經濟部智慧財產局員工消費合作社印製 593168 A7 B7_ 五、發明說明（l ) 發明領域 本發明係關於一種使用固定於多孔性擔體微生物的 廢水/水處理方法，尤其有關一種使用多孔性生物擔體的廢 水/水處理方法。 發明背景 水或廢水生物處理依微生物生長方式可以區分爲懸 浮生長（suspension growth)及固定生長（fixed-film growth)兩 種方式，兩種方式均被普遍採用。但在一些特殊情況如較 長污泥齡（SRT)、較短水力停留時間（HRT)或特殊污染 物的操作條件或處理時，採用微生物固定生長的方式具有 其優點。提供微生物生長及分解污染物之生物擔體可分爲 包埋式（immobilization)及附著式（fixed-film)兩大類。由於 包埋式生物擔體係將事先馴養特殊菌種包埋於生物擔體 中，製造成本較高且質傳效果較差，除特殊情況外，較少 使用。在環工應用上，一般採用附著式生物擔體以降低成 本。早期附著式生物擔體採用塑膠浪板，該材質取得容易 且性質穩定，故相當受歡迎。但由於此類材質比表面積小， 通常介於100〜200m2/m3之間，需要較大反應槽體積，而增 加槽體佔地面積與建造成本。另外，微生物需要較長時間， 才會慢慢附著於其上生長，故需要較長啓動期，操作上較 爲困擾。近年來針對傳統附著式生物擔體之缺點開發多孔 性生物擔體，尤其在比表面積方面，可從傳統的100〜200 m2/m3增加至1000m2/ m3左右或更大，可大幅縮小反應槽體 -4- ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ϋ ϋ i_i 1 I 1 I I I ϋ i-i ϋ 經濟部智慧財產局員工消費合作社印製 593168 A7 __B7_ 五、發明說明（2) 積，以降低操作成本。 反應槽中塡裝該多孔性生物擔體，雖可以加速將植種 的微生物捕捉或攔截於生物擔體之中，達到快速啓動目 的。但多孔性生物擔體通常爲疏水性材質，不僅不利於生 物擔體沈入水中，且不易吸附某些污染物如氨氮及造成色 度的污染物等，使反應槽中的微生物無法將這些污染物有 效率分解及利用。 發明槪要 本發明之一主要目的在於提供一種改良的多孔性生 物擔體，其不具有先前技藝的缺點。 本發明之另一目的在於提供一種使用該改良的多孔 性生物擔體的廢水/水處理方法。 爲達成上述本發明目的，本發明依據待處理水的性質 將多孔性生物擔體改質，改質後的多孔性生物擔體除維持 原有大比表面積特性外，使多孔性生物擔體具有不同特性 如親水性或污染物吸附性等，於是可有效提昇污染物去除 效果。本發明的改質方法包含使作爲多孔性擔體的高分子 發泡體與吸附劑微粒於一水溶液中充份接觸例如通過攪拌 或氣動的方式，而使得吸附劑微粒附著於該發泡體的孔隙 內。在多孔性擔體中添加矽藻土則可以改變擔體表面性質 由疏水性變爲較親水性，而容易沈入水中，不需再額外化 學品如醋酸丁酯以改變其表面性質。亦可以在處理受氨氮 污染的進流水時，在多孔性擔體中添加沸石，於是可以快 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593168 A7 B7_ V. Description of the Invention (1) Field of the Invention The present invention relates to a wastewater / water treatment method using microorganisms fixed on a porous support, and particularly to a method using a porous biological support. Wastewater / water treatment methods. BACKGROUND OF THE INVENTION Biological treatment of water or wastewater can be divided into suspension growth and fixed-film growth according to the growth mode of microorganisms, and both methods are commonly used. However, in some special situations, such as longer sludge age (SRT), short hydraulic retention time (HRT), or operating conditions or treatment of special pollutants, the method of fixed growth of microorganisms has its advantages. Biological carriers that provide microbial growth and decompose pollutants can be divided into two categories: immobilization and fixed-film. Since the embedded bio-burden system embeds the domesticated special bacteria in the bio-burden in advance, the manufacturing cost is high and the mass transfer effect is poor. Except in special cases, it is rarely used. In environmental engineering applications, attached bio-burdens are generally used to reduce costs. Early attached biological carriers used plastic wave boards, which are easy to obtain and stable in nature, so they are quite popular. However, due to the small specific surface area of such materials, which are usually between 100 ~ 200m2 / m3, a larger volume of the reaction tank is required, which increases the footprint and construction cost of the tank. In addition, it takes a long time for the microorganisms to slowly adhere to it and grow. Therefore, it takes a long start-up period, which is more troublesome in operation. In recent years, porous biosupports have been developed to address the shortcomings of traditional attached biosupports, especially in terms of specific surface area, which can be increased from the traditional 100 ~ 200 m2 / m3 to about 1000m2 / m3 or more, which can greatly reduce the reaction tank. -4- ^ The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ϋ ϋ i_i 1 I 1 III ϋ ii 智慧 Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative 593168 A7 __B7_ V. Description of the invention (2) to reduce operating costs. The porous biological support is installed in the reaction tank, although it can accelerate the capture or interception of the seeded microorganisms in the biological support, so as to achieve the quick start. However, porous biocarriers are usually hydrophobic materials, which not only does not help the biocarriers sink into the water, but also is not easy to adsorb certain pollutants such as ammonia nitrogen and pollutants that cause chromaticity, so that microorganisms in the reaction tank cannot contaminate these pollutants. Efficient decomposition and utilization of materials. Summary of the Invention One of the main objects of the present invention is to provide an improved porous biosupport which does not have the disadvantages of the prior art. Another object of the present invention is to provide a wastewater / water treatment method using the improved porous biological support. In order to achieve the above-mentioned object of the present invention, the present invention modifies the porous biological support according to the nature of the water to be treated. The modified porous biological support not only maintains the characteristics of the original large specific surface area, but also allows the porous biological support to have Different characteristics, such as hydrophilicity or pollutant adsorption, can effectively improve the effect of pollutant removal. The modification method of the present invention includes bringing a polymer foam that is a porous support into full contact with adsorbent particles in an aqueous solution, such as by stirring or pneumatically, so that the adsorbent particles are attached to the foam. Within the pores. Adding diatomite to the porous support can change the surface properties of the support from hydrophobic to more hydrophilic, and easily sink into water. No additional chemicals such as butyl acetate are needed to change its surface properties. It is also possible to add zeolite to the porous support when treating influent water contaminated with ammonia nitrogen, so the paper size can be adapted to Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the note on the back first) (Fill in this page again)
-I i_l I i_i I emme 1 一：OJ> ϋ I _1 n ϋ ϋ mam— I 經濟部智慧財產局員工消費合作社印製 593168 A7 __B7___ 五、發明說明（3 ) 速地將氨氮先行吸附於改質後的多孔性生物擔體，再由硝 化菌將氨氮轉化成硝酸氮，達到有效去除進流水中的氨氮 污染物的目的。此外，在多孔性擔體中添加活性碳則對廢 水的真色色度有良好去除效果。 多孔性生物擔體經過本發明方法改質後，除維持多孔 性生物擔體具有之優點如縮短啓動期、反應槽體積小（HRT 較短）外，能夠達到下列目的： a) 改善多孔性擔體親水性。 b) 可快速吸附污染物及微生物再生，以增加污染物去 除效果。 c) 污染物吸附、微生物脫附及微生物分解均在生物擔 體中進行，可縮短反應時間，以減少反應槽體積。 d) 藉由特定吸附劑改質，可以有效去除水或廢水中特 定污染物，達到去除特定污染物之效果。 圖式之簡單說明 圖1顯示本發明的一實施例及一對照例的長時間水處 理結果，其中橫軸爲時間（天）及縱軸爲真色色度値（ADMI 値，美國染料製造協會，American Dye Manufacturers Institute )，及其中圓圈代表進流水的値，正方形代表實施 例的値及三角形代表對照例的値。 較佳具體實施例之詳細說明 本發明揭示一種使用固定於多孔性擔體的微生物的廢 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝-I i_l I i_i I emme 1 I: OJ> ϋ I _1 n ϋ ϋ mam— I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593168 A7 __B7___ 5. Description of the invention (3) Quickly adsorb ammonia nitrogen to the modification After the subsequent porous biological carrier, ammonia nitrogen is converted into nitrate nitrogen by the nitrifying bacteria, so as to achieve the purpose of effectively removing the ammonia nitrogen pollutants in the inflow water. In addition, the addition of activated carbon to the porous support has a good removal effect on the true color and chromaticity of waste water. After the porous biological support is modified by the method of the present invention, in addition to maintaining the advantages of the porous biological support such as shortening the start-up period and small reaction tank volume (shorter HRT), the following objectives can be achieved: a) Improving the porous support Body hydrophilic. b) It can quickly absorb pollutants and regenerate microorganisms to increase the effect of pollutant removal. c) Pollutant adsorption, microbial desorption, and microbial decomposition are all performed in the biological carrier, which can shorten the reaction time and reduce the volume of the reaction tank. d) Modified by a specific adsorbent, it can effectively remove specific pollutants in water or wastewater to achieve the effect of removing specific pollutants. Brief Description of the Drawings Figure 1 shows the long-term water treatment results of an embodiment and a comparative example of the present invention, where the horizontal axis is time (days) and the vertical axis is true color chromaticity 値 (ADMI 値, American Dye Manufacturers Association, American Dye Manufacturers Institute), and in which the circle represents the inflow of 値, the square represents the 値 in the example and the triangle represents the 値 in the comparative example. Detailed description of a preferred embodiment The present invention discloses a waste using microorganisms fixed on a porous support. This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (please read the back first) (Please fill in this page again)
I ϋ I —m 一：^I ·1 1 Α— »ϋ a-ι ϋ I 593l68 A7 B7 $、發明說明（4) 水/水處理方法，包含將一進流水導入一反應槽中，使得該 進流水在該反應槽中滯留一段時間再從該反應槽流出，其 中該進流水中的污染物的一部份在該滯留時間爲反應槽中 的微生物所分解，於是從該反應槽流出的出流水相較於進 流水具有較低含量的污染物，其特徵包含該微生物係附著 於位於該反應槽中的一多孔性擔體，及該多孔性擔體包含 高分子發泡體及附著於該發泡體之孔隙內的吸附劑微粒。 較佳的，該高分子發泡體具有一介於20 kg/m3至60 kg/m3的密度，及一介於30%至100%的孔隙；及該吸附劑 微粒具有一介於0.1-60網目的大小。 較佳的，該多孔性擔體含有以高分子發泡體重量爲基 準的一介於1-100%的吸附劑微粒。 較佳的，該高分子發泡體爲聚胺基甲酸酯發泡體；該 吸附劑微粒爲活性碳，矽藻土或沸石。 較佳的，該多孔性擔體係通過將該高分子發泡體與該 吸附劑微粒於一水溶液中充份接觸，而使得該吸附劑微粒 附著於該高分子發泡體的孔隙內而製備。更佳的，該水溶 液係位於該反應槽中的進流水，及該充份接觸係通過將氣 泡打入該反應槽的底部而達成。 較佳的，該進流水含有氨氮污染物，而該吸附劑微粒 爲沸石。 較佳的，該進流水的真色度爲出流水的兩倍或更高， 而該吸附劑微粒爲活性碳。 較佳的，該多孔性擔體包含複數個體積介於8-125 cm3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) I ^1 ϋ ί ϋ ϋ ϋ 一 δ’ I ϋ ϋ I I i_i ί ·ϋ 經濟部智慧財產局員工消費合作社印製 593168 經濟部智慧財產局員工消費合作社印製 κι Β7_五、發明說明（5 ) 的立方體或球體，且該多孔性擔體的總體積爲該反應槽的 容量的80%。 本發明的一較佳實施例及一對照例被描述如下。使用 兩組反應槽，每個槽體材質均爲聚丙烯酸酯製成之直徑6 cm及高度60 cm的圓柱槽，有效水深50 cm，及有效體積 爲1.4公升（L)。槽體底部安裝曝氣設備以曝氣方式（流 量=1.0 L空氣/min)使槽體內的水溶液呈好氧狀態。 反應槽中添加多孔性擔體，爲PU材質發泡擔體，擔 體規格爲1 cm* 1 cm* 1 cm，故每顆擔體體積爲lcm3，其基 本性質如表1所示。兩槽均放入相同數目的多孔性擔體， 添加量約爲槽體積80%左右，相當於1100顆多孔性擔體。 僅於兩槽中的其中一槽中添加5 g活性碳（實施例）另一槽 則未添加（對照例）。活性碳添加至該反應槽的方式是將擔 體由槽底添加至五分之一槽高時，再將活性碳均勻放置於 槽中，再將其餘擔體裝入反應槽內，接著對實施例的反應 槽注滿進流水，及藉由曝氣所提供的動力使槽內的活性碳 附著於PU發泡擔體的孔隙內。活性碳規格如表2中所示。 該兩反應槽經過微生物植種、馴養後即進行試程實驗，其 實驗條件如表3所示。植種污泥來自工硏院光復院區SBR 廢棄污泥，每槽共植入2100 mg污泥量，故可以維持槽中 污泥濃度爲1500 mg/L，進流水由槽底送入，並進行內循環 一天即完成微生物植種、馴養。 本實施例及對照例所使用之進流水係人工合成基 質，其調配以AO-7爲主要成份，並另外添加尿素、磷酸 (請先閱讀背面之注意事項再填寫本頁) — — — — — — — — — lb. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 593168 κι ____Β7__ 五、發明說明（6) 及氯化鐵等微量成份，提供微生物足夠之養分。人工合成 基質成份如表4。 表1. PU發'? S擔體基本性質 項目 密度 抗張強度 引伸率 範圍 28±5(kg/m3) 0.8 〜0.84(kg/cm2) 240% 〜250% 表2.活性碳規格 項目 單位 範圍 顆粒大小 網目 24 碘値 Mg/g >=1000 苯吸附 Mg/g >450 比表面積 m2/g 900〜1100 強度 % 90 (請先閱讀背面之注意事項再填寫本頁) I ϋ 1 I I 一：OJ n ϋ ϋ ϋ I 1 1 經濟部智慧財產局員工消費合作社印製 表3.實驗條件 組別 對照例 實施例 PU泡綿添加量（顆） 1100 1100 空氣量（L /min ) 1.0 1.0 啓始污泥濃度（mg/L) 1500 1500 活性碳添加量（g ) 0 5 水力停留時間HRT (小時） 12 12 -9- lb. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 593168 A7 B7 五、發明說明（7 )I ϋ I —m One: ^ I · 1 1 Α— »ϋ a-ι ϋ I 593l68 A7 B7 $, Description of Invention (4) Water / water treatment method, which includes introducing an inflow water into a reaction tank, so that The inflow water stays in the reaction tank for a period of time and then flows out of the reaction tank, wherein a part of the pollutants in the inflow water is decomposed by the microorganisms in the reaction tank during the retention time, so the outflow from the reaction tank The flowing water has a lower content of pollutants than the flowing water, and is characterized in that the microorganism is attached to a porous support in the reaction tank, and the porous support includes a polymer foam and is attached to Adsorbent particles in the pores of the foam. Preferably, the polymer foam has a density between 20 kg / m3 and 60 kg / m3, and a pore between 30% and 100%; and the adsorbent particles have a size between 0.1 and 60 mesh. . Preferably, the porous support contains one to 100% of adsorbent particles based on the weight of the polymer foam. Preferably, the polymer foam is a polyurethane foam; the adsorbent particles are activated carbon, diatomaceous earth or zeolite. Preferably, the porous support system is prepared by fully contacting the polymer foam and the adsorbent particles in an aqueous solution so that the adsorbent particles adhere to the pores of the polymer foam. More preferably, the aqueous solution is the inflow water in the reaction tank, and the full contact is achieved by driving air bubbles into the bottom of the reaction tank. Preferably, the influent water contains ammonia nitrogen pollutants, and the adsorbent particles are zeolites. Preferably, the true color of the inflow water is twice or more than that of the outflow water, and the adsorbent particles are activated carbon. Preferably, the porous support includes a plurality of volumes ranging from 8 to 125 cm3. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page ) I ^ 1 ί ί ϋ ϋ ϋ 一 δ 'I ϋ ϋ II i_i ί · ϋ Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 593168 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics κ7 Ⅴ. Description of Invention (5 ), And the total volume of the porous support is 80% of the capacity of the reaction tank. A preferred embodiment and a comparative example of the present invention are described below. Two sets of reaction tanks are used, each of which is a cylindrical tank made of polyacrylate with a diameter of 6 cm and a height of 60 cm, an effective water depth of 50 cm, and an effective volume of 1.4 liters (L). Aeration equipment is installed at the bottom of the tank to make the aqueous solution in the tank aerobic by aeration (flow rate = 1.0 L air / min). A porous support is added to the reaction tank, which is a foamed support made of PU. The specifications of the support are 1 cm * 1 cm * 1 cm, so the volume of each support is 1 cm3. The basic properties are shown in Table 1. Both tanks are filled with the same number of porous supports, and the added amount is about 80% of the volume of the tank, which is equivalent to 1100 porous supports. Only 5 g of activated carbon was added to one of the two tanks (Example) and the other tank was not added (Comparative Example). The method for adding activated carbon to the reaction tank is to add the support from the bottom of the tank to one-fifth of the height of the tank, and then place the activated carbon evenly in the tank, and then load the remaining support into the reaction tank. The reaction tank of the example is filled with inflow water, and activated carbon in the tank is caused to adhere to the pores of the PU foamed support body by the power provided by the aeration. The activated carbon specifications are shown in Table 2. After the two reaction tanks were seeded and domesticated with microorganisms, trial experiments were performed. The experimental conditions are shown in Table 3. The planted sludge comes from the SBR waste sludge in Guangfuyuan of Gongyeyuan. A total of 2100 mg of sludge is implanted in each tank, so the sludge concentration in the tank can be maintained at 1500 mg / L. The inflow water is sent from the bottom of the tank. After the internal circulation is performed for one day, microbial planting and domestication are completed. The inflow water used in this example and the comparative example is an artificial synthetic substrate, which is formulated with AO-7 as the main component, and added with urea and phosphoric acid (please read the precautions on the back before filling this page) — — — — — — — — — Lb. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 593168 κι ____ Β7__ 5. Description of the invention (6) and trace elements such as ferric chloride, provide sufficient nutrients for microorganisms. Synthetic matrix components are shown in Table 4. Table 1. Basic properties of PU's S support. Density and tensile strength. Extension rate range 28 ± 5 (kg / m3) 0.8 to 0.84 (kg / cm2) 240% to 250%. Table 2. Unit range of activated carbon specifications Particle size mesh 24 Iodine 値 Mg / g > = 1000 Benzene adsorption Mg / g > 450 Specific surface area m2 / g 900 ~ 1100 Strength% 90 (Please read the precautions on the back before filling this page) I ϋ 1 II 1 ： OJ n ϋ ϋ ϋ I 1 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 3. Experimental Conditions Group Comparative Example Example PU Foam Addition (Pieces) 1100 1100 Air Volume (L / min) 1.0 1.0 Start Initial sludge concentration (mg / L) 1500 1500 Activated carbon addition (g) 0 5 Hydraulic retention time HRT (hours) 12 12 -9- lb. This paper size is applicable to China National Standard (CNS) A4 (210 X 297) Mm) 593168 A7 B7 V. Description of the invention (7)
_表4:人工合成基質成份 基質 成份 5 0 L廢水 AO-7 50000〜125000 ADMI 營養源 2〜6 ml 營養源（COD 6000 mg/L 添加 2 ml/L) 尿素（Urea) 160.5g/L KH2HPO4 ( K2HPO4) 70 g/L ( 84 g) FeCl3.6H2〇 36 g/L (請先閱讀背面之注意事項再填寫本頁) 從圖1的實驗結果可以看出，本發明實施例（在多孔 性擔體中添加活性碳）對真色色度有良好去除效果，可以使 真色色度從1000〜2500ADMI降至550ADMI (法規要求値） 以下。但在對照例中，無法將進流水中色度去除，出流水 幾乎與進流水的色度相當，並無法達到去除色度效果。 訂-------- •lb. 經濟部智慧財產局員工消費合作社印製 -10 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）_Table 4: Synthetic matrix components Matrix components 50 L wastewater AO-7 50000 ~ 125000 ADMI nutrition source 2 ~ 6 ml nutrition source (COD 6000 mg / L added 2 ml / L) urea (Urea) 160.5g / L KH2HPO4 (K2HPO4) 70 g / L (84 g) FeCl3.6H2〇36 g / L (Please read the precautions on the back before filling this page) From the experimental results in Figure 1, it can be seen that the embodiment of the present invention (in porous Adding activated carbon to the carrier) has a good removal effect on the true color chromaticity, which can reduce the true color chromaticity from 1000 ~ 2500ADMI to less than 550ADMI (regulation requirements 値). However, in the comparative example, the chromaticity of the inflow water cannot be removed, and the effluent water is almost the same as the chromaticity of the inflow water, and the chromaticity removal effect cannot be achieved. Order -------- • lb. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -10-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)