Micro-channel reactor, micro-channel reaction circulation system and reaction method

Abstract

The invention provides a micro-channel reactor, a micro-channel reaction circulation system and a reaction method, and relates to the technical field of micro-channel reaction.The micro-channel reactor comprises a gas plate, a liquid plate and a diffusion layer, and the gas plate and the liquid plate are oppositely arranged and connected; the diffusion layer is installed between the gas plate and the liquid plate, the gas plate is provided with a gas flow channel facing the diffusion layer, and the liquid plate is provided with a liquid flow channel facing the diffusion layer. By adopting the micro-channel reactor, reactants can be uniformly mixed within a short time, the specific surface area is increased, the heat transfer and mass transfer processes can be efficiently carried out, the reaction is more sufficient, and the reaction rate is increased.

Description

Technical Field

[0001] The present invention relates to the field of microfluidic channel reaction technology, and in particular to a microfluidic channel reactor, a microfluidic channel reaction circulation system and a reaction method. Background Art

[0002] Selective nitration, sulfonation, halogenation, hydrogenation and oxidation of organic matter are important in the chemical industry. The traditional production method is to use a reactor, and all the raw materials need to be added to react to generate the desired product. Taking the anthraquinone process to produce hydrogen peroxide as an example, the addition of all the raw materials leads to problems such as insufficient reaction, low reaction efficiency, high energy consumption, and high pollution. Summary of the invention

[0003] The object of the present invention is to provide a microfluidic reactor, a microfluidic reaction circulation system and a reaction method to alleviate the technical problems of insufficient reaction and low reaction efficiency in traditional reactors.

[0004] In a first aspect, the present invention provides a microfluidic reactor, comprising: a gas plate, a liquid plate and a diffusion layer, wherein the gas plate is arranged opposite to and connected to the liquid plate;

[0005] The diffusion layer is installed between the gas plate and the liquid plate. The gas plate is provided with a gas flow channel facing the diffusion layer, and the liquid plate is provided with a liquid flow channel facing the diffusion layer.

[0006] In combination with the first aspect, the present invention provides a first possible implementation manner of the first aspect, wherein a first gasket is installed between the gas plate and the diffusion layer, and a second gasket is installed between the liquid plate and the diffusion layer.

[0007] In combination with the first aspect, the present invention provides a second possible implementation of the first aspect, wherein the diffusion layer is made of at least one of polypropylene, polyethylene and foam metal and is configured as a porous component.

[0008] In combination with the first aspect, the present invention provides a third possible implementation of the first aspect, wherein a precious metal catalyst is provided in the gas flow channel.

[0009] In combination with the first aspect, the present invention provides a fourth possible implementation manner of the first aspect, wherein a transition metal catalyst is provided in the liquid flow channel.

[0010] In a second aspect, the present invention provides a microfluidic reaction circulation system, comprising: a circulation supply device and the microfluidic reactor described in the first aspect, wherein the gas flow channel and the liquid flow channel are respectively connected to the circulation supply device fluid.

[0011] In a third aspect, the present invention provides a microfluidic reaction circulation system, comprising: a circulation feeding device, a first reactor and a second reactor, wherein the first reactor and the second reactor respectively adopt the microfluidic reactor described in the first aspect;

[0012] The first reactor is used for hydrogenation reaction, the circulating supply device is in fluid communication with the liquid flow channel of the first reactor, and the gas flow channel of the first reactor is in fluid communication with the hydrogen tank;

[0013] The second reactor is used for performing an oxidation reaction, the hydrogenation reaction product outlet of the first reactor is in fluid communication with the liquid flow channel of the second reactor, and the gas flow channel of the second reactor is in fluid communication with the oxygen tank;

[0014] The oxidation reaction product outlet of the second reactor is in fluid communication with the circulating supply device.

[0015] In a fourth aspect, the microfluidic reaction method provided by the present invention adopts the microfluidic reactor described in the first aspect and comprises the following steps:

[0016] Passing hydrogen or oxygen into the gas flow channel, and passing a mixed solution consisting of a reaction substrate and an organic solvent into the liquid flow channel;

[0017] The reaction solution discharged from the microfluidic channel reactor is recovered and introduced into the liquid channel again.

[0018] In combination with the fourth aspect, the reaction substrate includes azobenzene or diphenylhydrazine, or the reaction substrate includes diphenylhydrazine and dichloromethane.

[0019] In a fifth aspect, the microfluidic reaction method provided by the present invention uses at least two microfluidic reactors described in the first aspect, one for hydrogenation reaction and the other for oxidation reaction;

[0020] The microfluidic channel reaction method comprises:

[0021] Passing a mixed solution of azobenzene and ethanol into a liquid flow channel of a microfluidic reactor for hydrogenation reaction, and passing hydrogen into a gas flow channel of the microfluidic reactor;

[0022] Passing the hydrogenation reaction product into the liquid flow channel of a microfluidic reactor for oxidation reaction, and passing oxygen into the gas flow channel of the microfluidic reactor;

[0023] The oxidation product is subjected to extraction separation to obtain hydrogen peroxide.

[0024] The embodiments of the present invention bring the following beneficial effects: a gas plate and a liquid plate are arranged opposite to and connected to each other, a diffusion layer is installed between the gas plate and the liquid plate, the gas plate is provided with a gas flow channel facing the diffusion layer, and the liquid plate is provided with a liquid flow channel facing the diffusion layer, so that the reactants can be evenly mixed in a shorter time, the specific surface area is increased, the heat transfer and mass transfer processes are efficient, the reaction is more complete, and the reaction rate is improved.

[0025] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the related technologies, the drawings required for use in the specific embodiments or the related technical descriptions will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 An exploded view of a microfluidic reactor provided by an embodiment of the present invention;

[0028] Figure 2 A schematic diagram of a microfluidic reaction circulation system provided by an embodiment of the present invention;

[0029] Figure 3 A schematic diagram of a reactor composed of multiple microfluidic channel reactors provided in an embodiment of the present invention;

[0030] Figure 4 A schematic diagram of multiple flow channel reactors in a microfluidic reaction circulation system provided by an embodiment of the present invention;

[0031] Figure 5 A schematic diagram of another microfluidic reaction circulation system provided in an embodiment of the present invention.

[0032] Icons: 001-gas plate; 002-liquid plate; 003-diffusion layer; 004-first gasket; 005-second gasket; 006-circulating feeding device; 601-liquid supply pipeline; 602-gas supply pipeline; 603-raw material tank; 604-hydrogen tank; 605-hydrogenation product tank; 606-oxygen tank; 607-oxidation product tank; 007-first reactor; 008-second reactor. DETAILED DESCRIPTION

[0033] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] In the description of the present invention, it should be noted that the terms "center", "up", "down", "left", "right", "vertical", "horizontal", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", and "third" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance. Physical quantities in formulas, if not separately marked, should be understood as basic quantities of the base units of the International System of Units, or derived quantities derived from the basic quantities through mathematical operations such as multiplication, division, differentiation or integration.

[0035] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0036] like Figure 1 As shown, the microfluidic reactor provided by the embodiment of the present invention includes: a gas plate 001, a liquid plate 002 and a diffusion layer 003, the gas plate 001 and the liquid plate 002 are arranged opposite to each other and connected; the diffusion layer 003 is installed between the gas plate 001 and the liquid plate 002, the gas plate 001 is provided with a gas flow channel toward the diffusion layer 003, and the liquid plate 002 is provided with a liquid flow channel toward the diffusion layer 003.

[0037] In the embodiment of the present invention, a first gasket 004 is installed between the gas plate 001 and the diffusion layer 003, and a second gasket 005 is installed between the liquid plate 002 and the diffusion layer 003. The first gasket 004 and the second gasket 005 respectively have openings facing the diffusion layer 003, and the diffusion layer 003 is sealed between the first gasket 004 and the second gasket 005. The gas plate 001 and the liquid plate 002 are connected by bolts, and the first gasket 004, the diffusion layer 003 and the second gasket 005 are pressed tightly.

[0038] The diffusion layer 003 is made of at least one of polypropylene, polyethylene and foamed metal and is configured as a porous member.

[0039] One or more noble metal catalysts such as platinum carbon, palladium carbon, etc. are arranged in the gas flow channel.

[0040] One or more transition metal catalysts such as nickel-based and copper-based are arranged in the liquid flow channel.

[0041] The gas plate 001 and the liquid plate 002 are made of one or more materials selected from the group consisting of stainless steel, graphite, titanium metal, and titanium alloy.

[0042] In this embodiment, the gas flow channel and the liquid flow channel can adopt one or more of serpentine flow channels, radial flow channels, grid flow channels, and bionic flow channels to improve the mass transfer and liquid transfer rate of the microfluidic reactor.

[0043] like Figure 2 As shown, the microfluidic reaction circulation system provided by the embodiment of the present invention includes: a circulation supply device 006 and the microfluidic reactor described in the above embodiment, and the gas flow channel and the liquid flow channel are respectively connected to the circulation supply device 006 fluid.

[0044] The circulating feeding device 006 includes a liquid storage tank and a power drive device, and the power drive device includes: one or more liquid control drive devices such as a peristaltic pump and a centrifugal pump, and also includes one or more gas control drive devices such as a mass flow meter and a glass rotor flow meter.

[0045] like Figure 3 , Figure 4 and Figure 5As shown, the microfluidic reaction circulation system provided by the embodiment of the present invention includes: a circulation feeding device 006, a first reactor 007 and a second reactor 008, the first reactor 007 and the second reactor 008 respectively adopt the microfluidic reactors recorded in the above-mentioned embodiments, and a plurality of microfluidic reactors are stacked and combined, and the plurality of microfluidic reactors are connected in parallel or in series through pipelines to form a multi-stage reactor; the first reactor 007 is used for hydrogenation reaction, the circulation feeding device 006 is fluidly connected with the liquid flow channel of the first reactor 007, and the gas flow channel of the first reactor 007 is fluidly connected with the hydrogen tank 604; the second reactor 008 is used for oxidation reaction, the hydrogenation reaction product outlet of the first reactor 007 is fluidly connected with the liquid flow channel of the second reactor 008, and the gas flow channel of the second reactor 008 is fluidly connected with the oxygen tank 606; the oxidation reaction product outlet of the second reactor 008 is fluidly connected with the circulation feeding device 006. Among them, the circulating feeding device 006 includes: a liquid supply pipeline 601, a gas supply pipeline 602, a raw material tank 603, a hydrogen tank 604, a hydrogenation product tank 605, an oxygen tank 606 and an oxidation product tank 607; the connection method of the circulating feeding device 006 includes: the raw material tank 603 and the liquid inlet of the first reactor 007, the liquid outlet of the first reactor 007 and the hydrogenation product tank 605, the hydrogenation product tank 605 and the liquid inlet of the second reactor 008, the liquid outlet of the second reactor 008 and the oxidation product tank 607, and the oxidation product tank 607 and the raw material tank 603 are connected through the liquid supply pipeline 601; the hydrogen tank 604 and the air inlet of the first reactor 007, and the oxygen tank and the air inlet of the second reactor are connected through the gas supply pipeline 602, and the air outlets of the first reactor 007 and the second reactor 008 are both blocked. During the experiment, a liquid pump is used to input the reaction solution in the raw material tank 603 into the liquid flow channel of the first reactor 007 through the liquid supply pipeline 601, and the hydrogen in the hydrogen tank 604 is input into the gas flow channel of the first reactor 007 through the gas supply pipeline 602. The hydrogenation reaction product is transported to the hydrogenation product tank 605, and the hydrogenation reaction product can be transported to the liquid flow channel of the second reactor 008 by the liquid pump. The oxygen in the oxygen tank 606 is transported to the gas flow channel of the second reactor 008, and the oxidation reaction product is transported to the oxidation product tank 607. The liquid in the oxidation product tank 607 can also be transported to the raw material tank 603 by the liquid pump to achieve circulation.

[0046] The microfluidic reaction method provided in an embodiment of the present invention adopts the microfluidic reactor described in the above-mentioned embodiment, and includes the following steps: introducing hydrogen or oxygen into the gas flow channel, and introducing a mixed solution consisting of a reaction substrate and an organic solvent into the liquid flow channel; recovering the reaction solution discharged from the microfluidic reactor, and introducing the reaction solution into the liquid flow channel again.

[0047] The organic solvent is one or more of cyclohexane, pentane, hexane, octane, dichloromethane, cyclohexanone, toluene cyclohexanone, methanol, ethanol, acetonitrile, pyridine and phenol.

[0048] The reaction substrate includes azobenzene or diphenylhydrazine, or the reaction substrate includes diphenylhydrazine and dichloromethane. By optimizing the reaction conditions, including the reaction solution ratio, the organic solvent selection, the diffusion layer selection, etc., the hydrogenation efficiency and oxidation efficiency of the organic compound in the microfluidic channel reactor reaction device are accelerated.

[0049] Embodiment 1: Figure 1 and Figure 2 As shown, the microfluidic reactor uses a diffusion layer 003 with a reaction area of ​​15 cm × 15 cm. Four microfluidic reactors can form a total active area of ​​4 × 15 × 15 cm 2 . A mixed solution of 200mL of organic solvent ethanol and 40mmol of azobenzene was used for hydrogenation reaction. The diffusion layer 003 is made of polyethylene material with a thickness of 0.1mm and a porosity of 90%. After assembly, the experiment was carried out at room temperature and pressure. The circulating feeding device 006 transports the reaction liquid and reaction gas to the gas flow channel and liquid flow channel of the four microchannel reactors through pipelines, and then transports the reaction solution back to the storage tank through pipelines, thereby reducing the yield loss between the two electrodes. The four microchannel reactors are all operated separately. When the hydrogenation reaction time is 150min, the conversion rate of aromatic azo compounds can reach more than 95%.

[0050] Example 2: Compared with Example 1, the difference is that the diffusion layer 003 is made of polypropylene, the reaction solution is a mixed solution of 200 mL ethanol and 40 mmol azobenzene for hydrogenation reaction, and when the hydrogenation reaction time is 180 min, the conversion rate of aromatic azo compounds can reach more than 95%.

[0051] Example 3: Compared with Example 1, this example performs a diphenylhydrazine oxidation reaction, the reaction solution is a mixed solution of 200 mL ethanol and 40 mmol diphenylhydrazine, and the diffusion layer 003 is made of polyethylene. When the oxidation reaction time is 150 min, the phenylhydrazine conversion rate reaches more than 95%.

[0052] Example 4: Compared with Example 1, the difference is that the diffusion layer 003 is made of nickel foam, with a thickness of 0.2 mm and a porosity of 95%. The reaction solution is 200 mL ethanol and 40 mmol azobenzene. When the hydrogenation reaction time is 150 min, the phenylhydrazine conversion rate reaches more than 95%.

[0053] Example 5: Compared with Example 4, the difference is that the reaction solution is a mixed solution of 200 mL ethanol, 40 mmol diphenylhydrazine, and 50 mL dichloromethane. When the oxidation reaction time is 150 min, the conversion rate of the aromatic azo compound reaches more than 95%.

[0054] Example 6: Compared with Example 1, the difference is that the reaction device consists of 10 microchannel reactors with a reaction area of ​​15 cm×15 cm, and the total active area is 10×15×15 cm 2 The reaction solution is a mixed solution of 500mL ethanol and 100mmol azobenzene for oxidation reaction. The diffusion layer 003 is made of polyethylene with a thickness of 0.1mm and a porosity of 90%. All 10 microfluidic reactors are used separately. When the hydrogenation reaction time is 150min, the conversion rate of aromatic azo compounds reaches more than 95%.

[0055] Example 7: Compared with Example 1, the difference is that multiple microchannel reactors are used to form a total active area of ​​500 cm 2 The reactor is a mixture of 500 mL ethanol and 100 mmol azobenzene for hydrogenation reaction. The diffusion layer 003 is made of polyethylene with a thickness of 0.1 mm and a porosity of 90%. When the hydrogenation reaction time is 150 min, the conversion rate of aromatic azo compounds reaches more than 95%.

[0056] Embodiment 8: The microfluidic reaction method uses at least two microfluidic reactors, one for hydrogenation reaction and the other for oxidation reaction;

[0057] The microfluidic reaction method comprises: passing a mixed solution of azobenzene and ethanol into a liquid flow channel of a microfluidic reactor for hydrogenation reaction, and passing hydrogen into a gas flow channel of the microfluidic reactor; passing a hydrogenation reaction product into a liquid flow channel of a microfluidic reactor for oxidation reaction, and passing oxygen into a gas flow channel of the microfluidic reactor; and extracting and separating the oxidation product to obtain hydrogen peroxide.

[0058] The microfluidic reactor, microfluidic reaction cycle system and reaction method described in the above embodiments have the following beneficial effects:

[0059] (1) It can ensure that the reactants are evenly mixed in a very short time, while providing a huge specific surface area, which is conducive to the efficient heat and mass transfer process and has industrial prospects;

[0060] (2) The precious metal catalyst selected for the gas flow channel can improve the catalytic activity for hydrogen and increase the reaction rate;

[0061] (3) The transition metal-based catalyst selected for the liquid flow channel can improve the catalytic activity of the reduction reaction of aromatic azo compounds and improve the yield and yield of the product;

[0062] (4) The gas flow channel and the liquid flow channel can be recycled together to reduce the osmotic pressure between the two electrodes and avoid yield loss;

[0063] (5) Using organic solvent as solvent ensures the sustainable progress of the reaction.

[0064] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A microfluidic reactor, characterized in that: include: A gas plate (001), a liquid plate (002) and a diffusion layer (003), wherein the gas plate (001) and the liquid plate (002) are arranged opposite to and connected to each other; The diffusion layer (003) is installed between the gas plate (001) and the liquid plate (002); the gas plate (001) is provided with a gas flow channel toward the diffusion layer (003); and the liquid plate (002) is provided with a liquid flow channel toward the diffusion layer (003).

2. The microfluidic reactor according to claim 1, characterized in that: A first gasket (004) is installed between the gas plate (001) and the diffusion layer (003), and a second gasket (005) is installed between the liquid plate (002) and the diffusion layer (003).

3. The microfluidic reactor according to claim 1, characterized in that: The diffusion layer (003) is made of at least one of polypropylene, polyethylene and foam metal and is configured as a porous component.

4. The microfluidic reactor according to claim 1, characterized in that: A noble metal catalyst is arranged in the gas flow channel.

5. The microfluidic reactor according to claim 1, characterized in that: A transition metal catalyst is arranged in the liquid flow channel.

6. A microfluidic reaction circulation system, characterized in that: include: A circulating supply device (006) and the microfluidic channel reactor as described in any one of claims 1 to 5, wherein the gas flow channel and the liquid flow channel are respectively connected to the fluid of the circulating supply device (006).

7. A microfluidic reaction circulation system, characterized in that: include: A circulating feed device (006), a first reactor (007) and a second reactor (008), wherein the first reactor (007) and the second reactor (008) respectively adopt the microfluidic channel reactor according to any one of claims 1 to 5; The first reactor (007) is used for performing a hydrogenation reaction, the circulating supply device (006) is in fluid communication with a liquid flow channel of the first reactor (007), and the gas flow channel of the first reactor (007) is in fluid communication with a hydrogen tank (604); The second reactor (008) is used for performing an oxidation reaction, the hydrogenation reaction product outlet of the first reactor (007) is fluidically connected to the liquid flow channel of the second reactor (008), and the gas flow channel of the second reactor (008) is fluidically connected to the oxygen tank (606); The oxidation reaction product outlet of the second reactor (008) is fluidically connected to the circulation supply device (006).

8. A microfluidic reaction method, characterized in that: The microfluidic reaction method adopts the microfluidic reactor according to any one of claims 1 to 5, and comprises the following steps: Passing hydrogen or oxygen into the gas flow channel, and passing a mixed solution consisting of a reaction substrate and an organic solvent into the liquid flow channel; The reaction solution discharged from the microfluidic channel reactor is recovered and introduced into the liquid channel again.

9. The microfluidic reaction method according to claim 8, characterized in that: The reaction substrate includes azobenzene or diphenylhydrazine, or the reaction substrate includes diphenylhydrazine and dichloromethane.

10. A microfluidic reaction method, characterized in that: The microfluidic reaction method uses at least two microfluidic reactors according to any one of claims 1 to 5, one for hydrogenation reaction and the other for oxidation reaction; The microfluidic channel reaction method comprises: Passing a mixed solution of azobenzene and ethanol into a liquid flow channel of a microfluidic reactor for hydrogenation reaction, and passing hydrogen into a gas flow channel of the microfluidic reactor; Passing the hydrogenation reaction product into the liquid flow channel of a microfluidic reactor for oxidation reaction, and passing oxygen into the gas flow channel of the microfluidic reactor; The oxidation product is subjected to extraction separation to obtain hydrogen peroxide.

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