201134552 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用具有原料氣體之分散裝置之流動層反 應器實施氣相反應之方法。 【先前技術】 於19世紀後半葉開發出流動層技術以來，其被應用於各 種製造技術。作為流動層之主要的工業性應用，可列舉： 煤氣爐、FCC 裝置（fluid catalytic cracking plant，流體化 媒裂裝置）、利用丙稀之氨氧化（aninioxidation)之丙烯腈製 造裝置、聚乙烯氣相聚合裝置、順丁烯二酸酐製造裝置。 於流動層反應器上設置有用以去除或附加反應熱而將反應 溫度控制為較佳溫度之除熱管或加熱管，通過配置於其下 部之原料氣體分散管及/或分散板向反應器内供給原料氣 體於反應器之上部設置有將流動層觸媒自反應氣體分離 之旋風分離器，由旋風分離器回收之觸媒係通過旋風分離 器浸入管（dipleg)返回反應區域。作為流動層反應方式之 優點，可列舉.反應熱之去除或附加較容易並可將層内維 持於均勻之溫度，可處理爆炸範圍之高濃度氣體，生產性 高’且今後亦期待各方面之應用、改良。 於流動層反應中，原料氣體均勻地分散於容器内於分子 間反應之效率之方面自不待言，就除熱及/或加熱之控制 之觀點而言亦成為重要之因素，因此進行了用以提昇原料 之均勻分散性之研究。 於專利文獻1中揭示有以T裝置：其係藉由將稀烴或第 153044.doc 201134552 二丁醇與氨氣之混合氣體自反應器入口喷嘴導入至該混合 氣體用散佈器之導管與散佈器之中心部位連通，而提昇混 合氣體之均勻分散性。 於專利文獻2中揭示有：藉由根據位置將多孔板之開孔 率设為不同之特定的分佈狀態，而增大流動層之粒子之循 環速度，從而使溫度控制變得容易之流動層反應器及流動 方法。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平8·208583號公報 [專利文獻2]曰本專利特開平號公報 【發明内容】 [發明所欲解決之問題] 然而’根據本發明者之研究，專利文獻所記載之分 散性之改良方法於進行最大限度地發揮流動層反應器之能 力之運轉，即以反應ϋ之能力之上限程度供給原料而運轉 之情形時，某種程度上為有效之方法，但是於降低原料之 流量而運轉之情形日夺，表現不出充分之均句分散性。實際 之化學裝置並不經常以最大限度之能力運轉流動層反應 器’而根據製品之需要或儲備、原料或製品之價格等頻够 地調整製造量’於降低生產量而運轉之情形時亦需要㈣ 料於反應器_句地分散而將產率維持於較高水平。就防 止由生成目標化合物以外之化合物所導致的設備之堵塞 或避免成本增加之觀點而言’即便於將生產量設為較：水 153044.doc 201134552 平之情形時亦可維持高產率具有重大意義。 本發明者發現：於使用具有原料氣體之分散裝置之流動 層反應器進行氣相反應之方法中，於降低生產量而運轉之 情形時，若將原料之流量降至分散裝置之壓力損失小於反 應器流動層之壓力損失之程度，則原料氣體之分散性惡 化，反應效果產生問題。然而，尚未發現即便於將原料之 流篁降至分散裝置之壓力損失小於反應器流動層之壓力損 失之程度之情形時亦可良好地保持原料氣體之分散性的方 法。 [解決問題之技術手段] 本發明者鑒於上述情況，對流動層反應器之原料氣體之 分散性進行潛心研究，結果發現··於將原料氣體之供給量 減^至分散裝置之壓力損失小於反應器流動層之壓力損失 之程度之情形時，藉由自分散裝置與原料氣體一起供給惰 性氣體，可改善原料氣體之分散性，從而達成本發明。 即本發明為如下所述。 [1] 種氣相反應方法，其係通過設置於流動層反應器内之 原料氣體之分散裝置將上述原料氣體供給至上述流動層反 應器而使上述原料氣體進行氣相反應者，且 包括於上述分散裝置之壓力損失相對於流動層之壓力損 失未達1 · 〇倍之情形時向上述分散裝置供給惰性氣體之步 驟0 [2] 153044.doc 201134552 之方法，其中上述分散裝置之壓力損失相對 於上述流動層之壓力損失為〇 12〜4 〇倍。 [3] 如上述[1]或[2]之方法，其中上述分散裝置之上述原料 氣體之壓力損失相對於上述流動層之慶力損失為〇柳以 下。 。 [4] 如上述[1]至[3]中任一Jg夕^ 項之方法，其中上述原料氣體為 選自由丙稀、異丁稀、丙院、異丁燒及第三丁醇所組成群 中之至少一種與氨氣之混合氣體。 [發明之效果] 根據本發明，於使用流動層反應器之氣相反應中，即便 於以/刀散裝置之壓力損失小於反應器流動層之壓力損失之 方式設定原料之流量而運轉之情形時，亦可良好地維持原 料氣體之分散性並可防止目標產物之產率。 【實施方式】 以下’對用以實施本路明夕π & / 不赞明之形態（以下稱為「本實施形 態」）進行詳細說明。再者，本發明並不限定於以下之本 貫施形態，可於其主旨之範圍内進行各種變形而實施。 、再者’於圖式中對相同要素附上相同符號而省略重複之 5、另卜上下左右等位置關係只要無特別說明，則視 為基於圖式所示之位置關係者。裝置或構件之尺寸比率並 不限定於圖示之比率。 本實施形態之氣相反應方法係、通過設置於流動層反應器 153044.doc 201134552 β之原料氣體之分散裝置將上述原料氣體供給至上述流動 層反應器而使上述原料氣體進行氣相反應之方法，其包括 於上述分散裝置之壓力損失相對於流動層之壓力損失未達 1 .〇倍之情形時向上述分散裝置供給惰性氣體之步驟。 圖1係概略表示可實施本實施形態之氣相反應方法之流 動層反應裝置之—例。流動層反應器i係立式圓筒型，於 下端之開口部連接有含有氧氣之氣體之導入管2,原料氣 體導入管4貫通側面，反應生成之氣體自上端之反應氣體 '' 嘗〜出於反應器1内存在觸媒流動而進行反應之觸 媒層9，觸媒層9揚起之觸媒由旋風分離器7回收而返回觸 媒層9。以縱貫觸媒層9之方式設置有複數個除熱管或加熱 管6 ’於發熱反應之情形時，利用除熱管㈣收反應熱，於 吸…、反應之情形時，利用加熱管6供給反應所需之熱量。 於原料氣體導人管4之内端連接有氣體之分散裝置5，原 料氣體通過刀散裝置5供給至反應器】内。分散裝置5包括 與原料氣體導入管4連接之供給管、及於其下端保持水平 且下面具有複數個噴嘴之歧管。分散裝置5之歧管於圓形 面之反應$ 1内分枝成格子狀或放射狀，因此原料氣體B 分散於反應器1之剖面方向’自各嗔嘴向反應器i之下方喷 出。原料氣體分散裝置5只要可遍及反應器ι之剖面 喷出氣體，則不抽拟4Λ 杓形式。作為原料氣體分散裝置5，較佳 為於等間隔或每單位剖面面積設置有相同數 氣體之喷嘴，為使各㈣ $出原枓 嘴上設置孔口部。 1更均句化，更佳為於各喷 153044.doc 201134552 於氣相反應為氧化反應之情形時，將空氣等含有氧氣之 氣體（或氧氣）A供給至反應器，就防止於供給導管内等進 行異常之氧化反應或爆炸之觀點而言，不與其他原料氣體 進行預混合而單獨供給。含有氧氣之氣體A經由導入管2自 分散板3分散至反應器1内。 分散板3之上端與原料氣體分散裝置5之下端之距離就達 成含有氧氣之氣體與原料氣體之良好混合之觀點而言，較 佳為25 mm〜500 mm，更佳為50 mm〜350 mm。 於圖1所示之例中，含有氧氣之氣體A係通過分散板3供 給至反應器1内，但於導入管2上安裝有分枝之分散管，則 亦可通過分散管供給。於不使用含有氧氣之氣體之情形 時’可省略分散板3。 分散裝置5之喷嘴向下開口，因此原料氣體b自噴嘴向下 喷出，含有氧氣之氣體A經由導入管2自分散板3之下方朝 上喷出，因此兩氣體於觸媒層9接觸而進行反應。為使原 料氣體B及含有氧氣之氣體八於觸媒層9高效地進行反應， 而分別設定及設置分散裝置5及分散板3以使原料氣體丑及 含有氧氣之氣體A均勻分散於反應器丨内。於流動層反應 中，藉由使原料氣體B及含有氧氣之氣體A均勻地分散， 可將反應器1内部之反應之進行率勻整化，藉此產生之反 應熱之控制變得容易。尤其原料氣體B之均勻分散係重 要，假设產生原料氣體B不均勻分散之情形時，則有不但 目私之反應產物之產率惡化，而且引起局部之發熱等異常 現象之虞。 I53044.doc 201134552 氣體分散裝置5係以遍及反應器剖面使原料氣體均勻地 喷出之方式設定。就確保氣體之良好之分散性之觀點而 言，當使氣體分散裝置5中通過特定之原料氣體流量而連 續反應時，較佳為以將該分散裝置之壓力損失設為流動層 之壓力損失之1 .〇〜4.0倍間的任意值之方式進行氣體分散裝 置5之流量設定。於分散裝置5之壓力損失相對於流動層之 壓力損失未達1.0倍之情形時，藉由向分散裝置5供給惰性 氣體而提高分散裝置與流動層之壓力損失比並調整為 1.0〜4.0倍之間《但是，於反應之啟動或終止之至少一部分 之過程中，將氣體分散裝置5之原料氣體流量設為較低水 平’使；7政裝置5之壓力損失相對於流動層之壓力損失為 未達1.0倍。其間，具體而言，於分散裝置5之壓力損失相 對於流動層之壓力損失為0.12倍以上且未達1〇倍之情形 時，就防止觸媒向分散裝置5内逆流之觀點而言，較佳為 自分散裝置5供給惰性氣體。 此處，使用下述式（1)，對氣體分散裝置5之流量設定方 法進行說明。 [(P0)-(P1)]/[(P1)-(P2)]=C1 (1) P0 :壓力計10之壓力 P1 :壓力計11之壓力 P2 :壓力計12之壓力 P0係表示由設置於原料氣體B之氣體分散裝置5入口之壓 力計10測定之壓力，P1係表示反應器！内 與空氣分散板3間之麼力。於將反應器i全長設二 153044.doc 201134552 時’壓力計12係由設置於距反應器下端〇 7 Lr以上之上部 之壓力計所測^之反應器1内之屡力。CM為常數，較佳為 LO〜4·0間之數值，更佳為1.5〜3.5。 於觸媒進行通常之流動之情形時，於例如反應器内上升 之氣體速度以反應器之有效剖面面積基準計為3〇〜9〇 _ 凊形夺將[(P1)-(P2)]稱為流動層之塵力損失該流動 層之屋力損失由觸媒量支配，不依存於流通觸媒内之氣體 流量而大致固定。 另一方面，原料氣體分散裝置5之壓力損失[(ρ〇) (ρι)】係 根據原料氣體流量之增減而變化。例如若原料氣體流量成 W倍，職體分散裝置之壓力損《大致成為4倍，若原料 氣體成為1/2倍，則該壓力損失大致成為1/4倍。 將氣體分散裝置5之壓力損失與流動層之壓力損失滿足 (1)式時之原料氣體流量稱為原料氣體分散裝置之設定流 量，將此時之原料氣體分散裝置之壓力損失稱為設定壓力 損失。如上所述，⑴式之〇較佳為i 〇〜4 〇之數值範圍， 故設定流量、設定壓力損失有增減之幅度，從而有選擇之 餘地。但是，於實際之設備設定中，藉由決定C1，而方便 地同時決定設定流量。產生由C1=1.0〜40計算之塵力損失 之原料氣體流量亦稱為氣體分散裝置流量範圍。 於具有根據上述（1)式所計算之幅度之設定流量下，即 便為可均勻地分散氣體之原料氣體分散裝置，於伴隨原料 氣體之供給量未達設定流量之下限值（以下亦稱為「設定 下限流量」（以下設為「F’」）），而原料氣體分散裝置之壓 153044.doc -10- 201134552 力損失未達下限值（以下亦稱為「設定下限壓力損失」（以 下設為「F」））之情形時，分散性亦惡化β例如於流動層 反應裝置之通常之啟動或終止之至少一部分之過程及生產 調整等所導致的低負荷運轉時’不得已使用未達設定下限 流量、設定下限壓力損失之原料氣體分散裝置，於此期間 有對原料氣體分散造成不良影響之虞。 即，於因自原料氣體導入管4供給之氣體之量未達設定 下限流量等而導致原料氣體分散裝置之壓力損失未達設定 下限壓力損失之情形時’氣體分散之均勻性易顯著惡化。 具體而言，當將分散裝置之壓力損失與流動層之壓力損失 之比即[(POHPDWOMHPWPKO之情形時的氣體分散裝 置5之壓力損失[(POXPi)]設為設定下限壓力損失F時於 氣體分散裝置5之壓力損失未達？之情形時，氣體之分散性 變差’若為0_64 F以下，則分散性有進一步惡化之傾向。 於本實施形態之氣相反應方法中，作為解決上述分散性 之問題之手段，於以未達設^下限壓力損失F之流量使用 原料氣體分散裝置5之情形，即分散裝置之壓力損失相對 於流動層之壓力損失未達Μ倍之情形時，將惰性氣體D自 惰性氣體導入管14供給至流動層反應器w側之原料氣體 導入管4 ’並與原料氣體Β一起供給至流動層反應器内之氣 體分散褒置5。所謂惰性氣體，只要為不參與反應之氣體 則其組成並無限;t，例如可列舉氮氣、氬氣、氦氣等。其 中，就經濟性之觀點而言較佳為氮氣。另夕卜，上述惰性氣 體可單獨使用，亦可併用2種以上。 153044.doc 201134552 就將反應之進行率句整化之觀點而言，較佳為自原料氣 體分散裝置5之喷嘴各處吹出之氣體量設為大致相同，另 外較佳為亦將自噴嘴各處吹出之氣體中之原料氣體濃度均 勻化:因此，較佳為於導入至分散裝置5之前於原料氣體 導入官4内連接惰性氣體導入管M。於惰性氣體導入管μ 較佳為設置有流量計以能測定惰性氣體之添加流量。再 者，對於自m管2供給之含有氧氣之氣體a，於將流 量設為未達設;t下限流量之情形時，亦認為分散性惡化。 但是，（雖亦取決於反應）氧化反應中，通常供給由空氣等 惰性，釋之氧氣作為含有氧氣之氣體A，因此導入管2 之流量與原料氣體導入管4相比通常較大。因&，於需要BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of performing a gas phase reaction using a fluidized bed reactor having a dispersion device of a material gas. [Prior Art] Since the development of the flow layer technology in the latter half of the 19th century, it has been applied to various manufacturing technologies. As a main industrial application of the fluidized bed, a gas furnace, a FCC (fluid catalytic cracking plant), an acrylonitrile production apparatus using an ammoxidation of propylene, and a polyethylene gas phase can be cited. A polymerization apparatus or a maleic anhydride production apparatus. A heat removal tube or a heating tube for removing or adding heat of reaction to control the reaction temperature to a preferred temperature is provided on the fluidized bed reactor, and is supplied into the reactor through a raw material gas dispersion tube and/or a dispersion plate disposed at a lower portion thereof. The raw material gas is provided on the upper portion of the reactor with a cyclone separating the fluidized bed catalyst from the reaction gas, and the catalyst recovered by the cyclone separator is returned to the reaction zone through a cyclone dip tube. As an advantage of the fluidized bed reaction mode, the removal or addition of the heat of reaction is relatively easy, and the temperature in the layer can be maintained at a uniform temperature, and the high-concentration gas in the explosion range can be treated, and the productivity is high, and various aspects are expected in the future. Application, improvement. In the fluidized bed reaction, the fact that the raw material gas is uniformly dispersed in the container in terms of the efficiency of the intermolecular reaction is self-evident, and is also an important factor in terms of heat and/or heating control, and thus Research to improve the uniform dispersion of raw materials. Patent Document 1 discloses a T device which introduces a mixed gas of a rare hydrocarbon or a 153044.doc 201134552 dibutanol and ammonia gas from a reactor inlet nozzle to a conduit and a dispersion of the mixed gas distributor. The center of the device is connected to enhance the uniform dispersion of the mixed gas. Patent Document 2 discloses that the flow rate of the particles of the fluidized bed is increased by setting the opening ratio of the porous plate to a specific distribution state according to the position, thereby making the temperature control easy. And flow methods. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 8 208 583 [Patent Document 2] Japanese Patent Application Laid-Open No. Publication No. [Invention] [The problem to be solved by the invention] However According to the study by the inventors of the present invention, the method for improving the dispersibility described in the patent document is performed when the operation of the fluidized bed reactor is maximized, that is, when the raw material is supplied at the upper limit of the capacity of the reaction enthalpy, To a certain extent, it is an effective method, but the situation in which the flow of raw materials is reduced and operated is not sufficient to exhibit sufficient uniformity of the sentence. The actual chemical equipment does not often operate the fluidized bed reactor with maximum capacity and the production quantity is adjusted according to the needs of the product or the price of the raw materials or products, etc. (iv) It is expected that the yield will be maintained at a high level in the reactor. From the viewpoint of preventing clogging of equipment caused by the generation of compounds other than the target compound or avoiding cost increase, it is of great significance to maintain a high yield even when the production amount is set to be equal to: water 153044.doc 201134552 . The present inventors have found that in the method of performing a gas phase reaction using a fluidized bed reactor having a dispersing device for a raw material gas, when the operation is reduced while reducing the throughput, the pressure loss of the raw material is reduced to less than the reaction of the dispersing device. The degree of pressure loss of the fluidized bed deteriorates the dispersibility of the material gas and causes a problem in the reaction effect. However, it has not been found that the method of maintaining the dispersibility of the material gas well can be maintained even when the pressure drop of the raw material is reduced to the extent that the pressure loss of the dispersing device is less than the pressure loss of the reactor fluidized bed. [Means for Solving the Problems] In view of the above, the present inventors conducted intensive studies on the dispersibility of the material gas in the fluidized bed reactor, and as a result, found that the pressure loss of the raw material gas is reduced to less than the reaction. In the case of the degree of pressure loss of the fluidized bed, the inert gas is supplied together with the material gas by the self-dispersing device, whereby the dispersibility of the material gas can be improved, thereby achieving the present invention. That is, the present invention is as follows. [1] A gas phase reaction method in which a raw material gas is supplied to a fluidized bed reactor through a dispersion device of a material gas provided in a fluidized bed reactor, and the raw material gas is subjected to a gas phase reaction, and is included in The method of the step of supplying the inert gas to the dispersing device in the case where the pressure loss of the dispersing device is less than 1 〇 times the pressure loss of the fluidized layer, wherein the pressure loss of the dispersing device is relatively The pressure loss in the above fluidized layer is 〇12 to 4 times. [3] The method according to [1] or [2] above, wherein the pressure loss of the raw material gas of the dispersing device is less than the creep loss of the fluidized layer. . [4] The method according to any one of the above [1] to [3] wherein the raw material gas is selected from the group consisting of acryl, isobutyl, propylene, isobutylidene and tert-butanol. At least one of a mixed gas with ammonia gas. [Effect of the Invention] According to the present invention, in the gas phase reaction using the fluidized bed reactor, even when the flow rate of the raw material is set to operate in such a manner that the pressure loss of the / knife-dispersing device is smaller than the pressure loss of the reactor fluidized bed It is also possible to maintain the dispersibility of the raw material gas well and prevent the yield of the target product. [Embodiment] The following is a detailed description of the form (hereinafter referred to as "this embodiment") for carrying out the present invention. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention. In the drawings, the same elements are denoted by the same reference numerals, and the overlapping is omitted. The positional relationship such as up, down, left, and right is regarded as the positional relationship based on the drawing unless otherwise specified. The size ratio of the device or member is not limited to the ratio shown. The gas phase reaction method of the present embodiment is a method for supplying the raw material gas to the vapor phase reaction by supplying the raw material gas to the fluidized bed reactor through a dispersion device of a raw material gas provided in the fluidized bed reactor 153044.doc 201134552β And the step of supplying an inert gas to the dispersing device when the pressure loss of the dispersing device is less than 1. 〇 times the pressure loss of the fluidized bed. Fig. 1 is a view schematically showing an example of a fluidized bed reaction apparatus which can carry out the gas phase reaction method of the present embodiment. The fluidized bed reactor i is a vertical cylindrical type, and the introduction pipe 2 containing a gas containing oxygen is connected to the opening of the lower end, and the raw material gas introduction pipe 4 penetrates the side surface, and the gas generated by the reaction is tasted from the upper end of the reaction gas. In the reactor 1, a catalyst layer 9 in which a catalyst flows and reacts, and a catalyst that is raised by the catalyst layer 9 is recovered by the cyclone 7 and returned to the catalyst layer 9. When a plurality of heat removal tubes or heating tubes 6' are disposed in the longitudinal direction of the catalyst layer 9, the heat is removed by the heat removal tubes (4), and when the reaction is taken, the reaction is performed by the heating tubes 6. The amount of heat needed. A gas dispersing device 5 is connected to the inner end of the material gas guiding tube 4, and the raw material gas is supplied to the reactor through the knife dispersing device 5. The dispersing device 5 includes a supply pipe connected to the material gas introduction pipe 4, and a manifold having a horizontal portion on the lower end and a plurality of nozzles on the lower surface. The manifold of the dispersing device 5 is branched into a lattice shape or a radial shape in the reaction of the circular surface. Therefore, the material gas B is dispersed in the cross-sectional direction of the reactor 1 and is ejected from the respective nozzles to the lower side of the reactor i. The material gas dispersing device 5 does not draw a 4 Λ form as long as the gas can be ejected across the cross section of the reactor ι. As the material gas dispersing device 5, it is preferable to provide nozzles of the same number of gases at equal intervals or per unit cross-sectional area, in order to provide the orifice portions in each of the four nozzles. 1 more uniform, more preferably in the case of the gas phase reaction 153044.doc 201134552, when the gas phase reaction is an oxidation reaction, a gas (or oxygen) A containing oxygen or the like is supplied to the reactor to prevent the supply into the conduit. From the viewpoint of performing an abnormal oxidation reaction or explosion, it is supplied separately without premixing with other material gases. The gas A containing oxygen is dispersed into the reactor 1 from the dispersion plate 3 via the introduction pipe 2. The distance between the upper end of the dispersion plate 3 and the lower end of the material gas dispersing device 5 is preferably from 25 mm to 500 mm, more preferably from 50 mm to 350 mm, from the viewpoint of good mixing of the oxygen-containing gas and the material gas. In the example shown in Fig. 1, the gas A containing oxygen is supplied to the reactor 1 through the dispersion plate 3. However, if the branch pipe is attached to the introduction pipe 2, it may be supplied through the dispersion pipe. The dispersion plate 3 can be omitted when the gas containing oxygen is not used. The nozzle of the dispersing device 5 is opened downward, so that the material gas b is ejected downward from the nozzle, and the gas A containing oxygen is ejected upward from the lower side of the dispersing plate 3 via the introduction pipe 2, so that the two gases are in contact with the catalyst layer 9. Carry out the reaction. In order to efficiently react the raw material gas B and the oxygen-containing gas VIII in the catalyst layer 9, the dispersing device 5 and the dispersing plate 3 are separately set and arranged to uniformly disperse the raw material gas and the oxygen-containing gas A in the reactor. Inside. In the fluidized bed reaction, by uniformly dispersing the material gas B and the gas A containing oxygen, the progress of the reaction inside the reactor 1 can be made uniform, whereby the control of the reaction heat generated can be easily performed. In particular, when the raw material gas B is uniformly dispersed, it is assumed that the raw material gas B is unevenly dispersed, and the yield of the reaction product is not deteriorated, and an abnormal phenomenon such as local heat generation is caused. I53044.doc 201134552 The gas dispersion device 5 is set so as to uniformly discharge the material gas throughout the cross section of the reactor. From the viewpoint of ensuring good dispersibility of the gas, when the gas dispersion device 5 is continuously reacted by a specific flow rate of the raw material gas, it is preferable to set the pressure loss of the dispersion device to the pressure loss of the fluidized bed. The flow rate setting of the gas dispersion device 5 is performed in a manner of an arbitrary value between 〇 and 4.0 times. When the pressure loss of the dispersion device 5 is less than 1.0 times the pressure loss of the fluidized bed, the pressure loss ratio of the dispersion device and the fluidized bed is increased by supplying the inert gas to the dispersion device 5, and is adjusted to 1.0 to 4.0 times. "However, in the process of at least part of the initiation or termination of the reaction, the flow rate of the raw material gas of the gas dispersing device 5 is set to a lower level"; the pressure loss of the political device 5 relative to the pressure loss of the fluidized bed is not Up to 1.0 times. In the meantime, when the pressure loss of the dispersion device 5 is 0.12 times or more and less than 1 time, the pressure loss of the flow medium is prevented from flowing back into the dispersion device 5, Preferably, the inert gas is supplied from the dispersion device 5. Here, the flow rate setting method of the gas dispersion device 5 will be described using the following formula (1). [(P0)-(P1)]/[(P1)-(P2)]=C1 (1) P0: Pressure P1 of pressure gauge 10: Pressure P2 of pressure gauge 11: Pressure P0 of pressure gauge 12 is indicated by setting The pressure measured by the pressure gauge 10 at the inlet of the gas dispersion device 5 of the raw material gas B, and P1 indicates the reactor! The force between the inner and the air dispersion plate 3. When the total length of the reactor i is set to two 153,044.doc 201134552, the pressure gauge 12 is an external force in the reactor 1 which is measured by a pressure gauge which is located above the upper end of the reactor 〇 7 Lr or more. The CM is a constant, preferably a value between LO and 4·0, more preferably 1.5 to 3.5. In the case where the catalyst is normally flowed, the gas velocity rising in, for example, the reactor is 3 〇 to 9 〇 based on the effective sectional area of the reactor _ 凊 夺 将 [(P1)-(P2)] The loss of dust force in the fluidized bed is dominated by the amount of catalyst and is not substantially dependent on the gas flow rate in the flow-through catalyst. On the other hand, the pressure loss [(ρ〇) (ρι)] of the material gas dispersion device 5 changes depending on the increase or decrease of the flow rate of the material gas. For example, if the flow rate of the raw material gas is W times, the pressure loss of the body dispersing device is "approximately four times, and if the raw material gas is 1/2 times, the pressure loss is approximately 1/4 times. The pressure loss of the gas dispersion device 5 and the pressure loss of the fluidized bed satisfying the formula (1) are referred to as the set flow rate of the raw material gas dispersion device, and the pressure loss of the raw material gas dispersion device at this time is referred to as the set pressure loss. . As described above, the value of the formula (1) is preferably a numerical range of i 〇 to 4 ,, so that the flow rate and the set pressure loss are increased or decreased, so that there is room for selection. However, in the actual device setting, it is convenient to simultaneously determine the set flow rate by determining C1. The flow rate of the raw material gas that produces the dust loss calculated from C1 = 1.0 to 40 is also referred to as the flow rate of the gas dispersion device. In the case of the raw material gas dispersing device which can uniformly disperse the gas at the set flow rate having the amplitude calculated according to the above formula (1), the supply amount of the raw material gas does not reach the lower limit of the set flow rate (hereinafter also referred to as "Set the lower limit flow rate" (hereinafter "F'")), and the pressure of the raw material gas dispersion device is 153044.doc -10- 201134552 The force loss does not reach the lower limit (hereinafter also referred to as the "set lower limit pressure loss" (below) In the case of "F")), the dispersibility is also deteriorated. For example, during the low-load operation caused by at least a part of the normal start or stop of the flow layer reaction device and the production adjustment, etc. The raw material gas dispersing device of the lower limit flow rate and the set lower limit pressure loss has an adverse effect on the dispersion of the raw material gas during this period. In other words, when the amount of gas supplied from the material gas introduction pipe 4 does not reach the set lower limit flow rate or the like, and the pressure loss of the material gas dispersion device does not reach the set lower limit pressure loss, the uniformity of the gas dispersion is remarkably deteriorated. Specifically, when the ratio of the pressure loss of the dispersion device to the pressure loss of the fluidized bed, that is, the pressure loss [(POXPi) of the gas dispersion device 5 in the case of POHPDWOMHPWPKO] is set as the lower limit pressure loss F, the gas is dispersed. When the pressure loss of the apparatus 5 is not reached, the dispersibility of the gas is deteriorated. When the pressure is 0 to 64 F or less, the dispersibility tends to be further deteriorated. In the gas phase reaction method of the present embodiment, the dispersibility is solved. The problem is that the raw material gas dispersing device 5 is used at a flow rate that does not reach the lower limit pressure loss F, that is, when the pressure loss of the dispersing device is less than twice the pressure loss of the fluidized layer, the inert gas is used. D is supplied from the inert gas introduction pipe 14 to the raw material gas introduction pipe 4' on the fluidized bed reactor w side, and is supplied to the gas dispersion pipe 5 in the fluidized bed reactor together with the material gas enthalpy. The so-called inert gas is not involved. The gas to be reacted has a composition and is infinite; for example, nitrogen, argon, helium, etc. may be mentioned, and among them, nitrogen is preferred from the viewpoint of economy. The inert gas may be used singly or in combination of two or more. 153044.doc 201134552 From the viewpoint of synthesizing the progress of the reaction, it is preferable to set the amount of gas blown from the nozzles of the raw material gas dispersing device 5 In the same manner, it is preferable to homogenize the concentration of the material gas in the gas blown from the nozzles. Therefore, it is preferable to connect the inert gas introduction pipe M to the raw material gas introduction unit 4 before being introduced into the dispersion device 5. Preferably, the inert gas introduction pipe μ is provided with a flow meter for measuring the addition flow rate of the inert gas. Further, for the gas a containing oxygen supplied from the m pipe 2, the flow rate is set to be less than the lower limit; In the case of the flow rate, the dispersibility is also considered to be deteriorated. However, (although depending on the reaction), the oxidation reaction is usually supplied with inert gas such as air, and oxygen is released as the gas A containing oxygen, so that the flow rate of the introduction pipe 2 and the material gas are The inlet tube 4 is usually larger than the &
調^量且㈣分散性之情料，與將含有氧氣之氣體A 之流量減少至未達設定下限流量並向其中供給惰性氣體相 2 ’較為合理的是將含有氧氣之氣體A之流量保持為設定 桃量内且利用原料氣體調整流量，自分散裝置供給惰性氣 體D而保持分散性。 較佳為於原料氣體導人管4内設置孔口板15以能夠將原 ;斗氣體B與〖月性氣體D預先混合。於將導入管4之内徑設為 D之情形時，就將原料氣體B與惰性氣體D有效地混合之觀 •、而口孔口板15之開口徑較佳為0.1 D〜0.8 D。孔口板15 &將氣體良好地混合之觀點而言’較佳為設置於自惰性氣 邑s位置之2 D以上之下游直至反應器1之入口之位 ^就把握原料氣體分散裝置5之分散性能之觀點而言， C力°十1 〇較佳為設置於可測定通過分散裝置5之全部氣體 153044.doc •12- 201134552 之壓力之位置。另外為了可測定穩定之壓力，較佳為設置 於距離惰性氣體混合部2 D以上之下游且距離孔口板1 5為2 D以上之處直至反應器丨入口之間。通過原料氣體分散裝置 之原料氣體與惰性氣體之合計流量’就防止觸媒向氣體分 散裝置内逆流之觀點而言較佳為設為〇·35 F，以上。再者， 此情形（0.35 F’之情形）之氣體分散裝置之壓力損失相當於 設定下限壓力損失F之〇.12倍。通過原料氣體分散裝置之 原料氣體及惰性氣體之合計流量之上限就防止原料氣體分 月文裝置之壓力損失變得過大而對供給原料氣體之裝置（未 圖示）之控製造成障礙之觀點而言，較佳為設為4 〇 F,以 下。另外，惰性氣體之流量較佳為〇.1〇 F，〜3.0 F,，更佳為 20 F 2.0 F，尤佳為〇·3〇 ρ'〜1.0 原料氣體之流量較 佳為0.80 F，以下，更佳為〇〇1 F，〜〇75 F·，尤佳為〇 ι〇 F'〜0.70 F'。 人於氧化反應中’自分散板3導入含有氧氣之氣體Α。至於 含有氧氣之氣體A向反應器【之導入量，為了以高產率獲得 目標產物，較佳為以與原料氣❹之莫耳比（a/b)成為由可 期待最高產率之預備實驗等求出之最佳莫耳比之方式進行 控制。此處’ a表示含有氧氣之氣體A所含之氧氣之莫耳 數’b表示原料氣體3之莫耳數。於原料氣體b包含2種以 上之咸合物之情形時，較佳為以a/bl、咖 之-種原料之莫耳—b〗與其他:： 莫耳數b2、b3之比達到最佳之方式加以控制。 所谓使莫耳比(a/b)為最佳，係指對應於原料氣體B之增 153044.doc -13- 201134552 減而成比例地控制含有氧氣之氣體A之流量。再者，由於 惰性氣體D不參與反應，因此與上述莫耳比之計算無關。 分散板3係以遍及反應器剖面使含有氧氣之氣體简勾地 嗔出之方式設定。為確保氣體之良好之分散性，較佳為於 使分散板3通過含有氧氣之氣體八而使用時，以將該分散板 之壓力損失設為流動層之壓力損失的〇 5〇〜2 5倍間之任意 值之方式進行分散板3之流量設定。 此處’使用下述式⑺對分散板3之流量設定方法進行說 明。 [(P3)-(P1)]/[(P1).(P2)]=C2 ⑺ P3 :壓力計13之壓力 P3係表示設置於分散板下部之㈣計13所料之屋力。 C2為常數’較佳為G.5G〜2·5間之數值，更佳為0.70〜20。 於反應器之使用開始，含有氧氣之氣體A先於原料氣體 B導入至反應器。較佳為於原料氣體b導人時之前，將含 有氧氣之氣體A之流量提高至式⑺中之以之下限以上之流 量而確保分散板3之氣體分散性。 惰性氣體D向分散裝置5之導入係於導入原料氣體B之前 向反應益1導入觸媒之前進行。此後開始導入原料氣體B =緩緩提高原料氣體B之流量。伴隨著原料氣體B導入之 2加’兩者之莫耳比（a/b)達到可期待最高反應效果之值 '人為保持此時點之供給量或視需要維持莫耳比（Μ)，而 使3有氧氣之氣體A及原料氣體b兩者 氣相反應生成之反廄4 士、# μ 〜生成軋體C係自反應氣體流出管8取 153044.doc -14· 201134552 出。 作為使用本實施形態之流動層反應裝置之氣相反應，例 如可列舉：以丙烧及/或丙烯為原料之氣相氨氧化，反應 之產物為丙烯腈之反應；以選自由正丁烷、丨_丁烯、2_丁 烯、丁二烯、苯所組成群中之丨種以上為原料之氣相氧 化，反應之產物為順丁烯二酸酐之反應；以異丁烯及/或 異丁烷為原料之氣相氨氧化，反應之產物為曱基丙烯腈之 反應；以鄰二甲苯及/或萘為原料之氣相氧化，反應之產 物為鄰苯二曱酸酐之反應；以羥基芳香族化合物及烷基醇 為原料之氣相烷基化，反應之產物為鄰位烷基化羥基芳香 族化合物之反應；作為具體例可列舉：以笨盼及甲醇為原 料之氣相烧基化，反應之產物為2,6-二曱苯酚及/或鄰曱酚 之反應；以曱烷及/或甲醇為原料之氣相氨氧化，反應之 產物為氰酸（HCN，hydrogencyanide)之反應；以選自由乙 燒、乙烯、乙醇所組成群中之1種以上為原料之氣相氨氧 化，反應之產物為乙腈之反應。 [實施例] 繼而，列舉實施例及比較例對本實施形態進行更具體地 說明，本實施形態只要不超出其主旨，則並不限定於以下 之實施例。再者’作為實施例及比較例中之流動層反應 器，可使用其下部具有原料氣體之分散管及空氣分散板 (於不使用空氣之反應中，無空氣分散板），内置有用以去 除反應熱之除熱管，具有用以測定反應溫度之溫度計，反 應器上部具有捕獲自反應器流出之反應氣體中之觸媒之旋 153044.doc 15 201134552 風分離器者。 計量器、附屬設備係、使用通常之化學裝置中所使 之產率係藉由對反應氣體取樣，根據利用氣相 層析法測疋之分析資料並藉由下式而進行計算。 丙婦腈產率（〇/〇)=(生成之丙稀腈之莫耳數）/(供給 之莫耳數）Χ100 ^ 丙烯腈產率㈤=(生成之丙烯腈之莫耳數)/(供給之丙烷 之莫耳數）xl00 順丁烯二酸酐產率（％)=(生成之順丁烯二酸酐之莫耳 數）/(供給之正丁烧之莫耳數）xl〇〇 鄰甲酚產率（％)=(生成之鄰甲酚之莫耳數）/(供給之苯酚 之莫耳數）xl〇〇 2,6-二甲本紛產率（％)=(生成之2,6·二甲苯齡之莫耳 數）/(供給之苯酚之莫耳數）xl〇〇 氣相層析法之測定設備及測定條件為如下所述。Adjusting the amount and (4) dispersing the situation, and reducing the flow rate of the gas A containing oxygen to the lower limit flow rate and supplying the inert gas phase thereto 2 ' It is more reasonable to maintain the flow rate of the gas A containing oxygen The amount of the peach was adjusted, and the flow rate was adjusted by the raw material gas, and the inert gas D was supplied from the dispersing device to maintain the dispersibility. Preferably, the orifice plate 15 is provided in the material gas guiding tube 4 so that the original gas B can be premixed with the moon gas D. When the inner diameter of the introduction tube 4 is set to D, the raw material gas B and the inert gas D are effectively mixed, and the opening diameter of the orifice plate 15 is preferably 0.1 D to 0.8 D. From the viewpoint that the gas is well mixed, the orifice plate 15 & preferably is disposed at a position downstream of 2 D or more from the position of the inert gas s to the inlet of the reactor 1 to grasp the material gas dispersing device 5 From the viewpoint of dispersion performance, the C force of 10 〇 is preferably set at a position at which the pressure of all the gases passing through the dispersing device 5 153044.doc • 12 - 201134552 can be measured. Further, in order to measure the stable pressure, it is preferably disposed downstream of the inert gas mixing portion 2 D or more and at a distance of 2 D or more from the orifice plate 15 to the reactor inlet. The total flow rate of the material gas and the inert gas in the raw material gas dispersing device is preferably set to 〇·35 F or more from the viewpoint of preventing the catalyst from flowing back into the gas dispersing device. Further, the pressure loss of the gas dispersing device in this case (in the case of 0.35 F') is equivalent to 12 times the set lower limit pressure loss F. The upper limit of the total flow rate of the material gas and the inert gas in the material gas dispersing device prevents the pressure loss of the material gas fractional device from becoming excessively large, and the control of the device (not shown) for supplying the material gas is hindered. Preferably, it is set to 4 〇F, below. Further, the flow rate of the inert gas is preferably 〇.1〇F, 〜3.0 F, more preferably 20 F 2.0 F, and particularly preferably 〇·3〇ρ'~1.0. The flow rate of the material gas is preferably 0.80 F, or less. More preferably 〇〇1 F, ~〇75 F·, especially good 〇ι〇F'~0.70 F'. A person introduces a gas containing oxygen gas into the self-dispersing plate 3 in the oxidation reaction. As for the introduction amount of the oxygen-containing gas A to the reactor, in order to obtain the target product in a high yield, it is preferred that the molar ratio (a/b) to the raw material gas is a preliminary experiment in which the highest yield can be expected. The way to find the best molar ratio is controlled. Here, 'a' indicates the number of moles of oxygen contained in the gas A containing oxygen, and b indicates the number of moles of the material gas 3. When the raw material gas b contains two or more kinds of salt compounds, it is preferable that the ratio of the moir-b of the a/bl, the coffee-type raw material and the other: the molar number b2 and the b3 are optimal. The way to control. The so-called molar ratio (a/b) is optimal, and the flow rate of the gas A containing oxygen is controlled in proportion to the increase of the raw material gas B 153044.doc -13 - 201134552. Furthermore, since the inert gas D does not participate in the reaction, it is irrelevant to the above calculation of the molar ratio. The dispersion plate 3 is set so that the gas containing oxygen is simply drawn over the cross section of the reactor. In order to ensure good dispersibility of the gas, it is preferred to use the pressure of the dispersion plate as the pressure loss of the fluidized layer when the dispersion plate 3 is used by the gas containing oxygen eight. The flow rate setting of the dispersion plate 3 is performed in any manner between the values. Here, the flow rate setting method of the dispersion plate 3 will be described using the following formula (7). [(P3)-(P1)]/[(P1).(P2)]=C2 (7) P3: Pressure of the pressure gauge 13 P3 indicates the house force of the (four) meter 13 placed in the lower part of the dispersion plate. C2 is a constant ', preferably a value between G. 5G and 2·5, more preferably 0.70 to 20. At the beginning of the use of the reactor, the gas A containing oxygen is introduced into the reactor prior to the source gas B. It is preferable to increase the flow rate of the gas A containing oxygen to a flow rate higher than the lower limit of the formula (7) before the introduction of the raw material gas b to ensure the gas dispersibility of the dispersion plate 3. The introduction of the inert gas D into the dispersing device 5 is performed before introducing the raw material gas B before introducing the catalyst into the reaction product 1. Thereafter, the introduction of the raw material gas B = the flow rate of the raw material gas B is gradually increased. With the introduction of the raw material gas B, the molar ratio (a/b) of both of them is the value that can be expected to have the highest reaction effect, and the amount of supply at this point is artificially maintained or the molar ratio (Μ) is maintained as needed. 3 There is a gas phase reaction between the gas A and the raw material gas b, which are generated by gas phase reaction, and the resulting product C is taken from the reaction gas outflow pipe 8 and taken 153044.doc -14·201134552. Examples of the gas phase reaction using the fluidized bed reactor of the present embodiment include a gas phase ammoxidation using a propane and/or propylene as a raw material, and the reaction product is an acrylonitrile reaction;丨-butene, 2-butene, butadiene, benzene, the above species are the gas phase oxidation of the raw materials, the reaction product is the reaction of maleic anhydride; isobutylene and / or isobutane For the gas phase ammoxidation of the raw material, the reaction product is a reaction of mercapto acrylonitrile; the gas phase oxidation of o-xylene and/or naphthalene as a raw material, the reaction product is a reaction of phthalic anhydride; The compound and the alkyl alcohol are gas phase alkylation of the raw material, and the product of the reaction is a reaction of ortho-alkylating the hydroxyaromatic compound; as a specific example, gas phase alkylation using porphyrin and methanol as a raw material may be mentioned. The reaction product is a reaction of 2,6-diphenylphenol and/or o-nonylphenol; a gas phase ammoxidation using decane and/or methanol as a raw material, and the reaction product is a reaction of cyanic acid (HCN, hydrogencyanide); Choose a group consisting of Ethylene, Ethylene, and Ethanol One or more kinds of the vapor phase ammoxidation of raw materials, the reaction product of the reaction is acetonitrile. [Examples] Hereinafter, the present embodiment will be described more specifically by way of examples and comparative examples, and the present embodiment is not limited to the following examples as long as the scope of the present invention is not exceeded. Further, as the fluidized bed reactor in the examples and the comparative examples, a dispersion pipe having a raw material gas and an air dispersion plate (in the reaction without using air, no air dispersion plate) may be used, and a built-in useful for removing the reaction may be used. The heat removal tube has a thermometer for measuring the reaction temperature, and the upper portion of the reactor has a catalyst for capturing the catalyst in the reaction gas flowing out of the reactor. 153044.doc 15 201134552 Air separator. The yield of the meter, the accessory equipment, and the use of a conventional chemical apparatus is calculated by sampling the reaction gas according to the analysis data measured by gas chromatography and by the following formula. Yield of acrylonitrile (〇/〇) = (molar number of acrylonitrile formed) / (mole of supply) Χ 100 ^ yield of acrylonitrile (5) = (molar number of acrylonitrile formed) / ( The number of moles of propane supplied) xl00 yield of maleic anhydride (%) = (the number of moles of maleic anhydride formed) / (the number of moles of n-butylene supplied) xl Phenol yield (%) = (molar number of ortho-cresol formed) / (molar number of phenol supplied) xl 〇〇 2,6-dimethyl phthalate yield (%) = (generated 2, 6. Mohr number of xylene age) / (molar number of phenol supplied) xl 测定 Gas chromatography method and measurement conditions are as follows.
氣相層析儀：島津GC-14B 管柱：Porapack-QS(50 〜80 篩孔） 檢測器：FID(Flame Ionization Detector，火焰離子檢測 器） 載流氣體··氮氣 [製造例] 如下述般藉由丙烯、氨氣及空氣進行丙烯之氨氧化反 應。 流動層反應裝置與圖1所示者相同，流動層反應器1係内 153044.doc -16 - 201134552 徑8 m、長度Lr20 m之立式圓筒型，距下方2 m之位置具有 空氣分散板3，其上具有丙烯及氨氣供給用原料氣體分散 管5 〇 原料氣體分散管5係根據（原料氣體分散管之壓力損 失）/(流動層壓力損失）=1.8而設定，設定流量=115〇〇 Nm3/h、設定下限流量=8570 Nm3/h。 將12個溫度計之平均值作為反應溫度並加以管理，該12 個溫度計係於距反應器下方5 m之高度之剖面具有8個，6 m之高度之剖面具有4個。 最初，自惰性氣體導入管14以4000 Nm3/h使氮氣流通至 原料氣體分散管5並加以保持。 自空氣分散板3向流動層反應器1供給經加熱之空氣。其 後，向反應器1導入流動層觸媒。 觸媒係使用粒徑10〜100 μιη、平均粒徑55 μπι之鉬_鉍-鐵 系承载觸媒，僅填充至靜止層高成為2.7①之程度。 [(Ρ1)-(Ρ2)]所表示之流動層壓力損失為〇 27 kg/cm2，設定 壓力損失=0.486 kg/cm2、設定下限壓力損失F = 〇 27 kg/cm2。 自原料氣體分散管5開始供給氨氣。緩緩提高氨氣流量 而達到規定流量後’自該原料氣體分散管5開始供給丙 烯。兩原料氣體之合計流量為7500 Nm3/h，向原料氣體分 散管5之原料氣體流量為設定下限流量之87 5%負荷。若包 含氮氣’則為134%負荷。[(P0)-(P1)]所示之分散裝置之壓 力損失為0.486 kg/cm2 ’為設定下限壓力損失ρ之18倍（1 8 153044.doc 17 201134552 F)。另外’流動層壓力損失仍然為0.27 kg/cm2。 [比較例1 ] 利用與製造例相同之方法藉由丙烯、氨氣及空氣開始丙 稀之數氧化反應後’停止自惰性氣體導入管丨4向原料氣體 分散管5供給氮氣。流動層壓力損失仍然為〇 27 kg/cm2， 但[(Ρ〇)-(Ρ1)]所表示之分散裝置之壓力損失低於〇 2〇7 kg/cm2。即，分散裝置之壓力損失為設定下限壓力損失F 之〇·77倍（0.77 F)。調整除熱管6而實施溫度控制以使反應 溫度為440°C。各流量條件及反應效果如下所述。 丙烯流量：3641 Nm3/h 氨氣流量：3859 Nm3/h 氮氣流量：0 Nm3/h 空氣流量：32767 Nm3/h 丙烯腈產率：80.4% [實施例1] 於比較例1之反應後，自惰性氣體導入管14向原料氣體 分散管5以4000 Nm3/h流通氮氣並加以保持。流動層壓力 才貝失仍然為0.27 kg/cm2 ’ [(Ρ〇)_(Ρ1)]所表示之分散裝置之 壓力損失自0.207 k g/cm2上升至0.486 kg/cm2。即，分散裝 置之壓力損失為設定下限壓力損失F之1.8倍（1.8 F)。各流 量條件及反應效果如下所述。 丙烯流量：3641 Nm3/h 氨氣流量：3859 Nm3/h 氮氣流量：4000 Nm3/h 153044.doc 201134552 空氣流量：32767 Nm3/h 丙烯腈產率：81.90/〇 產生CO及C02之反應減少，丙烯腈產率提昇。 使丙烯、氨氣及空氣之流量成比例地增加，將丙烯及氨 氣之合計流量設為11 500 Nm3/h，停止氮氣。其他條件與 上述相同。流動層壓力損失為0.27 kg/cm2，以及[(p〇)_ (P1)]所表示之分散裝置之壓力損失為0.486 kg/cm2，為設 定下限壓力損失F之1.8倍（1.8 F)。 各流量條件及反應效果如下所述。 丙烯流量：5583 Nm3/h 氨氣流量：5917 Nm3/h 氮氣流量：0 Nm3/h 空氣流量·· 50243 Nm3/h 丙烯腈產率：81.8% [比較例2] 於貫知例1之反應後，為進行生產調整而減少丙稀、氨 氣及空氣之流量並設為表1所示之原料氣體流量，但不自 惰性氣體導入管14向原料氣體分散管5供給氮氣。流動層 壓力損失仍然為0.27 kg/cm2，[(PO)-(Pl)]所表示之分散裝 置之塵力損失為0.269 kg/cm2。即，原料氣體引起之壓力 損失為設定下限壓力損失F之0.996倍（0.996 f)。 此時之丙烯腈產率為81.3%。 [實施例2] 於比較例2之反應後，自惰性氣體導入管14向原料氣體 153044.doc 19 201134552 分散官5以4000 Nm3/h流通氮氣並加以保持。流動層壓力 損失仍然為0.27 kg/cm2 ’ [(ροχρι)]所表示之分散裝置之 壓力損失自0.269 kg/cm2上升至0.579 kg/cm2。即，原料氣 體與氮氣引起之壓力損失為設定下限壓力損失F之21倍 (2.1 F)。 此時之丙烯腈產率為81.9%。產生CO及C02之反應減 少，丙烯腈產率提昇。 [比較例3] 於實施例2之反應後’為進行生產調整而減少丙烯、氨 氣及空氣之流量並設為表1所示之原料氣體流量，但不自 惰性氣體導入管14向原料氣體分散管5供給氮氣。流動層 壓力損失仍然為0.27 kg/cm2，[(Ρ〇)·(ρΐ)]所表示之分散裝 置之壓力損失為0.16，為設定下限壓力損失Fi 〇.59倍 (0.59 F)。此時之丙烯腈產率為79 7%。產生c〇及c〇2之反 應增加’丙浠腈產率下降β [實施例3〜7] 於比較例3之反應後，不改變丙烯、氨氣及空氣之流 量，自惰性氣體導入管14向原料氣體分散管5以表】所示之 流量流通氮氣。實施例3〜7中之流動層壓力損失於任一情 形時均為0.27 kg/cm2，[(Ρ〇)_(ρι)]所表示之分散裝置之壓 力損失於任一情形時均大於流動層壓力損失F，即[(p〇)_ (P1)]>F。實施例3〜7之反應效果如表1所示，丙烯腈產率 為 81.7〜81.9%。 [比較例4] 153044.doc -20_ 201134552 使用與製造例相同之流動層反應器1，開始準備丙稀之 氨氧化反應’不自惰性氣體導入管14向原料氣體分散管5 流通氮氣。 自空氣分散板3向流動層反應器1供給經加熱之空氣。其 後’向反應器1導入流動層觸媒。 觸媒係使用粒徑10〜100 μιη、平均粒徑55 之鉬-鉍-鐵 系承載觸媒，僅填充至靜止層高成為2 7爪之程度。 欲自原料氣體分散營5朗私祉^ 苽S開始供給氨氣，但無法流通氨 氣。 停止反應器，進行周祖々 原抖軋體導入管4及該分散管5之檢 .查，結果流動層觸媒堵塞。 153044.doc 201134552 卜 4¾) 〇 cs ο v〇 00 〇 〇 (Ν σν 〇 Ο 00 ΓΛ οο Os *η 00 *Τϊ 〇 00 (Ν Ο 对 (Ν 〇 (Ν^ rn ΓΟ S' οο CS Ο CN Ό 〇 Ό 〇 (Ν νγ CC 1 0.270 1 0.486 0.270 ο (Ν ΓΟ (Ν Os rn ΓΛ 5,000 28,800 0,494 Ο m 00 81.9 0,65 440 實施例5 〇 (Ν οο 0.270 0.486 0.270 3,200 (Ν Ον cn ro 2,000 ο 00Λ οο CN 0.271 1.004 81.7 °·65- 440 1 實施例4 〇 to rj Όχ οο 0.270 0.486 0.270 3,200 3,392 3,000 28,800 0.338 1.252 81.8 440 m 〇 yri CS ο VO 00 〇 ο (Ν Ον 〇 ο g (Ν ν〇 <Ν 81.8 ο 寸 οο (Ν Ο <Ν 〇 cs^ γι' 〇Λ οό， (Ν ^r Ο i〇 v〇 ο 〇 yn Ο V£> OO 〇 ο <Ν ΟΝ Ο 00 § m Os 卜 rv ir^ οο CNJ ο 寸 o CN 〇 <Ν cn <^γ cn ο 00 CS ο ο OS ν〇 Ο 實施例2 〇 »〇 οο Γ〇.270 1_ 0.486 0.270 Os ON ΓΊ 4,000 ΓΛ ΓΟ 0.579 2.144 81.9 0.65 440 比較例2 〇 ν*ϊ ri r·^ 8,572 0.270 0.486 0.270 寸Λ ON On fO 寸" ο 37,350 0.269 0.996 81.3 0.65 440 i 11,500 OJ οο 0.270 0.486 0.270 5,583 卜 Os ο ΓΛ 0.486 1.800 81.8 0.65 11,500 1_ οο 1 0.270 ι_ 0.486 0.270 3,641 ON 00^ rn Ρ,οοο ν〇 m 0.486 1.800 81.9 0.65 440 比較例1 ,11,500 ι_ (Ν yn^ οο 0.270 0.486 0.270 3,641 3,859 ο 32,767 0.207 0.767 80.4 0.65 5 <Ν ε ΓΊ ε <Ν ε ΓΊ ε Ο <Ν ε ε ε ε ε ε ε Ρ ζ 2： a a ζ ζ Μ Μ Ph φΐ < ♦ι R Η Θ a Μ Μ Μ π Μ Μ Θ 跑1 铋 e_ 邮 $ί φή «η Φ 咐j •Μ Φ *3?h ΤΡΊ Φ Φ 35 X 鋇 梃 靼 鋇 >d 装 Θ ㈣ Θ •22- 153044.doc 201134552 [實施例8] 如下述般使用與製造例相同之流動層反應裝置1，藉由 丙烷、氨氣及空氣進行丙烷之氨氧化反應》 . 最初’自惰性氣體導入管14向原料氣體分散管5以4000Gas Chromatograph: Shimadzu GC-14B Column: Porapack-QS (50 to 80 mesh) Detector: FID (Flame Ionization Detector), carrier gas, nitrogen gas [Production Example] The ammoxidation of propylene is carried out by propylene, ammonia and air. The fluidized bed reactor is the same as that shown in Fig. 1. The fluidized bed reactor 1 is a vertical cylindrical type with a diameter of 8 m and a length of Lr20 m, and an air dispersion plate at a position 2 m below. 3, the raw material gas dispersion pipe 5 for supplying propylene and ammonia gas, and the raw material gas dispersion pipe 5 are set according to (pressure loss of the raw material gas dispersion pipe) / (flow layer pressure loss) = 1.8, and the flow rate is set to 115 〇 〇Nm3/h, set lower limit flow = 8570 Nm3/h. The average of 12 thermometers was used as the reaction temperature, and the 12 thermometers had 8 profiles at a height of 5 m below the reactor, and 4 profiles at a height of 6 m. Initially, nitrogen gas is supplied to the raw material gas dispersion pipe 5 from the inert gas introduction pipe 14 at 4000 Nm3/h and held. The heated air is supplied from the air dispersion plate 3 to the fluidized bed reactor 1. Thereafter, a fluidized bed catalyst was introduced into the reactor 1. The catalyst was a molybdenum-niobium-iron-based catalyst having a particle diameter of 10 to 100 μm and an average particle diameter of 55 μm, and was filled only to a level of 2.71. The pressure loss of the fluidized bed represented by [(Ρ1)-(Ρ2)] is 〇 27 kg/cm2, the set pressure loss = 0.486 kg/cm2, and the set lower limit pressure loss F = 〇 27 kg/cm2. The supply of ammonia gas is started from the raw material gas dispersion pipe 5. When the flow rate of the ammonia gas is gradually increased and the predetermined flow rate is reached, the supply of propylene is started from the raw material gas dispersion pipe 5. The total flow rate of the two raw material gases was 7,500 Nm3/h, and the flow rate of the raw material gas to the raw material gas dispersion pipe 5 was 87 5% of the set lower limit flow rate. If nitrogen is included, it is 134% load. The pressure loss of the dispersing device shown in [(P0)-(P1)] was 0.486 kg/cm2', which was 18 times the set lower limit pressure loss ρ (1 8 153044.doc 17 201134552 F). In addition, the pressure loss of the flow layer is still 0.27 kg/cm2. [Comparative Example 1] After the oxidation reaction of propylene, ammonia gas and air was started in the same manner as in the production example, the supply of nitrogen gas to the raw material gas dispersion pipe 5 was stopped by the inert gas introduction pipe 4. The pressure loss of the fluidized bed is still 〇 27 kg/cm2, but the pressure loss of the dispersing device represented by [(Ρ〇)-(Ρ1)] is less than 〇 2〇7 kg/cm2. That is, the pressure loss of the dispersing device is 77 times (0.77 F) which is set to the lower limit pressure loss F. The heat removal tube 6 was adjusted to carry out temperature control so that the reaction temperature was 440 °C. The flow conditions and reaction effects are as follows. Propylene flow rate: 3641 Nm3/h Ammonia gas flow rate: 3859 Nm3/h Nitrogen gas flow rate: 0 Nm3/h Air flow rate: 32767 Nm3/h Acrylonitrile yield: 80.4% [Example 1] After the reaction of Comparative Example 1, The inert gas introduction pipe 14 supplies nitrogen gas to the raw material gas dispersion pipe 5 at 4000 Nm 3 /h and holds it. The pressure loss of the fluidized bed pressure is still 0.27 kg/cm2 ’ [(Ρ〇)_(Ρ1)] The pressure loss of the dispersing device rises from 0.207 k g/cm2 to 0.486 kg/cm2. That is, the pressure loss of the dispersing device is 1.8 times (1.8 F) which is the set lower limit pressure loss F. The respective flow conditions and reaction effects are as follows. Propylene flow: 3641 Nm3/h Ammonia flow: 3859 Nm3/h Nitrogen flow: 4000 Nm3/h 153044.doc 201134552 Air flow: 32767 Nm3/h Acrylonitrile yield: 81.90/〇Reduced CO and CO 2 reaction, propylene The yield of nitrile is increased. The flow rate of propylene, ammonia gas and air was increased in proportion, and the total flow rate of propylene and ammonia was set to 11 500 Nm3/h, and nitrogen gas was stopped. Other conditions are the same as above. The pressure loss of the fluidized bed was 0.27 kg/cm2, and the pressure loss of the dispersing device represented by [(p〇)_(P1)] was 0.486 kg/cm2, which was 1.8 times (1.8 F) of the set lower limit pressure loss F. The flow conditions and reaction effects are as follows. Propylene flow rate: 5583 Nm3/h Ammonia gas flow rate: 5917 Nm3/h Nitrogen gas flow rate: 0 Nm3/h Air flow rate·· 50243 Nm3/h Acrylonitrile yield: 81.8% [Comparative Example 2] After the reaction of Example 1 In order to reduce the flow rates of acryl, ammonia, and air for production adjustment, and to set the flow rate of the raw material gas shown in Table 1, the nitrogen gas is not supplied from the inert gas introduction pipe 14 to the raw material gas dispersion pipe 5. The pressure loss of the flowing layer was still 0.27 kg/cm2, and the dust loss of the dispersion device represented by [(PO)-(Pl)] was 0.269 kg/cm2. That is, the pressure loss caused by the material gas is 0.996 times (0.996 f) which is the set lower limit pressure loss F. The acrylonitrile yield at this time was 81.3%. [Example 2] After the reaction of Comparative Example 2, nitrogen was passed from the inert gas introduction pipe 14 to the raw material gas 153044.doc 19 201134552, and the nitrogen gas was kept at 4000 Nm 3 /h. The pressure loss of the fluidized bed is still 0.27 kg/cm2 ’ [(ροχρι)] The pressure loss of the dispersing device is increased from 0.269 kg/cm2 to 0.579 kg/cm2. That is, the pressure loss caused by the raw material gas and nitrogen gas is 21 times (2.1 F) which is the set lower limit pressure loss F. The acrylonitrile yield at this time was 81.9%. The reaction to produce CO and CO 2 is reduced, and the yield of acrylonitrile is increased. [Comparative Example 3] After the reaction of Example 2, the flow rate of propylene, ammonia gas and air was reduced for production adjustment, and the flow rate of the raw material gas shown in Table 1 was set, but not from the inert gas introduction pipe 14 to the raw material gas. The dispersion pipe 5 supplies nitrogen gas. The pressure loss of the fluidized bed was still 0.27 kg/cm2, and the pressure loss of the dispersion device represented by [(Ρ〇)·(ρΐ)] was 0.16, which was the set lower limit pressure loss Fi 〇.59 times (0.59 F). The yield of acrylonitrile at this time was 79 7%. The reaction for producing c〇 and c〇2 increased 'the yield of propionitrile was decreased β [Examples 3 to 7] After the reaction of Comparative Example 3, the flow rate of propylene, ammonia and air was not changed, and the inert gas was introduced into the tube 14 Nitrogen gas was flowed to the raw material gas dispersion pipe 5 at a flow rate shown in the table. The pressure loss of the fluidized bed in Examples 3 to 7 was 0.27 kg/cm 2 in either case, and the pressure loss of the dispersing device represented by [(Ρ〇)_(ρι)] was greater than that of the flowing layer in either case. Pressure loss F, ie [(p〇)_ (P1)] > F. The reaction effects of Examples 3 to 7 are shown in Table 1, and the yield of acrylonitrile was 81.7 to 81.9%. [Comparative Example 4] 153044.doc -20_ 201134552 The preparation of the ammoxidation reaction of propylene was started using the fluidized bed reactor 1 similar to the production example. The nitrogen gas was not supplied from the inert gas introduction pipe 14 to the raw material gas dispersion pipe 5. The heated air is supplied from the air dispersion plate 3 to the fluidized bed reactor 1. Thereafter, a fluidized bed catalyst is introduced into the reactor 1. The catalyst is a molybdenum-niobium-iron-based catalyst which has a particle diameter of 10 to 100 μm and an average particle diameter of 55, and is filled only to the extent that the height of the stationary layer is 27 claws. It is intended to supply ammonia gas from the raw material gas dispersion camp, but it is not possible to circulate ammonia. The reactor was stopped, and the inspection of the original rolling mill body introduction pipe 4 and the dispersion pipe 5 was carried out. As a result, the fluidized bed catalyst was clogged. 153044.doc 201134552 卜43⁄4) 〇cs ο v〇00 〇〇(Ν σν 〇Ο 00 ΓΛ οο Os *η 00 *Τϊ 〇00 (Ν Ο 对 (Ν 〇(Ν^ rn ΓΟ S' οο CS Ο CN Ό 〇Ό 〇 (Ν νγ CC 1 0.270 1 0.486 0.270 ο (Ν ΓΟ (Ν Os rn ΓΛ 5,000 28,800 0,494 Ο m 00 81.9 0, 65 440 Example 5 Ν (Ν οο 0.270 0.486 0.270 3,200 (Ν Ον cn ro 2,000 ο 00Λ οο CN 0.271 1.004 81.7 °·65- 440 1 Example 4 〇to rj Όχ οο 0.270 0.486 0.270 3,200 3,392 3,000 28,800 0.338 1.252 81.8 440 m 〇yri CS ο VO 00 〇ο (Ν Ον 〇ο g (Ν ν〇 <Ν 81.8 ο inchοο (Ν Ο <Ν 〇cs^ γι' 〇Λ οό, (Ν ^r Ο i〇v〇ο 〇yn Ο V£> OO 〇ο <Ν ΟΝ Ο 00 § m Os rv ir^ οο CNJ ο inch o CN 〇<Ν cn <^γ cn ο 00 CS ο ο OS ν〇Ο Example 2 〇»〇οο Γ〇.270 1_ 0.486 0.270 Os ON ΓΊ 4,000 ΓΛ ΓΟ 0.579 2.144 81.9 0.65 440 Comparative Example 2 〇ν*ϊ ri r·^ 8,572 0.270 0.486 0.270 inch Λ ON On fO inch" ο 37, 350 0.269 0.996 81.3 0.65 440 i 11,500 OJ οο 0.270 0.486 0.270 5,583 卜Os ο ΓΛ 0.486 1.800 81.8 0.65 11,500 1_ οο 1 0.270 ι_ 0.486 0.270 3,641 ON 00^ rn Ρ, οοο ν〇m 0.486 1.800 81.9 0.65 440 Comparative example 1, 11,500 ι_ (Ν yn^ οο 0.270 0.486 0.270 3,641 3,859 ο 32,767 0.207 0.767 80.4 0.65 5 <Ν ε ΓΊ ε <Ν ε ΓΊ ε Ο <Ν ε ε ε ε ε ε ε Ρ ζ 2: aa ζ ζ Μ Μ Ph φΐ < ♦ι R Η Θ a Μ Μ π π Μ Μ Θ Run 1 铋e_ Post $ί φή «η Φ 咐j •Μ Φ *3?h ΤΡΊ Φ Φ 35 X 钡梃靼钡>d (4) 22 • 22-153044.doc 201134552 [Example 8] The same flow-layer reaction apparatus 1 as in the production example was used, and ammoxidation of propane was carried out by propane, ammonia gas and air. Inert gas introduction pipe 14 to raw material Gas dispersion tube 5 to 4000
Nm3/h流通氮氣並加以保持。 自空氣分散板3向反應器1供給經加熱之空氣。其後，向 反應器1導入流動層觸媒。 觸媒係使用粒徑1 0〜1 〇〇 μηι、平均粒徑55 μηι之鉬-釩系 承載觸媒’僅填充至靜止層高成為2.7 m之程度。[(ρι)_(ρ2)] 所表示之流動層壓力損失為0.27 kg/cm2，設定壓力損失 =〇·486 kg/cm2、設定下限壓力損失 F=〇 27 kg/cm2。 自原料氣體分散管5開始供給氨氣◦緩緩提高氨氣流量 並達到規定流量後，自該原料氣體分散管5開始供給丙 烷。兩原料氣體之合計流量為6829 Nm3/h，向原料氣體分 散管5之原料氣體流量為設定下限流量之79 7%負荷，原料 氣體與氮氣之合計流量為126%負荷。_Μρι)]所表示之 分散裝置之壓力損失為0.431 kg/cm2，為設定下限壓力損 失F之^倍…F)。另外，流動層壓力損失仍然為⑶ . kg/Cm 。調整除熱管6而實施溫度控制以# & $ 44(Γ(：。 又k制以使反應溫度為 各"IL篁條件及丙稀腈產率如下所述。 丙烷流量：3449 Nm3/h 氨氣流量：3380 Nm3/h 氮氣流量：4000 Nm3/h 153044.doc -23- 201134552 空氣流量：51735 Nm3/h 丙烯腈產率：53.4% 僅將氣氣流量提高至4671 Nm3/h，其他反應條件設為與 上述相同。流動層壓力損失仍然為〇 27 kg/cm2，[(p〇)_ (P1)]所表示之分散裝置之壓力損失自〇 43i上升至〇 486 kg/cm2。即，原料氣體與氮氣引起之壓力損失為設定下限 壓力4貝失F之1.8倍（1.8 F)。丙稀腈產率如下所述。 丙烯腈產率：53.5% [比較例5] 除自實施例8之狀態停止氮氣以外，以實施例8所記載之 條件進行氣相反應。流動層壓力損失仍然為0.27 kg/cm2， [(Ρ〇)-(Ρ1)]所表示之分散裝置之壓力損失下降至0171 kg/cm2。即，原料氣體引起之壓力損失為設定了限壓力損 失 F之 0.6倍（0.6 F)。 丙烷流量：3449 Nm3/h 氨氣流量：3380 Nm3/h 氮氣流量：0 Nm3/h 空氣流量：51735 Nm3/h 丙烯腈產率：50.9% 與實施例8比較，產生CO及C02之反應增加’丙烯腈產 率下降。 153044.doc •24- 201134552 [表2] 實施例8 比較例5 氣體分散裝置設定流量 Nm3/h 11,500 11,500 11,500 氣體分散裝置設定下限流量 Nm3/h 8,572 8,572 8,572 ①流動層壓力損失 kg/cm2 0.270 0.270 0.270 氣體分散裝置設定壓力損失 kg/cm2 0.486 0.486 0.486 氣體分散裝置設定下限壓力損失F kg/cm2 0.270 0.270 0.270 丙烧流量 Nm3/h 3,449 3,449 3,449 氨氣流量 Nm3/h 3,380 3,380 3,380 氮氣流量 Nm3/h 4,000 4,671 0 空氣流量 Nm3/h 51,735 51,735 51,735 ②氣體分散裝置壓力損失 •y kg/cm 0.431 0.486 0.171 壓力損失比②/① 1.596 1.800 0.633 丙烯腈產率 % 53.4 53.5 50.9 反應器上部壓力 kg/cm2G 0.65 0.65 0.65 反應溫度 °C 440 440 440 [實施例9] 如下述般藉由正丁烧及空氣進行正丁烧之氧化反應。 反應器1係内徑6.8 m、長度Lr20 m之立式圓筒型，於距 下方2 m之位置具有空氣分散板3,其上具有正丁烷供給用 原料氣體分散管5。 原料氣體分散管5係根據（原料氣體分散管之壓力損 失）/(流動層壓力損失）=1.8而設定，設定流量=4696 Nm3/h、 設定下限流量=3500 Nm3/h。 將8個溫度計之平均值作為反應溫度並加以管理，該8個 溫度計於距反應器下方5 m之高度之剖面具有4個，6 m之 153044.doc -25- 201134552 高度之剖面具有4個。 最初，自惰性氣體導入管14向原料氣體分散管5以1000 Nm3/h流通氣氣並加以保持。 自空氣分散板3向反應器1供給經加熱之空氣。其後，向 反應器1導入流動層觸媒。 觸媒係使用粒徑1 〇〜1 00 μηι、平均粒徑60 μηι之鈒-填系 承載觸媒，僅填充至靜止層高成為2.9 m之程度。[(Ρ1)-(P2)]所表示之流動層壓力損失為0.29 kg/cm2，設定壓力損 失=0.522 kg/cm2、設定下限壓力損失F = 0.29 kg/cm2。 自原料氣體分散管5開始供給正丁烷。正丁烷之流量為 2450 Nm3/h，原料氣體分散管之流量為設定下限流量之 70.0%負荷，原料氣體與氮氣之合計流量為98.6%負荷。 [(P0)-(P1)]所表示之分散裝置之壓力損失為0.282 kg/cm2，為設定下限壓力損失F之0.972倍（0.972 F)。另 外，流動層壓力損失仍然為0.29 kg/cm2。 調整除熱管而實施溫度控制以使反應溫度為450°C。各 流量條件及反應效果如下所述。 正丁烷流量：2450 Nm3/h 氮氣流量：1000 Nm3/h 空氣流量：58200 Nm3/h 順丁烯二酸酐產率：49.6% [比較例6 ] 於實施例9之反應後，僅停止供給氮氣，其他條件設為 相同。[(PO)-(Pl)]所表示之分散裝置之壓力損失為0.142 153044.doc -26- 201134552 kg/cm2，為設定下限壓力損失F之0.49倍（0·49 F)。另外， 流動層壓力損失仍然為0.29 kg/cm2。順丁烯二酸酐產率成 為 48.2%。 使正丁烷及空氣之流量增加，其他條件設為相同。 [(P0)-(P1)]所表示之分散裝置之壓力損失為0.29 kg/cm2， 為設定下限壓力損失F之1.0倍（1.0 F)。另外，流動層壓力 損失仍然為0.29 kg/cm2。 各流量條件及反應效果如下所述。 正丁烷流量：3500 Nm3/h 氮氣流量：0 Nm3/h 空氣流量：83100 Nm3/h 順丁烯二酸酐產率：49.5% [表3] 實施例9 比較例6 氣體分散裝置設定流量 Nm3/h 4,696 4,696 4,696 氣體分散裝置設定下限流量 Nm3/h 3,500 3,500 3,500 ①流動層壓力損失 Λ kg/cm 0.290 0.290 0.290 氣體分散裝置設定壓力損失 λ kg/cm 0.522 0.522 0.522 氣體分散裝置設定下限壓力損失F kg/cm2 0.290 0.290 0.290 正丁烷流量 Nm3/h 2,450 2,450 3,500 氮氣流量 Nm3/h 1,000 0 0 空気流量 Nm3/h 58,200 58,200 83,100 ②氣體分散裝置壓力損失 kg/cm2 0.282 0.142 0.290 壓力損失比⑦/① 0.972 0.490 1.000 順丁烯二酸酐產率 % 49.6 48.2 49.5 反應溫度 °C 450 450 450 153044.doc •27- 201134552 [實施例ι〇] 如下述般藉由苯酚及甲醇進行烷基化反應。 反應器1係使用内徑2 m、長度Lr20 m之立式圓筒型，距 下方3 m之位置具有供給苯酚及曱醇之混合氣體之原料氣 體分散管5。 原料氣體分散管5係根據（原料氣體分散管之壓力損 失扒流動層壓力損失户:^而設定“文定流量邶川^!^%、 設定下限流量=5000 Nm3/h » 將4個溫度計之平均值作為反應溫度並加以管理，該4個 溫度計於距反應器下方5 m之高度之剖面具有2個，6爪之 高度之剖面具有2個。 最初，自惰性氣體導入管14向原料氣體分散管5以2〇〇〇 Nm3/h流通氮氣並力σ以保持〇 觸媒係使用粒徑10〜100 μιη、平均粒徑5〇 μηι之鐵_釩系 承載觸媒，僅填充至靜止層高成為8爪之程度。[(ρι)_(ρ2)] 所表示之流動層壓力損失為〇·8〇 kg/cm2，設定壓力損失 =1.44 kg/cm2、設定下限壓力損失F=〇 8〇 kg/cm2。 自原料氣體分散管5開始供給苯酚及甲醇混合氣體。該 混合氣體之流量為3〇〇〇 Nm3/h ’原料氣體分散管之流量為 設定下限流量之60.0%負荷，原料氣體與氣氣之合計流量 為100%負荷。 [(Ρ0)-(Ρ1)]所表示之分散裝置之壓力損失為〇 80 kg/cm2,為設定下限壓力損失F<i 〇倍（1 〇 f)。另外，流 動層壓力損失仍然為〇8〇 kg/cm2。調整除熱管而實施溫度 153044.doc -28- 201134552 控制以使反應溫度為330°C。各流量條件及反應效果如下 所述。 苯酚、甲醇合計流量：3000 Nm3/h 氮氣流量：2000 Nm3/h 鄰曱酚、2,6-二曱苯酚合計產率：93.8% [比較例7] 於實施例10之反應後，僅停止供給氮氣，其他條件設為 相同。[(PO)-(Pl)]所表示之分散裝置之壓力損失為0.288 kg/cm2，為設定下限壓力損失F之0.36倍（0.36 F)。另外， 流動層壓力損失仍然為0.80 kg/cm2。 鄰曱酚、2,6-二甲苯酚合計產率成為90.1%。 [表4] 實施例10 比較例7 氣體分散裝置設定流量 Nm3/h 6,708 6,708 氣體分散裝置設定下限流量 Nm3/h 5,000 5,000 ①流動層壓力損失 λ kg/cm 0.800 0.800 氣體分散裝置設定壓力損失 kg/cm2 1.440 1.440 氣體分散裝置設定下限壓力損失F kg/cm2 0.800 0.800 苯酚、曱醇混合氣體流量 Nm3/h 3,000 3,000 氮氣流量 Nm3/h 2,000 0 ②氣體分散裝置壓力損失 kg/cm 0.800 0.288 壓力損失比⑦/① 1.000 0.360 鄰曱酚、2,6-二曱苯酚合計產率 % 93.8 90.1 反應溫度 °c 330 330 本申請案係基於2010年1月25日向曰本專利廳申請之曰 本專利申請案（曰本專利特願2010-013265)者，其内容於此 153044.doc •29· 201134552 作為參照而引入。 [產業上之可利用性] 本發明之方法具有使用流動層反應器實施氣相反應之方 法的產業上之可利用性。 【圖式簡單說明】 圖1係表示具有原料氣體分散裝置之流動層反應裝置之 一例之概略圖。 【主要元件符號說明】 1 流動層反應器 2 空氣（氧氣）導入管 3 空氣（氧氣）分散板 4 原料氣體導入管 5 原料氣體分散管 6 除熱管或加熱管 7 旋風分離器裝置 8 反應氣體流出管 9 流動觸媒層 10 〜13 壓力計 14 惰性氣體導入管 15 孔口板 A 含有氧氣之氣體 B 原料氣體 C 反應生成氣體 D 惰性氣體 153044.doc •30· 201134552 P0 壓 P1 壓 P2 壓 P3 壓 力計ίο之壓力 力計11之壓力 力計12之壓力 力計13之壓力 153044.doc •31 -Nm3/h flows nitrogen and is maintained. The heated air is supplied from the air dispersion plate 3 to the reactor 1. Thereafter, a fluidized bed catalyst was introduced into the reactor 1. The catalyst was a molybdenum-vanadium-based carrier catalyst having a particle diameter of 10 0 to 1 〇〇 μηι and an average particle diameter of 55 μηι, and was filled only to a level of 2.7 m. [(ρι)_(ρ2)] The fluidized bed pressure loss is 0.27 kg/cm2, set pressure loss = 〇·486 kg/cm2, set lower limit pressure loss F=〇 27 kg/cm2. After the supply of the ammonia gas from the raw material gas dispersion pipe 5 is started, the flow rate of the ammonia gas is gradually increased, and the predetermined flow rate is reached, and then the propane gas is supplied from the raw material gas dispersion pipe 5. The total flow rate of the two raw material gases was 6829 Nm3/h, and the flow rate of the raw material gas to the raw material gas dispersion pipe 5 was 79 7% of the set lower limit flow rate, and the total flow rate of the raw material gas and the nitrogen gas was 126% load. The pressure loss of the dispersing device indicated by _Μρι) is 0.431 kg/cm2, which is the set lower limit pressure loss F times...F). In addition, the pressure loss of the fluidized bed is still (3). kg/Cm. Adjust the heat removal tube 6 and perform temperature control to # & $ 44 (Γ (:. and k to make the reaction temperature for each "IL篁 condition and acrylonitrile yield as follows. Propane flow: 3449 Nm3/h Ammonia flow rate: 3380 Nm3/h Nitrogen flow rate: 4000 Nm3/h 153044.doc -23- 201134552 Air flow rate: 51735 Nm3/h Acrylonitrile yield: 53.4% Only increase the gas flow rate to 4671 Nm3/h, other reactions The condition is set to be the same as above. The pressure loss of the fluidized bed is still 〇27 kg/cm2, and the pressure loss of the dispersing device represented by [(p〇)_(P1)] is increased from 〇43i to 〇486 kg/cm2. The pressure loss caused by the raw material gas and nitrogen gas was 1.8 times (1.8 F) of the set lower limit pressure of 4 ft. F. The acrylonitrile yield was as follows. Acrylonitrile yield: 53.5% [Comparative Example 5] Except for Example 8 The gas phase reaction was carried out under the conditions described in Example 8 except that the nitrogen gas was stopped. The pressure loss of the fluidized bed was still 0.27 kg/cm 2 , and the pressure loss of the dispersing device represented by [(Ρ〇)-(Ρ1)] was decreased to 0171 kg/cm2, that is, the pressure loss caused by the material gas is set to 0.6 times (0.6 F) of the limit pressure loss F. Alkane flow rate: 3449 Nm3/h Ammonia gas flow rate: 3380 Nm3/h Nitrogen gas flow rate: 0 Nm3/h Air flow rate: 51735 Nm3/h Acrylonitrile yield: 50.9% Compared with Example 8, the reaction of CO and CO 2 is increased. The yield of acrylonitrile decreased. 153044.doc •24- 201134552 [Table 2] Example 8 Comparative Example 5 Gas Dispersion Device Setting Flow Rate Nm3/h 11,500 11,500 11,500 Gas Dispersion Device Setting Lower Flow Rate Nm3/h 8,572 8,572 8,572 1 Flow Layer Pressure Loss kg/cm2 0.270 0.270 0.270 Gas dispersion device set pressure loss kg/cm2 0.486 0.486 0.486 Gas dispersion device set lower limit pressure loss F kg/cm2 0.270 0.270 0.270 Propane burn flow rate Nm3/h 3,449 3,449 3,449 Ammonia gas flow rate Nm3/h 3,380 3,380 3,380 Nitrogen flow rate Nm3/h 4,000 4,671 0 Air flow rate Nm3/h 51,735 51,735 51,735 2 Gas dispersion device pressure loss • y kg/cm 0.431 0.486 0.171 Pressure loss ratio 2/1 1.596 1.800 0.633 Acrylonitrile yield % 53.4 53.5 50.9 Reactor Upper pressure kg/cm2G 0.65 0.65 0.65 Reaction temperature °C 440 440 440 [Example 9] Normally calcined by n-butyl burning and air as follows The oxidation reaction. The reactor 1 has a vertical cylindrical shape having an inner diameter of 6.8 m and a length of Lr 20 m, and has an air dispersion plate 3 at a position 2 m below, and a raw material gas dispersion pipe 5 for supplying n-butane. The material gas dispersion pipe 5 is set according to (pressure loss of the material gas dispersion pipe) / (flow layer pressure loss) = 1.8, and the flow rate is set to 4696 Nm3/h, and the lower limit flow rate is set to 3500 Nm3/h. The average of the eight thermometers was used as the reaction temperature, and the eight thermometers had four profiles at a height of 5 m from the lower side of the reactor, and four sections of 153044.doc -25-201134552 at a height of 6 m. Initially, the inert gas introduction pipe 14 is ventilated at a flow rate of 1000 Nm 3 /h to the material gas dispersion pipe 5 and held. The heated air is supplied from the air dispersion plate 3 to the reactor 1. Thereafter, a fluidized bed catalyst was introduced into the reactor 1. The catalyst is used in a particle size of 1 〇1 to 00 μηι, and an average particle size of 60 μηι-filled with a catalyst, and only filled to a level of 2.9 m. The pressure loss of the fluidized bed represented by [(Ρ1)-(P2)] is 0.29 kg/cm2, the set pressure loss is = 0.522 kg/cm2, and the set lower limit pressure loss is F = 0.29 kg/cm2. The n-butane is supplied from the raw material gas dispersion pipe 5. The flow rate of n-butane was 2450 Nm3/h, the flow rate of the raw material gas dispersion pipe was 70.0% of the set lower limit flow rate, and the total flow rate of the raw material gas and nitrogen gas was 98.6% load. The pressure loss of the dispersing device represented by [(P0)-(P1)] was 0.282 kg/cm2, which was 0.972 times (0.972 F) of the set lower limit pressure loss F. In addition, the pressure loss of the flow layer is still 0.29 kg/cm2. Temperature control was carried out by adjusting the heat removal tube so that the reaction temperature was 450 °C. The flow conditions and reaction effects are as follows. N-butane flow rate: 2450 Nm3/h Nitrogen flow rate: 1000 Nm3/h Air flow rate: 58200 Nm3/h Maleic anhydride yield: 49.6% [Comparative Example 6] After the reaction of Example 9, only the supply of nitrogen was stopped. , other conditions are set to be the same. The pressure loss of the dispersing device represented by [(PO)-(Pl)] is 0.142 153044.doc -26-201134552 kg/cm2, which is 0.49 times (0·49 F) of the set lower limit pressure loss F. In addition, the flow layer pressure loss is still 0.29 kg/cm2. The yield of maleic anhydride was 48.2%. The flow rate of n-butane and air is increased, and other conditions are set to be the same. The pressure loss of the dispersing device represented by [(P0)-(P1)] was 0.29 kg/cm2, which was 1.0 times (1.0 F) of the set lower limit pressure loss F. In addition, the flow layer pressure loss is still 0.29 kg/cm2. The flow conditions and reaction effects are as follows. N-butane flow rate: 3500 Nm3/h Nitrogen flow rate: 0 Nm3/h Air flow rate: 83100 Nm3/h Maleic anhydride yield: 49.5% [Table 3] Example 9 Comparative Example 6 Gas dispersion device set flow rate Nm3/ h 4,696 4,696 4,696 Gas dispersion device set lower limit flow rate Nm3/h 3,500 3,500 3,500 1 Flow layer pressure loss Λ kg/cm 0.290 0.290 0.290 Gas dispersion device set pressure loss λ kg/cm 0.522 0.522 0.522 Gas dispersion device set lower limit pressure loss F kg /cm2 0.290 0.290 0.290 n-butane flow rate Nm3/h 2,450 2,450 3,500 nitrogen flow rate Nm3/h 1,000 0 0 air flow rate Nm3/h 58,200 58,200 83,100 2 gas dispersion device pressure loss kg/cm2 0.282 0.142 0.290 pressure loss ratio 7/1 0.972 0.490 1.000 Maleic anhydride yield % 49.6 48.2 49.5 Reaction temperature ° C 450 450 450 153044.doc • 27- 201134552 [Example ι] The alkylation reaction was carried out by phenol and methanol as follows. In the reactor 1, a vertical cylindrical type having an inner diameter of 2 m and a length of Lr 20 m was used, and a raw material gas dispersion pipe 5 for supplying a mixed gas of phenol and decyl alcohol was provided at a position 3 m below. The raw material gas dispersion pipe 5 is set according to (the pressure loss of the raw material gas dispersion pipe, the pressure loss of the fluidized bed: ^), and the setting of the "flow rate of the flow rate of the river ^^^^^, the lower limit flow rate = 5000 Nm3/h » 4 thermometers The average value is calculated as the reaction temperature, and the four thermometers have two profiles at a height of 5 m from the lower side of the reactor, and two profiles having a height of six claws. Initially, the inert gas introduction pipe 14 is dispersed to the raw material gas. The tube 5 is flowed with nitrogen gas at a pressure of 2〇〇〇Nm3/h and the force σ is used to maintain the iron-vanadium-bearing catalyst having a particle diameter of 10 to 100 μm and an average particle diameter of 5 〇μηι, which is only filled to the stationary layer. The degree of the 8 claws. The pressure loss of the fluidized bed represented by [(ρι)_(ρ2)] is 〇·8〇kg/cm2, the set pressure loss = 1.44 kg/cm2, the set lower limit pressure loss F=〇8〇kg /cm2. The phenol and methanol mixed gas is supplied from the raw material gas dispersion pipe 5. The flow rate of the mixed gas is 3〇〇〇Nm3/h 'The flow rate of the raw material gas dispersion pipe is 60.0% of the set lower limit flow rate, and the raw material gas and gas The total flow of gas is 100% load. [(Ρ0)-(Ρ1)] The pressure loss of the dispersing device is 〇80 kg/cm2, which is the set lower limit pressure loss F<i 〇 times (1 〇f). In addition, the pressure loss of the fluidized bed is still 〇8〇kg/cm2. 153044.doc -28- 201134552 Control so that the reaction temperature is 330 ° C. The flow conditions and reaction effects are as follows: phenol, methanol total flow: 3000 Nm3 / h nitrogen flow: 2000 Nm3 / h o-nonylphenol, 2, Total yield of 6-diphenyl phenol: 93.8% [Comparative Example 7] After the reaction of Example 10, only the supply of nitrogen gas was stopped, and other conditions were set to be the same. The dispersion device represented by [(PO)-(Pl)] The pressure loss is 0.288 kg/cm2, which is 0.36 times (0.36 F) of the set lower limit pressure loss F. In addition, the pressure loss of the fluidized bed is still 0.80 kg/cm2. The total yield of o-nonylphenol and 2,6-xylenol becomes 90.1% [Table 4] Example 10 Comparative Example 7 Gas Dispersing Device Setting Flow Rate Nm3/h 6,708 6,708 Gas Dispersing Device Setting Lower Limit Flow Rate Nm3/h 5,000 5,000 1 Flow Layer Pressure Loss λ kg/cm 0.800 0.800 Gas Dispersing Device Setting Pressure Loss kg/cm2 1.440 1.440 gas dispersion device Lower limit pressure loss F kg/cm2 0.800 0.800 Phenol, sterol mixed gas flow rate Nm3/h 3,000 3,000 Nitrogen flow rate Nm3/h 2,000 0 2 Gas dispersion device pressure loss kg/cm 0.800 0.288 Pressure loss ratio 7/1 1.000 0.360 Neighbor Phenol, 2,6-diphenyl phenol total yield% 93.8 90.1 Reaction temperature °c 330 330 This application is based on the patent application filed on January 25, 2010 from the Patent Office of Japan. -013265), the content of which is incorporated herein by reference to 153 044.doc. [Industrial Applicability] The method of the present invention has industrial applicability of a method of performing a gas phase reaction using a fluidized bed reactor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a fluidized bed reaction apparatus having a material gas dispersion device. [Main component symbol description] 1 Flow layer reactor 2 Air (oxygen) inlet pipe 3 Air (oxygen) dispersion plate 4 Raw material gas introduction pipe 5 Raw material gas dispersion pipe 6 Heat removal pipe or heating pipe 7 Cyclone separator device 8 Reaction gas outflow Tube 9 Flow catalyst layer 10 to 13 Pressure gauge 14 Inert gas introduction pipe 15 orifice plate A Gas containing oxygen B Raw material gas C Reaction gas D inert gas 153044.doc • 30· 201134552 P0 Pressure P1 Pressure P2 Pressure P3 Pressure Pressure gauge 11 pressure gauge 12 pressure gauge 13 pressure 153044.doc • 31 -