565547 A7 B7 五、發明說明（1) 相關申請案之對照 此申請案係美國專利申請案09/208/053號案（1998年12 月9日申請）之部份延續專利申請案。 發明背景 本發明係有關一種使醇混合物氨氧化成腈混合物之新 穎方法。特別地，本發明係有關增加丙烯氨化成丙烯腈期 間產生之共同產物氰化氫及乙腈之產率（較佳係比例）。 有數專利案係著重於使甲醇或乙醇注射於流體化床反 應器内以產生氰化氫或乙腈。此外，此等參考資料進一步 揭示甲醇或乙醇可被引入流體化床，以增加共同產物氰化 II或乙腈’且同時製造丙稀腈。例如，美國專利第 3,911，089 ; 4,485,079及5,288,473號案係有關藉由使甲醇 注射於含有適於生產丙烯腈之氨氧化催化劑之流體化床内 而使甲醇氨氧化以產生氰化氫。此等參考資料之每一者教 示甲醇之注射可與丙烯腈之製備同時為之。此外，日本專 利申請案74-87,474 ; 79-08,655 ;及78-35,232號案係有關 於製備丙稀腈期間增加氰化氫產率之相似方法。日本專利 申请案2[1990]-38,333號案係有關藉由使丙酮及/或乙醇注 射於含有氨氧化反應催化劑之氨氧化反應器内而改良乙腈 產率。曰本專利申凊案所揭示之方法包含同時使丙酮及/ 或乙醇注射於氨氧化反應器内及製造丙烯腈。所有此等專 利案係有關額外氰化氫或乙腈之生產。 本發明係有關一種於製備丙烯腈期間增加一或二種主 要共同產物（即，HCN及乙腈）且同時（1)節省與增加共同產 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------線遽 經濟部智慧財產局員工消費合作社印製 4 經濟部智慧財產局員工消費合作社印製 565547 A7 __B7 五、發明說明（2 ) 物產率有關之原料費用及（2)達成與使用淨醇（諸如，甲醇/ 乙醇）獲得者相同或更佳之所欲共同產物之轉化率及選擇 性（以奴為基準）之方法。氰化氫及乙腈之相對含量可藉由 本發明方法控制。 吾等不可預期地發現使用粗製之醇混合物可達成於生 產丙烯腈期間之乙腈及氰化氫之生產之所欲增加。 發明之概要說明 本發明之主要目的係提供一種大量增加自丙烯或丙院 製備丙烯腈期間產生之共同產物氰化氫及乙腈之一或多者 之產率之方法。 本發明之目的係提供一種於製備丙婦胯期間使含有甲 醇、乙醇、其它醇及水之粗製醇混合物轉化成氰化氫及乙 腈且不會實質影響丙烯胯產率之方法。 本發明之進一步目的係提供一種使包含乙醇之醇轉化 成乙腈之方法，其係包含或不包含曱醇。甲醇可以用以調 整產生之氰化氫及乙腈共同產物之相對量之所欲含量包含 於乙醇内。因此，當氰化氫之需求增加時，甲醇或額外之 甲醇可被添加至乙醇供料混合物，以達成促進含量之氰化 氫。另外，若乙腈之額外生產相對於氰化氫而言係所欲時， 醇供料中之乙醇含量可被增加，以促進產生之乙腈之相對 含量。 本發明之額外目的及優點與相穎特徵將部份示於描述 中，且部份對熟習此項技藝者於檢測下述者而變明顯，戈 可藉由實施本發明而學得。本發明之目的及優點可藉由 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -I n I ϋ ϋ I a n ϋ .^1 ϋ ϋ 565547 A7 五、發明說明（ 附申請專利範圍所特別指出之手段及組合而瞭解及達成。 (請先閱讀背面之注意事項再填寫本頁) 為依據此間廣泛描述之本發明目的達成前述目標，本 發明方法包含使選自丙烯及丙烷之烴、包含C〗至c4醇之 混合物之粗製醇、4及含氧氣體引人反應區域（例如，流體 化床反應器）内，以於催化劑（例如，流體化床催化劑）存在 中反應以生產包含丙烯腈、氰化氫及乙腈之反應器流出 物使δ有丙烯腈、氛化氮及乙勝之反應器流出物進至驟 冷管柱内，以使反應器流出物冷卻，及自驟冷管柱回收丙 烯腈、乙腈及氰化氫。 經濟部智慧財產局員工消費合作社印製 •於本發明之較佳具體例中，粗製醇之混合物係使用粗 製乙醇、粗製丙醇及/或粗製甲醇供應。為了本發明之目 的，粗製醇包含一種包含乙醇、丙醇、丁醇及水之混合物。 商業上可獲得之粗製乙醇之典型來源係含有86.34%之乙 醇、1.025%之異丙醇、i 266%之正丁醇及u 37%之水。雖 然非特別限於此組成物，任何粗製之乙醇、丙醇及/或甲醇 之混合物係適於本發明之實施。較佳係粗製醇亦含有水， 較佳係至少約3重量❽/〇,更佳係至少約5重量％，藉此， 進一步降低本發明方法之操作費用。本發明實施之一不可 預期之益處係發現當相較於使用純醇供料獲得之結果時， 使用粗製醇獲得之共同產物之選擇性及轉化率結果係相同 或更佳（以碳對碳之基準）。 於本發明之實施中，被擬想者係任何氨氧化反應催化 劑可被使用以達成增加共同產物乙腈及氰化氫之產率之所 欲結果。典型之氨氧化反應催化劑可藉由下述二化學式概 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 6 經濟部智慧財產局員工消費合作社印製 565547 A7 B7 五、發明說明（4 ) 括之：565547 A7 B7 V. Description of the invention (1) Comparison of related applications This application is part of the US Patent Application No. 09/208/053 (filed on December 9, 1998) for a continuation of the patent application. BACKGROUND OF THE INVENTION The present invention relates to a novel method for the ammoxidation of alcohol mixtures to nitrile mixtures. In particular, the present invention relates to increasing the yields of co-products hydrogen cyanide and acetonitrile produced during the amination of propylene to acrylonitrile (preferred ratios). Several patents focus on injecting methanol or ethanol into a fluidized bed reactor to produce hydrogen cyanide or acetonitrile. In addition, these references further reveal that methanol or ethanol can be introduced into the fluidized bed to increase the co-product cyanidation II or acetonitrile 'and simultaneously produce acrylic nitrile. For example, U.S. Patent Nos. 3,911,089; 4,485,079, and 5,288,473 are related to the ammonia oxidation of methanol to produce hydrogen cyanide by injecting the methanol into a fluidized bed containing an ammonia oxidation catalyst suitable for the production of acrylonitrile. Each of these references teaches that methanol injection can be done simultaneously with the preparation of acrylonitrile. In addition, Japanese patent applications 74-87,474; 79-08,655; and 78-35,232 are similar methods for increasing the yield of hydrogen cyanide during the preparation of acetonitrile. Japanese Patent Application No. 2 [1990] -38,333 relates to improving the yield of acetonitrile by injecting acetone and / or ethanol into an ammonia oxidation reactor containing an ammonia oxidation reaction catalyst. The method disclosed in the Japanese patent application involves the simultaneous injection of acetone and / or ethanol into an ammoxidation reactor and the production of acrylonitrile. All of these patents are related to the production of additional hydrogen cyanide or acetonitrile. The present invention relates to a method of adding one or two main common products (ie, HCN and acetonitrile) during the preparation of acrylonitrile and simultaneously (1) saving and increasing common production. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling out this page) -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative 565547 A7 __B7 V. Description of the invention (2) Raw material costs related to product yield and (2) Achieving the desired co-products that are the same as or better than those obtained using net alcohol (such as methanol / ethanol) Conversion rate and selectivity (based on slaves). The relative content of hydrogen cyanide and acetonitrile can be controlled by the method of the present invention. We unexpectedly found that the use of a crude alcohol mixture can achieve the desired increase in the production of acetonitrile and hydrogen cyanide during the production of acrylonitrile. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method for greatly increasing the yield of one or more of hydrogen cyanide and acetonitrile, which are co-products produced during the preparation of acrylonitrile from propylene or acrylic acid. An object of the present invention is to provide a method for converting a crude alcohol mixture containing methanol, ethanol, other alcohols, and water into hydrogen cyanide and acetonitrile during the preparation of fufangbu, without substantially affecting the yield of propylene. It is a further object of the present invention to provide a method for converting an alcohol containing ethanol to acetonitrile, which may or may not include methanol. Methanol can be used to adjust the relative amounts of the hydrogen cyanide and acetonitrile co-products produced to a desired content in ethanol. Therefore, as the demand for hydrogen cyanide increases, methanol or additional methanol can be added to the ethanol feed mixture to achieve a promoted content of hydrogen cyanide. In addition, if additional production of acetonitrile is desired relative to hydrogen cyanide, the ethanol content in the alcohol feed can be increased to promote the relative content of acetonitrile produced. The additional objects and advantages of the present invention and the distinguishing features will be shown in the description in part, and will become apparent to those skilled in the art when testing the following, which can be learned by implementing the present invention. The purpose and advantages of the present invention can be adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) by this paper size (please read the precautions on the back before filling this page) -I n I ϋ ϋ I an ϋ. ^ 1 ϋ ϋ 565547 A7 V. Description of the invention (with the means and combinations specifically pointed out in the scope of the patent application, to understand and achieve. (Please read the precautions on the back before filling this page) In order to achieve the purpose of the present invention, which is widely described here For the foregoing object, the method of the present invention includes introducing a hydrocarbon selected from propylene and propane, a crude alcohol containing a mixture of alcohols C to c4, 4 and an oxygen-containing gas into a reaction zone (for example, a fluidized bed reactor), so that A reaction in the presence of a catalyst (eg, a fluidized bed catalyst) to produce a reactor effluent containing acrylonitrile, hydrogen cyanide, and acetonitrile. A reactor effluent with acrylonitrile, nitrogenated nitrogen, and acetonitrile is passed to a quench column In order to cool the reactor effluent and recover acrylonitrile, acetonitrile and hydrogen cyanide from the quench column. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • In the preferred embodiment of the present invention, A mixture of crude alcohols is supplied using crude ethanol, crude propanol, and / or crude methanol. For the purposes of the present invention, a crude alcohol comprises a mixture comprising ethanol, propanol, butanol, and water. Commercially available crude ethanol Typical sources are 86.34% ethanol, 1.025% isopropanol, i 266% n-butanol, and u 37% water. Although not particularly limited to this composition, any crude ethanol, propanol, and / or methanol The mixture is suitable for the practice of the present invention. Preferably, the crude alcohol also contains water, preferably at least about 3% by weight ❽ / 0, more preferably at least about 5% by weight, thereby further reducing the operating cost of the method of the present invention. An unexpected benefit of the practice of the present invention is that the selectivity and conversion results of common products obtained using crude alcohols are the same or better when compared to the results obtained using pure alcohol feedstocks (carbon-to-carbon Benchmark). In the practice of the present invention, the proposed subject is any ammonia oxidation reaction catalyst that can be used to achieve the desired result of increasing the yield of the common products acetonitrile and hydrogen cyanide. Typical ammonia oxidation reaction The catalyst can be applied to the following two chemical formulas: paper size Applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 6 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565547 A7 B7 Of:
AaBbCcDdMo12Ox，其中 A=Li，Na, K，Cs, T1及其等之混合物，較佳係Cs及K B=Ni，Co, Mn，Mg，Ca及其等之混合物，較佳係Ni，Co 及Mg C=Fe，Cr，Ce，Cu，V，Sb，W，Sn，Ga，Ge，In，P 及其等之 混合物，較佳係Fe，Cr及Ce D=Bi及/或Te，較佳係Bi a=0.1-4.0，較佳係0.1至0.5，特別佳係0.1至0.2 b=0 · 1 -10 · 0 ’較佳係5至9，特別佳係6至8，且 c，d=0.1-10.0，較佳係0.5至4，特別佳係0.5至3 ; 及 AaBbSbi2〇x，其中 A=Fe，Cr，Ce，V，U, Sn，Ti，Nb及其等之混合物，較佳 係 Fe，V，Sn 及 Ti B=Mo, W，Co, Cu，Te，Bi，Zn，B，Ni，Ca，Ta 及其等之混 合物，較佳係Mo及Cu a=0.1-16，較佳係2至12，特別佳係4至10 b=0.0-12，較佳係1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。 此催化劑可以未被支撐或以矽石、氧化鋁、氧化鈦、 氧化錯等支樓而使用，但，石夕石係較佳之撑體。典型上， 被認為於本發明實施中適當之催化劑係揭示於美國專利第 3,642,930 ; 4,485,079 ; 3,911，089 ; 4,873,215 ; 5，134，105 及5,093,299號案，在此併入本案以為參考資料。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公t ) (請先閱讀背面之注咅？事項再填寫本頁)AaBbCcDdMo12Ox, where A = Li, Na, K, Cs, T1 and mixtures thereof, preferably Cs and KB = Ni, Co, Mn, Mg, Ca and mixtures thereof, preferably Ni, Co and Mg 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, more preferably Bi a = 0.1-4.0, preferably 0.1 to 0.5, particularly preferably 0.1 to 0.2 b = 0 · 1 -10 · 0 'preferably 5 to 9, particularly preferably 6 to 8, and c, d = 0.1 -10.0, preferably 0.5 to 4, particularly preferably 0.5 to 3; and AaBbSbi20x, where A = Fe, Cr, Ce, V, U, Sn, Ti, Nb, and mixtures thereof, preferably Fe , V, Sn and Ti B = Mo, W, Co, Cu, Te, Bi, Zn, B, Ni, Ca, Ta and mixtures thereof, preferably Mo and Cu a = 0.1-16, more preferably 2 to 12, particularly preferably 4 to 10 b = 0.0-12, preferably 1 to 10, particularly preferably 2 to 6, and the value of X depends on the oxidation state of the element used. This catalyst can be used unsupported or as a supporting structure such as silica, alumina, titanium oxide, or oxidized oxide. Typically, catalysts deemed suitable in the practice of the present invention are disclosed in U.S. Patent Nos. 3,642,930; 4,485,079; 3,911,089; 4,873,215; 5,134,105, and 5,093,299, which are incorporated herein by reference. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297mm t) (Please read the note on the back? Matters before filling out this page)
-^1 ϋ ϋ ϋ ϋ ϋ I 565547 * A7 _ B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（5 ) 現將詳細參考本發明之較佳具體例。 發明之詳細描述 本發明係有關使用含C!至C4醇之混合物之粗製醇作 為生產於丙烯腈製備期間產生之有用腈共同產物（氰化氮 及乙腈）之來源。此外，含有大量稀釋劑（諸如，水）之粗製 醇可於本發明實施中使用，藉此，進一步降低適於生產實 際共同產物之原料之費用。 於一方面，本發明包含一種於製備丙婦腈期間增加 HCN及乙腈之一或二者之產率之方法，包含使選自丙烯及 丙烷之烴、包含甲醇、乙醇或丙醇之混合物之粗製醇、氨 及空氣引至含有氨氧化反應催化劑之反應器區域内，於升 高溫度使烴、醇、氨及氧於該催化劑反應而產生丙烯腈、 氰化氫及乙腈，及自反應器回收丙烯腈、氰化氫及乙賸。 於此間使用時，粗製乙醇較佳係指包含約5至約95 重量％之乙醇（較佳係約5至約94重量％之乙醇，更佳係約 5〇至約90重量％之乙醇）之混合物（其選擇性地含有水）。 其匕組份可為，例如，水、甲醇、C3-C4醇，及其它有機 化合物。但是，較佳地，其它組份係選自水及醇之一或多 者，特別是上述之醇。於此間使用時，粗製丙醇係指包含 約5至約99重量％之一或多者之丙醇（較佳係約5〇至約％ 重ϊ %之一或多者之丙醇）之混合物（其選擇性含有水）。典 型上’丙醇（特別是粗製丙醇）係至少約50重量❻/〇(更佳係至 少約75重量％)之異丙醇之丙醇混合物之混合物。於此間 使用時’粗製甲醇較佳係指包含最高達約98重量％之甲醇 本紙張尺度翻格（21Q x 297公髮） f請先閲讀背面之注咅？事項再填寫本頁) 秦 — — — — — — — — -P— · 565547 A7 五、發明說明（6 ) (較佳係最高達約97重量％之甲醇，且更 文佳係最高達約95 重量％之曱醇）之混合物。若存在於醇内時，水可為約 至約10重量0/〇，較佳係3至約1()重量 …0·1 里篁/〇，其係以醇及 在之水之含量為基準計。 如上所述，於本發明之一具體例中，藉由本發明方法 產生之氰化氫及乙腈之相對含量可藉由調整添加至丙_ 方法之反應區域之相較於乙醇之甲醇相對含量而調整。= 此，若更大含量之氰化氫為所欲者時，甲醇對乙醇之比例 可被增加。相反地，若氫化氰為所欲時，此比例可被降低。 因此，本發明係-種藉由添加包含甲醇、乙醇或丙醇之混 合物及藉由控制添加至丙烯腈反應區域之曱醇及乙醇或丙 醇（較佳係乙醇）之比例而調整於丙烯腈製備期間產生之氰 化氫及乙腈之相對含量之方法。雖然任何等級之甲醇、乙 醇或丙醇可被用於此具體例，即使高純度之甲醇、乙醇或 丙醇，有利地係使用粗製之甲醇、乙醇或丙醇，較佳係粗 製之甲醇、乙醇及粗製丙醇（如此間於前所述者）。因此， 本發明亦係一種調整於製備丙烯腈期間產生之氰化氫及乙 腈之相對含量之方法，包含使選自丙烷及丙烯之烴、氨、 二氣及包§甲醇及第_醇（其包含乙醇、丙醇或其混合物） 之醇混合物引入含有氨氧化反應催化劑（諸如，此間所述之 催化劑）之反應區域内，於升高溫度時使烴、醇、氨及氧於 該催化劑反應以產生丙烯腈、氰化氫及乙腈，及 自此反應 回收丙婦胯、氰化氫及乙腈，其中醇混合物内之甲醇對乙 醇之重量比例係適當地為約99:1至約1:99,較佳係約98:2 本紙張尺度_巾國國家標準（CNS)A4規格（21〇 X 297公髮） (請先閱讀背面之注意事項再填寫本頁) --------tr---------線· 經濟部智慧財產局員工消費合作社印製 565547 A7 B7 五、發明說明（7 至約請’更佳係約95:5至約5:95。於醇混合物令，較佳 地，甲醇對乙醇(或甲醇對丙醇，或甲醇對乙醇及丙醇之混 合物）之重量比例適當地係約99:1至約1:99,較佳係約則 至約_’更佳I約95:5至約5:95。舉例而言，若欲共同 製備純於乙腈含量係相對較大含量之氰化氫時，供應至 反應器之醇比例可為，例如，9G重量％之乙醇及重量％ 之甲醇《乡所欲者係、增加氰化氫含量，供應至反應器 之醇比例可為10重量％之乙醇及9〇重量％之甲醇。需瞭 解供應至丙騎反應ϋ之較應物可於進人反應器前被混 合，或不同之醇可個別被添加且於反應器本身内混合。於 本發明之最佳具體例中，粗製乙醇被作為乙醇來源，且甲 醇被添加至粗製乙醇以達成氰化氫及乙腈共同產物之所欲 比例。 於本發明之較佳具體例中，需使反應器條件被調整以 獲得藉由使用粗製醇之混合物而獲得之乙腈及氰化氫之增 加產率。於本發明之實施中，氨氧化反應條件較佳應為於 下述參數内：粗製醇係1及50%間之丙烯或丙烷比例（以總 碳為基準）。反應溫度係於41〇°c至460°C (較佳係430°C至 460°C)之間。典型上，壓力係保持於1至5大氣壓之間， 較佳係1至3大氣壓 之間。 於本發明之較佳具體例中，粗製醇混合物包含一種含 有乙醇、丙醇、丁醇及水之混合物。 於本發明之進一步較佳具體例中，此方法係於流體化 床内施行。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） il· — — —.------- (請先閱讀背面之注意事項再填寫本頁) 1111111 經濟部智慧財產局員工消費合作社印製 10 565547 經濟部智慧財產局員工消費合作社印製 A7 -----------_B7__ 五、發明說明（8 ) ^美國專利申請案第〇9/2〇8/〇53號案⑽8年12月9日 申請）於此間特別被全部併人以為參考資料。 下列犯例係作為例示說明之目的，且不應被認為作為 實，本發明之限制。用於所有範例之催化劑係已知於使丙 婦氨氧化成丙烯腈之反應中適當之被促進之.eM〇〇x。 1 〇及15 /。之丙烯供料（以總碳而言）以粗製醇取代以產生 下這第1表所示之結果。於下述範例之每一者中，反應器 溫度係44(TC，壓力係9.5psig,且丙稀氨/空氣之^料 比例係1/1.2/9.3。wwh係〇.〇7(烴之克數/催化劑克數，小 時）。 範例編號 供應之EtOH% ί以C計） 第1表 AN產率％ Aceto 產康 〇/ft 6.5 U比較） 0 78.8 1.5 2 5 75.3 3.9 6.9 3 10 71.5 5.0 7.4 4 15 67.5 6.5 8.0 作為使用醇混合物之價值之進一步例子，30重量％之 甲醇與上述之粗製乙醇摻合，且此被共同供應至相同之丙 烯氨氧化反應器。結果係如下述第II表所示，且指示產物 中係位移至HCN。當高生產量之HCN為必需時，此供料 需以商業工廠使用。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 11-^ 1 ϋ ϋ ϋ ϋ ϋ I 565547 * A7 _ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (5) Reference will now be made in detail to the preferred specific examples of the present invention. Detailed description of the invention The present invention relates to the use of crude alcohols containing a mixture of C! To C4 alcohols as a source of useful nitrile co-products (nitrogen cyanide and acetonitrile) produced during the production of acrylonitrile. In addition, crude alcohols containing a large amount of diluent, such as water, can be used in the practice of the present invention, thereby further reducing the cost of raw materials suitable for the production of actual common products. In one aspect, the present invention comprises a method for increasing the yield of one or both of HCN and acetonitrile during the preparation of propionitrile, comprising crudely selecting a hydrocarbon selected from propylene and propane, a mixture comprising methanol, ethanol or propanol Alcohol, ammonia, and air are introduced into the area of the reactor containing the ammonia oxidation reaction catalyst, and hydrocarbons, alcohols, ammonia, and oxygen are reacted with the catalyst at an elevated temperature to produce acrylonitrile, hydrogen cyanide, and acetonitrile, and recovered from the reactor Acrylonitrile, hydrogen cyanide and ethyl residue. As used herein, crude ethanol preferably refers to ethanol containing about 5 to about 95% by weight of ethanol (preferably about 5 to about 94% by weight of ethanol, and more preferably about 50 to about 90% by weight of ethanol). Mixture (which optionally contains water). Its components can be, for example, water, methanol, C3-C4 alcohols, and other organic compounds. However, preferably, the other components are selected from one or more of water and alcohols, especially the alcohols described above. As used herein, crude propanol refers to a mixture containing from about 5 to about 99% by weight of one or more propanols, preferably from about 50 to about% by weight of one or more propanols. (It optionally contains water). A typical ' propanol (especially crude propanol) is a mixture of isopropanol and a propanol mixture of at least about 50 wt% / o (more preferably at least about 75 wt%). When used here, ‘crude methanol’ preferably means that it contains up to about 98% by weight of methanol. This paper is scaled (21Q x 297). F Please read the note on the back first? Please fill in this page again) Qin — — — — — — — — -P— · 565547 A7 V. Description of the invention (6) (preferably up to about 97% by weight of methanol, and more up to about 95%) % By weight of methanol). If present in alcohol, water can be from about to about 10 weight 0 / 〇, preferably from 3 to about 1 () weight ... 0.1 篁 篁 / 〇, which is based on the content of alcohol and water in it meter. As described above, in a specific example of the present invention, the relative content of hydrogen cyanide and acetonitrile produced by the method of the present invention can be adjusted by adjusting the relative content of methanol compared to ethanol added to the reaction zone of the propylene method. . = Therefore, if a larger content of hydrogen cyanide is desired, the ratio of methanol to ethanol can be increased. Conversely, if cyanogen is desired, this ratio can be reduced. Therefore, the present invention is a kind of acrylonitrile adjusted by adding a mixture containing methanol, ethanol, or propanol, and by controlling the ratio of methanol and ethanol or propanol (preferably ethanol) added to the acrylonitrile reaction zone. Method of relative content of hydrogen cyanide and acetonitrile produced during preparation. Although any grade of methanol, ethanol, or propanol can be used in this specific example, even high-purity methanol, ethanol, or propanol is favorably used with crude methanol, ethanol, or propanol, and preferably crude methanol, ethanol, or ethanol. And crude propanol (as described above). Therefore, the present invention is also a method for adjusting the relative content of hydrogen cyanide and acetonitrile produced during the preparation of acrylonitrile, which comprises making a hydrocarbon selected from the group consisting of propane and propylene, ammonia, two gases, and methanol and alkanol (which An alcohol mixture containing ethanol, propanol, or a mixture thereof) is introduced into a reaction zone containing an ammoxidation reaction catalyst (such as the catalyst described herein), and hydrocarbons, alcohols, ammonia, and oxygen are reacted with the catalyst at an elevated temperature to Producing acrylonitrile, hydrogen cyanide, and acetonitrile, and recovering propofol, hydrogen cyanide, and acetonitrile from this reaction, wherein the weight ratio of methanol to ethanol in the alcohol mixture is suitably about 99: 1 to about 1:99, The preferred size is about 98: 2. This paper size _ National Standard (CNS) A4 size (21〇X 297) (Please read the precautions on the back before filling this page) -------- tr --------- Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565547 A7 B7 V. Description of the invention (7 to about 'Please better about 95: 5 to about 5:95. In alcohol mixtures Let, preferably, methanol to ethanol (or methanol to propanol, or a mixture of methanol to ethanol and propanol). Weight ratio is suitably about 99: 1 to about 1:99, preferably about about to about _ 'more preferably I about 95: 5 to about 5:95. For example, if the pure When the acetonitrile content is a relatively large content of hydrogen cyanide, the proportion of alcohol supplied to the reactor may be, for example, 9G wt% ethanol and wt% methanol. The ratio of alcohol to the reactor can be 10% by weight of ethanol and 90% by weight of methanol. It should be understood that the counterparts supplied to the propane reaction can be mixed before entering the reactor, or different alcohols can be individually treated. It is added and mixed in the reactor itself. In the preferred embodiment of the present invention, crude ethanol is used as the ethanol source, and methanol is added to the crude ethanol to achieve the desired ratio of hydrogen cyanide and acetonitrile co-product. In a preferred specific example, the reactor conditions need to be adjusted to obtain increased yields of acetonitrile and hydrogen cyanide obtained by using a mixture of crude alcohols. In the practice of the present invention, the conditions of the ammoxidation reaction are preferably applied. Within the following parameters: between 1 and 50% of crude alcohol The ratio of ene or propane (based on total carbon). The reaction temperature is between 41 ° C to 460 ° C (preferably 430 ° C to 460 ° C). Typically, the pressure is maintained at 1 to 5 atmospheres It is preferably between 1 and 3 atmospheres. In a preferred embodiment of the present invention, the crude alcohol mixture includes a mixture containing ethanol, propanol, butanol, and water. In a further preferred embodiment of the present invention, This method is carried out in a fluidized bed. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) il · — — —.------- (Please read the Note for this page, please fill in this page) 1111111 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 565547 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 -----------_ B7__ V. Description of Invention (8) ^ U.S. Patent Application No. 09/208/053 (filed on December 9, 2008) is hereby incorporated by reference in its entirety. The following infringements are for illustrative purposes and should not be construed as limitations of the present invention. The catalyst used in all cases is known to be suitably promoted in the reaction for the ammoxidation of propylene to acrylonitrile. EMox. 10 and 15 /. The propylene feed (in terms of total carbon) was replaced with crude alcohol to produce the results shown in Table 1 below. In each of the following examples, the reactor temperature is 44 ° C., the pressure is 9.5 psig, and the ammonia / air ratio is 1 / 1.2 / 9.3. Wwh is 0.07 (g of hydrocarbon Number / gram of catalyst, hours). EtOH% supplied by the sample number (based on C) Table 1 AN Yield% Aceto production K / ft 6.5 U comparison) 0 78.8 1.5 2 5 75.3 3.9 6.9 3 10 71.5 5.0 7.4 4 15 67.5 6.5 8.0 As a further example of the value of using an alcohol mixture, 30% by weight of methanol is blended with the crude ethanol described above, and this is co-supplied to the same propylene ammoxidation reactor. The results are shown in Table II below, and indicate that the product is shifted to HCN. When high-volume HCN is required, this supply must be used in a commercial plant. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 11
-Λ --------tr--------- (請先閱讀背面之注意事項再填寫本頁) 565547 A7 B7 五、發明説明（9 ) 第90106356號專利申請案發明說明書修正頁91年9月30曰 第II表 供應之摻合物％ 範例編號 (以C計） 八^^產率％ Ace to產率％ HCN產率％ 5(比較例） 0 78.8 1.5 6.5 6 5 75.3 2.9 7.8 7 10 71.5 4.6 9.0 8 15 67.2 6.2 10.0 (請先閲讀背面之注意事項再填寫本頁) 一般，所有之醇被氨氧化成睛之混合物。較佳之醇包 含C!至C4之醇。含有數OH基之醇亦可被使用，例如， 乙二醇或丙二醇。 雖然此等範例係例示說明本發明之實施，其非用以將 申請人之發明限制於例示者，且明顯地，許多改良及變化 可基於上述教示而被使用。所欲者係申請人之發明之範圍 係以所附申請專利範圍界定。 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 12-Λ -------- tr --------- (Please read the notes on the back before filling out this page) 565547 A7 B7 V. Description of Invention (9) Patent Application No. 90106356 Correction page of the manual, September 30, 91. Blends supplied in Table II% Example No. (based on C) 8 ^^ Yield% Ace to Yield% HCN Yield% 5 (Comparative Example) 0 78.8 1.5 6.5 6 5 75.3 2.9 7.8 7 10 71.5 4.6 9.0 8 15 67.2 6.2 10.0 (Please read the notes on the back before filling out this page) Generally, all alcohols are oxidized by ammonia to form a mixture of eyes. Preferred alcohols include C! To C4 alcohols. Alcohols containing several OH groups can also be used, for example, ethylene glycol or propylene glycol. Although these examples illustrate the implementation of the present invention, they are not intended to limit the applicant's invention to the exemplifier, and obviously, many improvements and changes can be used based on the above teachings. The scope of the applicant's invention is defined by the scope of the attached patent application. This paper size applies to China National Standard (CNS) A4 (210X297 mm) 12