1377175 在從產物分離之後，將NO在單獨的環線中再氧化，以再循 環在此方法中所使用的硝酸。使用再循環的硝酸使得在此 方法中僅需要少的鎖酸初始量。 在較佳的具體實例中，反應基本上係在元素氧不存在 下進行。使用硝酸取代二氧化氮作為氧化劑允許元素氧不 存在於反應混合物中’因此避免二氧化氮的存在及形成， 該二氧化氮難以從包含乙二腈及一氧化氮的氣態產物氣體 合物分離。當反應係在元素氧不存在下進行時，不可能 測定出二氧化氮及對應之二聚物的形成。氣態產物混合物 亦完全無色。使用硝酸的另一優點是減少必須從此方法中 移出的二氧化碳及其他氣體的形成。 在較佳的具體貫例中’在反應混合物中存在的水$ 2〇 重量％之液相，更佳在從〇· 1至20重量％之範圍内，特別 佳從0.5至10重量％。 根據圖1及2，此方法可以分批或連續方式操作，其中 在水耗盡之混合物（視需要在添加補充（make_up )之溶劑 及銅催化劑之後）再循環至反應器之前，先抽取一部分反 應混合物及移出水》1377175 After separation from the product, NO is reoxidized in a separate loop to recycle the nitric acid used in the process. The use of recycled nitric acid makes only a small initial amount of lock acid required in this process. In a preferred embodiment, the reaction is carried out essentially in the absence of elemental oxygen. The use of nitric acid instead of nitrogen dioxide as the oxidant allows elemental oxygen to be absent from the reaction mixture' thus avoiding the presence and formation of nitrogen dioxide which is difficult to separate from gaseous product gases comprising ethanedinitrile and nitric oxide. When the reaction is carried out in the absence of elemental oxygen, it is impossible to determine the formation of nitrogen dioxide and the corresponding dimer. The gaseous product mixture is also completely colorless. Another advantage of using nitric acid is to reduce the formation of carbon dioxide and other gases that must be removed from the process. In a preferred embodiment, the liquid phase present in the reaction mixture is present in an amount of from 〇1 to 20% by weight, particularly preferably from 0.5 to 10% by weight. According to Figures 1 and 2, the process can be operated in a batch or continuous mode wherein a portion of the reaction is withdrawn before the water depleted mixture (if necessary after the addition of the make_up solvent and the copper catalyst) is recycled to the reactor. Mixture and remove water
酿胺、硫酿胺及極性芳族雜環化合物。 群： 溶劑無需具有長時間期拟_ Pα^ T u期間對抗硝酸的穩定性，因為Amine amine, sulfuric amine and polar aromatic heterocyclic compounds. Group: Solvents do not need to have a long-term stability against nitric acid during _ Pα ^ T u because
性，因為僅 乙腈、丙腈、 7 苯甲腈、丁腈、戍脾 猜、笨基乙腈及對甲苯腈。 丙酸曱 碳酸二 乙酸曱 酸二乙 較佳的酯係 -- %自由下列各物所組成之族群 s日、丙酸乙酯、 ^ 田此 G ^乙酯、乙酸丙酯、乙酸丁酯 曱酯、碳酸二己 3、三氣乙酸乙酯、氣乙酸乙酯 S曰、乙酸異丙輅、Sex, because only acetonitrile, propionitrile, 7 benzonitrile, butyronitrile, spleen guess, stupid acetonitrile and p-toluonitrile. Preferred ester of barium propionate diacetate diacetate diacetate - % free of the following groups of s day, ethyl propionate, ^ G ^ ethyl ester, propyl acetate, butyl acetate Ester, dihexyl carbonate, tri-acetic acid ethyl acetate, ethyl acetate S曰, isopropyl acetate,
st 本甲酸曱酯、苯甲酸乙酯、丙一吸二G 酯、乙醯乙酸乙 + ^ 本二曱酸二曱酯'丁内酯、碳酸丙烯 西日、石厌酸乙烯鲳及 久本二甲酸二丁酯。 較佳的二醇齡4 喊和二醇醚酯係選自由下列各物所組成之 孩群.乙二醇- 〜甲喊、乙二醇二乙醚、乙二醇二丙醚、乙 二醇二丁醚、19_ _ _ 丙二醇二曱鍵、1，2-丙二醇曱基乙喊.、12- 丙二醇二乙醚、丨 ’ ^ 丙二醇二丙醚、ι，2-丙二醇曱基丁醚、 ，丙一醇—甲醚、1，2_丁二醇二甲醚、甘油三曱醚、甘油 三乙喊 '甘油三丙喊 '甘油二甲_、二伸乙甘醇二甲醚’、 一伸乙甘醇二乙二伸丙甘醇二甲趟、三伸乙甘醇 醚及丙二醇單甲醚乙釀醋。 較佳的硝基化合物係選自由下列各物所組成之族群： 2-硝丙烧、1·硝丙烷、硝乙烷、硝甲烷及硝苯。 適合的硬為例如環丁礙。 佳的越係選自由下列各物所組成之族群：1 栌 够_ ，- — 1% 凡、第二丁基甲醚、二-異戊醚、呋喃、四氫呋喃' 甲| 技 7基 四氫0夫喃、大茴香驗、四氫β比喃、苯乙謎、ι，3·二氧雜戊严 (l，3-diox〇lane) ' 二·正丙醚、二異丙醚、二-正丁醚、一 丨· *· 第三丁醚'二苯醚及二苯甲醚。St Benzoate formate, ethyl benzoate, propionate G, ethyl acetoacetate B + ^ dinonyl phthalate 'butyrolactone, propylene carbonate, iron ruthenium ethoxide and long-standing dicarboxylic acid Dibutyl ester. Preferred diol age 4 and glycol ether esters are selected from the group consisting of the following: ethylene glycol - ~ A shout, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol Butyl ether, 19_ _ _ propylene glycol dioxime bond, 1,2-propanediol decyl ketone, 12-propylene glycol diethyl ether, 丨' ^ propylene glycol dipropyl ether, ι, 2-propanediol decyl butyl ether, propanol - methyl ether, 1,2-butanediol dimethyl ether, glycerol triterpene ether, glycerol triethyl singer 'glycerin tripropylene shouting 'glycerol dimethyl _, diethylene glycol dimethyl ether', one ethylene glycol Ethylene propylene glycol dimethyl hydrazine, triethylene glycol ether ether and propylene glycol monomethyl ether vinegar. Preferred nitro compounds are selected from the group consisting of 2-nitropropene, 1. nitropropane, nitrate, methane and nitrate. Suitable hard is, for example, a ring. The better the line is selected from the group consisting of: 1 栌 enough _ , - 1% where, second butyl methyl ether, di-isopentyl ether, furan, tetrahydrofuran ' A| | 7 base tetrahydrofuran , anise test, tetrahydro-β-pyran, benzene, ι, 3·dioxapentan (l,3-diox〇lane) 'di-n-propyl ether, diisopropyl ether, di-n-butyl ether , 一丨· *· Tert-butyl ether 'diphenyl ether and diphenyl ether.
較佳的醯胺係選自由下列各物所組成之族群：N N Ϊ377175 甲基甲醯胺、N，N-二乙基曱醯胺、四甲脲、四乙脲、n，n_ 一甲基乙酿胺、N，N-二乙基乙醯胺、N-甲基乙醯胺、义曱 基甲醯胺、曱醯胺、2-吡咯烷酮及卜甲基-2-吡咯烷酮。 較佳的極性芳族雜環化合物係選自由下列各物所組成 之族群：吡啶、甲基乙基吡啶、2,3-二甲基嘧啶-1-酮、ι，3· 二甲基嘧啶-2-酮及二甲吡啶（2,3·、2,4·、2,5·、2,6、3,4_ 或3,5-二甲吼啶）。 較佳的硫醯胺為例如i•甲基吡咯烷酮·2_硫酮。 在本發明的方法中，銅催化劑包含銅離子。 在硝酸存在下，幾乎任何銅合金、銅錯合物及鋼鹽會 被氧化’以提供銅離子。 因此，該銅離子係從金屬銅或銅合金、從銅錯合物、 銅⑴鹽或銅（I)錯合物、銅（11)鹽或銅（11)錯合物、及其混合 物所,產生。 術語、、銅（0)〃包含金屬銅及銅合金，甚至更佳地呈細 碎形式，例如研磨之金屬或合金。術語、、銅（0)化合物"包 含金屬錯合物，其包括在形式上未荷電銅原子。 術語、、銅（I)化合物"包含銅⑴鹽及包括CU+離子之金 屬錯合物。 適合的銅（I)鹽係選自乙酸Cu(I)、溴化Cu⑴、氯化 Cu⑴、碘化Cu(I)、氧化Cu(I)及氰化Cu(I)。 術語、、銅（II)化合物"包含銅（11)鹽及包括銅離子（cu+2) 之金屬錯合物。 可以上述溶劑中至少一者溶解之銅（π)鹽較佳地可於本 9 1377175 發明的方法中使用。適合的銅（π)鹽為例如硝酸銅（11)、氣化 銅（II)、溴化銅（II)、碘化銅（II)、硫酸銅（π)、氰化銅（π)、 氧化鋼（II)、焦璘酸銅（II)、硫化銅（II)、經基填酸銅（η)、碳 酸銅（II)、氫氧化銅（II)及非芳族和芳族叛酸之銅（II)鹽，諸 如乙酸銅（II)、曱酸銅（II)、乙醯乙酸銅（Π)、酒石酸銅（11)、 草酸銅（II)、檸檬酸銅（II)、苯甲酸銅（11)、曱基乙醯乙酸銅 (Π)、乙基乙醯乙酸銅（II)、乙基苯曱酿基乙酸銅（Η)、三氟 甲烧確酸銅（II)、苯二曱酸銅（π)或甲苯績酸銅（Η)。 在一個較佳的具體實例中，將氫氰酸放入反應容器 中’同時將硝酸進料至混合物中。 更有利地’僅將視需要溶解在溶劑中或與溶劑混合物 的催化劑放入反應容器中，並將硝酸及氫氰酸同時 '不連 續或連續添加至反應混合物中，同時使反應繼續進行。 若虱氰酸及确酸同時或以交替部分進料，則沒必要使 彼等在同時以化學計量方式進料。不過，為了避免過度氧 化及與溶劑的副反應，建議在反應器中具有大約根據方程 式1之化學計量比例的氳氰酸及硝酸。為了避免不完全的氫 氰酸轉化，亦可將硝酸以沒有不利影響的稍微過量進料。 此方法可在從15至150。(：，較佳從50至100°C，更佳 從60至90。(：之範圍内的溫度下進行。 在高壓下執行此方法可導致獲得呈氣態形式之產物的 問題’因此必須要從液體反應混合物回收產物。在硝酸存 在下’乙二腈或多或少與反應中形成的水快速地反應。因 此’液體反應溫度及壓力應在允許輕易地從反應器移出呈 1377175 ⑴吸附技術’ ％即將乙二腈吸附在固體吸附劑上及接著使 用適合的溶劑去吸附，或（H)液體-液體-萃取技藝，從其他 的反應伙伴分離乙二腈。在兩個實例中用於再循環溶劑的 必要裝置為熟習所屬技術領域者已知。 另一回收乙二腈的選擇係從氣態產物流直接冷凍乙二 腈此可使用兩個平行的熱交換管線執行，可擇一灌注產 物孔机。雖然乙二腈在一個管線中固化但是將固化之乙 二腈在其他管線中再蒸發且獲得幾乎純形式。 在管線38中，將部分量的反應混合物（該反應混合物 包含有機溶劑、水、催化劑、溶解之乙二腈及少量未反應 肖馱與氫氰酸）以連續或不連續模式從反應器〇 i排出及 進料至溶劑回收單元13。在溶劑回收單元13内，將水從反 應混合物分離，如下述更詳細的示例，並以管線“從此方 '、排出.同枯將回收的有機溶劑、催化劑及硝酸在管線4〇 中^循％至反應器〇1中。溶劑回收單元Η進一步包含旁 ，官線43，其包含溶劑、乙二猜與氮氛酸之混合物，亦將 八再循環至反應器中。 溶劑回收單元13 : 而定硯=3有機溶劑、水及催化劑之混合物的熱力學性質 進疒 離可在熟^所屬技術領域者已知適合的塔組構中 =例如使用簡單蒸館或精趨分離共沸混合物、以霧泳 塔可^ ^醚或烴）的變壓精餾或精餾分離共沸混合物》 拔等、。”有規律或不規律填料的層板、泡罩或泡盤塔或 5 可使用薄膜分離技術（諸如蒸發、透蒸發或 15 超過濾）分離反應水。除了上述方法以外，亦有可能使用 吸附、吸收或萃取步驟從反應混合物分離水。 圖2 : 圖2例示說明使用乙腈作為主要極性溶劑之方法的較 佳模式。根據圖1，反應器〇1配備有分別提供氫氰酸、硝 酸、催化劑及有機溶劑（亦即乙腈）進料的管線2丨、22 ' 23及24。硝酸、有機溶劑（亦即乙腈）及催化劑亦分別經 由再循環管線37 ' 40及43進料。管線22、23及24亦可 以補充為目的於此方法期間使用，而管線21亦用於提供在 反應期間需要的氫氰酸《管線33及34分別提供元素氧及 水，以再氧化一氧化氮。 將來自反應器01的產物氣流（包含乙二腈、一氧化氮、 有機溶劑（亦即乙腈）、水及微量二氧化碳）在管線25進 料至冷凝器02中。將包含有機溶劑（亦即乙腈）及水的冷 凝液經由管線26再循環至反應器01中，該再循環視需^ 在部分或完全移出水之後。將從冷凝器〇2所獲得在管線27 中伴有少量惰性氣！| (諸如二氧化碳）及很少的有機溶劑 (亦即乙腈）與水的氣態流出物（包含乙二腈及一氧化氮） 在管線27中裝入吸收塔〇3的塔底中，與在管線3〇中再循 裱至塔03的塔頂之有機溶劑（亦即乙腈）流逆流。在約_5 至:3〇C，較佳在從〇至+的之範圍内的溫度下操作的吸 收塔03可為以規律或不規律填料填充的填充塔，或層板' :罩或泡盤塔。包含乙腈及微量水的管線28之混合物經由 木。又塔的塔頂側面的出口管從塔03移出且再裝入反應器〇1Preferred guanamines are selected from the group consisting of NN Ϊ 377175 methyl methamine, N, N-diethyl decylamine, tetramethyl urea, tetraethyl urea, n, n _ methyl Amine, N,N-diethylacetamide, N-methylacetamide, decylcarbamide, decylamine, 2-pyrrolidone and benzyl-2-pyrrolidone. Preferred polar aromatic heterocyclic compounds are selected from the group consisting of pyridine, methylethylpyridine, 2,3-dimethylpyrimidin-1-one, iota, dimethylpyrimidine- 2-ketone and dimethylpyridine (2,3·, 2,4·, 2,5·, 2,6, 3,4_ or 3,5-dimethylacridine). A preferred thioguanamine is, for example, i.methylpyrrolidone-2-thione. In the process of the invention, the copper catalyst comprises copper ions. In the presence of nitric acid, almost any copper alloy, copper complex and steel salt will be oxidized to provide copper ions. Therefore, the copper ion is derived from a metallic copper or copper alloy, a copper complex, a copper (1) salt or a copper (I) complex, a copper (11) salt or a copper (11) complex, and a mixture thereof, produce. The term, copper (0) bismuth comprises metallic copper and a copper alloy, even more preferably in finely divided form, such as a ground metal or alloy. The term, copper (0) compound " contains a metal complex comprising a formally uncharged copper atom. The term, copper (I) compound " comprises a copper (1) salt and a metal complex comprising CU+ ions. Suitable copper (I) salts are selected from the group consisting of Cu(I) acetate, Cu(1) bromide, Cu(1) chloride, Cu(I) iodide, Cu(I) oxide and Cu(I) cyanide. The term, copper (II) compound " comprises a copper (11) salt and a metal complex comprising copper ions (cu+2). The copper (π) salt which can be dissolved in at least one of the above solvents is preferably used in the method of the present invention. Suitable copper (π) salts are, for example, copper nitrate (11), copper (II) vapor, copper (II) bromide, copper (II) iodide, copper (π) sulfate, copper cyanide (π), oxidation Steel (II), copper (II) pyroantimonate, copper (II) sulfide, copper (η) based on base, copper (II) carbonate, copper (II) hydroxide and non-aromatic and aromatic acid Copper (II) salt, such as copper (II) acetate, copper (II) citrate, copper acetate (yttrium), copper tartrate (11), copper (II) oxalate, copper (II) citrate, copper benzoate (11), mercaptoacetic acid copper (ruthenium), ethyl acetoacetate copper (II), ethyl benzoate copper acetate (ruthenium), trifluoromethane copper (II), benzodiazepine Copper acid (π) or toluene acid copper (Η). In a preferred embodiment, the hydrocyanic acid is placed in the reaction vessel while the nitric acid is fed to the mixture. More advantageously, only the catalyst dissolved in a solvent or a mixture with a solvent is placed in a reaction vessel as needed, and nitric acid and hydrocyanic acid are simultaneously 'discontinuously or continuously added to the reaction mixture while the reaction is continued. If the isocyanic acid and the acid are fed simultaneously or in alternating portions, it is not necessary to have them simultaneously fed stoichiometrically. However, in order to avoid excessive oxidation and side reactions with solvents, it is recommended to have cyanic acid and nitric acid in the reactor in a stoichiometric ratio according to Equation 1. In order to avoid incomplete conversion of the hydrocyanic acid, the nitric acid can also be fed in a slight excess without adverse effects. This method can be from 15 to 150. (:, preferably from 50 to 100 ° C, more preferably from 60 to 90. (: in the range of temperatures. Performing this method at high pressure can lead to the problem of obtaining a product in a gaseous form.) The liquid reaction mixture recovers the product. In the presence of nitric acid, 'ethane dinitrile reacts more or less with the water formed in the reaction. Therefore, the liquid reaction temperature and pressure should be allowed to be easily removed from the reactor to be 1377175 (1) adsorption technology' % is the adsorption of oxalylonitrile onto a solid adsorbent and subsequent adsorption using a suitable solvent, or (H) liquid-liquid-extraction technique to separate ethanedinitrile from other reaction partners. The necessary means of solvent are known to those skilled in the art. Another option for recovering ethanedinitrile is to directly freeze the ethanedonitrile from the gaseous product stream. This can be carried out using two parallel heat exchange lines, optionally with a perfusion product orifice machine. While ethanedinitrile is solidified in one line, the cured ethanedinitrile is re-evaporated in other lines and is obtained in almost pure form. In line 38, a portion of the reaction mixture is taken. (The reaction mixture comprises an organic solvent, water, a catalyst, dissolved ethanedinitrile and a small amount of unreacted xiaoxiong and hydrocyanic acid) and is discharged from the reactor 〇i and fed to the solvent recovery unit 13 in a continuous or discontinuous mode. In the solvent recovery unit 13, the water is separated from the reaction mixture, as exemplified in more detail below, and the pipeline is "from this side", discharged, and the recovered organic solvent, catalyst and nitric acid are in the pipeline 4% to In the reactor 。1, the solvent recovery unit Η further comprises a side, an official line 43, which comprises a solvent, a mixture of ethylene and nitrogen, and also recycles eight to the reactor. Solvent recovery unit 13: = 3 The thermodynamic properties of the mixture of organic solvent, water and catalyst can be selected in a suitable column structure known to those skilled in the art = for example using a simple steaming or fine separation azeotrope, with a mist swimming tower Separation of azeotropes by pressure swing distillation or rectification of ether or hydrocarbons. "Layer plates, blister or bubble trays with regular or irregular fillers or 5 may use membrane separation techniques (such as evaporation The reaction water is separated by evaporation or 15 ultrafiltration. In addition to the above methods, it is also possible to separate the water from the reaction mixture using an adsorption, absorption or extraction step. Figure 2: Figure 2 illustrates a preferred method of using acetonitrile as the primary polar solvent. According to Figure 1, the reactor crucible 1 is equipped with lines 2, 22' 23 and 24 which respectively supply hydrogen cyanate, nitric acid, a catalyst and an organic solvent (i.e., acetonitrile). Nitric acid, an organic solvent (i.e., acetonitrile) And the catalyst are also fed via recirculation lines 37' 40 and 43 respectively. Lines 22, 23 and 24 may also be supplemented for use during this process, while line 21 is also used to provide the hydrocyanic acid required during the reaction. Lines 33 and 34 provide elemental oxygen and water, respectively, to reoxidize nitric oxide. The product gas stream from reactor 01 (containing ethanedinitrile, nitrogen monoxide, organic solvent (ie, acetonitrile), water, and traces of carbon dioxide) Line 25 is fed to condenser 02. The condensate containing the organic solvent (i.e., acetonitrile) and water is recycled to reactor 01 via line 26, which is optionally followed by partial or complete removal of water. A small amount of inert gas in line 27 will be obtained from condenser 〇2! | (such as carbon dioxide) and a small amount of organic solvent (also known as acetonitrile) and water gaseous effluent (including ethanedinitrile and nitrogen monoxide) in line 27 into the bottom of the absorption tower 3, and in the pipeline The organic solvent (i.e., acetonitrile) flowing back to the top of column 03 was refluxed in the middle. The absorption column 03 which is operated at a temperature of from about _5 to: 3 〇C, preferably in the range from 〇 to +, may be a packed column filled with regular or irregular filler, or a laminate ': hood or bubble Pan tower. A mixture of line 28 comprising acetonitrile and traces of water is passed through the wood. The outlet pipe on the top side of the tower is removed from the column 03 and recharged into the reactor.