200922929 九、發明說明： ’尤其是製造環氧氯丙 【發明所屬之技術領域】 本發明涉及-_於製造魏化物的改良方法 烷之改良方法。 更詳細地，本發明涉及一種由氯丙烯製造環氧氣丙烷的方法。 【先前技術】 使用環氧氯时（EpiehlGIOhydrilKECH)最乡之處為製造環氧樹脂 y：Ep〇xyR£Sms> ’ 表面塗佈。一些表面活性劑亦是由環氧氯丙^^ 製成’做為洗、4#卜解乳化劑（demulsifiers)料之用。環氧氯丙院以應 用於一些藥物、紡織品柔軟劑和染色劑、紙漿劑等等之製備。環氧氯丙^ 用以作為-謂（例如：祕乙酸麟素）、用於餘乙浠的安定劑、氯化 橡膠和數種含氣殺蟲劑、以及潤滑油脂的添加劑。 在過去數十年中，發展出不同種類的製造方法，利用活性氧物種和無 ，鹽類將例如氯㈣（allyl ehlGride)的棘物（Qlefms)無為例如環氧 ^丙烧的環氧化物1例上’過量的氯丙麟由過氧乙酸㈤⑽价⑽） 溶液環氧化祕成環氧氯破。過量的氯丙肺所形成的環氧氯丙院藉由 蒸餾而分離。以上所述之慣用方法主要的缺點在於，由於乙酸（攝氏117 5 度）與環氧氯丙烷（攝氏116度）的沸點過於相近，因此要將乙酸從環氧 氯丙烷反應混合物中完全分離需要花費相當大的成本。在另一方法之中， 丙烯（Propylene)在鈀（Pd)催化劑和氧氣之下與乙酸（aceticadd)反應 產生喊（ether) ’該生成物在碳氧二氯（c〇ci2)和有機溶劑之下經氣化作 用產生2,3-二氣異構物（2,3-dichloroisomer)和1，2-二氯異構物的混合物。 此混合物加入水後產生U_二氣丙醇（1,2_dlchl〇r〇pr〇pan〇1)和2,3_二氣丙 醇的混合物’進一步加入氫氧化約（calciumhydroxide)後產生環氧氣丙烧。 然而，在氯化反應步驟中，所述C〇Cl2催化劑必須在反應完成後分離。此 外’產物的產率並不高（例如：47.5% - 84.2%)並因此必須分離和回收未 反應之氯丙烯。更在另一方法中’丙烯在Pd催化劑與氧氣之下與乙酸反應 產生醚。醚與氯化氫（hydrogen chloride)在氯化亞銅（CuCl)或氯化亞鐵 200922929 (FeCl2)以及有機溶劑之下反應產生氯丙烯與乙酸。該氯丙烯藉由氯/氧化 氫（Cl2/H2〇)次氯酸化（hypo chlorination)後產生 2, 3-二氣丙醇和 1,2-二 氣丙醇的混合物，該混合物與一種鹼--氫氧化鈣反應產生環氧氯丙烷。以上 所述之方法主要的缺點在於，反應在CuCl或？6(：12催化劑存在之下加入氯 化氫而進行，其為一非水系統以防止水解。 環氧氯丙烧的工業上製造係藉由氯化（chlorination)氣丙稀，該氯丙稀 係藉由在高溫下氯化丙烯（propylene)而得。氯化反應的副產物為順_i,3_ 一風> 丙稀、反-1，3-一風> 丙稀、以及1,2-二風丙烧。二氣丙醇（glycerol dichlorohydrin)係由氯丙烯而得，而副產物為l52,3-三氯丙烷（1, 2, 3-trichloropropane)。最後，環氧氯丙烷係由二氯丙醇混合物以鹼處理而產 生。其主要的缺點在於： 1) 所述方法使用石灰/氧化鈣（lime/CaO)、水、以及額外之氣，導致高成 本0 2) 使用需要蒸氣、電、冷卻水、以及空氣/氮（air/N2)的用具所需的支出 成本龐大。 3) 每生產一公噸的ECH產物的同時，所產生的15至20公噸的流出物 (effluents)係生產成本與法規限制上的一大難題。 美國專利號6720435、6288248、以及6350888揭露一製造環氧氯丙烧 的方法，藉由將氯丙稀與一過氧化合物在水、一催化劑、以及一溶劑中反 應，隨後藉由一液液萃取方式將所產生之環氧氯丙烷分離。其主要的缺點 在於，使用粉狀催化劑降低了過濾速率、由於液液萃取而使用另一氯化化 合物，因此使得回收成本以及所產生的流出液增加，導致處置與處理費用 增加。 美國專利號6380407揭露一製造環氧化物的方法，該方法為在一反應 益中，一烯烴物與一過氧化合物在一沸石型催化劑以及一溶劑下以液相 (aqueous phase)進行反應。氣體化合物以至少足夠載送些許所產生之環 氧化物的流速持續地加入反應器中，所述環氧化物在其離開反應器時與氣 體化合物一同回收。一些缺點在於，使用氣體化合物以進行反應導致預熱 化合物以及維持該固體催化劑的流體化需消耗額外的能量。 ‘ ' 200922929 美國專利號6677467、6723861、以及6838571揭露一製造環氧乙烷 (oxirane)的方法’該方法藉由一烯烴物與一過氧化合物在一催化劑以及 一溶劑之下，在一連串之反應器之令進行反應，每個反應器之中含有一部 分的催化劑’其中，所述過氧化合物僅加入至一連串之反應器的第一反應 器中而其後的反應器均未加入新鮮的過氧化合物，但所述過氧化合物係指 存在於前一反應器中所得之介質之十，而未在前一反應器中被消耗的過氧 化合物。 美國專利號6720435、6288248、以及6350888揭露一液液萃取的方法， 其中，一氯化化合物係用以在氯丙烯、曱醇、水、以及環氧氯丙烷的混合 物中選擇性萃取環氧氯丙院。該萃取相僅含有10%所產生之環氧氯丙烧而 其餘90%為在液相之中。從所述液相中分離出環氧氯丙烷係為一灰色地 帶，截至目前為止尚未有任何成果報告提出。 因此需要提出一種製造環氧氯丙燒的改良方法，其中，極少量的環氧 氯丙烷在失去在水層（aqU_ layer)中，並且藉由級聯反應（cascade reactions)提高產量百分率。本發明旨為滿足此需求。200922929 IX. INSTRUCTIONS: 'In particular, the production of epichlorohydrin. [Technical Field of the Invention] The present invention relates to an improved process for the manufacture of a derivative. In more detail, the present invention relates to a process for producing epoxidized propane from chloropropene. [Prior Art] When using epoxy chlorine (Epiehl GIOhydrilKECH), the most common place is to manufacture epoxy resin y: Ep 〇 R R £ Sms > ' Surface coating. Some surfactants are also made from epichlorohydrin, which is used as a wash and 4# demulsifiers. Epoxy chloride is used in the preparation of some pharmaceuticals, textile softeners and stains, pulps, and the like. Epoxy chloropropane ^ is used as an additive for - (for example, cytosine), a stabilizer for acetamidine, chlorinated rubber and several gas-containing insecticides, and lubricating grease. In the past few decades, different types of manufacturing methods have been developed, using reactive oxygen species and no, salts such as lyl ehlGride (Qlefms), such as epoxy epoxide epoxide 1 For example, 'excessive chloropropene is peroxyacetic acid (5) (10) valence (10)) solution epoxidized into epoxy chlorinated. The epichlorohydrin formed by an excess of chloropropene lungs was separated by distillation. The main disadvantage of the conventional method described above is that since acetic acid (117 degrees Celsius) is too close to the boiling point of epichlorohydrin (116 degrees Celsius), it takes time to completely separate acetic acid from the epichlorohydrin reaction mixture. Quite a big cost. In another method, Propylene reacts with acetic acid under palladium (Pd) catalyst and oxygen to produce an 'ether' in the carbon oxychloride (c〇ci2) and organic solvent. The gasification produces a mixture of the 2,3-dichloroisomer and the 1,2-dichloroisomer. When this mixture is added to water, a mixture of U_dipropanol (1,2_dlchl〇r〇pr〇pan〇1) and 2,3_dipropanol is produced. 'Additional addition of hydroxidehydroxide produces epoxy propylene. burn. However, in the chlorination reaction step, the C〇Cl2 catalyst must be separated after completion of the reaction. The yield of the product is not high (e.g., 47.5% - 84.2%) and therefore unreacted chloropropene must be separated and recovered. In still another method, propylene is reacted with acetic acid under Pd catalyst and oxygen to produce an ether. The ether is reacted with hydrogen chloride under cuprous chloride (CuCl) or ferrous chloride 200922929 (FeCl2) and an organic solvent to produce chloropropene and acetic acid. The chloropropene produces a mixture of 2,3-dipropanol and 1,2-dipropanol by chlorine/hydrogen peroxide (Cl2/H2 〇) hypochlorination, the mixture and a base- The calcium hydroxide reacts to produce epichlorohydrin. The main disadvantage of the above method is that the reaction is in CuCl or? 6 (: 12 catalyst is added in the presence of hydrogen chloride, which is a non-aqueous system to prevent hydrolysis. The industrial production of epichlorohydrin is chlorinated by chlorination. It is obtained by propylene chloride at a high temperature. The by-product of the chlorination reaction is cis_i, 3_一风> propylene, trans-1,3-one wind> propylene, and 1,2- The glycerol dichlorohydrin is derived from chloropropene, and the by-product is l52,3-trichloropropane. Finally, the epichlorohydrin is composed of two. The chloropropanol mixture is produced by alkali treatment. Its main disadvantages are: 1) The method uses lime/calcium oxide (lime/CaO), water, and extra gas, resulting in high cost 0 2) use of steam, electricity The cost of cooling water, and air/nitrogen (air/N2) appliances is enormous. 3) Each metric ton of ECH product produced, along with 15 to 20 metric tons of effluents, is a major challenge in terms of production costs and regulatory limits. U.S. Patent Nos. 6,720,435, 6,288,248, and 6,350, 888 disclose a process for the production of epichlorohydrin by reacting chloropropene with a peroxy compound in water, a catalyst, and a solvent, followed by extraction with a liquid-liquid The resulting epichlorohydrin is separated. The main disadvantage is that the use of a powdered catalyst reduces the filtration rate and the use of another chlorinated compound due to liquid-liquid extraction, thereby increasing the cost of recovery and the resulting effluent, resulting in increased disposal and disposal costs. U.S. Patent No. 6,380,407 discloses a process for the manufacture of epoxides in which a olefin is reacted with a peroxy compound in an aqueous phase under a zeolite-type catalyst and a solvent. The gaseous compound is continuously fed to the reactor at a flow rate that is at least sufficient to carry a portion of the resulting epoxide which is recovered with the gaseous compound as it exits the reactor. Some disadvantages are that the use of a gaseous compound to carry out the reaction results in the preheating of the compound and the maintenance of fluidization of the solid catalyst requires additional energy. A method for producing oxirane is disclosed in U.S. Patent Nos. 6,677,467, 6, 736, 861, and 6, 833, 851, the entire disclosure of which is incorporated by a olefin and a peroxy compound under a catalyst and a solvent in a series of reactions. The reaction is carried out, each reactor contains a part of the catalyst', wherein the peroxygen compound is only added to the first reactor of a series of reactors and the subsequent reactors are not added with fresh peroxygen A compound, but the peroxy compound refers to a peroxy compound which is present in the medium obtained in the previous reactor and which is not consumed in the previous reactor. U.S. Patent Nos. 6,720,435, 6,288,248, and 6,350, 888 disclose a liquid-liquid extraction process in which a monochlorinated compound is used for selective extraction of epichlorohydrin in a mixture of chloropropene, decyl alcohol, water, and epichlorohydrin. hospital. The extract phase contained only 10% of the produced epichlorohydrin and the remaining 90% was in the liquid phase. The epichlorohydrin was separated from the liquid phase into a gray band, and no results have been reported so far. There is therefore a need to provide an improved process for the manufacture of epichlorohydrin wherein a very small amount of epichlorohydrin is lost in the aqueous layer (aqU_layer) and the yield percentage is increased by cascade reactions. The present invention is intended to meet this need.
谷 J 本發明其中之-目的為，從根本上改良所述方法中環氧氯丙烧的總產 1百分率。 本發明之另-目的為’將反應財的混合產物分離為含有未轉化之氣 丙烯與甲醇的混合物，其適合循環再利用。 本發明更有另-目的為’使職丙烯從液相巾回收環氧氯丙烧。 本發明更有另—目的為’將水分離，ϋ適合循環再利用。 本發明更有另-目的為，大幅降低所產生的流出物。 ⑼t發明更有另—目的為，提高環魏峨在細目（―）中 的讀，以及儘可能地降低環氧氯丙燒在液相中的濃度。 本效有另一目的為，提出—種從氯丙烯生產環氧氯丙院，符合成 根據本發明，提出-種製備魏氯賊的方法，财法包含以下步驟： 200922929 5二:=匕劑的固定床管柱(flxed bed c〇1_)反應器中，於溫度約為 攝氏35度至=度之下，將氯_與—無機過氧化合物在至少—溶劑之下進 二生^物X得W 3有環氧氯丙烧、未反應之氯丙烯、溶劑、以及水的混 以水稀釋舰合物’其巾水與混合物的質量比為0.2至—稀釋混合 將遠稀釋混合物冷卻至_氏5至15度以_—冷卻觸混合物； 從該冷卻稀釋混合物分離有機相與液相； 藉由分顧技術輯有機相中_地分離與回收未反應之氯_鱗 烷；以及 ' 藉由分鶴技術以從液相中個別地分離與回收溶劑與水。 【實施方式】 請參閱圖1。 根據本發明，ax想一改良的方法用以在含有填充催化劑之套管式反應 器（R1與R2)中，藉由氣丙烯的催化氧化反應以生產環氧氯丙烷。入口流 (IS: inlet stream)包含反應物、氯丙烯、甲醇、以及一部分新鮮的過氧化 氫，其持續地向上流入所述反應器（R1)中。在所述尺丨的出口處的流含有 所述反應物以及所產生之3至5莫耳百分比的環氡氣丙烧，與另一部分新 I 鮮的過氧化氫混合後送入第二反應器（R2)，以有效利用催化劑的活性以 及高百分比的反應物轉化。二者擇一地，在反應結束後，從反應器流 出一約為攝氏45至50度的出口流（〇s :outlet stream)，其含有7至9莫耳 百分比的環氧氯丙烷、未反應之氯丙烯、曱醇、以及水，被傳送至一貯留 槽（T1)中。該從所述貯留槽（τι)流出之流出物流（Es:effluentstream) 後與從槽（T2)流出之程序用水（PW :process water)混合，並送入一萃 取室（ECl:extraction chamber)中。典型地，該萃取室（EC1與EC2)係 由3個單獨的組件構成：一混合器（M:mixer)、一冷萃取器（CE:cold extractor)、以及一傾析沈降器（DS:decanter settler)，其中從槽T1與T2流 出的流在混合器Μ中充分地混合，並且隨後向下流至盤管式冷萃取器（CE) 200922929 中，其中從混合器流出之反應器流出物與所述程序用水流入冷萃取器的盤 笞中並且冷卻劑在外威中環行以降低在盤管_混合物的溫度。從所述冷 萃取器流出之所述反應器流出物與所述程序用水的混合物流入在萃取室 (EC)中位於冷萃取器（CE)之下方的傾析沈降$ (DS)，其維持在一低 溫。在傾析沈降器（DS)中，有機相與液相藉由兩者密度不同而分離。該 有機相沈在傾析沈降ft (DS)的底部，並透過傾析沈降器（DS)的有機出 口（ orgamc outlet)進行萃取。該液相從傾析沈降器（m )的溶液出口（ omletj排^。進-步，包含主要為水與情、附加少量未反應之氯丙稀以 及微篁之環氧氣丙院的液相流人—萃取室（EC2)，以藉由加人氯丙婦而進 行第二次環氧氯丙烧的萃取，有機相（〇p: Grganiephase)與液相（Ap, aqueous phase)在萃取室中分離。該自EC2流出之处流入至一分館管柱 ci以回收氯丙烯與甲醇。該自EC1與EC2流出之〇p流入分鶴管柱c2以 得到粗環魏秘無質物（heavies)，其進—步在管柱C3巾進行分德， 環氧氯丙，從所述管柱α與α處戶_之f g_ =1並與反應斋R1的入口流18混合，並且從〇處所回收之水流入 水槽T2與冷萃取器組件的入口。 典型地，反應物氯丙烯的莫耳比為：進人反應器的過氧化物為m 〇 —般低；所述方法亦於莫耳比為U_6 Q : 1G之間些微修正之下執行。 典型地，所述反應係於溫度為攝氏％至乃度之範圍下進行。 5 (intermediate stream) 、、持在攝氏5至15度以得到最理想的成果。 之間典型地’ ES/PW的質量流率（massfl謝拙）維持在〇 2至〇 7的範圍 内。典型地，所述混合物在萃取器中的滯留時間在45至15〇分鐘的範圍之 典型地’沈降器中之液體的比重差異唯持在县一真$ Λ 1 ± / 以得到最理想的成果。 亶差異捕在母$升〇.2至0.7克(g/ml) 二型地’減所付狀輯魏氯祕純麟"·9 %，域雜豆他揮 ^ ^ ： f (methyl ethe〇 200922929 丙醇（2-methoxy-l_propan〇i)或其他任何含氯化合物。 典型地，以過氧化氫為基礎，環氧氣丙烷在通過反應器之後其產量為 97.1 /〇,通過萃取器之後其產量為98.1 〇4;以氯丙稀為基礎，所述方法的 產量為95.1 %。 圖1之詳細說明： 根據本發明，圖1揭露實施例的其中之一，其中，氯丙烯的所述催化 氧化反應在含有填充催化劑之套j管式反應器R1與幻中進行。入口流岱 包含反應物、氯丙烯ALC、甲醇MeOH、以及一部分新鮮的過氧化氫HP， 其流入所述反應器R1中，並且另一部分新鮮的過氧化氫流入第二反應器 R2中。在反應結束後，從反應器R2流出一出口流〇s，其含有環氧氣丙烷 ECH、未反應之氣丙烯、甲醇、以及水，被傳送至一貯留槽Ή中。該從所 述貯留槽Ή流出之流出物流Es隨後與程序用水pw混合，並送入一萃取 室EC1中。所述有機相〇p與液相处在萃取室Εα中分離。從Εα流出 之所述液相AP流入EC2中，藉由在萃取室EC2中加入ALC而進行第二次 ECH的萃取。從EC1與EC2流出之所述〇p流入所述管柱C2，然而從EC2 流出之AP流入所述Cl。從所述C1與^回收之alC、Me〇H、與從所 述ci回收之程序用水被循環再利用。從所述(：2處所得之所述粗ECH進 入C3以得到純ECH與重質物。所述ES/PW的質量流率維持在〇 2至〇 7 的範圍之間。如圖2所示’典型地，解取室Εα與EC2係由3個單獨的 組件構成.一預混合器Μ、一冷萃取器CE、以及一傾析沈降器DS。 所述預混合S Μ係為-紐實施湖於充分混合兩流。觸混合器M 包含玻璃珠’其中從T1與T2流出之流，在向下流人冷萃取器CE之前充 分地混合。所述冷萃取H CE係-盤管式冷郷，其巾所述反應器流出物與 所述程序用水流入盤官中，並且冷卻劑通過冷卻劑入口 1€在外殼中環行以 降低在盤^•巾混合物的溫度至攝氏5至15度，該冷卻劑並從出口 〇c棑出。 所述混合物在萃取器中的滞留時間在45至15〇分鐘的範圍之内。從所述冷 萃取器流ίΒ之所述反應1㈣物與所述程序肖水舰合物流人在萃取室 EC中位於冷萃取If CE之下方_析沈降器⑽），其中所述混合物的溫 11 200922929 度維持在攝氏5至15度。有機相與液相藉由兩者密度不同而分離，其中該 有機相沈在傾析沈降器DS的底部，並透過傾析沈降器ds的有機出口 (orgamc outlet)進行萃取。小心謹慎地控制所述分相含量浊脱 content)的滯留時間與兩相的量位〇evel)。該液相從傾析沈降器ds的液 相出口流出。該有機相與液相藉由虹吸管分別從各自的出口收集。從奶 流出^該液相’典型地包含主要為水與甲醇、附加少量未反應之氣丙稀以 及U量之ECH從官柱ci與C2所制之該有機相，典型地包含環氧氯丙 烷、未反應之氯丙烯、以及甲醇、附加微量之水。該有機相流入得到粗環 氧氯丙烧的所述管柱C2，並且流入管柱〇以得到作為一副產物的高纯产 Γ環氧氯丙院。從管柱cmc2處所回收之ALC與Me〇H被循環再利^ 與反應H R1的入口流^混合。該液流流入所述管柱c卜其為本質 醇與氣丙烯與水分離之處。從管柱α處所回收之虹 ' 他册、與水被 分別地送回至反應器R1的入口與冷萃取器組件的入口。 一 “二者擇-地，如圖3所示’從反應器幻流出之所述流出物流，可以 猎^適當地調整過氧化氫至氣丙烯的進料比（feedrati〇)於同一反應器之 再環行數次。 °° 此工業上由氯丙烯以製造環氧氣峨的方法較符合成本效益 出物形式之催化劑降低了·與再生的成本。大幅降低了回收未轉化 之氣丙烯的操作成本。本發日腾述之生纽法紅紅最佳現行之方法 較之下’本發明在整體上降低了用具蒸氣的消耗。因此，降低生產每— 位重量環魏秘雜作齡，增加環祕峨絲賴產量，並且 在液相中為較低濃度之ECH，減良所有下游之組件猶的安定性。因此 本發明中之方法與-般的方法嫌之下，本發明雜低的 到相對高產量之高品質產物。 #作成本传 本發明所浦的方法以較低的生絲作成本提供品紐良 烷產物。本發明之主要的優點在於： < 1.此方法容許個過氧成分的分流，在催化細固定床處進行氯 氧化反應（epoxidation reaction )。 、、 2·此-放熱反應藉錄麟量餘丙烯，有效地控綱過催化齡後上升 12 200922929 的溫度 3· 耗 4. 的消耗 5. 6. 過量的氯丙歸與？醇挪程中經回收與再利用，因而減少單位原料的消 =用水在術撕时、_與細，位程序用水 固體流出物的量為零，液體流出 本發明所含之此方法降低由氯丙歸生二二=降低處理成本。 因此藉由此方法，可細濟實*氧乳丙院的操作總成本。 產物，並代表-種適合_於^_ = = =的高品質環氧氯丙烧 丙烯生產環氧氯丙貌的新方法。、肖从成力的分流，持續由氣 本發^發明將透過以下的例子進行說明’惟所述例子僅為例示而並非限制 <例子1> 填充α 6G克/小時（gms/hr)的速率進料’利用 兴兀仏乐反應器中之15克的鈦矽分早益、μ _ 醇中反應，所述第-反應 r百^ ,分匕、甲醇（52.05莫耳百分比）、環氧氯丙院⑽莫 -二;1]^7莫耳百分比），其與另"^部分的過 抓入至第-反應μ，其固定床套管歧絲 莫耳百刀比）、甲醇（46·η莫耳百分比）、環氧氣丙烧（7 54莫耳百分 ^及水（20.91莫耳百分比）。所述第二反應器的流出物以％克/小時 (gms/hr)的速率與去礦物質水（DM:de_mineralizedwat^於降溫至攝 5度之前’在#門設計的萃取設備中混合。程序流與水的重量比維^在⑽。 在足夠的1〇〇分鐘的滞留時間後，兩個澄清相分離。該底層或有機層以2請 克/小時（gms/hr)的速率抽取，並含有氯丙烯（59 8〇莫耳百分比）、甲铲 (ii_5i莫耳百分比）、環氧氣丙烷（24 68莫耳百分比）、以及水（4〇〇 = 13 200922929 耳百刀比）最後，進一步以9 〇2克/小時的速率，在攝氏％度 ^下以新鮮的量的ALC萃取該上層或液層以收集環氧氯丙 96.45%^ 〇 里 <例子2> 複5液&有過1的虱丙稀，以21〇〇克/小時的速率進料，利 用填，於，-反應器中之8〇〇克的鈦石夕分子篩（TS])催化劑，與一部分 ，過氧化氫在-作為溶劑的甲醇中反應，所述第—反應器為—固定床套管 ^應器\持續生產核氧氯丙院。在所述第—反應器出口處的流含有氣丙 且（35.36莫耳百分比）、甲醇（45 87莫耳百分比）、環氧氯丙院（《μ莫 Z百分⑴、以及水（R48莫耳百分比），其與另—部分的過氧化氫混合並 二—反，器中’其亦為—固^床套管式反應器，含有_克的催化 2、續生產環氧氣丙烧。在所述第二反應器出口處的流含有氣丙稀(Μη 莫耳百分比）、甲醇（46.16莫耳百分比）、環氧氯丙烧（讓莫耳百分比）、 ^及水（19.57莫耳百分比）。所述第二反應器的流出物以遞克/小時 速率與去礦物f水（DM)於降溫至攝氏5度之前，在專門設 的滞中㉟合。程序流與水的重量比維持在〇.4。在足夠的100分鐘 守S < ，兩個澄清相分離。該底層或有機層以1233.52克厂_]、時 的速率抽取，並含有氯丙稀（6239莫耳百分比）、情（⑽ ^ 環氧氯 (19_93莫耳百分比）、以及水（3.42莫耳百分 比=敢後^進一步以331 73克/小時（gms/hr)的速率，在攝氏％度之下 以，的ALC萃取該上層或液層以收集環氧氯丙燒（產量=96 69%)。 料驟愈此處難實關之步驟與反應化合物的瞒，可對許多程 —ϋΐ 列與組合，並且在不偏離本發_原則之T可對較佳 露==:=中其他步驟 上所述内士顯得易僅，據此應請楚瞭解以 例為本發。前文係針對本伽之較佳實施 脫離太路” 明，唯熟悉此項技術之人士當可在不 脫離本發月之精神與原則下對本發明進行變更與修改，關等變更與修 14 200922929 改，皆應涵蓋於如下申請專利範圍所界定之範疇中。 【圖式簡單說明】 圖1為本發明所述方法之示意圖； 圖2為本發明於圖1中所示方法中之萃取器流程圖；以及 圖3為本發明其中之一實施例的套管式反應器之示意圖。 【主要元件符號說明】 C1 分餾管柱 C2 分餾管柱 C3 分餾管柱 CE 冷萃取器 DS 傾析沈降器 EC 萃取室 EC1 萃取室 EC2 萃取室 J 套 Μ 預混合器 R1 套管式反應器 R2 套管式反應器 Τ1 貯留槽 Τ2 貯留槽 15Valley J The present invention is directed to substantially improving the total yield of epichlorohydrin in the process by 1%. Another object of the present invention is to separate the reaction product of the reaction into a mixture containing unconverted gas propylene and methanol, which is suitable for recycling. The invention is furthermore directed to the recovery of epichlorohydrin from the liquid phase towel. The invention is furthermore directed to the separation of water which is suitable for recycling. The invention furthermore has the object of substantially reducing the effluent produced. (9) The invention is more unique—the purpose is to improve the reading of the ringworm in the detail (-) and to reduce the concentration of the epichlorohydrin in the liquid phase as much as possible. Another purpose of this effect is to propose a method for producing an epoxy chlorinated propyl sulfonate from chloropropene, which is in accordance with the present invention and proposes a method for preparing a chlorinated thief. The financial method comprises the following steps: 200922929 5:= tincture In a fixed bed column (flxed bed c〇1_) reactor, at a temperature of about 35 degrees Celsius to = degrees below, the chlorine-and-inorganic peroxy compound is passed into at least the solvent W 3 has epichlorohydrin, unreacted chloropropene, solvent, and water mixed with water to dilute the mixture. The mass ratio of the towel water to the mixture is 0.2 to - the dilution mixture cools the far dilution mixture to _ 5 to 15 degrees by _-cooling the mixture; separating the organic phase and the liquid phase from the cooled dilution mixture; separating and recovering unreacted chloro- tartan from the organic phase by the technique; and The crane technique separates and recovers solvent and water separately from the liquid phase. [Embodiment] Please refer to Figure 1. According to the present invention, ax is intended to improve the process for producing epichlorohydrin by catalytic oxidation of gaseous propylene in a jacketed reactor (R1 and R2) containing a packed catalyst. The inlet stream (IS: inlet stream) contains the reactants, chloropropene, methanol, and a portion of fresh hydrogen peroxide which continuously flows upward into the reactor (R1). The stream at the exit of the ruler contains the reactants and the resulting 3 to 5 mole percent of the helium helium burn, which is mixed with another portion of the fresh I fresh hydrogen peroxide and sent to the second reactor. (R2) to effectively utilize the activity of the catalyst and a high percentage of reactant conversion. Alternatively, after the reaction is completed, an exit stream (〇s : outlet stream) of about 45 to 50 degrees Celsius is discharged from the reactor, which contains 7 to 9 mole percent of epichlorohydrin, which is unreacted. The chloropropene, decyl alcohol, and water are transferred to a storage tank (T1). The effluent stream (Es: effluentstream) flowing out from the storage tank (τ1) is mixed with the process water (PW: process water) flowing out from the tank (T2), and sent to an extraction chamber (EC1: extraction chamber). . Typically, the extraction chambers (EC1 and EC2) are composed of three separate components: a mixer (M: mixer), a cold extractor (CE: cold extractor), and a decanter (DS: decanter) Settler), wherein the stream exiting from tanks T1 and T2 is thoroughly mixed in the mixer crucible and then flows down to the coiled cold extractor (CE) 200922929, where the reactor effluent from the mixer flows The procedure flows into the coil of the cold extractor and the coolant is looped in the outer tube to lower the temperature at the coil_mixture. The mixture of the reactor effluent flowing from the cold extractor and the process water flows into a decantation settlement $(DS) located below the cold extractor (CE) in the extraction chamber (EC), which is maintained at A low temperature. In the decanter settler (DS), the organic phase and the liquid phase are separated by the difference in density between the two. The organic phase is deposited at the bottom of the decantation settling ft (DS) and is extracted through an organic orgasc outlet of the decanter (DS). The liquid phase is discharged from the solution of the decanter (m) (omletj). The liquid phase flow consists mainly of water and moisture, with a small amount of unreacted chloropropene and micro oxime. Human-extraction chamber (EC2) for the second extraction of epichlorohydrin by addition of a chloropropene, organic phase (〇p: Grganiephase) and liquid phase (Ap, aqueous phase) in the extraction chamber Separation. From the point where EC2 flows out, it flows into a branch column ci to recover chloropropene and methanol. The 〇p flowing out from EC1 and EC2 flows into the branch pipe c2 to obtain the heavies. Further stepping on the column C3 towel, the epoxy chloropropene, from the column α and α, _ f g_ =1 and mixed with the inlet stream 18 of the reaction R1, and recovered from the sputum Water flows into the inlet of the trough T2 and the cold extractor assembly. Typically, the molar ratio of the reactant chloropropene is: the peroxide entering the reactor is m 〇 as low; the method is also U_6 in the molar ratio Q: Performed under slight correction between 1 G. Typically, the reaction is carried out at a temperature ranging from Celsius to Na. 5 (i Ntermediate stream), held at 5 to 15 degrees Celsius for the best results. The mass flow rate (massfl) of typically 'ES/PW' is maintained between 〇2 and 〇7. Typically, The residence time of the mixture in the extractor is typically in the range of 45 to 15 〇 minutes. The difference in the specific gravity of the liquid in the settler is only held in the county for a true $ Λ 1 ± / to get the best results. Captured in the mother's $ 〇 〇. 2 to 0.7 grams (g / ml) Type II land 'reduction of the type of Wei Chloric secret pure col · · 9%, domain miscellaneous beans he wave ^ ^ : f (methyl ethe〇200922929 Propyl alcohol (2-methoxy-l_propan〇i) or any other chlorine-containing compound. Typically, on the basis of hydrogen peroxide, the output of the epigas oxide propane is 97.1 / 〇 after passing through the reactor, and the yield after passing through the extractor is 98.1 〇4; based on chloropropene, the yield of the process is 95.1%. Figure 1 is a detailed description: According to the invention, Figure 1 discloses one of the examples, wherein the catalytic oxidation of chloropropene In a jacketed reactor R1 containing a packed catalyst and in the illusion. The inlet flow contains The reactants, chloropropene ALC, methanol MeOH, and a portion of fresh hydrogen peroxide HP, which flow into the reactor R1, and another portion of fresh hydrogen peroxide flows into the second reactor R2. The reactor R2 flows out of an outlet stream s containing ethylene oxide propane ECH, unreacted gaseous propylene, methanol, and water, and is sent to a storage tank. The effluent stream Es flowing out from the storage tank is subsequently It is mixed with the program water pw and sent to an extraction chamber EC1. The organic phase 〇p is separated from the liquid phase in the extraction chamber Εα. The liquid phase AP flowing out of Εα flows into the EC2, and the second extraction of ECH is performed by adding ALC to the extraction chamber EC2. The 〇p flowing out of EC1 and EC2 flows into the column C2, whereas the AP flowing out of EC2 flows into the Cl. The water recovered from the C1 and the recovered alC, Me〇H, and the process recovered from the ci is recycled. The crude ECH obtained from the (2) is introduced into C3 to obtain a pure ECH and a heavy substance. The mass flow rate of the ES/PW is maintained between 〇2 and 〇7. As shown in Fig. 2 Typically, the extraction chambers Εα and EC2 are composed of three separate components. A premixer 一, a cold extractor CE, and a decanter settler DS. The premixed S Μ is - New implementation lake The two streams are thoroughly mixed. The touch mixer M comprises glass beads 'where the flow from T1 and T2 is thoroughly mixed before flowing down the human cold extractor CE. The cold extraction H CE system - coil type cold heading, The reactor effluent and the process water are flowed into the tray, and the coolant is circulated in the outer casing through the coolant inlet 1 to lower the temperature of the tray mixture to 5 to 15 degrees Celsius, the cooling And withdrawing from the outlet 。c. The residence time of the mixture in the extractor is in the range of 45 to 15 〇 minutes. The reaction 1 (4) from the cold extractor is the same as the program Xiaoshui The hull stream is located in the extraction chamber EC below the cold extraction If CE - the settler (10), wherein the mixing The temperature of the object 11 is maintained at 5 to 15 degrees Celsius. The organic phase and the liquid phase are separated by a difference in density between the two, wherein the organic phase sinks at the bottom of the decanter settler DS and is extracted through an orgamc outlet of the decanter desiccator ds. Carefully control the retention time of the phase separation content and the amount of the two phases 〇evel). The liquid phase flows out of the liquid phase outlet of the decanter settler ds. The organic phase and the liquid phase are separately collected from the respective outlets by a siphon. From the milk stream, the liquid phase typically contains the organic phase consisting primarily of water and methanol, an additional small amount of unreacted propylene, and a U amount of ECH from the columns ci and C2, typically comprising epichlorohydrin. , unreacted chloropropene, and methanol, with an additional trace of water. The organic phase flows into the column C2 which is obtained by the crude chloropropane, and flows into the column to obtain a high-purity epoxidized chlorinated plant as a by-product. The ALC and Me〇H recovered from the column cmc2 are recycled and mixed with the inlet stream of the reaction H R1 . The liquid stream flows into the column c where it is the separation of the essential alcohol from the gas propylene and water. The rainbow recovered from the column α is sent back to the inlet of the reactor R1 and the inlet of the cold extractor assembly separately from the water. A "both-ground, as shown in Figure 3," the effluent stream exiting the reactor phantom, can properly adjust the feed ratio of hydrogen peroxide to gas propylene in the same reactor. Recirculating several times. °° This method of producing epoxies from chloropropene in the industry is more cost-effective than the catalysts in the form of cost-effective production. The cost of recovering unconverted propylene is greatly reduced. The best way to use this method is to reduce the consumption of steam in the appliance as a whole. Therefore, reduce the production weight per bit, and increase the ring. The secret is the yield, and the lower concentration of ECH in the liquid phase reduces the stability of all downstream components. Therefore, the method of the present invention and the general method are suspected, and the present invention is low. A relatively high-yield, high-quality product. The method of the present invention provides the product a naphtha product at a lower cost of raw silk. The main advantages of the present invention are: < 1. This method allows peroxygenation Dividing of components in catalysis The epoxidation reaction is carried out at the fine fixed bed. 2. The exothermic reaction borrows the amount of propylene from the arsenic, and effectively controls the temperature after the catalyst age rises 12 200922929 3. The consumption of 4. 6. Excessive chloropropane conversion and alcohol recovery and reuse, thus reducing the consumption of unit raw materials = water during the tearing, _ and fine, the amount of water used in the program effluent is zero, the liquid flows out of the present invention Including this method reduces the cost of chloropropion returning to the second two = reducing the processing cost. Therefore, by this method, the total operating cost of the oxy-lactic acid hospital can be fined. Product, and representative - suitable for _ ^ ^ = = = = A new method for the production of epoxy chloroforms from high-quality epoxy chloropropene propylene. The shunting of Xiao Congli is continued from the gas. The invention will be explained by the following examples. Rather than limiting <Example 1> filling rate of α 6 Gg/hr (gms/hr), the reaction was carried out using 15 g of titanium bismuth in the Xingle reactor, and in the μ _ alcohol. First-reaction r, ^, hydrazine, methanol (52.05 mole percent), epoxy chloride丙院(10)莫-二;1]^7mol%), which with the other part of the "catch-to-response μ, its fixed bed casing is a molar ratio", methanol (46 • η mole percentage), epoxide (7 54 mole percent ^ and water (20.91 mole percent). The effluent of the second reactor is at a rate of % grams per hour (gms/hr) Demineralized water (DM: de_mineralizedwat^ before cooling to 5 degrees) is mixed in the #gate design extraction equipment. The weight ratio of the program flow to the water is at (10). After a sufficient residence time of 1 minute The two clarified phases are separated. The bottom or organic layer is extracted at a rate of 2 g/hr (gms/hr) and contains chloropropene (59 8 mol%), nail shovel (ii_5 i mol percentage), ring Oxygen propane (24 68 mole percent), and water (4 〇〇 = 13 200922929 ear knives ratio) Finally, further extract with a fresh amount of ALC at a rate of 9 〇 2 g / h at Celsius The upper layer or the liquid layer to collect the epoxy chloropropane 96.45%^ 〇里<example 2> complex 5 liquid & 1 over propylene acrylate, 21 gram / Rate feed, using a 8 gram Titanium Zeolite (TS) catalyst in a reactor, and reacting with a portion of hydrogen peroxide in methanol as a solvent, said The reactor is - fixed bed casing ^ device / continuous production of nuclear oxygen chloride. The stream at the outlet of the first reactor contains aerobic and (35.36 mole percent), methanol (45 87 mole percent), epoxy chlorpheniramine ("μMo Z percent (1), and water (R48 Mo Percentage of the ear), which is mixed with another part of the hydrogen peroxide and is in the opposite direction. In the device, it is also a solid-bed type tubular reactor containing _ gram of catalysis 2. Continued production of epoxidized gas. The stream at the outlet of the second reactor contains propylene (% Μ% molar), methanol (46.16 mole percent), chlorinated chlorinated (percentage of molars), ^ and water (19.57 mole percent) The effluent of the second reactor is combined with demineralized f water (DM) to a temperature of 5 degrees Celsius before the demineralized f water (DM) is cooled to a temperature of 5 degrees Celsius. The weight ratio of the program stream to the water is maintained at 〇.4. Sufficient 100 minutes for S <, two clarification phase separation. The bottom or organic layer is extracted at a rate of 1233.52 g _], and contains chloropropene (6239 mol%), love ((10) ^ Epoxy chloride (19_93 mole percentage), and water (3.42 mole percentage = dare after ^ further to 3 At a rate of 31 73 g/h (gms/hr), the upper layer or the liquid layer was extracted by ALC below Celsius to collect epichlorohydrin (yield = 96 69%). The steps of the actual reaction and the reaction of the compound can be performed on a number of processes, and the TMS can be easily used in other steps of the preferred dew ==:= without departing from the T-principle. According to this, we should understand that the case is based on this issue. The previous article is aimed at the better implementation of this gamma, and only those who are familiar with the technology can use the invention without departing from the spirit and principles of this month. Changes and modifications, such as changes and modifications, should be included in the scope defined in the following patent application. [Simplified Schematic] Figure 1 is a schematic diagram of the method of the present invention; The extractor flow chart in the method shown in Fig. 1; and Fig. 3 is a schematic view of a cannulated reactor according to one embodiment of the present invention. [Key element symbol description] C1 fractionation column C2 fractionation column C3 fractionation Column CE cold extractor DS decanter settler EC extraction EC1 EC2 extraction chamber extraction chamber sets Μ J premixer tube reactor R1 R2 tube reactor Τ1 storage tank storage tank 15 Τ2