Mesoscale flow reactor and method of construction thereof

Abstract

The application discloses a mesoscale flow reactor and a construction method thereof. The construction method comprises the following steps: performing hydrophilic treatment on a hydrophobic flexible substrate surface to form at least one hydrophilic region, forming a water solution containing nanoparticles on the surface of the hydrophilic region, removing water in the water solution containing nanoparticles to deposit the nanoparticles on the surface of the hydrophilic region to form a nanoparticle layer, and winding the flexible substrate into a reaction channel after loading a catalyst on the surface of the nanoparticle layer to construct the mesoscale flow reactor. The reactor constructed by the application has the characteristics of novel structure and controllable size, the deposited nanoparticles can be efficiently loaded with the catalyst, and in terms of function, the stability and service life of the catalyst are improved, the reaction activity, selectivity and loading capacity of the catalyst are increased, the use amount of the catalyst can be controlled, and cost is reduced and benefit is increased.

Description

Technical Field

[0001] This invention relates to the field of microreactors, and more specifically to a mesoscale flow reactor and its construction method. Background Technology

[0002] A reactor is a device used to realize chemical processes, capable of performing single-phase liquid reactions and multiphase reactions such as liquid-liquid, gas-liquid, liquid-solid, and gas-liquid-solid reactions. It is widely used in chemistry, pharmaceuticals, and energy fields. Traditional reactors are characterized by their simple structure and ease of operation, typically consisting of a large reaction vessel containing one or more catalysts. Reactants undergo chemical reactions under catalysis to produce corresponding products. Typical reaction vessels include batch reactors and tubular reactors. Inside the reactor, the reaction process is often accompanied by high-temperature, strongly exothermic effects. The heat released from the reaction easily accumulates in the catalyst bed, especially during industrial scale-up. As the catalyst loading increases and the catalyst bed thickens, a large amount of reaction heat cannot be dissipated in time, leading to a rapid temperature rise in the catalyst bed. This results in problems such as difficulty in controlling the scaled-up reaction and an increase in byproducts. Therefore, researching efficient and safe reactors, improving catalyst utilization, and addressing the strong exothermic effect are particularly important for reactor process development.

[0003] With the continuous development of micro-nano fabrication technology, research on microreactors has become increasingly popular. A microreactor is a technology that places chemical synthesis reactions within microchannels. It is a novel, miniaturized, and continuously flowing tubular reactor that primarily achieves chemical synthesis through process intensification, exhibiting excellent mass and heat transfer efficiency, high reaction selectivity, and safety and stability. The reactor can contain numerous microchannels, allowing fluids to flow in combination under specific physical states. Simultaneously, by enhancing the rate and controllability of flow, mixing, and transfer processes within the system, the completion time of reaction and separation is shortened, the amount of material retained in the process is reduced, and the formation of byproducts is minimized, thereby achieving green, safe, and efficient chemical processes. Microreactors are a new type of technical equipment system developed in many process engineering fields such as chemical engineering, energy, environment, and materials. Existing research shows that the mass transfer rate of microreactors is several orders of magnitude higher than that of traditional reactors, and microreactors are suitable for reaction processes with high requirements for mass and heat transfer rates, especially strongly exothermic reactions. Therefore, research on the channel structure within the reactor and its enhanced mass and heat transfer processes is of great significance.

[0004] Currently, various microreactors have been developed for academic research and industrial applications, such as Corning's Advanced-Flow microreactor, Uniqsis' FlowSyn system, and Lonza's FlowPlate microreactor. These microreactors can perform chemical processes within confined spaces at the micrometer or millimeter scale. Through the spatial design of the channels, they reduce the dispersion scale of the system, enhance mixing and transport, and improve process controllability and efficiency. However, due to the small channel size of microreactors, catalyst accumulation can easily lead to channel blockage. Furthermore, the uniformity of the reaction process of reactant precursors in microchannels is difficult to guarantee. Therefore, there is still potential for further development in the structural design, fabrication, and material development of microreactors. Summary of the Invention

[0005] To address the aforementioned problems, one objective of this invention is to provide a mesoscale flow reactor and its construction method. By improving the uniformity of catalyst distribution on the reactor tube wall, the catalytic efficiency of the reactants is enhanced, the controllability of the reaction process and the mass and heat transfer efficiency are improved, and catalyst accumulation leading to channel blockage is avoided. At the same time, the reactor construction method is simple and can be scaled up for mass production.

[0006] As a first aspect of the present invention, a method for constructing a mesoscale flow reactor is provided, comprising the following steps:

[0007] S1, hydrophilic treatment is applied to the surface of a hydrophobic flexible substrate to form at least one hydrophilic region, and an aqueous solution containing nanoparticles is formed on the surface of the hydrophilic region;

[0008] S2, remove water from the aqueous solution containing nanoparticles so that the nanoparticles are deposited on the surface of the hydrophilic region to form a nanoparticle layer;

[0009] S3, after loading the catalyst onto the surface of the nanoparticle layer, the flexible substrate is rolled into a reaction channel to construct the mesoscale flow reactor.

[0010] Optionally, in step S1, the hydrophobic flexible substrate includes one or more of the following: polytetrafluoroethylene (PTFE), polytetrafluoroethylene-perfluoropropylene copolymer (PFA), polyetheretherketone (PEEK), polyimide (PI), perfluoroalkoxy resin, polydimethylsiloxane (PDMS), hydrophobic flexible glass, aluminum-plastic film, silicone sheet, stainless steel, and hydrophobically treated metal substrate, wherein the metal substrate includes titanium, magnesium, or copper.

[0011] Optionally, in the hydrophobically treated metal substrate, the hydrophobic treatment agent includes alkyl silanes or fluoropolymers; wherein the alkyl silane includes at least one of methyltrimethoxysilane, vinyltrimethoxysilane, hexadecyltrimethoxysilane chloride, and methacryloxypropyltrimethoxysilane, and the fluoropolymer includes at least one of perfluoroalkyl methacrylate and perfluoroalkyl acrylate.

[0012] Optionally, in step S1, the hydrophilic treatment of the hydrophobic flexible substrate surface to form at least one hydrophilic region includes: performing an array-based hydrophilic treatment on the hydrophobic flexible substrate surface to form a plurality of array-distributed hydrophilic regions.

[0013] Optionally, the arrayed hydrophilic treatment includes: performing plasma treatment or ozone treatment on the surface of the hydrophobic flexible substrate using a mask method, or performing laser ablation oxidation treatment at local locations on the surface of the hydrophobic flexible substrate.

[0014] Optionally, in step S1, the nanoparticles include unmodified and / or chemically modified nanoparticles; wherein the unmodified nanoparticles include one or more of silicon dioxide (SiO2), iron(II,III) oxide (Fe3O4), carbon nanotubes, cerium dioxide (CeO2), γ-alumina (γ-Al2O3), titanium dioxide (TiO2), zinc oxide (ZnO), polyethyleneimine, liquid crystal nanoparticles, dendritic polyamide-amine (PAMAM), polylactic acid (PLA), polyvinyl alcohol (PVA), and polyacrylamide (PAA); the chemical groups include at least one of amino (-NH2), carboxyl (-COOH), acyl (RM(O)-), olefin (-C=C-), hydroxyl (-OH), and mercapto (-SH).

[0015] Optionally, in step S1, the mass fraction of the nanoparticles in the aqueous solution containing nanoparticles is 10%-95%; wherein the degree of substitution of the chemically modified nanoparticles is 20%-90%.

[0016] Optionally, in step S2, removing water from the aqueous solution containing nanoparticles includes heating the flexible substrate at a temperature of 40°C to 200°C.

[0017] Optionally, in step S3, the catalyst includes at least one of a metal catalyst, a non-metal catalyst, a perovskite, and an enzyme; wherein the metal catalyst includes one or more of iron, cobalt, nickel, platinum, palladium, rhodium, zinc, manganese, copper, gold, silver, and lead; the non-metal catalyst includes one or more of carbon black, activated carbon, carbon nanotubes, silica, alumina, and iron oxide; and the perovskite includes inorganic perovskite ABO3, double perovskite configuration, or defective perovskite A2BX6, A2B... 1+ B 3+ X6, AB2X7, AB3X 10 And at least one of the following perovskite-like minerals: A3B2X9, wherein A is an alkali metal, alkaline earth metal, or rare earth element ion, B is a transition metal or some main group metal elements, and X is F. - I - ,Br - Cl - At least one of the following: enzymes including at least one of amylase, protease, lipase, cellulase, phosphodiesterase, superoxide dismutase, and glutamine synthase.

[0018] Optionally, in step S3, the method of loading the catalyst on the surface of the nanoparticle layer includes one or more of electrostatic adsorption, embedding blending, and covalent crosslinking.

[0019] Optionally, in step S3, after rolling the flexible substrate into a reaction channel, the method further includes: bonding the two ends of the flexible substrate with an adhesive to shape the reaction channel, wherein the adhesive includes at least one of silicone adhesive, polyimide adhesive, polyurethane adhesive, acrylate adhesive, PDMS and curing agent, two-component polyurethane adhesive, and epoxy resin adhesive.

[0020] Optionally, in step S3, the diameter of the reaction channel is 0.1-20 mm.

[0021] As a second aspect of the invention, a mesoscale flow reactor is also provided, which is prepared by the construction method described in any of the above aspects.

[0022] The mesoscale flow reactor and its construction method of the present invention involve forming a hydrophilic region on the surface of a hydrophobic flexible substrate with an aqueous solution containing nanoparticles. After forming a uniformly distributed aqueous solution, the substrate is subjected to high-temperature treatment. The deposition of nanoparticles enables efficient catalyst loading. Finally, the substrate is rolled into shape to prepare the mesoscale flow reactor. The hydrophilically treated flexible substrate allows for the localized attachment of nanoparticles. Furthermore, chemical modification of the nanoparticles can enhance their catalyst loading efficiency and catalytic activity. Optimization can also be performed for specific reactions, maintaining catalyst stability and improving utilization. Moreover, the prepared flow reactor can be reshaped and scaled down simultaneously according to actual needs, greatly improving the flexibility and adaptability of manufacturing processes, which is beneficial for large-scale industrial production. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort:

[0024] Figure 1 A flowchart illustrating the preparation method of a mesoscale flow reactor provided in an embodiment of the present invention;

[0025] Figure 2 A schematic diagram of the preparation process of the mesoscale flow reactor provided in an embodiment of the present invention;

[0026] Figure 3 This is a schematic diagram of the methane catalytic oxidation reaction process provided in an embodiment of the present invention;

[0027] Figure 4 The methane conversion rate of the reactor provided in the embodiments of the present invention at different times;

[0028] Figure 5 The methane conversion rate of the reactor provided in the embodiments of the present invention at different temperatures;

[0029] Figure 6 The hydrogen production rate of the reactor provided in the embodiments of the present invention at different temperatures. Detailed Implementation

[0030] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further clarifies the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0031] Various cross-sectional views of embodiments of the present invention are shown in the accompanying drawings. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0032] As a first aspect of the present invention, such as Figure 1 As shown, a method for constructing a mesoscale flow reactor is provided, comprising the following steps:

[0033] S1, hydrophilic treatment is applied to the surface of a hydrophobic flexible substrate to form at least one hydrophilic region, and an aqueous solution containing nanoparticles is formed on the surface of the hydrophilic region.

[0034] Specifically, the hydrophobic flexible substrate is used as the support substrate for the flow reactor. Organic, inorganic, or metallic materials with certain flexibility and strength can be selected as the substrate. For example, the hydrophobic flexible substrate includes one or more of the following: polytetrafluoroethylene (PTFE), polytetrafluoroethylene-perfluoropropylene copolymer (PFA), polyetheretherketone (PEEK), polyimide (PI), perfluoroalkoxy resin, polydimethylsiloxane (PDMS), hydrophobic flexible glass, aluminum-plastic film, silicone sheet, stainless steel, and hydrophobically treated metal substrates. The metal substrate includes titanium, magnesium, or copper. In the hydrophobically treated metal substrate, the hydrophobic treatment agent includes alkyl silanes or fluororesins; wherein the alkyl silane includes at least one of methyltrimethoxysilane, vinyltrimethoxysilane, hexadecyltrimethoxysilane chloride, and methacryloxypropyltrimethoxysilane, and the fluororesin includes at least one of perfluoroalkyl methacrylate and perfluoroalkyl acrylate.

[0035] A hydrophilic treatment is applied to the surface of a flexible substrate to form at least one hydrophilic region. Preferably, the number of hydrophilic regions can be one or more. If there is only one hydrophilic region, it can be formed in the central region of the flexible substrate surface. If there are multiple hydrophilic regions, they can be formed in an array on the flexible substrate surface to ensure uniform distribution. Specifically, the array of hydrophilic regions can be formed by performing an array-based hydrophilic treatment on the hydrophobic flexible substrate surface. This array-based hydrophilic treatment includes: plasma treatment or ozone treatment on the hydrophobic flexible substrate surface using a mask method, or laser ablation oxidation treatment at localized locations on the hydrophobic flexible substrate surface.

[0036] After forming at least one hydrophilic region, an aqueous solution containing nanoparticles is formed on the surface of the hydrophilic region. The aqueous solution containing nanoparticles refers to a homogeneous solution formed by uniformly dispersing nanoparticles in water. Since the surface of the flexible substrate is hydrophobic, the aqueous solution containing nanoparticles can be uniformly distributed on the surface of the at least one hydrophilic region without spreading to the surface of the flexible substrate outside the hydrophilic region. The nanoparticles include unmodified and / or chemically modified nanoparticles; wherein the unmodified nanoparticles include one or more of silicon dioxide (SiO2), iron(III) oxide (Fe3O4), carbon nanotubes, cerium dioxide (CeO2), γ-alumina (γ-Al2O3), titanium dioxide (TiO2), zinc oxide (ZnO), polyethyleneimine, liquid crystal nanoparticles, dendritic polyamide-amine (PAMAM), polylactic acid (PLA), polyvinyl alcohol (PVA), and polyacrylamide (PAA); the chemical groups include at least one of amino (-NH2), carboxyl (-COOH), acyl (RM(O)-), olefin (-C=C-), hydroxyl (-OH), and mercapto (-SH). In the aqueous solution containing the nanoparticles, the mass fraction of the nanoparticles is 10%-95%; wherein the degree of substitution of the chemically modified nanoparticles is 20%-90%.

[0037] Optionally, the aqueous solution containing nanoparticles can be formed on the surface of the hydrophilic region by immersing the flexible substrate in the aqueous solution containing nanoparticles; alternatively, the aqueous solution containing nanoparticles can be coated onto the surface of the flexible substrate by scraping. Since the local area of ​​the flexible substrate surface is hydrophilized, the aqueous solution containing nanoparticles will be uniformly distributed on the hydrophilic region under the action of surface tension. Preferably, there are multiple hydrophilic regions, so that the aqueous solution containing nanoparticles can be arrayed on the surface of the flexible substrate to form a droplet array, thereby forming a droplet printed substrate.

[0038] S2, remove water from the aqueous solution containing nanoparticles so that the nanoparticles are deposited on the surface of the hydrophilic region to form a nanoparticle layer.

[0039] Specifically, the flexible substrate can be heated to remove the moisture. The heating temperature can be 40℃-200℃, and the heating time can be selected from 1 minute to 300 minutes. The heating process allows the moisture to evaporate slowly until it is completely removed, causing the nanoparticles in the aqueous solution to deposit on the surface of the hydrophilic region. For nanoparticles modified with chemical groups, during the moisture removal process, the chemical groups on the surface of the nanoparticles can react with hydrophilic free radicals on the surface of the hydrophilic region or with chemical groups on the surface of other nanoparticles to form a self-assembled film. This allows the nanoparticle layer to be more firmly deposited and fixed on the surface of the hydrophilic region, and it will not easily peel off even when participating in high-throughput reactions later, thus improving the reliability of the reactor.

[0040] S3, after loading the catalyst onto the surface of the nanoparticle layer, the flexible substrate is rolled into a reaction channel to construct the mesoscale flow reactor.

[0041] Specifically, the nanoparticle layer formed in step S2 serves as a support, on which the target catalyst for catalyzing a specific reaction process is loaded, thereby forming catalytic reaction sites in the reactor. Optionally, depending on the catalytic reaction, the catalyst may be selected from at least one of metal catalysts, non-metal catalysts, perovskites, and enzymes. For example, the metal catalyst may include one or more of iron, cobalt, nickel, platinum, palladium, rhodium, zinc, manganese, copper, gold, silver, and lead; the non-metal catalyst may include one or more of carbon black, activated carbon, carbon nanotubes, silica, alumina, and iron oxide; and the perovskite may include inorganic perovskite ABO3, double perovskite configuration, or defective perovskite A2BX6, A2B... 1+ B 3+ X6, AB2X7, AB3X 10 And at least one of the following perovskite-like minerals: A3B2X9, wherein A is an alkali metal, alkaline earth metal, or rare earth element ion, B is a transition metal or some main group metal elements, and X is F. - I - ,Br - Cl - At least one of the following: enzymes including at least one of amylase, protease, lipase, cellulase, phosphodiesterase, superoxide dismutase, and glutamine synthase.

[0042] When loading catalysts onto the surface of nanoparticle layers, one or more loading methods, including electrostatic adsorption, embedding blending, and covalent cross-linking, can be selected depending on the type of catalyst and the surface characteristics of the nanoparticles. This allows the catalyst to be firmly attached to the surface of the nanoparticle layer, thereby forming catalytic reaction sites in the reactor. Simultaneously, the nanoparticle layer surface has a higher specific surface area, enabling it to load more catalyst, thus significantly improving the catalyst activity and enhancing the catalytic capacity of the microreactor.

[0043] After loading the catalyst onto the surface of the nanoparticle layer, since the flexible substrate is still in a planar state, it is necessary to roll the flexible substrate into a reaction channel. The cross-sectional shape of the reaction channel can be circular or regular polygonal, and the diameter of the reaction channel is 0.1-20 mm. Different reaction channel diameters can be selected according to the reaction flow rate and velocity of the reactor.

[0044] After the flexible substrate is rolled into a reaction channel, the two ends of the flexible substrate can be bonded with an adhesive to shape the reaction channel. The adhesive includes at least one of silicone adhesive, polyimide adhesive, polyurethane adhesive, acrylate adhesive, PDMS and curing agent, two-component polyurethane adhesive, and epoxy resin adhesive.

[0045] Furthermore, multiple reaction channels can be bundled together to form a multi-channel reactor according to the needs of the flow reactor, thereby increasing the reactor throughput and reaction efficiency.

[0046] Compared with the prior art, the technical solution disclosed in this invention has the following beneficial effects:

[0047] (1) The size and shape of the hydrophilic region prepared by the present invention are controllable, and the solution containing nanoparticles can be positioned and attached to form a droplet array by means of scraping or dipping.

[0048] (2) The mesoscale flow reactor of the present invention can efficiently fix the catalyst and activate the catalytic active center through the modification and localization deposition of nanoparticles, greatly improve the mass and heat transfer rate, and solve the problem of uneven reaction in the channel.

[0049] (3) The process conditions provided by the present invention are flexible, and the reactor can be rolled into different shapes according to actual needs. By adjusting the number and size of the reactor, large-scale production can be carried out relatively easily.

[0050] The technical solution of the present invention will be further described below with reference to specific embodiments and accompanying drawings, but this does not limit the present invention.

[0051] Example 1

[0052] like Figure 2 As shown, the construction of this mesoscale flow reactor mainly includes three steps: preparation of the droplet printing substrate, deposition of nanoparticles, and roll-up forming of the mesoscale flow reactor. The specific construction method steps are as follows:

[0053] 1. Preparation of droplet printing substrate

[0054] First, using a mask method, laser-perforated paper is attached to a silicone plate, leaving only the micropores intact. Then, it is placed in an oxygen plasma device for hydrophilic treatment, where the treated areas become hydrophilic, while the untreated areas remain hydrophobic. After removing the paper, 1 mL of an aqueous solution containing 10% silica nanoparticles is added to the treated silicone plate. This solution is then coated with a glass rod to form a droplet-printed substrate containing nanoparticles.

[0055] As an optional implementation, a high-precision laser drilling machine can be used to prepare paper of different shapes, and droplet lattice substrates of different shapes can be formed by masking, such as circles, ellipses, and snowmen.

[0056] 2. Deposition of nanoparticles

[0057] The droplet printing substrate formed above was placed in an oven at 100°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0058] 3. Rolling and shaping of mesoscale flow reactors

[0059] Nickel-based metal catalysts are loaded onto a substrate containing immobilized nanoparticles via physical embedding and blending. After folding and rolling, the substrate is connected end-to-end into a cylindrical shape using PDMS containing a curing agent, thus constructing a mesoscale flow reactor. Multiple prepared reactors can be assembled to form an integrated multi-channel flow reactor device.

[0060] Example 2

[0061] The construction method of this mesoscale flow reactor is as follows:

[0062] 1. Preparation of droplet printing substrate

[0063] First, the surface of metallic copper was treated with a perfluoroalkyl methacrylate reagent to achieve complete hydrophobicity. Then, it was etched using a high-precision laser drilling machine. The treated areas became hydrophilic, while the untreated areas remained hydrophobic. Next, 1 mL of an aqueous solution containing 20% ​​amination-modified cerium dioxide nanoparticles was added to the treated copper plate. This solution was then coated with a glass rod to form a droplet-printed substrate containing nanoparticles, with the amination degree of the nanoparticles reaching 90%.

[0064] 2. Deposition of nanoparticles

[0065] The droplet printing substrate formed above was placed in an oven at 200°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0066] 3. Rolling and shaping of mesoscale flow reactors

[0067] ABO3-type perovskite catalyst leucoxene was covalently cross-linked onto the aforementioned substrate with immobilized nanoparticles. After folding and rolling, the substrate was connected end to end with silicone adhesive to form a cylindrical shape, thus constructing a mesoscale flow reactor.

[0068] Figure 3This study demonstrates the catalytic oxidation process of methane gas using a perovskite catalyst. The feed gas is a mixture of methane and air. The introduction of inert argon gas helps maintain the stability of the pressure and gas composition within the reaction system. The flow rate of the reaction gas is regulated by a pressure regulating valve and a ball valve, and monitored in real time by a flow controller. After a heat treatment phase, the feed gas is delivered to the catalytic reaction module. Once the reaction is complete, the feed gas, the reactant gas, and the tail gas are analyzed online using gas chromatography.

[0069] Example 3

[0070] The construction method of this mesoscale flow reactor is as follows:

[0071] 1. Preparation of droplet printing substrate

[0072] First, using a mask method, laser-drilled paper is attached to a hydrophobic flexible glass substrate, leaving only the micropores intact. Then, it is placed in an oxygen plasma device for hydrophilic treatment, where the treated areas become hydrophilic, while the untreated areas remain hydrophobic. After removing the paper, the substrate is immersed in 5 mL of an aqueous solution containing 80% iron oxide nanoparticles, forming a droplet-printed substrate containing nanoparticles using an impregnation method.

[0073] 2. Deposition of nanoparticles

[0074] The droplet printing substrate formed above was placed in an oven at 200°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0075] 3. Rolling and shaping of mesoscale flow reactors

[0076] Non-metallic catalyst carbon nanotubes are loaded onto a substrate of fixed nanoparticles via electrostatic adsorption. After being folded and rolled up, the substrate is connected end to end into a cylindrical shape using a two-component polyurethane adhesive to construct a mesoscale flow reactor.

[0077] Example 4

[0078] The construction method of this mesoscale flow reactor is as follows:

[0079] 1. Preparation of droplet printing substrate

[0080] First, using a mask method, laser-drilled paper is attached to stainless steel, leaving only the micropores. Then, it is placed in an oxygen plasma device for hydrophilic treatment, where the treated areas become hydrophilic, while the untreated areas remain hydrophobic. After removing the paper, 1 mL of an aqueous solution containing 10% γ-alumina nanoparticles is added to the treated stainless steel. This solution is then coated with a glass rod to form a droplet-printed substrate containing nanoparticles.

[0081] 2. Deposition of nanoparticles

[0082] The droplet printing substrate formed above was placed in an oven at 200°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0083] 3. Rolling and shaping of mesoscale flow reactors

[0084] ABO3 type perovskite catalyst La 0.8 Ca 0.2 FeO3 perovskite type is loaded onto a substrate with fixed nanoparticles by embedding and blending. After being folded and rolled up, the substrate is connected end to end into a cylindrical shape with epoxy resin adhesive to construct a mesoscale flow reactor.

[0085] Figure 4 and Figure 5 The advantages of the prepared mesoscale flow reactor compared with other conventional reactors in methane conversion were demonstrated. The feed gas flow rate was 100 mL / min, and the argon gas flow rate was 40 mL / min. The temperature was controlled by heating from room temperature to 500℃, stabilizing for 10-30 min, and then starting the measurement. The measurement process was a heating process, and the selected temperature points were 200℃, 250℃, 300℃, 350℃, 400℃, 450℃, and 500℃. Samples were taken for analysis every 10 min.

[0086] refer to Figure 4 After heating to 500℃, the methane conversion rate in the reactor showed an upward trend followed by a downward trend. However, with increasing reaction time, the methane conversion rate of the constructed mesoscale flow reactor remained above 70%, which is generally higher than that of fixed-bed and fluidized-bed reactors. (Reference) Figure 5 As the reaction temperature gradually increases, the methane conversion efficiency in the reactor gradually increases. The methane conversion efficiency of the constructed mesoscale flow reactor is higher than that of the traditional reactor in the 200-500℃ range.

[0087] Example 5

[0088] The construction method of this mesoscale flow reactor is as follows:

[0089] 1. Preparation of droplet printing substrate

[0090] First, using a mask method, laser-perforated paper is attached to polyimide, leaving only the micropores. Then, it is placed in a plasma device for hydrophilic treatment, where the treated areas become hydrophilic and the untreated areas remain hydrophobic. After removing the paper, 1 mL of a 20% silica aqueous solution is added to the treated polyimide, and then coated with a glass rod to form a droplet printing substrate containing nanoparticles.

[0091] 2. Deposition of nanoparticles

[0092] The droplet printing substrate formed above was placed in an oven at 200°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0093] 3. Rolling and shaping of mesoscale flow reactors

[0094] ABO3 type perovskite catalyst La 0.8 Ca 0.2 FeO3 perovskite type was loaded onto a substrate with fixed nanoparticles by embedding and blending. After being folded and rolled up, the substrate was connected end to end with polyimide adhesive to form a cylindrical shape, thus constructing a mesoscale flow reactor.

[0095] Figure 6 The advantages of the prepared mesoscale flow reactor compared to other conventional reactors in methane reforming for hydrogen production are demonstrated. (Reference) Figure 3 During the reaction process, under reaction conditions of 400℃, 500℃, and 600℃, the hydrogen production rate of the mesoscale flow reactor can reach up to 74%, which is higher than the 62% of the fixed-bed reactor and the 54% of the fluidized-bed reactor. Among them, the hydrogen production rate of all three reactors reaches the highest at 500℃. The possible reason is that as the reaction gas loading increases, the catalyst activity shows a trend of first increasing and then decreasing. This means that after reaching a certain temperature, further increasing the temperature will lead to an accelerated catalyst deactivation rate and reduced stability.

[0096] Example 6

[0097] The construction method of this mesoscale flow reactor is as follows:

[0098] 1. Preparation of droplet printing substrate

[0099] First, laser-perforated paper is adhered to PDMS using a mask method, leaving only the micropores intact. Then, it is placed in an oxygen plasma device for hydrophilic treatment, where the treated areas become hydrophilic, while the untreated areas remain hydrophobic. After removing the paper, 1 mL of an aqueous solution containing 10% mercapto-modified iron oxide nanoparticles is added to the treated PDMS. This solution is then coated with a glass rod to form a droplet-printed substrate containing nanoparticles. The mercapto-modification degree is 60%.

[0100] 2. Deposition of nanoparticles

[0101] The droplet printing substrate formed above was placed in an oven at 200°C and heated for 2 hours. After the moisture was completely evaporated, the nanoparticles were deposited.

[0102] 3. Rolling and shaping of mesoscale flow reactors

[0103] Amylase was covalently cross-linked onto a substrate immobilized with nanoparticles. After folding and rolling, the substrate was bonded together end-to-end with PDMS containing a curing agent to form a cylindrical structure, thus constructing a mesoscale flow reactor. The nanoparticle-immobilized amylase exhibits higher stability and activity. Using a raw material liquid such as a starch solution, it can be directly introduced into the mesoscale flow reactor with a high loading of α-amylase, enabling efficient and large-scale glucose production.

[0104] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of the present invention without departing from the spirit and scope of the claims. All of these forms are within the protection scope of the present invention.

Claims

1. A method for constructing a mesoscale flow reactor, characterized in that, Includes the following steps: S1, hydrophilic treatment is applied to the surface of a hydrophobic flexible substrate to form at least one hydrophilic region, and an aqueous solution containing nanoparticles is formed on the surface of the hydrophilic region; S2, remove water from the aqueous solution containing nanoparticles so that the nanoparticles are deposited on the surface of the hydrophilic region to form a nanoparticle layer; S3, after loading the catalyst onto the surface of the nanoparticle layer, the flexible substrate is rolled into a reaction channel to construct the mesoscale flow reactor.

2. The construction method according to claim 1, characterized in that, In step S1, the hydrophobic flexible substrate includes one or more of the following: polytetrafluoroethylene, polytetrafluoroethylene-perfluoropropylene copolymer, polyetheretherketone, polyimide, perfluoroalkoxy resin, polydimethylsiloxane, hydrophobic flexible glass, aluminum-plastic film, silicone sheet, stainless steel, and hydrophobic treated metal substrate, wherein the metal substrate includes titanium, magnesium, or copper.

3. The construction method according to claim 2, characterized in that, In the hydrophobically treated metal substrate, the hydrophobic treatment agent includes alkyl silanes or fluoropolymers; wherein the alkyl silane includes at least one of methyltrimethoxysilane, vinyltrimethoxysilane, hexadecyltrimethoxysilane chloride, and methacryloxypropyltrimethoxysilane, and the fluoropolymer includes at least one of perfluoroalkyl methacrylate and perfluoroalkyl acrylate.

4. The construction method according to claim 1, characterized in that, In step S1, the hydrophilic treatment of the hydrophobic flexible substrate surface to form at least one hydrophilic region includes: performing an array-based hydrophilic treatment on the hydrophobic flexible substrate surface to form a plurality of array-distributed hydrophilic regions.

5. The construction method according to claim 1, characterized in that, In step S1, the nanoparticles include unmodified and / or chemically modified nanoparticles; wherein the unmodified nanoparticles include one or more of silicon dioxide, iron oxide, carbon nanotubes, cerium dioxide, γ-alumina, titanium dioxide, zinc oxide, polyethyleneimine, liquid crystal nanoparticles, dendritic polyamide-amine, polylactic acid, polyvinyl alcohol, and polyacrylamide; and the chemical groups include at least one of amino, carboxyl, olefinic, hydroxyl, and thiol groups.

6. The construction method according to claim 4, characterized in that, The arrayed hydrophilic treatment includes: using a mask method to perform plasma treatment or ozone treatment on the surface of the hydrophobic flexible substrate, or performing laser ablation oxidation treatment at local locations on the surface of the hydrophobic flexible substrate.

7. The construction method according to claim 1, characterized in that, In step S3, the catalyst comprises at least one of a metal catalyst, a non-metal catalyst, a perovskite, and an enzyme; wherein the metal catalyst comprises one or more of iron, cobalt, nickel, platinum, palladium, rhodium, zinc, manganese, copper, gold, silver, and lead; the non-metal catalyst comprises one or more of carbon black, activated carbon, carbon nanotubes, silica, alumina, and iron oxide; and the perovskite comprises inorganic perovskite ABO3, double perovskite configuration, or defective perovskite A2BX6, A2B 1+ B 3+ X6, AB2X7, AB3X 10 And at least one of the following perovskite-like minerals: A3B2X9, wherein A is an alkali metal, alkaline earth metal, or rare earth element ion, B is a transition metal or some main group metal elements, and X is F. - I - ,Br - Cl - At least one of the following: enzymes including at least one of amylase, protease, lipase, cellulase, phosphodiesterase, superoxide dismutase, and glutamine synthase.

8. The construction method according to claim 1, characterized in that, In step S3, the method of loading the catalyst on the surface of the nanoparticle layer includes one or more of electrostatic adsorption, embedding blending, and covalent crosslinking.

9. The construction method according to claim 1, characterized in that, In step S3, after rolling the flexible substrate into a reaction channel, the method further includes: bonding the two ends of the flexible substrate with an adhesive to shape the reaction channel. The adhesive includes at least one of silicone adhesive, polyimide adhesive, polyurethane adhesive, acrylate adhesive, PDMS and curing agent, two-component polyurethane adhesive, and epoxy resin adhesive.

10. A mesoscale flow reactor, characterized in that, The mesoscale flow reactor is prepared by the construction method according to any one of claims 1-9.

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