CN112973614A

CN112973614A - Gas-liquid reaction device, and use method and application thereof

Info

Publication number: CN112973614A
Application number: CN202110185045.0A
Authority: CN
Inventors: 周志茂
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2021-02-10
Filing date: 2021-02-10
Publication date: 2021-06-18

Abstract

The invention provides a gas-liquid reaction device, a use method and application thereof. The reaction device designed by the invention has the advantages of simple structure, large contact area of gas phase and liquid phase, no mechanical stirring part, difficult leakage, accurate control of reaction temperature, good mass transfer and heat transfer performance, large adjustable range of reaction pressure, adjustable reaction time, less material stock in the reaction process, strong safety, realization of continuous production, wide adaptability and the like.

Description

Gas-liquid reaction device, and use method and application thereof

Technical Field

The invention belongs to the technical field of gas-liquid reaction, and particularly relates to a gas-liquid reaction device, and a use method and application thereof.

Background

The tetrahydrophthalic anhydride is taken as a maleic anhydride derivative and is widely applied to the fields of resin curing agents, electronics, polyester high-grade coatings, green environment-friendly plasticizers, medicines, pesticides and the like. The cured product formed by the tetrahydrophthalic anhydride derivative and the epoxy resin is an ideal packaging material and is widely applied to packaging of basic electronic components such as resistors, capacitors, inductors, diodes, triodes and the like to complex devices such as semiconductor devices, integrated circuits and the like. As an important chemical intermediate, the demand of the product is increasing in China in recent years.

The market demand of tetrahydrophthalic anhydride is increasing at a rate of 15% per year, and China has no large-scale tetrahydrophthalic anhydride manufacturers. The domestic output of tetrahydrophthalic anhydride cannot meet the increasing market demand, and production enterprises adopt a parallel intermittent production line to expand production, but the intermittent production has the defects of large occupied area, low efficiency, small production capacity, complex production process, difficult automation control, difficult quality control, difficult reduction of production cost and the like.

The tetrahydrophthalic anhydride synthesis reaction is carried out on a two-phase interface of butadiene gas and maleic anhydride liquid, a fully contacted two-phase interface is formed firstly, and the forming mode of the gas-liquid phase interface has obvious influence on the heat transfer, mass transfer and reaction efficiency on the interface. The rate of the gas-liquid two-phase reaction is critically dependent on the contact area of the gas and liquid, with the larger the contact area, the faster the reaction and vice versa. The operating conditions of different reactors vary considerably, and it can be seen that the structure and operating parameters of the reactor have a great influence on the reaction process. The maximum contact interface is generated by changing the mixing mode of gas-liquid two-phase fluid in the reactor, so that the transfer-reaction coordination can be promoted, the efficiency of the tetrahydrophthalic anhydride synthesis reaction process is improved, the reaction time is shortened, and the continuous production is realized; the local temperature shock rise phenomenon is reduced, the side reaction is reduced, and the product quality is improved.

CN211847757U discloses a tetrahydrophthalic anhydride synthesizer, this synthesizer includes butadiene vaporization jar, maleic anhydride melting tank, circulating pump, heat exchanger, reactor and crosses hot water jar. The butadiene vaporization tank adopts an internal coil heating mode, hot water is introduced into the butadiene vaporization tank, and a gas phase outlet of the butadiene vaporization tank is connected with an aeration ring in the main reactor; the maleic anhydride dissolving tank adopts a structure with a jacket, superheated water is introduced into the jacket, and the maleic anhydride melting tank is connected with an inlet of a circulating pump; the other end of the circulating pump is connected with a heat exchanger, and the heat exchanger is connected with a Venturi ejector at the top of the reactor through a pipeline; the reactor consists of a Venturi jet reactor, a gas-liquid distributor and a tube-array pipeline mixer, wherein the main reactor is of a jacket type, and a mixed liquid jet area, a gas-liquid distribution area and a tube-array pipeline reaction area are sequentially arranged in the main reactor from top to bottom according to functional areas.

CN106824024A discloses a gas-liquid reactor, this gas-liquid reactor's barrel is equipped with the stainless steel casing with the barrel parcel outward, be equipped with on the stainless steel casing with the intake pipe, the outlet duct, first through-hole of feed liquor pipe and drain pipe complex and with sealing mechanism complex second through-hole, the intake pipe, the outlet duct, feed liquor pipe and drain pipe all stretch out from the first through-hole that corresponds, the feed liquor pipe, the drain pipe, the outer end of intake pipe and outlet duct all has the mouth of pipe flange, all overlap on every mouth of pipe flange and be equipped with the stainless steel flange, stainless steel flange and sealing mechanism all with stainless steel casing welded fastening, it has insulation material to fill between stainless steel casing and the barrel.

CN111167385A discloses an injection type gas-liquid reactor for preparing acid by using aldehyde raw material and air, wherein the gas-liquid reactor comprises an aldehyde feeding pipe, an air feeding pipe, a two-phase jet mixing nozzle and a heat exchange element. The aldehyde raw material is introduced into the two-phase jet flow mixing nozzle along the aldehyde feeding pipe and the pressurized air is introduced into the gas-liquid reactor after the mixture of the aldehyde raw material and the pressurized air is highly dispersed through the two-phase jet flow mixing nozzle. The aldehyde raw material and the air are subjected to oxidation reaction in the gas-liquid reactor to form acid, and heat released by the oxidation reaction is removed from the gas-liquid reactor through the heat exchange element arranged in the gas-liquid reactor.

At present, the synthesis reaction of tetrahydrophthalic anhydride mostly adopts an intermittent method, butadiene is gasified and then introduced into a maleic anhydride molten liquid, and gas-liquid phases are mixed and reacted in a reaction kettle in a mechanical stirring mode. Under the action of mechanical stirring, the butadiene gas is cut into millimeter-scale bubbles, the specific surface area is small, the phase interface transfer and reaction are slow, and the reaction time is long. The tetrahydrophthalic anhydride synthesis reaction is an exothermic reaction, the heat exchange area of a reaction kettle is small, the phenomenon of high local temperature exists, and the heat transfer problem limits the reaction efficiency.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a gas-liquid reaction device, a using method and application thereof, the reaction device designed by the invention has the advantages of simple structure, large gas-liquid two-phase contact area, no mechanical stirring part, difficulty in leakage, accurate control of reaction temperature, good mass transfer and heat transfer performance, large adjustable range of reaction pressure, adjustable reaction time, less material stock in the reaction process, strong safety, capability of realizing continuous production, wide adaptability and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a gas-liquid reaction apparatus, which includes a housing, and a gas dispersion module and a reaction module, which are sequentially connected to each other along a flow direction of a reaction liquid, are disposed in the housing.

The reaction module comprises at least two reaction pipe fittings which are connected in parallel or connected in series in sequence along the flow direction of reaction liquid.

When the reaction pipe fittings adopt the series connection mode, along the reaction liquid flow direction, the gas dispersion module insert the entry end of first reaction pipe fittings, gas raw materials and liquid phase raw materials flow through each reaction pipe fitting in proper order after the gas-liquid deconcentrator dispersion is even.

The gas-liquid reaction device provided by the invention is divided into a gas-liquid two-phase fluid mixing area and a main reaction area, the gas dispersion module is positioned in the gas-liquid two-phase fluid mixing area, the rapid and efficient mixing reaction of two immiscible fluids in large-scale production can be realized, meanwhile, the heat can be rapidly transferred, the side reaction is inhibited, the selectivity of the product is improved, the treatment capacity is large, and the energy consumption is low; the reaction pipe fittings are positioned in the main reaction zone, and when the gas-liquid multiphase material reaction time needs to be prolonged, the length of the reaction pipe fittings can be lengthened or the number of the reaction pipe fittings can be increased according to the needs. The reaction device designed by the invention has the advantages of simple structure, large contact area of gas phase and liquid phase, no mechanical stirring part, difficult leakage, accurate control of reaction temperature, good mass transfer and heat transfer performance, large adjustable range of reaction pressure, adjustable reaction time, less material stock in the reaction process, strong safety, realization of continuous production, wide adaptability and the like. The method can realize the rapid and efficient mixing reaction of gas and liquid in large-scale production, and simultaneously inhibit side reaction by accurately controlling reaction conditions, thereby improving the selectivity of products. Can be widely used in the field of petrochemical industry, and is particularly suitable for gas-liquid multiphase reactions, such as tetrahydrophthalic anhydride synthesis reaction and the like.

It should be particularly emphasized that the gas-liquid reaction apparatus provided by the present invention is not limited to synthesis of tetrahydrophthalic anhydride, other types of gas-liquid multiphase reactions can also adopt the gas-liquid reaction apparatus provided by the present invention, as long as a person skilled in the art can adaptively adjust the reaction raw materials and the reaction conditions, the technical effect produced by the gas-liquid reaction apparatus provided by the present invention is irrelevant to the reaction raw materials and the reaction conditions, and the technical effect of improving the reaction efficiency is brought by the structure of the apparatus, rather than by adjusting the reaction raw materials and the reaction conditions.

As a preferable technical scheme of the invention, the gas dispersion module comprises a shell, a microporous membrane component is arranged in the shell, one end of the microporous membrane component is sealed, the other end of the microporous membrane component is communicated with a gas inlet pipe, and the inlet end of the gas inlet pipe extends out of the shell.

Preferably, one end of the microporous membrane component is sealed by a closed end cap.

Preferably, the side wall of the shell is communicated with a liquid inlet pipe, the gas-phase raw material and the liquid-phase raw material are respectively introduced into the shell through an air inlet pipe and the liquid inlet pipe, and the gas-phase raw material passes through the microporous membrane component to form micro-bubbles and is diffused into the liquid-phase raw material to obtain a reaction liquid.

Preferably, the axis of the liquid inlet pipe is tangential to the shell, and the liquid is fed along the tangential direction of the shell.

Preferably, the top of the shell is communicated with a discharge pipe.

Preferably, the microporous membrane assembly is surrounded by a microporous membrane.

Preferably, the membrane material of the microporous membrane comprises any one of high molecular polymer, ceramic or metal.

Preferably, the pore size of the microporous membrane is 0.1 to 100. mu.m, and may be, for example, 0.1. mu.m, 1. mu.m, 10. mu.m, 20. mu.m, 30. mu.m, 40. mu.m, 50. mu.m, 60. mu.m, 70. mu.m, 80. mu.m, 90. mu.m or 100. mu.m, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

Preferably, the microporous membrane assembly is an inverted truncated cone structure.

Preferably, the included angle between the truncated cone generatrix of the microporous membrane assembly and the horizontal plane is 0 to 180 °, and may be, for example, 1 °, 10 °, 20 °, 30 °, 40 °, 50 °, 60 °, 70 °, 80 °, 90 °, 100 °, 110 °, 120 °, 130 °, 140 °, 150 °, 160 °, 170 ° or 180 °, but is not limited to the enumerated values, and other non-enumerated values within the range of the enumerated values are also applicable, and more preferably 45 to 135 °.

In the invention, all reaction raw materials are divided into a gas phase part and a liquid phase part according to the state, the liquid phase raw materials are introduced into the shell from the liquid inlet pipe, and the gas phase raw materials are introduced into the shell from the gas inlet pipe as a dispersion phase; the gas phase raw material forms micron-sized micro-bubbles after passing through the microporous membrane component, the micro-sized micro-bubbles are quickly diffused into the shell to be mixed with the liquid phase, the micro-bubbles enter the reaction pipe fitting from the discharge pipe of the gas dispersion module under certain pressure and temperature and flow in parallel for reaction, and the generated reaction product is discharged.

According to the invention, a gas phase raw material is uniformly dispersed into a liquid phase raw material in a microbubble mode through the microporous membrane structure of the gas dispersion module, the phase interface between gas and liquid is increased by more than 10 times compared with that of a traditional reactor, and the diameter of microbubbles can be adjusted to control the contact area through adjusting the aperture of the microporous membrane component, so that the miniaturization and high efficiency of a reaction system are realized; the reaction raw materials after gas-liquid mixing enter the reaction pipe fitting, and the turbulent flow stopper or the filling filler of the reaction pipe fitting ensures to control the efficient operation of the reaction pipe fitting, thereby improving the reaction efficiency.

As a preferable technical scheme of the invention, the reaction pipe fitting comprises an inner pipe body and an outer pipe body which are coaxially nested from inside to outside in sequence, a heat exchange medium is introduced into the inner pipe body, and an annular channel is formed between the inner pipe body and the outer pipe body.

Preferably, both ends of the annular channel are sealed, both ends of the inner tube body are open, the outer tube body is provided with a feed inlet and a discharge outlet, reaction liquid is introduced into the annular channel through the feed inlet on the outer tube body, and the reaction liquid exchanges heat with a heat exchange medium in the inner tube body.

Preferably, the annular channel has a radial width of 1 to 30mm, for example 1mm, 5mm, 10mm, 15mm, 20mm, 25mm or 30mm, but not limited to the values listed, and other values not listed in this range are equally applicable.

The reaction raw materials after gas-liquid mixing enter the reaction pipe fitting, and the turbulent flow stopper or the filling filler of the reaction pipe fitting ensures to control the efficient operation of the reaction pipe fitting, thereby improving the reaction efficiency. The shell of the reaction device is filled with heat exchange medium, the heat exchange area is more than 10 times of that of a common reactor, rapid heat transfer can be realized, and the reaction temperature can be accurately controlled. Taking the reaction for synthesizing tetrahydrophthalic anhydride as an example, the reactor of the invention increases the gas-liquid phase interface of butadiene and maleic anhydride, ensures that the two phases are fully contacted and react quickly. Through the aperture adjustment to microporous membrane subassembly, regulate and control butadiene bubble diameter and make its even entering maleic anhydride liquid phase, react in the annular channel, further strengthen the mixing degree between gaseous phase raw materials and the liquid phase raw materials through the vortex fender piece to improve mass transfer efficiency, realize serialization production, have the great characteristics that the handling capacity is big and the energy consumption is little.

As a preferable technical scheme of the invention, at least two groups of turbulence assemblies are arranged in the annular channel at intervals along the radial direction.

Preferably, each group of spoiler assemblies comprises at least three spoiler members arranged along the circumferential direction of the annular channel.

Preferably, the spoiler members included in two adjacent groups of spoiler assemblies are staggered.

Preferably, the shape of the spoiler comprises any one of a cylinder, a prism, a cone, a pyramid, a cube or a cuboid, or a combination of at least two groups.

Preferably, the material of the flow spoiler comprises any one or a combination of at least two groups of high molecular polymer, ceramic or metal.

The spoiler provided by the invention has the following effects: (1) the distance between the outer pipe and the inner pipe is strictly controlled, the concentricity of the outer pipe and the inner pipe is ensured, and the fluid does not generate a channeling effect; (2) the turbulence blocking piece in the annular channel can prevent bubbles or liquid drops from merging in the flowing process, simultaneously plays a role in turbulent flow of the fluid, increases the gas-liquid surface renewal and mass transfer in the flowing process, and improves the reaction efficiency.

Preferably, the annular channel is filled with filler.

Preferably, the shape of the filler comprises any one or a combination of at least two groups of spheres, rings, grids, waves or saddles.

Preferably, the filler material comprises any one or a combination of at least two groups of high molecular polymer, ceramic or metal.

The purpose of the filler is the same as that of the turbulence stopper, and the filler is used for preventing bubbles or liquid drops from being converged in the flowing process, playing a role in turbulent flow on fluid, increasing gas-liquid surface renewal and mass transfer in the flowing process and improving reaction efficiency. It can be understood that both packing and baffles can be used in the reaction tube of the present invention, or only packing or baffles can be used.

As a preferable technical scheme of the invention, the top and the bottom of the shell are respectively provided with a heat exchange medium outlet and a heat exchange medium inlet.

Preferably, the shell comprises a cylinder body and end sockets positioned at two ends of the cylinder body, and the end sockets are detachably connected with the cylinder body.

Preferably, the end socket is butted with the cylinder body through a flange.

Preferably, the shell is arranged vertically, and the reaction pipe fittings are longitudinally arranged in the shell side by side.

Preferably, both ends of the reaction pipe fitting are respectively provided with a fixing bracket, and the fixing brackets are used for fixing the reaction pipe fitting in the shell.

As a preferred technical scheme of the present invention, the reaction pipe fittings are connected in parallel, the reaction module further comprises a feeding main pipe and a discharging main pipe, and an inlet end and an outlet end of the reaction pipe fittings are respectively connected to the feeding main pipe and the discharging main pipe.

Preferably, the discharge pipe of the gas dispersion module is connected to the main feed pipe, and the reaction liquid discharged from the gas dispersion module is introduced into the main feed pipe through the discharge pipe and distributed to flow into the annular channels of the respective reaction pipe members.

Preferably, when the reaction pipe fitting adopts the series connection mode, along the reaction liquid flow direction, the row of gas dispersion module expect the feed inlet of pipe access first reaction pipe fitting, the feed inlet of next reaction pipe fitting is connected to the discharge gate of first reaction pipe fitting, according to this connected mode, each reaction pipe fitting is established ties in proper order along the reaction liquid flow direction, the reaction liquid through gas dispersion module exhaust lets in first reaction pipe fitting by arranging the material pipe, the annular channel of each reaction pipe fitting of flowing through in proper order afterwards.

In a second aspect, the present invention provides a method for using the gas-liquid reaction apparatus according to the first aspect, the method comprising:

and respectively introducing the gas-phase raw material and the liquid-phase raw material into the gas dispersion module, dispersing the gas-phase raw material into the liquid-phase raw material to form reaction liquid, and allowing the reaction liquid to enter the reaction module for reaction.

As a preferred technical solution of the present invention, the process of dispersing the gas-phase raw material in the gas dispersion module comprises: the gas phase raw material passes through the microporous membrane component to form micro bubbles and is diffused into the liquid phase raw material to obtain reaction liquid.

Preferably, the linear velocity of the gas-phase raw material passing through the microporous membrane module is 0.1 to 25m/s, for example, 0.1m/s, 1m/s, 5m/s, 10m/s, 15m/s, 20m/s or 25m/s, but is not limited to the above-mentioned values, and other values within the above-mentioned value range are also applicable, and more preferably 1 to 10 m/s.

Preferably, the reaction liquid flows into the annular channel of the reaction pipe fitting, meanwhile, a heat exchange medium is introduced into the inner pipe body of the reaction pipe fitting, the reaction liquid and the heat exchange medium are in contact for heat exchange, and the reaction temperature is controlled through the temperature of the heat exchange medium.

Preferably, the flow velocity of the reaction solution in the annular channel is 0.05 to 10m/s, for example, 0.05m/s, 1m/s, 2m/s, 3m/s, 4m/s, 5m/s, 6m/s, 7m/s, 8m/s, 9m/s, or 10m/s, but not limited to the values listed, and other values not listed in the range of the values are also applicable, and more preferably 1 to 5 m/s.

In a third aspect, the present invention provides a synthesis method for synthesizing tetrahydrophthalic anhydride by using the gas-liquid reaction apparatus of the first aspect, where the synthesis method includes:

and respectively introducing butadiene gas and maleic anhydride solution into the gas dispersion module, dispersing the butadiene gas into the maleic anhydride solution to form reaction liquid, and heating the reaction liquid after the reaction liquid enters the reaction pipe to perform a synthesis reaction to obtain tetrahydrophthalic anhydride.

As a preferred technical solution of the present invention, the solvent used in the maleic anhydride solution includes any one or a combination of at least two of maleic anhydride, tetrahydrophthalic anhydride, benzene, toluene, acetone, and chloroform.

Preferably, the mass ratio of the solvent to the maleic anhydride in the maleic anhydride solution is (0.1-2): 1, and may be, for example, 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1.0:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2.0:1, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and more preferably (0.5-1): 1.

The molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is preferably (1 to 1.6):1, and may be, for example, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1 or 1.6:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and more preferably (1 to 1.2): 1.

Preferably, the dispersing process of the butadiene gas in the gas dispersion module includes: and the butadiene gas passes through the microporous membrane component to form micro bubbles and diffuses into the maleic anhydride solution to obtain a reaction solution.

Preferably, the linear velocity of the butadiene gas passing through the microporous membrane module is 0.1 to 15m/s, for example, 0.1m/s, 1m/s, 5m/s, 10m/s, 15m/s, 20m/s or 25m/s, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and more preferably 1 to 10 m/s.

Preferably, the temperature of the synthesis reaction is controlled to 60 to 160 ℃, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃, but not limited to the values listed, and other values not listed within the range of the values are also applicable, and more preferably 100 to 140 ℃.

Preferably, the time of the synthesis reaction is 0.01 to 20min, for example, 0.01min, 1min, 2min, 4min, 6min, 8min, 10min, 12min, 14min, 16min, 18min or 20min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, and more preferably 0.1 to 10 min.

Preferably, the pressure of the synthesis reaction is 0.05 to 1.6MPa, and may be, for example, 0.05MPa, 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa or 1.6MPa, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable, and more preferably 0.2 to 0.6 MPa.

Compared with the prior art, the invention has the beneficial effects that:

Drawings

FIG. 1 is a schematic diagram of a gas dispersion module according to an embodiment of the present invention;

FIG. 2 is a schematic diagram of a reaction tube according to an embodiment of the present invention;

FIG. 3 is a schematic structural view of a gas-liquid reaction apparatus according to an embodiment of the present invention;

wherein, 1-microporous membrane component; 2-closing the end cover; 3-a discharge pipe; 4-a housing; 5-a liquid inlet pipe; 6, an air inlet pipe; 7-an outer body; 8-an inner tube; 9-an annular channel; 10-a spoiler; 11-a feed inlet; 12-a discharge hole; 13-heat exchange medium inlet; 14-a flange; 15-a housing; 16-a fixed support; 17-a heat exchange medium outlet; 18-reaction tube; 19-gas dispersion module.

Detailed Description

It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.

It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

It should be understood by those skilled in the art that the present invention necessarily includes necessary piping, conventional valves and general pump equipment for achieving the complete process, but the above contents do not belong to the main inventive points of the present invention, and those skilled in the art can select the layout of the additional equipment based on the process flow and the equipment structure, and the present invention is not particularly limited to this.

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

In one embodiment, the present invention provides a gas-liquid reaction apparatus, as shown in fig. 3, comprising a housing 15, wherein a gas dispersion module 19 and a reaction module are disposed in the housing 15, the gas dispersion module and the reaction module are sequentially connected along a flow direction of a reaction liquid, the reaction module comprises at least two reaction pipes 18, and the reaction pipes 18 are connected in parallel or sequentially connected in series along the flow direction of the reaction liquid. The top and the bottom of the shell 15 are respectively provided with a heat exchange medium outlet 17 and a heat exchange medium inlet 13. The shell 15 comprises a cylinder body and end sockets positioned at two ends of the cylinder body, the end sockets are detachably connected with the cylinder body, and further the end sockets are butted with the cylinder body through a flange 14. The housing 15 is arranged vertically, and the reaction tubes 18 are arranged longitudinally side by side inside the housing 15. Fixing brackets 16 are respectively provided at both ends of reaction pipe 18, and fixing brackets 16 are used to fix reaction pipe 18 in housing 15.

When the reaction pipe fittings 18 adopt a parallel connection mode, the reaction module further comprises a feeding main pipe and a discharging main pipe, the inlet end and the outlet end of the reaction pipe fittings 18 are respectively connected with the feeding main pipe and the discharging main pipe, the gas dispersion module 19 is connected with the feeding main pipe, and gas raw materials and liquid raw materials are uniformly dispersed by the gas-liquid disperser, then flow into the feeding main pipe and are distributed by the feeding main pipe to enter each reaction pipe fitting 18.

When the reaction pipe fittings 18 are connected in series, the gas dispersion module 19 is connected to the inlet end of the first reaction pipe fitting 18 along the flow direction of the reaction liquid, and the gas raw material and the liquid raw material are uniformly dispersed by the gas-liquid disperser and then sequentially flow through the reaction pipe fittings 18.

As shown in fig. 1, the gas dispersion module 19 includes a housing 4, a microporous membrane module 1 is disposed in the housing 4, one end of the microporous membrane module 1 is sealed, the other end is communicated with a gas inlet pipe 6, and an inlet end of the gas inlet pipe 6 extends out of the housing 4. Further, one end of the microporous membrane assembly 1 is sealed by a cap closure 2. The side wall of the shell 4 is communicated with a liquid inlet pipe 5, a gas phase raw material and a liquid phase raw material are respectively introduced into the shell 4 through an air inlet pipe 6 and the liquid inlet pipe 5, and the gas phase raw material forms micro bubbles after passing through the microporous membrane component 1 and is diffused into the liquid phase raw material to obtain a reaction liquid. The axis of the liquid inlet pipe 5 is tangential to the shell 4, and liquid is fed along the tangential direction of the shell 4. The top of the shell 4 is communicated with a discharge pipe 3.

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes comprises any one of high molecular polymer, ceramics or metal, and the aperture of the microporous membranes is 0.1-100 mu m. The microporous membrane component 1 is of an inverted round table-shaped structure, and the included angle between a round table bus of the microporous membrane component 1 and the horizontal plane is 0-180 degrees.

As shown in fig. 2, the reaction pipe 18 includes an inner pipe 8 and an outer pipe 7 coaxially nested from inside to outside, the inner pipe 8 is filled with a heat exchange medium, and an annular channel 9 is formed between the inner pipe 8 and the outer pipe 7. The two ends of the annular channel 9 are sealed, the two ends of the inner pipe body 8 are open, the outer pipe body 7 is provided with a feed inlet 11 and a discharge outlet 12, reaction liquid is introduced into the annular channel 9 through the feed inlet 11 on the outer pipe body 7, and the reaction liquid exchanges heat with a heat exchange medium in the inner pipe body 8. The radial width of the annular channel 9 is 1-30 mm.

At least two groups of turbulence components are arranged in the annular channel 9 at intervals along the radial direction, each group of turbulence components comprises at least three turbulence blocking pieces 10 arranged along the circumferential direction of the annular channel 9, and the turbulence blocking pieces 10 included in the two adjacent groups of turbulence components are distributed in a staggered mode. The shape of the turbulence stopper 10 includes any one or a combination of at least two groups of a cylinder, a prism, a cone, a pyramid, a cube or a cuboid, and the material of the turbulence stopper 10 includes any one or a combination of at least two groups of a high polymer, a ceramic or a metal. The annular channel 9 is also filled with a filler, the shape of the filler comprises any one or the combination of at least two groups of spherical, annular, grid-shaped, corrugated or saddle-shaped fillers, and the material of the filler comprises any one or the combination of at least two groups of high polymer, ceramic or metal.

The reaction pipe fittings 18 are connected in parallel, the discharge pipe 3 of the gas dispersion module 19 is connected to the feed main pipe, the feed ports 11 of the reaction pipe fittings 18 are respectively connected to the feed main pipe, and the reaction liquid discharged by the gas dispersion module 19 is introduced into the feed main pipe through the discharge pipe 3 and distributed to flow into the annular channels 9 of the reaction pipe fittings 18.

When the reaction pipe fittings 18 are connected in series, the discharge pipe 3 of the gas dispersion module 19 is connected to the feed inlet 11 of the first reaction pipe fitting 18 along the flow direction of the reaction liquid, the discharge outlet 12 of the first reaction pipe fitting 18 is connected to the feed inlet 11 of the next reaction pipe fitting 18, according to the connection mode, the reaction pipe fittings 18 are sequentially connected in series along the flow direction of the reaction liquid, the reaction liquid discharged by the gas dispersion module 19 is introduced into the first reaction pipe fitting 18 through the discharge pipe 3, and then sequentially flows through the annular channels 9 of the reaction pipe fittings 18.

In another embodiment, the present invention provides a method for using the gas-liquid reaction apparatus provided in the above embodiment, wherein the method specifically comprises the following steps:

(1) respectively introducing a gas-phase raw material and a liquid-phase raw material into a gas dispersion module 19, wherein the gas-phase raw material penetrates through the microporous membrane component 1 at a linear velocity of 0.1-25 m/s to form micro bubbles and diffuses into the liquid-phase raw material to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe 18 at a linear speed of 0.05-10 m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe 18, the reaction liquid and the heat exchange medium are in contact for heat exchange, and the reaction temperature is controlled through the temperature of the heat exchange medium.

Example 1

The present embodiment provides a gas-liquid reaction apparatus, which is provided according to a specific embodiment, wherein:

the reaction pipe fittings 18 are connected in series, the discharge pipe 3 of the gas dispersion module 19 is connected to the feed inlet 11 of the first reaction pipe fitting 18 along the flow direction of the reaction liquid, the discharge outlet 12 of the first reaction pipe fitting 18 is connected to the feed inlet 11 of the next reaction pipe fitting 18, according to the connection mode, the reaction pipe fittings 18 are sequentially connected in series along the flow direction of the reaction liquid, the reaction liquid discharged by the gas dispersion module 19 is introduced into the first reaction pipe fitting 18 through the discharge pipe 3, and then sequentially flows through the annular channels 9 of the reaction pipe fittings 18.

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes is high molecular polymer, and the aperture of the microporous membranes is 0.1 mu m. The microporous membrane component 1 is of an inverted round table structure, and the included angle between the round table generatrix of the microporous membrane component 1 and the horizontal plane is 20 degrees.

The radial width of annular channel 9 is 5mm, is provided with 8 groups of vortex subassemblies along radial interval in the annular channel 9, and every group vortex subassembly all includes 10 vortex fender spares 10 along the annular channel 9 circumference setting, and the vortex that includes in two sets of adjacent vortex subassemblies keeps off 10 staggered distribution. The turbulence blocking member 10 is cylindrical, and the material of the turbulence blocking member 10 is a high molecular polymer.

Example 2

The tetrahydrophthalic anhydride is synthesized by using the gas-liquid reaction device provided in example 1, and the synthesis method specifically comprises the following steps:

(1) mixing benzene and maleic anhydride according to the mass ratio of 0.1:1 to obtain a maleic anhydride solution, and respectively introducing butadiene gas and the maleic anhydride solution into the gas dispersion module 19, wherein the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is 1: 1;

after entering the gas dispersion module 19, the butadiene gas passes through the microporous membrane component 1 at a linear velocity of 0.1m/s to form micro bubbles and diffuses into a maleic anhydride solution to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe fitting 18 at a linear velocity of 0.05m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe fitting 18, the reaction liquid and the heat exchange medium are in contact for heat exchange to complete the synthesis reaction to obtain tetrahydrophthalic anhydride, the reaction temperature is controlled at 60 ℃ by controlling the temperature of the heat exchange medium, the time of the synthesis reaction is 0.01min, and the pressure of the synthesis reaction is 1.6 MPa.

The yield of tetrahydrophthalic anhydride was calculated to be 149% (based on the maleic anhydride feed).

Example 3

when the reaction pipe fittings 18 are connected in parallel, the inlet end and the outlet end of the reaction pipe fittings 18 are respectively connected to the feeding main pipe and the discharging main pipe, the discharging pipe 3 of the gas dispersion module 19 is connected to the feeding main pipe, the feed ports 11 of the reaction pipe fittings 18 are respectively connected to the feeding main pipe, and the reaction liquid discharged by the gas dispersion module 19 is introduced into the feeding main pipe through the discharging pipe 3 and distributed to flow into the annular channels 9 of the reaction pipe fittings 18.

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes is ceramic, and the aperture of the microporous membranes is 10 mu m. The microporous membrane component 1 is of an inverted round table structure, and the included angle between the round table generatrix of the microporous membrane component 1 and the horizontal plane is 45 degrees.

The radial width of the annular channel 9 is 10 mm. And 10 groups of turbulence assemblies are arranged in the annular channel 9 at intervals along the radial direction, each group of turbulence assemblies comprises 8 turbulence blocking pieces 10 arranged along the circumferential direction of the annular channel 9, and the turbulence blocking pieces 10 in the two adjacent groups of turbulence assemblies are distributed in a staggered manner. The spoiler 10 is prism-shaped, and the spoiler 10 is made of ceramic.

Example 4

The tetrahydrophthalic anhydride is synthesized by using the gas-liquid reaction device provided in example 3, and the synthesis method specifically comprises the following steps:

(1) mixing acetone and maleic anhydride according to the mass ratio of 0.5:1 to obtain a maleic anhydride solution, and respectively introducing butadiene gas and the maleic anhydride solution into the gas dispersion module 19, wherein the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is 1.2: 1;

after entering the gas dispersion module 19, the butadiene gas passes through the microporous membrane component 1 at a linear velocity of 5m/s to form micro bubbles and diffuses into a maleic anhydride solution to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe fitting 18 at a linear speed of 1m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe fitting 18, the reaction liquid and the heat exchange medium are in contact for heat exchange to complete the synthesis reaction to obtain tetrahydrophthalic anhydride, the reaction temperature is controlled at 80 ℃ by controlling the temperature of the heat exchange medium, the time of the synthesis reaction is 1min, and the pressure of the synthesis reaction is 1.5 MPa.

The yield of tetrahydrophthalic anhydride was calculated to be 150% (based on the maleic anhydride feed).

Example 5

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes is metal, and the aperture of the microporous membranes is 50 μm. The microporous membrane component 1 is of an inverted round table structure, and the included angle between the round table generatrix of the microporous membrane component 1 and the horizontal plane is 90 degrees.

The radial width of the annular channel 9 is 20mm, the annular channel is filled with filler, the filler is spherical, and the filler is made of high molecular polymer.

Example 6

The tetrahydrophthalic anhydride was synthesized using the gas-liquid reaction apparatus provided in example 5, and the synthesis method specifically included the following steps:

(1) mixing chloroform and maleic anhydride according to the mass ratio of 1:1 to obtain a maleic anhydride solution, and respectively introducing butadiene gas and the maleic anhydride solution into a gas dispersion module 19, wherein the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is 1.3: 1;

after entering the gas dispersion module 19, the butadiene gas passes through the microporous membrane component 1 at a linear velocity of 10m/s to form microbubbles and is diffused into a maleic anhydride solution to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe fitting 18 at a linear speed of 5m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe fitting 18, the reaction liquid and the heat exchange medium are in contact for heat exchange to complete the synthesis reaction to obtain tetrahydrophthalic anhydride, the reaction temperature is controlled at 100 ℃ by controlling the temperature of the heat exchange medium, the time of the synthesis reaction is 8min, and the pressure of the synthesis reaction is 1.3 MPa.

The yield of tetrahydrophthalic anhydride was calculated to be 152% (based on the maleic anhydride feed).

Example 7

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes is high molecular polymer, and the aperture of the microporous membranes is 80 μm. The microporous membrane component 1 is an inverted round table-shaped structure, and the included angle between the round table generatrix of the microporous membrane component 1 and the horizontal plane is 135 degrees.

The radial width of the annular channel 9 is 25mm, the annular channel is filled with filler, the filler is in a grid shape, and the filler is made of ceramic.

Example 8

The tetrahydrophthalic anhydride was synthesized using the gas-liquid reaction apparatus provided in example 7, and the synthesis method specifically included the following steps:

(1) mixing toluene and maleic anhydride according to the mass ratio of 1.5:1 to obtain a maleic anhydride solution, and respectively introducing butadiene gas and the maleic anhydride solution into the gas dispersion module 19, wherein the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is 1.5: 1;

after entering the gas dispersion module 19, the butadiene gas passes through the microporous membrane component 1 at a linear velocity of 15m/s to form micro bubbles and diffuses into a maleic anhydride solution to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe fitting 18 at a linear speed of 7m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe fitting 18, the reaction liquid and the heat exchange medium are in contact for heat exchange to complete the synthesis reaction to obtain tetrahydrophthalic anhydride, the reaction temperature is controlled at 130 ℃ by controlling the temperature of the heat exchange medium, the time of the synthesis reaction is 15min, and the pressure of the synthesis reaction is 1 MPa.

The yield of tetrahydrophthalic anhydride was calculated to be 153% (based on the maleic anhydride feed).

Example 9

The microporous membrane component 1 is surrounded by microporous membranes, the membrane material of the microporous membranes is high molecular polymer, and the aperture of the microporous membranes is 100 mu m. The microporous membrane component 1 is of an inverted round table structure, and the included angle between the round table generatrix of the microporous membrane component 1 and the horizontal plane is 150 degrees.

The radial width of annular channel 9 is 30mm, is provided with 12 groups of vortex subassemblies along radial interval in the annular channel 9, and every group vortex subassembly all includes 6 vortex fender spares 10 along annular channel 9 circumference setting, and the vortex fender spare 10 that includes in two sets of adjacent vortex subassemblies staggers the distribution. The shape of the turbulence blocking member 10 is conical, and the material of the turbulence blocking member 10 is metal. The annular channel is also filled with filler, the filler is corrugated, and the filler is made of metal.

Example 10

The tetrahydrophthalic anhydride was synthesized using the gas-liquid reaction apparatus provided in example 9, and the synthesis method specifically included the following steps:

(1) maleic anhydride and maleic anhydride are mixed according to the mass ratio of 2:1 to obtain a maleic anhydride solution, butadiene gas and the maleic anhydride solution are respectively introduced into the gas dispersion module 19, and the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is 1.6: 1;

after entering the gas dispersion module 19, the butadiene gas passes through the microporous membrane component 1 at a linear velocity of 25m/s to form microbubbles and is diffused into a maleic anhydride solution to obtain a reaction solution;

(2) the reaction liquid flows into the annular channel 9 of the reaction pipe fitting 18 at a linear speed of 10m/s, meanwhile, a heat exchange medium is introduced into the inner pipe 8 of the reaction pipe fitting 18, the reaction liquid and the heat exchange medium are in contact for heat exchange to complete the synthesis reaction to obtain tetrahydrophthalic anhydride, the reaction temperature is controlled at 160 ℃ by controlling the temperature of the heat exchange medium, the time of the synthesis reaction is 20min, and the pressure of the synthesis reaction is 0.05 MPa.

The yield of tetrahydrophthalic anhydride was calculated to be 150.5% (based on the maleic anhydride feed).

Example 11

This example provides a gas-liquid reaction apparatus, which is different from the gas-liquid reaction apparatus provided in example 9 in the structure that a turbulent flow member and a filler in an annular passage are omitted, and the structure and connection relationship of other apparatuses are completely the same as those of example 9.

The synthesis method provided in example 10 was carried out using the above-described gas-liquid reaction apparatus, and the yield of tetrahydrophthalic anhydride was calculated to be 129% (based on the maleic anhydride fed).

Comparative example 1

This comparative example provides a gas-liquid reaction apparatus, which is different from the gas-liquid reaction apparatus provided in example 9 in the structural point that the gas dispersion module 19 is omitted, the gas-phase raw material and the liquid-phase raw material are directly introduced into the reaction tube 18 to carry out the synthesis reaction, and the other apparatus structures and the connection relationship are completely the same as those of example 9.

The synthesis method provided in example 10 is performed by using the gas-liquid reaction apparatus, except that the gas dispersion module 9 is omitted, so that in step (1), the gas-phase raw material and the liquid-phase raw material are directly introduced into the reaction pipe 18 for the synthesis reaction without passing through the gas dispersion module 19, other process parameters and raw material ratios are completely the same as those in example 10, and the calculated yield of tetrahydrophthalic anhydride is 106% (based on the fed maleic anhydride).

As can be seen from the comparison among examples 9, 10 and 11, the yield of tetrahydrophthalic anhydride is reduced after the turbulence components and the fillers are omitted, and the main reason is that the turbulence components and the fillers can prevent bubbles or liquid drops from coalescing in the flowing process, play a role in turbulence on fluid, increase the gas-liquid surface renewal and mass transfer in the flowing process, and improve the reaction efficiency. Therefore, the turbulent flow component and the filler are omitted, the flowing state of the reaction liquid in the annular channel is influenced, the mixing efficiency and the mass transfer efficiency are reduced, and the reaction efficiency is influenced.

It can be seen from examples 9 and 10 and comparative example 1 that the yield of tetrahydrophthalic anhydride was greatly affected by directly introducing the gas-phase raw material and the liquid-phase raw material into the reaction tube without passing through the gas dispersion module, because the gas-phase raw material was uniformly dispersed into the liquid-phase raw material in the form of microbubbles by the gas dispersion module, the contact area between the gas-phase raw material and the liquid-phase raw material was increased, and the reaction efficiency was increased.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. The gas-liquid reaction device is characterized by comprising a shell, wherein a gas dispersion module and a reaction module which are sequentially connected along the flow direction of reaction liquid are arranged in the shell;

2. The gas-liquid reaction device as recited in claim 1, wherein the gas dispersion module includes a housing, a microporous membrane module is disposed in the housing, one end of the microporous membrane module is sealed, the other end of the microporous membrane module is communicated with a gas inlet pipe, and an inlet end of the gas inlet pipe extends out of the housing;

preferably, one end of the microporous membrane component is sealed by a closed end cover;

preferably, the side wall of the shell is communicated with a liquid inlet pipe, a gas-phase raw material and a liquid-phase raw material are respectively introduced into the shell through an air inlet pipe and the liquid inlet pipe, and the gas-phase raw material passes through the microporous membrane component to form micro-bubbles and is diffused into the liquid-phase raw material to obtain a reaction liquid;

preferably, the axis of the liquid inlet pipe is tangential to the shell, and the liquid is fed along the tangential direction of the shell;

preferably, the top of the shell is communicated with a discharge pipe;

preferably, the microporous membrane component is surrounded by a microporous membrane;

preferably, the membrane material of the microporous membrane comprises any one of high molecular polymer, ceramic or metal;

preferably, the aperture of the microporous membrane is 0.1-100 μm;

preferably, the microporous membrane component is in an inverted truncated cone-shaped structure;

preferably, the included angle between the circular truncated cone generatrix of the microporous membrane component and the horizontal plane is 0-180 degrees, and further preferably 45-135 degrees.

3. The gas-liquid reaction device as recited in claim 1 or 2, wherein the reaction pipe includes an inner pipe and an outer pipe coaxially nested in sequence from inside to outside, the inner pipe is fed with a heat exchange medium, and an annular channel is formed between the inner pipe and the outer pipe;

preferably, two ends of the annular channel are sealed, two ends of the inner tube body are open, the outer tube body is provided with a feed inlet and a discharge outlet, reaction liquid is introduced into the annular channel through the feed inlet on the outer tube body, and the reaction liquid exchanges heat with a heat exchange medium in the inner tube body;

preferably, the radial width of the annular channel is 1-30 mm.

4. A gas-liquid reactor as claimed in any one of claims 1-3, wherein at least two sets of flow-disturbing members are radially spaced in the annular passage;

preferably, each group of turbulence components comprises at least three turbulence stoppers arranged along the circumferential direction of the annular channel;

preferably, the spoiler components included in two adjacent groups of spoiler components are distributed in a staggered manner;

preferably, the shape of the spoiler comprises any one or a combination of at least two groups of a cylinder, a prism, a cone, a pyramid, a cube or a cuboid;

preferably, the material of the spoiler comprises any one or a combination of at least two groups of high molecular polymer, ceramic or metal;

preferably, the annular channel is filled with filler;

preferably, the shape of the filler comprises any one or a combination of at least two groups of spheres, rings, grids, waves or saddles;

5. The gas-liquid reaction device according to any one of claims 1 to 4, wherein the top and bottom of the shell are respectively provided with a heat exchange medium outlet and a heat exchange medium inlet;

preferably, the shell comprises a cylinder body and end sockets positioned at two ends of the cylinder body, and the end sockets are detachably connected with the cylinder body;

preferably, the end socket is butted with the cylinder body through a flange;

preferably, the shell is arranged vertically, and the reaction pipe fittings are longitudinally arranged in the shell side by side;

6. The gas-liquid reaction device according to any one of claims 1 to 5, wherein the reaction pipe members are connected in parallel, the reaction module further comprises a main feed pipe and a main discharge pipe, and an inlet end and an outlet end of the reaction pipe members are respectively connected to the main feed pipe and the main discharge pipe;

preferably, a discharge pipe of the gas dispersion module is connected to a main feed pipe, and the reaction liquid discharged by the gas dispersion module is introduced into the main feed pipe through the discharge pipe and distributed to flow into the annular channels of the reaction pipe fittings;

7. A method of using the gas-liquid reaction apparatus as recited in any one of claims 1 to 6, comprising:

8. The use method according to claim 7, wherein the dispersion process of the gas-phase raw material in the gas dispersion module comprises: the gas phase raw material passes through the microporous membrane component to form micro bubbles and is diffused into the liquid phase raw material to obtain reaction liquid;

preferably, the linear velocity of the gas-phase raw material passing through the microporous membrane component is 0.1-25 m/s, and more preferably 1-10 m/s;

preferably, the reaction liquid flows into the annular channel of the reaction pipe fitting, meanwhile, a heat exchange medium is introduced into the inner pipe body of the reaction pipe fitting, the reaction liquid and the heat exchange medium are in contact for heat exchange, and the reaction temperature is controlled through the temperature of the heat exchange medium;

preferably, the flow velocity of the reaction liquid in the annular channel is 0.05-10 m/s, and more preferably 1-5 m/s.

9. A synthesis method for synthesizing tetrahydrophthalic anhydride by using the gas-liquid reaction apparatus according to any of claims 1 to 6, comprising:

10. The method of claim 9, wherein the solvent used in the maleic anhydride solution comprises any one or a combination of at least two of maleic anhydride, tetrahydrophthalic anhydride, benzene, toluene, acetone, or chloroform;

preferably, in the maleic anhydride solution, the mass ratio of the solvent to the maleic anhydride is (0.1-2): 1, and more preferably (0.5-1): 1;

preferably, the molar ratio of the butadiene gas to the maleic anhydride in the maleic anhydride solution is (1-1.6): 1, and more preferably (1-1.2): 1;

preferably, the dispersing process of the butadiene gas in the gas dispersion module includes: the butadiene gas forms micro bubbles after passing through the microporous membrane component and diffuses into the maleic anhydride solution to obtain a reaction solution;

preferably, the linear speed of the butadiene gas passing through the microporous membrane component is 0.1-25 m/s, and further preferably 1-10 m/s;

preferably, the flow velocity of the reaction liquid in the annular channel is 0.05-10 m/s, and more preferably 1-5 m/s;

preferably, the temperature of the synthesis reaction is controlled to be 60-160 ℃, and further preferably 100-140 ℃;

preferably, the time of the synthesis reaction is 0.01-20 min, and further preferably 0.1-10 min;

preferably, the pressure of the synthesis reaction is 0.05-1.6 MPa, and more preferably 0.2-0.6 MPa.