200843854 九、發明說明： 【發明所屬之技術領域】 本發明係關於用於丙烯之觸媒氣相氧化製備丙烯醛、 或丙烯醛之觸媒氣相氧化製備丙烯酸的觸媒。更具體來 說’本發明係關於含鉬作爲主要成分之氧化觸媒，其具有 特定的粒徑分布。本發明亦關於使用該觸媒製備丙烯醛或 丙烯酸之方法，及使用如此製造之丙烯酸來製備吸水樹脂 的方法。 【先前技術】 丙烯醛於工業上已廣泛的用作丙烯酸等之起始材料， 而使用丙烯酸作爲吸水樹脂之起始材料。丙烯醛或丙烯酸 之一般實際製造方法，包括在氧化觸媒存在下，使用固定 床式殼-管反應器的丙烯之觸媒氣相氧化，或丙烯醛之觸媒 氣相氧化。 此觸媒氣相氧化反應係高度放熱反應，而因此於觸媒 層中形成局部異常高溫點（以下可稱爲“熱點”）。由於較其他 反應區域更高的溫度，氧化反應於熱點過度的進行，而減 少目標產物（即丙烯醛或丙烯酸）之產率。此外，由於熱點 曝於高溫，在該點之觸媒在短時間內顯示物理及化學性質 的變化，由於燒結等，其導致其活性或選擇性顯著的降低。 特別是當觸媒含鉬時，熱點之高溫加速鉬的昇華，而造成 觸媒組成成分（其組成比例）的改變，而使得觸媒的劣化程 度爲大。還有另一個問題爲，爲了提升丙烯醛或丙烯酸之 反應’當反應在高空間速度（space velocity)或高起始溫度濃 200843854 度下進行時（即進行高負載反應），此現象增加。 爲了妥善處理這些問題，已提出各種用於自丙烯製備 丙烯醛之改進方式，例如，包括以複數種類的佔據體積不 同之觸媒塡充反應管、於至少一個反應區域混合惰性物質 成形品（專利文獻 1 ·· JP 2005-320315A = USP 7，161，044);使 用受載觸媒之方法，包括以複數種類具有不同活性之觸媒 塡充反應管，該等觸媒係藉由改變觸媒上觸媒活性成分的 受載率及/或煅燒溫度而製備，以此方式，活性變成自起始 氣體的內側朝外側提高（專利文獻 2 : JP 平 10(1998)-168003A = USP6,028,2 00);或以複數之觸媒塡充反 應管之方式，於此方式，於反應管塡充之觸媒的佔據體積 變得自反應氣體的內側朝外側降低（專利文獻3 : JP平 4( 1 992)-2 1 793 2A = USP 5，1 98,5 8 1 )。 考慮自丙烯醛製備丙烯酸，已提出各種的改良，例如， 包括於起始氣體的內側以惰性物質稀釋觸媒的方法（專利 文獻 4: JP 昭 5 3 ( 1 97 8)-3 068 8B = USP 3,801，634);使用受載 觸媒之方法，包括觸媒塡充反應管，該觸媒之觸媒活性成 分的受載率變的自起始氣體的內側朝外側提高（專利文獻 5: JP平7(1995)-10802A);包括藉由改變加至觸媒之鹼金 屬的種類及/或數量，製備複數種具有不同活性觸媒，並將 其塡充至反應管之方法，於此方法中，觸媒活性自起始氣 體的內側朝外側提高（專利文獻 6 : JP2000_3 3 6060A = USP6,563,000);塡充反應管的方法，於此方法中包括以觸 媒粒子的體積自起始氣體的內側朝外側降低之方式（專利 200843854 文獻 7: JP 平 9( 1 997)-24 1 209A = USP5,719,318)。 然而，此種如以非活性物質稀釋、改變受載 具有不同活性之觸媒的方式，降低了對反應有效 成物數量，其係塡充於反應管，而減低了丙烯酸 與製備單一種類之觸媒相較起來，製備複數種的 要更多勞力及更大成本。 更且，在所有上述之提案完成了某種程度上 溫度的同時’效果仍不夠滿意。因此，於現況， 壽命及丙烯醛或丙烯酸的產率者，在這些方法中 空間。 【發明內容】 本發明之目標 因此，本發明之目標爲提供一種觸媒，其在 之觸媒氣相氧化製備丙烯醛，或藉由丙烯醛之觸 化製備丙烯酸時，可抑制觸媒層之局部異常高溫 的發生，並可長時間穩定提供丙烯醛或丙烯酸之 解決方法 我們發現：在藉由丙烯的觸媒氣相氧化製備 或藉由丙烯醛的觸媒氣相氧化製備丙烯酸之製造 用固定床式殼-管反應器，當塡充在反應器之觸媒 粒徑分布，觸媒粒子間之空隙可一致化並加大， 之局部異常高溫點（熱點）可被抑制，而不會降低 丙烯酸的產率，並可長時間穩地的獲得丙烯醛或 本發明係如此完成。 率或使用 的觸媒組 的產率。 觸媒亦需 抑制熱點 對於觸媒 仍有改進 藉由丙烯 媒氣相氧 .點（熱點） 高產率。 丙烯醛， 過程，使 具有特定 觸媒層中 丙烯醛或 丙烯酸。 200843854 因此，本發明提供一種含有鉬作爲主要成分之氧化觸 媒，其特徵在於其由下式（1)決定之粒徑的相對標準差爲至 少0.02且不大於0.20 : 粒徑之相對標準差=粒徑之標準差/平均粒徑 （1) 、r，丄 /一 ^ \ΝΣΧη2 -(ΣΧη)2 其中粒徑的標準差=—^'人、..."… y N(N -1) (N爲經測量粒徑之粒子的數目；Xn爲以三軸平均直徑 決定之各粒子之粒徑，其係由各粒子於三個方向所測得之 f 直徑的平均値）；而平均粒徑爲N個粒子之算術平均粒徑 本發明亦提供當存在有氧分子或含氧分子之氣體時， 藉由觸媒氣相氧化丙烯以製備丙烯醛之方法，或當存在有 氧分子或含氧分子之氣體時，藉由觸媒氣相氧化丙烯醛以 製備丙烯酸之方法，其特徵在於使用前述之觸媒。本發明 進一步提供用於製備吸水樹脂之方法，係使用得自本發明 之方法所得到的丙烯酸作爲起始材料。 本發明之影響 t ; 由於本發明之觸媒抑制觸媒層之局部異常高溫點（熱 點）的發生，並可長時間穩定的維持丙烯醛或丙烯酸之高產 率，本發明之觸媒可有利的使用作爲以固定床式殼-管反應 器，製備丙烯醛或丙烯酸之觸媒， 【實施方式】 實施本發明之最佳模式 本發明之觸媒適當的含鉬作爲主要成分，其粒徑並具 有由式（1)決定，範圍在至少0.02與不大於0.20之相對標 準差。當每一反應管之觸媒成分的塡充量充份維持時，觸 200843854 媒可抑制熱點的發生，並可使高負載之反應，長時間維持 丙烯醛或丙烯酸穩定之高產率。在觸媒粒徑之相對標準差 小於0.02時，即觸媒之粒徑一致時，一致的且大的空隙存 在於塡充於反應管中之粒子間。在此情形，可抑制熱點的 發生，但每一反應管塡充之觸媒成分的量減少，而變成需 要提升反應溫度以使反應之起始材料達到充分的轉化。結 果，因爲目標產物的選擇性下降，以及觸媒的加速劣化， 使得丙烯醛或丙烯酸的產率降低。另一方面，當觸媒粒徑 之相對標準差超過 0.20時，即觸媒具有過廣之粒徑分布 時，當其於塡充反應管時，小粒子進入大粒子間之空隙， 而顆粒間空隙劇烈減少。結果，雖然每一反應管塡充之觸 媒成分的量增加，但熱點的發生無法被抑制，而由於高溫 所造成之燃燒反應的增加以及觸媒的加速劣化，使得丙烯 醛或丙烯酸的產率降低。 本發明中，觸媒粒子不需要爲真正的球狀，只要大致 上爲球形便足夠。粒徑係以每一粒子於三個方向測量之直 徑的平均値來表示（三軸平均直徑）。當測量粒子的數目夠 多時，並不需要測量所有的粒子，而只要自整體隨機的採 樣測量便足夠。 觸媒之平均粒徑可依固定床式殻-管反應器之反應管 的內徑而適當的選擇。一般而言，用於上述反應之反應管 之內徑爲10-60毫米，而觸媒之平均粒徑較佳爲1-12毫米， 特別是3-10毫米。 將丙烯以氧分子或含氧分子之氣體，藉由觸媒氣相氧 200843854 化而便利的製備丙烯醛之該等依據本發明之氧化觸媒，含 由下式（2)表示之活性成分： M〇i2BiaFebAcBdCeDfOx ⑺ 其中Mo爲鉬，Bi爲鉍，Fe爲鐵，A爲至少一種選自 鈷、鎳之元素，B爲至少一種選自鹼金屬、鹼土金屬及鉈 之元素，C爲至少一種選自鎢、矽、鋁、鉻及鈦之元素，D 爲至少一種選自磷、碲、銻、錫、鈽、鉛、鈮、錳、砷及 鋅之元素，及〇爲氧；&、1)、〇、3、6^與\分別爲81、 Fe、A、B、C、D及〇之原子比例，其分別爲〇<a$ 1〇、〇<b $20、2$cS20、0<dS10、0€eS30、0$fS4、及 x 爲由 各元素之氧化態所決定之數値。 同樣的，將丙烯醛以氧分子或含氧分子之氣體，藉由 觸媒氣相氧化來製備丙烯酸之依據本發明的氧化觸媒，較 佳爲含由下式（3)表示之活性成分者：200843854 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalyst for the vapor phase oxidation of a catalyst for the aerobic oxidation of propylene to acrolein or acrolein to produce acrylic acid. More specifically, the present invention relates to an oxidation catalyst containing molybdenum as a main component, which has a specific particle size distribution. The present invention also relates to a process for producing acrolein or acrylic acid using the catalyst, and a process for producing a water-absorbent resin using the acrylic acid thus produced. [Prior Art] Acrolein has been widely used as a starting material for acrylic acid or the like in the industry, and acrylic acid is used as a starting material for a water absorbing resin. A general practical production process for acrolein or acrylic acid includes gas phase oxidation of propylene by a fixed bed type shell-and-tube reactor in the presence of an oxidation catalyst, or gas phase oxidation of acrolein. This catalytic gas phase oxidation reaction is highly exothermic and thus forms a local abnormally high temperature point (hereinafter referred to as "hot spot") in the catalyst layer. Due to the higher temperature than the other reaction zones, the oxidation reaction proceeds excessively in the hot spot, reducing the yield of the target product (i.e., acrolein or acrylic acid). Further, since the hot spot is exposed to a high temperature, the catalyst at this point exhibits a change in physical and chemical properties in a short time, which causes a significant decrease in its activity or selectivity due to sintering or the like. In particular, when the catalyst contains molybdenum, the high temperature of the hot spot accelerates the sublimation of the molybdenum, which causes a change in the composition of the catalyst (the composition ratio thereof), so that the degree of deterioration of the catalyst is large. Still another problem is that in order to enhance the reaction of acrolein or acrylic acid, this phenomenon increases when the reaction is carried out at a high space velocity or a high initial temperature concentration of 200843854 (i.e., a high load reaction). In order to properly handle these problems, various improvements have been proposed for the preparation of acrolein from propylene, for example, including mixing a reaction tube with a different type of catalyst occupying a different volume, and mixing an inert material molded article in at least one reaction zone (patent Document 1 ·· JP 2005-320315A = USP 7,161,044); using a method of loading a catalyst, comprising charging a reaction tube with a plurality of types of catalysts having different activities, the catalyst being changed by a catalyst Prepared by the loading rate of the upper catalytically active component and/or the calcination temperature, in such a manner that the activity becomes increased from the inner side to the outer side of the starting gas (Patent Document 2: JP Ping 10 (1998) -168003 A = USP 6,028, 2 00); or a plurality of catalysts to fill the reaction tube, in this way, the occupied volume of the catalyst in the reaction tube is reduced from the inside to the outside of the reaction gas (Patent Document 3: JP 4 (1 992)-2 1 793 2A = USP 5,1 98,5 8 1 ). Various improvements have been proposed in the preparation of acrylic acid from acrolein, for example, a method of diluting a catalyst with an inert substance on the inner side of a starting gas (Patent Document 4: JP ZHAO 5 3 (1 97 8)-3 068 8B = USP 3, 801, 634); using a catalyst-carrying method, including a catalyst-filled reaction tube, the loading rate of the catalytically active component of the catalyst increases from the inside to the outside of the starting gas (Patent Document 5: JP) Ping 7(1995)-10802A); comprising preparing a plurality of different active catalysts and charging them to a reaction tube by changing the kind and/or amount of alkali metal added to the catalyst. In the catalyst, the catalyst activity is increased from the inside to the outside of the starting gas (Patent Document 6: JP2000_3 3 6060A = USP 6, 563,000); the method of filling the reaction tube, which includes the volume of the catalyst particles from the starting gas. The way the inner side is lowered toward the outside (patent 200843854 document 7: JP flat 9 (1 997)-24 1 209A = USP 5, 719, 318). However, such a method of diluting the inactive material and changing the catalyst loaded with different activities reduces the amount of the effective product to the reaction, and the system is filled in the reaction tube, thereby reducing the contact between the acrylic acid and the preparation of a single species. Compared with the media, it takes more labor and more cost to prepare a plurality of species. Moreover, while all of the above proposals have achieved some degree of temperature, the effect is still not satisfactory. Therefore, in the current situation, the lifetime and the yield of acrolein or acrylic acid are in the space of these methods. DISCLOSURE OF THE INVENTION Objects of the Invention Accordingly, it is an object of the present invention to provide a catalyst which can inhibit the catalyst layer when it is subjected to gas phase oxidation to produce acrolein or when acrylic acid is prepared by the acupuncture of acrolein. The occurrence of local abnormally high temperature and stable supply of acrolein or acrylic acid for a long time. We have found that the production of acrylic acid is prepared by gas phase oxidation of propylene by catalyst or by catalytic gas phase oxidation of acrolein. In the bed type shell-tube reactor, when the catalyst particle size distribution in the reactor is filled, the gap between the catalyst particles can be uniformized and increased, and the local abnormal high temperature point (hot spot) can be suppressed without being lowered. The yield of acrylic acid, and the acrolein can be stably obtained over a long period of time or the present invention is thus completed. Rate or yield of the catalyst group used. The catalyst also needs to suppress hot spots. The catalyst is still improved by propylene gas phase oxygen. Point (hot spot) high yield. Acrolein, a process that imparts acrolein or acrylic acid to a specific catalyst layer. 200843854 Accordingly, the present invention provides an oxidation catalyst containing molybdenum as a main component, characterized in that the relative standard deviation of the particle diameter determined by the following formula (1) is at least 0.02 and not more than 0.20: relative standard deviation of particle diameter = Standard deviation/average particle size of particle size (1), r, 丄/一^ \ΝΣΧη2 -(ΣΧη)2 where the standard deviation of particle size = -^' person, ..."... y N(N -1 (N is the number of particles of the measured particle size; Xn is the particle size of each particle determined by the triaxial mean diameter, which is the average 値 of the diameter of f measured by each particle in three directions); The arithmetic mean particle diameter of the N particles is also provided. The present invention also provides a method for preparing acrolein by gas phase oxidation of propylene by a catalyst when a gas having oxygen molecules or oxygen-containing molecules is present, or when oxygen molecules are present or In the case of a gas containing oxygen molecules, a method of preparing acrylic acid by gas phase oxidation of acrolein by a catalyst is characterized in that the aforementioned catalyst is used. The present invention further provides a process for producing a water absorbing resin using acrylic acid obtained by the method of the present invention as a starting material. The effect of the present invention is because the catalyst of the present invention inhibits the occurrence of local abnormally high temperature points (hot spots) of the catalyst layer, and can stably maintain a high yield of acrolein or acrylic acid for a long period of time, and the catalyst of the present invention can be advantageously used. Use as a catalyst for preparing acrolein or acrylic acid in a fixed bed type shell-and-tube reactor, [Embodiment] Best Mode for Carrying Out the Invention The catalyst of the present invention suitably contains molybdenum as a main component, and has a particle size and has Determined by the formula (1), the range is at least 0.02 and a relative standard deviation of not more than 0.20. When the amount of the catalyst component of each reaction tube is sufficiently maintained, the catalyst can be inhibited from the occurrence of hot spots by the use of the medium, and a high load reaction can be maintained to maintain a high yield of acrolein or acrylic acid for a long period of time. When the relative standard deviation of the catalyst particle diameter is less than 0.02, that is, when the particle diameters of the catalysts are uniform, uniform and large voids exist between the particles in the reaction tube. In this case, the occurrence of hot spots can be suppressed, but the amount of the catalyst component for each reaction tube is reduced, and it becomes necessary to raise the reaction temperature so that the starting material of the reaction can be sufficiently converted. As a result, the yield of acrolein or acrylic acid is lowered because of the decrease in the selectivity of the target product and the accelerated deterioration of the catalyst. On the other hand, when the relative standard deviation of the catalyst particle diameter exceeds 0.20, that is, when the catalyst has an excessively large particle size distribution, when it is in the reaction tube, the small particles enter the gap between the large particles, and between the particles The gap is drastically reduced. As a result, although the amount of the catalyst component per unit of the reaction tube is increased, the occurrence of the hot spot cannot be suppressed, and the yield of acrolein or acrylic acid is increased due to an increase in the combustion reaction caused by the high temperature and accelerated deterioration of the catalyst. reduce. In the present invention, the catalyst particles need not be truly spherical, as long as they are substantially spherical. The particle size is expressed as the average 値 of the diameter of each particle measured in three directions (triaxial average diameter). When the number of measured particles is sufficient, it is not necessary to measure all the particles, as long as the measurement is accurate from the whole random sampling. The average particle diameter of the catalyst can be appropriately selected depending on the inner diameter of the reaction tube of the fixed bed type shell-and-tube reactor. In general, the inner diameter of the reaction tube for the above reaction is from 10 to 60 mm, and the average particle diameter of the catalyst is preferably from 1 to 12 mm, particularly from 3 to 10 mm. The oxidizing catalyst according to the present invention is preferably prepared by oxidizing a propylene with an oxygen molecule or a gas containing oxygen molecules by catalytic gas phase oxygen 200843854, and comprises an active ingredient represented by the following formula (2): M〇i2BiaFebAcBdCeDfOx (7) wherein Mo is molybdenum, Bi is ruthenium, Fe is iron, A is at least one element selected from the group consisting of cobalt and nickel, B is at least one element selected from the group consisting of alkali metals, alkaline earth metals and lanthanum, and C is at least one selected From elements of tungsten, rhenium, aluminum, chromium and titanium, D is at least one element selected from the group consisting of phosphorus, antimony, bismuth, tin, antimony, lead, antimony, manganese, arsenic and zinc, and antimony is oxygen; &, 1 ), 〇, 3, 6^ and \ are the atomic ratios of 81, Fe, A, B, C, D and 〇, respectively, which are 〇<a$ 1〇, 〇<b $20, 2$cS20, 0<dS10, 0€eS30, 0$fS4, and x are the number determined by the oxidation state of each element. Similarly, the oxidizing catalyst according to the present invention is prepared by subjecting acrolein to a gas of an oxygen molecule or an oxygen-containing molecule by gas phase oxidation of a catalyst, preferably an active component represented by the following formula (3). :
Mo^VgWhCu.EjFkGiHmOy (3) 其中Mo爲鉬，V爲釩，W爲鎢，Cu爲銅，E爲至少一 種選自鈷、鎳、鐵、鉛及鉍之元素，F爲至少一種選自銻、 銀及錫之兀素’ G爲至少一*種選自砂、錦、欽及銷之兀素’ Η爲至少一種選自鹼金屬之元素，及0爲氧；g、h、i、j、 k、1、m與y分別爲V、W、Cu、E、F、G、Η及◦之原子 比例，其分別爲 2S gg 15、〇$ 1〇、〇<!$ 6、OS 30、 0SkS6、0S1S60、〇$mg6、及y爲由各元素之氧化態 所決定之數値。 依據本發明之觸媒可爲藉由模製形成之成形觸媒的形 200843854 式或爲受載觸媒之形式，於受載觸媒之形式，觸媒活性成 分係承載於對反應爲惰性之載體上。如上述式之該等觸媒 活性成分可自通常用於製備此型觸媒之起始材料，藉由通 常所用之方式製備而得。至於起始材料，可使用例如氧化 物、氫氧化物、鹽（例如銨鹽、硝酸鹽、碳酸鹽、硫酸鹽、 有機酸鹽等）、其水溶液、其溶液、含複數種類之元素的化 合物等。 爲了製備成形觸媒，將起始材料接連的加入溶劑（如 I 水），以形成水溶液、懸浮液或漿液，並使用適當方式將所 得到的含觸媒成分之水溶液、懸浮液或漿液加以乾燥。至 於乾燥方法，例如，可使用蒸發乾燥，或使用噴霧乾燥器、 鼓乾燥器等形成乾燥粉末，或在以氣流進行加熱時可使用 箱型或隧道型乾燥器以提供乾燥塊或片。亦可使用真空乾 燥機以在減壓下有效乾燥，以提供乾燥塊或粉末。如此獲 得之乾燥產物，在需要時，經硏磨或分類之步驟後，送至 成形步驟，以得到粒徑適當的粉末。乾燥產物，在需要時， ^ 可在成形步驟前煅燒。只要可以成形爲大致上球狀之觸媒 粒子，觸媒之成形方式沒有特別的限制。可使用已知的成 形方式，例如以MarumerizerTM成形。在得到之成型產物乾 燥後，若需要，在300-600°C、較佳在350-500°C之溫度範 圍煅燒歷約1 -1 0小時，以提供氧化觸媒。 任何可均勻的承載前述觸媒活性成分於載體上之方 式，可有效的用來製備受載觸媒。例如，將含有上述任何 式所表示之觸媒活性成分之水溶液、懸浮液或漿液加以乾 -11- 200843854 燥、硏磨及視需要的煅燒，接著使用轉鼓型塗布設備、轉 鼓造粒機、旋轉及離散型混合機等，需要時，加入黏結劑（如 醇或水）。將載體浸漬於含有上述任何式所表示之觸媒活性 成分之水溶液、懸浮液或漿液亦爲有效。如此承載觸媒活 性成分之載體經乾燥，必要時，於範圍在300-600 °C、較佳 在35 0-500 °C之溫度加以煅燒歷約1-10小時，以提供受載 氧化觸媒。 至於用來承載觸媒之載體，任何用於各種已知之觸 ί 1 媒，特別是用於丙烯氧化反應之觸媒或丙烯醛氧化反應之 觸媒皆可使用。其較佳爲大致上球狀。更具體來說，可使 用氧化矽、氧化鋁、氧化矽-氧化鋁、碳化矽、硝化矽、氧 化鈦、氧化锆等，其中，較佳爲氧化鋁及氧化矽-氧化鋁。 載體可爲市售可得者，同時其亦可自含這些組成元素之起 始材料製備而得。 較佳之載體粒徑爲1-12毫米、特別是3-10毫米。具有 粒徑在前述特定範圍內、及依據式（1)所決定的相對標準差 ϋ 爲至少0.02且不大於0.20之載體爲特佳，因爲此種載體之 使用能夠以相對均勻含量之活性成分，簡單的製備具有粒 徑之相對標準差落在記載於本發明之範圍內的觸媒。在滿 足前述條件之載體可被直接製備的同時，亦可在製備後將 載體過篩以篩選出滿足前述條件之粒子。 成形觸媒可類似的直接製備以滿足式（1)之條件，或者 製備之觸媒本身可以篩子篩選出滿足式（1)之條件的觸媒 粒子。 -12- 200843854 對於本發明之觸媒，除了觸媒活性成分之外，尙可加 入成形助劑（如硝酸銨、纖維素等）、或強化劑（如玻璃纖維、 陶瓷纖維等）。 本發明可有效的用於所有的觸媒，包括特定觸媒活性 成分，特別是對高活性之觸媒，具有還要更高之效果。本 發明非常有效，特別是在進行高負載反應以提升丙烯醛或 丙烯酸之產率時。 在藉由丙烯之觸媒氣相氧化製備丙烯醛，或藉由丙烯 醛之觸媒氣相氧化製備丙烯酸的情況，使用存在有本發明 之觸媒的固定床式殼-管反應器時，不需要各別的、多層的 以觸媒塡充管，而只要簡單的以單一種類之觸媒塡充管即 可’則即便在高空間速度或高起始氣體濃度，熱點的發生 可被抑制，使丙烯醛或丙烯酸能夠保持高產率。不用說， 以各別的多層觸媒塡充管、以及用惰性物質稀釋部分觸 媒、或組合使用多種藉由各種成分、製備方式、煅燒條件 ., 等製備的氧化觸媒等方法的採用，並不會損害本發明之效 果。可使用具有不同佔據體積之多種氧化觸媒之各別的複 數觸媒層塡充反應管之方法，此時，每一各別層之氧化觸 媒係調整成具有記載於本發明之範圍內的相對標準差。 依據本發明，自丙烯製備丙烯醛之反應條件無特別限 制’反應可在通常用於此類反應之任何反應條件下操作。 例如，使用由1 -1 5體積％、較佳爲4 -1 2體積％之丙烯、較 佳爲0.5-25體積％、較佳爲2-20體積％之氧分子、〇-30體 積％、較佳爲0-25體積％之蒸汽、及平衡之惰性氣體（如氮 -13- 200843854 氣）所構成的氣體混合物爲起始氣體’其在範圍於 200-400 °C之溫度、〇.l-l.〇MPa 之壓力、及 300-5000 小時 _1(STP)之空間速度下與氧化觸媒接觸。 同樣地，自丙烯醛製備丙烯酸的反應條件無特別之限 制，而反應可在通常用於此類反應之任何反應條件下操 作。例如，可使用1 -1 5體積％、較佳爲4 -1 2體積％之丙烯 醛、0.5-25體積％、較佳爲2-20體積％之氧分子、0-30體積 %、較佳爲0-25體積％之蒸汽、及平衡之惰性氣體（如氮氣） 1 所構成的氣體混合物爲起始氣體，其在範圍於200-40(TC之 溫度、0.1-l.OMPa之壓力、及300-5000小時d(STP)之空間 速度下與氧化觸媒接觸。明顯的，可使用得自前述丙烯的 觸媒氣相氧化之含丙烯醛氣體，作爲本反應之含丙烯醛氣 體。在這種情況，可使用已知的方法，例如，藉由使用於 第一反應器塡充氧化丙烯用之觸媒及於第二反應器塡充氧 化丙烯醛用之觸媒的兩個反應器，將得自第一反應器之含 丙嫌醒氣體、循環氣體、氧氣或惰性氣體（如氮氣或蒸汽） " 導入第二反應器，以進一步將丙烯醛氧化爲丙烯酸；或使 用分割爲兩個反應區之反應器，於其中一反應區塡充氧化 丙烯用觸媒，而於另一反應區塡充氧化丙烯醛用觸媒。亦 可使用使用丙烯作爲起始材料而獲得之含有丙烯醛的混合 氣體。必要時可於此热體混合物中加入空氣或氧氣之類。 藉由此種觸媒氣相氧化所得之含丙烯酸之氣體，係藉 由將其吸收至溶劑（如水或高沸點疏水性有機溶劑之類）， 或藉由已知方式（如直接濃縮）加以處理，而轉化爲含丙烯 -14 - 200843854 酸之液體。如此所獲得的含丙烯酸之液體再藉由已知之萃 取、蒸餾或結晶方式加以純化，以提供純丙烯酸。吸水樹 脂可藉由使用所得到之純化丙烯酸及/或其鹽作爲基礎單 體而得到（較佳爲至少7 0莫耳％、特別爲至少9 0莫耳％)， 對其加入約0.001-5莫耳％之交聯劑與約0.001-2莫耳％之自 由基聚合起始劑（二者皆以丙烯酸計），以產生交聯聚合， 將所得到之聚合物加以乾燥，並加以硏磨。 吸水樹脂爲水可潤脹且水不可溶之具有交聯結構之聚 丙烯酸，其至少吸收3倍，較佳爲1 0 - 1 0 0 0倍於自身重量 之純水或生理食鹽水，以製備較佳含有不大於25質量％、 特別是不大於1 〇質量％之水可溶成分之水不可溶之水凝 膠。此種吸水樹脂的具體實例或其物理性質的測量方法敘 述於，例如美國專利 Nos.6，1 07,3 5 8、6，1 74,97 8 及 6,241，928。 [實施例] 以下，本發明藉由實施實例更具體的加以解釋，應了 解本發明並不僅限制於此等實例。於下面“質量份，，爲了方 便起見，簡易的寫爲“份”。於實例中，丙烯轉化率、丙烯 醛轉化率、丙烯醛產率及丙烯酸產率之定義如下： 丙烯轉化率（莫耳％)= (反應之丙烯的莫耳數) (供給之丙烯之莫耳數） 丙烯醛產率（莫耳％)= (形成之丙烯醛的莫耳數)Mo^VgWhCu.EjFkGiHmOy (3) wherein Mo is molybdenum, V is vanadium, W is tungsten, Cu is copper, E is at least one element selected from the group consisting of cobalt, nickel, iron, lead and antimony, and F is at least one selected from the group consisting of ruthenium , silver and tin bismuth 'G is at least one kind selected from the group consisting of sand, brocade, chin and pin ' ' ' Η is at least one element selected from alkali metals, and 0 is oxygen; g, h, i, j , k, 1, m, and y are atomic ratios of V, W, Cu, E, F, G, Η, and 分别, respectively, which are 2S gg 15, 〇$1〇, 〇<!$ 6, OS 30 0SkS6, 0S1S60, 〇$mg6, and y are the number determined by the oxidation state of each element. The catalyst according to the present invention may be in the form of a shaped catalyst formed by molding or in the form of a supported catalyst. In the form of a supported catalyst, the catalytically active component is carried inert to the reaction. On the carrier. The catalyst active ingredients of the above formula can be prepared from the usual starting materials for the preparation of the catalyst of this type by the usual methods. As the starting material, for example, an oxide, a hydroxide, a salt (for example, an ammonium salt, a nitrate, a carbonate, a sulfate, an organic acid salt, or the like), an aqueous solution thereof, a solution thereof, a compound containing a plurality of elements, and the like can be used. . In order to prepare the forming catalyst, the starting material is successively added to a solvent (such as I water) to form an aqueous solution, suspension or slurry, and the obtained aqueous solution, suspension or slurry containing the catalyst component is dried in an appropriate manner. . As for the drying method, for example, evaporative drying may be used, or a dry powder may be formed using a spray dryer, a drum dryer or the like, or a box type or tunnel type dryer may be used to provide a dry block or sheet when heating with a gas stream. A vacuum dryer can also be used to effectively dry under reduced pressure to provide a dry mass or powder. The dried product thus obtained is subjected to a honing or sorting step as needed, and then sent to a forming step to obtain a powder having an appropriate particle diameter. The product is dried and, if desired, ^ can be calcined prior to the forming step. The molding method of the catalyst is not particularly limited as long as it can be formed into substantially spherical catalyst particles. A known forming means can be used, for example, forming with a MarumerizerTM. After the obtained shaped product is dried, if necessary, it is calcined at a temperature of from 300 to 600 ° C, preferably from 350 to 500 ° C for about 1 to 10 hours to provide an oxidation catalyst. Any method which can uniformly carry the aforementioned catalytic active component on a carrier can be effectively used for preparing a supported catalyst. For example, an aqueous solution, suspension or slurry containing the catalytically active component represented by any of the above formulas is dried, honed, and optionally calcined, followed by a drum type coating apparatus, a drum granulator. , rotating and discrete mixers, etc., if necessary, add a binder (such as alcohol or water). It is also effective to immerse the carrier in an aqueous solution, suspension or slurry containing the catalytically active component represented by any of the above formulas. The carrier carrying the catalytically active component is dried and, if necessary, calcined at a temperature in the range of from 300 to 600 ° C, preferably from 35 to 500 ° C for about 1-10 hours to provide a supported oxidation catalyst. . As the carrier for carrying the catalyst, any catalyst for various known catalysts, particularly a catalyst for a propylene oxidation reaction or an acrolein oxidation reaction, can be used. It is preferably substantially spherical. More specifically, cerium oxide, aluminum oxide, cerium oxide-alumina, cerium carbide, cerium nitrate, titanium oxide, zirconium oxide or the like can be used, and among them, alumina and cerium oxide-alumina are preferable. The carrier may be a commercially available one, and it may also be prepared from the starting materials containing these constituent elements. Preferred carriers have a particle size of from 1 to 12 mm, especially from 3 to 10 mm. A carrier having a particle size within the above specific range and having a relative standard deviation ϋ determined according to formula (1) of at least 0.02 and not more than 0.20 is particularly preferred because such a carrier can be used in a relatively uniform amount of the active ingredient, A catalyst having a relative standard deviation of particle diameter falling within the scope of the present invention is simply prepared. While the carrier which satisfies the above conditions can be directly prepared, the carrier can also be sieved after preparation to screen out particles satisfying the above conditions. The forming catalyst can be similarly prepared directly to satisfy the condition of the formula (1), or the catalyst itself can be screened to filter the catalyst particles satisfying the conditions of the formula (1). -12- 200843854 For the catalyst of the present invention, in addition to the catalytically active component, cerium may be added with a forming aid (e.g., ammonium nitrate, cellulose, etc.), or a reinforcing agent (e.g., glass fiber, ceramic fiber, etc.). The present invention is effective for all catalysts, including specific catalyst active ingredients, particularly for highly active catalysts, with even higher effects. The present invention is very effective, especially when carrying out a high load reaction to increase the yield of acrolein or acrylic acid. In the case where acrolein is produced by gas phase oxidation of a catalyst of propylene or acrylic acid is produced by gas phase oxidation of a catalyst of acrolein, when a fixed bed type shell-and-tube reactor in which the catalyst of the present invention is present is used, It is necessary to use a separate, multi-layered catalyst to fill the tube, and simply fill the tube with a single type of catalyst. Even at high spatial velocities or high initial gas concentrations, the occurrence of hot spots can be suppressed. Acrolein or acrylic acid can be maintained in high yield. Needless to say, the use of a separate multi-layer catalyst to fill the tube, and to dilute a part of the catalyst with an inert substance, or a combination of various methods, preparation methods, calcination conditions, etc., is employed, It does not impair the effects of the present invention. The method of charging a reaction tube by using a plurality of complex catalyst layers having a plurality of oxidation catalysts having different occupied volumes, wherein the oxidation catalyst system of each individual layer is adjusted to have a range described in the present invention. Relative standard deviation. According to the present invention, the reaction conditions for producing acrolein from propylene are not particularly limited. The reaction can be carried out under any reaction conditions generally used for such reactions. For example, from 1 to 5% by volume, preferably from 4 to 12% by volume of propylene, preferably from 0.5 to 25% by volume, preferably from 2 to 20% by volume, of oxygen molecules, hydrazine - 30% by volume, Preferably, the gas mixture of 0-25% by volume of steam and a balanced inert gas (such as nitrogen-13-200843854 gas) is the starting gas 'which is in the range of 200-400 ° C, 〇.ll Contact with oxidizing catalyst at a pressure of 〇MPa and a space velocity of 300-5000 hours _1 (STP). Similarly, the reaction conditions for preparing acrylic acid from acrolein are not particularly limited, and the reaction can be carried out under any reaction conditions conventionally used for such a reaction. For example, 1 to 15% by volume, preferably 4 to 12% by volume of acrolein, 0.5 to 25% by volume, preferably 2 to 20% by volume of oxygen molecules, 0 to 30% by volume, preferably, may be used. a gas mixture of 0-25% by volume of steam and a balanced inert gas (such as nitrogen) 1 as a starting gas, which is in the range of 200-40 (TC temperature, 0.1-1.0 MPa pressure, and Contact with an oxidizing catalyst at a space velocity of 300-5000 hours d (STP). Obviously, an acrolein-containing gas obtained by gas phase oxidation of a catalyst derived from the above propylene can be used as the acrolein-containing gas of the present reaction. In a case, a known method can be used, for example, by using two catalysts for charging a catalyst for propylene oxide in a first reactor and a catalyst for activating acrolein in a second reactor. a propylene-containing awake gas, a recycle gas, an oxygen or an inert gas (such as nitrogen or steam) from the first reactor " introduced into the second reactor to further oxidize acrolein to acrylic acid; or split into two reactions a reactor in which one of the reaction zones is charged with a catalyst for propylene oxide, and The other reaction zone is charged with a catalyst for acrolein. A mixed gas containing acrolein obtained by using propylene as a starting material may be used, and if necessary, air or oxygen may be added to the hot body mixture. The acrylic acid-containing gas obtained by vapor phase oxidation of such a catalyst is treated by absorbing it into a solvent such as water or a high-boiling hydrophobic organic solvent, or by a known means such as direct concentration. Conversion to a liquid containing propylene-14 - 200843854 acid. The acrylic acid-containing liquid thus obtained is further purified by known extraction, distillation or crystallization to provide pure acrylic acid. The water absorbing resin can be obtained by using the obtained purified acrylic acid. And/or a salt thereof is obtained as a base monomer (preferably at least 70% by mole, particularly at least 90% by mole), to which about 0.001 to 5 mole % of crosslinking agent is added and about 0.001- 2 mol% of a radical polymerization initiator (both in terms of acrylic acid) to produce cross-linking polymerization, and the obtained polymer is dried and honed. The water absorbing resin is water swellable and water is not swellable. The polyacrylic acid having a crosslinked structure, which absorbs at least 3 times, preferably 10 to 1 000 times its own weight of pure water or physiological saline, is preferably prepared to contain not more than 25% by mass, particularly A water-insoluble hydrogel which is not more than 1% by mass of a water-soluble component. A specific example of such a water-absorbent resin or a method for measuring its physical properties is described, for example, in U.S. Patent No. 6,07,3 5 8, 6, 74, 97 8 and 6,241, 928. [Examples] Hereinafter, the present invention will be more specifically explained by way of examples, and it should be understood that the present invention is not limited by the examples. For the sake of convenience, the simple one is written as "parts." In the examples, the definitions of propylene conversion, acrolein conversion, acrolein yield, and acrylic acid yield are as follows: Propylene conversion (% by mole) = (molar number of propylene reacted) (Moir supplied to propylene) Number) Acrolein yield (% by mole) = (molar number of acrolein formed)
(供給之丙烯之莫耳數）X 丙烯醛轉化率（莫耳％)=(Molar number of propylene supplied) X Acrolein conversion rate (% by mole) =
(反應之丙烯酸的莫耳數)X (供給之丙烯醛之莫耳數)X -15- 200843854 丙烯酸產率（莫耳％)= (形成之丙烯酸的莫耳數)::1⑻ (供糸合之丙烯醛之莫耳數） 實例1 -載體之製備- 90份之平均粒徑爲2-1 Ομιη的α -氧化鋁粉末與5份作 爲有機黏著劑之甲基纖維素投入捏合機中充分混合。接 著，將3份（以Al2〇3含量計）平均粒徑2-20奈米之氧化鋁溶 膠與7份（以Si〇2含量計）平均粒徑2-20奈米之膠體氧化矽 加入混合物中。進一步將水倒入捏合機並充份混合，得到 添加氧化矽之氧化鋁混合物。將混合物擠壓成形，以形成 直徑約5.5毫米、長度約3.0-7.0毫米（平均5.5毫米）之圓 柱狀成形體，接著將其加以硏磨直到形成球形粒子。如此 乾燥，將粒子於1400°C煅燒2小時，接著藉由網目大小不 大於5.6毫米但不小於4.0毫米之篩子加以篩選。採樣1 00 克如此所獲得之載體，並測量其粒徑。平均粒徑爲5.00毫 米、於式（1)之標準差爲0.25及相對標準差爲0.05。 -觸媒之製備- 在加熱與攪拌下，將3 50份之鉬酸銨溶入2,000份之蒸 餾水（液A)。另外，將154份之硝酸鈷及144份之硝酸鎳溶 入5 00份之蒸餾水（液B)。進一步，另外將73.4份之硝酸 鐵及120份之硝酸鉍溶於3 50份之蒸餾水（液C)，該蒸餾水 係已藉由加入15份之濃硝酸（65量％)而酸化。將這些硝酸 溶液（液B及C)滴入液A。緊接著加入993份20質量％氧化 矽溶液及0.84份之硝酸鉀。將所得到的懸浮液加熱、攪拌 •16· 200843854 並汽化，乾燥之產物進一步於2 0 0 °C乾燥，並硏磨至不大於 1 5 Ο μιη以提供觸媒粉末。將1 7 5 0份前述之載體投入離心流 體塗布裝置，然後將觸媒粉末與作爲黏著劑之3 5質量％之 硝酸銨水溶液通過90 °C熱空氣流投入其中，使觸媒成份受 載於載體。其後，使受載觸媒接受在空氣大氣中之470 °C之 熱處理歷6小時，以提供氧化觸媒。除了氧之外，構成觸 媒活性成分的金屬元素的組成如下所示： M〇i2Bii.5C〇3.2Ni3.〇Fei.iK〇.〇sSi2〇 I 藉由下面方程式所計算得到之此氧化觸媒之承載率爲約30 質量％。 受載率（莫耳％)= (氧化觸媒之質量-載體之質量)碰 載體之質量 Χ 採樣1 00克之氧化觸媒並測量粒徑之結果如下：平均 粒徑：5.22毫米、標準差：0.31、及相對標準差0.06。 -反應- g 將氧化觸媒塡充入內徑25毫米、長度3,000毫米之鋼(molar number of acrylic acid reacted) X (molar number of acrolein supplied) X -15- 200843854 Acrylic acid yield (mol%) = (molar number of acrylic acid formed):: 1 (8) (for combination Example 1 - Preparation of Support - 90 parts of α-alumina powder having an average particle diameter of 2-1 Ομηη and 5 parts of methyl cellulose as an organic binder are mixed in a kneader . Next, 3 parts (as Al 2 〇 3 content) alumina sol having an average particle diameter of 2-20 nm and 7 parts (as Si 〇 2 content) colloidal cerium oxide having an average particle diameter of 2-20 nm are added to the mixture. in. Further, water was poured into a kneader and thoroughly mixed to obtain a cerium oxide-added alumina mixture. The mixture was extrusion molded to form a cylindrical shaped body having a diameter of about 5.5 mm and a length of about 3.0 to 7.0 mm (average 5.5 mm), which was then honed until spherical particles were formed. So dried, the particles were calcined at 1400 ° C for 2 hours and then screened by a sieve having a mesh size of not more than 5.6 mm but not less than 4.0 mm. One hundred thousand grams of the thus obtained carrier was sampled and its particle size was measured. The average particle diameter was 5.00 mm, the standard deviation of the formula (1) was 0.25, and the relative standard deviation was 0.05. - Preparation of catalyst - 3 50 parts of ammonium molybdate was dissolved in 2,000 parts of distilled water (Liquid A) under heating and stirring. Further, 154 parts of cobalt nitrate and 144 parts of nickel nitrate were dissolved in 500 parts of distilled water (Liquid B). Further, 73.4 parts of ferric nitrate and 120 parts of cerium nitrate were dissolved in 3 50 parts of distilled water (Liquid C) which had been acidified by adding 15 parts of concentrated nitric acid (65% by volume). These nitric acid solutions (Liquids B and C) were dropped into Liquid A. Next, 993 parts of a 20% by mass cerium oxide solution and 0.84 parts of potassium nitrate were added. The resulting suspension is heated, stirred, and centrifuged at 16·200843854, and the dried product is further dried at 200 ° C and honed to not more than 15 Ο μηη to provide a catalyst powder. 1705 parts of the aforementioned carrier was put into a centrifugal fluid coating device, and then the catalyst powder and a 35 mass% aqueous ammonium nitrate solution as an adhesive were introduced into the hot air stream at 90 ° C to cause the catalyst component to be carried. Carrier. Thereafter, the loaded catalyst was subjected to heat treatment at 470 ° C for 6 hours in an air atmosphere to provide an oxidation catalyst. In addition to oxygen, the composition of the metal element constituting the active component of the catalyst is as follows: M〇i2Bii.5C〇3.2Ni3.〇Fei.iK〇.〇sSi2〇I This oxidation catalyst is calculated by the following equation The load ratio was about 30% by mass. Loading rate (% by mole) = (mass of oxidation catalyst - mass of carrier) The mass of the carrier Χ The results of sampling the oxidation catalyst of 100 grams and measuring the particle size are as follows: average particle size: 5.22 mm, standard deviation: 0.31 and a relative standard deviation of 0.06. -Reaction - g The oxidation catalyst is filled into a steel with an inner diameter of 25 mm and a length of 3,000 mm.
U 反應管，使塡充的觸媒層之長度爲2,000毫米。在反應氣 體-觸媒層內側間插入平均粒徑5毫米之氧化鋁球，塡充長 度200毫米作爲預熱層。將由7.5體積％之丙烯、64體積％ 之空氣、2 1體積％之蒸汽、與平衡之情性氣體（如氮氣）所構 成的導入反應管，以對於氧化觸媒爲1，700小時^(STP)之空 間速度進行反應。在反應的起始階段及反應2,000個小時 後之性能示於表1。 m m 2 -17- 200843854 除了在載體製備階段以網目大小不大於5.6毫 小於3.4毫米之篩子加以篩選載體，重複實例1。結 表1。載體具有4.82毫米之平均粒徑、0.67之標準差 之相對標準差。所得到的氧化觸媒具有5.1 2毫米之 徑、0.56之標準差及0.11之相對標準差。 比較例 1 除了在載體製備階段以網目大小不大於5 · 6毫 小於2.4毫米之篩子加以篩選載體，重複實例1 °結 f 表1。載體具有4.99毫米之平均粒徑、1.05之標準差 之相對標準差。所得到的氧化觸媒具有5 · 1 7毫米之 徑、1.19之標準差及0.23之相對標準差。 比較例2 除了在載體製備階段以網目大小不大於5.6毫 小於4 · 6毫米之篩子加以篩選載體，重複實例1 °結 表1。載體具有5.00毫米之平均粒徑、0.05之標準差 之相對標準差。所得到的氧化觸媒具有5 · 20毫米之 1 ； 一 徑、0.05之標準差及〇.〇1之相對標準差。 米且不 果示於 及 0.14 平均粒 米且不 果示於 及 0.21 平均粒 米且不 果示於 及 0.01 平均粒 -18- 200843854U reaction tube so that the length of the charged catalyst layer is 2,000 mm. An alumina sphere having an average particle diameter of 5 mm was inserted between the inside of the reaction gas and the catalyst layer, and the length of the crucible was 200 mm as a preheating layer. Introducing a reaction tube consisting of 7.5 vol% propylene, 64 vol% air, 21 vol% steam, and a balanced inert gas (such as nitrogen) for 1,700 hours for the oxidation catalyst (STP The space velocity reacts. The properties at the initial stage of the reaction and after 2,000 hours of reaction are shown in Table 1. m m 2 -17- 200843854 Example 1 was repeated except that the vector was screened at a carrier preparation stage with a sieve having a mesh size of not more than 5.6 millimeters and less than 3.4 millimeters. Table 1. The carrier had an average particle diameter of 4.82 mm and a relative standard deviation of a standard deviation of 0.67. The resulting oxidation catalyst had a diameter of 5.1 2 mm, a standard deviation of 0.56, and a relative standard deviation of 0.11. Comparative Example 1 Except that the carrier was screened at a carrier preparation stage with a mesh size of not more than 5 · 6 millimeters and less than 2.4 mm, the example 1 ° knot f was repeated. The carrier had an average particle diameter of 4.99 mm and a relative standard deviation of a standard deviation of 1.05. The resulting oxidizing catalyst had a diameter of 5 · 17 mm, a standard deviation of 1.19, and a relative standard deviation of 0.23. Comparative Example 2 Example 1 ° Table 1 was repeated except that the carrier was screened at a carrier preparation stage with a mesh size of not more than 5.6 millimeters and less than 4.6 millimeters. The carrier had an average particle diameter of 5.00 mm and a relative standard deviation of a standard deviation of 0.05. The resulting oxidizing catalyst has a diameter of 5 · 20 mm; a diameter, a standard deviation of 0.05, and a relative standard deviation of 〇.〇1. The rice is not shown in the 0.14 average grain and is not shown in the 0.21 average grain and is not shown in the 0.01 and the average grain -18- 200843854
丙烯酸之產率 (莫耳％) Η CO oo 83.2 82.9 82.9 76.1 75.6 77.3 76.3 丙烯醛轉化率 (莫耳％) wn 〇6 ON 98.5 oo ON 98.5 99.1 98.9 98.2 97.5 熱點溫度(°c) s 04 VO S CN ON 〇\ OO … 反應溫度(°c) cn 1 < cn CO cn CO s m cn r—H cn m CN CO 操作時間(小時） 起始階段 _] 2000 起始階段 2000 起始階段 2000 起始階段 2000 觸媒 相對標準差 0.06 \,,mi r· H 0.23 Η Ο 平均粒徑(毫米） 5.22 5.12 5.20 載體 相對標準差 0.05 0.14 0.21 0.01 平均粒徑(毫米） 5.00 4.82 4.99 5.00 實例1 實例2 比較例1 比較例2 〇\ 200843854 實例3 -觸媒之製備- 在加熱與攪拌下，將5 1 3份之仲鉬酸銨、1 7 0份之偏釩 酸銨與78.5份之仲鎢酸銨溶入4,000份之蒸餾水。在加熱 與攪拌下，另外將146份之硝酸銅溶入200份之蒸餾水。 將如此所得到之二種水溶液混合，並進一步加入48.4份之 氧化鈦與3 5 .3份之氧化亞銻以提供懸浮液。將懸浮液置於 熱水浴上之瓷蒸發器，並於其中加入1 7 5 0份如實例1所製 ί ' 備之載體。在攪拌下將系統揮發，以乾燥固體，以將觸媒 組成物沉積於載體上。將如此所形成的受載觸媒取出，並 接受在空氣大氣中之4 00 °C之熱處理歷6小時，如此提供氧 化觸媒。除了氧之外，構成觸媒活性成分的金屬元素的組 成如下所示： M〇12V6W 1.2CU2.5SblTl2.5 此氧化觸媒之受載率爲約30質量％。氧化觸媒之平均粒徑 爲5.16毫米、標準差爲0.21及相對標準差爲0.04。 (-反應- 將氧化觸媒塡充入內徑25毫米、長度3,000毫米之鋼 反應管，使塡充的觸媒層之長度爲2,000毫米。在反應氣 體-觸媒層內側間插入平均粒徑5毫米之氧化銘球，塡充長 度200毫米作爲預熱層。將由7體積％之丙烯醛、35體積％ 之空氣、1 5體積％之蒸汽、與平衡之惰性氣體（如氮氣）所構 成的導入反應管，以對於氧化觸媒爲1，5〇〇小時"（STP)之空 間速度進行反應。在反應的起始階段及反應2,000個小時 後之性能示於表2。 -20- 200843854 實例4 除了使用實例2所得到之載體做爲載體以外’以 例3相同之方式進行觸媒之製備與反應。結果示於表 氧化觸媒具有5.16毫米之平均粒徑、〇· 67之標準差及 之相對標準差。 比較例3 除了使用比較例1所得到之載體做爲載體以外， 實例3相同之方式進行觸媒之製備與反應。結果示於_ f、 氧化觸媒具有5.16毫米之平均粒徑、1.08之標準差及 之相對標準差。 比較例4 除了使用比較例2所得到之載體做爲載體以外， 實例3相同之方式進行觸媒之製備與反應。結果示於I 氧化觸媒具有5.19毫米之平均粒徑、0.07之標準差及 之相對標準差。 實例5 Q 將比較例3所得到之觸媒以網目大小不大於5.6 且不小於3.4毫米之篩子加以篩選。除此之外，以與 例3相同之方式進行觸媒之製備與反應。氧化觸媒於 後具有5.13毫米之平均粒徑、0.77之標準差及〇·15之 標準差。結果示於表2。 實例6 -載體之製備- 75份之平均粒徑爲2-1 Ομιη的α -氧化鋁粉末與5 爲有機黏著劑之甲基纖維素投入捏合機中充分混合 與實 2 〇 0.13 以與 12° 0.21 以與 ft 2 〇 0.01 毫米 比較 篩選 相對 份作 。接 -21- 200843854 著，將8份（以Al2〇3含量計）平均粒徑2-20奈米之氧化鋁溶 膠與17份（以Si〇2含量計）平均粒徑2-20奈米之膠體氧化 矽加入混合物中。進一步將水倒入捏合機並充份混合，得 到添加氧化矽之氧化鋁混合物。將混合物擠壓成形，以形 成直徑約8.5毫米、長度約6.0-10.0毫米（平均8. 5毫米） 之圓柱狀成形體，接著將其加以硏磨直到得到球形粒子。 如此乾燥，將粒子於1400°C煅燒2小時，接著藉由網目大 小不大於8.5毫米且不小於7.2毫米之篩子加以篩選。如此 f 所得的載體具有8.00毫米之平均粒徑、0.32之標準差及 0.04之相對標準差。 -觸媒之製備- 在加熱與攪拌下，將5 30份之仲鉬酸銨、87.7份之偏 釩酸銨與74.2份之仲鎢酸銨溶入4,000份之蒸餾水。在加 熱與攪拌下，另外將72.4份之硝酸銅與14.5份之硝酸鈷溶 入2 00份之蒸餾水。將如此所得到之二種水溶液混合，並 進一步加入29.1份之氧化亞銻以提供懸浮液。將懸浮液置 Q 於熱水浴上之瓷蒸發器，並於其中加入1 750份前述之載 體。在攪拌下將系統蒸發以乾燥固體，以將觸煤成分沉積 於載體上。取出如此所製得的受載觸媒，使其於空氣大氣 中接受400°C之熱處理歷6小時，以提供氧化觸媒。此氧化 觸媒之受載率爲約3 0質量％，除了氧之外，構成觸媒活性 成分的金屬元素的組成如下所示： M〇l2V3Wl.lCUl.2Sb〇.8C〇0. 2 該氧化觸媒具有8.50毫米之平均粒徑、〇·34之標準差及 0.04之相對標準差。 -22- 200843854 -反應- 使用如此所得的氧化觸媒以與實例3相同之方式進行 反應。結果示於表2。 實例7 在加熱與攪拌下，將5 3 0份之仲鉬酸銨、87.7份之偏 釩酸銨與74.2份之仲鎢酸銨溶入4,000份之蒸餾水。在加 熱與攪拌下，分別將7 2 · 4份之硝酸銅與1 4 · 5份之硝酸鈷溶 入200份之蒸餾水。將如此所得到之二種水溶液混合，並 f 進一步加入29 · 1份之氧化亞銻以提供懸浮液。以噴霧乾燥 器乾燥懸浮液。將所得到的顆粒粉末於3 90°C煅燒約5小 時。此時將溫度計插入顆粒粉末，以控制之方式升高烤箱 溫度，如此以避免急速的溫度提升。將經煅燒之顆粒粉末 硏磨至不大於1 5 0 μπι之大小，以提供觸媒粉末。將1 7 5 0份 如實例6中所得到之載體投入離心流體塗布裝置，然後將 觸媒粉末與作爲黏著劑之20質量％之甘油水溶液經由90 °C 熱空氣流投入其中，使其受載於載體。使產物接受在空氣 I 大氣中之400T：之熱處理歷6小時，如此得到氧化觸媒。此 氧化觸媒之受載率爲約3 0質量％，除了氧之外’構成觸媒 活性成分的金屬元素的組成如下所示： MOi2V3Wl.lCUl.2Sbo.8COO.2 該氧化觸媒具有8.95毫米之平均粒徑、〇·36之標準差即 0.04之相對標準差。 -反應- 使用如上所得之觸媒，以與實例3相同之方式進行反 應。結果示於表2。 -23- 200843854 實例8 除了以網目大小不大於9.0毫米且不小於6 ·7毫米之篩 子篩選載體之外，重複實例6。結果示於表2。載體具有8.02 毫米之平均粒徑、0.64之標準差及0.08之相對標準差。所 得到之氧化觸媒具有8.52毫米之平均粒徑、〇· 68之標準 差、0.08之相對標準差。 實例9 將實例7所用之載體以網目大小不大於9.0毫米且不 小於6.7毫米之篩子篩選載體之外。除此之外’重複實例7。 結果示於表2。載體具有8.02毫米之平均粒徑、0.64之標 準差及0.08之相對標準差。所得到之氧化觸媒具有8.97毫 米之平均粒徑、0.72之標準差、〇.〇8之相對標準差。 比鮫例5 除了以網目大小不大於8.2毫米且不小於7 · 8毫米之篩 子篩選載體之外，重複實例6。結果示於表2。載體具有8.00 毫米之平均粒徑、0.0 8之標準差及〇 ·0 1之相對標準差。所 得到之氧化觸媒具有8.50毫米之平均粒徑、〇· 〇9之標準 差、0.01之相對標準差。 1±較例6 除了以網目大小不大於8 · 2毫米且不小於7 · 8毫米之篩 子篩選載體之外，重複實例7。結果示於表2。載體具有8.00 毫米之平均粒徑、0.08之標準差及〇·01之相對標準差。所 得到之氧化觸媒具有8.95毫米之平均粒徑、〇·〇9之標準 差、0.01之相對標準差。 -24- 200843854 比較例6 比較例5 實例9 實例8 實例7 實例6 實例5 比較例4 1 比較例3 實例4 實例3 8.00 8.00 8.02 8.02 8.00 8.00 4.99 5.00 4.99 4.82 5.00 |平均粒徑(毫米)| ΙτηΙΙι Μ 0.01 p 0.08 0.08 0.04 0.04 O to j 0.01 〇 0.14 0.05 相對標準差 藏 〇〇 8.50 8.97 8.52 OO 8.50 y\ LO 5.19 1 j 5.16 5.16 y\ a\ 1平均粒徑(毫米） 觸媒 ! 0.01 0.01 0.08 0.08 0.04 0.04 0.15 0.01 0.21 0.13 0.04 相對標準差 2000 起始階段 2000 I起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 2000 起始階段 操作時間(小時) to 〇〇 VO to oo oo oo oo to oo 〇\ to ON to to to OO to ->0 to On b〇 On to On to to OO N3 ^r\ oo σ\ to 〇\ σ\ OO to ON 反應溫度CC) h—* to un δ LA »—1 on |_k 1—-» 〇\ to LO H—^ oo vg S s OO 熱點溫度(°C) 97.8 98.0 97.9 98.2 98.3 98.3 Γ 98.2 98.2 98.4 98.6 98.2 98.3 98.4 j 98.6 97.7 98.3 98.7 99.5 98.3 98.4 98.4 98.4 丙烯醛轉化率 (莫耳％) 〇〇 87.6 87.9 88.1 93.4 1 93.4 uo ON 93.7 93.5 93.6 93.4 93.4 93.5 93.6 87.7 89.0 85.8 OO 93.4 93.5 93.4 93.4 丙烯酸之產率 (莫耳％) 200843854 實施例1 ο -反應- 由約8，5 Ο 0根反應管（各別之直徑爲2 5毫米、長度爲 5,000毫米）及用於流通覆蓋反應管之熱介質之殻組成固定 床式殻-管反應器，藉由將得自實例1之觸媒（“第一階段觸 媒，，）、外徑爲8毫米之SUS拉西環、與得自實例3之觸媒（“第 二階段觸媒”）連續的投入反應管頂部，將觸媒塡充入反應 管，使其各層之長度如下：第一階段觸媒爲2,300毫米、 f 拉西環爲400毫米及第二階段觸媒爲2,300毫米。在距離殻 之底部2，500毫米之位置，置入50毫米厚之隔板，將殼分 割爲上部及下部。在上部及下部殼之空間，熱介質向上循 環。自反應器的底部部分，導入由8體積％之丙烯、76體 積％之空氣、12體積％之蒸汽、及平衡之惰性氣體（如氮氣） 所組成的氣體混合物，反應係在1，600小時〃（STP)之對第一 階段觸媒的空間速度進行。在反應的起始階段及反應2,000 個小時後之性能示於表3 表3 操作時間 (小時） 第一階段觸媒 反應溫度(。。） 熱點溫度 CC) 第二階_某 鹏麵。C) 熱點溫度 CC) 丙烯轉化率 (莫耳％) 丙烯隨傾 (期%) 實例10 起始階段 315 61 270 60 98.5 89.6 2000 316 61 271 59 98.5 89.4 【圖式簡單說明】 無。 【元件符號說明】 Μ 〇 j\\\ -26-Acrylic acid yield (mol%) Η CO oo 83.2 82.9 82.9 76.1 75.6 77.3 76.3 Acrolein conversion (mol%) wn 〇6 ON 98.5 oo ON 98.5 99.1 98.9 98.2 97.5 Hot spot temperature (°c) s 04 VO S CN ON 〇\ OO ... reaction temperature (°c) cn 1 < cn CO cn CO sm cn r—H cn m CN CO operation time (hours) initial stage _] 2000 initial stage 2000 initial stage 2000 start Stage 2000 Catalyst relative standard deviation 0.06 \,, mi r· H 0.23 Η Ο Average particle size (mm) 5.22 5.12 5.20 Relative standard deviation of the carrier 0.05 0.14 0.21 0.01 Average particle size (mm) 5.00 4.82 4.99 5.00 Example 1 Example 2 Comparison Example 1 Comparative Example 2 〇\ 200843854 Example 3 - Preparation of Catalyst - 51 1 part of ammonium paramolybdate, 170 parts of ammonium metavanadate and 78.5 parts of ammonium paratungstate were dissolved in 4,000 under heating and stirring. Distilled water. Further, 146 parts of copper nitrate was dissolved in 200 parts of distilled water under heating and stirring. The two aqueous solutions thus obtained were mixed, and further, 48.4 parts of titanium oxide and 35.3 parts of cerium oxide were further added to provide a suspension. The suspension was placed in a porcelain evaporator on a hot water bath, and 175 parts of a carrier prepared as in Example 1 was added thereto. The system is volatilized with agitation to dry the solids to deposit the catalyst composition on the support. The carrier catalyst thus formed was taken out and subjected to heat treatment at 400 ° C for 6 hours in an air atmosphere, thus providing an oxidizing catalyst. In addition to oxygen, the composition of the metal element constituting the catalytically active component is as follows: M〇12V6W 1.2CU2.5SblTl2.5 The loading ratio of this oxidation catalyst is about 30% by mass. The average particle size of the oxidizing catalyst was 5.16 mm, the standard deviation was 0.21, and the relative standard deviation was 0.04. (-Reaction - The oxidation catalyst was filled into a steel reaction tube having an inner diameter of 25 mm and a length of 3,000 mm so that the length of the charged catalyst layer was 2,000 mm. The average particle diameter was inserted between the inside of the reaction gas and the catalyst layer. A 5 mm oxidized title ball with a length of 200 mm as a preheating layer consisting of 7 vol% acrolein, 35% by volume air, 15 vol% steam, and a balanced inert gas such as nitrogen. The reaction tube was introduced and reacted at a space velocity of 1,5 hrs (STP) for the oxidation catalyst. The properties at the initial stage of the reaction and after 2,000 hours of reaction are shown in Table 2. -20- 200843854 Example 4 The preparation and reaction of the catalyst were carried out in the same manner as in Example 3 except that the carrier obtained in Example 2 was used as a carrier. The results show that the oxidation catalyst has an average particle diameter of 5.16 mm and a standard deviation of 〇·67. And the relative standard deviation.Comparative Example 3 The preparation and reaction of the catalyst were carried out in the same manner as in Example 3 except that the carrier obtained in Comparative Example 1 was used as the carrier. The results are shown in _f, and the oxidation catalyst has an average of 5.16 mm. Particle size, 1. The standard deviation of 08 and the relative standard deviation.Comparative Example 4 The preparation and reaction of the catalyst were carried out in the same manner as in Example 3, except that the carrier obtained in Comparative Example 2 was used as the carrier. The results show that the I oxidation catalyst has 5.19 mm. Average particle size, standard deviation of 0.07, and relative standard deviation. Example 5 Q The catalyst obtained in Comparative Example 3 was screened with a sieve having a mesh size of not more than 5.6 and not less than 3.4 mm. The preparation and reaction of the catalyst were carried out in the same manner as in Example 3. The oxidation catalyst had an average particle diameter of 5.13 mm, a standard deviation of 0.77, and a standard deviation of 〇15. The results are shown in Table 2. Example 6 - Preparation of carrier - 75 parts of α-alumina powder having an average particle diameter of 2-1 Ομιη and 5 parts of methyl cellulose as an organic binder are put into the kneader and thoroughly mixed with 2 〇 0.13 to 12° 0.21 to ft 2 〇 0.01 mm compares and screens the relative parts. From 20 to 200843854, 8 parts (based on Al2〇3 content) average particle size 2-20 nm alumina sol and 17 parts (as Si〇2 content) average Colloidal cerium oxide with a particle size of 2-20 nm is added Further, the water was poured into a kneader and mixed thoroughly to obtain a cerium oxide-added alumina mixture. The mixture was extruded to form a diameter of about 8.5 mm and a length of about 6.0 to 10.0 mm (average 8.5 mm). The cylindrical shaped body was then honed until spherical particles were obtained. So dried, the particles were calcined at 1400 ° C for 2 hours, and then sieved by a sieve having a mesh size of not more than 8.5 mm and not less than 7.2 mm. The carrier thus obtained had an average particle diameter of 8.00 mm, a standard deviation of 0.32, and a relative standard deviation of 0.04. - Preparation of catalyst - 5 30 parts of ammonium paramolybdate, 87.7 parts of ammonium metavanadate and 74.2 parts of ammonium paratungstate were dissolved in 4,000 parts of distilled water under heating and stirring. Further, 72.4 parts of copper nitrate and 14.5 parts of cobalt nitrate were dissolved in 200 parts of distilled water under heating and stirring. The two aqueous solutions thus obtained were mixed, and 29.1 parts of cerium oxide was further added to provide a suspension. The suspension was placed in a porcelain evaporator on a hot water bath, and 1 750 parts of the aforementioned carrier was added thereto. The system was evaporated under agitation to dry the solids to deposit the coal contacting components on the support. The thus-loaded catalyst was taken out and subjected to heat treatment at 400 ° C for 6 hours in an air atmosphere to provide an oxidation catalyst. The loading ratio of the oxidation catalyst is about 30% by mass, and the composition of the metal element constituting the catalytically active component is as follows: M〇l2V3Wl.lCUl.2Sb〇.8C〇0. 2 The oxidation The catalyst has an average particle diameter of 8.50 mm, a standard deviation of 〇·34, and a relative standard deviation of 0.04. -22- 200843854 - Reaction - The reaction was carried out in the same manner as in Example 3 using the thus obtained oxidation catalyst. The results are shown in Table 2. Example 7 Under stirring and stirring, 530 parts of ammonium paramolybdate, 87.7 parts of ammonium metavanadate and 74.2 parts of ammonium paratungstate were dissolved in 4,000 parts of distilled water. Under heating and stirring, 7 2 · 4 parts of copper nitrate and 1 4 · 5 parts of cobalt nitrate were dissolved in 200 parts of distilled water, respectively. The two aqueous solutions thus obtained were mixed, and f further added 29.1 parts of cerium oxide to provide a suspension. The suspension was dried in a spray dryer. The obtained granule powder was calcined at 3 90 ° C for about 5 hours. At this point the thermometer is inserted into the granule powder and the oven temperature is raised in a controlled manner to avoid rapid temperature rise. The calcined granule powder is honed to a size of not more than 150 μm to provide a catalyst powder. 1705 parts of the carrier obtained in Example 6 was placed in a centrifugal fluid applicator, and then the catalyst powder and a 20% by mass aqueous glycerin solution as an adhesive were introduced into the hot air stream at 90 ° C to be loaded. For the carrier. The product was subjected to heat treatment at 400 T: in air I for 6 hours, thus obtaining an oxidation catalyst. The loading ratio of the oxidation catalyst is about 30% by mass, and the composition of the metal element constituting the catalytically active component other than oxygen is as follows: MOi2V3Wl.lCUl.2Sbo.8COO.2 The oxidation catalyst has 8.95 mm. The average particle size, the standard deviation of 〇·36 is the relative standard deviation of 0.04. - Reaction - The reaction was carried out in the same manner as in Example 3 using the catalyst obtained above. The results are shown in Table 2. -23- 200843854 Example 8 Example 6 was repeated except that the carrier was screened with a sieve having a mesh size of not more than 9.0 mm and not less than 6.7 mm. The results are shown in Table 2. The carrier had an average particle size of 8.02 mm, a standard deviation of 0.64, and a relative standard deviation of 0.08. The resulting oxidizing catalyst had an average particle diameter of 8.52 mm, a standard deviation of 〇·68, and a relative standard deviation of 0.08. Example 9 The carrier used in Example 7 was screened outside the carrier in a sieve having a mesh size of not more than 9.0 mm and not less than 6.7 mm. Except for this, repeat Example 7. The results are shown in Table 2. The carrier had an average particle size of 8.02 mm, a standard deviation of 0.64, and a relative standard deviation of 0.08. The resulting oxidizing catalyst had an average particle diameter of 8.97 mm, a standard deviation of 0.72, and a relative standard deviation of 〇.〇8. Comparative Example 5 Example 6 was repeated except that the carrier was screened with a sieve having a mesh size of not more than 8.2 mm and not less than 7.8 mm. The results are shown in Table 2. The carrier has an average particle diameter of 8.00 mm, a standard deviation of 0.08, and a relative standard deviation of 〇·0 1 . The resulting oxidizing catalyst has an average particle diameter of 8.50 mm, a standard deviation of 〇·〇9, and a relative standard deviation of 0.01. 1 ± Comparative Example 6 Example 7 was repeated except that the carrier was screened with a sieve having a mesh size of not more than 8.2 mm and not less than 7.8 mm. The results are shown in Table 2. The carrier has an average particle diameter of 8.00 mm, a standard deviation of 0.08, and a relative standard deviation of 〇·01. The resulting oxidizing catalyst has an average particle diameter of 8.95 mm, a standard deviation of 〇·〇9, and a relative standard deviation of 0.01. -24- 200843854 Comparative Example 6 Comparative Example 5 Example 9 Example 8 Example 7 Example 6 Example 5 Comparative Example 4 1 Comparative Example 3 Example 4 Example 3 8.00 8.00 8.02 8.02 8.00 8.00 4.99 5.00 4.99 4.82 5.00 | Average particle size (mm) | ΙτηΙΙι Μ 0.01 p 0.08 0.08 0.04 0.04 O to j 0.01 〇0.14 0.05 Relative standard deviation 〇〇 8.50 8.97 8.52 OO 8.50 y\ LO 5.19 1 j 5.16 5.16 y\ a\ 1 Average particle size (mm) Catalyst! 0.01 0.01 0.08 0.08 0.04 0.04 0.15 0.01 0.21 0.13 0.04 Relative standard deviation 2000 Initial stage 2000 I Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage 2000 Initial stage operation time (hours) to 〇〇VO to oo oo oo oo to oo 〇\ to ON to to OO to ->0 to On b〇On to On to to OO N3 ^r\ Oo σ\ to 〇\ σ\ OO to ON Reaction temperature CC) h—* to un δ LA »—1 on |_k 1—»» 〇\ to LO H—^ oo vg S s OO Hot spot temperature (°C) 97.8 98.0 97.9 98.2 98.3 98.3 Γ 98.2 98.2 98.4 98.6 98.2 98.3 98.4 j 98.6 97.7 98.3 98.7 99.5 98.3 98.4 98.4 98.4 Acrolein conversion (% by mole) 〇〇87.6 87.9 88.1 93.4 1 93.4 uo ON 93.7 93.5 93.6 93.4 93.4 93.5 93.6 87.7 89.0 85.8 OO 93.4 93.5 93.4 93.4 Yield of acrylic acid (% by mole) 200843854 Example 1 ο -Reaction - a fixed bed shell consisting of approximately 8,5 Ο 0 reaction tubes (each having a diameter of 25 mm and a length of 5,000 mm) and a shell for circulating a heat medium covering the reaction tube - tube reactor by using the catalyst from Example 1 ("first stage catalyst"), SUS Raschig ring with an outer diameter of 8 mm, and the catalyst from Example 3 ("Second stage The catalyst "" is continuously fed into the top of the reaction tube, and the catalyst cartridge is charged into the reaction tube so that the length of each layer is as follows: the first stage catalyst is 2,300 mm, the f-race ring is 400 mm, and the second stage catalyst is 2,300 mm. At a position of 2,500 mm from the bottom of the shell, a 50 mm thick partition was placed to divide the shell into upper and lower portions. In the space of the upper and lower shells, the heat medium circulates upward. From the bottom portion of the reactor, a gas mixture consisting of 8% by volume of propylene, 76% by volume of air, 12% by volume of steam, and a balanced inert gas such as nitrogen was introduced, and the reaction was carried out at 1,600 hours. (STP) is performed on the space velocity of the first-stage catalyst. The performance at the initial stage of the reaction and after 2,000 hours of reaction is shown in Table 3. Table 3 Operating time (hours) First stage catalyst Reaction temperature (.) Hot spot temperature CC) Second order _ a certain surface. C) Hot spot temperature CC) Propylene conversion (% by mole) Propylene with tilt (%) Example 10 Initial stage 315 61 270 60 98.5 89.6 2000 316 61 271 59 98.5 89.4 [Simple description] None. [Component Symbol Description] Μ 〇 j\\\ -26-