玖、發明說明： 本申凊案請求美國臨時專利申請序號60/381 066案 (2002年5月16日申請）。 【發明所屬技術領域】玖, invention description: This application filed a request for US Provisional Patent Application No. 60/381 066 (applied on May 16, 2002). [Technical Field of the Invention]
本發明係有關於一種使羧酸（特别係羧酸混合物）胺解 氧化成腈或腈混合物之方法。 t Λ. J 發明背景 丙烯腈係一重要化學物品，其主要係作為製造廣泛不 同的聚合物料(諸如，用於織物之丙烯系纖維之聚合物）及樹 月曰（遠如’ ABS及SAN樹脂）之早體。全世界地，丙稀腈係以 每年超過四百萬噸之量製造。製造丙烯腈之最普遍使用的 方法係於氨存在之胺解氧化反應器内使用空氣或其它分子 氧來源作為氧化劑使適當之烴(諸如，丙烯或丙烷)反應。此 等氧化反應（亦稱為胺解氧化反應）典型上係使用流體化催 化劑床之固體顆粒非均質催化劑催化胺解氧化反應，且提 供可接受轉化率及產率之所欲丙烯腈。除製造丙烯腈外， 此等胺解氧化反應一般亦產生乙腈、氰化氫(HCN)及其它有 價值之共產物。例如，乙腈係作為溶劑。烴供料催化胺解 氧化成丙烯腈之方法係揭示於，例如，美國專利第5,093,299; 4,863,891;4,767,878;4,503,001號案，其等在此皆被併入以 供參考之用。 廣泛用於商業上實施以回收此等烴胺解氧化反應（諸 如，丙烯之胺解氧化反應）之產物的方法一般包含步驟：a) 1322798 於驟冷塔使胺解氧化反應器之流出物與水性驟冷液體接觸 以使氣態流出物冷卻；b)於吸收器内使經驟冷之流出物與 水接觸，形成包含胺解氧化產物之水性溶液；c)使水性溶 液接受水萃取蒸餾；及d)自管柱頂部移除包含丙烯腈及一 5 些水之第一塔頂蒸氣流，及自管柱底部收集含有水及污染 物之液態廢料流。丙烯腈之進一步純化可藉由使塔頂蒸氣 流送至第二蒸餾管柱以自粗製丙烯腈移除至少一些雜質及 進一步蒸餾經部份純化之丙烯腈而完成。自胺解氧化反應 器之流出物一般含有一些含量之氨。因此，驟冷塔内所用 10 之驟冷流體亦可含有強礦物酸(諸如，硫酸）而反應且藉此形 成氨之水溶性鹽，諸如，硫酸銨。含有硫酸銨及其它組份 之用過或廢驟冷流體典型上係以環境安全方式處理或棄 置。 粗製之乙腈可以用以實施上述萃取蒸餾之管柱的底部 15 流體而被獲得，然後，接受進一步之純化程序，諸如，美 國專利第6,204,407號案所揭示之純化程序。 所欲地係能調整烴供料(諸如，丙烯或丙烷）之胺解氧化 反應製生之丙烯腈及乙腈之相對含量，因為有時欲具有額 外之可獲得符合變化或增加之市場需求的乙腈。另外，所 20 欲地係製造可於製造丙烯腈之方法中被循環回收（而非被 處理棄置）之用過的驟冷液體。本發明提供此等方法。 所欲地係能調整烴供料（諸如，丙烯或丙烷）之胺解氧化 反應製生之丙烯腈及乙腈之相對含量，因為有時欲具有額 外之可獲得符合變化或增加之市場需求的乙腈。另外，所 6 欲地係製造可於製造丙烯腈之方法中被循環回收（而非被 處理棄置）之用過的驟冷液體。本發明提供此等方法。 本發明係有關一種使羧酸(特別係羧酸混合物）胺解氧 化成腈或腈混合物之方法。本發明亦係有關增加產率，且 較佳係烴之胺解氧化反應（諸如，丙烯或丙烷變成丙烯腈） 期間產生之共產物乙腈對丙烯腈之比例。 本發明亦係有關於一種於藉由烴供料(諸如，丙烯或丙 烧）之胺解氧化反應製造丙烯腈期間增加共產物乙腈產率 且同時節省與共產物產率增加有關之原料費用之方法。乙 膀之相對量可藉由本發明之藉由調整添加至胺解氧化反應 之叛酸含量而控制。 已不可預期地發現使用羧酸（特別係粗製之羧酸混合 物）可達成於生產丙烯腈期間之乙腈生產之所欲增加。 本發明亦係有關於一種使用過之驟冷塔驟冷液體循環 回收至胺解氧化反應器之方法。 【發明内容】 發明概要 本發明包含一種大量增加自丙烯或丙烷或其混合物製 造丙烯腈期間產生之乙腈產量之方法。因此，本發明包含 一種增加於丙烯腈製造期間產生之共產物乙腈的產率之方 法，包含使包含至少一選自丙烯及丙烧所組成族群之烴、 羧酸、氨及含分子氧之氣體的反應物引入含有胺解氧化反 應催化劑之反應區域(例如，流體床反應器）内’使烴、緩酸、 氨及氧於升高溫度之催化劑上反應產生丙烯腈、氰化氫及 &精，及自反應區域回收包含丙烯腈、氰化氣及乙骑之產 物。 本發明包含一種於製造丙烯腈期間使羧酸（特別係粗 製緣酸’且更特別係粗製羧酸混合物)轉化成包含乙骑的混 合物真不會大量影響丙烯腈產率之方法。因此，本發明包 含使包含至少一選自丙烯及丙烷所組成族群之烴、至少一 線酸、氨及含分子氧之氣體的反應物引入含有胺解氧化反 舞催化劑之反應區域(例如’流體床反應器）内，及使烴、竣 酸、氨及分子氧於升高溫度之催化劑上反應產生丙稀猜、 氣化氫及乙腈。 本發明包含使至少一選自丙烯及丙烷所組成族群之 炫、裘少一幾酸、氨及含分子氧之氣體的反應物引入反應 處威（例如’流體床反應器）内以於胺解氧化反應催化劑（例 如，流體床胺解氧化反應催化劑)存在中反應以產生包含丙 稀腈、氰化氫及乙腈之反應器流出物，使包含丙歸腈、氰 化氮及乙猜之反應益流出物送至驟冷官柱内以使反應器流 出物冷卻’及自反應器流出物回收包含丙烯腈、乙腈及氰 化氫之至少一者之所欲產物。 於本發明之一實施例，一或更多之羧酸可被添加至驟 冷液體以與胺解氧化反應器之流出物内存在之過量氨反 應。較佳地，至少部份之包含藉由氨與一或更多之羧酸反 應形成之敍鹽的驟冷液體係被循環至胺解氧化反應器或反 應區域β 藉由本發明方法形成之產物（諸如，丙稀腈、乙腈及氰 1322798 化氫）可被回收，且藉由熟習此項技藝者已知之方法（例如， 美國專利第 4,234,501; 3,885,928; 3,352,764; 3，198,750及 3，(M4,966號案所揭示之方法’其等在此被併入以供參考之 用）純化。 5 於本發明之較佳實施例中，粗製之羧酸係作為羧酸來 源。於此使用時，粗製之羧酸包含尚未被純化成一般之商 業上可接受規格之純等級羧酸之羧酸或其混合物，且其較 佳係意指藉由一或更多之用以製造羧酸之方法製得但尚未 被純化成一般之商業上可接受規格之純等級羧酸之羧酸或 1〇 其混合物。粗製之羧酸或混合物可含有水、其它雜質或二 者°例如，粗製羧酸之水含量可為從約2，約5，或約1〇重 里/。，至隶南達約98重量％。粗製之乙酸係用於本發明實施 例之較佳羧酸。 任何胺解氧化催化劑可用於本發明之實施例。典型之 胺解氧化催化劑係以下列二化學式概括：This invention relates to a process for the deoxidation of a carboxylic acid, particularly a mixture of carboxylic acids, to a nitrile or mixture of nitriles. t Λ. J BACKGROUND OF THE INVENTION Acrylonitrile is an important chemical mainly used in the manufacture of a wide variety of polymer materials (such as polymers of propylene fibers for fabrics) and tree sap (as far as 'ABS and SAN resins') ) The early body. Worldwide, acrylonitrile is manufactured in quantities of more than four million tons per year. The most commonly used method of making acrylonitrile is to react a suitable hydrocarbon such as propylene or propane using an air or other molecular oxygen source as an oxidant in an ammonia desulfurization reactor. These oxidation reactions (also known as amine deoxidation reactions) typically catalyze the amine deoxidation using a solid particle heterogeneous catalyst of a fluidized catalyst bed and provide the desired conversion and yield of the desired acrylonitrile. In addition to the manufacture of acrylonitrile, such amine deoxidation reactions generally also produce acetonitrile, hydrogen cyanide (HCN) and other valuable co-products. For example, acetonitrile is used as a solvent. A method for the catalytic ammoxidation of a hydrocarbon feed to an acrylonitrile is disclosed, for example, in U.S. Patent Nos. 5,093,299, 4,863,891, 4,767,878, the disclosure of which is incorporated herein by reference. Processes widely used commercially to recover products of such hydrocarbon ammoxidation reactions, such as the amine deoxidation of propylene, generally comprise the steps of: a) 1322798 in a quench column to effect the effluent of the amine deoxidation reactor with The aqueous quench liquid is contacted to cool the gaseous effluent; b) contacting the quenched effluent with water in the absorber to form an aqueous solution comprising the amine deoxidation product; c) subjecting the aqueous solution to water extractive distillation; d) removing the first overhead vapor stream comprising acrylonitrile and a portion of water from the top of the column and collecting a liquid waste stream containing water and contaminants from the bottom of the column. Further purification of the acrylonitrile can be accomplished by passing the overhead vapor stream to a second distillation column to remove at least some of the impurities from the crude acrylonitrile and further distilling the partially purified acrylonitrile. The effluent from the amine deoxidation reactor typically contains some ammonia. Thus, the quench fluid used in the quench column may also contain a strong mineral acid such as sulfuric acid to react and thereby form a water soluble salt of ammonia, such as ammonium sulfate. Used or waste quench fluids containing ammonium sulphate and other components are typically disposed of or disposed of in an environmentally safe manner. The crude acetonitrile can be obtained by carrying out the bottom 15 fluid of the above-described extractive distillation column, and then subjected to a further purification procedure, such as the purification procedure disclosed in U.S. Patent No. 6,204,407. Desirably, the relative amount of acrylonitrile and acetonitrile produced by the amine deoxidation reaction of a hydrocarbon feedstock such as propylene or propane can be adjusted, as it is sometimes desirable to have additional acetonitrile which is available to meet changing or increasing market demand. . Further, it is desirable to produce a used quench liquid which can be recycled (not disposed of by disposal) in a process for producing acrylonitrile. The present invention provides such methods. Desirably, the relative amount of acrylonitrile and acetonitrile produced by the amine deoxidation reaction of a hydrocarbon feedstock such as propylene or propane can be adjusted, as it is sometimes desirable to have additional acetonitrile which is available to meet changing or increasing market demand. . Further, it is desirable to produce a used quench liquid which can be recycled (not disposed of by disposal) in a process for producing acrylonitrile. The present invention provides such methods. This invention relates to a process for the deoxidation of a carboxylic acid, particularly a mixture of carboxylic acids, to a nitrile or mixture of nitriles. The present invention is also directed to increasing the yield, and preferably the ratio of the co-product acetonitrile to acrylonitrile produced during the ammoxidation of a hydrocarbon such as propylene or propane to acrylonitrile. The present invention is also directed to a method for increasing the yield of co-product acetonitrile during the manufacture of acrylonitrile by amine deoxidation of a hydrocarbon feed such as propylene or propane, while at the same time saving material costs associated with increased coproduct yield. . The relative amount of the bladder can be controlled by adjusting the amount of tickic acid added to the amine deoxidation reaction of the present invention. It has been unexpectedly discovered that the use of carboxylic acids, particularly crude carboxylic acid mixtures, can achieve the desired increase in acetonitrile production during the production of acrylonitrile. The invention is also directed to a method of recycling a spent quench column quench liquid to an amine deoxidation reactor. SUMMARY OF THE INVENTION The present invention comprises a process for substantially increasing the yield of acetonitrile produced during the manufacture of acrylonitrile from propylene or propane or mixtures thereof. Accordingly, the present invention comprises a method of increasing the yield of a co-product acetonitrile produced during the manufacture of acrylonitrile, comprising reacting a hydrocarbon comprising at least one selected from the group consisting of propylene and propylene, a carboxylic acid, ammonia, and a molecular oxygen-containing gas. The reactants are introduced into a reaction zone containing an amine deoxidation catalyst (eg, a fluid bed reactor) to react a hydrocarbon, a slow acid, ammonia, and oxygen on an elevated temperature catalyst to produce acrylonitrile, hydrogen cyanide, and & Fine, and recovery of products containing acrylonitrile, cyanide gas and ethane from the reaction zone. The present invention comprises a process for converting a carboxylic acid, particularly a crude carboxylic acid mixture, and more particularly a crude carboxylic acid mixture, to a mixture comprising a cycline during the manufacture of acrylonitrile without substantially affecting the yield of acrylonitrile. Accordingly, the present invention comprises introducing a reactant comprising at least one hydrocarbon selected from the group consisting of propylene and propane, at least a line of acid, ammonia, and a molecular oxygen-containing gas into a reaction zone containing an amine deoxidation anti-race catalyst (eg, a fluid bed) In the reactor, the hydrocarbon, citric acid, ammonia and molecular oxygen are reacted on a catalyst having an elevated temperature to produce propylene, hydrogen sulfide and acetonitrile. The present invention comprises introducing at least one reactant selected from the group consisting of propylene and propane, a catalyst of a small amount of acid, ammonia and a molecular oxygen-containing gas into a reaction (for example, a 'fluid bed reactor) for amine hydrolysis. An oxidation reaction catalyst (for example, a fluid bed amine deoxidation catalyst) is reacted to produce a reactor effluent comprising acrylonitrile, hydrogen cyanide, and acetonitrile to provide a reaction benefit comprising azide, cyanide, and b. The effluent is sent to the quench column to cool the reactor effluent' and the desired product from at least one of acrylonitrile, acetonitrile and hydrogen cyanide is recovered from the reactor effluent. In one embodiment of the invention, one or more carboxylic acids may be added to the quench liquid to react with excess ammonia present in the effluent of the amine deoxidation reactor. Preferably, at least a portion of the quench liquid system comprising a salt formed by the reaction of ammonia with one or more carboxylic acids is recycled to the amine deoxidation reactor or reaction zone β by the process of the invention ( For example, acrylonitrile, acetonitrile, and cyanide 1322798 hydrogen can be recovered by methods known to those skilled in the art (e.g., U.S. Patent Nos. 4,234,501; 3,885,928; 3,352,764; 3,198,750 and 3, (M4,966) The method disclosed in the 'Recommendation, which is hereby incorporated by reference for reference, is hereby incorporated by reference. In the preferred embodiment of the invention, the crude carboxylic acid is used as a source of carboxylic acid. The carboxylic acid comprises a carboxylic acid or a mixture thereof of a pure grade carboxylic acid that has not been purified to a generally commercially acceptable specification, and preferably is derived from one or more processes for the manufacture of a carboxylic acid. A carboxylic acid or a mixture of pure carboxylic acids which have not been purified to a generally commercially acceptable specification. The crude carboxylic acid or mixture may contain water, other impurities or both. For example, the water content of the crude carboxylic acid may be For from about 2, about 5, or about The weight of acetic acid is about 98% by weight of the genus. The crude acetic acid is used in the preferred carboxylic acid of the examples of the present invention. Any amine deoxidation catalyst can be used in the examples of the present invention. It is summarized in the following two chemical formulas:
AaBbCjDcMouOx，其中 A=Li、Na、K、Ca、T1及其混合物，特別係Cs及K B Ni、c〇、Μη、Mg、Ca及其混合物，較佳係Ni、Co 及Mg 20 C=Fe、Cr ' Ce、Cu、V、Sb、W、Sn ' Ga、Ge、In、 p及其混合物，較佳係Fe、Cr及Ce D=Bi及/或Te ’較佳係Bi a==〇.l-4.〇 ’較佳係〇 1至〇 5 ’特別佳係〇丨至〇 2 b==〇.M〇.〇，較佳係5至9，特別佳係6至8，且 9 1322798 c，d=0.M0.0，較佳係〇 5至4，特別佳係0.5至3 ; 及AJBbSbnOx，其中 A=Fe、Cr、Ce、V、U、Sn、Ti ' Nb及其混合物，較 佳係Fe、V、Sn及Ti 5 B=M〇 ' W、Co、Cu、Te、Bi、Zn、B、Ni、Ca、Ta 及其混合物，較佳係Mo及Cu a=0.1-16’較佳係2至12，特別佳係4至1〇 b=0.0-12 ’較佳係丨至1〇，特別佳係2至6，且 X之值係依所用元素之氧化態而定。 10 本發明所用之適當胺解氧化催化劑可未被支撐地使 用，或可以石夕石、氧化鋁、氧化鈦、氧化結等支撑·，但是， 石夕石係較佳樓體。適用於本發明實施之催化劑的例子係揭 示於美國專利第 3,642,930; 4,485,079; 3,911，〇89; 4,873,215; 5，134，105及5,093,299號案，在此被併入以供參考之用。 15 【實施方式】 本發明之詳細說明 本發明係-種包含-或更多之丙烯及丙烧、氨、分子 氧來源及羧酸之混合物之胺解氧化反應方法。羧酸較佳係 粗製羧酸或粗製羧酸之混合物。本發明係—種使用羧酸(特 2〇別係粗製羧酸）作為製造於製造丙烯腈期間產生之有用| 腈共產物(諸如’乙猜）之供料。此外，含有大量稀釋劑^ 如，水)之羧酸或其混合物可用於實施本發明，藉此，進 步降低適於製造共產物之羧酸或含羧酸之原料的費用。 本發明亦係一種增加於製造丙烯腈期間之乙腈產率之 10 方法匕3使包含至少一選自丙烯及丙烷所組成族群之 至夕缓酸、氨及含分子氧之氣體(諸如，空氣)之反應 物引至含有胺解氧化催化劑之反應區域内 ，使烴、羧酸或 I混。物、氨及分子氧於升高溫度之此催化劑上反應產生 包3丙烯腈、氰化氫及乙腈之產物及自反應器回收一或 更^之包3丙稀腈、氰化氫及乙猜之-或更多之產物。 用於本發明之較佳敌酸係相對較低後數之缓酸，諸 如’'有8或更^個碳原子(較佳係6或更少個碳原子，且最 佳係3或更少個碳原子)者。紐可為飽和或不飽和，支化 或線性’ a可為芳香族或具有芳香族組份。用於本發明之 缓酸可為單紐，或其可為多㈣，π，具有數個酸基， 且因此TJj；例如，二…三_、四_幾酸。適當之緩酸包含， 例如，甲酸、乙酸、丙酸、丁酸、草酸、丙烯酸、丁烯酸、 馬來酸、琥珀酸、己二酸、苯曱酸、曱苯酸等之—或更多。 於此使用時，粗製綾酸（諸如，粗製乙酸）可為不多於約98 重量％純度（較佳係不多於約95重量％純度，更佳係不多於 約90重量％純度）之單—敌酸。較佳地，用於本發明之羧酸 係乙酸，更佳係粗製乙酸。用於本發明之另一較佳羧酸係 包含甲酸、乙酸及丙酸之混合物；例如，以自乙酸製造之 副產物或廢流體獲得之混合物。包含約5且最高達約98(戍 最南達約95或最南達約9〇或55)重量％之乙酸、約〇(或約1， 或約10)至最高達約2 5重量。/〇 t甲酸及約〇或約1且最高達約 20(或最高達約10，或最高遠約5)重量％之丙酸的粗製酸混 合物可用於本發明方法。此等粗製羧酸混合物可以製造純 1322798 乙酸之廢流或副流體獲得。 於本發明之方法中，一些或全部之羧酸可以鹽添加， 較佳係藉由羧酸與胺或氨混合而形成之鹽。較佳之鹽係錢 鹽。若羧酸被添加，且其一部份或全部係鹽（諸如，銨鹽）， 5則此鹽較佳係以水性溶液添加至胺解氧化反應器。例如， 最高達約33重量％鹽（較佳係約5至約33重量％之錢鹽）之水 性/谷液。當水性溶液被使用時’此水性溶液較佳係被喷灑 至胺解氧化反應區域（例如，胺解氧化催化劑之流體化床） 内。此銨鹽之較佳濃度係約與玎得自用於自胺解氧化反應 1〇器流出物回收丙烯腈之方法所用之驟冷操作之循環流體相 同之濃度。於如上所述之驟冷操作’胺解氧化反應器之熱 的氣態流出物係與驟冷液體(較佳係水性驟冷液體)接觸，以 使胺解氧化反應器流出物冷卻。於驟冷方法期間，胺解氧 化反應器流出物内之過量氨可與添加至水性驟冷液體之缓 15酸或羧酸混合物反應，形成缓酸-氨鹽（即，銨鹽ρ自此驟 冷操作獲得之用過或廢驟冷液體（包含羧酸或其混合物之 此銨鹽）係依據本發明之用於添加至胺解氧化反應器之本 發明較佳羧酸來源。添加至驟冷液體以與過量氨反應並將 此氨移除之羧酸可為此間所述之羧酸或其混合物之一或更 2〇多。因此，於本發明實施例，缓酸或其晃合物（較佳係如上 所述之羧酸之一或更多）被添加至用以使製造丙烯腈之胺 解乳化反應器之流出物驟冷之驟冷液體（較佳係水性驟A 液體）。於用以使胺解氧化反應器流出物驟冷且與胺解氧化 反應器流出物内存在之氨反應後，包含緩酸或其混合物之 12 5 錄鹽之液體係至少部份循環至胺解氧化反應器 。此循環驟 =液體内之㈣_銨鹽之量可為約5至最高達約3 3 (更佳係最 ^達、.勺15)重量％之細驗鹽。添加至料液體之較佳缓酸 ^ m係粗製乙gl另—較佳緩酸係如上所述之包 3曱‘、乙酸及丙酸之混合物^較佳係其間丙酸含量低(例 如人此現合物之不多於5重量％，更佳係不多則重量％)之 是合物’冷液體(較佳係水㈣冷㈣)較錢藉由使驟冷 液體噴壤至反應㈣（較佳係流體化床反應器之流體化床 内）而添加至胺解氧化反應器。 10 %、加至本發明方法中之反應區域之缓酸或其混合物 (以緩酸切(料，雜)之形仏力吹料財為基準可 為供應至反應區域之氨供料速率之最高達約5〇%，或最高 達約25或40%，例如，約丨與約15%之間。 15 20 於本發明之較佳實施例，胺解氧化反應器之條件可被 調整以於藉由利職酸或其混合物而獲得之乙腈獲得增加 之產率。於本發明之實施’贿氧化反應條件較佳係於下 列參數之震或鹽⑽如，_)科添力咬魏或其 混合物之供料速率以莫耳為基準可為氨供料速率之最高達 約观’或最高達約25或4〇%，例如，約i與約15%之= 胺解氧化反應之溫度可為約。至約誓c之間，較佳係 約430。至約4贼，壓力係被適當地維持於約i至約2大氣 壓之間，較佳係約1至約1_2或1.丨大氣屋。 乳 於本發明之較佳實施例，此方法係使用顆㈣胺解氣 化催化劑之流體床反應器内實施。 13 5 貫施例 下列實施例係用於例示目的，且不被認為係實施本發 明之限制。 10 15 ,使用空氣及氨之丙烯胺解氧化反應係於添加或未添加 竣酸而進行。所有實施财使狀催化_已知適於丙稀 胺解氧化成丙烯腈之經促進的BiFeMoOx。以莫耳為基準計 之氨供料之2·5、5及0%之量的粗製乙酸係與丙烯及空氣一 起添加至胺解氧化反應器，產生如下第丨表所示之結果。粗 製乙酸混合物係藉由添加氫氧化銨溶液變成ρΗ 5，且形成 之酸於供應至反應前稀釋至67%之水。於下列實施例之每 一者中’反應器溫度係440°C，壓力係1〇.〇 psig，且丙烯/ 氨/酸之莫耳供料比例係1/1.17/10.0/Χ (χ=〇·〇29，0.059 0.12)。wwh係0.08 (烴之克數/催化劑克數，小時）。 第1表 實施例編號乙酸，氨供料_丙烯腈產率乙腈產率％ HCN產生％ 之莫耳％ % 0 79.6 1.5 6.1 2.5 80.1 2.2 5.9 5 78.7 2.8 5.8 10 77.3 3.9 6.0 1(比較例） 2 3 4 第1表中之數據證明添加乙酸至胺解氧化反應形成產 生之乙腈的產率增加。 一般’所有羧酸可被胺解氧化成腈混合物。特別地， 乙酸且較佳係粗製乙酸可被胺解氧化成乙腈。較佳之酸包 含(^至〇4之羧酸。 20 本發明亦係一種方法，其係包含使包含至少一羧酸、 氨及含分子氧之氣體之反應物引至含有胺解氧化催化劑 14 1322798 (諸如，此間所述之催化劑之一）之反應區域(例如，流體床 反應）内，及使用諸如此間所述之溫度及壓力使包含羧酸、 氨及分子氧之反應物於升高溫度時於催化劑反應，以產生 包含腈之產物，較佳係其中羧酸包含乙酸，更佳係其中羧 5 酸包含粗製乙酸，且當羧酸包含乙酸或粗製乙酸時，腈較 佳係包含乙腊。 僅本發明之某些實施例及範例被例示，且另外之實施 例及各種改良對於熟習此項技藝者由如上之描述會變明 顯。此等及其它之另外實施例可被認為係等化物且係於本 10 發明之精神及範圍内。 美國臨時專利申請序號60/381,066案（2002年5月16曰 申請）在此被全部併入以供參考之用。 【圖式簡單說明3 (無） 15 【圖式之主要元件代表符號表】 (無） 15AaBbCjDcMouOx, wherein A=Li, Na, K, Ca, T1 and mixtures thereof, especially Cs and KB Ni, c〇, Μη, Mg, Ca and mixtures thereof, preferably Ni, Co and Mg 20 C=Fe, Cr ' Ce, Cu, V, Sb, W, Sn ' Ga, Ge, In, p and mixtures thereof, preferably Fe, Cr and Ce D = Bi and / or Te ' are preferably Bi a == 〇. L-4. 〇 'Better system 〇 1 to 〇 5 ' Particularly good system 〇丨 to 〇 2 b == 〇.M 〇. 〇, preferably 5 to 9, especially good 6 to 8, and 9 1322798 c, d = 0.1 M0.0, preferably 〇 5 to 4, particularly preferably 0.5 to 3; and AJBbSbnOx, wherein A = Fe, Cr, Ce, V, U, Sn, Ti ' Nb and mixtures thereof, Preferably, Fe, V, Sn and Ti 5 B=M〇' W, Co, Cu, Te, Bi, Zn, B, Ni, Ca, Ta and mixtures thereof, preferably Mo and Cu a = 0.1-16 Preferably, the ratio is from 2 to 12, particularly preferably from 4 to 1 〇 b = from 0.0 to 12, preferably from 1 to 6, especially from 2 to 6, and the value of X depends on the oxidation state of the element used. 10 The appropriate amine deoxidation catalyst used in the present invention may be used unsupported, or may be supported by Shishishi, alumina, titania, oxidized or the like. However, Shishishi is a preferred building. Examples of catalysts suitable for use in the practice of the present invention are disclosed in U.S. Patent Nos. 3,642,930, 4, 485, 079, 3, 911, 〇89, 4, 873, 215, 5, 134, and 5, 093, 299, incorporated herein by reference. [Embodiment] DETAILED DESCRIPTION OF THE INVENTION The present invention is an amine deoxidation reaction process comprising - or more of a mixture of propylene and propane, ammonia, a source of molecular oxygen and a mixture of carboxylic acids. The carboxylic acid is preferably a mixture of a crude carboxylic acid or a crude carboxylic acid. The present invention is the use of a carboxylic acid (a special carboxylic acid) as a feed for the useful nitrile co-products (such as ' B guess) produced during the manufacture of acrylonitrile. Further, a carboxylic acid containing a large amount of a diluent such as water or a mixture thereof can be used in the practice of the present invention, whereby the cost of a carboxylic acid or a carboxylic acid-containing raw material suitable for producing a coproduct is further reduced. The present invention is also a method for increasing the yield of acetonitrile during the production of acrylonitrile. The method 匕3 comprises at least one gas selected from the group consisting of propylene and propane, ammonia, and a molecular oxygen-containing gas (such as air). The reactants are introduced into a reaction zone containing an amine deoxidation catalyst to mix hydrocarbons, carboxylic acids or I. The product, ammonia and molecular oxygen are reacted on the catalyst at an elevated temperature to produce a product of the package 3 acrylonitrile, hydrogen cyanide and acetonitrile and recover one or more of the 3 acrylonitrile, hydrogen cyanide and B guess from the reactor. - or more products. A preferred latent acid used in the present invention is a relatively low number of slow acids, such as ''having 8 or more carbon atoms (preferably 6 or fewer carbon atoms, and preferably 3 or less) One carbon atom). The ketone may be saturated or unsaturated, and the branched or linear 'a' may be aromatic or have an aromatic component. The acid retardant used in the present invention may be a single bond, or it may be poly(tetra), π, having several acid groups, and thus TJj; for example, two...three_, tetra-acid. Suitable slow acids include, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, acrylic acid, crotonic acid, maleic acid, succinic acid, adipic acid, benzoic acid, phthalic acid, etc. - or more . As used herein, the crude citric acid (such as crude acetic acid) can be no more than about 98% by weight pure (preferably no more than about 95% by weight purity, more preferably no more than about 90% by weight purity). Single - enemy acid. Preferably, the carboxylic acid acetic acid used in the present invention is more preferably crude acetic acid. Another preferred carboxylic acid for use in the present invention comprises a mixture of formic acid, acetic acid and propionic acid; for example, a mixture obtained from by-products or waste fluids produced from acetic acid. It comprises about 5 and up to about 98 (戍 up to about 95 or up to about 9 or 55) wt% acetic acid, about 〇 (or about 1, or about 10) up to about 25 weight. A crude acid mixture of / formic acid and about 1 or up to about 20 (or up to about 10, or up to about 5) by weight of propionic acid can be used in the process of the invention. These crude carboxylic acid mixtures can be obtained by making a waste stream or a secondary fluid of pure 1322798 acetic acid. In the process of the present invention, some or all of the carboxylic acid may be added as a salt, preferably a salt formed by mixing a carboxylic acid with an amine or ammonia. The preferred salt is money salt. If a carboxylic acid is added and a portion or all of it is a salt (such as an ammonium salt), then the salt is preferably added to the amine deoxidation reactor as an aqueous solution. For example, an aqueous/troche liquid of up to about 33% by weight salt, preferably from about 5 to about 33% by weight of the salt of the salt. When the aqueous solution is used, the aqueous solution is preferably sprayed into the amine deoxidation reaction zone (e.g., a fluidized bed of an amine hydrolysis catalyst). The preferred concentration of the ammonium salt is about the same concentration as that of the quenching cycle fluid used in the process for recovering acrylonitrile from the amine effluent. The gaseous gaseous effluent from the quenching operation of the amine deoxidation reactor as described above is contacted with a quench liquid, preferably an aqueous quench liquid, to cool the amine deoxidation reactor effluent. During the quenching process, excess ammonia in the amine deoxidation reactor effluent can be reacted with a slow acid or carboxylic acid mixture added to the aqueous quench liquid to form a slow acid-ammonia salt (ie, ammonium salt ρ from this step) The used or waste quench liquid obtained by cold operation (containing this ammonium salt of a carboxylic acid or a mixture thereof) is a preferred carboxylic acid source of the present invention for addition to an amine deoxidation reactor according to the present invention. The carboxylic acid which reacts with the excess ammonia and removes the ammonia may be one or more of the carboxylic acids or mixtures thereof for this purpose. Therefore, in the examples of the present invention, the acid or its compound ( Preferably, one or more of the carboxylic acids as described above are added to the quench liquid (preferably aqueous A liquid) for quenching the effluent of the amine emulsification reactor for producing acrylonitrile. After the amine deoxidation reactor effluent is quenched and reacted with the ammonia present in the amine deoxidation reactor effluent, the liquid system comprising the slow acid or a mixture thereof is at least partially recycled to the amine hydrolysis. Reactor. This cycle is the amount of (tetra)-ammonium salt in the liquid. 5 to a maximum of about 3 3 (better than the most, up to 15) weight% of the salt. Adding to the liquid liquid is preferred to slow acid ^ m system crude B gl another - preferably slow acid is as above The mixture of 3', acetic acid and propionic acid is preferably a compound having a low propionic acid content (for example, no more than 5% by weight of the present invention, more preferably less than 5% by weight). The cold liquid (preferably water (4) cold (4)) is added to the amine deoxidation reactor by spraying the quench liquid to the reaction (4), preferably in a fluidized bed of a fluidized bed reactor. %, the slow acid or a mixture thereof added to the reaction zone in the process of the invention (the highest rate of ammonia supply to the reaction zone can be based on the shape of the acid-cutting material) About 5%, or up to about 25 or 40%, for example, between about 15% and about 15%. 15 20 In a preferred embodiment of the invention, the conditions of the amine deoxidation reactor can be adjusted to facilitate The acetonitrile obtained from the acid or a mixture thereof obtains an increased yield. In the practice of the present invention, the brittle oxidation reaction condition is preferably based on the following parameters of the earthquake or salt (10), for example, _) The feed rate of Ketianli Wei or its mixture may be up to about 25 or 4% of the ammonia feed rate on a molar basis, for example, about i and about 15%. The temperature of the amine hydrolysis reaction may be from about 约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约约To about 1 _2 or 1. 丨 atmosphere. Milk is a preferred embodiment of the invention, which is carried out in a fluid bed reactor using a quaternary amine desulfurization catalyst. 13 5 Examples The following examples are for illustration The purpose is not to be construed as limiting the practice of the invention. 10 15 . The acrylamide deoxidation reaction using air and ammonia is carried out with or without the addition of citric acid. All implementations of catalysis _ known to be suitable for propylene The amine is deoxidized to the promoted BiFeMoOx of acrylonitrile. The crude acetic acid in an amount of 2, 5, 5, and 0% of the ammonia feed based on moles was added to the amine deoxidation reactor together with propylene and air to produce the results shown in Table IX below. The crude acetic acid mixture was changed to pH 5 by the addition of an ammonium hydroxide solution, and the acid formed was diluted to 67% water before being supplied to the reaction. In each of the following examples, the reactor temperature was 440 ° C, the pressure system was 1 〇 〇 psig, and the propylene / ammonia / acid molar supply ratio was 1/1.17 / 10.0 / Χ (χ = 〇 ·〇29,0.059 0.12). Wwh is 0.08 (grams of hydrocarbons / grams of catalyst, hours). Table 1 Example No. Acetic Acid, Ammonia Feeding_Acrylonitrile Yield Acetonitrile Yield % HCN Production % Mo % % 0 79.6 1.5 6.1 2.5 80.1 2.2 5.9 5 78.7 2.8 5.8 10 77.3 3.9 6.0 1 (Comparative Example) 2 3 4 The data in Table 1 demonstrates the increase in the yield of acetonitrile produced by the addition of acetic acid to the amine deoxidation reaction. Generally, all carboxylic acids can be deoxidized by amines to a mixture of nitriles. In particular, acetic acid, and preferably crude acetic acid, can be deoxidized by amine to acetonitrile. Preferably, the acid comprises a carboxylic acid of (4 to 〇4). The invention is also a process comprising introducing a reactant comprising at least one carboxylic acid, ammonia and a molecular oxygen-containing gas to an amine-containing oxidation catalyst 14 1322798 In a reaction zone (such as a fluid bed reaction) (such as one of the catalysts described herein), and using a temperature and pressure such as described herein, the reactants comprising carboxylic acid, ammonia, and molecular oxygen are raised at elevated temperatures. The catalyst is reacted to produce a product comprising a nitrile, preferably wherein the carboxylic acid comprises acetic acid, more preferably wherein the carboxylic acid comprises crude acetic acid, and when the carboxylic acid comprises acetic acid or crude acetic acid, the nitrile preferably comprises acetonitrile. Only certain embodiments and examples of the invention are exemplified, and other embodiments and various modifications will become apparent to those skilled in the art from the foregoing description. These and other embodiments can be considered as equivalents. And is within the spirit and scope of the present invention. U.S. Provisional Patent Application Serial No. 60/381,066, filed on May 16, 2002, is hereby incorporated by reference in its entirety. ) 15 Formula [FIG principal element representing a symbol table] (none) 15