本發明係關於含油排水處理用之分離膜模組、使用該分離膜模組之含油排水處理方法及附設有分離膜模組的洗淨裝置之含油排水處理裝置，能長期有效率地將非水溶性油分從含油排水分離。The present invention relates to a separation membrane module for oily drainage treatment, an oily drainage treatment method using the separation membrane module, and an oily drainage treatment device for a cleaning device with a separation membrane module, which can efficiently and non-solutely dissolve for a long period of time. The oil is separated from the oily drainage.
習知，提供有從含有非水溶性油分之含油排水去除非水溶性油分之處理裝置及處理方法。It is known to provide a treatment apparatus and a treatment method for removing water-insoluble oil from an oil-containing drain containing water-insoluble oil.
油田含油汚水為含油排水的一種，必須將非水溶性油分從該油田含油汚水去除。亦即，原油開採時，一般會進行將海水注入地層中的油層，使非水溶性油分之壓力提高以確保生產量。由於被使用於這種原油開採的排水之「油田含油汚水」含有大量非水溶性油分，因此必須在進行非水溶性油分之去除處理後再加以廢棄。Oilfield oily sewage is a kind of oily drainage, and the water-insoluble oil must be removed from the oily wastewater of the oilfield. That is, when crude oil is mined, an oil layer that injects seawater into the formation is generally performed to increase the pressure of the water-insoluble oil to ensure production. Since the "oily oily sewage" used for the drainage of such crude oil contains a large amount of water-insoluble oil, it must be disposed of after the water-insoluble oil is removed.
但是，近年來，因成為引起海洋、湖沼等汚染之主要原因，所以逐漸加強排水中之非水溶性油分含量之限制，在最嚴格的國家和地區被要求非水溶性油分含量為未達5mg/L。However, in recent years, as a cause of pollution such as oceans and lakes, it has been stepped up to limit the amount of water-insoluble oil in the drainage. In the most stringent countries and regions, the water-insoluble oil content is required to be less than 5 mg/ L.
通常，油田含油汚水係經由藉由重力差分離、固/液水力旋流器等之固體分離後，再藉由板過濾器、液/液水力旋流器等之一次處理、利用凝聚沈澱/加壓浮選等之二次處理後，進行過濾或活性碳處理等之三次處理，但隨著一次、二次、三次處理和愈高次處理，處理水量則愈降低，因此有無法滿足被大量排出的油田含油汚水處理之問題。其結果，在大量排出之油田含油汚水處理中，精密的分離手段就其處理速度而言無法適用，結果據稱實際上極限是處理到非水溶性油分含量為20mg/L為止。又，處理成本也是問題所在。Generally, the oily oily water in the oil field is separated by solids such as gravity difference separation, solid/liquid hydrocyclone, and the like, and then treated by a plate filter, a liquid/liquid hydrocyclone, or the like, using coagulation sedimentation/addition. After secondary treatment such as pressure flotation, three treatments such as filtration or activated carbon treatment are performed, but with the treatment of primary, secondary, tertiary, and higher treatments, the amount of treated water is reduced, so that it is unable to satisfy a large amount of discharge. The problem of oily wastewater treatment in oil fields. As a result, in the treatment of oily sewage in a large amount of discharged oil fields, the precise separation means cannot be applied in terms of the processing speed, and as a result, it is said that the practical limit is to treat the water-insoluble oil content to 20 mg/L. Also, processing costs are also the problem.
因此，期待將分離膜模組利用於含油排水處理。分離膜模組具有可確保高處理水量，可進行高度之水處理的優點。例如，日本特開平5-245472號公報(專利文獻1)中，如第9圖所示提供一種處理方法，其係將含油排水100供給到具備有平均細孔徑比油粒子小的陶瓷分離膜101之過濾裝置102之一次側S1，從陶瓷分離膜101之二次側S2取出處理水並且將濃縮水循環供給到過濾裝置之一次側直到一次側之濃縮水成為既定濃度。Therefore, it is expected that the separation membrane module can be utilized for oily drainage treatment. The separation membrane module has the advantage of ensuring high treatment water volume and high water treatment. For example, Japanese Laid-Open Patent Publication No. Hei 5-245472 (Patent Document 1) provides a processing method for supplying an oil-containing drain 100 to a ceramic separation membrane 101 having an average pore diameter ratio oil particle as shown in FIG. The primary side S1 of the filtration device 102 takes out the treated water from the secondary side S2 of the ceramic separation membrane 101 and circulates the concentrated water to the primary side of the filtration device until the concentrated water on the primary side becomes a predetermined concentration.
[專利文獻1]日本特開平5-245472號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-245472
但是，在含油排水之持續處理中，非水溶性油分附著於分離膜的膜面會引起流量降低。因此，通常為了將非水溶性油分分解去除以持續進行過濾，必須進行使用氫氧化鈉等強鹼性藥劑之化學洗淨。但是，在分離膜使用陶瓷膜的專利文獻1中，對於在非水溶性油分之洗淨有效的高濃度鹼性水溶液之耐久性不充分，因而有無法充分地進行膜面之化學洗淨之問題。又，原本的物理強度較強，但因為當利用前述鹼等之藥液洗淨之累積頻率增加時，強度會開始劣化，雖然進行逆洗、散氣等物理洗淨實施時強度劣化很微量，但會受到負載之衝擊等的影響，亦容易產生因該衝擊而導致之龜裂等的問題。再者，在專利文獻1中由於分離膜為平膜，因此處理水量也會受到限制，不適於大量被排出之含油排水之持續處理。However, in the continuous treatment of the oil-containing drainage, the water-insoluble oil adheres to the membrane surface of the separation membrane to cause a decrease in flow rate. Therefore, in general, in order to decompose and remove the water-insoluble oil to continue filtration, it is necessary to perform chemical cleaning using a strong alkaline agent such as sodium hydroxide. However, in Patent Document 1 in which a ceramic membrane is used as the separation membrane, the durability of the high-concentration alkaline aqueous solution which is effective for washing the water-insoluble oil is insufficient, and thus the chemical cleaning of the membrane surface cannot be sufficiently performed. . In addition, the original physical strength is strong, but when the cumulative frequency of washing with the chemical solution such as the alkali is increased, the strength starts to deteriorate, and although the strength is deteriorated when performing physical washing such as backwashing and air diffusion, However, it is affected by the impact of the load, etc., and it is also likely to cause problems such as cracks due to the impact. Further, in Patent Document 1, since the separation membrane is a flat membrane, the amount of treated water is also limited, and it is not suitable for continuous treatment of a large amount of discharged oily drainage.
又，現在，耐藥品性優異之市售偏二氟乙烯(PVDF)所構成之分離膜亦與前述陶瓷膜同様，缺乏對高濃度鹼性水溶液之耐久性，由聚乙烯、聚丙烯所構成的分離膜有物理性強度不足之問題。Moreover, the separation membrane composed of commercially available vinylidene fluoride (PVDF) excellent in chemical resistance is also the same as the above-mentioned ceramic membrane, and lacks durability against a high-concentration alkaline aqueous solution, and is composed of polyethylene and polypropylene. The separation membrane has a problem of insufficient physical strength.
又，在不會造成加溫後之含油排水在溫度降低的情況下進行分離處理的裝置中，耐熱性及停止時之低溫和加熱時之高溫周期性地重複，對於含油排水處理裝置之設置場所，例如在寒冷地區低溫和高溫之差為100℃以上之熱循環也要求具有耐性。Further, in the apparatus which does not cause the oil-containing drainage after heating to be separated in the case where the temperature is lowered, the heat resistance and the low temperature at the time of stopping and the high temperature during heating are periodically repeated, and the installation place of the oil-containing drainage treatment apparatus is provided. For example, in a cold region, a thermal cycle in which the difference between low temperature and high temperature is 100 ° C or more is also required to have resistance.
但是，以往廣泛作為油水分離處理使用之樹脂製過濾膜的耐熱性不充分。However, the resin filter membrane which has been widely used as the oil-water separation treatment in the past has insufficient heat resistance.
例如，在PP、PE、PVDE中，若經常供給60℃以上之加熱含油排水，則軟化後孔徑會改變，在PE中容易產生破裂。For example, in PP, PE, and PVDE, if the oil-containing drainage water of 60 ° C or more is often supplied, the pore diameter changes after softening, and cracking easily occurs in the PE.
再者，習知使用的高溫油水分離裝置亦有以陶瓷粉末燒結體形成之情形，但該情形中，雖具有耐熱性但有重量増加等的問題，且在前述熱循環之溫度變化時受到熱障而容易產龜裂等。Further, the high-temperature oil-water separator used in the prior art may be formed of a ceramic powder sintered body. However, in this case, although it has heat resistance, it has a problem of weight increase, and is heated when the temperature of the heat cycle changes. It is easy to produce cracks and so on.
而且，具備陶瓷製分離裝置之習知裝置，由於每一膜面積之膜單元容積大，因而必須有較多的設置面積，另一方面也因此會有將膜裝置作成多段之情形，但是會成為裝置全體重量大的大型裝置，在洗淨時或檢査時，會有不易取下過濾裝置的問題。Further, in the conventional device including the ceramic separation device, since the membrane unit volume per membrane area is large, it is necessary to have a large installation area, and on the other hand, there is a case where the membrane device is formed in a plurality of stages, but it becomes A large-sized device having a large overall weight may have a problem that it is difficult to remove the filter device during cleaning or inspection.
本發明係鑒於前述問題而開發者，其課題在於對含油排水具有高性能的過濾性能，且對可有效去除非水溶性油分的鹼具有耐久性並能重複再生，更且耐熱性優異、能長期使高性能過濾持續進行。The present invention has been made in view of the above problems, and has an object of providing high performance filtration performance to oil-containing drainage, durability to a base capable of effectively removing water-insoluble oil, repeated regeneration, and excellent heat resistance and long-term durability. Enable high performance filtration.
為了解決前述課題，第一發明係一種含油排水處理用之分離膜模組，係將非水溶性油分自高濁度或/及高溫之含油排水分離的含油排水處理用之分離膜模組，其特徵為：使用由選自PTFE(聚四氟乙烯)、PSF(聚碸)及PES(聚醚碸)之具有耐鹼性的多孔質膜所構成且抗張力為30N以上之中空絲膜，前述中空絲膜之熱變形溫度為100℃以上，前述該中空絲膜的末端封止材係由熱變形溫度為100℃以上之熱硬化性樹脂、或熔點為使用溫度的1.5倍以上之熱熔融性樹脂所構成。In order to solve the above problems, the first invention is a separation membrane module for oil-containing drainage treatment, which is a separation membrane module for oil-containing drainage treatment in which water-insoluble oil is separated from high-turbidity and/or high-temperature oil-containing drainage. It is characterized in that a hollow fiber membrane composed of a porous membrane having alkali resistance selected from the group consisting of PTFE (polytetrafluoroethylene), PSF (polyfluorene) and PES (polyether oxime) and having a tensile strength of 30 N or more is used. The thermal deformation temperature of the silk film is 100° C. or higher, and the end sealing material of the hollow fiber membrane is a thermosetting resin having a heat distortion temperature of 100° C. or more or a hot melt resin having a melting point of 1.5 times or more the use temperature. Composition.
本發明人等發現，於將非水溶性油分從高濁度、高溫之含油排水分離之情形，使用之選自PTFE(聚四氟乙烯)、PSF(聚碸)、PES(聚醚碸)之多孔質分離膜的中空絲或平膜之分離膜模組，具備極為優異之非水溶性油分去除性能和耐藥性、特別是耐鹼性，且兼具耐久(發揮正常過濾性能的可使用期間)。其結果，可一面實現可降低非水溶性油分含量之至未達5mg/L，進一步為未達1mg/L之低濃度之高性能過濾，一面藉由利用鹼性水溶液之化學洗淨將附著於膜面之非水溶性油分溶解去除並可重複再生，因此能長期使高性能過濾持續進行。The present inventors have found that in the case of separating the water-insoluble oil component from the high turbidity and high-temperature oil-containing drainage, the use is selected from the group consisting of PTFE (polytetrafluoroethylene), PSF (polyfluorene), and PES (polyether oxime). The hollow fiber or flat membrane separation membrane module of the porous separation membrane has excellent water-insoluble oil removal performance and chemical resistance, particularly alkali resistance, and is durable (useful period of normal filtration performance) ). As a result, high-performance filtration which can reduce the water-insoluble oil content to less than 5 mg/L and further to a low concentration of less than 1 mg/L can be achieved while being chemically washed by using an alkaline aqueous solution. The water-insoluble oil of the membrane surface is dissolved and removed, and can be repeatedly regenerated, so that high-performance filtration can be continued for a long period of time.
構成前述過濾膜之PTFE(聚四氟乙烯)、PSF(聚碸)、PES(聚醚碸)的抗張力在25℃下，具備30N以上之強度。因此，即使以高濃度鹼性洗淨液重複過濾，過濾性能及強度亦不會降低，且能長期使高性能過濾持續進行。抗張力較佳為50N以上，上限為150N左右。The tensile strength of PTFE (polytetrafluoroethylene), PSF (polyfluorene), and PES (polyether oxime) constituting the filtration membrane is 30 N or more at 25 ° C. Therefore, even if the filtration is repeated with a high-concentration alkaline washing liquid, the filtration performance and strength are not lowered, and high-performance filtration can be continued for a long period of time. The tensile strength is preferably 50 N or more, and the upper limit is about 150 N.
此外，抗張力係以JIS K7161為依據，使用中空絲膜本身作為實驗體。實驗時，以拉伸速度為100mm/分鐘，標線間距離為50mm作測量。Further, the tensile strength is based on JIS K7161, and the hollow fiber membrane itself is used as an experimental body. In the experiment, the measurement was carried out at a stretching speed of 100 mm/min and a distance between the marking lines of 50 mm.
又，構成前述過濾膜之PTFE(聚四氟乙烯)、PSF(聚碸)、PES(聚醚碸)之熱變形溫度為100℃以上。具體而言，PTFE為121℃、PSF為181℃、PES為210℃。該熱變形溫度可依處理之含油排水溫度選擇上述膜。Further, the heat distortion temperature of PTFE (polytetrafluoroethylene), PSF (polyfluorene), and PES (polyether oxime) constituting the filtration membrane is 100 ° C or higher. Specifically, PTFE was 121 ° C, PSF was 181 ° C, and PES was 210 ° C. The heat distortion temperature can be selected from the above-mentioned film depending on the oil-containing drainage temperature to be treated.
又，過濾膜的末端封止材亦使用與前述過濾膜之形成材同様的熱變形溫度為100℃以上之樹脂，或者熱熔融性樹脂中耐熱溫度高之氟系樹脂形成。Further, the end seal material of the filtration membrane is also formed of a resin having a heat distortion temperature of 100 ° C or higher, or a fluorine resin having a high heat resistance temperature in the hot melt resin.
如此地，將過濾膜及末端封止材作成為耐熱性，因此即使常年使用使作為加熱含油排水之過濾膜，亦不易產生熱劣化。As described above, since the filtration membrane and the terminal sealing material are made heat-resistant, even if the filtration membrane which is a heating oil-containing drainage is used for many years, thermal deterioration is unlikely to occur.
利用前述過濾膜過濾之前述含油排水係含有：於40℃下動態黏度為1~600cSt，且於15℃下密度為0.7~1.0g/cm3之非水溶性油分較佳。該含油排水以60℃~200℃，較佳為以100℃~200℃過濾時，能將非水溶性油分以低黏度化的方式過濾。The oil-containing drainage system filtered by the filtration membrane preferably contains a water-insoluble oil having a dynamic viscosity of 1 to 600 cSt at 40 ° C and a density of 0.7 to 1.0 g/cm3 at 15 ° C. When the oil-containing drainage is filtered at 60 ° C to 200 ° C, preferably at 100 ° C to 200 ° C, the water-insoluble oil can be filtered in a low viscosity manner.
亦可適當使用非水溶性油分在20℃下黏度為0.1~5.0mPa.s之情況。已利用前述過濾膜進行過濾處理之水的油分含量為10mg/L~0.1mg/L。另一方面，排水之溫度為100℃等高溫之情形，由於黏度會降低，因此在常溫環境中黏度更大者亦可過濾。It is also possible to suitably use a water-insoluble oil having a viscosity of 0.1 to 5.0 mPa·s at 20 ° C. The water content of the water which has been subjected to the filtration treatment using the aforementioned filtration membrane is from 10 mg/L to 0.1 mg/L. On the other hand, in the case where the temperature of the drainage is a high temperature such as 100 ° C, since the viscosity is lowered, it is also possible to filter even if the viscosity is higher in a normal temperature environment.
將利用本發明之含油排水處理用分離膜模組處理之含油排水之動態黏度或者黏度設定在前述範圍，係因超過前述範圍時，對多孔質材料之附著力會變大，進而產生不可挽回的膜阻塞而不易確保充分的處理水量之故。另一方面，係因未達前述範圍時，微小的非水溶性油分彼此會結合而粗大化，不易粒子化之故。The dynamic viscosity or viscosity of the oil-containing drainage treated by the separation membrane module for oil-containing drainage treatment of the present invention is set within the above range, and when it exceeds the above range, the adhesion to the porous material becomes large, thereby causing irreparable Membrane occlusion does not easily ensure adequate treatment of water. On the other hand, when the above range is not reached, the minute water-insoluble oil components are combined and coarsened, and it is difficult to form particles.
含油排水所含有之非水溶性油分，只要是在前述黏度範圍且在水中與水分離形成粒子之非水溶性物質皆可，可舉出以石腦油等為主之石油系烴系溶劑。The water-insoluble oil component contained in the oil-containing water-containing water may be a water-insoluble hydrocarbon-based solvent mainly composed of naphtha or the like, as long as it is a water-insoluble substance which is separated from water by water in the above-mentioned viscosity range.
如後所述，前述含油排水係以可將可利用重量分離等分離之浮選油等預先去除，將非水溶性油分含量調整為10~2000mg/L，前述非水溶性油分係以微米(micron)到次微米(submicron)等級粒徑之微粒子於分散油狀態下存在於水中者較佳。As described later, the oil-containing drainage system is previously removed by a flotation oil or the like which can be separated by a usable weight separation, and the water-insoluble oil content is adjusted to 10 to 2000 mg/L, and the water-insoluble oil is divided into micrometers (micron). It is preferred that the fine particles of the submicron grade particle size are present in the dispersed oil state.
此外，前述非水溶性油分之黏度，係在20℃下使用英弘精機製黏彈性測量裝置(Rheomater)測量者。Further, the viscosity of the aforementioned water-insoluble oil component was measured at 20 ° C using an Invitrogen viscoelasticity measuring device (Rheomater).
又，利用前述過濾膜過濾之前述含油排水，適用於懸浮物質之濃度為5~20000mg/L，特別是100mm g/L以上的高濁度之含油排水。Further, the oil-containing drainage filtered by the filtration membrane is suitable for high-turbidity oily drainage having a suspended substance concentration of 5 to 20,000 mg/L, particularly 100 mm g/L or more.
如前述，亦可適用於利用過濾膜進行過濾之前述含油排水的溫度為經60~200℃加熱之高溫含油排水的情形。本發明中，因應含油排水之溫度，過濾膜及末端封止材具有於含油排水溫度下不會產生熱變形之耐熱溫度。As described above, it is also applicable to the case where the temperature of the oil-containing drainage filtered by the filtration membrane is a high-temperature oil-containing drainage heated at 60 to 200 °C. In the present invention, the filter membrane and the end sealant have a heat-resistant temperature which does not cause thermal deformation at the oil-containing drain temperature in response to the temperature of the oil-containing drain.
前述中空絲膜亦可為單層、或是具備支持層和層積在該支持層之至少外側的過濾層之多孔質複層或非對稱過濾膜之任一者。The hollow fiber membrane may be a single layer or a porous composite layer or an asymmetric filtration membrane having a support layer and a filtration layer laminated on at least the outer side of the support layer.
前述過濾膜之平均空孔徑以設成0.01~1μm較佳。The average pore diameter of the filtration membrane is preferably 0.01 to 1 μm.
前述中空絲膜係係以在中空絲膜全體具備內徑0.3~12mm、外徑0.8~14mm、起泡點50~400kPa、膜厚0.2~1mm、氣孔率30~90%、最大容許膜間壓差為0.1~1.0MPa之耐壓性者為佳。The hollow fiber membrane system 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 pressure in the entire hollow fiber membrane system. The pressure resistance of 0.1 to 1.0 MPa is preferred.
起泡點和前述同様，使用異丙醇(IPA)，以JIS K 3832所記載之方法為依據，實驗體係使用中空絲膜本身。The foaming point and the above-mentioned homogenate were based on the method described in JIS K 3832 using isopropyl alcohol (IPA), and the hollow fiber membrane itself was used in the experimental system.
中空絲膜之氣孔率係藉由阿基米德法求出。算出時，PTFE之比重為2.17。The porosity of the hollow fiber membrane was determined by the Archimedes method. When calculated, the specific gravity of PTFE was 2.17.
最大容許膜間壓差之測量在內壓過濾式之情況，係於中空絲膜面塗布矽油脂等且將加壓面非多孔化後，將分散有1500mg/l氫氧化鐵粒子之水作為媒體負載內壓。於負載前後之膜尺寸實質上沒有變化之範圍內，以每10kPa測量膜之1次側/2次側的壓力差。Measurement of the maximum allowable inter-membrane pressure difference In the case of the internal pressure filtration type, the surface of the hollow fiber membrane is coated with grease, etc., and the pressurized surface is non-porous, and the water in which 1500 mg/l of iron hydroxide particles are dispersed is used as a medium. Internal pressure of the load. The pressure difference between the primary side and the secondary side of the film was measured every 10 kPa within a range in which the film size before and after the load did not substantially change.
於外壓過濾式之情況，係將中空絲膜之兩端以預定長度於拘束狀態下固定，於使透過管內側之水從兩端流出的狀態下，於管外面相同地塗布有矽油脂之狀態下，將其收納在被密閉之外殼內並施加水壓。此時，當管開放負載壓力後，以每10kPa測量恢復到加壓前的外徑時之最大壓力。In the case of the external pressure filtration type, both ends of the hollow fiber membrane are fixed in a restrained state with a predetermined length, and in the state in which the water inside the permeation tube flows out from both ends, the crucible is similarly coated on the outside of the tube. In the state, it is housed in a sealed outer casing and water pressure is applied. At this time, when the tube is opened to the load pressure, the maximum pressure at the time of returning to the outer diameter before pressurization is measured every 10 kPa.
前述中空絲膜只要具備耐鹼性並且具有前述起泡點、氣孔率、最大容許膜間壓差者即可，如前述般，亦可為單層、複層之任一種中空絲膜。特別是在具有耐鹼性，且於強度、耐久性優異方面，該中空絲膜以多孔質延伸PTFE製為佳。The hollow fiber membrane may have any of the above-mentioned foaming point, porosity, and maximum allowable inter-membrane pressure difference as long as it has alkali resistance. As described above, it may be a single-layer or multi-layer hollow fiber membrane. In particular, in order to have alkali resistance and to be excellent in strength and durability, the hollow fiber membrane is preferably made of porous expanded PTFE.
前述中空絲膜係以於25℃下抗張力為30N以上、150N以下，IPA起泡點為50kPa以上、400kPa以下較佳。The hollow fiber membrane has a tensile strength of 30 N or more and 150 N or less at 25 ° C, and preferably has an IPA foaming point of 50 kPa or more and 400 kPa or less.
將前述中空絲膜之IPA起泡點設為50kPa以上、400kPa以下，係因若低於50kPa，則孔徑過大，無法獲得液狀非水溶性油分通過前述多孔質膜之孔的非水溶性油分含量為未達5mg/L之已處理的水。另一方面，若超過400kPa，則孔徑過小而不易確保處理水量，而且使用於膜之化學洗淨的洗淨液之浸透性差，因此洗淨恢復差。When the IPA foaming point of the hollow fiber membrane is 50 kPa or more and 400 kPa or less, if the pore diameter is less than 50 kPa, the pore diameter is too large, and the water-insoluble oil content of the liquid water-insoluble oil passing through the pores of the porous membrane cannot be obtained. It is less than 5 mg/L of treated water. On the other hand, when it exceeds 400 kPa, the pore diameter is too small, the amount of treated water is easily secured, and the permeability of the cleaning liquid used for chemical cleaning of the membrane is poor, so that the washing recovery is poor.
IPA起泡點之下限值較佳為80kPa以上，更佳為100kPa以上，上限值較佳為380kPa以下，更佳為350kPa以下。The lower limit of the IPA bubble point is preferably 80 kPa or more, more preferably 100 kPa or more, and the upper limit is preferably 380 kPa or less, more preferably 350 kPa or less.
此外，IPA起泡點係使用異丙醇(IPA)，以JIS K 3832記載之方法為依據，實驗體係使用中空絲膜本身。Further, the IPA foaming point was based on isopropyl alcohol (IPA), which was based on the method described in JIS K 3832, and the hollow fiber membrane itself was used in the experimental system.
作為前述中空絲膜而言，可適用在作為支持層之多孔質延伸PTFE管捲繞有作為過濾層之多孔質延伸PTFE薄片之多孔質複層中空絲膜。As the hollow fiber membrane, a porous multi-layer hollow fiber membrane in which a porous stretched PTFE sheet as a filtration layer is wound around a porous stretched PTFE tube as a support layer can be applied.
在前述PTFE多孔質複層中空絲膜中，將作為外層之過濾層設為薄片之捲繞構造，係因多孔質薄片容易一起作單軸向延伸、雙軸向延伸，表面之空孔形狀或大小等較容易調整，且在薄膜之層積亦容易進行。將內層支持層設為壓出成形之管，成形性亦佳，具有某種程度之厚度且容易具有充分強度，空孔率亦容易變大。In the PTFE porous multi-layer hollow fiber membrane, the filter layer as the outer layer is a sheet-like winding structure, and the porous sheet is easily uniaxially stretched and biaxially stretched together, and the pore shape of the surface or The size and the like are easier to adjust, and the lamination of the film is also easy. The inner support layer is a tube for extrusion molding, and the moldability is also good, and it has a certain thickness and is easy to have sufficient strength, and the porosity is also likely to become large.
只要支持層、過濾層一起至少作單軸向延伸即可，可朝向管之軸方向、圓周方向或徑方向等延伸，亦可朝向軸方向等單軸、或軸方向和圓周方向之雙軸等。延伸倍率可適當設定，但於壓出成形管的情況，在軸方向可設為50%~700%，在圓周方向可設為5%~100%，於多孔質薄膜的情況，在長邊方向可設為50%~1000%，在横方向可設為50%~2500%。特別是在使用多孔質延伸PTFE薄片時，横方向之延伸容易，因此在捲繞成管狀時，可提高圓周方向之強度，而可提高對於因散氣等造成的膜搖動或因逆洗淨造成的壓力負載之耐久性。As long as the support layer and the filter layer are at least uniaxially extended, they may extend in the axial direction, the circumferential direction, the radial direction, or the like of the tube, or may be oriented in a single axis such as an axial direction, or an axial direction, a biaxial direction in the circumferential direction, or the like. . The stretching ratio can be appropriately set. However, in the case of extruding the formed tube, it can be 50% to 700% in the axial direction and 5% to 100% in the circumferential direction, and in the case of the porous film in the longitudinal direction. It can be set to 50% to 1000%, and can be set to 50% to 2500% in the horizontal direction. In particular, when a porous stretched PTFE sheet is used, the elongation in the transverse direction is easy. Therefore, when it is wound into a tubular shape, the strength in the circumferential direction can be increased, and the film shake due to gas diffusion or the like can be improved. The durability of the pressure load.
再者，由多孔質延伸PTFE製之管所構成的支持層和過濾層係一體化，互相之空孔係連通成三次元，因此可獲得良好之透過性。Further, the support layer and the filter layer composed of the tube made of the porous stretched PTFE are integrated, and the pores of the two are connected to each other to form a three-dimensional element, so that good permeability can be obtained.
於過濾層之外周面存在多數的各空孔之平均最大長度，係比藉由在支持層中存在多數的纖維狀骨架所包圍之各空孔的平均最大長度還小。具體而言，以將過濾層之空孔的平均長度，設為前述支持層之空孔平均長度的1%~30%為佳，以盡量小為佳。藉此，可提高從外周面側朝內周面側之透過性。The average maximum length of each of the plurality of pores on the outer surface of the filter layer is smaller than the average maximum length of each of the pores surrounded by the plurality of fibrous skeletons in the support layer. Specifically, it is preferable that the average length of the pores of the filter layer is 1% to 30% of the average pore length of the support layer, and it is preferably as small as possible. Thereby, the permeability from the outer peripheral surface side to the inner peripheral surface side can be improved.
在過濾層之外表面，前述空孔對該外表面的全表面積之面積佔有率，以藉由畫像處理測量而成為30%~90%較佳。即使空孔之最大長度小，若空孔之面積佔有率某種程度較大時，亦不會減少流量，可有效率地提高過濾性能。On the outer surface of the filter layer, the area ratio of the total surface area of the outer surface to the outer surface is preferably 30% to 90% as measured by image processing. Even if the maximum length of the pores is small, if the area occupancy ratio of the pores is somewhat large, the flow rate is not reduced, and the filtration performance can be efficiently improved.
具體而言，以過濾層之空孔率為30%~80%、支持層之空孔率為50%~85%較佳。藉此，能夠一面保持與強度之平衡，一面進一步提高從中空絲膜之外周面側朝內周面側之透過性。若空孔率過小則流量容易降低，若空孔率過大則強度容易降低。Specifically, the porosity of the filter layer is 30% to 80%, and the porosity of the support layer is preferably 50% to 85%. Thereby, the permeability from the outer peripheral surface side to the inner peripheral surface side of the hollow fiber membrane can be further improved while maintaining the balance with the strength. If the porosity is too small, the flow rate is liable to decrease, and if the porosity is too large, the strength is liable to lower.
過濾層之厚度以5μm~100μm為佳。其係因若是小於前述範圍則難以形成過濾層，而即使大於前述範圍也難以期待對提高過濾性能有所影響。支持層之厚度以0.1mm~5mm為佳。藉此，在軸方向、徑方向、圓周方向之任一者皆可獲得良好之強度，可提高對內外壓或彎曲等之耐久性。此外，支持層之內徑以0.3mm~12mm mm為佳。The thickness of the filter layer is preferably from 5 μm to 100 μm. If it is less than the above range, it is difficult to form a filtration layer, and even if it is larger than the above range, it is difficult to expect an influence on the filtration performance. The thickness of the support layer is preferably 0.1 mm to 5 mm. Thereby, good strength can be obtained in any of the axial direction, the radial direction, and the circumferential direction, and durability against internal and external pressure, bending, and the like can be improved. Further, the inner diameter of the support layer is preferably 0.3 mm to 12 mm mm.
本發明之含油排水處理用之分離膜模組亦可為外壓式、外壓循環式、內壓式、內壓循環式、浸漬式之任一種。The separation membrane module for oil-containing drainage treatment of the present invention may be any of external pressure type, external pressure circulation type, internal pressure type, internal pressure circulation type, and immersion type.
具體而言，其具備由複數條前述中空絲膜構成之集束體，且將該集束體收容於外筒內，其作成為外壓過濾式或外壓循環過濾式，其中前述中空絲膜為一端開口、另一端封閉，具備用以將前述含油排水導入前述外筒內的導入部、以及與前述中空絲膜之一端開口連通之已過濾之處理液的導出部，且將未經過濾之非過濾液的排出部連通設置於前述外筒。Specifically, the present invention includes a bundle body comprising a plurality of the hollow fiber membranes, and the bundle body is housed in an outer cylinder, and is configured as an external pressure filtration type or an external pressure circulation filtration type, wherein the hollow fiber membrane is one end. The opening and the other end are closed, and have an introduction portion for introducing the oil-containing drainage into the outer cylinder, and a lead-out portion of the filtered treatment liquid that is open to communicate with one end of the hollow fiber membrane, and the unfiltered non-filter The liquid discharge portion is connected to the outer cylinder.
或者，亦可作成為內壓過濾式或內壓循環過濾式，其中前述中空絲膜為兩端開口，且具備從該中空絲膜之一端開口導入前述含油排水的導入部、從另一端開口導出未經過濾之非過濾液的排出部、以及與前述外筒內連通之已過濾之處理液的導出部。Alternatively, it may be an internal pressure filtration type or an internal pressure circulation filtration type, wherein the hollow fiber membrane is open at both ends, and has an introduction portion for introducing the oil-containing drainage from one end opening of the hollow fiber membrane, and is derived from the other end opening. a non-filtered discharge portion that is not filtered, and a discharge portion of the filtered treatment liquid that communicates with the inside of the outer cylinder.
於作成為浸漬過濾式之情況下，具備由複數條前述中空絲膜構成之集束體，將該集束體配置在前述含油排水的浸漬槽中，前述中空絲膜為一端開口、另一端封閉，且具備與前述中空絲膜之一端開口連通之已過濾之處理液的導出部。In the case of the immersion filtration type, a bundle body comprising a plurality of the hollow fiber membranes is disposed, and the bundle body is disposed in the immersion tank of the oil-containing drain, wherein the hollow fiber membrane is open at one end and closed at the other end. A lead-out portion having a filtered treatment liquid that is in communication with one end of the hollow fiber membrane is provided.
作為前述外壓過濾式或外壓循環過濾式使用之前述中空絲膜以外徑1~5mm、內徑0.5~4mm、氣孔率30~90%為佳。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%.
作為前述內壓過濾式或內壓循環式使用之前述中空絲膜以外徑1.3~20mm、內徑1~10mm、氣孔率30~90%為佳。The hollow fiber membrane used as the internal pressure filtration type or the 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%.
前述中空絲膜之集束體係具備500~8000左右之多數條耐藥品性和非水溶性油分的過濾性能優異之中空絲膜。The bundle system of the hollow fiber membranes has a plurality of hollow fiber membranes having excellent chemical resistance and water-soluble oil filtration performance of about 500 to 8,000.
該集束體中的中空絲膜充填率以設定為20~60%左右，擴大相鄰的中空絲之尺寸，使含油排水的流通路得以確保為佳。The filling rate of the hollow fiber membrane in the bundle is set to about 20 to 60%, and the size of the adjacent hollow fiber is enlarged to ensure the flow passage of the oil-containing drainage.
於將分離膜模組作成為使含油排水從中空絲膜的外側朝內側通過之外壓過濾式，使未經過濾之含油排水再度循環於分離膜模組之外壓循環式的情形下，可利用被處理液之流動剝除中空絲膜膜面之汚垢。因此，即使被處理液之非水溶性油分含量或懸浮物質之濃度高，仍可一面抑制膜面之汚垢或阻塞，一面持續過濾。在液體之過濾容易且不易阻塞之情形下，亦可作成為不使被處理液循環的全過濾外壓式。The separation membrane module is configured to pass the oil-containing drainage from the outer side of the hollow fiber membrane to the inner side through the external pressure filtration type, so that the unfiltered oil-containing drainage is recirculated to the separation membrane module outside the pressure circulation type, The dirt of the hollow fiber membrane surface is removed by the flow of the treated liquid. Therefore, even if the water-insoluble oil content of the liquid to be treated or the concentration of the suspended matter is high, it is possible to continue the filtration while suppressing the dirt or clogging of the film surface. In the case where the filtration of the liquid is easy and it is not easy to block, it may be a full filtration external pressure type which does not circulate the liquid to be treated.
另一方面，亦可作成內壓過濾、或者內壓循環過濾式，其等係於原水中的粒子較支持層的孔徑大很多之情形下，使已處理的水從中空絲膜的內側朝向外側透過。On the other hand, it may be used as an internal pressure filtration or an internal pressure circulation filtration type, in which the particles in the raw water are much larger than the pore diameter of the support layer, and the treated water is directed from the inside to the outside of the hollow fiber membrane. Through.
於處理對象之含油排水為高濁度且高溫之情形下，以將前述集束體中相鄰的中空絲膜之外周間的最短距離設成較廣之0.5mm~5mm為佳。又，前述中空絲膜對前述集束體的剖面積之充填率以20%~60%較佳。In the case where the oil-containing drainage to be treated is high in turbidity and high in temperature, it is preferable to set the shortest distance between the outer circumferences of the adjacent hollow fiber membranes in the above-mentioned bundle to be wider 0.5 mm to 5 mm. Further, the filling rate of the hollow fiber membrane to the cross-sectional area of the aggregate body is preferably 20% to 60%.
如此地藉由使中空絲膜間的分離尺寸較大，能一面抑制高濁度之含油排水在中空絲膜間產生阻塞，一面使高濁度之含油排水流動。By making the separation size between the hollow fiber membranes large, it is possible to prevent the high-turbidity oil-containing drainage from flowing between the hollow fiber membranes while suppressing the high-turbidity oil-containing drainage.
本發明中，如後述般，為了以鹼性水溶液洗淨中空絲膜，期待中空絲膜以外之固定材、集水集管、封止用樹脂、被處理液導入管及外筒等其他構件也用耐鹼性樹脂形成。In the present invention, in order to wash the hollow fiber membrane with an alkaline aqueous solution, it is expected that other components such as a fixing material, a water collecting header, a sealing resin, a liquid to be treated, and an outer cylinder other than the hollow fiber membrane are also used. It is formed with an alkali-resistant resin.
具體而言，關於將中空絲膜之一端開口封閉並且固定作為集束體的封止材、將中空絲膜之另一端開口固定為開口狀態之固定材，可使用環氧樹脂、聚氨酯樹脂、矽樹脂(橡膠)、不飽和聚酯樹脂等熱硬化性樹脂，或者使用聚烯烴樹脂、氟樹脂等熱可塑性樹脂。Specifically, regarding the sealing material which closes one end opening of the hollow fiber membrane and fixes the sealing material as a bundle body, and fixes the other end opening of the hollow fiber membrane to an open state, an epoxy resin, a urethane resin, a tantalum resin can be used. A thermosetting resin such as (rubber) or an unsaturated polyester resin, or a thermoplastic resin such as a polyolefin resin or a fluororesin.
關於前述外筒，以利用不銹鋼等金屬材料或ABS樹脂、PVC、FRP、PTFE、PSF、PES及PEEK等工程塑膠成形為佳。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.
配管或其附屬零件等同樣是以不銹鋼、PVC等構成。The piping or its accessory parts are also made of stainless steel, PVC, or the like.
構成前述中空絲膜模組之構件，為熱硬化性樹脂之情形係具有熱變形溫度為100℃以上之耐熱性者，或者為熱熔融性樹脂之情形係具有其熔點為使用溫度之1.5倍者。The member constituting the hollow fiber membrane module is a thermosetting resin having a heat distortion temperature of 100 ° C or higher, or a hot melt resin having a melting point of 1.5 times the use temperature. .
又，本發明之分離膜模組具備逆洗淨手段，其係於配置在垂直方向之中空絲膜的集束體下部，配置散氣用空氣配管，且自前述經處理之液體的導出部，將該經處理之液體作為逆洗淨液加壓送液至中空絲膜內部。Moreover, the separation membrane module of the present invention is provided with a reverse cleaning means for arranging a gas pipe for a gas distribution in a lower portion of a bundle body disposed in a vertical direction of the hollow fiber membrane, and from the outlet portion of the liquid to be treated The treated liquid is pressurized as a reverse washing liquid to the inside of the hollow fiber membrane.
藉由具備上述散氣用空氣配管，於通常的過濾運轉時，可從分離膜模組的下部或被連接在模組下部之配管，產生散氣用氣泡，而藉由使中空絲膜揺動的方式，可振落附著在中空絲膜外面的微粒子。By providing the above-described air-discharging air pipe, in the normal filtration operation, air bubbles can be generated from the lower portion of the separation membrane module or the pipe connected to the lower portion of the module, and the hollow fiber membrane can be moved by In a manner, the particles attached to the outside of the hollow fiber membrane can be shaken off.
又，定期地將已處理之液體作為逆洗淨水加壓送液至分離膜模組之中空絲膜內部，藉由進行逆洗淨，能謀求過濾性能之持續。Further, the treated liquid is periodically supplied as a backwash water to the inside of the hollow fiber membrane of the separation membrane module, and by performing reverse washing, filtration performance can be maintained.
作為第二發明而言，提供有使用前述含油排水處理用分離膜模組之含油排水處理方法。該含油排水處理方法，係將非水溶性油分含量(n-己烷值)為3~5000mg/L之含油排水，設成前述中空絲膜的IPA起泡點為50kPa以上而未達100kPa且膜間壓差50kPa以下、前述IPA起泡點為100kPa以上而未達150kPa且膜間壓差100kPa以下、前述IPA起泡點為150kPa以上、400kPa以下且膜間壓差200kPa以下之過濾條件，當含油排水之非水溶性油分含油量為10mg/L以上、2000mg/L以下時，已過濾處理之水的非水溶性油分含量為未達5mg/L，當含油排水之非水溶性油分含油量為3mg/L以上而未達10mg/L時，已過濾處理之水的非水溶性油分含量為未達1mg/L。As a second invention, there is provided an oily drainage treatment method using the separation membrane module for oil-containing drainage treatment. The oil-containing drainage treatment method is an oil-containing drainage having a water-insoluble oil content (n-hexane value) of 3 to 5000 mg/L, and the IPA bubble point of the hollow fiber membrane is 50 kPa or more and less than 100 kPa. The pressure difference of 50 kPa or less, the IPA bubble point is 100 kPa or more, less than 150 kPa, and the pressure difference between membranes is 100 kPa or less, and the IPA bubble point is 150 kPa or more, 400 kPa or less, and the membrane pressure difference is 200 kPa or less. When the oil content of the water-insoluble oil of the drainage is 10 mg/L or more and 2000 mg/L or less, the water-insoluble oil content of the filtered water is less than 5 mg/L, and the oil-insoluble oil content of the oil-containing drainage is 3 mg. When the amount of /L or more is less than 10 mg/L, the water-insoluble oil content of the filtered water is less than 1 mg/L.
本處理方法中，調整為藉由取得中空絲膜之IPA起泡點和膜間壓差的平衡之方式，使非水溶性油分不透過中空絲膜之多孔質膜之孔，即能有效率地將非水溶性油分從含油排水去除。In the treatment method, it is adjusted such that the water-insoluble oil does not permeate the pores of the porous membrane of the hollow fiber membrane by obtaining a balance between the IPA bubble point of the hollow fiber membrane and the pressure difference between the membranes, thereby efficiently The water-insoluble oil is removed from the oily drain.
在前述中空絲膜之IPA起泡點之各條件中，若超過規定之膜間壓差的上限值則非水溶性油分易透過多孔質膜之孔，變成不易獲得未達5mg/L或未達1mg/L之非水溶性油分含量而，因而不佳。In each of the conditions of the IPA bubble point of the hollow fiber membrane, if the upper limit value of the predetermined inter-membrane pressure difference is exceeded, the water-insoluble oil is easily permeated through the pores of the porous membrane, and it becomes difficult to obtain less than 5 mg/L or not. It is not as good as the water-insoluble oil content of 1 mg/L.
前述中空絲膜之IPA起泡點為50kPa以上而未達100kPa時的膜間壓差以50kPa以下為佳。The IPA bubble point of the hollow fiber membrane is preferably 50 kPa or more and less than 100 kPa, and the pressure difference between the membranes is preferably 50 kPa or less.
前述IPA起泡點為100kPa以上而未達150kPa時的膜間壓差以100kPa以下為佳。The pressure difference between the membranes when the IPA foaming point is 100 kPa or more and less than 150 kPa is preferably 100 kPa or less.
前述IPA起泡點為150kPa以上、400kPa以下時的膜間壓差以200kPa以下為佳。When the IPA foaming point is 150 kPa or more and 400 kPa or less, the pressure difference between the films is preferably 200 kPa or less.
關於下限值，期望維持更低壓，但隨著過濾之持續進行，壓差逐漸上升。期望在上升至前述記載的壓力之時點，實施鹼性水溶液等的藥品洗淨。Regarding the lower limit value, it is desirable to maintain a lower pressure, but as the filtration continues, the pressure difference gradually increases. It is desirable to carry out washing of a chemical such as an aqueous alkaline solution at the time of rising to the pressure described above.
此外，膜間壓差係測量運轉中的分離膜模組附近之原水入口壓力P1及模組透過水出口附近之壓力P2，從該等值算出(P1-P2)。Further, the inter-membrane pressure difference is obtained by measuring the raw water inlet pressure P1 in the vicinity of the separation membrane module during operation and the pressure P2 in the vicinity of the module permeated water outlet, from which the values are calculated (P1 - P2).
本處理方法中，將利用過濾膜處理之含油排水中的非水溶性油分含量(n-己烷值)設定為3~2000mg/L，係因若是超過2000mg/L則含有非水溶性油分量過多，中空絲膜易發生阻塞，而難以確保處理水量之故。In the treatment method, the water-insoluble oil content (n-hexane value) in the oil-containing drainage treated by the filtration membrane is set to 3 to 2000 mg/L, because if it exceeds 2000 mg/L, the water-insoluble oil component is excessive. The hollow fiber membrane is prone to blockage, and it is difficult to ensure the amount of water to be treated.
另一方面，若未達3mg/L則非水溶性油分以極小之粒子分散的情形下，在膜內部由於微小粒子不易會合粗大化，無法進行膜內部之穩定的補足，而無法確實地去除。On the other hand, when the water-insoluble oil is not dispersed at a minimum particle size of 3 mg/L, the fine particles are less likely to be coarsened in the film, and the inside of the film cannot be stably filled, and cannot be reliably removed.
本處理方法所處理之含抽排水之非水溶性油分含量以10~2000mg/L為佳，以20~1000mg/L尤佳。The water-insoluble oil content of the water-containing drainage treated by the treatment method is preferably from 10 to 2000 mg/L, more preferably from 20 to 1000 mg/L.
本發明之含油排水處理用分離膜模組，只要非水溶性油分含量為稀薄的，具體而言只要是未達30mg/L之含油排水，則當然可處理到5mg/L以下的程度，甚至還可處理到未達1mg/L的程度。The separation membrane module for oil-containing drainage treatment according to the present invention may be treated to an extent of 5 mg/L or less, as long as it is a water-insoluble oil content, as long as it is less than 30 mg/L. Can be processed to the extent of less than 1mg / L.
非水溶性油分含量係藉由利用依據JIS K 0102 24.2之測量方法之n-己烷值所獲得者。The water-insoluble oil content is obtained by using the n-hexane value according to the measurement method of JIS K 0102 24.2.
若前述含油排水之以JIS K 0102 14.1測量之懸浮物質(SS)之濃度為5~2000mg/L，則通常含油排水包含懸浮物質，成為不均勻系分散狀態。此外，要處理之含油排水之溫度通常為25~90℃左右。When the concentration of the suspended matter (SS) measured by JIS K 0102 14.1 of the oil-containing drainage is 5 to 2000 mg/L, the oil-containing drainage usually contains a suspended matter and becomes a state of uneven dispersion. In addition, the temperature of the oily drainage to be treated is usually about 25 to 90 °C.
又，本發明之含油排水之處理方法中，於含油排水之非水溶性油分含量為3~200mg/L、且懸浮物質(SS)之濃度為100mg/L以下之情形下，以利用使被處理液全量通過中空絲膜之外壓式全過濾來進行為佳。Further, in the method for treating oil-containing drainage of the present invention, in the case where the water-insoluble oil content of the oil-containing drainage is 3 to 200 mg/L and the concentration of the suspended matter (SS) is 100 mg/L or less, it is treated by use. It is preferred that the entire amount of the liquid is subjected to pressure filtration through the hollow fiber membrane.
非水溶性油分含量為超過200mg/L且為2000mg/L以下，懸浮物質(SS)為100~20000mg/L之情形下，以利用使被處理液循環流動之外壓循環式或內壓循環式的交叉流(Cross flow)方式進行為佳。When the water-insoluble oil content is more than 200 mg/L and 2000 mg/L or less, and the suspended matter (SS) is 100 to 20000 mg/L, the circulating liquid or internal pressure circulation type is used to circulate the liquid to be treated. The cross flow method is preferred.
特別是非水溶性油分為1000mg/L以上或者懸浮物質為500mg/L以上之情形，以利用循環過濾進行過濾為佳。In particular, when the water-insoluble oil is 1000 mg/L or more or the suspended matter is 500 mg/L or more, it is preferred to carry out filtration by circulation filtration.
如此地因應非水溶性油分或懸浮物質之濃度，利用變更處理方法，能有效率地進行處理，而能確保處理水量。In this way, depending on the concentration of the water-insoluble oil or suspended matter, the treatment can be efficiently performed by the modification treatment method, and the amount of treated water can be ensured.
前述含油排水處理方法係用於將油田含油汚水進行前處理，將非水溶性油分含量(n-己烷值)降低後之含油排水，利用前述分離膜模組進行精密過濾之情形。The oil-containing drainage treatment method is used for pre-treatment of oil-containing sewage in an oil field, and the oil-containing drainage water having a water-insoluble oil content (n-hexane value) is reduced, and the separation membrane module is used for precision filtration.
又，提供使用前述含油排水處理用之分離膜模組的含油排水處理方法，其中在含油排水中之含油量為20~2000mg/L、懸浮成分之含量為100~10000mg/L，且在60~200℃高溫的情形下，利用前述分離膜模組將該高溫含油排水進行過濾處理，使處理水中之非水溶性油分含量為5mg/L以下、懸浮成分含量為0~1mg/L。Further, an oily drainage treatment method using the separation membrane module for oily drainage treatment is provided, wherein the oil content in the oily drainage is 20 to 2000 mg/L, and the content of the suspended component is 100 to 10000 mg/L, and at 60~ In the case of a high temperature of 200 ° C, the high-temperature oil-containing drainage is filtered by the separation membrane module, so that 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.
再者，作為第三發明而言，提供有具備前述含油排水處理用之分離膜模的含油排水處理裝置。Further, as a third invention, an oil-containing drainage treatment apparatus including the separation membrane mold for the oil-containing drainage treatment is provided.
該含油排水處理裝置之特徴為具備洗淨手段，其將鹼性水溶液所構成之洗淨液送液至前述中空絲膜表面，作為附著於前述分離膜模組的中空絲膜表面之非水溶性油分去除用The oil-containing drainage treatment device is characterized in that it has a cleaning means for supplying a cleaning liquid composed of an alkaline aqueous solution to the surface of the hollow fiber membrane to be water-insoluble as a surface of the hollow fiber membrane attached to the separation membrane module. Oil removal
本發明所使用之含油排水處理用之分離膜模組係以PTFE等形成中空絲膜，由於具有極為優異之耐鹼性，因此即使將如4質量%氫氧化鈉水溶液(1mol/L)之高濃度鹼溶液之洗淨液送液，亦不損傷中空絲膜，能維持高性能之過濾性能。因此，充分地溶解、去除附著在表面之捕捉非水溶性油分，而能重複再生利用多孔質膜。The separation membrane module for oil-containing drainage treatment used in the present invention is a hollow fiber membrane formed of PTFE or the like, and has excellent alkali resistance, so that it is as high as a 4% by mass aqueous sodium hydroxide solution (1 mol/L). The cleaning solution of the concentrated alkali solution does not damage the hollow fiber membrane, and can maintain high performance filtration performance. Therefore, the water-insoluble oily component adhering to the surface is sufficiently dissolved and removed, and the porous membrane can be repeatedly used for regeneration.
本發明之含油排水處理裝置較佳係構成為：具備導入用配管和循環用配管；該導入用配管係將含油排水儲存槽、前述洗淨手段之洗淨液儲存槽、前述含油排水儲存槽及洗淨液儲存槽和前述分離膜模組之導入部連通並且介設有泵；該循環用配管係將前述含油排水儲存槽及洗淨液儲存槽和前述分離膜模組之非處理液排出部連通；以將前述導入用配管之分支管及循環用配管之分支管分別連通於前述含油排水儲存槽和洗淨液儲存槽為佳。The oil-containing wastewater treatment device of the present invention is preferably configured to include an introduction pipe and a circulation pipe, and the introduction pipe is an oil-containing drainage storage tank, a cleaning liquid storage tank of the cleaning means, and the oil-containing drainage storage tank; The cleaning liquid storage tank is connected to the introduction portion of the separation membrane module and is provided with a pump; the circulation piping system is configured to discharge the oil-containing drainage storage tank and the cleaning liquid storage tank and the non-treatment liquid discharge portion of the separation membrane module It is preferable that the branch pipe of the introduction pipe and the branch pipe of the circulation pipe are connected to the oil-containing drain storage tank and the cleaning liquid storage tank, respectively.
如前述，在含油排水儲存槽和分離膜模組之間裝設循環用配管，以循環式將被處理液之含油排水供給到分離膜模組以過濾含油排水。又，在用以儲存鹼性水溶液所構成之洗淨液之洗淨液儲存槽和分離膜模組之間亦裝設循環用配管，使洗淨液在分離膜模組循環並進行供給。As described above, a circulation pipe is installed between the oil-containing drain storage tank and the separation membrane module, and the oil-containing drainage of the liquid to be treated is supplied to the separation membrane module in a circulating manner to filter the oil-containing drainage. Further, a circulation pipe is installed between the cleaning liquid storage tank and the separation membrane module for storing the cleaning liquid composed of the alkaline aqueous solution, and the cleaning liquid is circulated and supplied to the separation membrane module.
前述被處理液之循環和洗淨液之循環係交互地進行，防止分離膜模組之過濾性能降低。The circulation of the treated liquid and the circulation of the cleaning liquid are alternately performed to prevent the filtration performance of the separation membrane module from being lowered.
介設在前述導入用配管之前述泵的吐出壓力以設在50~300kPa為佳。又，於前述分支管的分支位置介設切換閥，且將被處理液和洗淨液在分離膜模組作切換並進行送液。It is preferable that the discharge pressure of the pump interposed in the introduction pipe is set to 50 to 300 kPa. Further, a switching valve is disposed at a branching position of the branch pipe, and the liquid to be treated and the cleaning liquid are switched between the separation membrane module and the liquid is supplied.
如前述，藉由使含油排水在分離膜模組循環之交叉流方式，即使為非水溶性油分含量超過200mg/L且2000mg/L以下、懸浮物質(SS)為100~20000mg/L之被處理液，亦可處理至未達5mg/L的程度，而在懸浮物質(SS)、非水溶性油分少的情形下則可處理至未達1mg/L的程度。As described above, by the cross-flow method in which the oil-containing drainage is circulated in the separation membrane module, even if the water-insoluble oil content exceeds 200 mg/L and 2000 mg/L or less, and the suspended matter (SS) is 100 to 20000 mg/L, it is treated. The liquid can also be treated to a level of less than 5 mg/L, and can be treated to a level of less than 1 mg/L in the case of a suspended substance (SS) or a water-insoluble oil.
又，藉由將泵之吐出壓力設為50~300kPa而供給前述含油排水，能將具有前述IPA起泡點之中空絲膜之膜間壓差設定於前述範圍。Further, by supplying the oil-containing drainage water by setting the discharge pressure of the pump to 50 to 300 kPa, the pressure difference between the membranes of the hollow fiber membrane having the IPA bubble point can be set within the above range.
再者，藉由具備前述洗淨手段，能進行將含油排水的導入用配管切換至鹼性水溶液的洗淨液導入用配管，由於定期地進行中空絲膜之膜面的捕捉非水溶性油分之去除，而可易於進行過濾膜之再生。In addition, the cleaning liquid introduction pipe for switching the introduction pipe for oil-containing drainage to the alkaline aqueous solution can be performed by the above-described cleaning means, and the water-insoluble oil component can be captured by the film surface of the hollow fiber membrane periodically. It is removed, and the regeneration of the filter membrane can be easily performed.
本發明之含油排水處理裝置係將含油田油汚水進行前處理，使非水溶性油分含量降低，例如使非水溶性油分含油量(n-己烷值)成為10~2000mg/L後，可適當使用作為精密過濾該含油排水之裝置。The oil-containing drainage treatment device of the present invention pre-treats the oil-containing oily sewage to reduce the water-insoluble oil content, for example, after the oil content of the water-insoluble oil (n-hexane value) is 10 to 2000 mg/L, Use as a means of precision filtration of the oily drain.
具體而言，作為一種含油排水處理裝置使用，其中利用既存之油水分離處理手段將含油汚水分離成粗大的非水溶性油分和含油水分，再將經分離之含油水分利用電凝聚、浮選手段使非水溶性油分和金屬份之含油排水並予以粗略去除後之含油排水，作為被處理液進行精密過濾。Specifically, it is used as an oil-containing drainage treatment device, wherein the oil-containing sewage is separated into coarse water-insoluble oil and oil-containing water by using an existing oil-water separation treatment means, and the separated oil-containing water is electrically coagulated and floated. The oil-impregnated oily water and the oil-containing drainage of the metal parts are roughly removed, and the oil is drained as a liquid to be treated.
含油汚水之原水通常存在浮選油等大量的油並且含有汚泥，因此使用於將預先利用油水分離處理手段及電凝聚、浮選手段粗略去除非水溶性油分後之含油排水進行精密過濾之本發明之裝置。此時之含油量為10~100mg/L。The raw water of the oil-containing sewage usually contains a large amount of oil such as flotation oil and contains sludge, and therefore is used in the present invention for precisely filtering the oil-containing drain after the oil-water separation treatment means and the electrocoagulation and flotation means are used to roughly remove the water-insoluble oil. Device. The oil content at this time is 10 to 100 mg/L.
根據本構成，由於係預先去除浮選油等大部分的非水溶性油分，因此能一面確保處理水量，一面獲得清澈之已處理的水，所獲得之已處理的水，可作為例如灌溉用水使用。According to this configuration, since most of the water-insoluble oils such as flotation oil are removed in advance, it is possible to obtain clear treated water while ensuring the amount of treated water, and the obtained treated water can be used as, for example, irrigation water. .
作為前述高溫之含油排水處理使用之中空絲膜模具之分離膜模組中，集束體之中空絲膜間之尺寸平均值為較寬之0.5mm~5mm，且前述中空絲膜對集束體之剖面積之充填率以20%~60%為佳。In the separation membrane module of the hollow fiber membrane mold used for the high-temperature oil-containing drainage treatment, the average size between the hollow fiber membranes of the bundle body is 0.5 mm to 5 mm wide, and the hollow fiber membrane is cut into the bundle body. The filling rate of the area is preferably 20% to 60%.
如此地，將中空絲膜間之尺寸設定成較寬時，末端封止材容易產生因龜裂或者翹曲造成的洩漏。對此，本發明作為將多數條中空絲膜、及連結固定其至少一端之末端封止材之製造方法而言，利用下述方法不會使末端封止材產生龜裂。As described above, when the size between the hollow fiber membranes is set to be wide, the terminal sealing material is liable to cause leakage due to cracking or warping. On the other hand, in the present invention, as a method for producing a plurality of hollow fiber membranes and an end seal member for connecting and fixing at least one end thereof, the end seal material is not cracked by the following method.
例如在容器內注入、充填熱變形溫度為120℃以之耐熱環氧樹脂(芳香族胺系硬化劑)，以50℃~60℃預備加熱後，於常溫下至少保持3小時以上、較佳為保持6小時以上以進行預備硬化。For example, it is injected into a container and filled with a heat-resistant epoxy resin (aromatic amine-based curing agent) having a heat distortion temperature of 120 ° C, and is heated at 50 ° C to 60 ° C for at least 3 hours at room temperature, preferably Keep it for 6 hours or more for preliminary hardening.
接著，以使用溫度以上、熱變形溫度之120℃以下之溫度(於100℃下使用時，則為100℃以上、120℃以下)進行1小時以上加熱。Next, heating is performed for 1 hour or more at a temperature of 120 ° C or lower and a heat distortion temperature of 120 ° C or lower (100 ° C or higher and 120 ° C or lower when used at 100 ° C).
然後，以至少6小時以上且1℃/分鐘之溫度梯度保持且逐漸冷卻。Then, it is maintained at a temperature gradient of at least 6 hours and at 1 ° C/min and gradually cooled.
在預先成型為末端形狀的棒之預定位置配合中空絲膜之尺寸開孔，於該處插入中空絲膜且隔著預定間隔排列之狀態下，加熱且將末端封止材之實體溫度預備加熱至樹脂的熔點以上之溫度，進而以該熔融溫度加熱1小時以上，然後以至少6小時以上且1℃/分鐘之溫度梯度保持且逐漸除冷。The opening of the hollow fiber membrane is matched with a predetermined position of the rod which is pre-formed into the end shape, and the hollow fiber membrane is inserted therein and arranged at a predetermined interval, and the solid temperature of the end sealing material is heated and prepared. The temperature above the melting point of the resin is further heated at the melting temperature for 1 hour or more, and then maintained at a temperature gradient of at least 6 hours and at 1 ° C/min and gradually cooled.
如此地，預備加熱後保持預定時間，然後加熱成形，且在加熱後以所需時間進行逐漸冷卻。藉由此方法製造之中空絲膜分離模組中，即使以100℃左右之溫度差重複進行熱循環，仍可防止在末端封止材本身及末端封止材和中空絲之間產生龜裂，本發明者係藉由實驗得知。Thus, the preliminary heating is maintained for a predetermined time, then heat-formed, and gradually cooled after heating for a desired period of time. In the hollow fiber membrane separation module manufactured by the method, even if the thermal cycle is repeated at a temperature difference of about 100 ° C, cracks can be prevented from occurring between the terminal sealing material itself and the end sealing material and the hollow fiber. The inventors have learned from experiments.
如前述，若使用本發明之分離膜模組，則能實現將含油排水降低非水溶性油分含量至未達5mg/L，進而未達1mg/L之低濃度之高性能過濾。As described above, when the separation membrane module of the present invention is used, it is possible to achieve high-performance filtration in which the oil-containing drainage is reduced in water-insoluble oil content to less than 5 mg/L and further to a low concentration of less than 1 mg/L.
又，藉由本發明之含油排水處理方法，使用前述分離膜模組處理油田含油汚水之含油排水或經加溫之高溫含油排水時，不會使非水溶性油分透過，能有效率地將非水溶性油分從含油排水去除，可在不會使處理水量降低的情況下獲得清淨之經處理之液體。Moreover, according to the oil-containing drainage treatment method of the present invention, when the oil separation drainage oil of the oil-containing sewage in the oil field or the high-temperature oil-containing drainage water heated by the above-mentioned separation membrane module is used, the water-insoluble oil is not transmitted, and the water-soluble oil can be efficiently dissolved. The oil is removed from the oily drainage to obtain a clean treated liquid without reducing the amount of treated water.
又，藉由本發明之含油排水處理裝置，由於具備定期地洗淨分離膜模組之洗淨手段，藉由利用鹼性水溶液之化學洗淨將附著於中空絲膜膜面之非水溶性油分溶解去除且重複再生，因此能長期持續進行含油排水之高性能過濾。Moreover, the oil-containing drainage treatment apparatus of the present invention has a cleaning means for periodically cleaning the separation membrane module, and dissolves the water-insoluble oil adhering to the surface of the hollow fiber membrane by chemical cleaning with an alkaline aqueous solution. It is removed and regenerated, so high-performance filtration of oil-containing drainage can be continued for a long time.
使用於油田含油汚水之含油排水處理的情形下，由於係在預先去除浮選油等大部分的非水溶性油分之後，再以分離膜模組精密過濾，因此能一面確保高處理水量，一面獲得非水溶性油分含量未達5mg/L、更少時為未達1mg/L之清澄的經處理之液體。In the case of oil-containing drainage treatment of oily wastewater in an oil field, it is possible to ensure high treatment water volume while preliminarily removing most of the water-insoluble oil such as flotation oil and then filtering it with a separation membrane module. The water-insoluble oil content is less than 5 mg/L, and less is a clear liquid of less than 1 mg/L.
參照圖式說明本發明之實施形態。Embodiments of the present invention will be described with reference to the drawings.
第1圖至第3圖係顯示本發明之第1實施形態之含油排水處理用之分離膜模組1。Fig. 1 to Fig. 3 show a separation membrane module 1 for oil-containing drainage treatment according to the first embodiment of the present invention.
該第1實施形態之分離膜模組1，係用於預先將油田含油汚水加以粗分離處理所成之含油排水，精密地進行分離處理者。此外，不限於該油田含油汚水，亦可包含工廠排水或生活排水，例如可供從含有於40℃下動態黏度為1~600cSt且於15℃下密度為0.7~1/0g/cm3之非水溶性油分的含油排水，將非水溶性油分離使用。又，可供從含有20℃之黏度為0.1~5.0mPa.s之非水溶性油分的含油排水，將非水溶性油分分離使用。The separation membrane module 1 of the first embodiment is used for the oily drainage formed by coarsely separating the oil-containing oily sewage in advance, and is precisely separated and processed. In addition, it is not limited to oily sewage in the oil field, and may also include factory drainage or domestic drainage, for example, from a dynamic viscosity of 1 to 600 cSt at 40 ° C and a density of 0.7 to 1 / 0 g / cm3 at 15 ° C. Oil-soluble drainage of water-soluble oil, separation of water-insoluble oil. Further, the water-insoluble oil can be separated from the oil-containing water containing an insoluble oil having a viscosity of 0.1 to 5.0 mPa.s at 20 ° C.
前述分離膜模組1係作成為從非水溶性油分含量為3~2000mg/L之含油排水，獲得非水溶性油分含量未達1mg/L之已處理的水。The separation membrane module 1 is an oil-containing drainage water having a water-insoluble oil content of 3 to 2000 mg/L, and a treated water having a water-insoluble oil content of less than 1 mg/L is obtained.
分離膜模組1係作成為用於使前述含油排水循環流動之外壓循環過濾方式(外壓交叉流方式)者。The separation membrane module 1 is used as a pressure circulation filtration method (external pressure cross flow method) for circulating the oil-containing drainage circulation.
具備將中空絲膜2捆束複數條(本實施形態為3500條)之集束體3，將該集束體3之下端以封止材4封止，將各中空絲膜2之下端開口封閉。集束體3之上端，即中空絲膜2之上端開口2a係呈開口狀態，以固定材5固定。The bundle body 3 in which a plurality of hollow fiber membranes 2 (3,500 in the present embodiment) are bundled, and the lower end of the bundle body 3 is sealed with a sealing material 4, and the lower end of each hollow fiber membrane 2 is closed. The upper end of the bundle body 3, that is, the upper end opening 2a of the hollow fiber membrane 2 is in an open state, and is fixed by the fixing member 5.
將前述集束體3收容在外筒6內。在外筒6之上端黏接安裝上部罩蓋7，在該上部罩蓋7之內部設有用於使其與各中空絲膜2之中空部連通的導出口7a，將該導出口7a與處理液取出用之導出用配管8連接。The bundle body 3 is housed in the outer cylinder 6. An upper cover 7 is attached to the upper end of the outer cylinder 6, and an outlet port 7a for communicating with the hollow portion of each hollow fiber membrane 2 is provided inside the upper cover 7, and the outlet 7a and the treatment liquid are taken out. It is connected by the piping 8 for export.
在前述外筒6之下端黏接固定下部罩蓋9，在該下部罩蓋9設有由含油排水所構成之被處理液之導入口9a，將該導入口9a與導入被處理液之導入用配管10連接。The lower cover 9 is bonded and fixed to the lower end of the outer cylinder 6, and the lower cover 9 is provided with an inlet 9a for the liquid to be treated which is composed of oil-containing drainage, and the introduction port 9a and the introduction liquid to be treated are introduced. The piping 10 is connected.
在集束體3下端的封止材4和外筒6的內壁之間確保空間S，使自前述導入口9a導入之含油排水於外筒6內，迅速地朝集束體3流動。A space S is secured between the sealing material 4 at the lower end of the bundle body 3 and the inner wall of the outer cylinder 6, and the oil-impregnated water introduced from the introduction port 9a is drained into the outer cylinder 6, and rapidly flows toward the bundle body 3.
又，在外筒6上端附近的周壁，設有未經過濾之非處理液之排出口11，將該排出口11與循環用配管12連通。Further, a discharge port 11 for unfiltered non-treatment liquid is provided on the peripheral wall near the upper end of the outer cylinder 6, and the discharge port 11 is communicated with the circulation pipe 12.
再者，從外筒6的下部周壁插入散氣用空氣導入管14，連通到集束體3之內部。如第2圖所示，散氣用空氣導入管14係連接著鼓風機15。必要時藉由鼓風機15將既定量的空氣導入該散氣用空氣導入管14，朝向集束體3的各中空絲膜2散氣。藉此，使中空絲膜2振動，振落附著於其外周面之含油排水中所含之固形物等。Further, the air-exhausting air introduction pipe 14 is inserted from the lower peripheral wall of the outer cylinder 6, and communicates with the inside of the bundle body 3. As shown in Fig. 2, the air blowing air inlet pipe 14 is connected to the air blower 15. If necessary, a certain amount of air is introduced into the air-exhausting air introduction pipe 14 by the air blower 15, and the air is blown toward the respective hollow fiber membranes 2 of the bundle body 3. Thereby, the hollow fiber membrane 2 is vibrated, and the solid matter or the like contained in the oil-containing drainage adhered to the outer peripheral surface thereof is shaken off.
再者，利用補強棒16連結上部之固定材5和下部之封止材4的中央部。該補強棒16係用以防止不具剛性之中空絲膜2被來自下部的含油排水之水流力抬起，以確保垂直性。Further, the center portion of the upper fixing member 5 and the lower sealing member 4 is joined by the reinforcing rod 16. The reinforcing rod 16 is used to prevent the non-rigid hollow fiber membrane 2 from being lifted by the water from the lower oil-containing drainage to ensure verticality.
此外，外筒6、上部罩蓋7、下部罩蓋9係ABS樹脂，固定材5、封止材4係環氧樹脂，連通棒16係不鏽鋼或耐熱樹脂，模組全體為耐鹼性優異者。Further, the outer cylinder 6, the upper cover 7, and the lower cover 9 are ABS resin, the fixing material 5, the sealing material 4 are epoxy resin, the connecting rod 16 is stainless steel or heat resistant resin, and the entire module is excellent in alkali resistance. .
如第3圖所示，中空絲膜2係由多孔質複層中空絲膜所構成，該多孔質複層中空絲膜係具備由多孔質延伸PTFE製之管2b所構成之支持層、和在該支持層外表面由多孔質膜延伸PTFE薄片2c所構成之過濾層。As shown in Fig. 3, the hollow fiber membrane 2 is composed of a porous multi-layer hollow fiber membrane comprising a support layer composed of a tube 2b made of porous elongated PTFE, and The outer surface of the support layer is a filter layer composed of a porous film extending PTFE sheet 2c.
中空絲膜2係具備中空絲膜全體為內徑0.3~12mm、外徑0.8~14mm、IPA起泡點50kPa以上、400kPa以下、膜厚0.2~1mm、氣孔率50~90%、最大容許膜間壓差0.1~1.0MPa之耐壓性者，於25℃下抗張力為30~150N。此外，該等物性係利用和前述方法同様的方法測量。The hollow fiber membrane 2 includes a hollow fiber membrane having an inner diameter of 0.3 to 12 mm, an outer diameter of 0.8 to 14 mm, an IPA foaming point of 50 kPa or more, 400 kPa or less, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum allowable membrane interval. For pressure resistance with a pressure difference of 0.1 to 1.0 MPa, the tensile strength at 30 ° C is 30 to 150 N. Moreover, the physical properties are measured by the same method as described above.
前述多孔質複層中空絲膜所構成之中空絲膜2，係於由利用壓出成形所獲得之多孔質延伸PTFE管2b之外周面，捲繞多孔質延伸PTFE薄片2c所形成。具體而言，於利用火焰處理等在多孔質延伸PTFE管2b之外周面設置凹凸後，使多孔質延伸PTFE薄片2c位置不偏離地捲繞於全周後，通過模具(Dice)等附加荷重使其密合，然後以PTFE的熔點以上之溫度加熱燒結，使兩者融接一體化。The hollow fiber membrane 2 composed of the porous multi-layer hollow fiber membrane is formed by winding a porous stretched PTFE sheet 2c on the outer peripheral surface of the porous stretched PTFE tube 2b obtained by extrusion molding. Specifically, after the unevenness is provided on the outer peripheral surface of the porous stretched PTFE tube 2b by flame treatment or the like, the position of the porous stretched PTFE sheet 2c is wound around the entire circumference without being displaced, and then the load is added by a die (Dice) or the like. The mixture is in close contact with each other and then heated and sintered at a temperature higher than the melting point of PTFE to fuse the two.
具備前述分離膜模組1之含油排水處理裝置20係成為第2圖所示之構成。具備有前述導入用配管10和前述循環用配管12，前述導入用配管10係將從配管19被連續導入之含油排水OL之含油排水儲存槽21、和用以儲存鹼性水溶液之洗淨液(以下簡稱鹼洗淨液)AL之洗淨液儲存槽22、和含油排水儲存槽21及洗淨液儲存槽22與分離膜模組1的被處理液之導入口9a連通，並介設有泵23和切換閥24；前述循環用配管12係將含油排水儲存槽21及洗淨液儲存槽22和分離膜模組1之未經過濾之非處理液的排出口11連通。The oil-containing drainage treatment device 20 including the separation membrane module 1 is configured as shown in Fig. 2 . The introduction pipe 10 and the circulation pipe 12 are provided, and the introduction pipe 10 is an oily drainage storage tank 21 that continuously introduces the oil-containing drain OL from the pipe 19, and a washing liquid for storing an alkaline aqueous solution ( Hereinafter, the alkaline cleaning liquid storage tank 22 and the oil-containing drainage storage tank 21 and the cleaning liquid storage tank 22 communicate with the inlet port 9a of the liquid to be treated of the separation membrane module 1, and a pump is interposed. 23 and the switching valve 24; the circulation piping 12 communicates the oil-containing drain storage tank 21 and the cleaning liquid storage tank 22 with the unfiltered non-treatment liquid discharge port 11 of the separation membrane module 1.
前述導入用配管10係於泵23之上游具備切換閥24，利用該切換閥24將配管分支，使分支管10A連接含油排水儲存槽21，使分支管10B連接洗淨液儲存槽22。又，在導入用配管10，於泵23之下游經由切換閥25與逆洗淨水之排出管10C連接。The introduction pipe 10 is provided with a switching valve 24 upstream of the pump 23, and the switching valve 24 branches the pipe, connects the branch pipe 10A to the oil-containing drain storage tank 21, and connects the branch pipe 10B to the cleaning liquid storage tank 22. Moreover, the introduction pipe 10 is connected to the discharge pipe 10C of the reverse washing water via the switching valve 25 downstream of the pump 23.
亦將作為前述洗淨液路徑之循環用配管12分支，使分支管12A連接含油排水儲存槽21，使分支管12B連接洗淨液儲存槽22。而且，在該分支位置介設切換閥29，使未經過濾之非處理液返回含油排水儲存槽21，於鹼洗淨時使鹼洗淨液返回洗淨液儲存槽22進行循環。The branch pipe 12 is branched as the circulation pipe 12, and the branch pipe 12A is connected to the oil-containing drain storage tank 21, and the branch pipe 12B is connected to the cleaning liquid storage tank 22. Further, the switching valve 29 is interposed at the branching position, and the unfiltered non-treatment liquid is returned to the oil-containing drain storage tank 21, and the alkali washing liquid is returned to the cleaning liquid storage tank 22 for circulation during the alkali washing.
前述泵23之吐出壓力為50~300kPa，將含油排水OL和鹼洗淨液AL加壓並送液至分離膜模組1。The discharge pressure of the pump 23 is 50 to 300 kPa, and the oil-containing drain OL and the alkali washing liquid AL are pressurized and sent to the separation membrane module 1.
泵23之吐出壓力為50~300kPa，調整成中空絲膜2之IPA起泡點之膜間壓差。The discharge pressure of the pump 23 is 50 to 300 kPa, and is adjusted to the pressure difference between the membranes of the IPA bubble point of the hollow fiber membrane 2.
如此地，本裝置中，定期地交互供給鹼洗淨液AL和含油排水OL至分離膜模組1，且定期地以鹼洗淨液AL洗淨中空絲膜2。In this apparatus, the alkali cleaning liquid AL and the oil-containing drainage liquid OL are alternately supplied to the separation membrane module 1 periodically, and the hollow fiber membrane 2 is periodically washed with the alkali cleaning liquid AL.
作為鹼洗淨液AL而言係使用0.5~20質量%之氫氧化鈉水溶液。As the alkali cleaning solution AL, a 0.5 to 20% by mass aqueous sodium hydroxide solution is used.
與已過濾之處理液的導出口7a連接以取出處理液之導出用配管8，係與處理液儲存槽26連接。且，為了利用儲存在該處理液儲存槽26之處理液作為逆洗淨水，而將介設有逆洗用泵27之逆洗水的配管28，連接在處理液儲存槽26和前述導出用配管8之間。The piping 8 for discharging the processing liquid is connected to the outlet port 7a of the filtered processing liquid, and is connected to the processing liquid storage tank 26. In order to use the treatment liquid stored in the treatment liquid storage tank 26 as the backwash water, the piping 28 through which the backwash water of the backwashing pump 27 is interposed is connected to the treatment liquid storage tank 26 and the above-mentioned delivery. Between the pipes 8.
接著，說明有關具備前述分離膜模組1之含油排水處理裝置之作用。Next, the action of the oil-containing drainage treatment apparatus including the separation membrane module 1 will be described.
連續地被供給到前述含油排水儲存槽21之含油排水OL，係由利用油田含油汚水之油水分離處理手段分離成非水溶性油分和含油水分，將經分離之含油水分利用電凝聚、浮選手段凝聚非水溶性油分和金屬份並予以粗略去除後之非水溶性油分含量(n-己烷值)為約1000mg/L以下之含油排水所構成。The oil-containing drainage OL continuously supplied to the oil-containing drainage storage tank 21 is separated into water-insoluble oil and oil-containing water by oil-water separation treatment using oil-containing oily water, and the separated oil-containing water is electrocoagulated and floated. The water-insoluble oil component and the metal component are coagulated and roughly removed, and the water-insoluble oil content (n-hexane value) is about 1000 mg/L or less.
利用前述分離膜模組1過濾之含油排水係以60~200℃、較佳為100~200℃之溫度過濾。若設定於如此之溫度範圍，則於40℃下動態黏度為1~600cSt之非水溶性油分會低黏度化，易於過濾。The oil-containing drainage system filtered by the separation membrane module 1 is filtered at a temperature of 60 to 200 ° C, preferably 100 to 200 ° C. If it is set in such a temperature range, the water-insoluble oil having a dynamic viscosity of 1 to 600 cSt at 40 ° C will have a low viscosity and is easy to filter.
將含油排水OL加壓利用泵23，使之從含油排水儲存槽21經由從導入用配管10導入至分離膜模組1下端之導入口9a。被導入之含油排水OL係於外筒6內朝上方流動，於其間朝集束體3內的中空絲膜2之外周逐漸流入。從中空絲膜2之外周朝中空絲膜2之中空部被外壓過濾。The oil-containing drain OL is pressurized by the pump 23 and introduced from the oil-containing drain storage tank 21 through the introduction port 9a introduced from the introduction pipe 10 to the lower end of the separation membrane module 1. The introduced oil-containing drain OL flows upward in the outer cylinder 6, and gradually flows into the outer periphery of the hollow fiber membrane 2 in the bundle body 3 therebetween. From the outer periphery of the hollow fiber membrane 2, the hollow portion of the hollow fiber membrane 2 is externally filtered.
已過濾之處理液SL係從中空絲膜2之中空部通過上端之導出口7a，經由導出用配管8而被儲存於處理液儲存槽26。The filtered treatment liquid SL is stored in the treatment liquid storage tank 26 through the outlet pipe 8 from the hollow portion of the hollow fiber membrane 2 through the outlet port 7a at the upper end.
另一方面，未經過濾之非處理液係從排出口11被排出至循環用配管12，並經由分支管12A返回含油排水儲存槽21或洗淨液儲存槽22。On the other hand, the unfiltered non-treatment liquid is discharged from the discharge port 11 to the circulation pipe 12, and is returned to the oil-containing drain storage tank 21 or the cleaning liquid storage tank 22 via the branch pipe 12A.
如前述，利用中空絲膜2過濾含油排水OL時，於使用IPA起泡點為50kPa以上而未達100kPa者作為中空絲膜2之情形下，將膜間壓差調整為50kPa以下。As described above, when the oil-containing drainage OL is filtered by the hollow fiber membrane 2, when the IPA bubble point is 50 kPa or more and less than 100 kPa is used as the hollow fiber membrane 2, the pressure difference between the membranes is adjusted to 50 kPa or less.
於使用IPA起泡點為100kPa以上而未達150kPa者之情形下，將膜間壓差調整為100kPa以下。When the IPA bubble point is 100 kPa or more and less than 150 kPa, the pressure difference between the films is adjusted to 100 kPa or less.
於IPA起泡點為150kPa以上、200kPa以下之情形下，超過膜間壓差而設定為200kPa以下之過濾條件。When the IPA foaming point is 150 kPa or more and 200 kPa or less, the filtration conditions of 200 kPa or less are set to exceed the pressure difference between membranes.
如此地藉由取得中空絲膜2之IPA起泡點和膜間壓差的平衡之方式，使得在非水溶性油分不會透過中空絲膜2之孔的情況下，能有效率地從含油排水OL去除非水溶性油分，可獲得非水溶性油分含量未達1mg/L之已處理的水。By obtaining the balance between the IPA bubble point of the hollow fiber membrane 2 and the pressure difference between the membranes, the water-insoluble oil can be efficiently discharged from the oil-impregnated water without passing through the pores of the hollow fiber membrane 2. OL removes the water-insoluble oil to obtain treated water having a water-insoluble oil content of less than 1 mg/L.
此外，取代將含油排水OL連續供給至含油排水儲存槽21，亦可將含油排水OL間歇地供給至含油排水儲存槽21。於此情形，含油排水OL係以重複進行複數次循環過濾之方式，進行過濾並逐漸濃縮。亦可於含油排水OL之濃度為例如2000mg/L左右時，排出含油排水儲存槽21內殘存之被處理液，換入新的含油排水OL。Further, instead of continuously supplying the oil-containing drain OL to the oil-containing drain storage tank 21, the oil-containing drain OL may be intermittently supplied to the oil-containing drain storage tank 21. In this case, the oil-containing drainage OL is filtered and gradually concentrated by repeating a plurality of cycles of filtration. When the concentration of the oil-containing drain OL is, for example, about 2000 mg/L, the remaining liquid to be treated in the oil-containing drain storage tank 21 is discharged, and the new oil-containing drain OL is exchanged.
又，作為其他的運轉方法，亦可將含有與新導入之非水溶性油分、固形物的量之總量相等之量的濃縮排水排出系統外等，一面維持一定之非水溶性油分、固形物，一面持續過濾。In addition, as another method of operation, it is possible to maintain a certain amount of water-insoluble oil and solids by using a concentrated drainage discharge system having an amount equal to the total amount of newly introduced water-insoluble oil and solids. , while continuing to filter.
將含油排水OL之過濾運轉進行一定時間，於看見處理流量降低之時點，停止泵23之作動，將切換閥24切換至鹼洗淨用流路。然後，使泵23再作動，使鹼洗淨液AL通過導入用配管10，將鹼洗淨液AL導入至分離膜模組1的導入口9a。The filtration operation of the oil-containing drain OL is performed for a predetermined period of time, and when the treatment flow rate is lowered, the operation of the pump 23 is stopped, and the switching valve 24 is switched to the alkali washing flow path. Then, the pump 23 is reactivated, and the alkali cleaning liquid AL is introduced into the introduction port 9a of the separation membrane module 1 through the introduction pipe 10.
該鹼洗淨液AL流入外筒6內，將附著沉積在中空絲膜2表面之捕捉非水溶性油分加以洗淨去除。該鹼洗淨液AL係從排出口11排出至循環用配管12，從該循環用配管12循環至洗淨液儲存槽22進行。The alkali cleaning liquid AL flows into the outer tube 6, and the water-insoluble oil component deposited on the surface of the hollow fiber membrane 2 is adhered and removed. The alkali 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.
如此地，定期地交互進行含油排水OL之過濾和藉由鹼洗淨液AL之洗淨。In this manner, the filtration of the oil-containing drainage OL and the cleaning by the alkaline cleaning liquid AL are periodically performed alternately.
又，定期地從處理液儲存槽26將已過濾之處理液SL從導出用配管8壓送至中空絲膜2之中空部，將中空絲膜2從內側進行逆洗淨。該逆洗淨水係經切換切換閥25而通過排出管10C排出。Further, the filtered treatment liquid SL is pressure-fed from the discharge pipe 8 to the hollow portion of the hollow fiber membrane 2 from the treatment liquid storage tank 26, and the hollow fiber membrane 2 is backwashed from the inside. This reverse washing water is discharged through the discharge pipe 10C via the switching switching valve 25.
此外，亦可取代已過濾之處理液而使用鹼洗淨液作為逆洗淨水，亦可放置短時間例如1小時左右。Further, instead of the filtered treatment liquid, an alkali washing solution may be used as the backwash water, or may be left for a short period of time, for example, for about 1 hour.
於處理含油排水OL之非水溶性油分含量(n-己烷值)稀薄至3~200mg/L，特別是對膜之附著性少的含油排水時，以設為外壓過濾式較佳，其係從導入口9a供給含油排水，一面朝向集束體3之上端側流動，一面藉由中空絲膜2過濾，使已去除非水溶性油分之已處理水在中空絲膜2之內周側流通，從導出口7a導出至導出用配管8，將含油排水OL全部過濾，不使其循環。The oil-insoluble oil content (n-hexane value) of the oil-containing drainage OL is diluted to 3 to 200 mg/L, and particularly when the oil-containing drainage having little adhesion to the film is used, it is preferably an external pressure filtration type. The oil-containing drain water is supplied from the inlet port 9a, and flows toward the upper end side of the bundle body 3, and is filtered by the hollow fiber membrane 2, so that the treated water from which the water-insoluble oil has been removed flows through the inner peripheral side of the hollow fiber membrane 2, The outlet port 8a is led to the outlet pipe 8, and the oil-containing drain OL is completely filtered, and is not circulated.
於設為前述外壓過濾式之情形下，例如使逆洗泵27每30分鐘運作一次，使用已過濾之處理水對分離膜模組內的中空絲膜2施加逆壓(內壓)，拂拭沉積在外表面之固形物等。In the case where the external pressure filter type is used, for example, the backwash pump 27 is operated once every 30 minutes, and the back pressure (internal pressure) is applied to the hollow fiber membrane 2 in the separation membrane module using the filtered treated water, and wiped. Solid matter deposited on the outer surface, and the like.
此時，同時由鼓風機15送入空氣，使中空絲膜2振動，同樣地拂拭固形物。然後，從分離膜模組1之下部排出含有固形物之被處理液。此時之逆洗壓力為例如200kPa、時間為30秒、空氣量為在50L/min下20秒。如上所述，當非水溶性油分含量為稀薄之含油排水時，以進行全量過濾為佳。At this time, air is simultaneously supplied from the blower 15, and the hollow fiber membrane 2 is vibrated, and the solid matter is similarly swept. Then, the liquid to be treated containing the solid matter is discharged from the lower portion of the separation membrane module 1. The backwashing pressure at this time is, for example, 200 kPa, the time is 30 seconds, and the air amount is 20 seconds at 50 L/min. As described above, when the water-insoluble oil content is a lean oily drainage, it is preferred to carry out full filtration.
使用第4圖所示之測試用過濾系統，進行實施例1、2和比較例1之實驗。第4圖所示之過濾系統係與前述第一實施形態之過濾裝置為大致同様之構成，因此標註同一符號而省略說明。The experiments of Examples 1, 2 and Comparative Example 1 were carried out using the test filtration system shown in Fig. 4. The filtration system shown in Fig. 4 is substantially the same as the filtration device of the first embodiment, and therefore the same reference numerals will be given thereto, and the description thereof will be omitted.
各中空絲膜係外徑2.3mm、內徑1.1mm之交聯PVA且經親水處理之PTFE製，並且起泡點125kPa、氣孔率為77%，抗張力在25℃下為50~80N。其膜面積為0.1m2、末端封止材料為PFA之中空絲膜模組1，被裝入於第4圖所示之過濾系統。在含油排水儲存槽21(原水槽)導入下述「表1」所示之含油排水20L，溫度設為30℃。Each of the hollow fiber membranes was made of a crosslinked PVA having an outer diameter of 2.3 mm and an inner diameter of 1.1 mm and a hydrophilically treated PTFE, and had a bubble point of 125 kPa, a porosity of 77%, and a tensile strength of 50 to 80 N at 25 °C. The hollow fiber membrane module 1 having a membrane area of 0.1 m2 and a terminal sealing material of PFA was incorporated in the filtration system shown in Fig. 4. The oil-containing drain water 20L shown in the following "Table 1" was introduced into the oil-containing drain storage tank 21 (raw water tank), and the temperature was set to 30 °C.
設條件如下述「表2」，進行運轉，如第5(A)圖所示地顯示穩定之過濾流量。水質亦如「表3」所示地可充分去除油分。The conditions are as shown in the following "Table 2", and the operation is performed, and the stable filtration flow rate is shown as shown in Fig. 5(A). The water quality can also be fully removed as shown in Table 3.
非水溶性油分種類Mobil公司製 Super2000 10W-40(40℃動態黏度92cSt、密度0.869(at15℃))Insoluble oil type Mo2000 Co., Ltd. Super2000 10W-40 (40°C dynamic viscosity 92cSt, density 0.869 (at15°C))
濃度 145mg/lConcentration 145mg/l
懸浮物質(氫氧化鐵) 173mg/lSuspended matter (iron hydroxide) 173mg/l
TDS(溶解鹽分濃度)NaCl 10200mg/lTDS (dissolved salt concentration) NaCl 10200mg/l
「表2」"Table 2"
過濾入口壓力 80kPaFiltration inlet pressure 80kPa
透過水出口壓力 0kPaThrough water outlet pressure 0kPa
逆洗頻率：1次/30分Backwash frequency: 1 time / 30 points
逆洗壓力：200kPaBackwash pressure: 200kPa
負載時間：10秒Load time: 10 seconds
「表3」"table 3"
懸浮物質：1＞ mg/lSuspended material: 1> mg/l
非水溶性油分：1＞ mg/lWater-insoluble oil: 1> mg/l
中空絲膜係外徑2.3mm、內徑1.1mm之交聯PVA且經親水處理之PTFE製，並且起泡點55kPa、氣孔率為80%，抗張力在25℃下為40~60N。將以該中空絲膜構成、其膜面積為0.1m2、末端封止材料為PFA之中空絲膜模組1裝入前述第4圖所示之過濾系統。將下述「表4」所示之排水20L導入原水槽，溫度設為30℃。The hollow fiber membrane was a crosslinked PVA having an outer diameter of 2.3 mm and an inner diameter of 1.1 mm and was made of a hydrophilically treated PTFE, and had a bubble point of 55 kPa, a porosity of 80%, and a tensile strength of 40 to 60 N at 25 °C. The hollow fiber membrane module 1 comprising the hollow fiber membrane, having a membrane area of 0.1 m2 and a terminal sealing material of PFA was placed in the filtration system shown in Fig. 4 . 20L of the drainage shown in the following "Table 4" was introduced into the original water tank, and the temperature was set to 30 °C.
設條件如下述「表5」，進行運轉，如第5(B)圖所示般顯示穩定之過濾流量，但水質如下述「表6」所示般無法去除油分。The conditions are as shown in the following Table 5 and the operation is carried out. As shown in the fifth (B) diagram, the stable filtration flow rate is shown, but the water quality cannot be removed as shown in the following Table 6.
「表4」"Table 4"
非水溶性油分種類 Mobil公司製 Super2000 10W-40(40℃動態黏度92cSt、密度0.869(at15℃))Insoluble oil type Mo2000 Co., Ltd. Super2000 10W-40 (40°C dynamic viscosity 92cSt, density 0.869 (at15°C))
濃度 145mg/lConcentration 145mg/l
懸浮物質(氫氧化鐵) 173mg/lSuspended matter (iron hydroxide) 173mg/l
TDS(溶解鹽分濃度)NaCl 10200mg/lTDS (dissolved salt concentration) NaCl 10200mg/l
「表5」"table 5"
過濾入口壓力 85kPaFiltration inlet pressure 85kPa
過濾水出口壓力 0kPaFiltered water outlet pressure 0kPa
逆洗頻率：1次/30分鐘Backwash frequency: 1 time / 30 minutes
逆洗壓力：200kPaBackwash pressure: 200kPa
負載時間：10秒Load time: 10 seconds
「表6」"Table 6"
懸浮物質：2mg/lSuspended matter: 2mg/l
非水溶性油分：27mg/lWater-insoluble oil: 27mg/l
(實施例2)(Example 2)
中空絲膜係外徑2.3mm、內徑1.1mm之交聯PVA且經親水處理之PTFE製，並且起泡點125kPa、氣孔率為77%，抗張力在25℃下為50~80N。將以該中空絲膜構成、其膜面積為0.1m2、末端封止材料為PFA之中空絲膜模組1裝入前述第1圖所示之過濾系統。在原水槽導入下述「表7」所示之排水20L，溫度設為90℃。The hollow fiber membrane was made of crosslinked PVA having an outer diameter of 2.3 mm and an inner diameter of 1.1 mm and treated with hydrophilic treatment, and had a bubble point of 125 kPa, a porosity of 77%, and a tensile strength of 50 to 80 N at 25 °C. The hollow fiber membrane module 1 composed of the hollow fiber membrane, having a membrane area of 0.1 m2 and a terminal sealing material of PFA was placed in the filtration system shown in Fig. 1 described above. The drainage water 20L shown in the following "Table 7" was introduced into the raw water tank, and the temperature was 90 °C.
設條件如下述「表8」，進行運轉，如第5(C)圖所示般顯示穩定之過濾流量。水質亦如下述「表9」所示般可充分去除油分。The conditions are as shown in the following "Table 8", and the operation is carried out, and the stable filtration flow rate is shown as shown in Fig. 5(C). The water quality is also sufficient to remove oil as shown in Table 9 below.
「表7」"Table 7"
非水溶性油分種類 Mobil公司製Mobileagr SHC 320(40℃動態黏度320cSt、密度0.88(at15℃))Insoluble oil type Mobil's Mobileagr SHC 320 (40°C dynamic viscosity 320cSt, density 0.88 (at15°C))
濃度 153mg/lConcentration 153mg/l
懸浮物質(氫氧化鐵) 121mg/lSuspended matter (iron hydroxide) 121mg/l
TDS(溶解鹽分濃度)NaCl 10200mg/lTDS (dissolved salt concentration) NaCl 10200mg/l
「表8」"Table 8"
過濾入口壓力 80kPaFiltration inlet pressure 80kPa
過濾水出口壓力 0kPaFiltered water outlet pressure 0kPa
逆洗頻率：1次/30分鐘Backwash frequency: 1 time / 30 minutes
逆洗壓力：200kPaBackwash pressure: 200kPa
負載時間：10秒Load time: 10 seconds
「表9」"Table 9"
懸浮物質：1＞ mg/lSuspended material: 1> mg/l
非水溶性油分：1＞ mg/lWater-insoluble oil: 1> mg/l
於第6圖及第7圖顯示第2實施形態之內壓循環過濾式之含油排水處理裝置30。The internal pressure circulation filtration type oil-containing drainage treatment apparatus 30 of the second embodiment is shown in Figs. 6 and 7 .
該含油排水處理裝置30並非油田含油汚水用，而是作為含有油分之工廠排水之油水分離使用。此外，亦可與第1實施形態同様地作為油田含油汚水用之含油排水處理裝置使用。The oil-containing drainage treatment device 30 is not used for oil-containing sewage in an oil field, but is used as a separation of oil and water as a factory drain containing oil. Further, in the same manner as in the first embodiment, it can be used as an oily drainage treatment device for oily oily sewage.
第6圖所示之分離膜模組31係設為內壓循環過濾式模組，其係將中空絲膜32之兩端設為開口，使被處理液之含油排水OL通過中空絲膜32之中空部，從中空絲膜32之內側朝向外側過濾，使已過濾之處理液透過中空絲膜32之外側。The separation membrane module 31 shown in FIG. 6 is an internal pressure circulation filtration type module in which both ends of the hollow fiber membrane 32 are opened, and the oil-containing drainage OL of the liquid to be treated passes through the hollow fiber membrane 32. The hollow portion is filtered from the inner side of the hollow fiber membrane 32 toward the outside, and the filtered treatment liquid is passed through the outer side of the hollow fiber membrane 32.
具體而言，將作成有前述兩端開口之中空絲膜32的集束體33收容在外筒6。集束體33之上下兩側係將中空絲膜32之兩端開口作為開口狀態而以固定材34、35固定。在上端之固定材34連接固定有上部罩蓋37，該上部罩蓋37係設有未經過濾之非處理液的排出口37a，將上部罩蓋37和循環用配管12與排出口37a連接。Specifically, the bundle body 33 formed with the hollow fiber membranes 32 opened at both ends is housed in the outer cylinder 6. The upper and lower sides of the bundle body 33 are fixed to the fixing members 34 and 35 by opening the both ends of the hollow fiber membrane 32 as an open state. An upper cover 37 is attached and fixed to the fixing material 34 at the upper end, and the upper cover 37 is provided with a discharge port 37a for unfiltered non-treatment liquid, and the upper cover 37 and the circulation pipe 12 are connected to the discharge port 37a.
下端之固定材35係密合固定在外筒6之內周面，並且與下部罩蓋36固定，在該下部罩蓋36設有由含油排水所構成之被處理液的導入口36a，將該導入口36a與導入用配管10連接。The fixing material 35 at the lower end is closely fixed to the inner circumferential surface of the outer cylinder 6, and is fixed to the lower cover 36. The lower cover 36 is provided with an introduction port 36a for the liquid to be treated which is composed of oil-containing drainage, and the introduction is introduced. The port 36a is connected to the introduction pipe 10.
又，在外筒6上端附近之周壁設有已過濾之處理液的導出口6c，將該導出口6c連接處理液取出用之導出用配管8。Further, a discharge port 6c for filtering the treatment liquid is provided on the peripheral wall near the upper end of the outer cylinder 6, and the outlet 6c is connected to the outlet pipe 8 for taking out the treatment liquid.
具備前述內壓循環過濾式分離膜模組31之含油排水處理裝置30係如第7圖所示般，連接在分離膜模組31的導入口36a之導入用配管10係與第1實施形態同様地，經由泵23、切換閥24、分支管10A、10B，與含油排水儲存槽21、洗淨液儲存槽22連接。In the oil-containing drainage treatment device 30 including the internal pressure circulation filtration separation membrane module 31, as shown in Fig. 7, the introduction pipe 10 connected to the introduction port 36a of the separation membrane module 31 is the same as that of the first embodiment. The ground is connected to the oil-containing drain storage tank 21 and the cleaning liquid storage tank 22 via the pump 23, the switching valve 24, and the branch pipes 10A and 10B.
連接至分離膜模組31的排出口37a之循環用配管12亦與第1實施形態同様地，將分支管12A、12B與含油排水儲存槽21、洗淨液儲存槽22連接。In the same manner as in the first embodiment, the circulation pipe 12 connected to the discharge port 37a of the separation membrane module 31 is connected to the oil-containing drain storage tank 21 and the cleaning liquid storage tank 22 in the same manner as in the first embodiment.
連接至已過濾之處理液的導出口6c之導出用配管8，亦與第1實施形態同様地連接至處理液儲存槽26，且經由該處理液儲存槽26和逆洗用泵27，使逆洗用配管28與導出用配管8連接。使前述逆洗用泵27間歇地作動，將處理液導入外筒6的內部作為逆洗淨液，朝向中空絲膜32的外周面噴射，進行逆洗淨。The lead-out pipe 8 connected to the outlet 6c of the filtered processing liquid is also connected to the processing liquid storage tank 26 in the same manner as the first embodiment, and is reversed via the processing liquid storage tank 26 and the backwashing pump 27. The washing pipe 28 is connected to the outlet pipe 8. The backwashing pump 27 is intermittently operated, and the treatment liquid is introduced into the outer cylinder 6 as a backwashing liquid, and is sprayed toward the outer peripheral surface of the hollow fiber membrane 32 to be backwashed.
再者，將與鼓風機15連接之散氣用空氣導入管14，插入接近於分離膜模組31的導入口36a之配管10內，將散氣用空氣供給至各中空絲膜32的內部。In addition, the air-intake air introduction pipe 14 connected to the air blower 15 is inserted into the pipe 10 close to the introduction port 36a of the separation membrane module 31, and the air for air is supplied to the inside of each of the hollow fiber membranes 32.
本第2實施形態之中空絲膜32係與第1實施形態之第3圖同様，由多孔質延伸PTFE製單層管所構成。該多孔質中空絲膜32具備有內徑1~12mm、外徑1.6~14mm、IPA起泡點50kPa以上、400kPa以下、膜厚0.2~1mm、氣孔率50~90%、最大容許膜間壓差0.1~1.0MPa之耐壓性。該等物性係利用與前述方法同様的方法測量。The hollow fiber membrane 32 of the second embodiment is the same as the third embodiment of the first embodiment, and is composed of a porous tube made of porous PTFE. 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 foaming point of 50 kPa or more, 400 kPa or less, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum allowable inter-membrane pressure difference. Pressure resistance of 0.1~1.0MPa. These physical properties are measured by the same method as the aforementioned method.
前述分離膜模組31係將非水溶性油分含量(n-己烷值)為1000~2000mg/L之含油排水OL進行循環處理。於作成為內壓循環過濾方式之點，與第1實施形態之外壓循環過濾方式不同。The separation membrane module 31 is configured to circulate an oil-containing drainage OL having a water-insoluble oil content (n-hexane value) of 1000 to 2000 mg/L. The point of the internal pressure circulation filtration method is different from that of the first embodiment.
含油排水OL係如圖中箭號所示，從導入口36a被導入中空絲膜32的內部，朝向集束體33之上端側流動。在該流通過程中，藉由中空絲膜32過濾，去除非水溶性油分之已過濾之處理水係透過中空絲膜32的外周側，從設在外筒6的周壁之處理液的導出口6c，被導出至導出用配管8。The oil-containing drainage OL is introduced into the hollow fiber membrane 32 from the introduction port 36a as shown by an arrow in the figure, and flows toward the upper end side of the bundle body 33. In the flow, the filtered water treated by the hollow fiber membrane 32 is filtered to remove the water-insoluble oil, and the filtered treated water passes through the outer peripheral side of the hollow fiber membrane 32, and is guided from the outlet 6c of the treatment liquid provided on the peripheral wall of the outer cylinder 6. It is exported to the lead pipe 8 for export.
又，含有非水溶性油分或固形粒子等之未過濾之非處理液，係從設於上部罩蓋37之排出口37a，被排出至循環用配管12。In addition, the unfiltered non-treatment liquid containing water-insoluble oil or solid particles is discharged to the circulation pipe 12 from the discharge port 37a provided in the upper cover 37.
於內壓循環方式之情形下，即使是相同的循環流量，由於在分離膜模組31內流動之流路剖面積小，流速提高，沉積在中空絲膜32表面之固形物、非水溶性油分之剝離效果變大，因此特別是在非水溶性油分濃度大的區域可發揮功效。In the case of the internal pressure circulation mode, even if the same circulation flow rate is small, the flow path in the separation membrane module 31 is small, the flow velocity is increased, and the solid matter and the water-insoluble oil deposit deposited on the surface of the hollow fiber membrane 32 are formed. Since the peeling effect becomes large, it is effective especially in the area where the water-insoluble oil concentration is large.
本第2實施形態中，將高濃度非水溶性油分含量之含油排水OL作為被處理液，能以一次過濾獲得未達5mg/L之非水溶性油分含量之已處理之液體。In the second embodiment, the oil-containing drainage OL having a high concentration of the water-insoluble oil content is used as the liquid to be treated, and the treated liquid having a water-insoluble oil content of less than 5 mg/L can be obtained by one filtration.
由於其他構成及效果係與第1實施形態同様，因此對具有同一功能及作用之構件標註同一符號而省略說明。Since the other configurations and effects are the same as those in the first embodiment, members having the same functions and functions will be denoted by the same reference numerals and will not be described.
於第8圖及第9圖顯示第3實施形態之分離膜模組40及含油排水處理裝置60。The separation membrane module 40 and the oil-containing drainage treatment device 60 of the third embodiment are shown in Figs. 8 and 9.
含油排水處理用之分離膜模組40係浸漬型模組，其係將中空絲膜41之集束體42浸漬配置於儲存有含油排水OL之浸漬槽50內，藉由從中空絲膜41之內側吸引含油排水OL，而使含油排水OL從中空絲膜41之外側朝向內側透過。The separation membrane module 40 for oil-containing drainage treatment is an impregnation type module in which the bundle body 42 of the hollow fiber membrane 41 is immersed in the immersion tank 50 in which the oil-containing drainage OL is stored, from the inside of the hollow fiber membrane 41. The oil-containing drain OL is sucked, and the oil-containing drain OL is transmitted from the outer side to the inner side of the hollow fiber membrane 41.
中空絲膜41的集束體42之狀態係與第1實施形態同様地，於將中空絲膜之上端開口形成開口的狀態下以固定材5固定，將該固定材5與上部罩蓋7固定，且將該上部罩蓋7與用以取出已過濾之處理液之導出用配管8連接。In the same manner as in the first embodiment, the bundle body 42 of the hollow fiber membrane 41 is fixed to the fixing member 5 in a state in which the upper end of the hollow fiber membrane is opened, and the fixing member 5 and the upper cover 7 are fixed. The upper cover 7 is connected to a lead-out pipe 8 for taking out the filtered processing liquid.
集束體42之下端亦與第1實施形態同様地，以封閉中空絲膜41之下端開口之封止材4固定著。以連結棒43連結上端之固定材5和下端之封止材4的外周部，將集束體42保持於垂直方向並且予以補強。The lower end of the bundle body 42 is also fixed to the sealing material 4 that closes the lower end of the hollow fiber membrane 41 in the same manner as in the first embodiment. The fixing member 5 of the upper end and the outer peripheral portion of the sealing material 4 at the lower end are joined by the connecting rod 43, and the bundle body 42 is held in the vertical direction and reinforced.
將前述下端之封止材4和連結棒43之下端固定於裙形材46。在該裙形材46之下部配置有與鼓風機15連接之散氣用空氣導入管14之散氣口。於過濾運轉時長期從下方散氣，藉由其起泡，使浸漬槽50內之含油排水OL產生朝上方之循環流。The lower end sealing material 4 and the lower end of the connecting rod 43 are fixed to the skirt 46. An air diffusing port of the air blowing air introducing pipe 14 connected to the air blower 15 is disposed at a lower portion of the skirt 46. During the filtration operation, air is diffused from below for a long period of time, and by bubbling it, the oil-containing drainage OL in the immersion tank 50 generates a circulating flow upward.
如第9圖所示，處理液取出用之導出用配管8係與第1實施形態同様地，連接至處理液儲存槽26。在該處理液儲存槽26連接介設有逆洗用泵27之逆洗用之配管28，將該配管28與導出用配管8連接。As shown in Fig. 9, the delivery pipe 8 for taking out the treatment liquid is connected to the treatment liquid storage tank 26 in the same manner as in the first embodiment. The backwashing pipe 28 through which the backwashing pump 27 is interposed is connected to the process liquid storage tank 26, and the pipe 28 is connected to the lead pipe 8.
再者，將儲存有鹼洗淨液AL之洗淨液儲存槽22，藉由配管45導入浸漬槽50之內部，於去除浸漬槽50內之含油排水OL後，將鹼洗淨液AL導入浸漬槽50內，將集束體42浸漬所需時間並加以洗淨。Further, the cleaning liquid storage tank 22 in which the alkali cleaning liquid AL is stored is introduced into the immersion tank 50 through the pipe 45, and after the oil-containing drainage OL in the immersion tank 50 is removed, the alkali cleaning liquid AL is introduced into the immersion liquid. In the tank 50, the bundle 42 is immersed for a desired period of time and washed.
本第3實施形態之中空絲膜41係與第1實施形態之中空絲膜2同様，為一多孔質複層中空絲膜，其具備由多孔質延伸PTFE製之管所構成之支持層、及在該支持層外表面由多孔質膜延伸PTFE薄片所構成之過濾層。The hollow fiber membrane 41 of the third embodiment is the same as the hollow fiber membrane 2 of the first embodiment, and is a porous multi-layer hollow fiber membrane having a support layer made of a tube made of porous elongated PTFE. And a filter layer formed by extending a PTFE sheet on the outer surface of the support layer by a porous film.
中空絲膜41之內徑為0.3~2.0mm、外徑為0.8~3.0mm，在內面使用圓筒狀網等支持體之情形下，最大外徑為20mm。The hollow fiber membrane 41 has an inner diameter of 0.3 to 2.0 mm and an outer diameter of 0.8 to 3.0 mm. When a support such as a cylindrical mesh is used for the inner surface, the maximum outer diameter is 20 mm.
IPA起泡點係具備50kPa以上、400kPa以下、膜厚為0.2~1mm、氣孔率為50~90%、最大容許膜間壓差(外壓)0.1MPa之耐壓性者。此外，該等物性係利用與前述方法測量。本第3實施形態之浸漬型係作為非水溶性油分含量(n-己烷值)為10~200mg/L之含油排水OL處理使用。The IPA foaming point is a pressure resistance of 50 kPa or more, 400 kPa or less, a film thickness of 0.2 to 1 mm, a porosity of 50 to 90%, and a maximum allowable inter-membrane pressure difference (external pressure) of 0.1 MPa. Moreover, the physical properties are measured using the methods described above. The impregnation type of the third embodiment is used as an oil-containing drainage OL which has a water-insoluble oil content (n-hexane value) of 10 to 200 mg/L.
將含油排水OL經由配管19供給至浸漬槽50。含油排水OL從配管19供給至浸漬槽50係間歇地進行。The oil-containing drain water OL is supplied to the dipping tank 50 via the pipe 19 . The oil-containing drain OL is supplied from the pipe 19 to the dipping tank 50 intermittently.
具體而言，當浸漬槽50內之含油排水OL已過濾，未經過濾之含油排水OL之非水溶性油分含量到達200mg/L時，會從浸漬槽50被排出至系統外，將新的含油排水OL供給至浸漬槽50內。Specifically, when the oil-containing drainage OL in the immersion tank 50 has been filtered, and the water-insoluble oil content of the unfiltered oil-containing drainage OL reaches 200 mg/L, it is discharged from the immersion tank 50 to the outside of the system, and the new oil is contained. The drain OL is supplied into the dipping tank 50.
或者，當非水溶性油分含油量到達100mg/L時，在浸漬槽50內導入稀薄濃度之含油排水OL，當浸漬槽50內積存既定量非水溶性油分含油量為100mg/L之含油排水OL時，在短時間內排出至系統外。Alternatively, when the oil content of the water-insoluble oil reaches 100 mg/L, a thin-concentration oil-containing drainage OL is introduced into the immersion tank 50, and an oil-containing drainage OL having a water-insoluble oil content of 100 mg/L is accumulated in the immersion tank 50. When it is discharged to the outside of the system in a short time.
例如當導入1000公升之含油排水，被導入之含油排水之非水溶性油分為5000mg時，作為浸漬槽50內之非水溶性油分為100mg/L而言僅排出50公升。以保持該平衡的方式運轉，一面將浸漬槽50內之非水溶性油分保持固定，一面連續進行。For example, when 1000 liters of oil-containing drainage water is introduced and the water-insoluble oil to be introduced into the oil-containing drainage is divided into 5000 mg, only 50 liters is discharged as the water-insoluble oil in the immersion tank 50 is divided into 100 mg/L. The operation of maintaining the balance is carried out while maintaining the water-insoluble oil content in the dipping tank 50 constant.
本第3實施形態之浸漬型中，於過濾運轉時，經常從散氣用空氣插入管14噴射空氣至集束體42之下部，藉由其起泡而產生使浸漬槽50內之含油排水OL上升之循環流，一面振動中空絲膜41，一面將非水溶性油分及固形物附著於中空絲膜41之膜面，將附著之固形物及非水溶性油分振動剝離。In the immersion type according to the third embodiment, air is often ejected from the air-dissipating air insertion tube 14 to the lower portion of the concentrating body 42 during the filtration operation, and the oil-containing drainage OL in the immersion tank 50 is raised by the foaming. In the circulation flow, the water-insoluble oil component and the solid matter are adhered to the film surface of the hollow fiber membrane 41 while vibrating the hollow fiber membrane 41, and the adhered solid matter and the water-insoluble oil are vibrated and peeled off.
又，如前述，定期地從浸漬槽50將含抽排水排出系統外，排出後使鹼洗淨液AL通過配管45供給至浸漬槽50，將集束體42浸漬於鹼洗淨液AL進行洗淨。再者，驅動逆洗用泵27，將已過濾之處理液SL導入至中空絲膜41的內部作為逆洗淨液，將中空絲膜41進行逆洗淨。In addition, as described above, the drained water is discharged from the immersion tank 50 to the outside of the system, and after the discharge, the alkali cleaning liquid AL is supplied to the immersion tank 50 through the pipe 45, and the bundle 42 is immersed in the alkali cleaning liquid AL to be washed. . Further, the backwashing pump 27 is driven, and the filtered treatment liquid SL is introduced into the hollow fiber membrane 41 as a backwashing liquid, and the hollow fiber membrane 41 is backwashed.
如前述，藉由定期地洗淨之方式，利用鹼洗淨液AL去除附著沉積在中空絲膜42的膜面之捕捉非水溶性油分，能使中空絲膜之過濾性能大致完全地恢復。As described above, the alkali-washing liquid AL is used to remove the water-insoluble oil adhering to the film surface of the hollow fiber membrane 42 by means of the periodic cleaning, whereby the filtration performance of the hollow fiber membrane can be substantially completely restored.
其結果，可在不使處理水量降低的情況下，長期持續地獲得非水溶性油分含量未達5mg/L，進而成為1mg/L之已處理之液體，為優異之含油汚水之處理裝置。以此方式獲得之已處理之液體，可利用作為例如灌溉用水。As a result, it is possible to continuously obtain a treated liquid having a water-insoluble oil content of less than 5 mg/L and further to 1 mg/L without causing a decrease in the amount of treated water, and it is an excellent oily sewage treatment apparatus. The treated liquid obtained in this way can be utilized as, for example, irrigation water.
本第3實施形態之含油排水處理裝置係可作為油田含油汚水用、含有油分之工廠排水等任意領域之含油排水處理裝置使用。The oil-containing drainage treatment apparatus according to the third embodiment can be used as an oil-containing drainage treatment apparatus in any field such as an oil-containing sewage for oil field and a factory drainage containing oil.
於第10(A)、(B)圖顯示第4實施形態之高溫含油排水處理裝置。The high-temperature oil-containing drainage treatment apparatus according to the fourth embodiment is shown in Figs. 10(A) and (B).
要處理之含油排水，其溫度60~200℃、含油量為20~2000mg/L、懸浮成分之含量為100~10000mg/L，以具備分離膜模組62之過濾裝置(含油排水處理裝置)63進行精密過濾。The oil-containing drainage to be treated has a temperature of 60 to 200 ° C, an oil content of 20 to 2000 mg/L, and a suspended component content of 100 to 10000 mg/L, and a filtration device (oil-containing drainage treatment device) having the separation membrane module 62 63 Perform precision filtration.
前述過濾裝置63之分離膜模組62係使用與前述第1實施形態同様之由延伸PTFE多孔質管所構成之中空絲膜2，過濾裝置63之全體構成係前述第1圖所示之構成，亦配置有散氣手段，標註同一符號而省略說明。The separation membrane module 62 of the filtration device 63 is a hollow fiber membrane 2 composed of a porous PTFE porous tube which is the same as the above-described first embodiment, and the entire configuration of the filtration device 63 is the configuration shown in Fig. 1 described above. The means for dispersing air is also disposed, and the same reference numerals are used to omit the description.
前述分離膜模組62之各中空絲膜2亦可為單層、複層之其中之一，在各中空絲膜2係作為前述外壓過濾式或外壓循環過濾式使用之情形下，作成為外徑1~5mm、內徑0.5~4mm、過濾面之氣孔率30~90%而較佳為40~80%。Each of the hollow fiber membranes 2 of the separation membrane module 62 may be one of a single layer and a composite layer, and each of the hollow fiber membranes 2 is used as the external pressure filtration type or the external pressure circulation filtration type. The outer diameter is 1 to 5 mm, the inner diameter is 0.5 to 4 mm, and the porosity of the filtration surface is 30 to 90%, preferably 40 to 80%.
在作為前述內壓過濾式或內壓循環式使用之情形下，外徑1.3~20mm、內徑1~10mm、過濾面之氣孔率30~90%而較佳為40~80%。In the case of the internal pressure filtration type or the internal pressure circulation type, 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%.
又，將前述中空絲膜2之抗張力設為30N以上、150N以下，IPA起泡點為50kPa以上、400kPa以下。Moreover, the tensile strength of the hollow fiber membrane 2 is 30 N or more and 150 N or less, and the IPA foaming point is 50 kPa or more and 400 kPa or less.
具備集束有多數條中空絲膜2而成之集束體3的分離膜模組62係如第10(B)圖所示，為了讓較高黏度之含油排水流通，中空絲膜的充填面積相對於該分離膜模組之剖面積為20~60%。The separation membrane module 62 having the bundle body 3 in which a plurality of hollow fiber membranes 2 are bundled is shown in Fig. 10(B), and the filling area of the hollow fiber membrane is relatively large in order to allow the oily drainage of a higher viscosity to flow. The separation membrane module has a sectional area of 20 to 60%.
本實施形態中，分離膜模組62中，捆束中空絲膜2之集束體3下端之封止材4及打開上端開口且封止之固定材5(上端封止材)為直徑100~500mm之圓形，通常，中空絲膜模具分離膜模組的分離尺寸係廣泛使用相鄰的中空絲膜2之間隔(中空絲膜之分離尺寸)，在此，將中空絲膜模具分離膜模組的分離尺寸加寬至0.5mm~5mm，得以確保含油排水之流路。In the present embodiment, in the separation membrane module 62, the sealing material 4 at the lower end of the bundle 3 of the hollow fiber membrane 2 is bundled, and the fixing material 5 (upper end sealing material) having the upper end opened and sealed is 100 to 500 mm in diameter. The circular shape, usually, the separation size of the hollow fiber membrane mold separation membrane module is widely used by the interval between adjacent hollow fiber membranes 2 (the separation size of the hollow fiber membrane), here, the hollow fiber membrane mold separation membrane module The separation size is widened to 0.5mm~5mm to ensure the flow path of the oily drainage.
前述下端之封止材4及打開上端開口且封止之固定材5(上端封止材)、收容集束體3之外筒6、上部罩蓋7、下部罩蓋9係以熱變形溫度為120℃以上之耐熱性樹脂形成。The sealing material 4 at the lower end and the fixing material 5 (upper end sealing material) which is opened and closed at the upper end, and the outer tube 6, the upper cover 7, and the lower cover 9 which accommodate the bundle body 3 have a heat distortion temperature of 120. A heat resistant resin of ° C or more is formed.
該耐熱性樹脂係使用芳香族胺硬化系環氧樹脂、PFA、PEF、PVDE等。連結棒16係SUS。前述外筒亦可為SUS等金屬製。As the heat resistant resin, an aromatic amine hardening epoxy resin, PFA, PEF, PVDE or the like is used. The connecting rod 16 is a SUS. The outer cylinder may be made of metal such as SUS.
又，介設於上下罩蓋7、9和外筒6之間之O型環係鐵氟龍、氟橡膠、金屬和鐵氟龍併用型，具有耐熱性。Further, the O-ring type Teflon, fluorine rubber, metal and Teflon which are interposed between the upper and lower covers 7, 9 and the outer tube 6 have heat resistance.
在具備前述中空絲膜模組62之過濾裝置63中，將已加溫之含油排水利用與前述第1實施形態同様的方式進行過濾處理，使透過該分離膜模組62之處理液，處理至處理水中之非水溶性油分含量為5mg/L以下，懸浮成分含量為0~1mg/L。In the filtration device 63 including the hollow fiber membrane module 62, the oil-containing drainage water that has been heated 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 to 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.
又，將中空絲膜模組62與第1實施形態同様地進行洗淨處理。Further, the hollow fiber membrane module 62 is washed in the same manner as in the first embodiment.
由於前述分離膜模組62會形成停止時和運作時之溫差大的熱循環，因此中空絲膜2之分離距離設定成較大，所以在上下封止材容易產生龜裂。Since the separation membrane module 62 forms a thermal cycle having a large temperature difference between the stop and the operation, the separation distance of the hollow fiber membrane 2 is set to be large, so that the upper and lower sealing materials are likely to be cracked.
因此，本實施形態之分離膜模組62係以下述方法製造。Therefore, the separation membrane module 62 of the present embodiment is produced by the following method.
將複數條中空絲膜2隔著預定間隔配置在容器內。此時，如前述，中空絲膜間之分離距離L1隔開為較寬廣之0.5~5mm。The plurality of hollow fiber membranes 2 are placed in the container at predetermined intervals. At this time, as described above, the separation distance L1 between the hollow fiber membranes is spaced apart by a wide range of 0.5 to 5 mm.
在前述容器內充填前述熱變形溫度為120℃以上之熱硬化性樹脂，且在50℃下進行預備加熱後，於常溫下至少保持6小時進行預備硬化。The thermosetting resin having a heat distortion temperature of 120 ° C or higher is filled in the container, and after preliminary heating at 50 ° C, it is preliminarily cured at room temperature for at least 6 hours.
接著，以使用時之100℃溫度以上且熱變形溫度120℃以下之溫度條件，進行1小時以上加熱。Next, heating is performed for 1 hour or more at a temperature of 100 ° C or higher and a heat distortion temperature of 120 ° C or lower at the time of use.
然後，以至少6小時以上且1℃/分鐘之溫度梯度進行緩冷。Then, the slow cooling is carried out with a temperature gradient of at least 6 hours and 1 ° C/min.
如前述，藉由製造分離膜模組，即使使用時以前述熱循環使用，亦能降低或防止龜裂之產生，且即使中空絲膜間之分離距離寬大，亦不會在封止材產生龜裂，關於此情形，本發明者經由實驗已確認。As described above, by manufacturing the separation membrane module, even if it is used in the above-described thermal cycle, the occurrence of cracks can be reduced or prevented, and even if the separation distance between the hollow fiber membranes is large, the turtle is not produced in the sealing material. Crack, in this case, the inventors have confirmed through experiments.
在前述構成所成之加溫含油排水處理裝置中，由於中空絲膜係以具有耐熱性之PEFE形成，因此能防止軟化而使孔徑變化的情形，且能防止因反覆負載之熱震(thermal shock)而產生破裂或龜裂。再者，能使中空絲膜和上下封止材之間、或該封止材本身不易產生龜裂。In the warmed oil-containing drainage treatment apparatus formed as described above, since the hollow fiber membrane is formed of PEFE having heat resistance, it is possible to prevent softening and to change the pore diameter, and to prevent thermal shock due to repeated load (thermal shock) ) caused by cracking or cracking. Further, it is possible to prevent cracking between the hollow fiber membrane and the upper and lower sealing materials or the sealing material itself.
再者，相較於以往使用之處理裝置，能較為輕量化及小型化，不佔設置空間。且，具有於洗淨或膜狀態之調查時，能容易地取出分離膜模組之優點。Furthermore, compared with the conventionally used processing apparatus, it can be made lighter and smaller, and does not occupy an installation space. Moreover, it has the advantage of being able to easily take out the separation membrane module when investigating the state of washing or film.
本發明並不限定於前述實施形態，作為中空絲膜亦可使用由支持層和過濾層所構成之複層或者非對稱之中空絲膜，亦可以是由1個均勻之多孔質管所構成之單層。又，亦可將中空絲膜彎曲成U字狀，將上端兩側形成開口以固定材固定之集束體。再者，洗淨液係以使用鹼洗淨液進行洗淨為佳，但亦可以僅為使用已處理之液體的逆洗淨。The present invention is not limited to the above embodiment, and a hollow fiber membrane may be a multi-layer or asymmetric hollow fiber membrane composed of a support layer and a filter layer, or may be composed of one uniform porous tube. Single layer. Further, the hollow fiber membrane may be bent into a U shape, and a bundle body having an opening fixed to the fixing material may be formed on both sides of the upper end. Further, the cleaning liquid is preferably washed with an alkali cleaning solution, but may be used only for reverse washing using the treated liquid.
包含不超越本發明之要旨之範圍的各種形態。Various aspects are included that do not depart from the gist of the invention.
本發明所用之被處理液適合使用於實施形態中所述之油田含油污水之處理用，然而除了含有切削油劑等之工業排水之處理以外，亦可適用於含有非水溶性油分之食品排水等。The liquid to be treated used in the present invention is suitable for use in the treatment of oily wastewater in the oil field described in the embodiment. However, in addition to the treatment of industrial drainage including cutting oil, it can also be applied to food drainage containing water-insoluble oil. .
1、31、40、62．．．含油排水處理用之分離膜模組1, 31, 40, 62. . . Separation membrane module for oily drainage treatment
2、32、41．．．中空絲膜2, 32, 41. . . Hollow fiber membrane
2a．．．上端開口2a. . . Upper opening
2b．．．管2b. . . tube
2c．．．薄片2c. . . Thin slice
3、33、42．．．集束體3, 33, 42. . . Cluster
4．．．封止材4. . . Sealing material
5、34、35．．．固定材5, 34, 35. . . Fixing material
6．．．外筒6. . . Outer tube
6c、7a．．．導出口6c, 7a. . . Outlet
7、9、36、37．．．罩蓋7, 9, 36, 37. . . Cover
8．．．導出用配管8. . . Export piping
9a、36a．．．導入口9a, 36a. . . Guide
10．．．導入用配管10. . . Piping for introduction
10A、10B、12A、12B．．．分支管10A, 10B, 12A, 12B. . . Branch pipe
10C．．．排出管10C. . . Drain pipe
11、37a．．．排出口11, 37a. . . Discharge
12．．．循環用配管12. . . Cyclic piping
14．．．散氣用空氣導入管14. . . Air inlet pipe for air distribution
15．．．鼓風機15. . . Blower
16．．．補強棒16. . . Reinforcing rod
19、28、45．．．配管19, 28, 45. . . Piping
20、30、60．．．含油排水處理裝置20, 30, 60. . . Oily drainage treatment device
21．．．含油排水儲存槽twenty one. . . Oily drain storage tank
22．．．洗淨液儲存槽twenty two. . . Cleaning solution storage tank
24、25、29．．．切換閥24, 25, 29. . . Switching valve
23．．．泵twenty three. . . Pump
26．．．處理液儲存槽26. . . Treatment fluid storage tank
27．．．逆洗用泵27. . . Backwash pump
43．．．連結棒43. . . Link rod
46．．．裙形材46. . . Skirt
50．．．浸漬槽50. . . Dip tank
63、102．．．過濾裝置63, 102. . . filter
101．．．陶瓷分離膜101. . . Ceramic separation membrane
OL、100．．．含油排水OL, 100. . . Oily drainage
AL．．．鹼洗淨液AL. . . Alkali cleaning solution
SL．．．處理液SL. . . Treatment fluid
S．．．空間S. . . space
第1圖係第1實施形態之含油排水處理用之分離膜模組的剖視圖。Fig. 1 is a cross-sectional view showing a separation membrane module for oil-containing drainage treatment according to the first embodiment.
第2圖係顯示具備第1實施形態之分離膜模組的含油排水處理裝置之全體圖。Fig. 2 is a view showing the entire oil-containing drainage treatment apparatus including the separation membrane module of the first embodiment.
第3(A)、(B)圖係多孔質複層中空絲膜之示意構成圖。Fig. 3(A) and (B) are schematic diagrams showing the structure of a porous multi-layer hollow fiber membrane.
第4圖係顯示實施例、比較例的測試裝置之圖。Fig. 4 is a view showing the test apparatus of the examples and the comparative examples.
第5(A)、(B)、(C)圖係顯示實施例1、比較例1、實施例2的結果之圖表。The graphs of the results of Example 1, Comparative Example 1, and Example 2 are shown in Figs. 5(A), (B), and (C).
第6圖係第2實施形態之含油排水處理用之分離膜模組之剖視圖。Fig. 6 is a cross-sectional view showing a separation membrane module for oil-containing drainage treatment according to the second embodiment.
第7圖係顯示具備第2實施形態之分離膜模組的含油排水處理裝置之全體圖。Fig. 7 is a view showing the entire oil-containing drainage treatment apparatus including the separation membrane module of the second embodiment.
第8圖係第3實施形態之含油排水處理用之分離膜模組的剖視圖。Fig. 8 is a cross-sectional view showing a separation membrane module for oil-containing drainage treatment according to a third embodiment.
第9圖係顯示具備第3實施形態之分離膜模組的含油排水處理裝置之全體圖。Fig. 9 is a view showing the entire oil-containing drainage treatment apparatus including the separation membrane module of the third embodiment.
第10(A)、(B)圖係第4實施形態之分離膜模組的剖視圖。10(A) and (B) are cross-sectional views of the separation membrane module of the fourth embodiment.
第11圖係顯示習知例之圖。Figure 11 is a diagram showing a conventional example.
1．．．含油排水處理用之分離膜模組1. . . Separation membrane module for oily drainage treatment
2．．．中空絲膜2. . . Hollow fiber membrane
2a．．．上端開口2a. . . Upper opening
3．．．集束體3. . . Cluster
4．．．封止材4. . . Sealing material
5．．．固定材5. . . Fixing material
6．．．外筒6. . . Outer tube
7．．．上部罩蓋7. . . Upper cover
7a．．．導出口7a. . . Outlet
8．．．導出用配管8. . . Export piping
9．．．下部罩蓋9. . . Lower cover
9a．．．導入口9a. . . Guide
10．．．導入用配管10. . . Piping for introduction
11．．．排出口11. . . Discharge
12．．．循環用配管12. . . Cyclic piping
14．．．散氣用空氣導入管14. . . Air inlet pipe for air distribution
16．．．補強棒16. . . Reinforcing rod
S．．．空間S. . . space
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009100379AJP5446416B2 (en) | 2008-07-08 | 2009-04-16 | Separation membrane module for oil-containing wastewater treatment, oil-containing wastewater treatment method, and oil-containing wastewater treatment equipment |
| Publication Number | Publication Date |
|---|---|
| TW201038489A TW201038489A (en) | 2010-11-01 |
| TWI480231Btrue TWI480231B (en) | 2015-04-11 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW099104930ATWI480231B (en) | 2009-04-16 | 2010-02-17 | Method for processing oil-containing waste |
| Country | Link |
|---|---|
| TW (1) | TWI480231B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI648094B (en)* | 2015-11-18 | 2019-01-21 | 日商三菱重工環境 化學工程股份有限公司 | Water treatment system |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5564021B2 (en)* | 2011-09-05 | 2014-07-30 | 住友電気工業株式会社 | Oil-containing wastewater treatment system |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI252776B (en)* | 2000-09-21 | 2006-04-11 | Mitsubishi Rayon Co | The perforated membrane |
| TW200906477A (en)* | 2007-07-03 | 2009-02-16 | Sumitomo Elec Fine Polymer Inc | Flat film element for filtration and flat film filtrating modules |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI252776B (en)* | 2000-09-21 | 2006-04-11 | Mitsubishi Rayon Co | The perforated membrane |
| TW200906477A (en)* | 2007-07-03 | 2009-02-16 | Sumitomo Elec Fine Polymer Inc | Flat film element for filtration and flat film filtrating modules |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI648094B (en)* | 2015-11-18 | 2019-01-21 | 日商三菱重工環境 化學工程股份有限公司 | Water treatment system |
| Publication number | Publication date |
|---|---|
| TW201038489A (en) | 2010-11-01 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |