TWI328003B - Process for making dialkyl carbonates - Google Patents

Process for making dialkyl carbonates Download PDF

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TWI328003B
TWI328003B TW094107161A TW94107161A TWI328003B TW I328003 B TWI328003 B TW I328003B TW 094107161 A TW094107161 A TW 094107161A TW 94107161 A TW94107161 A TW 94107161A TW I328003 B TWI328003 B TW I328003B
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urea
stream
reaction
reactor
alcohol
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TW094107161A
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TW200609212A (en
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J Yong Ryu
Abraham P Gelbein
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Catalytic Distillation Tech
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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1328003 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種製備碳酸二烷酯、尤其C!_C3碳酸二院 酯之方法，其十反應與反應物及碳酸酯產物之分離同時發 生。更特定s之’本發明係關於一種方法，其中醇與尿素 及/或胺基甲酸院酯在錯合物催化劑之存在下反應。更特定 言之，本發明係關於一種方法，其中移除饋料流雜質以產 生穩定催化劑效能、改良之反應速率及設備之無故障下游 操作。 【先前技術】 碳酸二烷酯係重要商業化合物，其中最重要的係碳酸二 曱酯（DMC)。碳酸二曱酯用作甲基化劑及羰基化劑且用作 製備聚碳酸酯之原料。其亦可用作溶劑以替代諸如氣苯之 鹵化溶劑。雖然當前碳酸二甲酯及碳酸二乙酯兩者之價格 過於昂貴而不能用作燃料添加劑，但是兩者均可用作再重 組汽油中之氧化劑及辛烷組份。碳酸二甲酯具有比MTbe (曱基第三丁基醚）或TAME (第三戊基甲基醚）更十分高之 氧含量（53°/。）’且因此幾乎無需相同的量即可達成相同效 應。其具有為130之研究法辛烧值（R〇N)且揮發性小於 MTBE或TAME中之任一者。其具有舒適之氣味，且不像醚 類，其更易於生物降解。 在較老的商業方法中，碳酸二甲酯係自甲醇及碳醯氯製 備。由於碳醯氣之極度毒性及成本，曾努力開發更好、非 基於碳醯氯之方法。 99734-990412.doc : 八在斤新商業方法中，碳酸二曱酯係自甲醇、一氧化碳、 刀子乳及氯化亞鋼經由氧化性羰基化反應於兩步驟淤漿方 法中產生。此一古、 此方法揭示於EP 0 460 735八2中。該方法之 要缺點係低生產速率、產物及反應物分離之高成本、副 產物之形成、高再循環要求及對抗腐钱反應器及加工管線 之需要。 另一新方法揭示於Ep 〇 742 198 A2及Ep 〇 5〇5 374 B1 # 中其中碳酸一曱酯係經由形成亞硝酸甲酯代替上文所述 <甲氧基氯化銅而製備。副產物為氧化氮、二氧化碳、甲 , 酸曱S曰等。自反應器之產物流中之碳酸二甲酯係藉由溶劑 卒取蒸餾法使用草酸二曱酯作為溶劑以破壞共沸混合物而 分離。雖然該化學處理看似簡單且改良了生產速率，但該 方法由於許多物質之分離、方法各流段之平衡物質、複雜 之方法控制及對危險化學品亞硝酸甲酯之處理而十分複 雜。 _ 在另一商業方法中，碳酸二甲酯係自甲醇及二氧化碳於 兩步驟方法中產生。在第一步驟中，藉由使環氧化物與二 氧化碳反應而製備’如美國專利第4,786,741號、第4,85 1 555 號及第4,400,559號中所揭示》在第二步驟中，藉由環碳酸 醋與甲醇之交換反應，碳酸二甲酯隨乙二醇一起製備。參 見例如 Y. Okada專人’ "Dimethyl Carbonate Production for Fuel Additives", ACS, Div. Fuel Chem., Preprint, 41(3), 868, 1996 及 John F. Knifton 等人，"Ethylene Glycol-Dimethyl Carbonate Cogeneration", Journal of Molecular Chemistry， 99734-990412.doc 1328003 第67卷，第389-399頁，1991。雖然該方法具有其優點，但 環氧化物與二氧化碳之反應速率慢且需要高壓。此外，環 碳酸醋與曱醇之交換反應受平衡之限制且甲醇及碳酸二曱 酯形成之共沸物使得分離較為困難。 已知碳酸二烧酯可藉由使諸如曱醇之初級脂族醇與尿素 (1)在各種異質及同質催化劑（諸如二甲氧化二丁基錫、四笨 基錫等）之存在下反應來製備。參見例如p. Ball等人， "Synthesis of Carbonates and Polycarbonates by Reaction of1328003 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for the preparation of dialkyl carbonates, especially C?_C3 diesters, wherein the ten reactions occur simultaneously with the separation of the reactants and carbonate products. More particularly, the present invention relates to a process in which an alcohol is reacted with urea and/or a carbamic acid ester in the presence of a complex catalyst. More particularly, the present invention relates to a process wherein feed stream impurities are removed to produce stable catalyst performance, improved reaction rates, and trouble free downstream operation of the apparatus. [Prior Art] Dialkyl carbonate is an important commercial compound, the most important of which is dicaptanyl carbonate (DMC). Dinonyl carbonate is used as a methylating agent and a carbonylating agent and as a raw material for the preparation of polycarbonate. It can also be used as a solvent to replace a halogenated solvent such as benzene. Although both dimethyl carbonate and diethyl carbonate are too expensive to be used as fuel additives, both can be used as oxidants and octane components in reconstituted gasoline. Dimethyl carbonate has a much higher oxygen content (53°/.) than MTbe (decyl tertiary butyl ether) or TAME (third amyl methyl ether) and thus can be achieved with almost no need for the same amount The same effect. It has a research value of 130 (R〇N) and a volatility less than either MTBE or TAME. It has a pleasant odor and, unlike ethers, is more biodegradable. In older commercial processes, dimethyl carbonate was prepared from methanol and carbon ruthenium chloride. Due to the extreme toxicity and cost of carbon helium, efforts have been made to develop better, non-carbon based chlorine. 99734-990412.doc: In the new commercial process, dinonyl carbonate is produced from methanol, carbon monoxide, knife milk and chlorinated steel by an oxidative carbonylation reaction in a two-step slurry process. This method is disclosed in EP 0 460 735 VIII. The disadvantages of this process are low production rates, high cost of product and reactant separation, formation of by-products, high recycle requirements, and the need to combat rotten reactors and processing lines. Another new method is disclosed in Ep 742 742 198 A2 and Ep 〇 5〇5 374 B1 # in which mono-anthracene carbonate is prepared by forming methyl nitrite instead of the above-mentioned <methoxy copper chloride. The by-products are nitrogen oxide, carbon dioxide, methyl, acid bismuth S and the like. The dimethyl carbonate in the product stream from the reactor is separated by solvent draw distillation using dinonyl oxalate as a solvent to destroy the azeotrope. Although this chemical treatment appears to be simple and improves the production rate, the method is complicated by the separation of many substances, the balance of the various stages of the process, the complicated method control, and the treatment of the dangerous chemical methyl nitrite. In another commercial process, dimethyl carbonate is produced from methanol and carbon dioxide in a two-step process. In the first step, by reacting the epoxide with carbon dioxide, as disclosed in U.S. Patent Nos. 4,786,741, 4,85, 555, and 4,400,559, in the second step, by cyclic carbonic acid The exchange reaction of vinegar and methanol, dimethyl carbonate is prepared together with ethylene glycol. See, for example, Y. Okada Specialist "Dimethyl Carbonate Production for Fuel Additives", ACS, Div. Fuel Chem., Preprint, 41(3), 868, 1996 and John F. Knifton et al., "Ethylene Glycol-Dimethyl Carbonate Cogeneration ", Journal of Molecular Chemistry, 99734-990412.doc 1328003, Vol. 67, pp. 389-399, 1991. Although this method has its advantages, the reaction rate of epoxide with carbon dioxide is slow and requires high pressure. In addition, the exchange reaction of the carbonated vinegar with the decyl alcohol is limited by the balance and the azeotrope formed by methanol and dinonyl carbonate makes separation difficult. It is known that dialkyl carbonate can be prepared by reacting a primary aliphatic alcohol such as decyl alcohol with urea (1) in the presence of various heterogeneous and homogeneous catalysts such as dibutyltin dimethoxide, tetraphenyltin, and the like. See, for example, p. Ball et al., "Synthesis of Carbonates and Polycarbonates by Reaction of

Urea with Hydroxy Compounds"，Cl Mol. Chem·，第 1卷， 第95-108頁，1984。氨為一共產物且其可以下列反應序列 再循環至尿素（2)。 〇 〇Urea with Hydroxy Compounds", Cl Mol. Chem., Vol. 1, pp. 95-108, 1984. Ammonia is a co-product and it can be recycled to urea (2) in the following reaction sequence. 〇 〇

丨丨 II 2ROH + H2N-C-NH2 <=====> R〇.c.〇R + 2 NH3 ⑴ 醇 尿素 碳酸二烷酯 Ο丨丨 II 2ROH + H2N-C-NH2 <=====> R〇.c.〇R + 2 NH3 (1) Alcohol Urea Dialkyl carbonate Ο

I 2NH3 + C02 <====> H2N-C，NH2 + H20 (2) 胺基曱酸酯在低溫下產生接著在高溫下產生碳酸二烷 酯，在兩步驟中均產生氨。 99734-990412.doc 1328003 〇 οI 2NH3 + C02 <====> H2N-C, NH2 + H20 (2) Amino phthalate is produced at a low temperature to produce dialkyl carbonate at a high temperature, and ammonia is produced in both steps. 99734-990412.doc 1328003 〇 ο

. H II H2N-C：NH2 + ROH <=====> R0-C-NH2 + nh3 r 胺基甲酸烷酯 ο ο ο 8 R〇-C-NH2 + ROH <=====> RO-C-OR + NH3 ί 碳酸二烷酯 如所述，上文之兩個反應在反應條件下可逆。有機錫化 合物催化活性之順序為R4Sn<R3SnX«R2SnX2，其中x=cn、 Φ R0、RCOO、RCOS。報道了二烷基錫（IV)化合物之最大反 應速率及副產物之最小形成。對於大多數催化劑（路易斯酸） 而言，若反應係在適當共催化劑（路易斯鹼）之存在下進行， 則要求較高之催化活性。例如，用於諸如二曱氧化二丁基 錫、氧化二丁基錫等之有機錫（IV )催化劑之較佳共催化劑為 二苯基膦及4-二甲胺《比啶。然而，藉由胺基甲酸二烷酯之 合成中所採用之有機錫化合物（諸如二曱***或 氧化二丁基錯）亦便利了中間體胺基甲酸炫酯及尿素至異 • 氰酸（HNC0)或異三聚氰酸（(HNCO)3)及醇或氨（尿素分解 之共產物）之熱分解。WO 95/17369揭示了一種利用p. Ball 等人所公佈之化學處理及催化劑在兩步驟中自醇類及尿素 製備例如碳酸二曱酯之碳酸二烷酯之方法。在第一步驟 中’使醇與尿素反應以至被胺基甲酸烷酯。在第二步帮中， 藉由進一步使胺基甲酸烷酯與醇在高於第一步驟之溫度下 反應而製備碳酸二烧醋。採用高壓爸反應器來執行該 等反應。然而’當甲醇與胺基甲酸甲酷或展素反應時，諸 如N-甲基甲基胺基曱酸酯（N_MMC)& N烷基脲之n烷基副 99734-9904l2.doc •9· 1328003 產物亦根據下列反應而產生： 3 0 C NH2 + (CH30)2C0 ====> CH3-O-C-NH-CH3 + CH3OH+CO2 οH II H2N-C: NH2 + ROH <=====> R0-C-NH2 + nh3 r alkyl carbamate ο ο ο 8 R〇-C-NH2 + ROH <==== => RO-C-OR + NH3 ί Dialkyl carbonate As described above, the above two reactions are reversible under the reaction conditions. The order of catalytic activity of the organotin compound is R4Sn < R3SnX «R2SnX2, where x = cn, Φ R0, RCOO, RCOS. The maximum reaction rate of the dialkyltin (IV) compound and the minimum formation of by-products are reported. For most catalysts (Lewis acids), higher catalytic activity is required if the reaction is carried out in the presence of a suitable co-catalyst (Lewis base). For example, preferred co-catalysts for organotin (IV) catalysts such as dibutyltin dioxide, dibutyltin oxide, etc. are diphenylphosphine and 4-dimethylamine "bipyridine. However, the organotin compounds used in the synthesis of dialkyl carbamates (such as dibutyltin dioxide or dibutyl oxidized) also facilitate the intermediate amide and urea to iso- cyanate. Thermal decomposition of (HNC0) or iso-cyanuric acid ((HNCO) 3) and alcohol or ammonia (co-product of urea decomposition). WO 95/17369 discloses a process for the preparation of dialkyl carbonates such as dinonyl carbonate from alcohols and urea in two steps using chemical treatments as disclosed by p. Ball et al. In the first step, the alcohol is reacted with urea to be alkyl carbamate. In the second step, the second carbonated vinegar is prepared by further reacting the alkyl carbamate with the alcohol at a temperature higher than the first step. These reactions were carried out using a high pressure dad reactor. However, when methanol is reacted with carbamide or auxin, such as N-methylmethylamino phthalate (N_MMC) & N alkyl urea n-alkyl 99734-9904l2.doc • 9· The 1328003 product is also produced according to the following reaction: 3 0 C NH2 + (CH30)2C0 ====> CH3-OC-NH-CH3 + CH3OH+CO2 ο

II CH3-0:C-NH.CH3 + ch3oh <======> (ch3-0)2C=0 + ch3nh2 、 碳 酸二烷酯以基於反應器溶液之總胺基甲酸酯及醇含量之i 及3重量％之間之量存在於反應器中以使副產物之形成降 至最低。 在美國專利第6,010,976號中’石炭酸二甲酯（DMC)自尿素 及曱醇以高產率於單一步驟中在高沸點醚類及一新穎同質 錫錯合催化劑之存在下合成。 (NH2)2CO + 2 CH3OH =====> (CH30)2C0 + 2NH3f 驗溶劑亦用作錯合劑以自二甲氧化二丁基錫或氧化二丁 基錫就地形成同質錯合催化劑。 DMC方法中所涉及之物質之分離由於經濟原因對於 DMC之商業生產十分重要。EP 〇 742 198 A1&us 5,214185 中揭示藉由使用草酸二甲酯（DMOX)作為萃取溶劑而自曱 醇及DMC之蒸氣混合物中分離DMC。由於DM〇x之高熔點 (54°C)，因此使用DMOX係不方便的且增加了分離之額外成 本。 尿素及醇類均具高吸濕性。尿素含有胺基甲酸銨雜質。 因此，水及胺基甲酸銨為尿素及醇饋料中之雜質。已發現 99734-990412.doc •10· 展素及醇饋料中之雜質（諸如水、胺基甲酸銨等）導致催化劑 純化及官線堵塞於反應器之頂部蒸氣流之冷卻區段（冷凝 器）中之冷卻點。水導致含烷氧基之催化劑鈍化，舉例而 D ’有機錫錯合物分子上之甲氧基與水分子高度反應，導 致錫原子與甲氧基之氧原子之間之鍵水解。由於胺基曱酸 銨之先積，胺基曱酸銨導致控制碳酸二烷酯製備反應器中 月壓及自二烷基反應器之產物蒸氣流之冷卻系統（冷凝器） 堵塞之問題。 【發明内容】 簡。之’本發明係一種製備碳酸二烷酯之改良之方法， 其包含下列步驟： (a)將έ有尿素、醇、水及胺基曱酸鍵之物流饋入至第一 反應區； (b) 同時在該第一反應區中， (1)使水與尿素反應以形成胺基甲酸銨， ⑻使饋料中之胺基甲酸敍及自水與尿素反應而產生 胺基曱酸銨分解為氨及二氧化碳，及 (c) 將氨、二氧化碳及該醇作為第一塔頂產物自該第一 應區中移除； (d) 自該第一反應區移除尿素及該醇； (e) 將該尿素及該醇饋入至第二反應區； (f)使該醇與尿素在包含 的同質催化劑之存在下於 烧St，及 高沸點溶劑中反應以形成碳酸 99734-990412.doc -11· 1328003 (g)自該第二反應區中移除碳酸二烷酯及該醇β 藉由使醇（較佳c^c：3醇）與尿素或胺基曱酸烷酯或兩者在 有機錫化合物與作為溶劑之高沸點電子供體化合物之錯合 物（較佳二烷氧化二丁基錫錯合物及高沸點含氧有機溶劑） 之存在下反應來製備碳酸二烷酯，其中該反應較佳在蒸餾 爸或攢：拌槽反應器之再煮器中進行同時蒸餾碳酸二烷酯。 藉由移除水及胺基曱酸銨、N_烷基化副產物及少量餾份之 胺基曱酸烷酯來純化尿素及醇饋料。 藉由使水與尿素在具有預備反應區之預反應器中反應來 移除水。胺基甲酸銨藉由在預反應器中分解為氨及二氧化 碳而得以移除。此外’尿素在預反應器中部分且選擇性地 轉化為胺基曱酸烷酯’其導致主反應器中更快之反應迷 率、自碳酸二烧酯回收單元或管柱至主反應器之醇再循環 之減少及在子、主反應器之頂部物流中碳酸二烷酯之更高 濃度。在自主反應器之頂部物流中碳酸二烷酯之更高濃度 降低了分離碳酸二院酿之成本。 【實施方式】 藉由使水與尿素在預反應器中反應來移除尿素及醇饋料 中之水雜質’而胺基甲酸敍藉由在預反應器中分解為氨及 二氧化碳而得以移除。預反應器必須在對分解有利之條件 下操作以使氨及二氧化碳可作為蒸氣而移除。若分解不完 全’則未轉化之胺基甲酸銨將進入主反應器且可轉化為尿 素及水’由於其分解為氨及二氧化碳導致催化劑之鈍化。 尿素在預反應器中部分轉化為胺基曱酸烷酯。於預反應器 99734-990412.doc -12- 1328003 中發生下列必需之反應 * H20 + (NH2)2CO <-=-= ==--> NH2C02NH4 (1) nh2co2nh4 <-=====： => 2NH3 + C〇2 (2) nh2co2nh4 <-==-==： =>(NH2)2CO + h2o (3) 0 (NH2)2C0 + R0H <=—= 、 II —> R-0-C-NH2 + NH3 (4) 由於上文四個反應為平衡反應且必須同時出現於預反應 器中之預備反應區中，控制預反應器及主反應器之溫度及 壓力係重要的。在預反應器中，反應（1)、（2)、（3)及（4)在 200至380°F、較佳250至35 0T之溫度下於預反應器中之液 相中進行。預反應器頂部壓力之較佳範圍為約3〇至3〇〇 psig。然而’頂部壓力主要取決於預反應器管柱所要之溫度 及反應器中液體組合物。在無催化劑之狀況下反應（4)進入 平衡，但在承載於惰性支持物諸如矽石、高溫（>85〇<t)煅 燒氧化鋁之催化劑（諸如二烷氧化二丁基錫錯合催化劑之 催化劑及諸如氧化鋅、氧化錫、氧化鈦、氧化锆、氧化鉬、 滑塊石、碳酸鈣、碳酸鋅氫氧化物、碳酸鍅氫氧化物等之 弱酸性或鹼性異質催化劑）之存在下反應更快。在特定條件 下，預備反應區中液相中尿素之較佳濃度小於物败％， 較佳為50 wt·%。氨及二氧化碳之部分壓力必須保持低於胺 基甲酸敍之分解壓力以實現胺基甲酸狀分解。亦 望較佳將產物、氨及二氧化碳以暮 > ·、、、軋〜合物形式連同醇及 所採用的視情況之任何惰性汽提f 5, , ^ 飞杈虱體一起有效地自預反應 盗之預備反應區移除。若需要，則 ⑴醉療·乳可用作唯一汽提 99734-990412.doc -13- U28003 氣體。因此，改良之處係在製備碳酸二烷酯之方法中藉由 包含具有作為雜質之水及胺基甲酸銨的尿素及醇之反應物 反應’其包含下列步驟： (a) 將包含尿素及醇之反應物饋入至主反應區中； (b) 將有機錫化合物及高沸點含電子供體原子之溶劑饋 入至該主反應區中；且 (c) 同時在該主反應區中 (I) 使醇與尿素在該有機錫化合物及該高沸點含電子 供體原子之溶劑之存在下反應以製備碳酸二烷 酯；及 (II) 將碳酸二院醋及氨作為蒸氣自該主反應區中移除， 其中改良係在主反應區之前使用預備反應區以自該等反 應物移除水及胺基曱酸銨，其藉由首先在使該水與尿素反 應以形成胺基甲酸銨並使胺基甲酸銨分解為氨及二氧化碳 之條件下饋入該等反應物且在於步驟（b)中饋入反應物之前 自s玄等反應物移除氨及二氧化碳，較佳在2〇〇至38〇卞，更 佳250至350 F範圍内之溫度下且較佳於液相中之條件下。 在預備反應區中，較佳一部分尿素與醇反應形成胺基甲酸 烷酯。 製備碳酸二烷酯之方法之一較佳實施例包含下列步驟： (a)將尿素、Ci-C3醇饋入至預反應區中； (i)於預反應區中清除饋料中之雜質； (Π)將氨、二氧化碳及醇作為蒸氣移除； (iii)使一部分尿素與醇反應以製備胺基曱酸烷酯；及 99734.990412.doc 14 1328003 (iv)移除含有胺基甲酸烧醋、尿素及醇之液體流以引 入至主反應區中； (b) 將有機錫化合物及高沸點含電子供體原子之溶劑饋 入至該主反應區中； (c) 同時在該主反應區中 (i) 使匚广^醇、尿素及胺基甲酸烷酯在該有機錫化合 物及該高沸點含電子供體原子之溶劑之存在不反 應以製備碳酸二烷酯；且 (ii) 將碳酸二烷酯及氨、醚、二氧化碳、胺基曱酸N_ 烷基酯烷基酯及胺基甲酸烷酯作為蒸氣自該主反 應區中移除；及 (d) 在該第三清除反應區中，將自主反應器之蒸氣流分離 出之胺基甲酸N-烷基酯烷基酯及於主反應區之液體反應介 貝之小》月^IL中之胺基甲酸N -烧基g旨院基g旨轉化為該雜環化 合物（(RNCO)3 ’其中R為Η或CnH2n+1且n=l、2或3)且將胺 基甲酸烧酯轉化為碳酸二烧酯； (i) 將雜環化合物作為固體自該第三反應區物流中 移除； (ii) 使殘餘液體流返回主反應區及清除反應區，且 (iii) 將氨、醇及碳酸二烷酯作為頂部蒸氣流來移除。 該實施例提供下列改良，其包括預備反應區之使用以較 佳在200至380°F、更佳在250至350卞範圍内之溫度下且較 佳於液相中自該尿素及醇移除水及胺基甲酸銨，及清除反 應區之使用以在300至400T範圍内之溫度下於液相中將副 99734-990412.doc -15· 1328003 而作為 產物胺基甲酸N-院基㈣絲轉化為雜環化合物從 固體自系統移除。 U預反應器為雙直徑管柱反應器（下部區段直徑較 寬）。將醇中之尿素饋料溶液引入較窄直徑上部區段之中部 區奴處之官柱預反應器中。尿素饋料中之胺基甲酸銨分解 為氨及二氧化碳。在50至350 psigT管柱之溫度維持在約 2〇〇至約3崎。輕反應產物氨及二氧化碳作為頂部蒸氣流 隨醇蒸氣-起自管柱移除。饋料流中之尿素在該預反應器 中至少部分轉化為胺基甲酸烷酯。該反應放熱。尿素之轉 化大於10%，較佳大於50%。尿素至胺基甲酸烷酯之轉化可 在無錯合催化劑之狀況下進行。但在存在催化劑時轉化速 率更快。 移除饋料流中之水及胺基曱酸銨雜質解決了與保持催化 劑於活性狀態、控制蒸餾塔之頂部壓力及藉由胺基甲酸錄 沈積引起的主反應器頂部蒸氣流冷卻區之堵塞相關聯之問 題。饋料中雜質之清除在雙直徑蒸餾塔之預反應器中進 行。移除饋料流中之雜質為預反應器之主要目的。進一步 改良藉由於預反應器中將尿素至少部分轉化為胺基甲酸烧 醋而實現，其由於主反應器頂部流中碳酸二烷酯之較高濃 度而導致主反應器中製備碳酸二烷酯之更快反應速率、自 碳酸二烷酯回收單元至主反應器之醇再循環之減少。在碳 酸二烷酯之製備中，主反應器頂部物流中碳酸二烷酯之較 咼濃度降低了碳酸二院g旨之分離成本。 其中形成碳酸二烷酯之主反應器為配備有一熱交換器之 99734-990412.doc -16- 1328003II CH3-0:C-NH.CH3 + ch3oh <======> (ch3-0)2C=0 + ch3nh2, dialkyl carbonate with total urethane based on reactor solution and An amount between the i and 3% by weight of the alcohol content is present in the reactor to minimize the formation of by-products. In U.S. Patent No. 6,010,976, dimethyl phenolate (DMC) is synthesized from urea and decyl alcohol in high yield in a single step in the presence of high boiling ethers and a novel homogeneous tin-coupling catalyst. (NH2)2CO + 2 CH3OH =====> (CH30) 2C0 + 2NH3f The test solvent is also used as a binder to form a homogenous miscible catalyst in situ from dibutyltin dimethoxide or dibutyltin oxide. The separation of the substances involved in the DMC process is important for commercial production of DMC for economic reasons. It is disclosed in EP 742 198 198 A1 & 5,214185 that DMC is separated from a vapor mixture of decyl alcohol and DMC by using dimethyl oxalate (DMOX) as an extraction solvent. Due to the high melting point (54 ° C) of DM〇x, the use of DMOX is inconvenient and adds additional cost of separation. Both urea and alcohols are highly hygroscopic. Urea contains ammonium urethane impurities. Thus, water and ammonium urethane are impurities in the urea and alcohol feeds. It has been found that 99734-990412.doc •10· exhibiting impurities in impurities and alcohol feeds (such as water, ammonium urethane, etc.) leads to catalyst purification and cooling of the overhead vapor line in the reactor (condenser) The cooling point in the). Water causes the alkoxy-containing catalyst to passivate. For example, the methoxy group on the D' organotin complex molecule reacts highly with the water molecule, resulting in hydrolysis of the bond between the tin atom and the oxyl atom of the methoxy group. Ammonium ammonium amide causes a problem of clogging of the cooling system (condenser) that controls the monthly pressure in the dialkyl carbonate preparation reactor and the product vapor stream from the dialkyl reactor due to the pre-product of ammonium amide. [Summary of the Invention] Jane. The present invention is an improved process for the preparation of a dialkyl carbonate comprising the steps of: (a) feeding a stream of urea, alcohol, water and an amine ruthenium linkage to the first reaction zone; At the same time in the first reaction zone, (1) reacting water with urea to form ammonium urethane, (8) causing the aminocarboxylic acid in the feed to react with water to react with urea to produce ammonium amide ammonium Ammonia and carbon dioxide, and (c) removing ammonia, carbon dioxide and the alcohol as the first overhead product from the first zone; (d) removing urea and the alcohol from the first reaction zone; Feeding the urea and the alcohol to the second reaction zone; (f) reacting the alcohol with urea in the presence of a homogenous catalyst contained in the St. and high boiling solvent to form carbonic acid 99734-990412.doc -11 · 1328003 (g) removal of dialkyl carbonate and the alcohol β from the second reaction zone by making an alcohol (preferably c^c:3 alcohol) with urea or an alkyl decanoate or both a complex of a tin compound with a high boiling electron donor compound as a solvent (preferably dibutyltin dialkyl oxide complex and high boiling oxygen) The reaction is carried out in the presence of an organic solvent) to prepare a dialkyl carbonate, wherein the reaction is preferably carried out by simultaneously distilling the dialkyl carbonate in a distiller of a distilling dad or a retort reactor. Urea and alcohol feeds are purified by removal of water and ammonium ammonium citrate, N-alkylated by-products, and minor amounts of alkyl amides. Water is removed by reacting water with urea in a prereactor having a preliminary reaction zone. Ammonium ammonium amide is removed by decomposition into ammonia and carbon dioxide in a prereactor. In addition, 'the urea is partially and selectively converted to the alkyl amide in the pre-reactor' which results in a faster reaction rate in the main reactor, from the dialkyl carbonate recovery unit or column to the main reactor. The reduction in alcohol recycle and the higher concentration of dialkyl carbonate in the overhead stream of the sub and main reactors. The higher concentration of dialkyl carbonate in the overhead stream of the autoreactor reduces the cost of separating the distillate. [Embodiment] The removal of water impurities from urea and alcohol feeds by reacting water with urea in a prereactor, and the urethane is removed by decomposition into ammonia and carbon dioxide in the prereactor. . The pre-reactor must be operated under conditions favorable for decomposition to allow ammonia and carbon dioxide to be removed as a vapor. If the decomposition is not complete, the unconverted ammonium amide will enter the main reactor and can be converted to urea and water. The catalyst is passivated due to its decomposition into ammonia and carbon dioxide. The urea is partially converted to an alkyl phthalate in the prereactor. The following necessary reactions occur in the pre-reactor 99734-990412.doc -12- 1328003 * H20 + (NH2)2CO <-=-= ==--> NH2C02NH4 (1) nh2co2nh4 <-==== =: => 2NH3 + C〇2 (2) nh2co2nh4 <-==-==: =>(NH2)2CO + h2o (3) 0 (NH2)2C0 + R0H <=-= , II — > R-0-C-NH2 + NH3 (4) Since the above four reactions are equilibrium reactions and must be present in the preliminary reaction zone in the pre-reactor, the temperature and pressure of the pre-reactor and the main reactor are controlled. It is important. In the prereactor, the reactions (1), (2), (3) and (4) are carried out in the liquid phase in the prereactor at a temperature of from 200 to 380 °F, preferably from 250 to 550 °C. The pre-reactor top pressure preferably ranges from about 3 Torr to 3 psig. However, the top pressure is primarily dependent on the desired temperature of the prereactor column and the liquid composition in the reactor. In the absence of a catalyst, the reaction (4) enters equilibrium, but is supported on an inert support such as vermiculite, high temperature (>85 〇<t) calcined alumina catalyst (such as dibutyltin dialkyl oxidized catalyst). Reaction of a catalyst and a weakly acidic or basic heterogeneous catalyst such as zinc oxide, tin oxide, titanium oxide, zirconium oxide, molybdenum oxide, talc, calcium carbonate, zinc carbonate hydroxide, cesium carbonate hydroxide, etc. Faster. Under certain conditions, the preferred concentration of urea in the liquid phase in the preliminary reaction zone is less than the percent yield, preferably 50 wt.%. Part of the pressure of ammonia and carbon dioxide must be kept below the decomposition pressure of the aminocarboxylic acid to achieve the decomposition of the amine formate. It is also preferred that the product, ammonia and carbon dioxide are effectively pre-prepared together with the alcohol and any inert stripping f 5, , ^ as appropriate, in the form of 暮> The reaction zone for the reaction was removed. If necessary, (1) drunk therapy and milk can be used as the sole stripping 99734-990412.doc -13- U28003 gas. Therefore, the improvement is carried out in a process for producing a dialkyl carbonate by reacting a reactant comprising urea and an alcohol having ammonium as an impurity and ammonium carbamate, which comprises the following steps: (a) comprising urea and an alcohol The reactant is fed into the main reaction zone; (b) feeding an organotin compound and a solvent having a high boiling point electron donor atom into the main reaction zone; and (c) simultaneously in the main reaction zone (I And reacting the alcohol with urea in the presence of the organotin compound and the solvent of the high boiling electron donor atom to prepare a dialkyl carbonate; and (II) using the carbonated vinegar and ammonia as a vapor from the main reaction zone Removal, wherein the improvement uses a pre-reaction zone prior to the main reaction zone to remove water and ammonium ammonium citrate from the reactants by first reacting the water with urea to form ammonium urethane and Ammonia and carbon dioxide are preferably removed from the reactants such as smectic acid prior to the decomposition of the ammonium amide to ammonia and carbon dioxide, and the reactants are removed from the reactants prior to feeding the reactants in step (b). 38〇卞, better temperature in the range of 250 to 350 F The liquid phase and preferably under the conditions. In the preliminary reaction zone, a preferred portion of the urea reacts with the alcohol to form an alkyl carbamate. A preferred embodiment of the method for preparing a dialkyl carbonate comprises the steps of: (a) feeding urea, a Ci-C3 alcohol into a pre-reaction zone; (i) removing impurities in the feed in the pre-reaction zone; (Π) removing ammonia, carbon dioxide, and alcohol as a vapor; (iii) reacting a portion of the urea with an alcohol to prepare an alkyl phthalate; and 99734.990412.doc 14 1328003 (iv) removing the carboxylic acid containing carboxylic acid, a liquid stream of urea and an alcohol to be introduced into the main reaction zone; (b) feeding an organotin compound and a solvent having a high boiling point electron donor atom into the main reaction zone; (c) simultaneously in the main reaction zone (i) preparing a dialkyl carbonate in the presence of the organotin compound, the urea and the alkyl carbamate in the presence of the organotin compound and the solvent of the high boiling electron donor atom; and (ii) the carbonic acid An alkyl ester and ammonia, an ether, carbon dioxide, an alkyl sulfonate alkyl ester and an alkyl carbamate are removed as a vapor from the main reaction zone; and (d) in the third scavenging reaction zone, Separating the vapor stream of the autoreactor from the N-alkyl ester of urethane and the main reaction zone The liquid reaction 介 之 》 》 》 》 》 ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ ̄ 2 or 3) and converting the amine carboxylic acid to the dialkyl carbonate; (i) removing the heterocyclic compound as a solid from the third reaction zone stream; (ii) returning the residual liquid stream to the main reaction zone and The reaction zone is purged and (iii) ammonia, alcohol and dialkyl carbonate are removed as a top vapor stream. This embodiment provides the following modifications, including the use of a preliminary reaction zone, preferably at a temperature in the range of 200 to 380 °F, more preferably in the range of 250 to 350 °, and preferably in the liquid phase, from the urea and alcohol. The use of water and ammonium urethane, and the scavenging reaction zone, in the liquid phase at a temperature in the range of 300 to 400 T, the sub-99734-990412.doc -15·1328003 as the product urethane N-yard (four) wire Conversion to a heterocyclic compound is removed from the system from the solid. The U prereactor is a double diameter column reactor (the lower section has a larger diameter). The urea feed solution in the alcohol is introduced into the column pre-reactor of the slave in the middle of the narrower diameter upper section. The ammonium urethane in the urea feed is decomposed into ammonia and carbon dioxide. The temperature at the 50 to 350 psig T column is maintained at about 2 Torr to about 3 s. The light reaction products ammonia and carbon dioxide are removed from the column as a top vapor stream with alcohol vapor. The urea in the feed stream is at least partially converted to the alkyl carbamate in the prereactor. The reaction is exothermic. The conversion of urea is greater than 10%, preferably greater than 50%. The conversion of urea to alkyl carbamate can be carried out without a miscible catalyst. However, the conversion rate is faster in the presence of the catalyst. The removal of the water in the feed stream and the ammonium amide ammonium hydride solution solves the blockage of the cooling zone of the main reactor overhead vapor stream caused by maintaining the catalyst in an active state, controlling the pressure at the top of the distillation column, and depositing by the amine formate. Associated issues. The removal of impurities from the feed is carried out in a pre-reactor of a two-diameter distillation column. Removal of impurities in the feed stream is the primary purpose of the pre-reactor. Further improvement is achieved by the at least partial conversion of urea to the carboxylic acid sulphuric acid in the prereactor, which results in the preparation of the dialkyl carbonate in the main reactor due to the higher concentration of the dialkyl carbonate in the overhead stream of the main reactor. Faster reaction rate, reduction in alcohol recycle from the dialkyl carbonate recovery unit to the main reactor. In the preparation of the dialkyl carbonate, the higher concentration of the dialkyl carbonate in the overhead stream of the main reactor reduces the separation cost of the second plant. The main reactor in which the dialkyl carbonate is formed is equipped with a heat exchanger 99734-990412.doc -16-1328003

授拌槽反應器，以回收自主反應！I之產物蒸氣流之潛熱。 所回收之熱量用於使醇自醇回收管柱再循環至主反應器。 非必需但視情況可對液體反應介質進行機械攪拌。在本發 明中，非習知地操作主反應器之反應/蒸餾塔以使非所要之 N-烷基化副產物作為頂部產物流之部分自液體反應區移 除，其使副產物維持在最小含量以使反應器可在恆定的液 體含量下操作，而在連續的反應器操作之延長之時期内不 會以非所要副產物填充液體反應區。碳酸二烷酯之成功商 業製備高度需要此狀況。液體介質令低濃度之尿素、胺基 甲酸烷酯及碳酸二烷酯用於使义烷基化副產物之形成速率 降至最低，其藉由使用較高濃度的高沸點溶劑（諸如三乙二 醇一甲醚）來實現。然而，若胺基甲酸烷酯之濃度太低，則 可出現無法接受之DMC低空間產率。 為避免主反應器中諸如胺基曱酸N_烷基酯烷基酯及雜環 化合物之副產物之積聚，發現藉由控制主反應器蒸氣流之 瘵流管柱之溫度及壓力兩者，胺基甲酸义烷基酯烷基酯可 連續自液體反應介質中蒸餾出而同時執行碳酸二烷酯製備 反應，且轉化為可作為固體自系統移除之雜環化合物。換 言之，吾人發現可在穩態反應器操作條件下維持主反應區 之特定液體反應體積中的胺基曱酸N•烷基酯烷基酯及雜環 化合物之穩定濃度。亦發現維持主反應器任何内部之表面 溫度低於約550°F、較 <圭低於45〇卞+分有望使主反應區中 雜環化合物之形成降至最低。胺基甲酸Ν·烷基酯烷基酯至 雜環化合物之轉化藉由採用第三清除反應區來執行。 99734*990412.doc -17- 1328003 用於該目的之較佳清除反應器為一配備有附加蒸餾塔、 冷凝器及回流槽之攪拌槽反應器。藉由操作自主反應區之 蒸氣溫度處於高於約255T、較佳高於265T之管柱溫下， 使由胺基甲酸烧酯與碳酸二烧酯在主反應區中之烧基化而 產生之副產物胺基甲酸N-烷基酯烷基酯作為頂部蒸氣流之 一部分隨其它產物連續移除。 〇 〇 R-0-C-NH2 + (R0)2c=0-►R-O-H-NH-R + R-OH + C02 胺基甲酸N-烷基酯烷基酯自主反應器之頂部物流分離且 引入清除反應器中。清除反應器較佳在330至400〇F範圍内 之液體反應介質溫度下操作。控制管柱溫及管柱頂部壓力 以使頂部蒸氣流不含有胺基曱酸N_烷基酯烷基酯係重要 的。通常，清除反應器在高於主反應器中之反應溫度及頂 部壓力至少2°F及5 psig的反應溫度及頂部壓力下操作。 本發明中所揭示的移除副產物之技術可延伸至先前技 術，諸如 U.S. 6,359，163 B2 (2002)及 WO 95/17369 (1995)、 U.S. 6,031，122 (2000)及 EP 116733 9 (2002)自尿素及醇產生 碳酸二烷酯，無論溶劑是否用於主反應器及清除反應器中。 對於諸如碳酸二丙酯、碳酸二丁酯等之較重碳酸烷酯之 生產’將胺基甲酸N -院基S旨烧基醋作為頂部物流之部分自 主反應器移除變得困難。因此，液體滑流大量移出主反應 器至清除反應器中。將該滑流中之胺基曱酸N-烷基酯烷基 酯在如本發明所揭示之清除反應器中轉化為可分離之高沸 點物質。移除清除反應器底部物流中之高沸點廢料之後， 99734-990412.doc •18· 1328003 殘餘液體流可返回主反應器及清除反應器。 各種物理設備可用作預反應器。此等包括蒸餾管柱反應 态、攪拌槽反應器、氣泡反應器、管狀反應器、沸點反應 斋或其任何組合。較佳設備為蒸餾管柱反應器，其中在反 應/热餾條件下執行反應。不管反應及之平衡性 質，採用蒸餾管柱反應器允許推動三個反應向右，意即， 完全移除饋料流中之水及胺基曱酸銨。尿素在預反應器中 • 根據平衡反應（4)部分轉化為胺基甲酸烷酯。藉由將氨作為 頂部氣體混合物自反應區移除，亦可迫使反應（4)向反應之 右側進行。由於尿素與醇之反應產生碳酸二烷酯之反應於 兩步驟中進行且反應（4)為第一步驟，因此尿素至胺基甲酸 燒§日之部分轉化增加了主反應器中胺基甲酸烷酯至碳酸二 燒S曰之轉化速率且導致主反應器頂部物流中之碳酸二烷酯 之更高濃度。 石反酸—烧自旨形成之反應如下： R 〇-C-NH2 + R〇H<==s==> (R〇j2C=〇 + Nh,3 ο 反應（5)於主反應器中在高沸點溶劑之存在下以反應/蒸 鶴极式進行以建立用於一旦產生碳酸二烷酯即將其自反應 η質中快速移除之有利條件。由於化學熱力學，與於預反 應益中形成胺基甲酸烷酯之速率相比，於主反應器中形成 99734-990412.do. -19- 1328003 碳酸二烧酯之速率對主反應器反應介質中氨之濃度更為敏 感。形成碳酸二烷酯之速率變得更快，若在胺基曱酸烷酯 之特定濃度下，則在主反應器液體反應介質中具有更低氨 /辰度。在約環境壓力至150 psig、較佳30至120 psig之壓力 下’主反應器中反應介質之溫度為約3〇〇至約45〇下，較佳 為約320至4〇〇eF，最佳為約33〇至36〇卞。導致碳酸二烷酯 向選擇性之所要溫度及壓力之任何組合可藉由選擇適當高 彿點溶劑及控制溶劑在主反應器中之濃度來獲得。十分希 望操作主反應器以具有至少約300卞、較佳高於約32〇卞之 頂部浴氣溫度以用於回收頂部蒸氣流之潛熱用於醇作為超 熱醇蒸氣再循環至主反應器及預反應器中。 於主反應器中使用高沸點溶劑允許在低壓及低濃度胺基 曱酸酯於液體反應介質中進行該反應。低壓有利於碳酸二 烷酯自液體反應介質更快移除至蒸氣相，導致液體反應介 貝中較低浪度之碳酸二烧酯。液體反應介質中碳酸二烧酯 及胺基甲酸酯/尿素之濃度越低，主反應器中與N—烷基化及 尿素、胺基曱酸烷酯及N_烷基化產物分解產物相關之非所 要副產物越少。用於合成碳酸二烷酯之較佳溶劑應具有下 列特性.（1)溶劑應在高於碳酸二烧酯產物沸點至少2〇卞之 皿度下沸騰，且（2)其不應與碳酸二烷酯形成共沸混合物。 此'谷剤之貫例為咼沸點謎類、酮類、烴類及酯類或此等 之此〇物，二乙二醇二甲基醚、四乙二醇二烷基醚、茴香 喊、二甲氧基笨、二甲氧基甲苯、草酸烷酯、十氫萘、四 氫萘、二曱苯、癸烷等或此等之混合物。 99734-990412.doc -20. 1328003 將超熱醇蒸氣流直接引入液體反應區令以提供熱量用於 呈輕微吸熱反應的胺基曱酸烷酯轉化至碳酸二烷酯之反 應，且一旦產生碳酸二烷酯及氨則將其自液體反應介質中 汽提出。組合於反應介質中之胺基甲酸烷酯及尿素之所要 總濃度為液體反應介質中總物質之約1 〇至約60 wt·%，較佳 為約15至約50 wt.%。反應介質中碳酸二烷酯之所要濃度為 以液體反應介質總含量計約0.5至約12 wt.%，較佳為約2至 約9 wt. %。液體反應介質中胺基甲酸烷酯與醇之莫耳比為 0.2 : 1至2 : 1 ’較佳0.3 : 1至1.5 : 1。有機錫錯合催化劑之 濃度為以主反應器中液體反應區中所有物質之總含量計約 2至約20 wt.%錫’較佳為5至約17 wt·%錫。應注意，催化劑 亦催化上文所討論之非所要副反應。在低溫下執行反應減 少了副反應。然而，製備碳酸二烷酯之速率亦較低，其對 於DMC之商業生產可為不可接受。主反應器中反應介質中 问沸點溶劑之所要濃度為反應介質中總物質之約2至約65 〜[%，較佳為2.5至55评1.%。 在穩態反應條件下之工作催化劑為源自二烷氧化二烷基 錫R’4-nSn(〇R)n.xL (其中Ri為烷基、芳基或芳烷基；r=烷基； n= 1或2 ; X=1或2 ; ^為含電子供體原子之一齒或二齒配位 基）之有機錫錯合物之有機錫錯合催化劑系統。L之實例為 电子供體配位基分子，諸如鍵類、醋類 '綱類 '盤類、有 機膦或此等之混合物；1乙二醇二甲㈣、四乙二醇二甲 基醚草酸一曱酯、丙二酸二曱酯、琥珀酸二甲酯、茴香 醚、二甲氧基笨、二甲氧基甲苯、乙二醇、兒茶酚、1，4· 99734-990412.doc -21- 1328003 二噁烷-2,3-二醇、2-曱基四氫呋喃·3_酮、2,3_戍二酮、2,4_ · 戊二酮、3-曱基四氫"比喃、三笨基膦等。同質催化劑系統 為各種有機錫種類之准平衡混合物。該類型之適當催化劑 及其製造方法描述於美國專利第6 〇1〇 976號及第6 392 〇78 號中’其全文以引用方式併入本文中。 在穩態反應條件下之工作催化劑系統為藉由許多可能之 反應而產生的各種可溶性有機錫單體、二聚物及寡聚物物 貝之/扣合物。該4各種有機錫催化劑種類在特定反應條件 下多少處於准平衡狀態中。氧化二烷基錫、齒化二烷基錫、_ 雙（乙醯基丙酮酸）二烷基錫及羧酸二烷基錫（諸如二乙酸二 丁基錫、草酸二炫基錫、丙二酸二丁基錫、二乙酸二丁基 錫、雙（乙醯基丙酮酸）二丁基錫）等可用於在主反應器之起 始藉由在諸如三乙二醇二曱醚之高沸點溶劑之存在下與醇 反應就地形成可溶性錫錯合催化劑種類。附於錫原子之烷 基可相同或不同。例如’催化劑前驅體可為二丁基錫、丁 基卞基錫、丁基苯基錫、丁基辛基錫或二_2_苯基乙基錫二 烧氧化物、二鹵化物、羥基鹵化物、二乙酸鹽或氧化物。· 水、羧酸或鹽酸共產物作為頂部蒸氣流在高沸點溶劑之存 在下於低壓下自液體反應介質中連續移除。用於催化劑形 成反應之適當溫度為約2 〇 〇至約4 0 0 T且壓力自約環境壓力 至1 50 psig。在一較佳實施例中，取決於所要之碳酸二烧醋 產物之甲醇、乙醇或丙醇連泵入主反應器中。甲醇或乙醇 中之任一者可接受地用於MEC之生產。主反應器中催化劑 形成反應在稀釋胺基曱酸烷酯、胺基甲酸N_烷基酯烷基醋 99734-990412.doc -22· 1328003 化心rs旨溶液之存在τ有利地進行。應瞭解，在該傕 〇i? ^ ^ . '' °細作應在允許將共產物水、羧 或虱化虱作為頂部物流隨醇^ ^ ^ ^ ^ ^ ^ 野丨卜马頂部產物自反應區移除 條件下操作。對於碳酸二甲 τ知生產，可溶性有機錫錯合 催化劑系統藉由在啓動碳酸__ 烷酯形成反應之前在主反應 益中於高滞點溶劑之存在下簡單地將二甲氧化二丁基錫與 二乙二醇二甲_(作為錯合劑用於形成有機錫錯合催化劑） 及甲醇混合而形成。對於碳酸二乙醋生產，可溶性有機錫 錯合催化劑系統較佳藉由於主反應器中使用二甲氧化二丁 基錫與三乙二醇二甲醚及乙醇形成。隨著反應之進行，以 乙氧基置換催化劑上之甲氧基。 現在參看圖1 ’其展示本發明一實施例之簡化流程圖。圖 1說明去除了 DMC分離單元之改良方法之流程圖。讓❻ 離單元說明於圖2中。反應/蒸餾管柱反應器lu用作預反應 器以移除饋料流中之雜質且用於尿素至胺基甲酸甲酯之部 分轉化。藉由將尿素饋料i與甲醇流3混合於轉鼓丨3丨中製備 尿素溶液。曱醇流包含新鮮甲醇饋料流2及作為自DMC分離 單元之甲醇再循環流3〇之一部分的甲醇再循環流4。自DMc 分離單元（展示於圖2中）之甲醇再循環流30分為三個流（經 由31之4及33 ’及32)以用於尿素溶液之製備、主反應器112 及清除反應器113。自轉鼓131之尿素溶液饋料5引入雙直徑 管柱反應器111頂部狹窄管柱區段之中部。反應用作 預反應器以清除曱醇及尿素饋料中之雜質（水及胺基甲酸 銨）且用於將尿素部分轉化為MC。自預反應器1丨丨之蒸氣流 99734-990412.doc •23· 1328003 6包含氨、二氧化碳及曱醇。所清除之曱醇*2M(：及尿素 之混合溶液作為底部物流7自預反應器丨丨丨移除且與經由管 線20自冷卻/過濾系統133之再循環液體流22組合為物流 8。自冷卻/過濾系統133之液體再循環流20分為兩個物流（21 及22)以再循環至主反應器112及清除反應器113中。組合之 物流8引入主反應器（攪拌槽反應器或視情況之氣泡管柱反 應器）112。自DMC分離單元之再循環甲醇流33作為超熱甲 醇蒸氣引入主反應器112中。自閃蒸管柱132之頂部再循環 流14引入主反應器中。物流14主要包含MC及少量N-MMC 及甲醇。自主反應器112之頂部蒸氣流9包含氨、C〇2、二甲 基醚、曱醇、DMC '碳酸甲酯（MC) ' N-MMC '三甘醇（tg) 及少量有機錫催化劑。自主反應器112之該頂部物流9與自 清除擾拌槽反應器113之頂部物流17組合成物流1 〇。物流17 包含氨、C〇2、二甲基醚、甲醇及DMC。組合之物流1〇引 入蒸館塔15 1以自物流中其餘較重組份中分離出組份氧、 C〇2、二曱基趟、曱醇及DMC。自管柱1 5 1之頂部物流1 2與 預反應器反應器111之頂部物流6組合成物流23。組合之物 流23引入蒸德塔134。自管柱1 34之頂部物流25送至胺基甲 酸敍移除系統1 3 5，其中物流25適當冷卻以使C02與氨反應 生成胺基甲酸銨且使固體胺基甲酸銨沈澱。固體胺基曱酸 銨可藉由胺基曱酸銨移除系統135使用過濾器或水力旋流 器經物流26來移除。自胺基甲酸銨移除系統135之物流27 引入蒸餾塔136中以回收氨。自管柱136之頂部物流28送至 氨儲備槽中。自管柱136之底部物流29為主要包含二甲基醚 99734-990412.doc • 24 · 1328003 之有機廢料。自管柱134之底部物流24送至圖2中所示之 DMC分離單元。物流24包含DMC及甲醇。自管柱151之底 部物流13送至閃蒸管柱132。物流13包含甲醇、MC、 N-MMC、TG及少量催化劑。自閃蒸管柱132之底部物流15 包含N-MMC、MC(少量）、TG及少量有機錫催化劑。物流 15與自主反應器112之少量液體滑流η組合成物流16。組合 之物流16引入清除反應器113中（視情況自主反應器1丨2之 少量液體滑流11可引入管柱15 1或132中任一者之較低區 段）。將自清.除反應器113之底部物流1 8冷卻以沈殿物流中 之諸如異三聚氰酸、1，3,5-三曱基三》秦_2,4,6-三酮等之雜環 化合物且將沈澱作為固體經由管線19自過渡系統13 3移 除。自過濾系統13 3之液體過濾物流2〇分為兩個物流2丨及22 以再循環回主反應器112及清除反應器ι13。 主反應器視石反酸一烧醋之生產能力可為單授掉槽反應5| 或多攪拌槽反應器系統》例如’若主反應器包含一系列三 攪拌槽反應器’則自預反應器1 1 1清除之胺基甲酸燒酿/尿 素饋料流7適當分成三個物流且各物流直接引入三個反應 器中。自各反應器提取液體反應流且引入下一反應器中。 自第三反應器之液體反應流送至第一反應器中。自第三反 應益之液體反應流之少量滑流與自管柱13 2之底部物流1 5 組合為物流16，其送至清除反應器n 3中。醇再循環流諸 如自DMC分離單元之曱醇再循環流33作為超熱醇蒸氣引入 第一反應器中。自第一攪拌槽反應器之頂部蒸氣流引入第 一反應器中。自第一反應器之頂部蒸氣流引入第三反應器 99734-990412.doc -25· 1328003 中。隨著蒸氣流自第一反應器移動至第三反應器，自各反 應器之頂部物流中碳酸二烷酯之含量逐漸增加，導致自第 三反應器之頂部物流中DMC之最高濃度。自第三反應器之 頂部物流9與自/胃除反應器113之頂部物流17組合為物流 10，其引入蒸餾塔151。 自蒸餾塔134之底部物流24送至DMC分離單元（參看圖 2)。該物流含有約28 wt.%之DMC。自管柱134之物流24經 由管線34引入萃取蒸餾塔137。包含約98 wt %之甲醇及約2 wt.%之DMC的頂部物流35經由圖！中管線3〇再循環。底部物 流36引入萃取溶劑再循環管柱13卜將萃取溶劑茴香醚作為 自官柱13 8之底部物流3 8回收且經由管線3 8再循環回管柱 137。自管柱138之頂部物流37為產*DMC，其送至£)；^(：儲 備槽中。 可以上文用於生產DMC所述之類似方式生產碳酸二乙酯 (DEC)。由於乙醇及dec之混合物不形成共沸物，DEC自乙 醇之分離可以單蒸顧塔進行。 圖3說明用於生產DEC之方法之簡化流程圖。藉由於轉鼓 141中混合尿素饋料1〇1及乙醇流1〇3來製備尿素溶液。乙醇 流103包含新鮮乙醇饋料ι〇2及作為乙醇再循環流ι3〇之一 部分之乙醇再循環流155。乙醇再循環流13〇包含自蒸餾塔 146之頂部物流117及自蒸餾塔145(乙醇再循環管柱）之底部 物/;,L 129 °乙醇再循環流130分為兩個物流1 52及1 5 6。物流 152再循環至清除反應器123中。物流丨56再分為兩個物流 155及157以分別再循環至轉鼓141及主反應器122。乙醇再 99734-990412.doc •26- 1328003 循環流157引入主反應器122中。自轉鼓141之尿素溶液l〇4 引入雙直徑管柱反應器121頂部狹窄管柱區段之中部。反應 器121用作預反應器以清除饋料（乙醇及尿素）中之雜質（水 及胺基甲酸錄）且將尿素部分轉化為乙浠碳酸（EC)。自預反 應器121之蒸氣流1 〇5由氨、二氧化碳及乙醇組成。將所清 除之混合溶液作為底部物流1 〇6自預反應器121移除。物流 106引入主反應器（攪拌槽反應器或視情況之氣泡管柱反應 器）122中。再循環之乙醇流157(該物流為乙醇再循環流u〇 之主要部分）作為超熱乙醇蒸氣引入主反應器122中。自主 反應器122之少量滑流108與自DEC再循環管柱147之底部 物流120組合以形成物流1 61且組合之物流1 6 1引入清除反 應器123中。滑流1 〇8由乙醇、氨、二乙基醚、DEC、胺基 甲酸乙酯、N-乙基胺基曱酸乙酯、TG、諸如異三聚氰酸、 1，3,5-三甲基三嗪_2,4,6_三酮等之雜環化合物及有機錫錯 合催化劑組成。物流120包含乙醇、胺基曱酸乙酯、N_乙基 胺基曱酸酯、TG及痕量催化劑。自清除反應器123之頂部 物流160包含氨、c〇2、二乙基醚、乙醇及DEC。自清除反 應器123之底部物流159包含胺基甲酸乙酯、三乙二醇二曱 醚、N-乙基胺基甲酸乙酯、乙醇、雜環化合物及同質有機 錫催化劑。反應器123之底部物流159於冷卻/過濾系統148 中冷卻以沈澱雜環化合物。經由管線124將沈澱固體副產物 自系統148移除。自系統148之液體流125分為兩個物流126 及127以再循環至主反應器122及清除反應器123。自主反應 器122之頂部物流1〇7與自清除反應器123之頂部物流160組 99734-9904I2.doc •27· 1328003 合為物流109。自主反應器122之頂部蒸氣流ι〇7由氨、c〇2、 二乙基醚、乙醇、胺基曱酸乙酯、N_乙基胺基曱酸乙酯、 DEC、TG及痕量催化劑組成。物流1〇7與自清除反應器123 之頂部物流160組合為物流1〇9。頂部物流16〇包含氨、c〇2、 二乙基醚、乙醇及DEC。組合之物流1〇9引入蒸餾塔142中。 由氨、c〇2、二乙基醚及乙醇組成之管柱ι42之頂部物流u〇 引入蒸餾塔143。將自管柱143之頂部物流154冷卻以引起 C〇2與氨反應從而產生胺基曱酸銨。胺基甲酸銨沈澱於液體 氨中且作為固體經由管線115自冷卻/過濾系統丨44移除。自 冷卻/過遽系統144之液體氨流116送至氨儲備槽中。自管柱 142之底部物流150由DEC、乙醇、胺基甲酸乙酯、N_乙基 胺基甲酸乙酯、TG及痕量催化劑組成。物流丨5〇引入蒸餾 塔146(第一乙醇再循環管柱）中。自管柱146之頂部乙醇流 117與自蒸餾塔14 5 (第二乙醇再循環管柱）之乙醇底部物流 129組合為乙醇再循環流13〇。自管柱146之底部物流ιΐ8引 入蒸餾塔147 (DEC再循環管柱）。頂部物流丨19為產物 DEC，其送至DEC儲備槽。自管柱147之底部物流12〇與自 主反應器122之少量滑流108組合且組合之物流161引入攪Feed the tank reactor to recover the autoreactive reaction! The latent heat of the product vapor stream of I. The recovered heat is used to recycle the alcohol from the alcohol recovery column to the main reactor. It is not necessary but mechanical agitation of the liquid reaction medium as appropriate. In the present invention, the reaction/distillation column of the main reactor is not conventionally operated to remove undesired N-alkylated by-products from the liquid reaction zone as part of the overhead product stream, which maintains by-products to a minimum. The amount is such that the reactor can be operated at a constant liquid level without filling the liquid reaction zone with undesirable by-products over a prolonged period of continuous reactor operation. This situation is highly desirable for successful commercial preparation of dialkyl carbonate. The liquid medium allows low concentrations of urea, alkyl carbamate and dialkyl carbonate to minimize the rate of formation of the alkylation by-products by using higher concentrations of high boiling solvents such as triethylene Alcohol monomethyl ether) to achieve. However, if the concentration of the alkyl carbamate is too low, an unacceptable low spatial yield of DMC can occur. In order to avoid accumulation of by-products such as N-alkyl ester alkyl amide and heterocyclic compounds in the main reactor, it has been found that by controlling both the temperature and pressure of the turbulent column of the main reactor vapor stream, The alkyl alkyl carbamate can be continuously distilled from the liquid reaction medium while performing the dialkyl carbonate preparation reaction and converted into a heterocyclic compound which can be removed from the system as a solid. In other words, we have found that a stable concentration of the amino acid N-alkyl ester alkyl ester and the heterocyclic compound in the specific liquid reaction volume of the main reaction zone can be maintained under steady state reactor operating conditions. It has also been found that maintaining any internal surface temperature of the main reactor below about 550 °F is desirable to minimize the formation of heterocyclic compounds in the main reaction zone. The conversion of the guanidinium carbamate alkyl ester to the heterocyclic compound is carried out by employing a third scavenging reaction zone. 99734*990412.doc -17- 1328003 The preferred purge reactor for this purpose is a stirred tank reactor equipped with an additional distillation column, condenser and reflux tank. Producing the alkylation of the carbazate and the dialkyl carbonate in the main reaction zone by operating the vapor temperature of the autoreactive zone at a column temperature above about 255 T, preferably above 265 T. The by-product alkyl N-alkyl ester of carboxylic acid is continuously removed as part of the overhead vapor stream with the other products. 〇〇R-0-C-NH2 + (R0)2c=0-►ROH-NH-R + R-OH + C02 Aminoalkyl N-alkyl ester of carboxylic acid is separated from the top of the reactor and introduced into the purge In the reactor. The purge reactor is preferably operated at a liquid reaction medium temperature in the range of 330 to 400 F. It is important to control the temperature of the column and the pressure at the top of the column so that the overhead vapor stream does not contain the amine alkyl N-alkyl ester. Typically, the purge reactor is operated at a reaction temperature above the main reactor and at a top pressure of at least 2 °F and a reaction temperature of 5 psig and a top pressure. The techniques for removing by-products disclosed in the present invention can be extended to the prior art, such as US 6,359,163 B2 (2002) and WO 95/17369 (1995), US 6,031,122 (2000), and EP 116733 9 (2002). Dialkyl carbonate is produced from urea and alcohol, regardless of whether the solvent is used in the main reactor and in the purge reactor. For the production of lighter alkyl carbonates such as dipropyl carbonate, dibutyl carbonate, etc., it has become difficult to remove the amino N-based S-alkyl acetal as part of the overhead stream from the main reactor. Therefore, the liquid slip stream is largely removed from the main reactor to the purge reactor. The N-alkyl ester alkyl amide in the slip stream is converted to a separable high boiling material in a scavenging reactor as disclosed herein. After removing the high boiling waste in the bottom stream of the reactor, 99734-990412.doc •18·1328003 residual liquid stream can be returned to the main reactor and the reactor is purged. Various physical devices can be used as pre-reactors. These include distillation column reaction states, stirred tank reactors, bubble reactors, tubular reactors, boiling point reactions, or any combination thereof. A preferred apparatus is a distillation column reactor in which the reaction is carried out under reaction/heat distillation conditions. Regardless of the reaction and the balance of the nature, the use of a distillation column reactor allows the three reactions to be pushed to the right, meaning that the water in the feed stream and the ammonium ammonium citrate are completely removed. Urea in the pre-reactor • Partial conversion to alkyl carbamate according to equilibrium reaction (4). The reaction (4) can also be forced to the right side of the reaction by removing ammonia from the reaction zone as a top gas mixture. Since the reaction of the reaction of urea with an alcohol to produce a dialkyl carbonate is carried out in two steps and the reaction (4) is the first step, the partial conversion of the urea to the aminocarboxylic acid is increased by the amine carboxylic acid alkane in the main reactor. The conversion rate of the ester to the di-Sodium Carbonate and results in a higher concentration of the dialkyl carbonate in the overhead stream of the main reactor. The reaction of the stone acid-burning reaction is as follows: R 〇-C-NH2 + R〇H<==s==> (R〇j2C=〇+ Nh,3 ο Reaction (5) in the main reactor The reaction/distillation is carried out in the presence of a high boiling solvent to establish an advantageous condition for rapid removal of the dialkyl carbonate from the reaction η mass once it is produced. Due to chemical thermodynamics, it is formed in the pre-reaction The rate of alkyl carbamate is more sensitive to the formation of 99734-990412.do. -19-1328003 dialkyl carbonate in the main reactor. The concentration of ammonia in the main reactor reaction medium is more sensitive. The rate of ester becomes faster, if at a particular concentration of the alkyl phthalate, it has a lower ammonia/density in the main reactor liquid reaction medium. At about ambient pressure to 150 psig, preferably 30 to The temperature of the reaction medium in the main reactor at a pressure of 120 psig is from about 3 Torr to about 45 Torr, preferably from about 320 to 4 〇〇eF, most preferably from about 33 Torr to about 36 Torr. Any combination of the desired temperature and pressure of the alkyl ester to the selectivity can be determined by selecting the appropriate high point solvent and controlling the solvent in the main reaction. The concentration in the vessel is obtained. It is highly desirable to operate the main reactor to have a latent bath temperature of at least about 300 Torr, preferably above about 32 Torr for the recovery of the latent heat of the overhead vapor stream for the alcohol as the superheated alcohol vapor. Recycling to the main reactor and pre-reactor. The use of a high boiling point solvent in the main reactor allows the reaction to be carried out in a liquid reaction medium at low pressure and low concentration of amine phthalate. Low pressure favors dialkyl carbonate from liquid The reaction medium is removed to the vapor phase more quickly, resulting in a liquid reaction of the lower boiling dialkyl carbonate in the shell. The lower the concentration of the dialkyl carbonate and the urethane/urea in the liquid reaction medium, the main reactor The less the undesirable by-products associated with the N-alkylation and urea, the aminoalkyl decanoate and the N-alkylation product decomposition products, the preferred solvent for the synthesis of the dialkyl carbonate should have the following characteristics. (1) The solvent should boil at a temperature above the boiling point of the dialkyl carbonate product of at least 2 ,, and (2) it should not form an azeotrope with the dialkyl carbonate. Boiling point mystery, ketones, hydrocarbons and esters or Such sputum, diethylene glycol dimethyl ether, tetraethylene glycol dialkyl ether, fennel, dimethoxy studi, dimethoxytoluene, alkyl oxalate, decahydronaphthalene, tetrahydrogen Naphthalene, diphenylbenzene, decane, etc. or a mixture of these. 99734-990412.doc -20. 1328003 The superheated alcohol vapor stream is introduced directly into the liquid reaction zone to provide heat for the amino-based citric acid which is slightly endothermic. The reaction of converting the alkyl ester to dialkyl carbonate, and once the dialkyl carbonate and ammonia are produced, is stripped from the liquid reaction medium. The total concentration of the alkyl carbamate and urea combined in the reaction medium is liquid. The total amount of the material in the reaction medium is from about 1 Torr to about 60 wt.%, preferably from about 15 to about 50 wt.%. The desired concentration of the dialkyl carbonate in the reaction medium is from about 0.5 to about 12 wt.%, preferably from about 2 to about 9 wt.%, based on the total of the liquid reaction medium. The molar ratio of the alkyl carbamate to the alcohol in the liquid reaction medium is from 0.2:1 to 2:1', preferably from 0.3:1 to 1.5:1. The concentration of the organotin mismatch catalyst is from about 2 to about 20 wt.% tin', preferably from 5 to about 17 wt% tin, based on the total content of all materials in the liquid reaction zone of the main reactor. It should be noted that the catalyst also catalyzes the undesirable side reactions discussed above. Performing the reaction at low temperatures reduces side reactions. However, the rate of preparation of the dialkyl carbonate is also low, which may be unacceptable for commercial production of DMC. The desired concentration of the boiling point solvent in the reaction medium in the main reactor is from about 2 to about 65 to about [%, preferably from 2.5 to 55, 1.% of the total amount of the reaction medium. The working catalyst under steady state reaction conditions is derived from dialkyltin dialkyltin R'4-nSn(〇R)n.xL (wherein Ri is alkyl, aryl or aralkyl; r=alkyl; An organotin-coupling catalyst system of n=1 or 2; X=1 or 2; ^ is an organotin complex containing one or two bidentate ligands of an electron donor atom. Examples of L are electron donor ligand molecules such as a bond, a vinegar 'class' disk, an organophosphine or a mixture thereof; 1 ethylene glycol dimethyl (tetra), tetraethylene glycol dimethyl ether oxalic acid Monoterpene ester, dinonyl malonate, dimethyl succinate, anisole, dimethoxy stupyl, dimethoxytoluene, ethylene glycol, catechol, 1,4·99734-990412.doc - 21- 1328003 Dioxane-2,3-diol, 2-mercaptotetrahydrofuran·3-one, 2,3-dione, 2,4··pentanedione, 3-mercaptotetrahydro" , three stupyl phosphines, and the like. The homogeneous catalyst system is a quasi-equilibrium mixture of various organotin species. Suitable catalysts of this type and methods for their manufacture are described in U.S. Patent Nos. 6, 976, and 6, 392, the entire disclosure of each of which is incorporated herein by reference. The working catalyst system under steady state reaction conditions is a variety of soluble organotin monomers, dimers, and oligomers/buckling compounds produced by a number of possible reactions. The various organotin catalyst species are in a quasi-equilibrium state under certain reaction conditions. Dialkyltin oxide, dialkyltin dentate, dialkyltin bis(ethylmercaptopyruvate) and dialkyltin carboxylic acid (such as dibutyltin diacetate, dihydrogen tin oxalate, malonic acid II) Butyltin, dibutyltin diacetate, dibutyltin bis(ethylmercaptopyruvate), etc. can be used to react with the alcohol at the beginning of the main reactor by the presence of a high boiling solvent such as triethylene glycol dioxime ether. The formation of soluble tin mismatch catalyst species. The alkyl groups attached to the tin atoms may be the same or different. For example, the catalyst precursor may be dibutyltin, butyl-decyltin, butylphenyltin, butyloctyltin or di-2-phenylethyltin di-sinter oxide, dihalide, hydroxyhalide, diacetic acid. Salt or oxide. • The water, carboxylic acid or hydrochloric acid co-product is continuously removed from the liquid reaction medium as a top vapor stream in the presence of a high boiling solvent at low pressure. Suitable temperatures for the catalyst formation reaction range from about 2 Torr to about 4,000 Torr and the pressure is from about ambient pressure to 150 psig. In a preferred embodiment, methanol, ethanol or propanol, depending on the desired bicarbonate product, is pumped into the main reactor. Any of methanol or ethanol is acceptable for the production of MEC. The catalyst formation reaction in the main reactor is advantageously carried out in the presence of a dilute amine alkyl phthalate, an amino carboxylic acid N-alkyl ester alkyl vinegar 99734-990412.doc -22 1328003. It should be understood that in the 傕〇i? ^ ^ . '' ° fine work should be allowed to use the co-product water, carboxy or bismuth telluride as the top stream with the alcohol ^ ^ ^ ^ ^ ^ ^ wild 丨 顶部 顶部 顶部 顶部 顶部 自 自Action under removal conditions. For the production of dimethyl sulphate, the soluble organotin mis-synthesis catalyst system simply combines dibutyltin dimethoxide with two in the presence of a high stagnation solvent in the main reaction prior to initiating the formation of the alkyl carbonate. Ethylene glycol dimethyl _ (used as a binder for the formation of an organotin mis-coupling catalyst) and methanol are mixed to form. For the production of ethylene carbonate, the soluble organotin mismatch catalyst system is preferably formed by the use of dibutyltin dimethoxide and triethylene glycol dimethyl ether and ethanol in the main reactor. As the reaction proceeds, the methoxy group on the catalyst is replaced with an ethoxy group. Referring now to Figure 1 ', a simplified flow diagram of an embodiment of the present invention is shown. Figure 1 illustrates a flow chart of an improved method of removing a DMC separation unit. Let the unit be illustrated in Figure 2. The reaction/distillation column reactor lu is used as a pre-reactor to remove impurities in the feed stream and for partial conversion of urea to methyl carbamate. A urea solution is prepared by mixing urea feed i with methanol stream 3 in a rotary drum. The sterol stream comprises a fresh methanol feed stream 2 and a methanol recycle stream 4 as part of the methanol recycle stream 3 from the DMC separation unit. The methanol recycle stream 30 from the DMc separation unit (shown in Figure 2) is divided into three streams (via 31 of 4 and 33' and 32) for the preparation of the urea solution, the main reactor 112 and the purge reactor 113. . The urea solution feed 5 from the drum 131 is introduced into the middle of the narrow column section at the top of the double diameter column reactor 111. The reaction is used as a pre-reactor to remove impurities (water and ammonium aminate) from the sterol and urea feeds and to convert the urea fraction to MC. Vapor flow from pre-reactor 1 99 99734-990412.doc • 23· 1328003 6 Contains ammonia, carbon dioxide and sterols. The removed sterol*2M (: and urea mixed solution is removed from the pre-reactor 作为 as bottoms 7 and combined with the recycle liquid stream 22 from the cooling/filtration system 133 via line 20 to stream 8. The liquid recycle stream 20 of the cooling/filtration system 133 is split into two streams (21 and 22) for recycle to the main reactor 112 and the purge reactor 113. The combined stream 8 is introduced into the main reactor (stirred tank reactor or Optionally, bubble column reactor) 112. The recycle methanol stream 33 from the DMC separation unit is introduced as superheated methanol vapor into the main reactor 112. The recycle stream 14 from the top of the flash column 132 is introduced into the main reactor. Stream 14 mainly comprises MC and a small amount of N-MMC and methanol. The top vapor stream 9 of the autoreactor 112 comprises ammonia, C〇2, dimethyl ether, decyl alcohol, DMC 'methyl carbonate (MC) 'N-MMC 'Triglycol (tg) and a small amount of organotin catalyst. The overhead stream 9 of the autoreactor 112 is combined with the overhead stream 17 of the purge scavenger reactor 113 to form a stream 1 . Stream 17 comprises ammonia, C 2 Dimethyl ether, methanol and DMC. The combined logistics 1〇 is introduced into the steaming tower 1 5 1 separates component oxygen, C〇2, dimercaptopurine, decyl alcohol and DMC from the remaining comparative components in the stream. The top stream 1 2 from the column 15 and the prereactor reactor 111 The overhead stream 6 is combined into a stream 23. The combined stream 23 is introduced to a vapor deuterate 134. The overhead stream 25 from the column 134 is sent to the urethane removal system 135, wherein the stream 25 is suitably cooled to provide CO2 and ammonia. The reaction produces ammonium amide and precipitates the solid ammonium amide. The ammonium amine amide can be removed by the ammonium amide ammonium removal system 135 using a filter or hydrocyclone via stream 26. The stream 27 of the ammonium formate removal system 135 is introduced into the distillation column 136 to recover ammonia. The overhead stream 28 from the column 136 is sent to the ammonia storage tank. The bottom stream 29 from the column 136 is primarily comprising dimethyl ether 99734. -990412.doc • 24 · 1328003 organic waste. The bottom stream 24 from the column 134 is sent to the DMC separation unit shown in Figure 2. The stream 24 contains DMC and methanol. The bottom stream 13 from the column 151 is sent to the flash. Steam column 132. Stream 13 comprises methanol, MC, N-MMC, TG and a small amount of catalyst. The bottom stream 15 of 132 comprises N-MMC, MC (small amount), TG and a small amount of organotin catalyst. Stream 15 is combined with a small amount of liquid slip stream η of the autoreactor 112 into stream 16. The combined stream 16 is introduced into the purge reactor 113. (As appropriate, a small amount of liquid slipstream 11 of the autoreactor 1丨2 can be introduced into the lower section of either of the columns 15 1 or 132). The self-cleaning. The bottom stream of the reactor 113 is cooled 1 8 to cool the temple. a heterocyclic compound such as iso-cyanuric acid, 1,3,5-trimethyltris-trimethyl, 2,6,6-trione, etc. in the stream and moving the precipitate as a solid from the transition system 13 3 via line 19. except. The liquid filtration stream 2 from the filtration system 13 is divided into two streams 2 and 22 to be recycled back to the main reactor 112 and the purge reactor ι13. The main reactor can be used as a single-return tank reactor 5| or a stirred tank reactor system, for example, if the main reactor contains a series of three stirred tank reactors, then the pre-reactor The 1 1 1 purged aminocarboxylic acid brewing/urea feed stream 7 is suitably divided into three streams and each stream is introduced directly into the three reactors. The liquid reaction stream was withdrawn from each reactor and introduced into the next reactor. The liquid reaction stream from the third reactor is sent to the first reactor. A small amount of slip stream from the third reaction liquid reaction stream is combined with the bottom stream 1 5 from the column 13 to stream 16, which is sent to purge reactor n3. The alcohol recycle stream, such as the sterol recycle stream 33 from the DMC separation unit, is introduced into the first reactor as superheated alcohol vapor. The vapor stream from the top of the first stirred tank reactor is introduced into the first reactor. The vapor stream from the top of the first reactor is introduced into a third reactor 99734-990412.doc -25·1328003. As the vapor stream moves from the first reactor to the third reactor, the amount of dialkyl carbonate in the overhead stream from each reactor gradually increases, resulting in the highest concentration of DMC in the overhead stream from the third reactor. The overhead stream 9 from the third reactor is combined with the overhead stream 17 of the gas/gastric reactor 113 into a stream 10 which is introduced into a distillation column 151. The bottom stream 24 from the distillation column 134 is sent to the DMC separation unit (see Figure 2). This stream contains about 28 wt.% DMC. Stream 24 from column 134 is introduced into extractive distillation column 137 via line 34. The top stream 35 containing about 98 wt% methanol and about 2 wt.% DMC is shown in the figure! The pipeline is recirculated. The bottoms stream 36 is introduced into the extraction solvent recycle column 13 and the extraction solvent anisole is recovered as a bottoms stream 38 from the column 13 8 and recycled back to the column 137 via line 38. From the top stream 37 of the column 138 is a *DMC, which is sent to £); (: in a storage tank. Ethylene carbonate (DEC) can be produced in a similar manner as described above for the production of DMC. The mixture of dec does not form an azeotrope, and the separation of DEC from ethanol can be carried out by single distillation. Figure 3 illustrates a simplified flow chart of the process for producing DEC by mixing urea feed 1〇1 and ethanol in drum 141. A urea solution is prepared by flowing 1 to 3. The ethanol stream 103 comprises fresh ethanol feed ι 2 and an ethanol recycle stream 155 as part of the ethanol recycle stream ι3. The ethanol recycle stream 13 〇 is contained from the top of the distillation column 146. Stream 117 and bottoms from distillation column 145 (ethanol recycle column), L 129 ° ethanol recycle stream 130 is split into two streams 1 52 and 156. Stream 152 is recycled to purge reactor 123. The stream 56 is further divided into two streams 155 and 157 for recycling to the drum 141 and the main reactor 122, respectively. Ethanol 99734-990412.doc • 26-1328003 The recycle stream 157 is introduced into the main reactor 122. 141 urea solution l〇4 introduced into the double-diameter column reactor 121 top narrow tube In the middle of the column section, the reactor 121 acts as a pre-reactor to remove impurities (water and amine formate) from the feed (ethanol and urea) and convert the urea fraction to acetamethylene carbonate (EC). The vapor stream 1 〇 5 of the vessel 121 consists of ammonia, carbon dioxide and ethanol. The removed mixed solution is removed from the prereactor 121 as a bottoms stream 1 。 6. The stream 106 is introduced into the main reactor (stirred tank reactor or as appropriate) The bubble column reactor 122. The recycled ethanol stream 157 (which is a major portion of the ethanol recycle stream u) is introduced into the main reactor 122 as superheated ethanol vapor. A small amount of slipstream of the autoreactor 122 108 is combined with the bottoms stream 120 from the DEC recycle column 147 to form stream 1 61 and the combined stream 116 is introduced into the purge reactor 123. The slip stream 1 〇8 is comprised of ethanol, ammonia, diethyl ether, DEC, Ethyl carbamate, ethyl N-ethylamine decanoate, TG, heterocyclic ring such as iso-cyanuric acid, 1,3,5-trimethyltriazine-2,4,6-trione Compound and organotin mismatch catalyst composition. Stream 120 comprises ethanol, amine decanoic acid ethyl ester, N_ethyl Amino phthalate, TG, and a trace amount of catalyst. The overhead stream 160 from the purge reactor 123 comprises ammonia, c.2, diethyl ether, ethanol, and DEC. The bottoms stream 159 from the purge reactor 123 comprises the urethane. Ethyl ester, triethylene glycol dioxime ether, ethyl N-ethyl methacrylate, ethanol, heterocyclic compound and homogenous organotin catalyst. The bottoms stream 159 of reactor 123 is cooled in a cooling/filtration system 148 to precipitate impurities. Ring Compound. The precipitated solid by-product is removed from system 148 via line 124. The liquid stream 125 from system 148 is split into two streams 126 and 127 for recycle to main reactor 122 and purge reactor 123. The top stream 1〇7 of the autoreactor 122 and the top stream 160 of the self-cleaning reactor 123 are 99734-9904I2.doc • 27· 1328003 combined into stream 109. The vapor stream 7 of the autoreactor 122 is composed of ammonia, c〇2, diethyl ether, ethanol, ethyl decanoate, ethyl N-ethylamine decanoate, DEC, TG and trace catalyst. composition. The stream 1〇7 is combined with the overhead stream 160 of the purge reactor 123 to stream 1〇9. The overhead stream 16 contains ammonia, c〇2, diethyl ether, ethanol, and DEC. The combined stream 1〇9 is introduced into distillation column 142. The overhead stream u 管 of the column ι 42 composed of ammonia, c 〇 2, diethyl ether and ethanol is introduced into the distillation column 143. The overhead stream 154 from column 143 is cooled to cause C 〇 2 to react with ammonia to produce ammonium amide ammonium hydride. Ammonium ammonium amide is precipitated in liquid ammonia and removed as a solid via line 115 from a cooling/filtration system. The liquid ammonia stream 116 from the cooling/over-tank system 144 is sent to the ammonia storage tank. The bottom stream 150 from the column 142 is comprised of DEC, ethanol, ethyl urethane, ethyl N-ethyl methacrylate, TG, and a trace amount of catalyst. The stream 丨5〇 is introduced into a distillation column 146 (first ethanol recycle column). The ethanol stream 117 from the top of column 146 is combined with the ethanol bottoms stream 129 from distillation column 14 5 (second ethanol recycle column) to an ethanol recycle stream 13 . The bottom stream ι 8 from the column 146 is introduced into a distillation column 147 (DEC recycle column). The top stream 丨 19 is the product DEC which is sent to the DEC storage tank. The bottom stream 12 of the column 147 is combined with a small amount of slip stream 108 of the autoreactor 122 and the combined stream 161 is introduced.

拌槽清除反應器123中。由氨、C〇2、二乙基醚、乙醇及DEC 組成之頂部物流160經由管線109送至管柱142。自管柱143 之底部物流114送至蒸餾塔145以自物流中之乙醇分離二乙 基醚。頂部醚副產物流128送至醚儲備槽中。自管柱丨45之 底部物流129為乙醇，其經由管線13〇再循環至清除反應器 123及主反應器122。 99734-990412.doc •28- 1328003 藉由使用甲醇及乙醇之適當混合物作為饋料流代替甲醇 或乙醇饋料流至用於製備尿素溶液之轉鼓中來產生混合碳 酸二烷酯（諸如碳酸曱基乙基酯（MEC))。然而，自主反應器 及清除反應器之頂部物流除了包含碳酸甲乙酯（MEC)之外 亦含有一些DMC及DEC。自混合物分離DEC及DMC且在獨 立反應器（未圖示）中進行DEC及DMC至MEC之交換反應。 藉由使用異質鹼催化劑（諸如鹼性形式之沸石、鹼性滑塊石 等）或同質催化劑（諸如IV B族化合物諸如四乙氧化鈦或乙 氧碳酸鹽類）或二烷基錫化合物（諸如烷醇鹽、二烷基甲氧基 碳酸烷酯、碳酸二烷基錫）或上文所述之有機錫錯合催化劑 系統在存在或不存在溶劑之狀況下執行該交換反應。適當 溶劑將具有高於約265°F之沸點。此一溶劑之實例為烴類， 諸如十氫萘、癸烷、二曱苯、二乙二醇二甲醚、三乙二醇 二曱醚等，或此等之混合物。 圖4說明使用鹼性異質催化劑之反應/蒸餾管柱反應器。 DEC饋料經由管線22 1於催化劑床頂部區段之位置引入反 應/蒸餾管柱反應器153中。DMC饋料經由管線222於催化劑 床下部之位置引入153中。頂部物流223主要包含DMC及 MEC。物流223送至MEC分離單元。液體催化反應區之溫度 維持在約200至約450°F，較佳235至380°F之範圍内。為防 止重物形成於管柱反應器153之再煮器中，經由管線224提 取少量底部產物。 圖5說明具有附加蒸餾塔162之催化攪拌槽反應器158。使 用同質催化劑，諸如二曱氧化二丁基錫。將預定量之同質 99734-990412.doc -29- 1328003 催化劑在進行反應之前注入反應器158中。混合之 DEC/DMC饋料經由管線301引入反應器158。自162之頂部 物流303主要包含DMC且少量MEC再循環回反應器158。自 蒸餾塔162之濃縮有MEC之側取管柱流302送至蒸餾塔163 中以自DMC中分離MEC。自管柱163之頂部物流304再循環 回反應器158。自管柱163之底部MEC流305送至MEC儲備 槽。液體催化反應區之溫度维持在約200至約450eF，較佳 235至380°F之範圍内。管柱162頂部壓力之範圍為約2〇 psig 至約150 psig，較佳為約25至約12〇 psig。但管柱162之頂部 壓力藉由158中液體反應介質之所要溫度、反應介質之組合 物及是否使用溶劑來確定。 實例1 在該實例中進行水與尿素之反應。將下列物質注入一配 備有磁力攪拌器及水冷卻回流冷凝器之500 ml三頸燒瓶 中：229.67克三乙二醇二曱基醚（三乙二醇二曱醚）、158克 水、2.06克曱醇及15.89克尿素。當燒瓶中混合物之反應溫 度達到約100°C時，添加3.2克額外之曱醇。水與尿素之反 應在氮氣層下於128至140°C溫度下進行0.92小時。藉由GC 及HPLC對取自燒瓶之樣品進行分析。分析結果顯示尿素 22.4°/。轉化且水45.2%轉化。 實例2 實驗之概述 一升授拌向壓爸用作反應/蒸德管柱反應器之反應區及 再煮器’其連接至！英吋直徑x3 5英尺長之蒸餾塔❶蒸餾塔 99734-9904l2.doc 30· 1328003 具有可獨立控制之三個區加熱器。將自蒸餾塔之頂部蒸氣 流以氮氣流（800 cc/min)稀釋且隨後以冷凝器中之熱水部 分冷卻至約200T。將自冷凝器之蒸氣流冷卻至周圍溫度以 防止冷卻點及頂部背壓調節器之堵塞問題。自冷凝器之液 體流流至一較小的頂部液體回流轉鼓。液體回流轉鼓之溫 度維持在周圍溫度下。以LFM(液體流動儀）監測自頂部回流 轉鼓之液體產物之流動《自頂部回流轉鼓之液體流及冷卻 洛氣流組合為自反應/蒸餾反應器之產物流。樣品用於分析 以確定來自管柱之頂部蒸氣流之組合物。偶爾亦自再煮器 提取樣品以監測液體反應介質之組合物。一旦自再煮器提 取樣品’則泵入補充溶液以補償三乙二醇二甲醚及催化劑 之損失。在反應器自操作中，再煮器内液體含量維持在恆 定含量。一垂直視鏡附於再煮器用於視覺觀察操作中再煮 器内之液體含量。再煮器亦配備液體含量數位監測器用於 夜間及週末無人照看操作中的反應器之自動控制。 為進行主反應裔之操作以產生DMC，泵入MC饋料溶液 (甲醇中之胺基曱酸曱酯）及甲醇饋料且組合為單流。組合之 饋料流在300°F及230 psig下通過預反應器（垂直安裝之管 狀反應器上流）以移除饋料流中之水且隨後引入主反應器 中。藉由㈣蒸料之頂部壓力及蒸德塔再煮器中高沸點 溶劑之濃度來控制液體反應介質之溫度。產物DMC、氨及 其它輕副產物（諸如二甲基謎及c〇2)自液體介質中煮彿出 且隨甲醇蒸氣除去。以非f知模式進行蒸料柱之操作以 實現來自再煮器中液體介質之蒸氣之部分濃縮而無需藉由 99734-990412.doc 丄⑽υϋ3 控制瘵氣溫度來使自頂部回流轉鼓之液體回流，其藉由以 一個官柱區加熱器控制管柱之區溫度來進行，而蒸氣上升 至瘵餾塔之上部。吾人發現，非習知管柱操作保持三乙二 醇一甲醚溶劑處於反應器中且將副產物N_MMC連同作 為頂》p物流之一部分自液體反應介質中連續移除，其允許 在—延長之時期内操作反應器。吾人發現，高度要求無自 頂=卩回流轉鼓之液體回流以使副產物N_MMC及雜環化合 物之形成最小化。可不中斷地操作反應/蒸餾管柱反應器 1000小時以上直至再煮器之高壓氮氣閥偶然打開。因為由 於諸如N-MMC、三聚氰酸及τττ(1，3,5-三曱基三嗪_2,4,6_ 二_)等反應副產物之積聚所引起的再煮器之溢出，以習知 方式操作蒸餾塔導致物質自再煮器斷開或移除。 0The tank is purged from the reactor 123. A top stream 160 consisting of ammonia, C?2, diethyl ether, ethanol, and DEC is sent via line 109 to column 142. The bottom stream 114 from column 143 is sent to distillation column 145 to separate the diethyl ether from the ethanol in the stream. The overhead ether by-product stream 128 is sent to an ether storage tank. The bottom stream 129 from the column 45 is ethanol which is recycled via line 13 to the purge reactor 123 and the main reactor 122. 99734-990412.doc • 28- 1328003 to produce mixed dialkyl carbonates (such as cesium carbonate) by using a suitable mixture of methanol and ethanol as a feed stream instead of a methanol or ethanol feed to a drum for preparing a urea solution. Ethyl ethyl ester (MEC)). However, the top stream of the autoreactor and purge reactors also contains some DMC and DEC in addition to ethyl methyl carbonate (MEC). The DEC and DMC were separated from the mixture and the exchange reaction of DEC and DMC to MEC was carried out in a separate reactor (not shown). By using a heterogeneous base catalyst (such as a basic form of zeolite, alkaline talc, etc.) or a homogeneous catalyst (such as a Group IV B compound such as titanium tetraethoxide or oxycarbonate) or a dialkyl tin compound (such as The alkyl alkoxide, dialkyl methoxyalkyl carbonate, dialkyltin carbonate) or the organotin mismatch catalyst system described above is subjected to the exchange reaction in the presence or absence of a solvent. A suitable solvent will have a boiling point above about 265 °F. Examples of such a solvent are hydrocarbons such as decalin, decane, diphenylbenzene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like, or mixtures thereof. Figure 4 illustrates a reaction/distillation column reactor using a basic heterogeneous catalyst. The DEC feed is introduced into the reaction/distillation column reactor 153 via line 22 1 at the top of the catalyst bed section. The DMC feed is introduced into 153 via line 222 at a location below the catalyst bed. The overhead stream 223 mainly comprises DMC and MEC. Stream 223 is sent to the MEC separation unit. The temperature of the liquid catalytic reaction zone is maintained in the range of from about 200 to about 450 °F, preferably from 235 to 380 °F. To prevent heavy objects from forming in the re-cooker of column reactor 153, a small amount of bottoms is extracted via line 224. FIG. 5 illustrates a catalytic stirred tank reactor 158 having an additional distillation column 162. A homogeneous catalyst such as dibutyltin dioxide is used. A predetermined amount of homogenous 99734-990412.doc -29-1328003 catalyst is injected into reactor 158 prior to carrying out the reaction. The mixed DEC/DMC feed is introduced to reactor 158 via line 301. From the top of 162 stream 303 primarily contains DMC and a small amount of MEC is recycled back to reactor 158. The side stream of the MEC from the distillation column 162 is sent to the distillation column 163 to separate the MEC from the DMC. The overhead stream 304 from the column 163 is recycled back to the reactor 158. The bottom MEC stream 305 from the column 163 is sent to the MEC storage tank. The temperature of the liquid catalytic reaction zone is maintained in the range of from about 200 to about 450 eF, preferably from 235 to 380 °F. The pressure at the top of the column 162 ranges from about 2 psig to about 150 psig, preferably from about 25 to about 12 psig. However, the top pressure of the column 162 is determined by the desired temperature of the liquid reaction medium in 158, the composition of the reaction medium, and whether or not a solvent is used. Example 1 In this example, the reaction of water with urea was carried out. The following materials were poured into a 500 ml three-necked flask equipped with a magnetic stirrer and a water-cooled reflux condenser: 229.67 g of triethylene glycol didecyl ether (triethylene glycol dioxime ether), 158 g of water, 2.06 g Sterol and 15.89 grams of urea. When the reaction temperature of the mixture in the flask reached about 100 ° C, 3.2 g of additional sterol was added. The reaction of water and urea was carried out under a nitrogen atmosphere at a temperature of from 128 to 140 ° C for 0.92 hours. The samples taken from the flask were analyzed by GC and HPLC. The analysis showed urea 22.4 ° /. Conversion and 45.2% conversion of water. Example 2 Overview of the experiment One liter of the mixing reaction was used as the reaction zone for the reaction/steam column reactor and the re-cooker's connected to! Distillation column distillation column with a diameter of x 3 5 feet long 99734-9904l2.doc 30· 1328003 has three zone heaters that can be independently controlled. The vapor stream from the top of the distillation column was diluted with a stream of nitrogen (800 cc/min) and then cooled to about 200T with the hot water portion of the condenser. The vapor stream from the condenser is cooled to ambient temperature to prevent blockage of the cooling point and top back pressure regulator. The liquid from the condenser flows to a smaller top liquid reflux drum. The temperature of the liquid reflux drum is maintained at ambient temperature. The flow of liquid product from the top reflux drum is monitored by LFM (Liquid Flow Meter). The liquid stream from the top reflux drum and the cooling stream are combined into a product stream from the reaction/distillation reactor. The sample was used for analysis to determine the composition of the vapor stream from the top of the column. Occasionally, samples are taken from the re-cooker to monitor the composition of the liquid reaction medium. Once the sample is taken from the re-cooker, the replenishing solution is pumped to compensate for the loss of triethylene glycol dimethyl ether and the catalyst. In the reactor self-operation, the liquid content in the re-cooker is maintained at a constant level. A vertical view mirror is attached to the re-cooker for visual observation of the liquid content in the re-cooker during operation. The re-cooker is also equipped with a liquid content digital monitor for automatic control of the reactor during nighttime and weekend unattended operation. For the main reactive operation to produce DMC, the MC feed solution (ammonium decyl decanoate in methanol) and the methanol feed were pumped and combined into a single stream. The combined feed stream was passed through a pre-reactor (upper stage tubular reactor upflow) at 300 °F and 230 psig to remove water from the feed stream and subsequently introduced into the main reactor. The temperature of the liquid reaction medium is controlled by (iv) the top pressure of the steam and the concentration of the high boiling solvent in the steam de-cooker. The product DMC, ammonia and other light by-products (such as dimethyl mystery and c〇2) are boiled from the liquid medium and removed with methanol vapor. The operation of the steam column in a non-fusing mode to achieve partial concentration of the vapor from the liquid medium in the re-cooker without the need to control the helium temperature by 99734-990412.doc 10(10)υϋ3 to recirculate the liquid from the top reflux drum It is carried out by controlling the temperature of the column column with a column heater, and the vapor rises to the upper portion of the column. It has been found that the non-conventional column operation maintains the triethylene glycol monomethyl ether solvent in the reactor and continuously removes the by-product N_MMC from the liquid reaction medium as part of the top-p stream, which allows for -prolonged The reactor was operated during the period. It has been found that it is highly desirable to have no reflux of the liquid from the reflux drum to minimize the formation of by-products N_MMC and heterocyclic compounds. The reaction/distillation column reactor can be operated without interruption for more than 1000 hours until the high pressure nitrogen valve of the re-cooker is accidentally opened. Because of the overflow of the re-cooker caused by the accumulation of reaction by-products such as N-MMC, cyanuric acid, and τττ (1,3,5-trimercaptotriazine_2,4,6_di-) Operating the distillation column in a conventional manner causes the material to be disconnected or removed from the re-cooker. 0

3CH3-NH-C-0-CH3 -^ (CH3-NCO)3 + 3CH3OH τττ 使副反應降至最低同時保持可接受之DMC產率之其它重 要因素為平衡溶劑及催化劑之濃度、液體介質之温度及頂 部管柱壓力。用於再煮器溫度及頂部管柱壓力之最佳操作 範圍分別為：約330至約355°F之再煮器溫度及約80至約u〇 psig頂部管柱壓力。 實驗之詳細描述3CH3-NH-C-0-CH3 -^ (CH3-NCO)3 + 3CH3OH τττ Other important factors that minimize side reactions while maintaining acceptable DMC yield are equilibrium solvent and catalyst concentration, temperature of liquid medium And the top column pressure. The optimum operating range for reheater temperature and top column pressure is: reheater temperature of about 330 to about 355 °F and top column pressure of about 80 to about 〇 psig. Detailed description of the experiment

蒸餾塔之再煮器載有下列物質：285克三乙二醇二甲峻、 100克曱醇及100克二曱氧化二丁基錫。在以3_01 mi/min之 固定速率泵入曱醇（約280 ppm H2〇)中之13 3 wt % 2MC 99734-990412.doc •32· 1328003 並以1.92 ml/min之固定速率泵入曱醇（約80 ppm H2O)時， 獲得反應/蒸餾管柱反應器之穩態操作，其中再煮器中液體 反應介質為345°F，蒸餾管柱頂部區段之蒸氣溫度為260 °F 且頂部管柱壓力為90.8 psig。。調整曱醇之流速以維持液 體反應介質之345°F之恆定溫度。再煮器之攪拌速率為300 rpm。在該操作條件下，頂部產物流包含氨、二甲基謎、二 氧化碳、DMC、MC、NMMC、水、未知物及痕量（約1000 ppb) 催化劑。在流時間為926小時時，獲取頂部及底部樣品。此 等樣品之分析列於表1中。反應器液體介質中MC/CH3OH之 莫耳比及基於MC及CH3OH之DMC wt,%分別為1.01及4.49 〜[%，其與美國專利第5,5 61，094號（1996,£乂又〇1^(：1^111)中 所主張之2-10及1-3 wt.%有趣地比較。實驗結果符合優於95 莫耳％之MC至DMC之轉化。該實驗數據用於執行方法設計 之電腦模擬。The re-cooker of the distillation column contained the following materials: 285 g of triethylene glycol dimer, 100 g of sterol and 100 g of dibutyltin dioxide. Pumping 13 3 wt % 2MC 99734-990412.doc • 32· 1328003 in sterol (about 280 ppm H2 〇) at a fixed rate of 3_01 mi/min and pumping sterol at a fixed rate of 1.92 ml/min ( At about 80 ppm H2O), a steady state operation of the reaction/distillation column reactor is obtained, wherein the liquid reaction medium in the re-cooker is 345 °F, the vapor temperature in the top section of the distillation column is 260 °F, and the top column The pressure is 90.8 psig. . The flow rate of the sterol was adjusted to maintain a constant temperature of 345 °F of the liquid reaction medium. The re-cooker has a stirring rate of 300 rpm. Under this operating condition, the overhead product stream contains ammonia, dimethyl mystery, carbon dioxide, DMC, MC, NMMC, water, unknowns, and trace amounts (about 1000 ppb) of catalyst. At the 926 hour flow time, the top and bottom samples were taken. The analysis of these samples is shown in Table 1. The molar ratio of MC/CH3OH in the liquid medium of the reactor and the DMC wt% based on MC and CH3OH are 1.01 and 4.49 to [%, respectively, which are related to U.S. Patent No. 5,5 61,094 (1996, 乂 乂 〇 The 2-10 and 1-3 wt.% claimed in 1^(:1^111) are interestingly compared. The experimental results are in line with the conversion of MC to DMC which is better than 95%. The experimental data is used to implement the method design. Computer simulation.

99734-990412.doc -33- 1328003 表 分析(wt.%) 樣品 頂部(OVHD) 底部(ΒΊ C02 0.10 0.04 nh3 0.73 0.00 (ch3)20 0.04 0.00 甲醇 90.45 11.02 DMC 8.15 1.67 MC 0.36 26.17 N-MMC 0.17 1.88 TG 0.00 40.89 未知物 0.01 0.31 TTT 0.00 3.66 水(ppm) 87 - Sn (ppm) 約1 14.3599734-990412.doc -33- 1328003 Table Analysis (wt.%) Sample Top (OVHD) Bottom (ΒΊ C02 0.10 0.04 nh3 0.73 0.00 (ch3)20 0.04 0.00 Methanol 90.45 11.02 DMC 8.15 1.67 MC 0.36 26.17 N-MMC 0.17 1.88 TG 0.00 40.89 Unknown 0.01 0.31 TTT 0.00 3.66 Water (ppm) 87 - Sn (ppm) Approx. 1 14.35

*作為二曱氧化二丁基錫 實例3 具有蒸餾塔之一升攪拌反應器（高壓釜）用於移除甲醇中 之8.03 wt.%尿素溶液中之雜質且將尿素轉化為胺基曱酸甲 酯。無催化劑注入反應器中。實驗在200 psig於315 °F下及 在23 0 psig於328°F下藉由以具有2 ml/min之恒定底部流速 之4 ml/min持續27小時及具有1.5 ml/min之恆定底部流速之 3 ml/min至運行之最後（流時間為146小時）將尿素溶液泵入 至反應器中來進行。蒸餾塔以頂部回流操作。在操作中， 調整頂部物流以維持高壓釜中恆定液體含量（全部含量之 99734-990412.doc •34- 1328003 50%)。以自頂部回流轉鼓之頂部回流進行管柱操作。自高 壓爸之底部物流中2MC濃度平均為約2〇%，其符合尿素至 MC約97%之轉化。尿素饋料含有約2刚ppm之水。底部產 物在315 F下平均含有375 ppm之水而在328卞下平均含有 300 ppm之水。 實例4 該實驗之目的係例示包含多個反應器之主反應器系統。 φ 使用與實例2相同的實驗設置來例示第二主反應器之效 能。以類似於實驗2之方式進行該實驗。本實例與實例2之 不同之處在於此實例中使用甲醇中之8 wt·%之DMC溶液代 替貫驗2中之純甲醇且本蒸餾塔中之頂部壓力稍低（88 P si g)。蒸德4•之再煮器載有下列物質：285克三乙二醇二甲 醚、40克甲醇及100克二甲氧化二丁基錫。當將1^[(：溶液及 DMC-曱醇溶液泵入至反應器時獲得蒸餾塔反應器之穩態 操作。在再煮器中液體反應介質為345°F '蒸餾塔溫度為約 • 278 F且頂部管柱壓力為88 psig下’反應器操作無中斷持續*as dibutyltin dioxide. Example 3 A one-liter stirred reactor (autoclave) having a distillation column was used to remove impurities in a 8.03 wt.% urea solution in methanol and to convert urea into methyl decanoate. No catalyst was injected into the reactor. The experiment was carried out at 200 psig at 315 °F and at 23 psig at 328 °F for 4 hours with a constant bottom flow rate of 2 ml/min for 27 hours and with a constant bottom flow rate of 1.5 ml/min. From 3 ml/min to the end of the run (flow time 146 hours) the urea solution was pumped into the reactor. The distillation column was operated at the top reflux. In operation, the overhead stream is adjusted to maintain a constant liquid content in the autoclave (the total content is 99734-990412.doc • 34-1328003 50%). The column operation was carried out with reflux from the top of the top reflux drum. The 2MC concentration in the bottom stream from the high pressure dad averages about 2%, which is consistent with about 97% conversion of urea to MC. The urea feed contains about 2 ppm water. The bottom product contains an average of 375 ppm water at 315 F and an average of 300 ppm water at 328 Torr. Example 4 The purpose of this experiment is to exemplify a main reactor system comprising a plurality of reactors. φ The same experimental setup as in Example 2 was used to illustrate the effect of the second main reactor. The experiment was carried out in a manner similar to Experiment 2. This example differs from Example 2 in that the 8 wt.% DMC solution in methanol was used in this example to replace pure methanol in Run 2 and the top pressure in the distillation column was slightly lower (88 P si g). The steaming de-cooker contains the following materials: 285 g of triethylene glycol dimethyl ether, 40 g of methanol and 100 g of dibutyltin dimethoxide. The steady state operation of the distillation column reactor is obtained when pumping 1^[(: solution and DMC-sterol solution into the reactor. The liquid reaction medium in the re-cooker is 345 °F 'The distillation column temperature is about 278 F and the top column pressure is 88 psig 'reactor operation without interruption

1500小時以上。自流上時間1428小時至1482小時之54小時 中’反應器之頂部及底部產物之平均組合物列於表2中。在 該時期中，在345卞下，22.5 wt·%之MC溶液（約590 ppm之 H2O)之栗速率固定於1.97 ml/min且8 wt.%之DMC溶液（80 ppm ΚΟ)之泵速率為約3.2 ml/min。反應器液體介質中 MC/CH3OH之莫耳比及基於MC及CH3OH之DMC之wt.%分 別為0_915及6.40 wt.%。實驗之結果符合優於93莫耳％之MC 至DMC之轉化。 99734.990412.doc -35- 表2 樣品 OVHD BTM 分析(Wt.〇/〇) co2 nh3 極微量(tr) 0.89 ； (ch3)2o 0.06 - 甲醇 84.91 13.32 DMC 12.35 2.68 MC 1.41 28.58 N-MMC 0.36 2.28 TG 0 36.55 HC* 0 3.77 催化劑** 水(ppm) 39 12.83 Sn (ppm) 0.6 - 1328003 *HC:異氰酸及1,3,5-三甲基三嗪-2,4,6-三酮 **作為二曱氧化二丁基錫 實例5 該實驗之目的係例示碳酸二乙酯（DEC)之生產。藉由使胺 基甲酸乙酯（EC)與乙醇反應來產生DEC。以類似於實例2之 方法進行該實驗。分別使用乙醇中胺基曱酸乙酯之溶液及 乙醇來代替實例2中之MC溶液及曱醇。蒸餾塔之再煮器載 有下列物質·· 180克三乙二醇二甲醚、100克乙醇及100克二 甲氧化二丁基錫。當以一恆定流速泵入胺基曱酸乙酯（EC) 溶液且調整乙醇泵入速率以維持液體反應介質之恆定溫度 時獲得蒸餾塔反應器之穩態操作。在再煮器液體反應介質 為約345°F、蒸餾塔溫度為約282°F及66 psig之恆定頂部壓 力下，反應器操作以300 rpm之高壓釜攪拌速率無中斷持續 340小時〇 15.3 5 wt. %之EC溶液（約275 ppm H2O)之泵入速率 99734-990412.doc -36- 1328003 固定於2.69 ml/min下且乙醇（約106 ppm H20)之平均泵入速 率為2.36 ml/min。管柱頂部之頂部蒸氣流與氮氣稀釋氣體 (600 cc/min)混合且隨後在水冷卻之冷凝器中冷卻至約 200°F。整個運行之頂部產物之平均組合物及底部產物之組 合物列於表3中。74.2克固體物質在最後運行時自反應器移 除，其為雜環化合物之混合物且含有以重量計670 ppm之 Sn。表3中底部產物之分析表明反應器中液體介質中 EC/C2H5OH之莫耳比及基於EC及乙醇之DEC wt·%分別為 0.939及11.08 wt.%。整個運行之質量平衡及尿素莫耳平衡 分別為102%及101%。運行結果表明EC 57.5%之轉化及EC 至DEC之91莫耳％之選擇性。實驗結果轉換為1.60 Ib/h/ft3 之DEC空間產率。 表3 樣品 分析(Wt.0/o) OVHD BTM C〇2 tr - nh3 0.50 - 醚 0.02 0.11 乙醇 90.21 17.60 DEC 7.30 5.50 EC 1.74 32.00 N-EEC 0.15 1.75 TG 0.04 21.05 未知物 0.04 9.34 HC1 0.00 0.95 催化劑2 - 11.70 水(ppm) 148 - Sn (ppm) 1.7 - 99734-990412.doc •37· 1 HC:異氰酸及1，3,5-三曱基三嗪-2,4,6·三酮 2 作為二曱氧化二丁基錫 1328003 【圖式簡單說明】 圖1為根據本發明之製備DMC之一實施例之簡化流程圖。 圖2為DMC分離單元之簡化流程圖。 圖3為根據本發明之製備DEC之一實施例之圖示表示。 圖4為本方法之反應/蒸餾管柱反應器實施例之簡化流程 圖。 圖5為本方法之配備有附加蒸餾塔之催化攪拌槽反應器 實施例之簡化流程圖。 【主要元件符號說明】 1 尿素饋料 2 新鮮甲醇饋料流 3 曱醇流 4 甲醇再循環流 5 尿素溶液饋料 6 蒸氣流 7 底部物流 8 組合之物流 9 頂部蒸氣流 1 〇組合之物流 11少量液體滑流 1 2頂部物流 1 3 底部物流 14頂部再循環流 15底部物流 99734-990412.doc .38 - 1328003More than 1500 hours. The average composition of the top and bottom products of the reactor in the 54 hours from the 1428 hours to the 1482 hours of the self-flow time is listed in Table 2. During this period, at 345 Torr, the pump rate of 22.5 wt% of MC solution (about 590 ppm of H2O) was fixed at 1.97 ml/min and 8 wt.% of DMC solution (80 ppm ΚΟ) was About 3.2 ml/min. The molar ratio of MC/CH3OH in the liquid medium of the reactor and the wt.% of DMC based on MC and CH3OH were 0_915 and 6.40 wt.%, respectively. The results of the experiment were in line with the conversion of MC to DMC superior to 93 mol%. 99734.990412.doc -35- Table 2 Sample OVHD BTM analysis (Wt.〇/〇) co2 nh3 very small amount (tr) 0.89 ; (ch3) 2o 0.06 - methanol 84.91 13.32 DMC 12.35 2.68 MC 1.41 28.58 N-MMC 0.36 2.28 TG 0 36.55 HC* 0 3.77 Catalyst ** Water (ppm) 39 12.83 Sn (ppm) 0.6 - 1328003 *HC: Isocyanic acid and 1,3,5-trimethyltriazine-2,4,6-trione** Example 2 as dibutyltin dioxide. The purpose of this experiment is to illustrate the production of diethyl carbonate (DEC). DEC is produced by reacting ethyl carbamate (EC) with ethanol. The experiment was carried out in a manner similar to that of Example 2. The MC solution and sterol in Example 2 were replaced with a solution of ethyl amide in ethyl alcohol and ethanol, respectively. The re-cooker of the distillation column contains the following materials: 180 g of triethylene glycol dimethyl ether, 100 g of ethanol and 100 g of dibutyltin dioxide. Steady state operation of the distillation column reactor is obtained when the amine ruthenate (EC) solution is pumped at a constant flow rate and the ethanol pumping rate is adjusted to maintain a constant temperature of the liquid reaction medium. At a constant top pressure of the re-cooker liquid reaction medium of about 345 °F, distillation column temperature of about 282 °F and 66 psig, the reactor was operated at an autoclave agitation rate of 300 rpm without interruption for 340 hours 〇 15.3 5 wt The pumping rate of % EC solution (about 275 ppm H2O) is 99734-990412.doc -36-1328003 is fixed at 2.69 ml/min and the average pumping rate of ethanol (about 106 ppm H20) is 2.36 ml/min. The top vapor stream at the top of the column was mixed with a nitrogen diluent gas (600 cc/min) and then cooled to about 200 °F in a water cooled condenser. The composition of the average composition and the bottom product of the top product of the entire run is listed in Table 3. 74.2 grams of solid material was removed from the reactor during the final run, which was a mixture of heterocyclic compounds and contained 670 ppm by weight of Sn. Analysis of the bottom product in Table 3 indicates that the molar ratio of EC/C2H5OH in the liquid medium in the reactor and the DEC wt% based on EC and ethanol were 0.939 and 11.08 wt.%, respectively. The mass balance and urea molar balance of the entire operation were 102% and 101%, respectively. The results of the run showed a selectivity of 57.5% for EC and 91% for EC to DEC. The experimental results were converted to a DEC space yield of 1.60 Ib/h/ft3. Table 3 Sample Analysis (Wt.0/o) OVHD BTM C〇2 tr - nh3 0.50 - Ether 0.02 0.11 Ethanol 90.21 17.60 DEC 7.30 5.50 EC 1.74 32.00 N-EEC 0.15 1.75 TG 0.04 21.05 Unknown 0.04 9.34 HC1 0.00 0.95 Catalyst 2 - 11.70 Water (ppm) 148 - Sn (ppm) 1.7 - 99734-990412.doc • 37· 1 HC: Isocyanic acid and 1,3,5-trimethyltriazine-2,4,6·trione 2 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a simplified flow diagram of one embodiment of the preparation of a DMC in accordance with the present invention. Figure 2 is a simplified flow chart of the DMC separation unit. 3 is a pictorial representation of one embodiment of preparing DEC in accordance with the present invention. Figure 4 is a simplified flow diagram of an embodiment of a reaction/distillation column reactor of the present process. Figure 5 is a simplified flow diagram of an embodiment of a catalytic stirred tank reactor equipped with an additional distillation column of the present process. [Main component symbol description] 1 Urea feed 2 Fresh methanol feed stream 3 Sterol flow 4 Methanol recycle stream 5 Urea solution feed 6 Vapor flow 7 Bottom stream 8 Combined stream 9 Top vapour stream 1 〇Combined stream 11 Small liquid slipstream 1 2 top stream 1 3 bottom stream 14 top recycle stream 15 bottom stream 99734-990412.doc .38 - 1328003

16 組合之物流 17 頂部物流 18 底部物流 19 管線 20 液體過滤流、管線 21 物流 22 再循環液體流 23 組合之物流 24 底部物流 25 頂部物流 26 物流 27 物流 28 頂部物流 29 底部物流 30 甲醇再循環流 30 管線 31 物流 32 物流 33 再循環甲醇系統 34 管線 35 頂部物流 36 底部物流 37 頂部物流 38 底部物流、管線 99734-990412.doc -39- 1328003 101尿素饋料 102新鮮乙醇饋料 103乙醇流 104尿素溶液 105蒸氣流 106底部物流 107頂部物流 108少量滑流 109組合之物流、管線 110頂部物流 111反應/蒸餾管柱反應器/預反應器/雙直徑管柱反應器 112主反應器 113清除反應器 114底部物流 115管線 116液體氨流 117頂部乙醇流 11 8底部物流 119頂部物流 120底部物流 121雙直徑管柱反應器、預反應器反應器 122主反應器 123攪拌槽清除反應器 124管線 99734-990412.doc -40- 132800316 Combined stream 17 Top stream 18 Bottom stream 19 Line 20 Liquid filtered stream, line 21 stream 22 Recycled liquid stream 23 Combined stream 24 Bottom stream 25 Top stream 26 Stream 27 Stream 28 Top stream 29 Bottom stream 30 Methanol recycle stream 30 line 31 stream 32 stream 33 recycle methanol system 34 line 35 top stream 36 bottom stream 37 top stream 38 bottom stream, line 99734-990412.doc -39- 1328003 101 urea feed 102 fresh ethanol feed 103 ethanol stream 104 urea Solution 105 vapor stream 106 bottom stream 107 overhead stream 108 minor slip stream 109 combined stream, line 110 top stream 111 reaction / distillation column reactor / pre-reactor / double diameter column reactor 112 main reactor 113 purge reactor 114 bottom stream 115 line 116 liquid ammonia stream 117 top ethanol stream 11 8 bottom stream 119 top stream 120 bottom stream 121 double diameter column reactor, pre-reactor reactor 122 main reactor 123 agitation tank purge reactor 124 line 99734- 990412.doc -40- 1328003

125 液體流 126 物流 127 物流 128 頂部醚副產物流 129 乙醇底部物流 130 乙醇再循環流、 管線 131 轉鼓 132 閃蒸管柱 133 冷卻/過濾系統 134 蒸德塔 135 胺基甲酸銨移除 系統 136 蒸餾塔 137 萃取蒸餾塔 138 萃取溶劑再循環管柱 141 轉鼓 142 蒸餾塔 143 蒸餾塔 144 冷卻/過濾系統 145 蒸餾塔（第二乙醇再循環管柱） 146 蒸餾塔（第一乙醇再循環管柱） 147 蒸餾塔（DEC再揭 i環管柱） 148 冷卻/過濾系統 150 底部物流 151 蒸餾塔 99734-990412.doc 41 1328003 152 物流 153 反應/蒸餾管柱反應器 154 頂部物流 155 乙醇再循環流 156 物流 157 乙醇再循環流 158 催化攪拌槽反應器 159 底部物流 160 頂部物流 161 組合之物流 162 附加蒸德塔 163 蒸餾塔 221 管線 222 管線 223 頂部物流 224 管線 301 管線 302 側取管柱物流 303 頂部物流 304 頂部物流 305 底部MEC流 99734-990412.doc125 Liquid stream 126 Stream 127 Stream 128 Top ether byproduct stream 129 Ethanol bottoms stream 130 Ethanol recycle stream, line 131 drum 132 Flash tube column 133 Cooling/filtration system 134 Steamed Tower 135 Ammonium urethane removal system 136 Distillation column 137 Extractive distillation column 138 Extraction solvent Recirculation column 141 Drum 142 Distillation column 143 Distillation column 144 Cooling / filtration system 145 Distillation column (second ethanol recirculation column) 146 Distillation column (first ethanol recirculation column) 147 Distillation column (DEC re-issued i-ring column) 148 Cooling/filtration system 150 Bottom stream 151 Distillation column 99734-990412.doc 41 1328003 152 Stream 153 Reaction/distillation column reactor 154 Top stream 155 Ethanol recycle stream 156 Stream 157 Ethanol recycle stream 158 Catalytic stirred tank reactor 159 Bottom stream 160 Top stream 161 Combined stream 162 Additional steam tower 163 Distillation column 221 Line 222 Line 223 Top stream 224 Line 301 Line 302 Side take column column 303 Top stream 304 top stream 305 bottom MEC stream 99734-9 90412.doc

Claims (1)

J 申請專利範菌 〜種製備碳酸二烷酯之方法，其包含下列步驟： (a) 將包含尿素、醇、水及胺基甲酸銨之物流饋入至第 反應區； (b) 同時在該操作於溫度與壓力條件下之第一反應區 中， (0使水與尿素反應以形成胺基甲酸銨， (11)使胺基甲酸銨分解為氨及二氧化碳；及 (c) 自該第一反應區移除氨、二氧化碳及醇； (d) 自該第一反應區移除尿素及醇； (e) 將該尿素及醇饋入至第二反應區； (f) 使醇及尿素在包含二烷基烷氧化物之有機錫錯合物 文同貝催化劑之存在下於高沸點溶劑中反應以形成碳酸 〜燒醋，及 (g) 自該第二反應區移除碳酸二烷酯及醇，其中該高沸 •、占办劑之沸點溫度比該碳酸二烷酯之沸點溫度至少高出 2〇卞。 2. ^ 如請求項1之方法，其中醇與尿素在該第一反應區反應以 办成胺基甲酸燒酯。 如凊求項1之方法，其中該醇為<：1-(：3醇》 4’如請求項3之方法，其中該醇為c3醇。 種製備碳酸二甲酯之方法，其包含下列步驟： (a)將含有尿素、甲醇、水及胺基甲酸銨之該物流饋入 至第—反應區/蒸餾區； 99734-990412.doc 1328003 (b) 同時在該第一反應/蒸德區中， (i) 使水與尿素反應以形成胺基曱酸铵， (ii) 使饋料中之胺基甲酸銨及得自水與尿素反應 形成之胺基曱酸銨分解為氨及二氧化碳，及 (111)自尿素且藉由蒸餾分離氨、二氧化碳及曱醇； (c) 將氦、二氧化碳及曱醇作為第一頂部產物自該第一 反應/蒸餾區移除； (d)將尿素及甲醇作為第一底部產物自該第一反應/蒸 餾區移除； (e) 將該第一底部產物及甲醇饋入至第二反應/蒸餾區； (f) 同時在該第二反應/蒸餾區中， (Ο使甲醇與尿素在包含二烷基甲氧化物之有機錫 錯合物的同質催化劑之存在下於高沸點溶劑中 反應以形成碳酸二烷酯，其中該高沸點溶劑之沸 點溫度比該碳酸二烷酯之沸點溫度至少高出 20°F，且J. A method for preparing a dialkyl carbonate, comprising the steps of: (a) feeding a stream comprising urea, an alcohol, water and ammonium amide to a reaction zone; (b) simultaneously Operating in a first reaction zone under temperature and pressure conditions, (0 reacting water with urea to form ammonium urethane, (11) decomposing ammonium amide into ammonia and carbon dioxide; and (c) from the first The reaction zone removes ammonia, carbon dioxide and alcohol; (d) removes urea and alcohol from the first reaction zone; (e) feeds the urea and alcohol to the second reaction zone; (f) contains alcohol and urea An organotin complex of a dialkyl alkoxide is reacted in a high boiling solvent in the presence of a catalyst of the same type to form a carbonate to burned vinegar, and (g) a dialkyl carbonate and an alcohol are removed from the second reaction zone. Wherein the boiling point temperature of the high boiling agent and the agent is at least 2 高 higher than the boiling temperature of the dialkyl carbonate. 2. ^ The method of claim 1, wherein the alcohol and urea react in the first reaction zone The method of claim 1, wherein the alcohol is <: 1- (3) The method of claim 3, wherein the alcohol is a c3 alcohol. The method for preparing dimethyl carbonate comprises the following steps: (a) containing urea, methanol, water, and ammonium urinate The stream is fed to the first reaction zone/distillation zone; 99734-990412.doc 1328003 (b) simultaneously in the first reaction/steaming zone, (i) reacting water with urea to form ammonium amide ammonium citrate (ii) decomposing ammonium amide in the feed and ammonium amide ammonium formed from the reaction of water with urea into ammonia and carbon dioxide, and (111) from urea and separating ammonia, carbon dioxide and sterol by distillation. (c) removing ruthenium, carbon dioxide and decyl alcohol as the first top product from the first reaction/distillation zone; (d) removing urea and methanol as the first bottoms product from the first reaction/distillation zone; (e) feeding the first bottom product and methanol to the second reaction/distillation zone; (f) simultaneously in the second reaction/distillation zone, (make methanol and urea contain dialkyl methoxide The organotin complex is reacted in a high boiling solvent in the presence of a homogenous catalyst to form a carbonic acid An alkyl ester wherein the boiling point temperature of the high boiling solvent is at least 20 °F higher than the boiling temperature of the dialkyl carbonate, and 應/蒸餾區移除；且Should be removed from the distillation zone; 物中之碳酸二甲酯自曱醇分離。The dimethyl carbonate in the product was separated from decyl alcohol. 邵產物中。 99734-990412.doc 8. 如:求項5之方法，其中濃縮該第一頂部產物中之甲醇且 使*>亥/農縮之甲醇之一部分作為回流返回至接近該第一反 應/蒸餘區之頂部，且該濃縮甲醇之殘餘部分返回至該第 一反應/蒸館區之較低區段。 9·如請求項5之方法，其中將該第二底部產物之第—部分饋 入該第—反應/蒸餾區’將該第二底部產物之第二部 循環至該第二反應/蒸餾區且將該第二底部產物之第三部 分饋入第三蒸餾管柱反應器中用於催化劑再生及重物清 除。 ’月 10. 如請求項5之方法，其中濃縮該第二頂部產物且使該濃縮 之第二頂部產物之一部分以回流返回至該第二反應/蒸餾 1¾ 〇 11. 一種用於生產碳酸二曱酯之方法，其包含下列步驟： (a) 將含有尿素、甲醇、水及胺基甲酸銨之物流饋入至 第一蒸餾管柱反應器中； (b) 同時在該第一蒸餾管柱反應器中， (i)使該尿素之一部分與該甲醇之一部分反應以 產生胺基曱酸甲酯， (11)使水與尿素反應以形成胺基甲酸銨， (iii) 使饋料中之胺基甲酸銨及得自水與尿素反應 而產生之胺基甲酸銨分解為氨及二氧化碳，且 (iv) 藉由蒸餾自尿素及胺基甲酸甲酯分離氨、二氧 化碳及甲醇； (c) 將氨、二氧化碳及甲醇作為第一頂部產物自該第一 99734-990412.doc 1328003 蒸餾管枉反應器中移除； (d) 將尿素及胺基甲酸曱酯作為第一底部產物自該蒸餾 管柱反應器中移除； (e) 將該第一底部產物及曱醇饋入至第二蒸餾管枉反應 器中； (f) 同時在該第二蒸鶴管柱反應器中， ⑴使曱醇與尿素在包含二院基曱氧化物之有機錫 錯合物的同質催化劑之存在下於高沸點溶劑中 反應以形成碳酸二曱酯，其中該高沸點溶劑之沸· 點溫度比該碳酸二烷酯之沸點溫度至少高出 20°F，且 (Π)藉由蒸餾自該同質催化劑中分離碳酸二甲酯及 氨； ⑷將碳酸二甲醋及甲醇作為第二頂部產物自該第二蒸 德管柱反應器中移除； ⑻將均質催化劑作為第二底部產物自該第二蒸顧管柱 反應器中移除； ⑴藉由萃取蒸餾法自該 酸二甲酉旨；且 頂4產物中之甲醇分離碳 (j )將s亥第一底部產物之第一部分 柱反應器中； 饋入至該第一茱 鶴管 化 ⑻將該第二底部產物之第二部分“至其 劑且清除重物之第三蒸顧管柱反應器中；i 催 (1 )使δ亥第—底部產物之笛一 八κ / 之第二部分再猶環至該第二蒸館 99734-990412.doc 1328003 管柱反應器中。 12. —種藉由包含具有作為雜質之水及碳酸銨之尿素及醇的 反應物之反應而製備碳酸二坑酯之方法，其包含下列步 驟： (a) 將包含尿素及醇之反應物饋入至主反應區中； (b) 將有機錫化合物及高沸點溶劑饋入至該主反鹿區 中；且 (c) 同時在該主反應區中 (i) 使醇與尿素在該有機錫化合物及該高沸點溶劑 之存在下反應以產生碳酸二烷酯；且 (ii) 將該碳酸二烷酯及氨作為蒸氣自該主反應區中 移除’其中該高沸點溶劑之沸點溫度比該碳酸二 烷酯之沸點溫度至少高出20卞， 其中改良包含在主反應區之前之預備反應區，其用於 自該等反應物移除水及胺基甲酸銨，其係藉由首先在使 該水與尿素反應以形成胺基曱酸銨並使胺基曱酸銨分解 為氨及二氧化碳之條件下饋入該等反應物’且在於步驟（a) 中饋入反應物之前自該等反應物移除該氨及二氧化碳。 13. 如請求項12之方法，其中該預備反應區之該溫度為液相 中200至3 80°F之範圍内之溫度。 14. 如請求項13之方法，其中該預備反應區之該溫度在25〇至 350°F之範圍内。 15. 如請求項12之方法’其中在該預備反應區中該醇饋料之 一部分與該尿素饋料之一部分反應以形成胺基甲酸烷 99734-990412,doc 1328003 16. 17. 18. 19, 20. 21. 22. 23. 24. 酯。 如請求項12之方法，其中該預備反應區及主反應區在蒸 餾條件下操作。 如請求項12之方法，其中藉由使水與尿素反應以形成胺 基甲酸錄而胺基曱酸銨分解為氨及二氧化碳而將該水自 饋料中移除。 如請求項17之方法’其中該預備反應區之該溫度為液相 中200至380T之範圍内之溫度。 如請求項12之方法，其中該等胺基甲酸銨藉由分解為氨 及二氧化碳而自該等饋料中移除。 如明求項19之方法，其中該預備反應區之該溫度為液相 中200至380下之範圍内之溫度。 如凊求項12之方法，其中該高沸點溶劑包含四乙二醇二 曱基醚、一乙二醇二甲基醚及三乙二醇二甲基醚中之至 少一種。 如清求項12之方法，其中該醇包含甲醇及乙醇中之至少 一種。 如π求項12之方法，其中該醇包含甲醇且該石炭酸二烧酯 包含碳酸二甲酯。 如請求項12之方法，其中該醇包含乙醇且該碳酸二烷酯 包含碳酸二乙酯。 99734-990412.docIn the Shao product. 99734-990412.doc 8. The method of claim 5, wherein the methanol in the first top product is concentrated and one part of the methanol is returned as reflux to the first reaction/steaming At the top of the zone, and the remainder of the concentrated methanol is returned to the lower section of the first reaction/steam zone. 9. The method of claim 5, wherein the second portion of the second bottom product is fed to the first reaction/distillation zone to recycle the second portion of the second bottom product to the second reaction/distillation zone A third portion of the second bottoms product is fed to a third distillation column reactor for catalyst regeneration and heavy material removal. The method of claim 5, wherein the second top product is concentrated and a portion of the concentrated second top product is returned to the second reaction/distillation by reflux. 11. A method for producing bismuth carbonate An ester method comprising the steps of: (a) feeding a stream comprising urea, methanol, water, and ammonium urinate to a first distillation column reactor; (b) simultaneously reacting in the first distillation column (i) reacting a portion of the urea with a portion of the methanol to produce methyl amino decanoate, (11) reacting water with urea to form ammonium urethane, (iii) making an amine in the feed Ammonium formate and ammonium amide produced by reaction of water with urea are decomposed into ammonia and carbon dioxide, and (iv) ammonia, carbon dioxide and methanol are separated by distillation from urea and methyl carbamate; (c) ammonia , carbon dioxide and methanol as the first top product are removed from the first 99734-990412.doc 1328003 distillation tube reactor; (d) urea and guanidinium carbamate as the first bottom product from the distillation column reaction Removed from the device; (e) will The first bottom product and the sterol are fed to the second distillation tube reactor; (f) simultaneously in the second steaming column reactor, (1) the sterol and the urea are contained in the second hospital based cerium oxide The organotin complex is reacted in a high boiling solvent in the presence of a homogenous catalyst to form dinonyl carbonate, wherein the boiling point temperature of the high boiling solvent is at least 20 °F higher than the boiling temperature of the dialkyl carbonate, And (Π) separating dimethyl carbonate and ammonia from the homogenous catalyst by distillation; (4) removing dimethyl carbonate and methanol as the second top product from the second steam column reactor; (8) homogenizing The catalyst is removed from the second vapor column reactor as a second bottom product; (1) by extractive distillation from the acid dimethyl hydrazine; and the methanol in the top 4 product is separated from carbon (j) a first portion of the bottom product in the column reactor; fed to the first hydrazine tube (8) to the second portion of the second bottom product "to the agent and to remove the heavy material in the third vapor column reactor ;i reminder (1) to make δ Haidi - the bottom of the product of a flute The eighth κ / second part is re-circulated to the second steaming station 99734-990412.doc 1328003 in the column reactor. 12. a reactant comprising urea and alcohol having water as an impurity and ammonium carbonate A method for preparing dipoxy carbonate by the reaction comprising the steps of: (a) feeding a reactant comprising urea and an alcohol into the main reaction zone; (b) feeding the organotin compound and the high boiling solvent to the And (c) simultaneously reacting the alcohol with urea in the presence of the organotin compound and the high boiling solvent to produce a dialkyl carbonate in the main reaction zone; and (ii) The dialkyl carbonate and ammonia are removed from the main reaction zone as a vapor wherein the boiling point temperature of the high boiling solvent is at least 20 Torr higher than the boiling temperature of the dialkyl carbonate, wherein the improvement is included before the main reaction zone. a preliminary reaction zone for removing water and ammonium aminate from the reactants by first reacting the water with urea to form ammonium amide ammonium and decomposing ammonium ammonium citrate into ammonia And feeding the reactants under the conditions of carbon dioxide And wherein step (a) is fed from these reactants before removing the carbon dioxide and ammonia reactant. 13. The method of claim 12, wherein the temperature of the preliminary reaction zone is a temperature in the range of from 200 to 380 °F in the liquid phase. 14. The method of claim 13, wherein the temperature of the preliminary reaction zone is in the range of 25 〇 to 350 °F. 15. The method of claim 12, wherein a portion of the alcohol feed in the preliminary reaction zone partially reacts with a portion of the urea feed to form an alkyl carbamate 99734-990412, doc 1328003 16. 17. 18. 19, 20. 21. 22. 23. 24. Esters. The method of claim 12, wherein the preliminary reaction zone and the main reaction zone are operated under distillation conditions. The method of claim 12, wherein the water is removed from the feed by reacting water with urea to form an amine formate and decomposing ammonium ammonium citrate into ammonia and carbon dioxide. The method of claim 17 wherein the temperature of the preliminary reaction zone is a temperature in the range of from 200 to 380 T in the liquid phase. The method of claim 12, wherein the ammonium urethane is removed from the feed by decomposition into ammonia and carbon dioxide. The method of claim 19, wherein the temperature of the preliminary reaction zone is a temperature in the range of from 200 to 380 in the liquid phase. The method of claim 12, wherein the high boiling point solvent comprises at least one of tetraethylene glycol dimethyl ether, monoethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. The method of claim 12, wherein the alcohol comprises at least one of methanol and ethanol. A method of claim 12, wherein the alcohol comprises methanol and the dicocarbonate comprises dimethyl carbonate. The method of claim 12, wherein the alcohol comprises ethanol and the dialkyl carbonate comprises diethyl carbonate. 99734-990412.doc
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