200304853 (1) 玖、發明說明 【發明所屬之技術領域】 本發明爲關於不飽和醛類和/或不飽和羧酸之製造方 法。詳言之，爲關於使用塡充觸媒的固定床多管式反應器 ' ，且以丙烯、異丁烯、第三丁醇及甲基第三丁醚中選出之 至少一種化合物做爲原料，且經由分子狀氧氣或含分子狀 氧氣之氣體進行氣相接觸氧化，則可製造不飽和醛類和/ 或不飽和羧酸之方法。 φ 【先前技術】 關於使用塡充觸媒之固定床多管式反應器，且以丙烯 、異丁烯、第三丁醇及甲基-第三丁醚中選出之至少一種 化合物做爲原料’且經由分子狀氧氣或含分子狀氧氣之氣 體進行氣相接觸氧化，則可製造其分別對應之不飽和醛類 和/或不飽和羧酸之方法迄今已報導出數個提案（例如， 特公昭53- 30688號公報、特公昭63- 38331號公報、特 開平3- 29423 8號公報、特開平3_ 294239號公報、特開 平4· 217932號公報、特開平8- 3〇93號公報、特開平ίο· 168〇03號公報等），其中亦有已被工業上實施之方法。 此氣相接觸氧化反應爲伴隨非常的發熱反應，故於觸 媒層發生局部性的異常高溫部（以下，稱爲熱點部）。特 別’實施使用固定床多管式反應器之氧化反應上，並無法 避免觸媒層中熱點部的發生。 熱點部之溫度若高，則引起過度的氧化反應且產率降 -5- (2) (2)200304853 低，且於最壞之情況恐引起暴走反應。又，位於熱點部之 觸媒爲被曝露於高溫，故觸媒的物理性質及化學性質變化 ，令活性和目的產物之選擇降低等之觸媒惡化爲被加速。 特別，鉬系觸媒之情況，因爲鉬成分爲昇華且觸媒組成物 性易變化，故觸媒惡化之程度大。 上述之問題在以提高目的產物之生產性爲目的，且於 高空間速度下進行反應、和於高原料氣體濃度下進行反應 之情形中，更加顯著。 關於上述問題，若著眼於反應管中所塡充之觸媒層全 體，則位於熱點部之觸媒爲比其他部分之觸媒惡化更快， 經由長時間使用則目的產物之產率顯著降低，且難以安定 進行製造。如前述般，鉬系觸媒之情況、和於高空間速度 下進行反應和於高原料氣體濃度下進行反應之情況，觸媒 的惡化程度特別大。 【發明內容】 [發明所欲解決之課題] 前述先前公知的任一種提案，均爲著眼於壓低熱點部 溫度之提案。但是，實施使用固定床多管式反應器之氧化 反應時，於觸媒層並無法完全不發生熱點部，並無法解決 位於熱點部之觸媒惡化程度爲比位於其他部分之觸媒惡化 程度相對大之問題。特別，於使用鉬系觸媒之情況和高原 料氣體濃度下進行反應之情況中，此問題顯著。 因此，本發明之課題爲在於提供經由使用塡充鉬系觸 (3) (3)200304853 媒之固定床多管式反應器之氣相接觸氧化反應，製造不飽 和醛類和/或不飽和羧酸之情形中，抑制位於熱點部之觸 媒惡化，且於不取決於熱點部爲於何處發生和、原料氧體 濃度爲高之情形中，亦可一邊維持高產率一邊長期繼續反 應之方法。 [用以解決課題之手段] 本發明者爲了解決上述課題而進行致力檢討。其結果 ’著眼於相對於觸媒真密度之觸媒表觀密度比R (觸媒之 表觀密度/觸媒之真密度），並發現此R相對高之觸媒爲 比低觸媒即使於高溫中曝露亦令惡化程度小。於是，想到 準備R爲不同的觸媒，且經由將R高之觸媒以位於熱點 部和其附近般進行塡充，則可解決上述課題。 即，本發明之不飽和醛類和/或不飽和羧酸之製造方 法爲以使用塡充觸媒之固定床多管式反應器，且以丙烯、 異丁烯、第三丁醇、及甲基-第三丁醚中選出之至少一種 化合物做爲原料，並經由分子狀氧氣或含分子狀氧氣之氣 體進行氣相接觸氧化，製造對應原料之不飽和醛類和/或 不飽和羧酸之方法中，前述觸媒爲使用鉬、鉍及鐵做爲必 須成分之氧化物和/或複合氧化物，且將前述固定床多管 型反應器之各反應管內部於管軸方向上分割設置複數個反 應帶。並且於各反應帶中，分別塡充相對於觸媒真密度之 觸媒表觀密度比R (觸媒之表觀密度/觸媒之真密度）爲不 同的前述觸媒爲其特徵。 (4) (4)200304853 [發明之實施形態] _ 本發明所使用之以鉬、鉍及鐵做爲必須成分之觸媒， 若爲以丙烯、異丁烯、第三丁醇及甲基-第三丁醚中選出 ‘ 之至少一種化合物做爲原料，且經由氣相接觸氧化反應製 造對應之不飽和醛類和/或不飽和羧酸者則均可使用，並 以下述一般式（1)所示之複合氧化物觸媒爲適於使用。200304853 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for producing unsaturated aldehydes and / or unsaturated carboxylic acids. In detail, it is a fixed-bed multi-tubular reactor using a tritium-filled catalyst, using at least one compound selected from propylene, isobutylene, tertiary butanol, and methyl tertiary butyl ether as a raw material, and The method of producing unsaturated aldehydes and / or unsaturated carboxylic acids by molecular phase oxygen or gas containing molecular oxygen by gas phase contact oxidation. φ [Prior art] A fixed-bed multi-tubular reactor using a tritium-filled catalyst, using at least one compound selected from propylene, isobutylene, tertiary butanol, and methyl tertiary butyl ether as a raw material ', and via If molecular oxygen or a gas containing molecular oxygen is subjected to gas-phase contact oxidation, a method for producing the corresponding unsaturated aldehydes and / or unsaturated carboxylic acids, respectively, has been reported. So far, several proposals have been reported (for example, Special Publication 53- Gazette No. 30688, Gazette No. 63-38331, Gazette No. 3--29423 8, Gazette No. 3_294239, Gazette No. 4 217932, Gazette No. 8-30893, Gazette No. 8 No. 16803, etc.), among which there are also methods that have been implemented industrially. Since this gas-phase contact oxidation reaction is accompanied by an exothermic reaction, a locally abnormally high temperature portion (hereinafter, referred to as a hot spot portion) occurs in the catalyst layer. In particular, the implementation of an oxidation reaction using a fixed-bed multitubular reactor cannot prevent the occurrence of hot spots in the catalyst layer. If the temperature of the hot spot is high, it will cause excessive oxidation reaction and decrease the yield. -5- (2) (2) 200304853 is low, and in the worst case, it may cause a runaway reaction. In addition, the catalyst located in the hot spot is exposed to high temperature, so the physical and chemical properties of the catalyst change, and the catalyst, such as the reduction of the activity and the choice of the target product, is accelerated. In particular, in the case of a molybdenum-based catalyst, since the molybdenum component is sublimated and the properties of the catalyst composition are liable to change, the degree of deterioration of the catalyst is large. The above problems are more significant in the case where the reaction is performed at a high space velocity and the reaction is performed at a high raw material gas concentration for the purpose of improving the productivity of the target product. Regarding the above problems, if the entire catalyst layer filled in the reaction tube is focused on, the catalyst located in the hot spot will deteriorate faster than the catalyst in other parts. After a long time use, the yield of the target product will be significantly reduced. It is also difficult to manufacture stably. As described above, in the case of the molybdenum-based catalyst, and in the case where the reaction is performed at a high space velocity and the reaction is performed at a high raw material gas concentration, the catalyst is particularly deteriorated. [Summary of the Invention] [Problems to be Solved by the Invention] Any of the previously known proposals is a proposal focusing on reducing the temperature of a hot spot. However, when an oxidation reaction using a fixed-bed multitubular reactor is carried out, a hot spot cannot be completely prevented from occurring in the catalyst layer, and it is impossible to solve the deterioration of the catalyst located in the hot spot compared to the deterioration of the catalyst located in other parts. The big question. In particular, this problem is significant in the case where a molybdenum-based catalyst is used and the reaction is performed under a plateau gas concentration. Therefore, the subject of the present invention is to provide a gas-phase contact oxidation reaction through a fixed-bed multi-tubular reactor using a rhenium-filled molybdenum-based contact (3) (3) 200304853 medium to produce unsaturated aldehydes and / or unsaturated carboxylic acids. In the case of acid, it is possible to suppress the deterioration of the catalyst located in the hot spot and to continue the reaction for a long period of time while maintaining a high yield without depending on where the hot spot occurs and the concentration of the raw material oxygen is high. . [Means for Solving the Problems] The present inventors have conducted an intensive review in order to solve the problems described above. The result 'looks at the catalyst apparent density ratio R (the apparent density of the catalyst / the true density of the catalyst) relative to the catalyst's true density, and finds that this catalyst with a relatively high R is lower than the catalyst even with Exposure to high temperatures also causes less deterioration. Therefore, it is thought to prepare different catalysts for R, and to charge the catalysts with high R so that they are located near the hot spot and the vicinity thereof, and the above problems can be solved. That is, the method for producing the unsaturated aldehydes and / or unsaturated carboxylic acids of the present invention is a fixed-bed multitubular reactor using a tritium-filled catalyst, and using propylene, isobutylene, third butanol, and methyl- At least one compound selected from the third butyl ether is used as a raw material, and a method for producing unsaturated aldehydes and / or unsaturated carboxylic acids corresponding to the raw material by gas-phase contact oxidation through molecular oxygen or a gas containing molecular oxygen is used. The catalyst is an oxide and / or a composite oxide using molybdenum, bismuth, and iron as essential components, and a plurality of reactions are divided and arranged in the tube axis direction in each reaction tube of the fixed-bed multi-tube reactor. band. And in each reaction zone, it is characteristic that the catalyst apparent density ratio R (the apparent density of the catalyst / the true density of the catalyst) is different with respect to the true density of the catalyst. (4) (4) 200304853 [Embodiments of the invention] _ The catalyst used in the present invention is made of molybdenum, bismuth and iron as essential components, if it is propylene, isobutylene, third butanol and methyl-third At least one compound selected from butyl ether is used as a raw material, and the corresponding unsaturated aldehydes and / or unsaturated carboxylic acids can be used through gas-phase contact oxidation reaction, and can be used as shown in the following general formula (1) The composite oxide catalyst is suitable for use.
MoaWbBicFedAeBfCgDhEiOx (1) · (此處，Mo爲鉬，W爲鎢，Bi爲鉍，Fe爲鐵，A爲 由鈷及鎳中選出之至少一種元素，B爲由鈉、鉀、銷]、鉋 及鉈中選出之至少一種元素，C爲由硼、磷、鉻、錳、鋅 、砷、鈮、錫、銻、碲、鈽及鉛中選出之至少一種元素， D爲由矽、鋁、鈦及鉻中選出之至少一種元素，E爲由鹼 土金屬中選出之至少一種元素，Ο爲氧，a、b、c、d、e 、f、g、h、i 及 x 分別表示 Mo、W、Bi、Fe、A、B、C 、D、E 及 〇 之原子比，a·· 12 時，0SbS5、0.1$b$5、 _ O.lScSIO、0.1$dS20、l$e$20、0.001$f$5、OSg $10、0Sh$30、0$i^5、x爲根據各個元素之氧化狀態 所決定之數値）。 關於上述觸媒成分元素的起始原料並無特別限制，且 . 一般爲此種觸媒所使用之金屬元素的銨鹽、硝酸鹽、碳酸 鹽、氯化物、硫酸鹽、氫氧化物、有機酸鹽、氧化物或將 彼等之混合物組合使用亦可，但以銨鹽及硝酸鹽爲較佳使 用0 -8- (5) (5)200304853 觸媒原料鹽之混合水溶液或水性流漿可根據此種觸媒 所一般使用之方法進行調製，例如，以上述觸媒原料做爲 . 水溶液，並且將其依序混合即可。關於觸媒原料之混合條 件（混合順序、溫度、壓力、pH等）並無特別限制。如 · 此處理所得之觸媒原料鹽之混合水溶液或水性流漿有時視 需要進行濃縮乾燥，取得餅狀固形物。前述觸媒原料鹽混 合水溶液、水性流漿或餅狀固形物爲被加熱處理，取得觸 媒前體P1。 · 關於取得觸媒前體P1的加熱處理方法及觸媒前體的 形態並無特別限定，例如可使用噴霧乾燥器、鼓式乾燥器 等取得粉末狀之觸媒前體，且亦可使用箱型乾燥機、隧道 型乾燥機等在氣流中加熱取得塊狀或片狀之觸媒前體。 觸媒前體P 1較佳以減量率爲1 〇質量％以上且未滿 4 0質量％ 、更佳爲1 3質量％以上3 7質量％以下，再 佳爲1 5質量％以上3 5質量％以下般設定加熱處理條件 。但是，即使減量率爲上述範圍外之情況亦可使用。 · 觸媒前體之減量率爲將觸媒前體P1均勻混合且精秤 約1 〇克，並將其在空氣氛圍氣下以3 00 °C加熱1小時且 由下述算出。 減量率（質量％ )=(觸媒前體質量-加熱後之觸媒前 ， 體質量）/觸媒前體質量χίοο 減量部分爲經由加熱處理於分解、揮發、昇華之觸媒 * 前體P1中殘存的硝酸根、銨根等及水分。（意指觸媒前 體P1所含有之硝酸鹽、銨鹽爲經由高溫下加熱分解並由 -9 - (6) (6)200304853 觸媒前體P1中被除去。即，減量率愈高則含有愈高比例 之硝酸鹽、銨鹽等）。 上述之加熱處理條件爲根據加熱裝置（乾燥機）之種 類和加熱裝置之特性而適當選擇，無法一槪特定，例如’ 使用箱型乾燥機時，觸媒前體例如於氣體流通下，以23 0 °C以下之溫度進行3〜24小時加熱處理亦可取得。 如上述調整至較佳減量率的觸媒前體P1爲視需要經 過取得適當粒度之粉碎步驟和分級步驟，且接著送至成型 步驟。 對於減量率被調整至上述較佳範圍內之觸媒前體P1 ，接著添加、混合黏合劑，作成觸媒前質P2。 對於觸媒前體P1添加、混合之黏合劑種類並無特別 限定，可列舉例如觸媒成型中可使用之公知的黏合劑，較 佳爲水。 對於觸媒前體P1添加、混合之黏合劑份量，較佳爲 對於觸媒前體P1添加、混合之水量相對於該觸媒前體P1 之100質量份，較佳爲5質量份以上30質量份以下，更 佳爲8質量份以上27質量份以下，再佳爲1 1質量份以上 24質量份以下。 添加量若多於3 0質量份，則觸媒前體P2之成型性惡 化，且有時無法成型。添加量若未滿5質量份，則觸媒前 體P 2彼此間的結合弱’且本身無法成型或即使可成型， 亦令觸媒的機械強度降低。擠壓成型時，最壞之情況爲成 型機損壞。 -10- (7) (7)200304853 於觸媒前體P1中所添加之水可爲各種物質的水溶液 和各種物質與水之混合物形式均可添加。 與水共同添加之物質可列舉令成型性提高之成型助劑 ，令觸媒強度提高之增強劑和黏合劑，令觸媒形成細孔之 氣孔形成劑等一般使用之物質。此些物質爲經由添加對觸 媒性能（活性、目的產物之選擇性）不造成不良影響者爲 佳。即，（i)煅燒後未於觸媒中殘存物質的水溶液或與 水的混合物、（Π)煅燒後即使於觸媒中殘存亦對觸媒性 能不造成不良影響之物質所構成的水溶液或與水的混合物 〇 上述 （i)之具體例可列舉乙二醇、甘油、丙酸、馬 來酸、苄醇、丙醇、丁醇或苯酚等之有機化合物和硝酸、 硝酸銨、碳酸銨等。 上述（Π)之具體例可列舉一般已知做爲增強劑的矽 石、氧化鋁、玻璃纖維、碳化矽、氮化矽等。若根據本發 明則所製造之觸媒雖具有實用上充分的機械強度，但於再 必須更高機械強度之情況，則添加此些增強劑。 此些物質於添加量爲過剩之情況，則觸媒的機械強度 顯著降低，故在做爲工業觸媒之不可能實用程度爲止添加 不會令觸媒的機械強度降低程度之份量爲佳。 以上述各種物質之水溶液和各種物質與水之混合物型 式添加時，例如，對100質量份之觸媒前體P1，添加20 質量份之5質量％乙二醇水溶液並且予以成型時，於P1 中所添加之水量爲20x (1- 0.05) = 19質量份。 (8) (8)200304853 於本發明中所使用之觸媒可爲將觸媒前體P2成型爲 一定形狀的成型觸媒、或將觸媒前體P2於具有一定形狀 之任意惰性載體上承載的承載觸媒、或者此些成型觸媒與 承載型觸媒的組合，較佳爲將觸媒前體P2成型爲一定形 狀的成型觸媒。 關於上述觸媒之形狀並無特別限制，可爲球狀、圓柱 狀（九狀）、環狀、不定形等任何形狀。當然，球狀之情 況並非必須爲正球狀，而爲實質上呈球狀即可。關於圓柱 狀及環狀亦爲相同。又，於各反應帶中塡充之觸媒形狀可 爲相同、或爲不同亦可（例如，氣體入口側：球狀觸媒、 氣體出口側：九狀觸媒），但通常塡充相同形狀之成型觸 媒或相同形狀之承載型觸媒爲佳。 關於上述觸媒之大小於觸媒形狀爲球狀之情況，平均 觸媒粒徑爲1〜15mm爲佳，更佳爲1〜l〇mm，再佳爲3 〜10mm，再更佳爲3〜8mm之大小爲適於使用。 觸媒之細孔容積較佳爲0.2〜0.6cm3/g，更佳爲0.25 〜0.55m3/g 〇 承載觸媒之情況，對於載體材質本身並無特別限制， 於將丙烯醛類予以氣相氧化製造丙烯酸之製造觸媒時所通 常可用的載體均可使用。可使用載體之具體例可列舉氧化 銘、砂石、砂石-氧化銘、二氧化駄、氧化鎂、砂石-氧 化鎂、矽石-氧化鎂-氧化鋁、碳化矽、氮化矽、沸石等 〇 承載觸媒之情況，於各反應帶中塡充觸媒的承載率爲 -12- (9) (9)200304853 考慮氧化反應條件、觸媒活性、及強度等，適當決定取得 最適的活性及選擇性，但較佳爲5〜9 5 % ，更佳爲2 0〜 90% ，特佳爲30〜85% 。 還有’於本發明中，觸媒之承載率爲根據下式算出。 承載率（％ ) =[(锻燒後之觸媒重量-載體重量）/煅燒後之觸媒重 量]X 100 關於調製觸媒時之熱處理條件（所謂煅燒條件）亦無 特別限制，且於此種觸媒製造中可應用一般所採用的煅燒 條件。於各反應帶塡充之觸媒的熱處理溫度可爲相同或相 異，且熱處理溫度較佳爲350〜6〇〇 。(：，更佳爲400〜 5 5 0 °C，熱處理時間較佳爲1〜1 〇小時。 觸媒之成型方法可爲先前公知的方法，可應用例如擠 壓成型法、打錠成型法、造粒法（轉動造粒裝置、離心流 動塗層裝置）、揉圓法等之成型方法。其中以擠壓成型法 爲適當。 於本發明之不飽和醛類和/或不飽和羧酸之製造方法 中’將固定床多管式反應器之各反應管內部於管軸方向上 分割’設置複數個之反應帶，並於此各反應帶中，分別塡 充相對於觸媒真密度之觸媒表觀密度比R (觸媒之表觀密 度/觸媒之真密度）爲不同的前述觸媒爲其特徵。 還有’本發明中，觸媒之表觀密度=W (1/真密度+ 細孔容積）。 又’令載體承載觸媒活性物質之所謂承載型觸媒之情 (10) (10)200304853 形中，以任意方法僅由載體表面剝離觸媒活性物質，並且MoaWbBicFedAeBfCgDhEiOx (1) · (Here, Mo is molybdenum, W is tungsten, Bi is bismuth, Fe is iron, A is at least one element selected from cobalt and nickel, B is made of sodium, potassium, pin], planed and At least one element selected from hafnium, C is at least one element selected from boron, phosphorus, chromium, manganese, zinc, arsenic, niobium, tin, antimony, tellurium, thallium and lead, and D is selected from silicon, aluminum, titanium and At least one element selected from chromium, E is at least one element selected from alkaline earth metals, 0 is oxygen, a, b, c, d, e, f, g, h, i, and x represent Mo, W, Bi, respectively Atomic ratios of Fe, A, B, C, D, E and 0, at a · 12, 0SbS5, 0.1 $ b $ 5, _ O.lScSIO, 0.1 $ dS20, l $ e $ 20, 0.001 $ f $ 5, OSg $ 10, 0Sh $ 30, 0 $ i ^ 5, x is a number determined according to the oxidation state of each element 値). There are no particular restrictions on the starting materials of the above-mentioned catalyst component elements, and they are generally ammonium salts, nitrates, carbonates, chlorides, sulfates, hydroxides, organic acids of metal elements used in such catalysts It is also possible to use salts, oxides, or a combination of these mixtures, but ammonium salts and nitrates are preferred. 0 -8- (5) (5) 200304853 A mixed aqueous solution or aqueous slurry of catalyst raw materials can be used according to This catalyst is generally prepared by a method, for example, the above catalyst raw material is used as an aqueous solution, and it can be sequentially mixed. There are no particular restrictions on the mixing conditions (mixing sequence, temperature, pressure, pH, etc.) of the catalyst materials. For example, the mixed aqueous solution or aqueous slurry of the catalyst raw material salt obtained in this treatment may be concentrated and dried as necessary to obtain a cake-like solid. The catalyst raw material salt mixed aqueous solution, aqueous slurry, or cake-like solid is heat-treated to obtain a catalyst precursor P1. · There is no particular limitation on the heat treatment method for obtaining the catalyst precursor P1 and the form of the catalyst precursor. For example, a powdered catalyst precursor can be obtained using a spray dryer, a drum dryer, or the like, and a box can also be used. Type dryers, tunnel dryers, etc. are heated in the air stream to obtain block or sheet catalyst precursors. The catalyst precursor P 1 preferably has a weight loss rate of 10 mass% or more and less than 40 mass%, more preferably 13 mass% or more and 37 mass% or less, and still more preferably 15 mass% or more and 35 mass. The heat treatment conditions are set as below%. However, it can be used even when the reduction rate is outside the above range. · The reduction ratio of the catalyst precursor is uniformly mixed with the catalyst precursor P1 and finely weighed about 10 grams, and it is heated at 300 ° C in an air atmosphere for 1 hour and calculated from the following. Weight reduction rate (mass%) = (mass of catalyst precursor-mass of catalyst before heating) / mass of catalyst precursor χίοο The reduction is the decomposition, volatilization, and sublimation of the catalyst through heating treatment * precursor P1 Residual nitrate, ammonium, etc. and moisture. (It means that the nitrate and ammonium salts contained in the catalyst precursor P1 are decomposed by heating at high temperature and are removed from the catalyst precursor P1. That is, the higher the reduction rate, the Contains a higher proportion of nitrate, ammonium, etc.). The above-mentioned heat treatment conditions are appropriately selected according to the type of heating device (dryer) and the characteristics of the heating device, and cannot be specified at one time. For example, when using a box-type dryer, the catalyst precursor is, for example, under a gas flow, with a temperature of 23 It can also be obtained by heating for 3 to 24 hours at a temperature below 0 ° C. The catalyst precursor P1 adjusted to a better weight reduction rate as described above is subjected to a pulverization step and a classification step to obtain an appropriate particle size as necessary, and then sent to a molding step. For the catalyst precursor P1 whose weight loss rate is adjusted to be within the above-mentioned preferred range, a binder is then added and mixed to form a catalyst precursor P2. The type of the binder to be added and mixed in the catalyst precursor P1 is not particularly limited, and examples thereof include a known binder that can be used in catalyst molding, and water is more preferred. The amount of the binder added and mixed for the catalyst precursor P1 is preferably 100 parts by mass of the water added to and mixed with the catalyst precursor P1 relative to the catalyst precursor P1, and preferably 5 parts by mass or more and 30 parts by mass It is more preferably 8 parts by mass or more and 27 parts by mass or less, and still more preferably 11 parts by mass or more and 24 parts by mass or less. If the added amount is more than 30 parts by mass, the moldability of the catalyst precursor P2 is deteriorated, and molding may not be performed in some cases. If the added amount is less than 5 parts by mass, the binding of the catalyst precursors P 2 to each other is weak 'and the molding cannot be formed by itself, or even if it can be formed, the mechanical strength of the catalyst is reduced. The worst case during extrusion is damage to the molding machine. -10- (7) (7) 200304853 The water added to the catalyst precursor P1 can be added as an aqueous solution of various substances and as a mixture of various substances and water. Examples of substances commonly added with water include commonly used substances such as molding auxiliaries that improve moldability, enhancers and adhesives that improve catalyst strength, and pore-forming agents that form fine pores in catalysts. These substances are preferably added to the catalyst performance (activity, selectivity of the target product) without adverse effects. That is, (i) an aqueous solution or a mixture with water that does not remain in the catalyst after calcination, (ii) an aqueous solution composed of a substance that does not adversely affect the catalyst performance even after remaining in the catalyst after calcination, or Mixtures of water. Specific examples of the above (i) include organic compounds such as ethylene glycol, glycerol, propionic acid, maleic acid, benzyl alcohol, propanol, butanol, or phenol; nitric acid, ammonium nitrate, and ammonium carbonate. Specific examples of the above (Π) include silica, alumina, glass fiber, silicon carbide, silicon nitride, and the like generally known as reinforcing agents. If the catalyst produced in accordance with the present invention has practically sufficient mechanical strength, if a higher mechanical strength is required, these reinforcing agents are added. When the amount of these substances is excessive, the mechanical strength of the catalyst is significantly reduced. Therefore, it is better to add the amount that does not reduce the mechanical strength of the catalyst to the extent that it is impossible to use it as an industrial catalyst. When added in the form of an aqueous solution of various substances and a mixture of various substances and water, for example, when 100 parts by mass of the catalyst precursor P1 is added, and 20 parts by mass of a 5% by mass ethylene glycol aqueous solution is added and molded, it is added in P1. The amount of water added is 20x (1- 0.05) = 19 parts by mass. (8) (8) 200304853 The catalyst used in the present invention can be a shaped catalyst that forms the catalyst precursor P2 into a certain shape, or the catalyst precursor P2 can be carried on any inert carrier having a certain shape. The supporting catalyst, or a combination of these shaped catalysts and a supporting catalyst, is preferably a shaped catalyst in which the catalyst precursor P2 is shaped into a certain shape. The shape of the catalyst is not particularly limited, and may be any shape such as a spherical shape, a cylindrical shape (nine shape), a ring shape, and an irregular shape. Of course, the spherical shape does not have to be exactly spherical, but may be substantially spherical. The same applies to the cylindrical shape and the ring shape. In addition, the shape of the charged catalysts in each reaction zone may be the same or different (for example, the gas inlet side: a spherical catalyst, the gas outlet side: a nine-shaped catalyst), but usually the same shape. Molded catalysts or bearing catalysts of the same shape are preferred. Regarding the size of the catalyst when the catalyst shape is spherical, the average catalyst particle diameter is preferably 1 to 15 mm, more preferably 1 to 10 mm, even more preferably 3 to 10 mm, and even more preferably 3 to The size of 8mm is suitable for use. The pore volume of the catalyst is preferably 0.2 to 0.6 cm3 / g, and more preferably 0.25 to 0.55 m3 / g. When the catalyst is supported, there is no particular limitation on the carrier material itself, and acrolein is subjected to gas phase oxidation. Any carrier generally usable in the production of acrylic catalysts can be used. Specific examples of the carrier that can be used include oxide oxide, sandstone, sandstone-oxide oxide, hafnium dioxide, magnesium oxide, sandstone-magnesium oxide, silica-magnesium oxide-alumina, silicon carbide, silicon nitride, and zeolite. Waiting for the catalyst to be supported, the loading rate of the catalyst in each reaction zone is -12- (9) (9) 200304853 Considering the oxidation reaction conditions, catalyst activity, and strength, etc., it is appropriately determined to obtain the optimal activity. And selectivity, but preferably 5 to 95%, more preferably 20 to 90%, and particularly preferably 30 to 85%. In addition, in the present invention, the load factor of the catalyst is calculated by the following formula. Load factor (%) = [(Weight of catalyst after calcination-weight of carrier) / weight of catalyst after calcination] X 100 There are no special restrictions on the heat treatment conditions (the so-called calcination conditions) when the catalyst is prepared, and here In the manufacture of this catalyst, the commonly used calcining conditions can be applied. The heat treatment temperature of the catalyst charged in each reaction zone may be the same or different, and the heat treatment temperature is preferably 350 ~ 600. (:, More preferably 400 to 550 ° C, and heat treatment time is preferably 1 to 10 hours. The catalyst molding method may be a conventionally known method, and for example, an extrusion molding method, an ingot molding method, Granulation method (rotating granulation device, centrifugal flow coating device), kneading method, etc. Among them, extrusion molding method is suitable. Production of unsaturated aldehydes and / or unsaturated carboxylic acids in the present invention In the method, 'the interior of each reaction tube of the fixed-bed multi-tubular reactor is divided in the direction of the tube axis', a plurality of reaction zones are set, and in each of the reaction zones, catalysts corresponding to the true density of the catalyst are filled respectively. The apparent density ratio R (the apparent density of the catalyst / the true density of the catalyst) is characterized by the aforementioned catalyst being different. Also, in the present invention, the apparent density of the catalyst = W (1 / true density + Pore volume). Also, the so-called carrier-type catalyst (10) (10) 200304853 in which the carrier carries the catalyst active substance is that the catalyst active substance is peeled off only from the surface of the carrier by any method, and
僅測定觸媒活性物質之真密度及細孔容積且由上式算出R 〇 經由如此塡充相對於真密度之觸媒表觀密度比R爲不 同的觸媒，經由使用塡充鉬系觸媒之固定床多管式反應器 之氣相接觸氧化反應，製造不飽和醛類和/或不飽和羧酸 之情形中，不取決於熱點部爲於何處發生，又，於原料氣 體濃度爲高之情形中，可一邊維持高產率一邊長期繼續反 應。 相對於真密度之觸媒表觀密度比R爲不同之觸媒的製 造方法並無特別限定，例如，可根據如下之方法（1) 〜 (4)或其組合進行製造。 (1) 改變觸媒前體之減量率則可改變R。減量率若低 ，則觸媒之細孔形成減少，故觸媒的表觀密度變高。若觸 媒組成未極端改變，則即使製造方法改變亦不會令真空度 變化，故減量率若低則R變大。相反地，減量率若高，則 觸媒的表現密度變低，故R變小。 (2) 控制觸媒中添加之細孔形成劑的種類和/或添加 量。若對觸媒添加具有形成細孔作用之細孔形成劑，且其 添加量相對減少，則表現密度變高，R變大。相反地，若 添加量爲相對變多，則R變小。又，經由改變細孔形成劑 之種類亦可控制R。 (3) 改變R之效果雖小，但若改變觸媒組成（使用做 爲觸媒原料之金屬種類和添加比例），則真密度改變，故 -14- (11) (11)200304853 R亦改變。 (4)經由改變成型時之壓力亦可控制R。例如，打錠 . 成型之情況，若增高打壓則R變大’若降低打壓則R變 小。又，擠壓成型之情況，若增高擠出壓力則R變大，若 ‘ 降低擠出壓力則R變小。 相對於本發明所用觸媒之真密度之表觀密度比R (觸 媒之表觀密度/觸媒之真密度）之範圍並無特別限定，較 佳爲0.25〜0.55，更佳爲0.30〜0.50。 _ 相對於觸媒真密度之表觀密度比爲未滿0.25時，隨 著細孔容積之增加令細孔內擴散效率上升，此時，雖然觸 媒活性及對於目的產物之選擇率提高，但觸媒強度顯著降 氐，故爲不佳。 相對於觸媒真密度之表觀密度比大於〇 . 5 5時，則與 上述相反，觸媒強度雖提高，但觸媒活性及對於目的產物 之選擇率顯著降低，故爲不佳。 於本發明中，將固定床多管式反應器之各反應管內部 ® 於管軸方向上分割設置複數個反應帶，並且於此些複數個 反應帶中塡充根據上述方法所調製之R爲不同的複數個觸 關於上述塡充配置之方法並無特別限定，可列舉例如 . 由氣體入口側朝向氣體出口側以R爲變成更小般塡充的配 置、和由氣體入口側朝向氣體出口側以R爲暫時變大後變 小般塡充的配置等，較佳爲將R不同的觸媒由各反應管之 氣體入口側朝向氣體出口側以R爲變成更小般配置。即， -15- (12) (12)200304853 將R最大之觸媒配置於氣體入口側，則R最小之觸媒配 置於氣體出口側。又，由氣體入口側朝向氣體出口側以R . 爲暫時變大後變小般塡充配置中，氣體入口部分之R爲大 之觸媒的塡充層長度爲全觸媒層之60%以下爲佳，且以 ^ 5〜50% 爲更佳，10〜40% 爲再佳。 經由如此將相對於觸媒真密度之表觀密度比R (觸媒 之表觀密度/觸媒之真密度）不同之複數個觸媒，並且經 由使用塡充鉬系觸媒之固定床多管式反應器之氣相接觸氧 · 化反應，製造不飽和醛類和/或不飽和羧酸時，抑制位於 熱點部之觸媒惡化，且不根據熱點部爲於何處發生，又， 原料氣體濃度爲高之情況，亦可一邊維持高產率一邊長期 繼續反應。又，如以往僅使用活性不同的觸媒控制觸媒活 性下，特別於原料氣體濃度爲高之情形中具有界限，但若 使用本發明之方法，則即使於原料氣體濃度爲高之情形中 ，亦可不根據熱點部爲於何處發生，一邊維持高產率一邊 長期繼續反應。 Φ 於本發明之不飽和醛類和/或不飽和羧酸之製造方法 中，再令前述複數個反應帶中分別塡充之觸媒活性爲不同 爲佳。 上述活性不同觸媒之製造方法並無特別限定，例如， · 可使用先前公知的方法。具體而言，可列舉例如改變鈉、 鉀、細、鉋及鉈中選出之至少一種元素（本發明所用觸媒 之B成分）之種類和/或份量之方法，改變承載率之方法 ，改變煅燒溫度之方法、改變稀釋率之方法，組合承載觸 -16 - (13) (13)200304853 媒和成型觸媒之方法、改變觸媒粒徑之方法、和將其組合 之方法。 如此將活性不同之觸媒分別塡充至前述複數個反應帶 時，即，相對於觸媒真密度之觸媒表觀密度比R (觸媒之 表觀密度/觸媒之真密度）爲不同，且，活性亦不同之觸 媒分別塡充至前述複數個反應帶時，關於觸媒之塡充配置 方法並無特別限定，於著眼於R之情形爲如前述，可列舉 例如由氣體入口側朝向氣體出口側以R爲變成更小般塡充 的配置、和由氣體入口側朝向氣體出口側以R爲暫時變大 後變小般塡充的配置等，但於著眼於活性之情形中，可列 舉例如由氣體入口側朝向氣體出口側以活性爲依序變高般 塡充的配置、和由氣體入口側朝向氣體出口側以活性爲暫 時降低後變高般塡充的配置等，較佳，將活性不同之觸媒 由各反應管之氣體入口側朝向氣體出口側以活性爲依序變 高般配置。即，將活性最低之觸媒配置於氣體入口側、活 性最高之觸媒配置於氣體出口側。又，由氣體入口側朝向 氣體出口側以活性爲暫時降低後變高般塡充的配置中，氣 體入口部分之高活性觸媒的塡充層長度爲全觸媒層之60% 以下爲佳，且以5〜50%爲更佳，10〜40%爲再佳。 經由如此排列活性不同之複數個觸媒，並且經由使用 塡充鉬系觸媒之固定床多管式反應器之氣相接觸氧化反應 ，製造不飽和醛類和/或不飽和羧酸時，更加抑制位於熱 點部之觸媒惡化，且不取決於熱點部爲於何處發生，又， 原料氣體濃度爲高之情況，亦可一邊維持高產率一邊長期 -17- (14) (14)200304853 繼續反應。 觸媒之塡充配置的最佳形態，關於R爲由氣體入口側 朝向氣體出口側以R爲變成更小般塡充，且，關於活性爲 由氣體入口側朝向氣體出口側以活性爲依序變高般塡充配 置之形態。 反應帶之數目並無特別限定，愈多則愈易控制觸媒層 的熱點溫度，但於工業上以2或3個左右即可取得充分的 目的效果。又，關於觸媒層之分割比爲根據氧化反應條件 和對各層所塡充之觸媒組成、形狀、尺寸等而左右最適値 ，無法一槪特定，若適當選擇取得全體的最適活性及選擇 率即可。 觸媒對於各反應管塡充時，亦可將惰性物質所稀釋的 觸媒塡充至各反應帶。 以丙烯、異丁烯、第三丁醇、及甲基-第三丁醚中選 出之至少一種化合物做爲原料，並且經由分子狀氧氣或含 分子狀氧氣之氣體進行氣相接觸氧化，製造對應原料之不 飽和醛類和/或不飽和羧酸之方法除了使用本發明之觸媒 做爲觸媒以外並無特別限制，可在一般所用之裝置、方法 及條件下實施。 即，本發明中之氣相接觸反應可依據通常的單流通法 、或循環法進行，且反應器可使用固定床反應器、流動床 反應器、移動床反應器等。 上述之反應條件爲例如將做爲原料氣體之丙烯、異丁 烯、第三丁醇及甲基-第三丁醚中選出至少一種之化合物 -18- (15) (15)200304853 1〜1 5容量％ ，相對於此原料氣體容量比爲1〜1 0倍範 圍之分子狀氧氣及做爲稀釋劑之惰性氣體，例如，水蒸氣 、氮及碳酸氣體等所構成之混合氣體於250〜450 °C之溫 度範圍下，0·1〜IMPa壓力下以300〜5000hr· 1 (STP) 空間速度與本發明之觸媒接觸反應即可。 若根據本發明之方法，在提高生產性爲目的之高負荷 反應條件下，例如於更高原料氣體濃度、或更高空間速度 之條件下，可取得比先前法特別顯著佳之結果。特別，即 使使用原料氣體濃度爲7容量％以上，更嚴格爲9容量％ 以上般高濃度之原料氣體，亦可達成本發明之目的。 【實施方式】 [實施例] 以下，列舉實施例更加詳細說明本發明，但本發明並 非彼此些實施例所限制。還有，本說明書中之轉換率、選 擇率、及產率爲分別如下定義。 φ 轉換率（莫耳％ )=(反應之起始原料莫耳數）/ (供給 之起始原料莫耳數）x 1〇〇 選擇率（莫耳％ )=(生成之不飽和醛類和/或不飽和 竣酸之莫耳數）/(供給之起始原料莫耳數）X100 又’觸媒之真密度及細孔容積爲以下列之測定機器及 方法予以測定。 真密度： -19- (16) (16)200304853 測定機器：Micromeritics 公司製 Autopycnometer 1 3 20 . 測定方法：量取約4克觸媒，並放入測定用元件中且 安裝於上述之測定機器。 細孔容積： 測定機器：Micromeritics公司製 AutoPore III (水銀 壓入方式） 鲁 測定方法：量取約2克觸媒，並以壓力測定範圍〇〜 41 4MPa，等價時間1〇秒鐘進行測定。 (觸媒製造例1:觸媒（1)之調製） 將純水1 〇公升一邊加熱攪拌，一邊溶解鉬酸銨1 500 克，再加入20質量％矽石凝膠425克。對此混合液，將 硝酸鈷1 23 6克，硝酸鎳412克，硝酸鐵3 72克，硝酸鉀 5.7克溶於純水1〇〇〇毫升之液體一邊劇烈攪拌一邊滴下。 鲁 其後，對純水500毫升中加入濃硝酸250毫升之水溶液， 將溶解硝酸鉍446克之液體一邊劇烈攪拌一邊滴下。將生 成的懸浮液予以加熱攪拌，令大部分水蒸發，取得餅狀固 形物。將所得之餅狀固形物以箱型乾燥機予以加熱處理（ 加熱氣體溫度：170 °C，加熱氣體線速：1.2m/sec，加熱 處理時間：1 2小時），取得塊狀之觸媒前體。將此觸媒前 · 體弄碎後，測定減量率時，爲1 8 · 9質量％ 。其次，將5 〇 質量％之硝酸銨水溶液相對於觸媒前體粉末1公斤以 -20- (17) (17)200304853 260克之比例添加並且混練1小時後，擠壓成型爲外徑 6.0mm，內徑2.0mm，高度6.0mm的環狀。其次，將成型 體於空氣流通下以480 °C鍛燒5小時，取得觸媒（1)。 此觸媒除了氧以外的金屬元素組成爲如下。 觸媒（1) : MouCcuNhBiuFeuSisKo.os 觸媒 （1)之相對於真密度之表現密度比R (觸媒之 表觀密度/觸媒之真密度）爲0.35。 觸媒 （1)之觸媒組成，觸媒前體P1之減量率，相 對於觸媒前體P1 1〇〇質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ 觸媒之真密度）整理於表1。 (觸媒製造例2〜3:觸媒 （2)〜（3)之調製） 於上述觸媒製造例1之觸媒 （1)的調製方法中，除 了令添加至觸媒前體P1之50質量％硝酸銨水溶液份量 分別改變以外，同觸媒製造例1處理分別取得觸媒（2)〜 (3) 〇 觸媒（2)〜（3)之觸媒組成，觸媒前體P1之減量率 ，相對於觸媒前體P1 100質量份之黏合劑添加量，觸媒 之大小、及、相對於真密度之表觀密度比（觸媒之表觀密 度/觸媒之真密度）整理於表1。 (觸媒製造例4:觸媒 （4)之調製） 於上述觸媒製造例1之觸媒（1)的調製方法中，除 (18) (18)200304853 了令觸媒之大小改變成外徑7.〇mm、內徑2.0mm、高度 7.0mm以外，同觸媒製造例1處理取得觸媒 （4) 。 _ 觸媒 （4)之觸媒組成、觸媒前體P1之減量率’相 對於觸媒前體P1 1〇〇質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度R (觸媒之表觀密度/觸 媒之真密度）整理於表1。 (觸媒製造例5:觸媒（5)之調製） · 於上述觸媒製造例1之觸媒（1)的調製方法中，除 了令硝酸鉀之添加量改變成7.2克以外，同觸媒製造例1 處理取得觸媒 （5)。此觸媒除了氧以外的金屬元素組成 爲如下。 觸媒（5) ·· MouCosNhBiuFe^SizKo.i 觸媒 （5)之觸媒組成，觸媒前體P1之減量率，相 對於觸媒前體P1 1〇〇質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ ® 觸媒之真密度）整理於表1。 (觸媒製造例6:觸媒（6)之調製） 於上述觸媒製造例1之觸媒（1)的調製方法中，除 . 了令餅狀固形物之加熱處理條件中，加熱氣體溫度改變成 2 20 °C，並且令添加至觸媒前體P1之50質量％硝酸銨 水溶液份量改變以外，同觸媒製造例1處理取得觸媒 （6) -22· (19) (19)200304853 觸媒（6)之觸媒組成，觸媒前體P1之減量率’相 對於觸媒前體P1 100質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ 觸媒之真密度）整理於表1。 (觸媒製造例7:觸媒（7)之調製） 於上述觸媒製造例1之觸媒（1)的調製方法中’除 了令硝酸鉀之添加量改變成3.6克以外，並且令添加至觸 媒前體P1之50質量％硝酸銨水溶液份量、及、觸媒之 大小改變以外，同觸媒製造例1處理取得觸媒 （7)。此 觸媒除了氧以外的金屬元素組成爲如下。 觸媒（7) : MouCoeNhBUe^ShKo.os 觸媒 （7)之觸媒組成，觸媒前體P1之減量率’相 對於觸媒前體P1 1〇〇質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ 觸媒之真密度）整理於表1。 (觸媒製造例8:觸媒（8)之調製） 於上述觸媒製造例7之觸媒（7)的調製方法中’除 了令添加至觸媒前體P 1之50質量％硝酸銨水溶液份量 改變以外，同觸媒製造例7處理取得觸媒 （8)。 觸媒 （8)之觸媒組成，觸媒前體P1之減量率’相 對於觸媒前體P1 100質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ (20) (20)200304853 觸媒之真密度）整理於表1。 (觸媒製造例9:觸媒（9)之調製） 於上述觸媒製造例1之觸媒（1)的調製方法中，除 了使用硝酸鉋9.7克代替硝酸鉀，並且令添加至觸媒前體 P1之50質量％硝酸銨水溶液份量、及、觸媒之大小改 變以外’同觸媒製造例1處理取得觸媒（9)。此觸媒除 了氧以外的金屬元素組成爲如下。 觸媒（9) : MouCoeNhBi^FeuSizKo.o? 觸媒 （9)之觸媒組成，觸媒前體P1之減量率，相 對於觸媒前體P1 100質量份之黏合劑添加量，觸媒之大 小 '及、相對於真密度之表觀密度比R (觸媒之表現密度/ 觸媒之真密度）整理於表1。 (觸媒製造例10:觸媒（10)之調製） 於上述觸媒製造例9之觸媒（9)的調製方法中，除 了令添加至觸媒前體P1之50質量％硝酸銨水溶液份量 改變以外，同觸媒製造例9處理取得觸媒 （10)。 觸媒（10)之觸媒組成，觸媒前體P1之減量率，相 對於觸媒前體P1 100質量份之黏合劑添加量，觸媒之大 小、及、相對於真密度之表觀密度比R (觸媒之表現密度/ 觸媒之真密度）整理於表1。 (參考例1〜1 0 ；) (21) 200304853 於熔融硝酸鹽所加熱之內徑25mm不銹鋼製反應管中 ，將觸媒製造例1〜1〇所得之觸媒（1)〜（1〇)分別塡充 至層長200mm，並將下述組成之反應氣體以空間速度 1 5 001Γ 1 (STP)導入進行丙烯的氣相接觸氧化反應。結果 示於表2。 丙烯 3容量％ 空氣 3 〇容量％ 水蒸氣 4 〇容量％ 氮 2 7容量％ (實施例1) 於熔融硝酸鹽所加熱之內徑25rnm不銹鋼製反應管中 ，由反應氣體入口側朝向出口側之順序，將觸媒（〗）以 層長l5〇Omm，觸媒 （2)以層長l5〇〇mm塡充，並將下述 組成之反應氣體以空氣速度1500h 1 (STP)導入進行丙 烯的氣相接觸氧化反應。結果示於表3。 丙烯 5.5容量％ 空氣 5 〇 . 〇容量％ 水蒸氣 1 0.0容量％ 氮 3 4.5容量％Only the true density and pore volume of the catalyst active material are measured, and R is calculated from the above formula. Through such catalysts, the apparent density ratio R of the catalyst relative to the true density is different. In the case of the gas-phase contact oxidation reaction of a fixed-bed multitubular reactor, the production of unsaturated aldehydes and / or unsaturated carboxylic acids does not depend on where the hot spot occurs, and the concentration of the raw material gas is high. In this case, the reaction can be continued for a long time while maintaining a high yield. There are no particular limitations on the manufacturing method of the catalyst whose apparent density ratio R with respect to the true density is different. For example, it can be manufactured according to the following methods (1) to (4) or a combination thereof. (1) R can be changed by changing the reduction rate of the catalyst precursor. If the reduction rate is low, the pore formation of the catalyst is reduced, so the apparent density of the catalyst becomes high. If the catalyst composition is not extremely changed, the vacuum degree will not be changed even if the manufacturing method is changed. Therefore, if the reduction rate is low, R will increase. Conversely, if the weight loss rate is high, the expression density of the catalyst becomes low, so R becomes small. (2) Control the type and / or amount of the pore-forming agent added to the catalyst. When a pore-forming agent having a pore-forming effect is added to the catalyst, and the amount of the pore-forming agent is relatively reduced, the expression density becomes higher and R becomes larger. Conversely, if the amount of addition is relatively large, R becomes small. R can also be controlled by changing the type of the pore-forming agent. (3) Although the effect of changing R is small, if the composition of the catalyst is changed (the type of metal used as the raw material of the catalyst and the addition ratio), the true density changes, so -14- (11) (11) 200304853 R also changes . (4) R can also be controlled by changing the pressure during molding. For example, in the case of ingot molding, if the pressure is increased, R will increase. If the pressure is reduced, R will decrease. In the case of extrusion molding, if the extrusion pressure is increased, R is increased, and if ′ is decreased, R is decreased. The range of the apparent density ratio R (the apparent density of the catalyst / the true density of the catalyst) with respect to the true density of the catalyst used in the present invention is not particularly limited, but is preferably 0.25 to 0.55, and more preferably 0.30 to 0.50. . _ When the apparent density ratio relative to the true density of the catalyst is less than 0.25, the diffusion efficiency in the pores increases with the increase of the pore volume. At this time, although the catalyst activity and the selectivity for the target product increase, but The catalyst strength is significantly reduced, so it is not good. When the apparent density ratio relative to the true density of the catalyst is greater than 0.55, contrary to the above, although the catalyst strength is increased, the catalyst activity and the selectivity to the target product are significantly reduced, which is not good. In the present invention, the inside of each reaction tube of the fixed-bed multi-tubular reactor is divided into a plurality of reaction zones in the direction of the tube axis, and the plurality of reaction zones are filled with R prepared according to the above method as There are no particular restrictions on the method of contacting the above-mentioned charge arrangement, and examples include: a configuration in which the charge is made smaller from the gas inlet side to the gas outlet side, and from the gas inlet side to the gas outlet side It is preferable to use R as a configuration that temporarily becomes larger and then becomes smaller, and it is preferable to arrange a catalyst having a different R from the gas inlet side of each reaction tube toward the gas outlet side with R being smaller. That is, -15- (12) (12) 200304853 arranges the catalyst with the largest R on the gas inlet side, and places the catalyst with the smallest R on the gas outlet side. In addition, R is arranged from the gas inlet side to the gas outlet side. In the charge configuration, which is temporarily enlarged and then becomes smaller, the length of the charge layer of the catalyst where R is large is 60% or less of the full catalyst layer. It is better, and ^ 5 ~ 50% is more preferable, and 10 ~ 40% is even better. In this way, a plurality of catalysts having different apparent density ratios R (the apparent density of the catalyst / the true density of the catalyst) with respect to the true density of the catalyst are used, and the fixed-bed multi-tubes are used with a molybdenum-based catalyst. Gas-phase contact oxidation and oxidation reaction of the reactor, when producing unsaturated aldehydes and / or unsaturated carboxylic acids, suppress the deterioration of the catalyst located in the hot spot, and does not depend on where the hot spot occurs, and the raw material gas When the concentration is high, the reaction can be continued for a long time while maintaining a high yield. In addition, in the past, only using catalysts with different activities to control the catalyst activity has a limit, especially in the case where the concentration of the raw material gas is high. However, if the method of the present invention is used, even when the concentration of the raw material gas is high, It is also possible to continue the reaction for a long period of time while maintaining a high yield regardless of where the hot spot occurs. Φ In the method for producing an unsaturated aldehyde and / or an unsaturated carboxylic acid of the present invention, it is preferable that the catalytic activity of each of the plurality of reaction zones is different. The method for producing the above-mentioned different active catalysts is not particularly limited. For example, a conventionally known method can be used. Specifically, for example, a method of changing the type and / or amount of at least one element (the B component of the catalyst used in the present invention) selected from sodium, potassium, fine, planer, and gadolinium, a method of changing the load factor, and a change of calcination can be listed. A method of temperature, a method of changing the dilution rate, a method of combining a supported catalyst-16-(13) (13) 200304853, a method of molding a catalyst, a method of changing the particle diameter of a catalyst, and a method of combining them. In this way, when catalysts with different activities are respectively charged to the aforementioned plurality of reaction zones, that is, the apparent catalyst density ratio R (the apparent density of the catalyst / the true density of the catalyst) relative to the true density of the catalyst is different. In addition, when catalysts with different activities are charged to the aforementioned plurality of reaction zones, the method for disposing the catalyst is not particularly limited. In the case of focusing on R, as described above, for example, from the gas inlet side A configuration in which R is made smaller toward the gas outlet side, and a configuration in which R is temporarily made larger after the gas inlet side toward the gas outlet side becomes smaller, etc., but when focusing on activity, For example, a configuration in which charging is gradually increased from the gas inlet side toward the gas outlet side in order to increase the activity, and a configuration in which charging is gradually increased from the gas inlet side toward the gas outlet side after the activity is temporarily reduced, etc. are preferable. The catalysts with different activities are arranged from the gas inlet side of each reaction tube to the gas outlet side in order to increase the activity in order. That is, the catalyst with the lowest activity is arranged on the gas inlet side, and the catalyst with the highest activity is arranged on the gas outlet side. In addition, in the configuration where the charge is gradually increased from the gas inlet side to the gas outlet side, the activity is temporarily reduced and then becomes high. The charge layer length of the highly active catalyst at the gas inlet portion is preferably 60% or less of the full catalyst layer. 5 to 50% is more preferred, and 10 to 40% is even better. When a plurality of catalysts with different activities are arranged in this way, and through the gas-phase contact oxidation reaction of a fixed-bed multi-tubular reactor using a pseudo-molybdenum-based catalyst, unsaturated aldehydes and / or unsaturated carboxylic acids are produced even more Inhibit the deterioration of the catalyst located in the hot spot, and it does not depend on where the hot spot occurs, and if the concentration of the raw material gas is high, it can also maintain a high yield for a long time -17- (14) (14) 200304853 Continue reaction. The best configuration of the catalyst charge configuration is that R is from the gas inlet side to the gas outlet side, and R is smaller, and the activity is from the gas inlet side to the gas outlet side in order of activity. It looks like a high-profile configuration. The number of reaction zones is not particularly limited. The more the hot zone temperature, the easier it is to control the hotspot temperature of the catalyst layer. However, in the industry, about 2 or 3 can achieve sufficient results. In addition, the division ratio of the catalyst layer is optimized based on the oxidation reaction conditions and the catalyst composition, shape, and size of each layer. It cannot be specified at all, and if it is appropriately selected, the overall optimum activity and selectivity can be obtained. Just fine. When the catalyst is charged to each reaction tube, the catalyst diluted with an inert substance may also be charged to each reaction zone. At least one compound selected from propylene, isobutylene, tertiary butanol, and methyl tertiary butyl ether is used as a raw material, and gas phase contact oxidation is performed through molecular oxygen or a gas containing molecular oxygen to produce corresponding raw materials. The method of unsaturated aldehydes and / or unsaturated carboxylic acids is not particularly limited except that the catalyst of the present invention is used as the catalyst, and it can be carried out under the apparatus, method and conditions generally used. That is, the gas-phase contact reaction in the present invention can be performed according to a general single-flow method or a cyclic method, and the reactor can be a fixed-bed reactor, a fluid-bed reactor, a moving-bed reactor, or the like. The above reaction conditions are, for example, at least one compound selected from the group consisting of propylene, isobutylene, tertiary butanol, and methyl tertiary butyl ether as raw material gas. 18- (15) (15) 200 304 853 1 to 15% by volume Relative to this raw material gas capacity ratio is a molecular oxygen in the range of 1 to 10 times and an inert gas as a diluent, for example, a mixed gas composed of water vapor, nitrogen, and carbonic acid gas at a temperature of 250 to 450 ° C. In the temperature range, the catalyst of the present invention can be reacted at a space velocity of 300 to 5000 hr · 1 (STP) under a pressure of 0.1 to 1 MPa. According to the method of the present invention, under high-load reaction conditions for the purpose of improving productivity, for example, under conditions of higher raw material gas concentration or higher space velocity, a particularly remarkable result can be obtained. In particular, even if a high-concentration raw material gas having a raw material gas concentration of 7% by volume or more and more strictly 9% by volume or more is used, the purpose of the present invention can be achieved. [Embodiments] [Examples] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. The conversion rate, selectivity, and yield in this specification are defined as follows. φ conversion rate (mol%) = (mol number of starting materials for reaction) / (mol number of starting materials supplied) x 100 (selection rate (mol%)) = (unsaturated aldehydes and Moore number of unsaturated acid) / (Mole number of starting material supplied) X100 The true density and pore volume of the catalyst are measured by the following measuring machines and methods. True density: -19- (16) (16) 200304853 Measuring machine: Autopycnometer 1 3 20 manufactured by Micromeritics. Measuring method: Measure about 4 grams of catalyst, put it into the measuring element, and install it in the measuring machine. Pore volume: Measuring machine: AutoPore III (mercury press method) manufactured by Micromeritics. Measurement method: Measure about 2 g of catalyst and measure it in a pressure measuring range of 0 to 41 4 MPa for an equivalent time of 10 seconds. (Catalyst Production Example 1: Preparation of Catalyst (1)) While heating and stirring 10 liters of pure water, 1,500 g of ammonium molybdate was dissolved, and then 425 g of 20% by mass silica gel was added. For this mixed solution, 236 g of cobalt nitrate, 412 g of nickel nitrate, 3 72 g of iron nitrate, and 5.7 g of potassium nitrate dissolved in 1,000 ml of pure water were dropped while vigorously stirring. After that, an aqueous solution of 250 ml of concentrated nitric acid was added to 500 ml of pure water, and a liquid in which 446 g of bismuth nitrate was dissolved was dropped while vigorously stirring. The resulting suspension was heated and stirred to evaporate most of the water to obtain a cake-like solid. The obtained cake-like solids were heat-treated with a box dryer (heating gas temperature: 170 ° C, heating gas linear velocity: 1.2m / sec, heating processing time: 12 hours), before obtaining a block-shaped catalyst body. When the catalyst precursor and body were shattered and the weight loss rate was measured, it was 18 · 9% by mass. Next, a 50 mass% ammonium nitrate aqueous solution was added to -20 g of the catalyst precursor powder at a ratio of -20- (17) (17) 200304853 260 g and kneaded for 1 hour, and then extruded to an outer diameter of 6.0 mm. Ring with 2.0mm inner diameter and 6.0mm height. Next, the molded body was calcined at 480 ° C for 5 hours under air circulation to obtain a catalyst (1). The composition of metal elements other than oxygen of this catalyst is as follows. Catalyst (1): MouCcuNhBiuFeuSisKo.os Catalyst (1) The relative density R (actual density of catalyst / true density of catalyst) of true density is 0.35. The catalyst composition of the catalyst (1), the reduction rate of the catalyst precursor P1, the amount of binder added to the catalyst precursor P1 by 100 parts by mass, the size of the catalyst, and the table relative to the true density The apparent density ratio R (representative density of catalyst / true density of catalyst) is summarized in Table 1. (Catalyst Manufacturing Examples 2 to 3: Modulation of Catalysts (2) to (3)) In the method for preparing Catalyst (1) of Catalyst Manufacturing Example 1 described above, in addition to adding 50 to the catalyst precursor P1 The mass% ammonium nitrate aqueous solution was changed except that the catalysts (2) to (3) were obtained in the same manner as in Catalyst Production Example 1. The catalyst composition of catalysts (2) to (3) was reduced, and the catalyst precursor P1 was reduced. Ratio, the amount of binder added to 100 parts by mass of catalyst precursor P1, the size of the catalyst, and the apparent density ratio to the true density (apparent density of the catalyst / true density of the catalyst) Table 1. (Catalyst Manufacturing Example 4: Modulation of Catalyst (4)) In the method for preparing Catalyst (1) of Catalyst Manufacturing Example 1, except that (18) (18) 200304853 was used to change the size of the catalyst to The catalyst (4) was obtained in the same manner as in Catalyst Production Example 1 except that the diameter was 7.0 mm, the inner diameter was 2.0 mm, and the height was 7.0 mm. _ Catalyst composition of catalyst (4), reduction rate of catalyst precursor P1 '100% by mass of the amount of binder added to catalyst precursor P1, catalyst size, and relative to true density Apparent density R (apparent density of catalyst / true density of catalyst) is summarized in Table 1. (Catalyst Manufacturing Example 5: Modulation of Catalyst (5)) · In the method for preparing Catalyst (1) of Catalyst Manufacturing Example 1 above, except that the amount of potassium nitrate was changed to 7.2 g, the same as the catalyst Manufacturing example 1 Process acquisition catalyst (5). The composition of metal elements other than oxygen of this catalyst is as follows. Catalyst (5) ·· MouCosNhBiuFe ^ SizKo.i The catalyst composition of catalyst (5), the reduction rate of catalyst precursor P1, compared to the catalyst precursor P1, 100 parts by mass of the amount of binder added, the catalyst The size of the medium and the apparent density ratio R (actual density of the catalyst / true density of the catalyst) relative to the true density are summarized in Table 1. (Catalyst Manufacturing Example 6: Modulation of Catalyst (6)) In the method for preparing Catalyst (1) of Catalyst Manufacturing Example 1 described above, the temperature of the heated gas in the heating treatment conditions for making a cake-like solid was removed. The catalyst was changed to 2 20 ° C, and the amount of the 50% by mass ammonium nitrate aqueous solution added to the catalyst precursor P1 was changed, and the catalyst was obtained in the same manner as in Catalyst Production Example 1. (6) -22 · (19) (19) 200304853 The catalyst composition of the catalyst (6), the reduction rate of the catalyst precursor P1 'is 100 parts by mass of the added amount of the binder of the catalyst precursor P1, the size of the catalyst, and the apparent density relative to the true density The ratio R (performance density of catalyst / true density of catalyst) is summarized in Table 1. (Catalyst Manufacturing Example 7: Modulation of Catalyst (7)) In the method for preparing Catalyst (1) of Catalyst Manufacturing Example 1 above, 'apart from changing the amount of potassium nitrate to 3.6 g, and adding to The catalyst precursor P1 was treated in the same manner as in Catalyst Production Example 1 except that the amount of the 50 mass% ammonium nitrate aqueous solution and the catalyst size were changed to obtain the catalyst (7). The catalyst has a metal element composition other than oxygen as follows. Catalyst (7): MouCoeNhBUe ^ ShKo.os Catalyst composition of catalyst (7), the reduction rate of catalyst precursor P1 is 100% by mass of the amount of binder added to catalyst precursor P1, catalyst The size and the apparent density ratio R (actual density of the catalyst / true density of the catalyst) relative to the true density are summarized in Table 1. (Catalyst Production Example 8: Preparation of Catalyst (8)) In the preparation method of Catalyst (7) of Catalyst Production Example 7 above, except for a 50 mass% ammonium nitrate aqueous solution added to the catalyst precursor P1 The catalyst (8) was obtained in the same manner as in Catalyst Production Example 7 except that the weight was changed. The catalyst composition of catalyst (8), the reduction rate of catalyst precursor P1 'is 100 parts by mass of the amount of binder added to catalyst precursor P1, the size of the catalyst, and the apparent density relative to the true density The ratio R (performance density of the catalyst / (20) (20) 200304853 true density of the catalyst) is summarized in Table 1. (Catalyst Production Example 9: Preparation of Catalyst (9)) In the preparation method of Catalyst (1) of the above Catalyst Production Example 1, except that 9.7 g of nitric acid planer was used instead of potassium nitrate, and it was added before the catalyst. The amount of the 50% by mass aqueous solution of ammonium nitrate in the body P1 and the change in the size of the catalyst were changed in the same manner as in Catalyst Production Example 1 to obtain the catalyst (9). The composition of metal elements other than oxygen in this catalyst is as follows. Catalyst (9): MouCoeNhBi ^ FeuSizKo.o? The catalyst composition of catalyst (9). The reduction rate of catalyst precursor P1 is 100 parts by mass of the amount of binder added to catalyst precursor P1. The size 'and the apparent density ratio R (actual density of the catalyst / true density of the catalyst) relative to the true density are summarized in Table 1. (Catalyst Production Example 10: Preparation of Catalyst (10)) In the preparation method of Catalyst (9) of Catalyst Production Example 9 described above, the amount of 50% by mass ammonium nitrate solution added to the catalyst precursor P1 was added. Other than the change, the catalyst (10) was obtained in the same manner as in Catalyst Production Example 9. The catalyst composition of catalyst (10), the reduction rate of catalyst precursor P1, the amount of binder added to 100 parts by mass of catalyst precursor P1, the size of catalyst, and the apparent density relative to true density The ratio R (performance density of catalyst / true density of catalyst) is summarized in Table 1. (Reference examples 1 to 10;) (21) 200304853 In a 25 mm inner diameter stainless steel reaction tube heated by molten nitrate, the catalysts (1) to (1) obtained from catalyst manufacturing examples 1 to 10 Each was filled to a layer length of 200 mm, and a reaction gas having the following composition was introduced at a space velocity of 15 00 1 Γ 1 (STP) to perform a gas-phase contact oxidation reaction of propylene. The results are shown in Table 2. Propylene 3% by volume Air 3% by volume Water vapour 4% by volume Nitrogen 27% by volume (Example 1) In a reaction tube made of stainless steel with an inner diameter of 25rnm heated by molten nitrate, the reaction gas inlet side faces the outlet side In the order, the catalyst (?) Was charged with a layer length of 150 mm, the catalyst (2) was charged with a layer length of 15 mm, and a reaction gas having the following composition was introduced at an air velocity of 1500 h 1 (STP) for the propylene Gas-phase contact oxidation reaction. The results are shown in Table 3. Propylene 5.5% by volume Air 50.0% by volume Water vapor 1 0.0% by volume Nitrogen 3 4.5% by volume
(比較例1〜2) 於實施例1中’除了僅將觸媒（1)以靥長3000mm 、觸媒（2)以層長3 000mm塡充以外，同實施例i處理 -25- (22) (22)200304853 進行氧相接觸氧化反應。結果示於表3。 (實施例2、比較例3〜4) 於實施例1中，除了如表3所示般塡充觸媒，且反應 氣體組成如下改變以外，同實施例1處理進行氣相接觸氧 化反應。結果示於表3。 丙烯 6.5容量％ 空氣 5 7.0容量％ 水蒸氣 1 0.0容量％ 氮 2 6.5容量％ (實施例3〜5，比較例5) 於實施例1中，除了如表3所示般塡充觸媒，且反應 氣體組成如下改變以外，同實施例1處理進行氣相接觸氧 化反應。結果示於表3。 丙烯 8.0容量％ 空氣 7 0.0容量％ 水蒸氣 1 0.0 容量 °/〇 氮 1 2.0容量％ -26- (23) 200304853 (23)(Comparative Examples 1 to 2) In Example 1, except that the catalyst (1) was charged with a length of 3000 mm and the catalyst (2) was charged with a layer length of 3000 mm, the same treatment as in Example i was performed. 25- (22 ) (22) 200304853 Perform oxygen phase contact oxidation reaction. The results are shown in Table 3. (Example 2 and Comparative Examples 3 to 4) In Example 1, except that the catalyst was charged as shown in Table 3 and the reaction gas composition was changed as follows, a gas phase contact oxidation reaction was performed in the same manner as in Example 1. The results are shown in Table 3. Propylene 6.5% by volume Air 5 7.0% by volume Water vapor 1 0.0% by volume Nitrogen 2 6.5% by volume (Examples 3 to 5, Comparative Example 5) In Example 1, except that the catalyst was charged as shown in Table 3, and A gas-phase contact oxidation reaction was performed in the same manner as in Example 1 except that the reaction gas composition was changed as follows. The results are shown in Table 3. Acrylic 8.0% by volume Air 7 0.0% by volume Water vapor 1 0.0% ° / 〇 Nitrogen 1 2.0% by volume -26- (23) 200304853 (23)
表1 觸媒 觸媒組成 觸媒前體 黏合劑 觸媒大小 R(觸媒之表 編號 P1減量率 添加量 外徑X內徑X 現密度/觸媒 (質量％) (質量份) 高度（mm) 之真密度） ⑴ Mo12Co6Ni2BiuFe1.3Si2K0.08 18.9 26 6.0x 2.0x 6.0 0.35 ⑵ 个 18.8 40 个 0.30 ⑶ 个 19.0 20 个 0.43 ⑷ 个 19.0 26 7.0x 2.0x 7.0 0.35 (5) M〇i 2C〇6Ni2Bii jFei .3S12K0.1 19.1 26 6·0χ 2·0χ 6.0 0.35 ⑹ Mo12Co6Ni2Bi1.3FeuSi2K0.08 2.1 42 个 0.56 ⑺ Mo12Co0Ni2Bi1.3Fe1.3Si2K0.05 18.8 40 5.5χ 2.0χ 5.5 0.31 ⑻ 个 19.0 26 个 0.35 ⑼ Mo12Co6Ni2BiuFe1.3Si2K0.07 19.1 20 7.0χ 2.0χ 7.0 0.42 (10) 个 18.9 26 个 0.35Table 1 Catalyst catalyst composition Catalyst precursor binder Catalyst size R (catalyst table number P1 Addition rate reduction amount outer diameter X inner diameter X density / catalyst (mass%) (mass parts) height (mm ) True density) ⑴ Mo12Co6Ni2BiuFe1.3Si2K0.08 18.9 26 6.0x 2.0x 6.0 0.35 ⑵ 18.8 40 0.30 ⑶ 19.0 20 0.43 ⑷ 19.0 26 7.0x 2.0x 7.0 0.35 (5) M〇i 2C〇6Ni2Bii jFei .3S12K0.1 19.1 26 6 · 0χ 2 · 0χ 6.0 0.35 ⑹ Mo12Co6Ni2Bi1.3FeuSi2K0.08 2.1 42 0.56 ⑺ Mo12Co0Ni2Bi1.3Fe1.3Si2K0.05 18.8 40 5.5χ 2.0χ 5.5 0.31 ⑻ 19.0 26 0.35 ⑼ Mo12Co6Ni2BiuFe1. 3Si2K0.07 19.1 20 7.0χ 2.0χ 7.0 0.42 (10) 18.9 26 0.35
-27- (24)200304853 表2 參考例 觸媒編號 R(觸媒之表 現密度/觸媒 之真密度） 反應 酿 (°C) 丙烯轉換率 (莫耳％) 丙烯醛+丙烯 酸合計產率 (莫耳％) 丙烯醛+丙烯 酸合計選擇率 (莫耳％) 參考例1 (1) 0.35 310 98.2 92.4 94.1 參考例2 (2) 0.30 310 98.3 92.1 93.7 參考例3 (3) 0.43 310 96.8 91.8 94.8 參考例4 ⑷ 0.35 310 97.0 91.7 94.5 參考例5 (5) 0.35 310 96.7 91.5 94.6 參考例6 (6) 0.56 310 80.5 76.3 94.8 參考例7 (7) 0.31 310 99.3 90.6 91.2 參考例8 (8) 0.35 310 99.1 89.8 90.6 參考例9 (9) 0.42 310 81.2 77.9 95.9 參考例10 (10) 0.35 310 82.3 78.5 95.4 (25)200304853 表3 觸媒充塡方法 (氣體入口側—氣體出口側) 反應 時間 (小時) 反應 Μ (°C) 丙烯轉 換率 (莫耳％) 丙烯醛+ 丙烯酸合 計產率 (莫耳％) 丙烯醛+丙 烯酸合計選 擇率 (莫耳％) 實施例1 觸媒⑴腦媒⑵= 100 310 98.5 91.7 93.1 1500mm/l 500mm 4000 315 98.3 92.6 94.2 比較例1 觸媒⑴=3000mm 100 310 98.4 91.8 93.3 4000 314 98.3 92.0 93.6 比較例2 觸媒⑵=3000mm 100 310 98.5 91.5 92.9 4000 322 98.1 92.1 93.9 實施例2 觸媒⑶媒⑴= 100 310 97.8 91.3 93.4 1000mm/2000mm 4000 316 97.9 91.7 93.7 比較例3 觸媒⑷雇媒⑴= 100 310 97.7 90.9 93.0 1000mm/2000mm 4000 321 97.6 90.9 93.1 比較例4 觸媒(5)/觸媒⑴= 100 310 97.8 90.7 92.7 1000mm/2000mm 4000 323 97.6 90.6 92.8 實施例3 觸媒⑹/觸媒⑴= 100 320 97.6 89.5 91.7 1000mm/2000mm 4000 334 97.7 89.8 91.9 實施例4 觸媒（9)/觸媒（1)/觸媒 100 320 99.0 91.0 91.9 ⑺=1000mm/1400mm/600mm 4000 329 99.2 91.2 91.9 比較例5 觸媒（10)/觸媒（1)/觸媒 100 310 99.2 90.5 91.2 (8)=1000mm/1400mm/600mm 4000 337 99.0 89.8 90.8 實施例5 觸媒（1)/觸媒（9)/觸媒 100 310 99.2 90.6 91.3 ⑵=200mm/900mm/1900mm 4000 334 99.0 90.8 91.7 (26) (26)200304853 [發明之效果] 若根據本發明，則於經由使用塡充鉬系觸媒之固定床 多管式反應器之氣相接觸氧化反應，製造不飽和醛類類和 /或不飽和羧酸之情形中，可抑制位於熱點部之觸媒的惡 化，且於不取決於熱點部爲於何處發生，又，原料氣體濃 度爲高之情形中，亦可一邊維持局產率一邊長期繼續反應-27- (24) 200304853 Table 2 Reference example catalyst number R (representative density of catalyst / true density of catalyst) Reaction brewing (° C) Propylene conversion rate (mole%) Total yield of acrolein + acrylic acid ( Mole%) Total selectivity of acrolein + acrylic acid (Mole%) Reference example 1 (1) 0.35 310 98.2 92.4 94.1 Reference example 2 (2) 0.30 310 98.3 92.1 93.7 Reference example 3 (3) 0.43 310 96.8 91.8 94.8 Reference Example 4 ⑷ 0.35 310 97.0 91.7 94.5 Reference Example 5 (5) 0.35 310 96.7 91.5 94.6 Reference Example 6 (6) 0.56 310 80.5 76.3 94.8 Reference Example 7 (7) 0.31 310 99.3 90.6 91.2 Reference Example 8 (8) 0.35 310 99.1 89.8 90.6 Reference Example 9 (9) 0.42 310 81.2 77.9 95.9 Reference Example 10 (10) 0.35 310 82.3 78.5 95.4 (25) 200304853 Table 3 Catalyst charging method (gas inlet side-gas outlet side) Response time (hours) Response Μ (° C) Propylene conversion rate (mol%) Total acrolein + acrylic acid yield (mol%) Total selectivity of acrolein + acrylic acid (mol%) Example 1 Catalyst (brain media) = 100 310 98.5 91.7 93.1 1500mm / l 500mm 4000 315 98.3 92.6 94.2 Comparative Example 1 Catalyst ⑴ = 3000m m 100 310 98.4 91.8 93.3 4000 314 98.3 92.0 93.6 Comparative Example 2 Catalyst ⑵ = 3000mm 100 310 98.5 91.5 92.9 4000 322 98.1 92.1 93.9 Example 2 Catalyst ⑶ = 100 310 97.8 91.3 93.4 1000mm / 2000mm 4000 316 97.9 91.7 93.7 Comparative Example 3 Catalyst / Hydrogen = 100 310 97.7 90.9 93.0 1000mm / 2000mm 4000 321 97.6 90.9 93.1 Comparative Example 4 Catalyst (5) / catalyst⑴ = 100 310 97.8 90.7 92.7 1000mm / 2000mm 4000 323 97.6 90.6 92.8 Example 3 Catalyst ⑹ / catalyst ⑴ = 100 320 97.6 89.5 91.7 1000mm / 2000mm 4000 334 97.7 89.8 91.9 Example 4 Catalyst (9) / catalyst (1) / catalyst 100 320 99.0 91.0 91.9 ⑺ = 1000mm / 1400mm / 600mm 4000 329 99.2 91.2 91.9 Comparative Example 5 Catalyst (10) / catalyst (1) / catalyst 100 310 99.2 90.5 91.2 (8) = 1000mm / 1400mm / 600mm 4000 337 99.0 89.8 90.8 Example 5 Catalyst ( 1) / Catalyst (9) / Catalyst 100 310 99.2 90.6 91.3 ⑵ = 200mm / 900mm / 1900mm 4000 334 99.0 90.8 91.7 (26) (26) 200304853 [Effect of the invention] According to the present invention, the use of Gas phase contact of fixed bed multitubular reactor filled with molybdenum catalyst In the case of the production of unsaturated aldehydes and / or unsaturated carboxylic acids, the deterioration of the catalyst in the hot spot can be suppressed, and it does not depend on where the hot spot occurs, and the concentration of the raw material gas is In high cases, you can continue to react for a long time while maintaining the local yield.
-30--30-