200524673 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關在細粒固體觸媒存在中進行液體反應， 特別是液體-液體或液體-氣體反應所用的裝置。 【先前技術】 已知者，有許多化學反應可能要在增壓下且添加經分 散或懸浮的觸媒後進行。液體反應物可用液相，眾多液相 或另以反應氣體形式導到反應器內。液體反應的例子爲： 低聚合，交換反應，烷基化或異構化，以及異相生物化催 化反應。 於進行此等反應及在內反應動力學的測定中，較佳者 爲使用細分散觸媒，因其可相對於裝有觸媒九粒的固定床 反應器減低壓力降之故。此外，因爲外粒度的結果可大幅 地避免孔隙擴散限制且在放熱反應的情況中，因爲流化觸 媒的封流混合結果導致等溫反應器特性之故，通常不會有 如在固定床反應器中的局部溫度尖峰現象。 於反應中，固體觸媒通常不會被導致產物的反應所消 耗，使得該觸媒不必從反應區排放出。 爲此理由之故，此等懸浮反應時常是在反應器內利用 燒結金屬或陶瓷燒結塊或利用線網結構物所保留住的觸媒 而進行的。此處的一項問題爲在此等過濾元件上會隨著時 間發生濾餅的蓄積，尤其是在液體中有高固體含量之時， 因此會不利地影響觸媒的均勻分布且導致反應器的堵塞之 -5- 200524673 (2) 故。濾餅的蓄積常甚至不能利用攪拌器予以阻止。所以必 須定期地停止反應且必須淸潔過濾元件。 於此種程序的一種變化形式中，有提出於安裝另一過 濾元件讓氫氣通過之下進行氣體/液體反應（氫化反應） 者（U S 5，9 3 5，4 1 8 )。於一預定期間之後，將兩個過濾元 件交換使得於此時的反應液體係移動通過H2過濾元件而氫 氣在此係通過排放過濾元件導入。不過，於此情況中，要 維持住反應器內的精確液體水位會有問題，因爲有兩道獨 立的入流進入反應器內之故。特別是在高線性速度和低滯 留時間，爲動力學硏究所需者之下，此原則爲遭遇到問題 。於以此方式進行的液體反應之情況中，必須給入惰性氣 體，此舉代表一項本爲不需要的花費。 爲了避開此等問題，時常有提出不將觸媒保留在反應 器內而是隨產物排出且使用傳統分離裝置例如傾析器、過 广 濾器、濾棒、旋風器或類似者從液相分離出觸媒者（例如 US 3,901，660 )。此等方法的一項缺點爲若需要將固體作 爲觸媒回流到反應器系統時，隨後需要處置濕固體或濃懸 浮液。再者，當反應要連續進行而在反應器內有轉化率起 伏之下連續地進行之時，因爲觸媒後從反應器連續地取出 ，所以，難以控制要再循環回的觸媒量。 業經提出的另一替代法爲在反應器外部利用交流過濾 來分離觸媒與液體，其中將部份懸浮液從反應器分流出且 循環通過一微濾器，其係在相同壓力下且根據交流原理操 作，並於微爐器取出濾液形式之液體反應產物 -6 - 200524673 (3) (DE 3 2 4 5 3 1 8 )。此處的一項缺點爲同樣會隨時間而蓄 積一濾餅且必須定期淸除，此導致工廠的停機。再者，由 於已知的過濾器材料只能在有限溫度下操作，因此在反應 混合物進入過濾器單元之前，有時後需要減低反應混合物 的溫度。 所提及的所有外部分離方法都具有一項缺陷，亦即， 必須輸送一固體懸浮液。此舉需要額外的泵，其壽命會受 到固體所引起的磨蝕作用進一步限制。 於使用以漿液方式操作的噴佈槽（sparged tanks)或 泡沫塔，如業經對，例如Fischer-Tropsch合成所提出者， 其循環系統必須能夠由新注入的液體或上升泡沬所產生。 不過’因爲時常發生的在液體及/或固體之間的不合用之 質量傳送和熱傳送程序，所以在控制反應中可能在此發生 問題。會預期發生較低的轉化率或者，在放熱反應的情況 ‘ 中，會妨礙反應的反應器內熱分布情況。 ' 所以，本發明的一項目標爲找出一種方法和裝置使得 觸媒可在反應區內以完全有效形式利用而不需有定期中斷 程序用來再生或淸潔之舉。同時，反應粗產物應連續地以 無固體的液體形式獲得。 頃令人訝異地發現，可以從反應混合物連續地得到無 固體的產物，其中在反應器內進行反應之時，粉化觸媒係 以細分散液形式存在，該反應器在出口與出口具有一過濾 元件，且該入口和出口可互換使得入口可用爲出口且該出 口可用爲入口。將出口與入口互換可導致在過濾元件上存 -7- 200524673 (4) 在的任何沈積物沖回到反應器內。 【發明內容】 本發明因而提供一種用於連續操作催化液體反應的反 應器，其中該觸媒係以分散液形式存在於反應區內，其中 該反應器具有至少一入口和一出口，所有起始材料都是通 過一入口給入且所有產生都通過一出口排出，且入口與出 口都裝有一工具，該工具可使入口與出口轉換使得先前用 爲出口的排放處用爲入口的輸入處且於同時，用爲入□的 輸入處於此時用爲出口的排放處，且入口和出口分別裝有 一過濾元件，該等過濾元件將觸媒保持在反應器且該反應 器裝有一裝置，該裝置可確保觸媒和起始材料在反應器內 的均勻分布。 、 本發明同樣提供一種在至少一反應器內連續進行催化 液體反應之方法，其中該觸媒係以分散液形式存在於反應 區內，其中該方法係在至少一根據本發明的反應器內進行 的。 本發明也提供一種至少兩個根據本發明的反應器之組 裝體’彼等反應器係經倂行連接且提供給本發明方法所用 ’爲供局處理量篩選所用的一本發明的反應器或本發明的 組裝體。一般而言且爲本發明目的而言，高處理量篩選係 指觸媒組成與性質的快速檢驗以期將彼等對所探討的反應 或反應類別之工業使用的適當性予以最優化，以及將爲此 目的在倂行操作且較佳經微小化且自動化的裝置中所需的 -8- 200524673 (5) 反應參數（例如壓力、溫度、體積流速、流體動力學滯留 時間）予最最優化。 本發明裝置和本發明的反應器具有下列重要優點： •不需要在外部移除觸媒。因而可消除在懸浮液泵取 中可能發生的問題，例如有限的泵壽命，管路中的沈積， 等。 •可省卻複雜的程序步驟，例如具有高固體裝載率的 液體之輸送，冷卻和降壓到過濾器相容的壓力及將觸媒給 回到反應器內。 •本發明反應器原則上可在任何具有至少一入口和一 出口的商業攪拌槽反應器中實現。 •從裝置所得產物（濾液）通常不會固體，使得下游 程序設備，如蒸餾單元，的垢積爲之消除。 •可以採用的壓力和溫度只受容器的等級及所用的過 濾元件的材料性質所限制。 •本發明反應器展現出與攪拌槽反應器相同的特性。 •本發明反應器也可用於其中觸媒比例超過20體積％ ，較佳者超過30體積％且特別較佳者超過40體積％之反應 〇 本發明裝置也可有利地用來測定內在反應動力學，係 由於細分散觸媒粒子可使壓力降相對於使用觸媒九粒的固 定床反應器較爲減低，因此其使用係較佳者之故。此外， 因爲小粒度的結果，可大幅避免孔隙擴散抑制且於放熱反 應的情況中，因爲流化觸媒會因對流混合導致等溫反應器 -9- 200524673 (6) 行爲，所以常不會有局部溫度尖峰之出現。本發明反應器 可促成使用細分小觸媒粒子的反應以單純形式進行，此爲 此種反應器/反應組合特別可用來測定對反應器的規模擴 大具重要性的內在反應動力學之原因。 【實施方式】 下面要說明本發明裝置和本發明方法，但本發明不限 於此等具體實例。 供連續操作性催化液體反應所用，其中觸媒係以分散 液形式用於反應區內的本發明反應器具有至少一入口和至 少一出口，所有的起始材料都通過一入口給入且所有產物 係通過一出口排出。入口和出口都裝有一工具，該工具可 使入口和出口相連使得先前用的出口的排放處於此用爲入 ^ 口的輸入處且同時，用爲入口的輸入處改用的出口的排放 處。入口和出口各裝有一過濾元件用以將觸媒保持在反應 器之內。此外，反應器裝有一裝置用以確保觸媒和起始材 料在反應器中的均勻分布。此種裝置可爲，例如，馬達驅 動攪拌器，例如，葉輪攪拌器。 轉換入口和出口所用工具可爲，例如，一四向閥，其 中有兩對相連的排放處。若含有超過一個出口和一個入口 之時’必須使用一個具有相應較大數目排放處的閥，或者 對於每一對入口和出口分別有一個四向閥。所用的閥可人 工或自動地f架作（例如’電動或氣動），可通過一*習用的 程序控制系統進行調整。 -10- 200524673 (7) 轉換入口和出口所用工具 的轉換。不過，其也可以有利 的反應器，該感測器係連接到 根據反應器內的壓力控制該轉 於反應器入口和出口處的 器活性材料之例如，燒結金屬 物、陶瓷整體（monolith)、 編織金屬線構造物；或者可完 依照要在反應器內進行的 需要使反應器具有一設施用以 施可爲冷卻或加熱線圈，彼等 或在其壁內，且透過該設施可 〇 _ 過濾元件可爲具有各種幾 板或具有各種形狀的橫截面之 三角形、長方形、等。該等過 空環或中空壁（殻）之部份。 兩個過濾元件。該兩個或更多 的尺寸或具有至少相同面積的 換入口和出口時確保不會有因 橫截面所致無意的壓力蓄積。 過濾元件的內側及/或外側。 使彼等在組裝體上只形成圓筒 的尺寸可爲使彼等形成整個所 可裝有一裝置用以確保定期 地用於要裝置一壓力感測器 一程序控制系統，其轉而可 換工具。 過濾元件可包括作爲過濾器 熔塊、陶瓷熔塊、陶瓷複合 聚合物膜、不織布、針織或 全由此等所構成。 反應而定，可以有利地或視 導入或移除熱能量。此等設 可放置在反應器的內部及/ 流入恰當的冷卻或加熱介質 何的中空體。此等可爲平面 管柱，例如圓形、橢圓形、 濾元件可經成型，圓筒的中 於本發明反應器中含有至少 個過濾元件較佳者具有相同 過濾器活性材料，使得在轉 爲入口與出口中的不同流動 該過濾器活性材料可出現在 過濾元件的尺寸和形狀可爲 形外殼的一部份，或者彼等 過濾元件製成的中空圓筒。 -11 - 200524673 (8) 於最簡單的情況中’一完全中空圓筒係由兩部份所構成。 不過，爲了流體動力學理由，由也可以有利地使完全中空 圓筒由大於2的偶數段所構成，其中一過濾元件用爲入口 ，且較佳者有兩個過濾元件用爲毗鄰的出口。也可以有利 地將過濾元件以規則方式安排爲入和出口。還可以使過濾 元件的入口和出口合倂且只連接到一個轉換工具。不過， 業經發現者，對每一入口所含眾多過濾元件可以有利地通 過一轉換工具只連接到一出口以確保流過所有入口和出口 以及過濾元件之流都是在相同壓力之下（質量流）。不過 ，該轉換工具可經設計使其同時實施眾多所提及的轉換操 作。 於一較佳具體實例中，本發明反應器具有像一圓筒的 (中空）壁（殼）的一部份之形狀（於此等過濾元件中’ 從圓筒中空殼內部取掉滲透件（Permeate )而從部份圓筒 的內側及/或外側保留持留件（retentate )。再者，於此 較佳具體實例中的反應器具有裝在內側及/或外側（表面 )上的至少一個額外攪拌器，較佳者係在圓筒的內側與外 (表面）上，其係在超過過濾元件表面’特別者過濾元件 的過濾器活性部位，一小於，或等於1厘米’較佳者小於 或等於2厘米，更佳者小於或等於1毫米之距離處運轉。該 等過濾元件較佳者經成型爲一圓筒的半圓筒殼（半部）且 該攪拌器葉係在超過內和外表面一小於或等於2毫米，較 佳者1毫米，更佳者0.75毫米的距離處運轉。在超過該過 濾元件的外表面處運轉之攪拌器較佳者爲一錨式攪拌器。 •12- 200524673 Ο) 在超過該過濾元件內表面處運轉的攪拌 攪拌器，其較佳地具有從2至1 0片葉。 的過濾器活性表面一預定距離處運轉的 濾器活性表面上蓄積濾餅。 於本發明反應器一特別較佳具體實 同樣地經成型爲一圓筒的半圓筒殼（半 的內側（內表面）具有過濾器活性材料 性表面。此具體實例的特別特性在於該 筒形反應器壁（殻）的部份或甚至整個 再度地，可以存在者二或更多個過濾元 的過濾元件，且可如上述進行作爲入口 之轉換。再度地，其中較佳地存在著在 的過濾器活性部位表面一段距離過濾元 1厘米，較佳者小於或等於2毫米，更佳 米之處運轉之攪拌器。於本發明方法此 上的費用都保持在相當地小。此等係可 在只使用一攪拌器之時，將其形成爲使 的過濾、器活性部位表面一預定距離處運 反應器內令人滿意的混合。 有利者爲使該攪拌器配置成達到觸 該攪拌器或該等攪拌器在超過該等過濾 處在一軸上運轉。以此種方式，就裝置 持在非常小。不過，爲了達到甚至更佳 地使攪拌器裝設能讓攪拌器逆轉及/或 器較佳者爲一葉片 在超過該過爐兀件 攪拌器可防止在過 例中，該過濾元件 部），只在半圓筒 因而呈現過濾器活 過濾元件係形成圓 反應器壁（殼）。 件，較佳者爲偶數 和出口的過濾元件 超過該等過減元件 件表面小於或等於 :者小於或等於1毫 具體實例中，裝置 以達到者，特別是 其在超過過濾元件 轉且同時提供整個 媒的均勻分散且使 元件的內或外表面 而言的費用即可保 的混合’可以有利 以相異速度操作攪 - 13- 200524673 (10) 拌器之工具。 本發明擾伴窃可爲生產工廠，試驗工廠或小裝置所用 的反應器，因此，本發明反應器的尺寸可在從5毫升到1 00 立方米的範圍內變異，反應器尺寸或反應器體積能夠實質 自由地匹配到技術上所要求的條件。若反應器爲在工業規 模上所用的反應器，例如，用於烯烴特別是丁烯的低聚合 者，則本發明反應器具有從數升到數百立方米，特別者從 0.1立方米至200立方米，較佳者從1至1〇〇立方米且非常特 別較佳者從5至5 0立方米範圍之尺寸。若本發明反應器爲 ，例如實驗室反應器或用於高處理量硏究所用的反應器， 則可以有利地使反應器包括具有從10毫升至1 0 000毫升， 較佳者大於5 0毫升且非常特別較佳者大於1 〇 〇毫升之容積 〇 ^ 本發明反應器可促成達到在至少一個於其中觸媒係以 分散液形式存在於反應區內的反應器內連續地進行催化液 體反應之方法，其中該程序係在至少一個本發明反應器中 進行。於此反應器內，可以進行，例如，低聚合、交換反 應、烷基化或異構化反應與異相生物催化反應等根據本發 明的程序。本發明反應器特別較佳地係用來進行異相催化 高壓液體反應，例如烯烴的低聚合、氫化、交換反應、烷 基化、異構化及異相生物催化反應。使用本發明反應器的 一項特別優點在於，特別者，其也可進行其中觸媒在反應 器中的比例可高於20體積％，較佳者30至50體積％之程序 。對於觸媒比例的上限爲60 - 65體積％，因爲在更高觸媒 -14- 200524673 (11) 比例下，不能確定保有流體介質的存在之故。若能在更高 觸媒比例下繼續存在流體介質（分散物），則當然可以繼 續用本發明反應器因而使用本發明方法。 本發明方法較佳者係在進或出反應器的入流（inflow )與出流（outflow )經自動轉換之下進行使得在跨過過 濾元件的壓力差增加到使通過反應器的設定流係經維持在 只使反應器內的壓力增加到超過初始壓力或最後一次轉換 後的壓力5 %，較佳者超過1 %，特別較佳者超過〇. 5 %的 程度之時，或在最後一次轉換後經過一特別預設定的時間 期之時轉換。該時間期較佳者係選擇成使得其短於或等於 會導致明顯的，可測量的壓力增加之時間。此時間可能， 例如以簡單的預備試驗而定出。反應器內的壓力增加可利 用，例如在反應器內的壓力感測器予以測量。轉換可用人 ^ 工操作。特別較佳者的透過程序控制系統來進行轉換，該 系統可在反應器內的恰當壓力下或在一預設定的時間期之 後自動地觸發轉換。爲簡化工程，有利地爲定期發生轉換 。轉換必須根據所用觸媒的類型與特別者其尺寸及所用過 濾元件的孔隙尺寸而或高或低頻繁地進行。轉換較佳者爲 每隔2 4小時，較佳者每〇 · 5小時至1 2小時進行。 本發明方法可爲，例如，在從5 0至1 5 0。(：溫度範圍與 從10至70巴（bar)的壓力範圍內之丁烯低聚合。若此係 在，例如以從0.5至100毫升/分的體積流，使用有3.2厘 米X 4 · 2厘米尺寸及5微米網目開口之不銹鋼篩網及使用具 有15微米的粒徑之觸媒進行之時，經發現約3〇分鐘的轉換 -15- 200524673 (12) 時間係特別較佳者。 本發明方法也可以在倂行及/或串接操作的二或更多 個本發明反應器中進行。 於實驗室試驗中，該方法較佳者係在倂行操作的從2 至50，較佳者從4至25且非常特別較佳者9至16個反應器中 進行。以此方式進行本發明方法於使用經微小化的本發明 反應器時特別有利。 於本發明方法中以倂行操作的反應器可用相同方式或 相異方式操作。該等反應器可全部都供給相同的進料混合 物或個別反應器或倂行操作的反應器組可用不同進料混合 物供給。反應器中所得產物可個別地收拾處理或分析。不 過，也可以將全部反應器或分組反應器的產物合倂且分析 或收拾處理此等合倂產物。 除了變異起始材料的組成之外，也可以於本發明方法 中有利地對倂行操作，供給相同或不同進料組成物的個別 反應器或反應器組中設定相同的反應條件或不同的反應條 件。可用此種方式變異的反應條件較佳者爲壓力，溫度及 所用觸媒的量及/或類型。 要進行倂行反應時，較佳者係將本發明反應器排列形 成根據本發明的組合體，其具有至少兩個倂接的本發明反 應器。該組合體較佳地具有從2至50，較佳者從4至25且非 常特別較佳者從9至1 6個倂接的反應器。諸反應器的入口 和出口較佳地裝有轉換工具用以在反應器內的壓力增加超 過起始壓力或最後轉換時的壓力之5 %以上時，使入口和 -16- 200524673 (13) 出口交換。不過，也可以在經過一段預設定的時間期後自 動發生該入口和出口的轉換。 於本發明組合體中，於倂於操作的個別反應器或反應 器組中可以給入相同或相異的進料混合物，此可經由，例 如，利用分配器或計量裝置來進行。同樣地，在本發明組 合體中的諸反應器可分別具有至少一調整反應條件之工具 。此可爲，特別者，熱交換器，其供給反應混合物熱量或 移除反應熱，使得，可以設定，例如，等溫或擬等溫條件 。調整反應條件的其他工具爲，例如，壓力調節器、入流 及/或出流調節器、等。依應用而定，於本發明組合體中 倂行排列的諸反應器可完全彼此獨立，特別是在起始材料 與產物（彼此密封），方面，或者起始材料的供給及產物 的排放可通過共同的一入口 /出口而發生。個別反應器較 .佳者爲彼此密封以防止流體化合物從一反應器通到另一反 應器，使得在個別反應器內可以調整完全不同的反應條件 〇 眾多倂合操作的本發明反應器或一本發明組合體之使 用可使本發明方法用來快速地決定出最優反應產數（高處 理量篩選）。將本發明反應器微小化之機會也使此等，特 別是容積小於1 0 0毫升者，顯著地適合用於高處理量篩選 之中。 本發明要利用圖1至7闡明，但不對其給予限制。 圖1例舉闡示出本發明裝置對於在固體觸媒上的液體 反應之操作模式。於較佳地具有連續攪拌槽反應器流體動 •17- 200524673 (14) 力學且可在所需反應壓力與所需反應溫度下操作之一反應 區（3 )內裝設有至少兩個過濾單元（1和2 )。此等爲過 濾器活性介質，例如燒結金屬、陶瓷、陶瓷複合物，整體 陶瓷、聚合物膜、不織布、針織或編織的金屬線構成物。 液體或經飽和或富含氣體的液體係以進料（混合物）（b )形式通過第一過濾單元（1 )給到反應器內。反應後的 液體（產物）（7 )係通過第二過濾器單元（2 )從反應器 取出。反應器內的壓力可利用經安裝在排放處燒結塊的經 電磁或氣動控制的壓力維持閥（4 )維持住。於此方式中 ，過濾元件不會受到實際的壓力梯度且對彼等的機械應力 也爲最小。爲了要淸潔過濾元件及混合反應器內容物，乃 裝上眾多攪拌器（5a、5b和9 )。雖然利用攪拌器（5a和 5 b )淸潔過濾元件，不過，深度過濾可能導致排放處過濾 _ 元件的堵塞。爲此之故，在觀察到一特別的壓力增加之時 ，可利用一四向閥（8 )將過濾元件中的流向逆反使得入 流於此後係通過過濾器（2 )而出流係通過過濾器（1 )。 圖2 顯示出於彼此相對之處利用各具一鑽孔的兩個 固持器（l〇a和10b )固持住的過濾元件（1 )和（2 )之平 面與側視圖。箭號表進入的進料流（6a )與外流的產物流 (7a )。虛線顯示出可接到一或更多攪拌器的攪拌器驅動 軸（1 1 )。爲了更佳地導引攪拌器，該軸可安裝在一或兩 個鑽孔（1 〇a或1 Ob )中的軸承（1 2 )之中。此舉可以防止 可能的攪拌器偏心性，此偏心性可能導致攪拌器與過濾器 單元之間的接觸而可能損壞到過濾器單元。適當的軸承材 -18- 200524673 (15) 料爲，例如，軸承青銅或耐磨蝕性塑膠。 圖3示意地顯示出反應器另一構造的至平面圖與側視 圖。於此例中過濾元件（1 b和2b )係位於反應器內壁上的 嵌入物形式。於此構造中，反應器內壁的一半（圓筒的一 半加上視情況的底部一半）代表第一過濾單元1 b而另一半 代表第二過濾單元2b。反應器的外壁係由以嵌入物形式安 裝的過濾元件之非孔型背材所形成的，或者反應器的外壁 形成過濾元件的非孔型背材。第一和第二過濾元件的入口 (6b )與出口（ 7b )係由一不透性屏障（1 3 )彼此隔開。 中間的攪拌器（5 )用來淸潔過濾器表面且用以混合反應 器的內容物，並由軸（1 1 )所驅動。此種構造特別可用來 連續進行以相當大規模的本發明在分散物中的反應。 圖4例舉顯示出η個本發明反應器之組合體，其流動轉 換爲圖1或3中所示者。反應器（2 1 )的進料係利用調節器 (22 )計量且以合意量給到反應器之內。離開反應器的流 體係給入一選擇器（2 3 )中，於其中選出諸反應器中之一 者的出流且可使其通到一分析設施（2 4 )，例如氣體層析 儀或質譜儀或另一種分析儀器。其他物流則通到廢棄物處 理器（2 5 )或其他分析儀。 圖5顯示出一圖，其中將測量到的壓力相對於操作 時間標繪出。實驗係依實施例2中所述進行，不同處在於 該流向係在〇 · 7小時後逆反一次及在1小時後逆反一次。可 以淸楚地看出在設定約0 · 0 5小時後的反應壓力之後，壓力 於起始係保持固定直到0 · 3小時後穩定地增高，此可歸因 -19- 200524673 (16) 於過濾器活性層的堵塞。在約〇. 7小時後轉揆 洗過濾器活性層即造成反應壓力回復到起始 後的預防性轉換使反應壓力於初始時保持固 1.45小時處，反應壓力再穩定地上升。此實駿 ，流向的轉換可逆反過濾器活性層的堵塞及， 按時的預防性轉換可避免堵塞。 圖6和7顯示出實施例2的試驗物質在本 內之滯留時間曲線，且與此作比較者，也顯元 攪拌槽反應器對兩不同體積進料流之滯留時I 顯示出69毫升/分體積流速之曲線而圖7顯 /分的體積流之曲線。實驗測定値及歸一値另 形顯示出。計算値係以線條顯示。從此等圖瓦 驗曲線與計算曲線在形狀上沒有顯示明顯的差 以假設裝有過濾元件和攪拌器的反應容器所具 行爲大約對應於理想連續攪拌槽反應器之行爲 下面的實施例係闡述本發明而非限制其範 係由說明部份與申請專利範圍所界定。 實施例 爲了試驗本發明反應器的流動行爲，於T 實施例1和2 )中使用2 0重量％具有2 5微米的 鹽粉末在己烷（工業級正己烷，Aldrich )中 將此於開始即放在反應器內。然後於22巴的壓 別的己院流通過入口給到反應器內且再由出口 流向因而沖 値。於1小時 定，直到約 顯示，第一 第二，利用 發明反應器 出一理連續 0曲線。圖6 示出28毫升 別以黑色方 以看出，實 異。所以可 流體動力學 〇 圍，該範圍 「面諸實驗（ d 5 0値之矽酸 的分散液。 丨力下將一特 取出。 -20- 200524673 (17) 實施例l 使用安裝在— 3 00 —毫升攪拌槽反應器（Btuhi)中如 圖2中所不的一*包括~^個過漉器早兀之過減器組合。該過 濾器單元具有於各情況中於內側上爲2 · 8厘米X 3 . 8厘米之 過濾器活性面積。入口和出口橫截面分別爲1 / 8 〃 。從過 濾器活性表面到過濾元件背面的距離於各情況中同樣的爲 1 / 8 〃 。過濾器活性表面包括一有5微米網目開孔的不錄 鋼網/不銹鋼篩。該等過濾元件係利用兩個不銹鋼固持器 彼此接連，該等固持器各具一用於攪拌器軸的鑽孔且將內 表面保持3 · 4厘米間距。該攪拌器軸係於中心通過該等過 濾元件，使得接著到其之葉式攪拌器（5 a ) ( 5 一葉攪手半 器，高度二3厘米，個別葉的寬度=1.7厘米，V4 - A鋼， 總是以0 · 5毫米的相同距離通過圓筒形過濾元件的孔型0 側。此外，與該軸的下端固定有一具有4葉（對流動方@ 的角度：1 5 ° )之葉輪攪拌器以確保分散相的實質均勻分 布。該軸係以1〇〇〇 rpm的速度轉動。於10.6平方厘米每過 濾器單元的過濾器面積之下，可在長期操作（ > 1 000小時）於20體積％固體體積比例（矽酸鹽粉末， d5〇 = 15微米下可達到局達50毫升/分（己院）的流速。 轉換閥係每3 0分鐘觸發以逆沖洗篩孔內的堵塞物。於沒有 逆沖洗之下，過濾器的滲透率會在上述條件下0.5小時白勺 操作期後減低且在反應器中觀測到的壓力會增高。 200524673 (18) 實施例2 爲了增加過濾器面積，於第二實施例中使用將圓筒殼 外側也構成篩之過濾元件。該等過濾元件同樣地透過一穩 定棒焊接在一起。爲了避免在外過濾器表面上濾餅的蓄積 ，需要另加一攪拌器（如，一錨式攪拌器（5 b ))，其係 在與該葉式攪拌器相同的軸上運轉且以0 · 5毫米的距離通 過該過濾元件的外側。於長期操作（〉1 0 0 0小時）中’於 21.4平方厘米每過濾器單元的過濾器面積下，以20體積％ 的固體體積比例（矽酸鹽粉末，d5G = 1 5微米）達到高達 100毫升/分（己烷）之流速。轉換閥係每隔30分鐘觸發 以逆沖洗篩孔內的堵塞物。於沒有逆沖洗之下，於所述條 件下，過濾器的滲透率在約〇 . 5小時操作期後即下降，此 可由反應器內的壓力增加而指示出（參看圖5)。在過濾 元件之下，於底部附近，將一葉輪攪拌器接著到攪拌器軸 ，如實施例1中所述者，用以將懸浮固體沿過濾元件的方 向上輸送。以此種方式，可達到整個反應器內的固體均勻 分布。 於兩實施例中，沒有在< =1毫米的攪拌器間隙下觀 察到可看出的濾餅形式（使用玻璃反應器原位（in situ ) 觀察）。雖然有內部件，該反應器顯示出可與在充分高轉 速（依流速而定）下的理想連續攪拌槽反應器相比擬之流 體動力學。此可經由比較試驗物質的滯留時間曲線與在理 想連續攪拌槽反應器模型的曲線相比較而展現出（圖6與7 )。從圖6和7可以看出，兩曲線沒有顯示出不同處。 - 22- 200524673 (19) 實施例3 於一如實施例1中所述，裝有實施例2內建式過濾器組 合的反應器中，於8 0 °C或9 6 °C與2 5巴壓力（9 6 °C下的値顯 示於下面的括號中）下探討丁烯的低聚合（7 7.4重量％線 型丁烯與22·6重量％在反應條件下呈惰性的流體化合物） 。體積流速爲約5毫升/分。所用觸媒爲25克在 DE 3 9 1 4 8 1 7實施例2中低聚合所用類型之觸媒（平均粒 度dP=15微米）。觀察到25% (32%) C8至C2G低聚物轉 化率。每隔3 0分鐘，在兩過濾元件之間自動轉換進料。實 驗運轉2000小時後仍沒有可看出的過濾元件堵塞現象。 【圖式簡單說明】 圖1示範出用於在固體觸媒上進行液體反應之本發明 裝置之操作模式。 圖2顯示出本發明裝置中所包括的過濾元件之平面 圖和側視圖。 圖3示意地顯示出本發明反應器另一構造的平面圖和 側視圖。 圖4顯示出有圖1或3所示流向轉換之本發明反應器 組合體。 圖5顯示一圖，其中係將所測得之壓力相對於操作 時間標繪出。 圖6顯示出一試驗物質在實施例2的本發明反應器內 - 23- 200524673 (20) 於6 9毫升/分的體積流速之滯留時間曲線，及，作爲比較 者，一理想連續攪拌槽反應器模型的滯留時間曲線。 圖7顯示出一試驗物質在實施例2本發明反應器內 於2 8毫升/分體積流速下之滯留時間曲線，及，作爲比較 者，一理想連續攪拌槽反應器模型的滯留時間曲線。 【主要元件符號說明】 1 第一過濾單元 2 第_^過漉早兀 3 反應區 4 壓力維持閥 5a ， 5b ， 9 攪拌器 6，6 a 進料（混合物） 7，7a 產物 8 四向閥 10a，1 Ob 固持器 11 攪拌器驅動軸 12 軸承 13 不透性屏障 2 1 反應器 22 調節器 23 選擇器 24 分析設施 25 廢棄物處理 -24-200524673 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a device for performing a liquid reaction, particularly a liquid-liquid or liquid-gas reaction, in the presence of a fine-grained solid catalyst. [Prior art] It is known that there are many chemical reactions that may be performed under pressure and after adding dispersed or suspended catalysts. Liquid reactants can be introduced into the reactor in the liquid phase, a number of liquid phases, or in the form of reaction gases. Examples of liquid reactions are: oligomerization, exchange reactions, alkylation or isomerization, and heterogeneous biocatalysis reactions. In carrying out these reactions and the measurement of the internal reaction kinetics, it is preferable to use a finely divided catalyst because it can reduce the pressure drop compared to a fixed-bed reactor equipped with nine catalysts. In addition, because the results of external particle size can greatly avoid the pore diffusion limitation and in the case of exothermic reactions, because of the isothermal reactor characteristics due to the sealing and mixing results of the fluidized catalyst, it is usually not the same as in a fixed bed reactor. Local temperature spikes. In the reaction, the solid catalyst is usually not consumed by the reaction that causes the product, so that the catalyst does not have to be discharged from the reaction zone. For this reason, these suspension reactions are often carried out in the reactor by using sintered metal or ceramic sintered blocks or by using the catalyst retained by the wire mesh structure. One problem here is that the accumulation of filter cake on these filter elements will occur over time, especially when there is a high solid content in the liquid, so it will adversely affect the uniform distribution of the catalyst and lead to the reactor's -5- 200524673 (2) Therefore. The accumulation of filter cake is often not even prevented by agitators. Therefore, the reaction must be stopped periodically and the filter element must be cleaned. In a variation of this procedure, it is proposed to perform a gas / liquid reaction (hydrogenation reaction) under the installation of another filter element to allow hydrogen to pass through (U S 5, 9 3 5, 4 1 8). After a predetermined period, the two filter elements are exchanged so that the reaction liquid system at this time moves through the H2 filter element and hydrogen gas is introduced here through the exhaust filter element. However, in this case, maintaining accurate liquid levels in the reactor can be problematic because two separate inflows enter the reactor. Especially at high linear velocities and low residence times, which are needed for dynamics studies, this principle is a problem encountered. In the case of a liquid reaction performed in this manner, an inert gas must be introduced, which represents a cost that would otherwise be unnecessary. In order to avoid these problems, it is often proposed not to keep the catalyst in the reactor but to discharge it with the product and to separate it from the liquid phase using conventional separation devices such as decanters, over-filters, filter rods, cyclones or the like Catalyst (eg US 3,901,660). One disadvantage of these methods is that if solids need to be returned to the reactor system as a catalyst, then wet solids or concentrated suspensions need to be disposed of. Furthermore, when the reaction is to be performed continuously and continuously under the fluctuation of the conversion rate in the reactor, it is difficult to control the amount of catalyst to be recycled because the catalyst is continuously taken out from the reactor. Another alternative that has been proposed is to use alternating current filtration outside the reactor to separate the catalyst and liquid, in which part of the suspension is separated from the reactor and circulated through a microfilter, which is under the same pressure and according to the principle of exchange Operate and take out the liquid reaction product in the form of filtrate in a micro-furnace-6-200524673 (3) (DE 3 2 4 5 3 1 8). A disadvantage here is that a filter cake also accumulates over time and must be purged regularly, which results in plant shutdowns. Furthermore, since the known filter materials can only be operated at a limited temperature, it is sometimes necessary to reduce the temperature of the reaction mixture before the reaction mixture enters the filter unit. All of the external separation methods mentioned have the disadvantage that a solid suspension must be delivered. This requires an additional pump whose life is further limited by the abrasive effects caused by solids. For the use of slurry tanks or foam towers that operate in a slurry manner, such as those proposed by Fischer-Tropsch Synthesis, the circulation system must be capable of being generated by freshly injected liquid or rising foam. However, because of the undesired mass transfer and heat transfer procedures that often occur between liquids and / or solids, problems can occur in controlling the reaction. A lower conversion rate is expected or, in the case of an exothermic reaction, ′, the heat distribution in the reactor that hinders the reaction. '' Therefore, it is an object of the present invention to find a method and a device so that the catalyst can be used in the reaction zone in a completely effective form without the need to periodically interrupt the program for regeneration or cleaning. At the same time, the crude reaction product should be continuously obtained as a solid-free liquid. It was surprisingly found that a solid-free product can be continuously obtained from the reaction mixture, in which the pulverized catalyst exists in the form of a fine dispersion when the reaction is performed in the reactor, and the reactor has an outlet and an outlet. A filter element, and the inlet and outlet are interchangeable so that the inlet can be used as an outlet and the outlet can be used as an inlet. Interchanging the outlet with the inlet can cause any deposits on the filter element to be flushed back into the reactor. SUMMARY OF THE INVENTION The present invention thus provides a reactor for continuous operation of a catalytic liquid reaction, wherein the catalyst is present in the reaction zone as a dispersion, wherein the reactor has at least one inlet and one outlet, all starting The material is fed through an inlet and all production is discharged through an outlet, and the inlet and outlet are equipped with a tool that can switch the inlet and outlet so that the discharge previously used as the outlet is used as the input of the inlet and is At the same time, the input used as the inlet is at the discharge used as the outlet at this time, and the inlet and outlet are respectively equipped with a filter element, which holds the catalyst in the reactor and the reactor is equipped with a device, which can Ensure uniform distribution of catalyst and starting materials in the reactor. The present invention also provides a method for continuously performing a catalytic liquid reaction in at least one reactor, wherein the catalyst exists as a dispersion in the reaction zone, and the method is performed in at least one reactor according to the present invention. of. The present invention also provides an assembly of at least two reactors according to the present invention, 'these reactors are connected by a loop and provided to the method of the present invention' is a reactor or a reactor of the present invention used for screening of the throughput of the station. The assembly of the present invention. In general and for the purposes of the present invention, high throughput screening refers to rapid testing of catalyst composition and properties with a view to optimizing their suitability for the industrial use of the reaction or type of reaction in question, and will be -8-200524673 required for this purpose in limp operation and preferably miniaturized and automated devices (5) The reaction parameters (such as pressure, temperature, volume flow rate, hydrodynamic residence time) are optimized. The device of the invention and the reactor of the invention have the following important advantages: • The catalyst does not need to be removed externally. This eliminates problems that may occur during suspension pumping, such as limited pump life, deposits in the pipeline, etc. • Eliminates complex procedural steps, such as the transfer of liquids with high solids loading rates, cooling and depressurization to filter-compatible pressure, and return of catalyst to the reactor. • The reactor according to the invention can in principle be implemented in any commercial stirred tank reactor having at least one inlet and one outlet. • The product (filtrate) obtained from the plant is usually not solid, allowing the fouling of downstream process equipment, such as distillation units, to be eliminated. • The pressures and temperatures that can be used are limited only by the grade of the container and the material properties of the filter elements used. • The reactor of the invention exhibits the same characteristics as a stirred tank reactor. • The reactor of the present invention can also be used for reactions in which the catalyst ratio exceeds 20% by volume, preferably more than 30% by volume and particularly preferably more than 40% by volume. The device of the present invention can also be advantageously used to determine the intrinsic reaction kinetics Because the finely dispersed catalyst particles can reduce the pressure drop compared to the fixed-bed reactor using nine catalyst particles, its use is better. In addition, because of the small particle size, the inhibition of pore diffusion can be greatly avoided and in the case of exothermic reactions, because the fluidized catalyst will cause isothermal reactor-9-200524673 (6) behavior due to convective mixing, so there is often no The appearance of local temperature spikes. The reactor of the present invention enables the reaction using finely divided small catalyst particles to proceed in a simple form, which is the reason why such a reactor / reaction combination is particularly useful for determining the intrinsic reaction kinetics that is important for the scale-up of the reactor. [Embodiment] The device and method of the present invention will be described below, but the present invention is not limited to these specific examples. For continuous operational catalytic liquid reactions, the catalyst of the invention in which the catalyst is used in the reaction zone in the form of a dispersion has at least one inlet and at least one outlet, all starting materials are fed through one inlet and all products It is discharged through an outlet. Both the inlet and the outlet are equipped with a tool which can connect the inlet and the outlet so that the discharge of the previously used outlet is at the input of this inlet and at the same time, the outlet of the outlet changed to the input of the inlet. The inlet and outlet are each equipped with a filter element to hold the catalyst inside the reactor. In addition, the reactor is equipped with a device to ensure a uniform distribution of catalyst and starting materials in the reactor. Such a device may be, for example, a motor-driven agitator, such as an impeller agitator. The tool used to change the inlet and outlet can be, for example, a four-way valve with two pairs of connected discharges. Where more than one outlet and one inlet are included, 'a valve with a correspondingly large number of discharges must be used, or a four-way valve for each pair of inlets and outlets. The valves used can be operated manually or automatically (for example, 'electric or pneumatic') and can be adjusted by a conventional program control system. -10- 200524673 (7) Conversion of tools used for conversion entry and exit. However, it can also be an advantageous reactor, which is connected to an active material such as sintered metal, ceramic monolith, Braided metal wire structures; or the reactor can be provided with a facility for cooling or heating coils, either as they are in the wall, and through the facility, through which the facility can be provided. It can be a triangle, rectangle, etc. with various plates or a cross section with various shapes. These hollow rings or hollow wall (shell) parts. Two filter elements. These two or more dimensions or replacement inlets and outlets with at least the same area ensure that there is no unintentional pressure build-up due to the cross section. The inside and / or outside of the filter element. Dimensioning them to form only cylinders on the assembly may be such that they can be installed as a whole. A device can be installed to ensure regular use of a pressure sensor and a program control system, which can be replaced with tools. . The filter element may include a filter frit, a ceramic frit, a ceramic composite polymer film, a non-woven fabric, a knitted fabric, or the like. Depending on the reaction, thermal energy can be advantageously introduced or removed. These devices can be placed inside the reactor and / or flow into a suitable cooling or heating medium. These can be flat tubular columns, for example, round, oval, and filter elements can be formed. The cylindrical one contains at least one filter element in the reactor of the present invention, preferably the same filter active material. Different Flows in the Inlet and Outlet The filter active material may appear in the size and shape of the filter element, which may be part of a shaped housing, or a hollow cylinder made of their filter element. -11-200524673 (8) In the simplest case, a completely hollow cylinder is composed of two parts. However, for hydrodynamic reasons, it is also advantageous to make a completely hollow cylinder composed of an even number of segments greater than two, with one filter element used as the inlet and preferably two filter elements used as adjacent outlets. It may also be advantageous to arrange the filter elements in and out in a regular manner. It is also possible to combine the inlet and outlet of the filter element and connect to only one conversion tool. However, it has been found that for many filter elements contained in each inlet, it can be advantageously connected to only one outlet through a conversion tool to ensure that the flow through all inlets and outlets and the filter element is under the same pressure (mass flow ). However, the conversion tool can be designed to perform many of the mentioned conversion operations simultaneously. In a preferred embodiment, the reactor of the present invention has a shape like a part of a cylindrical (hollow) wall (shell) (in these filter elements' the permeate is removed from the inside of the hollow shell of the cylinder (Permeate ) While retaining retentates from the inside and / or outside of some cylinders. Furthermore, the reactor in this preferred embodiment has at least one additional agitation mounted on the inside and / or outside (surface) Device, preferably on the inside and outside (surface) of the cylinder, which is above the filter element surface, in particular, the active part of the filter, which is less than or equal to 1 cm, preferably less than or equal to 2 cm, more preferably at a distance of less than or equal to 1 mm. These filter elements are preferably formed into a cylindrical semi-cylindrical shell (half) and the agitator blades are less than Or equal to 2 mm, preferably 1 mm, and more preferably 0.75 mm. The stirrer that runs beyond the outer surface of the filter element is preferably an anchor stirrer. • 12- 200524673 〇) In over the filter element It was stirred at a stirrer running surface, which preferably has of from 2 to 10 leaves. The filter cake accumulates on the filter active surface running at a predetermined distance from the active surface of the filter. In a particularly preferred embodiment of the reactor of the present invention, a semi-cylindrical shell shaped like a cylinder (half inside (inner surface) has a filter active material surface. The special feature of this specific example is the cylindrical reactor Part or even the whole of the wall (shell) can again have filter elements of two or more filter elements, and can be converted as an inlet as described above. Again, there are preferably existing filters The surface of the active part is a centimeter from the filter element, preferably less than or equal to 2 millimeters, and more preferably a stirrer operated at a position of rice. The cost of the method of the present invention is kept relatively small. When using a stirrer, it is formed such that the filter and the active part surface of the stirrer are satisfactorily mixed within a predetermined distance. Advantageously, the stirrer is configured to reach the stirrer or the like. The stirrer runs on a shaft beyond the filtering point. In this way, the device is kept very small. However, in order to achieve or even better the stirrer installation allows the stirrer The rotor and / or device is preferably a blade that exceeds the furnace element stirrer to prevent the filter element in the previous example), only in the semi-cylindrical shape, so the filter or filter element system forms a round reactor wall. (shell). The number of filter elements, preferably even numbers and outlets, exceeds the surface of these over-reduction elements. The surface of the element is less than or equal to: less than or equal to 1 millimeter. In specific examples, the device is achieved, especially when it exceeds the filter element and is provided at the same time. The uniform dispersion of the entire medium and the cost-effective mixing of the internal or external surface of the component can be used to operate the stirrer at different speeds-13- 200524673 (10) The tool of the mixer. The disturbance companion of the present invention can be a reactor used in a production plant, a test plant or a small device. Therefore, the size of the reactor of the present invention can be varied from 5 ml to 100 cubic meters, and the reactor size or reactor volume Can be virtually free to match technically required conditions. If the reactor is a reactor used on an industrial scale, for example, for the oligomerization of olefins, especially butenes, the reactor of the present invention has from a few liters to hundreds of cubic meters, in particular from 0.1 cubic meters to 200 Cubic meters, preferably from 1 to 100 cubic meters and very particularly preferred sizes from 5 to 50 cubic meters. If the reactor according to the invention is, for example, a laboratory reactor or a reactor for high-throughput research, it can be advantageous to include a reactor having from 10 ml to 10,000 ml, preferably more than 50 ml And very particularly preferred is a volume greater than 100 milliliters. The reactor of the present invention can facilitate the continuous liquid catalytic reaction in at least one of the reactors in which the catalyst system exists as a dispersion in the reaction zone. A method, wherein the procedure is performed in at least one reactor of the invention. In this reactor, for example, oligomerization, exchange reaction, alkylation or isomerization reaction and heterogeneous biocatalytic reaction can be performed according to the procedure of the present invention. The reactor of the present invention is particularly preferably used for carrying out heterogeneous catalytic high-pressure liquid reactions, such as oligomerization, hydrogenation, exchange reaction, alkylation, isomerization, and heterogeneous biocatalytic reactions of olefins. A particular advantage of using the reactor of the present invention is that, in particular, it is also possible to perform procedures in which the proportion of catalyst in the reactor can be higher than 20% by volume, preferably 30 to 50% by volume. The upper limit for the catalyst ratio is 60-65% by volume, because at higher catalyst -14- 200524673 (11) ratios, the existence of a fluid medium cannot be determined. If the fluid medium (dispersion) can continue to exist at a higher catalyst ratio, it is of course possible to continue to use the reactor of the invention and thus use the method of the invention. The method of the present invention is preferably carried out under automatic conversion of inflow and outflow into or out of the reactor so that the pressure difference across the filter element is increased to allow the set flow through the reactor to pass through. It is maintained only when the pressure in the reactor is increased to an extent exceeding the initial pressure or the pressure after the last conversion by 5%, preferably more than 1%, particularly preferably more than 0.5%, or at the last conversion It then switches at a specific pre-set time period. The preferred time period is selected so that it is shorter than or equal to the time that results in a significant, measurable increase in pressure. This time may be determined, for example, by a simple preliminary test. The increase in pressure in the reactor can be used, for example, as measured by a pressure sensor in the reactor. Conversion can be performed manually. Particularly preferred is to carry out the conversion by means of a program control system which automatically triggers the conversion at the appropriate pressure in the reactor or after a pre-set time period. To simplify the project, it is advantageous for the conversion to occur on a regular basis. The conversion must be performed more or less frequently depending on the type of catalyst used and, in particular, its size and the pore size of the filter element used. The conversion is preferably performed every 24 hours, and more preferably every 0.5 to 12 hours. The method of the invention may be, for example, from 50 to 150. (: Temperature range and oligomerization of butene in the pressure range from 10 to 70 bar. If this is, for example, at a volume flow from 0.5 to 100 ml / min, use 3.2 cm X 4 · 2 cm When a stainless steel screen with a size of 5 micron mesh opening and a catalyst with a particle size of 15 micron are used, it is found that the conversion is about 30 minutes -15- 200524673 (12) The time is particularly preferred. The method of the present invention It can also be performed in two or more reactors of the present invention in limp and / or tandem operation. In laboratory tests, the method is preferably performed in limp operation from 2 to 50, more preferably from It is carried out in 4 to 25 and very particularly preferably in 9 to 16 reactors. Performing the method of the invention in this way is particularly advantageous when using miniaturized reactors of the invention. Reactions performed in limp operations in the method of the invention The reactors can be operated in the same way or in different ways. The reactors can all be supplied with the same feed mixture or individual reactors or groups of reactors operated in parallel can be supplied with different feed mixtures. The products obtained in the reactors can be individually Packing for processing or analysis. However, it is also possible to combine the products of all reactors or group reactors and analyze or pack these combined products. In addition to mutating the composition of the starting materials, it is also advantageous to carry out operations in the method of the present invention. The same or different reaction conditions are set in individual reactors or reactor groups that supply the same or different feed composition. The reaction conditions that can be varied in this way are preferably pressure, temperature, and the amount of catalyst used And / or type. To carry out a limp reaction, it is preferred to arrange the reactors of the present invention to form a combination according to the present invention, which has at least two reactors of the present invention connected. The combination preferably has From 2 to 50, preferably from 4 to 25 and very particularly preferably from 9 to 16 connected reactors. The inlets and outlets of the reactors are preferably equipped with conversion tools for use in the reactor. When the pressure increase exceeds 5% of the initial pressure or the pressure at the last transition, the inlet is exchanged with the -16-200524673 (13) outlet. However, the inlet can also occur automatically after a predetermined period of time has passed. Switching between mouth and outlet. In the combination according to the invention, the same or different feed mixtures can be fed into individual reactors or groups of reactors which are difficult to operate. This can be done, for example, by using distributors or metering devices. Similarly, the reactors in the combination of the present invention may each have at least one tool for adjusting reaction conditions. This may be, in particular, a heat exchanger that supplies heat to the reaction mixture or removes the heat of reaction so that Can be set, for example, isothermal or quasi-isothermal conditions. Other tools for adjusting reaction conditions are, for example, pressure regulators, inflow and / or outflow regulators, etc., depending on the application, in the composition of the invention The lined reactors can be completely independent of each other, especially in terms of starting materials and products (sealed to each other), or the supply of starting materials and the discharge of products can occur through a common inlet / outlet. The individual reactors are preferably sealed to each other to prevent fluid compounds from passing from one reactor to another, so that completely different reaction conditions can be adjusted in the individual reactors. Many reactors of the invention or The use of the combination of the present invention allows the method of the present invention to be used to quickly determine the optimal reaction yield (high throughput screening). The opportunity to miniaturize the reactor of the present invention also makes these, especially those with a volume less than 100 ml, remarkably suitable for high-throughput screening. The present invention is to be explained using Figs. 1 to 7, but is not limited thereto. Figure 1 illustrates the mode of operation of the device of the present invention for a liquid reaction on a solid catalyst. At least two filter units are installed in a reaction zone (3) which preferably has a continuous stirred tank reactor with fluid dynamics and is capable of operating at a desired reaction pressure and a desired reaction temperature. (1 and 2). These are filter active media such as sintered metals, ceramics, ceramic composites, monolithic ceramics, polymer membranes, non-woven fabrics, knitted or woven metal wire constructs. The liquid or saturated or gas-rich liquid system is fed into the reactor in the form of a feed (mixture) (b) through a first filter unit (1). The liquid (product) (7) after the reaction is taken out of the reactor through the second filter unit (2). The pressure in the reactor can be maintained by an electromagnetic or pneumatically controlled pressure maintaining valve (4) through a sintered block installed at the discharge. In this way, the filter elements are not subject to actual pressure gradients and their mechanical stress is minimal. In order to clean the filter element and the contents of the mixing reactor, many stirrers (5a, 5b and 9) are installed. Although the filter elements are cleaned with agitators (5a and 5b), deep filtration may cause clogging of the filter element at the discharge. For this reason, when a special pressure increase is observed, a four-way valve (8) can be used to reverse the flow direction in the filter element so that the inflow is then passed through the filter (2) and the outflow is passed through the filter. (1 ). Figure 2 shows a plan view and a side view of the filter elements (1) and (2) held by two holders (10a and 10b) each having a drilled hole, as opposed to each other. The arrows indicate the incoming feed stream (6a) and the outgoing product stream (7a). The dashed line shows the agitator drive shaft (1 1) that can be connected to one or more agitators. In order to better guide the agitator, the shaft can be mounted in a bearing (12) in one or two drilled holes (10a or 1 Ob). This will prevent possible eccentricity of the agitator, which may cause contact between the agitator and the filter unit and may damage the filter unit. Suitable bearing materials -18- 200524673 (15) Materials are, for example, bearing bronze or abrasion-resistant plastic. Fig. 3 schematically shows a plan view and a side view of another configuration of the reactor. The filter elements (1 b and 2b) are in the form of inserts on the inner wall of the reactor in this example. In this configuration, half of the inner wall of the reactor (half of the cylinder plus the bottom half of the case as appropriate) represents the first filter unit 1 b and the other half represents the second filter unit 2 b. The outer wall of the reactor is formed by the non-porous backing material of the filter element installed in the form of an insert, or the outer wall of the reactor forms the non-porous backing material of the filter element. The inlet (6b) and the outlet (7b) of the first and second filter elements are separated from each other by an impervious barrier (1 3). The middle agitator (5) is used to clean the filter surface and to mix the contents of the reactor, and is driven by a shaft (1 1). This configuration is particularly useful for continuous reactions of the present invention in dispersions on a relatively large scale. Fig. 4 illustrates an assembly of n reactors according to the present invention, the flow of which is converted to that shown in Fig. 1 or 3. The feed to the reactor (2 1) is metered with a regulator (22) and fed into the reactor in a desired amount. The stream system leaving the reactor is fed to a selector (23) in which the outflow of one of the reactors is selected and can be passed to an analysis facility (24) such as a gas chromatograph or Mass spectrometer or another analytical instrument. Other logistics go to waste processors (25) or other analyzers. Figure 5 shows a graph in which the measured pressure is plotted against the operating time. The experiment was performed as described in Example 2 except that the flow direction was reversed once after 0.7 hours and once after 1 hour. It can be clearly seen that after setting the reaction pressure after about 0.5 hours, the pressure remained fixed at the initial system until steadily increasing after 0.3 hours, which can be attributed to -19- 200524673 (16) in filtration The active layer of the device. After about 0.7 hours, turning the filter to wash the active layer of the filter caused the reaction pressure to return to the preventive switching after the start, so that the reaction pressure was kept solid at the initial 1.45 hours, and the reaction pressure rose steadily again. In this case, the change of flow direction can reverse the clogging of the active layer of the filter, and the preventive switching on time can avoid the clogging. Figures 6 and 7 show the internal retention time curves of the test substance of Example 2 and, compared to this, the retention time of the two-volume stirred feedstock reactor I showed 69 ml / The volumetric flow rate curve and the volumetric flow rate curve shown in FIG. Experimental measurements and normalization are shown differently. Calculations are shown as lines. From these figures, the tile inspection curve and the calculated curve did not show a significant difference in shape to assume that the behavior of the reaction vessel equipped with a filter element and a stirrer approximately corresponds to the behavior of an ideal continuous stirred tank reactor. The following examples explain this. The scope of the invention, rather than limiting, is defined by the description and the scope of the patent application. EXAMPLE In order to test the flow behavior of the reactor of the present invention, T Examples 1 and 2) were used in 20% by weight of a salt powder having 25 micrometers in hexane (industrial-grade hexane, Aldrich). Place in the reactor. Then at 22 bar, another courtyard flow is fed into the reactor through the inlet, and then flows out from the outlet to flush. Set it at 1 hour until about shows that the first and second, using the invention reactor to produce a rational continuous 0 curve. Figure 6 shows 28 ml. Don't see it in black. It's different. Therefore, the fluid dynamics can be ranged from the range of "experimental (d50) dispersion of silicic acid. Take out a special under force. -20- 200524673 (17) Example l Use installation at-3 00 —The one in the milliliter stirred tank reactor (Btuhi) as shown in Figure 2 * includes ~ ^ pre-subtractor pre-subtractor combinations. The filter unit has in each case 2 · 8 on the inside Filter active area of cm x 3.8 cm. Cross section of inlet and outlet are 1/8 分别 respectively. The distance from the active surface of the filter to the back of the filter element is also 1/8 1 in each case. Filter active The surface includes a non-recording steel mesh / stainless steel screen with 5 micron mesh openings. These filter elements are connected to each other by two stainless steel holders, each of which has a hole for the agitator shaft and the inner The surface is maintained at a distance of 3.4 cm. The agitator shaft is centered through the filter elements, so that it is followed by its leaf agitator (5 a) (5 one leaf agitator half, two 3 cm in height, the individual leaf Width = 1.7 cm, V4-A steel, always with 0.5 mm The same distance passes through the hole type 0 side of the cylindrical filter element. In addition, an impeller agitator with 4 leaves (angle to the flowing side @: 15 °) is fixed to the lower end of the shaft to ensure a substantially uniform distribution of the dispersed phase The shaft system rotates at 1000 rpm. Below the filter area of 10.6 square centimeters per filter unit, it can be operated for a long time (> 1 000 hours) at 20 vol% solid volume ratio (silicic acid Salt powder, d50 = 15 micron can reach a flow rate of up to 50 ml / min (the courtyard). The switching valve is triggered every 30 minutes to backwash the blockage in the sieve. Without the backwash, filter The permeability of the reactor will be reduced after 0.5 hours of operation under the above conditions and the pressure observed in the reactor will increase. 200524673 (18) Example 2 In order to increase the area of the filter, the second example uses the The outside of the cylindrical shell also forms the filter element of the sieve. These filter elements are also welded together through a stabilizer bar. In order to avoid the accumulation of filter cake on the surface of the external filter, an additional stirrer (such as an anchor stirrer) Device (5 b)), which runs on the same shaft as the paddle agitator and passes through the outside of the filter element at a distance of 0.5 mm. In long-term operation (> 100 hours)> 21.4 Under the filter area per square centimeter of the filter unit, a flow rate of up to 100 ml / min (hexane) is achieved at a solid volume ratio of 20% by volume (silicate powder, d5G = 15 microns). 30 minutes trigger to backwash the blockage in the sieve. Without the backwash, under the conditions, the filter's permeability decreases after about 0.5 hours of operation, which can be determined by the pressure in the reactor. Increase is indicated (see Figure 5). Below the filter element, near the bottom, an impeller stirrer is connected to the stirrer shaft, as described in Example 1, to convey suspended solids in the direction of the filter element. In this way, uniform distribution of solids throughout the reactor can be achieved. In both embodiments, no < Observable filter cake form was observed under agitator gap of = 1 mm (observed in situ with glass reactor). Despite the internal components, the reactor showed fluid dynamics comparable to an ideal continuous stirred tank reactor at sufficiently high speeds (depending on the flow rate). This can be demonstrated by comparing the residence time curve of the test substance with the curve in the ideal continuous stirred tank reactor model (Figures 6 and 7). As can be seen from Figures 6 and 7, the two curves do not show differences. -22- 200524673 (19) Example 3 In a reactor equipped with the built-in filter assembly of Example 2 as described in Example 1, at 80 ° C or 9 6 ° C and 25 bar The oligomerization of butene (7 7.4% by weight of linear butene and 22.6% by weight of a fluid compound that is inert under the reaction conditions) is explored under pressure (値 at 96 ° C is shown in parentheses below). The volume flow rate was about 5 ml / min. The catalyst used was 25 g of a catalyst of the type used for oligomerization in DE 3 9 1 4 8 1 7 Example 2 (average particle size dP = 15 microns). 25% (32%) C8 to C2G oligomer conversion was observed. The feed is automatically switched between the two filter elements every 30 minutes. After 2000 hours of experimental operation, no visible clogging of the filter element was observed. [Brief description of the drawings] Fig. 1 illustrates the operation mode of the device of the present invention for performing a liquid reaction on a solid catalyst. Fig. 2 shows a plan view and a side view of a filter element included in the apparatus of the present invention. Fig. 3 schematically shows a plan view and a side view of another configuration of the reactor of the present invention. Fig. 4 shows the reactor assembly of the present invention having the flow direction conversion shown in Fig. 1 or 3; Figure 5 shows a graph in which the measured pressure is plotted against operating time. Fig. 6 shows the retention time curve of a test substance in the reactor of the present invention in Example 2-23-200524673 (20) at a volume flow rate of 69 ml / min, and, as a comparator, an ideal continuous stirred tank reaction Residence time curve of the reactor model. Fig. 7 shows the retention time curve of a test substance in the reactor of the present invention at Example 2 at a volume flow rate of 28 ml / min, and, as a comparison, the retention time curve of an ideal continuous stirred tank reactor model. [Description of the main component symbols] 1 The first filter unit 2 The first ^^ premature 3 reaction zone 4 pressure maintenance valve 5a, 5b, 9 agitator 6, 6a feed (mixture) 7, 7a product 8 four-way valve 10a, 1 Ob holder 11 Agitator drive shaft 12 Bearing 13 Impervious barrier 2 1 Reactor 22 Regulator 23 Selector 24 Analysis facility 25 Waste treatment-24-