Microchannel reactor, method of making, use and method of making a low carbon alcohol aqueous solution

Abstract

The present application relates to the technical field of low carbon olefin hydration reaction, and discloses a micro-channel reactor, a preparation method and application thereof, and a method for preparing low carbon alcohol aqueous solution. The micro-channel reactor comprises a micro-channel reactor base body and a silane bottom layer, a reactant enrichment layer, a hydration layer and an olefin activation layer which are sequentially coated on the inner surface of the micro-channel reactor base body from inside to outside. The reactant enrichment layer contains amido, pyrrolyl and furanyl groups. The hydration layer contains amido, pyrrolyl, furanyl, phenoxy, sulfonic acid and phosphoric acid groups. The olefin activation layer contains phenoxy, sulfonic acid and phosphoric acid groups. The micro-channel reactor can significantly increase the contact area of water and olefin and promote the increase of hydration conversion rate.

Description

Technical Field

[0001] This invention relates to the technical field of low-carbon olefin hydration reactions, specifically to a microchannel reactor, its preparation method, application, and a method for preparing low-carbon alcohol aqueous solutions. Background Technology

[0002] Olefin hydration is an important organic reaction used to prepare alcohols such as sec-butanol, isopropanol, and cyclohexanol. Traditional olefin hydration generally employs the indirect sulfuric acid hydration method, which suffers from severe equipment corrosion and waste acid treatment problems, and has been gradually replaced by the catalytic direct hydration method. The catalytic direct hydration method typically uses a solid acid catalyst to directly generate the corresponding low-carbon alcohols from low-carbon olefins. However, since low-carbon olefins are almost immiscible with water, the reaction is a liquid-liquid-solid three-phase system, and the reaction yield is greatly affected by mass transfer efficiency. To improve the reaction yield, modified high-temperature resistant strong acid ion exchange resins with high reactivity and good temperature resistance are generally used as catalysts, or zeolite catalysts may also be used. The main process of the low-carbon olefin direct hydration process using solid acid as a catalyst generally involves mixing the olefin feedstock (olefin volume content 80-99%) with process water, preheating it to 70-250℃, and then introducing it into the hydration reactor for reaction at a pressure of 3.0-25.0 MPa. The reactor is equipped with multiple catalyst beds. The reactants are converted into low-carbon alcohols in the reactor bed, and then the low-carbon alcohol products are obtained by gradually removing components such as olefins, water, and olefin oligomers through a separation system.

[0003] To address the problem of uneven three-phase mixing, patent application CN114505017A discloses an olefin hydration reaction apparatus and method. The olefin hydration reaction apparatus includes a microchannel mixing device I, a microchannel mixing device II, and an olefin hydration reactor. The microchannel mixing device I has a shell-and-tube structure, with an inorganic membrane tube bundle installed inside the shell. The inlet end of the inorganic membrane tube bundle is connected to the aqueous phase pipeline, and the internal cavity outside the inorganic membrane tube bundle is connected to the olefin phase pipeline. The olefin phase expands from the internal cavity through the pores in the inorganic membrane tube wall. The mixture is dispersed into the aqueous phase inside the inorganic membrane tube, where it forms a homogeneous mixture under the shear force of the high-velocity aqueous phase. The microchannel mixing device II includes a microchannel assembly fixed within a housing. This assembly comprises multiple stacked thin sheets and oleophilic and hydrophilic fibers filling the gaps between adjacent sheets. These fibers form several microchannels, enabling water in the olefin and water feed to adhere, spread, and be cut into micron-sized particles along the fiber surface, thereby enhancing mass transfer and reducing the water-to-olefin ratio. The core of patent application CN114505017A lies in using microchannels to enhance liquid mixing. Specifically, it employs an inorganic membrane with pores to achieve cross-flow of two materials, or through repeated segmentation and mixing by packing material within the microchannels. The catalytic reaction still utilizes a conventional fixed-bed catalytic reactor, failing to achieve a high degree of integration of mixing, reaction, and separation within the microchannel reactor. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of small contact area and low hydration conversion rate of hydrates and olefins in the hydration process of low-carbon olefins in the prior art, and to provide a microchannel reactor, its preparation method, application, and method for preparing aqueous solutions of low-carbon alcohols. This microchannel reactor can significantly increase the contact area of ​​hydrates and olefins and promote the improvement of hydration conversion rate.

[0005] To achieve the above objectives, a first aspect of the present invention provides a microchannel reactor, wherein the microchannel reactor comprises a microchannel reactor substrate and, from the inside out, a silane underlayer, a reactant enrichment layer, a hydration layer, and an olefin activation layer sequentially coated on the inner surface of the microchannel reactor substrate; the reactant enrichment layer contains amide groups, pyrrole groups, and furan groups; the hydration layer contains amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups, and phosphoric acid groups; and the olefin activation layer contains phenoxy groups, sulfonic acid groups, and phosphoric acid groups.

[0006] A second aspect of the present invention provides a method for preparing a microchannel reactor, wherein the method includes:

[0007] (1) The inner surface of the microchannel reactor substrate is silanized by using a solution containing silane components to obtain a silanized microchannel reactor;

[0008] (2) The inner surface of the silanized microchannel reactor described in step (1) is subjected to reactant enrichment treatment using a solution containing reactant enrichment components to obtain a reactant enrichment microchannel reactor.

[0009] (3) The inner surface of the microchannel reactor enriched by the reactants in step (2) is hydrated using a solution containing hydration components to obtain a hydrated microchannel reactor.

[0010] (4) The inner surface of the microchannel reactor after hydration treatment in step (3) is subjected to olefin activation treatment using a solution containing olefin activation components to obtain the microchannel reactor.

[0011] The reactant enrichment component contains amide, pyrrole, and furanyl groups; the hydration component contains amide, pyrrole, furanyl, phenoxy, sulfonic acid, and phosphoric acid groups; and the olefin activation component contains phenoxy, sulfonic acid, and phosphoric acid groups.

[0012] The third aspect of this invention provides the application of the microchannel reactor described in the first aspect or the microchannel reactor prepared by the preparation method described in the second aspect in the hydration reaction of low-carbon olefins.

[0013] The fourth aspect of the present invention provides a method for preparing an aqueous solution of low-carbon alcohols, wherein the method comprises: hydrating olefin reaction raw materials with water in a microchannel reactor, wherein the microchannel reactor is the microchannel reactor described in the first aspect or the microchannel reactor prepared by the preparation method described in the second aspect.

[0014] During their research on the hydration of low-carbon olefins, the inventors of this invention discovered that using existing solid acid catalysts such as strong acid resins and ZSM-5 molecular sieves to catalyze olefin hydration resulted in a significantly lower single-pass conversion rate compared to the thermodynamic equilibrium conversion rate. This was mainly influenced by factors related to mass transfer and chemical equilibrium. Low-carbon olefins are generally poorly soluble in water; even with a significantly excess water-to-olefin ratio, the two remain incompatible. From the perspective of using excess reactants to further shift the hydration equilibrium to the right, the effect is not significant, only achieving a certain dilution effect on the product low-carbon alcohols. Solid acid catalysts have good water binding properties but poor compatibility with olefins. Olefins are difficult to adsorb onto the water-saturated solid acid catalyst surface, leading to difficulty in activating double bonds. To improve the catalytic effect of solid acids, modification mainly focuses on increasing acid strength and density. However, this approach can lead to side reactions such as olefin chelation, resulting in reduced yield and selectivity of low-carbon alcohols.

[0015] In this invention, the low-carbon olefin hydration microchannel uses a precision microchannel reactor as its substrate. Preferably, the inner diameter of the microchannel reactor substrate is controlled below 500 μm, so that the liquid-liquid contact area can reach 5000-15000 m². 2 / m 3 Compared to fixed-bed reactors or general structured packing materials, this reactor has a significantly increased surface area, providing favorable conditions for sufficient liquid-liquid contact. Using this precision microchannel reactor as a substrate, further modifications are made based on the components involved in the hydration reaction. From the inside out, the inner surface of the microchannel reactor substrate is coated with a silane underlayer, a reactant enrichment layer, a hydration layer, and an olefin activation layer, thereby addressing the problems of poor mass transfer and low yield and selectivity of low-carbon alcohols in existing technologies from a microscopic mechanism perspective. Detailed Implementation

[0016] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0017] In this invention, the functional groups and their contents in the coating were determined by infrared spectroscopy. The specific test conditions were KBr pellet pressing at 400 cm⁻¹. -1 -4000cm -1Within the range of scanning, the content of functional groups in each coating was obtained by step-by-step measurement during the preparation process.

[0018] In this invention, the thickness of the coatings involved is measured by an X-ray fluorescence thickness gauge.

[0019] The first aspect of the present invention provides a microchannel reactor, wherein the microchannel reactor comprises a microchannel reactor substrate and, from the inside out, a silane underlayer, a reactant enrichment layer, a hydration layer, and an olefin activation layer sequentially coated on the inner surface of the microchannel reactor substrate; the reactant enrichment layer contains amide groups, pyrrole groups, and furan groups; the hydration layer contains amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups, and phosphoric acid groups; and the olefin activation layer contains phenoxy groups, sulfonic acid groups, and phosphoric acid groups.

[0020] The silane substrate primarily functions as a connecting layer, linking the matrix and the reactant enrichment layer, thereby improving the stability of the reactant enrichment layer and extending the service life of the modified microchannels. The reactant enrichment layer is grafted with water-affinity groups (receptive to the hydration reaction feedstock) and low-carbon alcohol-repellent groups (repellent to the reaction products). The water-affinity groups form a water-rich layer on the inner surface of the matrix, providing excess water for the hydration reaction microenvironment. The low-carbon alcohol-repellent groups on the inner surface promote mass transfer of the low-carbon alcohols present in the reactant enrichment layer to the sub-outer layer.

[0021] The outermost layer of the reactant enrichment layer is the hydration layer, which is the main site of olefin hydration reactions. This layer is grafted with alkenophilic groups (for enriching olefins), hydrophilic groups (for enriching water), catalytic groups (for activating olefins, and through the synergistic combination of groups, the acid strength is rationally controlled), and low-carbon alcohol repulsion groups (for transferring the low-carbon alcohols generated in the reaction to the outside of the reaction system, promoting the hydration reaction to shift to the right). Water in the mixed liquid phase continuously accumulates from the liquid phase to the reaction enrichment layer based on the gradient change in hydrophilicity between the hydration layer and the reactant enrichment layer. The hydration layer is grafted with alkenophilic groups, which continuously receive olefin molecules captured by the outermost layer of the hydration layer. Under the activation of the catalytic groups with suitable acid strength, olefins undergo hydration reactions with the surrounding and bottom-enriched water molecules. The low-carbon alcohols generated by hydration continuously diffuse from the hydration layer and its outermost layer to the liquid phase under the impetus of the low-carbon alcohol repulsion groups, thereby shifting the hydration equilibrium to the right. The presence of hydrophilic groups in the reactant enrichment layer and the hydration layer results in a significant excess of microscopic water, thereby reducing the water-to-olefin ratio. This reduction in the water-to-olefin ratio promotes the enrichment of olefin molecules on the olefinic groups, further facilitating the shift in hydration equilibrium.

[0022] The outermost layer of the hydration layer is the olefin activation layer, which plays a role in enriching and activating olefins. This layer is grafted with alkenophilic groups and catalytic groups. The alkenophilic groups continuously capture olefin molecules from the mixed liquid phase, and the catalytic groups activate the captured olefin molecules. This layer is relatively thin, which can simultaneously meet the mass transfer requirements of olefin capture and low-carbon alcohol diffusion.

[0023] In this invention, there is no particular limitation on the structural type of the microchannel reactor substrate. Microchannel reactors conventionally defined in the art are all applicable to this invention, such as precision microchannel reactors. Preferably, the cross-section of the microchannel reactor is circular. Preferably, the inner diameter of the microchannel reactor substrate is 200-500 μm.

[0024] In this invention, there is no particular limitation on the preparation method of the microchannel reactor substrate. For example, it can be obtained by commercial purchase or by micro-cutting machining process. Those skilled in the art can choose according to actual needs.

[0025] In this invention, there is no particular limitation on the material of the microchannel reactor substrate. Preferably, the microchannel reactor substrate is made of metal, ceramic or glass.

[0026] In this invention, preferably, an isosceles triangular protrusion is provided on the inner wall of the microchannel reactor substrate. More preferably, the isosceles triangular protrusion is spirally distributed on the inner wall of the microchannel reactor substrate.

[0027] In this invention, preferably, the angle of the vertex angle of the isosceles triangular protrusion is 50°-130°.

[0028] In this invention, preferably, the ratio of the height of the isosceles triangular protrusion to the inner diameter of the microchannel reactor substrate is (1 / 8-1 / 4):1.

[0029] In this invention, preferably, the angle between the ridge of the isosceles triangular protrusion and the tangent of the cross-section of the microchannel reactor substrate is 15°-60°.

[0030] In this invention, the macroscopic mixing of water-based alkenes can be promoted by providing isosceles triangular protrusions with the above-mentioned preferred structure.

[0031] In this invention, the silane substrate serves as a dielectric layer, requiring only its ability to connect the microchannel reactor substrate and the reactant enrichment layer. The thickness of the silane substrate is not particularly limited. Preferably, the thickness of the silane substrate is 6-10 nm.

[0032] In this invention, there is no particular limitation on the specific type of silane substrate. Preferably, the silane substrate is provided by at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

[0033] In this invention, preferably, based on the inner surface area of ​​the dry-based microchannel reactor substrate per square meter, the content of amide groups in the reactant enrichment layer is 16-31 mmol / m². 2 The content of pyrrole groups is 11-19 mmol / m³. 2 The furanyl content is 1.8-4.7 mmol / m³. 2 By grafting different amounts of functional groups onto the inner surface of the microchannel reactor substrate, it has the advantage of microscopic water enrichment and repulsion of low-carbon alcohols.

[0034] In this invention, it should be noted that the inner surface area of ​​the microchannel reactor substrate refers to the surface area including the isosceles triangular protrusions.

[0035] In this invention, preferably, the thickness of the reactant enrichment layer is 4-7 nm.

[0036] In this invention, preferably, based on the inner surface area of ​​the dry-based microchannel reactor substrate per square meter, the amide group content in the hydration layer is 10-16 mmol / m². 2 The phenoxy group content is 11-20 mmol / m 2 The content of sulfonic acid groups is 21-40 mmol / m 2 The phosphate group content is 7.5-17 mmol / m³. 2 The content of pyrrole groups is 17-25 mmol / m³. 2 The furanyl content is 2.7-6.8 mmol / m³. 2 By grafting different amounts of functional groups onto the inner surface of the microchannel reactor substrate, it has the advantage of microscopically enriching water and alkenes while repelling lower alcohols.

[0037] In this invention, preferably, the thickness of the hydration layer is 10-17 nm.

[0038] In this invention, preferably, based on the inner surface area of ​​the dry-based microchannel reactor substrate per square meter, the phenoxy group content in the olefin activation layer is 1.3-1.9 mmol / m². 2 The content of sulfonic acid groups is 2.2-3.7 mmol / m. 2 The phosphate group content is 0.6-1.5 mmol / m 2 By grafting different amounts of functional groups onto the inner surface of the microchannel reactor substrate, it has the advantage of microscopic enrichment and activation of olefins.

[0039] In this invention, preferably, the thickness of the olefin activation layer is 1.1-1.8 nm.

[0040] A second aspect of the present invention provides a method for preparing a microchannel reactor, wherein the method includes:

[0041] (1) The inner surface of the microchannel reactor substrate is silanized by using a solution containing silane components to obtain a silanized microchannel reactor;

[0042] (2) The inner surface of the silanized microchannel reactor described in step (1) is subjected to reactant enrichment treatment using a solution containing reactant enrichment components to obtain a reactant enrichment microchannel reactor.

[0043] (3) The inner surface of the microchannel reactor enriched by the reactants in step (2) is hydrated using a solution containing hydration components to obtain a hydrated microchannel reactor.

[0044] (4) The inner surface of the microchannel reactor after hydration treatment in step (3) is subjected to olefin activation treatment using a solution containing olefin activation components to obtain the microchannel reactor.

[0045] The reactant enrichment component contains amide, pyrrole, and furanyl groups; the hydration component contains amide, pyrrole, furanyl, phenoxy, sulfonic acid, and phosphoric acid groups; and the olefin activation component contains phenoxy, sulfonic acid, and phosphoric acid groups.

[0046] In this invention, preferably, in step (1), the silanization treatment coats the inner surface of the microchannel reactor substrate with a silane underlayer, the thickness of which is 6-10 nm.

[0047] In this invention, there is no particular limitation on the method of silanization treatment. Preferably, the silanization treatment includes: contacting a solution containing silane components with a microchannel reactor substrate, followed by drying and curing.

[0048] In this invention, the source of the solution containing the silane component is not particularly limited, and it can be prepared by methods conventionally defined in the art. Preferably, in step (1), the solution containing the silane component is obtained by mixing a silane reagent, water, and anhydrous low alcohol, followed by pre-hydrolysis.

[0049] In this invention, there is no particular limitation on the amount of each component in the solution containing silane. Preferably, the volume ratio of silane reagent:water:lower alcohol is (1.9-4.4):(3.5-5.8):(89-95).

[0050] In this invention, preferably, the pH of the solution containing the silane component is 7.5-8.5.

[0051] In this invention, preferably, the pre-hydrolysis time is 12-30 hours.

[0052] In this invention, there is no particular limitation on the type of silane reagent. Preferably, the silane reagent is selected from at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

[0053] In this invention, preferably, in step (1), the amount of the solution containing the silane component is such that the thickness of the silane substrate is 6-10 nm.

[0054] In this invention, preferably, in step (2), the reactant enrichment treatment causes the inner surface of the silanized microchannel reactor described in step (1) to be coated with a reactant enrichment layer, wherein the reactant enrichment layer contains amide groups, pyrrole groups, and furan groups.

[0055] In this invention, preferably, based on the inner surface area of ​​the dry-based microchannel reactor substrate per square meter, the content of amide groups in the reactant enrichment layer is 16-31 mmol / m². 2 The content of pyrrole groups is 11-19 mmol / m³. 2 The furanyl content is 1.8-4.7 mmol / m³. 2 .

[0056] In this invention, the range of types of components in the solution containing the reactant enrichment component is relatively wide. Preferably, in step (2), the solution containing the reactant enrichment component contains the reactant enrichment component, a first initiator, and a first solvent.

[0057] In this invention, the range of selectable contents of each component in the solution containing the reactant enrichment component is relatively wide. Preferably, the mass ratio of reactant enrichment component: first initiator: first solvent is (3.8-6.7):(0.1-0.3):(93-97).

[0058] In this invention, the range of types of the first solvent is relatively wide. Preferably, in step (2), the first solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

[0059] In this invention, the range of types of the first initiator is relatively wide. Preferably, in step (2), the first initiator is selected from at least one of azo, organic peroxide, inorganic peroxide and redox initiators, preferably at least one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate and hydrogen peroxide, and more preferably benzoyl peroxide.

[0060] In this invention, preferably, in step (2), the reactant enrichment component contains amide derivatives, pyrrole derivatives, and furan derivatives.

[0061] In this invention, preferably, the molar ratio of amide derivatives: pyrrole derivatives: furan derivatives is (19-37): (13-23): (2.2-5.7).

[0062] In this invention, each group in each coating is provided by a derivative corresponding to that group. Preferably, the amide group is provided by an amide derivative, and more preferably by at least one of N,N'-dihydroxyethylbisacrylamide, N,N-methylenebisacrylamide, and hexamethylenebisacrylamide.

[0063] In this invention, preferably, the pyrrole group is provided by a pyrrole derivative, and more preferably by at least one of 3-isopropenyl-1-methyl-pyrrole, 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole, and 5-allyl-4-methoxy-1,5-dihydro-2H-pyrrole-2-one.

[0064] In this invention, preferably, the furanyl group is a furan derivative, and more preferably is provided by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

[0065] In this invention, the range of methods and conditions for reactant enrichment treatment is relatively wide. Preferably, in step (2), the reactant enrichment treatment includes: pumping a solution containing the reactant enrichment component into the inner cavity of the microchannel reactor described in step (1) for silanization; the linear velocity of the solution containing the reactant enrichment component on the inner surface of the microchannel reactor is 0.1-0.3 m / s; the treatment temperature is 60-80℃; and the treatment time is 1.5-3 h. The reactant enrichment treatment using the above flow treatment method can eliminate the capillary phenomenon during microchannel modification and prevent uneven modification.

[0066] In this invention, preferably, in step (3), the hydration treatment causes the inner surface of the microchannel reactor after the reactant enrichment treatment in step (2) to be coated with a hydration layer, wherein the hydration layer contains amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups, and phosphate groups.

[0067] In this invention, preferably, based on the inner surface area of ​​the dry-based microchannel reactor substrate per square meter, the amide group content in the hydration layer is 10-16 mmol / m². 2 The phenoxy group content is 11-20 mmol / m 2 The content of sulfonic acid groups is 21-40 mmol / m 2 The phosphate group content is 7.5-17 mmol / m³.2 The content of pyrrole groups is 17-25 mmol / m³. 2 The furanyl content is 2.7-6.8 mmol / m³. 2 .

[0068] In this invention, preferably, the thickness of the hydration layer is 10-17 nm.

[0069] In this invention, there is no particular limitation on the types of components in the solution containing the hydrated component, as long as the content of each group in the hydrated layer is satisfied. Preferably, in step (3), the solution containing the hydrated component contains the hydrated component, the second initiator, and the second solvent.

[0070] In this invention, there is no particular limitation on the content of each component in the solution containing the hydrated component, as long as the content of each group in the hydrated layer is satisfied. Preferably, the mass ratio of hydrated component: second initiator: second solvent is (4.7-8.8):(0.1-0.4):(92-96).

[0071] In this invention, preferably, in step (3), the hydrated component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives.

[0072] In this invention, preferably, the molar ratio of amide derivatives: phenoxy derivatives: sulfonic acid derivatives: phosphate derivatives: pyrrole derivatives: furan derivatives is (12-20): (13-24): (25-48): (9-21): (20-30): (3-8).

[0073] In this invention, preferably, the amide group is provided by an amide derivative. The specific types of amide derivatives have been described above and will not be repeated here.

[0074] In this invention, preferably, the phenoxy group is provided by a phenoxy derivative, and more preferably by at least one of 4-methoxystyrene, allyl phenyl ether, and phenyl vinyl ether.

[0075] In this invention, preferably, the phosphate group is provided by a phosphate derivative, and more preferably by at least one of (2-fluoro-3,7-dimethyloct-1,6-dien-3-yl)phosphonophosphate, [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate and 2-(phosphonooxy)propane-1,3-dimethyldimethacrylate.

[0076] In this invention, preferably, the sulfonic acid group is provided by a sulfonic acid derivative, and more preferably by at least one of 4-hydroxy-6-(prop-2-enoylamino)naphthalene-2-sulfonic acid, (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)) and 4-{(E)-2-[3,5-di(sulfonoxy)phenyl]vinyl}phenyl hydrosulfate.

[0077] In this invention, there are no particular limitations on the method and conditions of hydration treatment. Preferably, in step (3), the hydration treatment includes: pumping a solution containing hydration components into the inner cavity of the microchannel reactor after the reactant enrichment treatment in step (2), wherein the linear velocity of the solution containing hydration components on the inner surface of the microchannel reactor is 0.1-0.3 m / s, the treatment temperature is 70-90℃, and the treatment time is 1.5-3 h.

[0078] In this invention, preferably, step (3) further includes post-hydration treatment of the hydration product in a hydration post-treatment agent.

[0079] In this invention, there is no particular limitation on the type of post-hydration treatment agent. Preferably, the post-treatment agent is selected from at least one of anhydrous ethanol, anhydrous acetone, and anhydrous methanol, and more preferably anhydrous ethanol.

[0080] In this invention, there are no particular limitations on the conditions for post-hydration treatment. Preferably, the conditions for post-hydration treatment include: flow treatment time of 0.5-1 h, drying temperature of 100-120 °C, and drying time of 0.5-1 h.

[0081] In this invention, preferably, in step (4), the olefin activation treatment causes the inner surface of the microchannel reactor after the hydration treatment in step (3) to be coated with an olefin activation layer, wherein the olefin activation layer contains phenoxy, sulfonic acid, and phosphate groups.

[0082] In this invention, preferably, based on the surface area of ​​the dry-based microchannel matrix per square meter, the phenoxy group content in the olefin activation layer is 1.3-1.9 mmol / m². 2 The content of sulfonic acid groups is 2.2-3.7 mmol / m. 2 The phosphate group content is 0.6-1.5 mmol / m 2 .

[0083] In this invention, preferably, the thickness of the olefin activation layer is 1.1-1.8 nm.

[0084] In this invention, there is no particular limitation on the types of components in the solution containing the olefin activating component. Preferably, in step (4), the solution containing the olefin activating component contains the olefin activating component, a third initiator, and a third solvent.

[0085] In this invention, the content of each component in the solution containing the olefin activating component is not particularly limited. Preferably, the mass ratio of the olefin activating component: the third initiator: the third solvent is (0.5-0.9):(0.1-0.2):(96-98).

[0086] In this invention, preferably, in step (4), the olefin activating component contains phenoxy derivatives, sulfonic acid derivatives, and phosphoric acid derivatives.

[0087] In this invention, preferably, the molar ratio of phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives is (12-23): (24-46): (8-20).

[0088] In this invention, the phenoxy, phosphoric acid, and sulfonic acid groups are provided by their respective derivatives. The specific types of the derivatives have been described above and will not be repeated here.

[0089] In this invention, there are no particular limitations on the conditions for olefin activation treatment. Preferably, in step (4), the olefin activation treatment conditions include: pumping a solution containing olefin activation components into the inner cavity of the microchannel reactor after hydration treatment in step (3), the linear velocity of the solution containing olefin activation components flowing on the inner surface of the microchannel reactor being 0.15-0.45 m / s, the treatment temperature being 68-86℃, and the treatment time being 1.3-2.8 h.

[0090] In this invention, preferably, step (4) further includes post-activation treatment of the olefin activation product in an activation post-treatment agent.

[0091] In this invention, the range of types of activation post-treatment agents is relatively wide. Preferably, the activation post-treatment agent is selected from at least one of anhydrous ethanol, anhydrous acetone, and anhydrous methanol, and more preferably anhydrous ethanol.

[0092] In this invention, there is no particular limitation on the method of post-activation treatment; those skilled in the art can select according to actual needs, such as flow treatment. In this invention, the selection range of post-activation treatment conditions is relatively wide. Preferably, the post-activation treatment conditions include: flow treatment time of 0.5-1 hour, drying temperature of 100-120°C, and drying time of 0.5-1 hour.

[0093] The third aspect of this invention provides the application of the microchannel reactor described in the first aspect or the microchannel reactor prepared by the preparation method described in the second aspect in the hydration reaction of low-carbon olefins.

[0094] The fourth aspect of the present invention provides a method for preparing an aqueous solution of low-carbon alcohols, wherein the method comprises: hydrating olefin reaction raw materials with water in a microchannel reactor, wherein the microchannel reactor is the microchannel reactor described in the first aspect or the microchannel reactor prepared by the preparation method described in the second aspect.

[0095] In this invention, preferably, the olefin reaction feedstock is a low-carbon olefin feedstock containing C3 and / or C4. Preferably, based on the total amount of the olefin reaction feedstock, the content of the C3 and / or C4 low-carbon olefin is 10-100% by volume. The microchannel reactor provided by this invention, due to the grafting of different functional groups, is particularly suitable for hydration reactions where the reaction feedstock contains low-carbon olefins.

[0096] In this invention, the selection range of conditions for the hydration reaction is relatively wide. Preferably, the conditions for the hydration reaction include: a temperature of 100-170℃, a pressure of 1000-3000 kPa (gauge pressure), a flow linear velocity of 0.15-0.4 m / s in the olefin reaction feedstock within the microchannel reactor, a residence time of 6-10 minutes, and a molar ratio of water to olefin reaction feedstock of 1.8-5.5.

[0097] In this invention, there is no particular limitation on the contact method between the olefin reaction feedstock and water during the hydration reaction. Preferably, the olefin reaction feedstock stream and the aqueous phase stream are independently introduced into the inlet of the microchannel reactor and contact the inner surface of the microchannel reactor. More preferably, the olefin reaction feedstock stream and the aqueous phase stream enter the inner cavity of the microchannel reactor along the tangent direction of the cross-section of the microchannel reactor. Even more preferably, the angle between the flow direction of the olefin reaction feedstock stream and the tangent direction of the cross-section of the microchannel reactor is 25°-65°, and the angle between the flow direction of the aqueous phase stream and the tangent direction of the cross-section of the microchannel reactor is 25°-65°. Even more preferably, the angle between the flow direction of the olefin reaction feedstock stream and the tangent direction of the cross-section of the microchannel reactor is the same as the angle between the flow direction of the aqueous phase stream and the tangent direction of the cross-section of the microchannel reactor. The advantages of adopting the above preferred embodiments are that it promotes thorough mixing of water and olefins and is conducive to achieving the stability of water or olefin capture in the modified layer.

[0098] The present invention will be described in detail below through embodiments.

[0099] In this invention, the content of each group in the olefin hydration microchannel is determined by the test method described above.

[0100] In this invention, component analysis employed a 20A high-performance liquid chromatography (HPLC) system (Shimadzu Corporation, Japan, equipped with an autosampler, 10AT and 10AD pumps, and a 20A multi-wavelength UV detector); and an ACQUITY UPLC / Xevo G2 QTOF ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (Waters Corporation, USA, equipped with an autosampler and a diode array UV detector). HPLC conditions were as follows: column: Zorbax Eclipse Plus C18 (4.6 mm × 150 mm, 5 μm); mobile phase: water (containing 0.06% v phosphoric acid): acetonitrile = 95:5; flow rate: 1.0 mL / min; detection wavelength: 210 nm; column temperature: 35 °C; injection volume: 1 μL. Ultra-high performance liquid chromatography (UHPLC) conditions: Column: HSS T3 (2.1 mm × 100 mm, 1.7 μm); Mobile phase: water, methanol; Gradient elution (positive ion mode): 0 min V(water):V(methanol) = 85:15, after 2.5 min V(water):V(methanol) = 55:35, after 4 min V(water):V(methanol) = 10:90, flow rate: 0.45 mL / min; Gradient elution (negative ion mode): 0 min V(water):V(methanol) = 70:30, after 2.5 min V(water):V(methanol) = 55:35, after 3.5 min V(water):V(methanol) = 10:90; flow rate: 0.45 mL / min; Column temperature: 30 ℃; Injection volume: 3 μL. Mass spectrometry conditions: electrospray ionization source (ESI), positive or negative ion scanning mode, capillary voltage 2kV, cone voltage 30eV, ion source temperature: 120℃, desolventizing temperature 450℃, cone gas flow rate 50L / h, desolventizing gas (N2) flow rate 900L / h.

[0101] Example 1

[0102] In this embodiment, the olefin reaction feedstock composition, by volume percentage, includes: isobutane 33.9%, n-butane 8.7%, n-butene 55.7%, and pentane 1.7%.

[0103] In this embodiment, the microchannel reactor substrate is obtained through micro-machining. The microchannel reactor substrate has a circular cross-section and an inner diameter of 350 μm. A protrusion is formed on the inner wall of the substrate; the protrusion is an isosceles triangle with a 90° apex angle. The ratio of the height of the isosceles triangle to the inner diameter of the microchannel reactor substrate is 0.186:1, and the angle between the ridge of the isosceles triangle and the tangent to the cross-section of the microchannel reactor substrate is 38°. The substrate material is metal.

[0104] The solution containing the silane component was then brought into contact with the microchannel reactor substrate, followed by drying and curing. The contact conditions involved pumping the silane-containing solution into the inner cavity of the microchannel reactor substrate. The drying and curing conditions were 118°C for 45 minutes, conducted under a nitrogen atmosphere. The silane-containing solution was obtained by mixing a silane reagent, water, and anhydrous lower alcohol, followed by pre-hydrolysis. The pre-hydrolysis time was 21 hours. The volume ratio of silane reagent:water:anhydrous lower alcohol was 3.2:4.4:93. The pH of the silane-containing solution was 7.9. The silane reagent was methylvinyldiethoxysilane. The anhydrous lower alcohol was anhydrous methanol. The amount of silane-containing solution used resulted in a silane sublayer of 8.1 nm.

[0105] Then, a solution containing the reactant-enriched component is brought into contact with the inner surface of the silanized microchannel reactor, thereby coating the inner surface of the silanized microchannel reactor with a reactant-enriched layer. In the solution containing the reactant-enriched component, the mass ratio of reactant-enriched component: first initiator: first solvent is 5.3:0.2:95. The first solvent is toluene. The first initiator is benzoyl peroxide. The reactant-enriched component contains amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of amide derivative: pyrrole derivative: furan derivative is 27:18:3.9. The amide derivative is provided by N,N-methylenebisacrylamide. The pyrrole derivative is provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivative is provided by 2-(1-propen-2-yl)furan. The reactant enrichment treatment conditions included: a solution containing the reactant enrichment component was pumped into the inner cavity of the microchannel reactor after the silanization treatment in step (1); the linear velocity of the solution containing the reactant enrichment component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 70℃; and the treatment time was 2.3 h. Based on the inner surface area of ​​the dry-basis microchannel reactor substrate per square meter, the content of amide groups in the reactant enrichment layer was 23.6 mmol / m². 2 The pyrrole group content was 15.7 mmol / m³. 2 The furanyl content was 3.4 mmol / m³. 2 The thickness of the reactant enrichment layer is 5.4 nm.

[0106] A solution containing hydrated components is brought into contact with the inner surface of a microchannel reactor enriched with reactants, thereby coating the inner surface of the reactor with a hydrated layer. The mass ratio of the hydrated component to the second initiator to the second solvent in the solution is 6.8:0.2:94. The second solvent is toluene. The hydrated component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, with a molar ratio of amide derivatives: phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives of 16:19:36:15:25:5. The amide derivatives are provided by N,N-methylenebisacrylamide. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The pyrrole derivatives were provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives were provided by 2-(1-propen-2-yl)furan. The second initiator was benzoyl peroxide. The hydration treatment conditions included: the solution containing the hydrated component was pumped into the inner cavity of the microchannel reactor after reactant enrichment treatment; the linear velocity of the solution containing the hydrated component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 75 °C; and the treatment time was 2.3 h. Based on the inner surface area of ​​the dry microchannel reactor substrate per square meter, the content of amide groups in the hydrated layer was 13.1 mmol / m². 2 The phenoxy group content is 15.5 mmol / m 2 The content of sulfonic acid groups is 29.4 mmol / m 2 The phosphate group content is 12.3 mmol / m 2 The pyrrole group content was 20.4 mmol / m³. 2 The furanyl content was 4.1 mmol / m³. 2 The hydration layer thickness is 13.6 nm.

[0107] Following the hydration treatment, the hydration product undergoes post-treatment in a hydration post-treatment agent, which is anhydrous ethanol. The post-hydration post-treatment conditions include: pump-assisted flow treatment for 0.7 hours, drying at 110°C for 0.7 hours.

[0108] A solution containing an olefin-activating component is brought into contact with the inner surface of a hydrated microchannel reactor, resulting in an olefin-activating layer coating the inner surface of the reactor. The solution containing the olefin-activating component comprises the olefin-activating component, a third initiator, and a third solvent, with a mass ratio of olefin-activating component: third initiator: third solvent of 0.7:0.15:97. The olefin-activating component contains phenoxy derivatives, sulfonic acid derivatives, and phosphoric acid derivatives, with a molar ratio of phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives of 18:35:14. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivative was provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The olefin activation treatment conditions included: pumping a solution containing the olefin activation component into the inner cavity of a hydrated microchannel reactor; the linear velocity of the solution containing the olefin activation component on the inner surface of the microchannel reactor was 0.31 m / s; the treatment temperature was 76 °C; and the treatment time was 2 h. Based on the inner surface area of ​​the dry microchannel matrix per square meter, the phenoxy content in the olefin activation layer was 1.6 mmol / m². 2 The content of sulfonic acid groups is 3.1 mmol / m 2 The phosphate group content is 1.2 mmol / m 2 The thickness of the olefin activation layer is 1.4 nm.

[0109] The olefin activation treatment also includes a post-activation treatment of the olefin activation product in an anhydrous ethanol. The post-activation treatment conditions include: flow treatment time of 0.7 h, drying temperature of 110 °C, and drying time of 0.7 h.

[0110] The prepared microchannel reactor was applied to the hydration reaction of low-carbon olefins. The olefin reactants and demineralized water were mixed and contacted with the inner surface of the microchannel reactor to carry out the olefin hydration reaction, yielding an aqueous solution containing low-carbon alcohols. The water and olefin reactants flowed in a two-phase manner. The olefins and demineralized water entered the inner cavity of the microchannel reactor diagonally along the tangent of the circular cross-section, with both the olefin reactants and demineralized water forming an angle of 45° with the tangent of the microchannel reactor's cross-section.

[0111] The conditions for the hydration reaction include: a temperature of 130℃, a pressure of 2000 kPa (gauge pressure), a linear velocity of 0.27 m / s for the olefin reactants in the microchannel reactor, a residence time of 8 minutes, and a molar ratio of water to low-carbon olefin reactants of 3.5.

[0112] The single-pass olefin conversion rate of olefin hydration was 43.2%, and the selectivity for lower alcohols was 96.5%.

[0113] Example 2

[0114] The same olefin reaction feedstock as in Example 1 was selected.

[0115] In this embodiment, the microchannel reactor substrate is obtained through micro-machining. The microchannel reactor substrate has a circular cross-section and an inner diameter of 250 μm. A protrusion is formed on the inner wall of the substrate; the protrusion is an isosceles triangle with a 60° apex angle. The ratio of the height of the isosceles triangle to the inner diameter of the microchannel reactor substrate is 0.24:1. The angle between the ridge of the isosceles triangle and the tangent to the cross-section of the microchannel reactor substrate is 20°. The substrate material is metal.

[0116] The solution containing the silane component was then brought into contact with the microchannel reactor substrate, followed by drying and curing. The contact conditions involved pumping the silane-containing solution into the inner cavity of the microchannel reactor substrate. The drying and curing conditions were 124°C for 58 minutes, conducted under a nitrogen atmosphere. The silane-containing solution was obtained by mixing a silane reagent, water, and anhydrous lower alcohol, followed by pre-hydrolysis. The pre-hydrolysis time was 29 hours. The volume ratio of silane reagent:water:anhydrous lower alcohol was 4.3:5.7:95. The pH of the silane-containing solution was 8.2. The silane reagent was methylvinyldiethoxysilane. The anhydrous lower alcohol was anhydrous methanol. The amount of silane-containing solution used resulted in a silane sublayer of 9.7 nm.

[0117] Then, a solution containing the reactant-enriched component is brought into contact with the inner surface of the silanized microchannel reactor to coat the inner surface of the silanized microchannel reactor with a reactant-enriched layer. In the solution containing the reactant-enriched component, the mass ratio of reactant-enriched component: first initiator: first solvent is 6.6:0.2:94. The first solvent is toluene. The first initiator is benzoyl peroxide. The reactant-enriched component contains amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of amide derivative:pyrrole derivative:furan derivative is 36.2:22.4:5.6. The amide derivative is provided by N,N-methylenebisacrylamide. The pyrrole derivative is provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivative is provided by 2-(1-propen-2-yl)furan. The reactant enrichment treatment conditions included: a solution containing the reactant enrichment component was pumped into the inner cavity of a silanized microchannel reactor; the linear velocity of the solution containing the reactant enrichment component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 78℃; and the treatment time was 2.6 h. Based on the inner surface area of ​​the dry-based microchannel substrate reactor per square meter, the amide group content in the reactant enrichment layer was 30.6 mmol / m². 2 The content of pyrrole groups was 18.9 mmol / m³. 2 The furanyl content was 4.7 mmol / m³. 2 The reactant enrichment layer has a thickness of 6.5 nm.

[0118] A solution containing hydrated components is brought into contact with the inner surface of a microchannel reactor enriched with reactants, thereby coating the inner surface of the reactor with a hydrated layer. The mass ratio of hydrated component: second initiator: second solvent in the solution is 8.6:0.3:93. The second solvent is toluene. The hydrated component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, with a molar ratio of amide derivatives: phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives of 19.2:23.5:47.3:20.8:29.1:7.4. The amide derivatives are provided by N,N-methylenebisacrylamide. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The pyrrole derivatives were provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives were provided by 2-(1-propen-2-yl)furan. The second initiator was benzoyl peroxide. The hydration treatment conditions included: the solution containing the hydrated component was pumped into the inner cavity of the microchannel reactor after reactant enrichment treatment; the linear velocity of the solution containing the hydrated component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 87℃; and the treatment time was 2.5 h. Based on the inner surface area of ​​the dry-basis microchannel reactor substrate per square meter, the amide group content in the hydrated layer was 15.3 mmol / m². 2 The phenoxy group content was 18.7 mmol / m³. 2 The content of sulfonic acid groups is 37.6 mmol / m 2 The phosphate group content is 16.5 mmol / m 2 The pyrrole group content was 23.2 mmol / m³. 2 The furanyl content was 5.9 mmol / m³. 2 The hydration layer thickness is 16.2 nm.

[0119] Following the hydration treatment, the hydration product undergoes post-treatment in a hydration post-treatment agent, which is anhydrous ethanol. The post-hydration post-treatment conditions include: pump-assisted flow treatment for 0.9 hours, drying at 118°C for 0.9 hours.

[0120] A solution containing an olefin-activating component is brought into contact with the inner surface of a hydrated microchannel reactor, resulting in an olefin-activating layer coating the inner surface of the reactor. The solution containing the olefin-activating component comprises the olefin-activating component, a third initiator, and a third solvent, with a mass ratio of olefin-activating component: third initiator: third solvent of 0.8:0.17:96. The olefin-activating component contains phenoxy derivatives, sulfonic acid derivatives, and phosphoric acid derivatives, with a molar ratio of phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives of 22:43:19. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivative was provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The olefin activation treatment conditions included: pumping a solution containing the olefin activation component into the inner cavity of the microchannel reactor after hydration treatment as described in step (3); the linear velocity of the solution containing the olefin activation component on the inner surface of the microchannel reactor was 0.18 m / s; the treatment temperature was 85℃; and the treatment time was 2.5 h. Based on the inner surface area of ​​the dry microchannel matrix per square meter, the phenoxy content in the olefin activation layer was 1.8 mmol / m². 2 The content of sulfonic acid groups is 3.5 mmol / m 2 The phosphate group content is 1.5 mmol / m 2 The thickness of the olefin activation layer is 1.7 nm.

[0121] The olefin activation treatment also includes a post-activation treatment of the olefin activation product in an anhydrous ethanol. The post-activation treatment conditions include: flow treatment time of 0.9 h, drying temperature of 116 °C, and drying time of 0.8 h.

[0122] The reaction method is the same as in Example 1, except that the angle between the olefin reaction feedstock and the demineralized water and the tangent direction of the cross section of the microchannel reactor is 30°.

[0123] The conditions for the hydration reaction include: a temperature of 110℃, a pressure of 1500 kPa (gauge pressure), a linear velocity of 0.18 m / s for the olefin reactants in the microchannel reactor, a residence time of 9 minutes, and a molar ratio of water to low-carbon olefin reactants of 5.2.

[0124] The single-pass olefin conversion rate of olefin hydration was 48.6%, and the selectivity for lower alcohols was 97.2%.

[0125] Example 3

[0126] The same olefin reaction feedstock as in Example 1 was selected.

[0127] In this embodiment, the microchannel reactor substrate is obtained through micro-machining. The microchannel reactor substrate has a circular cross-section and an inner diameter of 450 μm. A protrusion, shaped like an isosceles triangle, is provided on the inner wall of the substrate. The apex angle of the isosceles triangle is 120°, and the ratio of the height of the isosceles triangle to the inner diameter of the microchannel reactor substrate is 0.13:1. The angle between the ridge of the isosceles triangle and the tangent to the cross-section of the microchannel reactor substrate is 55°. The substrate material is metal.

[0128] The solution containing the silane component was then brought into contact with the microchannel reactor substrate, followed by drying and curing. The contact conditions involved pumping the silane-containing solution into the cavity of the microchannel reactor substrate. The drying and curing conditions were a temperature of 112°C and a time of 33 minutes, conducted under a nitrogen atmosphere. The silane-containing solution was obtained by mixing a silane reagent, water, and anhydrous lower alcohol, followed by pre-hydrolysis. The pre-hydrolysis time was 13 hours. The volume ratio of silane reagent:water:anhydrous lower alcohol was 2.0:3.1:91. The pH of the silane-containing solution was 7.5. The silane reagent was methylvinyldiethoxysilane. The anhydrous lower alcohol was anhydrous methanol. The amount of silane-containing solution used resulted in a silane sublayer of 6.2 nm.

[0129] Then, a solution containing the reactant-enriched component is brought into contact with the inner surface of the silanized microchannel reactor to coat the inner surface of the silanized microchannel reactor with a reactant-enriched layer. In the solution containing the reactant-enriched component, the mass ratio of reactant-enriched component: first initiator: first solvent is 3.9:0.2:96. The first solvent is toluene. The first initiator is benzoyl peroxide. The reactant-enriched component contains amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of amide derivative:pyrrole derivative:furan derivative is 20.3:14.2:2.3. The amide derivative is provided by N,N-methylenebisacrylamide. The pyrrole derivative is provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivative is provided by 2-(1-propen-2-yl)furan. The reactant enrichment treatment conditions included: a solution containing the reactant enrichment component was pumped into the inner cavity of a silanized microchannel reactor; the linear velocity of the solution containing the reactant enrichment component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 62℃; and the treatment time was 1.7 h. Based on the inner surface area of ​​the dry-based microchannel substrate reactor per square meter, the amide group content in the reactant enrichment layer was 17.2 mmol / m². 2 The pyrrole group content is 12.0 mmol / m³. 2 The furanyl content was 1.9 mmol / m³. 2 The thickness of the reactant enrichment layer is 4.3 nm.

[0130] A solution containing hydrated components is brought into contact with the inner surface of a microchannel reactor enriched with reactants, thereby coating the inner surface of the reactor with a hydrated layer. The mass ratio of hydrated component: second initiator: second solvent in the solution is 4.8:0.2:95. The second solvent is toluene. The hydrated component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, with a molar ratio of amide derivatives: phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives of 13.2:14.1:26.3:9.5:20.6:3.5. The amide derivatives are provided by N,N-methylenebisacrylamide. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The pyrrole derivatives were provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives were provided by 2-(1-propen-2-yl)furan. The second initiator was benzoyl peroxide. The hydration treatment conditions included: the solution containing the hydrated component was pumped into the inner cavity of the microchannel reactor after reactant enrichment treatment; the linear velocity of the solution containing the hydrated component on the inner surface of the microchannel reactor was 0.2 m / s; the treatment temperature was 72℃; and the treatment time was 2 h. Based on the inner surface area of ​​the dry microchannel reactor substrate per square meter, the content of amide groups in the hydrated layer was 11.4 mmol / m². 2 The phenoxy group content was 12.1 mmol / m³. 2 The content of sulfonic acid groups is 22.7 mmol / m 2 The phosphate group content is 8.2 mmol / m 2 The content of pyrrole groups was 17.8 mmol / m³. 2 The furanyl content was 3.0 mmol / m³. 2 The hydration layer thickness is 12.4 nm.

[0131] Following the hydration treatment, the hydration product undergoes post-treatment in a hydration post-treatment agent, which is anhydrous ethanol. The post-hydration post-treatment conditions include: pump-assisted flow treatment for 0.6 hours, drying at 109°C for 0.6 hours.

[0132] A solution containing an olefin-activating component is brought into contact with the inner surface of a hydrated microchannel reactor, resulting in an olefin-activating layer coating the inner surface of the reactor. The solution containing the olefin-activating component comprises the olefin-activating component, a third initiator, and a third solvent, with a mass ratio of olefin-activating component: third initiator: third solvent of 0.6:0.12:98. The olefin-activating component contains phenoxy derivatives, sulfonic acid derivatives, and phosphoric acid derivatives, with a molar ratio of phenoxy derivatives: sulfonic acid derivatives: phosphoric acid derivatives of 13:26:9. The phenoxy derivatives are provided by allyl phenyl ether. The phosphoric acid derivatives are provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate hydrogen ester. The sulfonic acid derivative was provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The olefin activation treatment conditions included: pumping a solution containing the olefin activation component into the inner cavity of the microchannel reactor after hydration treatment as described in step (3); the linear velocity of the solution containing the olefin activation component on the inner surface of the microchannel reactor was 0.41 m / s; the treatment temperature was 70°C; and the treatment time was 1.5 h. Based on the inner surface area of ​​the dry microchannel matrix per square meter, the phenoxy content in the olefin activation layer was 1.4 mmol / m². 2 The content of sulfonic acid groups is 2.8 mmol / m 2 The phosphate group content is 0.9 mmol / m 2 The thickness of the olefin activation layer is 1.2 nm.

[0133] The olefin activation treatment also includes a post-activation treatment of the olefin activation product in an anhydrous ethanol. The post-activation treatment conditions include: flow treatment time of 0.6 h, drying temperature of 107 °C, and drying time of 0.6 h.

[0134] The reaction method is the same as in Example 1, except that the angle between the olefin reaction feedstock and the demineralized water and the tangent direction of the cross section of the microchannel reactor is 60°.

[0135] The conditions for the hydration reaction include: a temperature of 150℃, a pressure of 2500 kPa (gauge pressure), a linear velocity of 0.36 m / s for the olefin reactants in the microchannel reactor, a residence time of 7 minutes, and a molar ratio of water to low-carbon olefin reactants of 2.1.

[0136] The single-pass olefin conversion rate of olefin hydration was 38.6%, and the selectivity for lower alcohols was 95.3%.

[0137] Example 4

[0138] The method is the same as in Example 2, except that the composition of the olefin reaction feedstock in this example, by volume percentage, includes: 16.0% isobutane, 7.0% n-butane, 75.8% n-butene, and 1.2% pentane.

[0139] The single-pass olefin conversion rate of olefin hydration was 52.3%, and the selectivity for lower alcohols was 97.4%.

[0140] Example 5

[0141] The method is the same as in Example 2, except that the composition of the olefin reaction feedstock in this example, by volume percentage, includes: 6.9% isobutane, 2.2% n-butane, 90.5% n-butene, and 0.4% pentane.

[0142] The single-pass olefin conversion rate of olefin hydration was 55.4%, and the selectivity for lower alcohols was 97.6%.

[0143] Example 6

[0144] The method is the same as in Example 2, except that the composition of the olefin reaction feedstock in this example, by volume percentage, includes: 48.8% isobutane, 13.3% n-butane, 31.9% n-butene, and 5.9% pentane.

[0145] The single-pass olefin conversion rate of olefin hydration was 44.5%, and the selectivity for lower alcohols was 96.2%.

[0146] Comparative Example 1

[0147] The same olefin reaction feedstock as in Example 5 was used, namely, by volume percentage: 6.9% isobutane, 2.2% n-butane, 90.5% n-butene, and 0.4% pentane.

[0148] The olefin hydration reactor was packed with Suqing brand SQD-65 styrene-based macroporous strong acid cation exchange resin. The reaction temperature was 145℃, the reaction pressure was 85 kg, and the mass hourly space velocity (HHSV) was 1 h⁻¹. -1 The single-pass conversion rate of n-butene was 10.2%, and the selectivity was 95.7%.

[0149] Comparative Example 2

[0150] The method of Example 3 is different in that, in this comparative example, the silanized matrix (i.e., the silane reagent solution is brought into contact with the microchannel reactor matrix and then dried and cured) is directly brought into contact with the inner surface of the silanized microchannel reactor by a solution containing hydration components, without the process of bringing the inner surface of the silanized microchannel reactor into contact with a solution containing reactant enrichment components, and the subsequent treatments (hydration post-treatment, olefin activation treatment, olefin activation post-treatment) are omitted.

[0151] Following the reaction method and conditions of Example 3, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 15.8%, and the selectivity for lower alcohols was 80.1%.

[0152] Comparative Example 3

[0153] The method is the same as in Example 3, except that this comparative example directly uses a microchannel reactor substrate that has not undergone modification treatment.

[0154] Following the reaction method and conditions of Example 3, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 1.3%, and the selectivity for lower alcohols was 78.6%.

[0155] The embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A microchannel reactor characterized by, The micro-channel reactor comprises a micro-channel reactor base and, from inside to outside, a silane bottom layer, a reactant enrichment layer, a hydration layer and an olefin activation layer coated on the inner surface of the micro-channel reactor base; the reactant enrichment layer contains amide groups, pyrrole groups and furan groups; the hydration layer contains amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups and phosphoric acid groups; and the olefin activation layer contains phenoxy groups, sulfonic acid groups and phosphoric acid groups. The content of amide group in the reactant-rich layer is 16-31 mmol / m 2 , the content of pyrrole group is 11-19 mmol / m 2 , and the content of furan group is 1.8-4.7 mmol / m 2 , based on the inner surface area of the microchannel reactor substrate per square meter of dry base. The content of amide group in the hydration layer is 10-16 mmol / m 2 The content of phenoxy group is 11-20 mmol / m 2 The content of sulfonic acid group is 21-40 mmol / m 2 The content of phosphoric acid group is 7.5-17 mmol / m 2 The content of pyrrole group is 17-25 mmol / m 2 The content of furan group is 2.7-6.8 mmol / m 2 ; The content of the phenoxy group in the olefin activation layer is 1.3-1.9 mmol / m 2 The content of the sulfonic acid group is 2.2-3.7 mmol / m 2 The content of the phosphoric acid group is 0.6-1.5 mmol / m 2 .

2. The reactor of claim 1, wherein, The inner diameter of the micro-channel reactor base is 200-500 µm.

3. The reactor of claim 2, wherein, An isosceles triangle protrusion is arranged on the inner wall of the micro-channel reactor base.

4. The reactor of claim 3, wherein, The angle of the top corner of the isosceles triangle protrusion is 50°-130°.

5. The reactor of claim 3, wherein, The ratio of the height of the isosceles triangle protrusion to the inner diameter of the micro-channel reactor base is (1 / 8-1 / 4):

1.

6. The reactor of claim 3, wherein, The angle between the ridge line of the isosceles triangle protrusion and the tangent of the cross section of the micro-channel reactor base is 15°-60°.

7. The reactor of claim 1 or 2, wherein, The thickness of the silane bottom layer is 6-10 nm. And / or, the silane bottom layer is provided by at least one of 2-butenyl triethoxysilane, methyl vinyl diethoxysilane and allyl dimethoxysilane.

8. The reactor of claim 1 or 2, wherein, The thickness of the reactant enrichment layer is 4-7 nm.

9. The reactor of claim 1 or 2, wherein, The thickness of the hydration layer is 10-17 nm.

10. The reactor of claim 1 or 2, wherein, The thickness of the olefin activation layer is 1.1-1.8 nm.

11. A method of making a microchannel reactor, wherein, The method comprises: (1) silanization treatment is performed on the inner surface of the micro-channel reactor base by using a solution containing a silane component to obtain a silanized micro-channel reactor; (2) reactant enrichment treatment is performed on the inner surface of the silanized micro-channel reactor of step (1) by using a solution containing a reactant enrichment component to obtain a micro-channel reactor after reactant enrichment treatment; (3) hydration treatment is performed on the inner surface of the micro-channel reactor after reactant enrichment treatment of step (2) by using a solution containing a hydration component to obtain a micro-channel reactor after hydration treatment; (4) olefin activation treatment is performed on the inner surface of the micro-channel reactor after hydration treatment of step (3) by using a solution containing an olefin activation component to obtain a micro-channel reactor; The reactant enrichment component contains amide groups, pyrrole groups and furan groups; the hydration component contains amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups and phosphoric acid groups; and the olefin activation component contains phenoxy groups, sulfonic acid groups and phosphoric acid groups. In step (2), the reactant enrichment treatment is to coat the inner surface of the silanized microchannel reactor of step (1) with a reactant enrichment layer containing amide groups, pyrrole groups and furan groups; in the reactant enrichment layer, the content of amide groups is 16-31 mmol / m 2 , the content of pyrrole groups is 11-19 mmol / m 2 , and the content of furan groups is 1.8-4.7 mmol / m 2 , based on the inner surface area of the dry microchannel reactor substrate per square meter. 2 , the content of pyrrole groups is 11-19 mmol / m 2 , and the content of furan groups is 1.8-4.7 mmol / m 2 , based on the inner surface area of the dry microchannel reactor substrate per square meter. In step (3), the hydration treatment makes the inner surface of the microchannel reactor after the enrichment treatment of the reactants in step (2) coated with a hydration layer, the hydration layer containing amide groups, pyrrole groups, furan groups, phenoxy groups, sulfonic acid groups and phosphoric acid groups; in the hydration layer, the content of amide groups is 10-16 mmol / m 2 , the content of phenoxy groups is 11-20 mmol / m 2 , the content of sulfonic acid groups is 21-40 mmol / m 2 , the content of phosphoric acid groups is 7.5-17 mmol / m 2 , the content of pyrrole groups is 17-25 mmol / m 2 , and the content of furan groups is 2.7-6.8 mmol / m 2 . In step (4), the olefin activation treatment coats the inner surface of the microchannel reactor after the hydration treatment of step (3) with an olefin activation layer containing phenoxy groups, sulfonic acid groups, and phosphoric acid groups; the content of the phenoxy groups in the olefin activation layer is 1.3-1.9 mmol / m 2 , the content of the sulfonic acid groups is 2.2-3.7 mmol / m 2 , and the content of the phosphoric acid groups is 0.6-1.5 mmol / m 2 .

12. The method of claim 11, wherein, In step (1), the silanization treatment causes the inner surface of the micro-channel reactor base to be coated with a silane bottom layer, and the thickness of the silane bottom layer is 6-10 nm. And / or, the silanization treatment comprises: contacting the solution containing the silane component with the micro-channel reactor base, and then drying and curing.

13. The method of claim 12, wherein, In step (1), the solution containing the silane component is obtained by mixing a silane reagent, water and a low-carbon alcohol, and then pre-hydrolyzing.

14. The method of claim 13, wherein, In the solution containing the silane component, the volume ratio of the silane reagent: water: low-carbon alcohol is (1.9-4.4):(3.5-5.8):(89-95).

15. The method of claim 14, wherein, The silane reagent is selected from at least one of 2-butenyl triethoxysilane, methyl vinyl diethoxysilane and allyl dimethoxysilane.

16. The method of claim 11, wherein, In step (2), the solution containing the reactant-rich component contains the reactant-rich component, the first initiator and the first solvent.

17. The method of claim 16, wherein, The mass ratio of the reactant-rich component:the first initiator:the first solvent is (3.8-6.7):(0.1-0.3):(93-97).

18. The method of claim 16, wherein, In step (2), the first solvent is selected from at least one of toluene, p-xylene, m-xylene and o-xylene. And / or, in step (2), the first initiator is selected from at least one of azo, organic peroxide, inorganic peroxide and redox initiators. And / or, in step (2), the reactant-rich component contains amide derivatives, pyrrole derivatives and furan derivatives. And / or, in step (2), the reactant-rich component is treated by pumping the solution containing the reactant-rich component into the inner cavity of the silanized micro-channel reactor in step (1), the solution containing the reactant-rich component flows on the inner surface of the micro-channel reactor at a linear velocity of 0.1-0.3 m / s, the treatment temperature is 60-80℃, and the treatment time is 1.5-3 h.

19. The method of claim 18, wherein, In step (2), the first initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate and hydrogen peroxide.

20. The method of claim 19, wherein, In step (2), the first initiator is benzoyl peroxide.

21. The method of claim 18, wherein, The molar ratio of the amide derivatives:the pyrrole derivatives:the furan derivatives is (19-37):(13-23):(2.2-5.7).

22. The method of claim 18, wherein, The amido group is provided by the amide derivatives.

23. The method of claim 22, wherein, The amido group is provided by at least one of N,N'-dihydroxyethyl bisacrylamide, N,N-methylene bisacrylamide and hexamethylene bisacrylamide.

24. The method of claim 18, wherein, The pyrrolyl group is provided by the pyrrole derivatives.

25. The method of claim 24, wherein, The pyrrolyl group is provided by at least one of 3-isopropenyl-1-methyl-pyrrole, 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole and 5-allyl-4-methoxy-1,5-dihydro-2H-pyrrol-2-one.

26. The method of claim 18, wherein, The furanyl group is provided by the furan derivatives.

27. The method of claim 26, wherein, The furanyl group is provided by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

28. The method of claim 11, wherein, In step (3), the solution containing the hydration component contains the hydration component, the second initiator and the second solvent.

29. The method of claim 28, wherein, The mass ratio of the hydration component:the second initiator:the second solvent is (4.7-8.8):(0.1-0.4):(92-96). And / or, in step (3), the hydration component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives.

30. The method of claim 29, wherein, The molar ratio of the amide derivatives:the phenoxy derivatives:the sulfonic acid derivatives:the phosphoric acid derivatives:the pyrrole derivatives:the furan derivatives is (12-20):(13-24):(25-48):(9-21):(20-30):(3-8). And / or, the phenoxy group is provided by the phenoxy derivatives. And / or, the phosphoric acid group is provided by the phosphoric acid derivatives. And / or, the sulfonic acid group is provided by a sulfonic acid derivative; And / or, in step (3), the hydration treatment comprises: pumping a solution containing a hydration component into the inner cavity of the micro-channel reactor after the reactant enrichment treatment in step (2), and the solution containing the hydration component flows on the inner surface of the micro-channel reactor at a linear velocity of 0.1-0.3 m / s, the treatment temperature is 70-90℃, and the treatment time is 1.5-3h.

31. The method of claim 30, wherein, The phenoxy group is provided by at least one of 4-methoxystyrene, allyl phenyl ether and phenyl vinyl ether.

32. The method of claim 30, wherein, The phosphoric acid group is provided by at least one of (2-fluoro-3,7-dimethyloct-1,6-dien-3-yl) phosphorohydrogenophosphonate, [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl] methyl phosphorohydrogenophosphate and 2-(phosphoryloxy)propane-1,3-diyl dimethyl methacrylate.

33. The method of claim 30, wherein, The sulfonic acid group is provided by at least one of 4-hydroxy-6-(prop-2-enoylamino) naphthalene-2-sulfonic acid, (Z)-4',4'''-(ethene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)) and 4-{(E)-2-[3,5-bis(sulfooxy)phenyl]vinyl} phenyl hydrosulfate.

34. The method of claim 28, wherein, Step (3) further comprises performing hydration post-treatment on the hydration treatment product in a hydration post-treatment agent; The hydration post-treatment agent is selected from at least one of anhydrous ethanol, anhydrous acetone and anhydrous methanol; And / or, the conditions of the hydration post-treatment include: a flow treatment time of 0.5-1h, a drying temperature of 100-120℃, and a drying time of 0.5-1h.

35. The method of claim 34, wherein, The hydration post-treatment agent is anhydrous ethanol.

36. The method of claim 11, wherein, In step (4), the solution containing the olefin activation component contains an olefin activation component, a third initiator and a third solvent.

37. The method of claim 36, wherein, The mass ratio of the olefin activation component: the third initiator: the third solvent is (0.5-0.9):(0.1-0.2):(96-98); And / or, in step (4), the olefin activation component contains phenoxy derivatives, sulfonic acid derivatives and phosphoric acid derivatives; And / or, in step (4), the olefin activation treatment conditions include: pumping the solution containing the olefin activation component into the inner cavity of the micro-channel reactor after the hydration treatment in step (3), and the solution containing the olefin activation component flows on the inner surface of the micro-channel reactor at a linear velocity of 0.15-0.45 m / s, the treatment temperature is 68-86℃, and the treatment time is 1.3-2.8h.

38. The method of claim 37, wherein, The molar ratio of the phenoxy derivative: the sulfonic acid derivative: the phosphoric acid derivative is (12-23):(24-46):(8-20).

39. The method of claim 36, wherein, Step (4) further comprises performing activation post-treatment on the olefin activation treatment product in an activation post-treatment agent; The activation post-treatment agent is selected from at least one of anhydrous ethanol, anhydrous acetone and anhydrous methanol; And / or, the conditions of the activation post-treatment include: a flow treatment time of 0.5-1h, a drying temperature of 100-120℃, and a drying time of 0.5-1h.

40. The method of claim 39, wherein, The activation post-treatment agent is anhydrous ethanol.

41. Use of the microchannel reactor according to any one of claims 1 to 10 or the microchannel reactor prepared by the method according to any one of claims 11 to 40 in the hydration reaction of low carbon olefins.

42. A method of making an aqueous solution of a lower alkanol, wherein, The method comprises: carrying out a hydration reaction of an olefin reaction material with water in a microchannel reactor, wherein the microchannel reactor is the microchannel reactor according to any one of claims 1 to 10 or the microchannel reactor prepared by the method according to any one of claims 11 to 40.

43. The method of claim 42, wherein, The olefin reaction material is a low carbon olefin material containing C3 and / or C4.

44. The method of claim 42 or 43, wherein, The conditions of the hydration reaction include: a temperature of 100 to 170°C, a pressure of 1000 to 3000 kPa in terms of gauge pressure, a flow linear velocity of the olefin reaction material in the microchannel reactor of 0.15 to 0.40 m / s, a residence time of 6 to 10 minutes, and a molar ratio of water to the olefin reaction material of 1.8 to 5.5.