TWI590872B - A fluidized bed reactor and a method for producing a nitrile compound using the same - Google Patents
A fluidized bed reactor and a method for producing a nitrile compound using the same Download PDFInfo
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- TWI590872B TWI590872B TW104112157A TW104112157A TWI590872B TW I590872 B TWI590872 B TW I590872B TW 104112157 A TW104112157 A TW 104112157A TW 104112157 A TW104112157 A TW 104112157A TW I590872 B TWI590872 B TW I590872B
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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
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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
- B01J8/1872—Details of the fluidised bed reactor
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- 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
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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- 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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- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00946—Features relating to the reactants or products
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本發明是有關於一種流化床反應器，詳細而言是有關於一種在其內部防止觸媒粒子的堆積的流化床反應器及使用其的腈化合物的製造方法。 The present invention relates to a fluidized bed reactor, and more particularly to a fluidized bed reactor for preventing accumulation of catalyst particles therein and a method for producing a nitrile compound using the same.
流化床反應器用於各種工業反應。例如丙烯腈等腈化合物是利用丙烯等烴的氨氧化法(ammoxidation)而工業地製造。作為腈化合物的製造方法，通常已知有在金屬氧化物觸媒的存在下進行氣相氧化反應的方法。記載有該氣相氧化反應是將原料的烴、氨、及空氣等含氧氣體導入至反應器，在所述金屬氧化物觸媒的存在下進行氨氧化反應而製造腈化合物(專利文獻1、專利文獻2)。專利文獻1、專利文獻2中所使用的反應器為流化床反應器，在反應器的內部填充有所述觸媒，且在反應器的內壁通常具有人孔(manhole)或溫度計***孔等各種尺寸大小的凹部，該人孔用於檢查，該溫度計***孔用於將熱電偶溫度計***反應器內。此外，在專利文獻1、專利文獻2中所使用的反應器等流化床反應器的內部填充有所述觸媒，且通常具有梁、支柱(support)或旋風分離器(cyclone)上部等反應器內部的突出部。 Fluidized bed reactors are used in a variety of industrial reactions. For example, a nitrile compound such as acrylonitrile is industrially produced by ammoxidation of a hydrocarbon such as propylene. As a method for producing a nitrile compound, a method of performing a gas phase oxidation reaction in the presence of a metal oxide catalyst is generally known. In the gas phase oxidation reaction, an oxygen-containing gas such as a hydrocarbon, ammonia, or air of a raw material is introduced into a reactor, and an ammoxidation reaction is carried out in the presence of the metal oxide catalyst to produce a nitrile compound (Patent Document 1) Patent Document 2). The reactor used in Patent Document 1 and Patent Document 2 is a fluidized bed reactor in which the catalyst is filled, and the inner wall of the reactor usually has a manhole or a thermometer insertion hole. A recess of various sizes is used for inspection, and the thermometer insertion hole is used to insert a thermocouple thermometer into the reactor. Further, the fluidized bed reactor such as a reactor used in Patent Document 1 and Patent Document 2 is filled with the catalyst, and usually has a reaction such as a beam, a support, or a cyclone. a protrusion inside the device.
在流化床反應器的所述凹部及所述突出部，容易堆積所述金屬氧化物觸媒。 The metal oxide catalyst is easily deposited in the concave portion and the protruding portion of the fluidized bed reactor.
若在反應器的內部，觸媒堆積於凹部、突出部等，有如下情況：無法順利進行排熱，而在反應器內產生熱點(hotspot)，導致觸媒粒子的堆積部的反應器的材質劣化、噴嘴(nozzle)等的材質腐蝕。而且，有如下情況：因觸媒粒子堆積而導致觸媒粒子還原劣化，使目標的反應產量下降等，對氣相氧化反應產生不良影響。此外，當停止本反應並將人孔等所述凹部等開放時，有堆積的觸媒粒子接觸外部空氣後產生急遽的氧化反應而發熱的情況。 In the inside of the reactor, the catalyst is deposited on the concave portion, the protruding portion, and the like, and there is a case where the heat is not generated smoothly, and a hot spot is generated in the reactor, and the material of the reactor in which the catalyst particles are deposited is caused. Corrosion, material such as nozzles are corroded. Further, there is a case where the catalyst particles are reduced in the reduction due to the accumulation of the catalyst particles, and the target reaction yield is lowered, which adversely affects the gas phase oxidation reaction. In addition, when the reaction is stopped and the concave portion or the like such as a manhole is opened, the accumulated catalyst particles may contact the outside air to generate a rapid oxidation reaction and generate heat.
作為消除所述凹部等工業裝置的死空間(dead space)的一般方法，例如提出有在丙烯腈的工業製造製程(process)中，向脫氫氰酸脫水塔的死空間(人孔)***芯子(專利文獻3)。記載有利用專利文獻3中所使用的芯子，可防止丙烯腈及氫氰酸長時間滯留於所述死空間而產生聚合的情況。 As a general method for eliminating the dead space of an industrial device such as a recess, for example, it is proposed to insert a core into a dead space (manhole) of a dehydrocyanic acid dehydration column in an industrial manufacturing process of acrylonitrile. Child (Patent Document 3). The core used in Patent Document 3 is described, and it is possible to prevent acrylonitrile and hydrocyanic acid from staying in the dead space for a long time to cause polymerization.
[專利文獻1]日本公開專利公報「日本專利特開2005-193172號公報」 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-193172
[專利文獻2]日本公開專利公報「日本專利特開2006-247452號公報」 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2006-247452
[專利文獻3]日本公開專利公報「日本專利特開2007-39403 號公報」 [Patent Document 3] Japanese Laid-Open Patent Publication "Japanese Patent Laid-Open No. 2007-39403 Bulletin
然而，專利文獻3的方法中，關於自裝置內壁側安裝於脫氫氰酸脫水塔的人孔的芯子使用何種芯子為佳、如何設置可較佳地消除死空間，並無具體揭示，亦無通用方面的暗示。因此，需求如下對策：用於防止觸媒堆積於流化床反應器的內壁的凹部，而防止裝置的劣化或對反應的不良影響。 However, in the method of Patent Document 3, it is preferable to use a core for the core of the manhole attached to the dehydrocyanic acid dehydration tower from the inner wall side of the apparatus, and how to set it is preferable to eliminate the dead space, and there is no specific Revealed, there is no general implication. Therefore, there is a demand for a countermeasure for preventing the catalyst from accumulating in the concave portion of the inner wall of the fluidized bed reactor, thereby preventing deterioration of the device or adverse effect on the reaction.
另外，需求如下對策：用於防止觸媒粒子堆積於流化床反應器的內部的突出部，而防止裝置的材質劣化或對反應的不良影響。 Further, there is a demand for a countermeasure for preventing the catalyst particles from accumulating in the inside of the fluidized bed reactor, thereby preventing deterioration of the material of the apparatus or adverse effects on the reaction.
因此，本發明要解決所述以往的問題點，目的在於防止觸媒堆積於反應器的內壁的凹部，而防止裝置的劣化或對反應的不良影響。進而，目的在於防止堆積於反應器的內壁的凹部的觸媒因接觸外部空氣而急遽發熱。此外，本發明的目的在於防止觸媒粒子堆積於反應器內部的突出部，而防止裝置的材質劣化或對反應的不良影響。進而，目的在於防止堆積於反應器的突出部的觸媒粒子因接觸外部空氣而急遽發熱。 Accordingly, the present invention has been made to solve the above conventional problems, and an object thereof is to prevent a catalyst from accumulating in a concave portion of an inner wall of a reactor, thereby preventing deterioration of the device or adverse effect on the reaction. Further, it is an object of the invention to prevent the catalyst deposited in the concave portion of the inner wall of the reactor from being heated by the contact with the outside air. Further, an object of the present invention is to prevent the catalyst particles from accumulating in the protruding portion inside the reactor, and to prevent deterioration of the material of the device or adverse effects on the reaction. Further, it is an object of the invention to prevent the catalyst particles deposited on the protruding portion of the reactor from being heated rapidly by contact with the outside air.
本發明者發現，對於在流化床反應器的觸媒會接觸的反應器的內壁所設有的凹部，藉由設置觸媒堆積防止部件，可防止觸媒堆積於反應器的內壁的凹部，而防止裝置的劣化或對反應的 不良影響。而且發現，若設置觸媒堆積防止部件，可防止堆積於反應器的內壁的凹部的觸媒因接觸外部空氣而急遽發熱，從而解決所述課題。進而發現，藉由不在反應器的內壁形成凹部，亦可同樣地解決所述課題。 The present inventors have found that it is possible to prevent the catalyst from accumulating on the inner wall of the reactor by providing a catalyst accumulation preventing member for the concave portion provided in the inner wall of the reactor in which the catalyst of the fluidized bed reactor contacts. Concave, while preventing deterioration of the device or reaction Bad effects. Further, it has been found that by providing the catalyst deposition preventing member, it is possible to prevent the catalyst deposited in the concave portion of the inner wall of the reactor from being heated by contact with the outside air, thereby solving the above problem. Further, it has been found that the problem can be solved similarly by not forming a concave portion on the inner wall of the reactor.
另外，本發明者發現，對於在流化床反應器的觸媒粒子 會接觸的反應器內部的突出部或反應器內部的附帶裝置的水平部，藉由設置觸媒粒子的堆積防止部件，可防止觸媒粒子堆積於反應器內部的突出部或反應器內部的附帶裝置的水平部，而防止裝置的材質劣化或對反應的不良影響。進而發現，可防止堆積於反應器內部的突出部或反應器內部的附帶裝置的水平部的觸媒粒子因接觸外部空氣而急遽發熱，從而解決所述課題。 Additionally, the inventors have discovered that for catalyst particles in a fluidized bed reactor The protruding portion inside the reactor to be contacted or the horizontal portion of the attached device inside the reactor can prevent the catalyst particles from accumulating in the protruding portion inside the reactor or the inside of the reactor by providing the deposition preventing member of the catalyst particles. The horizontal portion of the device prevents deterioration of the material of the device or adverse effects on the reaction. Further, it has been found that it is possible to prevent the catalyst particles deposited in the inside of the reactor or the catalyst particles in the horizontal portion of the accessory device inside the reactor from being heated by contact with the outside air, thereby solving the above problem.
即，本發明是一種流化床反應器，是收納流化床的觸媒 粒子的反應器，且在所述反應器內的觸媒粒子會接觸的反應器的內壁不設有凹部，或者在設有的凹部設置堆積防止部件。 That is, the present invention is a fluidized bed reactor, which is a catalyst for containing a fluidized bed. In the reactor of the particles, the inner wall of the reactor in which the catalyst particles in the reactor are in contact with each other is not provided with a concave portion, or a deposition preventing member is provided in the recess provided.
另外，本發明如所述流化床反應器，其中所述堆積防止 部件包含封入材料，所述封入材料填充於所述凹部內。 Further, the present invention is as described in the fluidized bed reactor, wherein the accumulation prevention The component includes an encapsulating material that is filled within the recess.
另外，本發明如所述流化床反應器，其中所述堆積防止 部件包含：內蓋，材質與所述反應器的內壁相同；隔熱材料，填充於所述內蓋與所述反應器之間；以及封入材料，包含水泥(cement)且填充所述凹部的剩餘間隙。 Further, the present invention is as described in the fluidized bed reactor, wherein the accumulation prevention The component comprises: an inner cover having the same material as the inner wall of the reactor; an insulating material filled between the inner cover and the reactor; and a sealing material comprising a cement and filling the recess The remaining gap.
另外，本發明如所述流化床反應器，其中所述內蓋為碳 鋼(carbon steel)或者不鏽鋼(stainless steel)。 Further, the present invention is the fluidized bed reactor, wherein the inner cap is carbon Carbon steel or stainless steel.
另外，本發明如所述流化床反應器，其中調整成在設於所述凹部的堆積防止部件與反應器內壁面之間無階差。 Further, the present invention is the fluidized bed reactor, wherein the step is such that there is no step difference between the deposition preventing member provided in the concave portion and the inner wall surface of the reactor.
另外，本發明如所述流化床反應器，其中所述堆積防止部件為氣體吹入口，對所述凹部吹入氣體。 Further, the present invention is the fluidized bed reactor, wherein the deposition preventing member is a gas blowing inlet, and a gas is blown into the concave portion.
另外，本發明如所述流化床反應器，其中所述堆積防止部件是將所述突出部的上部以向上凸的傾斜構造或者向上凸的曲面構造而構成。 Further, according to the present invention, in the fluidized bed reactor, the stacking preventing member is configured by an upper portion of the protruding portion having an upwardly convex inclined structure or an upward convex curved surface structure.
另外，本發明如所述流化床反應器，其中突出部的上部構成的材質與所述反應器的內壁相同。 Further, the present invention is the fluidized bed reactor wherein the upper portion of the protruding portion is made of the same material as the inner wall of the reactor.
另外，本發明如所述流化床反應器，其中所述堆積防止部件是對所述突出部吹送氣體。 Further, the present invention is the fluidized bed reactor, wherein the accumulation preventing member blows gas to the protruding portion.
另外，本發明如所述流化床反應器，其中所述突出部為碳鋼或者不鏽鋼。 Further, the present invention is the fluidized bed reactor, wherein the protrusion is carbon steel or stainless steel.
此外，本發明是一種腈化合物的製造方法，使用所述流化床反應器，一面防止觸媒粒子堆積於反應器內所設有的、所述反應器內的觸媒粒子會接觸的突出部或者凹部，一面進行氨氧化反應。 Further, the present invention is a method for producing a nitrile compound, which uses the fluidized bed reactor to prevent a catalyst particle from being deposited in a protrusion provided in a reactor and in which a catalyst particle in the reactor is in contact with each other. Or the concave portion is subjected to an ammoxidation reaction.
若使用本發明的流化床反應器進行氧化反應，觸媒不會堆積於凹部，因此，可防止裝置的劣化或對反應的不良影響。 When the oxidation reaction is carried out using the fluidized bed reactor of the present invention, the catalyst does not accumulate in the concave portion, and therefore deterioration of the apparatus or adverse effect on the reaction can be prevented.
進而，在用於氨氧化反應的含有鉬的金屬氧化物觸媒等的情況下，當使反應停止並將反應器開放時，有接觸於反應器且 還原劣化的堆積觸媒接觸外部空氣而被氧化，發熱至150℃左右的情況，但藉由設置所述堆積防止部件或者不設有凹部，可防止觸媒的高溫發熱。 Further, in the case of a molybdenum-containing metal oxide catalyst used for the ammoxidation reaction, when the reaction is stopped and the reactor is opened, there is contact with the reactor and The reduced deposition catalyst is oxidized by contact with the outside air and is heated to about 150 ° C. However, by providing the deposition preventing member or not providing the concave portion, high temperature heat generation of the catalyst can be prevented.
另外，若使用本發明的流化床反應器進行氣相氧化反 應，觸媒粒子不會堆積於反應器內的突出部或反應器內部的附帶裝置的水平部，因此，可防止裝置的材質劣化或對反應的不良影響。 In addition, if the fluidized bed reactor of the present invention is used for gas phase oxidation reaction Therefore, the catalyst particles are not deposited on the protruding portion in the reactor or the horizontal portion of the accessory inside the reactor, and therefore, deterioration of the material of the device or adverse effect on the reaction can be prevented.
進而，在使用含有鉬的金屬氧化物觸媒進行氨氧化反應 的情況下，當使反應停止並將反應器開放時，有接觸於反應器且還原劣化的堆積觸媒接觸外部空氣而被急遽氧化，發熱至150℃左右的情況，但藉由設置所述堆積防止部件，可防止觸媒的高溫發熱。 Further, ammoxidation reaction is carried out using a metal oxide catalyst containing molybdenum In the case where the reaction is stopped and the reactor is opened, the deposition catalyst that has come into contact with the reactor and is reduced in reductiveness is exposed to the outside air and is rapidly oxidized to heat up to about 150 ° C. However, the deposition is performed by the deposition. Prevents parts from preventing high temperature heat generation of the catalyst.
11、111‧‧‧反應器本體 11, 111‧‧‧Reactor body
12、112‧‧‧空氣導入管 12, 112‧‧‧ air induction tube
13、113‧‧‧吹出口 13, 113‧‧‧ blown out
14、114‧‧‧觸媒 14, 114‧‧‧ catalyst
15、115‧‧‧原料導入管 15, 115‧‧‧ raw material introduction tube
16、116‧‧‧冷卻線圈 16, 116‧‧‧ Cooling coil
17、117‧‧‧製品抽出管 17, 117‧‧‧ product extraction tube
18、118‧‧‧熱交換器 18, 118‧‧‧ heat exchanger
19、119‧‧‧旋風分離器 19, 119‧‧ Cyclone separator
20、121‧‧‧凹部(人孔) 20, 121‧‧‧ recess (manhole)
21、122‧‧‧外蓋 21, 122‧‧‧ Cover
22‧‧‧凹部周壁 22‧‧‧ recessed wall
23‧‧‧凹部周緣 23‧‧‧The periphery of the recess
31‧‧‧內蓋 31‧‧‧ Inner cover
32‧‧‧隔熱材料 32‧‧‧Insulation materials
33‧‧‧封入材料 33‧‧‧Enclosed materials
41‧‧‧氣體吹入口 41‧‧‧ gas blowing inlet
120‧‧‧水平的突出部 120‧‧‧ horizontal projections
131‧‧‧突出部(梁) 131‧‧‧Protruding section (beam)
132‧‧‧三角材料 132‧‧‧Triangular materials
133‧‧‧寬度狹窄的突出部(梁) 133‧‧ ‧ narrow width projections (beams)
134‧‧‧三角材料 134‧‧‧Triangular materials
135‧‧‧支柱(支柱部) 135‧‧‧ pillars (pillars)
136‧‧‧寬度狹窄的突出部(梁) 136‧‧ ‧ narrow width projections (beams)
137‧‧‧氣體的吹送噴嘴 137‧‧‧ gas blowing nozzle
138‧‧‧突出部(梁) 138‧‧‧Protruding section (beam)
139‧‧‧圓筒狀構件 139‧‧‧Cylindrical members
a、a'‧‧‧空氣 a, a'‧‧‧ air
b、b'‧‧‧混合氣體 b, b'‧‧‧ mixed gas
c、c'‧‧‧反應氣體 c, c'‧‧‧ reaction gas
d、d'‧‧‧冷媒 d, d'‧‧‧ refrigerant
f‧‧‧氣體 F‧‧‧ gas
圖1是本發明的流化床反應器的實施方式例的概略圖。 Fig. 1 is a schematic view showing an embodiment of a fluidized bed reactor of the present invention.
圖2是表示本發明的設置堆積防止部件的凹部的一例的剖面圖。 2 is a cross-sectional view showing an example of a concave portion in which a deposition preventing member of the present invention is provided.
圖3是表示本發明的設置堆積防止部件的凹部的其他例的剖面圖。 3 is a cross-sectional view showing another example of a concave portion in which a deposition preventing member of the present invention is provided.
圖4是本發明的流化床反應器的其他實施方式例的概略圖。 Fig. 4 is a schematic view showing another embodiment of the fluidized bed reactor of the present invention.
圖5是本發明的設置堆積防止部件的部分的概略圖。 Fig. 5 is a schematic view showing a portion of a stacking preventing member of the present invention.
以下，對本發明的流化床反應器之一進行詳細說明。本發明之一關於一種流化床反應器，是收納流化床的觸媒粒子的反應器，且在所述反應器內的觸媒粒子會接觸的反應器的內壁不設有凹部，或者在所設有的凹部設置堆積防止部件。 Hereinafter, one of the fluidized bed reactors of the present invention will be described in detail. One of the aspects of the present invention relates to a fluidized bed reactor which is a reactor for containing catalyst particles of a fluidized bed, and the inner wall of the reactor in which the catalyst particles in the reactor are in contact is not provided with a recess, or A deposition preventing member is provided in the recess provided.
作為本發明的氣相氧化反應，例如可列舉：利用氨氧化 法由丙烯及/或丙烷、氨以及空氣等含氧氣體而製造丙烯腈的反應；或利用丙烯的氣相氧化法而製造丙烯酸等烷烴及/或烯烴的氧化反應。使用表示實施方式的例的圖1與圖2，對其中用於氨氧化反應的流化床反應器的概略進行說明。 As the gas phase oxidation reaction of the present invention, for example, oxidation with ammonia is exemplified. The process is a reaction for producing acrylonitrile from an oxygen-containing gas such as propylene and/or propane, ammonia or air; or an oxidation reaction of an alkane and/or an olefin such as acrylic acid by a vapor phase oxidation method of propylene. The outline of the fluidized bed reactor used for the ammoxidation reaction will be described using Figs. 1 and 2 showing an example of the embodiment.
本發明的氨氧化反應中，作為觸媒的代表例，可較佳地 使用含有鉬的金屬氧化物觸媒、或含有鐵、銻的金屬氧化物觸媒等。自下方的空氣導入管12對氣相反應裝置的反應器本體11導入空氣a，且自吹出口13吹出，藉此使觸媒14流動化。自原料導入管15導入丙烯與氨的混合氣體b作為反應原料，使丙烯、氨及空氣接觸，藉此，利用空氣中的氧進行氧化反應，使每1當量的丙烯生成1當量的丙烯腈與3當量的水。為了將該氨氧化反應保持在適當且固定的反應溫度，利用通入有冷媒d的冷卻線圈(coil)16使反應器本體11內部的反應氣體冷卻，從而一面進行溫度控制一面進行氨氧化反應。反應中生成的含有丙烯腈的反應氣體利用旋風分離器19而將觸媒分離，成為含有未反應的氨及副生成的丙烯酸等雜質的反應氣體c而自製品抽出管17被抽出。利用熱交換 器18使該反應氣體c冷卻之後，依次送入氨的吸收分離塔、丙烯腈的純化塔進行純化，藉此獲得製品的丙烯腈。 In the ammoxidation reaction of the present invention, as a representative example of the catalyst, it is preferred A metal oxide catalyst containing molybdenum or a metal oxide catalyst containing iron or ruthenium or the like is used. The air introduction pipe 12 from the lower side introduces the air a into the reactor main body 11 of the gas phase reaction apparatus, and blows it out from the air outlet 13 to thereby fluidize the catalyst 14. A mixed gas b of propylene and ammonia is introduced from the raw material introduction pipe 15 as a reaction raw material, and propylene, ammonia, and air are brought into contact with each other, whereby oxidation reaction is performed by oxygen in the air to generate 1 equivalent of acrylonitrile per equivalent of propylene. 3 equivalents of water. In order to maintain the ammonia oxidation reaction at an appropriate and fixed reaction temperature, the reaction gas inside the reactor body 11 is cooled by a cooling coil 16 through which the refrigerant d is passed, and the ammoxidation reaction is performed while performing temperature control. The acrylonitrile-containing reaction gas generated in the reaction is separated by a cyclone 19 to form a reaction gas c containing impurities such as unreacted ammonia and by-produced acrylic acid, and is extracted from the product extraction pipe 17. Use heat exchange After the reaction gas c is cooled, the reaction gas is sequentially sent to an absorption column of ammonia and a purification column of acrylonitrile for purification, whereby acrylonitrile of the product is obtained.
氣相反應裝置的反應器由於在開放檢查等時人要進入，故而通常安裝有作為相對較大的凹部的人孔20。所述人孔20在反應時由外蓋21堵住，但孔的部分在反應器內壁形成有凹部。此外，亦有檢查孔或在形成反應器的周壁時因焊接等的情況而產生的凹部，且作為相對較小的凹部，有存在用於將熱電偶溫度計***反應器內的溫度計***孔等各種尺寸大小的凹部的情況。 Since the reactor of the gas phase reaction apparatus is required to enter during an open inspection or the like, the manhole 20 as a relatively large concave portion is usually mounted. The manhole 20 is blocked by the outer cover 21 during the reaction, but the portion of the hole is formed with a recess in the inner wall of the reactor. Further, there are also inspection holes or recesses which are formed by welding or the like when forming the peripheral wall of the reactor, and as a relatively small recess, there are various types of thermometer insertion holes for inserting a thermocouple thermometer into the reactor. The case of a recess of a size.
在人孔20或檢查孔般相對較大的凹部的情況下，就凹部的大小而言，凹部的側主體部的直徑為0.5m~2m左右，凹部的側主體部的深度為10cm~80cm左右。在如用於將熱電偶溫度計***反應器內的溫度計***孔般相對較小的凹部的情況下，就凹部的大小而言，凹部的側主體部的直徑為2cm~50cm左右，凹部的側主體部的深度為2cm~30cm左右。 In the case of the manhole 20 or the recess having a relatively large hole like the inspection hole, the diameter of the side body portion of the recess portion is about 0.5 m to 2 m, and the depth of the side body portion of the recess portion is about 10 cm to 80 cm. . In the case of a recess such as a thermometer for inserting a thermocouple thermometer into a reactor into a relatively small recess, the diameter of the side body of the recess is about 2 cm to 50 cm in terms of the size of the recess, and the side body of the recess The depth of the part is about 2cm~30cm.
本發明的流化床反應器中，在如上所述般各式各樣的種類、大小的凹部設置堆積防止部件。例如可列舉填埋所述凹部的堆積防止部件。所謂填埋，即指以在凹部的內部不產生間隙的方式，利用所述堆積防止部件填充凹部的內部。此外，作為所述堆積防止部件，可列舉利用氣體進行沖洗以使觸媒不進入凹部內的部件。藉由設置該些堆積防止部件，可使觸媒14的微細粒子不進入凹部的內部而防止觸媒堆積於凹部。 In the fluidized bed reactor of the present invention, the deposition preventing members are provided in the recesses of various types and sizes as described above. For example, a deposition preventing member that fills the concave portion can be cited. The term "filling" means that the inside of the concave portion is filled by the deposition preventing member so that no gap is formed inside the concave portion. Further, as the deposition preventing member, a member that is flushed with a gas so that the catalyst does not enter the concave portion can be cited. By providing these deposition preventing members, the fine particles of the catalyst 14 can be prevented from accumulating in the concave portion without entering the inside of the concave portion.
當利用所述堆積防止部件填埋凹部時，較佳為使用在填 埋後可固化的水泥等封入材料33。而且，若在所述凹部的與反應器內壁側接觸的部位預先安裝材質與流化床反應器的內壁相同的內蓋31，凹部的內面亦可不利用水泥等封入材料進行固定，故而較佳。此外，若預先在內蓋31的更靠外側安裝隔熱材料32，熱不易自凹部逸散，故而較佳。若將所述內蓋與隔熱材料一併利用所述封入材料33包圍而填埋所述凹部的剩餘間隙，觸媒不易堆積於所述凹部，故而更佳。 When the recessed portion is filled by the stacking preventing member, it is preferably used in filling The material 33 which is solidified by embedding is sealed. Further, when the inner lid 31 having the same material as that of the inner wall of the fluidized bed reactor is attached to the portion of the recessed portion that is in contact with the inner wall side of the reactor, the inner surface of the recessed portion may be fixed without using a sealing material such as cement. Preferably. Further, if the heat insulating material 32 is attached to the outer side of the inner lid 31 in advance, heat is less likely to escape from the concave portion, which is preferable. When the inner lid and the heat insulating material are surrounded by the sealing material 33 to fill the remaining gap of the concave portion, the catalyst is less likely to accumulate in the concave portion, which is more preferable.
作為所述封入材料33，理想的是具有如下流動性且在塗 敷後可固化的材料，所述流動性為能夠以填埋凹部的孔或間隙的方式進行塗敷的程度。由於氣相氧化反應為發熱性，故而就耐熱性的觀點而言，所述封入材料33較佳為無機物，例如可列舉通常的波特蘭水泥(Portland cement)或耐火水泥等。 As the sealing material 33, it is desirable to have the following fluidity and to coat A material that is curable after application, the fluidity being such that it can be applied by filling holes or gaps of the recesses. Since the gas phase oxidation reaction is heat-generating, the sealing material 33 is preferably an inorganic material from the viewpoint of heat resistance, and examples thereof include ordinary Portland cement or refractory cement.
若在與反應氣體直接接觸的所述凹部的內面側，安裝材 質與反應器的內壁相同的內蓋31作為所述堆積防止部件的一部分，水泥等所述封入材料與反應氣體不會直接接觸，而可抑制對氣相氧化反應的不良影響。而且，即便當橫向安裝於反應器的側主體部的凹部為人孔時，亦可進行水泥的施工。當凹部為圓柱狀或者圓錐台時，內蓋31的大小較佳為覆蓋所述凹部的內面側即整個底面。 If the inner surface side of the recess is in direct contact with the reaction gas, the mounting material The inner lid 31 having the same inner wall as the reactor serves as a part of the deposition preventing member, and the sealing material such as cement does not directly contact the reaction gas, and the adverse effect on the gas phase oxidation reaction can be suppressed. Further, even when the concave portion laterally attached to the side main body portion of the reactor is a manhole, the construction of the cement can be performed. When the concave portion is a cylindrical shape or a truncated cone, the inner cover 31 preferably has a size that covers the inner surface side of the concave portion, that is, the entire bottom surface.
所述外蓋21、內蓋31、及反應器的內壁的材質只要為 可耐用於氣相氧化反應的金屬材質，便無特別限定，可採用碳鋼、不鏽鋼等。作為碳鋼，並無特別限定，可較佳地列舉S45C、S55C、 S65C等。作為不鏽鋼，並無特別限定，可較佳地列舉SUS27、SUS304、SUS304L、SUS316、SUS316L等。就材質的腐蝕劣化與耐熱性的觀點而言，更佳為不鏽鋼。 The material of the outer cover 21, the inner cover 31, and the inner wall of the reactor is only The metal material which can be used for the gas phase oxidation reaction is not particularly limited, and carbon steel, stainless steel or the like can be used. The carbon steel is not particularly limited, and examples thereof include S45C and S55C. S65C and so on. The stainless steel is not particularly limited, and examples thereof include SUS27, SUS304, SUS304L, SUS316, and SUS316L. From the viewpoint of corrosion deterioration and heat resistance of the material, stainless steel is more preferable.
所述金屬材質的部分視需要亦可藉由噴鍍或鍍敷處理 等而實施表面處理。作為構成藉由噴鍍或鍍敷處理等而形成的金屬皮膜的金屬，例如可列舉：鉬、銅、銀、鈦、鋁、鉻、鎳等金屬、或INCONEL(註冊商標，稱作「英高鎳」)等含有鎳-鉻-鉬-鐵的合金、INCOLOY(註冊商標，稱作「英高合金」)等含有鋁-鉻-鐵的合金、HASTELLOY(註冊商標，稱作「赫史特合金」)等含有鎳-鉬-鎢的合金、MONEL(註冊商標，稱作「莫內爾合金」)等含有鎳-銅的合金、STELLITE(註冊商標，稱作「史泰勒合金」)等含有鈷-鉻-鎢的合金、SUS304等包含鎳-鉻-鐵的不鏽鋼合金、金屬陶瓷(cermet)、碳化鉻(chromium carbide)、氧化鈦等，可將該些金屬單獨使用或者複合而使用。 The metal material may also be sprayed or plated as needed. Wait for the surface treatment. Examples of the metal constituting the metal film formed by the thermal spraying or the plating treatment include a metal such as molybdenum, copper, silver, titanium, aluminum, chromium, or nickel, or INCONEL (registered trademark, called "English" Nickel-chromium-molybdenum-iron-containing alloys such as nickel-chromium-molybdenum-iron, and alloys containing aluminum-chromium-iron such as INCOLOY (registered trademark, called "English high alloy"), HASTELLOY (registered trademark, called "Herstite alloy" ") alloy containing nickel-molybdenum-tungsten, alloy containing nickel-copper such as MONEL (registered trademark, called "Monel"), and cobalt containing STELLITE (registered trademark, "Steller alloy") - a chromium-tungsten alloy, a stainless steel alloy containing nickel-chromium-iron such as SUS304, a cermet, a chromium carbide, a titanium oxide, or the like, and these metals may be used singly or in combination.
另外，若預先在內蓋31與外蓋21之間安裝隔熱材料32 作為所述堆積防止部件的一部分，可防止熱自人孔等凹部逸散，從而保溫性提高，易於維持氣相氧化反應的條件，而可使反應產量提高。作為該隔熱材料32，例如可列舉矽酸鈣等無機多孔質、或對黏土進行素燒而成的耐火磚(fire brick)、向高爐石(blast furnace slag)及玄武岩(basalt)、其他天然岩石中添加石灰等而成的岩棉(rock wool)等。若形狀為磚狀或塊狀，則易於設置且易於利用封入材料33進行固定。 In addition, if the heat insulating material 32 is installed between the inner cover 31 and the outer cover 21 in advance, As a part of the deposition preventing member, heat can be prevented from escaping from the concave portion such as the manhole, and the heat retaining property can be improved, and the conditions for the gas phase oxidation reaction can be easily maintained, and the reaction yield can be improved. Examples of the heat insulating material 32 include inorganic porous materials such as calcium citrate, fire bricks which are fired from clay, blast furnace slag and basalt, and other natural materials. Rock wool or the like is added to the rock. If the shape is brick or block, it is easy to set and easy to fix by the sealing material 33.
關於由所述堆積防止部件形成的內蓋31的反應器內壁 側的面，較佳為調整成在與所述凹部周邊的反應器內壁面之間產生的階差為不受所述觸媒堆積的影響而可忽視的程度，即，實質上與凹部的周邊的面無階差。所述階差的大小通常較佳為5.0mm以下，更佳為1.0mm以下，進而較佳為0.05mm以下。藉此，可防止觸媒堆積於堆積防止部件的周邊。 The inner wall of the reactor with respect to the inner lid 31 formed by the stacking preventing member The side surface is preferably adjusted so that the step generated between the inner wall surface of the reactor and the inner wall surface of the recess is negligible from the influence of the catalyst accumulation, that is, substantially the periphery of the recess There is no step on the surface. The magnitude of the step is usually preferably 5.0 mm or less, more preferably 1.0 mm or less, still more preferably 0.05 mm or less. Thereby, it is possible to prevent the catalyst from accumulating on the periphery of the deposition preventing member.
當將所述內蓋31及隔熱材料32安裝於凹部時，以將它 們整體固定且包埋的方式塗敷封入材料33，若預先填埋與凹部周壁22之間的間隙或隔熱材料32與內蓋31的間隙、及隔熱材料32彼此的間隙等，可更確實地抑制觸媒堆積於凹部，故而較佳。當填充該封入材料33時，較佳為使內蓋31的反應器內壁側的面與反應器本體11的凹部周緣23的高度一致而調整成實質上無階差。若封入材料33自凹部周緣23與內蓋31的間隙突出，雖觸媒不易堆積於凹部20的內部，但在封入材料33的周邊產生的階差成為堆積坑而有少量觸媒堆積於此處的擔憂。即，若凹部周緣23與內蓋31有階差，觸媒會堆積於階差的部分，而對所述氣相氧化反應產生所述不良影響。 When the inner cover 31 and the heat insulating material 32 are mounted in the recess, to The sealing material 33 is applied to the entire fixed and embedded manner, and the gap between the recessed portion peripheral wall 22, the gap between the heat insulating material 32 and the inner lid 31, and the gap between the heat insulating materials 32 may be preliminarily filled. It is preferable to surely suppress the accumulation of the catalyst in the concave portion. When the sealing material 33 is filled, it is preferable to adjust the surface of the inner lid side of the inner lid 31 to the height of the concave peripheral edge 23 of the reactor main body 11 so as to have substantially no step. When the sealing material 33 protrudes from the gap between the peripheral edge 23 of the concave portion and the inner lid 31, the catalyst is less likely to accumulate inside the concave portion 20, but the step generated around the sealing material 33 becomes a deposition pit and a small amount of catalyst is deposited thereon. Worry. That is, if there is a step difference between the peripheral edge 23 of the concave portion and the inner lid 31, the catalyst will accumulate in the portion of the step, which adversely affects the gas phase oxidation reaction.
另外，作為所述堆積防止部件的其他實施方式，可如圖 3所示般在凹部設置氣體的吹入口41以吹入氣體f，而防止觸媒堆積於凹部。作為自吹入口吹入的氣體，可列舉空氣、惰性氣體、蒸氣(steam)等。 In addition, as another embodiment of the deposition preventing member, it may be as shown in the figure As shown in FIG. 3, a gas inlet port 41 is provided in the recess to blow the gas f, and the catalyst is prevented from accumulating in the recess. Examples of the gas blown into the inlet are air, inert gas, steam, and the like.
此外，作為所述堆積防止部件的其他實施方式，可藉由 在反應器本體11的內壁不設有凹部，而防止觸媒堆積於凹部。此處，所謂在反應器本體11的內部不設有凹部，是指自設計階段起設為不具有凹部的構造。 Further, as another embodiment of the stacking preventing member, The inner wall of the reactor body 11 is not provided with a recess, and the catalyst is prevented from accumulating in the recess. Here, the fact that the recessed portion is not provided inside the reactor main body 11 means that the recessed portion is not provided from the design stage.
藉由利用本發明的堆積防止部件來防止觸媒堆積於凹 部20及其周邊，可防止觸媒的多餘的堆積，因此，可防止裝置的劣化或對反應的不良影響。另外，藉由設為在反應器內部不設有凹部的構造，可獲得同樣的效果。進而，利用本發明，當凹部為人孔等可開放的部位時，可防止堆積的還原劣化觸媒在人孔開放時突然氧化發熱的情況。 Preventing catalyst from accumulating in the concave by using the deposition preventing member of the present invention The portion 20 and its periphery prevent excessive accumulation of the catalyst, and therefore, deterioration of the device or adverse effects on the reaction can be prevented. Further, the same effect can be obtained by providing a structure in which no concave portion is provided inside the reactor. Further, according to the present invention, when the concave portion is a portion that can be opened such as a manhole, it is possible to prevent the deposited reduction-degrading catalyst from suddenly oxidizing and generating heat when the manhole is opened.
以下，對本發明的其他流化床反應器進行詳細說明。本發明的流化床反應器之一是如下的流化床反應器，是收納流化床觸媒粒子的反應器，且在存在於反應器內的突出部設置有所述觸媒粒子的堆積防止部件。 Hereinafter, other fluidized bed reactors of the present invention will be described in detail. One of the fluidized bed reactors of the present invention is a fluidized bed reactor which is a reactor for containing fluidized bed catalyst particles, and is provided with a stack of the catalyst particles in a protruding portion existing in the reactor. Prevent parts.
作為本發明的氣相氧化反應，例如可列舉：利用氨氧化 法由丙烯及/或丙烷、氨及空氣等含氧氣體而製造丙烯腈的反應；或利用丙烯的氣相氧化法而製造丙烯酸的反應等烷烴及/或烯烴的氧化反應。使用圖4與圖5對其中用於氨氧化反應的流化床反應器的概略進行說明。 As the gas phase oxidation reaction of the present invention, for example, oxidation with ammonia is exemplified. The method is a reaction for producing acrylonitrile from an oxygen-containing gas such as propylene and/or propane, ammonia or air; or an oxidation reaction of an alkane and/or an olefin such as a reaction for producing acrylic acid by a vapor phase oxidation method of propylene. The outline of a fluidized bed reactor for ammoxidation reaction will be described with reference to Figs. 4 and 5.
本發明的氨氧化反應中，作為觸媒的代表例，可較佳地 使用含有鉬的金屬氧化物觸媒、或含有鐵、銻的金屬氧化物觸媒等。自下方的空氣導入管112對氣相反應裝置的反應器本體111 導入空氣a'，且自吹出口113吹出，藉此使觸媒114流動化。自原料導入管115導入丙烯與氨的混合氣體b'作為反應原料，使丙烯、氨及空氣接觸，藉此利用空氣中的氧進行氧化反應，使每1當量的丙烯生成1當量的丙烯腈與3當量的水。為了將該氨氧化反應保持在適當且固定的反應溫度，利用通入有冷媒d'的冷卻線圈116使反應器本體111內部的反應氣體冷卻，從而一面進行溫度控制一面進行氨氧化反應。反應中生成的含有丙烯腈的反應氣體利用旋風分離器119而將觸媒分離，成為含有未反應的氨及副生成的丙烯酸等雜質的反應氣體c'而自製品抽出管117被抽出。 利用熱交換器118使該反應氣體c'冷卻之後，依次送入氨的吸收分離塔、丙烯腈的純化塔進行純化，藉此獲得製品的丙烯腈。另外，設置有與本發明的流化床反應器1的人孔20同樣的人孔121，該人孔121在反應時由外蓋122堵住。關於人孔121的說明依照針對本發明的流化床反應器1進行的說明。 In the ammoxidation reaction of the present invention, as a representative example of the catalyst, it is preferred A metal oxide catalyst containing molybdenum or a metal oxide catalyst containing iron or ruthenium or the like is used. From the lower air introduction pipe 112 to the reactor body 111 of the gas phase reaction device The air a' is introduced and blown out from the air outlet 113, whereby the catalyst 114 is fluidized. A mixed gas b' of propylene and ammonia is introduced from the raw material introduction pipe 115 as a reaction raw material, and propylene, ammonia, and air are brought into contact, whereby an oxidation reaction is performed by oxygen in the air to generate 1 equivalent of acrylonitrile per equivalent of propylene. 3 equivalents of water. In order to maintain the ammonia oxidation reaction at an appropriate and fixed reaction temperature, the reaction gas inside the reactor body 111 is cooled by the cooling coil 116 to which the refrigerant d' is passed, and the ammoxidation reaction is performed while performing temperature control. The acrylonitrile-containing reaction gas generated in the reaction is separated from the catalyst by a cyclone 119 to form a reaction gas c' containing impurities such as unreacted ammonia and by-produced acrylic acid, and is extracted from the product extraction pipe 117. After the reaction gas c' is cooled by the heat exchanger 118, the absorption column of ammonia and the purification column of acrylonitrile are sequentially supplied and purified, whereby acrylonitrile of the product is obtained. Further, a manhole 121 similar to the manhole 20 of the fluidized bed reactor 1 of the present invention is provided, and the manhole 121 is blocked by the outer cover 122 during the reaction. The description of the manhole 121 will be described in accordance with the fluidized bed reactor 1 of the present invention.
在氣相反應裝置的反應器的內部，為了設置或固定冷卻管或旋風分離器，而安裝有梁或支柱等突出部120。 Inside the reactor of the gas phase reaction apparatus, a projection 120 such as a beam or a pillar is attached to fix or fix the cooling pipe or the cyclone.
反應器內的梁或支柱等突出部120的寬度為2cm~30cm左右，長度為30cm~8m左右。 The protruding portion 120 such as a beam or a pillar in the reactor has a width of about 2 cm to 30 cm and a length of about 30 cm to 8 m.
本發明的流化床反應器藉由將突出部的上部設為向上凸的傾斜構造或者向上凸的曲面構造，可防止觸媒粒子堆積於突出部。另外，藉由利用氣體沖洗所述突出部，可防止觸媒粒子堆積於突出部。藉由設置該些觸媒粒子的堆積防止部件，可防止觸 媒114的微細粒子堆積於突出部。 The fluidized bed reactor of the present invention can prevent the catalyst particles from accumulating on the protruding portion by setting the upper portion of the protruding portion to an upwardly convex inclined structure or an upward convex curved surface structure. Further, by rinsing the protruding portion with a gas, it is possible to prevent the catalyst particles from accumulating on the protruding portion. By preventing the accumulation preventing members of the catalyst particles, the touch can be prevented The fine particles of the medium 114 are deposited on the protruding portion.
所述突出部120、反應器的內壁的材質只要為可耐用於 氣相氧化反應的金屬材質，便無特別限定。其具體例依照針對本發明的流化床反應器1進行的說明。 The material of the protruding portion 120 and the inner wall of the reactor is only suitable for use. The metal material of the gas phase oxidation reaction is not particularly limited. Specific examples thereof are described in accordance with the fluidized bed reactor 1 of the present invention.
所述金屬材質視需要亦可藉由噴鍍或鍍敷處理等而實 施表面處理。作為構成藉由施於所述金屬材質的噴鍍或鍍敷處理等而形成的金屬皮膜的金屬的具體例，依照針對本發明的流化床反應器1進行的說明。 The metal material may also be sprayed or plated as needed. Apply surface treatment. A specific example of the metal constituting the metal film formed by the thermal spraying or plating treatment of the metal material is described in accordance with the fluidized bed reactor 1 of the present invention.
作為所述堆積防止部件，藉由在反應器內的突出部，即 梁131、梁133及梁138、或支柱部135或反應器內部的附帶裝置的水平部，即旋風分離器上部等，安裝三角材料132或三角材料134、外周面為曲面狀的圓筒狀構件139作為向上凸的傾斜構造或者向上凸的曲面構造的構件，觸媒粒子會自突出部的上部或反應器內部的附帶裝置的水平部的上部落下，因此，可防止觸媒粒子堆積於突出部的上部或反應器內部的附帶裝置的水平部的上部。 As the deposition preventing member, by the protruding portion in the reactor, that is, The beam 131, the beam 133 and the beam 138, or the pillar portion 135 or the horizontal portion of the attached device inside the reactor, that is, the upper portion of the cyclone, etc., is provided with a triangular material 132 or a triangular material 134, and a cylindrical member having a curved outer peripheral surface 139. As a member having an upwardly convex inclined structure or an upwardly convex curved surface, the catalyst particles may be from the upper portion of the protruding portion or the upper portion of the horizontal portion of the attached device inside the reactor, thereby preventing the catalyst particles from accumulating in the protruding portion. The upper part of the part or the upper part of the horizontal part of the attached device inside the reactor.
作為所述傾斜構造或者曲面構造的構件，可較佳地使用 傾斜構造或者曲面構造的構件的相對於長度方向的垂直剖面形狀為三角形狀的所述三角材料、為半圓形狀的所述圓筒狀構件、為梯形形狀的構件、為多邊形形狀的構件等。 As the member of the inclined structure or the curved surface structure, it can be preferably used The vertical cross-sectional shape of the member having the inclined structure or the curved surface structure with respect to the longitudinal direction is a triangular shape of the triangular material, a semicircular shape of the cylindrical member, a trapezoidal shape member, a polygonal shape member, or the like.
作為將本發明的堆積防止部件設於所述突出部的上部 的方法，可列舉將所述傾斜構造或者曲面構造的構件設置於突出部的上部的方法。另外，亦可列舉將所述傾斜構造或者曲面構造 的構件與所述突出部設為一體成型構造體的方法。 The deposition preventing member of the present invention is provided on the upper portion of the protruding portion A method of providing the member having the inclined structure or the curved surface structure on the upper portion of the protruding portion can be cited. In addition, the inclined structure or the curved surface structure may also be cited The member and the protruding portion are provided as a method of integrally forming the structure.
另外，作為所述堆積防止部件，亦可設置對寬度狹窄的 突出部(梁)136的氣體吹送構件。例如，對反應器內的突出部或反應器內部的附帶裝置的水平部設置氣體的吹送噴嘴137以吹送氣體，而可防止觸媒粒子堆積於反應器內的突出部或反應器內部的附帶裝置的水平部。作為自氣體的吹送噴嘴137吹送的氣體，可列舉空氣、惰性氣體、蒸氣等。 Further, as the deposition preventing member, it is also possible to provide a narrow width A gas blowing member of the protrusion (beam) 136. For example, a gas blowing nozzle 137 is provided to the protruding portion in the reactor or the horizontal portion of the accessory device inside the reactor to blow the gas, thereby preventing the catalyst particles from accumulating in the protruding portion of the reactor or the attached device inside the reactor. The horizontal part. Examples of the gas to be blown from the gas blowing nozzle 137 include air, an inert gas, steam, and the like.
利用本發明的堆積防止部件，可防止觸媒粒子堆積於突 出部或反應器內部的附帶裝置的水平部及其周邊，因此可防止裝置的材質劣化或對反應的不良影響。而且，利用本發明的堆積防止部件，可防止堆積的還原劣化觸媒在人孔開放時急遽氧化發熱的情況。 By using the deposition preventing member of the present invention, it is possible to prevent the catalyst particles from accumulating in the protrusion The horizontal portion of the attached device or the attached device inside the reactor and its periphery can prevent deterioration of the material of the device or adverse effects on the reaction. Further, according to the deposition preventing member of the present invention, it is possible to prevent the deposited reduction-degrading catalyst from rapidly oxidizing and generating heat when the manhole is opened.
以下，利用實施例對本發明進行具體說明，但本發明只要不超出其主旨，則並不限定於以下的實施例。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded.
在氣相氧化反應用流化床反應器的反應器本體的SUS27製的壁面安裝有人孔，所述氣相氧化反應用流化床反應器是使用含有鉬的金屬氧化物觸媒，利用丙烯的氨氧化反應進行丙烯腈的製造，將與人孔的內徑一致的SUS27製的內蓋(直徑900mm×深度300mm)自反應器的內壁側以凹部周緣與內蓋的內壁側的面不產生階差的方式安裝於人孔，且在內蓋的外側的凹部內部鋪滿矽酸 鈣製的隔熱材料(230mm×110mm×65mm的磚狀)之後，以在凹部周緣的面不產生階差的方式，利用波特蘭水泥填充包含隔熱材料的周圍的人孔內部的剩餘間隙整體，並進行乾燥後，蓋上SUS27製的外蓋。 A manhole is installed in a wall surface made of SUS27 of a reactor main body of a fluidized bed reactor for gas phase oxidation reaction, and the fluidized bed reactor for gas phase oxidation reaction uses a metal oxide catalyst containing molybdenum, and uses propylene. In the production of acrylonitrile by the ammoxidation reaction, the inner lid (900 mm in diameter × 300 mm in depth) made of SUS27 having the inner diameter of the manhole is not covered by the inner peripheral side of the reactor from the inner peripheral side of the recess and the inner wall side of the inner lid. The step is generated in the manhole, and the inside of the inner cover is covered with tannin After the calcium heat insulating material (230 mm × 110 mm × 65 mm brick shape), the remaining gap inside the manhole including the heat insulating material is filled with Portland cement so that no step is formed on the surface of the periphery of the concave portion. After drying, it is covered with a cover made of SUS27.
在設置所述堆積防止部件的前後，在下述反應條件下跨 及相同長度的期間，利用丙烯的氨氧化反應而製造丙烯腈。 Before and after setting the stacking prevention member, cross under the following reaction conditions During the same length, acrylonitrile is produced by ammoxidation of propylene.
向反應器內部，導入84kg的MoBi系觸媒(觸媒組成 為Mo：Bi：Fe：Ce：Cr：Ni：Mg：Co：K：Rb：O：SiO2=12：0.5：2：0.5：0.4：4：1.5：1：0.07：0.06：X：42)作為觸媒14。 在冷卻線圈16(傳熱面積：0.33m2)的內部，流通錶壓(gage pressure)為3kg/cm2的水蒸氣作為冷卻介質。然後，自原料導入管15向所述反應器的本體11，以流量7.8kg/h導入丙烯，以流量3.5kg/h導入氨，自空氣導入管12向所述反應器的本體11以流量54kg/h導入空氣，且在440℃的溫度環境下進行氨氧化反應。 To the inside of the reactor, 84 kg of MoBi-based catalyst was introduced (the composition of the catalyst was Mo:Bi:Fe:Ce:Cr:Ni:Mg:Co:K:Rb:O:SiO 2 =12:0.5:2:0.5: 0.4:4:1.5:1:0.07:0.06:X:42) as the catalyst 14. Inside the cooling coil 16 (heat transfer area: 0.33 m 2 ), water vapor having a gage pressure of 3 kg/cm 2 was passed as a cooling medium. Then, propylene was introduced into the main body 11 of the reactor from the raw material introduction pipe 15 at a flow rate of 7.8 kg/h, ammonia was introduced at a flow rate of 3.5 kg/h, and a flow rate of 54 kg from the air introduction pipe 12 to the main body 11 of the reactor was carried out. /h was introduced into the air, and the ammoxidation reaction was carried out at a temperature of 440 °C.
在設置堆積防止部件之前進行製造後的開放時，確認到 堆積於人孔的凹部的觸媒，而在設置堆積防止部件之後進行製造後的開放時，未確認到堆積於人孔的凹部的觸媒。而且，在設置堆積防止部件之前，因觸媒堆積所引起的異常加熱而產生鋼的石墨化現象，可見反應器的材質的劣化，相對於此，在設置堆積防止部件之後，無觸媒堆積，因此未見反應器的材質的劣化。 When opening after the manufacturing of the stacking prevention part, it is confirmed When the catalyst accumulated in the concave portion of the manhole was opened after the deposition preventing member was placed, the catalyst accumulated in the concave portion of the manhole was not confirmed. Further, before the deposition preventing member is provided, the graphitization of the steel occurs due to abnormal heating due to the accumulation of the catalyst, and the material of the reactor is deteriorated. On the other hand, after the deposition preventing member is provided, no catalyst is deposited. Therefore, deterioration of the material of the reactor was not observed.
在運轉停止後將外蓋開放時，在設置堆積防止部件之 前，人孔周邊加熱至150℃，而在設置堆積防止部件之後開放時， 未成為妨礙作業的程度的高溫。 When the outer cover is opened after the operation is stopped, the stacking prevention member is provided. Before, the periphery of the manhole is heated to 150 ° C, and when the stacking prevention member is opened, It is not a high temperature that hinders the work.
將矽酸鈣製的隔熱材料替換成耐火磚，將波特蘭水泥替換成耐火水泥，除此以外，進行與實施例1同樣的操作及該操作前後的比較，結果與實施例1同樣地，相對於設置堆積防止部件之前，在設置堆積防止部件之後，無觸媒堆積，因此未見材質的劣化。 The same operation as in Example 1 and comparison before and after the operation were carried out in the same manner as in Example 1 except that the insulating material made of calcium citrate was replaced with a refractory brick and the Portland cement was replaced with refractory cement. Before the deposition preventing member was placed, no catalyst was deposited after the deposition preventing member was placed, so that deterioration of the material was not observed.
在運轉停止後將外蓋開放時，在設置堆積防止部件之前，人孔周邊加熱至150℃，而在設置堆積防止部件之後開放時，未成為妨礙作業的程度的高溫。 When the outer lid is opened after the operation is stopped, the periphery of the manhole is heated to 150 ° C before the deposition preventing member is provided, and when the stacking preventing member is opened, it is not a high temperature that hinders the work.
將SUS27製替換成藉由鍍鎳進行過表面處理的SUS304製，除此以外，進行與實施例1同樣的操作及該操作前後的比較，結果與實施例1同樣地，相對於設置堆積防止部件之前，在設置堆積防止部件之後，無觸媒堆積，因此未見材質的劣化。 In the same manner as in the first embodiment and the comparison before and after the operation, the SUS27 system was replaced with the SUS304 system which was subjected to the surface treatment by nickel plating. As a result, in the same manner as in the first embodiment, the deposition preventing member was provided. Previously, after the deposition preventing member was provided, no catalyst was accumulated, and thus deterioration of the material was not observed.
在運轉停止後將外蓋開放時，在設置堆積防止部件之前，人孔周邊加熱至150℃，而在設置堆積防止部件之後開放時，未成為妨礙作業的程度的高溫。 When the outer lid is opened after the operation is stopped, the periphery of the manhole is heated to 150 ° C before the deposition preventing member is provided, and when the stacking preventing member is opened, it is not a high temperature that hinders the work.
在利用丙烯的氨氧化反應進行丙烯腈的製造的流化床反應器內部的SUS27製的梁的水平面的上部，安裝與梁的寬度及長度一致的SUS27製的三角材料作為堆積防止部件。 In the upper part of the horizontal surface of the beam made of SUS27 in the fluidized bed reactor in which the acrylonitrile is produced by the ammoxidation reaction of propylene, a triangular material made of SUS27 having the same width and length as the beam is attached as a deposition preventing member.
在設置所述堆積防止部件的前後，在下述反應條件下跨 及相同長度的期間，利用丙烯的氨氧化反應而製造丙烯腈。 Before and after setting the stacking prevention member, cross under the following reaction conditions During the same length, acrylonitrile is produced by ammoxidation of propylene.
向內壁為SUS27製的反應器內部，導入84kg的MoBi 系觸媒(觸媒組成為Mo：Bi：Fe：Ce：Cr：Ni：Mg：Co：K：Rb：O：SiO2=12：0.5：2：0.5：0.4：4：1.5：1：0.07：0.06：X：42)作為觸媒114。在冷卻線圈116(傳熱面積：0.33m2)的內部，流通錶壓為3kg/cm2的水蒸氣作為冷卻介質。然後，自原料導入管115向所述反應器的本體111以流量7.8kg/h導入丙烯，以流量3.5kg/h導入氨，自空氣導入管112向所述反應器的本體111以流量54kg/h導入空氣，且在440℃的溫度環境下進行氨氧化反應。 Into the inside of the reactor made of SUS27, 84 kg of MoBi-based catalyst was introduced (the composition of the catalyst was Mo:Bi:Fe:Ce:Cr:Ni:Mg:Co:K:Rb:O:SiO 2 =12: 0.5:2:0.5:0.4:4:1.5:1:0.07:0.06:X:42) as the catalyst 114. Inside the cooling coil 116 (heat transfer area: 0.33 m 2 ), steam having a gauge pressure of 3 kg/cm 2 was passed as a cooling medium. Then, propylene was introduced into the main body 111 of the reactor from a raw material introduction pipe 115 at a flow rate of 7.8 kg/h, ammonia was introduced at a flow rate of 3.5 kg/h, and a flow rate of 54 kg was applied from the air introduction pipe 112 to the body 111 of the reactor. h Air was introduced and the ammoxidation reaction was carried out at a temperature of 440 °C.
在設置堆積防止部件之前進行製造後的開放時，確認到 堆積於水平的梁的觸媒粒子，而在設置堆積防止部件之後進行製造後的開放時，未確認到堆積於水平的梁的觸媒粒子。而且，在設置堆積防止部件之前，因觸媒粒子的堆積所引起的異常加熱而產生鋼的石墨化現象，可見反應器內部的水平的梁的材質的劣化，相對於此，在設置堆積防止部件之後，無觸媒粒子的堆積，因此未見反應器內部的水平的梁的材質的劣化。 When opening after the manufacturing of the stacking prevention part, it is confirmed When the catalyst particles deposited on the horizontal beam were opened after the deposition preventing member was placed, the catalyst particles deposited on the horizontal beam were not confirmed. Further, before the deposition preventing member is provided, the graphitization of the steel occurs due to the abnormal heating due to the accumulation of the catalyst particles, and the material of the horizontal beam inside the reactor is deteriorated. On the other hand, the deposition preventing member is provided. After that, since no catalyst particles were deposited, the deterioration of the material of the horizontal beam inside the reactor was not observed.
在運轉停止後將外蓋開放時，在設置堆積防止部件之 前，水平的梁加熱至150℃，而在設置堆積防止部件之後開放時，未成為妨礙作業的程度的高溫。 When the outer cover is opened after the operation is stopped, the stacking prevention member is provided. In the front, the horizontal beam is heated to 150 ° C, and when it is opened after the deposition preventing member is installed, it does not become a high temperature that hinders the work.
在反應器內的冷卻用配管的支柱的水平面的上部，設置圓筒狀構件139作為向上凸的曲面構造構件，且進行與實施例4同樣 的操作及該操作前後的比較，結果與實施例4同樣地，相對於設置堆積防止部件之前，在設置堆積防止部件之後，無觸媒堆積，因此未見支柱的材質的劣化。 The cylindrical member 139 is provided as an upwardly convex curved structural member in the upper portion of the horizontal surface of the pillar of the cooling pipe in the reactor, and is carried out in the same manner as in the fourth embodiment. As a result of the operation and the comparison before and after the operation, as in the case of the fourth embodiment, since the deposition preventing member was provided before the deposition preventing member was provided, no catalyst was deposited, and thus the material of the pillar was not deteriorated.
在運轉停止後將外蓋開放時，在設置堆積防止部件之 前，支柱及支柱周邊加熱至150℃，而在設置堆積防止部件之後開放時，未成為妨礙作業的程度的高溫。 When the outer cover is opened after the operation is stopped, the stacking prevention member is provided. In the front, the pillars and the pillars are heated to 150 ° C, and when they are opened after the deposition preventing member is installed, the temperature is not high.
將SUS27製替換成藉由鍍鎳進行過表面處理的SUS304製，除此以外，進行與實施例4同樣的操作及該操作前後的比較，結果與實施例4同樣地，相對於設置堆積防止部件之前，在設置堆積防止部件之後，無觸媒堆積，因此未見水平的梁的材質的劣化。 In the same manner as in the example 4 and the comparison before and after the operation, the SUS27 system was replaced with the SUS304 system which was subjected to the surface treatment by the nickel plating. As a result, in the same manner as in the fourth embodiment, the deposition preventing member was provided. Previously, after the deposition preventing member was provided, no catalyst was accumulated, and thus the material of the horizontal beam was not deteriorated.
在運轉停止後將外蓋開放時，在設置堆積防止部件之 前，水平的梁加熱至150℃，而在設置堆積防止部件之後開放時，未成為妨礙作業的程度的高溫。 When the outer cover is opened after the operation is stopped, the stacking prevention member is provided. In the front, the horizontal beam is heated to 150 ° C, and when it is opened after the deposition preventing member is installed, it does not become a high temperature that hinders the work.
不安裝三角材料，一面自SUS27製的管(pipe)以流量5m3/h向SUS27製的梁的水平面的上部吹送空氣，一面進行與實施例4同樣的操作及該操作前後的比較，結果與實施例4同樣地，相對於設置堆積防止部件之前，在設置堆積防止部件之後，無觸媒堆積，因此未見水平的梁的材質的劣化。 The same operation as in the fourth embodiment and the comparison before and after the operation were carried out from a pipe made of SUS27 at a flow rate of 5 m 3 /h to the upper portion of the horizontal surface of the beam made of SUS27 without using a triangular material. In the same manner as in the fourth embodiment, since the deposition preventing member was provided before the deposition preventing member was provided, no catalyst was deposited, and thus the material of the horizontal beam was not deteriorated.
在運轉停止後將外蓋開放時，在設置堆積防止部件之 前，水平的梁加熱至150℃，而在設置堆積防止部件之後開放時， 未成為妨礙作業的程度的高溫。 When the outer cover is opened after the operation is stopped, the stacking prevention member is provided. Before, the horizontal beam is heated to 150 ° C, and when it is opened after the stacking prevention member is set, It is not a high temperature that hinders the work.
根據本發明，可廣泛用作如下方法：用於防止觸媒粒子堆積於流化床反應器的內部的凹部或突出部等，而防止裝置的材質劣化或對反應的不良影響。 According to the present invention, it can be widely used as a method for preventing the catalyst particles from being deposited on the inside of the fluidized bed reactor, such as a concave portion or a protruding portion, and preventing the deterioration of the material of the device or the adverse effect on the reaction.
11‧‧‧反應器本體 11‧‧‧Reactor body
12‧‧‧空氣導入管 12‧‧‧Air inlet tube
13‧‧‧吹出口 13‧‧‧Blowing out
14‧‧‧觸媒 14‧‧‧ catalyst
15‧‧‧原料導入管 15‧‧‧Material introduction tube
16‧‧‧冷卻線圈 16‧‧‧Cooling coil
17‧‧‧製品抽出管 17‧‧‧Product extraction tube
18‧‧‧熱交換器 18‧‧‧ heat exchanger
19‧‧‧旋風分離器 19‧‧‧Cyclone separator
20‧‧‧人孔 20‧‧‧Manhole
21‧‧‧外蓋 21‧‧‧ Cover
a‧‧‧空氣 A‧‧‧air
b‧‧‧混合氣體 B‧‧‧mixed gas
c‧‧‧反應氣體 c‧‧‧Reactive gas
d‧‧‧冷媒 d‧‧‧Refrigerant
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| JP2014090983A JP6486015B2 (en) | 2014-04-25 | 2014-04-25 | Fluidized bed reactor |
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