200734048 ^ (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於一種供製備不飽和醛與不飽和竣 之觸媒的製造方法。此外，本發明係關於一種使用 法所得觸媒製備不飽和醛與不飽和羧酸的方法。 【先前技術】 長久以來已經知悉者，關於氣相中使用分子氧 ® 氧化丙烯製造丙烯醛和丙烯酸所用的觸媒，或在氣 用分子氧而催化性氧化異丁烯或第三丁醇製造甲基 和甲基丙烯酸所用的觸媒，有效用者爲包括含鉬、 的混合氧化物之觸媒。此等供製備不飽和醛與不飽 所用的觸媒通常是經由將原料混合在水中所得水溶 淤漿予以乾燥，且於最後將所得觸媒先質煅燒而製 煅燒通常是在包含分子氧的氣體環境諸如空氣環境 φ 施，女口在，例女口， JP-A62-234548 、 JP-A-4-4048 、 1 24473、JP-A-2000-707 1 9 和 JP-A-2004 - 35 1 295 之 示者。 不過，供根據傳統方法製備不飽和醛與不飽和 用之觸媒都具有不足的催化活性，且因而，可能不 好的轉化率來氧化丙烯、異丁烯和第三丁醇，且不 人滿意的產率得到相應的不飽和醛與不飽和羧酸。 反應溫度以增加轉化率之時，會使副反應諸如接續 容易進行，由是可能不能以令人滿意的產率得到不 酸所用 上述方 催化性 相中使 丙烯醛 鉍和鐵 和羧酸 液或水 成。該 之下實 JP-A-7- 中所揭 羧酸所 能以良 能以令 在提局 的氧化 飽和醛 -5- 200734048 (2) 與不飽和羧酸。 因此，本發明的目的爲提供一種具有優良催化活性供 製造不飽和醛與不飽和羧酸所用之觸媒。此外，本發明的 目的爲提供一種製造方法，於其中使用以上面的方法所得 觸媒將丙烯、異丁烯或第三醇在良好轉化率下予以氧化而 以良好產率製得相對應的不飽和醛與不飽和羧酸。 | 【發明內容】 本發明提供一種製造觸媒的方法，該觸媒係用於將選 自丙烯、異丁烯和第三丁醇之中的化合物在氣相中利用分 子氧予以催化性氧化而製備不飽和醛與不飽和羧酸，該觸 媒包含含有鉬、鉍和鐵的混合氧化物，其中係將一觸媒先 質於包含分子氧的氣體環境下煅燒；然後在還原性物質的 存在下予以熱處理。 另外，本發明提供一種製造不飽和醛與不飽和羧酸的 φ 方法，該方法包括下述步驟：以上述方法製造觸媒，然後 將選自丙烯、異丁烯和第三丁醇之中的化合物在氣相中使 用分子氧於該觸媒存在下予以催化性氧化。 根據本發明，可以製造出具有優良催化活性的供製備 不飽和醛與不飽和羧酸所用之觸媒。此外，經由使用如此 所得觸媒’可以在良好轉化率之下將丙烯、異丁烯和第三 丁醇氧化而以良好的產率製造出對應的不飽和醛與不飽和 羧酸。 200734048 (3) 發明詳細說明 下面要詳細說明本發明。於本發明中，供製備不飽和 醛與不飽和羧酸所用之觸媒包括含有鉬、鉍和鐵作爲必要 成分的混合氧化物。該混合氧化物可包含鉬、鉍和鐵以外 元素，較佳者爲鎳及/或鈷與選自鉀、鉚、鉋和鉈之中的 元素。 較佳的混合物氧化物可由下面的通式（1 )例示： MoaBibFecAdBeCfDgOx ( 1 ) 其中Mo、Bi和Fe分別爲鉬、鉍和鐵；A爲鎳及/或鈷；B 爲選自錳、鋅、鈣、鎂、錫和鉛之中的元素；C爲選自磷 、硼、砷、碲、鎢、銻、矽、鋁、鈦、鉻和鈽之中的元素 ;D爲選自鉀、鉚、鉋和鉈之中的元素；當a=12，0<bSl0 ，0<c<10 » l<d<10 ， 0<e<10 ^ 0<f<10 » 且 0<g<2 ;且 x 爲 φ 取決於每一元素的氧化態之値。 於彼等之中，較佳者爲使用具有下面的組成（以不含 氧原子舉例說明）之化合物。200734048 ^ (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a process for producing a catalyst for preparing an unsaturated aldehyde and an unsaturated hydrazine. Further, the present invention relates to a process for producing an unsaturated aldehyde and an unsaturated carboxylic acid using a catalyst obtained by the method. [Prior Art] It has been known for a long time to use a catalyst for the production of acrolein and acrylic acid by using molecular oxygen® propylene oxide in the gas phase, or to catalytically oxidize isobutylene or tert-butanol to produce methyl groups by using molecular oxygen in the gas. The catalyst used for methacrylic acid is effectively used as a catalyst including a mixed oxide containing molybdenum. These catalysts for preparing unsaturated aldehydes and unsaturated are usually dried by mixing a raw material in water to obtain a water-soluble slurry, and finally calcining the obtained catalyst precursor to form a gas which is usually contained in molecular oxygen. Environment such as air environment φ application, female mouth in, female mouth, JP-A62-234548, JP-A-4-4048, 1 24473, JP-A-2000-707 1 9 and JP-A-2004 - 35 1 295. However, the catalyst for the preparation of unsaturated aldehydes and unsaturated catalysts according to conventional methods has insufficient catalytic activity, and thus, may have poor conversion to oxidize propylene, isobutylene and tert-butanol, and unsatisfactory production. The rate gives the corresponding unsaturated aldehyde and unsaturated carboxylic acid. When the reaction temperature is increased to increase the conversion rate, the side reaction such as the continuation proceeds easily, and the acrolein and the iron and the carboxylic acid solution may be used in the above catalytic phase which may not be obtained in a satisfactory yield. Water into. The carboxylic acid disclosed in JP-A-7- can be used as a catalyst for the oxidation of saturated aldehydes -5 - 200734048 (2) with unsaturated carboxylic acids. Accordingly, it is an object of the present invention to provide a catalyst for use in the production of unsaturated aldehydes and unsaturated carboxylic acids having excellent catalytic activity. Further, it is an object of the present invention to provide a process for producing a corresponding unsaturated aldehyde in a good yield by oxidizing propylene, isobutylene or a third alcohol at a good conversion rate using a catalyst obtained by the above method. With unsaturated carboxylic acids. SUMMARY OF THE INVENTION The present invention provides a method for producing a catalyst for catalytically oxidizing a compound selected from the group consisting of propylene, isobutylene, and third butanol by catalytic oxidation in the gas phase. a saturated aldehyde and an unsaturated carboxylic acid, the catalyst comprising a mixed oxide containing molybdenum, niobium and iron, wherein a catalyst is calcined in a gaseous environment containing molecular oxygen; and then in the presence of a reducing substance Heat treatment. Further, the present invention provides a φ method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, the method comprising the steps of: producing a catalyst by the above method, and then selecting a compound selected from the group consisting of propylene, isobutylene and tert-butanol Molecular oxygen is used in the gas phase for catalytic oxidation in the presence of the catalyst. According to the present invention, a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid having excellent catalytic activity can be produced. Further, by using the catalyst thus obtained, propylene, isobutylene and tert-butanol can be oxidized under a good conversion ratio to produce a corresponding unsaturated aldehyde and an unsaturated carboxylic acid in good yield. 200734048 (3) Detailed Description of the Invention The present invention will be described in detail below. In the present invention, the catalyst for the preparation of the unsaturated aldehyde and the unsaturated carboxylic acid includes a mixed oxide containing molybdenum, ruthenium and iron as essential components. The mixed oxide may contain elements other than molybdenum, niobium and iron, preferably nickel and/or cobalt and an element selected from the group consisting of potassium, riveting, planing and ruthenium. A preferred mixture oxide can be exemplified by the following formula (1): MoaBibFecAdBeCfDgOx ( 1 ) wherein Mo, Bi and Fe are molybdenum, niobium and iron, respectively; A is nickel and/or cobalt; and B is selected from the group consisting of manganese and zinc. An element selected from the group consisting of phosphorus, magnesium, tin, and lead; C is an element selected from the group consisting of phosphorus, boron, arsenic, antimony, tungsten, antimony, bismuth, aluminum, titanium, chromium, and antimony; and D is selected from the group consisting of potassium and riveting. The elements in the planing and raking; when a = 12, 0 < bSl0 , 0 < c < 10 » l < d < 10 , 0 < e < 10 ^ 0< f < 10 » and 0 < g <2; and x The value of φ depends on the oxidation state of each element. Among them, it is preferred to use a compound having the following composition (exemplified by an oxygen-free atom).
MoaBibF ecC〇dC Sg (a=12 ， 0.1<b<5 ， 0.5<c<5 ， 5<d<10 ， 0.01<g<l )MoaBibF ecC〇dC Sg (a=12, 0.1<b<5, 0.5<c<5, 5<d<10, 0.01<g<l)
MoaBibF ecC〇dSbfKg (a=12 ， 0.1<b<5 ， 0.5<c<5 ， 5<d<l 0 ^ 0.1<f<5 ， 0.01<g<l) 200734048 (4)MoaBibF ecC〇dSbfKg (a=12, 0.1<b<5, 0.5<c<5, 5<d<l 0 ^ 0.1<f<5, 0.01<g<l) 200734048 (4)
MoaBibFecNidSbflSif2Tlg (a=12 ^ 0.1<b<5 ^ 0.5<c<5 ^ 5<d<10 ? 0. 0· 1 <f2<5 ， 0.01 <g<l ) 作爲上述觸媒的原料者，係以滿足預定原子 例使用含有觸媒中所含各元素的化合物，諸如章 酸鹽、硫酸鹽、碳酸鹽、氫氧化物、氧基酸和伤 ，及鹵化物。例如，有關鉬化合物，可以使用三 鉬酸、鉬酸銨和類似者；有關鉍化合物，可以f妄 、硝酸鉍、硫酸鉍和類似者；且有關鐵化合物， 硝酸鐵（III )、硫酸鐵（III )、氯化鐵（III ) 於本發明製造觸媒所用方法中，係將從上紐 成的觸媒先質在含有分子氧的氣體環境下煅燒， Φ 原性物質存在中加熱處理。該觸媒先質通常可，稻 混合在水中而產生水溶液或水淤漿，然後將該才 淤漿乾燥而製得。該溶液或淤漿可藉由使用例贫 、箱式乾燥器、桶型流通式乾燥裝置、噴霧乾燥 乾燥器、和類似者，而予以乾燥。 如此所得觸媒先質係在含分子氧的氣體環境 分子氧於氣體中的濃度通常爲1至30體積％， 至25體積％。有關分子氧的來源，常使用空氣域 於需要時，利用氮氣、二氧化碳、水、氮氣、_ 1比例的比 L化物、硝 【等的銨鹽 :氧化鉬、 ί用氧化鉍 可以使用 和類似者 ^原料所製 然後在還 【由將原料 〔溶液或水 ]，捏合機 ^器、閃蒸 〖下煅燒。 較佳者10 5純氧，且 ，氣和類似 -8 - 200734048 (5) 者稀釋後才使用，將如此所得氣體利用作爲含分子氧的氣 體。煅燒溫度常爲300至600°C，較佳者400至5 50°C。 煅燒時間常爲5分至40小時，較佳者1小時至20小時。 於本發明中，於上述煅燒中所得經煅燒的觸媒先質係 在還原性物質中熱處理（後文中有時候將此處理稱爲還原 處理）。此一還原處理可以有效地改善觸媒活性。 還原性物質的例子包括例如，氫氣、氨、一氧化碳、 烴、醇類、醛類、胺類、和類似者。於需要時，可以將此 ® 等組合地使用。較佳者，該等烴類、醇類、醛類和胺類都 各具約1至約6個碳原子。烴的例子可包括飽和脂族烴諸 如甲烷、乙烷、丙烷、正丁烷和異丁烷；不飽和脂族烴諸 如乙烯、丙烯、α -丁烯、Θ -丁烯和異丁烯；苯、和類似 者。醇的例子可包括飽和脂族醇類諸如甲醇、乙醇、正丙 醇、異丙醇、正丁醇、異丁醇、第二丁醇和第三丁醇；不 飽和脂族醇類諸如烯丙醇、巴豆醇、和甲基烯丙醇；苯酚 φ ，和類似者。醛的例子可包括飽和脂族醛諸如甲醛、乙醛 、丙醛、正丁醛和異丁醛；不飽和脂族醛諸如丙烯醛、巴 豆醛和甲基丙烯醛、及類似者。胺的例子可包括飽和脂族 胺類諸如甲胺、二甲胺、三甲胺、乙胺、二乙胺和三乙胺 ;不飽和脂族胺類諸如烯丙胺和二-烯丙胺；苯胺，與類 似者。 該還原處理常經由將經煅燒的觸媒先質在包含上述還 原性物質的氣體環境下熱處理而實施。該還原性物質在該 氣體中的濃度常爲〇·1至50體積％，較佳者1至50體積％ 200734048 (6) ，更佳者3至3 0體積％。該還原性物質可用氮氣、二氧化 碳、水、氮氣、氬氣’或類似者予以稀釋以具有上述濃度 。氣體中可含分子氧’其含量係在不損及還原處理的效用 之範圍內，不過通常較佳者爲不含分子氧。 還原處理溫度常爲200至600°C，較佳者300至500 °C。還原處理時間常爲5分至20小時，較佳者30分至10 小時。較佳者，該還原處理係經由將煅燒過的觸媒先質置 $ 於一容器諸如管型容器或箱型容器，再將含還原性物質的 氣體通過其中而實施。於此一情況中，在需要時，可將來 自容器的廢氣再循環。例如，將煅燒觸媒先質塡充到氣態 催化性氧化所用反應管內，將含有還原性物質的氧體通過 其中以實質還原處理，其後可接著實施氣相催化性氧化。 通常，在還原處理後，觸媒質量會減低，此可能是因 爲晶格氧從煅燒觸媒先質流失所引起。質量流失率較佳者 爲0.05至6%，更佳者0.1至5%。在發生過份的還原且質 φ 量流失太高時，催化活性可能減低。於此一情況中，較佳 者爲在包含分子氧的氣體環境中再實施煅燒以降低質量流 失率。質量流失率係從下面的方程式計算的。 質量流失率（％ )=[(還原處理之前的煅燒觸媒先質之質 量·還原處理後的煅燒觸媒質量）/還原處理前的煅燒觸媒 質量]X100 當有實施還原處理時，在處理後，可將還原性物質本 -10 - 200734048 (7) 身及其分解產物保留在觸媒內，其取決於所用 的類別及熱處理條件。於此一情況中，係個別 中的殘留產物之質量，且將其從還原處理後的 物之觸媒質量予以減除之後所得之値則作爲處 質量。由於殘留產物典型地爲碳，其質量可經 碳（TC )測量和類似者而測得。 該觸媒通常經形成爲所欲形狀後才使用。 I 彼等經由壓錠或擠壓模塑形成爲環、小九、球 。該成形可在含分子氧的氣體環境下煅燒之前 狀態中實施，且可在煅燒後實施，或在還原處 在成形之中，爲了改善觸媒的機械強度，可以 反應實質惰性的無機纖維及類似者，如在JP-A 所述者。 經如此所得供製造不飽和醛與不飽和羧酸 具有優良的催化活性。經由使用該觸媒，可用 φ 相中將丙烯催化性氧化以在良好產率下製成丙 酸。另外，經由使用該觸媒，可用分子氧在氣 烯或第三丁醇催化性氧化而以良好產率製成甲 甲基丙烯酸。 根據氣相中的催化性氧化，通常將觸媒塡 多管狀反應容器內，再於該容器內供給包含分 氣體與選自丙烯、異丁烯和第三丁醇中的起始 可以使用流體床和移動床反應容器。分子氧的 空氣，且除了起始化合物和分子氧之外’起始 還原性物質 地測量觸媒 包含殘留產 理後的觸媒 由例如，總 較佳者，將 、和類似者 的觸媒先質 理後實施。 加入對氧化 -9-52053 中 所用的觸媒 分子氧在氣 烯醛和丙烯 相中將異丁 基丙烯醛和 充到固定床 子氧的起始 化合物。也 來源通常爲 氣體可包含 -11 - 200734048 (8) 氮氣、二氧化碳、一氧化碳、蒸汽和類似者。 反應溫度常爲250至400 °C，且反應壓力 50 OkP a，不過也可在減壓下實施反應。分子氧 至3莫耳/莫耳起始化合物。起始氣體的空間 常爲以STP (標準溫度和壓力）爲基準的500 時。 【實施方式】 實施例 下面係例示本發明之實施例，但本發明並 限制。實施例中，除非特別註明，否則標示氣 升/分鐘係根據STP。 比較例1 (a )觸媒之製造 將 13,241 克的鉬酸銨[(NH4 ) 6Mo7024 · 在1 5,000克溫水中，將其稱爲液體A。於另 6,060 克的硝酸鐵（III) [Fe(N03) 3· 9H20] 的硝酸鈷[Co ( N〇3 ) 2 · 6H20]和5 8 5克的硝睡 溶解在6,000克溫水中，接著，於其中溶解入 硝酸鉍[Bi ( N〇3 ) 3 · 5H20]，將此稱爲液體B A，於其中加入液體B而得一淤漿，且然後使 器乾燥該淤漿而得觸媒先質。於100質量份的 中加入6質量份的氧化矽氧化鋁纖維（ITM Co 营爲100至 的量常爲1 莖度（SV) 至5，0 0 0 /小 不受此等所 體流速的毫 4H20]溶解 一方面，將 ，13,096 克 Μ色[CsN〇3] 2,910克的 。攪拌液體 用閃蒸乾燥 該觸媒先質 ，Ltd.，所製 -12- 200734048 (9) ，RFC(400-SL)，且於其後將其形成爲具有 徑，2.5毫米內徑，及6毫米長度之環。將 5 1 6 °C空氣流中煅燒6小時而得觸媒。該觸媒^ 具有0.96鉍原子，2.4鐵原子，7.2銘原子和 (b )氧化反應 於一具有18毫米內徑的玻璃反應管中， 步驟（a )中所得觸媒，且在將異丁烯/ =1/2.2/6 · 7/2.1 (莫耳比）的混合氣體以（62, 的流速供給到該管中之時，在3 6 0 °C反應溫β 反應。表1中顯示異丁烯的轉化率及甲基丙少 烯酸的總產率。 實施例1 將50克比較例1 ( a )中所得觸媒塡充· ，且同時將氫氣/氮氣=10/90(體積比）的混名 毫升/分鐘的流速供給到該管內，於3 5 〇 〇c實J 小時。然後，停止氫氣的供給，接著在氮氣孩 溫而得到經還原處理的觸媒。該觸媒，經還原读 流失率爲0.84%。 實施比較例1 (b)中的相同氧化反應，^ 用上面所得觸媒且將反應溫度改變3 2 〇 ac。表 得結果。 6.3毫米外 該等環置於 ί 1 2鉬原子 〇 . 4 8鉋原子 眞充 13毫升 氧/氮/蒸汽 5毫升/分鐘 :下實施氧化 ¥醛和甲基丙 一玻璃管內 氣體以200 還原處理5 下冷卻到室 理所致質量 同處在於使 1顯示出所 -13- 200734048 (10) 實施例2 實施實施例1中的相同程序，不同處爲將還原處理中 所用的氣體改爲氫氣/氮氣=20/80 (體積比），還原處理溫 度改爲400°C，且將還原處理時間改爲3小時而得到經還 原處理的觸媒。該觸媒經還原處理所致質量流失率爲 3.52%。 實施比較例1 ( b )中的相同氧化反應，不同處在於使 用上面所得觸媒且將反應溫度改爲320。(：。表1顯示出所 得結果。 實施例3 實施實施例1中的相同程序，不同處爲將還原處理中 所用的氣體改爲氫氣/氮氣=20/80 (體積比），且將還原處 理溫度改爲400°C而得到經還原處理的觸媒。該觸媒經還 原處理所致質量流失率爲6.42%。 然後在200毫升/分鐘的氮氣流下將溫度增高到200°C ，且於以2 00毫升/分鐘間續地供給空氣之同時，於8小 時之內將溫度進一步升高到400°C，於空氣流下將溫度保 持在400°C下1小時，之後將其冷卻到室溫而得到經空氣 煅燒的經還原處理觸媒。還原處理後的流失率加上空氣煅 燒後的流失率所致該觸媒的總質量流失率爲〇·3 6%。 實施比較例1 ( b )中的相同氧化反應’不同處在於使 用上面所得觸媒且將反應溫度改爲3 20 °C。表1顯示示所 -14- 200734048 (11) 得結果。 實施例4 將25克比較例1 ( a )中所得觸媒塡充到 ，且同時將異丁烯/氮氣/蒸汽=6· 8/80.6/1 2.6 ( 混合氣體以600毫升/分鐘的流速供給到該管內 實施還原處理5小時。然後，停止異丁烯和蒸 接著在氮氣流下冷卻到室溫而得到經還原處理 觸媒經還原處理所致質量流失率爲1 . 1 8 %。 實施比較例1 ( b )中的相同氧化反應，不 用上面所得觸媒且將反應溫度改爲32(TC。表 得結果。 實施例5 實施實施例4中的相同程序，不同處爲使 異丁烯經還原處理的步驟。該觸媒經還原處理 失率爲3 . 1 1 %。 實施比較例1 ( b )中的相同氧化反應，不 用上面所得觸媒且將反應溫度改爲3 00 °C。表 得結果。 實施例6 將25克比較例1 ( a )中所得觸媒塡充到 ，且同時將甲基丙烯醛/氮氣/蒸汽=4.3/78.2/17 一玻璃管內 體積比）的 ，於 3 66〇C 汽的供給， 的觸媒。該 同處在於使 1顯示出所 用乙醇取代 所致質量流 同處在於使 1顯示出所 一玻璃管內 • 5 (體積比 15- 200734048 (12) )的混合氣體以1 00毫升/分鐘的流速供給到該管內，於 3 66 °C實施還原處理2.5小時。然後，停止甲基丙烯醛和 蒸汽的供給，接著在氮氣流下冷卻到室溫而得到經還原處 理的觸媒。該觸媒經還原處理所致質量流失率爲〇·58%。 實施例較例1 ( b )中的相同氧化反應，不同處在於使 用上面所得觸媒且將反應溫度改爲320 °C。表1顯示出所 得結果。 表 1 還原處理 氧化反應 還原性物質 溫度 時間 質量流失率 溫度 轉化率 產率 CC) (小時） (%) (°C) (%) (%) 比較例1 • - 360 99.0 76.6 實施例1 氫氣 350 5 0.84 320 99.4 79.0 實施例2 氫氣 400 3 3.52 320 99.3 77.6 實施例3 氫氣* 400* 5* 0.36* 320 99.1 78.1 實施例4 異丁烯 366 5 1.18 320 99.5 77.4 實施例5 乙醇 366 5 3.11 300 98.0 77.9 實施例6 甲基丙烯醛 366 2.5 0.58 320 99.3 78.0 於還原處理之後，再度實施空氣煅燒 根據本發明，提供下列發明。 [1 ]一種製造觸媒的方法，該觸媒係供將選自丙烯、異 丁烯和第三丁醇之中的化合物在氣相中利用分子氧予以催 化性氧化而製備不飽和醛與不飽和羧酸，該觸媒包含含有 鉬、鉍和鐵的混合氧化物，其中係將一觸媒先質於包含分 子氧的氣體環境下煅燒；然後在還原性物質的存在下予以 •16- 200734048 (13) 熱處理。 [2]根據[1]之方法，其中該混合氧化物係由下面的通 式（1 )所示：MoaBibFecNidSbflSif2Tlg (a=12^0.1<b<5^0.5<c<5^5<d<10?0.0·1<f2<5, 0.01<g<l) as a raw material of the above catalyst A compound containing a component contained in a catalyst such as a salt acid salt, a sulfate, a carbonate, a hydroxide, an acid acid, and a wound, and a halide are used in order to satisfy a predetermined atomic example. For example, regarding the molybdenum compound, trimolybdic acid, ammonium molybdate, and the like can be used; the ruthenium compound can be ruthenium, lanthanum nitrate, barium sulfate, and the like; and related iron compounds, iron (III) nitrate, iron sulfate ( III) Iron(III) Chloride In the method for producing a catalyst according to the present invention, the catalyst precursor formed from the above is calcined in a gas atmosphere containing molecular oxygen, and heat-treated in the presence of Φ-derived material. The catalyst precursor is usually prepared by mixing the rice in water to produce an aqueous solution or a water slurry, and then drying the slurry. The solution or slurry can be dried by use of a lean, box dryer, drum type flow dryer, spray dryer, and the like. The concentration of the catalyst precursor thus obtained in the molecular environment containing molecular oxygen is usually from 1 to 30% by volume to 25% by volume. Regarding the source of molecular oxygen, the air domain is often used when needed, using nitrogen, carbon dioxide, water, nitrogen, 1-1 ratio of L compound, nitrate, etc.: ammonium oxide: molybdenum oxide, yttrium oxide can be used and the like ^The raw material is prepared and then calcined under the raw material [solution or water], kneading machine, flashing. Preferably, 10 5 pure oxygen, and gas, and the like -8 - 200734048 (5) are used after dilution, and the gas thus obtained is utilized as a gas containing molecular oxygen. The calcination temperature is usually from 300 to 600 ° C, preferably from 400 to 550 ° C. The calcination time is usually from 5 minutes to 40 hours, preferably from 1 hour to 20 hours. In the present invention, the calcined catalyst precursor obtained in the above calcination is heat-treated in a reducing substance (this treatment is sometimes referred to as a reduction treatment hereinafter). This reduction treatment can effectively improve the activity of the catalyst. Examples of the reducing substance include, for example, hydrogen, ammonia, carbon monoxide, hydrocarbons, alcohols, aldehydes, amines, and the like. This ® can be used in combination when needed. Preferably, the hydrocarbons, alcohols, aldehydes and amines each have from about 1 to about 6 carbon atoms. Examples of the hydrocarbon may include saturated aliphatic hydrocarbons such as methane, ethane, propane, n-butane and isobutane; unsaturated aliphatic hydrocarbons such as ethylene, propylene, α-butene, oxime-butene and isobutylene; benzene, and Similar. Examples of the alcohol may include saturated aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol; unsaturated aliphatic alcohols such as allyl alcohol , crotyl alcohol, and methyl allyl alcohol; phenol φ, and the like. Examples of the aldehyde may include saturated aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde; unsaturated aliphatic aldehydes such as acrolein, crotonaldehyde and methacrolein, and the like. Examples of the amine may include saturated aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, and triethylamine; unsaturated aliphatic amines such as allylamine and di-allylamine; aniline, and Similar. This reduction treatment is usually carried out by heat-treating the calcined catalyst precursor in a gas atmosphere containing the above-mentioned reducing substance. The concentration of the reducing substance in the gas is usually from 1 to 50% by volume, preferably from 1 to 50% by volume, 200734048 (6), more preferably from 3 to 30% by volume. The reducing substance may be diluted with nitrogen, carbon dioxide, water, nitrogen, argon or the like to have the above concentration. The gas may contain molecular oxygen in the range which does not impair the effectiveness of the reduction treatment, but it is generally preferred that it does not contain molecular oxygen. The reduction treatment temperature is usually from 200 to 600 ° C, preferably from 300 to 500 ° C. The reduction treatment time is usually from 5 minutes to 20 hours, preferably from 30 minutes to 10 hours. Preferably, the reduction treatment is carried out by passing the calcined catalyst precursor to a vessel such as a tubular vessel or a tank vessel, and passing a gas containing a reducing substance therethrough. In this case, the exhaust gas from the container can be recycled as needed. For example, the calcination catalyst precursor is charged into a reaction tube for gaseous catalytic oxidation, and an oxygen containing a reducing substance is passed therethrough for substantial reduction treatment, after which gas phase catalytic oxidation can be carried out. Generally, the mass of the catalyst is reduced after the reduction treatment, which may be caused by the loss of lattice oxygen from the precursor of the calcination catalyst. The mass loss rate is preferably from 0.05 to 6%, more preferably from 0.1 to 5%. Catalytic activity may be reduced in the event of excessive reduction and loss of mass φ too high. In this case, it is preferred to carry out calcination in a gas atmosphere containing molecular oxygen to lower the mass loss rate. The mass loss rate is calculated from the equation below. Mass loss rate (%) = [(mass of calcination catalyst precursor before reduction treatment, calcination catalyst mass after reduction treatment) / calcination catalyst mass before reduction treatment] X100 When treatment is carried out, treatment is carried out Thereafter, the reducing substance Ben-10 - 200734048 (7) and its decomposition products may be retained in the catalyst depending on the type used and the heat treatment conditions. In this case, the mass of the residual product in the individual is subtracted from the mass of the catalyst after the reduction treatment as the mass. Since the residual product is typically carbon, its mass can be measured by carbon (TC) measurements and the like. The catalyst is typically used after being formed into the desired shape. I are formed into rings, small nines, balls by pressing or extrusion molding. The forming can be carried out in a state before calcination in a molecular oxygen-containing gas atmosphere, and can be carried out after calcination, or in the form of reduction, in order to improve the mechanical strength of the catalyst, it can react with substantially inert inorganic fibers and the like. As described in JP-A. The thus obtained unsaturated aldehyde and unsaturated carboxylic acid have excellent catalytic activity. By using the catalyst, propylene can be catalytically oxidized in the φ phase to produce propionic acid in a good yield. Further, by using the catalyst, methyl methacrylate can be produced in a good yield by catalytic oxidation of molecular oxygen in olefin or tert-butanol. According to the catalytic oxidation in the gas phase, the catalyst is usually used in a multi-tubular reaction vessel, and then the supply of the gas containing the gas and the starting from the propylene, isobutylene and the third butanol can be used in the vessel. Bed reaction vessel. The air of molecular oxygen, and in addition to the starting compound and molecular oxygen, the starting catalyst for measuring the reducing agent contains residual catalyst after the catalyst is, for example, always better, and the catalyst of the similar ones Implemented after quality. Addition of the catalyst molecular oxygen used in the oxidation of -9-52053 to the isobutyl acrolein in the alkenal and propylene phases and the starting compound charged to the fixed bed oxygen. Also sources are usually gases containing -11 - 200734048 (8) nitrogen, carbon dioxide, carbon monoxide, steam and the like. The reaction temperature is usually from 250 to 400 ° C and the reaction pressure is 50 OkP a, but the reaction can also be carried out under reduced pressure. Molecular oxygen to 3 moles/mole of starting compound. The starting gas space is often 500 hrs based on STP (standard temperature and pressure). [Embodiment] Embodiments of the present invention are exemplified below, but the present invention is not limited thereto. In the examples, unless otherwise specified, the mark gas/minute is based on STP. Comparative Example 1 (a) Production of catalyst A 13,241 g of ammonium molybdate [(NH4)6Mo7024· was referred to as liquid A in 15,000 g of warm water. On the other 6,060 grams of iron (III) nitrate [Fe(N03) 3 · 9H20] cobalt nitrate [Co (N〇3 ) 2 · 6H20] and 585 grams of nitrate sleep dissolved in 6,000 grams of warm water, then, Dissolving therein bismuth nitrate [Bi(N〇3) 3 · 5H20], this is called liquid BA, and liquid B is added thereto to obtain a slurry, and then the slurry is dried to obtain a catalyst precursor. . 6 parts by mass of cerium oxide alumina fiber is added to 100 parts by mass (the amount of ITM Co camp is 100 to 1 usually 1 stem (SV) to 5,0 0 /min is not subject to the flow rate of these bodies 4H20] Dissolved on the one hand, 13,096 g of ochre [CsN〇3] 2,910 g. Stirring liquid was flash dried to dry the catalyst precursor, Ltd., manufactured by -12-200734048 (9), RFC (400- SL), and thereafter formed into a ring having a diameter, an inner diameter of 2.5 mm, and a length of 6 mm. The catalyst was obtained by calcination in a stream of air at 5 1 6 ° C for 6 hours. The catalyst ^ had 0.96 铋Atom, 2.4 iron atom, 7.2 Ming atom and (b) oxidation reaction in a glass reaction tube having an inner diameter of 18 mm, the catalyst obtained in the step (a), and the isobutene / =1/2.2/6 · 7 The mixed gas of /2.1 (mole ratio) is reacted at a reaction temperature of 360 ° C at a flow rate of 62 °. The conversion of isobutylene and methacrylic acid are shown in Table 1. The total yield was obtained. Example 1 50 g of the catalyst obtained in Comparative Example 1 (a) was charged, and at the same time, a flow rate of a hydrogen/nitrogen = 10/90 (volume ratio) mixed cc/min was supplied thereto. In the tube, it was taken for 3 hours at 3 5 。c. Then, the supply of hydrogen gas was stopped, and then the reduced catalyst was obtained under nitrogen gas temperature. The catalytic read loss rate of the catalyst was 0.84%. The same oxidation reaction in 1 (b), using the catalyst obtained above and changing the reaction temperature by 3 2 〇 ac. The results are shown. 6.3 mm outside the ring is placed on ί 1 2 molybdenum atom 〇. 4 8 planing atom 眞Charge 13 ml of oxygen/nitrogen/steam 5 ml/min: Under the oxidation of aldehyde and methyl propylene, the gas in the glass tube is treated with 200 reduction. The cooling is carried out to the room for the same quality, so that 1 shows the -13- 200734048 (10) Example 2 The same procedure as in Example 1 was carried out, except that the gas used in the reduction treatment was changed to hydrogen/nitrogen=20/80 (volume ratio), and the reduction treatment temperature was changed to 400 ° C, and The reduction treatment time was changed to 3 hours to obtain a reduced catalyst. The mass loss rate of the catalyst after reduction treatment was 3.52%. The same oxidation reaction in Comparative Example 1 (b) was carried out, except that the above was used. The resulting catalyst was changed to a reaction temperature of 320. (:. Table The results obtained are shown in Example 1. Example 3 The same procedure as in Example 1 was carried out, except that the gas used in the reduction treatment was changed to hydrogen/nitrogen = 20/80 (volume ratio), and the reduction treatment temperature was changed to 400. The reduced catalyst was obtained at ° C. The mass loss rate of the catalyst after reduction treatment was 6.42%. Then, the temperature was increased to 200 ° C under a nitrogen flow of 200 ml / minute, and while continuously supplying air at 200 ml / minute, the temperature was further raised to 400 ° C in 8 hours, in the air. The temperature was maintained at 400 ° C for 1 hour, and then cooled to room temperature to obtain an air-calcined reduced treatment catalyst. The total mass loss rate of the catalyst due to the wastage rate after the reduction treatment plus the loss rate after air calcination was 〇·3 6%. The same oxidation reaction in Comparative Example 1 (b) was carried out except that the catalyst obtained above was used and the reaction temperature was changed to 3 20 °C. Table 1 shows the results of -14- 200734048 (11). Example 4 25 g of the catalyst enthalpy obtained in Comparative Example 1 (a) was charged while isobutylene/nitrogen/steam = 6.8/80.6/1 2.6 (mixed gas was supplied thereto at a flow rate of 600 ml/min) The reduction treatment was carried out for 5 hours in the tube. Then, the isobutene was stopped and steamed and then cooled to room temperature under a nitrogen stream to obtain a mass loss rate of 1.1% by reduction treatment of the reduction catalyst. Comparative Example 1 (b) The same oxidation reaction in the above, without the catalyst obtained above and changing the reaction temperature to 32 (TC. The results are shown. Example 5 The same procedure as in Example 4 was carried out, except that the step of subjecting isobutylene to reduction treatment was carried out. The catalyst was subjected to reduction treatment loss of 3.1%. The same oxidation reaction in Comparative Example 1 (b) was carried out without using the catalyst obtained above and the reaction temperature was changed to 300 ° C. The results are shown. 25 g of the catalyst obtained in Comparative Example 1 (a) was charged, and at the same time, methacrolein/nitrogen/steam = 4.3/78.2/17 in a glass tube volume ratio), at 3 66 ° C Supply, the catalyst. The same place is to make 1 show the replacement of the ethanol used. The mass flow is the same as that: 1 shows that the mixed gas in a glass tube • 5 (volume ratio 15-200734048 (12)) is supplied to the tube at a flow rate of 100 ml/min, and is reduced at 3 66 °C. After 2.5 hours, the supply of methacrolein and steam was stopped, and then cooled to room temperature under a nitrogen stream to obtain a reduced catalyst. The mass loss rate of the catalyst after reduction treatment was 〇·58%. The same oxidation reaction as in Example 1 (b) was carried out except that the catalyst obtained above was used and the reaction temperature was changed to 320 ° C. Table 1 shows the results obtained. Table 1 Reduction treatment Oxidation reaction Reducing substance temperature time quality Loss Rate Temperature Conversion Rate Yield CC) (hours) (%) (°C) (%) (%) Comparative Example 1 • - 360 99.0 76.6 Example 1 Hydrogen 350 5 0.84 320 99.4 79.0 Example 2 Hydrogen 400 3 3.52 320 99.3 77.6 Example 3 Hydrogen* 400* 5* 0.36* 320 99.1 78.1 Example 4 Isobutylene 366 5 1.18 320 99.5 77.4 Example 5 Ethanol 366 5 3.11 300 98.0 77.9 Example 6 Methacrolein 366 2.5 0.58 320 99.3 78.0 Yu also Air calcination after the original treatment According to the present invention, the following invention is provided. [1] A method for producing a catalyst for catalytically oxidizing a compound selected from the group consisting of propylene, isobutylene and tert-butanol by molecular oxygen in a gas phase to prepare an unsaturated aldehyde and an unsaturated carboxylic acid Acid, the catalyst comprising a mixed oxide containing molybdenum, niobium and iron, wherein a catalyst is calcined in a gaseous environment containing molecular oxygen; and then in the presence of a reducing substance. 16-200734048 (13 ) Heat treatment. [2] The method according to [1], wherein the mixed oxide is represented by the following general formula (1):
MoaBibFecAdBeCfDgOx (1) 其中Mo、Bi和Fe分別爲鉬、鉍和鐵；A爲鎳及/或鈷；B 爲選自錳、鋅、鈣、鎂、錫和鉛之中的元素；C爲選自磷 、硼、砷、碲、鎢、銻、矽、鋁、鈦、鉻和鈽之中的元素 ，〇爲選自绅、細、絶和銳之中的兀素；當a=12’ 0<b<10 ，0<c<10 » l<d<10 ， 0<e<10 ， 0<f<10 > 且 0<g<2 ;且 x 爲 取決於每一元素的氧化態之値。 [3] 根據[1]或[2]之方法，其中該煅燒係在300至600 °C下實施。 [4] 根據[1]至[3]中任一者之方法，其中該熱處理係在 200至600°C下實施。 [5] 根據[1]至[4]中任一者之方法，其中經由該熱處理 所造成的質量流失率爲〇.〇5至6質量％。 [6] 根據[1]至[5]中任一者之方法，其中該還原性物質 爲選自下列之中的化合物：氫、氨、一氧化碳、具有1至 6個碳原子的烴、具有1至6個碳原子的醇、具有1至6 個碳原子的醛、和具有1至6個碳原子的胺。 [7] —種製造不飽和醛與不飽和羧酸的方法，該方法包 括下述步驟：藉由[1]至[6]中任一者之方法製造觸媒，然 -17- 200734048 (14) 後將選自丙烯、異丁烯和第三丁醇之中的化合物在氣相中 利用分子氧於該觸媒存在下予以催化性氧化。MoaBibFecAdBeCfDgOx (1) wherein Mo, Bi and Fe are molybdenum, niobium and iron, respectively; A is nickel and/or cobalt; B is an element selected from the group consisting of manganese, zinc, calcium, magnesium, tin and lead; and C is selected from the group consisting of An element of phosphorus, boron, arsenic, antimony, tungsten, strontium, barium, aluminum, titanium, chromium and strontium, strontium is selected from the group consisting of strontium, fine, absolute and sharp; when a=12' 0< b < 10 , 0 < c < 10 » l < d < 10 , 0 < e < 10 , 0 < f < 10 > and 0 < g <2; and x is dependent on the oxidation state of each element. [3] The method according to [1] or [2], wherein the calcination system is carried out at 300 to 600 °C. [4] The method according to any one of [1] to [3] wherein the heat treatment is carried out at 200 to 600 °C. [5] The method according to any one of [1] to [4] wherein the mass loss rate by the heat treatment is 〇. 5 to 6 mass%. [6] The method according to any one of [1] to [5] wherein the reducing substance is a compound selected from the group consisting of hydrogen, ammonia, carbon monoxide, a hydrocarbon having 1 to 6 carbon atoms, having 1 An alcohol having 6 carbon atoms, an aldehyde having 1 to 6 carbon atoms, and an amine having 1 to 6 carbon atoms. [7] A method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, the method comprising the steps of: producing a catalyst by the method of any one of [1] to [6], and -17-200734048 (14) The compound selected from the group consisting of propylene, isobutylene and tert-butanol is then catalytically oxidized in the gas phase using molecular oxygen in the presence of the catalyst.
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