Modified hydrated fillers, their preparation methods and applications

Abstract

This invention relates to the technical field of low-carbon olefin hydration, and discloses a modified hydration filler, its preparation method, and its application. The modified hydration filler comprises a filler matrix, with a silane layer, a modified layer A, and a modified layer B sequentially coated on the outer surface of the filler matrix from the inside out. Modified layer A contains pyrrole groups, amide groups, and furan groups; modified layer B contains phenoxy groups, pyrrole groups, furan groups, sulfonic acid groups, phosphate groups, and amide groups. The modified hydration filler provided by this invention can significantly improve the mixing effect of hydrated olefins and promote the increase of low-carbon alcohol yield.

Description

Technical Field

[0001] This invention relates to the technical field of low-carbon olefin hydration, specifically to a modified hydration filler, its preparation method, and its application. 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 employed.

[0003] To promote the yield of lower alcohols in this three-phase reaction system, the reaction temperature, reaction pressure, and water-to-olefin ratio are generally high. However, olefin hydration is a strongly exothermic reaction, and runaway temperatures are prone to occur under high-temperature conditions, leading to sintering and deactivation of the resin or zeolite catalyst. High system reaction pressure can promote the dissolution of olefins in water, but it places higher demands on equipment and requires greater investment. Increasing the water-to-olefin ratio is beneficial to the formation of lower alcohols from a chemical equilibrium perspective, but it results in a larger water circulation volume within the entire system, a higher separation load, and higher energy consumption.

[0004] To address the issue of uneven three-phase mixing, the literature "Research on Phase Transfer Catalysis for Butene Hydration to sec-Butanol" (Zhang Yu and Qi Shixue, *Journal of Yantai University: Natural Science and Engineering Edition*, 2012, Vol. 2, pp. 111-116) describes the use of computer simulations to experimentally screen suitable phase transfer catalysts for the butene hydration reaction and conducts process research. Polyethylene glycol was determined to be the optimal phase transfer catalyst for this reaction system. The addition of the phase transfer catalyst at higher temperatures and water-to-olefin ratios, lower space velocities, and appropriate percentages significantly improved the single-pass conversion rate of butene hydration (from 5.5% to 6.5%). However, under these reaction conditions, the recovery and reuse of the phase transfer catalyst, as well as hydrothermal decomposition, leads to a complex process flow and reduced purity of the low-carbon alcohol product.

[0005] In existing technologies, the direct hydration process of low-carbon olefins using solid acids as catalysts generally employs a fixed-bed reactor. The solid acid is packed inside the reactor. The main process typically involves mixing olefin feedstock (olefin volume content 80-99%) with process water, preheating to 70-250°C, and then introducing the mixture into the hydration reactor for reaction at a pressure of 3.0-25.0 MPa. The feedstock is converted into low-carbon alcohols in the reactor bed. The reactor is generally packed with an H-type strong acid resin catalyst. Mixing within the reactor is primarily achieved through disturbance of catalyst particle morphology. H-type strong acid resin catalysts are highly active, influencing not only olefin hydration but also the self-complexation of olefins, leading to olefin polymerization and reduced low-carbon alcohol yield. Furthermore, relying solely on catalyst particle disturbance for mixing results in a relatively mild and ineffective mixing process. Therefore, adjusting catalytic activity, improving the water-olefin mixing effect, and promoting a rightward shift in the hydration equilibrium are pressing issues that need to be addressed in existing technologies. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of poor water-olefin mixing effect and low low-carbon alcohol yield in the hydration process of low-carbon olefins in the prior art, and to provide a modified hydration filler, its preparation method and application. The modified hydration filler can significantly improve the water-olefin mixing effect and promote the increase of low-carbon alcohol yield.

[0007] To achieve the above objectives, a first aspect of the present invention provides a modified hydrated filler, wherein the modified hydrated filler comprises a filler matrix, and a silane layer, a modified layer A, and a modified layer B are sequentially coated on the outer surface of the filler matrix from the inside to the outside; the modified layer A contains pyrrole groups, amide groups, and furan groups; the modified layer B contains phenoxy groups, pyrrole groups, furan groups, sulfonic acid groups, phosphoric acid groups, and amide groups.

[0008] A second aspect of the present invention provides a method for preparing a modified hydrated filler, wherein the method includes:

[0009] (1) In the presence of a solution containing silane components, the outer surface of the filler matrix is ​​subjected to silanization treatment to obtain a filler coated with a silane layer;

[0010] (2) In the presence of a solution containing modified component A, the outer surface of the filler coated with silane layer in step (1) is treated with modified component A to obtain a filler coated with modified component A.

[0011] (3) In the presence of a solution containing modified component B, the outer surface of the filler coated with modified layer A in step (2) is subjected to modification treatment B to obtain modified hydrated filler.

[0012] Modified component A contains pyrrole, amide, and furanyl groups, while modified component B contains phenoxy, pyrrole, furanyl, sulfonic acid, phosphoric acid, and amide groups.

[0013] The third aspect of this invention provides the application of the modified hydrated filler described in the first aspect or the modified hydrated filler prepared by the preparation method described in the second aspect in the preparation of aqueous solutions of low-carbon alcohols by the hydration reaction of low-carbon olefins.

[0014] During their research on the hydration of low-carbon olefins, the inventors of this invention discovered that when using existing solid acid catalysts such as strong acid resins and ZSM-5 molecular sieves to catalyze olefin hydration, the single-pass conversion rate of olefins is significantly lower than the thermodynamic equilibrium conversion rate. This is mainly affected by factors related to mass transfer and chemical equilibrium. Low-carbon olefins are generally poorly soluble in water. Even with a significantly excessive water-to-olefin ratio, the two remain immiscible. In a fixed bed with a generally low flow rate, the dispersed phase, acting as the oil phase, typically exists in the form of large droplets, resulting in a small oil-water contact area. Even increasing the water-to-olefin ratio only reduces the dispersion density of the large droplet oil phase in a macroscopic state, with virtually no significant change from the perspective of the oil-water contact surface. It also has no significant effect on shifting the hydration equilibrium to the right, only achieving a certain dilution effect on the product, the low-carbon alcohol. Solid acid catalysts have good water binding properties, but poor compatibility with olefins. After water saturation, olefins are difficult to adsorb on the solid acid catalyst surface, which makes it difficult to activate double bonds. In order to improve the catalytic effect of solid acids, solid acid modification mainly focuses on increasing acid strength and acid density. However, this direction will lead to side reactions such as olefin chelation, which in turn leads to a decrease in the yield and selectivity of lower alcohols.

[0015] The low-carbon olefin hydration filler provided by this invention solves the problems of poor water-olefin mixing effect and low low-carbon alcohol yield in existing technologies from a microscopic mechanism perspective. Using this filler as a matrix, it is further modified according to the components involved in the hydration reaction. A silane layer, a modified layer A, and a modified layer B are sequentially coated on the outer surface of the filler matrix from the inside out. The silane layer mainly acts as a connecting layer, linking the matrix and the secondary modified layer, improving the stability of the secondary modified layer and extending the service life of the modified filler. Modified layer A is grafted with water-affinity groups and low-carbon alcohol-repellent groups. The water-affinity groups form a water-rich layer on the outer surface of the matrix, providing excess water for the hydration reaction microenvironment. The low-carbon alcohol-repellent groups on the outer surface promote mass transfer of the low-carbon alcohol present in modified layer A to the secondary outer layer.

[0016] The outermost layer of modified layer A is modified layer B, which is the main site of olefin hydration reaction. 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 reasonably 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 towards modified layer A based on the gradient change in hydrophilicity between modified layer A and modified layer B. Modified layer B is grafted with alkenophilic groups that are slightly stronger than the hydrophilic groups. Through these alkenophilic groups, olefin molecules are continuously captured from the mixed liquid phase. Under the activation of the catalytic groups with suitable acid strength, olefins undergo hydration reactions with the water molecules enriched in the surrounding area and the bottom layer. The low-carbon alcohols generated by hydration continuously diffuse from modified layer B towards 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 modified layers A and B 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 shifting the hydration equilibrium to the right. Detailed Implementation

[0017] 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.

[0018] In this invention, the groups and their contents in the modified layer were determined by infrared spectroscopy. The specific test conditions were KBr tableting at 400 cm⁻¹. -1 -4000cm -1 Within the range of scanning, the content of each group in the modified layer was measured step by step during the preparation process.

[0019] In this invention, the thickness of the modified layer was measured by an X-ray fluorescence thickness gauge.

[0020] The first aspect of the present invention provides a modified hydrated filler, wherein the modified hydrated filler comprises a filler matrix, and a silane layer, a modified layer A, and a modified layer B are sequentially coated on the outer surface of the filler matrix from the inside to the outside; the modified layer A contains pyrrole groups, amide groups, and furan groups; the modified layer B contains phenoxy groups, pyrrole groups, furan groups, sulfonic acid groups, phosphate groups, and amide groups.

[0021] In this invention, the preparation method of the filler matrix is ​​not particularly limited and can be obtained by methods conventionally defined in the art. Preferably, the filler matrix is ​​made by winding and weaving corrugated wire mesh. According to a specific embodiment of the present invention, the filler matrix is ​​formed by winding corrugated wire mesh layer by layer. In this preferred embodiment, when the filler rotates around its center at a certain angular velocity, the oil-water mixture sprayed from the distributor located at the center of the filler matrix is ​​continuously divided, mixed, and re-divided by the wire mesh as it flows outwards, thereby greatly improving the oil-water mixing effect.

[0022] In this invention, preferably, the mesh count of the filler matrix is ​​70-150, the wire diameter is 0.07-0.12 mm, the fabric thickness is 0.2-0.5 mm, the peak height is 2-15 mm, and the wave pitch is 4-30 mm.

[0023] In this invention, there is no particular limitation on the material of the filler matrix. Preferably, the filler matrix is ​​made of metal and / or plastic, and more preferably metal.

[0024] In this invention, preferably, the thickness of the silane layer is 7-12 nm.

[0025] In this invention, preferably, the silane layer is provided by at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

[0026] In this invention, preferably, based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in the modified layer A is 13-23 mmol / m². 2 The content of amide groups is 18-38 mmol / m 2 The furanyl content is 2.2-5.9 mmol / m³. 2 .

[0027] In this invention, preferably, the thickness of the modified layer A is 4.5-8.2 nm.

[0028] In this invention, by selecting modified layer A with the above-mentioned group content and thickness, it is possible to achieve the enrichment of microscopic reaction raw material water and the driven separation of reaction product low-carbon alcohol.

[0029] In this invention, preferably, based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of phenoxy groups in modified layer B is 13-24 mmol / m². 2 The content of pyrrole groups is 19-36 mmol / m³. 2 The furanyl content is 3.2-8 mmol / m³. 2 The content of sulfonic acid groups is 25-47 mmol / m 2 The phosphate group content is 8.7-24.5 mmol / m2 The content of amide groups is 12-19 mmol / m 2 .

[0030] In this invention, preferably, the thickness of the modified layer B is 12-20 nm.

[0031] In this invention, by selecting modified layer B with the above-mentioned group content and thickness, it is possible to achieve the enrichment and activation of the reaction raw materials water and alkene, as well as the driven separation of the reaction product low alcohol, thereby promoting the equilibrium to shift to the right.

[0032] A second aspect of the present invention provides a method for preparing a modified hydrated filler, wherein the method includes:

[0033] (1) In the presence of a solution containing silane components, the outer surface of the filler matrix is ​​subjected to silanization treatment to obtain a filler coated with a silane layer;

[0034] (2) In the presence of a solution containing modified component A, the outer surface of the filler coated with silane layer in step (1) is treated with modified component A to obtain a filler coated with modified component A.

[0035] (3) In the presence of a solution containing modified component B, the outer surface of the filler coated with modified layer A in step (2) is subjected to modification treatment B to obtain modified hydrated filler coated with modified layer B.

[0036] Modified component A contains pyrrole, amide, and furanyl groups, while modified component B contains phenoxy, pyrrole, furanyl, sulfonic acid, phosphoric acid, and amide groups.

[0037] In this invention, the type, material, characteristic parameters and preparation method of the filler matrix in step (1) have been described in the first aspect and will not be repeated here.

[0038] In this invention, preferably, in step (1), the conditions of the silanization treatment and the amount of solution containing silane components are such that the thickness of the silane layer is 7-12 nm.

[0039] In this invention, the method of silanization is not particularly limited. Preferably, the silanization process includes: immersing a solution containing silane components in contact with the outer surface of the filler matrix, followed by drying and curing.

[0040] In this invention, the conditions for silanization treatment are not particularly limited. Preferably, the contact immersion treatment conditions include: an immersion temperature of 30-60°C, a time of 1.5-3 hours, and a liquid-to-solid volume of 1-3 cubic meters.

[0041] In this invention, there are no particular limitations on the drying and curing conditions. Preferably, the drying and curing conditions include: a temperature of 105-125°C and a time of 30-60 minutes.

[0042] In this invention, preferably, in step (1), the solution containing silane components is obtained by pre-hydrolysis of a mixture of silane reagent, water and low-carbon alcohol.

[0043] In this invention, preferably, the volume ratio of silane reagent: water: lower alcohol is (2.2-5.2):(3.5-5.9):(89-95).

[0044] In this invention, preferably, the pre-hydrolysis time is 15-30 hours.

[0045] In this invention, preferably, the pH of the solution containing the silane component is 7.5-8.5.

[0046] In this invention, preferably, the silane reagent is selected from at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

[0047] In this invention, preferably, based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in the modified layer A is 13-23 mmol / m². 2 The content of amide groups is 18-38 mmol / m 2 The furanyl content is 2.2-5.9 mmol / m³. 2 .

[0048] In this invention, preferably, in step (2), the thickness of the modified layer A is 4.5-8.2 nm.

[0049] In this invention, there is no particular limitation on the method of modification A treatment. Preferably, in step (2), the modification A treatment includes: immersing the solution containing modified component A in contact with the outer surface of the filler coated with the silane layer in step (1).

[0050] In this invention, preferably, in step (2), the solution containing modified component A contains modified component A, a first initiator and a first solvent, wherein the mass ratio of modified component A: first initiator: first solvent is (4.5-7.9):(0.1-0.4):(93-97).

[0051] In this invention, there is no particular limitation on the type of the first solvent. Preferably, in step (2), the first solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

[0052] In this invention, there is no particular limitation on the type of the first initiator. 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.

[0053] In this invention, preferably, in step (2), the modified component A contains pyrrole derivatives, amide derivatives, and furan derivatives, wherein the molar ratio of pyrrole derivatives: amide derivatives: furan derivatives is (15-27): (21-44): (2.7-6.8).

[0054] 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.

[0055] In this invention, preferably, the amide group is provided by an amide derivative, and more preferably by at least one of N,N'-dihydroxyethyl bisacrylamide, N,N-methylene bisacrylamide and hexamethylene bisacrylamide.

[0056] In this invention, preferably, the furanyl group is provided by a furan derivative, more preferably by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

[0057] In this invention, there are no particular limitations on the conditions for the modified A treatment. Preferably, in step (2), the conditions for the modified A treatment include: a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3h.

[0058] In this invention, preferably, based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of phenoxy groups in the modified layer B is 13-24 mmol / m². 2 The content of pyrrole groups is 19-36 mmol / m³. 2 The furanyl content is 3.2-8 mmol / m³. 2 The content of sulfonic acid groups is 25-47 mmol / m 2 The phosphate group content is 8.7-24.5 mmol / m 2 The content of amide groups is 12-19 mmol / m 2 .

[0059] In this invention, preferably, the thickness of the modified layer B is 12-20 nm.

[0060] In this invention, there is no particular limitation on the method of modifying B. Preferably, in step (3), the modification B treatment includes: immersing the solution containing the modified component B in contact with the outer surface of the filler coated with the modified layer A in step (2).

[0061] In this invention, preferably, in step (3), the solution containing modified component B contains modified component B, a second initiator, and a second solvent, wherein the mass ratio of modified component B: second initiator: second solvent is (5.5-10.4):(0.1-0.5):(92-96).

[0062] In this invention, preferably, in step (3), the modified component B contains phenoxy derivatives, pyrrole derivatives, furan derivatives, sulfonic acid derivatives, phosphoric acid derivatives, and amide derivatives, wherein the molar ratio of phenoxy derivatives: pyrrole derivatives: furan derivatives: sulfonic acid derivatives: phosphoric acid derivatives: amide derivatives is (15-29): (22-43): (3.9-9.5): (30-56): (10.3-28.9): (14.3-22.7).

[0063] 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.

[0064] 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.

[0065] 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.

[0066] In this invention, the pyrrole group, amide group, and furan group are provided by their respective derivatives. The specific types of the derivatives have been described above and will not be repeated here.

[0067] In this invention, there are no particular limitations on the conditions for the modified B treatment. Preferably, in step (3), the conditions for the modified B treatment include: a liquid-to-solid volume ratio of 1-3, a treatment temperature of 70-90℃, and a treatment time of 1.5-3h.

[0068] In this invention, preferably, step (3) further includes post-modification treatment of the modified B-treated product in a post-modification treatment agent. In this invention, the method of post-modification treatment is not particularly limited, but immersion post-modification treatment is preferred.

[0069] In this invention, there is no particular limitation on the type of modified post-treatment agent. Preferably, the modified post-treatment agent is selected from at least one of ethanol, acetone, and methanol, and more preferably ethanol.

[0070] In this invention, there are no particular limitations on the conditions for post-modification treatment. Preferably, the conditions for post-modification treatment include a treatment time of 0.5-1 hour.

[0071] In this invention, preferably, the post-modification treatment further includes drying the modified product. Preferably, the drying process is performed under a nitrogen atmosphere.

[0072] In this invention, preferably, the drying conditions include: a drying temperature of 100-120℃ and a drying time of 0.5-1h.

[0073] The third aspect of this invention provides the application of the modified hydrated filler described in the first aspect or the modified hydrated filler prepared by the preparation method described in the second aspect in the preparation of aqueous solutions of low-carbon alcohols by the hydration reaction of low-carbon olefins.

[0074] In this invention, preferably, the raw materials for the low-carbon olefin hydration reaction include reaction raw materials containing low-carbon olefins and water.

[0075] In this invention, preferably, the reaction raw materials containing low-carbon olefins contain C3 and / or C4 low-carbon olefins.

[0076] In this invention, preferably, the content of low-carbon olefins is 10-100% by volume, more preferably 25-95% by volume, based on the reaction raw materials containing low-carbon olefins.

[0077] In this invention, there is no particular limitation on the contact method for the hydration reaction of low-carbon olefins. Preferably, the reaction raw material containing low-carbon olefins and water are mixed in the modified hydration packing described in the first or third aspect and contacted with the outer surface of the modified hydration packing to carry out the low-carbon olefin hydration reaction, thereby obtaining an aqueous solution containing low-carbon alcohols; more preferably, the contact includes the mixture of reaction raw material containing low-carbon olefins and water entering the modified hydration packing through a modified hydration packing material distributor and contacting the outer surface of the modified hydration packing.

[0078] In this invention, preferably, the modified hydrated filler has a hypergravity factor of 100-200 during operation.

[0079] In this invention, preferably, the conditions for the hydration reaction of the low-carbon olefins include: a temperature of 100-160°C, a pressure of 1000-3000 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.1-0.3 seconds for the mixture of the reactants containing the low-carbon olefins and water, based on the macroscopic volume of the modified hydration filler. -1 The molar ratio of water to olefins in the reaction feedstock is 2-6.

[0080] In this invention, preferably, the single-pass olefin conversion rate of low-carbon olefin hydration is greater than 60%, and the selectivity of low-carbon alcohols is greater than 95%.

[0081] In this invention, the content of each group in the olefin hydration microchannel is determined by the test method described above.

[0082] 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.

[0083] The present invention will be described in detail below through embodiments.

[0084] Example 1

[0085] The composition of the reaction raw materials containing low-carbon olefins in this embodiment, by volume percentage, includes: 30.5% isobutane, 8.2% n-butane, 59.6% n-butene, and 1.7% pentane.

[0086] In this embodiment, the filler matrix is ​​prepared by the following method: a corrugated wire mesh is obtained through a weaving process, and then the filler matrix is ​​obtained by winding it along the central axis. The mesh count of the filler matrix is ​​120, the wire diameter is 0.1 mm, the wire thickness is 0.3 mm, the peak height is 8.5 mm, and the wave pitch is 17 mm. The filler material is metal.

[0087] In step (1), the silane component solution is brought into contact with the filler matrix, and then dried and cured to form a silane layer on the outer surface of the filler. The contact conditions are: immersion at a liquid-to-solid volume ratio of 2, treatment temperature of 45°C, and treatment time of 2.3 h. The drying temperature is 118°C, and the drying time is 45 minutes. Drying is carried out under a protective atmosphere of nitrogen. The silane component solution is obtained by mixing a silane reagent, water, and anhydrous low-carbon alcohol, followed by pre-hydrolysis. The pre-hydrolysis time is 22 hours. The volume ratio of silane reagent:water:anhydrous low-carbon alcohol is 3.7:4.5:93. The pH value of the silane component solution is 7.9. The silane reagent is methylvinyldiethoxysilane. The anhydrous low-carbon alcohol is anhydrous methanol. The amount of silane component solution used results in a silane layer thickness of 9.6 nm.

[0088] In step (2), the solution containing modified component A is brought into contact with the outer surface of the filler coated with a silane layer, so that the outer surface of the filler coated with the silane layer is coated with modified layer A. In the solution containing modified component A, the mass ratio of modified component A: first initiator: first solvent is 6.2:0.2:95. The first solvent is toluene. The first initiator is benzoyl peroxide. Modified component A contains pyrrole derivatives, amide derivatives, and furan derivatives, wherein the molar ratio of pyrrole derivatives: amide derivatives: furan derivatives is 21.2:32.4:4.7. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives are provided by 2-(1-propen-2-yl)furan. The amide derivatives are provided by N,N-methylenebisacrylamide. The modified A treatment conditions included: a solution containing modified component A was in contact with the outer surface of the filler coated with a silane layer as described in step (1); the liquid-to-solid volume ratio was 2; the treatment temperature was 70°C; and the treatment time was 2.3 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in modified layer A was 17.8 mmol / m². 2 The amide group content is 27.2 mmol / m 2 The furanyl content was 3.9 mmol / m³. 2 The thickness of modified layer A is 6.4 nm.

[0089] In step (3), the solution containing modified component B is brought into contact with the outer surface of the filler coated with modified layer A in step (2), so that the outer surface of the filler coated with modified layer A is coated with modified layer B. In the solution containing modified component B, the mass ratio of modified component B: second initiator: second solvent is 7.9:0.3:94. The second solvent is toluene. Modified component B contains phenoxy derivatives, pyrrole derivatives, furan derivatives, sulfonic acid derivatives, phosphoric acid derivatives, and amide derivatives, wherein the molar ratio of phenoxy derivatives: pyrrole derivatives: furan derivatives: sulfonic acid derivatives: phosphoric acid derivatives: amide derivatives is 21.8:32.4:6.6:43.1:19.5:18.4. The phenoxy derivatives are provided by allyl phenyl ether. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives were provided by 2-(1-propen-2-yl)furan. The amide derivatives were provided by N,N-methylenebisacrylamide. The phosphate derivatives were provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The second initiator was benzoyl peroxide. The modified B treatment conditions included: the solution containing modified component B was in contact with the outer surface of the filler coated with modified layer A in step (2), the liquid-to-solid volume ratio was 2, the treatment temperature was 80°C, and the treatment time was 2.3 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the phenoxy content in modified layer B was 18.4 mmol / m². 2 The pyrrole group content was 27.3 mmol / m 2 The furanyl content was 5.6 mmol / m³. 2 The content of sulfonic acid groups is 36.4 mmol / m 2 The phosphate group content is 16.4 mmol / m 2 The amide group content is 15.5 mmol / m 2 The thickness of modified layer B is 15.8 nm.

[0090] Step (3) further includes post-modifying the modified B-treated product in a post-modification treatment agent. The post-modification treatment agent is anhydrous ethanol. The post-modification treatment conditions include: soaking time of 0.7 h, drying temperature of 110 °C, and drying time of 0.7 h.

[0091] The modified hydrated packing material prepared in this embodiment is used in the hydration of low-carbon olefins. A packed bed is used, and the hypergravity factor is 150 when the modified hydrated packing material is running. The hydrated olefin mixture flows by spraying the olefin-containing reactant raw materials and desalinated water from the center of the modified hydrated packing material to the surrounding area. The olefin-containing reactant raw materials and desalinated water are mixed in the modified hydrated packing material and come into contact with the outer surface of the modified hydrated packing material to carry out a hydration reaction, thereby obtaining an aqueous solution containing low-carbon alcohols.

[0092] The olefin hydration reaction conditions included: a temperature of 130°C, a pressure of 2000 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.2 seconds for the mixture of reactants containing low-carbon olefins and water, based on the macroscopic volume of the modified hydration packing material. -1 The molar ratio of water to olefins in the reaction feedstock is 4.

[0093] The single-pass olefin conversion rate of olefin hydration was 68.2%, and the selectivity for lower alcohols was 96.7%.

[0094] Example 2

[0095] The same reaction feedstock containing low-carbon olefins as in Example 1 was selected.

[0096] In this embodiment, the filler matrix is ​​prepared by the following method: a corrugated wire mesh is obtained through a weaving process, and then the filler matrix is ​​obtained by winding it along the central axis. The mesh count of the filler matrix is ​​140, the wire diameter is 0.08 mm, the wire thickness is 0.3 mm, the peak height is 3 mm, and the wave pitch is 5 mm. The filler material is metal.

[0097] In step (1), the silane component solution is brought into contact with the filler matrix, and then dried and cured to form a modified layer A on the outer surface of the filler. The contact conditions are: immersion at a liquid-to-solid volume ratio of 3, treatment temperature of 57°C, and treatment time of 2.7 h. The drying temperature is 123°C, and the drying time is 56 minutes. Drying is carried out under a protective atmosphere of nitrogen. The silane component solution is obtained by mixing a silane reagent, water, and anhydrous low-carbon alcohol, followed by pre-hydrolysis. The pre-hydrolysis time is 29 hours. The volume ratio of silane reagent:water:anhydrous low-carbon alcohol is 5.1:5.6:92. The pH value of the silane component solution is 8.2. The silane reagent is methylvinyldiethoxysilane. The anhydrous low-carbon alcohol is anhydrous methanol. The amount of silane component solution used results in a silane layer thickness of 11.3 nm.

[0098] In step (2), the solution containing modified component A is brought into contact with the outer surface of the filler coated with a silane layer, so that the outer surface of the filler coated with the silane layer is coated with modified layer A. In the solution containing modified component A, the mass ratio of modified component A: first initiator: first solvent is 7.8:0.3:94. The first solvent is toluene. The first initiator is benzoyl peroxide. Modified component A contains pyrrole derivatives, amide derivatives, and furan derivatives, wherein the molar ratio of pyrrole derivatives: amide derivatives: furan derivatives is 26:43:6.7. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives are provided by 2-(1-propen-2-yl)furan. The amide derivatives are provided by N,N-methylenebisacrylamide. The modified A treatment conditions include: a solution containing modified component A is in contact with the outer surface of the filler coated with a silane layer as described in step (1); the liquid-to-solid volume ratio is 3; the treatment temperature is 79°C; and the treatment time is 2.7 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in the modified layer A is 22.6 mmol / m². 2 The content of amide groups is 37.4 mmol / m 2 The furanyl content was 5.8 mmol / m³. 2 The thickness of modified layer A is 7.9 nm.

[0099] In step (3), the solution containing modified component B is brought into contact with the outer surface of the filler coated with modified layer A in step (2), so that the outer surface of the filler coated with modified layer A is coated with modified layer B. In the solution containing modified component B, the mass ratio of modified component B: second initiator: second solvent is 10.2:0.4:93. The second solvent is toluene. Modified component B contains phenoxy derivatives, pyrrole derivatives, furan derivatives, sulfonic acid derivatives, phosphoric acid derivatives, and amide derivatives, wherein the molar ratio of phenoxy derivatives: pyrrole derivatives: furan derivatives: sulfonic acid derivatives: phosphoric acid derivatives: amide derivatives is 28:42:9.4:55:28.6:22.5. The phenoxy derivatives are provided by allyl phenyl ether. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives are provided by 2-(1-propen-2-yl)furan. The amide derivatives were provided by N,N-methylenebisacrylamide. The phosphate derivatives were provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The second initiator was benzoyl peroxide. The modified B treatment conditions included: the solution containing modified component B was in contact with the outer surface of the filler coated with modified layer A in step (2), the liquid-to-solid volume ratio was 3, the treatment temperature was 88°C, and the treatment time was 2.6 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the phenoxy content in modified layer B was 23.6 mmol / m². 2 The content of pyrrole groups was 35.4 mmol / m³. 2 The furanyl content was 7.9 mmol / m³. 2 The content of sulfonic acid groups is 46.3 mmol / m 2 The phosphate group content is 24.1 mmol / m 2 The amide group content is 18.9 mmol / m 2 The thickness of modified layer B is 19.1 nm.

[0100] Step (3) further includes post-modifying the modified B-treated product in a post-modification treatment agent. The post-modification treatment agent is anhydrous ethanol. The post-modification treatment conditions include: soaking time of 0.8 h, drying temperature of 116 °C, and drying time of 0.9 h.

[0101] According to the reaction method of Example 1, the hypergravity factor of the modified hydrated filler is 180 during operation.

[0102] The conditions for the olefin hydration reaction include: a temperature of 110°C, a pressure of 1500 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.1 s for the mixture of reactants containing low-carbon olefins and water, based on the macroscopic volume of the modified hydration packing material. -1 The molar ratio of water to olefins in the reaction feedstock is 5.

[0103] The single-pass olefin conversion rate of olefin hydration was 73.2%, and the selectivity for lower alcohols was 97.3%.

[0104] Example 3

[0105] The same olefin-containing reaction raw materials as in Example 1 were selected.

[0106] In this embodiment, the filler matrix is ​​prepared by the following method: a corrugated wire mesh is obtained through a weaving process, and then the filler matrix is ​​obtained by winding it along the central axis. The mesh count of the filler matrix is ​​80, the wire diameter is 0.11 mm, the wire thickness is 0.4 mm, the peak height is 12 mm, and the wave pitch is 20 mm. The filler material is metal.

[0107] In step (1), the silane component solution is brought into contact with the filler matrix, and then dried and cured to form a modified layer A on the outer surface of the filler. The contact conditions are: immersion at a liquid-to-solid volume ratio of 1, treatment temperature of 32°C, and treatment time of 1.7 h. The drying temperature is 112°C, and the drying time is 34 minutes. Drying is carried out under a protective atmosphere of nitrogen. The silane component solution is obtained by mixing a silane reagent, water, and anhydrous low-carbon alcohol, followed by pre-hydrolysis. The pre-hydrolysis time is 15 hours. The volume ratio of silane reagent:water:anhydrous low-carbon alcohol is 2.4:3.3:95. The pH value of the silane component solution is 7.8. The silane reagent is methylvinyldiethoxysilane. The anhydrous low-carbon alcohol is anhydrous methanol. The amount of silane component solution used results in a silane layer thickness of 8.2 nm.

[0108] In step (2), the solution containing modified component A is brought into contact with the outer surface of the filler coated with a silane layer, so that the outer surface of the filler coated with the silane layer is coated with modified layer A. In the solution containing modified component A, the mass ratio of modified component A: first initiator: first solvent is 4.7:0.2:96. The first solvent is toluene. The first initiator is benzoyl peroxide. Modified component A contains pyrrole derivatives, amide derivatives, and furan derivatives, wherein the molar ratio of pyrrole derivatives: amide derivatives: furan derivatives is 16.2:21.8:2.8. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives are provided by 2-(1-propen-2-yl)furan. The amide derivatives are provided by N,N-methylenebisacrylamide. The modified A treatment conditions included: a solution containing modified component A was in contact with the outer surface of the filler coated with a silane layer as described in step (1); the liquid-to-solid volume ratio was 1; the treatment temperature was 62°C; and the treatment time was 1.7 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in modified layer A was 13.8 mmol / m². 2 The amide group content is 18.6 mmol / m 2 The furanyl content was 2.4 mmol / m³. 2 The thickness of modified layer A is 4.6 nm.

[0109] In step (3), the solution containing modified component B is brought into contact with the outer surface of the filler coated with modified layer A in step (2), so that the outer surface of the filler coated with modified layer A is coated with modified layer B. In the solution containing modified component B, the mass ratio of modified component B: second initiator: second solvent is 5.7:0.2:95. The second solvent is toluene. Modified component B contains phenoxy derivatives, pyrrole derivatives, furan derivatives, sulfonic acid derivatives, phosphoric acid derivatives, and amide derivatives, wherein the molar ratio of phenoxy derivatives: pyrrole derivatives: furan derivatives: sulfonic acid derivatives: phosphoric acid derivatives: amide derivatives is 15.8:22.4:4.1:32:10.4:14.5. The phenoxy derivatives are provided by allyl phenyl ether. The pyrrole derivatives are provided by 1-(3-buten-1-yl)-2-vinyl-1H-pyrrole. The furan derivatives were provided by 2-(1-propen-2-yl)furan. The amide derivatives were provided by N,N-methylenebisacrylamide. The phosphate derivatives were provided by [2-methyl-2-(4-methylpent-3-enyl)cyclopropyl]methylphosphonophosphate. The sulfonic acid derivatives were provided by (Z)-4',4”'-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)). The second initiator was benzoyl peroxide. The modified B treatment conditions included: the solution containing modified component B was in contact with the outer surface of the filler coated with modified layer A in step (2), the liquid-to-solid volume ratio was 1, the treatment temperature was 72°C, and the treatment time was 1.6 h. Based on the outer surface area of ​​the dry-based filler matrix per square meter, the phenoxy content in modified layer B was 13.9 mmol / m². 2 The pyrrole group content was 19.7 mmol / m³. 2 The furanyl content was 3.6 mmol / m³. 2 The content of sulfonic acid groups is 28.1 mmol / m 2 The phosphate group content is 9.1 mmol / m 2 The amide group content is 12.7 mmol / m 2 The thickness of modified layer B is 12.7 nm.

[0110] Step (3) further includes post-modifying the modified B-treated product in a post-modification treatment agent. The post-modification treatment agent is anhydrous ethanol. The post-modification treatment conditions include: soaking time of 0.6 h, drying temperature of 104 °C, and drying time of 0.6 h.

[0111] According to the reaction method of Example 1, the hypergravity factor of the modified hydrated filler during operation is 120.

[0112] The conditions for the olefin hydration reaction include: a temperature of 150°C, a pressure of 2600 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.3 seconds for the mixture of reactants containing low-carbon olefins and water, based on the macroscopic volume of the modified hydration packing material. -1 The molar ratio of water to olefins in the reaction feedstock is 3.

[0113] The single-pass olefin conversion rate of olefin hydration was 62.7%, and the selectivity for lower alcohols was 95.8%.

[0114] Example 4

[0115] The method is the same as in Example 2, except that the reaction raw materials in this example contain low-carbon olefins, which, by volume percentage, include: 16.4% isobutane, 7.3% n-butane, 74.9% n-butene, and 1.4% pentane.

[0116] Following the reaction method and conditions of Example 2, the single-pass olefin conversion of olefin hydration was 74.6%, and the selectivity for lower alcohols was 97.5%.

[0117] Example 5

[0118] The method is the same as in Example 2, except that the reaction raw materials in this example contain low-carbon olefins, which, by volume percentage, include: 6.8% isobutane, 2.2% n-butane, 90.5% n-butene, and 0.5% pentane.

[0119] Following the reaction method and conditions of Example 2, the single-pass olefin conversion of olefin hydration was 75.3%, and the selectivity for lower alcohols was 97.6%.

[0120] Example 6

[0121] The method is the same as in Example 2, except that the reaction raw materials in this example contain low-carbon olefins, which, by volume percentage, include: 50.8% isobutane, 13.7% n-butane, 30.0% n-butene, and 5.5% pentane.

[0122] Following the reaction method and conditions of Example 2, the single-pass olefin conversion of olefin hydration was 70.3%, and the selectivity for lower alcohols was 97.1%.

[0123] Comparative Example 1

[0124] The same reaction feedstock containing low-carbon olefins as in Example 5 was selected, namely, by volume percentage: 6.8% isobutane, 2.2% n-butane, 90.5% n-butene, and 0.5% pentane.

[0125] The olefin hydration reactor was packed with Suqing brand SQD-69 styrene-based macroporous strong acid cation exchange resin. The reaction temperature was 155℃, the reaction pressure was 78 kg, and the mass hourly space velocity (HHSV) was 1 h⁻¹. -1The single-pass conversion rate of n-butene was 11.03%, and the selectivity was 95.7%.

[0126] Comparative Example 2

[0127] The method of Example 3 is different in that, in this comparative example, the silanized matrix (i.e., the silane reagent solution and the filler matrix are brought into contact and then dried and cured) is directly brought into contact with the outer surface of the filler coated with the silane layer by a solution containing the modifying component B, without going through the process of bringing the outer surface of the silanized filler into contact with a solution containing the modifying component A, and the subsequent modification post-treatment is omitted.

[0128] Following the reaction method and conditions of Example 3, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 37.6%, and the selectivity for lower alcohols was 87.3%.

[0129] Comparative Example 3

[0130] The method is the same as in Example 3, except that this comparative example directly uses an unmodified filler matrix.

[0131] Following the reaction method and conditions of Example 3, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 1.8%, and the selectivity for lower alcohols was 85.2%.

[0132] The preferred 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 combinations of 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 modified hydrated filler, characterized in that, The modified hydrated filler includes a filler matrix, and a silane layer, a modified layer A, and a modified layer B are sequentially coated on the outer surface of the filler matrix from the inside to the outside; the modified layer A contains pyrrole groups, amide groups, and furan groups; the modified layer B contains phenoxy groups, pyrrole groups, furan groups, sulfonic acid groups, phosphoric acid groups, and amide groups; Based on the surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in the modified layer A is 13-23 mmol / m². 2 The content of amide groups is 18-38 mmol / m 2 The furanyl content is 2.2-5.9 mmol / m³. 2 ; Based on the surface area of ​​the dry-based filler matrix per square meter, the phenoxy content in modified layer B is 13-24 mmol / m². 2 The content of pyrrole groups is 19-36 mmol / m³. 2 The furanyl content is 3.2-8 mmol / m³. 2 The content of sulfonic acid groups is 25-47 mmol / m 2 The phosphate group content is 8.7-24.5 mmol / m 2 The content of amide groups is 12-19 mmol / m 2 .

2. The modified hydrated filler according to claim 1, wherein, The filler matrix is ​​made by winding and weaving corrugated wire mesh.

3. The modified hydrated filler according to claim 2, wherein, The filler matrix has a mesh count of 70-150, a wire diameter of 0.07-0.12 mm, a fabric thickness of 0.2-0.5 mm, a peak height of 2-15 mm, and a wave pitch of 4-30 mm. And / or, the filler matrix is ​​made of metal and / or plastic.

4. The modified hydrated filler according to claim 3, wherein, The filler matrix is ​​made of metal.

5. The modified hydrated filler according to claim 1 or 2, wherein, The thickness of the silane layer is 7-12 nm.

6. The modified hydrated filler according to claim 1 or 2, wherein, The silane layer is provided by at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

7. The modified hydrated filler according to claim 1 or 2, wherein, The thickness of the modified layer A is 4.5-8.2 nm.

8. The modified hydrated filler according to claim 1 or 2, wherein, The thickness of the modified layer B is 12-20 nm.

9. A method for preparing a modified hydrated filler, wherein, The method includes: (1) In the presence of a solution containing silane components, the outer surface of the filler matrix is ​​subjected to silanization treatment to obtain a filler coated with a silane layer; (2) In the presence of a solution containing modified component A, the outer surface of the filler coated with silane layer in step (1) is subjected to modification A treatment to obtain the filler coated with modified layer A. (3) In the presence of a solution containing modified component B, the outer surface of the filler coated with modified layer A in step (2) is subjected to modification treatment B to obtain modified hydrated filler; Modified component A contains pyrrole, amide, and furanyl groups, while modified component B contains phenoxy, pyrrole, furanyl, sulfonic acid, phosphoric acid, and amide groups. Based on the surface area of ​​the dry-based filler matrix per square meter, the content of pyrrole groups in the modified layer A is 13-23 mmol / m². 2 The content of amide groups is 18-38 mmol / m 2 The furanyl content is 2.2-5.9 mmol / m³. 2 ; Based on the surface area of ​​the dry-based filler matrix per square meter, the content of phenoxy groups in the modified layer B is 13-24 mmol / m². 2 The content of pyrrole groups is 19-36 mmol / m³. 2 The furanyl content is 3.2-8 mmol / m³. 2 The content of sulfonic acid groups is 25-47 mmol / m 2 The phosphate group content is 8.7-24.5 mmol / m 2 The content of amide groups is 12-19 mmol / m 2 .

10. The method according to claim 9, wherein, In step (1), the filler matrix is ​​made by winding and weaving corrugated wire mesh.

11. The method according to claim 10, wherein, The filler matrix has a mesh count of 70-150, a wire diameter of 0.07-0.12 mm, a fabric thickness of 0.2-0.5 mm, a peak height of 2-15 mm, and a wave pitch of 4-30 mm. And / or, the filler matrix is ​​made of metal and / or plastic.

12. The method according to claim 11, wherein, The filler matrix is ​​made of metal.

13. The method according to claim 9 or 10, wherein, In step (1), the thickness of the silane layer is 7-12 nm; And / or, the silanization process includes: contact immersion treatment of a solution containing silane components with the outer surface of the filler matrix, followed by drying and curing; And / or, in step (1), the solution containing the silane component is obtained by pre-hydrolysis of a mixture of silane reagent, water and low alcohol.

14. The method according to claim 13, wherein, The volume ratio of silane reagent: water: lower alcohol is (2.2-5.2): (3.5-5.9): (89-95).

15. The method according to claim 13, wherein, The silane reagent is selected from at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

16. The method according to claim 9 or 10, wherein, In step (2), the thickness of the modified layer A is 4.5-8.2 nm.

17. The method according to claim 9 or 10, wherein, In step (2), the modified A treatment includes: immersing the solution containing modified component A in contact with the outer surface of the filler coated with silane layer in step (1); And / or, in step (2), the solution containing modified component A contains modified component A, a first initiator and a first solvent, wherein the mass ratio of modified component A: first initiator: first solvent is (4.5-7.9):(0.1-0.4):(93-97); In step (2), the first solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene; 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 modified component A contains pyrrole derivatives, amide derivatives, and furan derivatives, wherein the molar ratio of pyrrole derivatives: amide derivatives: furan derivatives is (15-27):(21-44):(2.7-6.8); And / or, the pyrrole group is provided by a pyrrole derivative; And / or, the amide group is provided by an amide derivative; And / or, the furan group is provided by a furan derivative; And / or, in step (2), the conditions for the modified A treatment include: a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3h.

18. The method according to claim 17, wherein, In step (2), the first initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate and hydrogen peroxide.

19. The method of claim 17, wherein, In step (2), the first initiator is benzoyl peroxide.

20. The method of claim 17, wherein, The pyrrole 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-pyrrole-2-one.

21. The method according to claim 17, wherein, The amide group is provided by at least one of N,N'-dihydroxyethylbisacrylamide, N,N-methylenebisacrylamide and hexamethylenebisacrylamide.

22. The method according to claim 17, wherein, The furanyl group is provided by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

23. The method according to claim 9 or 10, wherein, The thickness of the modified layer B is 12-20 nm.

24. The method according to claim 9 or 10, wherein, In step (3), the modified B treatment includes: immersing the solution containing modified component B in contact with the outer surface of the filler coated with modified layer A in step (2); And / or, in step (3), the solution containing modified component B contains modified component B, a second initiator, and a second solvent, wherein the mass ratio of modified component B: second initiator: second solvent is (5.5-10.4):(0.1-0.5):(92-96); In step (3), modified component B contains phenoxy derivatives, pyrrole derivatives, furan derivatives, sulfonic acid derivatives, phosphoric acid derivatives, and amide derivatives, wherein the molar ratio of phenoxy derivatives: pyrrole derivatives: furan derivatives: sulfonic acid derivatives: phosphoric acid derivatives: amide derivatives is (15-29): (22-43): (3.9-9.5): (30-56): (10.3-28.9): (14.3-22.7). And / or, the phenoxy group is provided by a phenoxy derivative; And / or, the phosphate group is provided by a phosphate derivative; And / or, the sulfonic acid group is provided by a sulfonic acid derivative; And / or, in step (3), the conditions for the modified B treatment include: a liquid-to-solid volume ratio of 1-3, a treatment temperature of 70-90℃, and a treatment time of 1.5-3h.

25. The method according to claim 24, wherein, The phenoxy group is provided by at least one of 4-methoxystyrene, allyl phenyl ether, and phenyl vinyl ether.

26. The method according to claim 24, wherein, The phosphate group is provided 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.

27. The method according to claim 24, 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'''-(ethylene-1,2-diyl)bis(([[1,1'-biphenyl]-4-sulfonic acid)) and 4-{(E)-2-[3,5-bis(sulfonoxy)phenyl]vinyl}phenyl hydrosulfate.

28. The method according to claim 24, wherein, Step (3) also includes post-modifying the modified B-treated product in a post-modifying agent; The modified post-treatment agent is selected from at least one of ethanol, acetone and methanol.

29. The method according to claim 28, wherein, The modified post-treatment agent is ethanol.

30. The method according to claim 28, wherein, The conditions for the post-modification treatment include a treatment time of 0.5-1 hour.

31. The method according to claim 28, wherein, The post-modification treatment also includes drying the modified post-treatment product.

32. The method according to claim 31, wherein, The drying conditions include: a drying temperature of 100-120℃ and a drying time of 0.5-1h.

33. The application of the modified hydrated filler according to any one of claims 1-8 or the modified hydrated filler prepared by the preparation method according to any one of claims 9-32 in the preparation of aqueous solutions of low-carbon alcohols by the hydration reaction of low-carbon olefins.