JP6486015B2 - Fluidized bed reactor - Google Patents
Fluidized bed reactor Download PDFInfo
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- JP6486015B2 JP6486015B2 JP2014090983A JP2014090983A JP6486015B2 JP 6486015 B2 JP6486015 B2 JP 6486015B2 JP 2014090983 A JP2014090983 A JP 2014090983A JP 2014090983 A JP2014090983 A JP 2014090983A JP 6486015 B2 JP6486015 B2 JP 6486015B2
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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
Description
本発明は、流動床反応器に関し、詳しくはその内部の触媒粒子の堆積防止された流動床反応器に関する。 The present invention relates to a fluidized bed reactor, and more particularly to a fluidized bed reactor in which catalyst particles are prevented from being deposited.
流動床反応器は様々な工業反応に用いられている。例えばアクリロニトリル等のニトリル化合物は、プロピレン等の炭化水素のアンモ酸化法により工業的に製造されている。ニトリル化合物の製造方法としては、金属酸化物触媒の存在下、気相酸化反応させる方法が一般的に知られている。この気相酸化反応は、原料の炭化水素と、アンモニアと、空気などの酸素含有ガスとを反応器に導入し、前記金属酸化物触媒の存在下、アンモ酸化反応を行ってニトリル化合物を製造することが記載されている（特許文献１、特許文献２）。特許文献１、２で使用する反応器は、流動床反応器であり、反応器の内部には前記触媒が充填され、梁、サポートやサイクロン上部などの反応器内部の張り出し部を有するものが一般的である。 Fluidized bed reactors are used for various industrial reactions. For example, nitrile compounds such as acrylonitrile are industrially produced by ammoxidation of hydrocarbons such as propylene. As a method for producing a nitrile compound, a method in which a gas phase oxidation reaction is performed in the presence of a metal oxide catalyst is generally known. In this gas phase oxidation reaction, a raw material hydrocarbon, ammonia, and an oxygen-containing gas such as air are introduced into a reactor, and an ammoxidation reaction is performed in the presence of the metal oxide catalyst to produce a nitrile compound. (Patent Document 1, Patent Document 2). The reactor used in Patent Documents 1 and 2 is a fluidized bed reactor, and the reactor is generally filled with the catalyst and has a projecting portion inside the reactor such as a beam, a support, or an upper part of a cyclone. Is.
流動床反応器の前記張り出し部には前記金属酸化物触媒が堆積しやすい。触媒粒子が堆積すると、除熱が上手くいかず反応器内にホットスポットを生じ、触媒粒子の堆積部で反応器の材質劣化や材質腐食を引き起こす事があった。また、触媒粒子が堆積することで触媒粒子が還元劣化を起こし、目的とする反応収率の低下等、気相酸化反応に悪影響を及ぼすことがあった。また、本反応を停止し開放した際、堆積した触媒粒子が外気に触れると、急激な酸化反応を起こして発熱することがあった。流動床反応器の内部の張り出し部に触媒粒子が堆積することを防止して装置の材質劣化や反応への悪影響を防止するための方策が求められていた。 The metal oxide catalyst tends to deposit on the overhanging portion of the fluidized bed reactor. When the catalyst particles are deposited, the heat removal is not successful and a hot spot is generated in the reactor, which may cause deterioration of the reactor material and corrosion of the material at the catalyst particle deposition portion. In addition, the catalyst particles may be deposited to cause reductive degradation, which may adversely affect the gas phase oxidation reaction, such as a reduction in the target reaction yield. Further, when this reaction was stopped and opened, if the deposited catalyst particles touched the outside air, a rapid oxidation reaction may occur and heat may be generated. There has been a demand for measures for preventing catalyst particles from accumulating on the overhanging portion of the fluidized bed reactor to prevent material deterioration of the apparatus and adverse effects on the reaction.
本発明は、反応器内部の張り出し部に触媒粒子が堆積することを防止して、装置の材質劣化や反応への悪影響を防止することを目的とする。更には、反応器の張り出し部に堆積した触媒粒子の外気接触による急激な発熱を防止することを目的とする。 An object of the present invention is to prevent catalyst particles from accumulating on the overhanging portion inside the reactor, thereby preventing deterioration of the material of the apparatus and adverse effects on the reaction. Furthermore, it aims at preventing the rapid heat_generation | fever by the external air contact of the catalyst particle deposited on the overhang | projection part of the reactor.
本発明は、流動床反応器の触媒粒子が接触する反応器内部の張り出し部や反応器内部の付帯装置の水平部に、触媒粒子の堆積防止手段を設けることで、反応器内部の張り出し部や反応器内部の付帯装置の水平部に触媒粒子が堆積することを防止して装置の材質劣化や反応への悪影響を防止できることを見出した。更には、反応器内部の張り出し部や反応器内部の付帯装置の水平部に堆積した触媒粒子の外気接触による急激な発熱を防止できることを見出し、上記の課題を解決した。 The present invention provides a catalyst particle accumulation preventing means in the overhanging portion inside the reactor where the catalyst particles of the fluidized bed reactor come into contact and the horizontal portion of the auxiliary device inside the reactor. It has been found that catalyst particles can be prevented from accumulating on the horizontal part of the auxiliary device inside the reactor, thereby preventing deterioration of the material of the device and adverse effects on the reaction. Furthermore, the present inventors have found that rapid heat generation due to outside air contact of catalyst particles deposited on the overhanging portion inside the reactor and the horizontal portion of the auxiliary device inside the reactor can be prevented, and the above problems have been solved.
即ち本発明は、流動床触媒粒子を収納する気相アンモ酸化反応を行う流動床反応器であって、反応器内に存在する張り出し部に前記触媒粒子の堆積防止手段を設けた、流動床反応器であって、前記張り出し部がサイクロン上部、およびサイクロンを固定するために取り付けられた梁またはサポート部より選ばれる少なくとも一つである流動床反応器である。
That is, the present invention is a fluidized bed reactor for conducting a gas phase ammoxidation reaction containing fluidized bed catalyst particles, wherein the catalyst particle accumulation preventing means is provided in an overhanging portion present in the reactor. The fluidized bed reactor, wherein the overhanging portion is at least one selected from a cyclone upper portion and a beam or a support portion attached to fix the cyclone .
また、本発明は、前記堆積防止手段が前記張り出し部の上部を上に凸の傾斜構造または上に凸の曲面構造で構成することである、前記の流動床反応器である。 Further, the present invention is the fluidized bed reactor according to the first aspect, wherein the accumulation preventing means is configured such that the upper portion of the projecting portion is configured with an upwardly inclined structure or an upwardly curved surface structure.
また、本発明は、張り出し部の上部構成が前記反応器の内壁と同じ材質である、前記の流動床反応器である。 Moreover, this invention is the said fluidized bed reactor whose upper part structure of an overhang | projection part is the same material as the inner wall of the said reactor.
また、本発明は、前記堆積防止手段が前記張り出し部に気体を吹き付ける事である、前記の流動床反応器である。 Further, the present invention is the fluidized bed reactor according to which the deposition preventing means blows gas to the overhanging portion.
更に本発明は、前記の流動床反応器を用いて、前記反応器内に存在する張り出し部への触媒粒子の堆積を防止しながらアンモ酸化反応を行う、ニトリル化合物の製造方法である。 Furthermore, the present invention is a method for producing a nitrile compound, wherein an ammoxidation reaction is performed using the fluidized bed reactor while preventing catalyst particles from being deposited on an overhanging portion existing in the reactor.
本発明にかかる流動床反応器を用いて気相酸化反応を行うと、反応器内の張り出し部や反応器内部の付帯装置の水平部に触媒粒子が堆積しなくなるため、装置の材質劣化や反応への悪影響を防止することができる。 When the gas phase oxidation reaction is performed using the fluidized bed reactor according to the present invention, catalyst particles do not accumulate on the overhanging portion in the reactor or the horizontal portion of the auxiliary device inside the reactor. Can prevent adverse effects.
更には、モリブデンを含有する金属酸化物触媒を用いてアンモ酸化反応を行った場合には、反応を停止させて反応器を開放する際に、反応器に接触して還元劣化していた堆積触媒が外気に触れて急激に酸化され１５０℃程度にまで発熱することがあったが、前記堆積防止手段を設けることで、触媒の高温発熱を防止することができる。 Furthermore, when an ammoxidation reaction was carried out using a metal oxide catalyst containing molybdenum, when the reaction was stopped and the reactor was opened, the deposited catalyst was brought into contact with the reactor and reduced and deteriorated. However, when the catalyst is exposed to the outside air, it is rapidly oxidized and generates heat up to about 150 ° C. However, by providing the deposition preventing means, high temperature heat generation of the catalyst can be prevented.
以下、本発明について詳細に説明する。本発明は、流動床触媒粒子を収納する反応器であって、反応器内に存在する張り出し部に前記触媒粒子の堆積防止手段を設けた、流動床反応器に関する。 Hereinafter, the present invention will be described in detail. The present invention relates to a reactor that contains fluidized bed catalyst particles, and relates to a fluidized bed reactor in which the catalyst particle accumulation preventing means is provided at an overhanging portion present in the reactor.
本発明の気相酸化反応としては、例えばアンモ酸化法によってプロピレン及び／又はプロパンとアンモニアと空気などの酸素含有ガスからアクリロニトリルを製造する反応や、プロピレンの気相酸化法によってアクリル酸を製造する反応など、アルカン及び／又はアルケンの酸化反応が挙げられる。このうち、アンモ酸化反応に用いる流動床反応器の概略を図１と図２を用いて説明する。 Examples of the gas phase oxidation reaction of the present invention include a reaction for producing acrylonitrile from an oxygen-containing gas such as propylene and / or propane, ammonia and air by an ammoxidation method, and a reaction for producing acrylic acid by a gas phase oxidation method of propylene. Etc., oxidation reaction of alkane and / or alkene. Among these, the outline of the fluidized bed reactor used for ammoxidation reaction is demonstrated using FIG. 1 and FIG.
本発明のアンモ酸化反応は、触媒の代表例としてはモリブデンを含有する金属酸化物触媒や鉄、アンチモンを含有する金属酸化物触媒などが好適に用いられる。気相反応装置の反応器本体１１に、下方の空気導入管１２から空気ａを導入して、吹き出し口１３から吹き出させることで触媒１４を流動化させる。原料導入管１５から反応原料としてプロピレンとアンモニアの混合気体ｂを導入し、プロピレンとアンモニアと空気を接触させることで、空気中の酸素により酸化反応を行って、プロピレン１当量辺り、１当量のアクリロニトリルと、３当量の水を生成させる。このアンモ酸化反応を適切な一定の反応温度に保つために、冷媒ｄを通した冷却コイル１６で反応器本体１１内部の反応気体を冷却して温度制御を行いながらアンモ酸化反応を行う。反応で生成したアクリロニトリルを含む反応気体は、サイクロン１９で触媒を分離し、未反応のアンモニアや副生したアクリル酸等の不純物を含んだ反応気体ｃとして製品抜出し管１７から抜き出される。この反応気体ｃを熱交換器１８で冷却した後、アンモニアの吸収分離塔、アクリロニトリルの精製塔に順次送って精製することで製品のアクリロニトリルを得る。 In the ammoxidation reaction of the present invention, as a typical example of a catalyst, a metal oxide catalyst containing molybdenum, a metal oxide catalyst containing iron or antimony, or the like is preferably used. The catalyst 14 is fluidized by introducing the air a into the reactor main body 11 of the gas phase reactor from the lower air introduction pipe 12 and blowing it out from the outlet 13. A mixed gas b of propylene and ammonia is introduced from the raw material introduction pipe 15 as a reaction raw material, and the propylene, ammonia and air are brought into contact with each other, so that an oxidation reaction is performed with oxygen in the air, and 1 equivalent of acrylonitrile per 1 equivalent of propylene. And 3 equivalents of water are produced. In order to maintain this ammoxidation reaction at an appropriate constant reaction temperature, the ammoxidation reaction is performed while cooling the reaction gas inside the reactor main body 11 with the cooling coil 16 through which the refrigerant d is passed and controlling the temperature. The reaction gas containing acrylonitrile produced by the reaction is separated from the catalyst by a cyclone 19 and is extracted from the product extraction pipe 17 as a reaction gas c containing impurities such as unreacted ammonia and by-produced acrylic acid. After the reaction gas c is cooled by the heat exchanger 18, the product acrylonitrile is obtained by sequentially sending it to an ammonia absorption separation tower and an acrylonitrile purification tower for purification.
気相反応装置の反応器の内部には、冷却管やサイクロンを設置したり固定したりするために、梁やサポート等の張り出し部２０が取り付けられている。 An overhanging portion 20 such as a beam or a support is attached inside the reactor of the gas phase reactor in order to install or fix a cooling pipe or a cyclone.
反応器内の梁やサポート等の張り出し部２０の幅は２〜３０ｃｍ程度で長さは３０ｃｍ〜８ｍ程度である。 The overhanging portions 20 such as beams and supports in the reactor have a width of about 2 to 30 cm and a length of about 30 cm to 8 m.
本発明にかかる流動床反応器は、張り出し部の上部を上に凸の傾斜構造または上に凸の曲面構造にする事で触媒粒子が張り出し部に堆積するのを防止することができる。また気体で前記張り出し部をパージする事で触媒粒子が張り出し部に堆積するのを防止することができる。これら触媒粒子の堆積防止手段を設けることにより、触媒１４の微細な粒子が張り出し部に堆積するのを防止することができる。 The fluidized bed reactor according to the present invention can prevent catalyst particles from accumulating on the overhanging portion by making the upper part of the overhanging portion have an upwardly inclined structure or an upwardly curved surface structure. Moreover, it is possible to prevent the catalyst particles from being deposited on the overhanging portion by purging the overhanging portion with a gas. By providing these catalyst particle accumulation preventing means, it is possible to prevent fine particles of the catalyst 14 from being deposited on the overhanging portion.
前記張り出し部２０、反応器の内壁の材質は、気相酸化反応の使用に耐えうる金属材質であれば、特に限定されないが、カーボンスチール、ステンレススチールなどが採用される。カーボンスチールとしては、特に限定されないが、好ましくはＳ４５Ｃ、Ｓ５５Ｃ、Ｓ６５Ｃなどが挙げられる。ステンレススチールとしては、特に限定されないが、好ましくはＳＵＳ２７、ＳＵＳ３０４、ＳＵＳ３０４Ｌ、ＳＵＳ３１６、ＳＵＳ３１６Ｌなどが挙げられる。材質の腐食劣化と耐熱性の観点から、ステンレススチールであることがより好ましい。 The material of the overhanging portion 20 and the inner wall of the reactor is not particularly limited as long as it is a metal material that can withstand the use of the gas phase oxidation reaction, and carbon steel, stainless steel, or the like is employed. Although it does not specifically limit as carbon steel, Preferably S45C, S55C, S65C etc. are mentioned. Although it does not specifically limit as stainless steel, Preferably SUS27, SUS304, SUS304L, SUS316, SUS316L etc. are mentioned. Stainless steel is more preferable from the viewpoint of corrosion deterioration and heat resistance of the material.
前記金属材質は、必要により溶射やメッキ処理等で表面処理を施すこともできる。溶射やメッキ処理等で形成される金属皮膜を構成する金属としては、例えば、モリブデン、銅、銀、チタン、アルミニウム、クロム、ニッケルなどの金属や、ＩＮＣＯＮＥＬ（登録商標、「インコネル」と呼称する。）などのニッケル−クロム−モリブデン−鉄を含む合金、ＩＮＣＯＬＯＹ（登録商標、「インコロイ」と呼称する。）などのアルミニウム−クロム−鉄を含む合金、ＨＡＳＴＥＬＬＯＹ（登録商標、「ハステロイ」と呼称する。）などのニッケル−モリブデン−タングステンを含む合金、ＭＯＮＥＬ（登録商標、「モネル」と呼称する。）などのニッケル−銅を含む合金、ＳＴＥＬＬＩＴＥ（登録商標、「ステライト」と呼称する。）などのコバルト−クロム−タングステンを含む合金、ＳＵＳ３０４などのニッケル−クロム−鉄からなるステンレス合金、サーメット、クロムカーバイド、酸化チタンなどが挙げられ、これらを単独、または複合して用いることができる。 If necessary, the metal material can be subjected to surface treatment by thermal spraying or plating treatment. As a metal constituting the metal film formed by thermal spraying or plating, for example, a metal such as molybdenum, copper, silver, titanium, aluminum, chromium, nickel, or INCONEL (registered trademark, “Inconel”) is used. ), An alloy containing nickel-chromium-molybdenum-iron, an alloy containing aluminum-chromium-iron such as INCOLOY (registered trademark, referred to as “Incoloy”), and HASTELLOY (registered trademark, referred to as “Hastelloy”). ) And other alloys containing nickel-molybdenum-tungsten, alloys containing nickel-copper such as MONEL (registered trademark, referred to as “Monel”), and cobalt such as STELLITE (registered trademark, referred to as “Stellite”). -Alloys containing chromium-tungsten, nickel-chromium such as SUS304 Stainless steel alloy consisting of iron, cermets, chromium carbide, titanium oxide and the like, can be used alone or in combination.
前記堆積防止手段として、反応器内の張り出し部である梁３１及び３３やサポート部３５や反応器内部の付帯装置の水平部であるサイクロン上部などに上に凸の傾斜構造または上に凸の曲面構造の部材として三角材３２や３４、外周面が曲面状の円筒状部材３９を取り付ける事で張り出し部の上部や反応器内部の付帯装置の水平部の上部から触媒粒子が落ちるため、張り出し部の上部や反応器内部の付帯装置の水平部の上部に触媒粒子が堆積するのを防止する事ができる。 As the deposition preventing means, an upwardly projecting inclined structure or an upwardly convex curved surface is formed on the beams 31 and 33 that are overhanging portions in the reactor, the support portion 35, the upper part of the cyclone that is the horizontal portion of the auxiliary device inside the reactor, or the like. By attaching the triangular members 32 and 34 as the structural members and the cylindrical member 39 having a curved outer peripheral surface, the catalyst particles fall from the upper part of the overhanging part or the horizontal part of the auxiliary device inside the reactor. It is possible to prevent the catalyst particles from being deposited on the upper part or the upper part of the horizontal part of the auxiliary device inside the reactor.
前記傾斜構造または曲面構造の部材としては、傾斜構造または曲面構造の部材の長手方向に対する垂直断面形状が三角形状の前記三角材、半円形状の前記円筒状部材、台形形状の部材、多角形形状の部材などを好適に使用することができる。 As the member having the inclined structure or the curved surface structure, the vertical cross-sectional shape with respect to the longitudinal direction of the member having the inclined structure or the curved structure is triangular, the semicircular cylindrical member, the trapezoidal member, or the polygonal shape. These members can be suitably used.
本発明の堆積防止手段を前記張り出し部の上部に設ける方法としては、前記傾斜構造または曲面構造の部材を張り出し部の上部に設置する方法が挙げられる。また、前記傾斜構造または曲面構造の部材と前記張り出し部を一体成型構造体とする方法も挙げられる。 Examples of the method of providing the deposition preventing means of the present invention on the upper portion of the overhanging portion include a method of installing the member having the inclined structure or the curved surface structure on the upper portion of the overhanging portion. Moreover, the method of making the member of the said inclination structure or a curved-surface structure and the said overhang | projection part into an integrally molded structure is also mentioned.
また、前記堆積防止手段として、反応器内の張り出し部や反応器内部の付帯装置の水平部に気体の吹き付けノズル３７を設けて気体を吹き付け、反応器内の張り出し部や反応器内部の付帯装置の水平部に触媒粒子が堆積するのを防止する事ができる。気体の吹き付けノズル３７から吹き付ける気体としては空気、不活性ガス、スチーム等が挙げられる。 Further, as the deposition preventing means, a gas blowing nozzle 37 is provided on the overhanging portion in the reactor or the horizontal portion of the auxiliary device inside the reactor to blow the gas, and the overhanging portion in the reactor or the auxiliary device inside the reactor is blown. It is possible to prevent the catalyst particles from accumulating on the horizontal portion. Examples of the gas blown from the gas blowing nozzle 37 include air, inert gas, and steam.
本発明の堆積防止手段により、張り出し部や反応器内部の付帯装置の水平部とその周辺への触媒粒子が堆積することを防止できるので装置の材質劣化や反応への悪影響を防止することができる。また、本発明の堆積防止手段により、堆積していた還元劣化触媒が、マンホール開放の際に急激に酸化発熱する事態を防止することができる。 By the deposition preventing means of the present invention, it is possible to prevent catalyst particles from being deposited on the overhanging portion or the horizontal portion of the auxiliary device inside the reactor and its surroundings, so that it is possible to prevent material deterioration of the device and adverse effects on the reaction. . In addition, the deposition preventing means of the present invention can prevent a situation in which the reduced and deteriorated catalyst is suddenly oxidized and heated when the manhole is opened.
以下、実施例により本発明を具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example, unless the summary is exceeded.
（実施例１）
プロピレンのアンモ酸化反応によりアクリロニトリルの製造を行う流動床反応器内部のＳＵＳ２７製の梁の水平面の上部に、堆積防止手段として梁の幅と長さに合わせたＳＵＳ２７製の三角材を取り付けた。
Example 1
An SUS27 triangular material matching the width and length of the beam was attached as an anti-deposition means to the upper part of the horizontal surface of the SUS27 beam inside the fluidized bed reactor for producing acrylonitrile by propylene ammoxidation reaction.
前記の堆積防止手段を設ける前と後について、下記の反応条件で同じ長さの期間に亘ってプロピレンのアンモ酸化反応によりアクリロニトリルを製造した。 Before and after the deposition preventing means was provided, acrylonitrile was produced by ammoxidation of propylene over the same length of time under the following reaction conditions.
内壁がＳＵＳ２７製の反応器内部には触媒１４として、ＭｏＢｉ系触媒（触媒組成、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）を８４ｋｇ導入した。冷却コイル１６（伝熱面積：０．３３ｍ２）の内部には、冷却媒体としてゲージ圧が３ｋｇ／ｃｍ２の水蒸気を流通させた。次いでこの本体１１に、原料導入管１５よりプロピレンを流量７．８ｋｇ／ｈで、アンモニアを流量３．５ｋｇ／ｈで導入し、空気導入管１２から空気を流量５４ｋｇ／ｈで導入して、４４０℃の温度環境でアンモ酸化反応を行った。 As a catalyst 14 inside the reactor whose inner wall is made of SUS27, a MoBi-based catalyst (catalyst composition, Mo: Bi: Fe: Ce: Cr: Ni: Mg: Co: K: Rb: O: SiO 2 = 12: 0. 84 kg of 5: 2: 0.5: 0.4: 4: 1.5: 1: 0.07: 0.06: X: 42) was introduced. Water vapor with a gauge pressure of 3 kg / cm 2 was circulated inside the cooling coil 16 (heat transfer area: 0.33 m 2 ) as a cooling medium. Next, propylene is introduced into the main body 11 at a flow rate of 7.8 kg / h and ammonia is introduced at a flow rate of 3.5 kg / h from the raw material introduction tube 15, and air is introduced from the air introduction tube 12 at a flow rate of 54 kg / h. The ammoxidation reaction was performed in a temperature environment of ° C.
堆積防止手段を設ける前に製造した後の開放の際には水平な梁に堆積した触媒粒子が確認されたが、堆積防止手段を設けた後に製造した後の開放の際には、水平な梁に堆積した触媒粒子は確認されなかった。また、堆積防止手段の設置前には触媒粒子の堆積による異常加熱で鋼の黒鉛化現象を生じ反応器内部の水平な梁の材質の劣化が認められたのに対して、堆積防止手段の設置後は、触媒粒子の堆積が無くなったため反応器内部の水平な梁の材質の劣化が認められなくなった。 The catalyst particles deposited on the horizontal beam were confirmed at the time of opening after manufacturing before providing the deposition preventing means, but the horizontal beam at the time of opening after manufacturing after providing the deposition preventing means. No catalyst particles deposited on the catalyst were confirmed. In addition, before the installation of deposition prevention means, abnormal heating due to the accumulation of catalyst particles caused the graphitization phenomenon of the steel, and deterioration of the material of the horizontal beam inside the reactor was observed. After that, there was no accumulation of catalyst particles, and no deterioration of the material of the horizontal beam inside the reactor was observed.
運転停止後に外蓋を開放する際には、堆積防止手段を設ける前は１５０℃まで水平な梁が加熱していたが、堆積防止手段を設けた後の開放の際には、作業の邪魔になるほどの高温にはならなかった。 When the outer lid is opened after the operation is stopped, the horizontal beam is heated to 150 ° C. before the deposition preventing means is provided. However, when opening after the deposition preventing means is provided, the work is disturbed. It wasn't hot enough.
（実施例２）
反応器内の冷却用配管のサポートの水平面の上部に上に凸の曲面構造部材として円筒形状部材３９を設置して実施例１と同様の操作、およびその操作前後の比較を行なったところ、実施例１と同様に堆積防止手段の設置前に対して堆積防止手段の設置後は、触媒堆積が無くなったためサポートの材質の劣化が認められなくなった。
(Example 2)
An operation similar to that in Example 1 was performed by installing a cylindrical member 39 as a convexly curved structural member on the upper horizontal surface of the support for the cooling pipe in the reactor, and comparison was made before and after the operation. As in Example 1, after the deposition preventing means was installed, the catalyst material was not deposited and the deterioration of the support material was not recognized after the deposition preventing means was installed.
運転停止後に外蓋を開放する際には、堆積防止手段を設ける前は１５０℃までサポート及びサポート周辺が加熱したが、堆積防止手段を設けた後の開放の際には、作業の邪魔になるほどの高温にはならなかった。 When the outer lid is opened after the operation is stopped, the support and the periphery of the support are heated to 150 ° C. before the deposition preventing means is provided. However, when opening after the deposition preventing means is provided, the operation is disturbed. The high temperature did not.
（実施例３）
ＳＵＳ２７製を、ニッケルメッキで表面処理したＳＵＳ３０４製に替えた以外は実施例１と同様の操作およびその操作前後の比較を行なったところ、実施例１と同様に堆積防止手段の設置前に対して堆積防止手段の設置後は、触媒堆積が無くなったため水平な梁の材質の劣化が認められなくなった。
(Example 3)
The same operation as in Example 1 and comparison before and after the operation except that SUS27 was replaced with SUS304 made by surface treatment with nickel plating were performed. After installation of the anti-deposition means, there was no catalyst build-up and no deterioration of the horizontal beam material was observed.
運転停止後に外蓋を開放する際には、堆積防止手段を設ける前は水平な梁が１５０℃までが加熱したが、堆積防止手段を設けた後の開放の際には、作業の邪魔になるほどの高温にはならなかった。 When the outer lid is opened after the operation is stopped, the horizontal beam is heated up to 150 ° C. before the deposition preventing means is provided. However, when the opening is opened after the deposition preventing means is provided, the operation is disturbed. The high temperature did not.
（実施例４）
三角材を取り付けないで、ＳＵＳ２７製のパイプから空気を流量５ｍ3／ｈでＳＵＳ２７製の梁の水平面の上部に吹き付けながら実施例１と同様の操作およびその操作前後の比較を行なったところ、実施例１と同様に堆積防止手段の設置前に対して堆積防止手段の設置後は、触媒堆積が無くなったため水平な梁の材質の劣化が認められなくなった。
Example 4
The same operation as in Example 1 and a comparison before and after the operation were performed while blowing air from the pipe made of SUS27 at a flow rate of 5 m 3 / h on the upper part of the horizontal surface of the beam made of SUS27 without attaching a triangular material. As in Example 1, after the deposition prevention means was installed, the deterioration of the material of the horizontal beam was not recognized after the deposition prevention means was installed because catalyst deposition was lost.
運転停止後に外蓋を開放する際には、堆積防止手段を設ける前は水平な梁が１５０℃までが加熱したが、堆積防止手段を設けた後の開放の際には、作業の邪魔になるほどの高温にはならなかった。 When the outer lid is opened after the operation is stopped, the horizontal beam is heated up to 150 ° C. before the deposition preventing means is provided. However, when the opening is opened after the deposition preventing means is provided, the operation is disturbed. The high temperature did not.
本発明によれば、流動床反応器の内部の張り出し部に触媒粒子が堆積することを防止して装置の材質劣化や反応への悪影響を防止するための方法として、広く適用できる。 INDUSTRIAL APPLICABILITY According to the present invention, the method can be widely applied as a method for preventing catalyst particles from accumulating on an overhanging portion inside a fluidized bed reactor and preventing adverse effects on the apparatus material deterioration and reaction.
ａ 空気
ｂ 混合気体
ｃ 反応気体
ｄ 冷媒
１１ 反応器本体
１２ 空気導入管
１３ 吹き出し口
１４ 触媒
１５ 原料導入管
１６ 冷却コイル
１７ 製品抜出し管
１８ 熱交換器
１９ サイクロン
２０ 水平な張り出し部
２１ 凹部（マンホール）
２２ 外蓋
３１ 張り出し部(梁)
３２ 三角材
３３ 幅の狭い張り出し部(梁)
３４ 三角材
３５ サポート
３６ 幅の狭い張り出し部(梁)
３７ 気体の吹き付けノズル
３８ 張り出し部(梁)
３９ 円筒状部材
a Air b Mixed gas c Reaction gas d Refrigerant 11 Reactor body 12 Air introduction pipe 13 Air outlet 14 Catalyst 15 Raw material introduction pipe 16 Cooling coil 17 Product extraction pipe 18 Heat exchanger 19 Cyclone 20 Horizontal overhanging part 21 Recess (manhole)
22 Outer lid 31 Overhang (beam)
32 Triangular material 33 Narrow overhang (beam)
34 Triangular material 35 Support 36 Narrow overhanging part (beam)
37 Gas spray nozzle 38 Overhang (beam)
39 Cylindrical member
Claims (4)
前記張り出し部がサイクロン上部、およびサイクロンを固定するために取り付けられた梁またはサポート部より選ばれる少なくとも一つである流動床反応器。 A fluidized bed reactor for performing a gas phase ammoxidation reaction containing fluidized bed catalyst particles, wherein the catalyst particles are prevented from depositing in an overhanging portion present in the reactor,
The fluidized bed reactor, wherein the overhanging portion is at least one selected from a cyclone upper part and a beam or a support portion attached to fix the cyclone.
Priority Applications (7)
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| JP2014090983A JP6486015B2 (en) | 2014-04-25 | 2014-04-25 | Fluidized bed reactor |
| TW104112157A TWI590872B (en) | 2014-04-25 | 2015-04-16 | A fluidized bed reactor and a method for producing a nitrile compound using the same |
| PCT/JP2015/061904 WO2015163260A1 (en) | 2014-04-25 | 2015-04-17 | Fluid bed reactor and method of producing nitrile compound using same |
| CN201910107932.9A CN109999733A (en) | 2014-04-25 | 2015-04-17 | The manufacturing method of fluidized-bed reactor and the nitrile compound using it |
| KR1020187018443A KR102005207B1 (en) | 2014-04-25 | 2015-04-17 | Fluid bed reactor and method of producing nitrile compound using same |
| KR1020167027399A KR101887293B1 (en) | 2014-04-25 | 2015-04-17 | Fluid bed reactor and method of producing nitrile compound using same |
| CN201580019487.0A CN106170335B (en) | 2014-04-25 | 2015-04-17 | The manufacturing method of fluidized-bed reactor and the nitrile compound using it |
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| CN110465253B (en) * | 2019-09-22 | 2021-06-22 | 太原理工大学 | Reaction and separation integrated corrosion-resistant and high-temperature-resistant reaction device |
| KR102404282B1 (en) * | 2019-09-24 | 2022-05-30 | 주식회사 엘지화학 | Fluidized bed reactor |
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| JPS4911550B1 (en) * | 1970-10-24 | 1974-03-18 | ||
| JPS5743286U (en) * | 1980-08-20 | 1982-03-09 | ||
| GB2134921A (en) * | 1983-02-14 | 1984-08-22 | Combustion Eng | High temperature pyrolysis process |
| JPS6058999U (en) * | 1983-09-30 | 1985-04-24 | 株式会社日立製作所 | Cover mounting structure |
| JPS6438136A (en) * | 1987-08-03 | 1989-02-08 | Mitsubishi Heavy Ind Ltd | Three phase fluidized reaction device |
| FR2648550B1 (en) * | 1989-06-16 | 1995-01-27 | Inst Francais Du Petrole | METHOD AND DEVICE FOR REGULATING OR CONTROLLING THE THERMAL LEVEL OF A POWDER SOLID COMPRISING A HEAT EXCHANGER WITH FLUIDIZED OR MOBILE BED COMPARTMENTS |
| JP2563045B2 (en) * | 1992-09-29 | 1996-12-11 | 川崎重工業株式会社 | Device to prevent particle deformation in centrifugal fluidized bed |
| JPH08219412A (en) * | 1995-02-10 | 1996-08-30 | Abb Kk | Discharging device for cyclone ash in pressurized fluidized bed combustion plant |
| JPH1019222A (en) * | 1996-06-28 | 1998-01-23 | Mitsubishi Heavy Ind Ltd | Fluidied bed incinerator |
| JP3741823B2 (en) * | 1997-05-20 | 2006-02-01 | 三井化学株式会社 | Gas phase polymerization equipment |
| CN1055916C (en) * | 1997-06-06 | 2000-08-30 | 中国石油化工总公司 | fluid bed reactor for ammoxidation of hydrocarbons |
| DE19851423A1 (en) * | 1998-11-07 | 2000-05-11 | Krupp Uhde Gmbh | Device for providing a block flange of a manhole opening or the like, in particular in the case of fluidized bed reactors |
| JP2000279751A (en) * | 1999-03-29 | 2000-10-10 | Electric Power Dev Co Ltd | Method and device for denitrating pressure fluidized bed boiler |
| JP4741766B2 (en) * | 2001-09-28 | 2011-08-10 | 住友化学株式会社 | Manhole structure of distillation tower |
| US20040052690A1 (en) * | 2002-09-12 | 2004-03-18 | Eaton Gerald B. | Polymerization reactant injection system |
| CA2522674A1 (en) * | 2003-05-09 | 2004-11-25 | The Standard Oil Company | Fluidized bed reactor with gas cooler |
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| KR101788476B1 (en) * | 2016-12-09 | 2017-10-20 | 오씨아이 주식회사 | Free board reactor haviing enhaced durability |
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| CN106170335A (en) | 2016-11-30 |
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| KR20180078333A (en) | 2018-07-09 |
| TWI590872B (en) | 2017-07-11 |
| WO2015163260A1 (en) | 2015-10-29 |
| CN106170335B (en) | 2019-05-31 |
| CN109999733A (en) | 2019-07-12 |
| TW201601839A (en) | 2016-01-16 |
| KR101887293B1 (en) | 2018-08-09 |
| JP2015208705A (en) | 2015-11-24 |
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