200819190 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種適用於廢水處理之濾材，特別是 指一種適用於固液分離型薄膜生物處理技術之濾材 (filtration media) 〇 【先前技術】 薄膜生物反應器（Membrane Bioreactor，簡稱MBR ) 技術，因為具有優質的出流水、污泥產量少、佔地面積小 # 、可去除難分解的有機物等優點，已應用於越來越多的商 業化廢水處理系統。 由於薄膜生物反應器處理技術是利用薄膜截留微生物 與固體物，而濾出淨化過的水，因此，薄膜被污染、阻塞 或積垢（fouling)導致薄膜通量降低，是MBR技術較常見 的問題。 早期薄膜（membrane)濾材大多為微孔性（microporous)( 孔徑大小0.1〜10/xm範圍）的聚合物材料或無機陶瓷材料，常 ® 見的聚合物濾材有中空纖維膜（hollow_fiber )，及利用相轉 換（phase inversion)技術，使聚合物溶液塗層上溶劑揮發後 - 產生的微孔性聚合物薄膜。其中陶瓷製的薄膜因為成本昂 貴且易碎，較少被使用，中空纖維膜則容易阻塞且不易清 洗，為其最大的缺點，而微孔性聚合物薄膜雖然成本較低 、清洗容易，但是機械強度較差，所以其應用範圍即受限 制。 近來已有人提出利用不織布作為濾材，由於不織布容 5 200819190 易製造’且機械強度良好’而具有極佳的發展潛力。缺而 ，不織布為多層纖維互相重疊的網狀結構物，具有多個相 連開放性孔隙，當水或廢水通過 +、哉布％，液相中的粒子 可被攔截而吸附在不織布表面上或孔隙内，經過_段時間 後，許多粒子會在纖維表面上集結成團粒，最後， 網表面形成滤餅，亦即所謂的積垢現象（fGuling)，而造成 薄膜通量降低。200819190 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a filter material suitable for wastewater treatment, and more particularly to a filtration medium suitable for solid-liquid separation type membrane biological treatment technology. Membrane Bioreactor (MBR) technology has been applied to more and more businesses because of its high quality outflow water, low sludge production, small footprint, and the removal of difficult organic materials. Wastewater treatment system. Since the membrane bioreactor treatment technology utilizes the membrane to trap microorganisms and solids, and filters out the purified water, the membrane is contaminated, blocked or fouled, resulting in a decrease in membrane flux, which is a common problem of MBR technology. . Most of the early membrane filters are microporous (pore size 0.1~10/xm range) polymer materials or inorganic ceramic materials. The polymer filters commonly used in the ® have hollow fiber membranes (hollow_fiber) and utilize them. A phase inversion technique that produces a microporous polymer film after evaporation of the solvent on the polymer solution coating. Among them, the ceramic film is less expensive because it is expensive and brittle, and the hollow fiber membrane is easy to block and difficult to clean, which is the biggest disadvantage, while the microporous polymer film is low in cost and easy to clean, but mechanical. The strength is poor, so its application range is limited. Recently, it has been proposed to use non-woven fabric as a filter material, and has excellent development potential due to the non-woven fabric 5 200819190 which is easy to manufacture and has good mechanical strength. In short, non-woven fabric is a network structure in which multi-layer fibers overlap each other, and has a plurality of connected open pores. When water or wastewater passes through +, 哉%%, particles in the liquid phase can be intercepted and adsorbed on the surface of the non-woven fabric or pores. Inside, after a period of time, many particles will aggregate into agglomerates on the surface of the fiber. Finally, the surface of the mesh forms a filter cake, also known as the fouling phenomenon (fGuling), which causes the film flux to decrease.
為了減少不織布濾材阻塞，已有商品於不織布表面塗 佈多孔性聚合«層’使該多孔性塗層的孔隙尺寸小於不 織布的孔隙尺寸，以減少進入不織布的粒子，而降低不織 布阻塞的機率’且以不織布為支撐結構可保有較佳的機械 強度。但疋，因多孔性聚合物塗層本身佈滿孔隙，造成塗 層的強度差變差，容易與不織布剝離，而減少據材的使用 壽命。 因此，如何減少濾材阻塞機率，以降低濾材清洗頻率 ’增加濾材使用壽命，仍為一待解決的課題。 【發明内容】 為了解決前述課題，發明人等經過多方研究與實驗， 發現以孔隙尺寸較一般不織布孔隙尺寸窄小的纖維薄層， 來取代現有的聚合物塗層作為過濾層，並可利用貼合方式 將至少一層的纖維薄層貼合於作為支撐結構的不織布之表 面’或可利用靜電紡絲法（electrostatic-spinniiig method)直 接在不織布表面形成纖維薄層，由於纖維薄層的結構為非 常細的纖維所組成，具有較佳的過濾效果。再者，以具疏 6 200819190 水2的纖維所製成的纖維薄層，較不易吸附液相中的粒子 ，能減少表面積垢以維持較大的薄膜通量，而具有較佳的 透膜性此（pernieability) 〇 因此，本發明之目的，即在提供一種表面不易積垢而 能維持較大的操作通量、具有較佳透膜性能的濾材。 於是，本發明一種固液分離型薄膜生物處理用的濾材 ’包含一不織布支撐層，及至少一層形成於該支撐層表面 的過濾層，其中，該過濾層係由直徑介於20〜1000奈米的 纖維構成，較佳為5G〜_奈米，且其厚度介於1()〜細微 米，較佳為10〜80微米，並具有介於〇 〇〇1〜15微米的孔隙 ，可依照出流水的水質需求而決定要採用的孔隙尺寸。 適用於製作本發明過濾層的材質為具有疏水性之聚烯 烴，可舉例如聚四氟乙烯（PTFE)、聚乙烯（pE)及聚丙烯 (PP)，其中以聚四氟乙烯為較佳。 適用於形成本發明之過濾層的方式可以是使過濾層先 形成薄膜再貼合於該支撐層上，貼合的方法可舉例如熱壓 黏合（thermal bonding)，亦可貼合較多層數的過濾層，以 增加過濾效率；另一方式是以靜電紡絲法（electr〇st如c spinning)直接於該支撐層上成膜而形成過濾層。 適用於本發明的不織布支撐層的基重介於1〇〜1〇〇〇克/ 平方公尺（g/nf)，其孔隙一般可在丨〜5〇微米，而用於製作 不織布的已知材質眾多，包括聚丙烯（pp)、聚乙烯（pE) 、聚對苯二甲酸乙二醇g旨（PET)、聚對苯二甲酸丁二醇醋 (PBT)及複合纖維等，適用於本發明之不織布的材質可依 7 200819190 製造成本及製程簡便性等考量選用。 本發明的另一目的，是提供一種以前述本發明的濾材 與支撐材（supporting me(iia)所構成的過濾器，以及一種由多 數個前述的過濾器所組合而成的過濾模組。 適用於本發明過濾器的支撐材可以是平面形（flat sheet) 或為多孔圓管形（perforated tube)，該支撐材的具體結構及 其與本發明的濾材之組裝方式，可參考現有的固液分離型 薄膜生物處理技術中所用的過濾器之製備方式，另外，將 多數個以本發明的濾材製成之過濾器組合成過濾模組的方 去亦可採用已知的組合技術，在此不再詳述。 本發明的濾材之過濾層係以纖維所製成，具有疏水性 且其孔隙尺寸小於該支撐層的孔隙尺寸，可減少表面積垢 的形成以維持較大的薄膜通量，而具有較佳的透膜性能。 【實施方式】 以下將藉實施例、實驗例及比較例更詳細地說明本發 明之内容。 <實施例> 參閱圖1，為本發明固液分離型薄膜生物處理用的濾材 之一較隹實施例的結構示意圖。濾材1是由過濾層η及支 揮層12所構成。過濾層11是由PTFE材質所製成，且其纖 維直梭為75 nm、孔隙尺寸0·5 μηι、厚度為18 μιη，並與聚 醋（ρΕΤ)不織布支撐層12貼合。支撐層η的纖維直徑 7·8 μιη、孔隙尺寸17 μηι、厚度為〇_5 mm，基重為25〇 g/m2 200819190 參閱圖2，為本發明固液分離型薄膜生物處理用的過濾 器之第一較佳實施例，過濾器2由平面形多孔支撐材21及 包覆於支撐材21兩面的濾材1所構成，並設有一出水口 22 用以連接抽水幫浦（圖未示）。濾材1的過渡層11位於最外 側’支撐層12位於過濾層11與支撐材21之間。污水是由 過;慮盗2四周先經由過慮層11過渡，再通過支擇層12後成 為淨水，並由出水口 22抽出放流。 參閱圖3,為本發明固液分離型薄膜生物處理用的過濾 器之第二較佳實施例，過濾器3由多孔圓管形支撐材31及 包覆於支撐材31外的濾材1所構成，並設有一出水口 32 用以連接抽水幫浦（圖未示）。濾材丨的過濾層u位於最外 側’過遽後的水經由出水口 32抽出。 參閱圖4,為本發明固液分離型薄膜生物處理用的過濾 模組之一較佳實施例，過濾模組4是利用框架41將多數個 過濾器2組合在一起，並將過濾器2的出水口 21 (參見圖 2)以管線（圖未示）連結至框架41上的出水口 42，並由 出水口 42連接抽水幫浦（圖未示），將過濾後的水抽出。 〈實驗例> 將單片平板形過濾器2(參見圖2)之出口水連接抽水 幫浦，置入體積為30公升的活性污泥反應槽體中，其活性 污泥濃度介於8100〜8500 mg/L，連續過濾三個月後，紀錄 其操作通量、透膜壓差及透膜性能如表1所示，其中濾材 的過濾面積為200 cm2。 ’、、 <比較例> 9 200819190 比車乂例所用的滤材為聚醋不織布，其不織布材質與每 驗例的支撐層相同。比較例的過_試條件比照實驗例^ 其結果亦示於表1。 實驗例 比較例 操作通量 (πι /m2*day) 0.4 0.15 表1 透膜壓差 (kg/cm2) 0.4 0.2 透膜性能 L0_ 0.75 曰由表1之操作通量顯示，實驗例具有較大薄膜操作通 量，亦即長時間操作下，所允許之通量較大，而其透膜性 能也優於比較例。 ' 歸納上述，本發明的濾材以纖維薄層所構成的過據層 具有疏水性且其孔隙尺寸小於該支撐層的孔隙尺寸，同時 ’其過滤層非常薄，可減少表面積垢的形成韓持較大的 薄膜通量’而具有較佳的透難能，故確實能達成本發明 之目的。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明中請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1為一示意圖，說明本發明固液分離型薄膜生物處 理用的濾材之一較佳實施例； 10 200819190 圖為伤剖視不意圖，說明本發明固液分離型薄 膜生物處理用的過濾、器之—第—較佳實施例； 圖3為不忍圖，說明本發明固液分離型薄膜生物處 理用的過濾器之一第二較佳實施例；及 圖4為一示意圖，說明本發明固液分離型薄膜生物處 理用的過濾模組之一較佳實施例。In order to reduce the clogging of the non-woven filter material, it has been commercially available to coat the surface of the non-woven fabric with a porous polymer layer to make the pore size of the porous coating layer smaller than the pore size of the non-woven fabric, so as to reduce the probability of non-woven fabric particles and reduce the probability of non-woven fabric clogging. The non-woven fabric is used as a support structure to maintain better mechanical strength. However, since the porous polymer coating itself is covered with pores, the difference in strength of the coating layer is deteriorated, and it is easy to peel off from the non-woven fabric, thereby reducing the service life of the material. Therefore, how to reduce the filter media blocking probability to reduce the filter media cleaning frequency ‘increasing the filter media life is still a problem to be solved. SUMMARY OF THE INVENTION In order to solve the above problems, the inventors have found through various studies and experiments that a thin layer of fibers having a pore size narrower than that of a general non-woven fabric is used as a filter layer instead of the existing polymer coating layer. In a manner, at least one layer of the fiber layer is attached to the surface of the non-woven fabric as a support structure' or a thin layer of fibers can be directly formed on the surface of the non-woven fabric by an electro-spinning method, because the structure of the thin layer of the fiber is very It is composed of fine fibers and has a better filtering effect. Furthermore, the thin layer of fibers made of fibers having the water of 200819190 water 2 is less likely to adsorb particles in the liquid phase, can reduce the surface area scale to maintain a larger film flux, and has better membrane permeability. Pernieability Therefore, it is an object of the present invention to provide a filter material which has a surface which is less prone to fouling and which can maintain a large operating flux and has a good membrane permeability. Therefore, the filter medium for solid-liquid separation type film biological treatment of the present invention comprises a non-woven support layer and at least one filter layer formed on the surface of the support layer, wherein the filter layer is composed of a diameter of 20 to 1000 nm. The fiber composition, preferably 5G~_nano, and having a thickness of 1 () to fine micron, preferably 10 to 80 micrometers, and having pores between 1 and 15 micrometers, can be The water quality requirements of the flowing water determine the pore size to be used. The material suitable for the production of the filter layer of the present invention is a hydrophobic polyolefin, and examples thereof include polytetrafluoroethylene (PTFE), polyethylene (pE) and polypropylene (PP), of which polytetrafluoroethylene is preferred. The method for forming the filter layer of the present invention may be that the filter layer is first formed into a film and then bonded to the support layer, and the bonding method may be, for example, thermal bonding or a plurality of layers. The filter layer is used to increase the filtration efficiency; the other method is to form a filter layer by directly forming a film on the support layer by an electrospinning method (electr〇st such as c spinning). The non-woven support layer suitable for use in the present invention has a basis weight of from 1 to 1 gram per square meter (g/nf), and its pores are generally 丨5 to 5 μm, and are known for making non-woven fabrics. A wide range of materials, including polypropylene (pp), polyethylene (pE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and composite fibers, suitable for this The material of the non-woven fabric of the invention can be selected according to the manufacturing cost of 7200819190 and the simplicity of the process. Another object of the present invention is to provide a filter comprising the filter medium and the support material (the support me (iia) of the present invention, and a filter module comprising a plurality of the aforementioned filters. The support material of the filter of the present invention may be a flat sheet or a perforated tube. The specific structure of the support material and the assembly method of the filter material of the present invention can be referred to the existing solid liquid. The preparation method of the filter used in the separation type membrane biological treatment technology, in addition, a plurality of filters made of the filter medium of the present invention are combined into a filter module, and a known combination technique can also be used. Further, the filter layer of the filter material of the present invention is made of fiber, has hydrophobicity and has a pore size smaller than the pore size of the support layer, and can reduce the formation of surface area scale to maintain a large film flux, and has [Embodiment] Hereinafter, the contents of the present invention will be described in more detail by way of examples, experimental examples and comparative examples. <Examples> Referring to Fig. 1, The filter medium 1 is composed of a filter layer η and a branch layer 12. The filter layer 11 is made of PTFE material, and The fiber straight shuttle is 75 nm, the pore size is 0·5 μηι, the thickness is 18 μηη, and it is bonded to the poly (vinegar) non-woven support layer 12. The fiber diameter of the support layer η is 7·8 μηη, the pore size is 17 μηι, and the thickness is 〇5 mm, basis weight is 25〇g/m2 200819190 Referring to FIG. 2, a first preferred embodiment of the filter for biological treatment of solid-liquid separation type film according to the present invention, the filter 2 is composed of a planar porous support material. 21 and a filter material 1 coated on both sides of the support material 21, and is provided with a water outlet 22 for connecting a pumping pump (not shown). The transition layer 11 of the filter material 1 is located at the outermost side, and the support layer 12 is located at the filter layer 11 Between the support material 21 and the support material 21, the sewage is passed; the thief is first transferred through the through-layer 11 and then passed through the support layer 12 to become purified water, and is discharged from the water outlet 22. Referring to Fig. 3, the present invention is solid. The second preferred filter for liquid separation type membrane biological treatment In the embodiment, the filter 3 is composed of a porous tubular support material 31 and a filter material 1 coated on the outside of the support material 31, and is provided with a water outlet 32 for connecting a pumping pump (not shown). Filtering of the filter material The water of the layer u located at the outermost side is extracted through the water outlet 32. Referring to Fig. 4, a preferred embodiment of the filter module for biological treatment of solid-liquid separation type film according to the present invention, the filter module 4 utilizes a frame. 41, a plurality of filters 2 are combined together, and the water outlet 21 (see FIG. 2) of the filter 2 is connected to the water outlet 42 on the frame 41 by a pipeline (not shown), and the water outlet 42 is connected to the water pumping port. Pu (not shown), the filtered water is pumped out. <Experimental Example> The outlet water of the single-plate filter 2 (see Fig. 2) was connected to a pumping pump and placed in a 30-liter activated sludge reaction tank with an activated sludge concentration of 8100~ 8500 mg / L, after continuous filtration for three months, record its operating flux, membrane pressure difference and membrane permeability as shown in Table 1, wherein the filter material has a filtration area of 200 cm2. ',, <Comparative Example> 9 200819190 The filter material used in the vehicle example is a polyester woven fabric, and the non-woven fabric material is the same as the support layer of each test case. The over-test conditions of the comparative examples are compared with the experimental examples. The results are also shown in Table 1. Experimental example Comparative operation flux (πι / m2*day) 0.4 0.15 Table 1 Membrane pressure difference (kg/cm2) 0.4 0.2 Permeation performance L0_ 0.75 曰 Displayed by the operating flux of Table 1, the experimental example has a larger film Operating flux, that is, long-term operation, allows for a larger flux, and its membrane permeability is superior to the comparative example. In summary, the filter material of the present invention has a hydrophobic layer composed of a thin layer of fibers and has a pore size smaller than the pore size of the support layer, and at the same time 'the filter layer is very thin, which can reduce the formation of surface area scale. The large film flux 'has better penetrating power, so the object of the present invention can be achieved. However, the above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent change and modification according to the scope of the patent and the description of the invention in the present invention. All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a preferred embodiment of a filter material for biological treatment of a solid-liquid separation type film of the present invention; 10 200819190 is a schematic view of a solid-liquid separation type film of the present invention. A filter for the biological treatment - a preferred embodiment; FIG. 3 is a second preferred embodiment of the filter for biological treatment of the solid-liquid separation type film of the present invention; and FIG. 4 is a BRIEF DESCRIPTION OF THE DRAWINGS A preferred embodiment of a filtration module for biological treatment of a solid-liquid separation membrane of the present invention is illustrated.
11 200819190 【主要元件符號說明】 1 ·· ·.·· 灑材 22 11…… •…過濾層 3 · 12…… •…支撐層 31 2…·· •…過濾器 32 21…… •…支撐材 4 · 21卜· •…第一側 41 212… •…第二側 42 出水口 過濾器 支撐材 出水口 過濾模組 框架 出水口11 200819190 [Explanation of main component symbols] 1 ·· ···· Sprinkling material 22 11... •...Filter layer 3 · 12... •...Support layer 31 2...··•...Filter 32 21...•...Support Material 4 · 21 Bu · •... First side 41 212... •...Second side 42 Outlet filter Support material Outlet filter module frame Outlet
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