TW448153B

TW448153B - Process of producing carbonicdisester

Info

Publication number: TW448153B
Application number: TW86109128A
Authority: TW
Inventors: Takeshi Minami; Noriyuki Yoneda; Yoshimi Shiroto; Haruto Kobayashi
Original assignee: Chiyoda Chem Eng Construct Co
Priority date: 1995-12-29
Filing date: 1997-06-28
Publication date: 2001-08-01

Abstract

This patent describe the novel catalysts and process which are used for producing of carbonicdisester. Carbonicdisester is generated from alcohol, carbon monoxide and oxide in the presence of catalysts. The reaction is performed at temperature in the range of 30 to 200 DEG C. the catalysts are homogenous and consist of copper compound, heterocyclic compound containing one or more nitrogen atom and glycol ester represented by the following formula (I): R1O-(CHR2-CH2O)nR3. Wherein R1 is an alkyl group having from 1 to 6 carbon atom. R2 is an alkyl group having from 1 to 2 carbon atom or hydrogen atom. R3 is an alkyl group having from 1 to 6 carbon atom. n is an integer of from 1 to 12.

Description

448153 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1 ) 本發明係有關碳酸二酯之製造方法。碳酸二甲酯等碳酸二酯類除了適用爲醫藥、赓藥等原料外，近年更成爲受入注目的汽油添加劑（辛烷增壓劑），或取代各種碳酸酯類之製造原料中的碳醯氯，以作爲反應原料使用。截至目前，已知的碳酸二酯之製造方法有，使碳醯氯及醇反應的方法，而且事實上此方式已工業化。但，其令產生副產品之鹽酸而腐蝕裝置材料及，碳醯氯具有刻毒性的問題，因此，希望能開發出不使用碳醯氯的非碳醯氯法之製造技術。爲了支援此需求，故Enichem公司已將，以氯化銅 (I )爲觸媒，並利用甲醇的氧化羰基化反應以製造碳酸一酯的技術工業化（Quad. Ind. Chim. Ital V" 〇 1 , 21 No. 1 (1985))。且其爲目前唯一的非碳醯氯法裝置。但，這樣的Eni c hero程序亦無法完全解決副產品鹽酸等所造成的腐蝕裝置材料等問題，因此，反應器內面需有玻璃襯底，如此一來會有裝置大型化的缺點。又’於Enichem程序中，爲了要得到充分反應速度，則需有1 4重量％以上高濃度的銅鹽，結果反應液因存在此固體成分而成爲水性泥漿液。因此，過程中需由所生成的碳酸酯分離出固體成分’故另需具備有膜分離或離心分離等特殊步驟。又’這些裝置需爲耐熱、耐壓、耐腐蝕性，故有成本非常两的問題存在。爲了解決上述問題’以避免使反應液成爲泥漿系的方法有’加入各種添加物，使其成爲均勻反應系，再以此均本紙張尺度適財關家標準（CNS)A4規格（21G X 297公楚)' ： — — — — Illllt— — - — lit — — — «flIlllla iiy · (請先閱讀背面之注意事項再填寫本頁) 448153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（2 ) 勻反應系製造碳酸二酯。例如，U.S.P.Re 2 9 3 3 8 ( Snam Prog-ett i )中所揭示的，利用由氯化銅及含氮化合物所形成之觸媒進行醇的氧化羰基化之實驗例》但，使用此觸媒時，會因氯化銅之溶.解度低而將觸媒濃度限制於很低，故無實用性。又，特開昭6 2 _ 8 1 3 5 6號公報（德士古· 雷洛普特）中則揭示了，反應系中添加吡啶類的例子，但，此反應液不會成爲均勻系而成爲泥漿系。 U. S. P. 4604242( Dow Chemical )中曾提案，使用 b i s ( 2，4— pentandianato) copper (.Π ) methox i de -吡啶，以達成均匀系之目的，但，此時之觸媒中所使用的銅化合物極爲特殊，並且有反應速度慢之缺點，故無實用性。特開平5 — 1 74 1 0號公報中揭示了，於 C u C 中加入喊土類金屬之氫氧化物 (Mg (011)2等）以使觸媒均勻化，因此，能抑制使用氯化第2銅時產生副產品氯化甲基、二甲基醚等的缺點。但，此觸媒仍未完全符合作爲工業性觸媒的條件。特開平6_2 5 1 0 5號公報中提到，利用共存的鈦 '錫 '鈮 '鉍、鉬及錳與金屬之鹵化物方式，以避免析出銅（1 ) ’但’這類的金屬鹵化物會因CO的燃燒，而使 co2之副產量有增加的傾向，故此使用方式並不佳。至於避免產生泥漿系的另一方法爲，廣爲人知的使用比較低濃度之C u C j?2/p d C艾3所形成的均勻觸媒本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） --------I----· I---I--訂—--!線 -· ; : : * ' v {锖先閱讀背面之注意事項再填寫本頁) -5 - 經濟部智慧財產局員工消費合作社印製 ^48153 Α7 ____Β7 五、發明說明（3 ) 系（特開平5 — 1 0 5 642號公報、特開平5 — 320098號公報、特開平5 — 320099號公報與 )。但’這些方法中會因使用Pd而產生副產物草酸，又 ’此草酸會與銅離子起反應而生成不溶性草酸銅，如此一來，會降低觸媒活性。，另一種避免產生泥漿系的方法爲，利用於固體上附載銅鹽或其配鹽所形成之觸媒，以進行氣相反應之方法。例如 ’U. S, P. 2625044( Dow Chemical )或特開平2 - 2 5 6 6 5 1號公報中所掲示的，以活性碳附載氯化銅或銅-吡啶配位化合物所形成之觸媒進行氣相反應β但，這些方法會有，碳酸二酯之選擇性（選擇率）低及’因鹵素等飛散而使觸媒活性惡化的問題存在，故此方法非好方法。特開平6 - 2 1 0 1 8 1號公報則揭示了，以活性碳附載銅-三苯基膦配位化合物所形成之觸媒進行反應。但 ’此時因亦需於觸媒上共存鹵素，故有因此鹵素或鹵化氫的飛散而使觸媒活性惡化的問題存在。另外，這類的固定化觸媒之再生法提案如，以鹵素氣體或鹵化氫氣體作爲再生氣體使用的處理方法（特開平6 — 2 1 〇 1 8 1號公報、特開平5 — 49947號公報、特開平5 — 2081 3 7號公報等）。但，這些觸媒再生法令有，再生氣體所造成的反應器與腐蝕，或殘留的再生氣體與原料乙醇反應而生成鹵化烷基，或製品的碳酸二酯之加水分解等問題存在本纸張尺度適用侧撕議臟格公楚）丨！II 丨丨！ I 丨丨 —1 —丨訂！I-- _| < (請先閱讀背面之注意事項再填k本頁) ^ 448 153 A7 _ B7 五、發明說明（4 ) 因此，本發明之目的如下。 (請先閲讀背面之注意事項再填窝本頁) (i )提供一種能提高碳酸二酯之選擇率，且腐蝕性低的碳酸二酯製造用觸媒液β (i i )提供一種使用上述觸媒液的碳酸二酯製造方法- *· (i i i )提供一種適合於使用上述觸媒液之碳酸二酯製造方法碳酸二酯製造裝置。至於本發明之其他目的則可由下面說明而得到理解。本發明者們爲了解決上述問題而經專心研究後，完成了本發明。即，本發明係提供一種，使醇與一氧化碳及氧起反應以製造碳酸二酯時所使用的觸媒液，其爲，由（i )銅化合物及（i i )環狀氮化合物、（i i i )下列一般式（ I ) R10[CH(R2)CH2〇]nR3 (I) 經濟部智慧財產局員工消費合作社印製 (其中’ R1爲碳數1〜6之烷基，R2爲碳數1〜2之烷基或氫，R3爲碳數1〜6之烷基或氫，η爲1〜1 2 之整數）所示的乙二醇酸所形成之，溶液所含有的銅化合物爲溶解狀之觸媒液^ 又，本發明係提供一種觸媒液之再生方法，其特徵爲 ’使活性變差之上述觸媒液接觸一氧化碳。另外，本發明係提供一種碳酸二酯製造方法，其特徵本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -7 - 448 1 53 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（5 ) 爲，於上述觸媒液中，使一氧化碳及氧在乙醇中起反應。本發明亦提供一種碳酸二酯製造方法，其係由’於上述觸媒液中使一氧化碳及氧在乙醇中起反應，而得到含碳酸二酯之反應溶液的生成碳酸二酯步驟及，由此反應溶液中分離出所含之碳酸二酯的分離碳酸二酯步驟及，分離出碳酸二酯後，再使所得之觸媒液接觸一氧化碳的觸媒液再生步驟所構成。又，本發明係提供一種裝置，其特徵爲，此使用上述觸媒液的碳酸二酯製造用裝置中具備有，（i )於上述觸媒液中，使一氧化碳及氧在乙醇中起反應，以生成碳酸二酯的反應裝置及，（i i )由此反應裝置所得之含碳酸二酯的反應溶液中，分離出碳酸二酯之分離裝置及，（ i i i )使至少部分的由分離裝置分離出碳酸二酯後所得之觸媒液接觸一氧化碳•使其再生之觸媒液再生裝置。另外，本發明係提供一種裝置，其特徵爲，此使用上述觸媒液的碳酸二酯製造用裝置中，（i)含有成爲碳酸二酯生成地帶之筒體及，成爲觸媒液再生地帶之筒體，（ i i ) 2個筒體的上端部及下端部能成爲液體性連絡處， (i i i )於成爲碳酸二酯生成地帶之筒體下方配設，可分別或混合供應一氧化碳及氧之供應管，以及供應乙醇之供應管，（i v )於成爲碳酸二酯生成地帶之筒體上方配設，排出碳酸二酯之排出管，（v)爲了將一氧化碳供應給成爲觸媒液再生地帶之筒體，而於此筒體上配設供應管 ’ （v i )於這2個筒體之頂端配設*排出含一氧化碳氣 ---------— — — illlll— ^illllln^i. 1- -(請先閱讀背面之注意事項再^',r本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 448 1 53 a7 B7 經濟部智慧財產局員工消費合作杜印製五、發明說明（6 ) 體的排出管。本發明亦提供~種裝置，其特徵爲，此使用上述觸媒液的碳酸二酯製造裝置中，（i )具有由外筒體及插在其中的內筒體所形成之，此內筒體內部成爲碳酸二酯生成地帶及，外筒體之內表面與內筒體旳外表面之間所形成的縫隙，成爲觸媒再生地帶的反應裝置，（i i )此外筒體及內筒體的上下端均成爲液體連絡處，（i i i )於內筒體下方配設，能分別或混合供應一氧化碳及氧的噴嘴及，供應乙醇之供應管，（i v )於此外筒材內表面與內筒材外表面所形成之縫隙部分配設，供應一氧化碳之噴嘴，（V )於此外筒體之上方配設，排出含碳酸二酯之溶液的排出管，（vi)此外筒體之頂端具有排出含一氧'化碳之氣體的排出管。本發明之觸媒液係由，銅化合物及環狀氮化合物及上述一般式（I )之乙二醇醚所形成。又，此觸媒液中所含的銅化合物爲均勻溶解狀》此銅化合物包含，銅齒化物、銅無機酸鹽、銅有機酸鹽及銅配鹽與。又，其可爲1價之銅（I )化合物及/或 2價銅（H )化合物β 上述之銅鹵化物則包含，氯化物、溴化物及碘化物。其具體例子如，CuCi2 、CuCJ?2 ' CuBr 、〇11312、（3111等- 上述之銅無機酸鹽包含，硝酸鹽、碳酸鹽、硼酸鹽及磷酸鹽等。其具體例子如，Cu (N〇3) 2、CuC03 請、先 S3. 讀· 背之注訂線本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 448153 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7 ) 、Cu (OH) 2 . h20、CuB4〇7、Cup〇4 等 ύ 上述之銅有機酸鹽包含，羧酸鹽、磺酸鹽、磷酸鹽、膦酸鹽等》其具體例子如，甲酸鹽、醋酸鹽、草酸鹽與β 上述之銅配鹽包含，以三甲基胺等鏈狀胺、吡啶等環狀胺或三苯基膦等有機磷化合物爲配位基之銅配鹽。就觸媒活性及碳酸二酯之選擇性觀點而言，本發明所使用之銅化合物又以氯化第1銅（C u C j?)或其配位化合物特別佳。本發明所使用的上述一般式（I )所示之乙二醇類中，：R1爲碳數1〜6，較佳爲碳數1〜4，又以碳數1〜 2更佳之烷基，R2爲碳數1〜2之烷基或氫，較佳爲氫或甲基，又以氫更佳，R3爲碳數1〜6，較佳爲碳數1 〜4 ，又以碳數1〜2更佳之烷基或氫，η爲1〜1 2，較佳爲1〜6，又以2〜4更佳之整數>若R1之碳數超過6時，會降低銅化合物之溶解度，故不合適》又，R2 之碳數超過2時，會降低銅化合物之溶解度，故不合適* R3之碳數超過6時，亦會降低銅化合物之溶解度，故不合適。另外，若η值超過1 2時，會有降低銅化合物之溶解度及增加觸媒液粘度之缺點，亦不合適。本發明所使用之乙二醇醚爲上述一般（I )所示之物，其代表例如，對甲醇、乙醇、丙醇及/或丁醇1克分子附加，氧化乙烯及/或氧化丙烯2〜1 2克分子所形成之乙二醇單烷基醚系化合物《又，這些代表性乙二醇醚以外本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ' · -10 - ---- ------I — illllll — — — — ^ J J (請先閱讀背面之注意事項再氣寫本頁) 經濟部智慧財產局員Η消費合作社印制取 448153 A7 —— ____ B7 五、發明說明（8 ) 的例子如，以甲基、乙基、丙基或丁基等低級烷基取代前述乙二醇單院基醚之末端0H基的Η之，乙二醇二烷基醚系化合物。又，這些乙二醇醚可單獨使用或2種以上混合使用。這類的乙二醇.酿除了可提高εο及co2之溶解度外，還可提高c u及環狀氮化合物之配位化合物的溶解度，故能避免析出c u化合物。這些乙二醇醚類雖易由合成乙二醇類與醇之醚化而得到，但，亦可使用市售品。市售品之例子如，東邦化學工業公司製的貝索普等。又，乙二醇醚類爲，被廣泛地作爲吸收劑使用之溶劑，其特徵爲，具有化學不活性、無腐蝕性、不會產生不溶物或沈澱及，熱安定性高、無溶劑惡化情形及，蒸氣壓低、溶劑損失情形少等。本發明所使用之環狀氮化合物爲，吡啶或吡啶骨幹上具有烷基、烷氧基、_原子等不會阻害碳酸二酯生成反應之取代基的吡啶類，其例如 > 吡啶、2 -羥基吡啶、2 -甲基吡啶、2 _乙基吡啶、2 ，4 _二甲基吡啶、2 -甲基一4 一羥基吡啶、2 —羥基4 一甲氧基吡啶、2 —羥基 6 —氯吡啶等》另外，亦可使用菲繞啉、二吡啶基、咪唑等環狀氮化合物。這些化合物係與觸媒之銅形成配位化合物後，再溶解於上述乙二醇醚類中》其中，又以使用吡啶、2 —羥基吡啶、2 —甲基吡啶、1，10 —菲繞啉、2 ，2’ —二吡啶基爲特別佳。本發明中作爲原料物質使用的醇類可爲，含羥基之廣本紙張尺度適用中國國家標準（CNS>A4規格<210 X 297公釐） ~ " 一 — If!! I - i I · I I Ϊ I I I I ^ — — — — — —— — — J.' -f ·' (請先閱讀背面之注*華項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 448 1 53 A7 _ B7 五、發明說明（9 ) 範圍的化合物，其例如，甲醇、乙醇、1 一丙醇、2 —丙醇、1— 丁醇、1 一戊醇、1一己醇、1 一辛醇、1—癸醇、1 一十八烷醇、烯丙醇、2 — 丁烯一 1 一基、2 —己烯一 1 一基等碳數1〜2 0的飽和或不飽和脂肪族醇，或環己醇、環戊醇等碳數3〜7的脂環族醇，或笮基醇、苯乙醇等芳香族醇等。又，所使用均醇不受限於一價醇，亦可爲乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇等二價醇’或甘油等多價醇。其中，就反應生成物之需求觀點而言，又以使用甲醇或乙醇爲佳。另外，作爲原料使用的一氧化碳及氧不需爲高純度之氣體’亦可爲利用氮、氬、二氧化碳等不活性氣體稀釋之氣體。尤其是反應條件下，爲了防止因氧而引起爆炸事件 ’較佳爲以不活性氣體稀釋之氣體。此意味著亦可使用空氣以取代氧。本發明所使用之碳酸二酯生成步驟爲，於上述觸媒液中’使醇、一氧化碳及氧起反應。此時所使用的銅化合物若爲C u CJ2時，其反應式如下。 (氧化） 2(R0H) + l/202 + 2(CuC 5 ) * Xn- 2[CuORC3Z ] * Xn + H2〇 (2) (羰基化） 2[CuORCίΜ . Xn + CO— (R0)2C0 + H20 + 2CuC1 · Xn (3) 集合上述2個反應式後可改成下列式。 2(R0H)+C0+1/20广（R0)2C0+H20 (4) 本紙張尺度適用中國國家標準(CNS)A4規格(綱靖）_ -- - - ---— — — — — I ' — ——111— ^ ·1111111 I). -m (請先間讀背面之注意事項再魂寫本頁) 448 153 A7 - —_______ B7 五、發明說明（10 > 其中’ R爲醇殘基，X爲配位基’ η爲結合於 CuCJ?的配位基數。本發明之觸媒液中的環狀氮化合物使用比率爲，對銅化合物之克分子比係〇_ 1〜100，又以〜50 爲佳’最佳爲1〜10。若此值抵於〇·1時，會存在著未溶解的銅化合物，而無法成爲均句觸媒系，故不合適，又，超過1 0 0時，會於存在醇之時期析出銅化合物，故不合適。乙二醇醚的使用比率爲，對銅化合物之克分子比係〇 5〜200’又以1〜100爲佳，最好爲3〜50 。若此值低於0_ 5時，觸媒系將無法成爲均勻系，又，超過2 0 0時，會降低觸媒液中的銅濃度，而無法得到充分的反應速度，故兩者均不合適。經濟部智慧財產局員工消費合作社印製原料醇的使用比率爲，對銅化合物之克分子比係1 〇〜700，又以30〜500爲佳1最佳爲50〜300 。若此值低於1 0時，將無法得到充分的反應速度，又，此值超過7 0 0時，會降低觸媒液中的銅濃度，而無法得到充分的反應速度，故兩者均不宜。本發明之碳酸二酯生成歩驟中的反應觸媒設定如下。即，其反應溫度爲30〜200 °C，較佳爲5 0〜1 50 °C，又以8 0〜1 4 0°C更佳，一氧化碳分壓（C Ο分壓 )爲 0· 1 〜50kg/cnf ，較佳爲 1 〜3 0 kg/ c nf ，又以1〜25kg/crri更佳，氧分壓（〇2分壓）爲 0. 001 〜10kg/cm，較佳爲〇· 005 -13 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐> 448153 A7 B7 經濟部智慧財產局員工消費合作社今製五、發明說明（U) 〜5kg/crri，又以0. 01〜3kg/crri 更佳。若反應溫度低於3 0°C時*將無法得到充分反應速度，又，超過2 0 0 °C時，副產物多，且乙二醇醚類會熱分解· 故兩者均不宜。另外，若CO分壓低於〇.lkg/ciri 時，將無法得到充分的反應速度*又，超過5 0 k g/ c m時，會提高麻壓容器（反應器）之製造成本，故不符合經濟性。至於〇2分壓若低於0. 001kg/cm2 時，將無法得到充分反應速度，又，超過1 0 k g/ciri 時，會使乙二醇醚類氧化分解，故兩者均不宜》進行本發明之碳酸二酯生成反應的方式可爲，分批式或流通式等任何方式。 (分批方式）先將觸媒液放入反應器中，再供應CO及〇2 -反應器的型式較好爲，能充分達成氣液接觸之反應器，故可使用攪拌槽或氣泡塔等目前已知的各種反應器，此分批方式之反應中的C 0供應量，對每1克分子銅化合物爲 8 〜200mo I/hr ，較佳爲 10 〜i〇〇mo 1 /hr，02供應量爲0. 08〜4mol/hr，較佳爲 0. 1 〜2mol/hre 所生成的碳酸二酯係由反應器以氣相方式回收，其後，於殘液中添加醇及吡啶類、乙二醇醚類之補充量，以進行第2回以下的反應。另外’若碳酸二酯係以液相方式由反應器回收時，亦本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — ！丨！— _!!1 訂！！線 J -- C (請先閱讀背面之注意事項再填寫本頁) -14 - 4481 53 Α7 Α7 Β7 五、發明說明（12 ) 可利用蒸餾塔將其蒸餾再回收》此時，可將蒸餾塔中的餐殘液（含C u觸媒、環狀氮化合物及乙二醇醚類）送回反應器內，然後再加入醇、環狀氮化合物及乙二醇醚類之補充量，以進行第二回以下的反應。於液相取出法中’因一般可用蒸餾塔分離生成物，故其效率比氣相取出法更佳β 碳酸二酯之生成步驟中的上述反應式（2 )及反應式 (3 )並不需要一次完成，亦可分別依序進行。即’首先先將觸媒液放入反應器中，以〇2分壓爲0. 001〜 10kg/ciri 、溫度爲30〜150 °C之條件進行反應，再去除〇2 »其次，以c〇分壓爲〇·1〜50kg /cnl、溫度爲3 0〜1 8 0°C之條件進行反應，以生成碳酸二酯。請先 Μ 讀背之注意事項再寫, 本頁經濟部智慧財產局員工消費合作社印製 (流通方式）其爲連續將醇、CO 合物、乙二醇醚類之補充出並回收反應生成物（碳式可爲，擾拌槽、氣泡塔反應生成物取出的方式可後者時，通常在反應器外應生成物，並且，將蒸餾狀氮化合物、乙二醇醚類 .出法中，因一般能利用蒸、〇2及必要時所需的環狀氮化量加入反應系中，同時連續地取酸二酯）的方法。此反應器的型等目前已知的各種反應器。至於爲，氣相取出或液相取出。若爲部設置有蒸餾裝置與，以分離反裝置之釜殘液（含C U觸媒、環 )連續送回反應器中β於液相取餾裝置分離生成物，故比氣相取出法更其效率本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15 - 448153 A7 B7 五、發明說明（13 ) (請先閱讀背面之注意事項再填贫本頁) 又，此流通方式之反應中的反應（2 )及反應（3 ) 亦可分開的進行。即，將2個反應器排成直列，再依序於各別反應器內進行反應（2 )之氧化步驟及反應（3 )的瑞基化步驟*這些步驟中的C 0分壓、〇2分壓、溫度等條件可同上述分批式。因係分開進行氧化步驟及羰化步驟，故可避免混合C 0與〇2時所形成的爆炸混合氣。若能組合成這樣的系統，就可使本發明之觸媒成爲安定之均勻系觸媒。經濟部智慧財產局員工消費合作社印製本發明之觸媒液於反應後會降低活性，但，利用一氧化碳接觸此類的活性下降之觸媒液的方式，可使觸媒液再生。爲了使觸媒液再生，而進行一氧化碳接觸此活性下降之觸媒液時的一氧化碳分壓爲0. lkg/crrf以上，又以0. 5kg/cnf以上爲佳。雖然一氧化碳分壓之上限值並無特別限制，但，一般爲50kg/ciri 。若此CO分壓低於〇. lkg/crrf時，將無法充分地進行觸媒液再生，又，超過5 0 k g / cm1時，會增加裝置成本，故兩者均不宜。另外•此觸媒液與C 0之接觸溫度爲50〜200 °C，又以70〜1 50 °C較佳。若此溫度低於5 0°C時，將無法充分地進行觸媒液再生，又，超過2 0 0°C時，會造成乙二醇醚類分解，故兩者均不宜》經此得到的再生觸媒液可繼續作爲碳酸二酯生成步驟中的觸媒液使用。使活性下降之觸媒液再生的情形，並不需全部再生處理，只需使部分的活性下降之觸媒液再生，並可將此再生觸媒液及未再生觸媒液混合供應給反應系。 Ϊ紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ~~ ： _ 16 一 448153 A7 B7 五、發明說明（14) 此觸媒液的再生可於製造碳酸二酯之反應裝置內進行，或於與反應裝置分，開設置的觸媒液再生裝置中進行β 下面請參照圖面說明本發明。圖1爲，實施本發明時之系統圖的一例。圖1中’ 5爲.反應裝置、6爲碳酸二酯分離裝置、9 爲觸媒再生裝置。反應裝置之目的爲，於觸媒液中使醇、C0、02起反應以生成碳酸二酯，其爲攪拌型之反應裝置。碳酸二酯分離裝置6之目的爲，由觸媒液中以蒸氣狀分離出碳酸二酯，所使用的分離裝置爲，閃沸裝置或蒸餾塔。觸媒液再生裝置9之目的爲，使分離出碳酸二酯後之觸媒液再生，所使用的裝置爲，氣液接觸裝置。依照圖1之系統以製造碳酸二酯時，係利用與填充著觸媒液之反應裝置5相通的管線11、12及13分別供應C0、〇2及醇，再於觸媒液中使醇、C0、〇2起反應以生成碳酸二酯》經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再,A寫本頁) 反應裝置5中所得到的由觸媒液、碳酸二酯及未反應醇所形成之反應溶液，則經過管線5 a導入碳酸二酯分離裝置6。未反應之〇2/(：0混合氣體係經由管線1 4，再經凝縮器1 5排出系外。於此凝縮器1 5中，可使含於氣體中的醇等凝縮性化合物凝縮》導入碳酸二酯分離裝置6中的反應生成液再經由管線本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17 - 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（15 ) 6 b ’以蒸氣方式將含於其中的碳酸二酯及未反應醇分離出’而觸媒液則以液體成分之方式殘留於分離裝置內。分離裝置6內的觸媒液再經由管線6 a導入再生裝置 9中，使其接觸C0而再生。於再生裝置9中接觸C 0而再生的觸媒液則經由管線 9 a送回反應裝置5，另外，未反應的C ◦係經由管線 9 b導入反應裝置5中。如上述般，此系統可連續生成碳酸二酯及，使觸媒液連續再生。圖1所示之系統中，原料醇並不一定要經由管線1 3 供應給反應裝置5，必要時亦可經由管線16將部分或全部導入再生裝置9中，再由此再生裝置9經過管線9 a供應給反應裝置5。又，由分離裝置6經過管線6 a而分離出的部分觸媒液亦可不送入再生裝置9，而係直接導入反應裝置5中。圖2爲，實施本發明之裝置模式圖。此裝置爲，氣泡反應器型之裝置，其係由，成爲碳酸二酯生成地帶Z1之筒狀反應筒體2 1及，成爲觸媒液再生之再生地帶Z2的筒狀再生筒體2 5所構成之，此筒體2 1及筒體25的上端係與相通筒體2 1 a相連結及，下端則與相通筒體 2 1 b相連結之，全體成爲環道構造的裝置。將觸媒液填入反應筒2 1及再生筒2 5中，此時的觸媒液可預先混合反應原料中的醇。再由反應筒2 1之下方以管線2 2導入〇2/CO混合氣體及，經由管線2 3導本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1---I ---I!訂-!-線 ΙΊ (請先閲讀背面之注$項再洗k本頁) —18 ^ 448153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（16 ) 入醇。因導入此〇2/CO混合氣體*故能於筒體2 1中產生含氣泡之反應溶液的上升液流。此成爲上升液流之反應溶液則可由筒體2 1之上方排放出氣泡，再流入筒體2 5 中，因其於筒體2 5內係呈下降狀’故能於筒體2 5內產生下降流。而於筒體2 1及筒體2 5之間形成如箭頭所示之流動方向的循環流。圖2所示之碳酸二酯製造用裝置中的碳酸二酯生成地帶Ζ1會因醇與C0、03之反應而產生碳酸二酯生成反應，又，於觸媒液再生地帶Ζ2會因觸媒液接觸C 0而造成觸媒液再生。經由管線2 2導入反應筒2 1的〇2/CO混合氣體中，C0之供應量在化學量論上因需比〇2的供應量爲多，即，每1克分子〇2的<：0使用量爲2克分子以上，因此，由反應筒2 1上方經過相通筒2 1 a而導入再生筒 2 5中之觸媒液中可溶存C 0，故此觸媒液可因液中的 C 0作用而再生。再生後的觸媒液則由筒體2 5下方經過相通筒而導入筒體2 1的下方。必要時亦可經由管線2 4 將可促進觸媒液再生之，不會造成此循環流大影響程度的 C0導入再生筒25中。由碳酸二酯及未反應醇所形成之反應生成液，則可由反應筒2 1之上方經過管線2 6排放至外部。又，未反應 C 0氣體係經由凝縮器2 7，再過管線2 8而排放至外部 (請先閲讀背面之注意事項再填寫本頁》本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 19 一 448153 A7 B7 經濟部智慧財產局員工消費合作社却製五、發明說明（17 > 圖3爲，實施本發明之方法時所使用的其他反應裝置模式圖。此裝置爲，筒體（外筒）3 1及插在此筒體3 1 內的同心狀筒體（內筒）3 5所構成之，於內筒3 5之上端3 5 a及下端3 5 b形成開口端，而與此外側的外筒 3 1相通之，使外筒體之內表面及內筒3 5的外表面之間所形成的間隙部3 1 a或爲觸媒液的再生地帶Z2及，內筒35之內部成爲碳酸二酯生成地帶Z1的裝置· 將觸媒液填入外筒3 1內及內筒3 5內。並由內筒 3 5之下方經過管線3 2及氣體噴嘴導入02/C0混合氣體及’經由管線3 3導入原料醇。因導入02/C0混合氣體，故能於內筒3 5內形成，由內含氣泡且密度低之反應溶液所形成的上升液流，當此上升液流由內筒3 5之上端開口 3 5 a排出後，其內含之氣體（c 0 )會散放出去，而使密度變大的觸媒液在外筒3 1中是下降狀，再經由內筒3 5之下端開口 3 5 b進入內筒3 5內。因此，外筒3 1與內筒3 5之間會形成如箭頭所示之流動方向的循環流。圖3所示之碳酸二醋製造用裝置中的破酸二酯生成地帶Z，會因醇、C0及〇2間的反應而產生碳酸二酯生成反應’又，觸媒液再生地帶Z2會因觸媒接觸c 0而造成觸媒液的再生。由管線3 2導入內筒3 5內之02/C0混合氣體中，C02之供應量在化學量論上需比〇2的供應量多，爲過剩量，因此’在間隙部3 1 a內下降的觸媒液中可溶存閲讀背面之注 |α 頁訂本紙張尺度適用尹國國家標準（CNS)A4規格（210 X 297公釐） -20 - 448 1 5 3 A7 B7 五、發明說明（18) -------------教— -- (請先閱讀背面之注意事項再填宵本頁) c 〇 ’又因此觸媒中的C0作用，而使觸媒液能再生。再生後的觸媒液則由間隙部3 1 a之下方經過開口端3 5 b 導入內筒3 5內。必要時，亦可經由管線3 4將能促進觸媒液再生且對循環流不會造成大影饗程度之c 0導入間隙部3 1 a中。至於由碳酸二酯及未反應醇所形成之反應生成液則由外筒3 1之上端經過管線3 6而排出至外部。又，未反應氣體則經由凝縮器3 7，再通過管線3 8而而排出至外部〇圖2及圖3所示之裝置因不需攪拌液體之動力等，故能減少能量的消耗，加上其形狀簡單、裝置構造亦簡單，因此*可成爲塔形狀，故具有易使裝置大型化等之優點β 下面將以實施例詳細說明本發明β -丨線· 實施例1 (調製觸媒液I ) 經濟部智慧財產局員工消費合作社印製準備一個附有螺旋栓的2 0 0m Ρ燒瓶，將吡啶 28.. 12放入其中《攪拌下再緩緩加入I2g的 C u C $。其後，馬上加入三乙二醇二甲基醚（東邦化學工業公司製、HISOLV HUM ) 6 9 . 2 g »若以添加 C u C j?後之狀態直接放置，結果會成爲固體，因此，在添加C u C 後仍爲溶液狀時需馬上加入三乙二醇二甲基 .醚。因僅存在著少許固體，故可使溫度大約升至5 0°C，又，此段時間內持續攪拌，以使其成爲均勻溶液。並以此本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） -21 - A7 ^48153 _________B7____ 五、發明說明（19 ) 均勻溶液作爲觸媒液I。接著，將甲醇51.lg加入其中，得未見Cu CJ2析出之濃綠色均勻溶液。 (請先閲讀背面之注意事項再填寫本頁) 實施例2 (調製觸媒液n ) -- 除了實施例1中所使用的CuCj?改爲13. 5g' 吡啶改爲31. 4g、三乙二醇二甲基醚改爲77. 3 g 外，其他同實施例1調製由均勻溶液形成之觸媒液Π。比較例1 (調製比較觸媒液I ) 除了不使用三乙二醇二甲基醚以外，其他同實施例1 。結果所得之觸媒液雖爲均勻溶液，但，加入甲醇後會析出固體成分，而得到泥漿液。既使攪拌下加熱至5 0°C，亦無法溶解固體成分，仍爲泥漿系。實施例3 經濟部智慧財產局員工消費合作社印製 (合成碳酸二甲酯）將實施例2所得之觸媒液Π 12 2. 2 g放入高壓鍋 (鎳基合C金製 '耐壓50kg/ciri )中，再加入甲醇 5 7 . 1 g。利用C 0_體使高壓鍋內純化後，再以C 0氣體使壓力升至 25kg/cirf 。其後，以 1 000 r. p . m 方式攪拌反應溶液，並將溫度升至1 3 0°C。當到達設定本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公釐） -22 - 4481 53 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（20 ) 溫度且狀態呈安定狀時分別開始供應CO氣體及〇2氧’ 以開始反應。又，此CO氣體之供應量爲1. 2 5 m ο 1 /hr、〇2之供應量爲0. lmo Ι/hr 。5小時後，採取反應溶液樣品，以氣相色譜測定二甲基碳酸鹽（碳酸二酯）（DM C.)之濃度。，結果，所生成之二甲基碳酸鹽（DMC)爲30. 9 g，銅利用率爲561%。又，試驗開始後第5小時的甲醇基準選擇率SM爲8 0%，CO基準選擇率Sco爲 60% (第2小時）〜40% (第4小時）。反應生成液確定爲均勻溶液，又，實驗結果後並未發現鎳基合金C製反應器內而任何腐蝕現象《至於上述的銅利用率（％)之定義爲，（DMC生成量 (mo 1 ) X2/放入之銅鹽（mo I ) X100。又，甲醇基準選擇率SM(%)的定義如下列式。 Sm=DMC生成量（mo丨）X2 /甲醇消耗量（ mol) X 1 〇 0 C 0基準選擇率sco(%)的定義如下列式。 Sco = DMC生成量（mo 1 ) / CO消耗量（ m ο 1 ) X 1 〇〇實施例4 (以方式合成碳酸二甲酯） p斤使用之實驗裝置爲，圖4所示之裝置系。j圖4中的 5 1爲反應裝置，5 2爲第1冷卻器、5 3爲碳酸二甲酯 --I---------i — 1 — m — — Ι — — — — — 1}-. -- .. . (請先閱讀背面之注意事項再填窝本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）一 23 _ 4481^3 經濟部智慧財產局員工消費合作社印製五、發明說明（21 ) 接收器’ 54爲第2冷卻器，55爲〇2計量器、56爲氣體計量器。將由CuCiZl. 3重量單位、肶啶2. 9重量單位及三乙二醇二甲基醚49. 6重量單位所形成之觸媒液與甲醇4 6. 2重量單位的混合液SO OmJ? ’放入錬合金 C製反應裝置51中。再以1OOOr. p‘ m方式攪拌混合液（反應溶液）’同時以1· 25mol/hr方式供應C 0 >並將、溫度升至1 〇〇°C ’其後’經過管線5 8 由反應裝置5 1之底部將〇2/C02混合氣體供應給反應裝置5 1 ，再經過管線5 7由反應裝置5 1之底部供應甲醇/吡啶混合液。此時，反應裝置5 1內之全分壓保持爲2 5化8/£；11120(〇0分壓約爲24.51^釔/<：11{ )，又，02之供應方式爲〇. lmo 1/hr 甲醇/毗啶混合液中的吡啶濃度爲〇· 5wt%，又，供應此混合液的方式爲，能使反應裝置內之液態水準保持一定般的方式。接著，由反應裝置5 1上方，以氣相方式取出碳酸二甲酯、甲醇、吡啶、H20及CO所形成的混合物，並將其導入第1冷卻器5 2中。又，此冷卻器5 2係保持爲，溫度1 0°C及壓力1 k g/crrfG之況態。將第1冷卻器5 2得到的凝縮液導入接收器5 3的同時，將另外的氣相混合物導入第2冷卻器54中。又’第2冷卻器5 4中係循環著4 °C之冷媒，並以大氣壓方式操作。由此冷卻器5 4得到的氣體狀物（排放氣 2 閲讀背之注意事項再 i 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -24 - 448153 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（22 ) 體）則經過02計量器及氣體計量器而排出。另外，凝縮液係導入接收器53中。開始實驗後，分別於經過0 . 5小時、1小時、2小時、3小時及4小時時段進行通過氣體計量器之排放氣體的取樣工作，並利用氣相色譜測定其中的C〇2、C0、碳酸二甲酯、甲醇及〇2之各濃度^同時亦以氣相色譜測定接收器5 3內的回收液狀物中之甲醇、吡啶、三乙二酸二甲基醚、碳酸二甲酯之各濃度，接著，再以卡爾費歇法測定液狀物中的水。根據上述結果算出與碳酸二甲酯有關之C 0基準選擇率S (C0)及甲醇基準選擇率S(M)，數值則記載於表1。又，此S (C0)係以下列式示之。 S(CO) = {1-A/(B-C) }/2X 100(¾) A:排放氣體中C〇2濃度（vol%) B:供應氣體中〇2濃度（vol%) C:排放氣體中02濃度（vol%) S(M)則以下列式示之。 S(M)=D/Ex2X 100(%) D:所生成之碳酸二甲基量（mol) E:消耗掉的甲醇量（mol ) 本紙張尺度適用中國國家標準（CNS)A4規輅（210 X 297公釐） -------------!丨訂！線- <請先閱讀背面之注意事項再%寫本頁) -25 - 448153 A7 B7_ 五、發明說明（23 ) 表 1 測定時間 r—— 0.5 *-〜— 1 2 3 4 s(co) 83 --- 77 78 72 59 S(M) 92 99 100 100 100 {請先朋讀背面之注意事項再填寫本頁) 此實驗經過4個小時操作後的每1β反應溶液之碳酸二甲酯生產性爲，〇 . 5 9 m i / h r . L。又’此實驗無c 以外之副產物產生。線· 實施例5 (合成碳酸二甲酯）經濟部智慧財產局員工消費合作社印製將實施例2之觸媒液及甲醇57.ig，放入3〇〇 m I?鎳基合金C製高壓鍋中。首先’進行氧化步驟。即，以〇2使高壓鍋內純化後 ’再以1400r. p. m方式攪拌反應溶液，同時將溫度升至7 0°C。其後，以〇2將壓力升至4kg/cma，以開始反應。2小時後，停止溫度調節，使反應液溫度降至4 0 °C以下》其次，進行羰基化步驟。即，脫壓後以C Ο使高壓鍋本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公釐） _ 26 - 448 1 53 Α7 Β7 經濟部智慧財產局員4消費合作社印製五、發明說明（24 ) 內純化，其後，以1400r. ρ· m方式攪拌反應溶液 ’並將溫度升至1 20 °C。接著，利用C0將壓力升至2 k g/c nf，以開始反應》2小時後停止溫度調節，使反應溶液溫度降至4 0eC以下。再採取反應溶液樣品及氣體樣品，並以氣相色譜分析，結果所生成之二甲基碳酸鹽爲 3. 8g，CO選擇性爲76%。比較例2 (合成碳酸二甲酯）同比較例1調製肶啶19g、CuC芡24g、甲醇 1 2 0 g所形成之混合液。結果混合液中存在著固體成分，爲泥漿狀。將此混合液放入3 0 OmJ?鎳基合金C製高壓鍋中。首先，進行氧化步驟。即，以02使高壓鍋內純化後 ’以1400r. P.m方式攪拌反應溶液，並將溫度升至70°C。其後，利用02將壓力升至4kg/crri，以開始反應。4 5分鐘後停止溫度調節，使反應液溫度降至 4 0 °C以下。其次’進行羰基化步驟。即，脫壓後以CO氣體使高壓鍋內純化’再以1400r. p. m方式攪拌反應溶液，並將溫度升至1 2 0°C。其後，利用CO氣體使壓力升至25kg/cni，以開始反應。45分鐘後停止調節，並將反應溶液溫度降至4 〇°C以下。接著，採取反應溶液樣品，以氣相色譜測定二甲基碳酸鹽（D M C )濃度。 ---------------：.款--- -_、 (請先閱讀背面之注意事項再株寫本頁) 訂· · --線. 本紙張尺度適用争國國家標準（CNS)A4規格（210 X 297公爱） -27 - 448153 A7 B7 五、發明說明（25) 結果雖可確定生成二甲基碳酸鹽，但，反應溶液約 8 0%爲凝膠狀固體，因此，不具實用性。實施例6〜1 0 (合成碳酸二甲酯）除了以表2所示之組成的混合液取代實施例3中之，放入高壓鍋中的觸媒液及甲醇混合液外，其他進行相同實驗。結果5小時後的碳酸二甲酯生成量記載於表2。 (請先閲讀背面之注意事項再氧寫本頁) 訂--------*線經濟部智慧財產局員工消費合作社印製448153 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (1) The present invention relates to a method for manufacturing carbonic acid diesters. Carbonic acid diesters such as dimethyl carbonate are not only suitable for use as raw materials for medicines, peony, etc. In recent years, they have also attracted attention as gasoline additives (octane booster), or they have replaced carbochlorine in the production materials of various carbonates To be used as a reaction raw material. Up to now, there are known methods for producing carbonic acid diesters in which carbochlorine and alcohol are reacted, and in fact this method has been industrialized. However, it causes corrosion of equipment materials and carbochlorine due to the generation of hydrochloric acid as a by-product. Therefore, it is desired to develop a non-carbochlorine method that does not use carbochlorine. In order to support this demand, Enichem has industrialized the technology of manufacturing monocarbonate with copper (I) as a catalyst and the oxidative carbonylation reaction of methanol (Quad. Ind. Chim. Ital V " 〇1 , 21 No. 1 (1985)). And it is currently the only non-carbon tritium chloride plant. However, such an Enic hero program cannot completely solve the problem of corrosion of the device materials caused by the by-product hydrochloric acid and the like. Therefore, a glass substrate is required on the inner surface of the reactor, so that the device has the disadvantage of large size. In the Enichem procedure, in order to obtain a sufficient reaction rate, a copper salt with a high concentration of 14% by weight or more is required. As a result, the reaction solution becomes an aqueous slurry because of the solid content. Therefore, in the process, it is necessary to separate solid components from the carbonate produced ', so it is necessary to have special steps such as membrane separation or centrifugation. Since these devices need to be heat-resistant, pressure-resistant, and corrosion-resistant, there are problems with very high cost. In order to solve the above problems, 'the method to avoid making the reaction liquid into a mud system is to add various additives to make it a uniform reaction system, and then use this paper to comply with CNS A4 specifications (21G X 297). (Gongchu) ': — — — — — Illllt — — — — lit — — — «flIlllla iiy · (Please read the notes on the back before filling out this page) 448153 A7 B7 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs DESCRIPTION OF THE INVENTION (2) A homogeneous reaction system produces a carbonic acid diester. For example, as disclosed in USPRe 2 9 3 3 8 (Snam Prog-ett i), an experimental example of the oxidative carbonylation of an alcohol using a catalyst formed from copper chloride and a nitrogen-containing compound is used. However, using this catalyst In the case of medium, the concentration of the catalyst is limited to a low level due to the low solubility and resolution of copper chloride, so it is not practical. Furthermore, Japanese Patent Application Laid-Open No. 6 2 _ 8 1 3 5 6 (Texaco Ralopte) discloses an example in which pyridines are added to the reaction system, but this reaction solution does not become a homogeneous system. Become a mud system. USP 4604242 (Dow Chemical) has proposed the use of bis (2,4— pentandianato) copper (.Π) methox i de-pyridine to achieve the purpose of homogeneity. However, the copper compound used in the catalyst at this time It is very special and has the disadvantage of slow response speed, so it is not practical. Japanese Patent Application Laid-Open No. 5-1 74 1 0 discloses that by adding a hydroxide (Mg (011) 2, etc.) of a shout earth metal to Cu C to homogenize the catalyst, the use of chlorination can be suppressed. In the second copper, there are disadvantages such as methyl chloride and dimethyl ether as by-products. However, this catalyst is still not fully qualified as an industrial catalyst. Japanese Unexamined Patent Publication No. 6_2 5 1 0 5 mentions the use of coexisting titanium 'tin' niobium bismuth, molybdenum, and manganese and metal halides to avoid the precipitation of copper (1) 'but' metal halide Due to the combustion of CO, the by-product of co2 tends to increase, so the use method is not good. As for another method to avoid the formation of mud system, it is widely known to use a relatively low concentration of C u C j 2 / pd C Ai 3 formed uniform catalyst This paper size applies Chinese National Standard (CNS) A4 specifications ( 210x297 mm) -------- I ---- · I --- I--Order ---! Line- ·;:: * 'v {锖 Read the notes on the back before filling in this Page) -5-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 48153 Α7 ____ Β7 V. Description of Invention (3) Department (Japanese Patent Application Laid-Open No. 5 — 1 0 5 642, Japanese Patent Laid-Open No. 5 — 320098, Japanese Patent Laid-Open No. 5 — Gazette No. 320099). However, in these methods, oxalic acid is produced as a by-product due to the use of Pd, and this oxalic acid reacts with copper ions to generate insoluble copper oxalate. As a result, the catalyst activity is reduced. Another method to avoid the generation of mud system is to use a catalyst formed by loading a copper salt or a complex salt thereof on a solid to perform a gas phase reaction. For example, as shown in 'U.S, P. 2625044 (Dow Chemical) or JP-A No. 2-2 5 6 6 5 1, a catalyst formed by supporting activated carbon with copper chloride or a copper-pyridine complex The gas phase reaction β is performed. However, these methods have problems such as low selectivity (selectivity) of carbonic acid diester and deterioration of catalyst activity due to scattering of halogen and the like, so this method is not a good method. Japanese Unexamined Patent Publication No. 6-2 0 1 81 discloses that a catalyst formed by supporting a copper-triphenylphosphine complex with activated carbon reacts. However, at this time, since it is necessary to coexist a halogen on the catalyst, there is a problem that the catalyst activity is deteriorated due to the scattering of the halogen or hydrogen halide. In addition, proposals for a regeneration method of such an immobilized catalyst include a treatment method using a halogen gas or a hydrogen halide gas as a regeneration gas (Japanese Laid-Open Patent Publication No. 6-2 1 010 81, Japanese Patent Laid-Open Publication No. 5-49947). JP 5-2081 3 7 etc.). However, these catalyst regeneration laws have problems with the reactor caused by the regeneration gas, corrosion, or the reaction of the remaining regeneration gas with the raw material ethanol to generate halogenated alkyl groups, or the hydrolysis of the carbonate diester of the product. Applicable side tearing dirty grid) 丨! II 丨丨! I 丨丨 —1 — 丨 Order! I-- _ | < (Please read the notes on the back before filling this page) ^ 448 153 A7 _ B7 V. Description of the invention (4) Therefore, the purpose of the present invention is as follows. (Please read the precautions on the back before filling in this page) (i) Provide a catalyst solution for carbonic acid diester production that can increase the selectivity of carbonic acid diesters and has low corrosivity β (ii) Provide a method using the above catalysts Method for producing carbonic acid diester of vehicle liquid-* · (iii) Provide a device for producing carbonic acid diester suitable for the method for producing carbonic acid diester using the catalyst liquid. The other objects of the present invention will be understood from the following description. The present inventors have intensively studied in order to solve the above problems, and have completed the present invention. That is, the present invention provides a catalyst liquid for reacting an alcohol with carbon monoxide and oxygen to produce a carbonic acid diester, comprising: (i) a copper compound; (ii) a cyclic nitrogen compound; and (iii) The following general formula (I) R10 [CH (R2) CH2〇] nR3 (I) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where 'R1 is an alkyl group with 1 to 6 carbon atoms, and R2 is an alkyl group with 1 to 2 carbon atoms Alkyl group or hydrogen, R3 is an alkyl group or hydrogen having 1 to 6 carbon atoms, η is an integer of 1 to 1 2), and the copper compound contained in the solution is dissolved. Vehicle fluid ^ Also, the present invention provides a method for regenerating a catalyst fluid, which is characterized in that the above-mentioned catalyst fluid whose activity is deteriorated is contacted with carbon monoxide. In addition, the present invention provides a method for manufacturing a carbonic acid diester, which is characterized in that the paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -7-448 1 53 A7 B7 employee consumption of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (5) In the above catalyst liquid, carbon monoxide and oxygen are reacted in ethanol. The present invention also provides a method for producing a carbonic acid diester, which comprises the steps of forming a carbonic acid diester by reacting carbon monoxide and oxygen in ethanol in the catalyst liquid to obtain a reaction solution containing a carbonic acid diester, and thereby The step of separating carbonic acid diester from the carbonic acid diester contained in the reaction solution and the catalyst liquid regeneration step of separating the carbonic acid diester and then contacting the obtained catalyst liquid with carbon monoxide. The present invention also provides a device, wherein the apparatus for producing a carbonic acid diester using the catalyst liquid is provided with (i) carbon monoxide and oxygen reacted in ethanol in the catalyst liquid, A carbonic acid diester reaction device and (ii) a carbonic acid diester-containing reaction solution obtained by the reaction device, a carbonic acid diester separation device and (iii) at least a portion of the carbonic acid diester separation device The catalyst liquid obtained after the carbonic acid diester is in contact with carbon monoxide. The catalyst liquid regeneration device for regeneration. In addition, the present invention provides a device characterized in that, in the apparatus for producing a carbonic acid diester using the catalyst liquid described above, (i) a cylinder which is a carbonic acid diester production zone and a catalyst liquid regeneration zone is included; The cylinder, (ii) the upper and lower ends of the two cylinders can become liquid contact points, and (iii) is arranged below the cylinder that becomes the carbonic acid diester formation zone, and can supply carbon monoxide and oxygen separately or in combination. The tube and the supply tube for ethanol are (iv) arranged above the cylinder which becomes the carbonic acid diester generating zone, and the carbonic acid ester is discharged into the tube, (v) in order to supply carbon monoxide to the cylinder which becomes the catalytic liquid regeneration zone And a supply pipe is provided on the cylinder '(vi) is arranged at the top of the two cylinders * to discharge carbon monoxide-containing gas ------------- — illlll— ^ illllln ^ i. 1--(Please read the precautions on the back before ^ ', r this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 448 1 53 a7 B7 Employees ’Intellectual Property Bureau, Ministry of Economic Affairs Cooperative Du Printing V. Invention Description (6) Exhaustion of the body . The present invention also provides a device characterized in that, in the carbonic acid diester manufacturing device using the catalyst liquid described above, (i) has an outer cylinder body and an inner cylinder body inserted therein, and the inner cylinder body The part becomes the carbonate diester formation zone and the gap formed between the inner surface of the outer cylinder and the outer surface of the inner cylinder 旳 becomes the reaction device of the catalyst regeneration zone. (Ii) The upper and lower sides of the outer cylinder and the inner cylinder. Both ends become liquid contact points, (iii) are arranged below the inner cylinder, and can supply carbon monoxide and oxygen nozzles and supply pipes for ethanol, respectively, or (iv) on the inner surface of the outer cylinder and the outer cylinder. The gap formed on the surface is distributed and a nozzle for supplying carbon monoxide is provided. (V) is arranged above the other cylinder to discharge a solution containing a carbonic acid diester. (Vi) In addition, the top of the cylinder is provided with an oxygen-containing gas. 'Exhaust pipe of carbonized gas. The catalyst liquid of the present invention is formed of a copper compound, a cyclic nitrogen compound, and a glycol ether of the general formula (I). The copper compound contained in the catalyst solution is uniformly dissolved. The copper compound includes copper dentate, copper inorganic acid salt, copper organic acid salt, and copper complex salt. It may be a monovalent copper (I) compound and / or a divalent copper (H) compound β. The above-mentioned copper halides include chloride, bromide, and iodide. Specific examples include CuCi2, CuCJ? 2 'CuBr, 〇11312, (3111, etc.-The above-mentioned copper inorganic acid salts include nitrate, carbonate, borate, and phosphate. Specific examples include Cu (N. 3) 2. CuC03 Please, first S3. Read · Back Note Binding This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 448153 Printed by A7 B7 of the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (7), Cu (OH) 2.h20, CuB407, Cup04, etc. The above copper organic acid salts include carboxylate, sulfonate, phosphate, phosphonate, etc. Examples include formate, acetate, oxalate and β. The copper complex salts described above include chain amines such as trimethylamine, cyclic amines such as pyridine, and organic phosphorus compounds such as triphenylphosphine as ligands. Copper complex salt. From the viewpoints of catalyst activity and carbonic acid diester selectivity, the copper compound used in the present invention is particularly preferably chlorinated first copper (C u C j?) Or a complex compound thereof. Among the ethylene glycols represented by the above general formula (I) used in the invention, R1 is 1 to 6 carbon atoms, preferably carbon. 1 ~ 4, more preferably an alkyl group having 1 to 2 carbons, R2 is an alkyl group or hydrogen having 1 to 2 carbons, preferably hydrogen or methyl, and more preferably hydrogen, R3 is 1 to 6 carbons , Preferably 1 to 4 carbons, and more preferably an alkyl or hydrogen having 1 to 2 carbons, η is 1 to 12, preferably 1 to 6, and more preferably an integer of 2 to 4 > if R1 When the carbon number exceeds 6, the solubility of the copper compound is reduced, so it is not suitable. Also, when the carbon number of R2 exceeds 2, the solubility of the copper compound is reduced, so it is not suitable. When the carbon number of R3 exceeds 6, it is also reduced. The solubility of copper compounds is not suitable. In addition, if the value of η exceeds 12, the disadvantages of reducing the solubility of copper compounds and increasing the viscosity of the catalyst liquid are not suitable. The glycol ether used in the present invention is the above General (I) is represented by, for example, ethylene glycol and / or propylene oxide added to 1 gram molecule of ethylene glycol and / or propylene oxide 2 to 12 molecules of ethylene glycol monomer Alkyl ether-based compounds "Also, other than these representative glycol ethers, the Chinese paper standard (CNS) A4 (210 X 297 mm) applies to this paper size" '-10-- --- ------ I — illllll — — — — ^ JJ (Please read the notes on the back before writing this page) Member of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives printed 448153 A7 —— ____ B7 5 Example of the invention description (8) For example, a lower alkyl group such as methyl, ethyl, propyl, or butyl is substituted for the terminal 0H group of the above ethylene glycol monoethyl ether, that is, ethylene glycol dialkyl ether These compounds can be used alone or in combination of two or more. In addition to this type of ethylene glycol, in addition to improving the solubility of εο and co2, it can also increase the solubility of the complex compounds of c u and cyclic nitrogen compounds, so it can avoid the precipitation of c u compounds. Although these glycol ethers are easily obtained by etherification of synthetic ethylene glycols and alcohols, commercially available products can also be used. Examples of commercially available products include Bessopp manufactured by Toho Chemical Industries. Glycol ethers are solvents that are widely used as absorbents. They are chemically inactive, non-corrosive, insoluble or precipitated, and have high thermal stability and no deterioration of solvents. In addition, the vapor pressure is low, and there is less solvent loss. The cyclic nitrogen compound used in the present invention is a pyridine having pyridine or a pyridine backbone having an alkyl group, an alkoxy group, an _ atom and the like that do not hinder the carbonic acid diester generation reaction, and examples thereof are > pyridine, 2- Hydroxypyridine, 2-methylpyridine, 2-ethylpyridine, 2,4-dimethylpyridine, 2-methyl-4 monohydroxypyridine, 2-hydroxy4-monomethoxypyridine, 2-hydroxy6-chloro Pyridine, etc. "In addition, cyclic nitrogen compounds such as phenanthroline, dipyridyl, and imidazole may be used. These compounds are complexed with copper of the catalyst, and then dissolved in the above glycol ethers. Among them, pyridine, 2-hydroxypyridine, 2-methylpyridine, and 1,10-phenanthroline are used. 2,2'-dipyridyl is particularly preferred. The alcohol used as a raw material in the present invention may be a wide range of hydroxyl groups. The paper size is applicable to Chinese national standards (CNS > A4 specifications). < 210 X 297 mm) ~ " 一 — If !! I-i I · II Ϊ IIII ^ — — — — — — — — J. '-f ·' (Please read the note on the back first * Hua Please fill in this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 448 1 53 A7 _ B7 V. Compounds in the scope of the invention (9), such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, 1-octadecanol, allyl alcohol, 2-butene-1, 1-yl, 2-hexene-1 Single-base saturated or unsaturated aliphatic alcohols having 1 to 20 carbon atoms, or cycloaliphatic alcohols having 3 to 7 carbon atoms such as cyclohexanol and cyclopentanol, or aromatic alcohols such as fluorenyl alcohol and phenylethanol . The homoalcohol used is not limited to a monovalent alcohol, and may be a divalent alcohol 'such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or propylene glycol, or a polyvalent alcohol such as glycerin. Among them, from the viewpoint of the demand of the reaction product, it is preferable to use methanol or ethanol. In addition, carbon monoxide and oxygen used as raw materials do not need to be high-purity gases', and they may be gases diluted with inert gases such as nitrogen, argon, and carbon dioxide. In particular, in order to prevent an explosion event caused by oxygen under reaction conditions, a gas diluted with an inert gas is preferred. This means that air can also be used instead of oxygen. The carbonic acid diester generation step used in the present invention is to react alcohol, carbon monoxide and oxygen in the catalyst liquid. When the copper compound used at this time is Cu CJ2, the reaction formula is as follows. (Oxidation) 2 (R0H) + 1/202 + 2 (CuC 5) * Xn- 2 [CuORC3Z] * Xn + H2 (2) (carbonylation) 2 [CuORCίΜ. Xn + CO— (R0) 2C0 + H20 + 2CuC1 · Xn (3) After combining the above two reaction formulas, the following formula can be changed. 2 (R0H) + C0 + 1/20 Cantonese (R0) 2C0 + H20 (4) This paper size applies to China National Standard (CNS) A4 specifications (Guang Jing) _-----------I '— ——111— ^ · 1111111 I). -M (Please read the notes on the back before writing this page) 448 153 A7-—_______ B7 V. Description of the invention (10 > where' R is alcohol residue X is a coordination group, 'η is the number of coordination groups bound to CuCJ ?. The cyclic nitrogen compound in the catalyst liquid of the present invention has a use ratio of 0-1 to 100, and It is better to be ~ 50. The best is 1 to 10. If this value is less than 0.1, there will be undissolved copper compounds, which cannot become a homogeneous catalyst system, so it is not suitable, and more than 10 At 0, copper compounds are precipitated in the presence of alcohol, so it is not suitable. The use ratio of glycol ether is that the molar ratio of copper compounds is from 0 to 200 ', and preferably from 1 to 100, most preferably 3 ~ 50. If the value is lower than 0_5, the catalyst system will not become a homogeneous system. When it exceeds 2 0, the copper concentration in the catalyst solution will be reduced, and a sufficient reaction speed cannot be obtained. The use ratio of the raw alcohol produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is: the molar ratio of copper compounds to copper compounds is 10 to 700, and 30 to 500 is preferred, and 1 is 50 to 300. If this value is less than 10, a sufficient reaction rate cannot be obtained, and if this value exceeds 7 0, the copper concentration in the catalyst solution will be reduced, and a sufficient reaction rate cannot be obtained, so neither is suitable. The reaction catalyst in the carbonic acid diester formation step of the present invention is set as follows. That is, the reaction temperature is 30 to 200 ° C, preferably 50 to 150 ° C, and 80 to 140 °. C is better, carbon monoxide partial pressure (C0 partial pressure) is from 0.1 to 50 kg / cnf, preferably from 1 to 30 kg / cnf, and more preferably from 1 to 25 kg / crri, and the oxygen partial pressure (〇2 Partial pressure) is 0.001 ~ 10kg / cm, preferably 0.005 -13-This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm > 448153 A7 B7 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperatives today. V. Invention description (U) ~ 5kg / crri, and more preferably 0.01 ~ 3kg / crri. If the reaction temperature is lower than 30 ° C *, it will not be available When the reaction rate is more than 200 ° C, there are many by-products and the glycol ethers are thermally decomposed. Therefore, both of them are not suitable. In addition, if the CO partial pressure is less than 0.1 kg / ciri, it will not be possible. A sufficient reaction speed * is obtained, and if it exceeds 50 kg / cm, the manufacturing cost of a hemp pressure vessel (reactor) will be increased, so it is not economical. If the partial pressure of 〇2 is less than 0.001 kg / cm2, a sufficient reaction speed cannot be obtained, and when it exceeds 10 kg / ciri, glycol ethers will be oxidatively decomposed, so neither is suitable. The method of the carbonic acid diester formation reaction of the present invention may be any method such as a batch method or a flow-through method. (Batch method) The catalyst liquid is first put into the reactor, and then the CO and 〇2-reactor are supplied. The type of the reactor is preferably a reactor that can fully achieve gas-liquid contact, so a stirred tank or bubble tower can be used. For various reactors currently known, the supply of C 0 in this batch reaction is 8 to 200 mo I / hr, preferably 10 to 100 hr 1 / hr, per 1 gram of copper compound. The supply amount is 0.08 to 4 mol / hr, preferably 0.1 to 2 mol / hre. The carbonic acid diester produced is recovered from the reactor in the gas phase, and then alcohol and pyridine are added to the residual liquid, The amount of glycol ethers is supplemented to carry out the second and subsequent reactions. In addition, if the carbonic acid diester is recovered from the reactor in liquid phase, the paper size is also applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) —!丨! — _ !! 1 Order! !! Line J-C (Please read the precautions on the back before filling this page) -14-4481 53 Α7 Α7 Β7 V. Description of the invention (12) Distillation column can be used for distillation and recovery "At this time, the distillation column can be Chinese meal residual liquid (containing Cu catalyst, cyclic nitrogen compounds and glycol ethers) is sent back to the reactor, and then the supplemental amounts of alcohol, cyclic nitrogen compounds and glycol ethers are added to carry out The following second response. In the liquid phase extraction method, because the product can generally be separated by a distillation column, its efficiency is better than that of the gas phase extraction method. The above reaction formula (2) and reaction formula (3) in the step of forming a carbonic acid diester are not required. It can be completed in one time, and can be performed in sequence. That is, "the catalyst liquid is first put into the reactor, and the reaction is performed under the condition of a partial pressure of 0.002 to 10 kg / ciri and a temperature of 30 to 150 ° C, and then the reaction is removed. The reaction is performed under the conditions of a partial pressure of 0.1 to 50 kg / cnl and a temperature of 30 to 180 ° C to form a carbonic acid diester. Please read the notes before reading. This page is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (circulation method). It is to continuously supplement the alcohol, CO compounds, and glycol ethers and recover the reaction products. (The carbon type can be the method of taking out the reaction products of the stirring tank and the bubble column. When the latter is used, the products are usually applied outside the reactor, and distilled nitrogen compounds and glycol ethers are used. Generally, the method of adding steam to the reaction system by adding cyclic nitriding amount of 0, and if necessary, and continuously taking the acid diester) can be used. The type of this reactor is various reactors currently known. As for the gas phase extraction or liquid phase extraction. If a distillation device is provided for the part, the residual liquid from the reactor (including the CU catalyst and the ring) is continuously returned to the reactor. Efficiency This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15-448153 A7 B7 V. Description of the invention (13) (Please read the precautions on the back before filling out the poor page) Also, this The reaction (2) and the reaction (3) in the flow-through reaction can also be performed separately. That is, the two reactors are arranged in a row, and then the oxidation step of reaction (2) and the refining step of reaction (3) are sequentially performed in the respective reactors. * In these steps, the C 0 partial pressure, 0 2 Conditions such as partial pressure and temperature can be the same as the above batch type. Because the oxidation step and the carbonylation step are performed separately, it is possible to avoid the explosive mixture formed when mixing C 0 and 〇 2. If such a system can be combined, the catalyst of the present invention can be made into a stable uniform catalyst. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the catalyst liquid of the present invention will reduce its activity after the reaction, but the catalyst liquid can be regenerated by using carbon monoxide to contact such a catalyst liquid whose activity decreases. In order to regenerate the catalyst liquid, the carbon monoxide partial pressure when the carbon monoxide is contacted with the catalyst liquid whose activity decreases is 0.1 kg / crrf or more, and preferably 0.5 kg / cnf or more. Although the upper limit of the carbon monoxide partial pressure is not particularly limited, it is generally 50 kg / ciri. If the partial pressure of CO is less than 0.1 kg / crrf, the catalyst liquid cannot be fully regenerated, and when it exceeds 50 kg / cm1, the cost of the equipment is increased, so neither is suitable. In addition, the contact temperature between this catalyst liquid and C 0 is 50 ~ 200 ° C, and preferably 70 ~ 1 50 ° C. If the temperature is lower than 50 ° C, the catalyst liquid cannot be fully regenerated, and when it exceeds 200 ° C, the glycol ethers will be decomposed, so neither is suitable. The regenerated catalyst liquid can continue to be used as the catalyst liquid in the carbonic acid diester generation step. In the case of regenerating the catalyst liquid with reduced activity, it is not necessary to regenerate the entire catalyst liquid. It is only necessary to regenerate a part of the catalyst liquid with reduced activity, and this regenerated catalyst liquid and unregenerated catalyst liquid can be mixed and supplied to the reaction system. . ΪThe paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ~~: _ 16 a 448 153 A7 B7 V. Description of the invention (14) The regeneration of this catalyst liquid can be used in the reaction device for the manufacture of carbonic acid diester It is carried out internally or in a catalyst liquid regeneration device which is separately provided from the reaction device, and β is described below with reference to the drawings. FIG. 1 is an example of a system diagram when the present invention is implemented. In Fig. 1, 5 is a reaction device, 6 is a carbonic acid diester separation device, and 9 is a catalyst regeneration device. The purpose of the reaction device is to react alcohol, CO, and 02 in a catalyst liquid to form a carbonic acid diester, and it is a stirring type reaction device. The purpose of the carbonic acid diester separation device 6 is to separate the carbonic acid diester in a vapor form from the catalyst liquid. The separation device used is a flash boiling device or a distillation column. The purpose of the catalyst liquid regeneration device 9 is to regenerate the catalyst liquid after the carbonic acid diester is separated. The device used is a gas-liquid contact device. When manufacturing a carbonic acid diester according to the system according to FIG. 1, the pipelines 11, 12, and 13 communicating with the reaction device 5 filled with a catalyst liquid are used to supply CO, O2, and alcohol, respectively, and the alcohol, C0 and 〇2 react to form carbonic acid diester. ”Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before writing this page). The catalyst liquid and carbonic acid obtained in the reaction device 5 The reaction solution formed by the diester and unreacted alcohol is introduced into the carbonic acid diester separation device 6 through the line 5a. The unreacted 〇2 / (: 0 mixed gas system is discharged out of the system through line 14 and then through condenser 15. In this condenser 15, condensable compounds such as alcohol contained in the gas can be condensed. " The reaction generated liquid in the carbonic acid diester separation device 6 passes through the pipeline. The paper size is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -17-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (15) 6 b 'Separate the carbonic acid diester and unreacted alcohol contained therein in a vapor manner', and the catalyst liquid remains as a liquid component in the separation device. The catalyst liquid in the separation device 6 It is then introduced into the regeneration device 9 through line 6a, and is brought into contact with C0 to be regenerated. The catalyst liquid that is regenerated by contacting C 0 in the regeneration device 9 is returned to the reaction device 5 through line 9a, and the unreacted C is It is introduced into the reaction device 5 through line 9b. As mentioned above, this system can continuously generate carbonic acid diester and continuously regenerate the catalyst liquid. In the system shown in Fig. 1, the raw alcohol does not necessarily need to go through line 1 3 Supply to reaction device 5, if necessary Some or all of the catalyst liquid can be introduced into the regeneration device 9 through the line 16, and then the regeneration device 9 is supplied to the reaction device 5 through the line 9a. In addition, part of the catalyst liquid separated by the separation device 6 through the line 6a can also be used. It is sent to the regeneration device 9 and directly introduced into the reaction device 5. Fig. 2 is a schematic diagram of a device for implementing the present invention. This device is a bubble reactor type device, which is made into a carbonate diester production zone Z1. The cylindrical reaction cylinder 21 and the cylindrical regeneration cylinder 25 which becomes the regeneration zone Z2 for the regeneration of the catalyst liquid are formed. The upper ends of the cylinder 21 and the cylinder 25 are in phase with the communicating cylinder 2 1 a. The connection and the lower end are connected to the communicating cylinder 2 1 b, and the whole is a device with a loop structure. The catalyst liquid is filled in the reaction cylinder 21 and the regeneration cylinder 25, and the catalyst liquid at this time can be mixed in advance. Alcohol in the reaction raw material. Then, the 〇2 / CO mixed gas is introduced from the bottom of the reaction tube 21 through the line 2 2 and is guided through the line 2 3. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). ) 1 --- I --- I! Order-!-Line IΊ (Please read the note on the back before washing Page) —18 ^ 448153 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (16) Into alcohol. Due to the introduction of this 〇2 / CO mixed gas *, air bubbles can be generated in the cylinder 21 The rising liquid flow of the reaction solution. The reaction solution that becomes the rising liquid flow can discharge bubbles from above the cylinder 21, and then flow into the cylinder 25, because it has a downward shape in the cylinder 25, so it can A downward flow is generated in the cylinder 25, and a circulating flow in a flow direction shown by an arrow is formed between the cylinder 21 and the cylinder 25. The carbonic acid diester production zone Z1 in the apparatus for producing a carbonic acid diester shown in FIG. 2 will generate a carbonic acid diester reaction due to the reaction of alcohols with CO and 03, and the catalytic liquid regeneration zone Z2 will be caused by the catalytic liquid. Contact with C 0 causes regeneration of the catalyst liquid. In the 〇2 / CO mixed gas introduced into the reaction tube 21 through the line 22, the supply amount of C0 is stoichiometrically larger than the supply amount of 〇2, that is, per gram molecule of 〇2. <: 0 is used for more than 2 mol molecules. Therefore, C 0 can be dissolved in the catalyst liquid introduced into the regeneration cylinder 25 from the top of the reaction cylinder 21 through the communication cylinder 2 1 a. C 0 in the role of regeneration. The regenerated catalyst liquid is introduced from below the cylinder 25 through the communicating cylinder and introduced below the cylinder 21. If necessary, C0, which can promote the regeneration of the catalyst liquid, can be introduced into the regeneration cylinder 25 through the pipeline 24 without causing a large degree of influence on this circulating flow. The reaction liquid formed from the carbonic acid diester and unreacted alcohol can be discharged to the outside through the line 2 6 above the reaction cylinder 21. In addition, the unreacted C 0 gas system is discharged to the outside through the condenser 2 7 and then through the pipeline 2 8 (please read the precautions on the back before filling in this page.) This paper standard is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) _ 19 a 448 153 A7 B7 Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, but the fifth, description of the invention (17 > Figure 3 is a schematic diagram of other reaction devices used in the implementation of the method of the present invention. This device The cylinder (outer cylinder) 3 1 and the concentric cylinder (inner cylinder) 3 5 inserted in the cylinder 3 1 are formed at the upper end 3 5 a and the lower end 3 5 b of the inner cylinder 3 5. The open end communicates with the outer cylinder 3 1 on the outer side, so that the gap portion 3 1 a formed between the inner surface of the outer cylinder and the outer surface of the inner cylinder 35 is the regeneration zone Z2 of the catalyst liquid and The inside of the inner cylinder 35 becomes the device of the carbonic acid diester generation zone Z1. The catalyst liquid is filled into the outer cylinder 3 1 and the inner cylinder 35, and is introduced from below the inner cylinder 35 through the pipeline 32 and the gas nozzle. The 02 / C0 mixed gas and the raw material alcohol are introduced through the pipeline 3 3. The 02 / C0 mixed gas is introduced, so it can be used in the inner cylinder 3 5 Formation, the rising liquid flow formed by the reaction solution containing bubbles and low density. When this rising liquid flow is discharged through the opening 3 5 a at the upper end of the inner cylinder 3 5, the gas (c 0) contained therein will be dispersed. It goes out and the catalyst liquid with a higher density is lowered in the outer cylinder 31, and then enters the inner cylinder 3 5 through the lower opening 3 5 b of the inner cylinder 35. Therefore, the outer cylinder 3 1 and the inner cylinder 3 5 A circulating flow in the flow direction shown by the arrows is formed between them. The acid-breaking diester generation zone Z in the apparatus for producing dicarbonate shown in Fig. 3 generates carbonic acid due to the reaction between alcohols, C0, and O2. Diester formation reaction 'Also, the catalyst liquid regeneration zone Z2 will cause the catalyst liquid to regenerate due to the catalyst's contact with c 0. It is introduced into the 02 / C0 mixed gas in the inner tube 3 5 from the line 3 2 and the supply amount of C02 In terms of stoichiometry, it is necessary to supply more than 〇2, which is an excess amount, so 'is soluble in the catalyst liquid falling within the gap 3 1 a. Read the note on the back | α page size is suitable for Yin Guo country Standard (CNS) A4 specification (210 X 297 mm) -20-448 1 5 3 A7 B7 V. Description of invention (18) ------------- Teach -(Please read the precautions on the back before filling in this page) c 〇 'and the catalyst's liquid can be regenerated due to the role of C0 in the catalyst. The regenerated catalyst liquid is provided by the gap 3 1 a. The lower part is introduced into the inner cylinder 35 through the open end 3 5 b. If necessary, c 0 can be introduced into the gap part 3 1 a through the pipeline 3 4 to promote the regeneration of the catalyst liquid without causing a large effect on the circulating flow. As for the reaction liquid formed by the carbonic acid diester and unreacted alcohol, it is discharged from the upper end of the outer cylinder 31 through the line 36 to the outside. In addition, the unreacted gas is discharged to the outside through the condenser 37 and then through the pipeline 38. The device shown in Figs. 2 and 3 can reduce the energy consumption because it does not require the power to stir the liquid. It has a simple shape and a simple device structure, so it can become a tower shape, so it has the advantage of making the device larger. Β The following will explain the β- 丨 line of the present invention in detail by way of Example 1. ) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed and prepared a 2000m flask with a screw cap. Pyridine 28 .. 12 was placed in it, and I 2g of C u C $ was slowly added under stirring. Immediately after that, triethylene glycol dimethyl ether (HISOLV HUM, manufactured by Toho Chemical Industry Co., Ltd.) 69.2 g was added. [C u C j? Add Triethylene Glycol Dimethyl Ether immediately after adding C u C as a solution. Because there is only a small amount of solids, the temperature can be raised to about 50 ° C, and stirring is continued during this period to make it a uniform solution. And on this paper scale, the Chinese national standard (CNS > A4 specification (210 X 297 mm) -21-A7 ^ 48153 _________B7____ V. Description of the invention (19) Homogeneous solution as catalyst liquid I. Next, methanol 51. lg was added to it, and no thick green uniform solution precipitated by Cu CJ2 was found. (Please read the precautions on the back before filling this page) Example 2 (Modulation of the catalyst solution n)-Except for the CuCj used in Example 1. ? Changed to 13.5g 'pyridine to 31.4 g, triethylene glycol dimethyl ether to 77.3 g, the other is prepared in the same manner as in Example 1 to form a catalyst solution Π. Comparative Example 1 ( Preparation and comparison of catalyst liquid I) The same as in Example 1 except that triethylene glycol dimethyl ether was not used. Although the obtained catalyst liquid was a homogeneous solution, solid components were precipitated after adding methanol to obtain a slurry. Even if it is heated to 50 ° C under stirring, it can not dissolve the solid content, and it is still a mud system. Example 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (synthesis of dimethyl carbonate). Catalyst liquid Π 12 2.2 g into a pressure cooker (nickel-based C gold '' Pressure 50kg / ciri), and then add 57.1 g of methanol. After purifying the inside of the autoclave by using C0_ body, the pressure was increased to 25kg / cirf with C0 gas. After that, 1 000 r. P Stir the reaction solution in m mode and raise the temperature to 130 ° C. When the paper size is reached, the Chinese National Standard (CNS) A4 specification (2〗 0 X 297 mm) will be applied. -22-4481 53 A7 B7 Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau. V. Invention Description (20) When the temperature and the state are stable, start to supply CO gas and O 2 oxygen 'to start the reaction. Also, the supply of this CO gas is 1.2 5 The supply of m ο 1 / hr and 〇2 was 0.1 l Ι / hr. After 5 hours, a sample of the reaction solution was taken, and the concentration of dimethyl carbonate (carbonic acid diester) (DM C.) was measured by gas chromatography. As a result, the dimethyl carbonate (DMC) produced was 30.9 g, and the copper utilization rate was 561%. In addition, the methanol base selection rate SM at the 5th hour after the test was started was 80%, and the CO base selection was The rate Sco is 60% (the second hour) to 40% (the fourth hour). The reaction solution was determined to be a homogeneous solution. Any corrosion phenomenon in the existing nickel-based alloy C reactor "As for the above-mentioned definition of copper utilization (%), (DMC production amount (mo 1) X 2 / put copper salt (mo I) X100." The definition of the methanol base selection rate SM (%) is as follows: Sm = DMC generation amount (mo 丨) X 2 / methanol consumption (mol) X 1 0 0 C 0 The base selection rate sco (%) is defined as the following formula. Sco = DMC production amount (mo 1) / CO consumption amount (m ο 1) X 1 〇〇 Example 4 (synthesis of dimethyl carbonate in a manner) The experimental device used for p kg is the device system shown in FIG. 4. j In Figure 4, 5 1 is a reaction device, 5 2 is a first cooler, and 5 3 is dimethyl carbonate --I --------- i — 1 — m — — Ι — — — — — 1}-.-... (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210x297 mm)-23 _ 4481 ^ 3 Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau V. Description of the Invention (21) The receiver '54 is the second cooler, 55 is the O2 meter, and 56 is the gas meter. A catalyst solution formed from CuCiZl. 3 weight unit, pteridine 2.9 weight unit and triethylene glycol dimethyl ether 49.6 weight unit and methanol 4 6.2 weight unit mixed solution SO OmJ? It is put into a reaction device 51 made of thorium alloy C. Then the mixed solution (reaction solution) was stirred in a 100Or.p'm mode, while C0 was supplied at a rate of 1.25mol / hr, and the temperature was raised to 100 ° C. 'Then' passed the line 5 8 to react by The bottom of the device 51 is supplied with a 0 2 / C02 mixed gas to the reaction device 5 1, and then a methanol / pyridine mixture is supplied from the bottom of the reaction device 51 through a line 57. At this time, the total partial pressure in the reaction device 51 is maintained at 25 ° / £; 11120 (the 00 partial pressure is about 24.51 ^ yttrium / <: 11 {), and the supply method of 02 is 0.1 lmo 1 / hr, the pyridine concentration in the methanol / pyridine mixture is 0.5 wt%, and the method of supplying this mixture is to enable the reaction device The level of liquid inside is maintained in a certain way. Next, from above the reaction device 51, a mixture of dimethyl carbonate, methanol, pyridine, H20, and CO was taken out in a gas phase, and introduced into the first cooler 52. The cooler 52 is maintained at a temperature of 10 ° C and a pressure of 1 kg / crrfG. While the condensate obtained from the first cooler 5 2 is introduced into the receiver 53, another gas-phase mixture is introduced into the second cooler 54. In the second cooler 54, a refrigerant at 4 ° C is circulated and operated at atmospheric pressure. The gaseous matter obtained from the cooler 5 4 (exhaust gas 2) Please read the precautions on the back of the paper again. I This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -24-448153 Intellectual Property Bureau, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Invention Description (22) body) is discharged through 02 gauge and gas gauge. The condensate is introduced into the receiver 53. After the experiment was started, the exhaust gas was sampled through the gas meter at intervals of 0.5 hours, 1 hour, 2 hours, 3 hours, and 4 hours, and C02, C0, Respective concentrations of dimethyl carbonate, methanol, and O2 ^ At the same time, methanol, pyridine, dimethyl trisuccinate, and dimethyl carbonate in the recovered liquid in the receiver 53 were also measured by gas chromatography. Each concentration was measured by Karl Fischer's method. Based on the above results, the C 0 reference selectivity S (C0) and the methanol reference selectivity S (M) related to dimethyl carbonate were calculated. The values are shown in Table 1. This S (C0) is represented by the following formula. S (CO) = {1-A / (BC)} / 2X 100 (¾) A: C02 concentration (vol%) in exhaust gas B: 02 concentration (vol%) in supply gas C: exhaust gas 02 concentration (vol%) S (M) is expressed by the following formula. S (M) = D / Ex2X 100 (%) D: The amount of dimethyl carbonate produced (mol) E: The amount of methanol consumed (mol) The paper size applies the Chinese National Standard (CNS) A4 Regulation (210 X 297 mm) -------------! 丨 Order! Line- < Please read the precautions on the back before writing this page) -25-448153 A7 B7_ V. Description of the invention (23) Table 1 Measurement time r—— 0.5 *-~ — 1 2 3 4 s (co) 83- -77 78 72 59 S (M) 92 99 100 100 100 (Please read the precautions on the back before filling this page) After 4 hours of operation in this experiment, the productivity of dimethyl carbonate per 1β reaction solution is , 0.5 9 mi / hr. L. Also, in this experiment, no by-products other than c were generated. Line Example 5 (Synthetic dimethyl carbonate) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The catalyst liquid and methanol 57.ig of Example 2 were placed in a 300m I? Nickel-based alloy C pressure cooker in. First, an oxidation step is performed. That is, after purifying the inside of the autoclave at 0 2 ′, the reaction solution was stirred at 1400 r.p.m., and the temperature was raised to 70 ° C. Thereafter, the pressure was raised to 4 kg / cma at 0 2 to start the reaction. After 2 hours, the temperature adjustment was stopped to reduce the temperature of the reaction solution to below 40 ° C. Second, a carbonylation step was performed. That is, after depressurization, the paper size of the pressure cooker is applied to the Chinese national standard (CNS > A4 (210 X 297 mm)) after depressurization. _ 26-448 1 53 Α7 Β7 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 Printed by a consumer cooperative Explanation (24) purification, after which, the reaction solution was stirred at 1400r.ρ · m and the temperature was raised to 1 20 ° C. Then, the pressure was increased to 2 kg / c nf using CO to start the reaction "2 8g ， CO selectivelyis for the dimethyl carbonate is 3. 8g, CO selectivity is as follows: the temperature adjustment is stopped after hours, so that the temperature of the reaction solution drops below 40 eC. Then take a sample of the reaction solution and a gas sample, and analyze by gas chromatography. 76%. Comparative Example 2 (Synthesis of Dimethyl Carbonate) A mixed solution of 19 g of pyridine, 24 g of CuC, and 120 g of methanol was prepared in the same manner as in Comparative Example 1. As a result, a solid component was present in the mixed solution, which was a slurry. This mixture was put into a 30 OmJ? Nickel-based alloy C pressure cooker. First, an oxidation step was performed. That is, after purifying the inside of the pressure cooker with 02, the reaction solution was stirred at 1400r.Pm, and the temperature was raised to 70 °. C. Thereafter, the pressure was increased to 4 kg / crri by using 02. In order to start the reaction. After 5 minutes, the temperature adjustment was stopped to reduce the temperature of the reaction solution to below 40 ° C. Secondly, the carbonylation step was performed. That is, the pressure in the autoclave was purified with CO gas after depressurization, and then 1400r. P The reaction solution was stirred in m mode, and the temperature was raised to 120 ° C. Thereafter, the pressure was increased to 25 kg / cni using CO gas to start the reaction. After 45 minutes, the adjustment was stopped, and the temperature of the reaction solution was reduced to 4 Below 0 ° C. Next, take a sample of the reaction solution and measure the dimethyl carbonate (DMC) concentration by gas chromatography. --------------- :. --- -_ (Please read the precautions on the back before writing this page) Order · · --- line. This paper size applies to the national standard (CNS) A4 (210 X 297 public love) -27-448153 A7 B7 V. Explanation of the invention (25) Although it is confirmed that dimethyl carbonate is formed, about 80% of the reaction solution is a gel-like solid, so it is not practical. Examples 6 to 10 (Synthesis of dimethyl carbonate) The mixture liquid of the composition shown in Table 2 was used in place of Example 3, and the catalyst liquid and the methanol liquid mixture were put in a pressure cooker. The same experiment was carried out. The results of dimethyl carbonate production after 5 hours are recorded in Table 2. (Please read the precautions on the back before writing this page) Order -------- * Intelligent Property Bureau, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

448153 A7 B7 五、發明說明（26 ) 表 2 經濟部智慧財產局員工消費合作社印製項目實施例 6 7 · 8 9 10 放入成分 CuCl 3. 38g 3. 38g 3. 38g 3. 38g 3. 38g 三乙二醇二甲基醚 T7. 3g 77. 3g T7.3g 77. 3g 77. 3g 甲醇 57. lg 57. lg 57. lg 57. lg 57. lg Hit啶 7. 9g — — — 羥基吡啶 — 9. 4g 1 — — — 甲基吡啶 — — 9. 4g — — 2, 2’ -吡啶基 - — — 8. Og 9. 2g 1, 1菲繞琳 — — — — 9. 2g 碳酸二甲基之生成量 28. Og 6. Og 20, Og 23. Og 19. 9g 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公釐）請先閱讀背 Φ 之注意事項再填寫頁 ~ 29 - 448153 A7 B7 五、發明說明（27 ) 實施例1 1〜1 5 觸 5 的，中又鍋。壓驗高實入行放進。代 3 3 取例表液施於合實載混同記之他量成其成組，生 } 示外酯醋所液甲甲 3 .合二二表混酸酸以醇碳碳了甲的成除及後合液時 { 媒小 ilIIIIIIIIII—— — —— — — II — — — ill— — — l]Jt I ! -1 (請先閱讀背面之注意事項再填寫本頁) .經濟部智慧財產局員工消費合作杜印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 448 153 A7 B7 五、發明說明（28 ) 表 3 經濟部智慧財產局員工消費合作社印製項目實施例 11 12 13 14 15 放入成分 CuCl 3. 38g 3. 38g 3. 38g 3. 38g 3. 38g 吡啶 7. 8g 7. 8g 7. 8g 7. 8g 7. 8g 甲醇 57. lg 57, lg 57. lg 57. lg 57. lg 乙二醇單苯基醚 77, 3g — — 丨 — _ " 三乙二醇單甲基醚 — 77. 3g — — — 丙二醇單甲基醚 — — 77. 3g — — 二乙二醇單丁基醚 — :- • — 77. 3g — 三乙二醇 — — — — 77. 3g 碳酸二甲基之生成量 20. lg 22. lg 28. Og 22. 4g 15. 6g 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) 31 - 448153 A7 B7 五、發明說明（29 ) 實施例1 6 (合成碳酸二甲酯）將3. 85g的CuCj?溶解於甲醇114. 2g: 吡啶7. 85g'三乙二醇二甲基醚77. 3所形成之混合液中，得觸媒液與甲醇之混合液。其後，將此混合液放入3 OOmj?高壓鍋（鈦製、耐壓5 Okg/cmaG)中〇以C Ο氣體使高壓鍋內純化後，再利用C 0氣體使壓力升至25kg/cnf，其後，以l〇〇〇r. p. m方式攪拌反應溶液，並將反應溫度升至1 0 o°c »當到達設定溫度後，再分別以1. 25mol/hr、〇. 10 mo 1/h r方式連續將CO及02供應給高壓鍋。反應中的壓力則利用控制閥保持爲2 5 k g/crri »反應開始後，以氣相色譜測定第3小時的反應溶液中之碳酸二甲酯濃度。又，測定每1小時後的排放氣體中之氧濃度及448153 A7 B7 V. Description of the invention (26) Table 2 Example 6 of the printed project of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 7 · 8 9 10 Ingredients CuCl 3. 38g 3. 38g 3. 38g 3. 38g 3. 38g Triethylene glycol dimethyl ether T7. 3g 77. 3g T7.3g 77. 3g 77.3g methanol 57. lg 57. lg 57. lg 57. lg 57. lg Hitidine 7. 9g — — — hydroxypyridine — 9. 4g 1 — — — Methylpyridine — — 9. 4g — — 2, 2 '-Pyridyl — — — 8. Og 9. 2g 1, 1 Pyreneline — — — — 9. 2g Dimethyl carbonate Yield: 28. Og 6. Og 20, Og 23. Og 19. 9g This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2) 0 X 297 mm. Please read the notes on the back Φ before filling in the page ~ 29-448153 A7 B7 V. Description of the invention (27) Example 1 1 ~ 1 5 If you touch 5, the pot is in the pot. Compression test Gao Shi Enter the line. Substitute 3 3 take the sample solution and mix it with other substances in the same amount to form a group, and then give a solution of the methyl ester 3, which is a mixture of acid and carbon. After the liquid is combined {介小 ilIIIIIIIIII—— — —— — — II — — — ill — — — l] Jt I! -1 (Please read the precautions on the back before filling this page). Employees of Intellectual Property Bureau, Ministry of Economic Affairs Consumption cooperation Du printed This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 448 153 A7 B7 V. Description of invention (28) Table 3 Examples of printed projects for employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs 11 12 13 14 15 Add ingredients CuCl 3. 38g 3. 38g 3. 38g 3. 38g 3. 38g pyridine 7. 8g 7. 8g 7. 8g 7. 8g 7. 8g methanol 57. lg 57, lg 57. lg 57. lg 57. lg ethylene glycol monophenyl ether 77, 3g — — 丨 — _ " triethylene glycol monomethyl ether — 77. 3g — — — propylene glycol monomethyl ether — 77. 3g — — Lg diethylene glycol monobutyl ether —:-• — 77.3 g — triethylene glycol — — — 77.3 g dimethyl carbonate production amount 20. lg 22. lg 28. Og 22. 4g 15. 6g This paper size applies to Chinese National Standard (CNS) A4 (210 χ 297 mm) (Please read the precautions on the back before filling this page) 31-448153 A7 B7 5 3. Description of the invention (29) Example 16 (Synthesis of dimethyl carbonate) 3.85g of CuCj? Dissolved in methanol 114.2g: pyridine 7. 85g of 'triethylene glycol dimethyl ether 77.3 In the mixed liquid, a mixed liquid of a catalyst liquid and methanol is obtained. Thereafter, the mixed solution was put into a 300 mj? Pressure cooker (made of titanium, pressure resistance 5 Okg / cmaG). After purifying the inside of the autoclave with C 0 gas, the pressure was increased to 25 kg / cnf by C 0 gas. After that, the reaction solution was stirred at 100 rpm and the reaction temperature was raised to 10 o ° c. When the set temperature was reached, it was continuously performed at 1.25mol / hr and 0.10 mo 1 / hr respectively. Supply CO and 02 to the autoclave. The pressure during the reaction was maintained at 25 k g / crri using a control valve. »After the reaction started, the concentration of dimethyl carbonate in the reaction solution at the 3rd hour was measured by gas chromatography. In addition, the oxygen concentration and

爲率用利銅 g 4 4 爲酯 D 甲 )二物酸產碳副的 < 成度生濃果 2 結ο CFor the use of copper g 4 4 as the ester D a) carbon dioxide produced by the di-acid acid < Cheng Dusheng concentrated fruit 2 C

請先 « . 讀背面之注意事項再 Ifk 本 · 頁 I ^ I I 1 I I I訂 I I I I 經濟部智慧財產总員工消費合作社印製 % ο 率 ο 擇〇 9 選 2 準時基ο C % 8 9 爲 Μ S 率擇選準基醇甲又Please «. Read the precautions on the back before Ifk this page · ^ II 1 Order IIII Printed by the Intellectual Property Chief Employees Consumer Cooperatives of the Ministry of Economic Affairs% ο Rate ο Select 〇 9 Select 2 Just-in-time base ο C% 8 9 is MS Selectivity

時小 1 第 % 8 7 爲 0 C S 小 3 第 /(\ % 8 6Hour Min. 1st% 8 7 is 0 C S Min. 3rd / (\% 8 6

分之行進所中 6 1 例施實行進器發蒸 3 轉生旋再以 7 的 } 1 液 1 例媒C 施觸實 C 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -32 - 448153 Λ/ _____Β7______-^- 五、發明說明（3〇 ) 批處理以製造碳酸二甲酯（DMC )實驗時，所回收的反應液之蒸發處理’以去除未反應之甲醇及生成的DMC、水，並同時去除部分的吡啶。其後，將同實施例1 6之放入量的甲醇及吡啶加入所得的觸媒液中，以調製成均勻浪合液，再將其放入高壓鍋中。 - (2 )其次，以CO氣體使高壓鍋內純化後，再利用 CO氣體使壓力升至25kg/cm*，其後，以1〇0〇 r . P m方式攪拌反應溶液，並將反應溫度升至1 0 0 °C ’維持3 0分鐘以使觸媒液再生。 (3)接著，分別以1. 25mol/hr及〇 l〇mol/hr比率將CO及02連續供應給高壓鍋’以開始反應》反應中的壓力則利用控制閥保持於2 5 kg/crri。反應開始後測定第3小時的反應溶液中 DMC。又，反應開始後測定每一個小時的排放氣體中之〇2濃度及co2濃度（副產物）。重覆操作3次上述（1) 、（2) 、（3)步驟。結果記載於表4 β又，實驗中鈦製高壓鍋未有腐蝕現 — — — — — — —— — — — — * I H I I II ^ illllil — -·r ( ' (請先閲讀背面之注意事項再#!'本頁) 經濟部智慧財產局員工消費合作社印製系勻均爲液溶應反且象本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 448153 A7 B7 經濟部智慧財產局員工消費合作杜印製五、發明說明（31 ) 表 4 實驗周期 1 回 2回 3回 D M G生成置（g ) 44.3 44. 8 42.5 G Ο 選擇 S c 〇〈％ ) (1 — 3時間） 78-^ 68 80—60 7 4—59 實施例1 8 (以流通方式合成碳酸二甲酯）所使用的實驗裝置爲，圖5所示之裝置系。圖5中 6 0爲循環唧筒，6 1爲反應裝置，6 2爲閃沸裝置， 6 3爲接收器’ 6 4爲冷卻器’ 6 5爲02計量器，6 6 爲氣體計量器。將由CuCJ?l. 3重量單位、Π比B定3. 9重量單位、三乙二醇二甲基醚3 8 · 1重量單位所形成之觸媒液與甲醇5 6 . 3重量單位的混合液2 0 Om j?放入鎳基合金 C製反應裝置6 1中，另外，將此混合液6 Omj?放入閃沸裝置62中。以1000r. p. m方式攪拌反應裝置 61中的混合液（反應溶液）的同時，並以1. 25 mo Ι/hr方式供應CO，又，將反應裝置61及閃沸本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）訂 -34 - 448 1 〇 3 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（32 ) 裝置6 2升溫至1 〇〇°C。以及使反應裝置6 1之壓力爲 251^2/(：1^〇，閃沸裝置62之壓力爲0. 8kg/ c πί。其次，經管線6 2將02 /CO混合氣體供應給反應裝置6 1及，經管，線6 2將甲醇〆吡啶混合液供應給反應裝置61。而02之供應速度爲0. lmo Ι/hr。又，由排放氣體之組成分析得知，反應裝置內的C Ο分壓爲 24〜24. 8kg/CIri，O2之分壓爲0.02〜 0-12kg/cnf。至於甲醇/吡啶混合液中的吡啶濃度爲0 . 7 5w t %，而供應此混合液的方式爲，其流量（1. 5〜2. 5 mo 1 /h r )能使閃沸裝置內的液態水準保持一定的方式。由反應裝置61以氣液混相方式取出部分的反應溶液，並將其導入閃沸裝置中，以進行閃沸處理。此閃沸裝置的溫度爲100 °C，壓力爲絕對壓0. 8kg/cni。於此閃沸裝置6 2中，由反應溶液分離出所含有之氣體（C 0 )的同時，將反應溶液所含之部分碳酸二甲酯、甲醇、吡啶、水及三乙二醇，以氣相方式送入冷卻器6 4 中’使其成爲凝縮液後再回收。至於由導入冷卻器6 4之 CO所形成的排放氣體則經由〇2計量器6 5及氣體計量器6 6而排出。閃沸裝置6 2內的殘液則利用循環唧筒6 0，以流量 i η方式送回反應裝置6 1 » (請先閱讀背面之注意事項再康驚本頁) ---..¼ 訂·· ，線· 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐） -〇5 ^ 448153 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（33 ) 供應給反應裝置6 1之02幾乎因此裝置內之反應而消耗掉，因此，閃沸裝置6 2內的氣體實際上僅爲C 0 ^ 故於此閃沸裝置內使觸媒液接觸C 0，可使觸媒液再生。又，上述過程係長時間連續運轉的。其反應結果則記載於表5。 *- 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）〇£? 一 36 — A7 448153 B7 五、發明說明（34 ) 表 5 經濟部智慧財產局員工消費合作社印製項目運轉時間（h r ) 1 2 4 6 8 12 16 22 23 選擇率 Sco (¾) 88 79 75 73 76 77 78 78 79 Sm (¾) 103 100 100 102 99.5 97.3 98. θ 102 101 生產性 (mol/L * hr) — — 0.67 0.77 0.75 0. 79 0. 70 0. 73 0. 70 排放氣體中〇2濃度 (vol%) 0. 48 0.20 0. 11 0.09 0. 14 0.45 0. 18 0. 18 0.25 ---------!!^^ *!1 訂-!-線 Id-„ {' (請先閱讀背面之注意事項再撕貧本頁) 本紙張尺度過甩令國國家標準（CNS)A4規格（210 X 297公釐） 448 1 53 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（35) 本發明之觸媒液除了具有優良的選擇性之生成反應的作用外，遺因此觸媒液含有醇銅化合物•而能使反應系內成爲均勻溶液。發明之觸媒液可製造出選擇性良好且收獲率酯，另外，易於回收來自所得反應生成物中又，使用本發明之觸媒液而得到的反應生成體成分之均勻溶液，‘故能直接進行蒸餾處理到高純度碳酸二酯。又，本發明之觸媒液能大幅減少目前作醇/C u C j混合液所造成的腐蝕情形，因明之觸媒液時，可使用比較便宜之鎳基合金反應裝置材料另外，本發明之觸媒液易於再生，即，活性下降之觸媒液的方式，可使觸媒液再生〔圖示主要元件符號說明〕 4、反應裝置 6、分離裝置 9、再生裝置 21、反應筒體 2 2、管線 25、再生筒體 31、外筒 35、內筒促進碳酸二酯，故不會析出因此，使用本良好的碳酸二的碳酸二酯。液因係不含固，因此，易得爲觸媒液之甲此’使用本發 C或鈦等作爲利用C 0接觸 — ίι — mlm -—— — — In ^ — — — — — — —— <請先閱讀背面之注$項再本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -38 - 448153 86109y>||專利申請案中文說明蓍修寶貪民國90年7 五、發明説明（35) 一本發明之觸媒液除了具有優良的選擇性促進碳酸二酯之生成反應的作用外，還因此觸媒液含有醇，故不會析出銅化合物，而能使反應系內成爲均勻溶液。因此，使用本發明之觸媒液可製造出選擇性良好且收獲率良好的碳酸二酯，另外，易於回收來自所得反應生成物中的碳酸二酯又，使用本發明之觸媒液而得到的反應生成液因.係不含固體成分之均勻溶液，故能直接進行蒸餾處理，因此，易得到高純度碳酸二酯》又，本發明之觸媒液能大幅減少目前作爲觸媒液之甲醇/C u C 混合液所造成的腐蝕情形，因此，使用本發明之觸媒液時，可使用比較便宜之鎳基合金C或鈦等作爲反應裝置材料。另外，本發明之觸媒液易於再生，即，利用C0接觸活性下降之觸媒液的方式，可使觸媒液再生· 〔圖示簡要說明〕圖1爲實施本發明時之反應系統圖之例。圖2爲實施本發明之裝置模式圖之例。圖3爲實施本發明之方法時所使用的其他反應裝置模式圖之例。圖4爲本發明實驗裝置之一例。圖5爲本發明實驗裝置之另一例。〔圓示主要元件符號說明〕本紙張尺度適用中國國家樣準（CNS > A4说格（210X297公釐） .^iT線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局工消費合作社印製 -38 - 448153 A7 B7 五、發明說明（36 ) 51、反應裝置 5 2、第1冷卻器 53、碳酸二甲酯接收器 54、第2冷卻器 55、〇2計量器 5 6、氣體計量器 6 0、循環唧筒 61、反應裝置 6 2、閃沸裝置 63、接收器 6 4、冷卻器 6 5、0 2計量器 6 6、氣體計量器 — — — III1—II1 — , I — 1 I I 1 — ^^ 11 — 1111· ^^^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） —〇 y — 4 4 8 153In the branch travel site, 6 1 cases were performed with steaming device 3 rebirth and then 7} 1 liquid 1 case medium C Shi Teng C This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) -32-448153 Λ / _____ Β7 ______- ^-V. Description of the invention (30) In the batch processing to produce dimethyl carbonate (DMC) experiment, the recovered reaction solution is evaporated to remove unreacted methanol and generate DMC, water, and at the same time removed part of the pyridine. Thereafter, the same amount of methanol and pyridine as those of Example 16 were added to the obtained catalyst liquid to prepare a homogeneous wave solution, and then placed in a pressure cooker. -(2) Secondly, after purifying the inside of the autoclave with CO gas, the CO gas was used to increase the pressure to 25 kg / cm *, and thereafter, the reaction solution was stirred in the manner of 1000 r .P m, and the reaction temperature was raised. To 100 ° C 'for 30 minutes to regenerate the catalyst liquid. (3) Next, CO and 02 were continuously supplied to the autoclave at a rate of 1.25 mol / hr and 0.1 mol / hr, respectively, to start the reaction. The pressure in the reaction was maintained at 25 kg / crri using a control valve. The DMC in the reaction solution at 3 hours after the start of the reaction was measured. In addition, after the reaction was started, the 02 concentration and the CO 2 concentration (by-products) in the exhaust gas were measured every hour. Repeat the above steps (1), (2), and (3) three times. The results are shown in Table 4 β. In the experiment, there was no corrosion in the titanium pressure cooker — — — — — — — — — — — * IHII II ^ illllil —-· r ('(Please read the precautions on the back before # ! 'This page) The printing department of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are all liquid-soluble and the Chinese national standard (CNS) A4 specification (210 X 297 mm) applies to this paper size. 448153 A7 B7 Printed by the staff of the Property Bureau, Du printed 5. Description of the invention (31) Table 4 Experiment cycle 1 time 2 times 3 times DMG generation device (g) 44.3 44. 8 42.5 G 〇 Select S c 〇 <%) (1-3 hours ) 78- ^ 68 80—60 7 4—59 Example 18 (Synthesis of dimethyl carbonate in a flow-through manner) The experimental device used was the device system shown in FIG. 5. In Fig. 5, 60 is a circulating drum, 6 1 is a reaction device, 6 2 is a flash boiling device, 6 3 is a receiver '6 4 is a cooler' 6 5 is a 02 meter, and 6 6 is a gas meter. A mixed solution of a catalyst liquid formed from CuCJ? 1.3 weight units, Π ratio B, 3.9 weight units, and triethylene glycol dimethyl ether 3 8 · 1 weight units, and methanol 5 6 3 weight units 2 0 Om j? Was placed in a nickel-based alloy C reaction device 61, and this mixed solution 6 Omj? Was placed in a flash boiling device 62. While stirring the mixed solution (reaction solution) in the reaction device 61 at 1000r.p.m, and supplying CO at 1.25 mo Ι / hr, the paper size of the reaction device 61 and flash boiling is applicable to China. Standard (CNS) A4 specification (210 X 297 mm) Order -34-448 1 〇3 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (32) Device 6 2 Warm up to 100 ° C . And the pressure of the reaction device 61 is 251 ^ 2 / (: 1 ^ 〇, the pressure of the flash boiling device 62 is 0.8kg / c πί. Second, the 02 / CO mixed gas is supplied to the reaction device 6 through the line 62. 1 and, via tube, line 6 2 The methanol / pyridine mixture was supplied to the reaction device 61. The supply speed of 02 was 0.1 lmo 1 / hr. In addition, from the analysis of the composition of the exhaust gas, it was found that C Ο in the reaction device The partial pressure is 24 ~ 24.8kg / CIri, and the partial pressure of O2 is 0.02 ~ 0-12kg / cnf. As for the pyridine concentration in the methanol / pyridine mixed solution is 0.75w t%, and the method of supplying this mixed solution is , Its flow rate (1. 5 ~ 2. 5 mo 1 / hr) can maintain a certain level of liquid level in the flash boiling device. A part of the reaction solution is taken out by the reaction device 61 in a gas-liquid mixed phase manner and introduced into the flash In the boiling device, a flash boiling process is performed. The temperature of the flash boiling device is 100 ° C and the pressure is 0.8 kg / cni. In this flash boiling device 62, the gas (C 0), at the same time, part of the dimethyl carbonate, methanol, pyridine, water and triethylene glycol contained in the reaction solution was vapor-phase After entering the cooler 6 4, it is made into a condensate and then recovered. As for the exhaust gas formed by the CO introduced into the cooler 6 4, it is discharged through the 0 2 meter 6 5 and the gas meter 6 6. Flash boiling device The residual liquid in 6 2 is returned to the reaction device 6 1 using the circulating cartridge 60 in a flow rate i η »(Please read the precautions on the back before shocking this page) --- .. ¼ Order ··, line · This paper size applies Chinese National Standard < CNS) A4 specification (210 X 297 mm)-0 5 ^ 448 153 A7 B7 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (33) Supply to the reaction device 6 1 of 02 is almost consumed by the reaction in the device. Therefore, the gas in the flash boiling device 62 is actually only C 0 ^ Therefore, contacting the catalyst liquid with C 0 in this flash boiling device can make the catalyst liquid regeneration. In addition, the above-mentioned process runs continuously for a long time. The reaction results are shown in Table 5. *-This paper size is in accordance with Chinese National Standard (CNS) A4 (210x297 mm) 〇 £? One 36 — A7 448153 B7 V. Description of Invention (34) Table 5 Printed Project Running Time of Employees' Cooperatives of Intellectual Property Bureau, Ministry of Economic Affairs (Hr) 1 2 4 6 8 12 16 22 23 Selectivity Sco (¾) 88 79 75 73 76 77 78 78 79 Sm (¾) 103 100 100 102 99.5 97.3 98. θ 102 101 Productivity (mol / L * hr ) — — 0.67 0.77 0.75 0. 79 0. 70 0. 73 0. 70 O2 concentration (vol%) in the exhaust gas 0.48 0.20 0. 11 0.09 0. 14 0.45 0. 18 0. 18 0.25 --- ------ !! ^^ *! 1 Order-!-Line Id- „{'(Please read the precautions on the back before tearing down this page) The paper size is too high and the national standard (CNS) A4 Specifications (210 X 297 mm) 448 1 53 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (35) In addition to the excellent selective formation reaction of the catalyst fluid of the present invention, Therefore, the catalyst liquid contains a copper alkoxide compound and can make the reaction system into a homogeneous solution. The catalyst liquid of the invention can produce a good selectivity. Yield ester, and it is easy to recover the homogeneous solution of the components of the reaction product obtained by using the catalyst solution of the present invention from the obtained reaction product, so it can be directly distilled to a high-purity carbonic acid diester. The catalyst liquid of the present invention can greatly reduce the corrosion caused by the current alcohol / C u C j mixed liquid. When the catalyst liquid of Ming is used, the relatively cheap nickel-based alloy reaction device material can be used. In addition, the catalyst of the present invention The liquid is easy to regenerate, that is, the catalyst liquid with reduced activity can regenerate the catalyst liquid [illustration of the main component symbols in the figure] 4. Reaction device 6, separation device 9, regeneration device 21, reaction cylinder 2 2, pipeline 25. The regeneration cylinder 31, the outer cylinder 35, and the inner cylinder promote the carbonic acid diester, so it will not be precipitated. Therefore, this good carbonic acid dicarbonate diester is used. Zhijia this' uses this hair C or titanium as the contact with C 0 — ίι — mlm -—— — — In ^ — — — — — — < Please read the note on the back first and then this page) Paper size Use Chinese National Standard (CNS) A4 specification (210 X 297 mm) -38-448153 86109y > || Chinese explanation of patent application Xiu Baobao 90 years of the Republic of China V. Description of invention (35) A catalyst for the invention In addition to its excellent selectivity to promote the formation of carbonate diesters, the catalyst solution also contains alcohol, so copper compounds will not be precipitated, and the reaction system can become a homogeneous solution. Therefore, by using the catalyst liquid of the present invention, a carbonic acid diester having good selectivity and good yield can be produced. In addition, it is easy to recover the carbonic acid diester derived from the obtained reaction product. The reaction solution is a homogeneous solution containing no solid components, so it can be directly distilled. Therefore, it is easy to obtain a high-purity carbonic acid diester. Also, the catalyst liquid of the present invention can greatly reduce the methanol / catalyst currently used as a catalyst liquid. Corrosion caused by the C u C mixed liquid. Therefore, when the catalyst liquid of the present invention is used, a relatively inexpensive nickel-based alloy C or titanium can be used as the material of the reaction device. In addition, the catalyst liquid of the present invention is easy to regenerate, that is, the catalyst liquid can be regenerated by using a method in which the contact activity of C0 is reduced. [Brief description of the figure] FIG. 1 is a diagram of a reaction system when the present invention is implemented. example. FIG. 2 is an example of a schematic diagram of a device for implementing the present invention. Fig. 3 is an example of a schematic diagram of another reaction apparatus used in carrying out the method of the present invention. FIG. 4 is an example of an experimental device of the present invention. FIG. 5 is another example of the experimental device of the present invention. [Symbol description of the main components of the circle] This paper size applies to the Chinese national standard (CNS > A4 grid (210X297 mm). ^ IT line (please read the precautions on the back before filling this page)) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Industrial and Commercial Cooperatives -38-448153 A7 B7 V. Description of the invention (36) 51, Reaction device 5 2, First cooler 53, Dimethyl carbonate receiver 54, Second cooler 55, 〇2 Meter 5 6. Gas meter 6 0, circulation drum 61, reaction device 6 2, flash boiling device 63, receiver 6 4, cooler 6 5, 0 2 meter 6 6, gas meter — — — III1—II1 —, I — 1 II 1 — ^^ 11 — 1111 · ^^^ (Please read the notes on the back before filling out this page) Printed on paper standards of the China National Standards (CNS) A4 standard printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (210x297 mm) —〇y — 4 4 8 153

經濟部智慧财產局員工消費合作社印®i 五、發明説明（36) 4、反應裝置 6、分離裝置 9、再生裝置 21、反應筒體 22、管線 25、再生筒體 31、外筒 35、內筒 51、反應裝置+ 52、第1冷卻器 53、碳酸二甲酯接收器 54、第2冷卻器 5 5、0 2計量器 5 6、氣體計量器 6 0、循環唧筒 61、反應裝置 62、閃沸裝置 63、接收器 64、冷卻器 65、 02計量器 66、氣體計量器 (谙先閲讀背面之注意事項再填窝本頁) .裝. 訂 .線本紙张尺度適用中國國家標準（CNS )八4说格（2IOX297公釐） -39 -Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives® i. 5. Description of the Invention (36) 4. Reaction device 6, separation device 9, regeneration device 21, reaction cylinder 22, pipeline 25, regeneration cylinder 31, outer cylinder 35, Inner tube 51, reaction device + 52, first cooler 53, dimethyl carbonate receiver 54, second cooler 5 5, 0 2 meter 5 6 gas meter 60, circulation drum 61, reaction device 62 , Flash boiling device 63, receiver 64, cooler 65, 02 meter 66, gas meter (谙 read the precautions on the back before filling in this page). Install. Order. Thread paper size applies to Chinese national standards ( CNS) 8 4 grids (2IOX297 mm) -39-

Claims

448153

A8 BS C8 D8 Amendments to this year's patent application Annex: No. 861 09 1 28 Patent application in Chinese Amendment of patent application scope Amendment in the Republic of China April 2009 (Please read the precautions on the back before filling out this page) 1 A catalyst liquid, which is a catalyst liquid used for reacting an alcohol with carbon monoxide and oxygen to produce a carbonic acid diester, and is further composed of (i) a copper compound, (ii) a cyclic nitrogen compound, and (iii) ) The following general formula (I) R1〇 [CH (R2) CH2〇] nR3 (I) (wherein R1 is an alkyl group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 2 carbon atoms or hydrogen, and R3 is Alkyl or hydrogen having 1 to 6 carbon atoms, wherein η is an integer of 1 to 1 2), and the solution contains a dissolved copper compound. 2. The catalyst liquid according to item 1 of the patent application scope, wherein the copper compound is copper halide. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. If the catalyst liquid of the second scope of the patent application, the copper halide is the first copper chloride (CuCl). 4. The catalyst liquid according to item 1 of the scope of patent application, wherein the glycol ether represented by formula (1) is composed of triethylene glycol dimethyl ether, propylene glycol dimethyl ether, and ethylene glycol monophenyl group. Ether, triethylene glycol-methyl ether, propylene glycol monomethyl ether, and diethylene glycol-butyl ether. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 448 1 53 A8 B8 D8 t. Application for patent scope 5. Such as the catalyst liquid of the first scope of the patent application 'Among them, cyclic nitrogen compounds Pyridine, 1, 1 0 _phenanthroline or 2, 2, dipyridyl < Please read the notes on the back before filling out this page) 6. For the catalyst liquid of the 1st or 2nd scope of patent application, Wherein, the molar ratio of the cyclic nitrogen compound to the copper compound is 0.1 to 30. 5〜100。 7. As claimed in the scope of the patent application of the catalyst liquid 1 or 2, wherein the molar ratio of ethylene glycol to copper compounds is 0. 5 ~ 100. 8. A method for regenerating a catalyst liquid, characterized in that at a temperature of 50 to 200 ° C and a partial pressure of carbon monoxide of 0.1 to 10 kg / crrf, the contact activity of carbon monoxide is reduced as in the scope of patent application Catalyst liquid Q 9 according to any one of items 1 to 7. A method for producing a carbonic acid diester, characterized in that carbon monoxide is used in the catalyst liquid according to any one of items 1 to 7 of the scope of patent application. And oxygen reacts in alcohol. 10. The method according to item 9 of the scope of patent application, wherein the oxygen partial pressure during the reaction is 0.001 to 10 kg / crrie 1 1. The method according to item 9 or 10 of the scope of patent application, wherein, during the reaction The carbon monoxide partial pressure is 1 ~ 30 kg / c m2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2. The method of item 9 or 10 of the scope of patent application, wherein the reaction temperature is 30 ~ 200 ° C. 1 3. A method for producing a carbonic acid diester, characterized in that carbon monoxide and oxygen are reacted in an alcohol, such as in a catalyst liquid according to any one of claims 1 to 7, to obtain Carbonic acid diester generation step of carbonic acid diester reaction solution and the carbonic acid diester separation step of carbonic acid diester contained in the reaction solution and 'making carbon monoxide contact to separate carbonic acid. The paper size is applicable to Chinese national standards (CNS ) A4 specification (2) 0 X 297 mm) 443153 A8 B8 C8 D8 Composition of the catalyst liquid regeneration step of the catalyst liquid obtained by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed and applied for a patent scope diester "1 4 .—A device for producing carbonic acid diester, characterized in that it is a device for producing a carbonic acid diester using a catalyst liquid as described in any one of items 1 to 7 of the scope of patent application, which is provided with: (i) the aforementioned catalyst A reaction device for reacting carbon monoxide and oxygen in an alcohol to generate a carbonic acid diester, and (ii) a carbonate production device using a catalyst liquid as described in any of claims 1 to 7 of the scope of patent application Carbonic acid In the reaction solution of the diester, a separating device for separating the carbonic acid diester, and (iii) a catalyst solution for contacting carbon monoxide with at least part of the catalyst liquid obtained after separating the carbonic acid diester by the separating device to regenerate the catalyst liquid Catalyst liquid regeneration device. 15. A device for producing a carbonic acid diester, which is characterized in that the device for producing a carbonic acid diester using a catalyst liquid as described in any one of claims 1 to 7 is provided, and (i) has The cylinder of the carbonic acid diester production zone and the cylinder that becomes the catalyst regeneration zone, (ii) The upper and lower ends of the two cylinders can become liquid contact points, and (iii) the carbonic acid diester production zone The lower part of the cylinder is equipped with a supply pipe that can supply carbon monoxide and oxygen, or a supply pipe for alcohol, respectively or mixedly. (Iv) A discharge pipe capable of discharging the carbonic acid diester is arranged above the cylinder that becomes the carbonic acid diester generating pool belt. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------ installation -------- order --------- (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 448 153 A8 B8 C8 D8 VI. Patent Application Scope (V) is arranged on the cylinder that becomes the catalyst regeneration zone A supply pipe capable of supplying carbon monoxide is provided, and (V i) is provided at the top of the two cylinders to discharge a gas containing carbon monoxide Discharge pipe. 16. A device for manufacturing a carbonic acid diester, which is characterized by using a catalyst liquid such as any one of claims 1 to 7 in the scope of a patent application to produce a dicarbonate, comprising: (i) The inside of the inner cylinder formed by the outer cylinder and the inner cylinder inserted therein becomes a carbonate diester formation zone, and the gap formed between the inner surface of the outer cylinder and the outer surface of the inner cylinder becomes a catalyst. The reaction device in the regeneration zone, (ii) the upper and lower ends of the cylinder and the inner cylinder can become liquid contact points, and (iii) are arranged below the inner cylinder, and can supply carbon monoxide and oxygen separately or in combination. Nozzle and alcohol supply pipe, (iv) a nozzle for supplying carbon monoxide is arranged on the gap formed between the surface of the outer cylinder and the outer surface of the inner cylinder, and (v) is arranged above the outer cylinder to discharge The discharge pipe of the solution containing the carbonic acid diester is provided with a discharge pipe for discharging a gas containing carbon monoxide on the top end of the outer cylinder. This paper size applies to China National Standard (CNS) A4 specifications (2) 0 X 297 mm) ------------- Installation ---- I--Order --- I! Green- -ί Please read the notes on the back before filling this page)