharged, and the oil-containing wastewater OL may be newly replaced.
Also, as another operation method, a certain amount of water-insoluble oil and solid content can be removed by discharging concentrated wastewater containing the same amount of the water-insoluble oil and solid content to be newly added to the system. You may filter continuously, maintaining.
含油排水OLの濾過運転を一定時間行い、処理流量の低下が見られた時点で、ポンプ23の作動を停止し、切替弁24をアルカリ洗浄用の流路に切り替る。その後、ポンプ23を再作動し、アルカリ洗浄液ALを導入用配管10を通して、分離膜モジュール1の導入口9aにアルカリ洗浄液ALを導入している。
該アルカリ洗浄液ALは外筒6内に流入し中空糸膜2の表面に付着堆積した捕捉非水溶性油分を洗浄除去している。該アルカリ洗浄液ALは排出口11より循環用配管12へ排出され、該循環用配管12より洗浄液貯留槽22に循環している。
このように、含油排水OLの濾過とアルカリ洗浄液ALによる洗浄とを、定期的に交互に行っている。
The filtration operation of the oil-containing wastewater OL is performed for a certain time, and when the processing flow rate is reduced, the operation of the pump 23 is stopped and the switching valve 24 is switched to the alkali cleaning flow path. Thereafter, the pump 23 is restarted, and the alkaline cleaning liquid AL is introduced into the inlet 9 a of the separation membrane module 1 through the introduction pipe 10.
The alkaline cleaning liquid AL flows into the outer cylinder 6 and cleans and removes the trapped water-insoluble oil component deposited and deposited on the surface of the hollow fiber membrane 2. The alkaline cleaning liquid AL is discharged from the discharge port 11 to the circulation pipe 12 and is circulated from the circulation pipe 12 to the cleaning liquid storage tank 22.
In this manner, the filtration of the oil-containing wastewater OL and the cleaning with the alkaline cleaning liquid AL are periodically performed alternately.
また、定期的に処理液貯留槽26より濾過済みの処理液SLを導出用配管8より中空糸膜2の中空部に圧送し、中空糸膜2を内側から逆洗浄している。該逆洗浄水は、切替弁25を切り替えて排出管10Cを通して排出している。
なお、濾過された処理液に変えて、アルカリ洗浄液を逆洗浄水として用い、短時間、たとえば1時間程度放置してもよい。
Further, the processing liquid SL that has been filtered from the processing liquid storage tank 26 is periodically pumped from the outlet pipe 8 to the hollow portion of the hollow fiber membrane 2, and the hollow fiber membrane 2 is back-washed from the inside. The backwash water is discharged through the discharge pipe 10C by switching the switching valve 25.
Note that instead of the filtered treatment liquid, an alkaline washing liquid may be used as the back washing water and left for a short time, for example, about 1 hour.
含油排水OLの非水溶性油分含有量(n−ヘキサン値)が3〜200mg/Lと希薄で、特に膜への付着性の少ない含油排水を処理する場合は、導入口9aから含油排水を供給し、集束体3の上端側に向かって流れながら中空糸膜2により濾過し、非水溶性油分が除去された処理済み水は中空糸膜2の内周側を流通させて導出口7aより導出用配管8へと導出し、含油排水OLを全濾過して、循環させない外圧濾過式とすることが好ましい。   When treating oil-containing wastewater with a non-water-soluble oil content (n-hexane value) of 3 to 200 mg / L, especially oily wastewater with little adhesion to the membrane, supply oil-containing wastewater from the inlet 9a. The treated water from which the water-insoluble oil has been removed while flowing toward the upper end side of the bundling body 3 is circulated on the inner peripheral side of the hollow fiber membrane 2 and led out from the outlet 7a. It is preferable to use an external pressure filtration type that is led out to the pipe 8 and oil-filtered wastewater OL is totally filtered and is not circulated.
前記外圧濾過式とする場合、例えば、30分に1回逆洗ポンプ27を稼働させ、濾過済みの処理水を使って分離膜モジュール内の中空糸膜2に逆圧(内圧)をかけ外表面に堆積する固形分などを払拭している。
その際、同時にブロア15より空気を送り込み、中空糸膜2を振動させて同じく固形分を払拭している。その後、分離膜モジュール1の下部より固形分を含む被処理液をドレンしている。このときの逆洗圧力は、例えば、200kPa、時間は30秒。空気の量は50L/minで20秒である。このように、非水溶性油分含有量が希薄な含油排水の場合は、全量濾過することが好ましい。
In the case of the external pressure filtration type, for example, the backwash pump 27 is operated once every 30 minutes, and the reverse pressure (internal pressure) is applied to the hollow fiber membrane 2 in the separation membrane module using the filtered treated water. Wipe away any solid matter that accumulates on the surface.
At that time, air is simultaneously fed from the blower 15 to vibrate the hollow fiber membrane 2 to wipe off the solid content. Thereafter, the liquid to be treated containing the solid content is drained from the lower part of the separation membrane module 1. The backwash pressure at this time is, for example, 200 kPa, and the time is 30 seconds. The amount of air is 50 L / min for 20 seconds. Thus, in the case of oil-containing wastewater with a lean water-insoluble oil content, it is preferable to filter the entire amount.
図4および図5に、第2実施形態の内圧循環濾過式の含油排水処理装置30を示す。
該含油排水処理装置30は、油田随伴水用ではなく、油分を含有する工場排水の油水分離用として用いている。なお、第1実施形態と同様に油田随伴水用の含油排水処理装置として用いてもよい。
図4に示す分離膜モジュール31は、中空糸膜32の両端を開口とし、中空糸膜32の中空部に被処理液の含油排水OLを通し、中空糸膜32の内側から外側に向けて濾過して、中空糸膜32の外側に濾過済みの処理液を透過させる内圧循環濾過式のモジュールとしている。
4 and 5 show an internal pressure circulation filtration type oil-containing wastewater treatment apparatus 30 of the second embodiment.
The oil-containing wastewater treatment device 30 is not used for oilfield associated water but for oily water separation of factory wastewater containing oil. In addition, you may use as an oil-containing wastewater treatment apparatus for oil field accompanying water similarly to 1st Embodiment.
The separation membrane module 31 shown in FIG. 4 has both ends of the hollow fiber membrane 32 as openings, the oil-containing wastewater OL of the liquid to be treated is passed through the hollow part of the hollow fiber membrane 32, and the filtration is performed from the inside to the outside of the hollow fiber membrane 32. Thus, an internal pressure circulation filtration type module that allows the filtered treatment liquid to permeate outside the hollow fiber membrane 32 is provided.
具体的には、前記両端開口とした中空糸膜32の集束体33を外筒6に収容している。集束体33の上下両側は中空糸膜32の両端開口を開口状態として固定材34、35で固定している。上端の固定材34に、濾過されていない非処理液の排出口37aを設けた上部キャップ37を接着固定し、上部キャップ37と循環用配管12を排出口37aと接続している。
下端の固定材35は外筒6の内周面に密着固定すると共に、下部キャップ36と固定し、該下部キャップ36に含油排水からなる被処理液の導入口36aを設け、該導入口36aを導入用配管10と接続している。
また、外筒6の上端近傍の周壁に濾過された処理液の導出口6cを設け、該導出口6cを処理液取出用の導出用配管8と接続している。
Specifically, the converging body 33 of the hollow fiber membrane 32 having the openings at both ends is accommodated in the outer cylinder 6. The upper and lower sides of the converging body 33 are fixed by fixing members 34 and 35 with both ends of the hollow fiber membrane 32 being opened. An upper cap 37 provided with a non-filtered non-processing liquid discharge port 37a is bonded and fixed to the fixing member 34 at the upper end, and the upper cap 37 and the circulation pipe 12 are connected to the discharge port 37a.
The fixing member 35 at the lower end is closely fixed to the inner peripheral surface of the outer cylinder 6 and is fixed to the lower cap 36. The lower cap 36 is provided with an inlet 36a for the liquid to be treated made of oil-containing waste water, and the inlet 36a is It is connected to the introduction pipe 10.
Further, a filtered processing liquid outlet 6c is provided on the peripheral wall near the upper end of the outer cylinder 6, and the outlet 6c is connected to a outlet pipe 8 for extracting the processing liquid.
前記内圧循環濾過式の分離膜モジュール31を備えた含油排水処理装置30は図5に示すように、分離膜モジュール31の導入口36aに接続した導入用配管10は、第1実施形態と同様に、ポンプ23、切替弁24、分岐管10A、10Bを介して含油排水貯留槽21、洗浄液貯留槽22と接続している。
分離膜モジュール31の排出口37aに接続する循環用配管12も第1実施形態と同様に、分岐管12A、12Bを含油排水貯留槽21、洗浄液貯留槽22と接続している。
濾過済みの処理液の導出口6cに接続する導出用配管8も、第1実施形態と同様に処理液貯留槽26に接続し、該処理液貯留槽26と逆洗用ポンプ27を介して逆洗用の配管28を導出用配管8と接続している。前記逆洗用ポンプ27を間歇的に作動して、外筒6の内部に処理液を逆洗浄液として導入して、中空糸膜32の外周面に向けて噴射して逆洗浄を行うようにしている。
さらに、ブロア15と接続した散気用空気導入管14を、分離膜モジュール31の導入口36aに近接した配管10内に挿入し、散気用空気を各中空糸膜32の内部へ供給している。
As shown in FIG. 5, the oil-containing wastewater treatment apparatus 30 having the internal pressure circulation filtration type separation membrane module 31 has an introduction pipe 10 connected to the introduction port 36a of the separation membrane module 31 as in the first embodiment. The oil-containing drainage storage tank 21 and the cleaning liquid storage tank 22 are connected via the pump 23, the switching valve 24, and the branch pipes 10A and 10B.
Similarly to the first embodiment, the circulation pipe 12 connected to the discharge port 37a of the separation membrane module 31 connects the branch pipes 12A and 12B to the oil-containing drainage storage tank 21 and the cleaning liquid storage tank 22, respectively.
Similarly to the first embodiment, the outlet piping 8 connected to the filtered processing liquid outlet 6 c is also connected to the processing liquid storage tank 26, and reversely passed through the processing liquid storage tank 26 and the backwash pump 27. The washing pipe 28 is connected to the outlet pipe 8. The back washing pump 27 is intermittently operated to introduce the treatment liquid into the outer cylinder 6 as a back washing liquid and spray it toward the outer peripheral surface of the hollow fiber membrane 32 to perform the back washing. Yes.
Further, the air diffuser introduction pipe 14 connected to the blower 15 is inserted into the pipe 10 close to the inlet 36a of the separation membrane module 31, and the air diffuser is supplied to the inside of each hollow fiber membrane 32. Yes.
本第2実施形態の中空糸膜32は第1実施形態の図3と同様に、多孔質延伸PTFE製の単層チューブからなる。該多孔質中空糸膜32は内径1〜12mm、外径1.6〜14mm、IPAバブルポイント50kPa以上400kPa以下、膜厚0.2〜1mm、気孔率50〜90%、最大許容膜間差圧0.1〜1.0MPaの耐圧性を備えている。これら物性は前記した方法と同様の方法で測定している。   The hollow fiber membrane 32 of the second embodiment is composed of a single-layer tube made of porous expanded PTFE, as in FIG. 3 of the first embodiment. The porous hollow fiber membrane 32 has an inner diameter of 1 to 12 mm, an outer diameter of 1.6 to 14 mm, an IPA bubble point of 50 kPa to 400 kPa, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum allowable transmembrane pressure. It has a pressure resistance of 0.1 to 1.0 MPa. These physical properties are measured by the same method as described above.
前記分離膜モジュール31は、非水溶性油分含有量(n−ヘキサン値)が1000〜2000mg/Lの含油排水OLを循環処理している。内圧循環濾過方式としている点で、第1実施形態の外圧循環濾過方式と相違する。
含油排水OLは、図中矢印に示すように、導入口36aから中空糸膜32の内部に導入され、集束体33の上端側に向かって流れる。この流通過程で中空糸膜32により濾過され、非水溶性油分が除去された濾過済みの処理水は中空糸膜32の外周側を透過し、外筒6の周壁に設けた処理液の導出口6cから導出用配管8へと導出される。
また、非水溶性油分や固形粒子等を含む濾過されていない非処理液は、上部キャップ37に設けられた排出口37aから循環用配管12に排出される。
内圧循環方式の場合、同じ循環流量でも、分離膜モジュール31内を流れる流路断面積が小さいため流速が上がり、中空糸膜32の表面に堆積する固形分、非水溶性油分の剥離効果が大きくなるため、特に、非水溶性油分濃度の大きい領域において有効である。
The separation membrane module 31 circulates oil-containing wastewater OL having a water-insoluble oil content (n-hexane value) of 1000 to 2000 mg / L. The internal pressure circulation filtration system is different from the external pressure circulation filtration system of the first embodiment.
The oil-containing wastewater OL is introduced into the hollow fiber membrane 32 from the introduction port 36a and flows toward the upper end side of the converging body 33, as indicated by an arrow in the figure. The treated water that has been filtered through the hollow fiber membrane 32 in this distribution process and from which the water-insoluble oil has been removed passes through the outer peripheral side of the hollow fiber membrane 32, and leads out the treatment liquid provided on the peripheral wall of the outer cylinder 6. 6c is led out to the lead-out piping 8.
Further, the non-filtered non-processed liquid containing water-insoluble oil and solid particles is discharged from the discharge port 37 a provided in the upper cap 37 to the circulation pipe 12.
In the case of the internal pressure circulation method, the flow rate increases because the flow passage cross-sectional area flowing through the separation membrane module 31 is small even at the same circulation flow rate, and the separation effect of the solid content and water-insoluble oil content deposited on the surface of the hollow fiber membrane 32 is large. Therefore, it is particularly effective in a region where the water-insoluble oil concentration is large.
本第2実施形態では、高濃度の非水溶性油分含有量の含油排水OLを被処理液とし、一度の濾過で5mg/L未満の非水溶性油分含有量の処理済み液を得ることができる。
他の構成及び効果は第1実施形態と同様のため、同一の機能及び作用を有する部材には同一符号を付して説明を省略する。
In the second embodiment, an oil-containing wastewater OL having a high concentration of a water-insoluble oil content is used as a liquid to be treated, and a treated liquid having a water-insoluble oil content of less than 5 mg / L can be obtained by a single filtration. .
Since other configurations and effects are the same as those of the first embodiment, members having the same functions and functions are denoted by the same reference numerals and description thereof is omitted.
図6および図7に、第3実施形態の分離膜モジュール40および含油排水処理装置60を示す。
含油排水処理用の分離膜モジュール40は、中空糸膜41の集束体42を含油排水OLを貯留した浸漬槽50内に浸漬配置し、中空糸膜41の内側から含油排水OLを吸引することにより中空糸膜41の外側から内側に向けて含油排水OLを透過させる浸漬型のモジュールとしている。
6 and 7 show the separation membrane module 40 and the oil-containing wastewater treatment apparatus 60 of the third embodiment.
The separation membrane module 40 for oil-containing wastewater treatment immerses and arranges the converging body 42 of the hollow fiber membrane 41 in the immersion tank 50 storing the oil-containing wastewater OL, and sucks the oil-containing wastewater OL from the inside of the hollow fiber membrane 41. The module is an immersion type that allows oil-containing wastewater OL to permeate from the outside to the inside of the hollow fiber membrane 41.
中空糸膜41の集束体42の状態は第1実施形態と同様に、中空糸膜の上端開口を開口した状態で固定材5で固定し、該固定材5を上部キャップ7と固定し、該上部キャップ7を濾過済みの処理液を取り出す導出用配管8と接続している。
集束体42の下端も第1実施形態と同様に、中空糸膜41の下端開口を閉鎖した封止材4で固定している。上端の固定材5と下端の封止材4との外周部を連結棒43で連結し、集束体42を鉛直方向に保持すると共に補強している。
前記下端の封止材4と連結棒43の下端とをスカート材46に固定している。該スカート材46の下部にブロア15と接続した散気用空気導入管14の散気口を配置している。濾過運転時には常時下方から散気して、そのバブリングにより、浸漬槽50内の含油排水OLに上向きの循環流れを生じさせている。
As in the first embodiment, the converging body 42 of the hollow fiber membrane 41 is fixed with the fixing material 5 with the upper end opening of the hollow fiber membrane being opened, and the fixing material 5 is fixed to the upper cap 7. The upper cap 7 is connected to an outlet piping 8 for taking out the filtered processing liquid.
Similarly to the first embodiment, the lower end of the converging body 42 is also fixed by the sealing material 4 with the lower end opening of the hollow fiber membrane 41 closed. The outer peripheral portions of the fixing member 5 at the upper end and the sealing member 4 at the lower end are connected by a connecting rod 43 to hold and reinforce the focusing body 42 in the vertical direction.
The sealing material 4 at the lower end and the lower end of the connecting rod 43 are fixed to the skirt material 46. A diffuser port of the diffuser air introduction pipe 14 connected to the blower 15 is disposed below the skirt member 46. During filtration operation, air is constantly diffused from below, and upward bubbling is caused in the oil-containing wastewater OL in the immersion tank 50 by bubbling.
図7に示すように、処理液取り出し用の導出用配管8は、第1実施形態と同様に、処理液貯留槽26に接続している。該処理液貯留槽26に逆洗用ポンプ27を介設した逆洗用の配管28を接続し、該配管28を導出用配管8と接続している。
さらに、アルカリ洗浄液ALを貯留した洗浄液貯留槽22を配管45を介して浸漬槽50の内部に導入し、浸漬槽50内の含油排水OLを除去した後にアルカリ洗浄液ALを浸漬槽50内に導入して、集束体42を所要時間浸漬して洗浄するようにしている。
As shown in FIG. 7, the lead-out piping 8 for taking out the processing liquid is connected to the processing liquid storage tank 26 as in the first embodiment. A backwash pipe 28 provided with a backwash pump 27 is connected to the treatment liquid storage tank 26, and the pipe 28 is connected to the outlet pipe 8.
Further, the cleaning liquid storage tank 22 storing the alkaline cleaning liquid AL is introduced into the immersion tank 50 through the pipe 45, and after removing the oil-containing wastewater OL in the immersion tank 50, the alkaline cleaning liquid AL is introduced into the immersion tank 50. Thus, the focusing body 42 is immersed and cleaned for a required time.
本第3実施形態の中空糸膜41は、第1実施形態の中空糸膜2と同様に、多孔質延伸PTFE製のチューブからなる支持層と、該支持層の外表面に多孔質膜延伸PTFEシートからなる濾過層を備えた多孔質複層中空糸膜としている。
中空糸膜41の内径は0.3〜2.0mm、外径は0.8〜3.0mm、内面に円筒状ネットなどの支持体を用いる場合は最大外径20mmとしている。
IPAバブルポイントは50kPa以上400kPa以下、膜厚は0.2〜1mm、気孔率は50〜90%、最大許容膜間差圧(外圧)0.1MPaの耐圧性を備えたものとしている。なお、これら物性は前記した方法と同様の方法で測定している。本第3実施形態の浸漬型は、非水溶性油分含有量(n−ヘキサン値)が10〜200mg/Lの含油排水OLの処理用として用いている。
Similar to the hollow fiber membrane 2 of the first embodiment, the hollow fiber membrane 41 of the third embodiment includes a support layer made of a porous stretched PTFE tube, and a porous membrane stretched PTFE on the outer surface of the support layer. It is set as the porous multilayer hollow fiber membrane provided with the filtration layer which consists of a sheet | seat.
The hollow fiber membrane 41 has an inner diameter of 0.3 to 2.0 mm, an outer diameter of 0.8 to 3.0 mm, and a maximum outer diameter of 20 mm when a support such as a cylindrical net is used on the inner surface.
The IPA bubble point has a pressure resistance of 50 kPa to 400 kPa, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum allowable transmembrane pressure (external pressure) of 0.1 MPa. These physical properties are measured by the same method as described above. The immersion type of the third embodiment is used for treating oil-containing wastewater OL having a water-insoluble oil content (n-hexane value) of 10 to 200 mg / L.
浸漬槽50に配管19を介して、含油排水OLを供給している。配管19から浸漬槽50への含油排水OLの供給は間歇的に行っている。
具体的には、浸漬槽50内の含油排水OLが濾過されて、濾過されていない含油排水OLの非水溶性油分含有量が200mg/Lになると、浸漬槽50から系外へ排出して、新たな含油排水OLを浸漬槽50内に供給している。
あるいは、非水溶性油分含油量が100mg/Lになると、浸漬槽50内に希薄濃度の含油排水OLを投入し、浸漬槽50内で非水溶性油分含油量が100mg/Lの所定量溜ると、系外に短時間で排出している。
例えば、含油排水を1000リットル投入し、投入される含油排水の非水溶性油分5000mgであると、浸漬槽50内の非水溶性油分100mg/Lとして、50リットルだけ排出している。このバランスが保てるように運転して浸漬槽50内の非水溶性油分を一定に保ちながら連続している。
Oil-containing wastewater OL is supplied to the immersion tank 50 via the pipe 19. The supply of the oil-containing wastewater OL from the pipe 19 to the immersion tank 50 is performed intermittently.
Specifically, when the oil-containing wastewater OL in the immersion tank 50 is filtered and the water-insoluble oil content of the oil-containing wastewater OL that has not been filtered becomes 200 mg / L, the oil-containing wastewater OL is discharged out of the system from the immersion tank 50, New oil-containing wastewater OL is supplied into the immersion tank 50.
Alternatively, when the water content of the water-insoluble oil content is 100 mg / L, the oil-contained waste water OL having a dilute concentration is introduced into the immersion tank 50, and a predetermined amount of water content of the water-insoluble oil content of 100 mg / L is accumulated in the immersion tank 50. It is discharged out of the system in a short time.
For example, when 1000 liters of oil-containing wastewater is added and the water-insoluble oil content of the oil-containing wastewater is 5000 mg, only 50 liters are discharged as the water-insoluble oil content in the immersion tank 50 is 100 mg / L. It operates so that this balance may be maintained, and it is continuing, maintaining the water-insoluble oil content in the immersion tank 50 constant.
本第3実施形態の浸漬型では、濾過運転時に、常時、集束体42の下部に散気用空気挿入管14より空気を噴射し、そのバブリングにより浸漬槽50内の含油排水OLを上昇させる循環流を発生させ、中空糸膜41を振動しつつ、中空糸膜41の膜面に非水溶性油分および固形分を付着し、付着した固形分および非水溶性油分をふるい剥ぎ取っている。
また、前記したように、定期的に浸漬槽50から含油排水を系外へ排出し、排出後にアルカリ洗浄液ALを配管45を通して浸漬槽50に供給し、集束体42をアルカリ洗浄液ALに浸漬して洗浄を行っている。さらに、逆洗用ポンプ27を駆動して、濾過済みの処理液SLを逆洗浄液として中空糸膜41の内部に導入し、中空糸膜41を逆洗浄している。
In the immersion type of the third embodiment, during the filtration operation, air is constantly sprayed from the air diffuser air insertion pipe 14 to the lower part of the focusing body 42, and the oil-containing wastewater OL in the immersion tank 50 is raised by the bubbling. While the flow is generated and the hollow fiber membrane 41 is vibrated, the water-insoluble oil component and the solid component are attached to the membrane surface of the hollow fiber membrane 41, and the attached solid component and the water-insoluble oil component are sieved off.
Further, as described above, the oil-containing wastewater is periodically discharged from the immersion tank 50 to the outside of the system, and after discharge, the alkaline cleaning liquid AL is supplied to the immersion tank 50 through the pipe 45, and the focusing body 42 is immersed in the alkaline cleaning liquid AL. Cleaning is performed. Further, the back washing pump 27 is driven to introduce the filtered processing liquid SL into the hollow fiber membrane 41 as a back washing liquid, and the hollow fiber membrane 41 is back washed.
前記のように定期的に洗浄することにより、アルカリ洗浄液ALにより中空糸膜42の膜面に付着堆積した捕捉非水溶性油分を除去し、中空糸膜の濾過性能をほぼ完全に回復させることができる。
その結果、非水溶性油分含有量5mg/L未満、さらには1mg/Lとなる処理済み液を処理水量を低下させずに長期に渡り持続的に得ることができ、油田随伴水の処理装置として優れている。このようにして得られた処理済み液は、例えば灌漑用水として利用することができる。
本第3実施形態の含油排水処理装置は油田随伴水用、油分を含有する工場排水等、いずれの分野の含油排水処理装置として用いることができる。
By periodically washing as described above, it is possible to remove the trapped water-insoluble oil adhering to the membrane surface of the hollow fiber membrane 42 with the alkaline washing liquid AL and almost completely restore the filtration performance of the hollow fiber membrane. it can.
As a result, a treated liquid having a water-insoluble oil content of less than 5 mg / L, and further 1 mg / L can be obtained continuously over a long period of time without reducing the amount of treated water. Are better. The treated liquid thus obtained can be used as irrigation water, for example.
The oil-containing wastewater treatment device of the third embodiment can be used as an oil-containing wastewater treatment device in any field, such as for oil field accompanying water and factory wastewater containing oil.
図8(A)(B)に第4実施形態の高温の含油排水処理装置を示す。
処理する含油排水は温度60〜200℃、油含有量が20〜2000mg/L、懸濁成分の含有量が100〜10000mg/Lであり、分離膜モジュール62を備えた濾過装置(含油排水処理装置)63で精密濾過している。
8A and 8B show a high-temperature oil-containing wastewater treatment apparatus according to the fourth embodiment.
The oil-containing wastewater to be treated has a temperature of 60 to 200 ° C., an oil content of 20 to 2000 mg / L, a suspended component content of 100 to 10,000 mg / L, and a filtration device (oil-containing wastewater treatment device) provided with a separation membrane module 62 ) 63 is microfiltered.
前記濾過装置63の分離膜モジュール62は前記第1実施形態と同様な延伸PTFE多孔質チューブからなる中空糸膜2を用い、濾過装置63の全体構成は前記図1に示す構成とし、散気手段も配置しており、同一符号を付して説明を省略する。   The separation membrane module 62 of the filtration device 63 uses a hollow fiber membrane 2 made of an expanded PTFE porous tube similar to that of the first embodiment, and the overall configuration of the filtration device 63 is as shown in FIG. Are also provided with the same reference numerals and the description thereof is omitted.
前記分離膜モジュール62の各中空糸膜2は単層、複層のいずれでもよく、各中空糸膜2は、前記外圧濾過式または外圧循環濾過式として用いる場合、外径1〜5mm、内径0.5〜4mm、濾過面の気孔率30〜90%、好ましくは40〜80%としている。
前記内圧濾過式または内圧循環式としている用いる場合は、外径1.3〜20mm、内径1〜10mm、濾過面の気孔率30〜90%、好ましくは40〜80%としている。
Each hollow fiber membrane 2 of the separation membrane module 62 may be either a single layer or a multi-layer, and each hollow fiber membrane 2 has an outer diameter of 1 to 5 mm and an inner diameter of 0 when used as the external pressure filtration type or the external pressure circulation filtration type. 0.5 to 4 mm, and the porosity of the filtration surface is 30 to 90%, preferably 40 to 80%.
When the internal pressure filtration type or the internal pressure circulation type is used, the outer diameter is 1.3 to 20 mm, the inner diameter is 1 to 10 mm, and the porosity of the filtration surface is 30 to 90%, preferably 40 to 80%.
また、前記中空糸膜2の抗張力を30N以上150N以下、IPAバブルポイントが50kPa以上400kPa以下としている。   Further, the tensile strength of the hollow fiber membrane 2 is 30 N or more and 150 N or less, and the IPA bubble point is 50 kPa or more and 400 kPa or less.
多数本の中空糸膜2を集束した集束体3を備えた分離膜モジュール62は、図8(B)に示すように、比較的高粘度の含油排水を流通させるため、該分離膜モジュールの断面積に対して中空糸膜の充填面積は20〜60%としている。
本実施形態では分離膜モジュール62は、中空糸膜2を束ねた集束体3の下端の封止材4および上端開口をあけて封止する固定材5(上端封止材)は直径100〜500mmの円形とし、隣接する中空糸膜2の間隔(中空糸膜の離間寸法)を汎用されている中空糸膜型分離膜モジュールの離間寸法は0.5mm〜5mmと広くし、含油排水の流路を確保している。
As shown in FIG. 8 (B), the separation membrane module 62 provided with the converging body 3 obtained by concentrating a large number of hollow fiber membranes 2 circulates a relatively high viscosity oil-containing wastewater. The filling area of the hollow fiber membrane is 20 to 60% with respect to the area.
In this embodiment, the separation membrane module 62 has a sealing material 4 at the lower end of the converging body 3 in which the hollow fiber membranes 2 are bundled and a fixing material 5 (upper end sealing material) that seals by opening an upper end opening, having a diameter of 100 to 500 mm. And the spacing between adjacent hollow fiber membranes 2 (separation dimension of the hollow fiber membrane) is widened as 0.5 mm to 5 mm for the widely used hollow fiber membrane type separation membrane module, and the flow path of the oil-containing drainage Is secured.
前記下端の封止材4および上端開口をあけて封止する固定材5(上端封止材)、集束体3を収容する外筒6、上部キャップ7、下部キャップ9は、熱変形温度が120℃以上の耐熱性樹脂で形成している。
該耐熱性樹脂としては、芳香族アミン硬化系エポキシ樹脂、PFA、PEF、PVDE等を用いている。連結棒16はSUSとしている。前記外筒もSUS等の金属製としてもよい。
また、上下キャップ7、9と外筒6との間に介在するOリングはテフロン、バイトン、金属とテフロン併用型として、耐熱性を持たせている。
The sealing material 4 at the lower end and the fixing material 5 (upper end sealing material) that seals by opening the upper end opening, the outer cylinder 6 that houses the focusing body 3, the upper cap 7, and the lower cap 9 have a heat deformation temperature of 120. It is made of a heat resistant resin at a temperature of ℃ or higher.
As the heat resistant resin, aromatic amine curable epoxy resin, PFA, PEF, PVDE, or the like is used. The connecting rod 16 is SUS. The outer cylinder may also be made of metal such as SUS.
The O-ring interposed between the upper and lower caps 7 and 9 and the outer cylinder 6 has heat resistance as Teflon, Viton, or a combination of metal and Teflon.
前記中空糸膜モジュール62を備えた濾過装置63で、加温された含油排水を前記第1実施形態と同様に濾過処理し、該分離膜モジュール62を透過した処理液を、処理水中の非水溶性油分含有量を5mg/L以下、懸濁成分含有量0〜1mg/Lとしている。
また、中空糸膜モジュール62を第1実施形態と同様に洗浄処理している。
In the filtration device 63 provided with the hollow fiber membrane module 62, the heated oil-containing wastewater is subjected to filtration treatment in the same manner as in the first embodiment, and the treatment liquid that has passed through the separation membrane module 62 is treated with water-insoluble water in the treated water. The essential oil content is 5 mg / L or less, and the suspended component content is 0 to 1 mg / L.
Further, the hollow fiber membrane module 62 is subjected to a cleaning process in the same manner as in the first embodiment.
前記した分離膜モジュール62は、停止時と稼働時との温度差が大きいヒートサイクルとなるため、中空糸膜2の離間距離を大きくしているため、上下封止材にクラックが発生しやすくなる。
よって、本実施形態の分離膜モジュール62は下記の方法で製造している。
Since the separation membrane module 62 has a heat cycle with a large temperature difference between the stop time and the operation time, the separation distance of the hollow fiber membrane 2 is increased, so that cracks are easily generated in the upper and lower sealing materials. .
Therefore, the separation membrane module 62 of this embodiment is manufactured by the following method.
容器内に複数本の中空糸膜2を所定間隔をあけて配置する。其の際、前記のように、中空糸膜間の離間距離L1を0.5〜5mmとして比較的広くあける。
前記容器内に、前記熱変形温度が120℃以上の熱硬化性樹脂を充填し、50℃で予備加熱したあと、常温で少なくとも6時間保持して予備硬化する。
ついで、使用時の100℃の温度以上で且つ熱変形温度120℃以下の温度条件で1時間以上加熱する。
その後、少なくとも6時間以上かつ1℃/分の温度勾配をもって除冷する。
A plurality of hollow fiber membranes 2 are arranged at predetermined intervals in the container. At that time, as described above, the separation distance L1 between the hollow fiber membranes is set to be relatively wide as 0.5 to 5 mm.
The container is filled with a thermosetting resin having a heat distortion temperature of 120 ° C. or higher, preheated at 50 ° C., and then preliminarily cured by holding at room temperature for at least 6 hours.
Next, heating is performed for 1 hour or more under a temperature condition of 100 ° C. or higher during use and a heat distortion temperature of 120 ° C. or lower.
Then, it cools with a temperature gradient of at least 6 hours and 1 ° C./min.
前記のように、分離膜モジュールを製造することで、使用時に前記ヒートサイクルで使用してもクラックの発生を低減または防止でき、かつ、中空糸膜間の離間距離を広くしても封止材にクラックが入らないことを、本発明者は実験によって確認した。   As described above, by producing the separation membrane module, it is possible to reduce or prevent the occurrence of cracks even when used in the heat cycle at the time of use, and the sealing material even if the separation distance between the hollow fiber membranes is widened The present inventor has confirmed through experiments that no cracks occur.
前記構成からなる加温含油排水処理装置では、中空糸膜を耐熱性を有するPEFEで形成しているため、軟化して孔径が変化することが防止でき、かつ、繰り返し負荷されるサーマルショックで破断やクラックが発生するのを防止できる。さらに、中空糸膜と上下の封止材との間や、該封止材自体にクラックが生じにくくすることができる。
さらに、従来用いられている処理装置と比較して軽量化および小型化でき、設置スペースをとらない。かつ、洗浄や膜状態の調査時に、分離膜モジュールを容易に取り出すことができる利点も有する。
In the heated oil-containing wastewater treatment apparatus having the above-described configuration, since the hollow fiber membrane is formed of heat-resistant PEFE, it can be prevented from softening and changing the pore diameter, and it can be broken by repeated thermal shock. And cracks can be prevented. Furthermore, it is possible to make it difficult for cracks to occur between the hollow fiber membrane and the upper and lower sealing materials or in the sealing material itself.
Furthermore, it can be reduced in weight and size as compared with conventionally used processing apparatuses, and does not take up installation space. In addition, there is also an advantage that the separation membrane module can be easily taken out at the time of cleaning or investigation of the membrane state.
本発明は前記実施形態に限定されず、中空糸膜として、支持層と濾過層とからなる複層もしくは非対称の中空糸膜を用いても良いし、1つの均一な多孔質チューブからなる単層としてもよい。また、中空糸膜をU字状に屈曲し、上端の両側を開口して固定材で固定した集束体としてもよい。さらに、洗浄液はアルカリ洗浄液を用いて洗浄することが好ましいが、処理済み液を用いた逆洗浄だけとしてもよい。
本発明の要旨を越えない範囲の種々の形態が含まれる。
The present invention is not limited to the above-described embodiment, and as the hollow fiber membrane, a multilayer or asymmetric hollow fiber membrane composed of a support layer and a filtration layer may be used, or a single layer composed of one uniform porous tube. It is good. Moreover, it is good also as a converging body which bent the hollow fiber membrane in U shape, opened both sides of the upper end, and was fixed with the fixing material. Furthermore, it is preferable that the cleaning liquid is cleaned using an alkaline cleaning liquid, but only back cleaning using the treated liquid may be performed.
Various forms within the scope of the present invention are included.
本発明に用いる被処理液としては、実施形態で述べた油田随伴水の処理用として好適に用いられるが、切削油剤等を含む工業排水の処理のほか、非水溶性油分を含む食品排水等にも適用することができる。   As the liquid to be treated used in the present invention, it is suitably used for the treatment of oilfield associated water described in the embodiment, but in addition to the treatment of industrial wastewater containing cutting oil, etc., food wastewater containing water-insoluble oil, etc. Can also be applied.
1、31、40、62 含油排水処理用の分離膜モジュール
20、30、60 含油排水処理装置
2、32、41 中空糸膜
3、33、42 集束体
6 外筒
8 導出用配管
10 導入用配管
12 循環用配管
21 含油排水貯留槽
22 洗浄液貯留槽
23 ポンプ
26 処理液貯留槽
OL 含油排水
AL アルカリ洗浄液
DESCRIPTION OF SYMBOLS 1, 31, 40, 62 Separation membrane module for oil-containing wastewater treatment 20, 30, 60 Oil-containing wastewater treatment device 2, 32, 41 Hollow fiber membrane 3, 33, 42 Converging body 6 Outer cylinder 8 Leading pipe 10 Introducing pipe 12 Pipe for Circulation 21 Oil-Containing Drainage Reservoir 22 Cleaning Liquid Reservoir 23 Pump 26 Treatment Liquid Reservoir OL Oil-Containing Drain AL Alkaline Cleaning Liquid

Claims (21)

  1. 高濁度あるいは/および高温の含油排水から非水溶性油分を分離する含油排水処理用の分離膜モジュールであって、
    PTFE(ポリテトラフルオロエチレン)、PSF(ポリスルホン)およびPES(ポリエーテルスルホン)から選択される耐アルカリ性を備えた多孔質膜からなり、抗張力が30N以上である中空糸膜を用い、
    前記中空糸膜の熱変形温度は100℃以上であり、
    前記該中空糸膜の端末封止材は、熱変形温度が100℃以上の熱硬化性樹脂、または融点が使用温度の1.5倍以上である熱溶融性樹脂からなることを特徴とする含油排水処理用の分離膜モジュール。
    A separation membrane module for oil-containing wastewater treatment that separates water-insoluble oil from high-turbidity or / and high-temperature oil-containing wastewater,
    Using a hollow membrane having an alkali resistance selected from PTFE (polytetrafluoroethylene), PSF (polysulfone) and PES (polyethersulfone), and having a tensile strength of 30 N or more,
    The hollow fiber membrane has a heat deformation temperature of 100 ° C. or higher,
    The hollow fiber membrane end-sealing material is composed of a thermosetting resin having a heat deformation temperature of 100 ° C. or higher, or a heat-melting resin having a melting point of 1.5 times or more of the use temperature. Separation membrane module for wastewater treatment.
  2. 前記濾過膜で濾過される前記含油排水は、20℃における粘度0.1〜5.0mPa・sの非水溶性油分を3mg/L〜2000mg/Lを含有する含油排水であり、前記濾過膜による濾過処理済み水の油分含有量を0.1mg/L〜10mg/Lとする請求項1に記載の含油排水処理用の分離膜モジュール。   The oil-containing wastewater filtered by the filtration membrane is an oil-containing wastewater containing 3 mg / L to 2000 mg / L of a water-insoluble oil having a viscosity of 0.1 to 5.0 mPa · s at 20 ° C., and depending on the filtration membrane. The separation membrane module for oil-containing wastewater treatment according to claim 1, wherein the oil content of the filtered water is 0.1 mg / L to 10 mg / L.
  3. 前記濾過膜で濾過される前記含油排水は懸濁物質の濃度は、5〜10000mg/Lである請求項1または請求項2に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to claim 1 or 2, wherein the oil-containing wastewater filtered by the filtration membrane has a suspended solid concentration of 5 to 10,000 mg / L.
  4. 前記濾過膜で濾過される前記含油排水の温度は60〜200℃である請求項1乃至請求項3のいずれか1項に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 3, wherein the temperature of the oil-containing wastewater filtered by the filtration membrane is 60 to 200 ° C.
  5. 前記中空糸膜は、単層、または支持層と該支持層の少なくとも外側に積層する濾過層を備えた多孔質複層あるいは非対称濾過膜である請求項1乃至請求項4のいずれか1項に記載の含油排水処理用の分離膜モジュール。   5. The hollow fiber membrane according to any one of claims 1 to 4, wherein the hollow fiber membrane is a single layer, or a porous multilayer or an asymmetric filtration membrane having a support layer and a filtration layer laminated at least outside the support layer. The separation membrane module for oil-containing wastewater treatment as described.
  6. 前記中空糸膜は前記抗張力が30N以上150N以下であり、IPAバブルポイントが50kPa以上400kPa以下である請求項1乃至請求項5のいずれか1項に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 5, wherein the hollow fiber membrane has a tensile strength of 30N to 150N and an IPA bubble point of 50kPa to 400kPa.
  7. 前記中空糸膜は多孔質延伸PTFEチューブに、多孔質延伸PTFEシート巻き付けた多孔質複層中空糸膜である請求項1乃至請求項6のいずれか1項に記載の含油排水処理用の分離膜モジュール。   The separation membrane for oil-containing wastewater treatment according to any one of claims 1 to 6, wherein the hollow fiber membrane is a porous multilayer hollow fiber membrane in which a porous expanded PTFE sheet is wound around a porous expanded PTFE tube. module.
  8. 前記中空糸膜の平均空孔径は0.01〜1μmである請求項1乃至請求項7のいずれか1項に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 7, wherein an average pore diameter of the hollow fiber membrane is 0.01 to 1 µm.
  9. 前記中空糸膜を複数本備えた集束体とし、該集束体を外筒内に収容しており、
    前記中空糸膜は一端開口、他端閉鎖とし、前記外筒内に前記含油排水を導入する導入部と、前記中空糸膜の一端開口と連通した濾過済み処理液の導出部と、濾過されなかった非濾過液の排出部を前記外筒に連通して備えた外圧濾過式または外圧循環濾過式とし、
    または、前記中空糸膜を両端開口とし、該中空糸膜の一端開口に前記含油排水を導入する導入部と、他端開口から濾過されなかった非濾過液を導出する排出部と、前記外筒内と連通した濾過済み処理液の導出部を備えた内圧濾過式または内圧循環濾過式とし、
    または、前記中空糸膜を複数本備えた集束体とし、該集束体を前記含油排水の浸漬槽中に配置し、前記中空糸膜は一端開口、他端閉鎖とし、前記中空糸膜の一端開口と連通した濾過済み処理液の導出部を備えた浸漬濾過式としている請求項1乃至請求項8のいずれか1項に記載の含油排水処理用の分離膜モジュール。
    A focusing body comprising a plurality of the hollow fiber membranes, the focusing body is accommodated in an outer cylinder,
    The hollow fiber membrane is open at one end and closed at the other end, an introduction portion for introducing the oil-containing drainage into the outer cylinder, a filtered treatment liquid outlet portion communicating with the one end opening of the hollow fiber membrane, and not filtered The non-filtrate discharge part is connected to the outer cylinder and is an external pressure filtration type or an external pressure circulation filtration type,
    Alternatively, the hollow fiber membrane is open at both ends, the introduction portion for introducing the oil-containing drainage into one end opening of the hollow fiber membrane, the discharge portion for leading the non-filtrated liquid not filtered from the other end opening, and the outer cylinder An internal pressure filtration type or an internal pressure circulation filtration type equipped with an outlet for the filtered treatment liquid communicating with the inside,
    Alternatively, a converging body provided with a plurality of the hollow fiber membranes, the converging body being disposed in the immersion tank of the oil-containing wastewater, the hollow fiber membrane being open at one end and the other end being closed, and being open at one end of the hollow fiber membrane The separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 8, wherein the separation membrane module is a submerged filtration type including a filtered treatment liquid lead-out portion in communication with the oil treatment waste water.
  10. 前記外圧濾過式または外圧循環濾過式として用いる前記中空糸膜は、外径1〜5mm、内径0.5〜4mm、気孔率30〜90%であり、
    前記内圧濾過式または内圧循環式としている用いる前記中空糸膜は、外径1.3〜20mm、内径1〜10mm、気孔率30〜90%である請求項9に記載の含油排水処理用の分離膜モジュール。
    The hollow fiber membrane used as the external pressure filtration type or external pressure circulation filtration type has an outer diameter of 1 to 5 mm, an inner diameter of 0.5 to 4 mm, and a porosity of 30 to 90%.
    The separation for oil-impregnated wastewater treatment according to claim 9, wherein the hollow fiber membrane used as the internal pressure filtration type or the internal pressure circulation type has an outer diameter of 1.3 to 20 mm, an inner diameter of 1 to 10 mm, and a porosity of 30 to 90%. Membrane module.
  11. 前記集束体における中空糸膜間の寸法平均値が0.5mm〜5mmである請求項9または請求項10に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to claim 9 or 10, wherein a dimensional average value between hollow fiber membranes in the converging body is 0.5 mm to 5 mm.
  12. 前記集束体の断面積に対する前記中空糸膜の充填率が20%〜60%である請求項9乃至請求項11のいずれか1項に記載の含油排水処理用の分離膜モジュール。   The separation membrane module for oil-containing wastewater treatment according to any one of claims 9 to 11, wherein a filling rate of the hollow fiber membrane with respect to a cross-sectional area of the converging body is 20% to 60%.
  13. 垂直方向に配置した中空糸膜の集束体の下部に、もしくは分離膜モジュールの外筒下部に接続される配管に対して散気用空気配管を配置し、かつ、前記処理済み液の導出部より中空糸膜の内部に処理済み液を逆洗浄液として加圧送液する逆洗浄手段を備えている請求項9乃至請求項12のいずれか1項に記載の含油排水処理用の分離膜モジュール。   An air pipe for aeration is arranged at the lower part of the concentrator of the hollow fiber membrane arranged in the vertical direction or the pipe connected to the lower part of the outer cylinder of the separation membrane module, and from the treated liquid outlet The separation membrane module for oil-containing wastewater treatment according to any one of claims 9 to 12, further comprising reverse cleaning means for pressure-feeding the treated liquid as a reverse cleaning liquid inside the hollow fiber membrane.
  14. 請求項1乃至請求項13のいずれか1項に記載の含油排水処理用の分離膜モジュールを用いた含油排水処理方法であって、
    非水溶性油分含有量(n−ヘキサン値)が3〜2000mg/Lである含油排水を、前記中空糸膜のIPAバブルポイントが50kPa以上100kPa未満で膜間差圧50kPa以下、前記IPAバブルポイントが100kPa以上150kPa未満で膜間差圧100kPa以下、前記IPAバブルポイントが150kPa以上400kPa以下で膜間差圧200kPa以下の濾過条件とし、含油排水の非水溶性油分含油量が10mg/L以上2000mg/L以下の場合は濾過処理済み水の非水溶性油分含有量を5mg/L未満、含油排水の非水溶性油分含油量が3mg/L以上10mg/L未満の場合は濾過処理済み水の非水溶性油分含有量を1mg/L未満としている含油排水処理方法。
    An oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 13,
    An oil-containing wastewater having a water-insoluble oil content (n-hexane value) of 3 to 2000 mg / L, the IPA bubble point of the hollow fiber membrane is 50 kPa or more and less than 100 kPa, the transmembrane pressure difference is 50 kPa or less, and the IPA bubble point is The filtration conditions are 100 kPa or more and less than 150 kPa and the transmembrane differential pressure is 100 kPa or less, the IPA bubble point is 150 kPa or more and 400 kPa or less and the transmembrane differential pressure is 200 kPa or less. In the following cases, the water-insoluble oil content of the filtered water is less than 5 mg / L, and the water-insoluble oil content of the oil-containing wastewater is 3 mg / L or more and less than 10 mg / L, water-insoluble in the filtered water An oil-containing wastewater treatment method in which the oil content is less than 1 mg / L.
  15. 請求項1乃至請求項13のいずれか1項に記載の含油排水処理用の分離膜モジュールを用いた含油排水処理方法であって、
    含油排水の非水溶性油分含有量が3〜200mg/L、かつ、懸濁物質(SS)の濃度が100mg/L以下は、被処理液の全量を中空糸膜を通過させる外圧式の全濾過とし、 含油排水の非水溶性油分含有量が200mg/Lを超えて2000mg/L以下、または懸濁物質(SS)が100〜20000mg/Lは、被処理液を循環させる内圧循環式または外圧循環式で濾過していることを特徴とする含油排水処理方法。
    An oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 13,
    When the water-insoluble oil content of the oil-containing wastewater is 3 to 200 mg / L and the concentration of the suspended solid (SS) is 100 mg / L or less, the total amount of liquid to be treated is externally filtered through the hollow fiber membrane. When the water-insoluble oil content of the oil-containing wastewater exceeds 200 mg / L and is 2000 mg / L or less, or the suspended solid (SS) is 100 to 20000 mg / L, the internal pressure circulation type or external pressure circulation for circulating the liquid to be treated An oil-containing wastewater treatment method characterized by being filtered by a formula.
  16. 請求項1乃至請求項13のいずれか1項に記載の含油排水処理用の分離膜モジュールを用いた含油排水処理方法であって、
    油田随伴水を前処理して非水溶性油分含有量(n−ヘキサン値)を低減した後の含油排水を前記分離膜モジュールで精密濾過している含油排水処理方法。
    An oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 13,
    An oil-containing wastewater treatment method in which oil-containing wastewater after pretreatment of oilfield-associated water and reducing the water-insoluble oil content (n-hexane value) is precisely filtered by the separation membrane module.
  17. 前記前処理が加圧浮上処理、電気凝集・電気浮上処理であり、その処理後のn−ヘキサン値が10〜100mg/Lである請求項16に記載の含油排水処理方法。   The oil-containing wastewater treatment method according to claim 16, wherein the pretreatment is pressure levitation treatment, electrocoagulation / electrolevitation treatment, and the n-hexane value after the treatment is 10 to 100 mg / L.
  18. 請求項1乃至請求項13のいずれか1項に記載の含油排水処理用の分離膜モジュールを用いた含油排水処理方法であって、
    前記含油排水は、加温含油排水は油含有量が20〜2000mg/L、懸濁成分の含有量が100〜10000mg/L、60〜200℃で加温されており、該含油排水を前記分離膜モジュールで濾過処理して、処理水中の非水溶性油分含有量を5mg/L以下、懸濁成分含有量を0〜1mg/Lとしている含油排水処理方法。
    An oil-containing wastewater treatment method using the separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 13,
    The oil-containing wastewater is heated at a temperature of 20-2000 mg / L, the content of suspended components is 100-10000 mg / L, 60-200 ° C., and the oil-containing wastewater is separated. An oil-containing wastewater treatment method in which a water-insoluble oil content in the treated water is 5 mg / L or less and a suspended component content is 0 to 1 mg / L by filtration with a membrane module.
  19. 請求項1乃至請求項13のいずれか1項に記載の含油排水処理用の分離膜モジュールを備えた濾過装置であって、
    前記分離膜モジュールの中空糸膜の表面に付着した非水溶性油分除去用として、アルカリ性水溶液からなる洗浄液を前記中空糸膜の表面に送液する洗浄手段を備えている含油排水処理装置。
    A filtration device comprising the separation membrane module for oil-containing wastewater treatment according to any one of claims 1 to 13,
    An oil-containing wastewater treatment apparatus comprising cleaning means for feeding a cleaning liquid made of an alkaline aqueous solution to the surface of the hollow fiber membrane for removing the water-insoluble oil adhering to the surface of the hollow fiber membrane of the separation membrane module.
  20. 含油排水貯留槽と、前記洗浄手段の洗浄液貯留槽と、前記含油排水貯留槽および洗浄液貯留槽と前記分離膜モジュールの導入部とを連通すると共にポンプを介設した導入用配管と、前記含油排水貯留槽および洗浄液貯留槽と前記分離膜モジュールの非処理液の排出部とを連通する循環用配管とを備え、
    前記導入用配管の分岐管および循環用配管の分岐管を、それぞれ前記含油排水貯留槽と洗浄液貯留槽に連通している請求項19に記載の含油排水処理装置。
    An oil-containing drainage storage tank, a cleaning liquid storage tank of the cleaning means, the oil-containing drainage storage tank and the cleaning liquid storage tank, and an introduction pipe having a pump interposed therebetween, and an introduction pipe connected to the separation membrane module, and the oil-containing drainage A circulation pipe that communicates the storage tank and the cleaning liquid storage tank and the discharge portion of the non-treatment liquid of the separation membrane module;
    20. The oil-containing wastewater treatment apparatus according to claim 19, wherein a branch pipe for the introduction pipe and a branch pipe for the circulation pipe are communicated with the oil-containing wastewater storage tank and the cleaning liquid storage tank, respectively.
  21. 前記導入用配管に介設した前記ポンプの吐出圧力は50〜300kPaとし、かつ、前記分岐管の分岐位置に切替弁を介設している請求項20に記載の含油排水処理装置。   21. The oil-containing wastewater treatment apparatus according to claim 20, wherein a discharge pressure of the pump provided in the introduction pipe is 50 to 300 kPa, and a switching valve is provided in a branch position of the branch pipe.
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