CN119657221B

CN119657221B - Low-carbon olefin hydration catalysts and their preparation methods, and methods for producing low-carbon alcohol aqueous solutions.

Info

Publication number: CN119657221B
Application number: CN202311218059.3A
Authority: CN
Inventors: 宋海峰; 黄谢君; 钟源
Original assignee: Sinopec Shanghai Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Current assignee: Sinopec Shanghai Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2023-09-20
Filing date: 2023-09-20
Publication date: 2025-10-31
Anticipated expiration: 2043-09-20
Also published as: CN119657221A

Abstract

本发明涉及低碳烯烃水合的技术领域，公开了一种低碳烯烃水合催化剂及其制备方法、生产低碳醇水溶液的方法。一种低碳烯烃水合催化剂，其中，所述水合催化剂包括树脂白球基体、吸附层和反应层，所述吸附层接枝于树脂白球基体的外表面，所述反应层接枝于树脂白球基体的内表面；所述吸附层中含有苯氧基、酰胺基、吡咯基、呋喃基；所述反应层中含有苯氧基、酰胺基、磺酸基、磷酸基、吡咯基、呋喃基。该低碳烯烃水合催化剂能够提高水烯的接触效果、促进水合平衡的移动、降低烯烃的叠合损失。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 the loss of olefin aggregation.

Description

Low-carbon olefin hydration catalyst, preparation method thereof and method for producing low-carbon alcohol aqueous solution

Technical Field

The invention relates to the technical field of low-carbon olefin hydration, in particular to a low-carbon olefin hydration catalyst, a preparation method thereof and a method for producing a low-carbon alcohol aqueous solution.

Background

Olefin hydration is one of the important organic reactions that can be used to prepare alcohols such as sec-butanol, isopropanol, cyclohexanol, and the like. The traditional olefin hydration generally adopts an indirect sulfuric acid hydration method, and the method has serious equipment corrosion problems, waste acid treatment problems and the like and is gradually replaced by a catalytic direct hydration method. The catalytic direct hydration method generally can directly generate corresponding low-carbon alcohol by the low-carbon olefin under the action of a catalyst of solid acid.

The solid acid catalysts commonly used in the art may be acidic zeolites, moO ₃/WO₃, ion exchange resins (e.g., DOWEXR, AMBERLYSTR, and D008 resins) and supported solid acid catalysts (e.g., phosphoric acid supported on silica). In order to promote the improvement of the conversion rate of olefin hydration reaction, patent application CN110665542A discloses a catalyst for isobutene hydration reaction and a preparation method thereof, wherein the catalyst adopts styrene, p-ethylstyrene, m-ethylstyrene, p-divinylbenzene and m-divinylbenzene as comonomers, and the comonomers are combined with a pore-forming agent, an initiator and a dispersing agent to perform suspension copolymerization to obtain copolymer spheres, and the copolymer spheres are prepared by extraction, drying, screening and sulfonation. The method is an in-situ modification method of the catalyst framework, the modification does not fully utilize the huge inner surface of the resin, meanwhile, the acid center adopts a conventional sulfonic group, the acid strength is high, and more side reactions are easy to generate when the reaction conditions are controlled improperly.

In view of the defects of the activity and the structure of the existing hydration catalyst, the development of the novel olefin hydration catalyst mainly improves the selective matching property of the catalytic hydration activity and the catalyst structure to the components by optimizing the catalyst formula and the preparation method, reduces the superposition catalysis effect of the active center of the catalyst on the olefin, further reduces the olefin polymerization, improves the yield of low-carbon alcohol and promotes the hydration balance to move rightwards.

Disclosure of Invention

The invention aims to solve the problems of insufficient low-carbon olefin hydration catalyst and low conversion rate in the low-carbon olefin hydration process in the prior art, and provides a low-carbon olefin hydration catalyst, a preparation method thereof and a method for producing a low-carbon alcohol aqueous solution.

In order to achieve the above purpose, the first aspect of the present invention provides a light olefin hydration catalyst, wherein the hydration catalyst comprises a resin white sphere matrix, an adsorption layer and a reaction layer, the adsorption layer is grafted on the outer surface of the resin white sphere matrix, the reaction layer is grafted on the inner surface of the resin white sphere matrix, the adsorption layer contains phenoxy, amido, pyrrolyl and furyl, and the reaction layer contains phenoxy, amido, sulfonic acid, phosphoric acid, pyrrolyl and furyl.

The second aspect of the invention provides a preparation method of a light olefin hydration catalyst, wherein the method comprises the following steps:

(1) Carrying out adsorption treatment on the outer surface of the resin white ball matrix in the presence of an adsorption component to obtain the resin white ball matrix after the adsorption treatment;

(2) In the presence of a reaction component, carrying out reaction treatment on the inner surface of the resin white ball matrix subjected to the adsorption treatment in the step (1) to obtain a low-carbon olefin hydration catalyst;

the adsorption component contains phenoxy, amido, pyrrolyl and furyl, and the reaction component contains phenoxy, amido, sulfonic acid, phosphoric acid, pyrrolyl and furyl.

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

The inventor of the invention finds that in the research process of low-carbon olefin hydration, the existing solid acid catalysts such as strong acid resin, ZSM-5 molecular sieve and the like are adopted to catalyze olefin hydration, the single-pass conversion rate of olefin is obviously lower than the thermodynamic equilibrium conversion rate, and the single-pass conversion rate of olefin is mainly influenced by factors in two aspects of mass transfer and chemical equilibrium. The low-carbon olefin is generally insoluble in water, and even if the ratio of the water to the olefin is greatly excessive, the low-carbon olefin and the water to the olefin are still incompatible, and the effect is not obvious from the aspect that the reaction raw materials are excessive to further push the hydration balance to move right. The solid acid catalyst has good combination property with water, but has poor compatibility with olefin, and the olefin on the catalytic surface of the solid acid after water saturation is difficult to adsorb, so that double bonds are difficult to activate.

The low-carbon olefin hydration catalyst provided by the invention solves the problems of poor contact of the water olefin on the catalytic surface and low yield and selectivity of low-carbon alcohol in the prior art in terms of microscopic mechanism. The hydration catalyst is preferably prepared by further modifying resin white balls with low crosslinking degree as a matrix, and the lower crosslinking degree can realize better swelling effect and provide possibility for good diffusion of reaction raw materials and reaction products.

The hydration catalyst provided by the invention is characterized in that an adsorption layer is grafted on the outer surface of a resin white ball substrate, and a reaction layer is grafted on the inner surface of the resin white ball substrate. The adsorption layer is grafted with a high-concentration alkenyl group, a hydrophilic group with a certain concentration and a low-carbon alcohol rejection group, and the high-concentration alkenyl group enables the outer surface of the resin white ball matrix to enrich low-concentration olefin in the aqueous emulsion and enable the low-concentration olefin to diffuse into the catalyst along the pore canal. The huge inner surface of the resin is grafted with a reaction layer which is a main place of olefin hydration reaction, the layer is grafted with high-concentration hydrophilic groups (used for enriching water, the water is diffused from a liquid phase main body to the inner surface through the outer surface of the catalyst by matching the hydrophilic groups at different concentrations of the outer surface and the inner surface), catalytic groups (used for activating olefin, the acid strength is reasonably regulated by the cooperative matching of the groups), low-carbon alcohol rejection groups (used for transmitting low-carbon alcohol generated by the reaction to the liquid phase main body through the outer surface by matching the rejection groups at different concentrations of the inner surface and the outer surface so as to promote the hydration reaction to move rightwards), and enophilic groups (used for enriching olefin and receiving the olefin enriched by the outer surface). The water in the mixed liquid phase main body is continuously enriched to the reaction layer from the liquid phase main body based on the gradient change of the hydrophilic intensity in the adsorption layer and the reaction layer, excessive water is provided for the hydration reaction microenvironment, the reaction layer is grafted with a high concentration of catalytic groups, after the olefin molecules are continuously captured from the mixed liquid phase to the inner surface through the outer surface by the alkenyl groups, the olefin and water molecules enriched on the inner surface generate hydration reaction under the activation of the catalytic groups with proper acid intensity, and the low-carbon alcohol generated by hydration is continuously diffused to the liquid phase main body from the inner surface through the outer surface under the pushing of the low-carbon alcohol repulsive groups, so that the hydration balance moves rightwards. The hydrophilic groups in the adsorption layer and the reaction layer realize large excess of microscopic water, so that the water-to-olefin ratio is reduced, the reduction of the water-to-olefin ratio simultaneously promotes the enrichment of olefin molecules on the enophilic groups, and further promotes the movement of hydration balance. The acid strength of the inner surface of the catalyst is proper, so that the side reaction of olefin superposition is inhibited, the resin pore canal is not easy to be blocked and deactivated, and the activity stability of the catalyst is good.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

In the invention, each group and the content thereof in the adsorption layer and the reaction layer are measured by infrared spectrum, the specific test condition is KBr tabletting, scanning is carried out within the range of 400cm ^-1-4000cm^-1, the content of each group in the adsorption layer and the reaction layer is obtained by stepwise measurement in the preparation process, namely, after the adsorption treatment is finished, the content of each group in the adsorption layer is measured by washing and drying, and then after the reaction treatment is finished, the content of each group in the adsorption layer is measured by washing and drying.

In the invention, the resin white ball matrix has a sphere or near-sphere structure with pore channels inside.

The invention provides a low-carbon olefin hydration catalyst, which comprises a resin white ball matrix, an adsorption layer and a reaction layer, wherein the adsorption layer is grafted on the outer surface of the resin white ball matrix, the reaction layer is grafted on the inner surface of the resin white ball matrix, the adsorption layer contains phenoxy, amido, pyrrolyl and furyl, and the reaction layer contains phenoxy, amido, sulfonic, phosphoric, pyrrolyl and furyl.

In the present invention, the specific kind of the resin white ball substrate is not particularly limited, and the resin white ball substrate conventionally defined in the art is applicable to the present invention. Preferably, the resin white ball matrix is styrene-divinylbenzene resin.

In the present invention, preferably, the styrene-divinylbenzene resin has a crosslinking degree of 3 to 6%.

In the present invention, preferably, the content of dangling double bonds of the resin white sphere matrix is 10-20mmol/g based on the dry resin white sphere matrix.

In the present invention, it is preferable that the average pore diameter of the resin white sphere matrix is 15 to 40nm.

In the present invention, the source of the resin white ball matrix is not particularly limited, and it may be commercially available or may be prepared according to a preparation method conventionally defined in the art, and the present invention is not particularly limited, and for example, a general-purpose resin white ball obtained by suspension polymerization may be purchased, and the present invention may be adapted as long as the above-mentioned parameters are satisfied.

In the invention, preferably, the total amount of the dry resin white ball matrix and the adsorption layer is taken as a reference, the content of phenoxy in the adsorption layer is 1.6-3.2mmol/g, the content of amide groups is 0.6-1.2mmol/g, the content of pyrrole groups is 0.85-1.7mmol/g, and the content of furan groups is 0.15-0.3mmol/g. By grafting an adsorption layer on the outer surface of the resin white ball matrix and controlling the content of each group in the adsorption layer, the olefin in the water-olefin emulsion can be enriched, and the movement of low-carbon alcohol into the liquid phase main body can be promoted.

In the invention, preferably, the total amount of the dry resin white ball matrix, the adsorption layer and the reaction layer is taken as a reference, the content of phenoxy in the reaction layer is 0.6-1.2mmol/g, the content of amide groups is 1-2mmol/g, the content of sulfonic acid groups is 1.4-2.8mmol/g, the content of phosphoric acid groups is 0.55-1.1mmol/g, the content of pyrrole groups is 1.25-2.5mmol/g, and the content of furan groups is 0.2-0.4mmol/g. By grafting a reaction layer on the inner surface of the resin white ball matrix and controlling the content of each group in the reaction layer, the contact and reaction of the water and the alkene can be promoted, and the mass transfer of the low carbon alcohol generated by the reaction to the outer surface can be realized.

In the present invention, in the step (1), the types, materials, characteristic parameters and sources of the resin white ball matrix are described in the first aspect, and will not be described herein.

In the present invention, preferably, in the step (1), the adsorption treatment grafts an adsorption layer on the outer surface of the resin white sphere matrix, and the adsorption layer contains phenoxy, amide, pyrrole and furan groups.

In the present invention, the content of each group in the adsorption layer is already described in the first aspect, and will not be described herein.

In the present invention, preferably, in the step (1), the adsorbing component is provided from a solution containing the adsorbing component, the solution containing the adsorbing component, the first initiator, the first solvent and the polyether.

In the invention, in the step (1), preferably, the mass ratio of the adsorption component to the first initiator to the first solvent to the polyether is (2.5-4.8): 0.1-0.2): 90-94): 3.2-4.6.

In the present invention, it is preferable that the polyether has an average molecular weight of 600 to 1500.

In the invention, the selection range of the type of the first solvent is wide, and the selection can be carried out by a person skilled in the art according to actual requirements. Preferably, in step (1), the first solvent is selected from at least one of toluene, para-xylene, meta-xylene and ortho-xylene.

In the invention, the selection range of the type of the first initiator is wide, and the selection can be carried out by a person skilled in the art according to actual requirements. Preferably, in the step (1), the first initiator is at least one selected from azo, organic peroxy, inorganic peroxy and redox initiators, more preferably at least one selected from azobisisobutyronitrile, benzoyl peroxide, potassium persulfate and hydrogen peroxide, and still more preferably benzoyl peroxide.

In the present invention, preferably, in the step (1), the adsorption component is provided by a phenoxy derivative, an amide derivative, a pyrrole derivative and a furan derivative.

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

In the present invention, the specific type of the phenoxy derivative is not particularly limited. Preferably, the phenoxy group is provided by a phenoxy derivative, preferably at least one of 4-methoxystyrene, allylphenyl ether and phenyl vinyl ether.

In the present invention, the specific type of the amide derivative is not particularly limited. Preferably, the amide group is provided by an amide derivative, preferably at least one of N, N' -dihydroxyethyl bisacrylamide, N-methylenebisacrylamide, and hexamethylenebisacrylamide.

In the present invention, the specific type of the azole derivative is not particularly limited. Preferably, the pyrrolyl group is provided by pyrrole derivatives, preferably at least one of 3-isopropenyl-1-methyl-pyrrole, 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole and 5-allyl-4-methoxy-1, 5-dihydro-2H-pyrrol-2-one.

In the present invention, the specific type of the furan derivative is not particularly limited. Preferably, the furyl group is provided by a furanic derivative, preferably by 2- (1-propen-2-yl) furan and/or 2- (2-pentenyl) furan.

In the present invention, the manner and condition of the adsorption treatment are not particularly limited. Preferably, in the step (1), the adsorption treatment comprises the step of soaking and contacting a solution containing an adsorption component with the resin white ball matrix, wherein the liquid-solid volume ratio is 1-3, the treatment temperature is 60-80 ℃, and the treatment time is 1.5-3h. In the invention, the outer surface of the resin white ball matrix is treated by adopting the solution containing the adsorption component, the outer edge of a pore canal of the resin white ball matrix close to the outer surface is plugged by polyether (polyether exists in the form of gel solution) in the adsorption treatment process, and the adsorption treatment only treats the outer surface of the resin white ball matrix, so that dangling double bonds on the outer surface of the resin white ball matrix are completely reacted, further, the outer surface is not grafted with the reaction groups again in the subsequent reaction treatment process, and the influence of the reaction treatment on the outer surface of the resin white ball matrix is avoided.

In the present invention, preferably, the step (1) further comprises subjecting the adsorption product after the adsorption treatment to an adsorption post-treatment in a post-treatment agent a. In the present invention, the specific mode of operation of the adsorption post-treatment is not particularly limited, and the adsorption product after the adsorption treatment may be subjected to an isovolumetric displacement in the post-treatment agent a.

In the present invention, the type of the post-treatment agent a is not particularly limited. Preferably, the aftertreatment agent a is benzene and/or acetonitrile, more preferably acetonitrile.

In the invention, the condition selection range of the adsorption post-treatment is wider, polyether residues attached to the outer surface of the adsorption treatment matrix can be removed through the adsorption post-treatment, and preparation is provided for subsequent further modification. Preferably, the conditions of the post-adsorption treatment comprise a soaking temperature of 50-70 ℃, a soaking time of 0.5-1h and a soaking time of 1-3 times. In the present invention, the number of soaking times is the aforementioned equivalent volume substitution times.

In the present invention, preferably, in the step (2), the reaction treatment grafts a reaction layer on the inner surface of the resin white sphere substrate after the adsorption treatment in the step (1), and the reaction layer contains phenoxy, amide, sulfonic acid, phosphoric acid, pyrrole and furan groups.

In the present invention, the content of each group in the reaction layer is already described in the first aspect, and will not be described herein.

In the present invention, preferably, in the step (2), the reaction component is provided from a reaction component-containing solution containing the reaction component, the second initiator, and the second solvent.

In the present invention, the content of each component in the solution containing the reaction component is not particularly limited. Preferably, in the 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.

In the present invention, preferably, the reaction component is selected from the group consisting of phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives.

In the present invention, the amount of each derivative in the reaction component is not particularly limited in order to satisfy the content of the desired group. Preferably, in the step (2), the molar ratio of the phenoxy derivative to the amide derivative to the sulfonic acid derivative to the phosphoric acid derivative to the pyrrole derivative to the furan derivative 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).

In the present invention, the selection of the specific types of the phenoxy derivative, the amide derivative, the pyrrole derivative and the furan derivative in the step (2) may be the same as or different from the types of the derivatives in the step (1), and preferably the same.

In the present invention, the phosphoric acid group is preferably provided by a phosphoric acid derivative, and more preferably by at least one of (2-fluoro-3, 7-dimethyloct-1, 6-dien-3-yl) phosphonohydrogen phosphate, [ 2-methyl-2- (4-methylpent-3-enyl) cyclopropyl ] methylphosphono-hydrogen phosphate, and 2- (phosphoryloxy) propane-1, 3-diyl dimethacrylate.

In the present invention, the sulfonic acid group is preferably provided by a sulfonic acid derivative, and more preferably by at least one of 4-hydroxy-6- (prop-2-enylamido) 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 (sulfooxy) phenyl ] vinyl } phenyl hydrosulfate.

In the present invention, the type of the second solvent is not particularly limited, and may be the same as or different from the type of the first solvent.

In the present invention, the type of the second initiator is not particularly limited, and may be the same as or different from the type of the first initiator.

In the present invention, the mode and condition of the reaction treatment are not particularly limited. Preferably, in the step (2), the reaction treatment comprises the steps of soaking and contacting the solution containing the reaction components with the resin white ball matrix subjected to the adsorption treatment in the step (1), wherein the liquid-solid volume ratio is 1-3, the treatment temperature is 60-80 ℃, and the treatment time is 1.5-3h.

In the present invention, preferably, step (2) further comprises subjecting the reaction treatment product to a reaction post-treatment in a post-treatment agent B. Preferably, the reaction product after the reaction treatment is subjected to the isovolumetric displacement in the aftertreatment agent B.

In the present invention, the type of the post-treatment agent B is selected in a wide range. Preferably, the post-treatment agent B is at least one selected from the group consisting of absolute ethanol, absolute acetone, and absolute methanol, and further preferably is absolute ethanol.

In the invention, the condition selection range of the post-reaction treatment is wider, and the residual monomer in the pore canal is removed and the pore canal structure is improved through the post-reaction treatment. Preferably, the conditions of the post-reaction treatment comprise a soaking temperature of 60-80 ℃, a soaking time of 1-2h and a soaking frequency of 1-3 times. In the present invention, the number of soaking times is the aforementioned equivalent volume substitution times.

In the present invention, preferably, the post-reaction treatment further comprises drying the post-reaction treatment product.

In the present invention, the condition selection range for the drying treatment is wide. Preferably, the drying treatment conditions include a drying temperature of 100-120 ℃ and a drying time of 0.5-1h. In the present invention, the drying treatment is preferably performed under a nitrogen atmosphere.

The third aspect of the invention provides a method for producing a low-carbon alcohol aqueous solution, wherein the method comprises the step of contacting a low-carbon olefin reaction raw material with water in the presence of a hydration catalyst to carry out hydration reaction to obtain the low-carbon alcohol aqueous solution, and the hydration catalyst is the low-carbon olefin hydration catalyst in the first aspect or the low-carbon olefin hydration catalyst prepared by the preparation method in the second aspect.

In the present invention, the content of the low-carbon olefin in the olefin reaction raw material is preferably 10 to 100% by volume based on the total amount of the olefin reaction raw material.

In the present invention, preferably, the lower olefins are C3 and/or C4 olefins.

In the present invention, preferably, the low-carbon olefin hydration reaction is performed in a fixed bed reactor.

In the present invention, the conditions for the hydration reaction are selected in a wide range. Preferably, the conditions of the hydration reaction include a temperature of 120-160 ℃, a pressure of 2000-4000kPa in terms of gauge pressure, a volume space velocity of the olefin reaction feedstock of 0.5-3h ^-1, and a molar ratio of water to olefin reaction feedstock of 6-15.

In the present invention, it is preferred that the once-through olefin conversion is greater than 32% and the low carbon alcohol selectivity is greater than 92%.

The present invention will be described in detail by examples.

In the present invention, the content of each group in the reaction layer and the adsorption layer was measured by the test method described above.

In the invention, a 20A high-performance liquid chromatography system (Japanese island fluid company, an automatic sampler, 10AT and 10AD pumps and a 20A multi-wavelength ultraviolet detector) is adopted for component analysis, and ACQUITYUPLC/XevoG2QTOF ultra-high-performance liquid chromatography high-resolution tandem mass spectrometry (U.S. Wo-tech, an automatic sampler and a diode array ultraviolet detector) is adopted for component analysis. High performance liquid chromatography conditions were ZorbaxEclipsePlusC 18:18 (4.6 mm. Times.150 mm,5 μm), mobile phase: water (0.06% v phosphoric acid): acetonitrile=95:5, flow rate: 1.0mL/min, detection wavelength: 210nm, column temperature: 35 ℃, sample injection amount: 1. Mu.L. Ultra-high performance liquid chromatography conditions were HSST3 (2.1 mm. Times.100 mm,1.7 μm), mobile phase water, methanol, gradient elution (positive ion mode) 0minV (water): V (methanol) =85:15, V (water) after 2.5min V (methanol) =55:35, V (water) after 4min V (methanol): 10:90, flow rate 0.45mL/min, gradient elution (negative ion mode) 0min with V (water): V (methanol): 70:30, V (water) after 2.5min V (methanol) =55:35, V (water) after 3.5min V (methanol) =10:90, flow rate 0.45mL/min, column temperature 30℃and sample injection amount 3. Mu.L. The mass spectrum conditions are electrospray ionization source (ESI), positive ion or negative ion scanning mode, capillary voltage of 2kV, taper hole voltage of 30eV, ion source temperature of 120 ℃ and desolventizing temperature of 450 ℃, taper hole gas flow rate of 50L/h and desolventizing gas (N ₂) flow rate of 900L/h.

Example 1

The olefin reaction raw material composition in this example comprises, by volume, 33.0% of isobutane, 8.7% of butane, 56.3% of normal butene and 2.0% of pentane.

In the embodiment, the resin white ball matrix is a general resin white ball obtained by purchased suspension polymerization, the product index is that the resin white ball matrix is styrene-divinylbenzene resin, the crosslinking degree of the styrene-divinylbenzene resin is 4.5 percent, the content of dangling double bonds of the dry resin white ball is 15.1mmol/g, and the average pore diameter is 27.6nm.

In the step (1), the solution containing the adsorption component is contacted with the resin white ball matrix, so that the outer surface of the resin white ball matrix is grafted with the adsorption layer. In the solution containing the adsorption component, the mass ratio of the adsorption component to the first initiator to the first solvent to the polyether (average molecular weight is 1000) is 3.6:0.1:92:3.9. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorption component contains phenoxy derivatives, amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the pyrrole derivatives to the furan derivatives is 2.9:1.1:1.6:0.26. The phenoxy derivative allyl phenyl ether is provided. The amide derivatives are provided by N, N-methylenebisacrylamide. Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The adsorption treatment condition comprises that the solution containing the adsorption component is in soaking contact with the resin white ball matrix in the step (1), the liquid-solid volume ratio is 2, the treatment temperature is 70 ℃, and the treatment time is 2.25h. The total amount of the dry resin white ball matrix and the adsorption layer is taken as a reference, the content of phenoxy in the adsorption layer is 2.3mmol/g, the content of amide group is 0.9mmol/g, the content of pyrrole group is 1.3mmol/g, and the content of furyl is 0.21mmol/g.

The step (1) also comprises the step of carrying out adsorption post-treatment on the resin white ball matrix after the adsorption component treatment in the post-treatment agent A. The post-treatment agent A is acetonitrile. The conditions of the post-adsorption treatment include soaking treatment time of 0.7h at 60 ℃ and 2 times of isovolumetric displacement.

In the step (2), the solution containing the reaction components is contacted with the resin white ball matrix after the adsorption treatment, so that the inner surface of the resin white ball matrix after the adsorption component treatment is grafted with the reaction layer. In the solution containing the reaction component, the mass ratio of the reaction component to the second initiator to the second solvent is 3.8:0.1:92. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components comprise phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 1.1:1.3:2.5:0.9:2.2:0.36. The phenoxy derivative is provided by allyl phenyl ether. The amide derivatives are provided by N, N-methylenebisacrylamide. Phosphoric acid derivatives are provided by [ 2-methyl-2- (4-methylpent-3-enyl) cyclopropyl ] methylphosphonic acid hydrogen phosphate. The sulfonic acid derivatives are provided by (Z) -4', 4' - (ethylene-1, 2-diyl) bis ([ [1,1' -biphenyl ] -4-sulfonic acid ]). Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The reaction treatment conditions comprise that the solution containing the reaction components is soaked and contacted with the resin white ball matrix after the adsorption treatment in the step (1), the liquid-solid volume ratio is 2, the treatment temperature is 70 ℃, and the treatment time is 2.3 hours. The total amount of the dry resin white ball matrix, the adsorption layer and the reaction layer is taken as a reference, the content of phenoxy in the reaction layer is 0.9mmol/g, the content of amide groups is 1.1mmol/g, the content of sulfonic acid groups is 2.0mmol/g, the content of phosphoric acid groups is 0.74mmol/g, the content of pyrrole groups is 1.8mmol/g, and the content of furyl groups is 0.3mmol/g.

Step (2) further comprises subjecting the reaction treatment product to a reaction aftertreatment in aftertreatment agent B. The post-treatment agent B is absolute ethyl alcohol. The conditions of the post-reaction treatment comprise a soaking temperature of 70 ℃, a soaking time of 1.5h, an equal volume soaking displacement of 2 times, a drying temperature of 110 ℃ and a drying time of 0.7h.

The prepared low-carbon olefin hydration catalyst is applied to low-carbon olefin hydration, the low-carbon olefin hydration catalyst is filled in a fixed bed reactor, and an olefin and desalted water mixture contacts with the low-carbon olefin hydration catalyst to carry out olefin hydration reaction to obtain an aqueous solution containing low-carbon alcohol. The conditions for the hydration reaction of the olefin include a temperature of 140 ℃, a pressure of 3000kPa in gauge, a volumetric space velocity of the olefin reaction feed of 1.7h ^-1, and a molar ratio of water to olefin reaction feed of 10.

The single pass olefin conversion of the olefin hydration was 37.5% and the low carbon alcohol selectivity was 95.3%.

Example 2

The olefin reaction feed of example 1 was selected.

In the embodiment, the resin white ball matrix is general resin white ball obtained by purchasing suspension polymerization, the resin white ball matrix is styrene-divinylbenzene resin, the crosslinking degree of the styrene-divinylbenzene resin is 3.2%, the content of dangling double bonds of the dry resin white ball is 18.7mmol/g, and the average pore diameter is 38.4nm.

In the step (1), the solution containing the adsorption component is contacted with the resin white ball matrix, so that the outer surface of the resin white ball matrix is grafted with the adsorption layer. In the solution containing the adsorption component, the mass ratio of the adsorption component to the first initiator to the first solvent to the polyether (average molecular weight: 700) was 4.7:0.2:91:3.3. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorption component contains phenoxy derivatives, amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the pyrrole derivatives to the furan derivatives is 3.8:1.4:2.0:0.36. The phenoxy derivative is provided by allyl phenyl ether. The amide derivatives are provided by N, N-methylenebisacrylamide. Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The adsorption treatment condition comprises that the solution containing the adsorption component is soaked and contacted with the resin white ball matrix in the step (1), the liquid-solid volume ratio is 3, the treatment temperature is 78 ℃, and the treatment time is 2.7h. The total amount of the dry resin white ball matrix and the adsorption layer is taken as a reference, the content of phenoxy in the adsorption layer is 3.1mmol/g, the content of amide group is 1.1mmol/g, the content of pyrrole group is 1.6mmol/g, and the content of furyl is 0.29mmol/g.

The step (1) further comprises the step of carrying out adsorption post-treatment on the resin white ball matrix subjected to the adsorption treatment in a post-treatment agent A. The post-treatment agent A is acetonitrile. The conditions of the post-adsorption treatment include soaking treatment time of 68 ℃ for 0.9h and 3 times of isovolumetric displacement.

In the step (2), the solution containing the reaction components is contacted with the resin white ball matrix after the adsorption treatment, so that the inner surface of the resin white ball matrix after the adsorption treatment is grafted with the reaction layer. In the solution containing the reaction component, the mass ratio of the reaction component to the second initiator to the second solvent is 4.8:0.2:91. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components comprise phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 1.4:2.4:3.3:1.3:2.8:0.47. The phenoxy derivative is provided by allyl phenyl ether. The amide derivatives are provided by N, N-methylenebisacrylamide. Phosphoric acid derivatives are provided by [ 2-methyl-2- (4-methylpent-3-enyl) cyclopropyl ] methylphosphonic acid hydrogen phosphate. The sulfonic acid derivatives are provided by (Z) -4', 4' - (ethylene-1, 2-diyl) bis ([ [1,1' -biphenyl ] -4-sulfonic acid ]). Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The reaction treatment conditions comprise that the solution containing the reaction components is soaked and contacted with the resin white ball matrix after the adsorption treatment in the step (1), the liquid-solid volume ratio is 3, the treatment temperature is 78 ℃, and the treatment time is 2.6h. The total amount of the dry resin white ball matrix, the adsorption layer and the reaction layer is taken as a reference, the content of phenoxy in the reaction layer is 1.1mmol/g, the content of amide groups is 1.9mmol/g, the content of sulfonic acid groups is 2.6mmol/g, the content of phosphoric acid groups is 1.02mmol/g, the content of pyrrole groups is 2.2mmol/g, and the content of furyl groups is 0.37mmol/g.

Step (2) further comprises subjecting the reaction treatment product to a reaction aftertreatment in aftertreatment agent B. The post-treatment agent B is absolute ethyl alcohol. The conditions for post-reaction treatment include a soaking temperature of 78 ℃, a soaking time of 1.7h, an isovolumetric soaking displacement of 3 times, a drying temperature of 117 ℃ and a drying time of 0.9h.

The reaction procedure of example 1 was followed except that the conditions for the hydration reaction of the olefin included a temperature of 130℃and a pressure of 2500kPa in gauge, the volume space velocity of the olefin reaction feed was 0.6h ^-1, and the molar ratio of water to the olefin reaction feed was 14.

The single pass olefin conversion of olefin hydration was 40.2% and the low carbon alcohol selectivity was 97.4%.

Example 3

The olefin reaction feed of example 1 was selected.

In the embodiment, the resin white ball matrix is general resin white ball obtained by purchasing suspension polymerization, the resin white ball matrix is styrene-divinylbenzene resin, the crosslinking degree of the styrene-divinylbenzene resin is 5.8%, the content of dangling double bonds of the dry resin white ball is 10.7mmol/g, and the average pore diameter is 16.4nm.

In the step (1), the solution containing the adsorption component is contacted with the resin white ball matrix, so that the outer surface of the resin white ball matrix is grafted with the adsorption layer. In the solution containing the adsorption component, the mass ratio of the adsorption component to the first initiator to the first solvent to the polyether (average molecular weight is 1400) is 2.6:0.2:93:4.5. The first solvent is toluene. The first initiator is benzoyl peroxide. The adsorption component contains phenoxy derivatives, amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the pyrrole derivatives to the furan derivatives is 2.0:0.8:1.2:0.18. The phenoxy derivative is provided by allyl phenyl ether. The amide derivatives are provided by N, N-methylenebisacrylamide. Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The adsorption treatment condition comprises that the solution containing the adsorption component is soaked and contacted with the resin white ball matrix in the step (1), the liquid-solid volume ratio is 1, the treatment temperature is 62 ℃, and the treatment time is 1.7h. The total amount of the dry resin white ball matrix and the adsorption layer is taken as a reference, the content of phenoxy in the adsorption layer is 1.7mmol/g, the content of amide groups is 0.68mmol/g, the content of pyrrole groups is 1.02mmol/g, and the content of furyl groups is 0.15mmol/g.

The step (1) further comprises the step of carrying out adsorption post-treatment on the resin white ball matrix subjected to the adsorption treatment in a post-treatment agent A. The post-treatment agent A is acetonitrile. The conditions of the post-adsorption treatment include soaking treatment time of 52 ℃ for 0.6h and 3 times of isovolumetric displacement.

In the step (2), the solution containing the reaction components is contacted with the resin white ball matrix after the adsorption treatment, so that the inner surface of the resin white ball matrix after the adsorption treatment is grafted with the reaction layer. In the solution containing the reaction component, the mass ratio of the reaction component to the second initiator to the second solvent is 2.8:0.2:93. The second solvent is toluene. The second initiator is benzoyl peroxide. The reaction components comprise phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the phenoxy derivatives to the amide derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 0.8:1.2:1.7:0.8:1.6:0.25. The phenoxy derivative is provided by allyl phenyl ether. The amide derivatives are provided by N, N-methylenebisacrylamide. Phosphoric acid derivatives are provided by [ 2-methyl-2- (4-methylpent-3-enyl) cyclopropyl ] methylphosphonic acid hydrogen phosphate. The sulfonic acid derivatives are provided by (Z) -4', 4' - (ethylene-1, 2-diyl) bis ([ [1,1' -biphenyl ] -4-sulfonic acid ]). Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. The furan derivative is provided by 2- (1-propylene-2-yl) furan. The reaction treatment conditions comprise that the solution containing the reaction components is soaked and contacted with the resin white ball matrix after the adsorption treatment in the step (1), the liquid-solid volume ratio is 1, the treatment temperature is 62 ℃, and the treatment time is 1.7h. The total amount of the dry resin white ball matrix, the adsorption layer and the reaction layer is taken as a reference, the content of phenoxy in the reaction layer is 0.7mmol/g, the content of amide groups is 1.05mmol/g, the content of sulfonic acid groups is 1.49mmol/g, the content of phosphoric acid groups is 0.7mmol/g, the content of pyrrole groups is 1.4mmol/g, and the content of furyl groups is 0.22mmol/g.

Step (2) further comprises subjecting the reaction treatment product to a reaction aftertreatment in aftertreatment agent B. The post-treatment agent B is absolute ethyl alcohol. The conditions for post-reaction treatment include a soaking temperature of 63 ℃, a soaking time of 1.4h, an isovolumetric soaking displacement of 1 time, a drying temperature of 103 ℃ and a drying time of 0.6h.

The reaction procedure of example 1 was followed except that the conditions for the hydration reaction of the olefin included a temperature of 150℃and a pressure of 3600kPa in terms of gauge pressure, the volume space velocity of the olefin reaction feed was 2.5h ^-1, and the molar ratio of water to the olefin reaction feed was 8.

The single pass olefin conversion of the olefin hydration was 33.7% and the low carbon alcohol selectivity was 93.5%.

Example 4

The procedure of example 2 was followed except that the olefin feed composition in this example, in volume percent, comprised 15.9% isobutane, 7.1% n-butane, 75.7% n-butene, and 1.3% pentane.

Following the reaction procedure and conditions of example 2, the single pass olefin conversion of the olefin hydration was 43.6% and the low carbon alcohol selectivity was 97.5% in the olefin hydration reactor.

Example 5

The procedure of example 2 was followed except that the olefin feed composition in this example, in volume percent, comprised 6.3% isobutane, 2.4% n-butane, 90.9% n-butene, and 0.4% pentane.

Following the reaction procedure and conditions of example 2, the single pass olefin conversion of the olefin hydration was 45.8% and the low carbon alcohol selectivity was 97.6% in the olefin hydration reactor.

Example 6

The procedure of example 2 was followed except that the olefin feed composition in this example, by volume, was composed of, isobutane 52.1%, n-butane 13.2%, n-butene 29.4% and pentane 5.3%.

Following the reaction procedure and conditions of example 2, the single pass olefin conversion of the olefin hydration was 38.2% and the low carbon alcohol selectivity was 97.1% in the olefin hydration reactor.

Comparative example 1

The olefin reaction feed was selected and used in example 5.

According to the reaction method of example 5, the olefin hydration reactor is filled with the Suqing macroporous strong acid resin D002GH, the reaction temperature is 170 ℃, the reaction pressure is 85 kg, the reaction mass space velocity is 1h ^-1, the single pass conversion of n-butene is 12.3%, and the selectivity of low carbon alcohol is 95.2%.

Comparative example 2

The procedure of example 3 was followed, except that the resin white sphere substrate was directly subjected to the step (2) reaction treatment using the reaction component without performing the step (1) adsorption treatment.

According to the reaction raw materials, the reaction method and the conditions of example 3, in the olefin hydration reactor, the single pass olefin conversion of olefin hydration was 20.4%, and the low carbon alcohol selectivity was 96.2%.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the 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, wherein 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; and 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 comprises:

(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;

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;

7. The method according to claim 6, wherein in step (1), the resin white ball 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 the 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, the solution containing the adsorbent component comprising 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 the 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 adsorbent component 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 of claim 14, wherein the first initiator is benzoyl peroxide.

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

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

18. The method of 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 of 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) further comprises performing an adsorption post-treatment on the adsorbed product after adsorption treatment in a post-treatment agent A; the 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, the solution containing the reaction component containing 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 are phenoxy derivatives, amide derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives.

26. The method according to 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 of 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-(propenylamino)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.

29. The method according to claim 20, wherein step (2) further comprises performing a post-reaction treatment on the reaction product in a post-treatment agent B, wherein the post-treatment agent B 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 1-2h, and soaking times of 1-3.

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 treatment further includes drying the post-reaction product.

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

34. A method for producing an aqueous solution of low-carbon alcohols, wherein the method comprises: hydrating a low-carbon olefin reaction feedstock with water in the presence of a hydration catalyst to obtain an aqueous solution of low-carbon alcohols, 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 of claim 35, wherein the low-carbon olefin is a C3 and/or C4 olefin;

And/or, the conditions for the hydration reaction include: a temperature of 120-160℃, a pressure of 2000-4000 kPa (gauge pressure), a volume hourly space velocity (VHSV) of 0.5-3 ^h⁻¹ for the olefin reaction feedstock, and a molar ratio of water to olefin reaction feedstock of 6-15.

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