201139363 六、發明說明： 【發明所屬之技術領域】 本發明係關於碳酸伸乙酯和/或乙二醇之製法。 【先前技術】 碳酸伸乙酯作爲，例如，各式各樣高分子量化合物之 溶劑，用於各式各樣化學反應的化學溶劑、用於鋰離子二 次電池的電解質溶液（電解液）之溶劑、萃取劑、發泡劑 、和潤滑油安定劑。通常，碳酸伸乙酯係藉由令環氧乙烷 與二氧化碳於高溫和高壓反應而合成。因此，碳酸伸乙酯 中含有二醇（包括，例如，源自於用於合成之材料的乙二 醇和二乙二醇）。例如，微小量的水亦與前述雜質含於碳 酸伸乙酯中。此水與碳酸伸乙酯反應而進一步產生乙二醇 0 較佳地，碳酸伸乙酯（其作爲各式各樣類型的溶劑） 不含任何極少量的雜質。各式各樣的方法，其包括，例如 ，蒸餾法和結晶法，曾建議用於純化碳酸伸乙酯之方法。 蒸餾法係工業上最常用的純化法。但是，碳酸伸乙酯 具有246 °c (大氣壓）的高沸點。因此，根據蒸餾法純化 碳酸伸乙酯時，即使於低壓下進行蒸餾，亦會引發任何熱 分解或受損，且碳酸伸乙酯會與二醇和水反應而形成高分 子量化合物。根據本發明者進行的硏究，發現下列事實。 即，高分子量乙二醇化合物的鍵經部分切斷而回到二醇狀 態。因此，即使進行蒸餾，二醇因此仍以約1 00 ppm的量 201139363 留在碳酸伸乙酯中。此外，蒸餾法需要對應於蒸發潛熱或 相關物質之蒸發的能量，此外，亦須提高回流比。因此， 相較於結晶法（其只要藉由移除可察覺的熱而冷卻便足以 實施），消耗的能量極大。 結晶法係純化法，其利用雜質組份（在某些目標組份 結晶的溫度下仍未結晶）未混入晶體中的事實。結晶法得 以藉由僅包括藉冷卻而結晶和藉略爲升溫而溶解的操作而 純化。因此，不易因副反應而引發分解，且消耗的能量小 。此外，日本專利申請公開第2007-284427號揭示施用此 專利文件中所述之結晶法時，可得到具有不低於99.999% 的高純度之碳酸伸乙酯。 但是，當碳酸伸乙酯藉由使用結晶法而純化時，些微 量的有色組份存在於已純化的碳酸伸乙酯中。此有色的組 份引發一些問題，尤其是在應用於須要高純度之供鋰離子 二次電池用的電解液之情況。 根據本發明者進行之硏究，逐漸顯露下列事實。即， 前述有色組份在例如英國專利案第2 0 9 8 9 8 5號和日本專利 申請公開第20〇4-2627 67號的方法中未移除，於此方法中 得到一部分含有觸媒的反應溶液以回收觸媒，於其中添加 水，使得溶液在回收觸媒之後循環回到方法。有色組份留 在待循環至方法的觸媒溶液中，且有色組份於實施連續操 作時被濃縮。 另一方面，已經知道製造乙二醇之方法，其中環氧乙 烷和二氧化碳於高溫和高壓反應而得到供製造碳酸伸乙酯 -6- 201139363 的反應溶液，於其中進一步添加水以引發水解反應，以藉 此製造乙二醇（日本專利公告第55-47617號和日本專利申 請公開第 59-13741 、 2000-128814和 2004-196722號）。於 實施連續操作並循環且使用觸媒時，前述方法引發水解反 應器（反應槽）中的輸出控制閥之類堵塞或阻塞的問題。 【發明內容】 發明總論 本發明的目的係提供用於製造碳酸伸乙酯之方法，其 中移除前述碳酸伸乙酯中所含的有色組份，及提供用於製 造乙二醇之方法，使得以長時間安定地操作且同時防止前 述乙二醇製法中之堵塞或阻塞》 本發明者致力於硏究以達到前述目的，結果發現下列 事實。即，在包含下列步驟之製造碳酸伸乙酯的方法（文 中有時稱爲“EC製法”）中可以製得已經移除有色組份的碳 酸伸乙酯：藉由令二氧化碳和環氧乙烷在觸媒存在下反應 而得到含有碳酸伸乙酯的反應溶液及藉結晶作用純化所製 得的碳酸伸乙酯，該除去有色組份的方法包含萃取一部份 之供製造碳酸伸乙酯的反應溶液（文中有時稱爲“碳酸化 反應溶液（供製造碳酸鹽的反應溶液）”），將不低於溶 於經萃取溶液中的觸媒的20倍重量的水加至經萃取的溶液 中以沉積未溶解的物質，自經萃取的溶液移除經沉積之未 溶解的物質，然後令該溶液循環至方法中。此外，本發明 者發現根據藉由進一步將水加至碳酸化反應溶液（下文中 201139363 有時稱爲“水解步驟”）中之製造乙二醇之方法，在水解步 驟中’不會在反應器（反應槽）的輸出控制閥造成任何堵 塞或阻塞，即使該操作持續進行1年亦然，該方法包含萃 取一部分的碳酸化反應溶液，將不低於溶於經萃取溶液中 的觸媒的2〇倍重量的水加至經萃取的溶液中以沉積未溶解 的物質’自經萃取的溶液移除經沉積之未溶解的物質，然 後令所得溶液循環至方法。藉此而完成本發明。 即，本發明具有下列特徵。 (1) 一種製造碳酸伸乙酯之方法，其包含藉由令二 氧化碳和環氧乙烷在觸媒存在下反應而得到含有碳酸伸乙 酯的反應溶液及藉結晶作用純化所製得的碳酸伸乙酯，該 方法包含自反應溶液萃取含有觸媒的溶液，將不低於溶於 經萃取溶液中的觸媒的2 0倍重量的水加至經萃取的溶液中 以沉積未溶解的物質，自經萃取的溶液移除經沉積之未溶 解的物質，然後令所得溶液循環至反應溶液。 (2) 根據（1)之方法’其中該含有觸媒之溶液係自 用以令二氧化碳與環氧乙烷反應以製造碳酸伸乙酯之反應 器得到之輸出溶液的一部分。 (3) —種製造乙二醇之方法，其包含藉由令二氧化 碳、環氧乙烷和水在觸媒存在下反應而得到含有碳酸伸乙 酯和乙二醇之反應溶液’及藉由進一步將水加至所得的反 應溶液中而將碳酸伸乙酯轉化成乙二醇，該方法包含自反 應溶液萃取含有觸媒的溶液，將不低於溶於經萃取溶液中 的觸媒的20倍重量的水加至經萃取的溶液中以沉積未溶解 201139363 的物質’自經萃取的溶液移除經沉積之未溶解的物 後令所得溶液循環至反應溶液。 (4) 根據（3)之方法，其中該含有觸媒之溶 用以令二氧化碳、環氧乙烷和水反應以製造碳酸伸 乙—·醇之反應器得到之輸出溶液的一部分和/或自 由添加水至所得反應溶液而將碳酸伸乙酯轉化成乙 反應器得到的輸出溶液的一部分。 (5) 根據（1)至（4)中任一者之方法，其 溶解的物質係藉靜態分離、過濾分離、或利用吸附 吸附移除而移除。 (6) 根據（1)至（5)中任一者之方法，其 媒係碘化或溴化四級鐄。 (7) —種碳酸伸乙酯，其有關色度的H azen値 1 0，且其純度不低於9 9.9 9 9 %。 (8 ) —種非水性電解質溶液，其含有（7 )項 之碳酸伸乙酯。 根據本發明，提供用於製造碳酸伸乙酯之方法 碳酸伸乙酯具有高純度，其中之有色組份經移除。 提供用於製造乙二醇之方法，其中該操作得以長時 地進行且未引發任何堵塞或任何阻塞，即使長時間 作亦然。 較佳體系之說明 (1 )關於有色組份 質，然 液係自 乙酯和 用以藉 二醇之 中該未 物質的 中該觸 不超過 所定義 ，其中 此外， 間安定 連續操 -9 201139363 碳酸伸乙酯中所含的有色組份，在根據本發明之用以 製造乙二醇之方法中移除之，其係在以紫外光照射時，會 發出螢光的物質。當以螢光分析在本發明之用於製造碳酸 伸乙酯的方法（包括藉由令二氧化碳和環氧乙烷在觸媒存 在下反應而製造碳酸伸乙酯及藉結晶作用純化製得的碳酸 伸乙酯之步驟）中追蹤到該物質存在來源時，則該物質已 存在於自用以製造環氧乙烷原料的氧化反應器得到的輸出 氣流中，然後，該物質通過環氧乙烷吸收塔和環氧乙烷汽 提塔，且該物質亦含於用於本發明之EC製法中之作爲原料 的環氧乙烷中。在EC製法中，有色組份與觸媒一起循環或 回收至方法中，且有色組份被濃縮。 試圖高純度地回收根據結晶法製得的碳酸伸乙酯時， 濃縮的有色組份以產物形式混入碳酸伸乙酯中，並導致淡 紅色。結構分析的結果中，有色組份係由聚乙二醇、聚乙 烯和芳族化合物所組成的組份所構成。有色組份溶於極性 溶劑（如甲醇之類）中。但在水中的溶解度低。因此，添 加某些量的水時，可沉積（沉澱）和移除該物質。 (2)碳酸伸乙酯之製法 本發明之製造碳酸伸乙酯之方法是包括下列步驟之方 法：藉由令二氧化碳和環氧乙烷在觸媒存在下反應而得到 含有碳酸伸乙酯的反應溶液（文中有時稱爲“供製造碳酸 鹽之反應”）及藉結晶作用純化碳酸伸乙酯。 可用於前述供製造碳酸伸乙酯之反應的觸媒適當地選 -10- 201139363 自已知的可用觸媒，包括，例如，鹼金屬的溴化物或碘化 物（述於，例如，日本專利公告第38-23175號者）、鹼土 金屬的鹵化物（述於，例如，美國專利案第2,667,497號者 )、烷基胺、四級銨鹽（述於，例如，美國專利案第 2,7 73,070號者）、有機錫、鍺或碲化合物（述於，例如， 日本專利申請公開第5 7 - 1 8 3 7 8 4號者）、和鹵化的有機鱗 鹽（述於，例如，日本專利申請公開第58-126884號者） 。特別地，較佳使用鹼金屬或鱗鹽的溴化物或碘化物。較 佳例子包括’例如，碘化鉀、溴化鉀、碘化四級鱗或溴化 四級鱗（例如，碘化三苯基甲基鱗、碘化三苯基丙基鳞、 碘化三苯基苄基鳞、碘化三丁基甲基鱗和彼等的溴化物。 形成鹼金屬碳酸鹽的化合物亦可與鐵鹽倂用。鹼金屬碳酸 鹽在碳酸化反應中抑制除了乙二醇和碳酸伸乙酯以外的任 何副產物之產生。溶解度高的鉀鹽和鹼金屬一樣爲較佳者 。當使用組合觸媒時，較佳的範例可使用日本專利申請公 開第2 0 0 0 - 1 2 8 8.1 4號中所述者。 也可以使用具有高純度的市售環氧乙烷作爲本發明之 碳酸化反應的環氧乙院原料。但是，如Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed., Vol. Al〇, p . 1 1 7中所述者’也可以在純化之後，使用，例如，下文 描述之藉由進行反應而合成得到的產物，其中該反應是使 主要含有乙烯（原料）、氧和甲烷（稀釋氣體）的氣體通 過裝有銀觸媒的多管狀反應器。通常，乙烯轉化爲環氧乙 烷的選擇率約80%。根據完全氧化反應，約20%殘渣轉化 -11 - 201139363 成二氧化碳和水。氧化反應氣體（其自反應器流出 例如，製得的環氧乙烷、未反應的乙烯、碳酸氣、 釋氣體所構成。製得的環氧乙烷被使用水作爲吸收 收塔中之液相所吸收。吸收液所吸收的環氧乙烷在 烷汽提塔中蒸餾或汽提，而環氧乙烷自塔頂以具有 環氧乙烷的水溶液形式回收。此外，在蒸餾塔中進 處理和純化處理。自前述塔頂得到之高濃度環氧乙 溶液亦可直接作爲原料。 可以藉由使用任何專用設備進行碳酸化反應。 泡罩塔（其在中間位置具有配備用於移除熱的熱交 用於循環的幫浦之液體循環導管）用以藉由令塔中 反應溶液經由液體循環導管循環而控制反應溫度。 塔底連續供應環氧乙烷和二氧化碳原料及觸媒，可 行此反應。亦較佳地，使用配備日本專利申請公p 269 1 1 0號揭示之噴射型噴嘴的反應器。反應溫度通 至200°C。但是，反應溫度較佳爲l〇〇°C至17〇°C。 反應壓力通常爲0.6至5.0 MPa。但是，反應壓 爲1.0至3.0 MP a。水可加至本發明的碳酸化反應中 在時，環氧乙烷不僅轉化成碳酸伸乙酯，亦轉化成 。因此，即使二氧化碳的供應量不超過環氧乙烷的 量，亦容易進行反應。二氧化碳相對於環氧乙烷的 耳比通常不超過5，且較佳爲0.5至3.0。 水相對於環氧乙烷的供應莫耳比通常不超過1 〇 佳爲0.5至5.0。此量不足以與泡罩塔中的環氧乙烷 )由， 氧和稀 液的吸 環氧乙 高濃度 行脫水 烷的水 例如， 換機及 含有的 藉由自 連續進 司第1 1- 常是70 力較佳 。水存 乙二醇 等莫耳 供應莫 ，且較 完全反 -12- 201139363 應。因此，亦較佳地，將管狀反應器配置於泡罩塔之後， 使溶液或液體中的環氧乙烷進一步反應。此程序中，觸媒 的添加量以相對於環氧乙烷之莫耳比表示爲1/1000至1/20 ，且較佳爲1 / 2 0 0至1/5 0。碳酸化反應中得到之反應溶液的 一部分可供至下文所述之純化碳酸伸乙酯的純化步驟，且 餘者可較佳地循環至碳酸化反應器，此可藉由在進行下文 所述之用以回收觸媒的操作之後，進行下文所述之移除有 色組份的操作的方式進行。或者，用於回收觸媒的操作和 用於移除有色組份的操作可以在不同的操作中進行。用於 回收觸媒的操作（其用以防止觸媒分解或受損）係例如， 藉，例如，日本專利申請公開第2004-262767、2004-284976和20〇4-292384號中所描述的方法進行。 通常，可以利用藉結晶而自碳酸化反應溶液分離碳酸 伸乙酯之方法，其中藉由冷卻碳酸化反應溶液製得粗製的 碳酸伸乙酯晶體。至於冷卻法，該冷卻可以根據已知方法 進行。特定言之，例如，可以使用日本專利申請公開第7-8 9905號中描述的方法，其中晶體沉積在冷的垂直間隔壁 上，之後溫熱，使得晶體的部分溶化，其向下流動而分離 ，並因此而回收純度提高的晶體。另一方面，也已經知道 對流接觸法作爲連續結晶法（述於，例如，日本專利申請 公開第2007-284427號、英國專利案第1〇86〇28號，和 “Separation Technology” ( The Society of Separation Process Engineers, Japan) , Vol. 35, No.6, pp.45-49 ( 2005 ))。對流接觸法係藉碳酸伸乙酯晶體和液體之間的 -13- 201139363 接觸而提高碳酸伸乙酯純度的方法。 本發明之EC製法中，自反應溶液萃取含有觸媒的溶液 ，之後，將不低於溶於經萃取溶液中的觸媒的20倍重量的 水加至經萃取的溶液中以沉積未溶解的物質。藉由移除經 沉積之未溶解的物質，移除有色組份（文中有時將此操作 稱爲“有色組份移除操作（用以移除有色組份之操作）”） 。含有觸媒的溶液經萃取之處可爲含有待循環的觸媒之溶 液的任何位置。但是，例如，較佳地，萃取在碳酸化反應 器的出口得到的輸出液或液體的一部分。適當地，萃取量 係有色組份不會在此方法中濃縮的量，此因在移除有色組 份之後，溶液或液體再度循環至EC製法之故。萃取量係在 碳酸化反應器出口處得到的輸出溶液的1/5 〇〇至W5 ’且較 佳爲 1/100 至 1/10。 至於加至含有觸媒之經萃取溶液中的水量’須添加沉 積有色組份所須的水量。水的添加量相對於所含觸媒重量 爲不低於20倍重量，較佳不低於50倍重量，且最佳不低於 6 0倍重量。至於最大S，若大量水含於方法中’則最後須 要極大量的能量來移除水。因此’適當地’相對於所含觸 媒重量，最大量是不超過100倍重量且較佳不超過200倍重 量。 前述之經萃取之含有觸媒的溶液亦可連續進行回收觸 媒之操作和移除有色組份之操作。首先’以前述方式自經 萃取之含有觸媒的溶液回收觸媒。回收的觸媒可以此狀態 使用，或者回收的觸媒可溶解，例如，於乙二醇中’以得 •14- 201139363 到可以作爲含有觸媒的溶液用之溶液。亦可於其中添加水 以移除有色組份。此程序所採取之水的添加量亦與前述者 對等。 關於添加水的方法，當觸媒濃度稀薄或低時，不須任 何特殊設備。例如，水管可連接至含觸媒的溶液以便在管 線中混合。另一方面，當觸媒濃度係，例如，40重量％的 高濃度時，在添加水時會使觸媒暫時沉積。因此，較佳地 ，在配備攪拌器的溶解器或槽中進行此操作。有色組份於 添加水之後沉積。因此，藉任何適當的方法分離並移除沉 積的有色組份。特定言之，分離和移除法可爲任何方法包 括，例如，靜態分離、過濾、和吸附移除。靜態分離的情 況中，溶液或液體必須留置足以使有色組份沉澱的一段時 間。溶液或液體靜置之後，較佳靜置不低於0.5小時且更 佳不低於1小時，回收上層清液作爲觸媒溶液。關於進行 靜態分離時所用的設備，例如，使用的設備可爲沉澱器或 槽’其中一般的沉澱器配備輸入管線和輸出管線，該管線 位於相反位置以降低在內部的流動速度。 在過濾分離的情況中，分離係藉由使用一般的過濾設 備或滲濾器而進行。但是，添加水之後，有色組份逐漸聚 集和凝聚，容易過濾。因此，較佳地，就有色組份的過濾 效能觀之，溶液或液體留置較佳不低於5分鐘且更佳不低 於3〇分鐘之後才過濾。關於用於過濾的設備，適當地使用 市售的一般過濾設備或滲濾器。吸附分離中，亦可使用吸 附劑包括，例如，一般的活性碳和沸石。但是，較佳使用 -15- 201139363 棉狀材料包括，例如，玻璃絨、聚丙烯絨、棉和金屬絨， 此因所具有的性質能夠無困難地物理性黏著或吸附有色組 份之故。特定言之，關於所用的設備，例如，令含有觸煤 並如前述地添加了水的溶液或液體通過塡有玻璃絨的吸附 容器或槽，並藉此而能夠令人滿意地移除有色組份。 對於令溶液或液體通過的期間沒有特定限制。當吸收 劑的密度稀薄或低時，須使得溶液緩慢流動。但是，當吸 收劑以緻密方式引入時，吸附處理可於短時間內進行。也 能夠使得在供至吸附容器之前，以一段時間凝聚有色組份 。但是，這兩種效果係藉由使得吸附時間約1 5分鐘至3小 時以同時在吸附容器中進行吸附和凝聚二者的方式實行。 移除有色組份之後得到之含有觸媒的溶液循環至EC製法的 碳酸化反應。含有觸媒的溶液回送的位置可爲任何位置， 只要觸媒於該位置循環即可。該位置包括，例如，碳酸化 反應器的入口、碳酸化反應器的出口、和觸媒分離步驟。 藉本發明之EC製法製造的碳酸伸乙酯不帶顏色且具有 高純度。因此，碳酸伸乙酯較佳可作爲原料，例如，非水 性電解質溶液（電解液）的原料。所謂“不帶顏色”特定指 Hazen値不超過10。Hazen値不超過1〇且純度不低於 99.999%的碳酸伸乙酯及含有該碳酸伸乙酯的非水性電解 質溶液亦含括於本發明中。本發明的非水性電解質溶液含 有電解質和用以藉任何一般非水性電解質溶液相同的方式 溶解彼的非水性溶劑。本發明的非水性電解質溶液含有這 些組份作爲主要成份’其根據一般使用的方法製造。 -16- 201139363 (3 )乙二醇之製法 本發明的另一方面係關於乙二醇之製法，其係基於包 含下列步驟的方法（文中有時稱爲“EG製法”：藉由令二 氧化碳、環氧乙烷和水在觸媒存在下反應而得到含有碳酸 伸乙酯和乙二醇之反應溶液，及藉由進一步將水加至所得 的反應溶液中而將碳酸伸乙酯轉化成乙二醇（水解步驟） ，該方法包含自反應溶液萃取含有觸媒的溶液，將不低於 溶於經萃取溶液中的觸媒的20倍重量的水加至經萃取的溶 液中以沉積未溶解的物質，自經萃取的溶液移除經沉積之 未溶解的物質，然後令所得溶液循環至方法。就另一觀點 ，碳酸伸乙酯的有色組份（於在前述用以製造碳酸伸乙酯 的方法中將被移除）在用以製造碳酸伸乙酯的方法的水解 步驟中造成堵塞或阻塞。因此，當有色組份根據相同或對 等方法移除時，能夠長時間安定地製造乙二醇。 在本發明之製造乙二醇的方法中，藉由令二氧化碳、 環氧乙烷和水在觸媒存在下反應得到含有碳酸伸乙酯和乙 二醇之反應溶液的步驟與前述EC製法相同或對等。碳酸化 反應溶液供至水解步驟。但是’一部分的碳酸伸乙酯可被 分離出並根據適當方法純化。此程序中，純化碳酸伸乙酯 之方法不僅限於前述的結晶法。也可以使用，例如，已知 蒸餾法。當然’根據前述結晶法純化時，可得到不帶顏色 且具有高純度的碳酸伸乙酯。 就反應速度觀點，有利地’水解步驟中，於高溫進行 -17- 201139363 反應。但是，若溫度過高，擔心乙二醇的品質受損。因此 ，通常較佳於1〇〇至180°C進行反應。反應壓力必須在至高 爲溶液或液體之沸點的範圍內。但是，通常較佳於大氣壓 至2.1 MPa的壓力下進行反應。此外，亦較佳地，進行水 解反應時，藉由提高反應溫度和/或降低反應壓力的方式 以有助於水解反應。特定言之，能夠使用，例如，日本專 利申請公開第59-13741和2000-128814號中所述的方法，例 如，有關原料和添加的水量的部份。 根據已知方法，由水解反應製造乙二醇之方法，可得 到乙二醇。通常，水藉蒸餾而分離，較佳地，在減低壓力 下蒸餾以得到粗製的乙二醇，其由，例如，乙二醇、二乙 二醇、其他高沸點組份、和碳酸化反應觸媒所構成。之後 ’欲自乙二醇分離觸媒，將粗製乙二醇供應至蒸發設備。 較大部分的乙二醇和一部分的高沸點組份蒸發並回收以得 到殘餘液體（其由，例如，觸媒、殘留的乙二醇和高沸點 組份所構成）。殘留液體以“觸媒溶液”形式供至前述碳酸 化反應。觸媒回收步驟亦於低壓進行，以有助於乙二醇和 高沸點組份的蒸發或氣化。配備再沸器的設備作爲蒸發設 備’其中補充蒸發所須能量，並控制蒸發量》 本發明之EG製法中，亦自反應溶液萃取含觸媒的溶液 °將不低於溶於經萃取溶液中的觸媒的20倍重量的水加至 經萃取的溶液中以沉積和移除未溶解的物質。之後，溶液 再度循環至方法。此程序中，含有觸媒的溶液可爲任何溶 液或液體，只要含有EG製法中所用的觸媒即可。但是，例 -18- 201139363 如，較佳使用在碳酸化反應器出口處或在水解步驟的反應 溶液處得到的輸出溶液。 在此EG製法中，關於觸媒回收步驟中回收的觸媒，亦 可進行觸媒回收操作以防止觸媒的任何進一步分解，且溶 液（藉由將回收的觸媒溶解於，例如，乙二醇，中而得者 )可以作爲含有觸媒的溶液。此程序中，循環溶液或液體 回送的位置亦包括，例如，碳酸化反應器和水解反應器。 【實施方式】 實例1 :碳酸伸乙酯之製造 (1 )碳酸化反應 藉由將5重量份/時之三丁基甲基碘化鱗、〇. 8重量份/ 時之碳酸鉀和78重量份/時之原料環氧乙烷水溶液（60重 量％ )供應至第一反應器（1 〇 0 °C，以二氧化碳加壓至2.0 MPa )，停留1小時，得到含有碳酸伸乙酯和乙二醇（EG )的碳酸化反應溶液。所得反應溶液以3重量份/時萃取， 於其中添加相對於所含觸媒量爲60倍重量的水。令此溶液 以SV=1通過已有聚丙烯絨（DCM Japan Co·，Ltd.製造）的 吸附器。通過的觸媒溶液具有淡黃色。使用此溶液並循環 至碳酸化反應器。 (2 )碳酸伸乙酯之純化 此操作持續一個月，之後，根據WO 2007/108213中描 述的方法，碳酸伸乙酯自碳酸化反應溶液結晶和純化。特 19- 201139363 定言之，使用日本專利申請公開第6-9 1 1 03號中描述 立型熔化純化設備作爲結晶設備。此純化設備配備攪 。所用的攪拌器配備具有水平攪拌棒的攪拌軸作爲攪 片。縫隙狀觀察孔（觀察孔或視窗，其用以確認晶體 積或沉降）配備於所用結晶設備側面上。 碳酸化反應中得到的反應溶液的一部分藉配備冷 套（述於日本專利申請公開第6-9 1 1 03號）的結晶設 卻至1 7°C。製得含有乙二醇晶體的淤漿，其由前述結 備的晶體供應管供應。晶體在結晶設備中沉降。過量 液以溢流液體形式自結晶器的上部回收，將之循環至 反應器。 晶體沉降，且晶體逐漸累積於塔底。晶體藉加熱 熱以熔化晶體，形成熔融液。此熔融液初時向上移動 時以對流方式與沉降的晶體（回流液體）接觸，熔融 上部萃取管萃出。此溶液經由結晶設備回到水解反應 此時間點，乙二醇未自產物萃取管萃出，在熔融液上 累積的晶體層。自觀察孔觀察累積的晶體層厚度，並 自產物萃取管萃取的S，使得累積的晶體層厚度爲結 備高度的95%。 此操作持續3天，使用氣相層析和卡爾費雪（ Fischer )濕度計評估碳酸伸乙酯產物的品質。結果， 中的乙二醇濃度爲1 ppm，濕氣含量或水含量爲2 ppm 言之，碳酸伸乙酯產物的純度不低於99.999%。至於 ，Hazen値（APHA)不超過 10。 的直 拌器 拌葉 的累 卻護 備冷 晶設 的母 水解 器加 ，同 液自 。於 形成 調整 晶設 Karl 產物 。換 色度 -20- 201139363 比較例1 以與實例1相同的方式製造碳酸伸乙酯，但未對自 酸化反應得到之反應溶液進行萃取且未進行添加水以移 沈積的物質的步驟。與實例1比較，操作一年之後得到 碳酸伸乙酯產物的乙二醇濃度和濕氣含量未改變。但是 色度略紅，且以Hazen値（APHA)表示之顏色的深度約 實例2至6 以與實例1相同的方式進行移除經沉積之未溶解的 質的步驟，但在萃取自碳酸化反應得到之反應溶液及添 水以移除沈積的物質的步驟中，改變添加的水量和移除 溶解的物質之方法。所得結果示於表1。如由表1顯見者 加至含有觸媒的溶液中之水量爲觸媒量的20倍重量時， 含有觸媒的溶液移除未溶解的物質或組份之後，所得溶 未觀察到任何顏色。 碳 除 的 25 物 加 未 白 液 -21 - 201139363 表1 添加的水量 (倍重量/觸媒量） 用以移除未溶解的物質或組份之方法 移除未溶解的物質之後的 狀態 實例2 200 靜置3小時 傾析上層清液 不帶顔色 實例3 80 以5C濾紙過濾 不帶顏色 實例4 60 於SV=8流動通過裝有聚丙烯絨的吸附容器 不帶顏色 不帶顏色 實例5 60 於SV=8流動通過裝有玻璃絨的吸附容器 實例6 40 以5C濾紙過濾 實質上不帶顔色 比較例2 10 以5C濾紙過濾 著色程度對等於過濾之前 比較例2 以與實例1相同的方式進行移除沉積之未溶解的物質 或組份的步驟，但在萃取自碳酸化反應得到之反應溶液及 添加水以移除沈積的物質的步驟中，添加的水量爲觸媒量 的10倍重量且移除未溶解的物質之方法改爲過濾法。所得 結果示於表1。如由表1顯見者，加至含有觸媒的溶液中之 水量爲觸媒量的10倍重量時，自含有觸媒的溶液移除未溶 解的物質之後，所得溶液與過濾之前者相同，有色組份未 被移除。 實例7 :乙二醇之製法 以與實例1相同的方式進行程序，直到碳酸化反應。 此碳酸化反應溶液轉移至第二皮應器，於其中的停留時間 爲2小時’壓力爲0.5 MPa，溫度爲150°C，含有的碳酸伸 乙酯經水解得到66.5重量份/時之含有觸媒的乙二醇水溶液 。此程序中，由第一反應器以3重量份/時萃取一部分的碳 酸化反應溶液。添加水，其量爲溶液中所含觸媒量的60倍 -22- 201139363 重量。令此溶液以sv=l通過裝有聚丙烯絨（DCM Japan Co·，Ltd.製造）的吸附容器。使用通過的溶液並循環至碳 酸化反應步驟。 水解反應所得反應溶液經蒸餾，例如，藉由在塔底於 低壓8 0托耳於1 40。(：蒸餾，自塔底得到經脫水的溶液。此 外’藉由在l4〇°C和60托耳操作的低壓蒸發器，較大部分 的乙二醇自彼蒸發。觸媒經濃縮的觸媒溶液以1 3重量份/ 時自蒸發器的底部回收。使用回收的觸媒溶液並以觸媒形 式循環至第一反應器。開始操作時，此觸媒溶液具有醋色 ’連續操作一年之後，未觀察到關於顏色的任何大幅改變 。水解反應器出口處的控制閥沒有任何堵塞或任何阻塞情 況’且此操作成功且安定地進行。 比較例3 以與實例7相同的方式操作一年，但未進行以添加的 水萃取碳酸化溶液及於移除沉積之未溶解的組份之後將溶 液循環的步驟。開始操作時，此觸媒溶液具有醋色，連續 操作一年之後，觸媒溶液的顏色改爲酒紅色。水解反應器 出口處的控制閥發生堵塞或阻塞情況，且難以進行任何安 定的操作。 實例8 程序以與實例7相同的方式進行，直到水解反應。萃 取來自水解反應器的輸出溶液，於其中添加水，添加量係 •23- 201139363 溶液中所含觸媒量的60倍重量’之後以 未溶解的組份。結果，移除混濁，成功 觸媒溶液。 實例9 程序以與實例7相同的方式進行， 二醇自水解反應溶液蒸發及觸媒溶液（ 以13重量份/時自蒸發器底部回收。添 所得觸媒溶液中所含觸媒量的18 0倍重 酒紅色的溶液變成混濁。沉積之未溶解 濾。結果，移除混濁，成功地回收不帶 黏著至濾紙的沉澱物以水清洗，之後， 洗。結果，甲醇具有深酒紅色，觸媒溶 份被分離出。 5C濾紙過濾沉積之 地回收不帶顔色的 直到較大部分的乙 其中觸媒被濃縮） 加水，其添加量係 量。結果，原來爲 的組份以5C濾紙過 顔色的觸媒溶液。 此沉澱物經甲醇清 液中含有的有色組 • 24-201139363 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing ethyl carbonate and/or ethylene glycol. [Prior Art] Ethyl carbonate is used as, for example, a solvent for various high molecular weight compounds, a chemical solvent for various chemical reactions, and a solvent for an electrolyte solution (electrolyte) for a lithium ion secondary battery. , extractant, foaming agent, and lubricant stabilizer. Usually, ethyl carbonate is synthesized by reacting ethylene oxide with carbon dioxide at a high temperature and a high pressure. Therefore, the ethyl carbonate contains diol (including, for example, ethylene glycol and diethylene glycol derived from materials for synthesis). For example, a small amount of water is also contained in the ethyl ester of carbonic acid with the aforementioned impurities. This water reacts with ethyl carbonate to further produce ethylene glycol. Preferably, ethyl carbonate (which acts as a solvent for a wide variety of types) does not contain any very small amounts of impurities. A wide variety of methods, including, for example, distillation and crystallization, have been proposed for the purification of ethyl carbonate. Distillation is the most commonly used purification method in the industry. However, ethyl carbonate has a high boiling point of 246 °c (atmospheric pressure). Therefore, when ethyl carbonate is purified by distillation, even if distillation is carried out at a low pressure, any thermal decomposition or damage is caused, and ethyl carbonate exhibits a high molecular weight compound by reacting with a diol and water. According to the study conducted by the inventors, the following facts were found. Namely, the bond of the high molecular weight ethylene glycol compound is partially cut off to return to the diol state. Therefore, even if distillation is carried out, the diol is thus left in the ethyl carbonate at a dose of about 100 ppm 201139363. Further, the distillation method requires energy corresponding to evaporation of latent heat of vaporization or related substances, and in addition, the reflux ratio must be increased. Therefore, the energy consumed is extremely large compared to the crystallization method, which is sufficient to be cooled by removing the perceptible heat. The crystallization method is a purification method which utilizes the fact that the impurity component (which is still not crystallized at the temperature at which some of the target components are crystallized) is not mixed into the crystal. The crystallization method is purified by an operation including only crystallization by cooling and dissolution by heating. Therefore, decomposition is not easily caused by side reactions, and the energy consumed is small. Further, Japanese Patent Application Publication No. 2007-284427 discloses that when the crystallization method described in this patent document is applied, ethyl carbonate having a high purity of not less than 99.999% can be obtained. However, when the ethyl carbonate is purified by using the crystallization method, a small amount of the colored component is present in the purified ethyl carbonate. This colored component causes some problems, especially in the case of an electrolyte for a lithium ion secondary battery requiring high purity. According to the study conducted by the inventors, the following facts are gradually revealed. That is, the aforementioned colored component is not removed in the method of, for example, the British Patent No. 2 0 9 8 9 5 and the Japanese Patent Application Laid-Open No. 20-4-2627 67, in which a part of the catalyst is contained. The reaction solution is used to recover a catalyst, and water is added thereto so that the solution is recycled back to the process after the catalyst is recovered. The colored component remains in the catalyst solution to be recycled to the process, and the colored component is concentrated during continuous operation. On the other hand, a method for producing ethylene glycol in which ethylene oxide and carbon dioxide are reacted at a high temperature and a high pressure to obtain a reaction solution for producing ethyl carbonate-6-201139363, in which water is further added to initiate a hydrolysis reaction, is known. In order to produce ethylene glycol (Japanese Patent Publication No. 55-47617 and Japanese Patent Application Laid-Open Nos. 59-13741, 2000-128814, and 2004-196722). The foregoing method causes a problem of clogging or clogging of an output control valve in the hydrolysis reactor (reaction tank) when continuous operation is carried out and cycled and a catalyst is used. SUMMARY OF THE INVENTION The present invention is directed to a method for producing ethyl carbonate, wherein the colored component contained in the aforementioned ethyl carbonate is removed, and a method for producing ethylene glycol is provided, In order to achieve the aforementioned object, the inventors of the present invention have made efforts to achieve the aforementioned object by operating stably for a long period of time while preventing the above-mentioned object in the ethylene glycol process. As a result, the following facts have been found. That is, an ethylene carbonate having been removed from the colored component can be obtained by a method of producing ethyl carbonate (including sometimes referred to as "EC process") comprising the following steps: by making carbon dioxide and ethylene oxide Reacting in the presence of a catalyst to obtain a reaction solution containing ethyl acetate and purifying the ethyl carbonate obtained by crystallization, the method of removing the colored component comprises extracting a part of the ethyl carbonate for the production of ethyl carbonate a reaction solution (sometimes referred to herein as "carbonation reaction solution (reaction solution for producing carbonate)"), and 20 times by weight of water not less than the catalyst dissolved in the extraction solution is added to the extracted solution. The undissolved material is deposited to remove the deposited undissolved material from the extracted solution, and the solution is then recycled to the process. Further, the inventors have found that according to the method of producing ethylene glycol by further adding water to a carbonation reaction solution (hereinafter referred to as "the hydrolysis step" in 201139363), it is not in the reactor in the hydrolysis step. The output control valve of the (reaction tank) causes any blockage or blockage, even if the operation continues for one year, the method involves extracting a portion of the carbonation reaction solution, which is not lower than the catalyst dissolved in the extracted solution. A weight of water is added to the extracted solution to deposit the undissolved material'. The deposited undissolved material is removed from the extracted solution, and the resulting solution is then recycled to the process. The present invention has thus been completed. That is, the present invention has the following features. (1) A method for producing ethyl carbonate, which comprises reacting carbon dioxide and ethylene oxide in the presence of a catalyst to obtain a reaction solution containing ethyl carbonate and purifying carbonic acid obtained by purification by crystallization Ethyl ester, the method comprising extracting a solution containing a catalyst from the reaction solution, adding 20 times by weight of water not less than a catalyst dissolved in the extraction solution to the extracted solution to deposit undissolved matter, The deposited undissolved material is removed from the extracted solution, and the resulting solution is then recycled to the reaction solution. (2) The method according to (1) wherein the catalyst-containing solution is a part of an output solution obtained by a reactor for reacting carbon dioxide with ethylene oxide to produce ethyl carbonate. (3) A method for producing ethylene glycol, comprising: reacting carbon dioxide, ethylene oxide, and water in the presence of a catalyst to obtain a reaction solution containing ethyl acetate and ethylene glycol and further Adding water to the obtained reaction solution to convert ethyl carbonate to ethylene glycol, the method comprising extracting a solution containing a catalyst from the reaction solution, which is not less than 20 times that of the catalyst dissolved in the extracted solution A weight of water is added to the extracted solution to deposit a substance that does not dissolve 201139363 'The deposited solution is recycled to the reaction solution after the deposited undissolved material is removed from the extracted solution. (4) A method according to (3), wherein the catalyst-containing solution is used to react carbon dioxide, ethylene oxide and water to produce a part of the output solution obtained by the reactor of the ethylene carbonate-alcohol and/or free Water is added to the resulting reaction solution to convert the ethyl carbonate to a portion of the output solution obtained in the ethylene reactor. (5) The method according to any one of (1) to (4), wherein the dissolved substance is removed by static separation, filtration separation, or removal by adsorption adsorption. (6) The method according to any one of (1) to (5), wherein the medium is iodinated or brominated to a quaternary phosphonium. (7) A kind of ethyl carbonate, which has a color of H azen 値 10 , and its purity is not less than 9 9.9 9 9 %. (8) A nonaqueous electrolyte solution containing the ethyl carbonate of (7). According to the present invention, there is provided a process for producing ethyl carbonate which has a high purity in which the colored component is removed. A method for producing ethylene glycol is provided, wherein the operation is carried out for a long period of time without causing any blockage or any blockage, even if it is used for a long period of time. DESCRIPTION OF THE PREFERRED SYSTEM (1) Regarding the color component, the liquid is from the ethyl ester and the unexposed substance in the diol is not more than defined, and in addition, the stability is continuously operated -9 201139363 The colored component contained in the ethyl carbonate is removed in the method for producing ethylene glycol according to the present invention, which is a substance which emits fluorescence when irradiated with ultraviolet light. A method for producing ethyl carbonate according to the present invention by fluorescence analysis (including production of ethyl carbonate by reaction of carbon dioxide and ethylene oxide in the presence of a catalyst, and purification of carbonic acid by crystallization) When the ethyl ester step is traced to the source of the material, the material is already present in the output gas stream obtained from the oxidation reactor used to make the ethylene oxide feedstock, and then the material is passed through the ethylene oxide absorber. And an ethylene oxide stripper, and this material is also contained in ethylene oxide as a raw material used in the EC process of the present invention. In the EC process, the colored component is recycled or recycled to the process with the catalyst, and the colored component is concentrated. In an attempt to recover the ethyl carbonate derived from the crystallization method in high purity, the concentrated colored component is incorporated as a product into the ethyl carbonate and results in a reddish color. As a result of the structural analysis, the colored component is composed of a component composed of polyethylene glycol, polyethylene, and an aromatic compound. The colored component is dissolved in a polar solvent such as methanol. However, the solubility in water is low. Therefore, when a certain amount of water is added, the substance can be deposited (precipitated) and removed. (2) Process for Producing Ethyl Carbonate The process for producing Ethyl Carbonate of the present invention is a process comprising the steps of: reacting carbonic acid and ethylene oxide in the presence of a catalyst to obtain a reaction containing ethyl carbonate The solution (sometimes referred to herein as "the reaction for the manufacture of carbonates") and the purification of ethyl acetate by crystallization. Catalysts which can be used in the above-mentioned reaction for producing ethyl carbonate are suitably selected from the known catalysts known from the Japanese Patent Publication No. 2011-038363, including, for example, alkali metal bromides or iodides (for example, Japanese Patent Publication No. No. 38-23175), an alkaline earth metal halide (described in, for example, U.S. Patent No. 2,667,497), an alkylamine, a quaternary ammonium salt (described in, for example, U.S. Patent No. 2,7,73,070) , an organotin, ruthenium or osmium compound (described in, for example, Japanese Patent Application Laid-Open No. 5 7 - No. 8 8 3 8 4), and a halogenated organic scale salt (described in, for example, Japanese Patent Application Publication) No. 58-126884). In particular, bromide or iodide of an alkali metal or a scaly salt is preferably used. Preferred examples include 'for example, potassium iodide, potassium bromide, iodinated quaternary scales or quaternary quaternary scales (for example, triphenylmethyl iodide scale, triphenylpropyl iodide scale, triphenyl iodide) Benzyl scales, tributylmethyl sulfonium iodide and their bromides. Compounds which form alkali metal carbonates can also be used with iron salts. Alkali metal carbonates inhibit ethylene glycol and ethyl carbonate in carbonation reactions. The production of any by-products other than the like. The potassium salt having a high solubility is preferably the same as the alkali metal. When a combined catalyst is used, a preferred example can be used in Japanese Patent Application Laid-Open No. 2 0 0 0 - 1 2 8 8.1 4 It is also possible to use commercially available ethylene oxide having high purity as the raw material of the carbonation reaction of the present invention. However, as in Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed., Vol. Al〇 , p. 1 1 7 ' can also be used after purification, for example, using the reaction described below to carry out the reaction, wherein the reaction is mainly composed of ethylene (raw material), oxygen and methane ( Diluent gas) A multi-tubular reactor equipped with a silver catalyst. Typically, the selectivity for the conversion of ethylene to ethylene oxide is about 80%. According to the complete oxidation reaction, about 20% of the residue is converted to -11 - 201139363 into carbon dioxide and water. Oxidation reaction gas ( It is formed from the reactor, for example, ethylene oxide, unreacted ethylene, carbonic acid gas, and released gas, and the obtained ethylene oxide is absorbed by using water as a liquid phase in the absorption tower. The ethylene oxide absorbed by the liquid is distilled or stripped in an alkane stripping column, and ethylene oxide is recovered from the top of the column as an aqueous solution having ethylene oxide. Further, it is subjected to treatment and purification treatment in a distillation column. The high concentration epoxy B solution obtained from the top of the column can also be used directly as a raw material. The carbonation reaction can be carried out by using any special equipment. The bubble column (which has a heat exchange for removing heat in the middle position) The circulating liquid circulation conduit of the pump is used to control the reaction temperature by circulating the reaction solution in the column through the liquid circulation conduit. The bottom of the column continuously supplies ethylene oxide and carbon dioxide raw materials and catalysts, which is feasible. It is also preferred to use a reactor equipped with a spray nozzle disclosed in Japanese Patent Application Laid-Open No. 269-110. The reaction temperature is to 200 ° C. However, the reaction temperature is preferably from 10 ° C to 17.反应 ° C. The reaction pressure is usually from 0.6 to 5.0 MPa. However, the reaction pressure is from 1.0 to 3.0 MP a. Water can be added to the carbonation reaction of the present invention, and ethylene oxide is not only converted into ethyl carbonate. It is also converted into. Therefore, even if the supply amount of carbon dioxide does not exceed the amount of ethylene oxide, the reaction is easy. The ear ratio of carbon dioxide to ethylene oxide is usually not more than 5, and preferably 0.5 to 3.0. The supply molar ratio of ethylene oxide is usually not more than 1 〇 preferably from 0.5 to 5.0. This amount is not sufficient with the ethylene oxide in the bubble column), the oxygen and the dilute liquid absorb the high concentration of ethylene oxide to dehydrate the water, for example, change the machine and contain the self-continuous It is better for 70. Water, ethylene glycol and other moirs supply Mo, and more completely reverse -12- 201139363 should. Therefore, it is also preferred to arrange the tubular reactor after the bubble column to further react the ethylene oxide in the solution or liquid. In this procedure, the amount of catalyst added is expressed as 1/1000 to 1/20, and preferably 1 / 2 0 0 to 1/5 0, with respect to the molar ratio of ethylene oxide. A portion of the reaction solution obtained in the carbonation reaction may be supplied to the purification step of the purified ethyl carbonate as described below, and the remainder may be preferably recycled to the carbonation reactor, which may be carried out by After the operation for recovering the catalyst, the operation of removing the colored component described below is performed. Alternatively, the operation for recovering the catalyst and the operation for removing the colored component can be performed in different operations. The operation for recovering the catalyst (which is used to prevent decomposition or damage of the catalyst) is, for example, the method described in, for example, Japanese Patent Application Laid-Open Nos. 2004-262767, 2004-284976, and No. 4-294384. get on. In general, a method of separating ethyl carbonate from a carbonation reaction solution by crystallization can be employed, wherein crude ethyl carbonate crystals are obtained by cooling a carbonation reaction solution. As for the cooling method, the cooling can be carried out according to a known method. Specifically, for example, the method described in Japanese Patent Laid-Open Publication No. 7-8 9905 in which crystals are deposited on a cold vertical partition wall, followed by warming, so that a part of the crystal melts, which flows downward and separates And thus recover crystals of increased purity. On the other hand, the convection contact method is also known as a continuous crystallization method (described in, for example, Japanese Patent Application Laid-Open No. 2007-284427, British Patent No. 1/86-28, and "Separation Technology" (The Society of Separation Process Engineers, Japan), Vol. 35, No. 6, pp. 45-49 (2005)). The convective contact method is a method for increasing the purity of ethyl carbonate by the contact of -13-201139363 between the crystal of ethyl carbonate and the liquid. In the EC process of the present invention, a catalyst-containing solution is extracted from the reaction solution, and then 20 times by weight of water not less than the catalyst dissolved in the extraction solution is added to the extracted solution to deposit undissolved. substance. The colored component is removed by removing the deposited undissolved material (this operation is sometimes referred to herein as "colored component removal operation (operation to remove colored components)"). The solution containing the catalyst may be extracted anywhere in the solution containing the catalyst to be recycled. However, for example, it is preferred to extract a portion of the output liquid or liquid obtained at the outlet of the carbonation reactor. Suitably, the amount of extraction is the amount by which the colored component will not be concentrated in the process, since the solution or liquid is recycled to the EC process after removal of the colored component. The extraction amount is from 1/5 Torr to W5' of the output solution obtained at the outlet of the carbonation reactor and is preferably from 1/100 to 1/10. The amount of water added to the extracted solution containing the catalyst must be added to the amount of water required to deposit the colored component. The amount of water added is not less than 20 times by weight, preferably not less than 50 times by weight, and most preferably not less than 60 times by weight, based on the weight of the catalyst contained. As for the maximum S, if a large amount of water is contained in the method, then a very large amount of energy is required to remove the water. Therefore, the maximum amount is 'appropriately' with respect to the weight of the contained catalyst, not more than 100 times by weight and preferably not more than 200 times by weight. The above-mentioned extracted catalyst-containing solution can also be continuously subjected to the operation of recovering the catalyst and the operation of removing the colored component. First, the catalyst is recovered from the extracted catalyst-containing solution in the manner described above. The recovered catalyst can be used in this state, or the recovered catalyst can be dissolved, for example, in ethylene glycol by -14-201139363 to a solution which can be used as a catalyst-containing solution. Water can also be added to remove colored components. The amount of water added by this procedure is also equal to the above. Regarding the method of adding water, when the catalyst concentration is thin or low, no special equipment is required. For example, a water pipe can be connected to the catalyst-containing solution for mixing in the pipe line. On the other hand, when the catalyst concentration is, for example, a high concentration of 40% by weight, the catalyst is temporarily deposited when water is added. Therefore, preferably, this operation is carried out in a dissolver or tank equipped with a stirrer. The colored component is deposited after the addition of water. Therefore, the deposited colored component is separated and removed by any suitable method. In particular, the separation and removal methods can be included for any method, such as static separation, filtration, and adsorption removal. In the case of static separation, the solution or liquid must be left for a period of time sufficient to precipitate the colored component. After the solution or liquid is allowed to stand, it is preferably allowed to stand for not less than 0.5 hours and more preferably not less than 1 hour, and the supernatant liquid is recovered as a catalyst solution. Regarding the apparatus used for performing static separation, for example, the apparatus used may be a precipitator or a tank' wherein a general precipitator is provided with an input line and an output line which are located at opposite positions to reduce the flow velocity inside. In the case of filtration separation, separation is carried out by using a general filtration apparatus or a percolator. However, after the addition of water, the colored components gradually aggregate and aggregate, and are easily filtered. Therefore, preferably, the filtration efficiency of the color component is determined, and the solution or liquid retention is preferably not less than 5 minutes and more preferably not less than 3 minutes before filtration. Regarding the apparatus for filtration, a commercially available general filtration apparatus or a percolator is suitably used. In the adsorption separation, adsorbents may also be used, including, for example, general activated carbon and zeolite. However, it is preferred to use -15-201139363 cotton-like materials including, for example, glass wool, polypropylene velvet, cotton, and metal velvet, which are capable of physically adhering or adsorbing colored components without difficulty due to their properties. Specifically, regarding the apparatus to be used, for example, a solution or a liquid containing a coal-contacting coal and adding water as described above is passed through a sorbent container or tank having a glass wool, and thereby the colored group can be satisfactorily removed. Share. There is no particular limitation on the period during which the solution or liquid is passed. When the density of the absorbent is thin or low, the solution must be allowed to flow slowly. However, when the adsorbent is introduced in a dense manner, the adsorption treatment can be carried out in a short time. It is also possible to agglomerate colored components for a period of time before being supplied to the adsorption vessel. However, these two effects are carried out by allowing the adsorption time to be about 15 minutes to 3 hours to simultaneously perform adsorption and agglomeration in the adsorption container. The solution containing the catalyst obtained after removal of the colored component is recycled to the carbonation reaction of the EC process. The position at which the solution containing the catalyst is returned can be any position as long as the catalyst circulates at the position. The location includes, for example, an inlet to the carbonation reactor, an outlet of the carbonation reactor, and a catalyst separation step. The ethyl carbonate which is produced by the EC process of the present invention is colorless and has high purity. Therefore, ethyl carbonate is preferably used as a raw material, for example, a raw material of a nonaqueous electrolyte solution (electrolyte). The so-called "no color" specific means that Hazen値 does not exceed 10. A non-aqueous electrolyte solution containing no more than 1 Å of Hazen and having a purity of not less than 99.999% and a non-aqueous electrolyte solution containing the ethyl carbonate are also included in the present invention. The non-aqueous electrolyte solution of the present invention contains an electrolyte and a non-aqueous solvent for dissolving it in the same manner as any of the general non-aqueous electrolyte solutions. The non-aqueous electrolyte solution of the present invention contains these components as a main component' which is produced according to a generally used method. -16- 201139363 (3) Method for Producing Ethylene Glycol Another aspect of the present invention relates to a process for producing ethylene glycol based on a method comprising the following steps (sometimes referred to herein as "the EG process": by making carbon dioxide, Ethylene oxide and water are reacted in the presence of a catalyst to obtain a reaction solution containing ethyl acetate and ethylene glycol, and ethylene carbonate is converted into ethylene glycol by further adding water to the obtained reaction solution. An alcohol (hydrolysis step), the method comprising extracting a solution containing a catalyst from the reaction solution, adding 20 times by weight of water not less than a catalyst dissolved in the extracted solution to the extracted solution to deposit undissolved a substance that removes the deposited undissolved material from the extracted solution and then circulates the resulting solution to the process. From another point of view, the colored component of the ethyl carbonate is used to produce ethyl carbonate at the foregoing. The method will be removed) causing clogging or clogging in the hydrolysis step of the process for making ethyl carbonate. Therefore, when the colored component is removed according to the same or equivalent method, the second can be stably produced for a long time. In the method for producing ethylene glycol of the present invention, the step of obtaining a reaction solution containing ethyl acetate and ethylene glycol by reacting carbon dioxide, ethylene oxide and water in the presence of a catalyst is the same as the above-mentioned EC production method. Or equivalent. The carbonation reaction solution is supplied to the hydrolysis step. However, a part of the ethyl carbonate can be isolated and purified according to an appropriate method. In this procedure, the method for purifying ethyl carbonate is not limited to the aforementioned crystallization method. It is possible to use, for example, a known distillation method. Of course, when purified according to the aforementioned crystallization method, ethyl carbonate which is colorless and has high purity can be obtained. From the viewpoint of the reaction rate, advantageously, in the hydrolysis step, at a high temperature - 17- 201139363 Reaction. However, if the temperature is too high, there is a concern that the quality of ethylene glycol is impaired. Therefore, it is usually preferred to carry out the reaction at a temperature of from 1 Torr to 180 ° C. The reaction pressure must be in the range of the boiling point of the solution or liquid. However, it is usually preferred to carry out the reaction at a pressure of from atmospheric pressure to 2.1 MPa. Further, it is also preferred to carry out the hydrolysis reaction by increasing the reaction temperature and/or A method of lowering the reaction pressure to facilitate the hydrolysis reaction. In particular, a method described in, for example, Japanese Patent Application Laid-Open Nos. 59-13741 and 2000-128814, for example, a portion related to a raw material and an amount of added water can be used. According to a known method, ethylene glycol can be obtained by a hydrolysis reaction to produce ethylene glycol. Usually, water is separated by distillation, preferably by distillation under reduced pressure to obtain crude ethylene glycol. For example, ethylene glycol, diethylene glycol, other high-boiling components, and a carbonation reaction catalyst. After that, the catalyst is separated from ethylene glycol to supply crude ethylene glycol to the evaporation equipment. A portion of the ethylene glycol and a portion of the high boiling component are evaporated and recovered to obtain a residual liquid (which is composed, for example, of a catalyst, residual ethylene glycol, and a high boiling component). The residual liquid is supplied as a "catalyst solution". To the aforementioned carbonation reaction. The catalyst recovery step is also carried out at a low pressure to facilitate evaporation or gasification of the ethylene glycol and high boiling components. The equipment equipped with the reboiler acts as an evaporation device, which supplements the energy required for evaporation, and controls the amount of evaporation. In the EG process of the present invention, the solution containing the catalyst is also extracted from the reaction solution, which is not lower than the solution in the extraction solution. 20 times by weight of water of the catalyst is added to the extracted solution to deposit and remove undissolved material. After that, the solution is recycled to the method again. In this procedure, the solution containing the catalyst may be any solution or liquid as long as it contains the catalyst used in the EG process. However, Example -18-201139363 For example, it is preferred to use an output solution obtained at the outlet of the carbonation reactor or at the reaction solution of the hydrolysis step. In the EG process, the catalyst recovered in the catalyst recovery step may also be subjected to a catalyst recovery operation to prevent any further decomposition of the catalyst, and the solution (by dissolving the recovered catalyst, for example, Alcohol, whichever is obtained, can be used as a solution containing a catalyst. In this procedure, the location where the circulating solution or liquid is returned also includes, for example, a carbonation reactor and a hydrolysis reactor. [Examples] Example 1: Production of ethyl carbonate (1) Carbonation reaction by adding 5 parts by weight of tributylmethyl iodide, 〇. 8 parts by weight of potassium carbonate and 78 parts by weight / The raw material ethylene oxide aqueous solution (60% by weight) was supplied to the first reactor (1 〇 0 ° C, pressurized with carbon dioxide to 2.0 MPa), and left for 1 hour to obtain ethyl carbonate and ethylene glycol (obtained). Carbonation reaction solution of EG). The resulting reaction solution was extracted at 3 parts by weight/hour, and water was added thereto in an amount of 60 times by weight based on the amount of the catalyst contained. This solution was passed through an adsorber of an existing polypropylene velvet (manufactured by DCM Japan Co., Ltd.) at SV = 1. The catalyst solution passed has a pale yellow color. This solution was used and recycled to the carbonation reactor. (2) Purification of ethyl carbonate. This operation was continued for one month, after which ethyl carbonate was crystallized and purified from the carbonation reaction solution according to the method described in WO 2007/108213. In particular, the vertical melting purification apparatus described in Japanese Patent Application Laid-Open No. Hei 6-9 1 1 03 is used as a crystallization apparatus. This purification equipment is equipped with agitating. The agitator used was equipped with a stirring shaft having a horizontal stirring bar as a stirrer. A slit-like observation hole (observation hole or window for confirming crystallinity or sedimentation) is provided on the side of the crystallization apparatus used. A part of the reaction solution obtained in the carbonation reaction was set to 17 ° C by a crystal equipped with a cold jacket (described in Japanese Patent Application Laid-Open No. 6-9 1 1 03). A slurry containing ethylene glycol crystals was produced which was supplied from the crystal supply tube prepared as described above. The crystals settle in the crystallization apparatus. The excess liquid is recovered from the upper portion of the crystallizer as an overflow liquid and recycled to the reactor. The crystals settle and the crystals gradually accumulate at the bottom of the column. The crystal is heated by heating to melt the crystal to form a melt. When the melt is moved upward at the beginning, it is convectively contacted with the settled crystal (reflux liquid), and the molten upper extraction tube is extracted. This solution was returned to the hydrolysis reaction via the crystallization apparatus. At this point in time, ethylene glycol was not extracted from the product extraction tube, and the crystal layer accumulated on the melt. The cumulative crystal layer thickness was observed from the observation hole, and S extracted from the product extraction tube, so that the accumulated crystal layer thickness was 95% of the preparation height. This operation was continued for 3 days, and the quality of the ethyl carbonate product was evaluated using gas chromatography and a Fischer hygrometer. As a result, the ethylene glycol concentration was 1 ppm, the moisture content or the water content was 2 ppm, and the purity of the ethyl carbonate product was not less than 99.999%. As for, Hazen値 (APHA) does not exceed 10. The straight mixer is mixed with the mother to prepare the cold crystallizer, and the same liquid. The formation of the modified crystal Karl product is formed. Color change degree -20-201139363 Comparative Example 1 Ethyl carbonate was produced in the same manner as in Example 1, except that the reaction solution obtained by the acidification reaction was not subjected to extraction and no water was added to remove the deposited material. The ethylene glycol concentration and the moisture content of the ethyl carbonate derived product obtained after one year of operation were not changed as compared with Example 1. However, the chromaticity was slightly red, and the depth of the color represented by Hazen(R) (APHA) was about Example 2 to 6 in the same manner as in Example 1 except that the deposited undissolved substance was removed, but in the extraction of the self-carbonation reaction. In the step of obtaining the reaction solution and adding water to remove the deposited substance, the amount of added water and the method of removing the dissolved substance are changed. The results obtained are shown in Table 1. As apparent from Table 1, when the amount of water added to the catalyst-containing solution was 20 times the amount of the catalyst, after the catalyst-containing solution was removed from the undissolved substance or component, no color was observed in the obtained solution. 25 addition of carbon plus unwhite liquid-21 - 201139363 Table 1 Amount of water added (double weight / amount of catalyst) State of removal after removal of undissolved substances by means of undissolved substances or components 200 Stand for 3 hours, decanter the supernatant without color Example 3 80 Filter with 5C filter paper without color Example 4 60 Flow at SV=8 through the adsorption container with polypropylene fleece without color without color Example 5 60 SV=8 flow through the glass wool sorption container Example 6 40 Filtered with 5C filter paper substantially without color Comparative Example 2 10 Filtered with 5C filter paper Coloration degree equal to filtration Comparative Example 2 Moved in the same manner as Example 1 In addition to the step of depositing the undissolved substance or component, but in the step of extracting the reaction solution obtained by the carbonation reaction and adding water to remove the deposited substance, the amount of water added is 10 times the weight of the catalyst and is shifted The method of removing the undissolved matter was changed to the filtration method. The results obtained are shown in Table 1. As apparent from Table 1, when the amount of water added to the solution containing the catalyst is 10 times the amount of the catalyst, after the undissolved substance is removed from the solution containing the catalyst, the resulting solution is the same as that before the filtration, and the color is the same. The component was not removed. Example 7: Preparation of ethylene glycol The procedure was carried out in the same manner as in Example 1 until the carbonation reaction. The carbonation reaction solution is transferred to the second dermal device, wherein the residence time is 2 hours, the pressure is 0.5 MPa, the temperature is 150 ° C, and the ethyl carbonate containing ethyl ester is hydrolyzed to obtain 66.5 parts by weight/time. Medium glycol aqueous solution. In this procedure, a part of the carbonic acid reaction solution was extracted from the first reactor at 3 parts by weight/hour. Add water in an amount of 60 times the amount of catalyst contained in the solution -22- 201139363 by weight. This solution was passed through a adsorption vessel equipped with polypropylene velvet (manufactured by DCM Japan Co., Ltd.) at sv = 1. The passed solution is used and recycled to the carbonation reaction step. The reaction solution obtained by the hydrolysis reaction is subjected to distillation, for example, at a low pressure of 80 Torr at 140 ° at the bottom of the column. (: Distillation, dehydrated solution is obtained from the bottom of the column. In addition, by the low pressure evaporator operating at 14 ° C and 60 Torr, a larger portion of the ethylene glycol evaporates from the catalyst. The catalyst is concentrated. The solution was recovered from the bottom of the evaporator at 13 parts by weight/time. The recovered catalyst solution was used and recycled to the first reactor as a catalyst. At the start of the operation, the catalyst solution had a vinegar color for one year after continuous operation. No significant change in color was observed. The control valve at the outlet of the hydrolysis reactor did not have any blockage or any blocking condition' and this operation was carried out successfully and safely. Comparative Example 3 was operated in the same manner as in Example 7 for one year. However, the step of extracting the carbonation solution with added water and recycling the solution after removing the deposited undissolved component is not performed. When the operation is started, the catalyst solution has a vinegar color, and after one year of continuous operation, the catalyst solution The color is changed to wine red. The control valve at the outlet of the hydrolysis reactor is clogged or blocked, and it is difficult to perform any stable operation. Example 8 The procedure was carried out in the same manner as in Example 7. Until the hydrolysis reaction, the output solution from the hydrolysis reactor is extracted, and water is added thereto, and the amount is added to the undissolved component after 60 times the weight of the catalyst contained in the solution. 23, 2011, the turbidity is removed. , Successful catalyst solution. Example 9 The procedure was carried out in the same manner as in Example 7, the diol was hydrolyzed from the hydrolysis reaction solution and the catalyst solution was recovered from the bottom of the evaporator at 13 parts by weight per hour. The solution of the 18% red wine solution became turbid. The undissolved sediment was deposited. As a result, the turbidity was removed, and the precipitate which was adhered to the filter paper was successfully recovered and washed with water, and then washed. As a result, methanol had Deep burgundy, the solvent is separated. 5C filter paper is filtered to deposit the unrecovered color until the larger part of B is concentrated.) The water is added and the amount is added. As a result, the original component is 5C filter paper over color catalyst solution. This precipitate is colored group contained in methanol clear solution. 24-