M418125 • « • 係經由擔體結合诸（例如共價鍵結合法、離子結合法及物理吸附 法等）或截留法（例如格子型及微膠囊型），將酵素或微生物固定 於一介質中，再使反應所須之原料通過該結合有微生物或酵素之 介質，以產生所欲之產物。此反應器使微生物或酵素不會流失而 可重複使用，且可提高單位體積内活性物質之濃度及耐受性，故 可增加反應效率，因而被運用於多項工業製程（如異構糖之製造） 中。然而，充填型生物反應器亦非全無缺點，其缺點包括：固定 化過程易導致微生物死亡或酵素失活、介質間之立體障礙與擴散 • 特性不利於穩定的反應速率、介質容易堵塞故原料必須限制為不 含微粒之澄清液體等。因此，充填型生物反應器仍有待改進之處。 至於膜型生物反應器，因其不具充填型生物反應器之缺點，復 具有分離功能，故於近年來廣受矚目，主要可分為游離型及強制 透過型二類。游離型膜生物反應器係結合一攪拌槽型生物反應器 與一膜裝置，其中，微生物或酵素係在反應器内保持游離狀態而 進行所欲反應（一般為分解反應），反應後之低分子量產物則可通 過該膜裝置而於透過端收集取出。此反應器多應用於製備澱粉、 ® 纖維素、或蛋白質等高分子物質的水解產物。強制透過型膜生物 反應器則係於一膜内固定一酵素，並於施加壓力下使反應原料通 過該膜以進行酵素反應，所得之透過物質即為所欲之產物。 儘管膜型生物反應器於反應效率及製程操作上具有許多優點， 但受限於各種不同生物反應製程所須之反應器的規格與形式，故 於可實際應用之範疇仍相當有限。因此，仍有設計出一種具高度 運用彈性及適應性之膜型生物反應器的需求，以達到大量生產或 處理之目標。 5 M418125 另一方面，廢水中之氨氮污染物（例如NH/)主要係來自家庭 污水、工業廢水及農業化學肥料，該氨氮污染物具生物毒性、會 消耗水中溶氧，造成水庫優養化等環境問題。因此，於廢（污） 水處理過程中，必須先將氨氮污染物移除，方可排放。傳統上會 使用氣以移除氨氮污染物，然此將增加廢水處理成本，且於水中 生成對環境及生物體有害之氣化物，故現多改以生物處理程序進 行氨氮之去除。 傳統之生物除氮過程包括硝化程序與脫硝程序。硝化程序係先 於好氧條件下，藉由氨氧化菌（ammoniaoxidizing bacteria，下文 簡稱為「AOB菌」）將氨氮氧化為亞硝酸鹽（N02_)，再經由亞硝 酸鹽氧化菌（nitrite oxidizing bacteria，下文簡稱為「NOB菌」）’ 將亞硝酸鹽氧化成硝酸鹽（no3_)，其反應方程式如下式（1)所 示。 NH4++ 1.82 〇2 +0.13 C〇2-> 0.026 C5H7O2N + 0.97 NO3' + 0.92 H20 + 1.97 IT ( 1 ) 其中，AOB菌與NOB菌多屬化學自營性（autotrophic)，其生長 所須的碳源僅為水中之二氧化碳或無機之碳酸氫根（HCO，）。 脫硝程序則係於厭氧條件下，藉由脫硝菌將硝酸鹽或亞硝酸鹽 還原成氮氣（N2)，再經由排出氮氣而完成生物除氮的過程，其反 應方程式如下式（2)所示。 4 N03- + 5 C + 2 H20 — C02 + 4 HC〇3· + 2 N2 (2) 脫硝菌以化學異營性（heterotrophic )為主，其生長須要如曱醇、 乙醇、醋酸鈉、或葡萄糖等有機碳作為碳源。 業經開發出許多應用上述硝化/脫硝程序以移除廢水中之氨氮 M418125 的生物反應器，此等生物反應器，須結合好氧自營性硝化作用與 厭氧異營性脫硝作用二種截然不同、甚至相反的程序，始能達成 生物除氮之目的，故產生以下不利之處：（〇須大片土地面積以 串聯兩種程序之處理/反應槽，使操作變得複雜且提升成本；（？） 異營性脫硝程序中須添加有機碳作為脫硝菌之生長碳源，以確保 脫硝反應順利進行，因而會有殘留碳源及產生大量污泥此會增 加後續污泥處理及去除殘留碳源的困難度與成本；（3)硝化作用 會產生酸，脫硝作用則產生鹼，故於操作時須分別添加鹼劑及酸 劑，以維持微生物生長所須之pH值，確保反應穩定進行，而此增 加操作複雜度與成本；以及（4)硝化作用須於好氧環境了進行， 而脫硝作用須於厭氧環境下進行，此二階段之廢水中溶氧濃度的 控制與轉換，亦將增加操作的困難性。 針對上述缺失，儘管已有許多改良方法被提出’例如利用單槽 式生物反應器於單槽内進行硝化/脫硝作用、利用生物固定化技術 及改良反應器之設計等。然而，由於無法有效阻隔硝化/脫硝兩種 反應環境之相互干擾’亦無法避免有機碳源之使用，故改善效果 相當有限。 為解決使用有機碳源所衍生出之各項問題•，已有「完全自營性 生物除氮技術」之相關研究被提出。其中，係於硝化過程中進行 「部分硝化（partial nitrification)」，使氨氧化菌（AOB菌）將氨 氣氧化為亞硝酸鹽後即停止’木再繼續將亞硝酸鹽氧化為硝酸 鹽，如下式（3)所示： NHt+ + 1.5 02 + 2 HC03' ^ N02' + 3 H20 + 2 C02 ( 3 ) 接著’於脫硝過程中，使用一種自營性厭氧氨氧化菌（anaer〇bic M418125 體及至少-上述<微生物反應模組，其中，該至少—微生物反應 模組係設置於該槽體中。 本創作之詳細技術及較佳實施態樣，將描述於以下内容中以 供本創作所屬領域具通常知識者據以明瞭本創作之特徵。 【實施方式】 ° ^本文尤其後附中請專利範圍中）’除非另外說明，所使用 之「一」、「該」及類似用語應理解為包含單數及複數形式。 本創作係關於一種微生物反應模組，其係包含一支架結構該 支架結構係定義出-由至少三個表面所環繞之立體㈣，其中， 〜等表面之至）—者之至少—部分係由透氣性親水性薄膜構成， 其餘表面則由相同或不同之不透氣層所構成，從而使該立體空間 為-役閉空間以容納微生物，以進行生化反應，且直中*多於一 表面為由錢性親水㈣輯成時，料透氣簡水性=膜係相 同或不同。 寺疋。之本創作微生物反應模組係藉由—支架結構而定義出 :供容納微生_的立財間，該立體㈣係由至少三個表面所 環^於本創作微生物反應模組之某些實施態樣中，該支架結構 例如—圓柱體、多角錐或多角柱空間’其Μ繞出該圓 :工間之上下表面係為圓形或_形，環繞出該圓柱體或多肖 ^ J次不问，％繞出該多角錐或多角柱空間 之各側表面係相同或不同。 舉例言之，如第I薗所+ π 圖斤 可經由二圓形框架ΗΗ與二或多根 條狀支架102之纟且合，定義+ , 疋義出一由二個表面（即上表面103、下表 面104及側表面105)環繞 田町圓柱體空間106。其t，視構成側 9 M418125 表面105之材質硬度，可視需要而省略條狀支架102。又，如第2 圖所示，可經由十二根條狀支架201之組合，定義出一由六個表 面（即上表面202、下表面203、左表面204、右表面205、前表 面206及後表面207)所環繞出的長方體空間208。或者，如第3 圖所示，可經由六根條狀支架301之組合，定義出一由四個表面 (即，下表面302及三側之側表面303)所環繞出的三角錐空間 304 等。 於本創作微生物反應模組中，該由支架結構所定義出之立體空 間，其環繞表面之至少一者之至少一部分係由透氣性親水性薄膜 構成，其餘則分別由相同或不同之不透氣層所構成。較佳地，本 創作微生物反應模組之支架結構係定義出一圓柱體空間或多角柱 體空間，且環繞出該圓柱體空間或多角柱體空間之上下表面之一 或二者係由透氣性親水性薄膜構成，其餘則由不透氣層構成。更 佳地，該支架結構係定義出一多角柱空間，例如四角柱空間，且 環繞出該多角柱空間之上下表面之一或二者係由透氣性親水性薄 膜構成，其餘表面則由不透氣層構成。於本創作微生物反應模組 之一具體實施態樣中，支架結構係定義出一長方體空間，且環繞 出該長方體空間之上下表面之一或二者係由透氣性親水性薄膜構 成，其餘表面則由不透氣層構成。 於本創作微生物反應模組，當環繞立體空間之多於一表面係由 透氣性親水性薄膜構成時（如該長方體之上下二表面皆由透氣性 親水性薄膜構成），各該透氣性親水性薄膜可為相同或不同，即， 可由相同或不同之材料所構成，視實際需求而定。 根據本創作，可以該支架結構之一部份作為環繞該立體空間之 M418.125 一❹個表面’即二者[體成型之結構。舉例言之如下文配 合弟4圖與第5圖說明之態樣，可經由一長方體中空支架而定義 出一長方體《，該支架結構搬本身即作為構成環繞該長方體 空間之前後左右側之表面4〇5、4〇6、術、之不透氣層（第* 圖）；亦可經由-圓柱體中空支架定義出—圓柱體空間，該支架結 構502本身即作為構成環繞該圓柱體空間之側表面5〇5之不透氣 層（第5圖）。 藉由透氣性親水性薄膜與不透氣層構成環繞微生物反應模組 之立體空間的各表面，可使該立體空間形成一「密閉空間」。於本 文中，所謂「密閉空間」，係指對於微生物或酵素等高分子物質而 言，皆無法通過該透氣性親水性薄膜與不透氣層而進出該立體空 間，故其對於前述物質便形成一「密閉空間」，惟對於小分子、離 子或氣體等物質而言，仍可通過該透氣性親水性薄膜之孔隙而進 出該立體空間’故其對於彼等小分子物質而言仍為一「開放空 間」。因此，本創作微生物反應模組之立體空間屬一「密閉空間」 以包覆微生物。 以該呈密閉空間之立體空間來容納微生物，係具有諸多優點。 如上所述，於習知之連續式攪拌槽型生物反應器中，須要避免流 體相中雜菌的汙染及防止微生物隨流體相而流失；而於充填型生 物反應器中’則易於微生物之固定化過程中導致微生物死亡而喪 失活性。於本創作微生物反應模組之立體空間中，由於微生物係 呈游離態而侷限於密閉空間内，故不會隨流體相而流失，且其他 雜菌亦無法進入該密閉空間而造成污染；此外，將微生物侷限於 密閉空間内並不須要固定化處理，可避免導致微生物死亡。因此， 11 M418125 相較於習知生物反應器，本創作微生物反應模組可更廣泛地應用 於各種生物反應製程中。 根據本創作之微生物反應模組，所使用之支架結構與不透氣層 之材質並無特別限制，惟應具有使實質上任何物質皆無法通過之 性質且不會與所容納之微生物及所處理之對象物發生反應，可使 用如木材、金屬或高分子聚合物（如壓克力）等材料且可任意組 合使用。 此外，基於本說明書之教導，熟習此項技藝者可視需要選擇任 何合宜之材料以提供透氣性親水性薄膜，只要可提供能使離子或 氣體等小分子物質通過，微生物或酵素等高分子物質則無法通過 之功能。一般而言，人工合成之材料具有較佳之抗機械力及耐久 度，而天然材料則較不具生物毒性。 舉例言之，本創作所採之透氣性親水性薄膜可由選自以下群組 之材料所構成：洋菜膠、明膠、褐藻膠、鹿角菜膠（carrageenan )、 聚丙烯醯胺、聚苯乙烯、聚乙烯醇、聚乙二醇、及前述之組合； 較佳地，係由選自以下群組之材料所構成：聚乙烯醇、褐藻膠、 及前述之組合。聚乙烯醇因具有價格便宜、不具生物毒性及強度 高等優點，且成形方式亦較多元且易於操作，尤其適用於提供本 創作所需之透氣性親水性薄膜。再者，透氣性親水性薄膜可呈較 厚之層狀形式或較薄之薄膜形式，較佳為薄膜形式，如具有厚度 0.5毫米至10毫米之薄膜，較佳為0.8毫米至3毫米，可視實際應 用而加以調整。 可視需要選擇任何合宜之方式，以透氣性親水性薄膜或不透氣 層構成環繞立體空間之表面。舉例言之，可使用如黏著劑或釘子 12 M418125,. 等將透氣性親水性薄膜或不透氣層固定於支架結構上構成環繞表 面；或可選用具有黏性之材料作為支架結構、透氣性親水性薄膜 或不透氣層，則可直接將透氣性親水性薄膜或不透氣層覆於支架 結構上，而毋須使用黏著劑或釘子；或者，亦可使用前述之組合 方式。 根據本創作，可於製作微生物反應模組之過程中，將具有所欲 反應活性之微生物先注入該立體空間内，再將構成最後一面環繞 表面之透氣性親水性薄膜（或不透氣層）覆於框架上，提供該微 • 生物反應模組。或者，可進一步於環繞立體空間之該等表面之至 少一者上，設置一可開啟之填料口，以利於視需要裝填、補充微 生物至該立體空間，增加本創作微生物反應模組之操作便利性。 本創作微生物反應模組之一實施態樣係如第4圖所示。微生物 反應模組401係包含由一長方體中空木材框架所形成之支架結構 402，其定義出由上表面403、下表面404、左表面405、右表面 406、前表面407及後表面408共六個表面所環繞之立體空間409。 上表面403及下表面404係由聚乙烯醇透氣性親水性薄膜構成， 且左表面405設置有一填料口 410。於進行生物反應前，將一具有 所欲反應活性之微生物經由填料口 410注入至立體空間409中 後，關閉填料口 410,並將微生物反應模組401置入一適當之設備 或裝置中，以進行生物反應。較佳地，係以避免使由透氣性親水 性薄膜構成的上表面403及下表面404朝下的方式，將微生物反 應模組401置放於反應設備或裝置中。於進行反應時，實質上沒 有任何物質可通過由木材骨架所構成之左表面405、右表面406、 前表面407及後表面408 (由不透氣層構成），且如微生物或酵素 13 M418125 等大分子物質及大部分的水（或其他流體），亦無法通過由透氣性 親水性薄賴構成之上表面及τ表面·僅有如氣體或離子 等小分子物質可通過上表面403及下表面綱而進出立體空間 409’故該具所欲反應活性之微生物係被偈限於呈密閉空間之立體 空間409内，而不會流失。 本創作微生物反應模組之另_實施態樣係如第5圖所示。微生 物反應核組5G1包含由-壓克力中空圓柱形框架所形成之支架結 構502，其定義出由上表面503、下表面5〇4及側表面5〇5共三個 表面所環繞之立體空間506。上表面5〇3係由聚乙烯醇透氣性親水 性薄膜構成，下表面504係由壓克力不透氣層構成，側表面5〇5 則由支架結構502構成’且側表面5〇5上係設置有—填料口 507。 於進行生物反應之前，將一具有所欲反應活性之微生物經由填料 口 507注入至立體空間506中後，關閉填料口 507，並將微生物反 應模組501置入一適當之設備或裝置中，即可進行生物反應。較 佳地，係以避免使由透氣性親水性薄膜構成的上表面5〇3朝下的 方式，將微生物反應模組501置放於反應設備或裝置中。於進行 反應時，實質上沒有任何物質可通過由壓克力側表面505 (形成一 不透氣層）及下表面504，且如微生物或酵素等大分子物質及大部 分的水（或其他流體），亦無法通過由透氣性親水性薄膜構成之上 表面503’僅有如氣體或離子等小分子物質 <通過上表面503而進 出立體空間506,故該具所欲反應活性之微生物係被侷限於呈密閉 空間之立體空間506内，而不會流失。 [本創作微生物反應模纽於污水處理之應用】 M418125 (3) 微生物生長所須之養分可通過透氣性親水性薄膜而到達立體 空間内，使生長速率極為緩慢且難以语養的ANAMM〇X菌可源源 不絕地於該立體空間内生^，並保留於其内，而毋須額外補充； (4) 即使ANAMMOX菌於反應過赛中死亡，因其被侷限於立體 空間内，而不會流至反應模組外，故降低了後續處理因微生物死 亡所產生之污泥的困難度，例如吁免除於一般污水處理廠為處理 污泥所設置之沉澱槽，從而降低成本；另一方面’亦可經由於表 面所設置之填料口，補充新鮮的ANAMMOX菌，故操作方便； (5) 將ANAMMOX菌侷限於立體空間内，提高了微生物單位體 乃 積的濃度及密度’增加細胞間之聯繫作用，使其脫硝反應速率遠 較一般含有呈游離態之ANAMMOX菌的活性污泥者為高；以及 (6) 已知可見光對ANAMMOX菌之活性具有抑制作用，而本創 作微生物反應模組係經透氣性親水性薄膜及不透氣層所覆蓋，具 阻隔可見光之效果’使可見光不會直接照射到ANAMMOX菌，因 而確保了 ANAMMOX菌的反應活性。 本創作亦提供一種生物反應裝置，其係包含一槽體及至少一本 創作之微生物反應模組，其中，該至少一微生物反應模組係設置 ） 於該槽體中》該槽體之規格、尺寸、形式與材料並無特別限制， 熟習此項技藝者基於本說明書之敎示，可端視所欲進行之生物反 應的種類與目的、工薇或設備的規模大小、或程序設計之規劃等 因素而定。該槽體可為開放式或密閉式，舉例言之，當該槽體為 密閉式時，可於該槽體上方提供有一密封蓋，使本創作生物反應 裝置形成一密閉系統；而當須要開放式之槽體時，則可移除該密 封盘，使本創作生物反應裝置形成一開放系統，使裝置内部可與 16 M418125. 外界空氣直接接觸。、此外，可視實際需要而調整生物反應裝置内 微生物反應模組的數量及配置方式。 由於本創作微生物反應模組具有高度運用彈性，故本創作生物 反應裝置亦可應用於各種生物反應之領域中。於一實施態樣中， 係將本創作生物反應裝置用於污水處理，其中待處理之污水係置 於該槽體内而淹沒該微生物反應模組之至少一部分。於此，可依 照實際污水濃度負荷調整微生物反應模組之數量與配置方式。 茲以下列具體實施態樣以進一步例示說明本創作。其中該些實 Λ 施態樣僅提供作為說明，而非用以限制本創作之範疇。 實施例1、透氣性親水性薄膜製作及通透性測試 [製作透氣性親水性薄膜] 首先，於100克之水中加入16克之聚乙烯醇及0至4克之褐 藻膠，並置於加熱板上加熱溶解並持續攪拌約2小時，當溶液達 到透明無色的程度時，再將其置於室溫下無塵處冷卻12小時。最 後，將溶液注入一長30公分、寬20公分、高1毫米之壓克力平 ; 板内，再浸置於無菌之成形液（50% NaN03)中約40分鐘使其硬 化，即可製得厚度為1毫米之透氣性親水性薄膜，以無菌水沖洗 數次，並浸泡於無菌食鹽水中，保存於4°C乏冰箱中備用。 [測試透氣性親水性薄膜之通透性】 為測試透氣性親水性薄膜之基質通透性，另設計一透氣性親水 性薄膜通透性測試反應槽，如第6圖所示。槽體601主要係由雙 層壓克力構成，且為長30公分、寬20公分、高25公分之長方體， 槽體中央則以面積為5公分χ5公分之透氣性親水性薄膜602阻隔 17M418125 • « • The enzyme or microorganism is fixed in a medium by means of a combination of carriers (for example, covalent bond bonding, ion bonding, physical adsorption, etc.) or a retention method (for example, a lattice type and a microcapsule type). The raw materials required for the reaction are passed through the medium to which the microorganisms or enzymes are combined to produce the desired product. The reactor can be reused without losing the microorganisms or enzymes, and can increase the concentration and tolerance of the active substance per unit volume, thereby increasing the reaction efficiency, and thus is used in various industrial processes (such as the manufacture of isomerized sugars). ). However, the filling bioreactor is not completely flawless. The disadvantages include: the immobilization process is easy to cause microbial death or enzyme inactivation, and the steric obstacle and diffusion between the media. The characteristics are not conducive to stable reaction rate, and the medium is easily blocked. It must be limited to a clear liquid containing no particles, and the like. Therefore, there is still room for improvement in the packed bioreactor. As for the membrane type bioreactor, since it has the disadvantage of not filling the bioreactor and has a separation function, it has been widely recognized in recent years, and can be mainly classified into a free type and a forced transmission type. The free membrane bioreactor is combined with a stirred tank bioreactor and a membrane device, wherein the microorganism or enzyme is kept in a free state in the reactor to carry out the desired reaction (generally a decomposition reaction), and the low molecular weight after the reaction The product can be collected and removed at the transmissive end by the membrane device. This reactor is widely used to prepare hydrolysates of high molecular substances such as starch, cellulose, or protein. The forced-transmissive membrane bioreactor is a method in which an enzyme is immobilized in a membrane, and a reaction raw material is passed through the membrane under pressure to carry out an enzyme reaction, and the obtained permeate is a desired product. Although membrane type bioreactors have many advantages in terms of reaction efficiency and process operation, they are limited by the specifications and forms of the reactors required for various biological reaction processes, and thus are still quite limited in practical applications. Therefore, there is still a need to design a membrane type bioreactor with high flexibility and adaptability to achieve mass production or processing goals. 5 M418125 On the other hand, ammonia nitrogen pollutants (such as NH/) in wastewater mainly come from domestic sewage, industrial wastewater and agricultural chemical fertilizers. The ammonia nitrogen pollutants are biologically toxic and will consume dissolved oxygen in water, resulting in reservoir maintenance. Environmental issues. Therefore, in the process of waste (sewage) water treatment, ammonia nitrogen pollutants must be removed before they can be discharged. Traditionally, gas is used to remove ammonia nitrogen contaminants, which will increase the cost of wastewater treatment and create a gasification that is harmful to the environment and organisms in the water. Therefore, the removal of ammonia nitrogen by biological treatment procedures has been changed. The traditional biological nitrogen removal process includes a nitrification process and a denitration process. The nitrification process prior to aerobic conditions, the ammonia nitrogen is oxidized to nitrite (N02_) by ammonia oxidizing bacteria (hereinafter referred to as "AOB bacteria"), and then nitrite oxidizing bacteria (nitrite oxidizing bacteria, Hereinafter, it is simply referred to as "NOB bacteria"). The nitrite is oxidized to nitrate (no3_), and the reaction equation is as shown in the following formula (1). NH4++ 1.82 〇2 +0.13 C〇2-> 0.026 C5H7O2N + 0.97 NO3' + 0.92 H20 + 1.97 IT ( 1 ) Among them, AOB and NOB are mostly autotrophic, and the carbon required for their growth The source is only carbon dioxide in water or inorganic bicarbonate (HCO,). The denitration process is based on anaerobic conditions, the nitrate or nitrite is reduced to nitrogen (N2) by denitrifying bacteria, and the biological nitrogen removal process is completed by discharging nitrogen. The reaction equation is as follows (2) Shown. 4 N03- + 5 C + 2 H20 — C02 + 4 HC〇3· + 2 N2 (2) Denitrifying bacteria are mainly chemically heterotrophic, and their growth needs to be sterol, ethanol, sodium acetate, or Organic carbon such as glucose is used as a carbon source. Many bioreactors have been developed to remove the ammonia nitrogen M418125 from wastewater by using the above-mentioned nitrification/denitration procedure. These bioreactors must be combined with aerobic self-nitration and anaerobic denitrification. A completely different or even the opposite procedure can achieve the purpose of biological nitrogen removal, which has the following disadvantages: (there is no need to process large areas of land to connect the two processing/reaction tanks in series, which complicates the operation and increases the cost; (?) Organic carbon should be added as a carbon source for denitrifying bacteria in the heterotrophic denitrification process to ensure smooth denitrification, so there will be residual carbon sources and large amounts of sludge, which will increase subsequent sludge treatment and removal. Difficulty and cost of residual carbon source; (3) Nitrification will produce acid, and denitrification will produce alkali. Therefore, alkali and acid should be added separately during operation to maintain the pH required for microbial growth and ensure the reaction. Stable, which increases operational complexity and cost; and (4) nitrification must be carried out in an aerobic environment, and denitrification must be carried out in an anaerobic environment. The control and conversion of the dissolved oxygen concentration will also increase the difficulty of operation. In view of the above-mentioned shortcomings, although many improved methods have been proposed, for example, the use of a single-tank bioreactor for nitrification/denitration in a single tank, utilization Bio-immobilization technology and design of improved reactors, etc. However, due to the inability to effectively block the mutual interference of the nitrification/denitration reaction environments, the use of organic carbon sources cannot be avoided, so the improvement effect is rather limited. Issues arising from the source • Relevant research on “completely self-supporting biological nitrogen removal technology” has been proposed. Among them, “partial nitrification” is carried out in the nitrification process to make ammonia oxidizing bacteria ( AOB bacteria will stop the oxidation of ammonia to nitrite and then stop the oxidation of nitrite to nitrate, as shown in the following formula (3): NHt+ + 1.5 02 + 2 HC03' ^ N02' + 3 H20 + 2 C02 (3) then 'in the denitration process, a self-supporting anammox bacteria (anaer〇bic M418125 body and at least - the above <microbial reaction module, wherein, at least - The microbial reaction module is disposed in the trough. The detailed techniques and preferred embodiments of the present invention will be described in the following content for those of ordinary skill in the art to which the present invention pertains. The present invention relates to a singular and plural form. Unless otherwise stated, the terms "a", "the" and the like are used in the singular and plural. , the system comprising a stent structure defining a three-dimensional (four) surrounded by at least three surfaces, wherein at least a portion of the surface is composed of a gas permeable hydrophilic film, the remaining surface It is composed of the same or different gas-impermeable layers, so that the three-dimensional space is a closed space for accommodating microorganisms for biochemical reaction, and when more than one surface is composed of money hydrophilic (four), Breathable water=The film system is the same or different. Temple 疋. The creation of the microbial reaction module is defined by a scaffolding structure: for the purpose of accommodating the micro-library, which is surrounded by at least three surfaces and implemented in some embodiments of the microbial reaction module of the present invention. In the aspect, the support structure, for example, a cylinder, a polygonal pyramid or a polygonal column space, is wound around the circle: the upper surface of the work surface is circular or _-shaped, and the cylinder is surrounded or multi-dimensionally Regardless, % surrounds the side surfaces of the polygonal or polygonal column space to be the same or different. For example, if the 第 + + 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由 经由The lower surface 104 and the side surface 105) surround the Tamachi cylindrical space 106. The t, depending on the material hardness of the surface 105 of the constituting side 9 M418125, the strip-shaped bracket 102 may be omitted as needed. Moreover, as shown in FIG. 2, six surfaces (ie, upper surface 202, lower surface 203, left surface 204, right surface 205, front surface 206, and the like) may be defined via a combination of twelve strip-shaped brackets 201. The cuboid space 208 surrounded by the rear surface 207). Alternatively, as shown in Fig. 3, a triangular pyramid space 304 surrounded by four surfaces (i.e., the lower surface 302 and the side surfaces 303 on the three sides) may be defined via a combination of six strip brackets 301. In the present microbial reaction module, the three-dimensional space defined by the stent structure, at least a part of at least one of the surrounding surfaces is composed of a gas permeable hydrophilic film, and the rest are respectively made of the same or different gas impermeable layers. Composition. Preferably, the scaffolding structure of the present microbial reaction module defines a cylindrical space or a polygonal cylindrical space, and one or both of the lower surfaces surrounding the cylindrical space or the polygonal cylindrical space are breathable. It is composed of a hydrophilic film, and the rest is composed of a gas-impermeable layer. More preferably, the support structure defines a polygonal column space, such as a quadrangular prism space, and one or both of the lower surfaces surrounding the polygonal column space are composed of a gas permeable hydrophilic film, and the remaining surfaces are airtight. Layer composition. In one embodiment of the present microbial reaction module, the scaffold structure defines a cuboid space, and one or both of the lower surfaces surrounding the cuboid space are composed of a gas permeable hydrophilic film, and the remaining surfaces are It consists of a gas impermeable layer. In the present microbial reaction module, when more than one surface surrounding the three-dimensional space is composed of a gas permeable hydrophilic film (for example, the upper and lower surfaces of the cuboid are composed of a gas permeable hydrophilic film), each of the gas permeable hydrophilicity The films may be the same or different, i.e., may be composed of the same or different materials, depending on actual needs. According to the present invention, one part of the support structure can be used as a structure of M418.125 which surrounds the three-dimensional space. For example, as shown in the following figure, in conjunction with the description of FIG. 4 and FIG. 5, a rectangular parallelepiped may be defined via a rectangular hollow support, which itself acts as a surface 4 around the front and rear sides of the rectangular space. 〇5,4〇6, surgery, the gas-impermeable layer (Fig.*); or a cylindrical space defined by a cylindrical hollow support, the support structure 502 itself as a side surface constituting the space surrounding the cylinder 5 〇 5 of the gas-tight layer (Figure 5). The space surrounding the three-dimensional space of the microbial reaction module is formed by the gas permeable hydrophilic film and the gas impermeable layer, so that the three-dimensional space can form a "closed space". As used herein, the term "closed space" means that a polymer material such as a microorganism or an enzyme cannot enter or exit the three-dimensional space through the gas permeable hydrophilic film and the gas impermeable layer, so that a substance is formed in the space. "Confined space", but for small molecules, ions or gases, the space can still enter and exit through the pores of the gas permeable hydrophilic film, so it is still "open" for their small molecules. space". Therefore, the three-dimensional space of the present microbial reaction module belongs to a "closed space" to coat microorganisms. The use of the three-dimensional space in a confined space to accommodate microorganisms has many advantages. As described above, in the conventional continuous stirred tank type bioreactor, it is necessary to avoid contamination of the bacteria in the fluid phase and prevent the loss of microorganisms with the fluid phase; in the packed bioreactor, it is easy to immobilize the microorganisms. The process causes microbial death and loss of activity. In the three-dimensional space of the microbial reaction module of the present invention, since the microorganisms are in a free state and are confined in a confined space, they are not lost with the fluid phase, and other bacteria cannot enter the confined space to cause pollution; Microorganisms are confined to confined spaces and do not require immobilization to avoid microbial death. Therefore, 11 M418125 is a more widely used bioreactor process than traditional bioreactors. According to the microbial reaction module of the present invention, the material of the stent structure and the gas-impermeable layer used is not particularly limited, but has the property that substantially no substance can pass, and does not interfere with the microorganisms and the processed microorganisms. The object reacts, and materials such as wood, metal, or high molecular polymer (such as acrylic) can be used and can be used in any combination. In addition, based on the teachings of the present specification, those skilled in the art can select any suitable material to provide a gas permeable hydrophilic film as long as it can provide a small molecule such as ions or gas, and a high molecular substance such as a microorganism or an enzyme. Unable to pass the function. In general, synthetic materials have better resistance to mechanical and durability, while natural materials are less biotoxic. For example, the breathable hydrophilic film taken in the present invention may be composed of materials selected from the group consisting of agar extract, gelatin, alginate, carrageenan, polyacrylamide, polystyrene, Polyvinyl alcohol, polyethylene glycol, and combinations of the foregoing; preferably, are comprised of materials selected from the group consisting of polyvinyl alcohol, alginate, and combinations of the foregoing. Polyvinyl alcohol has the advantages of being inexpensive, non-biotoxic and high in strength, and is also versatile and easy to handle, and is particularly suitable for providing a breathable hydrophilic film required for the present creation. Further, the gas permeable hydrophilic film may be in the form of a thick layer or a thin film, preferably in the form of a film, such as a film having a thickness of 0.5 mm to 10 mm, preferably 0.8 mm to 3 mm, visible. Adjusted for practical use. Any suitable method may be selected as needed to form a surface surrounding the three-dimensional space with a gas permeable hydrophilic film or a gas impermeable layer. For example, a gas permeable hydrophilic film or a gas impermeable layer may be fixed on the stent structure to form a surrounding surface, such as an adhesive or a nail 12 M418125, or the like; or a viscous material may be used as the stent structure, and the gas permeability is hydrophilic. The film or the gas impermeable layer may directly coat the gas permeable hydrophilic film or the gas impermeable layer on the stent structure without using an adhesive or a nail; or, a combination of the foregoing may be used. According to the present invention, in the process of fabricating the microbial reaction module, the microorganism having the desired activity is first injected into the three-dimensional space, and then the gas permeable hydrophilic film (or gas impermeable layer) constituting the last side is covered. The micro-bioreactor module is provided on the frame. Alternatively, an openable filler port may be further disposed on at least one of the surfaces surrounding the three-dimensional space to facilitate loading and replenishing microorganisms to the three-dimensional space as needed, thereby increasing the operational convenience of the microbial reaction module of the present invention. . An embodiment of the present microbial reaction module is shown in Figure 4. The microbial reaction module 401 comprises a support structure 402 formed by a rectangular hollow wood frame defining six surfaces of an upper surface 403, a lower surface 404, a left surface 405, a right surface 406, a front surface 407 and a rear surface 408. A three-dimensional space 409 surrounded by a surface. The upper surface 403 and the lower surface 404 are composed of a polyvinyl alcohol gas permeable hydrophilic film, and the left surface 405 is provided with a filler opening 410. Before the biological reaction, a microorganism having the desired reactivity is injected into the three-dimensional space 409 through the filling port 410, the filling port 410 is closed, and the microbial reaction module 401 is placed in a suitable device or device. Carry out a biological reaction. Preferably, the microbial reaction module 401 is placed in a reaction apparatus or apparatus in such a manner as to prevent the upper surface 403 and the lower surface 404 composed of the gas permeable hydrophilic film from facing downward. When the reaction is carried out, substantially no substance can pass through the left surface 405, the right surface 406, the front surface 407 and the rear surface 408 (consisting of a gas impermeable layer) composed of a wood skeleton, and is as large as a microorganism or an enzyme 13 M418125. Molecular substances and most of the water (or other fluids) cannot form the upper surface and the surface of the τ by the gas permeable hydrophilic thin layer. Only small molecules such as gases or ions can pass through the upper surface 403 and the lower surface. In and out of the three-dimensional space 409', the microorganisms having the desired reactivity are confined to the three-dimensional space 409 in a confined space without being lost. Another embodiment of the present microbial reaction module is shown in Figure 5. The microbial reaction nuclear group 5G1 comprises a support structure 502 formed of an acrylic hollow cylindrical frame, which defines a three-dimensional space surrounded by three surfaces of an upper surface 503, a lower surface 5〇4 and a side surface 5〇5. 506. The upper surface 5〇3 is composed of a polyvinyl alcohol gas permeable hydrophilic film, the lower surface 504 is composed of an acrylic gas impermeable layer, and the side surface 5〇5 is composed of a stent structure 502 and the side surface 5〇5 is attached. A packing port 507 is provided. Before the biological reaction, a microorganism having the desired reactivity is injected into the three-dimensional space 506 via the filling port 507, the filling port 507 is closed, and the microbial reaction module 501 is placed in a suitable device or device, that is, A biological reaction can be performed. Preferably, the microbial reaction module 501 is placed in a reaction apparatus or apparatus in such a manner as to prevent the upper surface 5?3 composed of the gas permeable hydrophilic film from facing downward. When the reaction is carried out, substantially no substance can pass through the acrylic side surface 505 (forming a gas impermeable layer) and the lower surface 504, and macromolecules such as microorganisms or enzymes and most of the water (or other fluid) It is also impossible to form the upper surface 503' by the gas permeable hydrophilic film, and only the small molecule substance such as gas or ion < enters the three-dimensional space 506 through the upper surface 503, so that the microorganism having the desired reactivity is limited. It is in the three-dimensional space 506 of the closed space without being lost. [Application of the microbial reaction module in wastewater treatment] M418125 (3) The nutrients required for microbial growth can reach the three-dimensional space through the gas permeable hydrophilic film, making the growth rate extremely slow and difficult to maintain ANAMM〇X bacteria. It can be continuously sourced in the three-dimensional space and retained in it without additional supplementation; (4) Even if ANAMMOX bacteria die in the reaction, they are confined to the three-dimensional space and will not flow to Outside the reaction module, it reduces the difficulty of subsequent treatment of sludge caused by microbial death, such as calling for the removal of the sedimentation tank provided by the general sewage treatment plant for sludge treatment, thereby reducing costs; The fresh ANAMMOX bacteria are supplemented by the filling port provided on the surface, so the operation is convenient; (5) The ANAMMOX bacteria are confined to the three-dimensional space, and the concentration and density of the microbial unit body are increased to increase the intercellular connection. The denitration reaction rate is much higher than that of the activated sludge generally containing the free ANAMMOX bacteria; and (6) the known visible light has an inhibitory effect on the activity of ANAMMOX bacteria. Effect, and the present microorganism reactor module authoring system covered by the gas-permeable gas-impermeable film and a hydrophilic layer having a barrier effect of visible light 'so that the visible light is not irradiated directly ANAMMOX bacteria, because reactivity is ensured ANAMMOX bacteria. The present invention also provides a biological reaction device comprising a tank body and at least one of the created microbial reaction modules, wherein the at least one microbial reaction module is disposed in the tank body, the size of the tank body, Dimensions, forms and materials are not particularly limited, and those skilled in the art will be able to look at the type and purpose of the desired biological reaction, the size of the work or equipment, or the planning of the program based on the description of the present specification. Depending on the factors. The tank body may be open or closed. For example, when the tank body is closed, a sealing cover may be provided above the tank body to form a closed system of the present bioreactor; and when it is required to be opened In the case of the tank, the sealing disc can be removed to form an open system for the creation of the bioreactor, so that the interior of the device can be in direct contact with 16 M418125. of outside air. In addition, the number and arrangement of microbial reaction modules in the bioreactor can be adjusted according to actual needs. Due to the high flexibility of the creative microbial reaction module, the bioreactor can also be applied to various biological reaction fields. In one embodiment, the inventive bioreactor is used in sewage treatment, wherein the sewage to be treated is placed in the tank to flood at least a portion of the microbial reaction module. Here, the number and configuration of the microbial reaction modules can be adjusted according to the actual sewage concentration load. The following specific implementations are used to further illustrate the creation. These examples are provided for illustrative purposes only and are not intended to limit the scope of the present invention. Example 1. Preparation and permeability test of gas permeable hydrophilic film [Preparation of gas permeable hydrophilic film] First, 16 g of polyvinyl alcohol and 0 to 4 g of alginate were added to 100 g of water, and placed on a hot plate to be heated and dissolved. Stirring was continued for about 2 hours, and when the solution reached a level of clear colorlessness, it was allowed to cool at room temperature for 12 hours in a dust-free place. Finally, the solution is injected into a zipper of 30 cm in length, 20 cm in width and 1 mm in height; the plate is then immersed in a sterile forming solution (50% NaN03) for about 40 minutes to harden it. A gas permeable hydrophilic film having a thickness of 1 mm was washed several times with sterile water, immersed in a sterile saline solution, and stored in a refrigerator at 4 ° C for use. [Testing the permeability of the gas permeable hydrophilic film] To test the matrix permeability of the gas permeable hydrophilic film, a gas permeable hydrophilic film permeability test reaction tank was further designed as shown in Fig. 6. The tank body 601 is mainly composed of a double laminated gram force, and is a rectangular parallelepiped of 30 cm in length, 20 cm in width and 25 cm in height, and a gas permeable hydrophilic film 602 having an area of 5 cm to 5 cm is blocked in the center of the tank.