玫、發明說明： 【發明所屬^技術4員域】 發明領域 本發明係關於一種可供用於將—種不飽和碳氫化合物 予以氨氧化成對應之不飽和晴的改良催化劑。特別地，本 發明係針對一種可供用於將丙烯及/或異丁烯個別地予以 氨氧化成丙烯晴及/或甲基丙烯晴的方法以及催化劑。更特 別地，本發明係關於一種新穎且改良的氨氧化催化劑，該 催化劑是在實質不包含任何一種錳及鋅之下，包含一種由 鉀、鉋、鈽、鉻、鈷、鎳、鐵、鉍及鉬之催化性氧化物所 構成之複合物。 ilyT 】 習知技藝内容 諸等包含鐵、鉍及鉬之氧化物催化劑係以適合的元素 來增進反應，此等催化劑已於長久以來被使用來供用於升 向>孤度及氨與氧(通常是來自空氣)存在之下，藉由轉化丙稀 來製備丙烯晴。特別地，英國專利案編號：1436475、美國 專利案編號：4,766,232、4,377,534、4,040,978、4，168,246、 5,223,469及 4,863,891 係個別 針對該等可以第II族元素增進丙烯晴製備之鉍_鉬_鐵 催化劑。此外，美國專利案編號·· 4，190,608揭露類似之可 供用以增進烯烴氧化之鐵、鉍及鉬催化劑。美國專利案編 號：5,093,299、5,212，137、5,658,842以及5,834,394係針對 該等展現高丙烯晴產率之鉍-鉬-鐵增進催化劑。 200422101 _本發明的一個標的是一種新穎的催化劑，該催化劑包 s種獨特之增進劑組合，藉此使該催化劑於個別催化丙 烯、異τ：)#或其混合物進行缝化產μ烯晴、甲基丙烯 晴及其混合物時，會具有更佳的效力。 【潑^明内容】 發明概要 本發明係針對一種可供用於將丙烯及/或異丁烯個別 地予以氨氧化成丙烯晴及/或甲基丙烯晴的方法以及催化 劑0 10 於一個具體例中，本發明催化劑包含一種由催化性氧 化物所構成的複合物，該催化性氧化物包含：钟、铯、鈽、 鉻、始、鎳、鐵、级及銦，且其中此等元素之相對比例是 以下列通式來表示：Description of the invention: [Technical field of 4 members of the invention] Field of the invention The present invention relates to an improved catalyst that can be used for the ammoxidation of an unsaturated hydrocarbon to the corresponding unsaturated clear. In particular, the present invention is directed to a method and a catalyst that can be used for the ammoxidation of propylene and / or isobutylene individually to propylene and / or methacrylic. More specifically, the present invention relates to a novel and improved ammonia oxidation catalyst. The catalyst does not substantially contain any of manganese and zinc, and includes a catalyst consisting of potassium, planer, thorium, chromium, cobalt, nickel, iron, and bismuth. And a composite of molybdenum's catalytic oxide. ilyT] Known technical content. Various oxide catalysts containing iron, bismuth, and molybdenum are used to enhance the reaction with suitable elements. These catalysts have been used for a long time for ascent > orphanness and ammonia and oxygen ( In the presence of air), acrylonitrile is produced by converting propylene. In particular, the British patent case number: 1434675, the U.S. patent case number: 4,766,232, 4,377,534, 4,040,978, 4,168,246, 5,223,469, and 4,863,891 are individual bismuth_molybdenum_iron catalysts which can be prepared by Group II elements to promote acrylonitrile. In addition, U.S. Patent No. 4,190,608 discloses similar iron, bismuth, and molybdenum catalysts that can be used to enhance the oxidation of olefins. U.S. Patent Nos. 5,093,299, 5,212,137, 5,658,842, and 5,834,394 are directed to these bismuth-molybdenum-iron enhancement catalysts that exhibit high acrylonitrile yields. 200422101 _ An object of the present invention is a novel catalyst comprising a unique combination of promoters, thereby enabling the catalyst to sew the individual catalysts of propylene, isoτ:) # or mixtures thereof to produce μene, Methacrylic acid and its mixture will have better efficacy. [Abstract] Summary of the Invention The present invention is directed to a method and a catalyst which can be used for the ammoxidation of propylene and / or isobutylene individually to propylene and / or methacrylic acid. In a specific example, the present invention The catalyst of the invention comprises a composite composed of a catalytic oxide, the catalytic oxide comprising: bell, cesium, rubidium, chromium, starting, nickel, iron, grade and indium, and the relative proportions of these elements are as follows Column formula to represent:
AaKbCscCedCreCofNigXhFejBijMo^Ox 15 其中 A是铷(Rb)、鈉(Na)、鋰(U)、鉈(T1)、或由此等所構 成之混合物， X是磷(P)、銻（Sb)、碲(Te)、侧(B)、鍺(Ge)、鎢（W)、 鈣(Ca)、鎂(Mg)、一種稀土元素、或由此等所構成之 混合物， 2〇 a是大約〇至大約1， b是大約0.01至大約1， c是大約0.01至大約1， d是大約0.01至大約3， e是大約0.01至大約2， 7 200422101 f是大約0.01至大約10， g是大約0.1至大約10， . h是大約0至大約3， i是大約0.1至大約4， 5 j是大約0.05至大約4， X是一個視其他存在元素之價數需求來決定之數目， 且其中該催化劑是實質不包含錳及鋅。 本發明亦係針對諸等可供用以將一種選自於該包含： 丙烯、異丁烯或其混合物群組之烯烴，個別轉變成丙烯晴、 · 10 甲基丙烯晴及其混合物之方法，該等方法是藉由在一種混 合金屬氧化物催化劑存在之下，令一種包含氧分子之氣體 及氨與該等烯烴反應於氣相及一升高之溫度與壓力下，其 中該催化劑係如上文所述。 I：實施方式3 15 較佳實施例之詳細說明 本發明是一種新穎的催化劑，該催化劑包含一種獨特 之增進劑組合，藉此使該催化劑於個別催化丙烯、異丁烯 ® 或其混合物進行氨氧化產生丙烯晴、甲基丙烯晴及其混合 物時，會具有更佳的效力。 20 本發明是一種氨氧化催化劑，該催化劑包含一種由鉀 (K)、铯(Cs)、鈽(Ce)、鉻(Cr)、鈷(Co)、鎳(Ni)、鐵(Fe)、 鉍(Bi)及鉬（Mo)之催化性氧化物所構成的複合物，其中此等 元素之相對比例是以下列通式來表示： AaKbCscCedCreC〇fNigXhFeiBijM〇i2〇x 8 200422101 其中 A是#〇(Rb)、鈉(Na)、經(Li)、I它(ΤΙ)、或由此等戶斤構 成之混合物， X是磷(Ρ)、銻(Sb)、碲(Te)、硼(Β)、鍺(Ge)、鎢(W)、 鎂(Mg)、一種稀土元素、或由此等所構成之混合物， 5 a是大約0至大約1， b是大約0.01至大約1， c是大約0·01至大約1， d是大約0.01至大約3， e是大約0.01至大約2， 10 f是大約〇·〇1至大約10， g是大約0.1至大約10， h是大約0至大約3， i是大約〇·1至大約4， j是大約〇·〇5至大約4， 15 x是一個視其他存在元素之價數需求來決定之數目， 且其中該催化劑是實質不包含錳及辞。 於一個具體例中，該鈽(Ce)加鉻(Cr)之數量[以原子計] 大於鉍(Bi)之數量[意即〃b"+〃c〃大於〃 g〃]。於另一個具體例 中，該鈽(Ce)之數量[以原子計]大於鉻(Cr)之數量[意即 20 大於〃c〃]。 本案所述之基本催化劑組成物是一種由鉀（K)、铯 (Cs)、鈽(Ce)、鉻(Cr)、鈷(c〇)、鎳(Ni)、鐵(Fe)、鉍(Bi)及 鉬（Mo)之催化性氧化物所構成的複合物。除了特定排除之 元素以外，可包含其他的元素或增進劑。於一個具體例中， 9 200422101 本發明催化劑可以包含一種或數種铷（Rb)、鈉（Na)、鋰 · (Li)、鉈(T1)、磷(P)、銻（Sb)、碲(Te)、侧(B)、鍺(Ge)、鎢 · (W)、鈣(Ca)、鎂(Mg)、及一種稀土元素(本案定義為鑭(La)、 . 镨(Pr)、鈥(Nd)、鉅(Pm)、釤（Sm)、銪(Eu)、釓(Gd)、铽(Tb)、 5 (Dy)、鈥(Ho)、铒(Er)、铥(Tm)、鎰(Yb)之任何一個）。於尚 有另一個具體例中，本發明催化劑包含一少量的磷(p)(意即 "X〃至少是〃磷(P)"，且〃h"大於〇)，藉此可使本發明催化劑 具有一種有利之耐磨損性。於尚有另一個具體例中，本發 明催化劑包含#〇(Rb)(意即"A"至少是〃#a(Rb)〃，且〃a"大於 馨 10 0)。於尚有另一個具體例中，本發明催化劑包含鋰(Li)(意 即"A"至少是〃鋰(Li)"，且"a"大於〇)。於尚有另一個具體例 中，本發明催化劑實質不包含銷(Sr)的化合物，且較佳是不 包含鳃(Sr)。 額外地，對於供用於將丙烯、氨及氧轉變持成丙烯晴 15而言，已確認包含某些元素會不利於製得一種具有改良丙 烯晴產率之催化劑。這些元素是錳與辞。催化劑中包含錳 與鋅會產生-種具有較低活性之催化劑，導致丙烯晴產帛 φ 降低。因此，本案所述之本發明催化劑是實質不包含錳與 辞。對於錳而言，本案所使用之"實質不包含〃係意指具有 2〇 一個低於0.1 : 12之錳對比鉬原子比例。對於鋅而言，本案 所使用之"實質不包含"係意指具有一個低於i : 12之辞對比 鉬原子比例。較佳地，本發明催化劑不包含錳及/或鋅。 本發明催化劑之使用可以具有擔體或不具有擔體（意 即催化劑包含一個擔體）。適合的擔體是氧化石夕、氧化銘、 10 200422101 氧化锆、氧化鈦或其混合物。一典型之擔體可供用為一種 催化劑基石（binder)，俾以產生一種更硬且更具有财磨損性 之催化劑。然而，對於商業應用而言，一種適合之活化相（意 即該上述之催化性氧化物複合物）與基石之攙合是製得一 5 個具有可接受活性及硬度（耐磨損性)之催化劑的關鍵。解析 而言，任何一種活化相增加皆會增進催化劑活性，但卻會 降低該催化劑之硬度。典型地，該具有擔體之催化劑會包 含40-60wt%之擔體。於一個本發明具體例中，該具有擔體 之催化劑可以包含少至大約30wt%之擔體。於另一個本發 1〇明具體例中，該具有擔體之催化劑可以包含多達大約 70wt%之擔體。 、 -——-厂但羊U匕矽溶膠來 為擔體。設若氧化碎溶膠之膠體粒徑太小時，該製成之 15 20AaKbCscCedCreCofNigXhFejBijMo ^ Ox 15 where A is thorium (Rb), sodium (Na), lithium (U), thorium (T1), or a mixture thereof, and X is phosphorus (P), antimony (Sb), tellurium ( Te), side (B), germanium (Ge), tungsten (W), calcium (Ca), magnesium (Mg), a rare earth element, or a mixture thereof, and 20a is about 0 to about 1 B is about 0.01 to about 1, c is about 0.01 to about 1, d is about 0.01 to about 3, e is about 0.01 to about 2, 7 200422101 f is about 0.01 to about 10, and g is about 0.1 to about 10 , H is about 0 to about 3, i is about 0.1 to about 4, 5 j is about 0.05 to about 4, X is a number that depends on the valence requirements of other existing elements, and the catalyst is substantially non-existent. Contains manganese and zinc. The present invention is also directed to methods for individually converting an olefin selected from the group consisting of: propylene, isobutylene, or a mixture thereof into acrylonitrile, 10 methacrylic acid, and mixtures thereof. By reacting a gas containing oxygen molecules and ammonia with the olefins in the gas phase and an elevated temperature and pressure in the presence of a mixed metal oxide catalyst, the catalyst is as described above. I: Embodiment 3 15 Detailed description of the preferred embodiment The present invention is a novel catalyst containing a unique combination of promoters, whereby the catalyst is used to catalyze the ammoxidation of propylene, isobutylene® or mixtures thereof Acrylic sunny, methacrylic sunny and their mixtures will have better efficacy. 20 The present invention is an ammonia oxidation catalyst. The catalyst comprises a catalyst consisting of potassium (K), cesium (Cs), rubidium (Ce), chromium (Cr), cobalt (Co), nickel (Ni), iron (Fe), and bismuth. (Bi) and molybdenum (Mo) composite oxide, in which the relative proportion of these elements is expressed by the following general formula: AaKbCscCedCreC〇fNigXhFeiBijM〇i2〇x 8 200422101 where A is # 〇 (Rb ), Sodium (Na), via (Li), it (TI), or a mixture thereof, X is phosphorus (P), antimony (Sb), tellurium (Te), boron (B), Germanium (Ge), tungsten (W), magnesium (Mg), a rare earth element, or a mixture of these, 5 a is about 0 to about 1, b is about 0.01 to about 1, and c is about 0 · 01 to about 1, d is about 0.01 to about 3, e is about 0.01 to about 2, 10 f is about 0.01 to about 10, g is about 0.1 to about 10, h is about 0 to about 3, i Is about 0.1 to about 4, j is about 0.05 to about 4, 15 x is a number that depends on the valence requirements of other existing elements, and wherein the catalyst does not substantially contain manganese. In a specific example, the amount of [Ce] plus chromium (Cr) is [atom] greater than the amount of Bi ([i.e., 〃b " + 〃c〃 is greater than 〃g〃]. In another specific example, the amount (in terms of atomic) of the plutonium (Ce) is greater than the amount of chromium (Cr) [meaning 20 is greater than 〃c〃]. The basic catalyst composition described in this case is a potassium (K), cesium (Cs), rubidium (Ce), chromium (Cr), cobalt (c0), nickel (Ni), iron (Fe), and bismuth (Bi ) And molybdenum (Mo) composite oxide. In addition to the specifically excluded elements, other elements or enhancers may be included. In a specific example, 9 200422101 the catalyst of the present invention may include one or more of rhenium (Rb), sodium (Na), lithium (Li), rhenium (T1), phosphorus (P), antimony (Sb), tellurium ( Te), side (B), germanium (Ge), tungsten (W), calcium (Ca), magnesium (Mg), and a rare earth element (defined in the present case as lanthanum (La), ytterbium (Pr), " Nd), giant (Pm), 钐 (Sm), 铕 (Eu), 釓 (Gd), 铽 (Tb), 5 (Dy), '(Ho), 铒 (Er), 铥 (Tm), 镒 ( Yb) any one). In yet another specific example, the catalyst of the present invention contains a small amount of phosphorus (p) (meaning that "X〃 is at least 〃phosphorus (P)", and 〃h " is greater than 0), thereby enabling the present invention The inventive catalyst has an advantageous abrasion resistance. In yet another specific example, the catalyst of the present invention contains # 〇 (Rb) (meaning that "A" is at least 〃 # a (Rb) 〃, and 〃a " is greater than Xin 10 0). In yet another specific example, the catalyst of the present invention includes lithium (Li) (meaning " A " at least Lithium (Li) ", and " a " is greater than 0). In yet another specific example, the catalyst of the present invention does not substantially contain a pin (Sr) compound, and preferably does not include a gill (Sr). Additionally, for the conversion of propylene, ammonia, and oxygen to propylene oxide 15, it has been confirmed that the inclusion of certain elements is detrimental to the production of a catalyst with improved propylene oxide yield. These elements are manganese and words. The inclusion of manganese and zinc in the catalyst will produce a catalyst with lower activity, resulting in a decrease in the 帛 φ of propylene sunny production. Therefore, the catalyst of the present invention described in this case is substantially free of manganese. For manganese, the use of "substantially free" means that it has a manganese to molybdenum atomic ratio of less than 0.1: 12. For zinc, the term "substantially not included" used in this case means a phrase with a molybdenum atom ratio of less than i: 12. Preferably, the catalyst of the present invention does not include manganese and / or zinc. The catalyst of the present invention may be used with or without a support (that is, the catalyst includes one support). Suitable supports are stone oxide, oxide oxide, 10 200422101 zirconia, titanium oxide or mixtures thereof. A typical support is available as a catalyst binder to produce a harder and more abrasive catalyst. However, for commercial applications, the combination of a suitable activating phase (meaning the above-mentioned catalytic oxide complex) with the cornerstone is to produce 5 active compounds with acceptable activity and hardness (wear resistance). The key to the catalyst. In terms of analysis, the increase of any one of the activated phases will increase the catalyst activity, but will decrease the hardness of the catalyst. Typically, the supported catalyst will contain 40-60 wt% of the support. In one embodiment of the present invention, the catalyst having a support may include as little as about 30% by weight of the support. In another embodiment of the present invention, the catalyst with a support may include up to about 70% by weight of the support. , ------ Factory but U U. Silica gel for the load. If the colloidal particle size of the oxidized crushed sol is too small, the produced 15 20
化劑表面積會增加，藉此使該催化劑展現之選擇性降低The surface area of the chemical agent will increase, thereby reducing the selectivity exhibited by the catalyst
=若氧切_之雜粒社㈣，該製叙催化劑脅 =不良的抗磨損力1型地’氧切溶膠之平均 疋居於大約l5nm至大約50nm之間。於一狄，、 中’乳化石夕溶膠之平均膠體粒徑是大約1〇她 8 n m。於另—個本發明具額巾，氧切溶 "T以伯 徑是大約lGGnm。於另—個本發明具體例中，^均膠楚 平均膠體_是大約2Gnm。 錢石夕溶| 本發明催化劑可藉綠種為那些熟習此 已知之催化劑製備方法的任何—種來- 藉由共同⑽各種不同的成份來製造催化劑。其2如: 11 200422101 燥ό亥共同/儿;殿團塊，然後予以研磨成一個適合的尺寸。可 選擇性地，將該共同沉澱之材料形成漿液，然後參照習知 技術來予以噴射乾燥。可以如本技藝中所熟知地，將催化 劑擠壓成丸粒，或者製成油包水之圓球。特定之供用以製 5備催化劑的方法，請筝閱美國專利案編號：5,093,299、 4,863,891及4,766,232，其等在此併入本案作為參考資料。 於一個具體例中，本發明催化劑組份會呈一種漿液形式與 種擔體援合，知之乾無该漿液，或者將本發明催化劑組 份灌注於氧化矽或其他擔體上。 10 導入催化劑之麵可以是一種氧化物或者一種於鍛燒之 下會形成其氧化物之鹽。如同其他元素，鉍鹽較佳是使其 可均勻分散於催化劑中之水溶性鹽。最佳是硝酸鉍。 配製入催化劑之鐵組份可以得自任何一種於鍛燒之下 會形成其氧化物之鐵的化合物。如同其他元素，鐵鹽較佳 15是使其可均勻分散於催化劑中之水溶性鹽。最佳是硝酸鐵。 導入催化劑之鉬組份可以是任何一種鉬之氧化物，例 如· 一氧化物、三氧化物或七氧化物。然而，較佳是一種 可水解或可分解來供用為一種鉬源之鉬鹽。最佳之起始材 料是七翻酸銨。 20 催化劑之其他所需組份及任擇之增進劑（例如：鎳 (Ni)、鈷(Co)、鎂(Mg)、鉻(〇)、磷(P)、錫（Sn)、碲(Te)、 石朋（B)、錯（Ge)、辞（Zn)、姻（In)、#5(Ca)、鶴（W)可以得自 任何一種適合的來源。例如：鈷、鎳、及鎂可以其硝酸鹽 來導入催化劑中。額外地，導入之鎂可以是一種於加熱處 12 之下產生—種氧化物之不可溶碳酸鹽或氫氧化物。導入 4匕密丨丨夕2T# — ^可以是一種鹼金屬或鹼土金屬或鏔鹽，但較佳 是鱗酸。 所需及任擇之催化劑鹼組份(例如：铷(Rb)、鋰(U)、 鈉(Na)、鉀(κ)、铯(Cs)、鉈(η)或其混合物可以一種於鍛燒 之下產生一種氧化物氧化物或鹽來導入催化劑中。較佳 地’於將此種元素攙合入催化劑之方法中是使用諸等容易 使用且易溶解之鹽（例如硝酸鹽）。 本發明催化劑之製備，典型地是以一種氧化矽溶膠攙 合一種七銦酸銨水性溶液，對此攙合物添加一種包含該等 化合物(較佳是其他元素之硝酸鹽）漿液。其後該固體材料被 乾燥、去硝基化、然後鍛燒。較佳地，喷射乾燥該催化劑 是於一個居於11〇-35〇1之溫度下，更佳是居於110-25(rc， 最佳是110-180°c。去硝基化溫度較佳是l〇〇-500°C，更佳是 250-450°C。最後，一個鍛燒溫度是居於300-700°C，較佳是 居於350-65(TC。 本發明催化劑可供用於將一種選自該包含：丙烯、異 丁烯或其混合物群組之烯烴，個別地予以轉化為丙烯晴、 甲基丙稀晴或其混合物之氨氧化方法，該方法是藉由在本 發明催化劑存在之下，令該等烯烴與一種包含氧分子之氣 體及氨反應於氣相及一升高之温度與壓力下。 雖然可使用其他型式的反應槽（例如：輸送管路反應 槽），但較佳地該氨氧化反應是施行於一種流體基床反應槽 中。供用於製造丙烯晴之流體基床反應槽是習知技藝所熟 200422101 知。適用之反應槽是例如··美國專利案編號·· 3,23〇,246所 · 提供之反應槽設計，該案在此併入本案作為參考資料。 · 氨氧化反應條件亦為習知技藝所熟知，可參閱例如： _ 美國專利案編號：5,093,299、4, 863,891、4,767,878及4， ’ 5 503,，該等在此併人本案作為參考資料。典型地，氨氧 化反應S在升高之溫度以及氨純存在下，以—種雜& 床催化劑來接觸丙烯或異丁稀，藉此產生丙缔晴或甲基丙 稀晴。可使用任何-種氧供應源。然而為了經濟理由，較 佳是使用空氣。典型地，該進料氧對比烯烴莫耳比例是居 寒 10於0·5:1至4:1之範圍内，較佳是居於i:i至3:1之範圍内。 反應之進料氨對比烯烴莫耳比例可以落在〇.5:丨至 2:1。貫際上氨對比烯烴莫耳比例並沒有上限，但因為經濟 理由，通#不會超過一個2:1之比例。適合供本發明催化劑 自丙烯製造丙烯晴的進料比例是一個氨對比丙烯比例居於 I5 0.9.1至1.3:1 ’以及空氣對比丙烯比例為8〇:1至12众丨。本 發明催化劑是藉由大約1:1至纟約1〇5:1之相當低的氛對比 丙烯進料比例來提供一個高丙烯晴產率。此等"低氨反應條 鲁 件可協助減少該居於反應槽流體之未反應氨，這是一種已 知為〃氨耗盡〃反應條件，該條件可實質減少製程浪費。特 2〇別地，未反應氨必須在回收丙稀晴之前自反應槽流出物移 除。未反應氨之移除典型地是以硫酸接觸反應槽流出物， 藉此產生硫酸銨，或以丙烯酸接觸反應槽流出物，藉此產 生丙烯酸銨，這兩種情形皆導致必須處理及/或棄置之製程 廢液流。 14 200422101 氨氧化反應是進行於一個大約260°C至600°C之溫度範 ， 圍内，較佳是310°C至500°C，特佳是350°C至480°C。接觸 . 時間雖非關鍵，但通常是落在0.1至50秒之範圍内，較佳是 ， 一個歷時1至15秒的接觸時間。 5 反應產物可藉由那些熟習此項技藝人士所已知之任何 一種方法來予以回收及純化。一種方法是涉及以冷水或一 種適合的溶劑洗滌來移除反應產物，其後以蒸餾來純化反 應產物。 本發明催化劑之主要用途是供用於將丙烯氨氧化成丙 ® 10 烯晴。然而，本發明催化劑亦可供用於將丙烯氧化成丙烯 酸。此種製程典型地是兩階段製程，其中丙烯是於第一階 段中，在一種催化劑存在之下，被轉變為一級丙烯醛，其 後該丙烯醛會於第二階段中，在一種催化劑存在之下，被 轉變為丙烯酸。本案所述之催化劑適合供用於第一階段， 15 藉此將丙烯氧化成丙烯醛。 特定具體例 為了闡釋本發明，製備本發明催化劑以及類似但省略 ® 一個或數個（或額外包含）諸等會不利於丙烯晴產生元素之 催化劑，其後於類似反應條件下，予以評估。這些實施例 20 僅供闡釋之目的。 製備催化劑 實施例1 : 一個具有化學式：50wt%= If the oxygen cut _ is mixed, the production catalyst is threatened = the average wear resistance of type 1 ground "oxy cut sol with poor abrasion resistance is between about 15nm to about 50nm. In Yidi, the average colloidal particle size of the emulsified stone sol is about 10 nm 8 nm. In another aspect of the present invention, the oxygen-cutting " T diameter is about 1 GGnm. In another specific example of the present invention, the average colloid is about 2 Gnm. Qian Shixiong | The catalyst of the present invention can be made by using green seeds for any of those who are familiar with this known catalyst preparation method-by preparing various catalysts together. The 2 such as: 11 200422101 Dang Hai Hai Common / Er; Hall clumps, and then grind to a suitable size. Alternatively, the co-precipitated material is formed into a slurry and then spray-dried with reference to conventional techniques. The catalyst can be extruded into pellets or made into water-in-oil spheres as is well known in the art. For specific methods for preparing 5 catalysts, please refer to U.S. Patent Nos .: 5,093,299, 4,863,891, and 4,766,232, which are incorporated herein by reference. In a specific example, the catalyst component of the present invention will be in the form of a slurry to assist the support, and it is known that the slurry is dry or the catalyst component of the present invention is poured on silica or other supports. 10 The side where the catalyst is introduced can be an oxide or a salt that will form its oxide upon calcination. Like the other elements, the bismuth salt is preferably a water-soluble salt which makes it uniformly dispersible in the catalyst. Most preferred is bismuth nitrate. The iron component formulated into the catalyst can be obtained from any compound that will form iron oxides upon calcination. As with other elements, the iron salt is preferably a water-soluble salt which makes it uniformly dispersible in the catalyst. The best is iron nitrate. The molybdenum component introduced into the catalyst may be any oxide of molybdenum, such as · monoxide, trioxide, or heptaoxide. However, a molybdenum salt that is hydrolyzable or decomposable for use as a source of molybdenum is preferred. The best starting material is ammonium heptarate. 20 Other required components of the catalyst and optional enhancers (for example: nickel (Ni), cobalt (Co), magnesium (Mg), chromium (〇), phosphorus (P), tin (Sn), tellurium (Te ), Shi Peng (B), Ge (Ge), Ci (Zn), Marriage (In), # 5 (Ca), Crane (W) can be obtained from any suitable source. For example: cobalt, nickel, and magnesium The nitrate can be introduced into the catalyst. In addition, the introduced magnesium can be an insoluble carbonate or hydroxide which is produced under the heating place 12-an oxide. Introduced in 4mm 丨 丨 夕 2T # — ^ It may be an alkali metal or alkaline earth metal or a phosphonium salt, but is preferably a scale acid. The required and optional catalyst base components (for example: rhenium (Rb), lithium (U), sodium (Na), potassium (κ) ), Cesium (Cs), rubidium (η), or a mixture thereof can be introduced into the catalyst by generating an oxide oxide or salt under calcination. Preferably, in the method of incorporating such elements into the catalyst It uses various easy-to-use and easily soluble salts (such as nitrates). The preparation of the catalyst of the present invention is typically a silica oxide sol combined with an aqueous solution of ammonium heptainate. A solid slurry containing the compounds (preferably nitrates of other elements) is added to the mixture. Thereafter, the solid material is dried, denitrified, and then calcined. Preferably, the catalyst is spray-dried at At a temperature of 〇-35〇1, it is more preferably at 110-25 (rc, most preferably 110-180 ° c. The denitrification temperature is preferably 100-500 ° C, more preferably 250-450 ° C. Finally, a calcination temperature is in the range of 300-700 ° C, preferably 350-65 ° C. The catalyst of the present invention can be used to select an olefin selected from the group consisting of: propylene, isobutylene, or a mixture thereof. Ammonia oxidation method which is individually converted into acrylonitrile, methacrylonil or a mixture thereof. The method is to react these olefins with a gas containing oxygen molecules and ammonia in the presence of the catalyst of the present invention. Gas phase and an elevated temperature and pressure. Although other types of reaction tanks (eg, pipeline reaction tanks) can be used, the ammoxidation reaction is preferably performed in a fluid-based bed reaction tank. For use It is well known to make acrylonitrile-based fluid bed reaction tanks. It is well known in the art. 200422101. The applicable reaction tank is, for example, the design of the reaction tank provided by the US Patent Case No. 3,23,246, which is incorporated herein as a reference. Ammonia oxidation reaction conditions It is also well known in the art, and can be referred to, for example: _ US Patent Case Numbers: 5,093,299, 4, 863,891, 4,767,878, and 4, 5503, which are incorporated herein by reference. Typically, the ammonia oxidation reaction In the presence of elevated temperature and the presence of pure ammonia, S is used to contact propylene or isobutylene with a heterogeneous & bed catalyst, thereby producing cyanine or methacrylic acid. Any source of oxygen can be used. For economic reasons, however, it is better to use air. Typically, the feed oxygen to olefin mole ratio is in the range of 10 to 0.5: 1 to 4: 1, preferably in the range of i: i to 3: 1. The molar ratio of ammonia to olefin in the reaction feed can fall from 0.5: 2 to 2: 1. In general, there is no upper limit on the molar ratio of ammonia to olefins, but for economic reasons, the ratio of ## will not exceed a 2: 1 ratio. A suitable feed ratio for the catalyst of the present invention to produce acrylonitrile from propylene is an ammonia to propylene ratio ranging from 0.9.1 to 1.3: 1 'and an air to propylene ratio of 80: 1 to 12. The catalyst of the present invention provides a high propylene yield by a relatively low atmospheric to propylene feed ratio of about 1: 1 to about 105: 1. These " low ammonia reaction conditions can help reduce the unreacted ammonia that resides in the reaction tank fluid, a reaction condition known as ammonia depletion, which can substantially reduce process waste. In particular, 20 otherwise, unreacted ammonia must be removed from the reaction tank effluent before propylene is recovered. The removal of unreacted ammonia is typically contacting the reaction tank effluent with sulfuric acid to produce ammonium sulfate, or contacting the reaction tank effluent with acrylic acid to produce ammonium acrylate, both of which lead to the need for treatment and / or disposal Process waste stream. 14 200422101 The ammoxidation reaction is carried out in a temperature range of about 260 ° C to 600 ° C, preferably within a range of 310 ° C to 500 ° C, and particularly preferably 350 ° C to 480 ° C. Contact. Although not critical, it usually falls within the range of 0.1 to 50 seconds, preferably, a contact time of 1 to 15 seconds. 5 The reaction product can be recovered and purified by any method known to those skilled in the art. One method involves washing with cold water or a suitable solvent to remove the reaction product, followed by purification by distillation. The main use of the catalyst of the present invention is for the ammonia oxidation of propylene to propylene ® 10 ene. However, the catalysts of the present invention are also useful for the oxidation of propylene to acrylic acid. This process is typically a two-stage process, in which propylene is converted to first-grade acrolein in the first stage in the presence of a catalyst, and then the acrolein is in the second stage in the presence of a catalyst. It is converted to acrylic acid. The catalyst described in this case is suitable for use in the first stage, whereby the propylene is oxidized to acrolein. Specific Examples For the purpose of illustrating the present invention, the catalysts of the present invention and similar but omitted o (one or several (or additionally included)) catalysts which are not conducive to the generation of acrylonitrile, were evaluated under similar reaction conditions. These examples 20 are for illustrative purposes only. Preparation of catalyst Example 1: One with chemical formula: 50wt%
Cs〇iiK〇.iCe〇>75Cr〇.3C〇4.3Ni4.4Fe2.〇Bi〇.5M〇i4.425〇57.775 + 5〇Wt%Cs〇iiK〇.iCe〇 > 75Cr〇.3C〇4.3Ni4.4Fe2.〇Bi〇.5M〇i4.425〇57.775 + 5〇Wt%
Si02之催化劑的製備如下：將下列硝酸鹽：硝酸铯 15 (CsN03)(1.535 克）、硝酸鉀(ΚΝΟ3)(0·796 克）、硝酸鐵 (Fe(N03)3 · 9Η20)(63·643 克）、硝酸鎳（Ni(N〇3)2 · 6Η20)(100·778克）、硝酸鈷(Co(N03)2 · 6Η20)(98·572克）、 硝酸鉍（Bi(N03)3 · 5Η2Ο)(19·104克）、以及硝酸#二銨 5 ((NH4)2Ce(N03)6)(64.773克之一個50%溶液），以〜7〇°C 一併 熔解於一個1000毫升之燒杯中。溶解七鉬酸銨（AHM) (200.603克)於310毫升之蒸餾水中。對此溶液添加一個溶解 於20毫升水之三氧化鉻(Cr03)(2.363克）。接續於金屬硝酸鹽 熔解之後添加氧化矽（自一個40%二氧化矽（Si02)溶液取得 10 625克）。其後將所產生之黃色漿液喷射乾燥。該製得之材 料於空氣中，以290°C/3小時、繼之425°C/3小時來予以去硝 基化，其後以57CTC/3小時來予以鍛燒。 比較實施例A(不具有鎳）：使用上述實施例1所述之製 備方法，並依照下列配方來配製一個具有化學式： 15 50Wt%Cs〇 ]Κ〇 1Ceo.75Cro.3CO8.7F^2.〇Bi〇.5M〇]4.425〇57.775~^50wt %Si〇2之催化劑··將下列硝酸鹽··硝酸铯(CsN03)(1.535克）、 硝酸鉀(ΚΝΟ3)(0·796克）、硝酸鐵(Fe(N03)3 · 9H20)(63.623 克）、硝酸鎳（Ni(N03)2 · 6Η2Ο)(100·778 克）、硝酸鈷 (Co(N03)2 · 6Η20)(98·572 克）、硝酸鉍（Bi(N03)3 · 20 5Η2Ο)(19·098克）、以及硝酸鈽二銨((NH4)2Ce(N03)6)(64.753 克之一個50%溶液），以〜7〇°C —併熔解於一個1000毫升之燒 杯中。溶解七鉬酸銨(ΑΗΜ)(200·603克)於310毫升之蒸餾水 中。對此溶液添加一個溶解於20毫升水之三氧化鉻 (Cr03)(2.362克）。接續於金屬硝酸鹽熔解之後添加氧化石夕 16 200422101 (625克之一個40%二氧化石夕（gi〇2)溶液）。 比較貫施例B(不具有鉀）：使用上述實施例1所述之製 備方法’並依照下列配方來配製一個具有化學式： 50wt%Cs〇.1Ce〇.75Cr〇.3Co8.7Fe2.〇Bi〇.5Mo14.425〇57.775+5〇wt%Si 5 〇2之催化劑：將下列硝酸鹽：硝酸鉋(CsNO3)(3.061克）、硝 酸鐵（Fe(N03)3 · 9Η20)(63·456 克）、硝酸鎳（Ni(N〇3)2 · 6Η20)(100·481 克）、硝酸鈷（Co(N〇3)2 · 6h2〇x98.282克）、 硝酸鉍（Bi(N03)3 · 5Η2Ο)(19·047克）、以及硝酸鈽二銨 ((NH4)2Ce(N03)6)(64.582克之一個50%溶液），以〜70°C—併 10 熔解於一個1000毫升之燒杯中。溶解七鉬酸銨 (ΑΗΜ)(200·603克)於310毫升之蒸餾水中。對此溶液添加一 個溶解於20毫升水之三氧化鉻(Cr03)(2.356克）。接續於金屬 硝酸鹽熔解之後添加氧化矽（625克之一個40%二氧化矽 (Si02)溶液）。 15 比較實施例C(具有錳）：使用上述實施例1所述之製備 方法，並依照下列配方來配製一個具有化學式： 50wt%Cs〇.iK〇.iCe〇.75Cr〇.3C〇4.3Ni4.4Mn〇.5Fe2.〇Bi〇.5M〇i4.425〇57. 775+50wt%SiO2之催化劑：將下列硝酸鹽：硝酸鉋 (CsN03)(1.485 克）、硝酸鉀（ΚΝΟ3)(0·77 克）、硝酸鐵 20 (Fe(N03)3 · 9Η20)(61·559 克）、硝酸鎳（Ni(N03)2 · 6Η20)(97·478克）、硝酸鈷(Co(N03)2 · 6Η20)(95·345克）、硝 酸猛（Μη(Ν〇3)2)(13·34克之一個50%溶液）、硝酸絲 (Bi(N03)3 · 5Η20)(18·478 克）、以及硝酸鈽二銨 ((NH4)2Ce(N03)6)(62.653克之一個50%溶液），以〜70°C—併 17 200422101 溶解於一個1000宅升之燒杯中。溶解七鉬酸銨 (ΑΗΜ)(200·761克)於310毫升之蒸餾水中。對此溶液添加一 個溶解於20毫升水之三氧化鉻(Cr〇3x2 286克接續於金屬 硝酸鹽熔解之後添加氧化矽（625克之一個4〇%二氧化矽 5 (Si02)溶液）。 比較實施例D(具有鋅）：使用上述實施例丨所述之製備 方法，並依照下列配方來配製一個具有化學式： 50wt%Cs〇.iK〇.iCe〇.75Cr〇.3C〇4.3Ni2.2Zn2.〇Fe2.〇Bi〇.5Mo14.425〇57.7 75+50wt%Si〇2之催化劑：將下列硝酸鹽：硝酸铯 10 (CsN03)(1.55 克）、、硝酸鉀（ΚΝΟ3)(0·8·4 克）、硝酸鐵 (Fe(N03)3 · 9Η20)(64·244 克）、硝酸鎳（Ni(N03)2 · 6Η2Ο)(50·865克）、硝酸鈷(Co(N03)2 · 6Η2Ο)(99·503克）、硝 酸鋅（Zn(N03)2 · 6Η2Ο)(47·301 克）、硝酸鉍（Bi(N03)3 · 5Η20)(19·284 克）、以及硝酸鈽二銨（(NH4)2Ce(N03)6) 15 (65.385克之一個50%溶液），以〜70°C —併熔解於一個1000 毫升之燒杯中。溶解七鉬酸銨(AHM)(199.759克)於310毫升 之蒸餾水中。對此溶液添加一個溶解於2〇毫升水之三氧化 鉻(Cr03)(2.385克）。接續於金屬硝酸鹽熔解之後添加氧化矽 (625克之一個40%二氧化石夕（SiOJ溶液）。 20 測試催化劑 所有的測試皆進行於一個40 cc流體基床反應槽内。丙 烯是以一個〇·〇6 WWH(意即丙烯重量/催化劑重量/小時)之 速率，來予以進料入反應槽。反應槽内的壓力維持於10 psig。反應溫度430°C。俟安定〜2〇小時之後’收集反應產物 18 200422101 樣品。反應槽流出物是以包含冷鹽酸(HC1)溶液之氣泡式洗 滌器來予以收集。以肥皂薄膜測定儀量測排氣速率，其後 以配備有一種分流管柱氣體分析儀之氣相層析儀來協助測 定運作最終之排氣組成物。於最終回收運作時，以蒸餾水 5 將所有的洗滌液體稀釋至大約200公克。使用定量的2-丁酮 做為已知標準物，並配製為〜50公克之稀釋分液。於一部配 備有一部火談離子偵測儀及一部交聯乙二醇(Carbowax)管 柱之氣相層析儀(GC)中，分析一個2μ1樣品。氨(NH3)的數 量是以氫氧化鈉(NaOH)溶液滴定過量的自由鹽酸(HC1)來 10 予以測定。下列樣品可闡釋本發明。 表1 ¥ 品 活性相組成物 Toatal C3X011V· Conv. To AN Sel. To AN 1 CSo.1KojCeo.75Cro.3CO4.3Ni4.4Fe2.oBio 5M〇i4 425〇57 77S 98.5 82.6 83.9 —__ A Cs〇.iK〇.iCe〇.75Cr〇.3C〇8.7Fe2.〇Bi〇.5M〇i4 425Ο57 775 95.8 80.6 84.4 B Cs〇.iCe〇.75Cr〇.3C〇8.7Fe2.〇Bi〇.5M〇i4 425Ο57 775 Γ 96.6 80.5 83.3 C Cs〇.iK〇.1Ce〇i75Cr〇.3C〇4.3Ni4.4Mn〇.5Fe2.〇Bi〇 5Mo14 77, 99.4 81.6 82.0 D CS〇.lK〇.lCe〇J5Cr〇.3C〇4.3Ni2.2Zn2.〇Fe2.〇Bi〇 5MOM 49^0^7 77^ 96.4 81.0 84.0 注釋： 1.所有的測試催化劑皆包含50%活性相及50%二氧化石夕(Si〇2) 15 ，::i=al 是每一回通入之丙稀轉變為所有產物的莫耳百分比。 4·"，。ΑΝ"是丙稀晴莫耳百分比對比丙烯莫耳 本發明催化劑組成物獨特之處在於其係於實質不包含 锰與鋅之下，包含卸、铯、#、鉻、録、鎳、鐵、減钥。 此種王本案所述之相對比例的元素組合，尚未被使用於一 種單一氨氧化催化劑配方中。如表丨所闡釋，對於供用以將 丙烯轉、交成丙烯晴而言，本發明催化劑會展現較諸等包含 19 20 200422101 類似（但不盡相同）之習知技藝專利案所述的元素組合，具有 、 更佳的功能。更特別地，當丙烯於一升高溫度以及氨與空 ， 氣存在之下，於一種實質不包含錳與辞之包含鉀、鉋、鈽、 鬌 鉻、始、鎳、鐵、叙及I目的催化劑作用下，會顯現較諸該 5 等偏離本發明範疇以外之類似催化劑，具有更高的總轉變 率以及丙稀晴轉變率。 雖然上述說明及上述具體例皆為實施本發明之典型， 然而對那些熟習此項技藝人士而言，多種改變、修改及變 化是顯而知悉的。因此，所欲的是所有的此等改變、修改 0 10 及變化皆涵概且落在本發明精義以及由檢附申請專利範圍 所定義之寬廣範脅内。 L圖式簡單說明3 (無） 【圖式之主要元件代表符號表】 (無） 20The catalyst for Si02 was prepared as follows: The following nitrates were: cesium nitrate 15 (CsN03) (1.535 g), potassium nitrate (KNO3) (0.796 g), iron nitrate (Fe (N03) 3 · 9Η20) (63 · 643 G), nickel nitrate (Ni (N〇3) 2 · 6Η20) (100 · 778 g), cobalt nitrate (Co (N03) 2 · 6Η20) (98 · 572 g), bismuth nitrate (Bi (N03) 3 · 5Η20) (19.104 g), and #diammonium nitrate 5 ((NH4) 2Ce (N03) 6) (a 50% solution of 64.773 g), and melted at ~ 70 ° C in a 1000 ml beaker . Dissolve ammonium heptamolybdate (AHM) (200.603 g) in 310 ml of distilled water. To this solution was added chromium trioxide (Cr03) (2.363 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, silicon oxide was added (10 625 g obtained from a 40% silicon dioxide (SiO2) solution). The resulting yellow slurry was then spray-dried. The obtained material was denitrified in air at 290 ° C / 3 hours, followed by 425 ° C / 3 hours, and then calcined at 57CTC / 3 hours. Comparative Example A (without nickel): using the preparation method described in Example 1 above, and formulating a chemical formula according to the following formula: 15 50Wt% Cs〇] Κ〇1Ceo.75Cro.3CO8.7F ^ 2.〇 Bi〇.5M〇] 4.425〇57.775 ~ ^ 50wt% Si〇2 catalyst ... The following nitrate salts ... Cesium nitrate (CsN03) (1.535 g), potassium nitrate (KNO3) (0.796 g) (Fe (N03) 3 · 9H20) (63.623 g), nickel nitrate (Ni (N03) 2 · 6Η20) (100 · 778 g), cobalt nitrate (Co (N03) 2 · 6Η20) (98 · 572 g), Bismuth nitrate (Bi (N03) 3 · 20 5Η20) (19.098 g), and diammonium hafnium nitrate ((NH4) 2Ce (N03) 6) (a 50% solution of 64.753 g), at ~ 7 ° C — And melt in a 1000 ml beaker. Dissolve ammonium heptamolybdate (ΑΜΜ) (200 · 603 g) in 310 ml of distilled water. To this solution was added chromium trioxide (Cr03) (2.362 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, oxidized stone oxide 16 200422101 (625 g of a 40% SiO2 solution) was added. Comparative Example B (without potassium): using the preparation method described in Example 1 above and formulating a chemical formula according to the following formula: 50wt% Cs〇.1Ce.75Cr〇.3Co8.7Fe2.〇Bi. .5Mo14.425〇57.775 + 50wt% Si 5 〇2 catalyst: the following nitrates: nitrate shavings (CsNO3) (3.061 g), iron nitrate (Fe (N03) 3 · 9Η20) (63 · 456 g) , Nickel nitrate (Ni (N〇3) 2 · 6Η20) (100 · 481 g), cobalt nitrate (Co (N〇3) 2 · 6h2 0x98.282 g), bismuth nitrate (Bi (N03) 3 · 5Η2〇 ) (19.047 g), and diammonium osmium nitrate ((NH4) 2Ce (N03) 6) (a 50% solution of 64.582 g), melt at ~ 70 ° C and 10 in a 1000 ml beaker. Dissolve ammonium heptamolybdate (AΗM) (200 · 603 g) in 310 ml of distilled water. To this solution was added chromium trioxide (Cr03) (2.356 g) dissolved in 20 ml of water. Following the melting of the metal nitrate, silicon oxide (625 g of a 40% silicon dioxide (Si02) solution) was added. 15 Comparative Example C (with manganese): using the preparation method described in Example 1 above, and formulating a chemical formula according to the following formula: 50wt% Cs〇.iK〇.iCe〇75Cr〇3Ni.4.3Ni4. 4Mn〇.5Fe2.〇Bi〇.5M〇i4.425〇57. 775 + 50wt% SiO2 catalyst: the following nitrates: nitrate planing (CsN03) (1.485 g), potassium nitrate (KNO 0) (0.77 g ), Iron nitrate 20 (Fe (N03) 3 · 9Η20) (61 · 559 g), nickel nitrate (Ni (N03) 2 · 6Η20) (97 · 478 g), cobalt nitrate (Co (N03) 2 · 6Η20) (95 · 345 g), nitric acid (Μη (Ν〇3) 2) (a 50% solution of 13.34 g), nitric acid filaments (Bi (N03) 3.5 · 20) (18.478 g), and thallium nitrate Diammonium ((NH4) 2Ce (N03) 6) (a 50% solution of 62.653 grams) was dissolved at ~ 70 ° C and 17 200422101 in a 1000 liter beaker. Dissolve ammonium heptamolybdate (AΗM) (200.761 g) in 310 ml of distilled water. To this solution was added a solution of chromium trioxide dissolved in 20 ml of water (CrO3x2 286g was followed by melting of the metal nitrate and silicon oxide (625g of a 40% silicon dioxide 5 (SiO2) solution) was added. Comparative Examples D (with zinc): Use the preparation method described in Example 丨 above, and formulate one with the following formula according to the following formula: 50wt% Cs〇.iK〇.iCe〇75Cr〇.3C〇4.3Ni2.2Zn2.〇Fe2 .〇Bi〇.5Mo14.425〇57.7 75 + 50wt% Si〇2 catalyst: the following nitrates: cesium nitrate 10 (CsN03) (1.55 g), potassium nitrate (KNO 0) (0 · 8 · 4 g) , Iron nitrate (Fe (N03) 3 · 9Η20) (64 · 244 g), nickel nitrate (Ni (N03) 2 · 6Η2〇) (50 · 865 g), cobalt nitrate (Co (N03) 2 · 6Η20) (99 · 503 g), zinc nitrate (Zn (N03) 2 · 6Η2Ο) (47 · 301 g), bismuth nitrate (Bi (N03) 3 · 5Η20) (19 · 284 g), and diammonium nitrate ((NH4) 2Ce (N03) 6) 15 (65.385 g of a 50% solution) at ~ 70 ° C-and melt in a 1000 ml beaker. Dissolve ammonium heptamolybdate (AHM) (199.759 g) in 310 ml of distilled water Add a dissolve to this solution Chromium trioxide (Cr03) (2.385 g) in 20 ml of water. Following the melting of the metal nitrate, silicon oxide (625 g of a 40% silica dioxide (SiOJ solution) was added. 20 Test catalyst All tests were performed In a 40 cc fluid-based bed reaction tank. Propylene was fed into the reaction tank at a rate of 0.06 WWH (meaning propylene weight / catalyst weight / hour). The pressure in the reaction tank was maintained at 10 psig. Reaction temperature 430 ° C. After stabilization ~ 20 hours, 'Collect reaction product 18 200422101 sample. The reaction tank effluent was collected in a bubble scrubber containing cold hydrochloric acid (HC1) solution. Soap film tester Measure the exhaust rate, and then use a gas chromatograph equipped with a split-column gas analyzer to help determine the final exhaust composition during operation. During the final recovery operation, dilute all the washing liquid with distilled water 5 Up to about 200 grams. A quantitative standard of 2-butanone is used as a known standard, and it is formulated as a ~ 50 grams dilution. It is equipped with a flame ionizer and a crosslinked glycol A (Carbowax) column was analyzed by a gas chromatograph (GC), and a 2 µ1 sample was analyzed. The amount of ammonia (NH3) was determined by titrating an excess of free hydrochloric acid (HC1) with a sodium hydroxide (NaOH) solution. The following samples illustrate the invention. Table 1 ¥ Active phase composition Toatal C3X011V · Conv. To AN Sel. To AN 1 CSo.1 KojCeo.75Cro.3CO4.3Ni4.4Fe2.oBio 5M〇i4 425〇57 77S 98.5 82.6 83.9 —__ A Cs〇.iK 〇.iCe〇.75Cr〇.3C〇8.7Fe2.〇Bi0.5.05M〇i4 425Ο57 775 95.8 80.6 84.4 B Cs〇.iCe.75Cr〇.3C〇8.7Fe2.〇Bi〇.5M〇i4 425〇57 775 Γ 96.6 80.5 83.3 C Cs〇.iK〇.1Ce〇i75Cr〇.3C〇4.3Ni4.4Mn〇.5Fe2.〇Bi〇5Mo14 77, 99.4 81.6 82.0 D CS〇.1Ke.1Ce〇J5Cr0.3C04.3Ni2 .2Zn2.〇Fe2.〇Bi〇5MOM 49 ^ 0 ^ 7 77 ^ 96.4 81.0 84.0 Notes: 1. All tested catalysts contain 50% active phase and 50% dioxide (Si〇2) 15 :: i = al is the mole percentage of each pass of propylene into all products. 4 · ". ΑΝ "is the percentage of propylene moire to propylene moire. The catalyst composition of the present invention is unique in that it is substantially free of manganese and zinc, including unloading, cesium, #, chromium, chromium, nickel, iron, key. The relative proportions of element combinations described in the King's case have not yet been used in a single ammonia oxidation catalyst formulation. As explained in Table 丨, for the purpose of converting and delivering propylene to propylene, the catalyst of the present invention will exhibit a combination of elements as described in conventional art patents containing similar (but not identical) 19 20 200422101 , With, better features. More specifically, when propylene is present at an elevated temperature and in the presence of ammonia and air, it contains potassium, planer, osmium, rhenium, chromium, nickel, iron, iron, and aluminum for a purpose that does not substantially contain manganese. Under the action of the catalyst, it will appear to have a higher total conversion rate and acrylonitrile conversion rate than similar catalysts outside the scope of the present invention. Although the above description and the above specific examples are typical for implementing the present invention, for those skilled in the art, many changes, modifications and variations are obvious. Therefore, what is desired is that all such changes, modifications, and changes are intended to be within the broad meaning of the present invention and defined by the scope of the attached patent application. L Schematic Illustration 3 (None) [Representative Symbols for Main Components of the Schematic] (None) 20