Low-carbon olefin hydration catalysts and their preparation methods, and methods for producing low-carbon alcohol aqueous solutions.

Abstract

This invention relates to the technical field of low-carbon olefin hydration, and discloses a low-carbon olefin hydration catalyst and its preparation method, as well as a method for producing low-carbon alcohol aqueous solutions. The low-carbon olefin hydration catalyst comprises a resin white sphere matrix, an adsorption layer, and a reaction layer. The adsorption layer is grafted onto the outer surface of the resin white sphere matrix, and the reaction layer is grafted onto the inner surface of the resin white sphere matrix. The adsorption layer contains phenoxy, amide, pyrrole, and furanyl groups; the reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups. This low-carbon olefin hydration catalyst can improve the contact effect between water and olefins, promote the shift of hydration equilibrium, and reduce olefin aggregation loss.

Description

Technical Field

[0001] This invention relates to the technical field of low-carbon olefin hydration, specifically to a low-carbon olefin hydration catalyst and its preparation method, and a method for producing 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 serious equipment corrosion and waste acid disposal 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 lower alcohols from lower olefins.

[0003] Commonly used solid acid catalysts include acidic zeolites, MoO3 / WO3, ion exchange resins (such as DOWEXR50, AMBERLYSTR 15, and D008 resins), and supported solid acid catalysts (such as phosphoric acid supported on silica). To improve the conversion rate of olefin hydration reactions, patent application CN110665542A discloses a catalyst for isobutylene hydration and its preparation method. The catalyst uses styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene, and m-divinylbenzene as comonomers, which are suspended copolymerized with a porogen, initiator, and dispersant to obtain copolymer spheres. The copolymer spheres are then extracted, dried, sieved, and sulfonated. This is an in-situ modification method of the catalyst skeleton. The modification does not fully utilize the large internal surface area of ​​the resin. Furthermore, the acid centers use conventional sulfonic acid groups, resulting in high acid strength. If the reaction conditions are not properly controlled, numerous side reactions can easily occur.

[0004] Given the shortcomings of existing hydration catalysts in terms of activity and structure, the development of novel olefin hydration catalysts currently focuses on optimizing catalyst formulations and preparation methods to improve catalytic hydration activity and the selectivity and matching of catalyst structure to components, thereby reducing the catalytic superposition effect of active centers on olefins, and ultimately reducing olefin polymerization, increasing the yield of lower alcohols, and promoting a rightward shift of the hydration equilibrium. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing low-carbon olefin hydration catalysts and the problem of low conversion rate during the hydration process of low-carbon olefins, and to provide a low-carbon olefin hydration catalyst and its preparation method, as well as a method for producing low-carbon alcohol aqueous solutions. This low-carbon olefin hydration catalyst can significantly improve the contact between hydrated olefins and the catalyst surface and promote the improvement of hydration conversion rate.

[0006] To achieve the above objectives, a first aspect of the present invention provides a low-carbon olefin hydration catalyst, wherein the hydration catalyst comprises a resin white sphere matrix, an adsorption layer, and a reaction layer, the adsorption layer being grafted onto the outer surface of the resin white sphere matrix, and the reaction layer being grafted onto the inner surface of the resin white sphere matrix; the adsorption layer contains phenoxy, amide, pyrrole, and furanyl groups; and the reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups.

[0007] A second aspect of the present invention provides a method for preparing a low-carbon olefin hydration catalyst, wherein the method includes:

[0008] (1) In the presence of the adsorption component, the outer surface of the resin white ball matrix is ​​subjected to adsorption treatment to obtain the resin white ball matrix after adsorption treatment;

[0009] (2) In the presence of the reaction components, the inner surface of the resin white ball matrix after the adsorption treatment in step (1) is subjected to reaction treatment to obtain a low-carbon olefin hydration catalyst.

[0010] The adsorbent component contains phenoxy, amide, pyrrole, and furanyl groups, and the reaction component contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups.

[0011] A third aspect of the present invention provides a method for producing an aqueous solution of low-carbon alcohols, wherein the method comprises: contacting a low-carbon olefin reaction raw material with water in the presence of an olefin hydration catalyst to perform a hydration reaction, thereby obtaining an aqueous solution of low-carbon alcohols, wherein the hydration catalyst is the low-carbon olefin hydration catalyst described in the first aspect or the low-carbon olefin hydration catalyst prepared by the preparation method described in the second aspect.

[0012] 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, and the effect of using excess reactants to further shift the hydration equilibrium to the right is not significant. Solid acid catalysts exhibit good water binding properties but poor compatibility with olefins. Olefins are difficult to adsorb onto the water-saturated surface of the solid acid catalyst, 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 yields and selectivity of low-carbon alcohols.

[0013] The low-carbon olefin hydration catalyst provided by this invention solves the problems of poor contact between hydrated olefins and catalytic surfaces, and low yields and selectivity of low-carbon alcohols in existing technologies from a microscopic mechanism perspective. Preferably, the hydration catalyst of this invention is further modified from a low-crosslinked resin white sphere matrix. The lower degree of crosslinking enables better swelling effects, providing the possibility for good diffusion of reactants and products.

[0014] The hydration catalyst provided by this invention has an adsorption layer grafted onto the outer surface of a resin white sphere matrix and a reaction layer grafted onto the inner surface of the resin white sphere matrix. The adsorption layer is grafted with a high concentration of alkenophilic groups and a certain concentration of hydrophilic groups and low-carbon alcohol repellent groups. The high concentration of alkenophilic groups enables the enrichment of low-concentration olefins in the aqueous emulsion on the outer surface of the resin white sphere matrix and allows them to diffuse along the pores into the catalyst interior. The large inner surface of the resin is grafted with a reaction layer, which is the main site of the olefin hydration reaction. This layer is grafted with a high concentration of hydrophilic groups (used to enrich water, and the matching of different concentrations of hydrophilic groups on the outer and inner surfaces enables water to diffuse from the liquid phase bulk through the catalyst outer surface to the inner surface), catalytic groups (used to activate olefins, and the acid strength is reasonably controlled through the synergistic combination of groups), low-carbon alcohol repellent groups (used to transfer the low-carbon alcohols generated in the reaction to the liquid phase bulk through the matching of different concentrations of repellent groups on the inner and outer surfaces, promoting the hydration reaction to the right), and alkenophilic groups (used to enrich olefins and receive olefins enriched on the outer surface). Water in the mixed liquid phase continuously accumulates in the reaction layer due to the gradient of hydrophilicity in the adsorption and reaction layers, providing excess water for the hydration reaction microenvironment. The reaction layer is grafted with a high concentration of catalytic groups. As the alkenophilic groups continuously capture olefin molecules from the mixed liquid phase via the outer surface to the inner surface, under the activation of the catalytic groups with suitable acid strength, the olefins undergo a hydration reaction with the water molecules enriched on the inner surface. The resulting lower alcohols, driven by the lower alcohol repulsion groups, continuously diffuse from the inner surface to the liquid phase via the outer surface, thus shifting the hydration equilibrium to the right. The presence of hydrophilic groups in the adsorption and reaction layers achieves a significant excess of microscopic water, thereby reducing the water-to-olefin ratio. This reduction in the water-to-olefin ratio simultaneously promotes the enrichment of olefin molecules on the alkenophilic groups, further facilitating the shift in hydration equilibrium. The suitable acid strength on the inner surface of the catalyst suppresses side reactions of olefin aggregation, prevents resin pore blockage and deactivation, and ensures good catalyst activity stability. Detailed Implementation

[0015] 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.

[0016] In this invention, the groups and their contents in the adsorption layer and reaction layer were determined by infrared spectroscopy. The specific testing conditions were KBr pellet compression at 400 cm⁻¹. -1 -4000cm -1 The content of each group in the adsorption layer and the reaction layer is obtained by step-by-step measurement during the preparation process. That is, after the adsorption treatment is completed, the content of each group in the adsorption layer is measured after washing and drying; then after the reaction treatment is completed, the content of each group in the adsorption layer is measured again after washing and drying. In this invention, there are no special limitations on the test conditions. For example, 0.1g of dried resin white balls grafted with the adsorption layer can be randomly selected to measure the content of each group in the adsorption layer.

[0017] In this invention, the resin white sphere matrix is ​​a sphere or near-sphere structure containing internal channels.

[0018] The first aspect of this invention provides a low-carbon olefin hydration catalyst, wherein the hydration catalyst comprises a resin white sphere matrix, an adsorption layer, and a reaction layer, the adsorption layer being grafted onto the outer surface of the resin white sphere matrix, and the reaction layer being grafted onto the inner surface of the resin white sphere matrix; the adsorption layer contains phenoxy, amide, pyrrole, and furanyl groups; and the reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups.

[0019] In this invention, there is no particular limitation on the specific type of resin white sphere matrix; all resin white sphere matrices conventionally defined in the art are applicable to this invention. Preferably, the resin white sphere matrix is ​​styrene-divinylbenzene resin.

[0020] In this invention, preferably, the degree of crosslinking of the styrene-divinylbenzene resin is 3-6%.

[0021] In this invention, preferably, the content of dangling double bonds in the resin white sphere matrix is ​​10-20 mmol / g, based on the dry-based resin white sphere matrix.

[0022] In this invention, preferably, the average pore size of the resin white sphere matrix is ​​15-40 nm.

[0023] In this invention, there is no particular limitation on the source of the resin white sphere matrix. It can be obtained commercially or prepared according to the preparation methods conventionally defined in the art. This invention does not particularly limit its preparation method. For example, general resin white spheres formed by suspension polymerization can be purchased. As long as the above parameters are met, it can be adapted to this invention.

[0024] In this invention, preferably, based on the total amount of the dry-based resin white sphere matrix and the adsorption layer, the adsorption layer contains 1.6-3.2 mmol / g of phenoxy groups, 0.6-1.2 mmol / g of amide groups, 0.85-1.7 mmol / g of pyrrole groups, and 0.15-0.3 mmol / g of furanyl groups. By grafting an adsorption layer onto the outer surface of the resin white sphere matrix and controlling the content of each group in the adsorption layer, olefins in the aqueous olefin emulsion can be enriched, and the movement of lower alcohols into the liquid phase bulk can be promoted.

[0025] In this invention, preferably, based on the total amount of the dry-based resin white sphere matrix, the adsorption layer, and the reaction layer, the reaction layer contains 0.6-1.2 mmol / g of phenoxy groups, 1-2 mmol / g of amide groups, 1.4-2.8 mmol / g of sulfonic acid groups, 0.55-1.1 mmol / g of phosphate groups, 1.25-2.5 mmol / g of pyrrole groups, and 0.2-0.4 mmol / g of furanyl groups. By grafting the reaction layer onto the inner surface of the resin white sphere matrix and controlling the content of each group in the reaction layer, the contact and reaction between the water and olefin phases can be promoted, and the low-carbon alcohols produced in the reaction can be transported to the outer surface by mass transfer.

[0026] A second aspect of the present invention provides a method for preparing a low-carbon olefin hydration catalyst, wherein the method includes:

[0027] (1) In the presence of the adsorption component, the outer surface of the resin white ball matrix is ​​subjected to adsorption treatment to obtain the resin white ball matrix after adsorption treatment;

[0028] (2) In the presence of the reaction components, the inner surface of the resin white ball matrix after the adsorption treatment in step (1) is subjected to reaction treatment to obtain a low-carbon olefin hydration catalyst.

[0029] The adsorption component contains phenoxy, amide, pyrrole, and furanyl groups, and the reaction component contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups.

[0030] In this invention, the type, material, characteristic parameters and source of the resin white sphere matrix in step (1) have been described in the first aspect and will not be repeated here.

[0031] In this invention, preferably, in step (1), the adsorption treatment causes an adsorption layer to be grafted onto the outer surface of the resin white sphere matrix, and the adsorption layer contains phenoxy, amide, pyrrole, and furan groups.

[0032] In this invention, the content of each group in the adsorption layer has been described in the first aspect and will not be repeated here.

[0033] In this invention, preferably, in step (1), the adsorbent component is provided by a solution containing the adsorbent component, wherein the solution contains the adsorbent component, a first initiator, a first solvent and a polyether.

[0034] In this invention, preferably, in step (1), the mass ratio of adsorbent component: first initiator: first solvent: polyether in the solution containing adsorbent component is (2.5-4.8):(0.1-0.2):(90-94):(3.2-4.6).

[0035] In this invention, preferably, the polyether has an average molecular weight of 600-1500.

[0036] In this invention, the range of types of the first solvent is relatively wide, and those skilled in the art can select it according to actual needs. Preferably, in step (1), the first solvent is selected from at least one of toluene, p-xylene, m-xylene, and o-xylene.

[0037] In this invention, the range of types of the first initiator is relatively wide, and those skilled in the art can select according to actual needs. Preferably, in step (1), the first initiator is selected from at least one of azo, organic peroxide, inorganic peroxide and redox initiators, more preferably at least one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate and hydrogen peroxide, and even more preferably benzoyl peroxide.

[0038] In this invention, preferably, in step (1), the adsorption component is provided by phenoxy derivatives, amide derivatives, pyrrole derivatives and furan derivatives.

[0039] In this invention, preferably, the molar ratio of phenoxy derivatives: amide derivatives: pyrrole derivatives: furan derivatives in the adsorption component is (1.9-3.9): (0.7-1.5): (1.0-2.1): (0.16-0.37).

[0040] In this invention, there is no particular limitation on the specific type of phenoxy derivative. 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.

[0041] In this invention, there is no particular limitation on the specific type of amide derivative. 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.

[0042] In this invention, there is no particular limitation on the specific type of pyrrole derivative. Preferably, the pyrrole group is provided by a pyrrole derivative, 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.

[0043] In this invention, there is no particular limitation on the specific types of furan derivatives. Preferably, the furan group is provided by furan derivatives, preferably by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

[0044] In this invention, there are no particular limitations on the method and conditions of the adsorption treatment. Preferably, in step (1), the adsorption treatment includes: immersing the resin white sphere matrix in a solution containing the adsorption component, with a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3 hours. In this invention, the outer surface of the resin white sphere matrix is ​​treated with a solution containing the adsorption component. During the adsorption treatment, polyether (existing in the form of a gel solution) is used to seal the pores near the outer surface of the resin white sphere matrix. The adsorption treatment only treats the outer surface of the resin white sphere matrix, ensuring that the dangling double bonds on the outer surface of the resin white sphere matrix are completely reacted. This prevents the outer surface from being grafted with reactive groups again during subsequent reaction treatments, thus avoiding any impact on the outer surface of the resin white sphere matrix from the reaction treatment.

[0045] In this invention, preferably, step (1) further includes post-adsorption treatment of the adsorbed product in post-treatment agent A. The specific operation method of the post-adsorption treatment is not particularly limited in this invention; preferably, the adsorbed product after adsorption treatment is subjected to equal-volume displacement in post-treatment agent A.

[0046] In this invention, the type of post-treatment agent A is not particularly limited. Preferably, the post-treatment agent A is benzene and / or acetonitrile, and more preferably acetonitrile.

[0047] In this invention, the selection range of post-adsorption treatment conditions is relatively wide. Post-adsorption treatment can remove polyether residues adhering to the outer surface of the adsorption-treated matrix, preparing it for further modification. Preferably, the post-adsorption treatment conditions include: an immersion temperature of 50-70℃, an immersion time of 0.5-1 h, and 1-3 immersion cycles. In this invention, the number of immersion cycles refers to the aforementioned number of equal-volume replacement cycles.

[0048] In this invention, preferably, in step (2), the reaction treatment causes the inner surface of the resin white sphere matrix after the adsorption treatment in step (1) to be grafted with a reaction layer, wherein the reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furan groups.

[0049] In this invention, the content of each group in the reaction layer has been described in the first aspect and will not be repeated here.

[0050] In this invention, preferably, in step (2), the reaction component is provided by a solution containing the reaction component, the solution containing the reaction component contains the reaction component, a second initiator and a second solvent.

[0051] In this invention, there is no particular limitation on the content of each component in the solution containing the reaction components. Preferably, in step (2), the mass ratio of the reaction component: the second initiator: the second solvent in the solution containing the reaction components is (2.7-4.9):(0.1-0.2):(90-94).

[0052] In this invention, preferably, the reaction components consist of phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives.

[0053] In this invention, there is no particular limitation on the amount of each derivative in the reaction components, with the aim of satisfying the required content of functional groups. Preferably, in step (2), the molar ratio of phenoxy derivatives: amide derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives in the reaction components is (0.7-1.5): (1.1-2.5): (1.6-3.4): (0.7-1.4): (1.5-2.9): (0.23-0.49).

[0054] In this invention, the specific types of phenoxy derivatives, amide derivatives, pyrrole derivatives, and furan derivatives selected in step (2) can be the same as or different from the types of derivatives in step (1) above, but are preferably the same.

[0055] 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.

[0056] 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.

[0057] In this invention, there is no particular limitation on the type of the second solvent; it can be the same as or different from the type of the first solvent.

[0058] In this invention, there is no particular limitation on the type of the second initiator; it can be the same as or different from the type of the first initiator.

[0059] In this invention, there are no particular limitations on the reaction treatment method and conditions. Preferably, in step (2), the reaction treatment includes: immersing and contacting the solution containing the reaction components with the resin white sphere matrix after the adsorption treatment in step (1), with a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3h.

[0060] In this invention, preferably, step (2) further includes post-reaction treatment of the reaction product in post-treatment agent B. Preferably, the reaction product after reaction treatment can be subjected to equal-volume displacement in post-treatment agent B.

[0061] In this invention, the range of types of post-treatment agent B is relatively wide. Preferably, the post-treatment agent B is selected from at least one of anhydrous ethanol, anhydrous acetone, and anhydrous methanol, and more preferably anhydrous ethanol.

[0062] In this invention, the selection range of post-reaction treatment conditions is relatively wide, and the post-reaction treatment removes residual monomers from the pores and improves the pore structure. Preferably, the post-reaction treatment conditions include: an immersion temperature of 60-80℃, an immersion time of 1-2 hours, and 1-3 immersion cycles. In this invention, the number of immersion cycles refers to the aforementioned number of equal-volume displacement cycles.

[0063] In this invention, preferably, the post-reaction treatment further includes drying the post-reaction product.

[0064] In this invention, the selection range for drying conditions is relatively wide. Preferably, the drying conditions include: a drying temperature of 100-120℃ and a drying time of 0.5-1 hour. In a preferred embodiment, the drying process is carried out under a nitrogen atmosphere.

[0065] A third aspect of the present invention provides a method for producing an aqueous solution of a low-carbon alcohol, wherein the method comprises: contacting a low-carbon olefin reaction raw material with water in the presence of a hydration catalyst to carry out a hydration reaction to obtain an aqueous solution of the low-carbon alcohol, wherein the hydration catalyst is the low-carbon olefin hydration catalyst described in the first aspect or the low-carbon olefin hydration catalyst prepared by the preparation method described in the second aspect.

[0066] In this invention, preferably, based on the total amount of olefin reaction raw materials, the content of low-carbon olefins in the olefin reaction raw materials is 10-100% by volume.

[0067] In this invention, preferably, the low-carbon olefin is a C3 and / or C4 olefin.

[0068] In this invention, preferably, the low-carbon olefin hydration reaction is carried out in a fixed-bed reactor.

[0069] 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 120-160℃, a pressure of 2000-4000 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.5-3 h⁻¹ for the olefin reaction feedstock. -1 The molar ratio of water to olefin reactants is 6-15.

[0070] In this invention, preferably, the single-pass olefin conversion rate is greater than 32%, and the low-carbon alcohol selectivity is greater than 92%.

[0071] The present invention will be described in detail below through embodiments.

[0072] In this invention, the content of each group in the reaction layer and the adsorption layer is determined by the test method described above.

[0073] 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 ACQUITYUPLC / XevoG2QTOF 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: HSST3 (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.

[0074] Example 1

[0075] In this embodiment, the olefin reaction feedstock composition, by volume percentage, includes: isobutane 33.0%, butane 8.7%, n-butene 56.3%, and pentane 2.0%.

[0076] In this embodiment, the resin white sphere matrix is ​​a general-purpose resin white sphere produced by suspension polymerization. The product specifications are as follows: the resin white sphere matrix is ​​styrene-divinylbenzene resin; the degree of crosslinking of styrene-divinylbenzene resin is 4.5%; the content of suspended double bonds in the dry basis resin white sphere is 15.1 mmol / g; and the average pore size is 27.6 nm.

[0077] In step (1), the solution containing the adsorbent component is brought into contact with the resin white sphere matrix, so that the outer surface of the resin white sphere matrix is ​​grafted with an adsorbent layer. In the solution containing the adsorbent component, the mass ratio of adsorbent component: first initiator: first solvent: polyether (average molecular weight of 1000) is 3.6:0.1:92:3.9. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorbent component contains phenoxy derivatives, amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: pyrrole derivatives: furan derivatives is 2.9:1.1:1.6:0.26. The phenoxy derivative is provided by allyl phenyl ether. 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 adsorption treatment conditions included: immersion contact between the solution containing the adsorbent components and the resin white sphere matrix from step (1), a liquid-to-solid volume ratio of 2, a treatment temperature of 70℃, and a treatment time of 2.25 h. Based on the total amount of dry resin white sphere matrix and adsorption layer, the adsorption layer contained 2.3 mmol / g of phenoxy groups, 0.9 mmol / g of amide groups, 1.3 mmol / g of pyrrole groups, and 0.21 mmol / g of furanyl groups.

[0078] Step (1) also includes post-adsorption treatment of the resin white sphere matrix after adsorption component treatment in post-treatment agent A. Post-treatment agent A is acetonitrile. The post-adsorption treatment conditions include: immersion treatment at 60℃ for 0.7h, and two equal-volume replacements.

[0079] In step (2), the solution containing the reaction components is brought into contact with the resin white sphere matrix after adsorption treatment, so that the inner surface of the resin white sphere matrix after adsorption treatment is grafted with a reaction layer. In the solution containing the reaction components, the mass ratio of reaction components: second initiator: second solvent is 3.8:0.1:92. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components contain phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives is 1.1:1.3:2.5:0.9:2.2:0.36. The phenoxy derivatives are provided by allyl phenyl ether. The amide derivatives are provided by N,N-methylenebisacrylamide. 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 reaction conditions included: immersion contact between the solution containing the reaction components and the resin white sphere matrix after adsorption treatment as described in step (1), a liquid-to-solid volume ratio of 2, a treatment temperature of 70°C, and a treatment time of 2.3 h. Based on the total amount of dry resin white sphere matrix, adsorption layer, and reaction layer, the reaction layer contained 0.9 mmol / g of phenoxy groups, 1.1 mmol / g of amide groups, 2.0 mmol / g of sulfonic acid groups, 0.74 mmol / g of phosphate groups, 1.8 mmol / g of pyrrole groups, and 0.3 mmol / g of furan groups.

[0080] Step (2) also includes post-treatment of the reaction product in post-treatment agent B. Post-treatment agent B is anhydrous ethanol. The post-treatment conditions include: soaking temperature of 70°C, soaking time of 1.5 h, two equal-volume soaking replacements, drying temperature of 110°C, and drying time of 0.7 h.

[0081] The prepared low-carbon olefin hydration catalyst was applied in the hydration of low-carbon olefins. The catalyst was packed in a fixed-bed reactor, and a mixture of olefins and demineralized water was contacted with the catalyst to carry out the olefin hydration reaction, yielding an aqueous solution containing low-carbon alcohols. The conditions for the olefin hydration reaction included: a temperature of 140℃, a pressure of 3000 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 1.7 h⁻¹ for the olefin reactants. -1 The molar ratio of water to olefins in the reaction feedstock is 10.

[0082] The single-pass olefin conversion rate of olefin hydration was 37.5%, and the selectivity for lower alcohols was 95.3%.

[0083] Example 2

[0084] The olefin reaction feedstock from Example 1 was selected.

[0085] In this embodiment, the resin white sphere matrix is ​​a general-purpose resin white sphere produced by suspension polymerization. The resin white sphere matrix is ​​styrene-divinylbenzene resin. The degree of crosslinking of styrene-divinylbenzene resin is 3.2%, the content of dangling double bonds in the dry-basis resin white sphere is 18.7 mmol / g, and the average pore size is 38.4 nm.

[0086] In step (1), the solution containing the adsorbent component is brought into contact with the resin white sphere matrix, so that the outer surface of the resin white sphere matrix is ​​grafted with an adsorbent layer. In the solution containing the adsorbent component, the mass ratio of adsorbent component: first initiator: first solvent: polyether (average molecular weight of 700) is 4.7:0.2:91:3.3. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorbent component contains phenoxy derivatives, amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: pyrrole derivatives: furan derivatives is 3.8:1.4:2.0:0.36. The phenoxy derivatives are provided by allyl phenyl ether. The amide derivatives are provided by N,N-methylenebisacrylamide. 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 adsorption treatment conditions included: the solution containing the adsorbent components was immersed in the resin white sphere matrix of step (1) for contact, the liquid-to-solid volume ratio was 3, the treatment temperature was 78℃, and the treatment time was 2.7h. Based on the total amount of dry resin white sphere matrix and adsorption layer, the adsorption layer contained 3.1 mmol / g of phenoxy groups, 1.1 mmol / g of amide groups, 1.6 mmol / g of pyrrole groups, and 0.29 mmol / g of furanyl groups.

[0087] Step (1) also includes post-adsorption treatment of the adsorption-treated resin white sphere matrix in post-treatment agent A. Post-treatment agent A is acetonitrile. The post-adsorption treatment conditions include: immersion treatment at 68℃ for 0.9h, and three equal-volume replacements.

[0088] In step (2), the solution containing the reaction components is brought into contact with the adsorption-treated resin white sphere matrix, so that the inner surface of the adsorption-treated resin white sphere matrix is ​​grafted with a reaction layer. In the solution containing the reaction components, the mass ratio of reaction components: second initiator: second solvent is 4.8:0.2:91. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components contain phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives is 1.4:2.4:3.3:1.3:2.8:0.47. The phenoxy derivatives are provided by allyl phenyl ether. The amide derivatives are provided by N,N-methylenebisacrylamide. 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 reaction conditions included: immersion contact between the solution containing the reaction components and the resin white sphere matrix after adsorption treatment in step (1), a liquid-to-solid volume ratio of 3, a treatment temperature of 78°C, and a treatment time of 2.6 h. Based on the total amount of dry resin white sphere matrix, adsorption layer, and reaction layer, the reaction layer contained 1.1 mmol / g of phenoxy groups, 1.9 mmol / g of amide groups, 2.6 mmol / g of sulfonic acid groups, 1.02 mmol / g of phosphate groups, 2.2 mmol / g of pyrrole groups, and 0.37 mmol / g of furan groups.

[0089] Step (2) also includes post-treatment of the reaction product in post-treatment agent B. Post-treatment agent B is anhydrous ethanol. The post-treatment conditions include: soaking temperature of 78°C, soaking time of 1.7 h, three equal-volume soaking replacements, drying temperature of 117°C, and drying time of 0.9 h.

[0090] The reaction method was the same as in Example 1, except that the conditions for the olefin hydration reaction included: a temperature of 130°C, a pressure of 2500 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.6 h⁻¹ for the olefin reactants. -1 The molar ratio of water to olefins in the reaction feedstock is 14.

[0091] The single-pass olefin conversion rate of olefin hydration was 40.2%, and the selectivity for lower alcohols was 97.4%.

[0092] Example 3

[0093] The olefin reaction feedstock from Example 1 was selected.

[0094] In this embodiment, the resin white sphere matrix is ​​a general-purpose resin white sphere produced by suspension polymerization. The resin white sphere matrix is ​​styrene-divinylbenzene resin. The degree of crosslinking of styrene-divinylbenzene resin is 5.8%, the content of dangling double bonds in the dry-basis resin white sphere is 10.7 mmol / g, and the average pore size is 16.4 nm.

[0095] In step (1), the solution containing the adsorbent component is brought into contact with the resin white sphere matrix, so that the outer surface of the resin white sphere matrix is ​​grafted with an adsorbent layer. In the solution containing the adsorbent component, the mass ratio of adsorbent component: first initiator: first solvent: polyether (average molecular weight of 1400) is 2.6:0.2:93:4.5. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorbent component contains phenoxy derivatives, amide derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: pyrrole derivatives: furan derivatives is 2.0:0.8:1.2:0.18. The phenoxy derivatives are provided by allyl phenyl ether. The amide derivatives are provided by N,N-methylenebisacrylamide. 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 adsorption treatment conditions included: the solution containing the adsorbent components was immersed in contact with the resin white sphere matrix from step (1), the liquid-to-solid volume ratio was 1, the treatment temperature was 62℃, and the treatment time was 1.7h. Based on the total amount of dry resin white sphere matrix and adsorption layer, the adsorption layer contained 1.7 mmol / g of phenoxy groups, 0.68 mmol / g of amide groups, 1.02 mmol / g of pyrrole groups, and 0.15 mmol / g of furanyl groups.

[0096] Step (1) also includes post-adsorption treatment of the adsorption-treated resin white sphere matrix in post-treatment agent A. Post-treatment agent A is acetonitrile. The post-adsorption treatment conditions include: immersion treatment at 52℃ for 0.6h, and three equal-volume replacements.

[0097] In step (2), the solution containing the reaction components is brought into contact with the adsorption-treated resin white sphere matrix, so that the inner surface of the adsorption-treated resin white sphere matrix is ​​grafted with a reaction layer. In the solution containing the reaction components, the mass ratio of reaction components: second initiator: second solvent is 2.8:0.2:93. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components contain phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives, and furan derivatives, wherein the molar ratio of phenoxy derivatives: amide derivatives: sulfonic acid derivatives: phosphoric acid derivatives: pyrrole derivatives: furan derivatives is 0.8:1.2:1.7:0.8:1.6:0.25. The phenoxy derivatives are provided by allyl phenyl ether. The amide derivatives are provided by N,N-methylenebisacrylamide. 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 reaction conditions included: immersion contact between the solution containing the reaction components and the resin white sphere matrix after adsorption treatment in step (1), a liquid-to-solid volume ratio of 1, a treatment temperature of 62°C, and a treatment time of 1.7 h. Based on the total amount of dry resin white sphere matrix, adsorption layer, and reaction layer, the reaction layer contained 0.7 mmol / g of phenoxy groups, 1.05 mmol / g of amide groups, 1.49 mmol / g of sulfonic acid groups, 0.7 mmol / g of phosphate groups, 1.4 mmol / g of pyrrole groups, and 0.22 mmol / g of furan groups.

[0098] Step (2) also includes post-treatment of the reaction product in post-treatment agent B. Post-treatment agent B is anhydrous ethanol. The post-treatment conditions include: soaking temperature of 63°C, soaking time of 1.4 h, one equal-volume soaking replacement, drying temperature of 103°C, and drying time of 0.6 h.

[0099] The reaction method was the same as in Example 1, except that the conditions for the olefin hydration reaction included: a temperature of 150°C, a pressure of 3600 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 2.5 h⁻¹ for the olefin reactants. -1 The molar ratio of water to olefins in the reaction feedstock is 8.

[0100] The single-pass olefin conversion rate of olefin hydration was 33.7%, and the selectivity for lower alcohols was 93.5%.

[0101] Example 4

[0102] 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: 15.9% isobutane, 7.1% n-butane, 75.7% n-butene, and 1.3% pentane.

[0103] Following the reaction method and conditions of Example 2, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 43.6%, and the selectivity for lower alcohols was 97.5%.

[0104] Example 5

[0105] 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: 6.3% isobutane, 2.4% n-butane, 90.9% n-butene, and 0.4% pentane.

[0106] Following the reaction method and conditions of Example 2, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 45.8%, and the selectivity for lower alcohols was 97.6%.

[0107] Example 6

[0108] 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: 52.1% isobutane, 13.2% n-butane, 29.4% n-butene, and 5.3% pentane.

[0109] Following the reaction method and conditions of Example 2, in the olefin hydration reactor, the single-pass olefin conversion rate of olefin hydration was 38.2%, and the selectivity for lower alcohols was 97.1%.

[0110] Comparative Example 1

[0111] The olefin reaction feedstock selected is the same as that in Example 5.

[0112] Following the reaction method of Example 5, the olefin hydration reactor was packed with Suqing brand macroporous strong acid resin D002GH, the reaction temperature was 170℃, 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 12.3%, and the selectivity for lower alcohols was 95.2%.

[0113] Comparative Example 2

[0114] The method of Example 3 is different in that this comparative example does not perform step (1) adsorption treatment, but directly uses the reaction components to perform step (2) reaction treatment on the resin white ball matrix.

[0115] According to the reaction raw materials, reaction method and conditions of Example 3, the single-pass olefin conversion rate of olefin hydration in the olefin hydration reactor was 20.4%, and the selectivity of lower alcohols was 96.2%.

[0116] 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 low-carbon olefin hydration catalyst, characterized in that, The hydration catalyst comprises a resin white sphere matrix, an adsorption layer, and a reaction layer. The adsorption layer is grafted onto the outer surface of the resin white sphere matrix, and the reaction layer is grafted onto the inner surface of the resin white sphere matrix. The adsorption layer contains phenoxy, amide, pyrrole, and furanyl groups. The reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups. Based on the total amount of dry-based resin white sphere matrix and adsorption layer, the adsorption layer contains 1.6-3.2 mmol / g of phenoxy groups, 0.6-1.2 mmol / g of amide groups, 0.85-1.7 mmol / g of pyrrole groups, and 0.15-0.3 mmol / g of furanyl groups. Based on the total amount of dry-based resin white sphere matrix, adsorption layer and reaction layer, the reaction layer contains 0.6-1.2 mmol / g of phenoxy groups, 1-2 mmol / g of amide groups, 1.4-2.8 mmol / g of sulfonic acid groups, 0.55-1.1 mmol / g of phosphate groups, 1.25-2.5 mmol / g of pyrrole groups, and 0.2-0.4 mmol / g of furanyl groups.

2. The low-carbon olefin hydration catalyst according to claim 1, wherein, The resin white sphere matrix is ​​styrene-divinylbenzene resin.

3. The low-carbon olefin hydration catalyst according to claim 2, wherein, The degree of crosslinking of the styrene-divinylbenzene resin is 3-6%.

4. The low-carbon olefin hydration catalyst according to claim 1 or 2, wherein, Based on a dry-based resin white sphere matrix, the content of dangling double bonds in the resin white sphere matrix is ​​10-20 mmol / g.

5. The low-carbon olefin hydration catalyst according to claim 1 or 2, wherein, The average pore size of the resin white sphere matrix is ​​15-40 nm.

6. A method for preparing a low-carbon olefin hydration catalyst, wherein, The method includes: (1) In the presence of the adsorbent component, the outer surface of the resin white ball matrix is ​​subjected to adsorption treatment to obtain the resin white ball matrix after adsorption treatment; (2) In the presence of the reaction components, the inner surface of the resin white ball matrix after the adsorption treatment in step (1) is subjected to reaction treatment to obtain a low-carbon olefin hydration catalyst. The adsorption component contains phenoxy, amide, pyrrole, and furanyl groups, and the reaction component contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furanyl groups. In step (1), the adsorption treatment results in an adsorption layer being grafted onto the outer surface of the resin white sphere matrix, wherein the adsorption layer contains phenoxy, amide, pyrrole, and furan groups; Based on the total amount of dry-based resin white sphere matrix and adsorption layer, the adsorption layer contains 1.6-3.2 mmol / g of phenoxy groups, 0.6-1.2 mmol / g of amide groups, 0.85-1.7 mmol / g of pyrrole groups, and 0.15-0.3 mmol / g of furanyl groups. In step (2), the reaction treatment causes the inner surface of the resin white sphere matrix after the adsorption treatment in step (1) to be grafted with a reaction layer, the reaction layer containing phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole, and furan groups; Based on the total amount of dry-based resin white sphere matrix, adsorption layer and reaction layer, the reaction layer contains 0.6-1.2 mmol / g of phenoxy groups, 1-2 mmol / g of amide groups, 1.4-2.8 mmol / g of sulfonic acid groups, 0.55-1.1 mmol / g of phosphate groups, 1.25-2.5 mmol / g of pyrrole groups, and 0.2-0.4 mmol / g of furanyl groups.

7. The method according to claim 6, wherein, In step (1), the resin white sphere matrix is ​​styrene-divinylbenzene resin.

8. The method according to claim 7, wherein, The degree of crosslinking of the styrene-divinylbenzene resin is 3-6%.

9. The method according to claim 6, wherein, Based on a dry-based resin white sphere matrix, the content of dangling double bonds in the resin white sphere matrix is ​​10-20 mmol / g.

10. The method according to claim 6, wherein, The average pore size of the resin white sphere matrix is ​​15-40 nm.

11. The method according to any one of claims 6-10, wherein, In step (1), the adsorbent component is provided by a solution containing the adsorbent component, which contains the adsorbent component, a first initiator, a first solvent and a polyether.

12. The method according to claim 11, wherein, In step (1), the mass ratio of adsorbent component: first initiator: first solvent: polyether in the solution containing adsorbent component is (2.5-4.8): (0.1-0.2): (90-94): (3.2-4.6). And / or, the average molecular weight of the polyether is 600-1500; And / or, in step (1), the first solvent is selected from at least one of toluene, p-xylene, m-xylene and o-xylene; And / or, in step (1), the first initiator is selected from at least one of azo, organic peroxide, inorganic peroxide and redox initiators; And / or, in step (1), the adsorbent component is provided by phenoxy derivatives, amide derivatives, pyrrole derivatives and furan derivatives.

13. The method according to claim 12, wherein, In step (1), the molar ratio of phenoxy derivatives: amide derivatives: pyrrole derivatives: furan derivatives in the adsorbed components is (1.9-3.9): (0.7-1.5): (1.0-2.1): (0.16-0.37). And / or, the phenoxy group is provided by a phenoxy derivative; And / or, the amide group is provided by an amide derivative; And / or, the pyrrole group is provided by a pyrrole derivative; And / or, the furanyl group is a furan derivative; And / or, in step (1), the adsorption treatment includes: immersing the solution containing the adsorbent component in contact with the resin white ball matrix, with a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3h.

14. The method according to claim 12, wherein, The first initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, and hydrogen peroxide.

15. The method according to claim 14, wherein, The first initiator is benzoyl peroxide.

16. The method according to claim 13, wherein, The phenoxy group is provided by at least one of 4-methoxystyrene, allyl phenyl ether, and phenyl vinyl ether.

17. The method according to claim 13, wherein, The amide group is provided by at least one of N,N'-dihydroxyethylbisacrylamide, N,N-methylenebisacrylamide and hexamethylenebisacrylamide.

18. The method according to claim 13, 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.

19. The method according to claim 13, wherein, The furanyl group is provided by 2-(1-propen-2-yl)furan and / or 2-(2-pentenyl)furan.

20. The method according to claim 12, wherein, Step (1) also includes post-adsorption treatment of the adsorption product after adsorption treatment in post-treatment agent A; post-treatment agent A is benzene and / or acetonitrile.

21. The method according to claim 20, wherein, The conditions for post-adsorption treatment include: soaking temperature of 50-70℃, soaking time of 0.5-1h, and soaking times of 1-3 times.

22. The method according to claim 20, wherein, The post-treatment agent A is acetonitrile.

23. The method according to any one of claims 6-10, wherein, In step (2), the reaction component is provided by a solution containing the reaction component, which contains the reaction component, a second initiator, and a second solvent.

24. The method according to claim 23, wherein, In step (2), the mass ratio of the reaction component to the second initiator to the second solvent in the solution containing the reaction component is (2.7-4.9):(0.1-0.2):(90-94).

25. The method according to claim 24, wherein, In step (2), the reaction components consist of phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives.

26. The method of claim 25, wherein, In step (2), the molar ratio of phenoxy derivatives: amide derivatives: sulfonic acid derivatives: phosphate derivatives: pyrrole derivatives: furan derivatives in the reaction components is (0.7-1.5): (1.1-2.5): (1.6-3.4): (0.7-1.4): (1.5-2.9): (0.23-0.49). 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 (2), the reaction treatment includes: immersing the solution containing the reaction components in contact with the resin white ball matrix after the adsorption treatment in step (1), with a liquid-to-solid volume ratio of 1-3, a treatment temperature of 60-80℃, and a treatment time of 1.5-3h.

27. The method according to claim 26, 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.

28. The method according to claim 26, 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.

29. The method according to claim 20, wherein, Step (2) further includes post-reaction treatment of the reaction product in post-treatment agent B, which is selected from at least one of anhydrous ethanol, anhydrous acetone and anhydrous methanol.

30. The method according to claim 29, wherein, The post-reaction treatment conditions include: soaking temperature of 60-80℃, soaking time of 1-2 hours, and soaking times of 1-3 times.

31. The method according to claim 29, wherein, The post-treatment agent B is anhydrous ethanol.

32. The method according to claim 29, wherein, The post-reaction processing also includes drying the post-reaction product.

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

34. A method for producing an aqueous solution of a low-carbon alcohol, wherein, The method includes: in the presence of a hydration catalyst, contacting a low-carbon olefin reaction raw material with water to carry out a hydration reaction to obtain a low-carbon alcohol aqueous solution, wherein the hydration catalyst is a low-carbon olefin hydration catalyst according to any one of claims 1-5 or a low-carbon olefin hydration catalyst prepared by any one of claims 6-33.

35. The method according to claim 34, wherein, Based on the total amount of olefin reaction feedstock, the content of low-carbon olefins in the olefin reaction feedstock is 10-100% by volume.

36. The method according to claim 35, wherein, The low-carbon olefins are C3 and / or C4 olefins; And / or, the conditions for the hydration reaction include: a temperature of 120-160°C, a pressure of 2000-4000 kPa (gauge pressure), and a volume hourly space velocity (VHSV) of 0.5-3 h⁻¹ for the olefin reactants. -1 The molar ratio of water to olefin reactants is 6-15.

37. The method of claim 36, wherein, The low-carbon olefin hydration reaction is carried out in a fixed-bed reactor.