201124342 六、發明說明： 本發明關於一種用於從氫氰酸製備乙二腈之方法。 乙二腈（氰’（CN)2 )為一種穩定的無色氣體，其最先 係在1815年於實驗室中藉由氰化銀之熱分解而製備。由於 其反應性，使乙二腈為合成有機化合物之有希望的建構單 元（building block)，如由 Roesky 及 Hofmann 於 Chemiker201124342 VI. INSTRUCTIONS: The present invention relates to a process for the preparation of ethanedinitrile from hydrocyanic acid. Ethylene nitrile (cyanide' (CN) 2 ) is a stable, colorless gas which was first prepared by thermal decomposition of silver cyanide in the laboratory in 1815. Due to its reactivity, ethanedinitrile is a promising building block for the synthesis of organic compounds, such as by Roesky and Hofmann in Chemiker.
Zeitung 1984, 7-8, 231-238中所評論。亦以其用作燻蒸劑， 如在US 6,001，383及W02005/037332中所示。此外，乙二 腈顯示出作為火箭發射藥系統中的活性成分之希望。 在已知的方法中’乙二腈係從氫氰酸在氧、硝酸鹽及 銅催化劑存在下形成。 在US 3,135，5 82中，其揭示藉由氧及氮氧化物與氫氰 酸在催化劑存在下在從1〇〇至l〇〇(TC之溫度下反應的乙二 腈製備。 在US 3,949,061中，其揭示藉由在水溶液中的氫氰酸 在元素氧、硝酸銅存在下反應的乙二腈製備。 在US 3,769,388中，其揭示在氧、實質上無水液體介 質、催化量銀、釕或汞及硝酸鹽存在下氧化氫氰酸。 在US 3,494,734中’其揭示氫氰酸與二氧化氮在作為 催化劑的銅離子存在下反應。 在DE 11633 02 A中，其揭示氫氰酸在銅鹽存在下於強 酸性溶液中的氧化，而在實施例及說明書中，氧化係在約 4 201124342 pH 2.8下進行。根據實施例，反應係在銨鹽及元素氧以及 活化元素氧的額外試劑存在下進行。Comments by Zeitung 1984, 7-8, 231-238. It is also used as a fumigant as shown in US 6,001,383 and WO2005/037332. In addition, acetonitrile shows promise as an active ingredient in rocket propellant systems. In the known method, ethanedicarbonitrile is formed from hydrocyanic acid in the presence of oxygen, nitrate and copper catalysts. In U.S. Patent 3,135,5,82, the disclosure of which is incorporated herein by reference in its entirety in U.S. Patent No. 3,949,061, the disclosure of which is incorporated herein by reference. , which discloses the preparation of oxalylonitrile by reaction of hydrocyanic acid in aqueous solution in the presence of elemental oxygen, copper nitrate. In US 3,769,388, it is disclosed in oxygen, substantially anhydrous liquid medium, catalytic amount of silver, cerium or mercury. Hydrogen cyanide is present in the presence of a nitrate. It is disclosed in US Pat. No. 3,494,734, which discloses the reaction of hydrocyanic acid with nitrogen dioxide in the presence of copper ions as a catalyst. In DE 11633 02 A, it is disclosed that hydrocyanic acid is present in the presence of a copper salt. Oxidation in a strongly acidic solution, while in the examples and the description, the oxidation system is carried out at about 4 201124342 pH 2.8. According to an embodiment, the reaction is carried out in the presence of an ammonium salt and an elemental oxygen and an additional reagent that activates elemental oxygen. .
Riemenschneider，W.在 Chemtech 1976, 658-661 中揭示 建議在二氧化氮與氫氰酸的反應中使用稍微過量的氧。 到今日為止’用於製備之可用方法就產率及選擇性而 論仍不令人滿意。亦難以從流出氣體發現乙二腈，特別在 過量二氧化氮存在下。 欲解決之技術問題是提供用於製備乙二腈之替換方 法。 問題已由申請專利範圍第丨項之方法解決。 所明為一種用於在液相中從氫氰酸（HCN )製備乙二 腈（（C )2 )之方法，其係藉由氫氰酸在銅離子催化劑及非 質子極性溶劑存在下的催化氧化，其特徵在於添加石肖酸 (HN〇3)作為氫I酸氧化期間唯—的氧化劑。因此，既沒 有NO、N02，亦沒有ν2〇4直接添加至反應混合物中。 在反應期間，在氫氰酸與確酸一經接觸時，主要包含 乙二腈、NO及水的無色氣體從反應混合物釋出。該無色氣 體顯然沒有NxOy，其中v A 9 w | , χ y /、τ y 為 2X (例如，N〇2 或 n2〇4)。乙 一猜可輕易地從Ν Ο及水-去八她 久Α —者分離。Ν〇可在再氧化成硝酸 之後再猶環至此方法中。出半音 出子忍枓地，包含在流出氣體中 的NO不在流出氣體中進一 步反應且可從產物輕易地分 離。在主要產物環線中減至啬 碼至取少的Nx〇y (其中y為2X，例 如N〇2或N2〇4 )量亦減低峰能 以王恶危害的可能性。 5 201124342 式（i)描述本方法的化學計量： 6 HCN + 2 N〇3 - 3 (CN)2 + 2 NO + 4 H20 ⑴ 根據式I，在與6莫耳氫氰酸反應的此方法中消耗2莫 耳硝酸，以獲得3莫耳乙二腈、2莫耳一氧化氮及4莫耳水。 然而’所獲得的-氧化氮可以元素氧再氧化及與水反應成 硝酸，至少在理論上，此係在連續操作的方法中，其中僅 需要起始的硝酸量+。 在較佳的具體實例中，硝酸及氫氰酸係以從丨：25至 1 : 3.5之範圍内的莫耳比同時添加至此方法中。 在本方法中，硝酸意謂包含至少4〇重量％，較佳為至 少60重量％，更佳為約65重量％之HN〇3的'、濃,，硝酸。 至高達發煙硝酸（〜100重量％之HN〇3)之較高濃度的硝酸 亦可用於此方法中。本發明的進一步態樣係在封閉環線中 再循環氧化劑，如在例如圖丨及2中所描述。在此方法中 所獲得的一氧化氮（NO)可以氧氧化成二氧化氮（N〇2或 N2〇4 )，其可與水反應，得到具有約65重量％之最大濃度 的硝酸。 在較佳的具體貫例中’該硕酸可直接再用於此方法 中，因此將硝酸貯存及運輸的需求減至最低。 石肖酸係以化學S十直消耗於此方法中。因此，當石肖酸及 虱氰酸以大約化學計量比例同時進料時，則沒有或僅少許 過置硝酸存在於此方法中。因此，反應可以非常安全處置。 6 » 201124342 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 方法中僅需要少的硝酸初始量。 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 混合物分離。當反應係在元素氧不存在下進行時，不可能 測疋出一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 移出的二氡化碳及其他氣體的形成。 在較佳的具體實例中，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2〇重量％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。 適合的非質子極性溶劑可選自由下列各物所組成之族 群··腈、醚、二醇醚和二醇醚酯、硝基化合物、砜、醋、 醯胺、硫醯胺及極性芳族雜環化合物。 溶劑無需具有長時間期間對抗硝酸的穩定性，因為僅 有少許過量硝酸存在於此方法中。 猜較佳地選自由下列各物所組成之族群：乙腈、丙腈、 201124342 苯曱腈、丁腈、rfe «Λ 戍腈、苯基乙腈及對甲苯腈。 較佳的g旨孫a 货、選自由下列各物所組成之族群：丙酸甲 酯、丙酸乙酯、7祕 心乙酯、乙酸丙酯、乙酸丁酯、碳酸二 甲酉旨、碳酸二乙_ 9 二氣乙酸乙醋、氣乙酸乙g旨、乙酸甲 i:乙S夂異丙酯、笨曱酸甲酯、苯曱酸乙酯、丙二酸二乙 乙S欠乙酯、笨二甲酸二曱酯、丁内酯、碳酸丙烯 酷、碳酸乙烯酯及笨二甲酸二丁酿。 ^ 的醇醚和二醇醚酯係選自由下列各物所組成之 知群.乙二醇二甲_、乙二醇二乙醚、乙二醇二丙醚、乙 二醇二丁 _ ， 一醇一曱醚、1，2 -丙二醇曱基乙醚、I，〗， 醇乙醚1}2 -丙二醇二丙醚、1，2 -丙二醇甲基丁喊、 1，3-丙二醇二曱醚、丁二醇二曱醚、甘油三曱醚 '甘油 ，乙醚、甘油三丙醚、甘油二甲鍵、二伸乙甘醇二甲醚’、 一伸乙甘醇二乙醚、二伸丙甘醇二曱醚、三伸乙 驗及丙二醇單曱醚乙酸酯。 _ 較佳的硝基化合物係選自由下列各物所組成之族群： 2-硝丙烷、1 -硝丙烷、硝乙烷、硝曱烷及硝苯。 適合的砜為例如環丁砜。 較佳的醚係選自由下列各物所組成之族群：丨，4-二聘 烷、第三丁基甲醚、二_異戊醚、呋喃、四氫呋喃、甲基 四氫呋喃、大茴香醚、四氫吡喃、苯乙醚、13__ 、 5 一氧雜戊環 (1,3-diojcolane )、二·正丙醚、二異丙醚、二 _ ~~止丁喊、- 第三丁謎、二苯醚及二苯甲醚。 較佳的醯胺係選自由下列各物所組成之族群. 3 人 ’ ，》_»% 201124342 甲基曱醢胺、N，N-二乙其田減 基曱醯胺、四甲脲、四乙脲、NN 二甲基乙醯胺、N，N- - 7 # ，Ν· ^ w Λ —乙基乙醯胺、Ν-甲基乙醯胺、Ν_ 基曱醯胺、曱醯胺、2 甲 也咯烷酮及1-曱基-2-吡咯烷酮。 較佳的極性芳族雜王班儿人a, 之族群：…甲基乙： 選自由下列各物所組成 丞乙基吡啶、2,3_二曱基嘧啶酮、丨 二甲基密咬-2 -酮及二甲％ 彳 ， T 比啶（2,3_、2,4-、2,5-、2,6…3,4· 或3,5 -二曱。比。定）。 較佳的硫醯胺為例如κ甲基。比嘻烧綱-2_硫嗣。 在本發明的方法中，銅催化劑包含銅離子。 、在石肖酸存在下，幾乎任何銅合金、銅錯合物及銅鹽會 被氧化，以提供銅離子。 因此，忒銅離子係從金屬銅或銅合金、從鋼（〇)錯合物、 銅⑴鹽或銅⑴錯合物、銅（Η)鹽或銅（η)錯合物、及其混合 物所產生。 口 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Cu(I)、氣化 Cu(I)、職化 cu(l)、氧化 Cu(I)及氮化 Cu(I)。 術語''、銅（II)化合物"包含銅（π)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 201124342 發明的方法中使用。適合的銅（π)鹽為例如硝酸銅（11)、氣化 銅（Π)、溴化銅（II)、碘化銅（Π)、硫酸銅（11)、氰化銅、 氧化銅（II)、焦磷酸銅（II) '硫化銅（11)、羥基磷酸銅（11)、碳 酸銅（II)、氫氧化銅（II)及非芳族和芳族羧酸之銅（π)鹽，諸 如乙酸銅（II)、甲酸銅（II)、乙醯乙酸銅（11)、酒石酸銅（11)、 草酸銅（II)、檸檬酸銅（II)、苯曱酸銅（11)、甲基乙醯乙酸銅 (Π)、乙基乙醯乙酸銅（11)、乙基苯曱醯基乙酸銅（11)、三氟 曱烧磺酸銅（II)、苯二甲酸銅（11)或曱苯磺酸銅（π)。 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。 若虱氰酸及石肖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 弋I之化學叶量比例的氫氰酸及硕酸。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loot：，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 。戏’因此必須要從液體反應混合物回收產物。在硝酸存 —卜-· ’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 10 201124342 氣態形式之產物的範圍内。最佳地，反應係在約大氣壓力 下進行。 在氫氰酸與硝酸混合之後，立即形成包含乙二腈及一 氧化氮之產物氣流。有利地，該產物氣流係從反應器連續 排出且接受進一步的處理（work_up)，其中將乙二腈從產 物氣流分離。 有可能以不同的方式從產物氣流分離乙二腈，例如藉 由冷/東、冷凝、吸收/去吸附或吸附/去吸附乙二腈。 特別佳地，將產物氣流中的乙二腈吸收於溶劑中及從 該溶劑回收。 、為了使廢料處理、成本、所使用的硝酸量及環境危害 減至最低，本發明的方法提供再循環在氫氰酸與硝酸的反 應中所獲得的-氧化氣的可能性。有利地，將以工業規模 的流出-氧化氮（N0)氧化，以獲得二氧化氮（N〇2)。、 在：素氧（〇2)存在下的N0氧化為所屬技藝中所熟知。將 °從排氣NO獲得的遠n〇2進料至水中導致硝酸（hn〇 ) =液，其可直接用於此方法中,2與水反應亦為所屬技 二中t已知。當此方法-開始，就將此方法的排氣NO再循環 因此可使hno3進料減至最少。 因此，在較佳的具體實例中 谁祖石貝” τ將產物氣流的-氧化氮 —至早獨的反應器中，在此以 _ 虱之軋體氧化，以獲得 一氧化氮，其被吸收於水中， 于 I _ ’斤k得的硝酸再循環至 與虱氰酸的反應中。 主 —個較佳的反應具體實例係 j你以連續方法進行反應，其 11 201124342 — 方决内僅需要氫氰酸、元素氧及補充流之進料。合 X再循環法需要將具有適當純度及高產率的溶劑及 催劑有效再循環。較佳的每個經回收之組份具有適合的 、屯度以向純度較佳，因為富集副產物及/或分解產物會對 此=法的壽命有不利的影響。在硝酸與氫氰酸的反應中使 用门沸點岭劑具有可輕易地進行從反應混合物分離氰的優 點。 在車又佳的具體實例中，本發明的方法係以連續方法進 行，視需要於其中回收至少有機溶劑及催化劑。 項酸與氫氰酸的反應合宜地在有機溶劑中進行，該溶 劑基本上與用於乙二腈處理的溶劑相同。 在較佳的具體實例中，乙二腈的處理係使用溶劑進 行，從產物氣流混合物回收乙二腈。較佳地，該溶劑在約 + 30C或更低的溫度下具有對乙二腈而言好的吸收性質及 對一氧化氮而言差的吸收性質。 在從-5至+3 0°C之溫度下，以乙腈溶解乙二腈還更優於 溶解一氧化氮’因此可用於有效地分離兩種化合物。 因此，在更佳的具體實例中，有機溶劑為乙腈。 在特別佳的具體實例中’硝酸與氫氰酸的反應係以乙 腈作為有機溶劑進行’並視需要在通過冷凝器之後，將產 物氣流進料至以乙腈逆流的吸收塔中。逆流的乙腈主要吸 收乙二腈，而一氧化氮仍維持氣態形式，且最終將乙二猜 產物從乙腈回收且從此方法移出’同時將回收的乙腈再揭 環至此方法中。反應及從產物氣流回收乙二腈二者皆使用 12 201124342 乙腈，以提供有效的化合物再猶 .s 衣次同產率的產物回收。 在更特別佳的具體實例中， T 在從一氧化氮分離之後， 乙二腈產物係在去吸附塔中從乙腈回收。 回收的一氧化氮視需要在含氧之氣體存在下氧化 獲得二氧化氮’將其與水反應， '· 乂獲付硝酸。該再循環的 硝酸亦可再用於此方法中。 衣的 圖1及圖2例證在較佳的具體實例中的本發明方法， 其中將硝酸及有機溶劑再循環至此方法中（圖ο，且 詳細的形式巾，制採取乙腈㈣為極性錢溶#1(圖 圖形的說明： 圖1 : 圖1例示說明以琐酸再循環之方法的通用模式。反應 器（H配備有分別提供氫氛酸、石肖酸、催化劑及溶劑進料的 管線2卜22、23及24。雖然在連續方法中，大部分的硝酸、 溶劑及催化劑係經由再循環管線37、40及43再循環，但 是管線2 2、2 3及2 4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氮氮酸。管線η 及34分別提供元素氧及水，以再氧化一氧化氮。 將從反應盗01排出在管線25中的產物氣流（包含乙 一腈、一氧化氮、有機溶劑及水與微量二氧化碳）進料至 冷凝器02中’其中將大部分的有機溶劑及水冷凝，並將管 線26中的冷凝液再循環至反應器〇1中，該再循環視需要 在部分或完全移出水之後。將來自冷凝器〇2的剩餘產物氣 13 201124342 流在官線2 7中進料至虚裡留, Λ 竹芏恩理早兀12中，用於隔離乙二腈。 在管線27中的產物ϋ奋&人， | J座初轧"IL包a乙二腈、一氧化氮及少量惰性 氣體’諸如二氧化碳’且實質上耗盡溶劑及水。處理單元 1 2包3⑴用於主要由純乙二猜所組成的氣態產物之管線 32，（η)用於主要由回收的有機溶劑與微量水所組成的流出 冲洗液之s線28 ’將§玄沖洗液再裝入反應器〇i中，以抑制 不必要的化合物（例如，水）累積在處理單元㈣，及㈣ 主要由-氧化氮及惰性氣體（諸如二氧化碳）戶斤組成的管 線29。 將管線29的氣流再裝入氧化反應器〇7中，其中將— 氧^氮在經由管線33進料的含氧之氣體存在下氧化成二氧 :氮：有利地在催化劑存在下。將管線35的流出氣流（包 含一軋化氮）視需要再循環至反應器〇8中及與經由管線Η 進料的水反應，以獲得硝酸。反應器〇8包含移出排氣，諸 如二氧化碳的管線36。硝酸視需要以管線37裝入反.應器 01中或於別處使用。 處理單元1 2 : 一視管線27令的熱力學性質而定，可使用不同的分離技 術回收乙二腈。適合的具體實例為吸收塔與用於再循環溶 劑的再生單元之組合。將乙二腈吸收在具有高選擇性的吸 ^塔溶劑中且釋出在包含去吸附、蒸餾或精餾的隨後再生 早元令。可能發生的進一步處理係使惰性氣體吸收在適合 的溶劑中。乙二腈於是為第一塔的塔頂產物。 〇 可擇-以吸收/再生來回收乙二腈’亦有可能使用例如 14 201124342 ⑴吸附技術，/亦即將乙二腈 -¾ Tv - ^ . *你u體及附劑上及接著使 用適S的浴劑去吸附，或⑻液體.液體·萃取技藝，從其他 的反應伙伴分離乙二猜。在 、 τ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束乙二 腈》此可使用兩個平行的熱交換f線執行，可擇—灌注產 物乳流。雖然乙二腈在—個管線中固〖，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。 在官線38巾，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 之硝酸與氫氰酸）以連續或不連續模式從反應器〇1排出及 進料至岭劑回收單元丨3。在溶劑回收單元Η内，將水從反 應混合物分離’如下述更詳細的示例’並以管線41從此方 法排出，同時將回收的有機溶劑、催化劑及硝酸在管線40 中再循環至反應器01中。溶劑回收單元進一步包含旁 通管線43，其包含溶劑、乙二腈與氫氰酸之混合物，亦將 其再循環至反應器中。 溶劑回收單元13 : 視包含有機溶劑、水及催化劑之混合物的熱力學性質 而疋’分離可在熟習所屬技術領域者已知適合的塔組構中 進行’例如使用簡單蒸餾或精餾分離共沸混合物、以霧沫 劑（例如’醚或烴）的變壓精餾或精餾分離共沸混合物。 D °選自具有規律或不規律填料的層板、泡罩或泡盤塔或 。号。或者’可使用薄膜分離技術（諸如蒸發、透蒸發或 15 201124342 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配備有分別提供氫氮酸、确 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，該再循環視需要 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 中伴有少量惰性氣體（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⑯（包含乙二腈及一氧化氮) =管線27中裝入吸收塔03的塔底中，與在管線3〇中再循 %至塔03的塔頂之有機溶劑（亦即乙腈）流逆流。在約_5 至30 C，較佳在從〇至+15<»c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 架设塔的塔頂側面的出口管從塔〇3移出且再裝入反應器 16 201124342 中。到達反應器0 1的再循環管線28阻止水及有機溶劑（亦 即乙猜）在連續操作期間的吸收/去吸附系列中累積在塔03 中。 塔〇3的塔底產物（包含有機溶劑（亦即乙腈）、乙二 月及水）以$線31排出’進料至加熱器〇*中及接著再循 %至去吸附塔05的塔頂中。塔〇3的塔頂流（包含一氧化 氮與微量惰性氣體，諸如二氧化碳）有利地在管線29中進 料至氧化反應器07中，以獲得硝酸，如以下所概述。 從不利於此方法的雜質及其他化合物（亦即水）分離 乙腈係根據熟習所屬技術領域者已知的最新技藝於去吸附 塔〇5内進行，例如使用低壓及/或上升溫度。有利地塔 〇5經組構成以規律或不規律填料填充的填充塔，或成為層 板、泡罩或泡盤塔。仍可能包含水的精製之有機溶劑流（亦 ^乙腈）從塔05的塔底排出及在管線3〇中進料至熱交換 器06中。接著將乙腈加熱塔03的操作溫度，並接著再循 環至塔03的塔頂中。塔〇5的塔頂流（包含幾乎純的氣態 產物乙二腈）以管線32排出，其可直接使用或可在例如冷 卻及冷凝之後回收。亦有可能使氣態或液化乙二猜通過 驗’以獲得其水解化合物。 太如以上圖1中所概述，將在塔〇3中從管線25的氣能 產物流回收的-氧化氮再氧化成硝酸及作為在管線37中= t再裝入反應器01中，以減少進行此方法所需之氧化試 在管線3 8中 將部分量的反應混合物 (S亥反應混合物 17 201124342 包含有機溶劑（亦即乙腈）、水'催化劑、溶解之乙二腈 及少量未反應之硝酸與氫氰酸）以連續或不連續模式從反 應器01排出及進料至精餾塔09中，該精餾塔係在〇 8至 20巴之範圍内，較佳在〇 8至8巴之範圍内，特別佳在4 至6巴之範圍内的壓力下操作。產物氣流在塔〇9中分離成 ⑴塔頂流，其包含有機溶劑（亦即乙腈）、水與微量乙二 腈之幾乎共沸組成物及氫氰酸，將其在管線39中進料至蒸 餾塔10中，及（ii)塔底產物，其包含有機溶劑（亦即乙腈）、 催化劑、硝酸及微量水，將其在管線4C)中再 。…蒸德…在約。.0…巴，較佳在至。 之範圍内的低壓下加工。將管線39之混合物（其為塔〇9 的塔頂流）在塔10内分離成⑴塔頂流及（Η)塔底產物。將塔 頂流⑴在管線42中進料至冷凝器u中，同時將主要由水 所組成的塔底產物（ii)以管線41從此方法排出。當以連續模 式操作時’若整個水量經控制在固定值，則以管線41排出 的水大約相當於在反應器01中所獲得的水莫耳量。以管線 42進料的過多流在冷凝器u内分離成⑴冷凝之液體部分， 其包含有機溶劑（亦即乙腈）與水之幾乎共沸組成物，將 其^管線44 +再循環至塔〇9之塔頂巾，及⑻氣態流，其 包含乙二腈、氫氰酸及有機溶劑（亦即乙猜），將其在管 線43中再循環至反應器〇 1中。 圖1與2之具體實例表列 01 :反應器 02 :熱交換器（冷凝器） 18 201124342 03 :吸收塔 04 :熱交換器 05 :去吸附塔 06 :熱交換器 07 :反應器 08 :反應器 09 :精镏塔 10 :蒸镏塔 11 :熱交換器 12:用於一氧化氮之產物回收的處理單元 13 :溶劑回收單元 21 :氫氰酸進料 22 :硝酸進料 23 :催化劑酸進料 24 :溶劑進料 25 :來自反應器的氣態產物流 26 :產物耗盡之溶劑流 27 :溶劑耗盡之產物氣流" 28 :沖洗流（經冷凝之水及產物耗盡之溶劑流） 29 :包含一氧化氮及惰性氣體的氣態流 30 :用於回收乙二腈之清洗溶劑 3 1 :具有乙二腈及水之溶劑 32 :乙二腈產物氣流 33 :含氧之氣體 19 201124342 34 水 進 料 35 二 氧化 氮 氣 流 36 排 氣流 37 再循 環 之 硝 酸 38 部 分 量 的 反 應 混 39 溶 劑 及 水 流 40 用 於 回 收 的 催 化 41 從 方 法 移 出 之 水 42 塔頂 流 43 溶 劑 乙 二 腈 及 44 溶 劑 與 水 之 混 合 合物 劑之再循環迴線 氫氰酸之旁通流 物的經冷凝之液體部分 實施例： 僅在以輕易地測定乙二腈產率為目的實施例中，將流 出之產物氣體通過鹼性汽提劑（KOH溶液），其幾乎完全 吸收乙二腈’與NO及&形成對比’彼等繼續維持氣態形 式。如在實施例中所示，本發明的方法避免發展出二氧化 碳及其他較高的氧化之氮化合物，總結為Nx0y，其中y為 2χ 0 貫施例1 : 將在乙腈（694毫升）中的硝酸銅（Π)彡水合物（95重 量％ ’ 10.5公克，42毫莫耳）放入在氮氣Τ的2公升容器 (Labmax，Mettler )中且加熱至70°C »將氮氰酸（HCN， 1 〇〇% ’ 63.1公克）及硝酸（65重量％，84.5公克）同時於 20 201124342 2小時之内進料至在該溫度下的混合物中。在完全添加之 後’將混合物再攪拌3〇分鐘。在一經添加HCN時，無色 氣體從合物釋出’表明沒有Ν Ο2存在。根據氣體層析術 分析，流出之氣體產物具有下列組成物：乙二腈（（cn)2 ): 64.9% ’ NO 與 N2 : 32.5%，C02 : 2.6%，HCN : 0%，h2〇 : 0%及乙腈（溶劑峰）。 在溫度經調整至-15°C之冷卻器中從氣態混合物汽提出 乙腈。接著將剩餘氣態混合物通過水性KOH溶液（1 〇重量 % )。吸收之（CN)2經測定為54公克，相當於85%之產率。 實施例2 : 將在乙腈（902毫升）中的硝酸銅（II)三水合物（95重 量％，7公克，30毫莫耳）放入在氮氣下的2公升容器 (Labmax，Mettler)中且加熱至 7(TC。將 HCN ( 81·6 公克） 及硝酸（65重量％，1〇2_6公克）同時於2.5小時之内進料 至在s亥溫度下的混合物中。在完全添加之後，將混合物再 攪拌60分鐘。在一經添加HCN時，無色氣體從混合物釋 出’表明沒有Ν〇2存在。根據氣體層析術分析，流出之氣 體產物具有下列組成物：（CN)2 : 65.6%，NO與Ν2 : 31.7 %，C〇2 : 2.8%，HCN : 0%，Η20 : 0%及乙腈（溶劑峰）。 在溫度經調整至-1 5 °C之冷卻器中從氣態混合物汽提出乙 腈。接著將剩餘氣態混合物通過水性KOH溶液（1 0重量 % ) 。（CN)2及C〇2幾乎完全被吸收。吸收之（CN)2經測定 為65公克，相當於80%之產率。 實施例3 : 21 201124342 將在乙腈（660毫升）及h20 ( 63.0毫升）中的硝酸銅 (II)三水合物（95重量％，lo o公克，40毫莫耳）放入在 氮氣下的2公升容器（Labmax，Mettler )中且加熱至70°C。 將HCN ( 100%，149.8公克）及硝酸（65重量％，194公 克）同時於4·5小時之内進料至在該溫度下的混合物中。在 完全添加之後，將混合物再攪拌6〇分鐘。在一經添加HCN 時’無色氣體從混合物釋出，表明沒有Ν02存在。根據氣 體層析術分析，流出氣體具有下列組成物：（cn)2 : 69.3%， NO 與 N2 : 28.5%，C02 : 0.5%，HCN : 1.3%，H20 : 0% 及乙腈（溶劑峰）。在溫度經調整至_15〇c之冷卻器中從氣 態混合物汽提出乙腈。接著將剩餘氣態混合物通過水性 K0H溶液（10重量％ )，其中（CN)2及C〇2被吸收。吸收 之（CN)2經測定為116公克，相當於78%之產率。 實施例4 : 將在環丁砜（ 356毫升）中的硝酸銅（Π)三水合物（95 重量％ ’ 10.0公克，40毫莫耳）放入在氮氣下的2公升容 器（Labmax，Mettler)中且加熱至 7CTC。將 HCN ( 100%， 99.7公克）及硝酸（65重量％，129.6公克）同時於3小時 之内進料至在該溫度下的混合物中。在完全添加之後，將 混合物再攪拌30分鐘。在一經添加HCN時，無色氣體從 混合物釋出’表明沒有N02存在。根據氣體層析術分析， 流出之氣體產物具有下列組成物：（cn)2 : 46.1 %，NO + N2 : 42.0% ’ C02 : 1〇_7% ’ HCN : 0.3%，H20 : 0.3%。將氣態 混合物通過水性KOH溶液（10重量％)，其中（CN)2及C02 22 201124342 二腈經測定為 72公克，相當於54%之產 被吸收。吸收之乙 率。 實施例5 : 在氮氣下於2八_^六 A开谷4 ( Labmax，Mettler)中製備硝酸 銅（II)三水合物（9 旦 3重置％，10.0公克，40毫莫耳）、乙 腈（ 600毫升）斑水主 〃尺（63毫升）之混合物且加熱至7(rc。將 氫氰酸（100重量％ , Λ ς/| 、丄 里/〇 0.54公克/分鐘）及硝酸（65重量％， 〇·72公克/分鐘）同昧於2 , 士 J守於3小時之内進料至在該溫度下的混 合物中及接著再谱主·^ Λ a 丹視件30分鐘。在整個反應時間内，從反應 此口物連續排出量且亦連續以在乙腈（咖毫升）中的硝酸 銅(11)一水合物（1 〇.〇公克）之混合物歸還該量。排出及裝 入一者白在1.5公克/分鐘之進料速度下進行。在一經添加 HCN時’直接靠近於混合物的氣流為無色。在一經添加hCN 時，無色氣體從混合物釋出，表明沒冑n〇2存在。根據氣 體層析術分析’流出之氣體產物在整個反應時間内具有下 列組成物：（CN)2: 70.6 至 71.4%，NO+N2: 27.9 至 29.9%， C02 : 0.3 至 0.8%，HCN : 〇 至 0.5%，H20 : 0 至 0.1%。 將氣態產物流通過維持在_15〇c之冷卻器，以移出乙腈。最 終獲得80%產率之（cn)2 ( 79公克）。 比較實施例1 : 根據US 3,949506 1之實施例2的運轉4,將水性硝酸銅 (H)溶液（500毫升，包含19〇 5公克硝酸銅（11)，75〇毫莫 耳）放入在氮氣下的2公升容器（Labmax，Mettler )中，並 將pH以65重量％之硝酸（79公克）調整至約pH 〇。在2〇 23 201124342 C及攪拌下於30分鐘之内進料HCN( 1〇〇% , 415公克）。 在一經添加HCN時，棕色氣體從混合物釋出，表明有N〇2 存在將混σ物於3 〇分鐘之内加熱至3 〇 t且不斷地再授拌 3〇分鐘。接著將額外的HCN(15 5公克）在3代下進料。 將品。物在30 C下再授拌3〇分鐘。以最先的HCN劑量開 始，將氧以0.23莫耳/小時經由玻璃料經15分鐘進料至混 5物中帛著減少至〇」2莫耳/小時，持續進料，直到反應 停止為止。排氣的氣體層析術分析顯露出（CN)2含量在反應 過程中從22.3%降低至4_5%。由於低產率及甚至降低在排 氣中的（CN)2含量，使反應溫度從20°C上升至30°C且以平 行的HCN及〇2劑量再持續3小時。不過’（cn)2下降至* 6 /6 , NO、NxOY (其中y為2χ )及n2增加至74%，且 增加至約20%。在反應期間，透明的藍色溶液轉變成在白 色落塵下的淺綠色懸浮液。該白色落塵經測定為不可溶的 CuCN及草醯胺（NC_C(〇)NH2 )，後者為水解之（cn)2的產 物。（CN)2的最終產率：13%。 比較實施例2 : 根據US 3997653 ’將1〇.5公克硝酸鋼三水合物（％ 重量％，10.5公克，42毫莫耳）與乙腈（693毫升）之混 合物放入2公升容器（Labmax，Mettler)中且加熱至7(rc。 以0.54莫耳/小時（0_35毫升/分鐘）之進料速度添加HCN。 在一經添加HCN時，棕色氣體從混合物釋出，表明有n〇2 存在。以最先的hcn劑量開始，將氡以〇 34莫耳/小時（6〇 毫升/分鐘）經由玻璃料以3小時期間進料至混合物中。在 24 201124342 反應過程中，藍色溶液轉變成淺綠色懸浮液及出現白色沉 澱物。排氣的氣體層析術分析顯露出（CN)2含量從35降低 至27%。NO、NxOY (其中y為2x)及N2維持在約56%， C02含量從7.6至0%，且HCN含量從0增加至14%。（CN)2 的最終產率：38%。 25Riemenschneider, W., Chemtech 1976, 658-661 discloses the use of a slight excess of oxygen in the reaction of nitrogen dioxide with hydrocyanic acid. As far as today's available methods for preparation are still unsatisfactory in terms of yield and selectivity. It is also difficult to find ethanedinitrile from the effluent gas, especially in the presence of excess nitrogen dioxide. The technical problem to be solved is to provide an alternative method for preparing ethanedinitrile. The problem has been solved by the method of applying for the scope of patents. It is a method for preparing ethanedinitrile ((C)2) from hydrocyanic acid (HCN) in a liquid phase, which is catalyzed by hydrocyanic acid in the presence of a copper ion catalyst and an aprotic polar solvent. Oxidation, characterized by the addition of oxalic acid (HN〇3) as the only oxidant during the oxidation of hydrogen acid. Therefore, neither NO nor N02 nor ν2〇4 was directly added to the reaction mixture. During the reaction, a colorless gas mainly comprising ethanedinitrile, NO and water is released from the reaction mixture upon contact of the hydrogen cyanate with the acid. The colorless gas apparently has no NxOy, where v A 9 w | , χ y /, τ y is 2X (for example, N〇2 or n2〇4). B. I can easily separate from the Ν Ο and the water - go to eight her long time. Ν〇 can be recycled to this method after reoxidation to nitric acid. The semi-tone is endless, and the NO contained in the effluent gas does not react further in the effluent gas and can be easily separated from the product. The amount of Nx〇y (where y is 2X, such as N〇2 or N2〇4) is reduced to a small amount in the main product loop to reduce the likelihood of peak damage. 5 201124342 Formula (i) describes the stoichiometry of the process: 6 HCN + 2 N〇3 - 3 (CN) 2 + 2 NO + 4 H20 (1) According to formula I, in this method of reaction with 6 mol hydrocyanic acid 2 moles of nitric acid was consumed to obtain 3 moles of oxalylonitrile, 2 moles of nitric oxide, and 4 moles of water. However, the obtained nitrogen oxide can be reoxidized by elemental oxygen and reacted with water to form nitric acid, at least in theory, in a continuously operated process in which only the initial amount of nitric acid + is required. In a preferred embodiment, nitric acid and hydrocyanic acid are simultaneously added to the process at a molar ratio ranging from 丨:25 to 1:3.5. In the present process, nitric acid means ', concentrated, nitric acid comprising at least 4% by weight, preferably at least 60% by weight, more preferably about 65% by weight of HN〇3. Higher concentrations of nitric acid up to fuming nitric acid (~100% by weight of HN〇3) can also be used in this process. A further aspect of the invention recycles the oxidant in a closed loop, as described, for example, in Figures 2 and 2. The nitrogen monoxide (NO) obtained in this method can be oxidized to nitrogen dioxide (N〇2 or N2〇4), which can react with water to obtain nitric acid having a maximum concentration of about 65% by weight. In a preferred embodiment, the acid can be reused directly in the process, thereby minimizing the need for nitric acid storage and transportation. The diaphoric acid is consumed in this method by chemical S. Therefore, when the diaphoric acid and the phthalocyanine are simultaneously fed in approximately stoichiometric proportions, no or only a little excess of nitric acid is present in the process. Therefore, the reaction can be handled very safely. 6 » 201124342 After separation from the product, NO is reoxidized in a separate loop to recycle the nitric acid used in this process. The use of recycled nitric acid makes only a small initial amount of nitric 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 the gaseous product gas mixture comprising ethanedinitrile and nitric oxide. When the reaction is carried out in the absence of elemental oxygen, it is impossible to detect the formation of nitric oxide and the corresponding dimer. The gaseous product mixture is also completely colorless. Another advantage of using nitric acid is to reduce the formation of diuterated carbon 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 2% 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 water-depleted mixture (if necessary after the addition of the solvent and copper catalyst) is recycled to the reactor. The reaction mixture was removed and water was removed. Suitable aprotic polar solvents may be selected from the group consisting of nitriles, ethers, glycol ethers and glycol ether esters, nitro compounds, sulfones, vinegars, decylamines, thiosamines and polar aromatics. Ring compound. The solvent need not have stability against nitric acid during prolonged periods of time since only a small excess of nitric acid is present in the process. It is guessed that it is preferably selected from the group consisting of acetonitrile, propionitrile, 201124342 benzoquinone, butyronitrile, rfe «indole nitrile, phenylacetonitrile and p-toluonitrile. Preferably, the product is selected from the group consisting of methyl propionate, ethyl propionate, 7 secret ethyl ester, propyl acetate, butyl acetate, dimethyl carbonate, carbonic acid. Diethyl -9 non-acetic acid ethyl acetate, gaseous acetic acid, ethyl acetate, acetic acid, i: ethyl sulphide isopropyl ester, methyl benzoate, ethyl benzoate, ethyl diethyl succinate Di-decyl dibenzoate, butyrolactone, propylene carbonate, ethylene carbonate and dibutyl benzoate. The alcohol ether and glycol ether ester are selected from the group consisting of ethylene glycol dimethyl ketone, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ketone, and monool. Monoterpene ether, 1,2-propanediol decyl ether, I, 〗 〖, alcohol ether 1} 2 - propylene glycol dipropyl ether, 1,2-propylene glycol methyl butyl, 1,3-propanediol dioxime ether, butanediol Dimethyl ether, glycerol triglyceride 'glycerol, ether, triglyceride, glycerol dimethyl bond, diethylene glycol dimethyl ether', one ethylene glycol diethyl ether, diethylene glycol diethylene ether, three Examined and tested with propylene glycol monoterpene ether acetate. Preferred nitro compounds are selected from the group consisting of 2-nitropropane, 1-nitropropane, nitrate, nitroxane and nifediene. Suitable sulfones are, for example, sulfolane. Preferred ethers are selected from the group consisting of hydrazine, 4-dihydroalkane, tert-butyl methyl ether, di-isoamyl ether, furan, tetrahydrofuran, methyltetrahydrofuran, anisole, tetrahydropyran. , phenylethyl ether, 13__, 5, 1,3-dioxcolane, di-n-propyl ether, diisopropyl ether, two _~~ 止丁, - third 谜, diphenyl ether and two Anisole. Preferred amides are selected from the group consisting of the following: 3 person's, _»% 201124342 methyl decylamine, N,N-diethyl hydrazine decylamine, tetramethylurea, tetraethyl Urea, NN dimethyl acetamide, N, N- - 7 # , Ν · ^ w Λ - ethyl acetamide, hydrazine - methyl acetamide, hydrazine hydrazide, guanamine, 2 A Also a pyrrolidone and 1-mercapto-2-pyrrolidone. Preferred polar aromatic miscellaneous class A, the group of: methyl ethyl: the following components are composed of 丞ethylpyridine, 2,3-dimercaptopyrimidinone, dimethyl dimethyl ketone - 2-ketone and dimethyl hydrazine, T is pyridine (2,3_, 2,4-, 2,5-, 2,6...3,4· or 3,5-dioxime. ratio). A preferred thioguanamine is, for example, a κ methyl group. Than 嘻 纲 -2 嗣 嗣. In the process of the invention, the copper catalyst comprises copper ions. In the presence of lithospermic acid, almost any copper alloy, copper complex and copper salt are oxidized to provide copper ions. Therefore, the beryllium copper ion is derived from a metallic copper or copper alloy, a steel (〇) complex, a copper (1) salt or a copper (1) complex, a copper (Η) salt or a copper (η) complex, and a mixture thereof. produce. The term, copper (0) 〃 contains metallic copper and copper alloys, and even more preferably in finely divided form, such as ground metal or alloy. The term, copper (0) compound 〃 comprises 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(I) bromide, vaporized Cu(I), cu(l), Cu(I) oxide, and Cu(I) nitride. The term '', copper (II) compound" comprises a copper (π) salt and a metal complex comprising copper ions (Cu + 2). The copper (π) salt which may be dissolved in at least one of the above solvents is preferably It is used in the method of the invention of 201124342. Suitable copper (π) salts are, for example, copper nitrate (11), vaporized copper (ruthenium), copper (II) bromide, copper iodide (ruthenium), copper sulfate (11). , copper cyanide, copper (II) oxide, copper (II) pyrophosphate, copper sulfide (11), copper hydroxyphosphate (11), copper (II) carbonate, copper (II) hydroxide and non-aromatic and aromatic Copper (π) salt of carboxylic acid, such as copper (II) acetate, copper (II) formate, copper (11) acetate, copper tartrate (11), copper (II) oxalate, copper (II) citrate, benzene Copper ruthenate (11), copper methyl phthalate (yttrium), copper ethyl acetate (11), copper ethyl phenyl phthalate (11), copper (II) trifluorosulfonate, Copper (11) phthalate or copper (π) benzene sulfonate. In a preferred embodiment, hydrocyanic acid is placed in the reaction vessel while simultaneously feeding nitric acid into the mixture. More advantageously Will be dissolved in the solvent as needed or The catalyst mixture with the solvent is placed in the reaction vessel, and the nitric acid and hydrocyanic acid are simultaneously, discontinuously or continuously added to the reaction mixture while the reaction is continued. If the phthalocyanic acid and the tartaric acid are simultaneously or alternately It is not necessary for them to be fed stoichiometrically at the same time. However, in order to avoid excessive oxidation and side reactions with solvents, it is recommended to have hydrocyanic acid in the reactor according to the ratio of the chemical leaf amount according to the equation 弋I. And sour acid. In order to avoid incomplete conversion of hydrocyanic acid, nitric acid can also be fed in a slight excess without adverse effects. This method can be from 15 to 150. (: 'better from 50 to loot:, better It is carried out at temperatures in the range of 60 to 90. Execution of this method at high pressure can result in the production of the product in gaseous form. Therefore, it is necessary to recover the product from the liquid reaction mixture. The nitrile reacts more or less rapidly with the water formed in the reaction. Therefore, the liquid reaction temperature and pressure should be in a range that allows easy removal of the product in the gaseous form of 10 201124342 from the reactor. Preferably, the reaction is carried out at about atmospheric pressure. Immediately after the hydrocyanic acid is mixed with the nitric acid, a product gas stream comprising ethanedinitrile and nitrogen monoxide is formed. Advantageously, the product gas stream is continuously discharged from the reactor. And subject to further work (work_up) in which ethanedinitrile is separated from the product gas stream. It is possible to separate the ethanedinitrile from the product gas stream in different ways, for example by cold/east, condensation, absorption/desorption or adsorption/desorption. Adsorption of ethanedinitrile. Particularly preferably, the ethanedinitrile in the product gas stream is absorbed in and recovered from the solvent. In order to minimize waste disposal, cost, amount of nitric acid used and environmental hazards, the present invention The method provides the possibility of recycling the oxidizing gas obtained in the reaction of hydrocyanic acid with nitric acid. Advantageously, the industrial scale effluent-nitrogen oxide (N0) is oxidized to obtain nitrogen dioxide (N〇2). Oxidation of N0 in the presence of: alkoxy (?2) is well known in the art. Feeding far n〇2 from the exhaust NO to the water results in nitric acid (hn〇) = liquid, which can be used directly in this process, and 2 reacting with water is also known in the art. When this method begins, the exhaust NO of this process is recycled so that the hno3 feed can be minimized. Therefore, in a preferred embodiment, the sulphate τ τ will be the product gas stream - the nitrogen oxide - to the reactor alone, where it is oxidized to obtain nitric oxide, which is absorbed. In water, the nitric acid obtained in I _ 'kgk is recycled to the reaction with phthalocyanine. The main preferred reaction example is that you carry out the reaction in a continuous process, 11 201124342 — only need to be determined within the The feed of hydrocyanic acid, elemental oxygen and make-up streams. The X-recycle method requires efficient recycling of solvents and catalysts of appropriate purity and high yield. Preferably each recycled component has a suitable hydrazine. The degree of purity is preferred because the enriched by-products and/or decomposition products may have an adverse effect on the life of the method. The use of a gate boiling agent in the reaction of nitric acid with hydrocyanic acid can be easily carried out from the reaction. The advantage of separating the cyanide from the mixture. In a preferred embodiment of the vehicle, the process of the invention is carried out in a continuous process, in which at least the organic solvent and the catalyst are recovered as needed. The reaction of the acid with hydrocyanic acid is conveniently carried out in an organic solvent. get on, The solvent is substantially the same as the solvent used for the oxalylonitrile treatment. In a preferred embodiment, the treatment of ethanedinitrile is carried out using a solvent to recover ethanedinitrile from the product gas stream mixture. Preferably, the solvent is about + 30C or lower temperature with good absorption properties for oxalylonitrile and poor absorption properties for nitric oxide. Dissolve ethylene in acetonitrile at temperatures from -5 to +30 °C Nitrile is also better than dissolved nitric oxide. It can therefore be used to effectively separate two compounds. Thus, in a more specific embodiment, the organic solvent is acetonitrile. In a particularly preferred embodiment, the reaction of nitric acid with hydrocyanic acid Ethyl acetonitrile is used as an organic solvent' and, after passing through the condenser, the product gas stream is fed to an absorption column countercurrent to acetonitrile. The countercurrent acetonitrile mainly absorbs ethanedinitrile while the nitric oxide remains in gaseous form, and Finally, the second guess product is recovered from acetonitrile and removed from the process. The recovered acetonitrile is then re-extracted to the process. The reaction and recovery of the ethanedonitrile from the product gas stream are all carried out using 12 201124342 acetonitrile. The product is recovered from the acetonitrile in a desorption column. The nitric oxide is oxidized as needed in the presence of an oxygen-containing gas to obtain nitrogen dioxide, which reacts with water, and the nitric acid is recovered. The recycled nitric acid can be reused in this method. And Figure 2 illustrates the process of the invention in a preferred embodiment wherein nitric acid and an organic solvent are recycled to the process (Fig. ο, and the detailed form of the towel, taken from acetonitrile (4) as polar money solution #1 (Figure graphic Description of the drawings: Figure 1 : Figure 1 illustrates a general mode for the recycling of tribasic acid. The reactor (H is equipped with a line 2, 22, 23, respectively, which provides a hydrogen acid, a sulphuric acid, a catalyst and a solvent feed. twenty four. Although in the continuous process most of the nitric acid, solvent and catalyst are recycled via recycle lines 37, 40 and 43, pipelines 2, 2 3 and 24 may also be supplemented for the purpose of use during this process, while pipelines 21 is also used to provide the nitrogen nitro acid required during the reaction. Lines η and 34 provide elemental oxygen and water, respectively, to reoxidize nitric oxide. The product gas stream (containing acetonitrile, nitrogen monoxide, organic solvent and water and trace carbon dioxide) discharged from the reaction pirates 01 is fed to the condenser 02 where it condenses most of the organic solvent and water, and The condensate in line 26 is recycled to reactor crucible 1 as needed after partial or complete removal of water. The remaining product gas from the condenser 〇2, 13 201124342, is fed to the virgin lining in the official line 27, and is used to isolate the ethanedinitrile. The product in line 27 is Hyper & People, | Block J is rolled "IL package a ethanedinitrile, nitric oxide and a small amount of inert gas such as carbon dioxide' and substantially depleted solvent and water. Processing unit 1 2 package 3 (1) for line 32 of gaseous products consisting mainly of pure Ethylene, (η) for s line 28' of the effluent rinsing liquid consisting mainly of recovered organic solvent and traces of water. The scouring rinsing liquid is recharged into the reactor 〇i to suppress accumulation of unnecessary compounds (e.g., water) in the processing unit (4), and (d) a line 29 consisting mainly of nitrogen oxide and an inert gas such as carbon dioxide. The gas stream from line 29 is recharged into oxidation reactor crucible 7, wherein the oxygen is oxidized to the dioxane: nitrogen in the presence of an oxygen-containing gas fed via line 33: advantageously in the presence of a catalyst. The effluent stream of line 35 (comprising a nitrogen stream) is recycled to reactor enthalpy 8 as needed and reacted with water fed via a hydrazine line to obtain nitric acid. Reactor 〇 8 contains a line 36 that removes exhaust gases, such as carbon dioxide. Nitric acid is required to be loaded into the reactor 01 in line 37 or used elsewhere. Treatment Unit 1 2: Depending on the thermodynamic properties of line 27, acetylonitrile can be recovered using different separation techniques. A suitable specific example is the combination of an absorption column and a regeneration unit for recycling the solvent. The ethanedinitrile is taken up in a solvent having a high selectivity and released in a subsequent regeneration of the early dehydration including desorption, distillation or rectification. Further processing that may occur is to trap the inert gas in a suitable solvent. The ethanedinitrile is then the top product of the first column. 〇 Optional - to recover acetonitrile by absorption / regeneration 'It is also possible to use, for example, 14 201124342 (1) adsorption technology, / also ethanedinitrile -3⁄4 Tv - ^. * The bath is desorbed, or (8) liquid, liquid, and extraction techniques are separated from other reaction partners. The necessary means for recycling the solvent at τ are known to those skilled in the art. Another option for recovering ethanedinitrile is to direct cold acetonitrile from the gaseous product stream. This can be performed using two parallel heat exchange f-lines, optionally injecting the product emulsion. Although ethanedinitrile is solidified in one line, the solidified acetonitrile is re-evaporated in other lines and obtained in almost pure form. In the official line 38, a portion of the reaction mixture (the reaction mixture comprising an organic solvent, water, a catalyst, dissolved ethanedinitrile and a small amount of unreacted nitric acid and hydrocyanic acid) is discharged from the reactor in a continuous or discontinuous mode. 1 Discharge and feed to the ridge recovery unit 丨3. Within the solvent recovery unit, water is separated from the reaction mixture as described in more detail below and discharged from the process in line 41 while the recovered organic solvent, catalyst and nitric acid are recycled to reactor 01 in line 40. . The solvent recovery unit further comprises a bypass line 43 comprising a solvent, a mixture of ethanedinitrile and hydrocyanic acid, which is also recycled to the reactor. Solvent recovery unit 13: Depending on the thermodynamic properties of the mixture comprising the organic solvent, water and catalyst, the separation can be carried out in a suitable column configuration known to those skilled in the art, for example by using simple distillation or rectification to separate the azeotrope. The azeotrope is separated by pressure swing rectification or rectification of a misting agent such as an 'ether or a hydrocarbon. D ° is selected from laminates, blister or bubble trays with regular or irregular fillers. number. Alternatively, the reaction water can be separated using a membrane separation technique such as evaporation, pervaporation or 15 201124342 ultrafiltration. In addition to the above methods, it is also possible to separate water from the reaction mixture using an adsorption, absorption or extraction step. Figure 2: Figure 2 illustrates a preferred mode of the process using acetonitrile as the primary polar solvent. According to Figure 1, reactor 〇 1 is equipped with lines 2, 22, 23 and 24 which respectively provide a feed of hydroquinic acid, acid, catalyst and organic solvent (i.e., acetonitrile). Nitric acid, an organic solvent (i.e., acetonitrile), and a catalyst are also fed through recirculation lines 37, 40, and 43, respectively. Lines 22, 23 and 24 may also be used during this process for supplemental purposes, 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 (i.e., acetonitrile), water, and traces of carbon dioxide) is fed to condenser 02 in line 25. The condensate containing the organic solvent (i.e., acetonitrile) and water is recycled to reactor 01 via line 26, which is optionally removed after partial or complete removal of water. The gaseous effluent 16 (containing ethanedinitrile and nitric oxide) from the condenser 〇2 with a small amount of inert gas (such as carbon dioxide) and a small amount of organic solvent (ie acetonitrile) and water in line 27 is obtained. 27 is charged into the bottom of the absorption column 03, and countercurrent to the organic solvent (i.e., acetonitrile) flowing in the column 3 to the top of the column 03. The absorption column 03 operating at a temperature of from about _5 to 30 C, preferably in the range from 〇 to +15<»c, may be a packed column filled with regular or irregular fillers, or a laminate, = hood or Bubble tray tower. A mixture of line 28 comprising acetonitrile and traces of water is removed from column 3 via an outlet tube on the top side of the overhead column and recharged into reactor 16 201124342. Recirculation line 28 to reactor 0 1 prevents water and organic solvents (i.e., B guess) from accumulating in column 03 during the absorption/desorption series during continuous operation. The bottom product of Taman 3 (containing organic solvent (ie acetonitrile), ethylene February and water) is discharged at $31 to the feed 〇* and then to the top of the desorption column 05. in. The overhead stream of column 3 (comprising nitric oxide with a trace amount of inert gas, such as carbon dioxide) is advantageously fed to oxidation reactor 07 in line 29 to obtain nitric acid, as outlined below. Separation of impurities and other compounds (i.e., water) which are disadvantageous to this process is carried out in the desorption column 5 according to the latest art known to those skilled in the art, for example, using a low pressure and/or a rising temperature. Advantageously, the tower 5 is formed into a packed column filled with regular or irregular packing, or as a laminate, blister or bubble tray. The refined organic solvent stream (also acetonitrile), which may still contain water, is withdrawn from the bottom of column 05 and fed to heat exchanger 06 in line 3〇. The acetonitrile is then heated to the operating temperature of column 03 and then recycled to the top of column 03. The overhead stream of the column 5 (containing the almost pure gaseous product ethanedinitrile) is withdrawn via line 32, which may be used directly or may be recovered after, for example, cooling and condensation. It is also possible to pass a gaseous or liquefied acetylation test to obtain a hydrolyzed compound. As outlined above in Figure 1, the nitrogen oxide recovered from the gas product stream of line 25 in the column 3 is reoxidized to nitric acid and recharged into reactor 01 in line 37 to reduce Oxidation test required for this method A partial amount of the reaction mixture is carried out in line 38 (Shai reaction mixture 17 201124342 contains organic solvent (ie acetonitrile), water 'catalyst, dissolved ethanedinitrile and a small amount of unreacted nitric acid With hydrocyanic acid, it is discharged from the reactor 01 in a continuous or discontinuous mode and fed to the rectification column 09, which is in the range of 8 to 20 bar, preferably 8 to 8 bar. Within the range, it is particularly good to operate at pressures in the range of 4 to 6 bar. The product gas stream is separated in column column 9 into (1) overhead stream comprising an organic solvent (i.e., acetonitrile), an almost azeotropic composition of water and traces of ethanedinitrile, and hydrocyanic acid, which are fed to line 39 to In the distillation column 10, and (ii) a bottom product comprising an organic solvent (i.e., acetonitrile), a catalyst, nitric acid, and a trace amount of water, which is further recharged in line 4C). ... steamed de... in about. .0...bar, preferably at. Processing at low pressure within the range. A mixture of line 39, which is the overhead stream of column 9, is separated in column 10 into (1) overhead stream and (Η) bottoms product. The overhead stream (1) is fed in line 42 to condenser u while the bottoms product (ii) consisting essentially of water is withdrawn from this process as line 41. When operating in the continuous mode, if the entire amount of water is controlled to a fixed value, the water discharged in line 41 is approximately equivalent to the amount of water obtained in the reactor 01. The excess stream fed in line 42 is separated in condenser u into (1) a condensed liquid portion comprising an almost azeotropic composition of organic solvent (i.e., acetonitrile) and water, which is recycled to the column. A topsheet of 9 and (8) a gaseous stream comprising ethanedinitrile, hydrocyanic acid and an organic solvent (i.e., B guess) which is recycled to reactor 〇1 in line 43. Specific examples of Figures 1 and 2 Table 01: Reactor 02: Heat exchanger (condenser) 18 201124342 03: Absorption column 04: Heat exchanger 05: Desorption column 06: Heat exchanger 07: Reactor 08: Reaction 09: Refinery column 10: distillation column 11: heat exchanger 12: treatment unit 13 for product recovery of nitric oxide: solvent recovery unit 21: hydrocyanic acid feed 22: nitric acid feed 23: catalyst acid Feed 24: solvent feed 25: gaseous product stream from the reactor 26: product depleted solvent stream 27: solvent depleted product gas stream " 28: flushing stream (condensed water and product depleted solvent stream) 29: a gaseous stream comprising nitric oxide and an inert gas 30: a cleaning solvent for recovering ethanedinitrile 3 1 : a solvent having ethanedinitrile and water 32: an ethanedinitrile product stream 33: an oxygen-containing gas 19 201124342 34 Water feed 35 Nitrogen dioxide stream 36 Exhaust stream 37 Recycled nitric acid 38 Partial reaction mixture 39 Solvent and water stream 40 Catalyst for recovery 41 Water removed from the process 42 Top stream 43 Solvent ethanedinitrile and 44 Part of the condensed liquid of the bypass stream of the hydrocyanic acid in the recycle loop of the solvent and water mixture. Example: Only in the case of the purpose of easily determining the yield of ethanedinitrile, the effluent will be discharged. The product gas passes through an alkaline stripping agent (KOH solution) which almost completely absorbs the ethanedinitrile' in contrast to NO and & 'they continue to maintain the gaseous form. As shown in the examples, the process of the present invention avoids the development of carbon dioxide and other higher nitrogen oxide compounds, summarized as Nx0y, where y is 2 χ Example 1 : Nitric acid in acetonitrile (694 ml) Copper (Π) hydrazine hydrate (95% by weight '10.5 g, 42 mmol) was placed in a 2 liter vessel (Labmax, Mettler) in a nitrogen atmosphere and heated to 70 ° C » Nitric acid cyanide (HCN, 1 〇〇% '63.1 gram) and nitric acid (65% by weight, 84.5 gram) were simultaneously fed to the mixture at this temperature within 2 hours of 201124342. The mixture was stirred for a further 3 minutes after it was completely added. When the HCN was added, the colorless gas was released from the compound, indicating that no Ν2 was present. According to gas chromatography analysis, the effluent gas product had the following composition: ethanedinitrile ((cn) 2 ): 64.9% 'NO and N2: 32.5%, C02: 2.6%, HCN: 0%, h2 〇: 0 % and acetonitrile (solvent peak). The acetonitrile was stripped from the gaseous mixture in a cooler adjusted to a temperature of -15 °C. The remaining gaseous mixture was then passed through an aqueous KOH solution (1% by weight). The absorbed (CN) 2 was determined to be 54 grams, which corresponds to a yield of 85%. Example 2: Copper (II) nitrate trihydrate (95% by weight, 7 grams, 30 millimoles) in acetonitrile (902 ml) was placed in a 2 liter vessel (Labmax, Mettler) under nitrogen and Heat to 7 (TC. HCN (81·6 g) and nitric acid (65 wt%, 1〇2_6 g) are simultaneously fed to the mixture at s sea temperature within 2.5 hours. After complete addition, The mixture was stirred for a further 60 minutes. Upon addition of HCN, a colorless gas evolved from the mixture indicated that no Ν〇2 was present. According to gas chromatography analysis, the effluent gas product had the following composition: (CN) 2: 65.6%, NO and Ν2: 31.7 %, C〇2: 2.8%, HCN: 0%, Η20: 0% and acetonitrile (solvent peak). Vapor acetonitrile from gaseous mixture in a cooler adjusted to -1 5 °C The remaining gaseous mixture was then passed through an aqueous KOH solution (10% by weight). (CN) 2 and C 〇 2 were almost completely absorbed. The absorbed (CN) 2 was determined to be 65 grams, corresponding to an 80% yield. Example 3: 21 201124342 Copper (II) nitrate in acetonitrile (660 ml) and h20 (63.0 ml) Hydrate (95% by weight, lo og, 40 mmol) was placed in a 2 liter vessel (Labmax, Mettler) under nitrogen and heated to 70 ° C. HCN (100%, 149.8 g) and nitric acid ( 65 wt%, 194 g) was simultaneously fed to the mixture at this temperature within 4.5 hours. After complete addition, the mixture was stirred for a further 6 minutes. Upon addition of HCN, a colorless gas was released from the mixture. Out, indicating that no Ν02 exists. According to gas chromatography analysis, the effluent gas has the following composition: (cn) 2: 69.3%, NO and N2: 28.5%, C02: 0.5%, HCN: 1.3%, H20: 0% And acetonitrile (solvent peak). The acetonitrile is stripped from the gaseous mixture in a cooler adjusted to _15 ° C. The remaining gaseous mixture is then passed through an aqueous K0H solution (10% by weight), wherein (CN) 2 and C 〇 2 was absorbed. The absorbed (CN) 2 was determined to be 116 g, which corresponds to a yield of 78%. Example 4: Copper nitrate (Π) trihydrate (95% by weight) in sulfolane (356 ml) 10.0 gram, 40 millimoles) placed in a 2 liter container under nitrogen (Labmax, Mettler) and heated to 7 CTC. HCN (100%, 99.7 g) and nitric acid (65 wt%, 129.6 g) were simultaneously fed to the mixture at this temperature within 3 hours. After complete addition, The mixture was stirred for a further 30 minutes. Upon the addition of HCN, the colorless gas was released from the mixture, indicating that no N02 was present. According to gas chromatography analysis, the effluent gas product had the following composition: (cn) 2 : 46.1 %, NO + N2 : 42.0% 'C02 : 1 〇 _ 7% 'HCN: 0.3%, H20: 0.3%. The gaseous mixture was passed through an aqueous KOH solution (10% by weight), wherein (CN) 2 and C02 22 201124342 dinitrile were determined to be 72 grams, equivalent to 54% of the product being absorbed. The rate of absorption. Example 5: Preparation of copper (II) nitrate trihydrate (9 denier 3 reset %, 10.0 g, 40 mmol), acetonitrile in a nitrogen solution (Labmax, Mettler) under nitrogen (600 ml) a mixture of spotted water master ruler (63 ml) and heated to 7 (rc. Hydrogen cyanide (100% by weight, Λ ς / |, 丄 / 〇 0.54 g / min) and nitric acid (65 weight) %, 〇·72 g/min) with the same 22, 士J kept within 3 hours of feeding to the mixture at this temperature and then re-sampling the main ^^ Λ a Dan visuals for 30 minutes. The amount is continuously recovered from the reaction and is also continuously returned as a mixture of copper nitrate (11) monohydrate (1 〇. 〇g) in acetonitrile (caffe). White was carried out at a feed rate of 1.5 g/min. The air flow directly adjacent to the mixture was colorless upon addition of HCN. Upon addition of hCN, a colorless gas was released from the mixture, indicating that no n胄2 was present. Gas Chromatography Analysis 'Exhausted gas products have the following composition throughout the reaction time: (CN) 2 : 70.6 to 71.4%, NO+N2: 27.9 to 29.9%, C02: 0.3 to 0.8%, HCN: 〇 to 0.5%, H20: 0 to 0.1%. Pass the gaseous product stream through a chiller maintained at _15〇c To remove acetonitrile. Finally, 80% yield of (cn) 2 (79 g) was obtained. Comparative Example 1: According to the operation 4 of Example 2 of US Pat. No. 3,949,506, an aqueous copper nitrate (H) solution (500) Millimeter, containing 19 〇 5 g of copper nitrate (11), 75 〇 millimoles) was placed in a 2 liter vessel (Labmax, Mettler) under nitrogen, and the pH was adjusted to 65% by weight of nitric acid (79 grams) to About pH 〇. HCN (1〇〇%, 415 g) was fed in 30 minutes with stirring at 2〇23 201124342 C. Upon addition of HCN, brown gas was released from the mixture, indicating the presence of N〇2 The mixed slag was heated to 3 〇t in 3 且 minutes and continuously re-mixed for 3 。 minutes. Then additional HCN (15 5 gram) was fed in 3 generations. The product was at 30 C. Mix for another 3 minutes. Start with the first HCN dose and reduce the oxygen to 0.25 mol/hr via the frit for 15 minutes. At the same time, the feed was continued until the reaction was stopped. Gas chromatographic analysis of the exhaust revealed that the (CN)2 content decreased from 22.3% to 4_5% during the reaction. Due to low yield and even reduced in the exhaust gas ( CN) 2 content, the reaction temperature was raised from 20 ° C to 30 ° C and continued in parallel with HCN and 〇 2 dose for 3 hours. However, '(cn)2 drops to *6/6, NO, NxOY (where y is 2χ) and n2 increases to 74% and increases to about 20%. During the reaction, the clear blue solution turned into a light green suspension under white dust. The white dust was determined to be insoluble CuCN and oxalylamine (NC_C(〇)NH2), which was a product of hydrolysis of (cn)2. Final yield of (CN) 2: 13%. Comparative Example 2: A mixture of 1 〇.5 gram of nitric acid steel trihydrate (% by weight, 10.5 gram, 42 mM) and acetonitrile (693 cc) was placed in a 2 liter container according to US 3,997,653 (Labmax, Mettler) And heated to 7 (rc. HCN was added at a feed rate of 0.54 mol/hr (0-35 ml/min). Upon addition of HCN, brown gas was released from the mixture, indicating the presence of n〇2. The first hcn dose was started and the crucible was fed to the mixture via a frit over a period of 3 hours at 〇34 mol/hr (6 〇 ml/min). During the 24 201124342 reaction, the blue solution turned into a light green suspension. Liquid and white precipitate appeared. Gas chromatographic analysis of the exhaust revealed a decrease in (CN)2 content from 35 to 27%. NO, NxOY (where y was 2x) and N2 maintained at about 56%, C02 content from 7.6 To 0%, and the HCN content increased from 0 to 14%. The final yield of (CN)2: 38%.