CN102059081A - Tubular reactor for performing liquid phase oxidation on cyclohexane by utilizing pure oxygen (enriched oxygen) - Google Patents

Tubular reactor for performing liquid phase oxidation on cyclohexane by utilizing pure oxygen (enriched oxygen) Download PDF

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CN102059081A
CN102059081A CN2010105840445A CN201010584044A CN102059081A CN 102059081 A CN102059081 A CN 102059081A CN 2010105840445 A CN2010105840445 A CN 2010105840445A CN 201010584044 A CN201010584044 A CN 201010584044A CN 102059081 A CN102059081 A CN 102059081A
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liquid
reaction
reactor
tube
gas
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刘长军
唐盛伟
张海广
梁斌
闵恩泽
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四川大学
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Abstract

The invention belongs to the field of energy resource and chemical industry, and relates to a tubular reactor for performing liquid phase oxidation on hydrocarbons by utilizing pure oxygen (enriched oxygen). The tubular reactor comprises a gas distribution unit, a tubular reactor and a highly integrated reaction heat removal and utilization mode. A gas forms a large number of bubbles with the diameters below 2 mm by the shearing action of liquid in a cross-flow aeration unit; the bubbles are uniformly mixed with a reaction liquid phase; the obtained gas-liquid mixture passes through a tubular reaction area with a high slenderness ratio in a laminar flow mode; and oxygen in a gas phase is completely transformed in the process. The reactor and a heat exchanger are highly integrated; and high degree of energy integration is realized by combining reaction heat removal with liquid-phase raw material preheating. The reactor designed in the invention has the advantages that: the structure is compact, the space utilization ratio is high, the highly integrated design greatly improves the comprehensive utilization level of heat energy, the internal security is high, the temperature is controlled accurately, products have high selectivity and high yield, and the tubular reactor can be used for pure oxygen and enriched oxygen oxidation, has a simple structure, is easy to maintain and enlarge and the like.

Description

一种利用纯氧(富氧)进行环己烷液相氧化的管式反应器 Utilizing pure oxygen (oxygen-rich) for liquid phase oxidation of cyclohexane tubular reactor

技术领域 FIELD

[0001] 本发明涉及能源和化工领域,涉及含氧有机化合物的生产制备,属于清洁绿色化工过程,是一种烃类液相氧化反应器。 [0001] The present invention relates to the field of energy and chemical industry, involving the preparation of oxygenated organic compounds produced, which belongs to the green chemical cleaning processes, liquid-phase reactor is a hydrocarbon oxidation reactor. 特别涉及一种适用于强放热的气液反应的管式反应器,特别适用于以纯氧(富氧)作为氧化剂进行的烃类液相氧化反应。 Particularly relates to a gas-liquid reaction is strongly exothermic suitable for tubular reactors, especially for pure oxygen (oxygen-rich) as a hydrocarbon liquid phase oxidation reaction of an oxidizing agent. 气体经错流曝气机构形成大量微小气泡并与液相环己烷均勻混合,混合后气液物料以平推流的方式并流通过反应区,其中气相中的氧气在此过程中实现完全转化。 Gas through the cross flow aerating means is formed with a large number of fine bubbles and liquid cyclohexane uniformly mixed, the mixed material liquid so as to plug flow and flow through the reaction zone, wherein the gas phase to achieve complete conversion of oxygen in the process .

背景技术 Background technique

[0002] 氧化反应是化学品加工过程中最重要的反应之一,是以烃类化合物生产含氧有机物的一步关键转化反应。 [0002] Chemical oxidation reaction is one of the most important processes of the reaction, the hydrocarbon compound is a key step in the production of oxygenates conversion reaction. 如已内酰胺生产中的甲苯氧化制苯甲酸、环已烷氧化制环已酮、尼龙6生产中的对二甲苯氧化制对二苯甲酸等过程,以及异丁烷氧化为叔丁基过氧化氢和叔丁醇等工业化过程,都是石油化工中典型的强放热气液反应。 The oxidation of toluene caprolactam acid production, oxidation of cyclohexane cyclohexanone, nylon 6 Production of p-xylene oxidation process acid, etc., and the oxidation of isobutane to tertiary butyl peroxide t-butanol and hydrogen industrial processes, are typically petrochemical strongly exothermic gas-liquid reaction. 很多氧化反应采用液相氧化工艺,与气相氧化工艺相比具有反应条件温和、选择性高等优点。 Many liquid phase oxidation process using an oxidation reaction, and vapor phase oxidation process as compared with mild reaction conditions, selective advantages. 现有工业化烃类液相氧化反应器通常采用带搅拌的釜式反应器或鼓泡塔。 Current commercial liquid-phase oxidation of hydrocarbons is commonly used tank reactor or a bubble column reactor with stirring. 搅拌釜带有运动部件,其密封困难,设备的运行和维护费用高。 Stirred autoclave with a moving member that seals difficult, high operating and maintenance costs of the equipment. 同时搅拌釜和鼓泡塔反应器中液相返混严重,给提高液相氧化产物的选择性带来不利影响。 While stirred tank and bubble column reactor in the liquid phase backmixing serious, to improve the liquid-phase oxidation product selectivity adversely affected.

[0003] 烃类液相氧化反应在热力学上是高度有利的,通常情况下为强放热的自由基链式反应,容易发生热爆炸或支链爆炸。 [0003] The hydrocarbon liquid phase oxidation reaction is thermodynamically highly advantageous, is usually highly exothermic free radical chain reactions, thermal explosion prone to explosion or branched. 鼓泡塔或搅拌鼓泡反应器中,空气通过鼓泡的形式穿越反应器,在反应器的上部存在较大的气相空间,容易引起爆炸危险。 Sparged bubble column or a stirred reactor in the form of air bubbled through the reactor, there is a large vapor space in the upper portion of the reactor, a potentially explosive hazard. 现有反应器气液返混严重,气液返混不仅影响反应的选择性,还导致气泡停留时间分布宽化,尾气氧浓度控制更加困难。 Existing reactors liquid backmixing serious, not only affects the liquid backmixing selectivity of the reaction, but also leads to a broad distribution of the residence time of the bubbles, the exhaust gas oxygen concentration control is more difficult. 生产中为了保证安全,采用限制供氧量或反应气中氧含量的方式控制尾气中的氧浓度不超过爆炸极限。 To ensure the safety in production, the use of limited supply of oxygen or the amount of the reaction gas is controlled oxygen content in the oxygen concentration in the exhaust gas does not exceed the explosion limit. 这使得反应过程始终处于供氧不足的状态,并导致反应器体积庞大,空间的利用率低,生产效率低。 This makes the reaction process in a state of oxygen shortage, leading to the reactor and bulky, space utilization is low, production efficiency is low. 工业氧化反应过程中,烃的单程转化率低,大量的反应液循环导致分离过程流程长,能耗高。 Industrial oxidation reaction process, a low per pass conversion of hydrocarbons, a large amount of the reaction liquid separation process resulting in long process cycle, high energy consumption.

[0004] 通过调整反应器或气体分布器的结构型式和改善气液混合状况,提高反应器的供氧能力有望提高反应器生成能力和产物选择性。 [0004] By adjusting the structure type reactor or the gas distributor and improved gas-liquid mixing condition, improve the oxygen supply capacity of the reactor is expected to improve the ability to produce a reactor and product selectivity. 专利CN 1090165C在将立式反应器用金属多孔板分割成多个反应室,采用气液逆流的方式进行操作,使得气体分散均勻,从而提高环己烷的转化率和环己醇、环己酮的选择性。 Patent No. CN 1090165C divided in the vertical reactor porous metal plate into a plurality of reaction chambers, gas-liquid countercurrent flow operation, so that a uniform gas dispersion, thereby improving the conversion rate of cyclohexane and cyclohexanol, cyclohexanone selectivity. 专利CN 1142129C通过为现有的搅拌鼓泡反应器增设供气和曝气单元,提高反应器的供氧能力,可将装置的生产能力从100吨/天提高到133吨/天。 Patent No. CN 1142129C conventional bubble reactor is stirred by additional supply and aeration unit, to improve the oxygen supply capacity of the reactor, the production capacity of the device can be increased from 100 t / day to 133 tons / day. 专利CN 100522897C则通过对鼓泡塔内设置一定的填料段,并采用分段曝气的方式进行改造,使得反应液相以平推流的方式通过反应器,有效改善反应物的返混问题,提高环己烷的选择性。 Patent CN 100522897C by setting a certain segment of the bubble column filler, and piecewise transformation aeration manner, such that a liquid phase reaction in a plug flow manner through the reactor, back mixing issues effectively improve reactant, cyclohexane improve selectivity. 专利CN 1243704C对搅拌反应器内的搅拌桨、挡板和通气方式进行了调整,改善了氧化反应器中物料的分散情况,提高了气体处理能力。 Patent No. CN 1243704C stirring blade, a baffle and the ventilation mode in the reactor was stirred adjusted, improved dispersion of the material in the oxidation reactor, increase the processing capability of the gas. 专利CN 101143811A将鼓泡塔分为上下两个相对独立的反应区,鼓泡塔下部还增加了机械搅拌来提高混合效率, 提高反应的效率和选择性。 Patent CN 101143811A the bubble column is divided into two independent reaction zones, the lower portion of a bubble column also increases the mechanical agitation to improve the mixing efficiency, to improve the efficiency and selectivity of the reaction.

[0005] 最新的研究表明,环己烷液相氧化过程受氧浓度和传质的影响较大,环己烷催化 [0005] A recent study showed that the liquid phase oxidation of cyclohexane greatly influenced by the oxygen concentration and mass transfer in cyclohexane catalytic

3氧化动力学对氧为一级反应动力学。 3 is an oxygen oxidation kinetics of the reaction kinetics. 因此采用纯氧(富氧)进行烃类液相氧化可以提高氧浓度,从而提高反应速率和选择性。 Thus pure oxygen (oxygen-rich) for liquid-phase oxidation of hydrocarbons can increase the oxygen concentration, thereby increasing the reaction rate and selectivity. 同时采用纯氧(富氧)进行烃类液相氧化,可以降低尾气量,减少尾气处理成本。 While pure oxygen (oxygen-rich) for liquid-phase oxidation of hydrocarbons, the amount of exhaust gas can be reduced, reducing the cost of tail gas treatment. 但是在现有的搅拌鼓泡反应器和鼓泡塔反应器中使用纯氧(富氧) 氧化剂,对于像环己烷液相氧化这样的反应来说,会带来尾气中氧浓度不易控制的缺点,存在安全隐患。 However, use of pure oxygen (oxygen-rich) an oxidizing agent in a conventional stirred reactor and sparged bubble column reactors, liquid-phase oxidation of cyclohexane as for such reactions, the oxygen concentration in the exhaust gas will bring difficult to control shortcomings, there are security risks.

[0006] 对于纯氧(富氧)氧化,台湾学者陈政任提出利用水和环己烷形成共沸物的特点,以水蒸气作为惰性介质对气相空间的氧浓度进行稀释,保证反应器的安全。 [0006] For pure oxygen (oxygen-rich) oxide, Taiwan scholars Chen Zheng raised features of any forms an azeotrope with water and cyclohexane, water vapor concentration in the vapor space of the oxygen is diluted, to ensure the safety of the reactor as the inert medium. 专利US 5880683公开了一种机械搅拌反应器用于纯氧(富氧)液相氧化,采用涡轮搅拌器强力搅拌将气泡破碎分散,并增设导流筒来强化气液两相的混合,尽量提高氧气的反应深度。 Patent US 5880683 discloses a mechanically stirred reactor for the liquid-phase oxidation of pure oxygen (oxygen-rich), using a turbine agitator vigorous stirring dispersing bubble breaker, and to strengthen the Draft Tube mixed gas-liquid two-phase, to maximize oxygen the depth of reaction. 同时在反应器顶端采用开孔隔板将顶部的气相空间与液相主体分隔开,并通入氮气对顶部气相空间进行稀释以保证反应器的安全。 While using an opening in the top of the reactor space at the top of the separator the gas phase and the liquid phase separated from the body, and into a top vapor space of nitrogen was diluted to ensure the safety of the reactor. 但结果是机械搅拌会加大液相返混,而运动部件的存在使反应器的维护困难。 But the result is a mechanically stirred liquid phase backmixing will increase, and the presence of moving parts makes difficult to maintain the reactor. 同时,加入氮气稀释尾气使尾气处理负荷额外加大。 Meanwhile, the exhaust gas diluted with nitrogen so that the exhaust gas treating additional load increase.

发明内容 SUMMARY

[0007] 本发明针对现有液相氧化反应器的不足,提供一种能用于烃类液相氧化的新型反应器,特别是针对于环已烷液相纯氧(富氧)氧化反应、甲苯液相纯氧(富氧)氧化反应等烃类液相氧化反应的一种管式反应器。 [0007] The present invention is directed to a liquid phase oxidation reactor prior deficiencies and to provide a novel reactor for liquid-phase oxidation of hydrocarbons which can be used, in particular, directed to a liquid phase pure cyclohexane (oxygen-rich) the oxidation reaction, a tubular oxygen toluene phase oxidation reactor (oxygen-rich) hydrocarbons such as liquid phase oxidation reaction. 要提高氧化反应器的效率和安全性,必须突破现有的反应技术,提高反应速率、缩小反应器自由空间。 To improve the efficiency and safety of the oxidation reactor, the reaction must break the existing technology to improve response rates, reduce reactor free space. 以小直径气泡强化传质,利用通道直径限制反应程度,并强化传热以及时移走反应热是确保反应安全的基本措施。 A small diameter of the bubbles transfer enhancement by channel diameter limits the extent of reaction, and enhanced heat transfer and reaction heat removal during the reaction substantially to ensure the safety measures. 本发明专利基于这一原理设计出一种能用于烃类液相氧化的管式反应器,具有安全性高、反应选择性好、反应转化率高,便于放大等优点。 The present invention patented design based on the principle that a tubular reactor can be used in one kind of liquid-phase oxidation of hydrocarbons, with high safety, good reaction selectivity, reaction conversion rate, etc. to facilitate amplification.

[0008] 一般情况下的多孔曝气,由于气泡在空口聚并成大气泡,离开孔口后,大气泡破碎成小气泡。 [0008] Porous aeration in the general case, because bubbles larger than the air interface bubble coalescence, after leaving the orifice, breaking large bubbles into small bubbles. 由于最大稳定气泡尺寸的限制,一般只能得到最大稳定气泡尺寸大小的气泡。 Since the maximum stable bubble size limit, generally only obtain maximum bubble size of the bubble stability. 一般情况下最大稳定气泡尺寸在remm左右,一般的多孔曝气很难得到具有高传质表面的更小的气泡。 Normally the maximum stable bubble size is about remm, aeration is generally difficult to obtain a porous smaller bubbles have a high mass transfer surface. 根据我们的研究,错流微孔曝气可以得到小于最大稳定气泡尺寸的初始气泡错流微孔曝气方式的气体分布器可以产生Sauter平均直径不大于2. 0 mm (或者1. 5 mm)的微小氧气气泡。 According to our study, cross-flow microporous aeration bubbles can obtain an initial bubble size of less than the maximum steady cross-flow microporous aeration gas distributor may generate a Sauter mean diameter of no greater than 2. 0 mm (or 1. 5 mm) tiny oxygen bubbles. 因此,错流曝气可以得到较高的气液传质效率。 Accordingly, the cross flow aeration can obtain a high efficiency of gas-liquid mass transfer.

[0009] 有研究表明,液相分散的气泡发生延时爆炸的可能性发生在大于4飞mm的大气泡中,对于错流微孔曝气产生的1. 5^2. Omm以下的气泡,在反应管中是安全的。 [0009] Studies have shown that the possibility of bubble generation liquid phase dispersion explosion delay occurs in large bubbles fly greater than 4 mm, the cross-flow for the bubble 2. Omm microporous aeration below 1.5 ^ produced, in the reaction tube is safe. 由于套管管式反应器的传热效率高,也可有效地避免反应出现热爆炸的情况。 Due to the high heat transfer efficiency of the tube of the tubular reactor, can be effectively avoid thermal runaway reactions. 采用单管反应器,氧气在反应过程中大量被消耗掉,可以减小氧气(或富氧)尾气在气液分离后的气体空间,也减少了气相空间的爆炸危险。 Explosion hazard using a single reactor, a large amount of oxygen during the reaction is consumed can be reduced oxygen (or oxygen) in the exhaust gas after gas-liquid separation space, but also reduces the vapor space.

[0010] 实现上述目的的技术方案如下: [0010] The technical solution to achieve the above object are as follows:

以环己烷、甲苯、对二甲苯、异丁烷、异丙苯等液态烃为原料,纯氧或富氧空气为氧化剂。 Cyclohexane, toluene, p-xylene, isobutane, cumene and other liquid hydrocarbons as starting material, pure oxygen or oxygen-enriched air as the oxidant. 液体原料先与给定量的催化剂(如环烷酸钴、醋酸钴等)混合,然后气液两相流体经预热升温至反应温度12(T220°C后,在微孔错流曝气单元进行混合,得到气泡直径小、数量大,且分布均勻的气液混合物流,气液混合物流在管式反应器中进行充分反应,并将其中的氧气消耗完全。 First liquid feedstock, with a given amount of a catalyst (such as cobalt naphthenate, cobalt acetate, etc.), and then the reaction liquid was heated to a temperature of two-phase fluid 12 (T220 ° C after preheated at a microporous cross-flow aeration unit mixed to obtain small diameter gas bubbles, a large number of, and uniform distribution of the gas-liquid mixed stream, the mixed gas-liquid stream in the tubular reactor sufficiently reactor, and wherein oxygen is completely consumed.

[0011] 本发明的所描述的反应装置包括单通道和多通道两种类型,以及单级和多级两种型式。 The reaction apparatus [0011] according to the present invention as described include two types of single and multi-channel, multi-stage and single-stage and two types.

[0012] 单通道反应装置由气液错流方式曝气元件和管式反应器构成。 [0012] The reaction apparatus is constituted by a single-channel gas-liquid cross-flow mode and aeration element tubular reactor. 气液错流曝气元件结构如附图1所示,在液体以一定流速通过内管的过程中,氧气(或富氧)通过一个多孔金属膜管(或陶瓷烧结膜管)分布到液相中,在液体错流剪切作用下,分散为Sauter平均直径小于2. Omm的气泡,随液流进入反应管。 A gas-liquid cross flow shown in Figure 1, a constant liquid flow rate through the inner tube of the process, the oxygen (or oxygen enriched) through a metal film perforated tube (or the ceramic sintered membrane tube) to the liquid distribution element structure such as aeration , in the liquid crossflow shear, the Sauter mean diameter is smaller than the dispersion of bubbles of 2. Omm, with the flow into the reaction tube. 反应管设计如附图2所示,为套管结构,管外通冷却流体及时移走反应热,保证反应温度恒定。 The reaction tube design as shown in Figure 2, a sleeve structure, the outer tube of the cooling fluid through the heat of reaction is removed in a timely manner, to ensure a constant reaction temperature. 反应管内气液两相分散并并流通过,反应物料以平推流方式流过反应器。 Gas-liquid two-phase dispersion and the reaction tube and flows through the reaction mass to a plug flow manner through the reactor.

[0013] 管式反应区由直径为2〜50 mm的不锈钢管构成,反应区内气液混合物的流型接近平推流。 [0013] a tubular reaction zone having a diameter of 2~50 mm stainless steel tubes, the gas-liquid mixture flow pattern near the plug flow reaction zone. 通过错流曝气式气体分布器可得到气泡直径小且分布均勻气液混合物流,气液两相混合充分,可有效促进反应的进行。 By cross-flow aeration gas distributor to obtain a uniform distribution of small liquid stream and a mixing cell diameter, sufficient gas-liquid two-phase mixture, which can effectively promote the reaction.

[0014] 反应段圆管的外侧为走冷却介质的壳程,冷却介质可以是专门的冷却剂如冷却水,也可以是待预热的原料烃。 [0014] The reaction tube outer segment of the cooling medium to take the shell, the cooling medium may be a special coolant such as cooling water, may also be preheated hydrocarbon feedstock. 由此将原本独立运行的反应器和换热器集成为反应换热一体化的反应器,既能有效移走反应热,又能实现反应热的综合利用,降低装置能耗。 The independent operation whereby the original reactor and the heat exchanger integrated into an integrated reaction reactor, can effectively remove the reaction heat, but also to achieve utilization of reaction heat, reduce energy consumption devices. 其优良的传热性能保证了反应的精确控制,缩小了反应温度的波动范围,使釜式反应器出现的温度超过控制温度的现象得到根本解决。 Its excellent heat transfer performance ensures precise control of the reaction, the reaction temperature reduces the fluctuation range of the temperature of the tank reactor phenomenon occurring over a temperature controlled to be solved. 反应温度的精确控制一方面使得由温度升高引起的副反应发生的程度降低,从而提高目的产物的收率。 Precise control of the reaction temperature on the one hand such an extent that side reactions occur by the rise in temperature is reduced, thereby increasing the yield of the desired product.

[0015] 多通道反应器则由多通道曝气单元和多通道反应单元构成。 [0015] Multi-channel reactor unit by the multi-channel and multi-channel aeration reactor units. 多通道反应器由多个错流微孔曝气单管反应器并联排布组成,各管式反应元件设计为管壳式换热器结构,反应管外是壳程冷却介质。 A plurality of multi-channel reactor aeration a microporous cross-flow reactor in parallel with a single composition arrangement, each element is designed as a tube reactor shell and tube configuration heat exchanger, the reaction tube is an outer shell of the cooling medium. 多通道曝气单元结构为如附图3所示的多微孔膜管阵列,多通道反应单元为如附图4所示的阵列,曝气单元的通道的排布形式与反应单元通道的排布形式一一对应。 Multichannel aeration unit such as a microporous membrane structure is a tube array shown in Figure 3, the multi-channel array of figures as the reaction units, arranged in the form of channels with the reaction unit aeration unit shown in Figure 4 exhaust passage cloth in the form of correspondence. 其组装结构如附图5所示。 Assembling structure as shown in Figure 5. 由于气体分布器和反应区均为管状结构,形式简单, 因此通过增加平行的管状结构的数量即可实现反应器放大。 Since the gas distributor and the reaction zone are tubular structures, in the form of simple, so the reactor can be realized by increasing the number of parallel amplification of the tubular structure. 数增放大的方式可以避免传统反应器在尺寸放大中遇到的流动,传质情况发生变化的问题,使得该反应器具有放大简单易行的特点。 Increasing the number of amplification may avoid flow encountered in conventional reactors size is enlarged, the problem of mass transfer conditions change, so that the characteristics of the reactor having a simple amplification. 当反应停留时间较长时,可根据需要将单通道和多通道反应器按照附图6所示的形式进行多级串联,冷却介质可采用与反应液成并流或逆流的形式。 When the reaction residence time is longer, single and multi-channel reactor may be in the form of multi-level series shown in FIG. 6 as necessary, with the reaction liquid cooling medium may take the form of a cocurrent or countercurrent.

[0016] 本发明有益结果有: [0016] Advantageous results of the invention are:

1.设备结构紧凑,反应器空间利用率高。 1. compact structure, high reactor space utilization.

[0017] 反应器和换热器高度集成,可实现反应物料预热和反应器移热的热量集成,降低生产能耗。 [0017] The reactor and the heat exchanger highly integrated, the reaction mass can be achieved preheater and reactor heat removal heat integration, reduce energy consumption. 同时高的换热效率使得无需另设外循环换热器。 While the high heat transfer efficiency so that without a separate external circulation heat exchanger.

[0018] 反应温度的控制精确高,目标反应的选择性好,目的产物的收率高。 [0018] The precise control of the reaction temperature is high, the target reaction good selectivity, high yield of the desired product.

[0019] 反应器内在安全性高,可利用富氧或纯氧进行烃类液相氧化反应。 [0019] The intrinsic safety of the reactor, can be a hydrocarbon or oxygen-enriched liquid-phase oxidation reaction using pure oxygen.

[0020] 结构简单,维护费用低,且容易实现工业放大。 Simple [0020] structure, low maintenance, and easy to implement industrial scale.

附图说明 BRIEF DESCRIPTION

[0021] 图1单通道气液错流微孔曝气单元结构示意图;图中1为气体进口,2为液体进口,3为气液混合物出口,4为多孔膜管。 [0021] Fig 1 a schematic view of a single-channel gas-liquid cross-flow microporous aeration cell structure; FIG. 1 is a gas inlet, a liquid inlet 2, gas-liquid mixture outlet 3, 4 is a porous membrane tube.

[0022] 图2单通道管式反应器结构示意图;图中1为气体进口,2为液体进口,3为液体出口,4为冷却剂进口,5为冷却剂出口。 [0022] 2 a schematic diagram of a single channel tube reactor configuration; Figure 1 is a gas inlet, a liquid inlet 2, a liquid outlet 3, the coolant inlet 4, an outlet 5 for the coolant.

[0023] 图3多通道反应器曝气单元结构示意图;图中1为气体进口。 [0023] FIG multichannel reactor structural diagram of the aeration unit; FIG. 1 is a gas inlet. [0024] 图4多通道反应器反应段结构示意图;图中1为冷却剂进口,2为冷却剂出口。 [0024] Figure 4 a schematic section structure of a multi-channel reactor the reaction; FIG. 1 is a coolant inlet, a coolant outlet 2.

[0025] 图5多通道反应器组装示意图;图中1为气体进口,2为液体进口,3为液体出口, 4为冷却剂进口,5为冷却剂出口,6为整流挡板。 [0025] FIG. 5 schematic multichannel reactor assembly; FIG. 1 is a gas inlet, a liquid inlet 2, a liquid outlet 3, 4 to the coolant inlet, a coolant outlet 5, 6 for the rectifier baffle.

[0026] 图6单/多通道反应器多级串联示意图;(a)冷却剂管路并联结构;(b)冷却剂管路串联结构;1、气体供给总管;2、气体供给支路;3、冷却剂供给总管;4、冷却剂供给支路; 5、冷却剂出口管路;6、冷却剂汇集总管,7、反应液进口;8、反应液出口。 [0026] FIG. 6 single / multi-stage series reactor multichannel schematic; (A) the coolant line parallel configuration; (b) a series arrangement of a coolant piping; 1, gas supply manifold; 2, a gas supply section; 3 , coolant supply manifold; 4, a coolant supply branch; 5, the coolant outlet line; 6, coolant collection manifold, 7, the reaction liquid inlet; 8, the reaction liquid outlet.

具体实施方式 Detailed ways

[0027] 实施方式1 : [0027] Embodiment 1:

本实施例中的气液错流曝气单元基本结构如图1所示。 In this embodiment a gas-liquid cross flow aeration unit shown in Figure 1 the basic structure. 反应器组装后的基本结构如图2所示。 The basic structure of the reactor assembly shown in FIG. 其中曝气单元为套管结构,内管为微孔膜管,膜管长度和直径可根据实际需要通过计算得到。 Wherein the aeration unit is a double pipe structure, the inner tube is a microporous membrane tubes, tube length and diameter of the membrane may be obtained by calculation based on the actual need. 通常膜管长度为0.003、. 03 m,膜管直径为0.002、. 10 m,膜管上微孔的平均孔径为0.0广1000 μπι。 Typically membrane tube length 0.003 ,. 03 m, film tube diameter of 0.002 ,. 10 m, the microporous membrane, 0.0 average pore wide tube 1000 μπι. 反应段的长度和直径按照实际需要的反应所需停留时间和氧气被完全吸收所需的时间进行设计。 Length and diameter of the reaction zone according to the actual needs of the reaction and oxygen is the desired residence time of the time required for complete absorption of the design. 其中长度的范围为0.5〜500 m;反应管的直径为0.002、. 10 m,其大小可与曝气单元膜管的直径一致,也可以大于膜管的直径。 Wherein the range of the length of 0.5~500 m; diameter of the reaction tube is 0.002 ,. 10 m, the diameter of the same size with the aeration unit membrane tubes, it may be larger than the diameter membrane tubes. 其制作材质可为不锈钢等金属材料和陶瓷等非金属材料。 Its production may be made of a metal material such as stainless steel and non-metallic materials such as ceramic.

[0028] 其中氧气(或富氧)由图1中的气体进口进入曝气单元套管的环隙,并经微孔穿透过微孔膜管在其内侧与液态反应原料混合。 [0028] wherein the oxygen (or oxygen) into the casing annulus from the aeration gas inlet means in FIG 1, and penetrates through the microporous membrane material microporous by mixing the reaction tube at its inner side with a liquid. 液态烃的流动方向与气体流动方向相互垂直, 由此产生的剪切作用使得气泡的直径分布均勻,且平均直径不大于2.0 mm。 The flow direction of the gas flow in a direction perpendicular to each other liquid hydrocarbons, such shearing action resulting bubble diameter distribution and an average diameter no greater than 2.0 mm. 曝气单元产生的小气泡在形成后迅速被流动的反应液带走,离开曝气区,均勻地分散在液相中,从而有效地抑制了气泡间的聚并作用。 Small bubble aeration unit is produced in the reaction solution after the formation of the flow away quickly, leaving the aeration zone, uniformly dispersed in the liquid phase, thereby effectively suppressing the interaction between bubble coalescence.

[0029] 气液混合物离开曝气单元后进入反应区。 [0029] The liquid mixture leaving the reaction zone after the aeration unit. 反应区同样为套管结构,其中套管内侧走气液反应混合物,反应混合物在此充分反应直至氧气消耗完全;套管的环隙走冷却介质(冷态原料烃或冷却水等),冷却介质可以以并流或逆流的方式与管内的气液混合物进行换热。 Also the reaction zone is a double pipe structure, wherein the inner sleeve away liquid reaction mixture, the reaction mixture was sufficiently react until this complete oxygen consumption; annulus sleeve away cooling medium (cold starting hydrocarbon or cooling water, etc.), a cooling medium and heat exchange can be performed in a manner gas-liquid mixture within the tube with cocurrent or countercurrent. 由于套管结构的管径小,换热面积大,换热效率高,因此能有效避免反应器中出现热点。 Due to the small diameter of the pipe structure, large heat transfer area, heat transfer efficiency, it is possible to effectively avoid the occurrence of hot spots in the reactor. 同时在高长径比下气液混合物在管内的流动接近平推流,大大减少了氧化中间产物如醇、 酮的返混,避免其发生深度氧化,能在一定程度上提高了对目的产物的选择性。 While flowing in the tube close to the plug flow in the gas-liquid mixture at a high aspect ratio, greatly reducing the oxidation of the intermediate product, such as alcohols, ketones backmixing, avoid the occurrence of deep oxidation, the purpose can be improved to some extent, the product selectivity. 气相中的氧气在反应中被完全吸收或几乎完全吸收,因而不存在大量的含氧尾气。 Gas phase oxygen is absorbed completely or nearly completely absorbed in the reaction, and thus a large amount of oxygen-containing off-gas does not exist. 这不仅保证了反应器的安全性,还能节约了尾气处理的费用,减少了反应原料随尾气的流失。 This not only ensures the safety of the reactor, but also saves the cost of tail gas treatment, reducing the loss of the starting material with the exhaust gas.

[0030] 实施方式2 : [0030] Embodiment 2:

实施方式1的基础上采用五级串联方式构建多级分段进气反应器。 Construction intake multistage reactor embodiment employs five series based on 1. 其中各级的气体分布器均为长10 mm、内径4 mm、外径8 mm的多孔金属膜管;各级反应段均为内径50 mm的不锈钢圆管,其中前四级反应区的长度均为2 m,第五级反应区的长度为4 m。 Wherein the gas distributor levels are length 10 mm, an inner diameter of 4 mm, an outer diameter of 8 mm perforated metal film tube; reaction zone levels are stainless steel pipe of 50 mm inner diameter, wherein the length of the previous four reaction zones are is 2 m, the length of the fifth stage of the reaction zone is 4 m. 以环烷酸钴为催化剂,Co2+的质量分数为1X10_6,反应温度165°C,压力1. IMI^a下,以纯氧为氧化剂进行环己烷液相氧化生产KA油。 Cobalt naphthenate as catalyst, Co2 + mass fraction 1X10_6, the reaction temperature of 165 ° C, under pressure of 1. IMI ^ a, pure oxygen for the production of liquid-phase oxidation of cyclohexane to KA oil oxidant. 液态热环己烷流量为0.105 m_3 ^tT1,各级气体分布器的氧气流量均为0.0276 πΓ3化-1,停留时间10. 7 min,气泡Sauter平均直径1. 68 Xl(T3m,环己烷转化率为3. 5%,KA油选择性85%。环己烷氧化反应的时空产率为:1. 00 mol · m_3 · IT1。 Liquid flow hot cyclohexane 0.105 m_3 ^ tT1, oxygen flow rate of the gas distributor of 0.0276 πΓ3 levels are -1 and the residence time of 10. 7 min, Sauter mean bubble diameter of 1. 68 Xl (T3m, the conversion of cyclohexane It was 3. 5%, KA selectivity of 85% oil space-time yield of the oxidation of cyclohexane:.. 1 00 mol · m_3 · IT1.

[0031] 实施方式3: [0031] Embodiment 3:

以实施方式1为基础构建多通道反应器。 In Embodiment 1 constructed based on a multi-channel reactor. 本实施例中的气液错流曝气单元结构如图3 In this embodiment a gas-liquid cross flow aeration unit structure shown in Figure 3

6所示,反应段的结构如图4所示。 6, the structure of the reaction section as shown in FIG. 其反应器组装结构如图5所示。 Reaction assembly structure shown in Figure 5. 其中曝气单元的结构(图3)为微孔膜管阵列,微孔膜管的长度和直径同实施方式1的要求,微孔膜管的数量则根据生产能力的要求进行增减。 Wherein the structure (FIG. 3) to the aeration units tube array microporous membrane, a microporous membrane tube length and diameter of the same embodiment of claim 1, the number of the microporous membrane tube is increased or decreased in accordance with the requirements of production capacity. 曝气单元处氧气首先通过气体进口进入微孔膜管外侧的腔体, 再透过各微孔膜管进入反应液相并与之均勻混合。 First, the aeration unit from the oxygen into the cavity through the outer microporous membrane gas inlet tube, and then the reaction liquid into the microporous film through the respective tubes and uniformly mixed therewith. 反应液通过液相进口进入反应器,经挡板对流速分布进行适当调整后分别流入各微孔膜管,并通过剪切作用将透过膜管的气体分散为直径不大于2mm的气泡。 The reaction liquid by liquid inlet into the reactor, the velocity profile of the tailgate appropriately adjusted flows into each of the microporous film tube, and dispersed by a shearing action of the gas permeable membrane tube is not larger than the diameter of the bubbles of 2mm. 同时液流迅速将形成的小气泡带离曝气区并均勻分散反应液相中。 While rapid stream of small bubbles will form away from the aeration zone and uniformly dispersed in the reaction liquid phase. 反应段结构如图4所示,其中各管的布局与曝气单元各微孔膜管的布局一一对应。 The reaction section configuration shown in Figure 4, wherein the aeration unit layout is the microporous membrane tubes each tube one correspondence.

[0032] 反应段与曝气段的连接方式可以采用法兰连接或焊接。 [0032] reaction zone and the aeration connection sections may be welded or flange connection. 同样反应段的长度和直径如实施方式1的要求,并根据实际需要的反应所需停留时间和氧气被完全吸收所需的时间进行设计。 Segment length and diameter of the same reaction as described in claim 1 of the embodiment, and the required residence time, and oxygen is the time required for complete absorption designed according to the actual needs of the reaction. 反应管的数量与曝气单元中微孔膜管的数量一致。 Consistent with the number of the microporous membrane aeration tube unit reaction tube. 在这里各管的流动和反应状态是一致的,不存在传统的放大过程中存在流动状态发生变化等问题,只须根据生产能力的要求,对曝气单元和反应单元进行数增,并进行经适当布局即可完成装置的放大。 Here the state of the flow tubes and the reaction is the same, and so there is no problem to change the flow state in the presence of conventional amplification process, only according to the requirements of production capacity of the reaction aeration unit and increase the number of units, and by amplifying means to a suitable layout is completed. 气液混合物充分反应后气相氧被完全吸收或几乎完全吸收,反应后的液相在反应管的出口端会合后流出反应器进入下一工段进行处理。 Gaseous oxygen is completely absorbed, or nearly completely absorbed liquid reaction mixture sufficiently, the reaction liquid after the outlet end of the reactor effluent after the convergence of the reactor tube into the next processing station.

[0033] 实施方式4 : [0033] Embodiment 4:

以实施方式1为基础,如图6所示构建多级串联单通道反应器,各反应单元冷却介质可以为串联或并联,与反应液流动方向为并流或逆流。 In Embodiment 1 is constructed based on a single channel multi-stage series reactor shown in Figure 6, each of the reaction unit cooling medium may be a series or parallel with the direction of flow of the reaction liquid cocurrent or countercurrent.

[0034] 实施方式5 : [0034] Embodiment 5:

以实施方式3为基础,如图6所示构建多级串联多通道反应器,各反应单元冷却介质可以为串联或并联,与反应液流动方向为并流或逆流。 In the third embodiment constructed based on the multi-channel multi-stage series reactor shown in Figure 6, each of the reaction unit cooling medium may be a series or parallel with the direction of flow of the reaction liquid cocurrent or countercurrent.

Claims (10)

1. 一种用于烃类氧化的管式反应器,该反应器适用于换热负荷很大的烃类液相氧化反应,其特征在于该反应器主要由气液错流微孔曝气单元、管式气液两相反应单元以及走冷却介质的壳体组成。 A hydrocarbon oxidation tubular reactor for the reactor heat load applied to a large liquid-phase oxidation reaction of hydrocarbons, wherein the reactor is mainly composed of a gas-liquid cross-flow microporous aeration unit , gas-liquid two-phase reaction tube housing unit and a cooling medium consisting of walking.
2.根据权利要求1所述,曝气单元的特征为液体流动的通道中有一段由微孔膜管或侧壁开孔的圆管构成,其材质可以是金属或陶瓷,膜管长度为0.003 - 0. 03 m,膜管内径/外径为0.002 - 0. 10 m,膜管微孔的平均孔径范围为0.01 - 1000 μ m。 2. The method of claim 1, wherein the aeration unit is a liquid flow path from the opening there is a microporous membrane or a tube constituting the tube side wall, the material may be metal or ceramic membrane tube length 0.003 - 0. 03 m, the film tube diameter / outer diameter of 0.002 - 0. 10 m, an average pore size of the microporous membrane tube is 0.01 - 1000 μ m.
3.根据权利要求1所述,反应单元的特征为套管结构,内管长度为0.5 - 500 m,内径/外径为0.002 - 0. 10 m,其大小可与曝气单元的内/外径一致,也可以比曝气单元的内/ 外径大。 3. The method of claim 1, wherein the reaction unit is a double pipe structure, the inner tube length is 0.5 - 500 m, an inner diameter / outer diameter of 0.002 - 0. 10 m, and its size may be within the aeration unit / outer same diameter, may be / is larger than the outer diameter of the aeration unit.
4.根据权利要求1所述,管式反应器可采用气液错流微孔曝气单元与管式气液两相反应单元串联的单通道结构,反应器可竖直放置或水平放置,竖直放置时曝气单元可以连接在反应单元顶部,此时气液混合物并流向下,曝气单元可以连接在反应单位的底部,此时气液混合物并流向上。 4. The method of claim 1, the tubular reactor can be a single-channel structure cross-flow liquid porous aeration unit and a tubular gas-liquid two-phase reaction units connected in series, the reactor may be placed vertically or horizontally, vertical when direct aeration unit is placed at the top of the reaction unit may be connected, and at this time the flow of the liquid mixture, the aeration unit may be attached to the bottom of the reaction units, and at this time the flow of the liquid mixture.
5.根据权利要求1所述,管式反应器可采用由曝气单元阵列和反应单元阵列共同构成的多通道结构,微孔膜管和反应单元圆管的几何排列形式可以为正三角形,正方形或正方形错列等形式,所有膜管包含在同一个壳体内,壳体上有一个或多个对称分布的进气口,反应单元的所有圆管则被包裹在另一个壳体内,壳内间隙为冷却介质流动空间,壳体上有一个或多个对称分布的冷却介质进出口。 5. The method of claim 1, the tubular reactor may employ multichannel structure array by the aeration unit and together constitute the reaction cell array, a microporous membrane tube and the reaction tube are arranged in the form of geometric means may be an equilateral triangle, square staggered squares or the like forms, all membrane tube contained in the same housing, an air inlet or a plurality of symmetrically distributed on the casing, all the reaction tube units were wrapped in the other housing shell gap the flow space for the cooling medium, a cooling medium to one or more export symmetrically distributed on the housing.
6.根据权利要求1所述,多通道结构管式反应器的液相进料口架设有适当尺寸的挡板或多孔板对液体进料的流速分布进行调整,使得液体流速在整个空间上分布均勻,各膜管内的液体流速基本一致。 6. The method of claim 1, liquid multichannel structure in the tubular reactor inlet bridged or baffle plates of appropriate size for the feed liquid flow rate distribution is adjusted, so that the liquid flow velocity distribution across the entire space uniform, the flow rate of the liquid in each membrane tube substantially uniform.
7.根据权利要求1所述,反应器反应单元圆管内为气液两相反应混合物的流动通道, 圆管与外壳之间的空间为冷却剂的流动空间,冷却剂可为待加热的液态烃,也可以是冷却水等专用冷却介质,并且冷却剂与反应物流的流向可以为并流或逆流。 7. The method of claim 1, the reactor is a pipe reactor unit gas-liquid two-phase reaction mixture flow path, the space between the tube and the housing space for the coolant flow, the coolant can be heated hydrocarbon liquid , may be a special cooling medium such as cooling water, and the reaction with the flow of the coolant stream can be cocurrent or countercurrent.
8.根据权利要求1所述,曝气单元的膜管内液速为0.25 m. S-1- 25 m. s—1,微孔孔口处的气速为0. 1 m. s—1 - 50 m. s—1,所得气泡直径不大于2. 0 mm。 According to claim 1, film tube means is a liquid aeration velocity 0.25 m S-1- 25 m s-1, a microporous gas velocity at the orifice is 0. 1 m s-1... - 50 m. s-1, the resulting bubble diameter no greater than 2. 0 mm.
9.根据权利要求1所述,单通道和多通道管式反应器均可直接利用纯氧或氧浓度大于30%的含氧气体进行烃类液相氧化反应,根据烃类原料的不同反应温度为100°C -250°C。 According to claim 1, single and multi-channel tube as claimed in claim reactor can be directly or using an oxygen-containing gas is pure oxygen concentration of greater than 30% of the liquid phase oxidation reaction of hydrocarbons carried out, the reaction temperature varies depending on the different hydrocarbon feedstock of 100 ° C -250 ° C.
10.根据权利要求1所述,管式反应器的结构可以是由多个单通道曝气单元和单通道反应单元,以及多个多通道曝气单元和多通道反应单元,按照曝气单元、反应单元交替的方式串联形成的多级反应系统。 10. The method of claim 1, the structure of the tubular reactor may be a plurality of single-channel and single-channel units reaction aeration unit, an aeration unit and a plurality of multi-channel and multi-channel reactor unit, in accordance with the aeration unit, multistage reactor system reaction unit formed in series in an alternating manner.
CN2010105840445A 2010-12-13 2010-12-13 Tubular reactor for performing liquid phase oxidation on cyclohexane by utilizing pure oxygen (enriched oxygen) CN102059081A (en)

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