TW201904660A - Method for producing reaction product gas and fluidized bed gas phase reaction device - Google Patents

Method for producing reaction product gas and fluidized bed gas phase reaction device

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Publication number
TW201904660A
TW201904660A TW107103378A TW107103378A TW201904660A TW 201904660 A TW201904660 A TW 201904660A TW 107103378 A TW107103378 A TW 107103378A TW 107103378 A TW107103378 A TW 107103378A TW 201904660 A TW201904660 A TW 201904660A
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Taiwan
Prior art keywords
value
gas
reaction
reactor
reference value
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TW107103378A
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Chinese (zh)
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TWI652109B (en
Inventor
佐野和彦
古谷泰章
藤田一之
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日商旭化成股份有限公司
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Publication of TWI652109B publication Critical patent/TWI652109B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/07—Mononitriles
    • C07C255/08—Acrylonitrile; Methacrylonitrile

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

This method for producing a reaction-generating gas comprises a reaction step for feeding a starting gas for a fluidized bed gas-phase reaction in the presence of a catalyst, the reaction step including a shutdown step in which, when at least one of prescribed conditions is satisfied, emergency shutdown of a fluidized bed gas-phase reactor operation is performed by cutting off at least a first feed tube.

Description

反應生成氣體之製造方法及流動層氣相反應裝置Method for producing reaction generated gas and fluid layer gas phase reaction device

本發明係關於一種反應生成氣體之製造方法及流動層氣相反應裝置。The invention relates to a method for producing a reaction-produced gas and a fluid-phase gas-phase reaction device.

流動層技術自19世紀後半期被開發以來，已應用於各種製造技術。作為流動層之主要工業應用，可列舉：煤氣化爐、FCC(Fluid Catalytic Cracking，流體化煤裂)設備、利用丙烯之氨氧化之丙烯腈製造設備、聚乙烯氣相聚合設備、順丁烯二酸酐製造設備等。流動層反應器由於容易去除或施加反應熱，故而可列舉可將層內維持為均一溫度而可避免反應不均、可進行爆炸範圍之高濃度氣體之處理、生產性較高等作為特徵，今後亦期待於各方面之應用、改良。 圖1表示先前技術之流動層氣相反應裝置。進行氣相反應之流動層反應器1於其內部具有：分散板3，其供給含氧氣體A；或分散管5，其供給空氣等原料氣體B。進而具有冷卻盤管6，藉由使水或蒸氣流通而去除反應熱，控制反應溫度。反應中之流動層反應器1之內部空間具有位於下部之觸媒之空間密度較高之濃厚層9a、及位於上部之觸媒之空間密度較低之稀薄層9b。反應主要係於濃厚層9a中進行。稀薄層9b中之反應氣體中之流動層觸媒係利用旋風分離器7自反應氣體分離，並返回至反應器下部之濃厚層9a中。 一種以上之單獨或混合原料氣體B之流量係利用流量感測器進行測定，且利用流量指示計FI1顯示流量。同樣地，視需要導入之含氧氣體A之流量係利用流量感測器進行測定，且利用流量指示計FI2顯示流量。為了測定反應器內之溫度，於濃厚層9a設置溫度計TI1，於稀薄層9b設置TI2。反應壓力係利用設置於稀薄層9b例如反應器上部之壓力計PI1而進行測定 作為與流動層氣相反應裝置之反應之穩定性相關之發明，例如於專利文獻1中揭示有於溫度不穩定系統之流動層反應器中，實現精密之溫度控制之設計方法及流動層反應器。 於專利文獻2中揭示有非常規反應器之關閉法。認為係藉由如下安全地對化學反應製程進行操作之方法而達成，該方法包括：檢測有可能對製程造成影響之不理想之狀態之步驟；將反應物質之反應抑制為最低限度之步驟；及以自反應區移出反應混合物之方式維持通過製程之反應區之物質流之步驟。 於專利文獻3中揭示有一種用以省略運轉之不必要之緊急停止，僅確實地進行必要之緊急停止之不飽和烴之利用含分子氧之氣體之氣相部分氧化反應裝置的緊急停止方法。 [先前技術文獻] [專利文獻] 專利文獻1：日本專利特開2015-174063號公報 專利文獻2：日本專利特開2006-143730號公報 專利文獻3：日本專利特開2004-277339號公報Since the development of the fluid layer technology in the second half of the 19th century, it has been applied to various manufacturing technologies. As the main industrial applications of the fluidized layer, gasification furnaces, FCC (Fluid Catalytic Cracking) equipment, acrylonitrile manufacturing equipment using ammoxidation of propylene, polyethylene gas phase polymerization equipment, butadiene diene Acid anhydride manufacturing equipment. The fluidized bed reactor is easy to remove or apply reaction heat, so it can be characterized by maintaining a uniform temperature in the layer to avoid uneven reaction, handling high-concentration gas in the explosive range, and high productivity. Looking forward to application and improvement in various aspects. Fig. 1 shows a prior art fluidized bed gas phase reaction apparatus. The fluidized-layer reactor 1 that performs a gas-phase reaction includes a dispersion plate 3 which supplies an oxygen-containing gas A, or a dispersion pipe 5 which supplies a raw material gas B such as air. Furthermore, a cooling coil 6 is provided, and the reaction heat is removed by circulating water or steam to control the reaction temperature. The internal space of the flowing layer reactor 1 in the reaction includes a thick layer 9a having a higher spatial density of the catalyst located at the lower portion and a thin layer 9b having a lower spatial density of the catalyst located at the upper portion. The reaction proceeds mainly in the thick layer 9a. The flowing layer catalyst in the reaction gas in the thin layer 9b is separated from the reaction gas by the cyclone 7 and returned to the thick layer 9a in the lower part of the reactor. The flow rate of more than one type of single or mixed source gas B is measured by a flow sensor, and the flow rate is displayed by a flow indicator FI1. Similarly, the flow rate of the oxygen-containing gas A introduced as necessary is measured by a flow rate sensor, and the flow rate is displayed by a flow rate indicator FI2. In order to measure the temperature in the reactor, a thermometer TI1 is provided in the thick layer 9a, and TI2 is provided in the thin layer 9b. The reaction pressure is measured by using a pressure gauge PI1 provided on the thin layer 9b, such as the upper part of the reactor, as an invention related to the stability of the reaction of the fluid-phase gas-phase reaction device. For example, Patent Document 1 discloses a temperature unstable system In the flow layer reactor, a design method for realizing precise temperature control and the flow layer reactor are realized. Patent Document 2 discloses a method for closing an unconventional reactor. It is believed that this was achieved by a method of safely operating a chemical reaction process, which includes: a step of detecting an undesired state that may affect the process; a step of suppressing a reaction of a reaction substance to a minimum; and A step of maintaining a flow of material through the reaction zone of the process by removing the reaction mixture from the reaction zone. Patent Document 3 discloses an emergency stop method for a gas phase partial oxidation reaction device using unsaturated oxygen gas and a gas phase partial oxidation reaction device for omitting unnecessary emergency stop of an operation and performing only the necessary emergency stop. [Prior Art Literature] [Patent Literature] Patent Literature 1: Japanese Patent Laid-Open No. 2015-174063 Patent Literature 2: Japanese Patent Laid-Open No. 2006-143730 Patent Literature 3: Japanese Patent Laid-Open No. 2004-277339

[發明所欲解決之問題] 流動層氣相反應裝置之穩定化就將目標產物之產率維持為高位之觀點、及安全運轉之觀點而言為必需之事項，且業界進行有大量發明。然而，關於防止流動層氣相反應裝置中之製程值因某些影響而紊亂，從而導致事故之流動層氣相反應裝置之運轉方法之發明，仍不充分，尚有改善之餘地。 專利文獻2係與監視部分氧化反應製程，必要時安全地關閉反應製程之方法相關之發明。為了實施上述發明之方法，製作需要關閉反應器裝置之不理想之反應製程條件之清單，特定出表示經清單化之不理想之條件之各者的臨界製程測定值。認為所使用之臨界製程測定值之種類可包含選自如下清單中的1種以上，該清單包含溫度、壓力、流向、供給比、可燃性計算值、及流動組成(例如利用線上分析儀決定)、以及反應器裝置內之支援裝置之操作狀態(例如反應器冷卻循環泵、反應物質饋送氣化裝置)及分離裝置及相關之裝置、及廢棄物減少裝置及相關之裝置之下游裝置之操作狀態。然而，由於上述臨界製程測定值之種類涉及多方面及未具體化，採用全部認為較為過量，並且緊急停止系統變得較複雜，故而認為有產生由較多測定器之任一者發生故障所引起之誤檢測之發生率上升之作動上的問題之虞。進而於經濟方面亦較困難。為了避免上述問題，於選擇採用有效之測定值之情形時亦未對選擇方法進行記載，而根據實施者之衡量加以選擇，有遺漏本來應選擇者等無法達成安全地關閉之目的之虞。 本發明之目的在於提供一種於使用流動層氣相反應裝置之氣相反應中，可防止異常之未檢測(係指將異常檢測為正常)及異常之誤檢測(係指將正常檢測為異常)，正確地檢測異常並停止運轉之確保充分之製程安全性的反應生成氣體之製造方法；及達成該方法之流動層氣相反應裝置。 [解決問題之技術手段] 本發明者等人對在使用流動層氣相反應裝置之氣相反應中，確實地檢測異常反應，防止災害於未然之方法進行努力研究，結果發現，藉由對特定部位之製程值及氣體分析值與預先決定之基準值進行比較監視，可解決該課題，從而完成本發明。 即，本發明如下所述。 [1] 一種反應生成氣體之製造方法，其係使用流動層氣相反應裝置並利用原料氣體製造反應生成氣體之方法，且 上述流動層氣相反應裝置具有：反應器，其可流動地收納觸媒；第一供給管，其向上述反應器中供給上述原料氣體；流出管，其自上述反應器中排出上述反應生成氣體；冗餘之複數個溫度計TI，該等係設置於上述反應器；冗餘之複數個壓力計PI，該等係位於上述反應器之稀薄層部；及冗餘之複數個反應生成氣體分析器DI，該等係位於上述流出管之下游；並且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第一至第六基準值之各者之實測值下，產生下述(a1)至(c3)之6種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟。 (a1)將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值，顯示大於第一基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (a2)將觸媒之活性降低而增加未反應，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值，顯示小於第二基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (b)將反應器之設計壓力之70〜85%之值設為第三基準值，顯示大於第三基準值之實測值之上述壓力計PI之數量超過壓力計PI之總數的過半數之狀態 (c1)將爆炸極限氧濃度之40〜100%之值設為第四基準值，顯示大於第四基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c2)將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值，顯示小於第五基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c3)將原料氣體濃度之設計值之150〜300%之值設為第六基準值，顯示大於第六基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 [2] 如[1]中所記載之製造方法，其中上述流動層氣相反應裝置進而具有冗餘之複數個原料氣體流量計FI，該等係設置於上述第一供給管；且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第七至第八基準值之各者之實測值下，產生下述(d1)至(d2)之2種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟。 (d1)將成為觸媒失活之氧濃度之假定原料氣體流量值、成為反應器之設計溫度之假定原料氣體流量值、及成為觸媒劣化之溫度之假定原料氣體流量值中之最低之流量值的85〜100%之值設為第七基準值，顯示大於第七基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 (d2)將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值，顯示小於第八基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 [3] 如[1]或[2]中所記載之製造方法，其中上述流動層氣相反應裝置進而具有：第二供給管，其向上述反應器中供給含氧氣體；及冗餘之複數個含氧氣體流量計FI，該等係設置於上述第二供給管；且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第九至第十基準值之各者之實測值下，產生下述(e1)至(e2)之2種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管、或上述第一供給管及上述第二供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟。 (e1)將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值，顯示大於第九基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 (e2)將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值，顯示小於第十基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 [4] 如[1]至[3]中任一項所記載之製造方法，其中上述原料氣體包含烷烴及/或烯烴。 [5] 如[4]中所記載之製造方法，其中上述烷烴為丙烷及/或異丁烷。 [6] 如[4]中所記載之製造方法，其中上述烯烴為丙烯及/或異丁烯。 [7] 如[1]至[6]中任一項所記載之製造方法，其中上述氣相反應為氨氧化反應。 [8] 一種流動層氣相反應裝置，其具有：反應器，其可流動地收納觸媒；第一供給管，其向上述反應器中供給原料氣體；流出管，其自上述反應器中排出反應生成氣體；冗餘之複數個溫度計TI，該等係設置於上述反應器；冗餘之複數個壓力計PI，該等係位於上述反應器之稀薄層部；冗餘之複數個反應生成氣體分析器DI，該等係位於上述流出管之下游；及緊急反應停止控制部；且 於監視相對於下述第一至第六基準值之各者之實測值下，產生下述(a1)至(c3)之6種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止者。 (a1)將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值，顯示大於第一基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (a2)將觸媒之活性降低而增加未反應，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值，顯示小於第二基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (b)將反應器之設計壓力之70〜85%之值設為第三基準值，顯示大於第三基準值之實測值之上述壓力計PI之數量超過壓力計PI之總數的過半數之狀態 (c1)將爆炸極限氧濃度之40〜100%之值設為第四基準值，顯示大於第四基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c2)將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值，顯示小於第五基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c3)將原料氣體濃度之設計值之150〜300%之值設為第六基準值，顯示大於第六基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 [9] 如[8]中所記載之流動層氣相反應裝置，其中上述流動層氣相反應裝置進而具有冗餘之複數個原料氣體流量計FI，該等係設置於上述第一供給管；且 於監視相對於下述第七至第八基準值之各者之實測值下，產生下述(d1)至(d2)之2種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止者。 (d1)將成為觸媒失活之氧濃度之假定原料氣體流量值、成為反應器之設計溫度之假定原料氣體流量值、及成為觸媒劣化之溫度之假定原料氣體流量值中之最低之流量值的85〜100%之值設為第七基準值，顯示大於第七基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 (d2)將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值，顯示小於第八基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 [10] 如[8]或[9]中所記載之流動層氣相反應裝置，其中上述流動層氣相反應裝置進而具有：第二供給管，其向上述反應器中供給含氧氣體；及冗餘之複數個含氧氣體流量計FI，該等係設置於上述第二供給管；且 於監視相對於下述第九至第十基準值之各者之實測值下，產生下述(e1)至(e2)之2種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管、或 上述第一供給管及上述第二供給管，而使上述流動層氣相反應裝置之運轉緊急停止者。 (e1)將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值，顯示大於第九基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 (e2)將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值，顯示小於第十基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 [發明之效果] 根據本發明，可提供一種於使用流動層氣相反應裝置之氣相反應中，可正確地檢測異常並停止運轉之確保充分之製程安全性的反應生成氣體之製造方法；及達成該方法之流動層氣相反應裝置。[Problems to be Solved by the Invention] The stabilization of the fluidized-phase gas-phase reaction device is necessary from the viewpoint of maintaining a high yield of a target product and the viewpoint of safe operation, and a large number of inventions have been made in the industry. However, the invention of a method for operating a fluidized-phase gas phase reaction device that prevents the process value in the fluidized-phase gas phase reaction device from being disturbed due to certain influences is still insufficient, and there is still room for improvement. Patent Document 2 relates to a method for monitoring a partial oxidation reaction process and safely shutting down the reaction process when necessary. In order to implement the method of the invention described above, a list of undesired reaction process conditions requiring the reactor device to be shut down is made, and critical process measurement values indicating each of the list of undesired conditions are specified. It is considered that the type of the critical process measurement value used may include one or more selected from the following list, which includes temperature, pressure, flow direction, supply ratio, calculated flammability, and flow composition (e.g., determined by an online analyzer) And the operating status of the supporting devices in the reactor device (such as the reactor cooling circulation pump, the reaction material feed gasification device) and the separation device and related devices, and the waste reduction device and related devices downstream devices . However, since the types of the above-mentioned critical process measurement values involve many aspects and are not specified, all of them are considered to be excessive, and the emergency stop system has become more complicated. Therefore, it is considered that there is a problem caused by failure of any one of the plurality of measuring devices. There is a risk of an increase in the rate of false detections and a problem with the operation. It is also more difficult economically. In order to avoid the above problems, the selection method is not documented when the effective measurement value is selected, and it is selected based on the implementer's measurement. There is a risk that the selector and the like cannot achieve the purpose of safe shutdown. An object of the present invention is to provide an abnormal detection (referring to detecting abnormality as normal) and erroneous detection of abnormality (referring to detecting normality as abnormality) in a gas phase reaction using a fluidized-phase gas phase reaction device. , A method for producing a reaction gas that accurately detects abnormality and stops operation to ensure sufficient process safety; and a flow-layer gas-phase reaction device that achieves the method. [Technical means to solve the problem] The inventors of the present inventors made efforts to study methods for reliably detecting abnormal reactions and preventing disasters in a gas phase reaction using a fluidized-phase gas phase reaction device, and found that, Comparing and monitoring the process value and gas analysis value of the part with a predetermined reference value can solve this problem and complete the present invention. That is, the present invention is as follows. [1] A method for producing a reaction-generating gas, which is a method for producing a reaction-generating gas by using a fluid-phase gas-phase reaction device and using a raw material gas, and the fluid-phase gas-phase reaction device described above includes a reactor that can house a contact A medium; a first supply pipe that supplies the raw material gas to the reactor; an outflow pipe that discharges the reaction generated gas from the reactor; a redundant plurality of thermometers TI, which are arranged in the reactor; The redundant plurality of pressure gauges PI are located in the thin layer portion of the above-mentioned reactor; and the redundant plurality of reaction-generating gas analyzers DI are located downstream of the above-mentioned outflow pipe; and the manufacturing method includes: In the reaction step in which the above-mentioned raw material gas is supplied to the gas-phase reaction in the presence of the catalyst in the above-mentioned reactor, the actual measured values with respect to each of the first to sixth reference values described below are monitored to produce In the case of at least one of the following six states (a1) to (c3), the operation of the fluidized-phase gas phase reaction device is performed by blocking at least the first supply pipe. Turn to the stop step of emergency stop. (a1) Set the value of 90 ~ 100% of the lower one of the design temperature of the reactor or the highest temperature based on the viewpoint of protecting the catalyst as the first reference value, and display the value greater than the first reference value. The state of the measured value of the above-mentioned thermometer TI exceeds more than half of the total number of thermometers TI (a2) reduces the activity of the catalyst and increases unreacted, the temperature at which an explosive mixture is formed in the reactor or abnormal combustion occurs in downstream equipment A value of 100 to 120% of any higher temperature is set as a second reference value, and a state in which the number of the above-mentioned thermometers TI smaller than the measured value of the second reference value exceeds more than half of the total number of thermometers TI ( b) Set the value of 70 ~ 85% of the design pressure of the reactor as the third reference value, and display the state where the number of the above-mentioned pressure gauge PI exceeds the actual value of the third reference value by more than half of the total number of the pressure gauge PI ( c1) Set the value of 40 to 100% of the explosive limit oxygen concentration as the fourth reference value, and display the measured value of the above-mentioned reaction generated gas analyzer DI exceeding the total measured value of the fourth reference value exceeds the total number of reaction generated gas analyzer DI More than half In the state (c2), the value of 100 to 120% of the oxygen concentration at which the reduction degradation of the catalyst is generated is set to a fifth reference value, and the number of the above-mentioned reaction-produced gas analyzer DI exceeding the measured value showing the measured value less than the fifth reference value exceeds the reaction. The state (c3) of more than half of the total number of generated gas analyzer DI. Set the value of 150 to 300% of the design value of the raw material gas concentration as the sixth reference value, and display the above-mentioned reaction generated gas that is greater than the measured value of the sixth reference value. A state where the number of analyzers DI exceeds more than half of the total number of reaction-produced gas analyzers DI [2] The manufacturing method described in [1], wherein the fluidized-phase gas phase reaction device described above further has a plurality of redundant source gases The flow meters FI are arranged in the first supply pipe; and the manufacturing method includes: in the reaction step of supplying the raw material gas to a gas phase reaction in the presence of the catalyst in the reactor, and When at least one of the following two states (d1) to (d2) occurs when the actual measured values relative to each of the following seventh to eighth reference values are monitored, at least blocking is performed by Above the first supply pipe , And the stopping step of emergency stopping the operation of the above-mentioned fluidized bed gas phase reaction device. (d1) The lowest flow rate of the assumed raw material gas flow value which will be the oxygen concentration of the catalyst deactivation, the assumed raw material gas flow value which will be the design temperature of the reactor, and the assumed raw material gas flow value which will be the temperature at which the catalyst will deteriorate. The value of 85 to 100% of the value is set as the seventh reference value, and the case where the number of the above-mentioned raw material gas flow meter FI which exceeds the actual measured value of the seventh reference value exceeds more than half of the total number of the raw material gas flow meter FI (d2) will be The value of 100 to 120% of the assumed raw material gas flow value at which the oxygen concentration in the outflow pipe becomes the limit oxygen concentration is set to the eighth reference value, and the number of the above-mentioned raw material gas flow meter FI showing the measured value less than the eighth reference value exceeds the raw material. Case of more than half of the total number of gas flow meters FI [3] The manufacturing method described in [1] or [2], wherein the fluidized-phase gas-phase reaction device further includes a second supply pipe to the reactor Supply oxygen-containing gas; and a plurality of redundant oxygen-containing gas flow meters FI, which are provided in the second supply pipe; and the manufacturing method includes: in the reactor, in the presence of the catalyst In the reaction step in which the above-mentioned raw material gas is supplied to a gas-phase reaction, monitoring the actual measured values with respect to each of the following ninth to tenth reference values produces two states (e1) to (e2) below In the case of at least one state, a stopping step is performed to stop the operation of the fluidized-phase gas phase reaction apparatus by stopping at least the first supply pipe, or the first supply pipe and the second supply pipe. . (e1) Set the value of 85 to 100% of the assumed oxygen-containing gas flow value of the oxygen concentration in the outflow pipe to the limit oxygen concentration as the ninth reference value, and display the above-mentioned oxygen-containing gas flow rate that is greater than the ninth reference value of the measured value In the case where the number of FI is calculated to exceed more than half of the total number of oxygen-containing gas flow meters FI2 (e2), the value of 100 to 120% of the assumed oxygen-containing gas flow rate which becomes the oxygen concentration of the catalyst deactivation is set as the tenth reference value. In the case where the number of the above-mentioned oxygen-containing gas flow meter FI showing an actual measured value smaller than the tenth reference value exceeds more than half of the total number of oxygen-containing gas flow meter FI2 [4] As described in any one of [1] to [3] The production method, wherein the raw material gas includes an alkane and / or an olefin. [5] The production method according to [4], wherein the alkane is propane and / or isobutane. [6] The production method according to [4], wherein the olefin is propylene and / or isobutylene. [7] The production method according to any one of [1] to [6], wherein the gas-phase reaction is an ammoxidation reaction. [8] A fluidized-phase gas-phase reaction device comprising: a reactor that can accommodate a catalyst in a flowable manner; a first supply pipe that supplies a raw material gas to the reactor; and an outflow pipe that discharges from the reactor Gas produced by the reaction; redundant thermometers TI, these are installed in the above-mentioned reactor; redundant pressure gauges PI, these are located in the thin layer portion of the above-mentioned reactor; redundant plural reaction-generated gases Analyzers DI, which are located downstream of the above-mentioned outflow pipe; and emergency response stop control section; and monitor the actual measured values with respect to each of the first to sixth reference values below to produce the following (a1) to In the case of at least one of the six states (c3), the emergency response stop control unit is an emergency stop of the operation of the fluidized bed gas phase reaction device by blocking at least the first supply pipe. (a1) Set the value of 90 ~ 100% of the lower one of the design temperature of the reactor or the highest temperature based on the viewpoint of protecting the catalyst as the first reference value, and display the value greater than the first reference value. The state of the measured value of the above-mentioned thermometer TI exceeds more than half of the total number of thermometers TI (a2) reduces the activity of the catalyst and increases unreacted, the temperature at which an explosive mixture is formed in the reactor or abnormal combustion occurs in downstream equipment A value of 100 to 120% of any higher temperature is set as a second reference value, and a state in which the number of the above-mentioned thermometers TI smaller than the measured value of the second reference value exceeds more than half of the total number of thermometers TI ( b) Set the value of 70 ~ 85% of the design pressure of the reactor as the third reference value, and display the state where the number of the above-mentioned pressure gauge PI exceeds the actual value of the third reference value by more than half of the total number of the pressure gauge PI ( c1) Set the value of 40 to 100% of the explosive limit oxygen concentration as the fourth reference value, and display the measured value of the above-mentioned reaction generated gas analyzer DI exceeding the total measured value of the fourth reference value exceeds the total number of reaction generated gas analyzer DI More than half In the state (c2), the value of 100 to 120% of the oxygen concentration at which the reduction degradation of the catalyst is generated is set to a fifth reference value, and the number of the above-mentioned reaction-produced gas analyzer DI exceeding the measured value showing the measured value less than the fifth reference value exceeds the reaction The state (c3) of more than half of the total number of generated gas analyzer DI. Set the value of 150 to 300% of the design value of the raw material gas concentration as the sixth reference value, and display the above-mentioned reaction generated gas that is greater than the measured value of the sixth reference value. A state where the number of analyzers DI exceeds more than half of the total number of reaction-produced gas analyzers DI [9] The fluid layer gas phase reaction device described in [8], wherein the above-mentioned fluid layer gas phase reaction device further has a redundant A plurality of raw material gas flowmeters FI, which are provided in the first supply pipe; and upon monitoring actual measured values with respect to each of the seventh to eighth reference values described below, the following (d1) to (d2) are generated In the case of at least one of the two states, the emergency response stop control unit is an emergency stop of the operation of the fluidized bed gas phase reaction device by blocking at least the first supply pipe. (d1) The lowest flow rate of the assumed raw material gas flow value which will be the oxygen concentration of the catalyst deactivation, the assumed raw material gas flow value which will be the design temperature of the reactor, and the assumed raw material gas flow value which will be the temperature at which the catalyst will deteriorate. The value of 85 to 100% of the value is set as the seventh reference value, and the case where the number of the above-mentioned raw material gas flow meter FI which exceeds the actual measured value of the seventh reference value exceeds more than half of the total number of the raw material gas flow meter FI (d2) will be The value of 100 to 120% of the assumed raw material gas flow value at which the oxygen concentration in the outflow pipe becomes the limit oxygen concentration is set to the eighth reference value, and the number of the above-mentioned raw material gas flow meter FI showing the measured value less than the eighth reference value exceeds the raw material. Case of more than half of the total number of gas flow meters FI [10] The fluidized bed gas phase reaction device described in [8] or [9], wherein the fluidized bed gas phase reaction device further includes a second supply pipe, Supply of oxygen-containing gas to the above-mentioned reactor; and a plurality of redundant oxygen-containing gas flow meters FI, which are provided in the above-mentioned second supply pipe; and monitor each of the following ninth to tenth reference values Of the When at least one of the following two states (e1) to (e2) occurs under the actual measured value, the emergency response stop control unit is to block at least the first supply pipe or the first The supply pipe and the second supply pipe, and the emergency stop of the operation of the fluidized bed gas phase reaction device. (e1) Set the value of 85 to 100% of the assumed oxygen-containing gas flow value of the oxygen concentration in the outflow pipe to the limit oxygen concentration as the ninth reference value, and display the above-mentioned oxygen-containing gas flow rate that is greater than the ninth reference value of the measured value In the case where the number of FI is calculated to exceed more than half of the total number of oxygen-containing gas flow meters FI2 (e2), the value of 100 to 120% of the assumed oxygen-containing gas flow rate which becomes the oxygen concentration of the catalyst deactivation is set as the tenth reference value. A case where the number of the above-mentioned oxygen-containing gas flow meter FI, which shows an actual measured value smaller than the tenth reference value, exceeds more than half of the total number of oxygen-containing gas flow meter FI2 [Effect of the invention] According to the present invention, it is possible to provide In the gas phase reaction of the reaction device, a manufacturing method of a reaction gas capable of correctly detecting abnormality and stopping the operation to ensure sufficient process safety; and a flow-layer gas phase reaction device that achieves the method.

以下，視需要一面參照圖式，一面對本發明之實施形態(以下，稱為「本實施形態」)詳細地進行說明，但本發明並不限定於此，可於不脫離其主旨之範圍內進行各種變化。再者，圖式中，對相同要素標註相同符號，且省略重複之說明。又，上下左右等位置關係只要未特別說明，則設為基於圖式所示之位置關係者。進而，裝置或構件之尺寸比率並不限定於圖示之比率。 再者，於本說明書中，存在將正常運轉與人該應對之異常運轉之邊界稱為「閾值1」，將人該應對之異常運轉與應自動進行緊急停止之異常運轉之邊界稱為「閾值2」之情形。又，存在將閾值2更具體而言，藉由壓力或氧濃度等進行數值化而加以表述者稱為「基準值」之情形。 [具有緊急反應停止控制部之流動層氣相反應裝置及使用該裝置之反應生成氣體之製造方法] 本實施形態之流動層氣相反應裝置具有：反應器，其可流動地收納觸媒；第一供給管，其向反應器中供給原料氣體；流出管，其自反應器中排出反應生成氣體；冗餘之複數個溫度計TI，該等係設置於反應器；冗餘之複數個壓力計PI，該等係位於反應器之稀薄層部；冗餘之複數個反應生成氣體分析器DI，該等係位於流出管之下游；及緊急反應停止控制部。 首先，於異常狀態下作動之緊急反應停止控制部與於正常狀態下進行反應控制之系統(例如分散控制系統(DCS))於概念上不同。反應控制係根據運轉狀態而進行。所謂此處所指之運轉狀態，可列舉：監視對象之測定值(實測值)在正常運轉之範圍(為方便起見而稱為「藍色區域」)、危險運轉之範圍(為方便起見而稱為「紅色區域」)、於正常運轉之範圍外且亦於危險運轉之範圍外之具有冗餘性之範圍(為方便起見而稱為「黃色區域」)。以下亦將成為藍色區域與黃色區域之邊界之監視對象的測定值稱為閾值1，將成為黃色區域與紅色區域之邊界之監視對象的測定值稱為閾值2。 作為監視對象，若以溫度為例，則分散控制系統係監視特定之部位之溫度是否處於藍色區域內，於可見溫度即將偏離藍色區域之傾向時，藉由反饋及/或前饋控制而控制使溫度上升或下降之因素，藉此以溫度不偏離藍色區域之方式進行控制者。又，於溫度超過閾值1而自藍色區域進入至黃色區域時，分散控制系統亦以溫度再次返回至藍色區域之方式加以控制。又，於溫度進入至黃色區域時，亦存在反應裝置之監視者人為地進行反應控制，以溫度再次返回至藍色區域之方式加以控制之情形。 另一方面，於異常狀態下作動之緊急反應停止控制部係監視溫度是否超過閾值2而自黃色區域進入至紅色區域，於溫度超出黃色區域而進入至紅色區域時，強制地使反應裝置緊急停止者。 上述中係以溫度為例，但由於緊急反應停止控制部係為了防止流動層氣相反應裝置之事故於未然而構築者，故而必須應對流動層氣相反應裝置之所有事故。若基於此種觀點而進行研究，則可知流動層氣相反應裝置之事故可大致區分成火災、爆炸及破壞。首先，根據潛在危險及風險分析中所使用之方法例如FTA(Fault Tree Analysis，故障樹分析)或HAZOP(Hazard And Operability，危險與可操作性)等抽選異常檢測中所使用之儀器等。結果可知，反應器溫度、反應器壓力、原料氣體流量、含氧氣體流量、氣體流量/含氧氣體流量、反應生成氣體組成、冷卻盤管冷媒流量、流動層觸媒量、反應生成氣體配管之閥、原料氣體蒸發器之運轉條件、空氣壓縮機之運轉條件係產生流動層氣相反應裝置之異常之儀器或運轉條件。 如此，緊急反應停止控制部所檢測之對象除溫度以外，有壓力、各種氣體流量、氣體組成等，又，所檢測之場所有反應器、向反應器中供給原料之各種供給管、流出管等。於檢測流動層氣相反應裝置之運轉中之異常時，自設置於此種流動層氣相反應裝置之所有儀器及與流動層氣相反應裝置連接之所有設備之異常中檢測出1種以上為一種理想形態。然而，於在高溫高壓下運行之流動層氣相反應裝置中，無法排除產生儀器之故障及誤動作、不動作之可能性，若不擔保該方面而始終監視設置於流動層氣相反應裝置之所有儀器及與流動層氣相反應裝置連接之所有設備，即便為1種亦欲於進入至紅色區域之時刻進行緊急停止，則實際上亦容易弄錯正常地運轉者而進行緊急停止。又，即便自流動層氣相反應裝置之費用方面考慮，將所有儀器設置於流動層氣相反應裝置之各處亦缺乏現實性。又，進行假想實驗，單獨地對設置於流動層氣相反應裝置之各處之各儀器獨立設定自藍色區域至紅色區域之規定值亦不容易。 因此，就使緊急反應停止控制部正常地運行之觀點而言，必須不多不少地選擇必要之檢測機構。又，就排除產生儀器之故障及誤動作、不動作之可能性之觀點而言，關於異常檢測中所使用之儀器，必須以可確保相應之可靠性之方式構成。基於此種前提，本發明者等人對儀器之可靠性之擔保及必要之檢測機構之選擇進行研究，從而構成具有緊急反應停止控制部之流動層氣相反應裝置。以下，首先對儀器之可靠性之擔保進行說明，其後對檢測機構之選擇進行說明。 本實施形態之流動層氣相反應裝置中，作為異常檢測用之儀器，具有：冗餘之複數個溫度計TI，該等係設置於反應器；冗餘之複數個壓力計PI，該等係位於反應器之稀薄層部；及冗餘之複數個反應生成氣體分析器DI，該等係位於流出管之下游；於在各場所中顯示異常值(紅色區域之範圍)之儀器超過所設置之儀器總數的過半數之情形，信任該儀器之值，使流動層氣相反應裝置緊急停止。其原因在於，於如圖1所示般各場所之儀器數為1個之情形時，防止因該唯一之儀器產生故障及誤動作、不動作而弄錯實際上正常地運轉者而進行緊急停止之情形、或將實際上異常地運轉者誤認為正常運轉並使之持續運行。此處，所謂「冗餘之複數個」係指利用複數個測定器對相同之對象進行測定。於該含義之範圍內，除將相同之種類之測定器設置於相同之位置而進行測定以外，且可使用測定方式不同之複數種測定器對相同對象(例如溫度)進行測定，可於即便測定位置完全不同亦將所測定之值視為計算上相同之位置範圍內設置複數個測定器，亦可將該等予以組合。例如，於圖5中，係利用TI1、TI2、TI3之3個溫度計對濃厚層9a之溫度進行測定，但若為將該等之溫度視為相同之範圍，則可相當於「冗餘之複數個」。又，關於測定稀薄層9b之溫度之溫度計TI4、TI5、或測定稀薄層9b之壓力之壓力計PI1、PI2亦同樣。 緊急反應停止控制部係自流動層氣相反應裝置之溫度計、壓力計、及反應生成氣體分析器之各者接收測量值，於該等測量值根據多數決選定方式判斷為異常之情形時，藉由至少阻斷第一供給管，而使流動層氣相反應裝置之運轉緊急停止者。 就使用三取二(2 out of 3)之多數決選定方式之觀點而言，異常檢測用之儀器數較佳為3個。於將儀器三重化，即便3個輸出中之任一個發出錯誤之信號，剩餘之2個信號亦相同之情形時，藉由採用此，可提高可靠性。 再者，關於流量異常，亦可藉由反應器溫度及反應生成氣體分析代替地進行異常檢測，但為了判斷緊急停止，可進行流量計之監視。由於藉由直接監視流量，可發現更早期之異常，故而較佳為進行流量計之監視。流量計由於多數情況下於技術上或經濟上難以獨立設置多個，故而可為進行二重化者。於將儀器二重化之情形時，就防止誤動作之觀點而言，較佳為採用二取二(2 out of 2)之多數決選定方式。 圖2及圖3表示溫度計、壓力計及流量計進行二重化之態樣，圖4表示流量計進行二重化，溫度計與壓力計進行三重化之態樣。再者，於圖中，TI表示溫度計，PI表示壓力計，FI表示流量計。溫度計TI係分別設置於反應器1之觸媒以高濃度存在之濃厚層9a、及觸媒以相對低濃度存在之稀薄層9b。又，溫度計就監視反應溫度之觀點而言必須設置於濃厚層9a，進而亦可設置於稀薄層9b。又，壓力計PI係設置於較旋風分離器之入口更靠上之反應器上部。進而，流量計FI係分別設置於供給原料之供給管，於具有2根以上之供給管於進入至反應器中之前於中途合流之構造之情形時，係設置於各供給管。 該等溫度計與壓力計係與複數個反應生成氣體分析器組合而使用。圖7表示於較流動層氣相反應裝置之流出管更靠下游處，反應生成氣體分析器於不同之部位進行二重化之態樣。再者，於圖中，DI表示反應生成氣體分析器。 其次，於對異常檢測中所使用之儀器等進行說明前，對本實施形態之流動層氣相反應裝置之整體之構成態樣進行說明。 圖2係表示表示本實施形態之流動層氣相反應裝置之第1態樣之模式圖。於反應器1中，除具有可流動地收納觸媒，且自反應生成氣體中分離回收觸媒之旋風分離器7以外，視需要具有冷卻盤管6，其係主要用以去除反應器1之濃厚層9a之反應熱，控制反應溫度。 又，於反應器1上連接有供給原料氣體B之第一供給管4。原料氣體B係自與反應器1之下方連接之第一供給管4經由分散管5而向反應器1內供給。第一供給管4之上游可具有另一原料氣體D等各氣體種類之供給管進行合流之構造，於該情形時，較佳為於各氣體種類之供給管上分別設置冗餘之複數個流量計。 觸媒係於觸媒本身之自重及體積、以及原料氣體B及下述含氧氣體A之供給量等之平衡之中，於反應器1內流動。觸媒之每一單元空間之存在量(分佈)於較分散管5更靠上之空間中，隨著自反應器1之下向上而減少。 設置於反應器1之冷卻盤管6係以控制反應器1之反應熱之方式發揮作用，故而主要設置於觸媒濃度較高之反應器1之濃厚層9a。氣相反應中所產生之熱係利用流通於作為除熱管之冷卻盤管6內之冷媒而進行除熱，從而控制反應溫度。 反應器1具有：旋風分離器7，其於反應器1內自反應生成氣體C中分離回收觸媒；及流出管8，其自反應器1中排出利用旋風分離器7分離之反應生成氣體C。於旋風分離器7中，伴有觸媒之反應生成氣體C自其入口進入。進入至旋風分離器7中之觸媒於旋風分離器7之圓錐部分以描繪螺旋之方式向下方掉落，反應生成氣體C係自從旋風分離器7之上部向上方延伸之管被引導至流出管8。於旋風分離器7之圓錐部分之下方，管進而朝向反應器3之下方延伸，觸媒通過該管中而被引導至反應器1之下方。另一方面，被引導至設置於反應器1之下游之流出管8之反應生成氣體C係由流出管8輸送至下游步驟。 自流出管8流出之反應生成氣體C係視需要於位於下游之反應器出口熱交換器(未圖示)中經空氣及/或鍋爐水冷卻。其後，於急冷塔(參照圖7)中，利用硫酸中和反應生成氣體中之氨，去除高沸點物質等及觸媒，進而進行冷卻。自急冷塔流出之反應生成氣體被供於吸收塔(參照圖7)。於吸收塔中，使產物吸收至水等溶劑中，並向回收步驟輸送。自吸收塔頂流出之未反應氣體、包含未回收有機物等之未冷凝氣體係利用廢氣焚燒設備(參照圖7)進行焚燒處理。 圖3係表示表示本實施形態之流動層氣相反應裝置之第2態樣之模式圖。第2態樣之流動層氣相反應裝置係除於反應器1上連接有供給包含氧之含氧氣體A之第二供給管2以外，與第1態樣同樣地構成者。含氧氣體A係自與反應器1之下方連接之第二供給管2經由分散板3而向反應器1內供給。自複數個供給口4供給之原料氣體B與經分散板5分散而供給之含氧氣體A係以相互對向之方式供給，並一面交絡一面混合。 圖4係表示表示本實施形態之流動層氣相反應裝置之第3態樣之模式圖。第3態樣之流動層氣相反應裝置係除將溫度計與壓力計之各儀器三重化以外，與第2態樣同樣地構成者。於第3態樣中，可使用三取二之多數決選定方式。 圖5係表示表示本實施形態之流動層氣相反應裝置之第4態樣之模式圖。第4態樣之流動層氣相反應裝置係除將濃厚層之溫度計三重化以外，與第2態樣同樣地構成者。於第4態樣中，可使用三取二之多數決選定方式。於第4態樣中，變更水平方向及高度方向之位置，並且於溫度視為相同之範圍內利用TI1、TI2、TI3之3個溫度計對濃厚層9a之溫度進行測定，變更水平方向及高度方向之位置，並且於溫度視為相同之範圍內利用TI4、TI5之2個溫度計對稀薄層9b之溫度進行測定，變更水平方向之位置，並且於壓力視為相同之範圍內利用PI1、PI2之2個壓力計對稀薄層9b之壓力進行測定。如此，藉由在測定值視為實質上相同之範圍內設置冗餘之複數個測定器，可監視由測定器所圍成之一定之空間範圍之流動層氣相反應裝置之運轉狀態。又，於圖5中，雖未圖示，但可設為溫度計TI1等分別進行冗餘化之構成。 (異常檢測中所使用之儀器等) 其次，就降低誤動作及不動作之風險等級之觀點而言，對上述異常檢測中所使用之儀器、運轉條件等之層級劃分進行說明。如以下之記載及圖6所示，檢測直接導致火災、爆炸、破壞或對設備造成致命之損害(例如觸媒之失活等)之事故之異常現象的儀器、及就運轉管理之觀點而言較重要之儀器均可設為異常檢測用之儀器。 反應器內之溫度計： 若反應器內之溫度超過反應器之設計溫度，且仍上升，則會導致反應器之熔損(破壞)事故。另一方面，於反應器內之溫度降低之情形時，有向反應器1供給之原料氣體或含氧氣體中之未反應物增加，自排出口流出之反應生成氣體C、或反應器1內部之氣體容易形成爆炸混合氣之傾向。由於爆炸混合氣有導致爆炸事故之虞，故而反應器內之溫度為重要之運轉管理值。又，根據溫度高低，亦存在規定流動層觸媒進行過度氧化或過度還原等對觸媒造成不良影響之溫度之情形。因此，關於反應器內之溫度，特定之上限值及下限值被作為用以判斷緊急停止之值而進行選擇設定。於圖6中，係以粗線表示。 反應器內之溫度計係設置於濃厚層9a、或濃厚層9a與稀薄層9b之兩者。具體而言，可設置於低於冷卻盤管6之上端之位置及/或高於冷卻盤管6之上端之位置。溫度計係測定反應器1內部之溫度者，較佳為具備信號傳輸功能者。作為溫度計之種類，並無特別限制，只要為可於石油化學設備中測定溫度者即可，較佳為熱電偶、電阻溫度計。 流動層反應之溫度之特徵為相對較均一，但根據觸媒存在之有無、反應率、冷卻盤管之使用等有可能產生溫度分佈。因此，較佳為利用位於低於冷卻盤管之上端之位置之冗餘的複數個溫度計TI，監視主要活躍地產生氣相反應之觸媒濃度較高之反應器1之下部(濃厚層9a)的溫度，且利用高於冷卻盤管之上端之位置之冗餘的複數個溫度計TI，監視反應器1之上部(稀薄層9b)之溫度。於圖2及圖3之例中，利用2個溫度計TI3及TI4對濃厚層9a內之1個部位進行測定，且利用2個溫度計TI1及TI2對稀薄層9b之1個部位進行測定。於圖4之例中，利用3個溫度計TI4、TI5及TI6對濃厚層9a內之1個部位進行測定，且利用3個溫度計TI1、TI2及TI3對稀薄層9b之1個部位進行測定。假定發生由溫度計之斷線或接線不良等所引起之故障，較佳為進行如成為故障無礙(fail safe)側之故障之考慮。即，分別設置檢測溫度高及溫度低之溫度計。由此，於溫度高檢測用之溫度計發生故障之情形時，指示溫度高，於溫度低檢測用之溫度計發生故障之情形時，指示溫度低。例如，較佳為於將圖2之TI3及TI4設為檢測溫度高之溫度計之情形時，檢測溫度低之其他溫度計TI3'及TI4'係設置於濃厚層9a內之1個部位。 反應器內之壓力計： 若反應器內之壓力超過反應器之設計壓力，且仍上升，則會導致反應器之破壞。另一方面，反應器內之壓力之降低或許會對反應造成某些影響，但較少情況下會直接與事故相關聯。因此，關於反應器內之壓力，特定之上限值被作為用以判斷緊急停止之值而進行選擇設定。 反應器內之壓力計可設置於反應器1之稀薄層9b尤其是塔頂部。壓力計係測定反應器1內部之壓力者，較佳為顯示表壓力，且具備信號傳輸功能者。作為壓力計之種類，並無特別限制，只要為可用於石油化學設備者即可，較佳為布爾登管、波紋管式、膜片式等。壓力計只要設置於可測定反應器之內部壓力之位置即可，並無特別限定，但由於流動層觸媒內之壓力會受到觸媒量或觸媒流動之影響，故而較佳為設置於稀薄層9b。 又，由於噴嘴阻塞等噴嘴之不良情況會對複數個壓力計造成影響，故而就儀器可靠性之觀點而言，與自1個取出噴嘴進行分支而與2個以上之壓力計連接之態樣相比，較佳為壓力計與反應器1通過噴嘴而以1對1連接。 原料氣體流量計： 原料氣體流量計可設置於第1供給管。若原料氣體流量增加，則下述原料氣體流量/含氧氣體流量亦發生變化。若原料氣體流量增加，則反應量增多，故而反應發熱熱增加，反應器溫度上升。若能夠以冷卻裝置應對，則可控制反應器溫度，但於因急劇之增加等而應對不充分之情形時，反應器溫度仍上升，而導致反應器之熔損(破壞)事故。作為因原料氣體流量之增加而未反應原料氣體異常增加之情形，例如可考慮無因原料氣體之急劇之增加、原料之不平衡而反應之對象之情形、流動層觸媒相對於增加氣體量不足之情形、因氣體之單向流動等而未反應原料氣體增加之情形等。於該等情形時，產生反應器下游機器尤其是廢氣焚燒設備中之異常燃燒或爆炸之危險性。又，未反應原料氣體之變化亦可藉由下述反應生成氣體組成分析而加以檢測。 另一方面，若原料氣體流量減少，則反應熱減少，反應器溫度降低。若反應器溫度降低，則原料氣體或含氧氣體之未反應物增加，形成爆炸混合氣而導致爆炸。於原料氣體流量減少之情形時，原料氣體流量/含氧氣體流量、及反應生成氣體組成分析值亦發生變化。 根據以上，原料氣體流量之增減就時間序列而言，經過原料氣體流量/含氧氣體流量之增減、反應器溫度之增減及反應生成氣體組成分析值之變化而與事故相關聯。此處，原料氣體流量為流動層氣相反應裝置之重要之運轉條件之一，考慮進行頻繁之運轉操作、原料氣體流量變化為引起異常現象之開端、流量計之測定值之可靠性相對較高。因此，雖然有可能不直接與事故相關聯，但關於原料氣體流量，特定之上限值及下限值可作為用以判斷緊急停止之值而進行選擇設定。 再者，流量計係測定向反應器1供給之氣體之流量者，較佳為設置於各種流體，且具備信號傳輸功能者。流量計之種類只要為可測定石油化學設備中之氣體流體者，則並無特別限制，較佳為差壓式流量計、面積式李流量計、渦式流量計、渦輪式流量計、容積式流量計、科利奧利式流量計、超音波流量計。以下，於含氧氣體流量計方面亦同樣。 含氧氣體流量計： 若含氧氣體流量增加，則由作為可燃性氣體之原料氣體及生成氣體與氧形成爆炸混合氣，而導致爆炸。另一方面，若含氧氣體流量減少，則原料氣體無法充分地反應，未反應之原料氣體增加。該等現象有於廢氣焚燒裝置等反應器下游機器中導致異常燃燒、爆炸之虞。含氧氣體流量之變化亦會使原料氣體流量/含氧氣體流量及反應生成氣體組成分析值產生變化。含氧氣體流量之異常雖然不直接與事故相關聯，但與原料氣體之情形同樣地，較妥當的是作為必須選擇之測定值而進行處理。因此，關於含氧氣體流量，特定之上限值及下限值可作為用以判斷緊急停止之值而進行選擇設定。 含氧氣體流量/原料氣體流量計： 雖然能夠以含氧氣體流量及原料氣體流量進行代替，但亦可進而進行含氧氣體流量/原料氣體之監視。由於含氧氣體流量/原料氣體係來自2個儀器之運算值，故而於不使用分散控制系統(DCS)之情形時，另外需要進行運算之系統例如安全儀器等。於圖6中，係以細線表示。 反應生成氣體分析器： 反應生成氣體包含生成氣體、未反應原料氣體，若為氧化反應，則進而添加氧、或視情形之氮等。於通常運轉中，反應生成氣體中之氧濃度就防止爆炸之觀點而言，係管理為未達極限氧濃度。進而，於如觸媒於還原氣氛下劣化之情形時，係以觸媒不進行還原劣化之氧濃度以上進行管理。然而，於在反應場中產生某些異常之情形時，反應生成氣體組成發生變化。關於此種情形，即便尚不明確反應場中之異常之詳情，只要可監視反應生成氣體之組成是否產生異常，則亦可獲知異常之產生。例如，若氣層接觸反應為氧化反應，則將反應生成氣體中所含之氧濃度設為必需之測定對象。其原因在於，即便為可燃物，只要不存在氧則亦不會產生爆炸，故而就防止爆炸之觀點而言，較重要的是將氧濃度設為必需之測定對象。又，若為氧化反應以外，則測定原料氣體濃度及/或生成氣體濃度。因此，關於反應生成氣體分析，特定之上限值係作為用以判斷緊急停止之值而進行選擇設定。 利用反應生成氣體分析器DI進行之反應生成氣體之分析可連續對自反應器1中流出之反應生成氣體取樣而進行。反應生成氣體之取樣部位(反應生成氣體分析器之設置部位)如圖7中所記載般，較佳為反應器(出口熱交換器)〜急冷塔間或急冷塔〜吸收塔間。作為於進行氧分析之情形時之分析器，並無特別限制，例如可列舉：氧化鋯式、磁式、雷射分光式、電極式之分析器。又，反應產物及/或反應未反應物之分析較佳為使用氣相層析法。為了可減少分析器之污垢，更佳為於急冷塔〜吸收塔間進行反應生成氣體之分析。 冷卻盤管冷媒流量計： 就提高正確性之方面而言，可進而進行冷卻盤管之冷媒流量之監視。若冷卻盤管冷媒流量發生變動，則對反應溫度造成影響。作為與冷卻盤管相連通之冷媒，多數可使用飽和溫度之水及/或蒸氣。與冷卻盤管相連通之飽和溫度之水吸收於反應中所產生之熱，且其一部分(蒸發率5〜30%)蒸發。於飽和溫度之水之流量增加之情形時，該類型之冷卻盤管之除熱量亦幾乎無變化。於冷媒為蒸氣之情形時，若蒸氣流量增加，則成為除熱量增加之傾向，但由於可使用之蒸氣流量之上限存在限制及/或使用蒸氣之冷卻盤管數相對較少，故而對反應溫度造成之影響較少。另一方面，於冷媒流量減少之情形時，無法去除反應熱，而反應溫度上升。即，考慮冷卻盤管冷媒流量之減少之結果帶來反應器溫度高，通常不進行冷卻盤管流量之變更。因此，關於冷卻盤管冷媒流量，特定之上限值及下限值可作為用以判斷緊急停止之值而進行選擇設定。 流動層觸媒量之測定： 可進而進行流動層觸媒量之監視。未假定於正常運轉中流動層觸媒增加。然而，因某些原因例如旋風分離器之不正常而無法捕捉流動層觸媒，於流動層觸媒量減少之情形時，有可能不進行反應而使未反應物增加。於此種情形時，反應生成氣體中之原料氣體濃度上升，或於氧化反應之情形時，氧濃度上升。因此，於觸媒量減少之情形時，可藉由上述反應生成氣體組成之分析而代替地進行檢測。又，關於觸媒量之減少，即便反應器內之溫度降低，亦可代替地進行檢測。進而，流動層觸媒量亦可利用複數個壓力計等儀器而間接地算出。如此，關於流動層觸媒量，可利用已說明之其他儀器進行代替之檢測。因此，如上所述，就費用方面或實現性、或預先防止錯誤之緊急停止之觀點而言，可不作為用以判斷緊急停止之值而進行選擇設定，只要擔保該等，則亦可作為用以判斷緊急停止之值而進行選擇設定。 反應生成氣體配管之閥： 可進而進行反應生成氣體配管之閥關閉之觀測。於安裝於用以移送自反應器中流出之反應生成氣體之配管之閥因某些原因而向關閉方向作動之情形時，反應器之壓力上升，有可能會導致反應器之破壞。因此，閥之關閉由於反應器壓力較高等，故而可利用壓力計代替地進行檢測。如此，關於反應生成氣體配管之閥關閉，可利用已說明之其他儀器進行代替之檢測。因此，如上所述，就費用方面或實現性、或預先防止錯誤之緊急停止之觀點而言，可不作為用以判斷緊急停止之值而進行選擇設定，只要擔保該等，則亦可作為用以判斷緊急停止之值而進行選擇設定。 原料氣體蒸發器之運轉條件、狀態： 可進而進行原料氣體蒸發器之運轉異常之觀測。原料氣體蒸發器之運轉受到熱媒之流量及溫度、原料氣體蒸發器內之原料液位、原料氣體蒸發器內之壓力等之影響，且影響波及原料氣體流量。因此，原料氣體蒸發器之運轉異常可利用原料氣體流量代替地進行檢測。又，對原料氣體蒸發器之運轉造成影響之各條件有不易直接對反應器運轉造成影響之傾向。如此，與原料氣體蒸發器之運轉條件、狀態相關之檢測異常可利用已說明之其他儀器進行代替之檢測。因此，如上所述，就費用方面或實現性、或預先防止錯誤之緊急停止之觀點而言，可不作為用以判斷緊急停止之值而進行選擇設定，只要擔保該等，則亦可作為用以判斷緊急停止之值而進行選擇設定。 空氣壓縮機之運轉條件、狀態： 可進而進行空氣壓縮機之運轉異常之觀測。空氣壓縮機之運轉受到作為壓縮機之驅動源之蒸氣或電之供給狀況、作為空氣供給對象之反應器之壓力之影響，且影響波及含氧氣體流量。因此，空氣壓縮機之運轉異常可利用含氧氣體流量代替地進行檢測。如此，與空氣壓縮機之運轉條件、狀態相關之檢測異常可利用已說明之其他儀器進行代替之檢測。因此，如上所述，就費用方面或實現性、或預先防止錯誤之緊急停止之觀點而言，可不作為用以判斷緊急停止之值而進行選擇設定，只要擔保該等，則亦可作為用以判斷緊急停止之值而進行選擇設定。 (閾值) 於本實施形態中，於對複數個溫度計TI、壓力計PI、及反應生成氣體分析器DI應用多數決選定方式而獲得之值超過特定之閾值之情形，緊急反應停止控制部係藉由至少阻斷第一供給管，而使流動層氣相反應裝置之運轉緊急停止。具體而言，於在觸媒之存在下將原料氣體供於氣相反應之反應步驟中，於監視相對於下述第一至第六基準值之各者之實測值下，產生下述(a1)至(c3)之6種狀態中之至少1種狀態之情形時，使流動層氣相反應裝置之運轉緊急停止。 (a1)將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值，顯示大於第一基準值之實測值之溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (a2)將觸媒之活性降低而未反應增加，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值，顯示小於第二基準值之實測值之溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (b)將反應器之設計壓力之70〜85%之值設為第三基準值，顯示大於第三基準值之實測值之壓力計PI之數量超過壓力計PI之總數的過半數之狀態 (c1)將爆炸極限氧濃度之40〜100%之值設為第四基準值，顯示大於第四基準值之實測值之反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c2)將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值，顯示小於第五基準值之實測值之反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c3)將原料氣體濃度之設計值之150〜300%之值設為第六基準值，顯示大於第六基準值之實測值之反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 又，本實施形態之流動層氣相反應裝置進而具有設置於第一供給管之冗餘之複數個原料氣體流量計FI，且於監視相對於下述第七至第八基準值之各者之實測值下，產生下述(d1)至(d2)之2種狀態中之至少1種狀態之情形時，緊急反應停止控制部可藉由至少阻斷第一供給管，而使流動層氣相反應裝置之運轉緊急停止。 (d1)將成為觸媒失活之氧濃度之假定原料氣體流量值、成為反應器之設計溫度之假定原料氣體流量值、及成為觸媒劣化之溫度之假定原料氣體流量值中之最低之流量值的85〜100%之值設為第七基準值，顯示大於第七基準值之實測值之原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 (d2)將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值，顯示小於第八基準值之實測值之原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 進而，流動層氣相反應裝置進而具有：第二供給管，其向反應器中供給含氧氣體；及設置於第二供給管之冗餘之複數個含氧氣體流量計FI，且於監視相對於下述第九至第十基準值之各者之實測值下，產生下述(e1)至(e2)之2種狀態中之至少1種狀態之情形時，緊急反應停止控制部可藉由至少阻斷第一供給管，而使流動層氣相反應裝置之運轉緊急停止。 (e1)將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值，顯示大於第九基準值之實測值之含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 (e2)將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值，顯示小於第十基準值之實測值之含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 反應器溫度之上限及下限之閾值： 狀態(a1)係決定反應器溫度之上限之閾值之條件，將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值。又，狀態(a2)係決定反應器溫度之下限之閾值之條件，將藉由反應溫度降低，觸媒之活性降低而未反應增加，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值。 關於狀態(a1)，本發明者等人藉由模擬對反應溫度之動態特性進行研究。據此得知，反應溫度自穩態值達到上限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則反應溫度即時降低。基於該等見解，第一基準值之上限可設為使用最高溫度(反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低者)之100%。又，關於第一基準值之下限，就早期檢測之觀點而言，較佳為較低，但考慮到由條件變動時等之溫度變動所引起之誤動作而採用90%。 關於狀態(a2)，與狀態(a1)同樣地進行模擬，並對反應溫度之動態特性進行研究。據此得知，反應溫度自穩態值達到下限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則爆炸混合氣之形成立即消除。基於該等見解，第二基準值之下限可設為使用最低溫度(於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高者)之100%。又，關於第二基準值之上限，就早期檢測之觀點而言，較佳為較高，但考慮到由條件變動時等之溫度變動所引起之誤動作而採用120%。 圖8中表示狀態(a1)及狀態(a2)中之緊急停止流程圖。如圖8所示，冗餘之複數個溫度計TI持續監視設置場所中之溫度直至反應結束。於圖8中，判斷根據多數決決定方式而被認為具有可靠性之溫度是否超過溫度之上限閾值1而進入至黃色區域，於進入至黃色區域之情形時，向降低溫度之方向施加反饋及/或前饋控制。即便藉由該控制而溫度仍繼續上升，於根據多數決決定方式而被認為具有可靠性之溫度超過溫度之上限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。再者，此處，上限閾值2係於狀態(a1)中被決定為第一基準值者。 另一方面，冗餘之複數個溫度計TI亦對根據多數決決定方式而被認為具有可靠性之溫度是否超過溫度之下限閾值1而進入至黃色區域進行判斷，於進入至黃色區域之情形時，對使溫度上升之方向施加反饋及/或前饋控制。即便藉由該控制而溫度仍繼續下降，於根據多數決決定方式而被認為具有可靠性之溫度超過溫度之下限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。此處，下限閾值2係於狀態(a2)中被決定為第二基準值者。於圖8中，成為於進行重大性相對較高之狀態(a1)之判斷後判斷狀態(a2)之流程，但對此並無特別限制。 反應器壓力之上限之閾值： 狀態(b)係決定反應器壓力之上限之閾值之條件，將反應器之設計壓力之70〜85%之值設為第三基準值。又，如上所述，對於反應器壓力之下限之閾值，並無特別限制。 關於狀態(b)，本發明者等人藉由模擬而對反應器壓力之動態特性進行研究。據此得知，反應器壓力自穩態值達到上限之閾值之時間為幾十秒之等級，相對較快。根據實際機器裝置之運轉實績等發現，氣相反應若藉由緊急停止而停止氣體供給，則反應器壓力即時降低。考慮壓力上升相對較快地產生之模擬結果，第三基準值之上限係設為設計壓力之85%，具有相對於啟動緊急停止後之動作例如控制閥之關閉動作時間等之裕度。又，關於第三基準值之下限，就早期檢測之觀點而言，較佳為較低，但考慮由條件調整時之壓力增高所引起之誤動作而採用70%。 圖9中表示狀態(b)中之緊急停止流程圖。如圖9所示，冗餘之複數個壓力計PI持續監視設置場所中之溫度直至反應結束。於圖9中，判斷根據多數決決定方式而被認為具有可靠性之壓力是否超過壓力之上限閾值1而進入至黃色區域，於進入至黃色區域之情形時，向降低壓力之方向施加反饋及/或前饋控制。即便藉由該控制而壓力仍繼續上升，於根據多數決決定方式而被認為具有可靠性之壓力超過壓力之上限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。再者，此處，上限閾值2係於狀態(b)中被決定為第三基準值者。 反應生成氣體組成之上限之閾值： 狀態(c1)就防止爆炸之觀點而言，係決定反應生成氣體之氧濃度之上限之閾值之條件，將爆炸極限氧濃度之40〜100%之值設為第四基準值。又，狀態(c2)就防止觸媒劣化之觀點而言，係決定反應生成氣體之氧濃度之下限之閾值之條件，將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值。進而，狀態(c3)就廢氣焚燒裝置中之處理能力之觀點而言，係決定反應生成氣體中之原料氣體濃度之上限之閾值之條件，將原料氣體濃度之設計值之150〜300%之值設為第六基準值。再者，此處，所謂「原料氣體濃度之設計值」係指向反應器供給之原料氣體之0.5〜10%之值。通常，於反應器中，原料氣體之轉化率並非100%，相當於上述原料氣體濃度之設計值之原料氣體於未反應之狀態下殘留。於反應器中，於因某些原因而原料氣體之轉化率降低之情形時，向對原料氣體進行焚燒處理之廢氣焚燒裝置中供給過量之原料氣體。如此，成為原料氣體處理過多，而有廢氣焚燒裝置失控之虞。 關於狀態(c1)，本發明者等人藉由模擬而對反應生成氣體之氧濃度之動態特性進行研究。據此得知，氧濃度自穩態值達到上限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則氧濃度即時降低。基於該等見解，第四基準值之上限可設為爆炸極限氧濃度之100%。又，關於第四基準值之下限，就早期檢測之觀點而言，較佳為較低，但考慮到條件變動時之誤動作而採用40%。 關於狀態(c2)，與狀態(c1)同樣地進行模擬，並對反應生成氣體之氧濃度之動態特性進行研究。據此得知，氧濃度自穩態值達到下限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則藉由溫度降低立即抑制觸媒之劣化。基於該等見解，第五基準值之下限可設為使用最低氧濃度之100%。又，關於第五基準值之上限，就早期檢測之觀點而言，較佳為較高，但考慮到條件變動時之誤動作而採用120%。 關於狀態(c3)，與狀態(c1)同樣地進行模擬，並對反應生成氣體之原料氣體濃度之動態特性進行研究。據此得知，反應生成氣體中之原料氣體濃度自穩態值達到上限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則反應生成氣體中之原料氣體流量立即降低。基於該等見解，第六基準值之下限設定就防止誤動作及早期檢測之觀點而言，可設為原料氣體濃度之設計值之150%。又，第六基準值之上限取決於廢氣焚燒裝置之設備能力而採用300%。 圖10中表示於狀態(c1)〜狀態(c3)下監視氧濃度及原料氣體濃度之情形時之緊急停止流程圖。如圖10所示，冗餘之複數個反應生成氣體分析器DI持續監視設置場所中之反應生成氣體組成直至反應結束。於圖10中，判斷根據多數決決定方式而被認為具有可靠性之反應生成氣體組成(氧濃度、原料氣體濃度、或其他可燃性氣體濃度)是否超過反應生成氣體組成之上限閾值1而進入至黃色區域，於進入至黃色區域之情形時，向使反應生成氣體組成正常化之方向施加反饋及/或前饋控制。即便藉由該控制而反應生成氣體組成仍繼續變化，於根據多數決決定方式而被認為具有可靠性之反應生成氣體組成超過反應生成氣體組成之上限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。再者，此處，上限閾值2就防止爆炸之觀點而言，係決定反應生成氣體之氧濃度之上限之閾值之條件，係於狀態(c1)中被決定為第四基準值者，或者，就廢氣焚燒裝置中之處理能力之觀點而言，係決定反應生成氣體中之原料氣體濃度之上限之閾值之條件，係於狀態(c3)中被決定為第六基準值者。 另一方面，冗餘之複數個反應生成氣體分析器DI判斷根據多數決決定方式而被認為具有可靠性之反應生成氣體組成(氧濃度、原料氣體濃度、或其他可燃性氣體濃度)是否超過反應生成氣體組成之下限閾值1而進入至黃色區域，於進入至黃色區域之情形時，向使反應生成氣體組成正常化之方向施加反饋及/或前饋控制。即便藉由該控制而反應生成氣體組成仍繼續變化，於根據多數決決定方式而被認為具有可靠性之反應生成氣體組成超過反應生成氣體組成之下限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。再者，此處，下限閾值2就防止觸媒劣化之觀點而言，係決定反應生成氣體之氧濃度之下限之閾值之條件，係於狀態(c2)中被決定為第五基準值者。 原料氣體流量之上限及下限之閾值： 狀態(d1)係決定原料氣體流量之上限之閾值之條件，係基於檢測由原料氣體供給系統之異常所引起之流量增加之觀點、及檢測導致異常現象之流量增加之觀點而決定。然而，定量地推定原料氣體流量之變化對溫度、壓力、氣體組成造成之影響需要各條件之前提，多數情況下難以實質地進行流量值之特定。因此，單純地藉由計算求出僅原料氣體流量增加之情形之影響，而決定流量值。具體而言，(1)若原料氣體流量增加，則反應器溫度上升且氧消耗量增加，而氧濃度降低。若將由低氧氣氛下之觸媒之還原所引起之失活假定為異常現象，則可計算成為觸媒失活之氧濃度之假定原料氣體流量值。(2)若原料氣體流量增加，則反應器溫度上升。若將反應器之熔損假定為異常現象，則可計算成為反應器之設計溫度之假定原料氣體流量值。(3)若原料氣體流量增加，則反應器溫度上升。若將高反應溫度氣氛下之觸媒之劣化假定為異常現象，則可計算成為觸媒劣化之溫度之假定原料氣體流量值。採用以上(1)〜(3)中所求出之假定原料氣體流量值中之最小值，於狀態(d1)中，將該最小值之85〜100%設為第七基準值。 關於狀態(d1)，本發明者等人藉由模擬而對原料氣體流量對溫度、壓力、氣體組成造成之影響之動態特性進行研究。據此得知，原料氣體流量自穩態值達到上限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，藉由緊急停止可立即停止原料氣體。基於該等見解，第七基準值之上限可設為假定原料氣體流量值之100%。又，關於第七基準值之下限，就早期檢測之觀點而言，較佳為較低，但考慮到條件變動時之誤動作而採用85%。 又，作為抑制於反應器下游產生之其他異常現象之觀點，可考慮原料氣體流量之增加部分於未反應器內未反應，而於後續步驟之廢氣焚燒裝置中焚燒之情形。由於基於廢氣焚燒裝置之焚燒能力及燃燒生成氣體之處理之觀點而決定可燃燒之可燃性氣體量，故而亦可將可燃燒之可燃性氣體量之85〜100%設為基準而併用。 又，狀態(d2)係決定原料氣體流量之下限之閾值之條件，係基於檢測由原料氣體供給系統之異常所引起之流量減少之觀點、及檢測導致異常現象之流量減少之觀點而決定。然而，定量地推定原料氣體流量之變化對溫度、壓力、氣體組成造成之影響需要各條件之前提，多數情況下難以實質地進行流量值之特定。因此，單純地藉由計算求出僅原料氣體流量減少之情形之影響，而決定流量值。具體而言，若原料氣體流量減少，則氧消耗量減少，氧濃度上升。若將爆炸混合氣形成假定為異常現象，則可計算流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值。於狀態(d2)中，將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值。 關於狀態(d2)，本發明者等人藉由模擬而對原料氣體流量對溫度、壓力、氣體組成造成之影響之動態特性進行研究。據此得知，原料氣體流量自穩態值達到下限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則爆炸混合氣之形成立即消失。基於該等見解，第八基準值之下限可設為設最低流量之100%。又，關於第八基準值之上限，就早期檢測之觀點而言，較佳為較高，但考慮到條件變動時之誤動作而採用120%。 含氧氣體流量之上限及下限之閾值： 狀態(e1)係決定含氧氣體流量之上限之條件，係基於檢測由含氧氣體供給系統之異常所引起之流量增加之觀點、及檢測導致異常現象之流量增加之觀點而決定。然而，定量地推定含氧氣體流量之變化對溫度、壓力、氣體組成造成之影響需要各條件之前提，多數情況下難以實質地進行流量值之特定。因此，單純地藉由計算求出僅含氧氣體流量增加之情形之影響，而決定流量值。具體而言，若含氧氣體流量增加，則氧濃度上升，形成爆炸混合氣，而導致爆炸。若將爆炸混合氣形成假定為異常現象，則可計算流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值。於狀態(e1)中，將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值。 關於狀態(e1)，本發明者等人藉由模擬而對含氧氣體流量對溫度、壓力、氣體組成造成之影響之動態特性進行研究。據此得知，含氧氣體流量自穩態值達到上限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，藉由緊急停止可立即停止含氧氣體。基於該等見解，第九基準值之上限可設為上述假定含氧氣體流量值之100%。又，關於第九基準值之下限，就早期檢測之觀點而言，較佳為較低，但考慮到條件變動時之誤動作而採用85%。 狀態(e2)係決定含氧氣體流量之下限之條件，係基於檢測由含氧氣體供給系統之異常所引起之流量減少之觀點、及檢測導致異常現象之流量減少之觀點而決定。然而，定量地推定含氧氣體流量之變化對溫度、壓力、氣體組成造成之影響需要各條件之前提，多數情況下難以實質地進行流量值之特定。因此，單純地藉由計算求出僅含氧氣體流量減少之情形之影響，而決定流量值。具體而言，若含氧氣體流量減少，則氧濃度降低。若將由低氧氣氛下之觸媒之還原所引起之失活假定為異常現象，則可計算成為觸媒失活之氧濃度之假定原料氣體流量值。於狀態(e2)中，將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值。 又，作為抑制於反應器下游產生之其他異常現象之觀點，可考慮若含氧氣體流量減少，則原料氣體之一部分無法與氧於反應器內反應成為未反應，而於後續步驟之廢氣焚燒裝置中焚燒之情形。由於基於廢氣焚燒裝置之焚燒能力及燃燒生成氣體之處理之觀點而決定可燃燒之可燃性氣體量，故而亦可將可燃燒之可燃性氣體量之100〜120%設為基準而併用。 關於狀態(e2)，本發明者等人藉由模擬而對含氧氣體流量對溫度、壓力、氣體組成造成之影響之動態特性進行研究。據此得知，含氧氣體流量自穩態值達到下限之閾值之時間為幾分鐘〜幾十分鐘，為相對較和緩之速度。進而，根據實際機器裝置之運轉實績等亦發現，氣相反應若藉由緊急停止而停止反應，則藉由溫度降低立即抑制觸媒之劣化及可燃性氣體之生成立即消失。基於該等見解，第十基準值之下限可設為設最低流量之100%。又，關於第十基準值之上限，就早期檢測之觀點而言，較佳為較高，但考慮到條件變動時之誤動作而採用120%。 圖11中表示狀態(d1)〜(e2)中之緊急停止流程圖。如圖11所示，冗餘之複數個原料氣體流量計FI及含氧氣體流量計FI(以下，亦一併稱為「流量計FI」)持續監視設置場所中之流量直至反應結束。於圖11中，判斷根據多數決決定方式而被認為具有可靠性之流量是否超過流量之上限閾值1而進入至黃色區域，於進入至黃色區域之情形時，向降低流量之方向施加反饋及/或前饋控制。即便藉由該控制而流量亦繼續上升，於根據多數決決定方式而被認為具有可靠性之流量超過流量之上限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。再者，此處，上限閾值2係於狀態(d1)及(e1)中被決定為第七基準值及第九基準值者。 另一方面，冗餘之複數個流量計FI亦對根據多數決決定方式而被認為具有可靠性之流量是否超過流量之下限閾值1而進入至黃色區域進行判斷，於進入至黃色區域之情形時，向使流量上升之方向施加反饋及/或前饋控制。即便藉由該控制而流量仍繼續下降，於根據多數決決定方式而被認為具有可靠性之流量超過流量之下限閾值2而進入至紅色區域之情形時，本實施形態之緊急停止進行作動。此處，下限閾值2係於狀態(d2)及(e2)中被決定為第八基準值及第十基準值者。於圖11中，成為於進行重大性相對較高之狀態(d1)及(e1)之判斷後判斷狀態(d2)及(e2)之流程，但對此並無特別限制。 (檢測到異常之情形時之動作) 於檢測異常之儀器之任一者檢測到異常之情形時，反應器係向停止方向操作。就停止反應之觀點而言，向反應器之供給氣體均阻斷。即，停止向反應器供給原料氣體及含氧氣體。氣體之阻斷除控制流量之控制閥(CV)之關閉以外，較佳為設置阻斷閥而將其關閉。其原因在於，假定來自CV之洩漏，就防止洩漏之觀點而言，較佳為設置阻斷閥，預先進行二重化。確保自反應器中流出之氣體之目的地，防止反應器加壓而破壞。通常，自反應器中流出之氣體係依反應器→急冷塔→吸收塔→廢氣焚燒設施→大氣之順序流動，但於緊急停止時，使阻斷閥自動作動，設為反應器→急冷塔→廢氣焚燒設備→大氣。不與吸收塔連接之原因在於，反應器有複數台，於共用吸收塔之情形時，不向連接有正常之反應生成氣體之吸收塔中導入不穩定時之氣體。反應器內之氣體之利用惰性氣體進行之沖洗並非必須，但就防止高溫且反應生成氣體氣氛下之性能劣化之觀點而言，亦可對流動層觸媒進行利用惰性氣體之反應生成氣體之清理。於未利用惰性氣體對反應器內之氣體進行沖洗之情形時，停止後，反應器溫度降低，故而作為反應器之負壓對策，宜以不成為負壓之方式適量流通惰性氣體。惰性氣體較佳為使用氮。 由於向停止之反應器供給之空氣並非必要，故而空氣壓縮機較佳為停止。向冷卻盤管之冷媒供給可於原樣之狀態下維持。 (反應) 作為使用本實施形態之流動層氣相反應裝置進行之流動層氣相反應，並無特別限定，例如可列舉：氧化反應、氨氧化反應、烷基化反應。又，氣相反應可為發熱反應，亦可為吸熱反應，就本實施形態之緊急停止之必要性之觀點而言，較佳為發熱反應。 作為反應原料，只要係成為氣相反應之原料者，則並無特別限定，例如可列舉：烷烴、烯烴、醇、芳香族烴。具體而言，於上述氨氧化反應之情形時，可使用烴等有機化合物、氧或空氣等氧化劑、及氨作為反應原料。作為成為氨氧化反應之原料之一之烴之例，可列舉烷烴及/或烯烴。有機化合物及氧化劑分別可單獨使用一種或組合兩種以上而使用。 作為烷烴，並無特別限制，例如可列舉：甲烷、乙烷、丙烷、正丁烷、異丁烷。又，作為烯烴，並無特別限制，例如可列舉：乙烯、丙烯、正丁烯、異丁烯、第三丁烯。該等之中，就所生成之腈化合物之作為化學品中間原料之價值之觀點而言，作為烷烴，較佳為丙烷及/或異丁烷，作為烯烴，較佳為丙烯及/或異丁烯。 又，作為填充至反應器內之氣相反應之觸媒，只要為於該反應中通常所使用之固體觸媒，則並無特別限定，例如可列舉擔載於二氧化矽等之金屬氧化物觸媒。 實施例 以下，為了更具體地說明本發明，對將丙烯、氨及空氣供於立式圓筒型之流動層反應器，實施丙烯之氨氧化反應之情形時之模擬結果進行說明。但本發明並不受到以下之實施例之任何限定。 首先，將實施之模擬條件示於表1。再者，作為流動層氣相反應裝置，假定具有圖3之構成者。再者，作為氣相反應，原料氣體係設為丙烯，其他原料氣體係設為氨，含氧氣體係設為空氣，假定氨氧化反應。 [表1] [實施例1] 於在上述表1中所記載之條件下保持原料氣體流量及空氣流量之狀態下進行假定冷卻盤管之冷媒喪失之反應溫度之模擬。將冷卻盤管之冷媒喪失時刻設為0 min，將自冷卻盤管之冷媒喪失起之反應器內之溫度變化(實線)示於圖12。若藉由冗餘之複數個溫度計TI測定之反應器內之溫度成為500℃(表1之反應溫度之高基準值(第一基準值))而達到狀態(a1)，則緊急停止進行作動而阻斷向反應器之原料氣體及空氣之供給。其結果為，反應溫度如虛線般降溫。 [實施例2] 於上述表1中所記載之條件下進行假定丙烯之供給減少之模擬。將丙烯流量之減少開始時刻設為0 min，將丙烯流量每1分鐘減少1%之實例(實線)與丙烯流量每1分鐘減少5%之實例(虛線)之反應溫度的推移示於圖13。若藉由冗餘之複數個溫度計TI測定之反應器內之溫度成為410℃(表1之反應溫度之低基準值(第二基準值))而達到狀態(a2)，則緊急停止進行作動而阻斷向反應器之原料氣體及空氣之供給。其結果為，確認到爆炸混合氣之形成消除。 [實施例3] 於上述表1中所記載之條件下進行假定關閉急冷塔出口之閥，反應生成氣體未自反應器中排出之模擬。將急冷塔出口之閥之關閉時刻設為0 sec，將自急冷塔出口之閥之關閉起之反應器內之壓力變化(實線)示於圖14。若藉由冗餘之複數個壓力計PI測定之反應器內之壓力成為1.5 kg/cm2 G(表1之反應器壓力之高基準值(第三基準值))而達到狀態(b)，則緊急停止進行作動而阻斷向反應器之原料氣體及空氣之供給，排氣閥打開。其結果為，反應器壓力如虛線般降低。 [實施例4] 於上述表1中所記載之條件下進行假定空氣供給之增加之模擬。將原料空氣流量之增加開始時刻設為0 min，將空氣流量每1分鐘增加5%之實例(實線)與空氣流量每1分鐘增加10%之實例(虛線)之氧濃度的推移示於圖15。若藉由冗餘之複數個反應生成氣體分析器DI測定之氧濃度成為7%(表1之氧濃度之高基準值(第四基準值))而達到狀態(c1)，則緊急停止進行作動而阻斷向反應器之原料氣體及空氣之供給。其結果為，氧濃度如點劃線般降低。 [比較例1-1] 將反應溫度之高基準值設為445℃(閾值之89%)，除此以外，進行與實施例1同樣之模擬。其結果為，雖然處於正常運轉之範圍內，但存在反應步驟中之反應溫度因上下浮動(波動)而達到445℃之情形，故而反應器之緊急停止錯誤地進行作動。 [比較例1-2] 將反應溫度之高基準值設為510℃(閾值之102%)，除此以外，進行與實施例1同樣之模擬。其結果為，有於反應器之緊急停止進行作動前，對反應器之材質造成不良影響之虞。 [比較例2-1] 將反應溫度之低基準值設為350℃(閾值之97%)，除此以外，進行與實施例2同樣之模擬。其結果為，有反應氣體形成爆炸混合氣，產生反應器下游機器中之火災、爆炸現象之虞。 [比較例2-2] 將反應溫度之低基準值設為435℃(閾值之121%)，除此以外，進行與實施例2同樣之模擬。其結果為，雖然處於正常運轉之範圍內，但存在反應步驟中之反應溫度因上下浮動(波動)而達到435℃之情形，故而反應器之緊急停止錯誤地進行作動。 [比較例3-1] 將反應器壓力之高基準值設為1.3 kg/cm2 G(閾值之65%)，除此以外，進行與實施例3同樣之模擬。其結果為，雖然處於正常運轉之範圍內，但存在於實際機器運轉之啟動及/或關閉操作時反應器壓力接近1.3 kg/cm2 G之情形，故而反應器之緊急停止錯誤地進行作動。 [比較例3-2] 將反應器壓力之高基準值設為1.8 kg/cm2 G(閾值之90%)，除此以外，進行與實施例3同樣之模擬。其結果得知，若由緊急停止所引起之降壓較慢，則有可能接近2.0 kg/cm2 G(反應器之設計壓力)。 [比較例4-1] 將氧濃度之高基準值設為4%(閾值之33%)，除此以外，進行與實施例4同樣之模擬。其結果為，雖然處於正常運轉之範圍內，但存在於實際機器運轉之啟動及/或關閉操作時氧濃度接近4%之情形，反應器之緊急停止錯誤地進行作動。 [比較例4-2] 將氧濃度之高基準值設為13%(閾值之108%)，除此以外，進行與實施例4同樣之模擬。結果得知，於緊急停止進行作動前超過極限氧濃度，為火災、爆炸之可能性較高之狀態。 [產業上之可利用性] 本發明之方法可有效地用作使用流動層氣相反應裝置並利用原料氣體製造反應生成氣體之方法。尤其是就流動層氣相反應裝置之安全之運轉之觀點而言，作為流動層氣相反應裝置之緊急停止方法較有用。the following, Refer to the drawings as needed. Faced with an embodiment of the present invention (hereinafter, (Referred to as "this embodiment") to explain in detail, However, the present invention is not limited to this, Various changes can be made without departing from its spirit. Furthermore, In the diagram, Label the same elements with the same symbols, Repeated description is omitted. also, As long as the positional relationship between up, down, left, and right is not specified, It is assumed to be based on the positional relationship shown in the figure. and then, The size ratio of the device or component is not limited to the ratio shown in the figure. Furthermore, In this manual, There is a boundary between normal operation and abnormal operation that people should cope with. This is called "threshold value 1." The case where the boundary between the abnormal operation that a person should respond to and the abnormal operation that should be emergency stop automatically is called "threshold 2". also, There is a threshold value 2 more specifically, A case where the expression is expressed as a "reference value" by digitizing the pressure, the oxygen concentration, and the like. [Flow-layer gas-phase reaction device having an emergency reaction stop control unit and a method for producing a reaction-generating gas using the device] The flow-layer gas-phase reaction device of this embodiment has: reactor, It can accommodate the catalyst fluidly; First supply pipe, It supplies raw material gas into the reactor; Outflow tube, It discharges reaction generated gas from the reactor; Redundant thermometers TI, These are arranged in the reactor; Redundant multiple pressure gauges PI, These are located in the thin layer of the reactor; Redundant reactions generate gas analyzer DI, These are located downstream of the outflow pipe; And emergency response stop control. First of all, The emergency response stop control unit that operates in an abnormal state is conceptually different from a system (such as a distributed control system (DCS)) that performs reaction control in a normal state. The response control is performed according to the operation state. The so-called operating state here, Can be enumerated: The measured value (actual measured value) of the monitored object is within the range of normal operation (referred to as "blue area" for convenience), Range of dangerous operation (referred to as `` red area '' for convenience), Redundant areas (referred to as "yellow areas" for convenience) outside the range of normal operation and also outside the range of dangerous operation. Hereinafter, the measurement value of the monitoring object that is the boundary between the blue region and the yellow region is also referred to as a threshold value 1, The measurement value of the monitoring target that is the boundary between the yellow region and the red region is referred to as a threshold value 2. As a monitoring object, Using temperature as an example, The distributed control system monitors whether the temperature of a specific part is within the blue area. When the visible temperature is about to deviate from the blue area, Controlling the factors that increase or decrease the temperature through feedback and / or feedforward control, In this way, the controller is controlled so that the temperature does not deviate from the blue region. also, When the temperature exceeds the threshold value 1 and enters from the blue area to the yellow area, The decentralized control system is also controlled in such a way that the temperature returns to the blue area again. also, When the temperature enters the yellow area, There is also a monitor of the reaction device to artificially control the reaction, Controlled in such a way that the temperature returns to the blue area again. on the other hand, The emergency response stop control unit operating in an abnormal state monitors whether the temperature exceeds the threshold 2 and enters from the yellow area to the red area. When the temperature exceeds the yellow area and enters the red area, Forced emergency stop of the reaction device. The above system takes temperature as an example. However, because the emergency response stop control unit is an engineer who has not constructed in order to prevent the accident of the fluid layer gas phase reaction device, Therefore, it is necessary to deal with all accidents in the gas-phase reaction device of the fluidized bed. If we conduct research based on this view, It can be known that the accidents of the gas-phase reaction device in the fluid layer can be roughly divided into fire, Explosion and destruction. First of all, According to the methods used in the analysis of potential hazards and risks such as FTA (Fault Tree Analysis, Fault Tree Analysis) or HAZOP (Hazard And Operability, Danger and operability), etc. Select the equipment used for abnormal detection. It turns out that Reactor temperature, Reactor pressure, Raw gas flow, Oxygen-containing gas flow, Gas flow / oxygen gas flow, Gas composition of reaction, Cooling coil refrigerant flow, Flow layer catalyst amount, Valves for reaction to produce gas piping, Operating conditions of the raw material gas evaporator, The operating conditions of the air compressor are the instruments or operating conditions that cause abnormalities in the fluid-phase gas-phase reaction device. in this way, In addition to the temperature detected by the emergency stop control unit, under pressure, Various gas flows, Gas composition, etc. also, All reactors in the tested field, Various supply pipes for supplying raw materials to the reactor, Outflow pipe and so on. When detecting an abnormality in the operation of the fluid-phase gas-phase reaction device, It is an ideal form to detect more than one type from all the abnormalities of all the instruments installed in such a fluidized-phase gas phase reaction device and all the equipment connected to the fluidized-phase gas phase reaction device. however, In a fluidized bed gas phase reaction device operating at high temperature and pressure, Cannot rule out the malfunction and malfunction of the instrument, The possibility of no action, If this aspect is not guaranteed and all instruments installed in the fluidized-phase gas phase reaction device and all equipment connected to the fluidized-phase gas phase reaction device are always monitored, Even if it is one type, it is necessary to perform an emergency stop when entering the red area. In fact, it is also easy to make an emergency stop by mistakenly performing a normal operation. also, Even considering the cost of a gas-phase reaction device from a fluidized bed, It is also impractical to place all the instruments everywhere in the fluidized-phase gas-phase reaction apparatus. also, Conducting hypothetical experiments, It is also not easy to independently set the respective values from the blue region to the red region for each of the instruments provided in each place of the fluidized-phase gas phase reaction apparatus. therefore, From the standpoint of normal operation of the emergency stop control unit, The necessary testing agencies must be selected not less. also, To troubleshoot and malfunction the instrument, From the standpoint of the possibility of inaction, Regarding the equipment used in abnormal detection, It must be constructed in such a way as to ensure corresponding reliability. Based on this premise, The inventors and others have studied the guarantee of the reliability of the instrument and the selection of the necessary testing institutions, Thus, a fluidized bed gas phase reaction device having an emergency response stop control unit is constructed. the following, First explain the reliability of the instrument, The selection of the testing agency will be described later. In the fluidized bed gas phase reaction apparatus of this embodiment, As an instrument for abnormal detection, have: Redundant thermometers TI, These are arranged in the reactor; Redundant multiple pressure gauges PI, These are located in the thin layer of the reactor; And redundant multiple reactions to generate a gas analyzer DI, These are located downstream of the outflow pipe; When the number of instruments displaying abnormal values (the range of the red area) in each place exceeds more than half of the total number of instruments set, Trust the value of the instrument, The fluidized-phase gas-phase reaction apparatus was stopped urgently. The reason is that When the number of instruments in each location is one as shown in FIG. 1, To prevent malfunctions and malfunctions due to the sole instrument, A case where an emergency stop is performed without a person performing a normal operation without making a mistake, Or, a person who actually operates abnormally may mistake it for normal operation and keep it running. Here, The so-called "redundant plurality" means that the same object is measured by a plurality of measuring devices. Within this meaning, Except for setting the same type of measuring device at the same position for measurement, In addition, multiple measuring devices with different measuring methods can be used to measure the same object (such as temperature). It is possible to install a plurality of measuring devices within the same range of positions even if the measurement positions are completely different. These may be combined. E.g, In Figure 5, Use TI1, TI2, The three thermometers of TI3 measure the temperature of the thick layer 9a. However, if these temperatures are regarded as the same range, It may be equivalent to "a plurality of redundancy". also, Thermometer TI4 for measuring the temperature of the thin layer 9b, TI5, Or pressure gauge PI1 for measuring the pressure of thin layer 9b The same is true for PI2. The emergency reaction stop control unit is a thermometer from a gas-phase reaction device of a fluidized bed, pressure gauge, And each of the reaction generating gas analyzer receives the measurement value, When the measured values are judged abnormal by the majority selection method, By blocking at least the first supply tube, The emergency stop of the operation of the fluidized bed gas phase reaction device. From the standpoint of using a 2 out of 3 majority decision method, The number of anomaly detection instruments is preferably three. Yu tripled the instrument, Even if any of the 3 outputs signal an error, When the remaining two signals are the same, By adopting this, Can improve reliability. Furthermore, Regarding traffic anomalies, Anomaly detection can also be performed by analysis of reactor temperature and reaction generated gas, But to judge the emergency stop, It can monitor the flow meter. Because by monitoring traffic directly, Early anomalies can be found, Therefore, it is preferable to monitor the flow meter. Since it is technically or economically difficult to set multiple flow meters independently in most cases, Therefore, it can be a dual. In the case of dual instrumentation, From the standpoint of preventing malfunction, Preferably, a 2 out of 2 majority selection method is used. Figures 2 and 3 show thermometers, The pressure gauge and flow meter are dualized, Figure 4 shows the dual flowmeter, Thermometer and pressure gauge are tripled. Furthermore, In the figure, TI stands for thermometer, PI stands for pressure gauge, FI stands for flow meter. The thermometer TI is a thick layer 9a, which is provided at a high concentration in the catalyst of the reactor 1, respectively. And the catalyst is present in a thin layer 9b at a relatively low concentration. also, The thermometer must be provided in the thick layer 9a from the viewpoint of monitoring the reaction temperature, Furthermore, it can be provided in the thin layer 9b. also, The pressure gauge PI is arranged on the upper part of the reactor which is higher than the inlet of the cyclone separator. and then, The flow meter FI is installed in a supply pipe for supplying raw materials. In the case of a structure having two or more supply pipes converging halfway before entering the reactor, It is installed in each supply pipe. These thermometers and pressure gauges are used in combination with a plurality of reaction-producing gas analyzers. Fig. 7 shows that it is further downstream than the outflow pipe of the gas-phase reaction device of the fluidized bed. The reaction produces a gas analyzer that is duplexed at different locations. Furthermore, In the figure, DI stands for Reaction Generated Gas Analyzer. Secondly, Before explaining the equipment used in abnormal detection, The overall configuration of the fluidized bed gas phase reaction apparatus of this embodiment will be described. FIG. 2 is a schematic diagram showing a first aspect of the fluidized bed gas phase reaction apparatus according to this embodiment. In reactor 1, In addition to having a fluid storage catalyst, In addition to the cyclone separator 7 that separates and recovers the catalyst from the reaction generated gas, With cooling coils 6 as required, It is mainly used to remove the reaction heat of the thick layer 9a of the reactor 1, Control the reaction temperature. also, A first supply pipe 4 for supplying a raw material gas B is connected to the reactor 1. The raw material gas B is supplied into the reactor 1 from the first supply pipe 4 connected below the reactor 1 through the dispersion pipe 5. The upstream of the first supply pipe 4 may have a structure in which another supply pipe of each gas type such as a source gas D is merged, In that case, Preferably, a plurality of redundant flow meters are provided on the supply pipes of each gas type. The catalyst is based on the weight and volume of the catalyst itself, And the balance between the supply of raw material gas B and the following oxygen-containing gas A, It flows in the reactor 1. The presence (distribution) of each unit space of the catalyst is in a space higher than the dispersion tube 5, It decreases as it rises from below reactor 1. The cooling coil 6 provided in the reactor 1 functions to control the reaction heat of the reactor 1, Therefore, it is mainly provided in the thick layer 9a of the reactor 1 with a higher catalyst concentration. The heat generated in the gas-phase reaction is removed by using a refrigerant flowing in the cooling coil 6 as a heat removal pipe. Thereby controlling the reaction temperature. Reactor 1 has: Cyclone separator 7, The catalyst is separated and recovered from the reaction generated gas C in the reactor 1; And outflow pipe 8, It discharges the reaction-generated gas C separated by the cyclone 7 from the reactor 1. In cyclone separator 7, The gas C generated by the reaction of the catalyst enters from its inlet. The catalyst entering the cyclone separator 7 falls downward in a spiral manner on the cone portion of the cyclone separator 7, The reaction generated gas C is guided to the outflow pipe 8 from a pipe extending upward from the upper part of the cyclone 7. Below the conical part of cyclone separator 7, The tube further extends below the reactor 3, The catalyst is guided under the reactor 1 through the tube. on the other hand, The reaction-generating gas C guided to the outflow pipe 8 provided downstream of the reactor 1 is transported from the outflow pipe 8 to a downstream step. The reaction generated gas C flowing out of the outflow pipe 8 is cooled by air and / or boiler water in a reactor outlet heat exchanger (not shown) located downstream as needed. Since then, In the quench tower (see Figure 7), Use sulfuric acid to neutralize ammonia in the gas, Remove high boiling point substances and catalysts, Further cooling is performed. The reaction generated gas flowing from the quench tower is supplied to an absorption tower (see FIG. 7). In the absorption tower, The product is absorbed into a solvent such as water, And conveyed to the recovery step. Unreacted gas flowing from the top of the absorption tower, An uncondensed gas system containing unrecovered organic matter and the like is incinerated using an exhaust gas incinerator (see FIG. 7). FIG. 3 is a schematic diagram showing a second aspect of the fluidized bed gas phase reaction apparatus according to this embodiment. The second aspect of the fluidized-phase gas phase reaction apparatus is in addition to a second supply pipe 2 for supplying an oxygen-containing gas A containing oxygen to the reactor 1, It is the same as the first aspect. The oxygen-containing gas A is supplied into the reactor 1 from the second supply pipe 2 connected below the reactor 1 through the dispersion plate 3. The raw material gas B supplied from the plurality of supply ports 4 and the oxygen-containing gas A supplied by being dispersed by the dispersion plate 5 are supplied to face each other. Blend while blending. FIG. 4 is a schematic diagram showing a third aspect of the fluidized bed gas phase reaction apparatus according to this embodiment. In the third aspect, the fluidized-phase gas phase reaction device is a triple-layered instrument, except that the thermometer and the pressure gauge are tripled. The same structure as the second aspect. In the third aspect, A two-to-three majority selection method can be used. FIG. 5 is a schematic diagram showing a fourth aspect of the fluidized-bed gas-phase reaction apparatus according to this embodiment. The fourth aspect of the fluidized-phase gas-phase reaction device is a triple-layer thermometer. The same structure as the second aspect. In the fourth aspect, A two-to-three majority selection method can be used. In the fourth aspect, Change the position in the horizontal and height directions. And use TI1 in a range where the temperature is considered to be the same TI2, The three thermometers of TI3 measure the temperature of the thick layer 9a. Change the position in the horizontal and height directions. In addition, TI4, The two thermometers of TI5 measure the temperature of thin layer 9b. Change the horizontal position, And use PI1 to the extent that pressure is considered the same The two pressure gauges of PI2 measure the pressure of the thin layer 9b. in this way, By providing a plurality of redundant measuring devices within a range where the measured values are considered to be substantially the same, It can monitor the operation status of the mobile layer gas-phase reaction device in a certain spatial range surrounded by the measuring device. also, In Figure 5, Although not shown, However, a configuration in which the thermometer TI1 and the like are separately redundant may be adopted. (Equipment used in abnormality detection, etc.) Second, From the standpoint of reducing the risk level of malfunction and inaction, For the instruments used in the above abnormality detection, Hierarchical division of operating conditions will be described. As shown below and shown in Figure 6, Detection directly leads to fire, explosion, An instrument or an abnormal phenomenon that damages or causes fatal damage to the equipment (such as the inactivation of a catalyst), And from the viewpoint of operation management, instruments which are more important can be set as instruments for abnormal detection. Thermometer inside the reactor: If the temperature in the reactor exceeds the design temperature of the reactor, And still rising, It will lead to a meltdown (destruction) accident of the reactor. on the other hand, When the temperature in the reactor decreases, There is an increase in unreacted materials in the raw material gas or oxygen-containing gas supplied to the reactor 1, Reaction generated gas C, Or the gas in the reactor 1 tends to form an explosive mixture. Because the explosion mixture may cause an explosion accident, Therefore, the temperature in the reactor is an important operation management value. also, According to the temperature, There are also cases where the temperature of the fluid layer catalyst, such as excessive oxidation or excessive reduction, which adversely affects the catalyst, is required. therefore, Regarding the temperature in the reactor, The specific upper limit value and the lower limit value are selected and set as values for determining the emergency stop. In Figure 6, It is indicated by a thick line. The thermometer in the reactor is provided in the thick layer 9a, Or, both the thick layer 9a and the thin layer 9b. in particular, It may be provided at a position lower than the upper end of the cooling coil 6 and / or at a position higher than the upper end of the cooling coil 6. The thermometer measures the temperature inside the reactor 1, Those with a signal transmission function are preferred. As the type of thermometer, There are no special restrictions. As long as the temperature can be measured in petrochemical equipment, Preferably a thermocouple, Resistance thermometer. The temperature of the fluid layer reaction is characterized by relatively uniformity, But according to the existence of the catalyst, Response rate, The use of cooling coils, etc. may cause temperature distribution. therefore, It is preferable to use a plurality of redundant thermometers TI located below the upper end of the cooling coil, Monitoring the temperature of the lower part (thick layer 9a) of the reactor 1, which has a high concentration of catalyst, which mainly produces a gas phase reaction And using a plurality of redundant thermometers TI above the upper end of the cooling coil, The temperature of the upper part (thin layer 9b) of the reactor 1 was monitored. In the examples of FIGS. 2 and 3, Using two thermometers TI3 and TI4 to measure one part in the thick layer 9a, In addition, two thermometers TI1 and TI2 were used to measure one part of the thin layer 9b. In the example of Figure 4, Using 3 thermometers TI4, TI5 and TI6 measure one part in the thick layer 9a. And use three thermometers TI1, TI2 and TI3 were measured on one part of the thin layer 9b. Assume that a malfunction is caused by a broken or poorly connected thermometer, etc. It is preferable to consider such a failure as a fail safe side. which is, Set thermometers that detect high and low temperatures, respectively. thus, In case of failure of the thermometer for high temperature detection, Indicates high temperature, In the case of failure of the thermometer for low temperature detection, Indicates low temperature. E.g, Preferably, when TI3 and TI4 in FIG. 2 are set as thermometers with high detection temperature, The other thermometers TI3 'and TI4', which have a low detection temperature, are provided at one location in the thick layer 9a. Pressure gauge in the reactor: If the pressure in the reactor exceeds the design pressure of the reactor, And still rising, Will cause damage to the reactor. on the other hand, The reduction in pressure in the reactor may have some effects on the reaction, In rare cases, however, it is directly linked to the accident. therefore, Regarding the pressure in the reactor, The specific upper limit value is selected and set as a value for determining the emergency stop. The pressure gauge in the reactor can be arranged on the thin layer 9b of the reactor 1 especially the top of the column. The pressure gauge is a person who measures the pressure inside the reactor 1, It is better to display the gauge pressure, And have signal transmission function. As the type of pressure gauge, There are no special restrictions. As long as it can be used in petrochemical equipment, Bourdon tube is preferred, Bellows, Diaphragm type and so on. The pressure gauge only needs to be set at a position where the internal pressure of the reactor can be measured, It is not particularly limited. However, because the pressure in the fluid layer catalyst is affected by the amount of catalyst or the catalyst flow, Therefore, it is preferably provided on the thin layer 9b. also, Defective nozzles, such as nozzle clogging, can affect multiple pressure gauges, So from the standpoint of instrument reliability, Compared with the case where one nozzle is branched out and two or more pressure gauges are connected, Preferably, the pressure gauge and the reactor 1 are connected one to one through a nozzle. Raw material gas flow meter: The raw material gas flowmeter may be provided in the first supply pipe. If the feed gas flow increases, Then, the following raw material gas flow rate / oxygen-containing gas flow rate also changes. If the feed gas flow increases, The reaction volume increases, Therefore, the reaction fever increases, The reactor temperature rose. If you can respond with a cooling device, You can control the reactor temperature, However, in the case of insufficient response due to a sharp increase, etc., The reactor temperature is still rising, This results in a meltdown (destruction) accident of the reactor. As an abnormal increase in unreacted source gas due to an increase in the flow rate of the source gas, For example, consider the rapid increase of non-caused source gas, The imbalance of raw materials Compared with the case where the fluid layer catalyst is insufficient, Increasing unreacted source gas due to unidirectional flow of gas, etc. In such cases, Risk of abnormal combustion or explosion in the machinery downstream of the reactor, especially in the waste gas incineration plant. also, Changes in the unreacted raw material gas can also be detected by the composition analysis of the reaction generated gas described below. on the other hand, If the feed gas flow decreases, The heat of reaction decreases, The reactor temperature decreased. If the reactor temperature decreases, The unreacted material of the raw material gas or oxygen-containing gas increases, An explosive mixture is formed which causes an explosion. When the flow of raw material gas decreases, Feed gas flow / oxygen gas flow, And the analysis value of the composition of the reaction gas also changed. Based on the above, Increase or decrease of the feed gas flow After the increase or decrease of the flow of the raw material gas / the flow of the oxygen-containing gas, The increase and decrease in the reactor temperature and the change in the analysis value of the composition of the reaction generated gas are related to the accident. Here, The flow of the raw material gas is one of the important operating conditions of the gas-phase reaction device in the fluidized bed. Consider performing frequent operating operations, The change in the flow rate of the raw material gas is the beginning of causing abnormal phenomena. The reliability of the measured value of the flow meter is relatively high. therefore, Although it may not be directly related to the accident, But regarding the raw gas flow, The specific upper limit value and lower limit value can be selected and set as values for judging the emergency stop. Furthermore, The flow meter measures the flow rate of the gas supplied to the reactor 1, It is preferably provided in various fluids, And have signal transmission function. As long as the type of flow meter is capable of measuring gaseous fluid in petrochemical equipment, There are no special restrictions. Preferably a differential pressure flowmeter, Area type Lee flowmeter, Vortex flowmeter, Turbine flowmeter, Positive displacement flowmeter, Coriolis flowmeter, Ultrasonic flowmeter. the following, The same applies to the oxygen-containing gas flow meter. Oxygen-containing gas flow meter: If the flow of oxygen-containing gas increases, The raw gas and the generated gas, which are flammable gases, form an explosive mixture with oxygen, It caused an explosion. on the other hand, If the flow of oxygen-containing gas decreases, The raw material gas cannot fully react, Unreacted raw material gas increases. These phenomena can cause abnormal combustion in the equipment downstream of the reactor such as the waste gas incinerator, Risk of explosion. Changes in the flow rate of oxygen-containing gas will also change the analysis value of the flow rate of raw material gas / flow of oxygen-containing gas and the composition of the reaction gas. Although the abnormality of oxygen-containing gas flow is not directly related to the accident, But as in the case of the raw gas, It is more appropriate to process as a measurement value that must be selected. therefore, Regarding oxygen-containing gas flow, The specific upper limit value and lower limit value can be selected and set as values for judging the emergency stop. Oxygen-containing gas flow / raw gas flow meter: Although the oxygen-containing gas flow rate and the raw material gas flow rate can be used instead, However, it is also possible to monitor the flow of oxygen-containing gas / raw gas. Since the oxygen-containing gas flow / feed gas system is calculated from two instruments, Therefore, when the distributed control system (DCS) is not used, In addition, systems that require calculations, such as safety equipment. In Figure 6, They are shown in thin lines. Reaction gas analyzer: The reaction generated gas includes generated gas, Unreacted source gas, If it is an oxidation reaction, Then add oxygen, Or nitrogen as the case may be. During normal operation, From the standpoint of preventing explosion, the oxygen concentration in the reaction generated gas, The system is managed as below the limit oxygen concentration. and then, When the catalyst deteriorates in a reducing atmosphere, The catalyst is managed at an oxygen concentration that is not reduced by the catalyst. however, When something abnormal happens in the reaction field, The composition of the reaction gas changes. Regarding this situation, Even if the details of the anomaly in the reaction field are not clear, As long as the composition of the reaction generated gas can be monitored for abnormalities, You can also know the occurrence of anomalies. E.g, If the gas-layer contact reaction is an oxidation reaction, The concentration of oxygen contained in the reaction gas is set as a necessary measurement object. The reason is that Even if it is combustible, As long as there is no oxygen, no explosion will occur, So from the standpoint of preventing explosions, It is important to set the oxygen concentration as a necessary measurement object. also, If it is not an oxidation reaction, Then, the concentration of the source gas and / or the concentration of the generated gas is measured. therefore, With regard to the reaction generated gas analysis, The specific upper limit value is selected and set as a value for determining the emergency stop. The analysis of the reaction generated gas using the reaction generated gas analyzer DI can be performed by continuously sampling the reaction generated gas flowing out of the reactor 1. The sampling location of the reaction generated gas (the installation location of the reaction generated gas analyzer) is as described in FIG. 7. Preferably, it is between a reactor (exit heat exchanger)-a quenching tower, or between a quenching tower-an absorption tower. As an analyzer in the case of oxygen analysis, There are no special restrictions. For example: Zirconia type, Magnetic, Laser spectroscopic, Electrode type analyzer. also, The analysis of the reaction products and / or unreacted products is preferably performed by gas chromatography. In order to reduce the dirt on the analyzer, It is more preferable to analyze the reaction generated gas between the quench tower and the absorption tower. Cooling coil refrigerant flow meter: In terms of improving accuracy, Further, the refrigerant flow rate of the cooling coil can be monitored. If the cooling coil refrigerant flow changes, It will affect the reaction temperature. As the refrigerant connected to the cooling coil, Most can use saturated water and / or steam. The water at the saturation temperature connected to the cooling coil absorbs the heat generated in the reaction, And a part of it (evaporation rate 5-30%) evaporates. When the flow of water at saturation temperature increases, This type of cooling coil also has almost no heat removal. When the refrigerant is vapor, If the vapor flow increases, Becomes a tendency to remove heat, However, due to the upper limit of the steam flow rate that can be used and / or the relatively small number of cooling coils using steam, Therefore, the effect on the reaction temperature is small. on the other hand, When the refrigerant flow decreases, The heat of reaction cannot be removed, The reaction temperature rises. which is, Considering that the reduction of the refrigerant coil flow of the cooling coil brings high reactor temperature, The cooling coil flow rate is usually not changed. therefore, Regarding the cooling coil refrigerant flow, The specific upper limit value and lower limit value can be selected and set as values for judging the emergency stop. Determination of the amount of fluid layer catalyst: Further monitoring of the amount of catalyst in the flow layer is possible. It is not assumed that the fluid layer catalyst will increase during normal operation. however, For some reason, such as the abnormality of the cyclone, unable to capture the fluid layer catalyst, When the amount of catalyst in the mobile layer decreases, There may be an increase in unreacted substances without performing the reaction. In this case, The concentration of the source gas in the reaction gas increases, Or in the case of an oxidation reaction, The oxygen concentration rises. therefore, When the amount of catalyst decreases, The detection can be performed instead by analysis of the composition of the reaction generated gas. also, Regarding the reduction in catalyst volume, Even if the temperature in the reactor decreases, Detection can also be performed instead. and then, The amount of catalyst in the flow layer can also be calculated indirectly using a plurality of instruments such as pressure gauges. in this way, Regarding the amount of fluid layer catalyst, Alternative tests may be performed using other instruments as described. therefore, As mentioned above, In terms of cost or achievability, Or from the perspective of preventing false emergency stops in advance, It can be selected and set instead of the value used to judge the emergency stop. As long as these are guaranteed, It can also be selected and set as the value for judging the emergency stop. Valves for reaction to produce gas piping: Observation of valve closing of the reaction gas piping can be further performed. When the valve installed in the pipe for transferring the reaction generated gas flowing out of the reactor is closed for some reason, The pressure in the reactor rises, May cause damage to the reactor. therefore, The valve is closed due to the high pressure in the reactor, etc. Therefore, a pressure gauge can be used instead for testing. in this way, Regarding the closing of the valve of the reaction gas piping, Alternative tests may be performed using other instruments as described. therefore, As mentioned above, In terms of cost or achievability, Or from the perspective of preventing false emergency stops in advance, It can be selected and set instead of the value used to judge the emergency stop. As long as these are guaranteed, It can also be selected and set as the value for judging the emergency stop. Operating conditions of the raw material gas evaporator, status: Further observation of abnormal operation of the raw material gas evaporator can be performed. The operation of the raw material gas evaporator is subject to the flow and temperature of the heat medium, Raw material liquid level in raw material gas evaporator, The influence of the pressure in the raw material gas evaporator, And affect the flow of the raw material gas. therefore, The abnormal operation of the raw material gas evaporator can be detected by using the raw material gas flow rate instead. also, Each condition that affects the operation of the raw material gas evaporator has a tendency not to directly affect the operation of the reactor. in this way, And the operating conditions of the raw material gas evaporator, State-related detection anomalies can be replaced by other instruments as described. therefore, As mentioned above, In terms of cost or achievability, Or from the perspective of preventing false emergency stops in advance, It can be selected and set instead of the value used to judge the emergency stop. As long as these are guaranteed, It can also be selected and set as the value for judging the emergency stop. Operating conditions of air compressors, status: Further observation of abnormal operation of the air compressor is possible. The operation of the air compressor is subject to the supply of steam or electricity as the drive source of the compressor, The influence of the pressure of the reactor as the air supply target, And affect the flow of oxygen-containing gas. therefore, The abnormal operation of the air compressor can be detected using the oxygen-containing gas flow instead. in this way, With the operating conditions of the air compressor, State-related detection anomalies can be replaced by other instruments as described. therefore, As mentioned above, In terms of cost or achievability, Or from the perspective of preventing false emergency stops in advance, It can be selected and set instead of the value used to judge the emergency stop. As long as these are guaranteed, It can also be selected and set as the value for judging the emergency stop. (Threshold) In this embodiment, For multiple thermometers TI, Pressure gauge PI, And the case where the value obtained by applying the majority selection method to the reaction gas analyzer DI exceeds a specific threshold, The emergency response stop control unit blocks at least the first supply pipe, The operation of the fluidized-phase gas-phase reaction device is stopped urgently. in particular, In the reaction step of supplying a raw material gas to a gas phase reaction in the presence of a catalyst, Under monitoring actual measured values with respect to each of the following first to sixth reference values, When at least one of the following six states (a1) to (c3) occurs, The operation of the gas-phase reaction device of the fluidized bed is stopped urgently. (a1) the value of 90 to 100% of any lower temperature among the design temperature of the reactor or the highest temperature determined based on the viewpoint of protecting the catalyst is set as the first reference value The state (a2) showing that the number of thermometers TI that is greater than the measured value of the first reference value exceeds more than half of the total number of thermometers TI reduces the activity of the catalyst and increases unreacted, The value of 100 ~ 120% of any higher temperature of the temperature at which an explosive mixture is formed in the reactor or the temperature at which abnormal combustion occurs in downstream equipment is set as the second reference value, A state where the number of thermometers TI showing an actual measured value less than the second reference value exceeds more than half of the total number of thermometers TI (b) Set a value of 70 to 85% of the design pressure of the reactor as the third reference value A state where the number of pressure gauges PI showing an actual measured value larger than the third reference value exceeds more than half of the total number of pressure gauges PI (c1) Set a value of 40 to 100% of the explosive limit oxygen concentration as the fourth reference value, A state in which the number of reaction generated gas analyzer DIs showing an actual measured value greater than the fourth reference value exceeds more than half of the total number of reaction generated gas analyzers DI (c2) will generate 100 to 120% of the oxygen concentration of the catalyst for reduction degradation The value is set to the fifth reference value, Shows a state where the number of reaction generated gas analyzer DI is less than the fifth reference value and exceeds half of the total number of reaction generated gas analyzer DI (c3) Set a value of 150 to 300% of the design value of the raw material gas concentration Is the sixth reference value, A state where the number of reaction generated gas analyzer DI exceeding the measured value of the sixth reference value exceeds more than half of the total number of reaction generated gas analyzer DI is displayed, The fluidized bed gas phase reaction apparatus of this embodiment further has a plurality of redundant raw material gas flow meters FI provided in the first supply pipe, And under monitoring actual measured values with respect to each of the following seventh to eighth reference values, When at least one of the following two states (d1) to (d2) occurs, The emergency response stop control unit may block at least the first supply pipe, The operation of the fluidized-phase gas-phase reaction device is stopped urgently. (d1) The assumed raw material gas flow value that will be the oxygen concentration of the catalyst deactivation, The assumed raw material gas flow value that becomes the design temperature of the reactor, And the value of 85 to 100% of the lowest flow value among the assumed raw material gas flow values which is the temperature at which the catalyst deteriorates is set as the seventh reference value, In the case where the number of raw material gas flow meters FI showing an actual measured value greater than the seventh reference value exceeds more than half of the total number of raw material gas flow meters FI (d2) the assumed raw material gas flow value in which the oxygen concentration in the outflow tube becomes the limit The value of 100 to 120% of the Cases where the number of raw material gas flow meters FI showing an actual measured value less than the eighth reference value exceeds more than half of the total number of raw material gas flow meters FI The fluidized-phase gas-phase reaction device further includes: Second supply pipe, It supplies oxygen-containing gas to the reactor; And a plurality of redundant oxygen-containing gas flow meters FI arranged in the second supply pipe, And under monitoring the actual measured values with respect to each of the following ninth to tenth reference values, When at least one of the following two states (e1) to (e2) occurs, The emergency response stop control unit may block at least the first supply pipe, The operation of the fluidized-phase gas-phase reaction device is stopped urgently. (e1) Set the value of 85 to 100% of the assumed oxygen-containing gas flow value at which the oxygen concentration in the outflow pipe becomes the limit oxygen concentration, The case where the number of oxygen-containing gas flow meters FI showing an actual measured value greater than the ninth reference value exceeds more than half of the total number of oxygen-containing gas flow meters FI2 (e2) will be the assumed oxygen-containing gas flow rate of the catalyst deactivation oxygen concentration 100 ~ 120% of the value is set as the tenth reference value, The upper and lower thresholds of the reactor temperature when the number of oxygen-containing gas flow meters FI showing an actual measured value less than the tenth reference value exceeds more than half of the total number of oxygen-containing gas flow meters FI2: State (a1) is a condition that determines the upper threshold of the reactor temperature, A value of 90 to 100% of any lower temperature among the design temperature of the reactor or the highest temperature determined from the viewpoint of protecting the catalyst is set as the first reference value. also, State (a2) is a condition that determines the lower threshold of the reactor temperature, By reducing the reaction temperature, The activity of the catalyst decreases but the unreaction increases. A value of 100 to 120% of any higher temperature of the temperature at which the explosive mixture is formed in the reactor or the temperature at which abnormal combustion occurs in the downstream equipment is set as the second reference value. Regarding state (a1), The present inventors have studied the dynamic characteristics of the reaction temperature by simulation. Based on this, The time for the reaction temperature to reach the upper threshold is from several minutes to several tens of minutes. For relatively modest speed. and then, According to the actual operating results of actual equipment, If the gas phase reaction is stopped by an emergency stop, The reaction temperature immediately decreases. Based on these insights, The upper limit of the first reference value can be set to 100% of the highest temperature used (whichever is the lower of the design temperature of the reactor or the highest temperature determined from the viewpoint of protecting the catalyst). also, Regarding the lower limit of the first reference value, From the perspective of early detection, Preferably lower However, 90% is used in consideration of malfunction caused by temperature fluctuations such as when conditions change. Regarding state (a2), Perform the simulation in the same way as state (a1), The dynamic characteristics of reaction temperature were studied. Based on this, The time for the reaction temperature to reach the lower threshold threshold from a few minutes to several tens of minutes. For relatively modest speed. and then, According to the actual operating results of actual equipment, If the gas phase reaction is stopped by an emergency stop, The formation of explosive mixtures is immediately eliminated. Based on these insights, The lower limit of the second reference value may be set to 100% of the lowest temperature (any one of the temperature at which an explosive mixture is formed in the reactor or the temperature at which abnormal combustion occurs in downstream equipment). also, Regarding the upper limit of the second reference value, From the perspective of early detection, Preferably higher However, 120% is adopted in consideration of malfunction caused by temperature fluctuations such as when conditions change. FIG. 8 shows a flowchart of the emergency stop in the state (a1) and the state (a2). As shown in Figure 8, The redundant multiple thermometers TI continuously monitor the temperature in the setting place until the reaction is completed. In Figure 8, Determine whether the temperature considered to be reliable according to the majority decision method exceeds the upper limit threshold 1 of the temperature and enters the yellow area, When entering the yellow area, Apply feedback and / or feedforward control in the direction of decreasing temperature. Even with this control, the temperature continues to rise, When the temperature considered to be reliable according to the majority decision method exceeds the upper limit threshold 2 of the temperature and enters the red region, The emergency stop of this embodiment operates. Furthermore, Here, The upper limit threshold 2 is determined in the state (a1) as the first reference value. on the other hand, The redundant multiple thermometers TI also judge whether the temperature considered to be reliable according to the majority decision method exceeds the lower temperature threshold 1 and enters the yellow area. When entering the yellow area, Apply feedback and / or feed-forward control to the direction of increasing temperature. Even with this control, the temperature continues to drop, When the temperature deemed reliable by the majority decision method exceeds the lower temperature threshold value 2 and enters the red area, The emergency stop of this embodiment operates. Here, The lower limit threshold 2 is a value determined as the second reference value in the state (a2). In Figure 8, It becomes the process of judging the state (a2) after the judgment of the state (a1) of relatively high significance, There is no particular restriction on this. Threshold of the upper limit of the reactor pressure: State (b) is a condition that determines the threshold of the upper limit of the reactor pressure, The value of 70 to 85% of the design pressure of the reactor was set as a third reference value. also, As mentioned above, For the lower threshold of the reactor pressure, There are no particular restrictions. Regarding state (b), The inventors have studied the dynamic characteristics of the reactor pressure by simulation. Based on this, The time for the pressure of the reactor to reach the upper limit threshold is in the order of tens of seconds. Relatively fast. According to the actual operating results of actual equipment, If the gas phase reaction stops the gas supply by an emergency stop, The reactor pressure immediately decreases. Considering the results of simulations where pressure rises relatively quickly, The upper limit of the third reference value is set to 85% of the design pressure. It has a margin for actions such as the closing operation time of a control valve after an emergency stop is activated. also, Regarding the lower limit of the third reference value, From the perspective of early detection, Preferably lower However, considering the misoperation caused by the increased pressure during condition adjustment, 70% is used. The emergency stop flowchart in the state (b) is shown in FIG. As shown in Figure 9, The redundant multiple pressure gauges PI continuously monitor the temperature in the setting place until the reaction is completed. In Figure 9, Judging whether the pressure considered to be reliable according to the majority decision method exceeds the upper pressure threshold value 1 of the pressure and enters the yellow area, When entering the yellow area, Apply feedback and / or feedforward control in the direction of reduced pressure. Even though the pressure continues to rise through this control, When the pressure considered reliable by the majority decision method exceeds the upper limit threshold 2 of the pressure and enters the red area, The emergency stop of this embodiment operates. Furthermore, Here, The upper threshold value 2 is determined as the third reference value in the state (b). Threshold of the upper limit of the composition of the reaction gas: State (c1) from the standpoint of preventing explosions, Is the condition that determines the upper limit of the oxygen concentration of the reaction generated gas, A value of 40 to 100% of the explosive limit oxygen concentration is set as a fourth reference value. also, State (c2) is from the viewpoint of preventing catalyst deterioration, Is the condition that determines the lower limit of the oxygen concentration of the reaction generated gas, A value of 100 to 120% of the oxygen concentration at which the reduction degradation of the catalyst occurs is set as a fifth reference value. and then, State (c3) from the standpoint of the processing capacity in the exhaust gas incinerator, Is the condition that determines the upper limit of the upper limit of the concentration of the source gas in the reaction generated gas, A value of 150 to 300% of the design value of the raw material gas concentration is set as a sixth reference value. Furthermore, Here, The so-called `` design value of the raw material gas concentration '' refers to 0 of the raw material gas supplied by the reactor. A value of 5 to 10%. Generally, in the reactor, the conversion rate of the source gas is not 100%, and the source gas corresponding to the design value of the above-mentioned concentration of the source gas remains in an unreacted state. In the reactor, when the conversion rate of the raw material gas is reduced for some reason, an excessive amount of the raw material gas is supplied to the exhaust gas incineration device that performs the incineration treatment of the raw material gas. In this way, the raw material gas is treated too much, and the exhaust gas incinerator may run out of control. Regarding the state (c1), the inventors of the present invention studied the dynamic characteristics of the oxygen concentration of the gas produced by the reaction by simulation. According to this, it is known that the time when the oxygen concentration self-steady-state value reaches the upper limit threshold is several minutes to several tens of minutes, which is a relatively gentle speed. Furthermore, based on actual operating results of actual equipment, it has been found that if the gas phase reaction is stopped by an emergency stop, the oxygen concentration will immediately decrease. Based on these insights, the upper limit of the fourth reference value may be set to 100% of the explosive limit oxygen concentration. In addition, the lower limit of the fourth reference value is preferably lower from the viewpoint of early detection, but 40% is adopted in consideration of erroneous operation when conditions change. The state (c2) was simulated in the same manner as the state (c1), and the dynamic characteristics of the oxygen concentration of the reaction generated gas were studied. According to this, it is known that the time from the steady-state value of the oxygen concentration to the lower limit threshold is several minutes to several tens of minutes, which is a relatively gentle speed. Furthermore, based on the actual operating results of actual equipment, it has been found that if the gas phase reaction is stopped by an emergency stop, the catalyst degradation is immediately suppressed by the temperature decrease. Based on these insights, the lower limit of the fifth reference value may be set to 100% of the minimum oxygen concentration used. The upper limit of the fifth reference value is preferably higher from the viewpoint of early detection, but 120% is adopted in consideration of erroneous operation when conditions change. Regarding the state (c3), simulation was performed in the same manner as the state (c1), and the dynamic characteristics of the raw material gas concentration of the reaction generated gas were studied. According to this, it is known that the time from when the concentration of the raw material gas in the reaction generated gas reaches the upper limit threshold is several minutes to several tens of minutes, which is a relatively slow speed. Furthermore, based on the actual operating results of actual equipment, it was also found that if the gas phase reaction is stopped by an emergency stop, the flow rate of the raw material gas in the reaction generated gas is immediately reduced. Based on these insights, the lower limit setting of the sixth reference value can be set to 150% of the design value of the raw material gas concentration from the viewpoint of preventing malfunction and early detection. The upper limit of the sixth reference value depends on the equipment capacity of the exhaust gas incinerator, and 300% is adopted. FIG. 10 is a flowchart of an emergency stop when monitoring the oxygen concentration and the source gas concentration in the states (c1) to (c3). As shown in FIG. 10, the plurality of redundant reaction gas analyzers DI continuously monitor the reaction gas composition in the installation site until the reaction is completed. In FIG. 10, it is determined whether the composition of the reaction generated gas (oxygen concentration, raw material gas concentration, or other flammable gas concentration) considered to be reliable according to the majority decision method exceeds the upper threshold value 1 of the reaction generated gas composition and enters In the yellow region, when entering the yellow region, feedback and / or feedforward control is applied in a direction to normalize the composition of the reaction generated gas. Even if the composition of the reaction generated gas continues to change by this control, when the reaction generated gas composition considered to be reliable according to the majority decision method exceeds the upper limit threshold 2 of the reaction generated gas composition and enters the red region, this The emergency stop of the implementation form operates. Here, the upper threshold value 2 is a condition that determines the upper limit of the oxygen concentration of the reaction generated gas from the viewpoint of explosion prevention, and is determined by the state (c1) as the fourth reference value, or, From the viewpoint of the processing capacity in the exhaust gas incineration device, it is a condition that determines the threshold value of the upper limit of the concentration of the raw material gas in the reaction generated gas, and it is a condition determined as the sixth reference value in the state (c3). On the other hand, the plurality of redundant reaction gas analyzers DI determine whether the composition of the reaction gas (oxygen concentration, raw material gas concentration, or other flammable gas concentration) considered to be reliable according to the majority decision method exceeds the reaction. The lower limit of the generated gas composition threshold value 1 enters the yellow region. When entering the yellow region, feedback and / or feedforward control is applied in a direction to normalize the reaction generated gas composition. Even with this control, the composition of the reaction gas continues to change. When the composition of the reaction gas considered to be reliable according to the majority decision method exceeds the lower threshold 2 of the reaction gas composition and enters the red region, this The emergency stop of the implementation form operates. Here, the lower limit threshold value 2 is a condition for determining the lower limit value of the oxygen concentration of the reaction generated gas from the viewpoint of preventing catalyst deterioration, and is determined as the fifth reference value in the state (c2). Upper and lower thresholds of the raw material gas flow rate: State (d1) is a condition that determines the upper threshold of the raw material gas flow rate, and is based on the viewpoint of detecting an increase in the flow rate caused by an abnormality of the raw material gas supply system, and detecting abnormalities that cause the phenomenon. It depends on the viewpoint of increasing traffic. However, quantitatively estimating the effects of changes in the flow rate of the raw material gas on temperature, pressure, and gas composition requires advancement of each condition, and in many cases it is difficult to actually specify the flow rate value. Therefore, the value of the flow rate is determined simply by calculating the influence of the case where only the flow rate of the raw material gas increases. Specifically, (1) if the flow rate of the raw material gas is increased, the reactor temperature is increased, the oxygen consumption is increased, and the oxygen concentration is decreased. If the deactivation caused by the reduction of the catalyst in a low-oxygen atmosphere is assumed to be an abnormal phenomenon, the hypothesized raw material gas flow value that becomes the concentration of the catalyst deactivated oxygen can be calculated. (2) When the flow rate of the raw material gas increases, the temperature of the reactor increases. If the melting loss of the reactor is assumed to be an abnormal phenomenon, the assumed raw material gas flow value that becomes the design temperature of the reactor can be calculated. (3) When the flow rate of the raw material gas increases, the temperature of the reactor increases. If the deterioration of the catalyst in a high-reaction temperature atmosphere is assumed to be an abnormal phenomenon, the assumed raw material gas flow value that is the temperature at which the catalyst deteriorates can be calculated. Using the minimum value of the assumed raw material gas flow value obtained in (1) to (3) above, in the state (d1), 85 to 100% of the minimum value is set as the seventh reference value. Regarding the state (d1), the present inventors have studied the dynamic characteristics of the influence of the flow rate of the raw material gas on the temperature, pressure, and gas composition through simulation. According to this, it is known that the time from when the flow rate of the raw material gas reaches the upper limit threshold is several minutes to several tens of minutes, which is a relatively slow speed. Furthermore, based on actual operating results of actual equipment, it was found that the raw gas can be stopped immediately by an emergency stop. Based on these insights, the upper limit of the seventh reference value may be set to 100% of the assumed feed gas flow value. The lower limit of the seventh reference value is preferably lower from the viewpoint of early detection, but 85% is adopted in consideration of a malfunction when conditions change. In addition, as a viewpoint of suppressing other abnormal phenomena generated downstream of the reactor, it may be considered that an increase in the flow rate of the raw material gas is not reacted in the unreactor and is incinerated in a waste gas incinerator in a subsequent step. Since the combustible flammable gas amount is determined based on the viewpoint of the incineration capacity of the exhaust gas incineration device and the treatment of the combustion-generated gas, it is also possible to use 85 to 100% of the combustible flammable gas amount as a reference and use them together. The state (d2) is a condition that determines the lower limit of the flow rate of the raw material gas, and is determined based on the viewpoint of detecting a decrease in the flow rate caused by an abnormality of the raw material gas supply system, and the viewpoint of detecting a decrease in the flow rate that causes an abnormal phenomenon. However, quantitatively estimating the effects of changes in the flow rate of the raw material gas on temperature, pressure, and gas composition requires advancement of each condition, and in many cases it is difficult to actually specify the flow rate value. Therefore, the value of the flow rate is determined simply by calculating the influence of the case where only the flow rate of the raw material gas is reduced. Specifically, when the flow rate of the raw material gas is reduced, the oxygen consumption amount is reduced and the oxygen concentration is increased. If the formation of the explosive mixture is assumed to be an abnormal phenomenon, the hypothetical raw material gas flow value in which the oxygen concentration in the outflow pipe becomes the limiting oxygen concentration can be calculated. In the state (d2), the value of 100 to 120% of the assumed raw material gas flow value at which the oxygen concentration in the outflow pipe becomes the limit oxygen concentration is set as the eighth reference value. Regarding the state (d2), the present inventors have studied the dynamic characteristics of the influence of the flow rate of the raw material gas on the temperature, pressure, and gas composition through simulation. According to this, it is known that the time from when the flow rate of the raw material gas reaches the lower limit threshold is several minutes to several tens of minutes, which is a relatively slow speed. Furthermore, based on actual operating results of actual equipment, it was also found that if the gas phase reaction is stopped by an emergency stop, the formation of an explosive mixture disappears immediately. Based on these insights, the lower limit of the eighth reference value can be set to 100% of the set minimum flow. The upper limit of the eighth reference value is preferably higher from the viewpoint of early detection, but 120% is adopted in consideration of a malfunction when conditions change. Threshold of the upper limit and lower limit of the oxygen-containing gas flow rate: State (e1) is a condition that determines the upper limit of the oxygen-containing gas flow rate, based on the viewpoint of detecting an increase in the flow rate caused by an abnormality of the oxygen-containing gas supply system, and detecting an abnormal phenomenon caused From the perspective of increased traffic. However, quantitatively estimating the effects of changes in the oxygen-containing gas flow rate on temperature, pressure, and gas composition requires advancement of each condition, and in many cases it is difficult to actually specify the flow rate value. Therefore, the influence of the case where only the flow rate of the oxygen-containing gas increases is determined by calculation, and the flow rate value is determined. Specifically, if the flow rate of the oxygen-containing gas increases, the oxygen concentration rises, an explosive mixture is formed, and an explosion is caused. If the formation of the explosive mixture is assumed to be abnormal, the hypothetical oxygen-containing gas flow value at which the oxygen concentration in the outflow pipe becomes the limiting oxygen concentration can be calculated. In the state (e1), the value of 85 to 100% of the assumed oxygen-containing gas flow value of the oxygen concentration in the outflow pipe to the limit oxygen concentration is set as the ninth reference value. Regarding the state (e1), the present inventors have studied the dynamic characteristics of the influence of the oxygen-containing gas flow rate on temperature, pressure, and gas composition through simulation. According to this, it is known that the time from the steady state value of the oxygen-containing gas flow to the upper limit threshold is several minutes to several tens of minutes, which is a relatively slow speed. Furthermore, based on actual operating results of actual equipment, it was found that the oxygen-containing gas can be stopped immediately by an emergency stop. Based on these insights, the upper limit of the ninth reference value may be set to 100% of the aforementioned assumed oxygen-containing gas flow value. The lower limit of the ninth reference value is preferably lower from the viewpoint of early detection, but 85% is adopted in consideration of a malfunction when conditions change. State (e2) is a condition that determines the lower limit of the flow rate of the oxygen-containing gas, and is determined based on the viewpoint of detecting a decrease in the flow rate caused by an abnormality of the oxygen-containing gas supply system, and the viewpoint of detecting a decrease in the flow rate that causes an abnormal phenomenon. However, quantitatively estimating the effects of changes in the oxygen-containing gas flow rate on temperature, pressure, and gas composition requires advancement of each condition, and in many cases it is difficult to actually specify the flow rate value. Therefore, the influence of the case where only the flow rate of the oxygen-containing gas is reduced is calculated simply by calculation to determine the flow rate value. Specifically, as the flow rate of the oxygen-containing gas decreases, the oxygen concentration decreases. If the deactivation caused by the reduction of the catalyst in a low-oxygen atmosphere is assumed to be an abnormal phenomenon, the hypothesized raw material gas flow value that becomes the concentration of the catalyst deactivated oxygen can be calculated. In the state (e2), the value of 100 to 120% of the assumed oxygen-containing gas flow rate which becomes the oxygen concentration of the catalyst deactivation is set as the tenth reference value. In addition, as a viewpoint of suppressing other abnormal phenomena generated downstream of the reactor, it can be considered that if the flow rate of the oxygen-containing gas is reduced, a part of the raw material gas cannot react with oxygen in the reactor to become unreacted, and an exhaust gas incineration device in a subsequent step may be considered. In the case of incineration. Since the combustible flammable gas amount is determined based on the viewpoint of the incineration capacity of the exhaust gas incineration device and the treatment of the combustion-generated gas, 100 to 120% of the combustible flammable gas amount can also be used as a reference and used in combination. Regarding the state (e2), the present inventors have studied the dynamic characteristics of the influence of the flow rate of the oxygen-containing gas on the temperature, pressure, and gas composition through simulation. According to this, it is known that the time from the steady-state value of the flow rate of the oxygen-containing gas to the lower limit is several minutes to several tens of minutes, which is a relatively slow speed. Furthermore, based on the actual operating results of actual equipment, it has been found that if the gas phase reaction is stopped by an emergency stop, the deterioration of the catalyst is immediately suppressed by the decrease in temperature and the generation of flammable gas disappears immediately. Based on these insights, the lower limit of the tenth benchmark value can be set to 100% of the minimum flow rate. The upper limit of the tenth reference value is preferably higher from the viewpoint of early detection, but 120% is adopted in consideration of erroneous operation when conditions change. An emergency stop flowchart in states (d1) to (e2) is shown in FIG. 11. As shown in FIG. 11, a plurality of redundant raw material gas flow meters FI and oxygen-containing gas flow meters FI (hereinafter, also collectively referred to as “flow meters FI”) continuously monitor the flow rate in the installation place until the end of the reaction. In FIG. 11, it is judged whether the flow considered to be reliable according to the majority decision method exceeds the upper limit threshold 1 of the flow and enters the yellow area. When entering the yellow area, feedback is provided in the direction of reducing the flow rate and / Or feedforward control. Even with this control, the flow rate continues to increase. When the flow rate considered to be reliable according to the majority decision method exceeds the upper limit threshold 2 of the flow rate and enters the red area, the emergency stop of this embodiment operates. In addition, here, the upper limit threshold 2 is determined in the states (d1) and (e1) as the seventh reference value and the ninth reference value. On the other hand, the redundant flowmeters FI also judge whether the flow considered to be reliable according to the majority decision method exceeds the lower limit of flow threshold 1 and enters the yellow area. When entering the yellow area, , Apply feedback and / or feedforward control in the direction that increases the flow. Even if the flow rate continues to decrease by this control, when the flow rate considered to be reliable according to the majority decision method exceeds the lower flow rate threshold value 2 and enters the red area, the emergency stop of this embodiment operates. Here, the lower limit threshold value 2 is determined as the eighth reference value and the tenth reference value in the states (d2) and (e2). In FIG. 11, the process of judging the states (d2) and (e2) after judging the states (d1) and (e1) of relatively high significance is performed, but there is no particular limitation on this. (Operation when abnormal condition is detected) When any abnormal condition is detected by any one of the abnormality detecting devices, the reactor is operated in the stop direction. From the standpoint of stopping the reaction, the supply of gas to the reactor was blocked. That is, the supply of the raw material gas and the oxygen-containing gas to the reactor is stopped. In addition to the closing of the control valve (CV) that controls the flow, it is preferable to block the gas by closing it. The reason for this is that, assuming a leak from the CV, it is preferable to provide a blocking valve from the standpoint of preventing leakage, and to perform a duplexing in advance. Ensure the destination of the gas flowing from the reactor to prevent the reactor from being pressurized and damaged. Generally, the gas system flowing out of the reactor flows in the order of reactor → quenching tower → absorption tower → exhaust gas incineration facility → atmosphere, but in the case of emergency stop, the blocking valve is automatically actuated to set the reactor → quenching tower → Exhaust gas incineration equipment → atmosphere. The reason why it is not connected to the absorption tower is that there are a plurality of reactors. When the absorption tower is shared, the gas in the unstable state is not introduced into the absorption tower to which the normal reaction-generating gas is connected. The flushing of the gas in the reactor with an inert gas is not necessary, but from the viewpoint of preventing high temperature and performance degradation in the reaction-generating gas atmosphere, it is also possible to clean up the flow-layer catalyst using the reaction-generating gas generated by the inert gas. . When the inert gas is not used to flush the gas in the reactor, the temperature of the reactor decreases after stopping. Therefore, as a countermeasure for the negative pressure of the reactor, it is appropriate to circulate an appropriate amount of inert gas in a manner that does not become a negative pressure. The inert gas is preferably nitrogen. Since the air supplied to the stopped reactor is not necessary, the air compressor is preferably stopped. The supply of the refrigerant to the cooling coil can be maintained as it is. (Reaction) The fluidized-layer gas phase reaction using the fluidized-layer gas-phase reaction apparatus of the present embodiment is not particularly limited, and examples thereof include an oxidation reaction, an ammoxidation reaction, and an alkylation reaction. In addition, the gas-phase reaction may be an exothermic reaction or an endothermic reaction. From the viewpoint of the necessity of an emergency stop in this embodiment, an exothermic reaction is preferred. The reaction raw material is not particularly limited as long as it is a raw material for a gas phase reaction, and examples thereof include alkanes, olefins, alcohols, and aromatic hydrocarbons. Specifically, in the case of the above-mentioned ammonia oxidation reaction, an organic compound such as a hydrocarbon, an oxidant such as oxygen or air, and ammonia can be used as a reaction raw material. Examples of the hydrocarbon that is one of the raw materials for the ammoxidation reaction include alkanes and / or olefins. The organic compound and the oxidant may be used singly or in combination of two or more kinds. The alkane is not particularly limited, and examples thereof include methane, ethane, propane, n-butane, and isobutane. The olefin is not particularly limited, and examples thereof include ethylene, propylene, n-butene, isobutylene, and third butene. Among these, from the viewpoint of the value of the produced nitrile compound as a chemical intermediate raw material, propane and / or isobutane are preferred as the alkane, and propylene and / or isobutene are preferred as the olefin. The catalyst for the gas-phase reaction filled in the reactor is not particularly limited as long as it is a solid catalyst usually used in the reaction, and examples thereof include metal oxides supported on silicon dioxide and the like. catalyst. EXAMPLES Hereinafter, in order to explain the present invention more specifically, simulation results in a case where propylene, ammonia, and air are supplied to a vertical cylindrical flow-layer reactor and the ammoxidation reaction of propylene is performed will be described. However, the present invention is not limited in any way by the following examples. First, the simulation conditions performed are shown in Table 1. In addition, as a fluidized-phase gas phase reaction apparatus, it is assumed that it has the structure of FIG. In addition, as the gas phase reaction, the source gas system is propylene, the other source gas systems are ammonia, and the oxygen-containing system is air, and an ammonia oxidation reaction is assumed. [Table 1] [Example 1] A simulation of the reaction temperature assuming the loss of refrigerant in the cooling coil was performed while maintaining the flow rate of the raw material gas and the air flow under the conditions described in Table 1 above. The refrigerant loss time of the cooling coil is set to 0 min, and the temperature change (solid line) in the reactor from the refrigerant loss of the cooling coil is shown in FIG. 12. If the temperature in the reactor measured by redundant thermometers TI reaches 500 ° C (high reference value (first reference value) of the reaction temperature in Table 1) and reaches the state (a1), the emergency stop operation is performed and The supply of feed gas and air to the reactor was blocked. As a result, the reaction temperature decreased as a dotted line. [Example 2] A simulation assuming a decrease in the supply of propylene was performed under the conditions described in Table 1 above. The transition of the reaction temperature between the case where the reduction of propylene flow is started at 0 min and the case where the flow of propylene is reduced by 1% every 1 minute (solid line) and the case where the flow of propylene is reduced by 5% every 1 minute (dashed line) . If the temperature in the reactor measured by the redundant thermometers TI reaches 410 ° C (the low reference value (second reference value of the reaction temperature in Table 1)) and reaches the state (a2), the emergency stop operation is performed and The supply of feed gas and air to the reactor was blocked. As a result, it was confirmed that the formation of the explosive mixture was eliminated. [Example 3] A simulation was performed under the conditions described in Table 1 above, assuming that the valve at the outlet of the quench tower was closed and the reaction generated gas was not discharged from the reactor. The closing time of the valve at the exit of the quench tower is set to 0 sec, and the pressure change (solid line) in the reactor from the closing of the valve at the exit of the quench tower is shown in FIG. 14. If the pressure in the reactor measured by redundant pressure gauges PI becomes 1.5 kg / cm 2 When G (the high reference value (third reference value) of the reactor pressure in Table 1) reaches the state (b), the emergency stop operation is performed to block the supply of raw material gas and air to the reactor, and the exhaust valve is opened. As a result, the reactor pressure was reduced like a dotted line. [Example 4] A simulation assuming an increase in air supply was performed under the conditions described in Table 1 above. The transition time of the oxygen concentration of the raw material air flow increase starting time is set to 0 min, the example of increasing the air flow by 5% every 1 minute (solid line) and the example of increasing the air flow by 1% (dotted line) 15. If the oxygen concentration measured by the redundant reaction gas analyzer DI becomes 7% (the high reference value of the oxygen concentration in Table 1 (the fourth reference value)) and reaches the state (c1), the emergency stop operation is performed. The supply of raw gas and air to the reactor is blocked. As a result, the oxygen concentration decreases like a chain line. [Comparative Example 1-1] A simulation similar to that of Example 1 was performed except that the high reference value of the reaction temperature was 445 ° C (89% of the threshold value). As a result, although it is within the range of normal operation, the reaction temperature in the reaction step may reach 445 ° C due to fluctuations (fluctuations), and therefore the emergency stop of the reactor may be operated by mistake. [Comparative Example 1-2] A simulation similar to that of Example 1 was performed except that the high reference value of the reaction temperature was 510 ° C (102% of the threshold value). As a result, the material of the reactor may be adversely affected before the emergency stop of the reactor is operated. [Comparative Example 2-1] A simulation similar to Example 2 was performed except that the low reference value of the reaction temperature was set to 350 ° C (97% of the threshold value). As a result, the reaction gas may form an explosive mixture, which may cause fire and explosion in the equipment downstream of the reactor. [Comparative Example 2-2] A simulation similar to that of Example 2 was performed except that the low reference value of the reaction temperature was 435 ° C (121% of the threshold value). As a result, although it is within the range of normal operation, the reaction temperature in the reaction step may reach 435 ° C due to fluctuations (fluctuations), so the emergency stop of the reactor may be operated by mistake. [Comparative Example 3-1] The high reference value of the reactor pressure was set to 1.3 kg / cm 2 Except for G (65% of the threshold), the same simulation as in Example 3 was performed. As a result, although it is within the range of normal operation, the reactor pressure is close to 1.3 kg / cm during the startup and / or shutdown operation of the actual machine operation. 2 In the case of G, the emergency stop of the reactor was operated by mistake. [Comparative Example 3-2] The high reference value of the reactor pressure was set to 1.8 kg / cm 2 Except for G (90% of the threshold), the same simulation as in Example 3 was performed. As a result, if the pressure drop caused by the emergency stop is slow, it may be close to 2.0 kg / cm 2 G (design pressure of the reactor). [Comparative Example 4-1] A simulation similar to that of Example 4 was performed except that the high reference value of the oxygen concentration was set to 4% (33% of the threshold value). As a result, although it is within the range of normal operation, the oxygen concentration may be close to 4% during the start-up and / or shutdown operation of the actual machine operation, and the emergency stop of the reactor may be operated by mistake. [Comparative Example 4-2] A simulation similar to that of Example 4 was performed except that the high reference value of the oxygen concentration was set to 13% (108% of the threshold value). As a result, it was found that the limit oxygen concentration was exceeded before the emergency stop operation was performed, and it was in a state of high possibility of fire and explosion. [Industrial Applicability] The method of the present invention can be effectively used as a method for producing a reaction-producing gas by using a fluid-phase gas-phase reaction device and using a raw material gas. Especially from the viewpoint of safe operation of the fluidized bed gas phase reaction device, it is useful as an emergency stop method of the fluidized bed gas phase reaction device.

1‧‧‧反應器1‧‧‧ reactor

2‧‧‧含氧氣體導入管2‧‧‧ oxygen-containing gas introduction pipe

3‧‧‧含氧氣體分散板3‧‧‧ oxygen-containing gas dispersion plate

4‧‧‧原料氣體導入管4‧‧‧ material gas introduction pipe

5‧‧‧原料氣體分散管5‧‧‧ raw material gas dispersion tube

6‧‧‧冷卻盤管6‧‧‧ cooling coil

7‧‧‧旋風分離器7‧‧‧ cyclone separator

8‧‧‧流出管8‧‧‧ Outflow tube

9a‧‧‧濃厚層9a‧‧‧ thick layer

9b‧‧‧稀薄層9b‧‧‧ thin layer

A‧‧‧含氧氣體A‧‧‧Oxygen-containing gas

B‧‧‧原料氣體B‧‧‧ raw gas

C‧‧‧反應生成氣體C‧‧‧ reaction to generate gas

D‧‧‧另一原料氣體D‧‧‧ Another raw gas

DI‧‧‧反應生成氣體分析器DI‧‧‧Reaction gas analyzer

DI1‧‧‧反應生成氣體分析器DI1‧‧‧Reaction gas analyzer

DI2‧‧‧反應生成氣體分析器DI2‧‧‧Reaction gas analyzer

DI3‧‧‧反應生成氣體分析器DI3‧‧‧Reaction gas analyzer

DI4‧‧‧反應生成氣體分析器DI4‧‧‧Reaction gas analyzer

FI‧‧‧流量指示計FI‧‧‧ Flow Indicator

FI1‧‧‧流量指示計FI1‧‧‧Flow indicator

FI2‧‧‧流量指示計FI2‧‧‧Flow indicator

FI3‧‧‧流量指示計FI3‧‧‧ Flow Indicator

FI4‧‧‧流量指示計FI4‧‧‧Flow indicator

FI5‧‧‧流量指示計FI5‧‧‧ Flow Indicator

FI6‧‧‧流量指示計FI6‧‧‧flow indicator

PI‧‧‧壓力指示計PI‧‧‧Pressure Indicator

PI1‧‧‧壓力指示計PI1‧‧‧pressure indicator

PI2‧‧‧壓力指示計PI2‧‧‧pressure indicator

PI3‧‧‧壓力指示計PI3‧‧‧pressure indicator

TI‧‧‧溫度指示計TI‧‧‧Temperature Indicator

TI1‧‧‧溫度指示計TI1‧‧‧Temperature Indicator

TI2‧‧‧溫度指示計TI2‧‧‧Temperature Indicator

TI3‧‧‧溫度指示計TI3‧‧‧Temperature Indicator

TI4‧‧‧溫度指示計TI4‧‧‧Temperature Indicator

TI5‧‧‧溫度指示計TI5‧‧‧Temperature Indicator

TI6‧‧‧溫度指示計TI6‧‧‧Temperature Indicator

圖1係表示先前技術之流動層氣相反應裝置之概略圖。 圖2係表示本實施形態之流動層氣相反應裝置之一例的概略圖。 圖3係表示另一本實施形態之流動層氣相反應裝置之一例的概略圖。 圖4係表示另一本實施形態之流動層氣相反應裝置之一例的概略圖。 圖5係表示另一本實施形態之小型流動層氣相反應裝置之一例的概略圖。 圖6係表示導致災害現象之現象與異常檢測之一例的概念圖。 圖7係表示較本實施形態之流動層氣相反應裝置之流出管8更靠下游的概念圖。 圖8為條件(a1)及條件(a2)中之緊急停止流程圖。 圖9為條件(b)中之緊急停止流程圖。 圖10係於在條件(c)中監視氧濃度之情形之緊急停止流程圖。 圖11為條件(d1)〜(e2)中之緊急停止流程圖。 圖12係表示實施例1之模擬結果之曲線圖。 圖13係表示實施例2之模擬結果之曲線圖。 圖14係表示實施例3之模擬結果之曲線圖。 圖15係表示實施例4之模擬結果之曲線圖。FIG. 1 is a schematic diagram showing a fluidized bed gas phase reaction apparatus of the prior art. FIG. 2 is a schematic diagram showing an example of a fluidized bed gas phase reaction apparatus according to this embodiment. Fig. 3 is a schematic diagram showing an example of a fluidized bed gas phase reaction apparatus according to another embodiment. FIG. 4 is a schematic view showing an example of a fluidized-phase gas phase reaction apparatus according to another embodiment. FIG. 5 is a schematic diagram showing an example of a small-scale fluidized-bed gas-phase reaction apparatus according to this embodiment. FIG. 6 is a conceptual diagram showing an example of a phenomenon that causes a disaster phenomenon and abnormal detection. FIG. 7 is a conceptual diagram showing a downstream side of the outflow pipe 8 of the fluidized-bed gas-phase reaction apparatus of this embodiment. FIG. 8 is a flowchart of the emergency stop in the condition (a1) and the condition (a2). Fig. 9 is a flowchart of the emergency stop in the condition (b). Fig. 10 is a flowchart of an emergency stop in the case where the oxygen concentration is monitored in the condition (c). FIG. 11 is a flowchart of the emergency stop in the conditions (d1) to (e2). FIG. 12 is a graph showing simulation results of Example 1. FIG. FIG. 13 is a graph showing a simulation result of Example 2. FIG. FIG. 14 is a graph showing a simulation result of Example 3. FIG. FIG. 15 is a graph showing a simulation result of Example 4. FIG.

Claims (10)

一種反應生成氣體之製造方法，其係使用流動層氣相反應裝置而利用原料氣體製造反應生成氣體之方法，且 上述流動層氣相反應裝置具有：反應器，其可流動地收納觸媒；第一供給管，其向上述反應器中供給上述原料氣體；流出管，其自上述反應器中排出上述反應生成氣體；冗餘之複數個溫度計TI，該等係設置於上述反應器；冗餘之複數個壓力計PI，該等係位於上述反應器之稀薄層部；及冗餘之複數個反應生成氣體分析器DI，該等係位於上述流出管之下游；並且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第一至第六基準值之各者之實測值下，產生下述(a1)至(c3)之6種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟， (a1)將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值，顯示大於第一基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (a2)將觸媒之活性降低而未反應增加，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值，顯示小於第二基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (b)將反應器之設計壓力之70〜85%之值設為第三基準值，顯示大於第三基準值之實測值之上述壓力計PI之數量超過壓力計PI之總數的過半數之狀態 (c1)將爆炸極限氧濃度之40〜100%之值設為第四基準值，顯示大於第四基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c2)將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值，顯示小於第五基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c3)將原料氣體濃度之設計值之150〜300%之值設為第六基準值，顯示大於第六基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態。A method for producing a reaction-generating gas is a method for producing a reaction-generating gas by using a fluid-phase gas-phase reaction device and using a raw material gas, and the fluid-phase gas-phase reaction device has a reactor that can accommodate a catalyst in a flowable manner; A supply pipe that supplies the above-mentioned raw material gas to the reactor; an outflow pipe that discharges the above-mentioned reaction-produced gas from the reactor; a plurality of redundant thermometers TI, which are arranged in the reactor; and a redundant one A plurality of pressure gauges PI, which are located in the thin layer portion of the above-mentioned reactor; and a redundant plurality of reaction-producing gas analyzers DI, which are located downstream of the above-mentioned outflow pipe; and the manufacturing method includes: In the reactor, in the reaction step of supplying the above-mentioned raw material gas to the gas-phase reaction in the presence of the above-mentioned catalyst, the following measured values are monitored with respect to each of the following first to sixth reference values to produce the following ( In the case of at least one of the six states from a1) to (c3), the operation of the fluidized-phase gas phase reaction device is performed by blocking at least the first supply pipe. The stopping step of emergency stop, (a1) Set the value of 90 ~ 100% of the lower one of the design temperature of the reactor or the highest temperature determined based on the viewpoint of protecting the catalyst as the first reference value, and display The state where the number of the above-mentioned thermometers TI which is greater than the measured value of the first reference value exceeds more than half of the total number of thermometers TI (a2) reduces the activity of the catalyst without increasing the reaction, and the temperature at which an explosive mixture is formed in the reactor is The value of 100 ~ 120% of any higher temperature at which abnormal combustion occurs in the downstream machine is set as the second reference value, and the number of the above-mentioned thermometers TI, which shows the measured value less than the second reference value, exceeds the total number of the thermometers TI (B) Set the value of 70 ~ 85% of the design pressure of the reactor to the third reference value, and the number of the above-mentioned pressure gauge PI that exceeds the measured value of the third reference value exceeds the total number of pressure gauge PI More than half of the states (c1) set the value of 40 to 100% of the explosive limit oxygen concentration as the fourth reference value, and the number of the above-mentioned reaction generated gas analyzer DI exceeding the measured value of the fourth reference value exceeds the reaction generated gas The state (c2) of more than half of the total number of analyzer DI sets the value of 100 to 120% of the concentration of oxygen that reduces the degradation of the catalyst as the fifth reference value, and the above-mentioned reaction generation that shows the measured value less than the fifth reference value is generated A state where the number of gas analyzer DI exceeds more than half of the total number of reaction-produced gas analyzer DI (c3) Set a value of 150 to 300% of the design value of the raw material gas concentration as the sixth reference value, and display greater than the sixth reference value It is a state where the number of the above-mentioned reaction-generating gas analyzer DI of the measured value exceeds more than half of the total number of the reaction-generating gas analyzer DI. 如請求項1之製造方法，其中上述流動層氣相反應裝置進而具有冗餘之複數個原料氣體流量計FI，該等係設置於上述第一供給管；且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第七至第八基準值之各者之實測值下，產生下述(d1)至(d2)之2種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟， (d1)將成為觸媒失活之氧濃度之假定原料氣體流量值、成為反應器之設計溫度之假定原料氣體流量值、及成為觸媒劣化之溫度之假定原料氣體流量值中之最低之流量值的85〜100%之值設為第七基準值，顯示大於第七基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 (d2)將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值，顯示小於第八基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形。For example, the manufacturing method of claim 1, wherein the fluidized-phase gas phase reaction device further has a plurality of redundant raw material gas flow meters FI, which are provided in the first supply pipe; and the manufacturing method includes: In the device, in the reaction step of supplying the above-mentioned raw material gas to the gas-phase reaction in the presence of the above-mentioned catalyst, the following (d1) is generated by monitoring the actual measured values with respect to each of the following seventh to eighth reference values. In the case of at least one of the two states of (d2) to (d2), a stopping step is performed to stop the operation of the fluidized-phase gas phase reaction apparatus by stopping at least the first supply pipe, (d1 ) Will be the lowest of the assumed raw material gas flow value that will become the catalyst's deactivated oxygen concentration, the assumed raw material gas flow value that will be the design temperature of the reactor, and the assumed raw material gas flow value that will be the temperature at which the catalyst will deteriorate. The value of 85 to 100% is set as the seventh reference value, and the case where the number of the above-mentioned raw material gas flow meter FI which exceeds the actual measured value of the seventh reference value exceeds more than half of the total number of the raw material gas flow meter FI (d2) will flow out The value of 100 to 120% of the assumed raw material gas flow value of the oxygen concentration in the tube as the limit oxygen concentration is set to the eighth reference value, and the number of the above-mentioned raw material gas flow meter FI showing the measured value less than the eighth reference value exceeds the raw material gas. In the case of more than half of the total number of flow meters FI. 如請求項1或2之製造方法，其中上述流動層氣相反應裝置進而具有：第二供給管，其向上述反應器中供給含氧氣體；及冗餘之複數個含氧氣體流量計FI，該等係設置於上述第二供給管；且 該製造方法包括：於在上述反應器內，於上述觸媒之存在下將上述原料氣體供於氣相反應之反應步驟中，於監視相對於下述第九至第十基準值之各者之實測值下，產生下述(e1)至(e2)之2種狀態中之至少1種狀態之情形時，進行藉由至少阻斷上述第一供給管、或上述第一供給管及上述第二供給管，而使上述流動層氣相反應裝置之運轉緊急停止之停止步驟， (e1)將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值，顯示大於第九基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 (e2)將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值，顯示小於第十基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形。The manufacturing method according to claim 1 or 2, wherein the fluidized-phase gas-phase reaction device further includes: a second supply pipe that supplies an oxygen-containing gas to the reactor; and a plurality of redundant oxygen-containing gas flow meters FI, These are provided in the second supply pipe; and the manufacturing method includes: in the reaction step of supplying the raw material gas to a gas phase reaction in the presence of the catalyst in the reactor, and monitoring the relative When at least one of the following two states (e1) to (e2) occurs under the actual measured values of each of the ninth to tenth reference values, at least the first supply is blocked by Or the first supply pipe and the second supply pipe to stop the operation of the fluidized-phase gas phase reaction apparatus in an emergency stop step, (e1) assuming that the oxygen concentration in the outflow pipe is the limit oxygen concentration When the value of 85 to 100% of the gas flow value is set as the ninth reference value, and the number of the above-mentioned oxygen-containing gas flow meter FI that exceeds the measured value of the ninth reference value exceeds more than half of the total number of oxygen-containing gas flow meters FI2 (e2) will become a catalyst loss The oxygen concentration of 100 to 120% of the oxygen-containing gas flow rate is set to the tenth reference value, and the number of the above-mentioned oxygen-containing gas flow meter FI, which shows an actual measured value less than the tenth reference value, exceeds that of the oxygen-containing gas flow meter FI2. In the case of more than half of the total. 如請求項1至3中任一項之製造方法，其中上述原料氣體包含烷烴及/或烯烴。The production method according to any one of claims 1 to 3, wherein the raw material gas contains an alkane and / or an olefin. 如請求項4之製造方法，其中上述烷烴為丙烷及/或異丁烷。The method according to claim 4, wherein the alkane is propane and / or isobutane. 如請求項4之製造方法，其中上述烯烴為丙烯及/或異丁烯。The method according to claim 4, wherein the olefin is propylene and / or isobutylene. 如請求項1至6中任一項之製造方法，其中上述氣相反應為氨氧化反應。The manufacturing method according to any one of claims 1 to 6, wherein the gas-phase reaction is an ammoxidation reaction. 一種流動層氣相反應裝置，其具有：反應器，其可流動地收納觸媒；第一供給管，其向上述反應器中供給原料氣體；流出管，其自上述反應器中排出反應生成氣體；冗餘之複數個溫度計TI，該等係設置於上述反應器；冗餘之複數個壓力計PI，該等係位於上述反應器之稀薄層部；冗餘之複數個反應生成氣體分析器DI，該等係位於上述流出管之下游；及緊急反應停止控制部；且 於監視相對於下述第一至第六基準值之各者之實測值下，產生下述(a1)至(c3)之6種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止者， (a1)將反應器之設計溫度或基於保護觸媒之觀點而決定之最高溫度中之任一較低之溫度的90〜100%之值設為第一基準值，顯示大於第一基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (a2)將觸媒之活性降低從而未反應增加，於反應器中形成爆炸混合氣之溫度或於下游機器中發生異常燃燒之溫度中之任一較高之溫度的100〜120%之值設為第二基準值，顯示小於第二基準值之實測值之上述溫度計TI之數量超過溫度計TI之總數的過半數之狀態 (b)將反應器之設計壓力之70〜85%之值設為第三基準值，顯示大於第三基準值之實測值之上述壓力計PI之數量超過壓力計PI之總數的過半數之狀態 (c1)將爆炸極限氧濃度之40〜100%之值設為第四基準值，顯示大於第四基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c2)將產生觸媒之還原劣化之氧濃度之100〜120%之值設為第五基準值，顯示小於第五基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態 (c3)將原料氣體濃度之設計值之150〜300%之值設為第六基準值，顯示大於第六基準值之實測值之上述反應生成氣體分析器DI之數量超過反應生成氣體分析器DI之總數的過半數之狀態。A fluidized layer gas-phase reaction device includes a reactor that can accommodate a catalyst in a flowable manner, a first supply pipe that supplies a raw material gas to the reactor, and an outflow pipe that discharges a reaction-produced gas from the reactor. ; Redundant multiple thermometers TI, these are installed in the above-mentioned reactor; redundant multiple pressure gauges PI, these are located in the thin layer part of the above-mentioned reactor; redundant multiple reactions generate a gas analyzer DI These are located downstream of the above-mentioned outflow pipe; and the emergency response stop control section; and under monitoring the actual measured values with respect to each of the first to sixth reference values described below, the following (a1) to (c3) are generated In the case of at least one of the six states, the emergency response stop control section is to stop the operation of the fluidized-phase gas phase reaction device by stopping at least the first supply pipe, (a1) Set the value of 90 ~ 100% of the lower one of the design temperature of the reactor or the highest temperature determined based on the viewpoint of protecting the catalyst as the first reference value, and display the measured value greater than the first reference value. Above thermometer T The state where the number of I exceeds more than half of the total number of thermometers TI (a2) reduces the activity of the catalyst and increases the unreaction, either the temperature at which an explosive mixture is formed in the reactor or the temperature at which abnormal combustion occurs in downstream equipment A value of 100 to 120% of a higher temperature is set as a second reference value, and a state where the number of the above-mentioned thermometer TI is smaller than the measured value of the second reference value exceeds more than half of the total number of thermometers TI (b) the reactor The value of 70 to 85% of the design pressure is set as the third reference value, and the state where the number of the above-mentioned pressure gauge PI is greater than the measured value of the third reference value exceeds more than half of the total number of pressure gauge PI (c1) will explode the limit A value of 40 to 100% of the oxygen concentration is set as a fourth reference value, and a state in which the number of the above-mentioned reaction-produced gas analyzer DI exceeds the total value of the reaction-produced gas analyzer DI by more than the actual measured value of the fourth reference value ( c2) Set the value of 100 to 120% of the oxygen concentration of the catalyst that reduces the degradation to the fifth reference value, and the number of the above-mentioned reaction generated gas analyzer DI that exceeds the measured value of the fifth reference value exceeds the reaction generated gas The state (c3) of more than half of the total number of analyzers DI sets the value of 150 to 300% of the design value of the raw material gas concentration as the sixth reference value, and displays the above-mentioned reaction generated gas analyzer with the measured value greater than the sixth reference value. A state where the number of DI exceeds more than half of the total number of reaction-producing gas analyzer DI. 如請求項8之流動層氣相反應裝置，其中上述流動層氣相反應裝置進而具有冗餘之複數個原料氣體流量計FI，該等係設置於上述第一供給管；且 於監視相對於下述第七至第八基準值之各者之實測值下，產生下述(d1)至(d2)之2種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管，而使上述流動層氣相反應裝置之運轉緊急停止者， (d1)將成為觸媒失活之氧濃度之假定原料氣體流量值、成為反應器之設計溫度之假定原料氣體流量值、及成為觸媒劣化之溫度之假定原料氣體流量值中之最低之流量值的85〜100%之值設為第七基準值，顯示大於第七基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形 (d2)將流出管中之氧濃度成為極限氧濃度之假定原料氣體流量值的100〜120%之值設為第八基準值，顯示小於第八基準值之實測值之上述原料氣體流量計FI之數量超過原料氣體流量計FI之總數的過半數之情形。For example, the fluidized bed gas phase reaction device of claim 8, wherein the fluidized bed gas phase reaction device further has a plurality of redundant raw material gas flow meters FI, which are arranged on the first supply pipe; When at least one of the following two states (d1) to (d2) occurs under the actual measured values of each of the seventh to eighth reference values, the above-mentioned emergency response stop control unit is at least If the first supply pipe is blocked and the operation of the fluidized-phase gas phase reaction device is stopped urgently, (d1) the assumed raw material gas flow value of the oxygen concentration of the catalyst deactivation, and the assumed design temperature of the reactor The raw material gas flow value and the value of 85 to 100% of the lowest flow value of the assumed raw material gas flow value which is the temperature at which the catalyst deteriorates is set as the seventh reference value, and the above-mentioned raw material showing an actual measured value greater than the seventh reference value is displayed. In the case where the number of gas flow meters FI exceeds more than half of the total number of raw material gas flow meters FI (d2), the value of 100 to 120% of the assumed raw material gas flow value of the oxygen concentration in the outflow pipe to the limit oxygen concentration is set to eighth base Value, the display smaller than the number of the raw material gas flow meter FI Found exceeds the reference value on the eighth case of the majority of the total feed gas flow meter FI. 如請求項8或9之流動層氣相反應裝置，其中上述流動層氣相反應裝置進而具有：第二供給管，其向上述反應器中供給含氧氣體；及冗餘之複數個含氧氣體流量計FI，該等係設置於上述第二供給管；且 於監視相對於下述第九至第十基準值之各者之實測值下，產生下述(e1)至(e2)之2種狀態中之至少1種狀態之情形時，上述緊急反應停止控制部係藉由至少阻斷上述第一供給管、或上述第一供給管及上述第二供給管，而使上述流動層氣相反應裝置之運轉緊急停止者， (e1)將流出管中之氧濃度成為極限氧濃度之假定含氧氣體流量值的85〜100%之值設為第九基準值，顯示大於第九基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形 (e2)將成為觸媒失活之氧濃度之假定含氧氣體流量的100〜120%之值設為第十基準值，顯示小於第十基準值之實測值之上述含氧氣體流量計FI之數量超過含氧氣體流量計FI2之總數的過半數之情形。The fluidized-phase gas phase reaction device according to claim 8 or 9, wherein the fluidized-phase gas phase reaction device further includes: a second supply pipe that supplies an oxygen-containing gas to the reactor; and a plurality of redundant oxygen-containing gases Flowmeters FI, which are installed in the above-mentioned second supply pipe; and monitor the actual measured values with respect to each of the following ninth to tenth reference values to produce two of the following (e1) to (e2) In the case of at least one of the states, the emergency response stop control unit causes the fluid layer gas phase reaction by blocking at least the first supply pipe, or the first supply pipe and the second supply pipe. For the emergency stop of the operation of the device, (e1) Set the value of 85 to 100% of the assumed oxygen-containing gas flow value of the oxygen concentration in the outflow pipe to the limit oxygen concentration as the ninth reference value, and display the measured value greater than the ninth reference value. If the number of the above-mentioned oxygen-containing gas flow meter FI exceeds more than half of the total number of oxygen-containing gas flow meter FI2 (e2), it will become a value of 100 to 120% of the assumed oxygen-containing gas flow rate of the oxygen concentration of the catalyst inactivation. Set as the tenth reference value, display less than tenth base In the case where the actual value of the standard value of the oxygen-containing gas flow meter FI exceeds more than half of the total number of the oxygen-containing gas flow meter FI2.
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