CN119680652A - Low-carbon olefin hydrated fiber membrane and its preparation method and application - Google Patents

Abstract

The present invention relates to the field of olefin hydration, and discloses a low-carbon olefin hydration fiber membrane and its preparation method and application. A low-carbon olefin hydration fiber membrane, wherein the low-carbon olefin hydration fiber membrane comprises a hollow fiber membrane substrate, a first silane layer, a first functional layer and a first olefin-philic layer sequentially coated on the inner surface of the hollow fiber membrane substrate from the inside to the outside, and a second silane layer and a second functional layer sequentially coated on the outer surface of the hollow fiber membrane substrate from the inside to the outside; the first functional layer contains amide, phenoxy, sulfonic acid, phosphoric acid, pyrrol and furan groups; the first olefin-philic layer contains phenoxy; the second functional layer contains amide, pyrrol and furan groups. The low-carbon olefin hydration fiber membrane can improve the contact effect of water and olefin, promote the movement of hydration equilibrium, and reduce the superposition loss of olefins.

Description

Low-carbon olefin hydrated fiber membrane and preparation method and application thereof

Technical Field

The invention relates to the technical field of olefin hydration, in particular to a low-carbon olefin hydrated fiber membrane, a preparation method and application thereof.

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 sec-butyl alcohol can be used as solvent in industry, and mixed with methanol in certain proportion to prepare components for raising octane number of gasoline, and may be used in producing mineral dressing agent, herbicide, plasticizer, etc. its main application is to produce methyl ethyl ketone, which is one excellent organic solvent and organic synthetic material, and is widely used in oil refining, fuel, high grade paint, medicine, etc.

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.

Patent application CN104039435A discloses an integrated membrane hydration reactor for producing a related alcohol product from an olefin using water, comprising a solid acid olefin hydration catalyst located in a production zone, and a hydrophilic membrane located in a separation zone, capable of selectively unidirectionally pervaporating water under olefin hydration process conditions, and capable of preventing pervaporation of the related alcohol and permeation of the olefin. The production zone is effective to form a production zone product mixture formed from the relevant alcohol and any unreacted water. The associated separation zone is effective to form and produce an associated alcohol product and a pervaporated water product from the production zone product mixture. An olefin hydration process utilizing water to form a related alcohol product from an olefin utilizes the integrated membrane hydration reactor under olefin hydration process conditions.

Patent application CN104039435A discloses a combination of a hydration catalytic bed and a pervaporation membrane, a water-alcohol mixture is formed through a conventional catalytic bed, an alcohol-water emulsion with higher concentration is gradually layered into an alcohol-rich layer and an water-rich layer under a relatively static condition, unreacted water from hydration reaction in the water-rich layer is recovered by the pervaporation membrane to obtain pure water, the pure water is used for continuously carrying out the present-stage hydration reaction or the next-stage hydration reaction, a small amount of alcohol dissolved in the water-rich layer intercepted by the pervaporation membrane is continuously concentrated and separated out to the alcohol-rich layer, and the alcohol in the alcohol-rich layer is continuously extracted out of the system through an alcohol pipeline. The catalytic bed layer can be not contacted with the pervaporation membrane, can also be contacted with the pervaporation membrane, can be arranged along the outer surface of the hollow membrane under the condition that the catalytic bed layer is contacted with the pervaporation membrane, and can also be filled in the inner cavity of the hollow membrane. The pervaporation membrane can be directly prepared from inorganic materials, polymeric materials or organic-inorganic composite materials. The alcohol or alcohol concentrated solution and water are obtained by separation by using a pervaporation membrane to replace a conventional rectifying tower for dehydration, so that the alcohol as a reaction product is removed, and the water is reused again, thereby promoting the hydration balance to move rightwards. However, the catalytic hydration layer and the pervaporation membrane are macroscopic combination, and have the effects of recovering water, separating alcohols and promoting balance movement, but lack comprehensive microscopic affinity treatment modification on water, alkene and alcohol involved in hydration reaction. On the other hand, the catalytic layer and the membrane are separated to further realize smaller-scale integration so as to reduce the volume of the reactor and the occupied space of the industrial device.

Disclosure of Invention

The invention aims to solve the problems of poor contact of water and olefin, overlarge water and olefin ratio and low selectivity of target products in the low-carbon olefin hydration process in the prior art, and provides a low-carbon olefin hydrated fiber membrane, a preparation method and application thereof.

In order to achieve the above purpose, the first aspect of the present invention provides a low-carbon olefin hydrated fiber membrane, wherein the low-carbon olefin hydrated fiber membrane comprises a hollow fiber membrane substrate, a first silane layer, a first functional layer and a first enophilic layer which are sequentially coated on the inner surface of the hollow fiber membrane substrate from inside to outside, and a second silane layer and a second functional layer which are sequentially coated on the outer surface of the hollow fiber membrane substrate from inside to outside, wherein the first functional layer contains an amide group, a phenoxy group, a sulfonic group, a phosphoric group, a pyrrole group and a furan group, the first enophilic layer contains a phenoxy group, and the second functional layer contains an amide group, a pyrrole group and a furan group.

The second aspect of the invention provides a preparation method of a light olefin hydrated fiber membrane, wherein the method comprises the following steps:

(1) Performing silanization treatment on the hollow fiber membrane matrix to obtain a silanized hollow fiber membrane;

(2) Performing first functional treatment on the inner surface of the silanized hollow fiber membrane in the step (1) in the presence of a first functional component, and then performing first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment in the presence of a first enophilic component to obtain a hollow fiber membrane subjected to the first enophilic treatment;

(3) Performing a second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment in the step (2) in the presence of a second functional component to obtain a low-carbon olefin hydrated fiber membrane;

The first functional component contains amide, phenoxy, sulfonic acid, phosphoric acid, pyrrole and furan groups, the first enophilic component contains phenoxy, and the second functional component contains amide, pyrrole and furan groups.

The third aspect of the invention provides an application of the light olefin hydrated fiber membrane in the first aspect or the light olefin hydrated fiber membrane prepared by the preparation method in the second aspect in the light olefin hydration reaction.

The inventor of the invention discovers that the single pass conversion rate of olefin is obviously lower (generally 3-8%) than the thermodynamic equilibrium conversion rate by adopting the existing solid acid catalysts such as strong acid resin, ZSM-5 molecular sieve and the like to catalyze olefin hydration in the research process of low-carbon olefin hydration. The low-carbon olefin is generally insoluble in water, even if the water content is excessive, the low-carbon olefin and the water content are still incompatible, and the effect is not obvious from the perspective that the reaction raw materials are excessive to further push the hydration balance to move rightwards, so that the dilution effect on the low-carbon alcohol of the product can be realized. 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.

According to the low-carbon olefin hydrated fiber membrane provided by the invention, the stability and the service life of the subsequent first functional layer, the first enophilic layer and the second functional layer can be improved by the first silane layer and the second silane layer, the mass transfer problem, the balance pushing problem and the product yield selectivity problem in the prior art are solved by the first functional layer, the first enophilic layer and the second functional layer from the microscopic mechanism, and the selectivity of a product is improved.

The low-carbon olefin hydrated fiber membrane provided by the invention not only can be suitable for olefin hydration reaction with olefin content of more than 80%, but also can be suitable for olefin hydration reaction with low-carbon olefin content of less than 80%, so that the material treatable range of the olefin hydration reaction is greatly expanded, and the low-carbon olefin hydrated fiber membrane is particularly suitable for the situation of olefin hydration.

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 first silane layer, the second silane layer, the first functional layer, the first enophilic layer and the second functional layer are all measured by infrared spectroscopy, the specific test condition is KBr tabletting, scanning is carried out within the range of 400cm ^-1-4000cm^-1, and the group content in each layer is obtained by step measurement in the preparation process.

In the invention, the thicknesses of the first silane layer, the second silane layer, the first functional layer, the first enophilic layer and the second functional layer are all measured by an X-ray fluorescence thickness gauge.

The invention provides a low-carbon olefin hydrated fiber membrane, which comprises a hollow fiber membrane matrix, a first silane layer, a first functional layer, a first enophilic layer and a second silane layer and a second functional layer, wherein the first silane layer, the first functional layer and the first enophilic layer are sequentially coated on the inner surface of the hollow fiber membrane matrix from inside to outside, the second silane layer and the second functional layer are sequentially coated on the outer surface of the hollow fiber membrane matrix from inside to outside, the first functional layer contains an amide group, a phenoxy group, a sulfonic group, a phosphate group, a pyrrole group and a furan group, the first enophilic layer contains a phenoxy group, and the second functional layer contains an amide group, a pyrrole group and a furan group.

The inner surface of the hollow fiber membrane matrix is coated with a first functional layer and a first enophilic layer, wherein the first functional layer is a main place of olefin hydration reaction, and contains enophilic groups (used for enriching olefins), hydrophilic groups (used for enriching water), catalytic groups (used for activating olefins, and reasonably regulating acid strength through group cooperative collocation), and low-carbon alcohol rejection groups (used for transmitting low-carbon alcohol generated by the reaction out of a reaction system and promoting hydration reaction to move rightwards).

The first enophilic layer is coated to enrich olefin. The olefin enriched in the first enophilic layer reacts with water transferred through the pore canal of the hollow fiber membrane matrix on the inner side of the first enophilic layer (namely the first functional layer), and the conditions of sintering or deactivation of the catalyst caused by the fact that the reaction interface is small in thickness, limited in hydration exothermic heat effect and free from occurrence of temperature runaway are avoided. The catalyst has moderate acid strength, no side reaction such as olefin superposition, low-carbon alcohol condensation and the like, and obviously improved low-carbon alcohol yield and selectivity, and furthermore, the first functional layer (the reaction layer) contains a low-carbon alcohol rejection group, so that the low-carbon alcohol generated by hydration can gradually transfer to the water phase outside the matrix along the pore channels of the first functional layer and the matrix under the action of molecular force, thereby promoting the hydration balance to continuously move rightwards.

The second functional layer is coated, the layer contains hydrophilic groups and low-carbon alcohol repulsive groups, water is enriched on the outer surface of the substrate and in the pore canal through the hydrophilic groups, microscopic excessive water is provided for hydration reaction, and the requirement of macroscopic water-to-olefin ratio of the film is obviously reduced due to the existence of the hydrophilic groups, so that the water circulation and separation load of the whole system is obviously reduced, and the low-carbon alcohol repulsive groups in the first functional layer and the repulsive groups in the second functional layer act together in a relay manner to continuously transfer low-carbon alcohol generated by hydration from a reaction zone to a water phase.

In the present invention, the hollow fiber membrane matrix is a hollow cylinder with a hollow structure inside, which is conventionally defined in the art, the inner surface refers to the inner surface of the hollow cylinder, and the outer surface refers to the outer surface of the hollow cylinder.

In the present invention, the type of the low-carbon olefin hydrated fiber film is not particularly limited. Preferably, the hollow fiber membrane substrate is a hollow ceramic fiber membrane.

In the present invention, the properties of the hollow fiber membrane matrix are not particularly limited. Preferably, the inner diameter of the hollow fiber membrane matrix is 0.1-0.5mm, the outer diameter is 1.1-2.5mm, the pore diameter of the fiber membrane wall is 30-80nm, and the porosity is 40-60%.

In the present invention, the material of the hollow fiber membrane substrate is not particularly limited. Preferably, the hollow fiber membrane substrate is made of silicon dioxide and/or aluminum oxide.

In the present invention, it is preferable that the thickness of the first silane layer and the second silane layer is 5 to 8nm each independently.

In the present invention, it is understood that the first silane layer and the second silane layer are prepared by immersing the hollow fiber membrane substrate in a solution containing a silane component, and the inner surface and the outer surface of the hollow fiber membrane are in contact with the silane component, so that the thicknesses of the first silane layer and the second silane layer are the same.

In the present invention, preferably, the first silane layer and the second silane layer are each independently provided by at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

In the present invention, preferably, the first functional layer has an amide group content of 10-17mmol/m ², a phenoxy group content of 9-16mmol/m ², a sulfonic acid group content of 16-30mmol/m ², a phosphoric acid group content of 7-15mmol/m ², a pyrrole group content of 18-26mmol/m ², and a furan group content of 3-7mmol/m ², based on the inner surface area of the dry-based hollow fiber membrane matrix per square meter. The advantage of adopting this kind of preferred embodiment is that can realize enrichment and activation of reaction raw materials, timely removal of reaction products.

In the present invention, preferably, the thickness of the first functional layer is 7 to 11nm. The advantage of using such a preferred embodiment is that both the reaction rate and the thermal effect of the reaction can be achieved.

In the present invention, preferably, the phenoxy group content in the first enophilic layer is 14-30mmol/m ² based on the inner surface area of the dry basis hollow fiber membrane matrix per square meter. An advantage of using such a preferred embodiment is that a captured enrichment of olefins in the raw olefin feed can be achieved.

In the present invention, preferably, the thickness of the first enophilic layer is 4-6nm. The advantage of adopting this preferred embodiment is that it can combine olefin enrichment and mass transfer and improve the reaction performance.

In the present invention, preferably, the second functional layer has an amide group content of 18 to 35mmol/m ², a pyrrole group content of13 to 21mmol/m ², and a furan group content of2 to 5mmol/m ², based on the external surface area of the dry-based hollow fiber membrane substrate per square meter. An advantage of using such a preferred embodiment is that both moisture enrichment and lower alcohol separation can be achieved.

In the present invention, preferably, the thickness of the second functional layer is 5-8nm. The advantage of adopting this preferred embodiment is that moisture enrichment, low carbon alcohol separation and mass transfer resistance can be compromised.

The second aspect of the invention provides a preparation method of a light olefin hydrated fiber membrane, wherein the method comprises the following steps:

(1) Performing silanization treatment on the hollow fiber membrane matrix to obtain a silanized hollow fiber membrane;

(2) Performing first functional treatment on the inner surface of the silanized hollow fiber membrane in the step (1) in the presence of a first functional component, and then performing first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment in the presence of a first enophilic component to obtain a hollow fiber membrane subjected to the first enophilic treatment;

(3) Performing a second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment in the step (2) in the presence of a second functional component to obtain a low-carbon olefin hydrated fiber membrane;

The first functional component contains amide, phenoxy, sulfonic acid, phosphoric acid, pyrrole and furan groups, the first enophilic component contains phenoxy, and the second functional component contains amide, pyrrole and furan groups.

In the present invention, in the step (1), the types, materials and characteristic parameters of the hollow fiber membrane matrix are described in the first aspect, and will not be described herein.

In the present invention, the method for preparing the hollow fiber membrane substrate is not particularly limited, and for example, the hollow fiber membrane substrate can be prepared by preparing a casting solution, preparing a hollow fiber blank through a spinning molding-phase inversion process, drying and roasting to obtain a hollow ceramic fiber, wherein the hollow ceramic fiber is prepared by polyether sulfone (average molecular weight of 1500-3800), N-methylpyrrolidone, ceramic precursor (silica and/or alumina) and polyvinylpyrrolidone K90 in a mass ratio of (9-18): (65-95): (170-330): (4-9), stirring at 75-95 ℃ for 40-60 hours, and standing and defoaming for 7-12 hours to obtain the casting solution. The inner and outer gel baths of the spinning nozzle are deionized water at 0-3 ℃, the inner diameter of the spinning nozzle is 0.3-0.7 mm, the outer diameter of the spinning nozzle is 1.3-2.7 mm, the flow rate of casting solution is 4-8 ml/min, the casting solution pressure in the spinning nozzle is 150-300kPa (gauge pressure), the ambient temperature is 20-30 ℃, the ambient humidity is 45-60%, and the casting solution and the inner and outer gel baths are subjected to solvent exchange and phase separation solidification to form a hollow fiber blank. Washing the hollow fiber membrane blank for 4-8 times by desalted water, drying with air at 20-30 ℃, then heating to 1600-1800 ℃ by adopting a 0.5-1 ℃ per minute program, keeping the temperature for 4-8 hours, and then naturally cooling to 20-30 ℃ to obtain the hollow ceramic fiber membrane substrate.

In the present invention, preferably, in the step (1), the silylation treatment is performed such that the inner surface and the outer surface of the hollow fiber membrane are coated with a first silane layer and a second silane layer, respectively, each of which has a thickness of 5 to 8nm independently.

In the present invention, the manner of the silylation treatment is not particularly limited as long as the first silane layer and the second silane layer can be formed. Preferably, in step (1), the silylation treatment comprises contacting a silane reagent solution with a hollow fiber membrane matrix and then drying and curing. In the present invention, the manner and condition of contact are not particularly limited. Preferably, the contact mode is soaking, and the soaking time is 90-150 seconds. In the present invention, the conditions for drying and curing are not particularly limited. Preferably, the temperature is 100-120 ℃ and the time is 30-60 minutes. In the present invention, the drying and curing are preferably performed under a protective atmosphere, preferably an inert atmosphere and/or nitrogen.

In the present invention, preferably, in the step (1), the silane reagent solution is obtained by prehydrolysis of a silane reagent, water and a lower alcohol. In the present invention, the conditions for the pre-hydrolysis are not particularly limited, and the pre-hydrolysis time is preferably 12 to 24 hours.

In the present invention, the content of each component in the silane reagent solution is not particularly limited as long as the thickness requirements of the first silane layer and the second silane layer are satisfied. Preferably, the volume ratio of the silane reagent to the water to the lower alcohol is (1.7-3.8): 3-5): 90-96.

In the present invention, preferably, the pH of the silane reagent solution is 7.4 to 8.3.

In the present invention, preferably, the silane reagent is at least one selected from the group consisting of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

In the present invention, the specific type of the lower alcohol is not particularly limited. Preferably, the water lower alcohol is anhydrous methanol and/or anhydrous ethanol.

In the present invention, it is preferable that the silane reagent solution is used in such an amount that the thicknesses of the first silane layer and the second silane layer are each independently 5 to 8nm.

In the present invention, preferably, in the step (2), the first functional treatment coats the inner surface of the silanized hollow fiber membrane in the step (1) with a first functional layer, and the first functional layer contains an amide group, a phenoxy group, a sulfonic acid group, a phosphoric acid group, a pyrrole group and a furan group.

In the present invention, preferably, the first functional layer has an amide group content of 10-17mmol/m ², a phenoxy group content of 9-16mmol/m ², a sulfonic acid group content of 16-30mmol/m ², a phosphoric acid group content of 7-15mmol/m ², a pyrrole group content of 18-26mmol/m ², and a furan group content of 3-7mmol/m ², based on the inner surface area of the dry-based hollow fiber membrane matrix per square meter.

In the present invention, preferably, in the step (2), the first enophilic treatment coats the inner surface of the hollow fiber membrane after the first functional treatment with a first enophilic layer, and the first enophilic layer contains phenoxy.

In the present invention, preferably, the phenoxy group content in the first enophilic layer is 14-30mmol/m ² based on the inner surface area of the dry basis hollow fiber membrane matrix per square meter.

In the present invention, the mode of the first function processing is not particularly limited. Preferably, in step (2), the first functional treatment comprises contacting a solution containing a first functional component with the inner surface of the silanized hollow fiber membrane of step (1).

In the present invention, the kind of each component in the solution containing the first functional component is not particularly limited as long as the requirement of the first functional layer is satisfied. Preferably, in the step (2), the solution containing the first functional component contains the first polyether, the first functional component, the first initiator and water.

In the present invention, the content of each component in the solution containing the first functional component is not particularly limited as long as the requirement of the first functional layer is satisfied. Preferably, in the solution containing the first functional component, the mass ratio of the first polyether to the first initiator to the water is 100 (3.2-5.3) (0.2-0.6) (1-2).

In the present invention, preferably, the average molecular weight of the first polyether is 500 to 1000.

In the present invention, the kind of the first initiator is not particularly limited. Preferably, 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, still more preferably benzoyl peroxide.

In the present invention, preferably, the first functional component is provided by an amide derivative, a phenoxy derivative, a sulfonic acid derivative, a phosphoric acid derivative, a pyrrole derivative, and a furan derivative.

In the invention, preferably, in the solution containing the first functional component, the molar ratio of (13-23): (12-21): (21-39): (9-20): (24-34): (4-9) of the amide derivative to the sulfonic acid derivative to the phosphoric acid derivative to the pyrrole derivative to the furan derivative.

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

In the present invention, the 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, allyl phenyl ether and phenyl vinyl ether.

In the present invention, the type of the phosphoric acid derivative is not particularly limited. Preferably, the phosphoric acid derivative is at least one selected from (2-fluoro-3, 7-dimethyloct-1, 6-dien-3-yl) phosphonohydrogen phosphate, [ 2-methyl-2- (4-methylpent-3-enyl) cyclopropyl ] methylphosphonic acid hydrogen phosphate and 2- (phosphoryloxy) propane-1, 3-diyl dimethacrylate.

In the present invention, the type of the sulfonic acid derivative is not particularly limited. Preferably, the sulfonic acid group is provided by a sulfonic acid derivative, preferably the sulfonic acid derivative is selected from 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 pyrrole derivative is not particularly limited. Preferably, the pyrrolyl group is provided by a pyrrole derivative, preferably at least one selected from the group consisting 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 kind of the furan derivative is not particularly limited. Preferably, the furanyl group is provided by a furanyl derivative, preferably the furanyl derivative is 2- (1-propen-2-yl) furan and/or 2- (2-pentenyl) furan.

In the invention, the inner cavity of the hollow fiber membrane is completely filled through the first functional treatment, so that the first polyether gel solution is only coated on the inner surface and a part of pore channels close to the inner surface of the hollow fiber membrane, and the outer surface is not coated. In the present invention, the conditions of the first functional process are not particularly limited. Preferably, in the step (2), the conditions of the first functional treatment include introducing a solution containing the first functional component into the inner cavity of the silanized hollow fiber membrane of the step (1), and the back pressure of the outlet of the inner cavity in gauge is 10-20 kg. Preferably, the first functional treatment further comprises introducing the solution containing the first functional component, then treating for 0.7 to 1.5 hours under a protective atmosphere (preferably nitrogen) at 80 to 100 ℃, cooling to normal temperature, immersing and washing for 4 to 8 times with an organic solvent (preferably benzene) at 70 to 80 ℃, and then drying under nitrogen. The first polyether gel is pumped into the inner cavity of the hollow fiber membrane under pressure, so that the inner cavity is completely filled, the first functional component is prevented from being coated on the outer surface of the hollow fiber membrane, and the first polyether is removed by benzene washing, so that the operation is simple and the cost is low.

In the present invention, the amount of the solution containing the first functional component is not particularly limited, and preferably, the amount of the solution containing the first functional component is such that the thickness of the first functional layer of the produced low-carbon olefin hydrated fiber film is 7 to 11nm.

In the present invention, the mode of the first enophilic treatment is not particularly limited. Preferably, in step (2), the first enophilic treatment comprises contacting a solution containing a first enophilic component with the inner surface of the hollow fiber membrane after the first functional treatment.

In the present invention, preferably, in the step (2), the solution containing the first enophilic component contains a second polyether, the first enophilic component, a second initiator and water.

In the present invention, the content of each component in the solution containing the first enophilic component is not particularly limited. Preferably, in the solution containing the first enophilic component, the mass ratio of the second polyether to the first enophilic component to the second initiator to water is 100 (3.8-6.2): 0.3-0.6): 1-2.

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

In the present invention, preferably, the second polyether has an average molecular weight of 800 to 2000.

In the present invention, preferably, the first enophilic component is provided by a phenoxy derivative, and further preferably at least one selected from the group consisting of 4-methoxystyrene, allyl phenyl ether and phenyl vinyl ether.

In the invention, the solution containing the first enophilic component contains second polyether, and the viscosity of the second polyether is larger than that of the first polyether, so that the solution containing the first enophilic component cannot permeate into the pore channels and is only used for modifying the inner surface of the hollow fiber membrane matrix. The conditions for the first enophilic treatment in the present invention are not particularly limited. Preferably, in the step (2), the condition of the first enophilic treatment comprises introducing a solution containing a first enophilic component into the inner cavity of the hollow fiber membrane after the first functional treatment, wherein the back pressure of the outlet of the inner cavity is 6-13 kg in terms of gauge pressure. Preferably, the first enophilic treatment further comprises introducing the solution containing the first enophilic component followed by treatment under a protective atmosphere (preferably nitrogen) at 85-110 ℃ for 0.8-1.5 hours and cooling to ambient temperature. Preferably, the back pressure of the first enophilic treatment is less than the back pressure of the first functional treatment.

In the present invention, the amount of the solution containing the first enophilic component is not particularly limited, and it is preferable that the amount of the solution containing the first enophilic component is such that the thickness of the first enophilic layer of the produced low-carbon olefin hydrated fiber membrane is 4 to 6nm.

In the present invention, it is understood that the first functional treatment and the first enophilic treatment have been a filling treatment of the hollow fiber membrane lumens with a first polyether and a second polyether, respectively, and the lumens have been completely filled during operation, and thus, the first functional treatment and the first enophilic treatment primarily treat only the inner surface portions of the hollow fiber membranes, and the subsequent second functional treatment treats only the outer surface portions of the hollow fiber membranes.

In the present invention, preferably, in the step (2), the second functional treatment coats the outer surface of the hollow fiber membrane after the first enophilic treatment with a second functional layer, where the second functional layer contains an amide group, a pyrrole group, and a furan group.

In the present invention, preferably, the second functional layer has an amide group content of 18 to 35mmol/m ², a pyrrole group content of 13 to 21mmol/m ², and a furan group content of 2 to 5mmol/m ², based on the external surface area of the dry-based hollow fiber membrane substrate per square meter.

In the present invention, the mode of the second function processing is not particularly limited. Preferably, in step (2), the second functional treatment comprises contacting a solution containing a second functional component with the outer surface of the hollow fiber membrane after the first enophilic treatment.

In the present invention, preferably, in the step (3), the solution containing the second functional component contains the second functional component, the third initiator and the first solvent.

In the present invention, the content of each component in the solution containing the second functional component is not particularly limited. Preferably, in the solution containing the second functional component in the step (2), the mass ratio of the second functional component to the third initiator to the first solvent is (4.2-7.5): 0.1-0.4): 92-96.

In the present invention, the type of the first solvent is not particularly limited. Preferably, in step (2), the first solvent is selected from at least one of toluene, para-xylene, meta-xylene and ortho-xylene.

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

In the present invention, preferably, in step (2), the second functional component is provided by an amide derivative, a pyrrole derivative, or a furan derivative.

In the invention, preferably, the molar ratio of the amide derivative to the pyrrole derivative to the furan derivative in the solution containing the second functional component is (23-46): 16-28): 2-7.

In the invention, the amide derivatives and the pyrrole derivatives, namely the furan derivatives, are already described in the previous description, and are not repeated here.

In the present invention, the conditions for the second functional processing are not particularly limited as long as the requirements of the second functional layer are satisfied. Preferably, in the step (3), the conditions of the second functional treatment comprise that the liquid-solid volume ratio of the solution containing the second functional component to the hollow fiber membrane after the first enophilic treatment is 2-4, the soaking temperature is 60-80 ℃ and the time is 1.5-3h. Preferably, the second functional treatment further comprises immersing and washing the immersed product in an organic solvent (preferably benzene) at 70-80 ℃ for 4-8 times. The second polyether is removed by washing with an organic solvent.

In the present invention, the amount of the solution containing the second functional component is not particularly limited, and preferably, the amount of the solution containing the second functional component is such that the thickness of the second functional layer of the produced low-carbon olefin hydrated fiber film is 5 to 8nm.

In the present invention, preferably, step (3) further comprises a post-treatment performed in the presence of a post-treatment agent. The advantage of using this preferred embodiment is the removal of residual monomer and the perfecting of the tunnel structure.

In the present invention, the specific mode of operation of the post-treatment is not limited. Preferably, the post-treatment includes immersing a second functional treatment product obtained by the second functional treatment in a post-treatment agent, and then drying.

In the present invention, the kind of the post-treatment agent is not particularly limited. Preferably, the post-treatment agent is at least one selected from the group consisting of absolute ethanol, absolute acetone, and absolute methanol, and further preferably, absolute acetone.

In the present invention, the conditions for the post-treatment are not particularly limited. Preferably and, the post-treatment conditions include a soaking time of 0.5-1h, a drying temperature of 120-150 ℃ and a drying time of 0.5-1h.

The third aspect of the invention provides an application of the light olefin hydrated fiber membrane in the first aspect or the light olefin hydrated fiber membrane prepared by the preparation method in the second aspect in the light olefin hydration reaction.

In the present invention, the content of the low-carbon olefin in the olefin reaction raw material for the hydration reaction of the low-carbon olefin 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 invention, preferably, the low-carbon olefin hydration reaction comprises the steps of respectively contacting olefin reaction raw materials and the inner surface and the outer surface of the low-carbon olefin hydration fiber membrane to carry out olefin hydration reaction to obtain an aqueous solution containing low-carbon alcohol.

In the present invention, the equipment used for the hydration reaction of olefins is not particularly limited. Preferably, the olefin hydration reaction is performed in an olefin hydration reactor, and further preferably, a shell-and-tube structured olefin hydration reactor is adopted, and the low-carbon olefin hydrated fiber membranes are arranged in parallel in the olefin hydration reactor. In the present invention, it is understood that water (preferably desalted water) flows through the shell side of the olefin hydration reactor (i.e., water contacts the outer surfaces of the hollow fiber membranes), and light olefins flow through the tube side of the olefin hydration reactor (i.e., light olefins contact the inner surfaces of the hollow fiber membranes).

In the invention, the condition selection range of the hydration reaction of the low-carbon olefin is wider. Preferably, the conditions of the hydration reaction of the low-carbon olefin comprise the temperature of 80-150 ℃, the pressure of 500-2000kPa by a gauge pressure, the molar ratio of water to the low-carbon olefin of 1.5-4.5, and the treatment capacity of the olefin reaction raw material of 520-860L.m ^-2﹒h^-1 by taking the inner surface area of a dry basis hollow fiber membrane matrix per square meter as a reference.

In the present invention, the single pass olefin conversion of olefin hydration is preferably greater than 62% and the lower alcohols selectivity is preferably greater than 95%.

The present invention will be described in detail by examples.

In the present invention, the content of each group in the olefin hydrated fiber film was measured by the foregoing test method.

In the invention, a 20A high performance liquid chromatography system (Japanese island fluid company, an autosampler, 10AT and 10AD pumps and a 20A multi-wavelength ultraviolet detector) is adopted for component analysis, and an ACQUITY UPLC/XeFo G2 QTOF ultra-high performance liquid chromatography high resolution tandem mass spectrum (U.S. Wo-Tech company, an autosampler and a diode array ultraviolet detector) is adopted for component analysis. High performance liquid chromatography conditions were Zorbax Eclipse Plus C18:18 (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 column HSS T3 (2.1 mm. Times.100 mm,1.7 μm), mobile phase water, methanol, gradient elution (positive ion mode) 0min V (water): V (methanol) =85:15, 2.5min after V (water): V (methanol) =55:35, 4min after V (water): V (methanol): 10:90, flow rate 0.45mL/min, gradient elution (negative ion mode) 0min with V (methanol): 70:30,2.5min after V (water): V (methanol) =55:35, 3.5min after V (water): V (methanol) =10:90, flow rate 0.45mL/min, column temperature 30 ℃ C, 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, 33.1% of isobutane, 8.5% of n-butane, 56.7% of n-butene and 1.7% of pentane.

The preparation method of the low-carbon olefin hydrated fiber membrane comprises (1) carrying out silanization treatment on the inner surface and the outer surface of a hollow fiber membrane matrix to obtain a silanized hollow fiber membrane, (2) sequentially carrying out first functional treatment and first enophilic treatment on the inner surface of the silanized hollow ceramic fiber membrane obtained in the step (1), and then carrying out second functional treatment on the outer surface to obtain the low-carbon olefin hydrated fiber membrane.

In the embodiment, the hollow fiber membrane matrix can be prepared by preparing a casting solution, preparing a hollow fiber blank through a spinning molding-phase inversion process, drying and roasting to obtain hollow ceramic fibers, wherein the hollow ceramic fibers are prepared by polyether sulfone (with an average molecular weight of 2600), N-methylpyrrolidone, a ceramic precursor (silicon dioxide) and polyvinylpyrrolidone K90 according to a mass ratio of 13.5:80:250:6.5, stirring at 85 ℃ for 50 hours, standing and defoaming for 9.5 hours to obtain the casting solution. The inner and outer gel baths of the spinneret are deionized water at 1.5 ℃, the inner diameter of the spinneret is 0.5 mm, the outer diameter of the spinneret is 2mm, the flow rate of casting solution is 6 ml/min, the casting solution pressure in the spinneret is 225kPa (gauge pressure), the ambient temperature is 25 ℃, the ambient humidity is 52.5%, and the casting solution is subjected to solvent exchange with the inner and outer gel baths and phase separation and solidification to form a hollow fiber blank. Washing the hollow fiber membrane blank for 6 times by desalted water, drying by air at 25 ℃, then heating to 1700 ℃ by adopting a 0.7 ℃ per minute program, keeping the temperature for 6 hours, and then naturally cooling to 25 ℃ to obtain the hollow ceramic fiber membrane substrate. The inner diameter of the hollow ceramic fiber is 0.3mm, the outer diameter is 1.3mm, the pore diameter of the fiber membrane wall is 55nm, and the porosity is 50%.

The hollow fiber membrane substrate is then contacted with a silane reagent solution and then dried and cured to yield a silanized hollow fiber membrane. The silane reagent solution is obtained by mixing a silane reagent, water and anhydrous lower alcohol, and then performing pre-hydrolysis. The prehydrolysis time was 18 hours. The volume ratio of the silane reagent to the water to the anhydrous low-carbon alcohol is 2.7:4:93. The pH of the silane reagent solution was 7.8. The silane reagent is methyl vinyl diethoxy silane. The anhydrous low carbon alcohol is anhydrous methanol. The contact condition is soaking, and the soaking time is 120 seconds. The drying and curing conditions were 110 ℃ for 45 minutes with nitrogen as the drying atmosphere. The silane reagent solution was used in such an amount that the thickness of the first and second silane layers was each independently 6.5nm.

And then treating the inner surface of the silanized hollow fiber membrane by adopting a solution containing the first functional component to obtain the hollow fiber membrane after the first functional treatment. The solution containing the first functional component comprises first polyether, the first functional component, a first initiator and water, wherein the mass ratio of the first polyether to the first functional component to the first initiator to the water is 100:4.2:0.4:1.5. The average molecular weight of the first polyether was 750. The first initiator is benzoyl peroxide. The first functional component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the phenoxy derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 18:16.5:30:14.5:29:6.5. The amide derivatives are provided by N, N-methylenebisacrylamide. The phenoxy derivative is provided by allyl phenyl ether. 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. Furanyl is provided by furan derivatives from 2- (1-propen-2-yl) furan. The first functional treatment condition comprises that a solution containing a first functional component is introduced into the inner cavity of the hollow fiber membrane subjected to silanization treatment in the step (1), the back pressure of the outlet of the inner cavity is 15 kg according to the gauge pressure, then the hollow fiber membrane is treated for 1.1 hours under the condition of nitrogen atmosphere and 90 ℃, and after the hollow fiber membrane is cooled to normal temperature, the hollow fiber membrane is soaked and washed for 6 times by hot benzene at 75 ℃ and then is dried in the nitrogen atmosphere. Based on the inner surface area of the dry-basis hollow fiber membrane matrix per square meter, the content of amide groups in the first functional layer is 13.5mmol/m ², the content of phenoxy groups is 12.4mmol/m ², the content of sulfonic acid groups is 22.5mmol/m ², the content of phosphoric acid groups is 10.9mmol/m ², the content of pyrrole groups is 21.7mmol/m ², the content of furan groups is 4.9mmol/m ², and the thickness of the first functional layer is 9nm.

And then carrying out first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment by adopting a first enophilic component to obtain the hollow fiber membrane subjected to the first enophilic treatment. The solution of the first enophilic component comprises second polyether, the first enophilic component, a second initiator and water, wherein the mass ratio of the second polyether to the first enophilic component to the second initiator to the water is 100:5:0.45:1.5. The average molecular weight of the second polyether was 1500. The second initiator is benzoyl peroxide. The first enophilic component is provided by a phenoxy derivative (allyl phenyl ether). The conditions for the first enophilic treatment include introducing a solution containing a first enophilic component into the inner cavity of the hollow fiber membrane after the first functional treatment in the step (2), carrying out treatment for 1.1 hour under the condition of nitrogen atmosphere and 97 ℃ after the back pressure of the outlet of the inner cavity is 9.5 kg based on the gauge pressure, cooling to normal temperature, and then drying in the nitrogen atmosphere. The phenoxy content in the first enophile layer is 22mmol/m ² based on the internal surface area of the dry-based hollow fiber membrane substrate per square meter, and the thickness of the first enophile layer is 5.1nm.

And then carrying out second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment by adopting a second functional component to obtain the low-carbon olefin hydrated fiber membrane. In the solution containing the second functional component, the mass ratio of the second functional component to the third initiator to the second solvent is 5.8:0.2:94. The second solvent is toluene. The second functional component contains amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the pyrrole derivatives to the furan derivatives is 34.5:22:4.5. The amide derivative is N, N-methylene bisacrylamide. 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 second functional treatment condition comprises that the liquid-solid volume ratio of the solution containing the second functional component to the hollow fiber membrane after the first enophilic treatment is 3, the soaking temperature is 70 ℃ and the soaking time is 2.2h, and the hollow fiber membrane is soaked and washed 6 times by hot benzene at 75 ℃. And carrying out post-treatment on the second functional treatment product in a post-treatment agent. The post-treatment agent is anhydrous acetone. The post-treatment conditions included a soak time of 0.7h, a drying temperature of 135 ℃ and a drying time of 0.7h. Based on the external surface area of the dry-based hollow fiber membrane substrate per square meter, the content of the amide group in the second functional layer is 26.5mmol/m ², the content of the pyrrole group is 17mmol/m ², the content of the furan group is 3.5mmol/m ², and the thickness of the second functional layer is 6.4nm.

The prepared low-carbon olefin hydration fiber membrane is applied to low-carbon olefin hydration, an olefin hydration reactor with a tube shell structure is adopted, the low-carbon olefin hydration fiber membrane is arranged in parallel in the olefin hydration reactor, and olefin and desalted water are respectively contacted with the inner surface and the outer surface of the low-carbon olefin hydration fiber membrane to carry out olefin hydration reaction, so that an aqueous solution containing low-carbon alcohol is obtained. The conditions for the olefin hydration reaction include a temperature of 115℃and a pressure of 1250kPa in terms of gauge pressure, a treatment amount of 687L.m ^-2﹒h^-1 of the olefin reaction raw material per square meter of the internal surface area of the hollow fiber membrane matrix, a molar ratio of water to light olefins of 3.1, a single pass olefin conversion of olefin hydration of 68.4% and a low carbon alcohol selectivity of 97.6%.

Example 2

The same olefin reaction feed as in example 1 was selected.

In the embodiment, the hollow fiber membrane matrix can be prepared by preparing a casting solution, preparing a hollow fiber blank through a spinning molding-phase inversion process, drying and roasting to obtain hollow ceramic fibers, wherein the hollow ceramic fibers are prepared by stirring polyethersulfone (with an average molecular weight of 1600), N-methylpyrrolidone, a ceramic precursor (silicon dioxide) and polyvinylpyrrolidone K90 in a mass ratio of 10:68:320:5 at 94 ℃ for 58 hours, and standing and defoaming for 11 hours to obtain the casting solution. The inner and outer gel baths of the spinneret were 0.5 ℃ deionized water, the spinneret had an inner diameter of 0.4 mm and an outer diameter of 1.4 mm, the casting solution flow rate was 4.3 ml/min, the casting solution pressure in the spinneret was 155kPa (gauge pressure), the ambient temperature was 23 ℃ and the ambient humidity was 58%, and the casting solution was solvent exchanged with the inner and outer gel baths and phase-separated and solidified to form a hollow fiber body. Washing the hollow fiber membrane blank for 8 times by desalted water, drying by air at 29 ℃, then heating to 1780 ℃ by adopting a 0.6 ℃ per minute program, keeping the temperature for 7 hours, and then naturally cooling to 23 ℃ to obtain the hollow ceramic fiber membrane substrate. The inner diameter of the hollow ceramic fiber is 0.2mm, the outer diameter is 1.2mm, the pore diameter of the fiber membrane wall is 35nm, and the porosity is 45%.

The hollow fiber membrane substrate is then contacted with a silane reagent solution and then dried and cured to yield a silanized hollow fiber membrane. The silane reagent solution is obtained by mixing a silane reagent, water and anhydrous lower alcohol, and then performing pre-hydrolysis. The prehydrolysis time was 23 hours. The volume ratio of the silane reagent to the water to the anhydrous low-carbon alcohol is 3.7:4.8:92. The pH of the silane reagent solution was 8.1. The silane reagent is methyl vinyl diethoxy silane. The anhydrous low carbon alcohol is anhydrous methanol. The contact condition is soaking, and the soaking time is 140 seconds. The drying and curing conditions were 115 ℃ for 56 minutes with nitrogen as the drying atmosphere. The silane reagent solution was used in such an amount that the thickness of the first and second silane layers was 7.7nm each independently.

And then treating the inner surface of the silanized hollow fiber membrane by adopting a solution containing the first functional component to obtain the hollow fiber membrane after the first functional treatment. The solution containing the first functional component comprises first polyether, the first functional component, a first initiator and water, wherein the mass ratio of the first polyether to the first functional component to the first initiator to the water is 100:5.2:0.5:1.8. The average molecular weight of the first polyether was 700. The first initiator is benzoyl peroxide. The first functional component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the phenoxy derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 22:20:38:19:33:8. The amide derivatives are provided by N, N-methylenebisacrylamide. The phenoxy derivative is provided by allyl phenyl ether. 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. Furyl is provided by furan derivatives, preferably 2- (1-propen-2-yl) furan. The first functional treatment condition comprises that a solution containing a first functional component is introduced into the inner cavity of the hollow fiber membrane subjected to silanization treatment in the step (1), the back pressure of the outlet of the inner cavity is 18 kg according to the gauge pressure, then the hollow fiber membrane is treated for 1.4 hours under the condition of nitrogen atmosphere and 95 ℃, and after the hollow fiber membrane is cooled to normal temperature, the hollow fiber membrane is soaked and washed for 7 times by hot benzene at 78 ℃ and then is dried in the nitrogen atmosphere. Based on the inner surface area of the dry-basis hollow fiber membrane matrix per square meter, the content of amide groups in the first functional layer is 16.3mmol/m ², the content of phenoxy groups is 14.8mmol/m ², the content of sulfonic acid groups is 28.1mmol/m ², the content of phosphoric acid groups is 14.0mmol/m ², the content of pyrrole groups is 24.5mmol/m ², the content of furan groups is 5.9mmol/m ², and the thickness of the first functional layer is 10nm.

And then carrying out first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment by adopting a first enophilic component to obtain the hollow fiber membrane subjected to the first enophilic treatment. The solution of the first enophilic component comprises second polyether, the first enophilic component, a second initiator and water, wherein the mass ratio of the second polyether to the first enophilic component to the second initiator to the water is 100:6.1:0.5:1.8. The average molecular weight of the second polyether was 1000. The second initiator is benzoyl peroxide. The first enophilic component is provided by a phenoxy derivative (allyl phenyl ether). The conditions for the first enophilic treatment comprise introducing a solution containing a first enophilic component into the inner cavity of the hollow fiber membrane subjected to the first functional treatment in the step (2), carrying out treatment for 1.4 hours under the condition of nitrogen atmosphere and 106 ℃ at the back pressure of the outlet of the inner cavity in terms of gauge pressure, cooling to normal temperature, and then drying in the nitrogen atmosphere. The phenoxy content in the first enophile layer is 28.6mmol/m ² based on the internal surface area of the dry-based hollow fiber membrane substrate per square meter, and the thickness of the first enophile layer is 5.8nm.

And then carrying out second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment by adopting a second functional component to obtain the low-carbon olefin hydrated fiber membrane. In the solution containing the second functional component, the mass ratio of the second functional component to the third initiator to the second solvent is 7.4:0.3:93. The second solvent is toluene. The second functional component contains amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the pyrrole derivatives to the furan derivatives is 45:27:6. 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 second functional treatment condition comprises that the liquid-solid volume ratio of the solution containing the second functional component to the hollow fiber membrane after the first enophilic treatment in the step (2) is 4, the soaking temperature is 77 ℃ and the time is 2.6h, and the hollow fiber membrane is soaked and washed for 7 times by hot benzene at 78 ℃. And carrying out post-treatment on the second functional treatment product in a post-treatment agent. The post-treatment agent is anhydrous acetone. The post-treatment conditions included a soak time of 0.8h, a drying temperature of 146 ℃ and a drying time of 0.8h. In the second functional layer, the content of amide groups is 34.2mmol/m ², the content of pyrrole groups is 20.6mmol/m ², the content of furan groups is 4.5mmol/m ², and the thickness of the second functional layer is 7.7nm based on the external surface area of the dry-basis hollow fiber membrane substrate per square meter.

According to the reaction method of example 1, the conditions for the olefin hydration reaction include a temperature of 90℃at a pressure of 800kPa on a gauge pressure, a molar ratio of water to light olefins of 4.2, a treatment amount of the olefin reaction raw material of 550L.m ^-2﹒h^-1 on the basis of the inner surface area of the hollow fiber membrane matrix per square meter dry basis, a single pass olefin conversion of olefin hydration of 73.5%, and a low carbon alcohol selectivity of 98.3%.

Example 3

The same olefin reaction feed as in example 1 was selected.

In the embodiment, the hollow fiber membrane matrix can be prepared by preparing a casting solution, preparing a hollow fiber blank through a spinning molding-phase inversion process, drying and roasting to obtain hollow ceramic fibers, wherein the hollow ceramic fibers are prepared by stirring polyether sulfone (with an average molecular weight of 3700), N-methylpyrrolidone, a ceramic precursor (silicon dioxide) and polyvinylpyrrolidone K90 in a mass ratio of 17:93:180:8 at 78 ℃ for 43 hours, and standing and defoaming for 8 hours to obtain the casting solution. The inner and outer gel baths of the spinneret were 2.5 ℃ deionized water, the spinneret had an inner diameter of 0.6 mm and an outer diameter of 1.6 mm, the casting solution flow rate was 7.6 ml/min, the casting solution pressure in the spinneret was 280kPa (gauge pressure), the ambient temperature was 27 ℃ and the ambient humidity was 50%, and the casting solution was solvent exchanged with the inner and outer gel baths and phase-separated and solidified to form a hollow fiber body. Washing the hollow fiber membrane blank for 5 times by desalted water, drying by air at 23 ℃, then heating to 1650 ℃ by adopting a 0.9 ℃ per minute program, keeping the temperature for 5 hours, and then naturally cooling to 27 ℃ to obtain the hollow ceramic fiber membrane substrate. The inner diameter of the hollow ceramic fiber is 0.4mm, the outer diameter is 1.4mm, the pore diameter of the fiber membrane wall is 73nm, and the porosity is 56%.

The hollow fiber membrane substrate is then contacted with a silane reagent solution and then dried and cured to yield a silanized hollow fiber membrane. The silane reagent solution is obtained by mixing a silane reagent, water and anhydrous lower alcohol, and then performing pre-hydrolysis. The prehydrolysis time was 14 hours. The volume ratio of the silane reagent to the water to the anhydrous low-carbon alcohol is 1.8:3.2:94. The pH of the silane reagent solution was 7.6. The silane reagent is methyl vinyl diethoxy silane. The anhydrous low carbon alcohol is anhydrous methanol. The contact condition is soaking, and the soaking time is 100 seconds. The drying and curing conditions were 106 ℃ for 34 minutes with nitrogen as the drying atmosphere. The silane reagent solution was used in such an amount that the thickness of the first and second silane layers was 5.3nm each independently.

And then treating the inner surface of the silanized hollow fiber membrane by adopting a solution containing the first functional component to obtain the hollow fiber membrane after the first functional treatment. The solution containing the first functional component comprises polyether, the first functional component, a first initiator and water, wherein the mass ratio of the first polyether to the first functional component to the first initiator to the water is 100:3.6:0.3:1.3. The first polyether had an average molecular weight of 900. The first initiator is benzoyl peroxide. The first functional component contains amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the sulfonic acid derivatives to the phosphoric acid derivatives to the pyrrole derivatives to the furan derivatives is 14:13:22:10:25:5. The amide derivatives are provided by N, N-methylenebisacrylamide. The phenoxy derivative is provided by allyl phenyl ether. 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 first functional treatment condition comprises that a solution containing a first functional component is introduced into the inner cavity of the hollow fiber membrane subjected to silanization treatment in the step (1), the back pressure of the outlet of the inner cavity is 12 kg according to the gauge pressure, then the hollow fiber membrane is treated for 0.9 hour under the condition of nitrogen atmosphere and 83 ℃, and after the hollow fiber membrane is cooled to normal temperature, the hollow fiber membrane is soaked and washed for 5 times by hot benzene at 73 ℃ and then is dried in the nitrogen atmosphere. Based on the inner surface area of the dry-basis hollow fiber membrane matrix per square meter, the content of amide groups in the first functional layer is 11.2mmol/m ², the content of phenoxy groups is 10.3mmol/m ², the content of sulfonic acid groups is 17.5mmol/m ², the content of phosphoric acid groups is 7.9mmol/m ², the content of pyrrole groups is 20mmol/m ², the content of furan groups is 4mmol/m ², and the thickness of the first functional layer is 7.6nm.

And then carrying out first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment by adopting a first enophilic component to obtain the hollow fiber membrane subjected to the first enophilic treatment. The solution of the first enophilic component comprises polyether, the first enophilic component, a second initiator and water, wherein the mass ratio of the second polyether to the first enophilic component to the second initiator to the water is 100:3.9:0.4:1.2. The second polyether has an average molecular weight of 1800. The second initiator is benzoyl peroxide. The first enophilic component is provided by a phenoxy derivative (allyl phenyl ether). The conditions for the first enophilic treatment comprise introducing a solution containing a first enophilic component into the inner cavity of the hollow fiber membrane subjected to the first functional treatment in the step (2), carrying out back pressure of 8 kg at the outlet of the inner cavity according to a gauge pressure, then treating for 0.9 hour under the condition of nitrogen atmosphere and 88 ℃, cooling to normal temperature, and then drying in the nitrogen atmosphere. The phenoxy content in the first enophile layer is 15.3mmol/m ² based on the internal surface area of the dry-based hollow fiber membrane substrate per square meter, and the thickness of the first enophile layer is 4.3nm.

And then carrying out second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment by adopting a second functional component to obtain the low-carbon olefin hydrated fiber membrane. In the solution containing the second functional component, the mass ratio of the second functional component to the third initiator to the second solvent is 4.3:0.2:95. The second solvent is toluene. The second functional component contains amide derivatives, pyrrole derivatives and furan derivatives, wherein the molar ratio of the amide derivatives to the pyrrole derivatives to the furan derivatives is 24:17:3. The amide derivatives are provided by N, N-methylenebisacrylamide. Pyrrole derivatives are provided by 1- (3-buten-1-yl) -2-vinyl-1H-pyrrole. Furanyl is provided by furan derivatives from 2- (1-propen-2-yl) furan. The second functional treatment condition comprises that the liquid-solid volume ratio of the solution containing the second functional component to the hollow fiber membrane after the first enophilic treatment in the step (2) is 3, the soaking temperature is 65 ℃ and the time is 1.7h, and the hollow fiber membrane is soaked and washed for 5 times by hot benzene at 73 ℃. And carrying out post-treatment on the second functional treatment product in a post-treatment agent. The post-treatment agent is anhydrous acetone. The post-treatment conditions included a soak time of 0.7h, a drying temperature of 131 ℃ and a drying time of 0.7h. In the second functional layer, the content of amide groups is 19.5mmol/m ², the content of pyrrole groups is 13.8mmol/m ², the content of furan groups is 2.43mmol/m ², and the thickness of the second functional layer is 5.3nm based on the external surface area of each square meter of dry-based hollow fiber membrane substrate.

According to the reaction method of example 1, the conditions for the olefin hydration reaction include a temperature of 140℃at a pressure of 1600kPa on a gauge pressure, a molar ratio of water to light olefins of 1.8, an olefin reaction raw material throughput of 850L.m ^-2﹒h^-1 on a per square meter basis of the inner surface area of the hollow fiber membrane matrix, a single pass olefin conversion of olefin hydration of 63.2%, and a low carbon alcohol selectivity of 96.3%.

Example 4

The procedure of example 2 was followed except that the olefin feed composition in this example, in volume percent, comprised 15.6% isobutane, 6.7% n-butane, 76.5% n-butene and 1.2% pentane.

Following the reaction procedure and conditions of example 2, the single pass olefin conversion of the olefin hydration was 77.2% and the low carbon alcohol selectivity was 98.5% 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 6.2% isobutane, 2.1% n-butane, 91.3% 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 79.3% and the low carbon alcohol selectivity was 98.7% in the olefin hydration reactor.

Example 6

The procedure of example 2 was followed except that the olefin feed composition in this example was 50.4% by volume of isobutane, 13.8% by volume of n-butane, 30.3% by volume of n-butene and 5.5% by volume of pentane.

Following the reaction procedure and conditions of example 2, the single pass olefin conversion of olefin hydration was 69.9% and the low carbon alcohol selectivity was 98.1% in the olefin hydration reactor.

Example 7

The procedure of example 3 was followed, except that the product after the second functional treatment in this example was not subjected to post-treatment with a post-treatment agent.

Following the reaction procedure and conditions of example 3, the single pass olefin conversion of the olefin hydration was 62.5% and the low carbon alcohol selectivity was 95.2% in the olefin hydration reactor.

Comparative example 1

The same olefin reaction raw materials as in example 5 are selected, and the raw materials comprise 6.2% of isobutane, 2.1% of n-butane, 91.3% of n-butene and 0.4% of pentane by volume.

The olefin hydration reactor is filled with Su Qing brand SQD-67 styrene series macroporous strong acid cation exchange resin, the reaction temperature is 150 ℃, the reaction pressure is 75 kg, the reaction mass space velocity is 1h ^-1, the single pass conversion of n-butene is 11.32%, and the selectivity of low carbon alcohol is 95.6%.

Comparative example 2

According to the method of embodiment 3, except that only the first functional processing is performed.

Following the reaction procedure and conditions of example 3, the single pass olefin conversion of the olefin hydration was 32.3% and the low carbon alcohol selectivity was 87.9% in the olefin hydration reactor.

Comparative example 3

The procedure of example 3 was followed except that the first enophilic treatment was not performed, and the other preparation steps and processes were the same as in example 3.

Following the reaction procedure and conditions of example 3, the single pass olefin conversion of the olefin hydration was 38.5% and the low carbon alcohol selectivity was 88.2% in the olefin hydration reactor.

Comparative example 4

The procedure of example 3 was followed except that the second functional treatment was not performed, and the other preparation steps and processes were the same as in example 3.

Following the reaction procedure and conditions of example 3, the single pass olefin conversion of the olefin hydration was 39.6% and the low carbon alcohol selectivity was 88.4% in the olefin hydration reactor.

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 (16)

1. The low-carbon olefin hydrated fiber membrane is characterized by comprising a hollow fiber membrane matrix, a first silane layer, a first functional layer, a first enophilic layer and a second silane layer and a second functional layer, wherein the first silane layer, the first functional layer and the first enophilic layer are sequentially coated on the inner surface of the hollow fiber membrane matrix from inside to outside, the second silane layer and the second functional layer are sequentially coated on the outer surface of the hollow fiber membrane matrix from inside to outside, the first functional layer contains an amide group, a phenoxy group, a sulfonic group, a phosphoric group, a pyrrole group and a furan group, the first enophilic layer contains a phenoxy group, and the second functional layer contains an amide group, a pyrrole group and a furan group.

2. The low-carbon olefin hydrated fiber membrane of claim 1 wherein the hollow fiber membrane matrix is a hollow ceramic fiber membrane;

And/or the inner diameter of the hollow fiber membrane matrix is 0.1-0.5mm, the outer diameter is 1.1-2.5mm, the pore diameter of the fiber membrane wall is 30-80nm, and the porosity is 40-60%;

and/or the hollow fiber membrane substrate is made of silicon dioxide and/or aluminum oxide.

3. The low-carbon olefin hydrated fibrous membrane of claim 1 or 2 wherein the thickness of the first silane layer and the second silane layer are each independently 5-8nm;

and/or, the first and second silane layers are each independently provided by at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

4. The hydrated fiber membrane of low-carbon olefin according to any one of claims 1 to 3, wherein the first functional layer has an amide group content of 10 to 17mmol/m ², a phenoxy group content of 9 to 16mmol/m ², a sulfonic acid group content of 16 to 30mmol/m ², a phosphoric acid group content of 7 to 15mmol/m ², a pyrrole group content of 18 to 26mmol/m ², and a furanyl group content of 3 to 7mmol/m ², based on the inner surface area of the hollow fiber membrane matrix on a dry basis per square meter;

and/or the thickness of the first functional layer is 7-11nm.

5. The low-carbon olefin hydrated fiber membrane of any one of claims 1 to 4 wherein the phenoxy content in the first enophile layer is 14 to 30mmol/m ² on a per square meter dry basis of the internal surface area of the hollow fiber membrane matrix;

And/or the thickness of the first enophilic layer is 4-6nm.

6. The hydrated fiber membrane of any one of claims 1 to 5, wherein the second functional layer has an amide group content of 18 to 35mmol/m ², a pyrrole group content of 13 to 21mmol/m ², and a furan group content of 2 to 5mmol/m ² on the basis of the outer surface area of the hollow fiber membrane matrix on a dry basis per square meter;

preferably, the thickness of the second functional layer is 5-8nm.

7. A method for preparing a light olefin hydrated fiber membrane, wherein the method comprises the following steps:

(1) Performing silanization treatment on the hollow fiber membrane matrix to obtain a silanized hollow fiber membrane;

(2) Performing first functional treatment on the inner surface of the silanized hollow fiber membrane in the step (1) in the presence of a first functional component, and then performing first enophilic treatment on the inner surface of the hollow fiber membrane subjected to the first functional treatment in the presence of a first enophilic component to obtain a hollow fiber membrane subjected to the first enophilic treatment;

(3) Performing a second functional treatment on the outer surface of the hollow fiber membrane subjected to the first enophilic treatment in the step (2) in the presence of a second functional component to obtain a low-carbon olefin hydrated fiber membrane;

The first functional component contains amide, phenoxy, sulfonic acid, phosphoric acid, pyrrole and furan groups, the first enophilic component contains phenoxy, and the second functional component contains amide, pyrrole and furan groups.

8. The method of claim 7, wherein in step (1), the hollow fiber membrane matrix is a hollow ceramic fiber membrane;

And/or the inner diameter of the hollow fiber membrane matrix is 0.1-0.5mm, the outer diameter is 1.1-2.5mm, the pore diameter of the fiber membrane wall is 30-80nm, and the porosity is 40-60%;

and/or the hollow fiber membrane substrate is made of silicon dioxide and/or aluminum oxide.

9. The method according to claim 7 or 8, wherein in step (1), the silylation treatment coats the inner and outer surfaces of the hollow fiber membrane with a first and a second silane layer, respectively, each having a thickness of 5-8nm independently;

And/or, in the step (1), the silanization treatment comprises the steps of contacting a silane reagent solution with a hollow fiber membrane matrix, and then drying and curing;

and/or, in the step (1), the silane reagent solution is obtained by prehydrolysis of a silane reagent, water and lower alcohols;

Preferably, the volume ratio of the silane reagent to the water to the lower alcohol is (1.7-3.8): 3-5): 90-96;

Preferably, the silane reagent is selected from at least one of 2-butenyltriethoxysilane, methylvinyldiethoxysilane, and allyldimethoxysilane.

10. The method according to any one of claims 7 to 9, wherein in step (2), the first functional treatment coats the inner surface of the silanized hollow fiber membrane of step (1) with a first functional layer containing amide groups, phenoxy groups, sulfonic groups, phosphoric groups, pyrrole groups, furan groups;

Preferably, the first functional layer has an amide group content of 10-17mmol/m ², a phenoxy group content of 9-16mmol/m ², a sulfonic acid group content of 16-30mmol/m ², a phosphate group content of 7-15mmol/m ², a pyrrole group content of 18-26mmol/m ², and a furanyl group content of 3-7mmol/m ², based on the inner surface area of the hollow fiber membrane matrix on a dry basis per square meter;

and/or in the step (2), the first enophilic treatment enables the inner surface of the hollow fiber membrane after the first functional treatment to be coated with a first enophilic layer, wherein the first enophilic layer contains phenoxy;

preferably, the phenoxy content in the first enophilic layer is 14-30mmol/m ² based on the internal surface area of the dry basis hollow fiber membrane matrix per square meter.

11. The method according to any one of claims 7 to 10, wherein in step (2), the first functional treatment comprises contacting a solution containing a first functional component with the inner surface of the silanized hollow fiber membrane of step (1);

And/or, in the step (2), the solution containing the first functional component contains first polyether, the first functional component, a first initiator and water;

and/or the mass ratio of the first polyether to the first initiator to the water in the solution containing the first functional component is 100 (3.2-5.3) (0.2-0.6) (1-2);

and/or the average molecular weight of the first polyether is 500-1000;

And/or the first functional component is provided by amide derivatives, phenoxy derivatives, sulfonic acid derivatives, phosphoric acid derivatives, pyrrole derivatives and furan derivatives;

Preferably, the molar ratio of the amide derivatives to the phenoxy derivatives to the sulfonic derivatives to the phosphoric derivatives to the pyrrole derivatives to the furan derivatives is (13-23): (12-21): (21-39): (9-20): (24-34): (4-9);

preferably, the amide group is provided by an amide derivative, preferably the amide derivative is at least one selected from the group consisting of N, N' -dihydroxyethyl bisacrylamide, N-methylenebisacrylamide and hexamethylenebisacrylamide;

Preferably, the phenoxy group is provided by a phenoxy derivative, preferably the phenoxy derivative is selected from at least one of 4-methoxystyrene, allyl phenyl ether and phenyl vinyl ether;

Preferably, the phosphate group is provided by a phosphoric acid derivative, preferably the phosphoric acid derivative is selected from 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;

preferably, the sulfonic acid group is provided by a sulfonic acid derivative, preferably at least one selected from the group consisting 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;

preferably, the pyrrolyl group is provided by a pyrrole derivative, preferably the pyrrole derivative is selected from 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;

preferably, the furanyl group is provided by a furanyl derivative, preferably the furanyl derivative is 2- (1-propen-2-yl) furan and/or 2- (2-pentenyl) furan;

and/or, in the step (2), the condition of the first functional treatment comprises the steps of introducing a solution containing a first functional component into the inner cavity of the silanized hollow fiber membrane in the step (1), wherein the back pressure of the outlet of the inner cavity is 10-20 kg in terms of gauge pressure.

12. The method according to any one of claims 7 to 11, wherein in step (2), the first enophilic treatment comprises contacting a solution containing a first enophilic component with the inner surface of the hollow fiber membrane after the first functional treatment;

and/or, in the step (2), the solution containing the first enophilic component contains second polyether, the first enophilic component, a second initiator and water;

And/or the mass ratio of the second polyether to the first enophilic component to the second initiator to the water in the solution containing the first enophilic component is 100 (3.8-6.2): 0.3-0.6): 1-2;

And/or, the second polyether has an average molecular weight of 800-2000;

And/or the first enophilic component is provided by a phenoxy derivative, preferably at least one selected from 4-methoxystyrene, allyl phenyl ether and phenyl vinyl ether;

And/or in the step (2), the condition of the first enophilic treatment comprises the steps of introducing a solution containing a first enophilic component into the inner cavity of the hollow fiber membrane after the first functional treatment, wherein the back pressure of the outlet of the inner cavity is 6-13 kg based on the gauge pressure.

13. The method according to any one of claims 7 to 12, wherein in the step (3), the second functional treatment coats the outer surface of the hollow fiber membrane after the first enophilic treatment with a second functional layer, and the second functional layer contains an amide group, a pyrrole group and a furan group;

And/or, based on the external surface area of the dry-basis hollow fiber membrane substrate per square meter, the content of the amide groups in the second functional layer is 18-35mmol/m ², the content of the pyrrole groups is 13-21mmol/m ², and the content of the furan groups is 2-5mmol/m ².

14. The method according to any one of claims 7 to 13, wherein in the step (3), the second functional treatment comprises contacting a solution containing a second functional component with the outer surface of the hollow fiber membrane after the first enophilic treatment;

and/or, in the step (3), the solution containing the second functional component contains the second functional component, a third initiator and a first solvent;

And/or in the step (3), the mass ratio of the second functional component to the third initiator to the first solvent in the solution containing the second functional component is (4.2-7.5) (0.1-0.4) (92-96);

And/or, in the step (3), the first solvent is selected from at least one of toluene, para-xylene, meta-xylene and ortho-xylene;

And/or in the step (3), the second functional component is provided by amide derivatives, pyrrole derivatives and furan derivatives;

Preferably, in the solution containing the second functional component, the molar ratio of the amide derivative to the pyrrole derivative to the furan derivative is (23-46): (16-28): (2-7);

Preferably, in the step (3), the conditions of the second functional treatment comprise that the liquid-solid volume ratio of the solution containing the second functional component to the hollow fiber membrane after the first enophilic treatment is 2-4, the soaking temperature is 60-80 ℃ and the time is 1.5-3h.

15. The method of claim 14, wherein step (3) further comprises a post-treatment, the post-treatment being performed in the presence of a post-treatment agent;

And/or the post-treatment agent is at least one selected from absolute ethyl alcohol, absolute acetone and absolute methyl alcohol, preferably absolute acetone;

And/or the post-treatment conditions comprise soaking time of 0.5-1h, drying temperature of 120-150 ℃ and drying time of 0.5-1h.

16. Use of the low-carbon olefin hydrated fiber membrane according to any one of claims 1 to 6 or the low-carbon olefin hydrated fiber membrane produced by the production method according to any one of claims 7 to 15 in a low-carbon olefin hydration reaction;

Preferably, the raw materials for the hydration reaction of the low-carbon olefin comprise olefin reaction raw materials and water;

preferably, the content of the low-carbon olefin in the olefin reaction raw material is 10-100% by volume based on the total amount of the olefin reaction raw material;

Preferably, the lower olefins are C3 and/or C4 olefins;

Preferably, the low-carbon olefin hydration reaction comprises the steps of respectively contacting an olefin reaction raw material and the inner surface and the outer surface of a low-carbon olefin hydration fibrous membrane to carry out the low-carbon olefin hydration reaction to obtain an aqueous solution containing low-carbon alcohol;

Preferably, the conditions of the hydration reaction of the low-carbon olefin comprise the temperature of 80-150 ℃, the pressure of 500-2000kPa by a gauge pressure, the molar ratio of water to the low-carbon olefin of 1.5-4.5, and the treatment capacity of the olefin reaction raw material of 520-860L.m ^-2﹒h^-1 by taking the inner surface area of a dry basis hollow fiber membrane matrix per square meter as a reference.