201242958 六、發明說明： 本申請要求於20 11年1月27日提交的歐洲專利申請 號EP 11152407.0的權益，其內容藉由引用結合在此。 若任何藉由引用結合在此的專利案、專利申請案以及 公開物中的揭露內容與本說明書相衝突的程度至它可能使 —術語不清楚，則本說明書應該優先。 【發明所屬之技術領域】 本發明涉及一種用於藉由氯丙稀與過氧化氫之間的反 應製造1，2-環氧-3-氯丙烷的方法。 【先前技術】 已知在甲醇作爲溶劑存在下，並且在包括TS-1的催 化劑存在下，如在M.G. Clerici (克萊裡希）等人，催化 雜誌（Journal of Catalysis) ，140，71-83 (1993)中揭露 的那樣，用過氧化氫，藉由氯丙烯的環氧化作用製造1，2-環氧-3-氯丙烷（或環氧氯丙烷）。要求使用甲醇作爲溶劑以 獲得催化劑的良好活性以及對環氧氯丙烷的良好選擇性。 然而使用大量溶劑存在涉及需要對其進行分離、回收和再 利用的缺陷，它們給本方法增加了複雜性。 中國專利申請1〇 1 48 1 3 64的Derwent (德溫特）摘要 說明了在最小量的作爲溶劑的甲醇存在下，以及在鈦-矽 分子篩催化劑存在下，借助過氧化氫，藉由氯丙烯的環氧 化作用製造環氧氯丙烷。該催化劑係一粉末。該催化劑藉 -5- 201242958 由過濾分離，用溶劑再懸浮，並且再循環至該反Μ。使用 —粉末催化劑表現出催化劑回收操作和再循環使該方法更 複雜的缺點。 【發明內容】 本發明目標在於藉由提供一新穎的方法來克服前面的 缺點，其中與溶劑以及反應器複雜性相關的該等缺點大大 減少，然而基本上沒有減小催化劑的活性（或反應物的轉 化度、或環氧化作用反應的速率）以及催化劑壽命，並且 基本上沒有增加副產物的形成。 本發明因此涉及在環氧化作用介質中、固體催化劑存 在下，有可能在至少一種溶劑存在下，藉由氯丙烯和過氧 化氫之間的反應製造1,2-環氧-3-氯丙烷的一種方法，該介 質包括在反應條件下的至少兩個液相，其中該催化劑表現 出低於或等於2.4x1 Ο4 πΓ1的外表面/體積比。 將使用表現出低於或等於2.4χ104 πΓ1的外表面/體積 比的催化劑與雙液相反應混合物結合呈現出至少以下優點 之一： • 提供一催化劑，其具有的形狀使得它易於從反應 混合物分離，並且有助於催化劑的再生： • 在其中使用一醇作爲溶劑的情況下，減少醇解副 產物； • 藉由減少最終產物被溶劑和由溶劑形成的副產物 污染，增強環氧氯丙烷純度； -6 - 201242958 • 減少並且可能地移除溶劑的分離操作； • 減少溶劑再循環回路的體積，並且可能地移除該 回路； • 易於連續進行全過程； • 有可能使用具有可容許的壓降的催化的固定床或 流化床反應器； - • 藉由減少過程的下游步驟的數目減少該方法的總 成本； • 減小該方法的複雜性和成本。 可以獲得那些優點而幾乎沒有影響反應速率和環氧氯 丙烷選擇性。這係出人意料地的，因爲不願受任何理論束 縛，將雙相性環氧化作用條件與一表現出要求的表面/體 積比率特徵的催化劑結合，由於反應物的液相分離的累積 的負面效應（質量傳遞問題）和催化劑顆粒內的擴散問題 ’人們會期待一非常慢的反應速率。此外，由於環氧氯丙 烷溶劑分解的二次後繼反應，爲了對環氧氯丙烷選擇性具 有負面影響的環氧氯丙烷的可接受的生產能力，這樣的條 件此外會要求更高的反應時間。 催化劑的體積應理解爲是指宏觀催化劑的床的幾何體 積。該床可以具有像例如固定床、流化床、移動床、載流 床或循環床的任何類型。固定床和移動床係較佳的，固定 床係最佳的。該催化劑床的體積應理解爲是指在該方法過 程中的操作中催化劑的體積。 催化劑的“外表面”應理解爲是指構成催化劑床的催化 201242958 劑顆粒的表面。由於催化劑顆粒的可能的大孔隙度、中孔 隙度、和/或微孔隙度，該外表面並不包括催化劑顆粒的1 表面。這樣的孔隙度總體上是使得等價的孔徑低於5 μιη ，通常低於2 μηι，並且時常地低於1 μιη。催化劑顆粒旨 在指固體成分的催化劑（例如粉末、擠出物、小粒等）， 蜂窩狀結構，催化的微反應器以及結構化塡料（類似 Katapack®、Melapack®、等）。催化劑可以是一本體催化 劑或一載體催化劑。 可以從催化劑床的的幾何尺寸計算體積。 外表面可以從催化劑顆粒的平均幾何外部尺寸，使用 經典表面和體積公式計算。如果對於該等催化劑顆粒沒有 形狀可以用來限定，它們可以被認爲是球體，並且其幾何 外部尺寸係等效球體的直徑。 在根據本發明的方法中，催化劑可以表現出任何形狀 。該催化劑顆粒總體上以選自由以下各項組成之群組的形 式存在：環，珠粒，小粒，片劑，擠出物，粒料，壓碎的 、鞍狀的、小片，蜂窩狀的結構、浸漬的結構化塡料以及 它們的任何混合物。 當該催化劑係以珠粒的形式存在時，該等珠粒被認爲 是球體，並且其幾何外部尺寸係等效球體的直徑。 當催化劑係以圓柱形顆粒（例如小粒、擠出物）的形 式存在時，該等催化劑顆粒被認爲是圓柱體，並且其幾何 外部尺寸係平均粒徑和平均顆粒長度。平均可以是幾何平 均、算術平均或對數平均。例如算術平均係特別方便的。 201242958 當該等催化劑顆粒不具有簡單幾何形狀，像例如具有 不同形狀（星形、等）的壓碎物、小片、鞍狀物、擠出物 時，它們被認爲是球體並且其幾何外部尺寸係等效球體的 直徑。 當該等催化劑顆粒係以圓柱環的形式存在時，該等催 化劑顆粒被認爲是空心的圓筒並且其幾何尺寸係該等圓筒 的平均直徑（內徑和外徑），以及該等圓筒的平均長度》 當該催化劑係以具有圓柱形通道的蜂窩狀結構的形式 存在時，其幾何尺寸係該等通道的平均長度和直徑。 那些僅是關於如何可以限定對於計算催化劑的外表面 /體積比需要的該等催化劑顆粒的幾何外部尺寸的一些實 例。熟習該項技術者將容易地理解如何獲得任何催化劑形 狀的那些尺寸，包括這以上未揭露的形狀。 可以藉由任何手段，例如藉由對個體催化劑顆粒的視 覺或顯微測量，隨後對於統計可靠的足夠大數量的顆粒（ 例如多於1 〇〇 )的測量進行平均，或者從藉由例如篩選、 沉降（自然的或受迫的）方法或光散射法的細微性分佈， 來獲得該等催化劑顆粒的特徵外部尺寸的値。 在根據本發明的方法中，催化劑表現出一外表面/體 積比，該値通常低於或等於2.ΟΧΙΟ4 ηΓ1，時常地低於或等 於1.5Μ Ο4 ηΤ1，確切地低於或等於1.0x1 〇4 «Γ1，更通常 低於或等於〇.75χ1 04 m·1，更時常地低於或等於0.6χ1 04 πΓ1，確切地低於或等於0.5 xlO4 m·1，更特別地低於或等 於0.3χ104 ηΤ1 ，並且在很多情況下低於或等於O.lxlO4 -9- 201242958 m 。這個比率總體上尚於或等於10 m·1，通常高於20 m_ ^時常地高於或等於50 m·1，確切地高於或等於75 m·1 ，特別地高於或等於100 m·1，並且在很多情況下高於或 等於 1 50 πΓ1。 在根據本發明的方法中，該催化劑較佳的是以選自由 以下各項組成之群組的形式提供：珠粒、擠出物、蜂窩狀 結構以及它們的任何混合物。 在根據本發明的方法的一第一較佳的方面，該催化劑 有利地以藉由任何已知方法獲得的珠粒（球形顆粒）的形 式提供》—特別好地適合的方法係在來自蘇威股份有限公 司（Soci6t6 Anonyme)的國際申請 WO 99/24164中揭露 的方法。催化劑顆粒表現出大於0.10 mm的一平均直徑， 更佳的是大於或等於0.25 mm，並且最佳的是大於或等於 0.4 mm。這個平均直徑通常小於或等於5 mm，較佳的是 小於或等於2 mm，更佳的是小於或等於1 mm並且最佳的 是小於或等於0.8 mm。該等催化劑顆粒總體上表現出大 於或等於1 m2/g並且小於或等於900 m2/g的一比表面積 (根據氮吸附法確定），在0.1和1.〇 g/ml之間的堆密度 ，在0.25和2.5 ml/g之間的孔體積，以及具有在15和 2000 A之間的最大値的孔的直徑的分佈。 在根據本發明的方法的一第二較佳的方面，有利地以 所獲得的非球形顆粒的形式提供催化劑，例如像藉由如在 來自蘇威股份有限公司（Soci0t0 Anonyme)的國際申請 WO 99/2 8 029中揭露的擠出獲得的擠出物。該等擠出粒料 201242958 的形狀係任意的。它們可以是實心的或空心的。它們可以 具有圓的或矩形的截面，或者可替代地是具有更大外表面 積的一不同截面。圓柱形狀係較佳的。當它們具有圓柱形 狀時，該等擠出粒料有利地具有至少0 · 5 mm的平均直徑 ，較佳的是至少1 mm。該平均直徑通常是最多5 mm，較 佳的是最多2 mm。該等圓柱形具有通常至少1 mm的平均 長度，特別地至少2 mm。最多8 mm的平均長度係通用的 ，最多4 mm的那些給出了良好的結果。合適的是該等圓 柱形狀具有從0.5至5 mm的平均直徑，較佳的是從1至 2 mm，並且具有從1至8 mm的平均長度，較佳的是從2 至 4 mm ° 在根據本發明的方法的一第三較佳的方面，有利地以 蜂窩狀結構的形式提供催化劑。“蜂窩”結構應理解爲是指 由具有室狀結構（不論該等室的形狀如何）的組分組成的 —形狀。一般以筒（cartridge )的形式提供蜂窩狀物，該 筒包括每平方英寸（cpi2)高於或等於1〇個的多個室，較 佳的是高於或等於50個，並且更佳的是高於或等於70個 。每平方英寸（cpi2 )的室的這一數目通常低於或等於 1 20 0 ’較佳的是低於或等於900，更佳的是低於或等於 8 00 ’仍更佳的是低於或等於450，並且仍更佳的是低於或 等於4 0 0。 在根據本發明的方法中，催化劑較佳的是包括沸石。 沸石應S解爲是指一固體，該固體包括表現出微孔晶 體結構的矽石。沸石有利地沒有鋁。沸石包括鈦。根據本 -11 - 201242958 發明的沸石較佳的是其中若干矽原子已經被鈦原子替換的 沸石。 用鈦矽沸石類型的沸石已經獲得良好結果。後者有利 地表現出ZSM-5、ZSM-11或MCM-41類型或β類型的一晶 體結構。它們較佳的是表現出在約950-960 cnT1的一紅外 吸收譜帶。高度有效的是對應於化學式xTi02(l-x)Si02的 那些，其中X係從0.000 1至0.5，較佳的是從0.001至 〇.〇5。這一類型的材料（在TS-1名下已知）表現出類似 于沸石ZSM-5的微孔晶體沸石結構。該等化合物的特性和 主要應用係已知的（B. Notari，多相催化中的結構活性和 選擇性關係（Structure-Activity and Selectivity Relationship in Heterogeneous Catalysis )，編輯 R.K. Grasselli 和 A.W. Sleight，愛思唯爾（Elsevier) ，1991 ，第243-256頁）。具體地已經由A. Van der Poel和J. Van Hooff (應用合成（Applied Catalysis A) ，1992，卷 92，第 93-111頁），以及由 Thangaraj等人（沸石 (Zeolites)，12 (1992)，943-950)硏究了 它們的合成。 在根據本發明的催化劑中的沸石含量，表示爲按重量 計催化劑中的沸石的百分比，總體上是大於或等於1 %， 並且小於或等於60%。沸石含量較佳的是大於或等於5% ，並且小於或等於40%。 在根據本發明的第三較佳的方面，該催化劑包括一種 鈦，該鈦含有如以上所述，藉由在一蜂窩狀物形的支持物 上的浸漬而沉積的沸石。該蜂窩狀物形的支持物有利地由 -12- 201242958 一惰性材料組成’該材料經受再生條件並且在其上有可能 藉由一黏合劑使沸石附著。作爲支持物，矽石係高度合適 的。它可以涉及例如與其他鎂或鋁的氧化物或它們的混合 物結合的矽石。該支持物較佳的是堇青石或莫來石。對於 堇青石’示出了一特別的優先，因爲它導致沸石更好地附 著到該支持物上。 在根據本發明的方法中，可隨意地使用的溶劑係一很 好地溶解環氧氯丙烷並且通常在其中水係略微可溶的溶劑 。較佳的是，還可以使用很好地溶解起始氯丙烯的一溶劑 〇 該溶劑較佳的是一有機溶劑。該溶劑可以選自由以下 各項組成之群組：醇，有可能含有至少一個鹵素原子的飽 和脂肪族烴’有可能含有至少一個鹵素原子的不飽和脂肪 族烴’有可能含有鹵素原子、氮原子和烷基中至少之一的 芳香族烴，以及它們中的至少兩種的任意混合物。 該醇通常含有從1至5個碳原子並且僅包括一個-OH 基團。可以提及的例子係甲醇、乙醇、正丙醇、異丙醇、 正丁醇、異丁醇、仲丁醇、叔丁醇以及戊醇。通常，該醇 係甲醇或叔丁醇。甲醇係特別佳的。 當該溶劑係一種醇時，更確切地是一種與水完全易混 合的醇時，這種醇在環氧化作用介質中的含量係使得在環 氧化作用反應的條件下，該環氧化作用介質包括至少兩個 液相。 該可隨意地鹵化的、不飽和烴較佳的是包括從3至 -13- 201242958 20個碳原子。 該芳香族烴有可能含有一鹵素原子、一氮原子和一烷 基中至少之一’較佳的是包括從6至12個碳原子。 該溶劑較佳的是選自由以下各項組成之群組：正癸烷 、正十三烷、1，2,3-三氯丙烷、十氫萘、鄰-二氯苯、間· 二氯苯、對-二氯苯、鄰-二甲苯、間-二甲苯、對-二甲苯 、1，3,5-三甲苯、十氫化萘、鄰-氯甲苯、間-氯甲苯、對_ 氯甲苯、硝基苯、以及它們的混合物。該溶劑通常是甲醇 〇 在根據本發明的方法中，術語“環氧化作用介質”（在 其中發生根據本發明的方法的環氧化作用）應理解爲是指 包括至少兩個液相的一介質，包括氯丙烯、過氧化氫，適 當時，包括溶劑、形成的1，2-環氧-3-氯丙烷和可隨意的副 產物、水以及包括催化劑的一固相。 在根據本發明的方法中，該環氧化作用介質包括至少 兩個液相，至少一個第一液相，實質上是水性的，包括過 氧化氫和至少一部分溶劑（適當時）：以及至少一個第二 液相’實質上是有機的，包括氯丙烯、形成的1，2-環氧-3-氯丙烷、可隨意的副產物以及至少一個其他部分的溶劑（ 適當時）。該第一液相可以包括除了該溶劑的有機化合物 。該第二液相可以包括水。該環氧化作用介質可以沒有溶 劑。 在根據本發明的方法中，此外，可以證明在該環氧化 作用過程中保持環氧化作用介質的pH在一選擇的値下是 rs -14- 201242958 有利的，如在國際申請WO 2004/048353中揭露的。在環 境溫度下、在用一Metr〇hm®6.0239.1 00電極（電解液3M KC1 )對環氧化作用介質的抽出的樣品上所進行的測量過 程中，該pH對應大於或等於1.5的値，特別是大於或等 於3，更特別大於或等於3.2。該pH有利地保持在小於或 等於5的値，更尤其是小於或等於4.8，小於或等於4.5 並且特別是小於4的値給出良好的結果。當該pH保持在 大於或等於3並且小於或等於4.5的値時，與在自然的而 沒有控制的pH時進行的方法相比，觀察到了選擇性更高 而不會減少活性的優點。 藉由添加一種鹼，或者一種鹽以及其共軛鹼或酸的混 合物，可以控制該pH。該鹼可以選自水溶性鹼。它們可 以是強鹼或弱鹼。作爲實例，可以提及一種鹼金屬或鹼土 金屬的氫氧化物、碳酸鹽或乙酸鹽。氫氧化鈉係較佳的。 如以上所述，在有力攪拌這兩個液相時測量該pH，以獲 得遍及該攪拌的介質的一恒定的並且可再現的pH測量。 在根據本發明的方法中，此外，可以證明使用一純化 的使得它包括小於2000 ppm的1，5-己二烯的氯丙烯係有 利的，如在國際申請WO 2004/043941中揭露的。這係因 爲已經發現，使用純化的氯丙烯使之有可能增加使用催化 劑的持續時間（並且因此減少了爲了取代或再生，必需從 該環氧化作用介質除去催化劑的頻率），同時保持高活性 和高選擇性。 純化的氯丙烯可以藉由任何適當的已知方法（例如藉 -15- 201242958 由氯化）獲得，如在國際申請wo 96/033 62中揭露的。該 純化還可以藉由蒸餾進行》 該純化的氯丙烯總體上包括小於按重量計1〇〇〇 ppm 的量的1,5-己二烯，並且較佳的是小於或等於按重量計 500 ppm;小於或等於按重量計400 ppm，並且特別是小 於或等於300 ppm的値係最有利的。在純化的氯丙烯中存 在的1，5-己二烯的量通常是大於或等於按重量計1 ppm， 總體上大於或等於按重量計10 ppm。 在根據本發明的方法中，過氧化氣有利地以一種水溶 液的形式使用。該水溶液總體上包括按重量計至少1 0%的 過氧化氫，特別是按重量計至少20%。它通常包括按重量 計最多70%的過氧化氫，特別是按重量計最多50% » 總體上，使用的氯丙烯的量與使用的過氧化氫的量的 莫耳比係大於或等於0.1，特別是大於或等於0.5，並且較 佳的是大於或等於1。這個比率通常是小於或等於1〇〇， 更尤其是小於或等於50，總體上是小於或等於25。在根 據本發明的方法的一特別有利的替代形式中，利用過量的 氯两烯’使得所使用的氯丙烯的量與所使用的過氧化氫的 量的莫耳比大於或等於1，特別是大於或等於2，非常特 別地大於或等於4。在這一有利的替代形式中，該比率總 體上是小於或等於10，更尤其是小於或等於8，並且通常 小於或等於7 »約爲5的比率係特別好地適合的。在這一 替代形式中使用過量氯丙烯使之有可能獲得在選擇性上甚 至更大的增加’並且結合純化的氯丙烯，使之有可能還獲 rs -16- 201242958 得催化劑的失活上的減少。 在根據本發明的方法中，催化劑可以按一床的形式存 在。它可以是一固定床或流化床。固定床係較佳的。當該 等催化劑顆粒係以環、珠粒、小粒、片劑、擠出物、粒料 、壓碎的小片、蜂窩狀的結構或它們的混合物的形式存在 時，有利地使用此種類型的床。 由珠粒、擠出物或蜂窩狀結構製成的固定床係較佳的 0 可以在任何類型的適當的反應器中進行根據本發明的 方法的環氧化作用反應。例如它可以是一單道（singlepass ) 的床 。它 還可以 是包括 環氧化 作用介 質的再 循環的 一回路型反應器，較佳的是沒有催化劑的再循環。 可以進行該環氧化作用反應的溫度總體上是大於或等 於〇°C，特別是大於或等於35°C，更特別是大於或等於 45°C，並且較佳的是大於或等於55°C。該溫度通常是小 於或等於120°C，更尤其地小於或等於100°C，總體上小 於或等於80°C，小於或等於65°C的溫度給出了高度滿意 的結果。當該溫度係從45 °C至80°C時，與更低的溫度相 比，例如約3 5 °C，觀察到減少了催化劑的失活速率的優 點。 可以在至少等於該環氧化作用介質的組分的蒸氣壓力 的任何壓力下，進行根據本發明的方法。 根據本發明的方法可以連續或分批地進行，較佳的是 連續地進行。 -17- 201242958 當連續進行時，根據本發明的方法通常包括向一包括 該催化劑的反應區連續地加入至少氯丙烯、過氧化氫和有 可能地至少一種溶劑。該進料速率係使得總的液體線速度 總體上是高於或等於0.01 m/s，通常高於或等於0.02 m/s ，時常地高於或等於0.0 3 m/s，在很多情況下，高於或等 於0.1 m/s，並且確切地高於或等於0.2 m/s。這個液體的 進料速率係使得總的液體線速度總體上是低於或等於1 m/s，通常低於或等於0.8 m/s，時常地低於或等於0.6 m/s ，並且確切地低於或等於0.5 m/s。在這樣的總液體線速 度的條件下，橫過該反應區的壓降通常是低於或等於25 kPa/m，時常地低於或等於20 kPa/m，通常低於或等於15 kPa/m，更時常地低於或等於12 kPa/m，通常低於或等於 1 0 kPa/m，更確切地低於5 kPa/m。橫過該反應區的這一 壓降通常是高於或等於〇.〇2 kPa/m ’時常地高於或等於 0.05 kPa/m，通常高於或等於0.08 kPa/m，更時常地高於 或等於0.1 kPa/m，更通常高於或等於〇·4 kPa/m，確切地 高於或等於0.5 kPa/m，並且更確切地高於或等於〇.8 kPa/m 〇 總的液體線速度應理解爲是指含有催化劑的反應區的 總液體進料的線速度。 總的線速度藉由含有催化劑的反應區的總液體進料的 流除以所述區的截面獲得。 總液體進料可以藉由像例如經由孔口、文氏管、噴嘴 、轉子流量計、皮託管、量熱、渦輪、渦流、電磁、多普 • 18- 201242958 勒效應、超聲、熱或寇里奧利的流量計的任何手 所述反應區的截面應理解爲是指沿所述反應 的平均截面。所述反應區可以是水平的或豎直的 橫過該含有催化劑的反應區的壓降被理解爲 壓降，包括對應連接到該區的流體裝置的壓降。 壓降可以藉由像例如，壓差（Dp )計、壓力 U形管壓力計、杯式壓力計、波爾登壓力計、皮 計、電離壓力計、薄膜壓力計、壓電壓力計）、 的任何組合的任何手段測量。較佳的手段選自由 組成之群組：Dp計、U形管壓力計、波爾登壓 膜壓力計、壓電壓力計、以及它們的任何組合。 段選自由以下各項組成之群組：Dp計、薄膜壓 電壓力計、以及它們的任何組合。 對於環氧氯丙烷，根據本發明的方法使之有 總體上大於或等於90 mol%的選擇性，特別是大 95%，如在稍後說明的實例中計算的。該選擇性 於或等於99.5%，更尤其地小於或等於99%« 【實施方式】 然而，以下實例旨在說明本發明而非限制它 實例 這些測試在實質上由具有再迴圈的回路的、 液體-固體固定床（蜂窩狀結構，3個疊加的 段測量。 區的長度 〇 是指動態 計（例如 拉尼壓力 以及它們 以下各項 力計、薄 更佳的手 力計、壓 可能獲得 於或等於 通常是小201242958 VI. OBJECTS: This application claims the benefit of the European Patent Application No. EP 11152407.0, filed on Jan. 27, 2011, the content of which is incorporated herein by reference. In the event that any of the disclosures of the patents, patent applications, and publications cited herein are inconsistent with this specification to the extent that it may render the term unclear, the specification should be preferred. TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing 1,2-epoxy-3-chloropropane by a reaction between chloropropene and hydrogen peroxide. [Prior Art] It is known in the presence of methanol as a solvent, and in the presence of a catalyst including TS-1, as in MG Clerici et al., Journal of Catalysis, 140, 71-83. As disclosed in (1993), 1,2-epoxy-3-chloropropane (or epichlorohydrin) was produced by epoxidation of chloropropene using hydrogen peroxide. It is required to use methanol as a solvent to obtain good activity of the catalyst and good selectivity to epichlorohydrin. However, the use of large amounts of solvent involves defects that require separation, recovery, and reuse, which adds complexity to the process. The Derwent abstract of Chinese patent application 1 〇 1 48 1 3 64 illustrates the use of hydrogen peroxide by means of chloropropene in the presence of a minimum amount of methanol as a solvent and in the presence of a titanium-strontium molecular sieve catalyst. The epoxidation produces epichlorohydrin. The catalyst is a powder. The catalyst was separated by filtration from -5 to 201242958, resuspended with solvent, and recycled to the ruthenium. The use of a powder catalyst demonstrates the disadvantages of catalyst recovery operations and recycle making the process more complicated. SUMMARY OF THE INVENTION The object of the present invention is to overcome the aforementioned disadvantages by providing a novel method in which these disadvantages associated with solvent and reactor complexity are greatly reduced, while substantially no reduction in catalyst activity (or reactants) The degree of conversion, or the rate of epoxidation reaction) and catalyst life, and substantially no increase in the formation of by-products. The invention therefore relates to the production of 1,2-epoxy-3-chloropropane by the reaction between chloropropene and hydrogen peroxide in the presence of at least one solvent in the presence of a solid catalyst in an epoxidation medium. In one method, the medium comprises at least two liquid phases under reaction conditions, wherein the catalyst exhibits an outer surface to volume ratio of less than or equal to 2.4 x 1 Ο 4 π Γ 1 . Combining a catalyst exhibiting an outer surface/volume ratio of less than or equal to 2.4 χ 104 π Γ 1 with a two-liquid phase reaction mixture exhibits at least one of the following advantages: • Providing a catalyst having a shape such that it is easily separated from the reaction mixture And contribute to the regeneration of the catalyst: • Reduce the alcoholysis by-product in the case where a monol is used as a solvent; • Enhance the purity of the epichlorohydrin by reducing the contamination of the final product by the solvent and by-products formed by the solvent ; -6 - 201242958 • Separation operation to reduce and possibly remove solvent; • Reduce the volume of the solvent recirculation loop and possibly remove the loop; • Easily perform the entire process continuously; • It is possible to use a tolerable pressure Reduced catalytic fixed bed or fluidized bed reactor; - • Reduce the total cost of the process by reducing the number of downstream steps of the process; • Reduce the complexity and cost of the process. Those advantages are obtained with little effect on the reaction rate and the epichlorohydrin selectivity. This is unexpected because it is not intended to be bound by any theory, combining biphasic epoxidation conditions with a catalyst exhibiting the desired surface/volume ratio characteristics due to the cumulative negative effects of the liquid phase separation of the reactants (quality) Transfer problems) and diffusion problems within the catalyst particles 'people will expect a very slow reaction rate. In addition, such conditions may require higher reaction times due to the secondary subsequent reaction of the epichlorohydrin solvolysis, in order to have an acceptable production capacity for epichlorohydrin having a negative impact on the epichlorohydrin selectivity. The volume of the catalyst is understood to mean the geometric volume of the bed of the macrocatalyst. The bed may have any type such as, for example, a fixed bed, a fluidized bed, a moving bed, a carrier bed or a circulating bed. Fixed and moving beds are preferred, and fixed bed systems are preferred. The volume of the catalyst bed is understood to mean the volume of the catalyst during the operation in the process. The "outer surface" of a catalyst is understood to mean the surface of the catalyzed 201242958 granule constituting the catalyst bed. The outer surface does not include the surface 1 of the catalyst particles due to the possible large porosity, mesoporosity, and/or microporosity of the catalyst particles. Such porosity is generally such that the equivalent pore size is below 5 μηη, typically below 2 μηι, and often below 1 μηη. The catalyst particles are intended to refer to solid component catalysts (e.g., powders, extrudates, pellets, etc.), honeycomb structures, catalyzed microreactors, and structured tanning materials (like Katapack®, Melapack®, etc.). The catalyst can be a bulk catalyst or a supported catalyst. The volume can be calculated from the geometry of the catalyst bed. The outer surface can be calculated from the average geometric outer dimensions of the catalyst particles using classical surface and volume formulas. If no shape can be used for the definition of the catalyst particles, they can be considered as spheres and their geometric outer dimensions are equivalent to the diameter of the sphere. In the process according to the invention, the catalyst can exhibit any shape. The catalyst particles are generally present in a form selected from the group consisting of rings, beads, granules, tablets, extrudates, pellets, crushed, saddle-shaped, small pieces, honeycomb structures. , impregnated structured tanning materials and any mixtures thereof. When the catalyst is present in the form of beads, the beads are considered to be spheres and their geometric outer dimensions are equivalent to the diameter of the sphere. When the catalyst is present in the form of cylindrical particles (e.g., granules, extrudates), the catalyst particles are considered to be cylinders, and their geometric outer dimensions are average particle size and average particle length. The average can be geometric mean, arithmetic mean or log average. For example, arithmetic averaging is particularly convenient. 201242958 When the catalyst particles do not have simple geometric shapes, such as crushes, chips, saddles, extrudates having different shapes (stars, etc.), they are considered to be spheres and their geometric outer dimensions The diameter of the equivalent sphere. When the catalyst particles are present in the form of a cylindrical ring, the catalyst particles are considered to be hollow cylinders and their geometrical dimensions are the average diameter (inner diameter and outer diameter) of the cylinders, and the Average Length of the Cartridge When the catalyst is in the form of a honeycomb structure having a cylindrical passage, its geometry is the average length and diameter of the channels. Those are only examples of how the geometric outer dimensions of the catalyst particles required to calculate the outer surface/volume ratio of the catalyst can be defined. Those skilled in the art will readily understand how to obtain those dimensions of any catalyst shape, including those not disclosed above. The measurement can be averaged by any means, such as by visual or microscopic measurement of individual catalyst particles, followed by statistically reliable measurements of a sufficiently large number of particles (eg, more than 1 〇〇), or by, for example, screening, The fineness distribution of the sedimentation (natural or forced) method or light scattering method to obtain the enthalpy of the characteristic outer dimensions of the catalyst particles. In the process according to the invention, the catalyst exhibits an outer surface/volume ratio, which is usually lower than or equal to 2. ΟΧΙΟ4 ηΓ1, often lower than or equal to 1.5Μ Ο4 ηΤ1, and indeed lower than or equal to 1.0x1 〇 4 «Γ1, more usually less than or equal to 〇.75χ1 04 m·1, more often less than or equal to 0.6χ1 04 πΓ1, exactly lower than or equal to 0.5 xlO4 m·1, more particularly lower than or equal to 0.3 Χ104 ηΤ1 , and in many cases lower than or equal to O.lxlO4 -9- 201242958 m. This ratio is generally equal to or equal to 10 m·1, usually higher than or equal to 50 m·1 when it is higher than 20 m_^, and is preferably higher than or equal to 75 m·1, in particular higher than or equal to 100 m· 1, and in many cases higher than or equal to 1 50 πΓ1. In the process according to the invention, the catalyst is preferably provided in the form of a group selected from the group consisting of beads, extrudates, honeycomb structures and any mixtures thereof. In a first preferred aspect of the method according to the invention, the catalyst is advantageously provided in the form of beads (spherical particles) obtained by any known method - a particularly well-suited method is derived from Solvay The method disclosed in International Application No. WO 99/24164 to Soci6t6 Anonyme. The catalyst particles exhibit an average diameter greater than 0.10 mm, more preferably greater than or equal to 0.25 mm, and most preferably greater than or equal to 0.4 mm. This average diameter is usually less than or equal to 5 mm, preferably less than or equal to 2 mm, more preferably less than or equal to 1 mm and most preferably less than or equal to 0.8 mm. The catalyst particles generally exhibit a specific surface area (determined by nitrogen adsorption method) of greater than or equal to 1 m2/g and less than or equal to 900 m2/g, a bulk density between 0.1 and 1. 〇g/ml, The pore volume between 0.25 and 2.5 ml/g, and the distribution of the diameter of the pores with a maximum enthalpy between 15 and 2000 A. In a second preferred aspect of the method according to the invention, the catalyst is advantageously provided in the form of the obtained non-spherical particles, for example by, for example, the international application WO 99 from Soci0t0 Anonyme The extrudate obtained by extrusion disclosed in /2 8 029. The shape of the extruded pellets 201242958 is arbitrary. They can be solid or hollow. They may have a round or rectangular cross section or alternatively a different cross section with a larger outer surface area. A cylindrical shape is preferred. When they have a cylindrical shape, the extruded pellets advantageously have an average diameter of at least 0. 5 mm, preferably at least 1 mm. The average diameter is usually up to 5 mm, preferably up to 2 mm. The cylinders have an average length of usually at least 1 mm, in particular at least 2 mm. Average lengths of up to 8 mm are common, and those up to 4 mm give good results. Suitably the cylindrical shapes have an average diameter of from 0.5 to 5 mm, preferably from 1 to 2 mm, and have an average length of from 1 to 8 mm, preferably from 2 to 4 mm ° In a third preferred aspect of the method of the present invention, the catalyst is advantageously provided in the form of a honeycomb structure. "Honeycomb" structure is understood to mean a shape consisting of components having a chamber-like structure, regardless of the shape of the chambers. The honeycomb is typically provided in the form of a cartridge comprising a plurality of chambers per square inch (cpi2) greater than or equal to one, preferably greater than or equal to 50, and more preferably high Or equal to 70. This number per square inch (cpi2) of the chamber is typically less than or equal to 1200's preferably less than or equal to 900, more preferably less than or equal to 800' or still more preferably less than or It is equal to 450, and still better is lower than or equal to 400. In the process according to the invention, the catalyst preferably comprises a zeolite. Zeolite should be interpreted as a solid which comprises vermiculite which exhibits a microporous crystal structure. The zeolite advantageously has no aluminum. Zeolites include titanium. The zeolite according to the invention of -11 - 201242958 is preferably a zeolite in which a plurality of ruthenium atoms have been replaced by titanium atoms. Good results have been obtained with zeolites of the titanium strontium zeolite type. The latter advantageously exhibits a crystal structure of ZSM-5, ZSM-11 or MCM-41 type or β type. They preferably exhibit an infrared absorption band at about 950-960 cnT1. Highly effective are those corresponding to the chemical formula xTi02(l-x)SiO 2 wherein X is from 0.000 1 to 0.5, preferably from 0.001 to 〇.〇5. This type of material (known under the TS-1 name) exhibits a microporous crystalline zeolite structure similar to zeolite ZSM-5. The properties and main applications of these compounds are known (B. Notari, Structure-Activity and Selectivity Relationship in Heterogeneous Catalysis), edited by RK Grasselli and AW Sleight, Ai Siwei Elsevier, 1991, pp. 243-256). Specifically by A. Van der Poel and J. Van Hooff (Applied Catalysis A, 1992, Vol. 92, pp. 93-111), and by Thangaraj et al. (Zeolites), 12 (1992) , 943-950) studied their synthesis. The zeolite content in the catalyst according to the present invention is expressed as a percentage of the zeolite in the catalyst by weight, which is generally greater than or equal to 1% and less than or equal to 60%. The zeolite content is preferably greater than or equal to 5% and less than or equal to 40%. In a third preferred aspect according to the present invention, the catalyst comprises a titanium comprising a zeolite deposited by impregnation on a honeycomb-shaped support as described above. The honeycomb-shaped support is advantageously composed of an inert material of -12-201242958. The material is subjected to regeneration conditions and it is possible to attach the zeolite by a binder. As a support, the meteorite system is highly suitable. It may involve, for example, vermiculite combined with other oxides of magnesium or aluminum or mixtures thereof. The support is preferably cordierite or mullite. A particular preference is shown for cordierite as it results in a better attachment of the zeolite to the support. In the process according to the present invention, the solvent which can be optionally used is a solvent which dissolves epichlorohydrin very well and is usually slightly soluble in the water system. Preferably, a solvent which dissolves the starting chloropropene well is also used. The solvent is preferably an organic solvent. The solvent may be selected from the group consisting of alcohols, saturated aliphatic hydrocarbons which may contain at least one halogen atom, 'unsaturated aliphatic hydrocarbons which may contain at least one halogen atom', possibly containing a halogen atom, a nitrogen atom And an aromatic hydrocarbon of at least one of the alkyl groups, and any mixture of at least two of them. The alcohol typically contains from 1 to 5 carbon atoms and includes only one -OH group. Examples which may be mentioned are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and pentanol. Usually, the alcohol is methanol or tert-butanol. Methanol is particularly good. When the solvent is an alcohol, more specifically an alcohol which is completely miscible with water, the content of the alcohol in the epoxidation medium is such that, under the conditions of the epoxidation reaction, the epoxidation medium comprises At least two liquid phases. The optionally halogenated, unsaturated hydrocarbon preferably comprises from 3 to -13 to 201242958 20 carbon atoms. The aromatic hydrocarbon may have at least one of a halogen atom, a nitrogen atom and a monoalkyl group. Preferably, it comprises from 6 to 12 carbon atoms. The solvent is preferably selected from the group consisting of n-decane, n-tridecane, 1,2,3-trichloropropane, decahydronaphthalene, o-dichlorobenzene, m-dichlorobenzene. , p-dichlorobenzene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, decalin, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, Nitrobenzene, and mixtures thereof. The solvent is usually methanol oxime. In the process according to the invention, the term "epoxidation medium" in which the epoxidation of the process according to the invention takes place is understood to mean a medium comprising at least two liquid phases, Included are chloropropene, hydrogen peroxide, and, where appropriate, a solvent, formed 1,2-epoxy-3-chloropropane and optionally by-products, water, and a solid phase comprising a catalyst. In the process according to the invention, the epoxidation medium comprises at least two liquid phases, at least one first liquid phase, substantially aqueous, comprising hydrogen peroxide and at least a portion of the solvent (where appropriate): and at least one The two liquid phases are substantially organic, including chloropropene, formed 1,2-epoxy-3-chloropropane, optionally by-products, and at least one other portion of the solvent (where appropriate). The first liquid phase may include an organic compound other than the solvent. The second liquid phase can include water. The epoxidation medium may be free of solvent. In the process according to the invention, in addition, it can be demonstrated that it is advantageous to maintain the pH of the epoxidation medium during the epoxidation under rs -14 - 201242958, as in the international application WO 2004/048353. Revealed. In the measurement of the extracted sample of the epoxidation medium with a Metr〇hm® 6.0239.1 00 electrode (electrolyte 3M KC1 ) at ambient temperature, the pH corresponds to a enthalpy greater than or equal to 1.5. In particular, it is greater than or equal to 3, more particularly greater than or equal to 3.2. The pH is advantageously maintained at enthalpy of less than or equal to 5, more particularly less than or equal to 4.8, and less than or equal to 4.5 and especially less than 4 gives good results. When the pH is maintained at 大于 greater than or equal to 3 and less than or equal to 4.5, the advantage of higher selectivity without reducing activity is observed as compared to the method performed at a natural, uncontrolled pH. The pH can be controlled by the addition of a base, or a salt and a mixture of its conjugate base or acid. The base can be selected from water soluble bases. They can be strong bases or weak bases. As an example, mention may be made of an alkali metal or alkaline earth metal hydroxide, carbonate or acetate. Sodium hydroxide is preferred. As described above, the pH is measured while vigorously agitating the two liquid phases to obtain a constant and reproducible pH measurement throughout the agitated medium. In the process according to the invention, in addition, it can be demonstrated that the use of a purified chloropropene which makes it comprise less than 2000 ppm of 1,5-hexadiene is advantageous, as disclosed in the international application WO 2004/043941. This is because it has been found that the use of purified chloropropene makes it possible to increase the duration of use of the catalyst (and thus reduce the frequency of removal of the catalyst from the epoxidation medium for substitution or regeneration) while maintaining high activity and high Selectivity. Purified chloropropene can be obtained by any suitable known method (e.g., by -15-201242958 from chlorination) as disclosed in International Application WO 96/03362. The purification may also be carried out by distillation. The purified chloropropene generally comprises less than or equal to 1 〇〇〇ppm of 1,5-hexadiene, and preferably less than or equal to 500 ppm by weight. A lanthanide system of less than or equal to 400 ppm by weight, and especially less than or equal to 300 ppm, is most advantageous. The amount of 1,5-hexadiene present in the purified chloropropene is usually greater than or equal to 1 ppm by weight, and is generally greater than or equal to 10 ppm by weight. In the process according to the invention, the peroxygen gas is advantageously used in the form of an aqueous solution. The aqueous solution generally comprises at least 10% by weight hydrogen peroxide, especially at least 20% by weight. It usually comprises up to 70% by weight of hydrogen peroxide, especially up to 50% by weight » overall, the amount of chloropropene used is greater than or equal to 0.1 for the amount of hydrogen peroxide used. In particular, it is greater than or equal to 0.5, and preferably greater than or equal to 1. This ratio is typically less than or equal to 1 〇〇, more specifically less than or equal to 50, and is generally less than or equal to 25. In a particularly advantageous alternative form of the process according to the invention, the excess chlorodiene is used such that the molar ratio of the amount of chloropropene used to the amount of hydrogen peroxide used is greater than or equal to 1, in particular Greater than or equal to 2, very particularly greater than or equal to 4. In this advantageous alternative, the ratio is generally less than or equal to 10, more particularly less than or equal to 8, and a ratio of typically less than or equal to 7 » about 5 is particularly well suited. The use of excess chloropropene in this alternative form makes it possible to obtain even greater increases in selectivity' and in combination with purified chloropropene, making it possible to obtain the deactivation of the catalyst from rs-16-201242958. cut back. In the process according to the invention, the catalyst may be present in the form of a bed. It can be a fixed bed or a fluidized bed. A fixed bed system is preferred. This type of bed is advantageously used when the catalyst particles are present in the form of rings, beads, granules, tablets, extrudates, pellets, crushed tablets, honeycomb structures or mixtures thereof. . The fixed bed made of beads, extrudate or honeycomb structure is preferably 0. The epoxidation reaction of the process according to the invention can be carried out in any type of suitable reactor. For example it can be a singlepass bed. It may also be a primary loop reactor comprising a recirculating epoxidation medium, preferably without catalyst recycle. The temperature at which the epoxidation reaction can be carried out is generally greater than or equal to 〇 ° C, especially greater than or equal to 35 ° C, more specifically greater than or equal to 45 ° C, and preferably greater than or equal to 55 ° C. The temperature is usually less than or equal to 120 ° C, more specifically less than or equal to 100 ° C, and generally less than or equal to 80 ° C, and temperatures less than or equal to 65 ° C give highly satisfactory results. When the temperature is from 45 ° C to 80 ° C, an advantage of reducing the rate of deactivation of the catalyst is observed in comparison with a lower temperature, for example, about 35 ° C. The process according to the invention can be carried out at any pressure at least equal to the vapor pressure of the components of the epoxidation medium. The process according to the invention can be carried out continuously or batchwise, preferably continuously. -17- 201242958 When continuously carried out, the process according to the invention generally comprises continuously adding at least chloropropene, hydrogen peroxide and possibly at least one solvent to a reaction zone comprising the catalyst. The feed rate is such that the total liquid linear velocity is generally greater than or equal to 0.01 m/s, typically greater than or equal to 0.02 m/s, and often greater than or equal to 0.03 m/s, in many cases, Higher than or equal to 0.1 m/s, and specifically higher than or equal to 0.2 m/s. The feed rate of this liquid is such that the total liquid linear velocity is generally less than or equal to 1 m/s, typically less than or equal to 0.8 m/s, often less than or equal to 0.6 m/s, and is substantially low At or equal to 0.5 m/s. At such total liquid line velocity conditions, the pressure drop across the reaction zone is typically less than or equal to 25 kPa/m, often less than or equal to 20 kPa/m, and typically less than or equal to 15 kPa/m. , more often less than or equal to 12 kPa/m, usually less than or equal to 10 kPa/m, and more specifically less than 5 kPa/m. This pressure drop across the reaction zone is typically greater than or equal to 〇.〇2 kPa/m', often higher than or equal to 0.05 kPa/m, usually greater than or equal to 0.08 kPa/m, and more often higher than Or equal to 0.1 kPa/m, more usually higher than or equal to 〇·4 kPa/m, specifically higher than or equal to 0.5 kPa/m, and more specifically higher than or equal to 〇.8 kPa/m 〇 total liquid line Speed is understood to mean the linear velocity of the total liquid feed to the reaction zone containing the catalyst. The total linear velocity is obtained by dividing the flow of the total liquid feed of the reaction zone containing the catalyst by the cross section of the zone. The total liquid feed can be by, for example, via orifices, venturis, nozzles, rotameters, pitot tubes, calorimetry, turbines, eddy currents, electromagnetics, Doppler 18-201242958, effect, ultrasound, heat or enthalpy The cross section of the reaction zone of any hand of Orly's flow meter is understood to mean the average cross section along the reaction. The reaction zone may be horizontal or vertical. The pressure drop across the reaction zone containing the catalyst is understood to be a pressure drop, including the pressure drop corresponding to the fluidic device connected to the zone. The pressure drop can be obtained by, for example, a differential pressure (Dp) meter, a pressure U-tube pressure gauge, a cup gauge, a Bourdon gauge, a skin gauge, an ionization gauge, a membrane pressure gauge, a piezoelectric pressure gauge, Any means of any combination of measurements. Preferred means are selected from the group consisting of Dp meters, U-tube pressure gauges, Bolden pressure gauges, piezoelectric pressure gauges, and any combination thereof. The segments are selected from the group consisting of Dp meters, thin film piezoelectric pressure gauges, and any combination thereof. For epichlorohydrin, the process according to the invention has a selectivity which is generally greater than or equal to 90 mol%, in particular 95% greater, as calculated in the examples illustrated later. The selectivity is equal to or equal to 99.5%, more particularly less than or equal to 99%. [Embodiment] However, the following examples are intended to illustrate the invention and not to limit its examples. These tests are essentially by loops with recirculating loops. Liquid-solid fixed bed (honeycomb structure, measured in 3 superimposed sections. The length of the zone 〇 refers to the dynamic gauge (eg Rani pressure and their force gauges below, thinner hand gauges, pressures may be obtained from Or equal to usually small
處於一台 orning C -19 - 201242958 119筒，對於一個筒具有以下特徵：直徑：2.6 cm，高度 :10 cm，每平方英寸400個通道，lxl mm的正方形通道 ，每立方英寸68.8平方英寸）中的管式反應器（在壓力 下帶夾套的）組成的裝置中進行。具體是該回路包括一回 流冷凝器，該冷凝器在大氣壓下，直接位於該反應器的出 口（冷凝氯丙烯）。該器件的總體積爲約3 1 0 ml。 使用一低溫恒溫器穩定該反應器的溫度。 使用一氣壓閥將該反應器內的壓力穩定在1.0巴。 從該環氧化作用介質從該反應器的出口處，對其減壓 ，並且藉由穿過進入一帶夾套的玻璃盤管冷卻由此生成的 液體-氣體混合物。該低溫恒溫器的溫度設定點固定在-20°C。 在該冷凝器的出口，該液相被分爲兩個流： • 液體流出物，它的流速對應反應物進料的流速， • 以及一第二更大的流出物，它形成再循環穿梭。 向這一再循環流添加H202、氯丙烯（ALC )和有可能地甲 醇（MeOH)進料。 使用一隔膜泵提供朝向該反應器的運動。使用一流量 計測量該再循環流速，並且將其調節至600 Ι/h。該總的液 體線速度爲0.33 m/s。在進入該反應器以前，該液體穿過 一預熱器。已經估算該壓降爲低於7 kPa/m。藉由按照由 G Germain (熱爾曼）、C Chandellier (康得里爾）和 C Blarel (貝拉熱）在第 10 期 J〇urn0e de l’hydrodynamique Nantes 7-9/3/20 05中提出的方法和資料進行該估算。 -20- 201242958 在該等測試中，利用以由3個疊加的Corning C 119 筒製成的蜂窩狀結構的形式提供的16 g催化劑，該等筒 具有在由Ti矽沸石組成的蜂窩狀物室的表面上沉積的TS-1沸石。已經根據如蘇威股份有限公司的揭露的國際申請 WO 1 999/2803 5製備該等筒。在該空的Corning C筒的外 表面/體積比的基礎上，估算該催化劑的外表面/體積比小 於 2800 ηΤ1。 使用了具有75 ml/h的流速的35重量％1〇2。調整了 氯丙烯以及有可能地甲醇的進料流速，以獲得包括 ALC/H202兩個液相的一環氧化作用介質以及 表1中給定的Me0H/(Me0H + H202)比率。 從H2〇2的進口和出口流速計算H202的轉化度（DC )，後者使用溢流液體中的殘留H202的碘量滴定測定的 結果來確定： DC(%)=100x(按mol/h的使用的H202-按mol/h的未轉 化的H202)/按mol/h的使用的H202 同時未轉化的H202 =按mol/kg的溢流中的H2〇2的濃 度X按kg/h的溢流流速。 術語“形成的C3”應理解爲是指環氧氯丙烷（EPI)以 及從環氧乙烷環的開環生成的不同副產物，即1 1-氯-3 -甲 氧基-2-丙醇（記作lC130Me2Pol) 、1-氯-2-甲氧基-3-丙 醇（記作 lC120Me3Pol) 、3-氯-1,3-丙二醇（記作 MCG) 以及1,3-二氯-2-丙醇（記作l,3DCPol)。 因此可以從藉由液體流出物的氣相色譜法獲得的色譜 -21 - 201242958 圖，使用以下運算式計算形成的EPI/C3的選擇性： EPI/C3f 選擇性（％)=l〇〇x 按 mol/h 的 ΕΡΙ®α 的/按 mol/h 的 Z(EPI+lC130Me2Pol + lC120Me3Pol + MCG + l，3DCPol)形成的。 實例1至5 (根據本發明） 在下表1中給出了該等測試的條件和結果。 表1In an orning C -19 - 201242958 119 cylinder, for a cylinder with the following characteristics: diameter: 2.6 cm, height: 10 cm, 400 channels per square inch, lxl mm square channel, 68.8 square inches per cubic inch) It is carried out in a device consisting of a tubular reactor (with a jacket under pressure). Specifically, the circuit includes a reflux condenser that is directly at the outlet of the reactor (condensed chloropropene) at atmospheric pressure. The total volume of the device is approximately 310 ml. The temperature of the reactor was stabilized using a cryostat. The pressure in the reactor was stabilized at 1.0 bar using a pneumatic valve. From the epoxidation medium, it is decompressed from the outlet of the reactor, and the thus produced liquid-gas mixture is cooled by passing through a glass coil entering a jacket. The temperature set point of the cryostat is fixed at -20 °C. At the outlet of the condenser, the liquid phase is split into two streams: • a liquid effluent whose flow rate corresponds to the flow rate of the reactant feed, and a second, larger effluent which forms a recirculation shuttle. To this recycle stream was added H202, chloropropene (ALC) and possibly methanol (MeOH) feed. A diaphragm pump is used to provide motion towards the reactor. The recirculation flow rate was measured using a flow meter and adjusted to 600 Ι/h. The total liquid line speed is 0.33 m/s. The liquid passes through a preheater before entering the reactor. This pressure drop has been estimated to be below 7 kPa/m. Proposed by G Germain, C Chandellier and C Blarel in the 10th issue of J〇urn0e de l'hydrodynamique Nantes 7-9/3/20 05 The method and information are used to make this estimate. -20- 201242958 In these tests, 16 g of catalyst was provided in the form of a honeycomb structure made of 3 superimposed Corning C 119 cartridges having a honeycomb chamber composed of Ti yttrium zeolite. TS-1 zeolite deposited on the surface. The cartridges have been prepared in accordance with the international application WO 1 999/2803 5, which is incorporated herein by reference. Based on the outer surface/volume ratio of the empty Corning C cartridge, the outer surface/volume ratio of the catalyst was estimated to be less than 2800 η Τ 1 . A 35 wt% 1 〇 2 flow rate of 75 ml/h was used. The feed flow rate of chloropropene and possibly methanol was adjusted to obtain an epoxidation medium comprising two liquid phases of ALC/H202 and a Me0H/(Me0H + H202) ratio given in Table 1. Calculate the degree of conversion (DC) of H202 from the inlet and outlet flow rates of H2〇2, which is determined by the results of iodometric titration of residual H202 in the overflow liquid: DC (%) = 100x (by mol/h) H202-based as mol/h of unconverted H202)/mol/h used H202 simultaneously unconverted H202 = concentration of H2〇2 in the overflow of mol/kg X by overflow of kg/h Flow rate. The term "formed C3" is understood to mean epichlorohydrin (EPI) and different by-products formed from the ring opening of the oxirane ring, ie 1-chloro-3-methoxy-2-propanol (denoted as lC130Me2Pol), 1-chloro-2-methoxy-3-propanol (denoted as lC120Me3Pol), 3-chloro-1,3-propanediol (denoted as MCG) and 1,3-dichloro-2- Propanol (denoted as l, 3DCPol). Therefore, the selectivity of the formed EPI/C3 can be calculated from the chromatogram of the liquid effluent obtained by gas chromatography of the liquid effluent from 21 to 201242958: EPI/C3f selectivity (%) = l〇〇x The mol/h of ΕΡΙ®α is formed by mol/h of Z (EPI+lC130Me2Pol + lC120Me3Pol + MCG + l, 3DCPol). Examples 1 to 5 (according to the invention) The conditions and results of the tests are given in Table 1 below. Table 1
實例 alc/h2o2 (mol/mol) Me0H/(Me0H+H202) (wt%) T (°C) DC (%) EPI/C3f選擇性 (mol%) 1 1.43 21 25 60 96.9 2 1.97 9 35 67 94.9 3 2.06 33 35 76 95.0 4 4.06 21 45 90 92.3 5 1.76 34 45 81 90.7 -22-Example alc/h2o2 (mol/mol) Me0H/(Me0H+H202) (wt%) T (°C) DC (%) EPI/C3f selectivity (mol%) 1 1.43 21 25 60 96.9 2 1.97 9 35 67 94.9 3 2.06 33 35 76 95.0 4 4.06 21 45 90 92.3 5 1.76 34 45 81 90.7 -22-