CN114768690A - Reactor and method for gas-solid continuous photocatalytic direct oxidation of methane to methanol - Google Patents

Abstract

A reactor and a method for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis are disclosed, wherein a cylindrical reactor main body is arranged on a bottom plate, a reaction plate is arranged in the middle of the reactor main body, a light-transmitting sheet is arranged on the reactor main body above the reaction plate, a reaction cavity is formed between the reaction plate and the light-transmitting sheet, an air inlet channel and an air outlet channel which are communicated with the reaction cavity are processed on the reactor main body, and an annular cover plate is connected to the reactor main body above the light-transmitting sheet; spreading a certain amount of catalyst powder in a catalyst filling area, pressing the catalyst powder by using an in-situ pressing die, allowing a mixed gas of methane and oxidizing gas to enter a reaction cavity under the reaction conditions of low temperature and normal pressure, contacting the mixed gas with a catalyst under illumination and reacting, and condensing the reacted mixed gas to separate out methanol. The invention has the advantages of high catalytic efficiency, easy unloading and recovery of the catalyst and easy cleaning.

Description

Translated fromChinese

气固相连续光催化甲烷直接氧化制甲醇的反应器及方法Reactor and method for gas-solid continuous photocatalytic direct oxidation of methane to methanol

技术领域technical field

本发明属于化学反应设备技术领域，具体涉及到一种气固相连续光催化甲烷直接氧化制甲醇的反应器及方法。The invention belongs to the technical field of chemical reaction equipment, and particularly relates to a reactor and a method for producing methanol by gas-solid continuous photocatalytic direct oxidation of methane.

背景技术Background technique

甲烷是天然气、页岩气、煤层气、可燃冰等含碳资源的主要成分，在世界范围内储量可观，除了被直接用作燃料之外，还可以作为原料来合成高附加值产品。甲醇是重要的基础化工原料，又可以作为清洁燃料，是甲烷转化的最理想产品，保留了甲烷的绝大部分能量。将甲烷转化合成甲醇，有利于实现甲烷资源的高效利用，同时解决了气态甲烷储存和输送成本高的问题，是天然气优化利用中极具吸引力的途径之一。Methane is the main component of carbon-containing resources such as natural gas, shale gas, coalbed methane, and combustible ice. It has considerable reserves around the world. In addition to being directly used as fuel, it can also be used as a raw material to synthesize high value-added products. Methanol is an important basic chemical raw material and can also be used as a clean fuel. It is the most ideal product for methane conversion and retains most of the energy of methane. Converting methane into methanol is conducive to the efficient utilization of methane resources, and at the same time solves the problem of high storage and transportation costs of gaseous methane, which is one of the most attractive ways to optimize the utilization of natural gas.

目前工业上通常采用甲烷间接合成甲醇法，即先由甲烷和水蒸气反应生成合成气，再由合成气生产甲醇，存在反应温度高，工艺流程长，能耗和设备投资均较大等缺点。甲烷直接氧化制甲醇可大幅缩短工艺流程，降低能耗。该技术主要面临两大难题：一是甲烷分子的碳氢键解离能很大(439.3kJ/mol)，活化困难；二是甲醇分子较活泼，容易被过度氧化为二氧化碳。因此高效活化甲烷并控制其氧化程度，抑制甲醇的过度氧化显得尤为重要。At present, the industry usually adopts the indirect method of synthesizing methanol from methane, that is, the synthesis gas is first produced by the reaction of methane and water vapor, and then methanol is produced from the synthesis gas, which has disadvantages such as high reaction temperature, long process flow, large energy consumption and equipment investment. The direct oxidation of methane to methanol can greatly shorten the process flow and reduce energy consumption. This technology mainly faces two major problems: first, the dissociation energy of carbon-hydrogen bond of methane molecule is very large (439.3kJ/mol), and activation is difficult; second, methanol molecule is relatively active and easily over-oxidized to carbon dioxide. Therefore, it is particularly important to efficiently activate methane and control its oxidation degree to inhibit the over-oxidation of methanol.

光催化甲烷直接氧化为甲醇是理想的反应途径。与传统热催化反应相比，光催化反应从高能量的甲烷激发态出发，能够实现很多传统基态条件下无法自发进行的转化过程或降低催化反应所需要的温度，实现在温和条件下甲烷的转化，并减少副反应的发生。随着光催化甲烷制甲醇技术的发展，可分为气液固多相和气固相反应，多为间歇过程。迄今为止，鲜见关于气固相光催化甲烷直接氧化制甲醇反应的研究报道。The photocatalytic direct oxidation of methane to methanol is an ideal reaction pathway. Compared with the traditional thermocatalytic reaction, the photocatalytic reaction starts from the high-energy methane excited state, and can realize many conversion processes that cannot be carried out spontaneously under the traditional ground state conditions or reduce the temperature required for the catalytic reaction, and realize the conversion of methane under mild conditions. , and reduce the occurrence of side reactions. With the development of photocatalytic methane-to-methanol technology, it can be divided into gas-liquid-solid multiphase and gas-solid phase reactions, mostly batch processes. So far, there are few reports on the gas-solid photocatalytic direct oxidation of methane to methanol.

光反应器是光催化反应过程的核心设备，然而有关气固相光催化甲烷直接氧化制甲醇的反应器的开发严重滞后于光催化剂的研究和发展。目前，用于气固相光催化甲烷直接氧化制甲醇的反应器主要有流化床光反应器和固定床光反应器，存在以下问题：(1)流化床光反应器通过催化剂的悬浮分散提高了催化剂的有效利用面积，但催化剂回收和后处理较困难，重复使用性差，反应器内光分布不均匀。(2)固定床光反应器虽然解决了催化剂回收和重复使用的问题，但存在有效催化面积小、传质传热效率不高、床层温度不容易控制等缺点。(3)目前光反应器内的流体通道都处于常规尺度，不可避免地存在热质传递受限、光子传输受限、反应器体积大、处理量小等缺点。The photoreactor is the core equipment of the photocatalytic reaction process, however, the development of the reactor for the direct oxidation of methane to methanol by gas-solid photocatalysis is seriously lagging behind the research and development of photocatalysts. At present, the reactors used for gas-solid photocatalytic direct oxidation of methane to methanol mainly include fluidized bed photoreactors and fixed bed photoreactors, which have the following problems: (1) The fluidized bed photoreactors are used for the suspension and dispersion of catalysts. The effective utilization area of the catalyst is improved, but the recovery and post-treatment of the catalyst are difficult, the reusability is poor, and the light distribution in the reactor is uneven. (2) Although the fixed bed photoreactor solves the problem of catalyst recovery and reuse, it has shortcomings such as small effective catalytic area, low mass transfer and heat transfer efficiency, and difficult bed temperature control. (3) At present, the fluid channels in photoreactors are all at conventional scales, which inevitably have disadvantages such as limited heat and mass transfer, limited photon transmission, large reactor volume, and small processing capacity.

发明内容SUMMARY OF THE INVENTION

本发明所要解决的技术在于克服现有技术的缺点，提供一种设计合理、操作方便、催化剂容易卸载和回收、催化效率高的气固相连续光催化甲烷直接氧化制甲醇的反应器及方法。The technology to be solved by the present invention is to overcome the shortcomings of the prior art, and to provide a reactor and method for producing methanol by gas-solid continuous photocatalytic direct oxidation of methane with reasonable design, convenient operation, easy unloading and recovery of catalyst, and high catalytic efficiency.

解决上述技术问题所采用的技术方案是：一种气固相连续光催化甲烷直接氧化制甲醇的反应器，底板上设置有圆柱形的反应器主体，反应器主体底部设置有换热槽，底板上设置有与换热槽相连通的入口和出口，反应器主体中部设置有反应板，位于反应板上方反应器主体上设置有透光片，反应板与透光片之间形成反应腔体，反应器主体上加工有与反应腔体相连通的进气通道和出气通道，位于透光片上方反应器主体上可拆卸连接有环形的盖板；所述反应板为反应板本体上表面上从一端到另一端依次加工有相连通的原料气混合槽、气体分布槽、反应通道区、气体收集槽，原料气混合槽底部加工有与进气通道相连通的第一通气孔，气体收集槽底部加工有与出气通道相连通的第二通气孔，原料气混合槽和气体分布槽及气体收集槽的深度相同，反应通道区由至少条反应通道组成，反应通道的底低于原料气混合槽的底形成催化剂装填区。The technical solution adopted to solve the above technical problems is: a reactor for the direct oxidation of methane to methanol by gas-solid phase continuous photocatalysis, the bottom plate is provided with a cylindrical reactor main body, the bottom of the reactor main body is provided with a heat exchange tank, and the bottom plate is provided with a heat exchange tank. The upper part is provided with an inlet and an outlet that communicate with the heat exchange tank, a reaction plate is arranged in the middle of the reactor main body, a light-transmitting sheet is arranged on the reactor main body above the reaction plate, and a reaction cavity is formed between the reaction plate and the light-transmitting sheet, The main body of the reactor is machined with an air inlet channel and an air outlet channel that communicate with the reaction cavity, and a ring-shaped cover plate is detachably connected to the main body of the reactor above the light-transmitting sheet; From one end to the other end, the raw material gas mixing tank, the gas distribution tank, the reaction channel area, and the gas collection tank are processed in sequence. There is a second ventilation hole communicated with the gas outlet channel, the depth of the raw gas mixing tank, the gas distribution tank and the gas collection tank are the same, the reaction channel area is composed of at least one reaction channel, and the bottom of the reaction channel is lower than the raw material gas mixing tank. The bottom forms a catalyst packing area.

作为一种优选的技术方案，所述反应板的原料气混合槽是一长边为圆弧的长方形槽，所述气体分布槽是等腰梯形槽，所述气体收集槽是等腰三角形槽。As a preferred technical solution, the raw material gas mixing tank of the reaction plate is a rectangular tank with a long side arc, the gas distribution tank is an isosceles trapezoid tank, and the gas collection tank is an isosceles triangle tank.

作为一种优选的技术方案，所述反应通道的宽度为0.5～3mm、深度为0.5～3mm。As a preferred technical solution, the reaction channel has a width of 0.5-3 mm and a depth of 0.5-3 mm.

作为一种优选的技术方案，所述反应通道的底比原料气混合槽e的底低0.1～1mm。As a preferred technical solution, the bottom of the reaction channel is 0.1-1 mm lower than the bottom of the raw gas mixing tank e.

作为一种优选的技术方案，所述相邻两条反应通道之间的距离为1～3mm。As a preferred technical solution, the distance between the two adjacent reaction channels is 1-3 mm.

作为一种优选的技术方案，所述透光片分别与反应器主体和盖板之间均设置有密封圈。As a preferred technical solution, a sealing ring is provided between the light-transmitting sheet, the main body of the reactor and the cover plate, respectively.

作为一种优选的技术方案，所述的反应板用3D打印方法加工制成，材料为树脂或不锈钢或合金或聚合物材料。As a preferred technical solution, the reaction plate is processed by 3D printing method, and the material is resin or stainless steel or alloy or polymer material.

一种用于气固相连续光催化甲烷直接氧化制甲醇的方法，包括以下步骤组成：A method for gas-solid continuous photocatalytic direct oxidation of methane to methanol, comprising the following steps:

S1.将一定量催化剂粉末均匀地平铺于反应板上的催化剂装填区，用原位压制模具对催化剂粉末进行压制，将催化剂固定于催化剂装填区，压制后催化剂表面与原料气混合槽底面平齐；S1. Spread a certain amount of catalyst powder evenly on the catalyst loading area on the reaction plate, press the catalyst powder with an in-situ pressing mold, fix the catalyst in the catalyst loading area, and the surface of the catalyst after pressing is flush with the bottom surface of the raw gas mixing tank ;

S2.将反应板置于反应器主体中，在其上依次放置密封圈、透光片和盖板，并用螺栓进行紧固，保证反应腔体的密封性；S2. Place the reaction plate in the main body of the reactor, place a sealing ring, a light-transmitting sheet and a cover plate on it in sequence, and fasten them with bolts to ensure the tightness of the reaction chamber;

S3.将光源置于反应器上方，使光束垂直于透光片入射；向反应器主体中换热槽通入换热介质，控制反应体系的温度；S3. Place the light source above the reactor, so that the light beam is incident perpendicular to the light-transmitting sheet; enter the heat exchange medium into the heat exchange tank in the main body of the reactor to control the temperature of the reaction system;

S4.在低温、常压的反应条件下，将甲烷和氧化气按照一定比例混合，由进气通道进入反应腔体内，流经反应通道区时，在光照下与催化剂接触并发生反应，反应后的混合气体由出气通道流出，经冷凝分离出甲醇，未反应的气体组分可循环至进气通道前，并与原料气混合后继续反应。S4. Under the reaction conditions of low temperature and normal pressure, mix methane and oxidizing gas according to a certain proportion, enter the reaction chamber through the air inlet channel, and when flowing through the reaction channel area, contact with the catalyst under illumination and react, after the reaction The mixed gas flows out from the gas outlet channel, and the methanol is separated by condensation. The unreacted gas components can be recycled to the front of the gas inlet channel, and continue to react after being mixed with the raw material gas.

作为一种优选的技术方案，所述原位压制模具为基座上加工与反应通道相匹配的压条，压条的高度大于反应通道的深度、长度大于反应通道的长度。As a preferred technical solution, the in-situ pressing mold is a bead that is processed on the base to match the reaction channel, and the height of the bead is greater than the depth and length of the reaction channel.

作为一种优选的技术方案，所述原位压制模具用3D打印方法加工制成，材料为树脂或聚合物材料。As a preferred technical solution, the in-situ pressing mold is processed by a 3D printing method, and the material is resin or polymer material.

本发明的有益效果如下：The beneficial effects of the present invention are as follows:

(1)本发明光反应器的通道尺度小，比表面积大，强化了光催化甲烷直接氧化制甲醇过程的传质传热，加快反应速率，及时移出甲烷氧化释放的热量，同时可以精确控制物料的停留时间，避免因温度过高、反应时间过长而使甲醇过度氧化产生副产物，提高了目的产物甲醇的选择性，同时提高了催化剂的稳定性和使用寿命；(1) The channel size of the photoreactor of the present invention is small, the specific surface area is large, the mass and heat transfer in the process of photocatalytic direct oxidation of methane to methanol is strengthened, the reaction rate is accelerated, the heat released by the oxidation of methane can be removed in time, and the material can be accurately controlled at the same time. The residence time is longer, avoiding excessive oxidation of methanol to produce by-products due to excessive temperature and excessive reaction time, improving the selectivity of the target product methanol, and at the same time improving the stability and service life of the catalyst;

(2)本发明可实现连续的气固相光催化甲烷直接氧化制甲醇反应；(2) the present invention can realize continuous gas-solid-phase photocatalytic direct oxidation of methane to methanol reaction;

(3)本发明光反应器的高径比小，光在传输过程中衰减少，且光在催化剂床层上的分布均匀；(3) the aspect ratio of the photoreactor of the present invention is small, the attenuation of light is reduced in the transmission process, and the distribution of light on the catalyst bed is uniform;

(4)可根据实际需要灵活更换反应板，调整反应板上各区域和反应通道的形状和尺寸。相比于传统催化剂装填法，“粉末装填-原位压片”的催化剂装填方法操作方便，且催化剂容易卸载和回收；(4) The reaction plate can be flexibly replaced according to actual needs, and the shape and size of each area and reaction channel on the reaction plate can be adjusted. Compared with the traditional catalyst filling method, the "powder filling-in-situ tableting" catalyst filling method is easy to operate, and the catalyst is easy to unload and recover;

(5)本发明为组合式结构，易于拆卸清洗。(5) The present invention is a combined structure, which is easy to disassemble and clean.

附图说明Description of drawings

图1是本发明气固相连续光催化甲烷直接氧化制甲醇的反应器的结构示意图。1 is a schematic structural diagram of a reactor for the direct oxidation of methane to methanol by gas-solid-phase continuous photocatalysis of the present invention.

图2是图1的爆炸示意图。FIG. 2 is an exploded schematic diagram of FIG. 1 .

图3是图2中反应板3的结构示意图。FIG. 3 is a schematic structural diagram of thereaction plate 3 in FIG. 2 .

图4是原位压制模具7的结构示意图。FIG. 4 is a schematic structural diagram of the in-situpressing mold 7 .

具体实施方式Detailed ways

下面结合附图和实施例对本发明进一步详细说明，但本发明不限于下述的实施方式。The present invention will be further described in detail below with reference to the accompanying drawings and examples, but the present invention is not limited to the following embodiments.

在图1～3中，本实施例的气固相连续光催化甲烷直接氧化制甲醇的反应器由盖板1、透光片2、反应板3、反应器主体4、密封圈5、底板6连接构成，圆形的底板6上粘接有圆柱形的反应器主体4，反应器主体4底部加工有换热槽j，底板6上加工有与换热槽j相连通的入口和出口，反应过程中通过底板6上的入口和出口向换热槽j内通入热蒸汽或热水为反应提供合适的温度，反应器主体4中部安装有反应板3，反应板3为反应板3本体上表面上从一端到另一端依次加工有相连通的原料气混合槽e、气体分布槽f、反应通道g区、气体收集槽h，原料气混合槽e为一长边为圆弧的长方形槽，原料气混合槽e底部加工有与进气通道d相连通的第一通气孔c，气体分布槽f为等腰梯形槽，气体收集槽h是等腰三角形槽，气体收集槽h底部加工有与出气通道b相连通的第二通气孔a，原料气混合槽e和气体分布槽f及气体收集槽h的深度相同，反应通道g区由16条间距相等且相互平行的反应通道g组成，反应通道g的底低于原料气混合槽e的底形成催化剂装填区，相邻两反应通道g之间的距离为1.5mm，反应通道g的宽度为1.5mm、深度为2mm、长度为36mm，反应通道g的底比原料气混合槽e的底低0.7mm，反应板3用3D打印方法加工制成，位于反应板3上方反应器主体4上安装有透光片2，反应板3与透光片2之间形成反应腔体，反应器主体4上加工有进气通道d和出气通道b，进气通道d和出气通道b的直径均为2mm，进气通道d通过第一通气孔c与反应腔体相连通，出气通道b通过第二通气孔a与反应腔体相连通，位于透光片2上方反应器主体4上通过螺纹紧固件固定连接有环形的盖板1。本实施例盖板1、反应板3、反应器主体4和底板6的材质均为不锈钢。In FIGS. 1 to 3 , the reactor for the gas-solid phase continuous photocatalytic direct oxidation of methane to methanol in this embodiment consists of a cover plate 1 , a light-transmitting sheet 2 , areaction plate 3 , a reactor main body 4 , asealing ring 5 , and abottom plate 6 The connection structure is that a cylindrical reactor main body 4 is bonded on thecircular bottom plate 6, a heat exchange tank j is processed at the bottom of the reactor main body 4, and an inlet and an outlet that communicate with the heat exchange tank j are processed on thebottom plate 6. In the process, hot steam or hot water is introduced into the heat exchange tank j through the inlet and outlet on thebottom plate 6 to provide a suitable temperature for the reaction. Thereaction plate 3 is installed in the middle of the reactor main body 4, and thereaction plate 3 is on the body of thereaction plate 3. The raw material gas mixing tank e, the gas distribution tank f, the reaction channel g area, and the gas collection tank h are processed in sequence from one end to the other end on the surface. The bottom of the raw gas mixing tank e is processed with a first ventilation hole c that communicates with the air inlet channel d, the gas distribution tank f is an isosceles trapezoid groove, the gas collection tank h is an isosceles triangle groove, and the bottom of the gas collection tank h is processed with a The second vent hole a connected with the gas outlet channel b, the raw gas mixing tank e, the gas distribution tank f and the gas collection tank h have the same depth, and the reaction channel g area is composed of 16 reaction channels g with equal spacing and parallel to each other. The bottom of the channel g is lower than the bottom of the raw gas mixing tank e to form a catalyst loading area, the distance between two adjacent reaction channels g is 1.5mm, the width of the reaction channel g is 1.5mm, the depth is 2mm, and the length is 36mm. The bottom of the channel g is 0.7mm lower than the bottom of the raw gas mixing tank e. Thereaction plate 3 is processed by 3D printing method. The light-transmitting sheet 2 is installed on the reactor main body 4 above thereaction plate 3. A reaction cavity is formed between the sheets 2, and an inlet channel d and an outlet channel b are processed on the main body 4 of the reactor. The reaction chamber is communicated, the gas outlet channel b is communicated with the reaction chamber through the second vent hole a, and an annular cover plate 1 is fixedly connected to the reactor main body 4 above the light-transmitting sheet 2 by threaded fasteners. In this embodiment, the cover plate 1 , thereaction plate 3 , the reactor main body 4 and thebottom plate 6 are all made of stainless steel.

本实施例所述反应器用于气固相连续光催化甲烷直接氧化制甲醇的方法，由以下步骤组成：The reactor described in this embodiment is used for the method for the direct oxidation of methane to methanol by gas-solid phase continuous photocatalysis, which is composed of the following steps:

S1.将0.43g催化剂粉末均匀地平铺于反应板3上的催化剂装填区，用原位压制模具7对催化剂粉末进行压制，将催化剂固定于催化剂装填区，压制后催化剂表面与原料气混合槽e底面平齐；S1. Spread 0.43 g of catalyst powder evenly on the catalyst loading area on thereaction plate 3, use the in-situ pressing mold 7 to press the catalyst powder, fix the catalyst in the catalyst loading area, and the surface of the catalyst and the raw gas mixing tank e after pressing the bottom surface is flush;

催化剂为掺杂了Pt的MoO₃/HZSM-5(n_Pt/n_Mo＝0.02)分子筛基催化剂；The catalyst is MoO₃ /HZSM-5 (n_Pt /n_Mo =0.02) molecular sieve-based catalyst doped with Pt;

原位压制模具7为圆形基座上加工与反应通道g相匹配的压条，相邻两压条之间的距离为1.55mm，压条的高度为3mm、长度为40mm、宽度为1.45mm，原位压制模具7的材料为树脂，用3D打印方法加工制成，如图4；The in-situ pressing mold 7 is a bead that matches the reaction channel g processed on the circular base, the distance between the adjacent two bead is 1.55mm, the height of the bead is 3mm, the length is 40mm, and the width is 1.45mm. The material of thepressing mold 7 is resin, which is processed by the 3D printing method, as shown in Figure 4;

S2.将反应板3置于反应器主体4中，在其上依次放置密封圈5、透光片2和盖板1，并用螺栓进行紧固，保证反应腔体的密封性；S2. Place thereaction plate 3 in the reactor main body 4, place the sealingring 5, the light-transmitting sheet 2 and the cover plate 1 on it in turn, and fasten them with bolts to ensure the tightness of the reaction chamber;

S3.将氙灯光源置于反应器上方，使光束垂直于透光片2入射；向反应器主体4的换热槽j通入80℃循环水，控制反应体系的温度；S3. Place the xenon lamp light source above the reactor so that the light beam is incident perpendicular to the light-transmitting sheet 2; feed 80°C circulating water into the heat exchange tank j of the main body 4 of the reactor to control the temperature of the reaction system;

S4.将甲烷、氧气和氮气按照8：1：10的体积比混合，总流率为75mL/min，由进气通道d进入反应腔体内，流经反应通道g区时，在光照下与催化剂接触并发生反应，反应后的混合气体由出气通道b流出，经冷凝分离出甲醇，未反应的气体组分可循环至进气通道d前，并与原料气混合后继续反应。S4. Mix methane, oxygen and nitrogen according to the volume ratio of 8:1:10, the total flow rate is 75mL/min, enter the reaction chamber through the inlet channel d, and flow through the reaction channel g area, under the illumination with the catalyst After contacting and reacting, the mixed gas after the reaction flows out from the gas outlet channel b, and the methanol is separated by condensation.

连续反应1h后,出口气体经气相色谱仪检测，甲烷转化率为67％，甲醇选择性为95％。After continuous reaction for 1h, the outlet gas was detected by gas chromatograph, the conversion rate of methane was 67%, and the selectivity of methanol was 95%.

实施例2Example 2

在本实施例中，反应板3为反应板3本体上表面上从一端到另一端依次加工有相连通的原料气混合槽e、气体分布槽f、反应通道g区、气体收集槽h，原料气混合槽e是一长边为圆弧的长方形槽，原料气混合槽e底部加工有与进气通道d相连通的第一通气孔c，气体分布槽f是等腰梯形槽，气体收集槽h是等腰三角形槽，气体收集槽h底部加工有与出气通道b相连通的第二通气孔a，原料气混合槽e和气体分布槽f及气体收集槽h的深度相同，反应通道g区由1条反应通道g构成，反应通道g的底低于原料气混合槽e的底形成催化剂装填区，反应通道g的宽度为3mm、深度为3mm、长度为30mm，反应通道g的底比原料气混合槽e的底低1mm，反应板3用3D打印方法加工制成，材料为聚四氟。其他零部件及零部件的连接关系与实施例1相同。In this embodiment, the upper surface of thereaction plate 3 is formed with a raw material gas mixing tank e, a gas distribution tank f, a reaction channel g area, and a gas collection tank h which are connected in sequence from one end to the other end. The gas mixing tank e is a rectangular tank with a long side of an arc, the bottom of the raw gas mixing tank e is machined with a first ventilation hole c that communicates with the air inlet channel d, the gas distribution tank f is an isosceles trapezoidal tank, and the gas collection tank h is an isosceles triangular groove, the bottom of the gas collection groove h is machined with a second vent hole a that communicates with the gas outlet channel b, the raw gas mixing groove e, the gas distribution groove f and the gas collection groove h have the same depth, and the reaction channel g area It consists of one reaction channel g. The bottom of the reaction channel g is lower than the bottom of the raw gas mixing tank e to form a catalyst loading area. The width of the reaction channel g is 3mm, the depth is 3mm, and the length is 30mm. The bottom of the reaction channel g is higher than the raw material. The bottom of the gas mixing tank e is 1 mm lower, and thereaction plate 3 is processed by 3D printing method, and the material is polytetrafluoroethylene. The other parts and the connection relationship of the parts are the same as those in the first embodiment.

本实施例的原位压制模具7为圆形基座上加工与反应通道g相匹配的压条，压条的高度为4.5mm、长度为34mm、宽度为2.95mm，相邻两压条之间的距离为3.05mm，原位压制模具7的材料为树脂，用3D打印方法加工制成。The in-situ pressing mold 7 in this embodiment is a bead that is processed on a circular base to match the reaction channel g. The height of the bead is 4.5 mm, the length is 34 mm, and the width is 2.95 mm, and the distance between the adjacent two beading is 3.05mm, the material of the in-situ pressing mold 7 is resin, which is processed by 3D printing method.

本实施例的反应器用于气固相连续光催化甲烷直接氧化制甲醇的方法与实施例1相同。The reactor in this embodiment is used in the same method as in Embodiment 1 for the gas-solid phase continuous photocatalytic direct oxidation of methane to methanol.

实施例3Example 3

在本实施例中，反应板3为反应板3本体上表面上从一端到另一端依次加工有相连通的原料气混合槽e、气体分布槽f、反应通道g区、气体收集槽h，原料气混合槽e是一长边为圆弧的长方形槽，原料气混合槽e底部加工有与进气通道d相连通的第一通气孔c，气体分布槽f是等腰梯形槽，气体收集槽h是等腰三角形槽，气体收集槽h底部加工有与出气通道b相连通的第二通气孔a，原料气混合槽e和气体分布槽f及气体收集槽h的深度相同，反应通道g区由30条反应通道g构成，反应通道g的底低于原料气混合槽e的底形成催化剂装填区，反应通道g的宽度为0.5mm、深度为0.5mm、长度为40mm，反应通道g的底比原料气混合槽e的底低0.1mm，反应板3用3D打印方法加工制成，材料为钛合金。其他零部件及零部件的连接关系与实施例1相同。In this embodiment, the upper surface of thereaction plate 3 is formed with a raw material gas mixing tank e, a gas distribution tank f, a reaction channel g area, and a gas collection tank h which are connected in sequence from one end to the other end. The gas mixing tank e is a rectangular tank with a long side of an arc, the bottom of the raw gas mixing tank e is machined with a first ventilation hole c that communicates with the air inlet channel d, the gas distribution tank f is an isosceles trapezoidal tank, and the gas collection tank h is an isosceles triangular groove, the bottom of the gas collection groove h is machined with a second vent hole a that communicates with the gas outlet channel b, the raw gas mixing groove e, the gas distribution groove f and the gas collection groove h have the same depth, and the reaction channel g area It is composed of 30 reaction channels g. The bottom of the reaction channel g is lower than the bottom of the raw gas mixing tank e to form a catalyst loading area. The width of the reaction channel g is 0.5mm, the depth is 0.5mm, and the length is 40mm. The bottom of the reaction channel g is It is 0.1 mm lower than the bottom of the raw gas mixing tank e, and thereaction plate 3 is processed by the 3D printing method, and the material is titanium alloy. The other parts and the connection relationship of the parts are the same as those in the first embodiment.

本实施例的原位压制模具7为圆形基座上加工与反应通道g相匹配的压条，压条的高度为1mm、长度为44mm、宽度为0.45mm，相邻两压条之间的距离为0.55mm，原位压制模具7的材料为聚四氟，用3D打印方法加工制成。The in-situ pressing mold 7 in this embodiment is a bead that matches the reaction channel g processed on the circular base. The height of the bead is 1 mm, the length is 44 mm, the width is 0.45 mm, and the distance between two adjacent beading is 0.55 mm. mm, the material of the in-situ pressing mold 7 is polytetrafluoroethylene, which is processed by the 3D printing method.

本实施例的反应器用于气固相连续光催化甲烷直接氧化制甲醇的方法与实施例1相同。The reactor in this embodiment is used in the same method as in Embodiment 1 for the gas-solid phase continuous photocatalytic direct oxidation of methane to methanol.

Claims (10)

1. A reactor for preparing methanol by directly oxidizing methane through gas-solid phase continuous photocatalysis is characterized in that: a cylindrical reactor main body (4) is arranged on the bottom plate (6), a heat exchange groove (j) is arranged at the bottom of the reactor main body (4), an inlet and an outlet which are communicated with the heat exchange groove (j) are arranged on the bottom plate (6), a reaction plate (3) is arranged in the middle of the reactor main body (4), a light-transmitting sheet (2) is arranged on the reactor main body (4) above the reaction plate (3), a reaction cavity is formed between the reaction plate (3) and the light-transmitting sheet (2), an air inlet channel (d) and an air outlet channel (b) which are communicated with the reaction cavity are processed on the reactor main body (4), and an annular cover plate (1) is detachably connected on the reactor main body (4) above the light-transmitting sheet (2); reaction plate (3) is processed in proper order from one end to the other end on the reaction plate body upper surface and has feed gas mixing tank (e) that are linked together, gas distribution groove (f), reaction channel (g) district, gas collecting tank (h), feed gas mixing tank (e) bottom processing has first air vent (c) that are linked together with inlet channel (d), gas collecting tank (h) bottom processing has second air vent (a) that are linked together with outlet channel (b), the degree of depth of feed gas mixing tank (e) and gas distribution groove (f) and gas collecting tank (h) is the same, reaction channel (g) district comprises 10 at least reaction channel (g), the end of reaction channel (g) is less than the end of feed gas mixing tank (e) and forms catalyst loading district.

2. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, is characterized in that: the feed gas mixing tank (e) of the reaction plate (3) is a rectangular tank with a long edge being a circular arc, the gas distribution tank (f) is an isosceles trapezoid tank, and the gas collection tank (h) is an isosceles triangle tank.

3. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, which is characterized in that: the width of the reaction channel (g) is 0.5-3 mm, and the depth is 0.5-3 mm.

4. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, which is characterized in that: the bottom of the reaction channel (g) is 0.1-1 mm lower than that of the raw material gas mixing tank (e).

5. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, 3 or 4, is characterized in that: the distance between two adjacent reaction channels (g) is 1-3 mm.

6. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, is characterized in that: and sealing rings (5) are respectively arranged between the light-transmitting sheet (2) and the reactor main body (4) and between the light-transmitting sheet and the cover plate (1).

7. The reactor for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis according to claim 1, which is characterized in that: the reaction plate (3) is processed and manufactured by a 3D printing method, and the material is resin or stainless steel or alloy or polymer material.

8. The method for preparing the methanol by the direct oxidation of the methane through the gas-solid phase continuous photocatalysis by the reactor according to claim 1, which is characterized by comprising the following steps:

s1, uniformly and flatly paving a certain amount of catalyst powder in a catalyst filling area on a reaction plate (3), pressing the catalyst powder by using an in-situ pressing die (7), fixing the catalyst in the catalyst filling area, and enabling the surface of the pressed catalyst to be flush with the bottom surface of a raw material gas mixing tank (e);

s2, placing a reaction plate (3) in a reactor main body (4), sequentially placing a sealing ring (5), a light-transmitting sheet (2) and a cover plate (1) on the reaction plate, and fastening the reaction plate and the cover plate by using bolts to ensure the sealing property of a reaction cavity;

s3, placing a light source above the reactor to enable light beams to be incident perpendicularly to the light-transmitting sheet (2); introducing a heat exchange medium into a heat exchange groove in the reactor main body (4) and controlling the temperature of a reaction system;

s4, under the reaction conditions of low temperature and normal pressure, mixing methane and oxidizing gas according to a certain proportion, entering a reaction cavity from an air inlet channel (d), contacting with a catalyst under illumination and reacting when flowing through a reaction channel (g) region, allowing the reacted mixed gas to flow out from an air outlet channel (b), separating out methanol through condensation, and allowing unreacted gas components to circulate to the front of the air inlet channel (d) and react continuously after being mixed with feed gas.

9. The method for preparing methanol by the direct oxidation of methane through gas-solid phase continuous photocatalysis by using the reactor according to claim 8, which is characterized by comprising the following steps: the in-situ pressing die (7) is used for processing a pressing strip matched with the reaction channel (g) on the base, and the height of the pressing strip is greater than the depth of the reaction channel (g) and the length of the pressing strip is greater than the length of the reaction channel (g).

10. The method for preparing methanol by direct oxidation of methane through gas-solid phase continuous photocatalysis by using the reactor according to claim 8 or 9, is characterized in that: the in-situ pressing die (7) is processed and manufactured by a 3D printing method, and is made of resin or polymer materials.

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