CN109651552B

CN109651552B - Strong alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material

Info

Publication number: CN109651552B
Application number: CN201710945903.0A
Authority: CN
Inventors: 李亚男; 何文军
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2017-10-11
Filing date: 2017-10-11
Publication date: 2021-03-30
Anticipated expiration: 2037-10-11
Also published as: CN109651552A

Abstract

The invention relates to a strong-basicity ternary composite type nano inorganic oxide-graphene-ion exchange resin material and a preparation method thereof, and mainly solves the problems that in the prior art, a strong-basicity ion exchange resin catalyst is low in basic active group content and correspondingly low in activity in the application process of the catalyst. The invention comprises the following components in percentage by weight based on the total weight of the resin material: (a) 70-85 parts of a polymerized monomer; (b) 3-15 parts of a comonomer; (c) 0.1-10 parts of graphene; (d) 0.1-1 part of a nano inorganic oxide component; (e) the technical scheme of 0.1-10 parts of initiator well solves the problem and can be used in industrial production of strong-basicity composite ion exchange resin material catalysts.

Description

Strong alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material

Technical Field

The invention relates to a strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material and a preparation method thereof.

Background

Graphene is a novel nano-carbon material, and in view of the outstanding properties of high strength, high conductivity, high strength, flexibility, bending and the like of graphene, graphene provides a wide development space for a novel and high-performance polymer matrix composite material. The graphene and the polymer matrix are compounded to prepare the composite material, so that the physical and mechanical properties, the electrical properties and the like of the material can be obviously improved, and the composite material has a wide application prospect.

The nano oxide has excellent performance due to the unique properties of the nano material, and the existing researchers can prepare composite materials with different shapes by further researching doping, coating, modifying and the like by using the nano oxide, so that the nano oxide becomes a new research hotspot. The hydrothermal method is one of the more studied synthesis methods of nano oxide, when the soluble precursor salt of inorganic oxide is heated in a closed reaction container, water is used as a medium, and many compounds in the reaction system show physicochemical properties different from normal temperature, such as increased solubility and chemical combinationThe crystal structure of the product is easy to transform, and the like, and the oxide product obtained by recrystallization has small particles, uniform distribution and high purity. Adopts polyethylene glycol as a surfactant, and prepares Co with high purity and different shapes under hydrothermal conditions by using a cobalt oxalate precursor₃O₄And the grain size is uniform (young poplar, Huangkelong, Liuhe, etc., school newspaper of Chinese and south university, 2006, 37, 1103). Pires et al SnCl₂·2H₂O is soluble precursor salt, SnO powder is synthesized by a microwave-assisted hydrothermal method, and nanocrystals with different sizes and shapes can be obtained by adjusting hydrothermal synthesis time, temperature and concentration (Pires F I, Joanni E, Savu R et al, Material Letters,2008,62, 239). Document CN106340633A discloses that SnO is obtained by hydrothermal synthesis method₂Carbon Material and V₂O₅The/graphene composite material is further prepared into SnO by a ball milling and blending method₂carbon/V₂O₅A graphene composite nanomaterial. However, in the above technology, since the hydrothermal system has a strong hydrophilic requirement for the material deposited by the nano-oxide, the uniform dispersion of the aqueous solution and the deposited material can be promoted by using liquid glucose or graphene oxide having a strong hydrophilic property, so as to obtain a stable and uniform suspension, thereby achieving a good deposition effect, and the two different oxides are separately synthesized and further physically mixed and formed. Document CN104356258A discloses a method for modifying adsorption performance of aldehyde-removed resin with rare earth elements, but in the above technique, it is necessary to prepare sulfonated acidic resin by polymerization process, and then add rare earth element nitric acid solution into the molded resin for modification. The full exchange capacity of the commercially available strong base styrenic anion exchange resin type 201 is about 3.4 mmol/g.

Disclosure of Invention

One of the problems to be solved by the invention is that the prior art has the problems of low content of basic active groups of a strong-basic ion exchange resin catalyst and low activity in the application process of the catalyst correspondingly, and provides a novel strong-basic ternary composite nano inorganic oxide-graphene-ion exchange resin material which has the characteristics of high content of basic functional groups and high activity in the reaction process.

The second technical problem to be solved by the invention is to provide a preparation method of the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material corresponding to the first technical problem.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material is characterized by comprising the following components in parts by weight:

(a) 70-85 parts of a polymerized monomer;

(b) 3-15 parts of a comonomer;

(c) 0.1-10 parts of graphene;

(d) 0.1-1 part of a nano inorganic oxide component;

(e) 0.1-10 parts of an initiator;

wherein the polymerized monomer is selected from at least one of the compounds of the following structure;

the polymerized monomer is preferably at least one selected from p-chloromethyl styrene, 4- (3-chloropropyl) styrene, 4- (3-bromopropyl) styrene, 4- (4-chlorobutyl) styrene, 4- (4-bromobutyl) styrene, 4- (5-chloropentyl) styrene or 4- (5-bromopentyl) styrene;

the polymerized monomer in the technical scheme is more preferably selected from p-chloromethyl styrene and 4- (3-chloropropyl) styrene;

the comonomer is selected from at least one of the compounds of the following structure;

the comonomer is preferably at least one of ethylene glycol dimethacrylate, diacrylene, divinylphenylmethane and divinylbenzene;

in the technical scheme, the comonomer is more preferably selected from dipropenyl benzene and divinyl benzene; the nano inorganic oxide component is selected from at least one of nano oxides of metals in the second subgroup or/and nano oxides of metals in the sixth subgroup.

In the above-mentioned embodiment, it is preferable that the second subgroup metal is selected from zinc.

In the above-mentioned aspect, a preferable aspect is that the sixth subgroup is at least one selected from chromium and molybdenum.

In the above technical solution, the nano inorganic oxide component is preferably a nano oxide of zinc from a second subgroup metal and a nano oxide of chromium from a sixth subgroup; the molar ratio of zinc oxide to chromium oxide is (1: 4) to (4: 1), and both have a synergistic effect in enhancing the high activity of the resin material.

In the above technical solution, the nano inorganic oxide component is preferably a nano oxide of zinc from a second subgroup metal and a nano oxide of molybdenum from a sixth subgroup, and the molar ratio of zinc oxide to molybdenum oxide is (1: 4) - (4: 1); the two have synergistic effect in improving high activity of resin material.

In the above technical solution, the nano inorganic oxide component is preferably a nano oxide of chromium from the sixth subgroup and molybdenum metal, and the molar ratio of chromium oxide to molybdenum oxide is (1: 4) - (4: 1); the two have synergistic effect in improving high activity of resin material.

In the above technical solution, the nano inorganic oxide component is more preferably a composition of three nano oxides, namely zinc oxide, chromium oxide and molybdenum oxide, and the molar ratio of zinc oxide, chromium oxide and molybdenum oxide is 1: (0.25-4): (0.25-4), the three nano oxides are used together, and have a synergistic effect on the aspect of improving the high activity of the resin material.

The initiator is at least one selected from benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide and cumene hydroperoxide.

To solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material comprises the following steps:

(1) preparing a nano inorganic oxide soluble precursor salt into an aqueous solution A with the molar concentration of 0.01-4 mol/L; wherein the nano inorganic oxide component is selected from at least one of nano oxides of metals in a second subgroup and/or soluble precursor salts corresponding to nano oxides in a sixth subgroup;

(2) dipping the solution A into graphene, performing ultrasonic oscillation for 1-6 hours at normal temperature, adding a precipitator into a high-pressure reactor, performing hydrothermal decomposition for 2-24 hours at the temperature of 100-500 ℃, then slowly cooling, and washing to room temperature to obtain a nano inorganic oxide-graphene binary material B; wherein the precipitant is selected from at least one of deionized water, ammonia water, urea, sodium hydroxide or potassium hydroxide.

(3) Preparing a polymerization auxiliary agent into an aqueous solution C with the weight percentage concentration of 0.3-3%; wherein the polymerization auxiliary agent is selected from at least one of polyvinyl alcohol, gelatin, starch, methyl cellulose, bentonite or calcium carbonate; the amount of the polymerization assistant is 5-50% of the weight of the polymerization monomer;

(4) mixing a required amount of polymerization monomer, comonomer, initiator and the nano inorganic oxide-graphene binary material B prepared in the step (2) into a solution D;

(5) pre-polymerizing the solution D at 40-60 ℃ for 0.5-2.5 hours; stirring and mixing the solution D and the solution B, heating to 55-85 ℃, reacting for 3-10 hours, then heating to 80-95 ℃, reacting for 3-10 hours, and curing and forming; after the reaction is finished, pouring out the upper layer liquid, washing, filtering, drying and sieving, and collecting the ternary composite nano inorganic oxide-graphene-ion exchange resin microspheres with the particle size range of 0.35-0.60 mm;

(6) adding a swelling agent accounting for 100-200% of the weight of the composite microspheres, an amination reagent accounting for 50-150% of the weight of the composite microspheres and an alkali accounting for 50-150% of the weight of the composite microspheres into the ternary composite microspheres, and reacting for about 3-20 hours at 25-40 ℃; after the reaction is finished, washing with water, adding alkali for transformation, and washing with water to be neutral to obtain the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material.

Wherein the swelling agent is at least one selected from dichloromethane, 1, 2-dichloroethane, chloroform, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran; the amination reagent is selected from at least one of trimethylamine salt, triethylamine salt, diethylamine salt or tributylamine salt; the alkali is at least one of sodium hydroxide, potassium hydroxide or sodium bicarbonate.

In the above technical solution, preferably, the precipitating agent is selected from at least one of water and sodium hydroxide.

In the above technical solution, preferably, the polymerization assistant is at least one selected from polyvinyl alcohol and gelatin.

In the above technical solution, preferably, the swelling agent is at least one selected from dichloromethane and tetrahydrofuran.

In the above technical solution, preferably, the amination reagent is selected from at least one of trimethylamine salt and triethylamine salt.

The single-layer graphene and the multilayer graphene adopted in the invention can be prepared by methods such as an epitaxial growth method, a chemical vapor deposition method, a graphene oxide reduction method and the like. This is a well-known graphene preparation technique in the art and is published in document CN 201210561249.0.

The cross-linked skeleton of the ion exchange resin is styrene, and after the copolymerization skeleton is synthesized through polymerization reaction, functional group quaternary ammonium group is introduced through amination reaction. Specifically, the inorganic oxide soluble precursor salt is directly subjected to a hydrothermal method to generate a nano inorganic substance and loaded on the surface of graphene, so that the nano inorganic oxide-graphene binary compound with small particle size and uniform dispersion is obtained. The nano inorganic oxide-graphene binary compound participates in polymerization reaction, the nano inorganic oxide-graphene binary compound is grafted with a polymer carbon chain, and finally the ternary composite nano inorganic oxide-graphene-ion exchange resin bead is obtained. Introducing a functional group quaternary ammonium group through amination reaction to obtain the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material.

By adopting the technical scheme of the invention, the nano inorganic oxide is loaded and dispersed on the surface of the nano material graphene by utilizing a hydrothermal deposition method, and the graphene deposited with the nano oxide is applied to a polymerization reaction, so that the preparation of a novel strong-basicity ternary composite nano inorganic oxide-graphene-ion exchange resin material is realized, and the problems of low content of basic active groups of a strong-basicity graphene composite ion exchange resin catalyst and correspondingly low activity in the application process of the catalyst are solved. The strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material has the characteristics of high content of basic functional groups and strong activity in the reaction process, and achieves better technical effect in the practical application process.

The method for measuring the content of the basic group of the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material comprises the following steps: by adopting a hydrochloric acid standard solution titration method, 2.5 g of resin material is taken, 100 ml of 0.1 mol/L hydrochloric acid standard solution is added, and the resin material is heated in a water bath for 2 hours at the temperature of 40 ℃ and then cooled. And taking 25 ml of the soak solution, adding 50 ml of deionized water, and dropwise adding 2-3 drops of phenolphthalein indicator solution. Titrating with 0.1 mol/L sodium hydroxide standard solution, and recording the volume V of the sodium hydroxide standard solution₁And (4) milliliters. Taking another 1 g of resin material, drying at 105 ℃ to constant weight, and recording the mass m at the moment₁And g.

The water content of the resin is calculated by the formula

The calculation formula of the content of the basic groups on the surface of the resin is

The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

50 ml of deionized water solution (molar concentration is 0.1 mol/L) in which 2.001 g of chromium nitrate nonahydrate is dissolved is poured into 2.5 g of multilayer graphene, the mixture is stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, the temperature is kept for 24 hours at 160 ℃, the mixture is cooled to room temperature, the mixture is washed by deionized water, the mixture is poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and the mixture is stirred for 2 hours at 60 ℃ to carry out prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres A with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of the ternary composite microspheres A and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and the mixture is washed with water, and is further washed with water to be neutral after being transformed by adding sodium hydroxide, so that the ternary composite ion exchange resin material A is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material A is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano chromium oxide-graphene-ion exchange resin material A.

[ example 2 ]

Preparing 50 ml of deionized water solution (the molar concentration is 0.1 mol/L) from 1.487 g of zinc nitrate hexahydrate, soaking the solution into 2.5 g of multilayer graphene powder, stirring the solution and pouring the solution into a hydrothermal kettle, ultrasonically oscillating the solution for 1 hour, keeping the temperature of the hydrothermal kettle at 160 ℃ for 24 hours, cooling the solution to room temperature, and washing the solution with deionized water to obtain a nano zinc oxide-graphene binary composite sample. In a 250 ml three-necked flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide as an initiator were charged, and stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres B with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of the ternary composite microspheres B and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and the mixture is washed with water, and is further washed with water to be neutral after being transformed by adding sodium hydroxide, so that the ternary composite ion exchange resin material B is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material B is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano zinc oxide-graphene-ion exchange resin material B.

[ example 3 ]

A deionized water solution (molar concentration is 0.1 mol/L) in which 6.179 g of ammonium molybdate tetrahydrate is dissolved is poured into 2.5 g of multilayer graphene, the mixture is stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, the temperature is kept for 24 hours at 160 ℃, the mixture is cooled to room temperature, the mixture is washed by deionized water, the mixture is poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and the mixture is stirred for 2 hours at 60 ℃ for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres C with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of the ternary composite microsphere C and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microsphere was allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and the mixture is washed with water, and is further washed with water to be neutral after being transformed by adding sodium hydroxide, so that the ternary composite ion exchange resin material C is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material C is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline ternary composite nano molybdenum oxide-graphene-ion exchange resin material C.

[ example 4 ]

50 ml of deionized water solution (the molar concentrations are 0.02 mol/L and 0.08 mol/L respectively, and the molar concentration ratio is 1:4) of 0.400 g of chromium nitrate nonahydrate and 1.190 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres D with the particle size of 0.35-0.60 mm.

In a 250 ml three-necked flask, 30 g of the ternary composite microsphere D and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃ and the ternary composite microsphere was allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and the mixture is washed with water, and is further washed with water to be neutral after being transformed by adding sodium hydroxide, so that the ternary composite ion exchange resin material D is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material D is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material D.

[ example 5 ]

50 ml of deionized water solution (the molar concentrations are 0.04 mol/L and 0.06 mol/L respectively and the molar concentration ratio is 2:3) of dissolved 0.800 g of chromium nitrate nonahydrate and 0.892 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres E with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material E and the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material E is the same as that in example 4.

[ example 6 ]

50 ml of deionized water solution (the molar concentrations are 0.05 mol/L and 0.05 mol/L respectively, and the molar concentration ratio is 1:1) of dissolved 1.000 g of chromium nitrate nonahydrate and 0.744 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres F with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material F and the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material F is the same as that in example 4.

[ example 7 ]

50 ml of deionized water solution (the molar concentrations are 0.06 mol/L and 0.04 mol/L respectively and the molar concentration ratio is 3:2) of dissolved 1.200 g of chromium nitrate nonahydrate and 0.595 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres G with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material G and the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material G is the same as that in example 4.

[ example 8 ]

50 ml of deionized water solution (molar concentrations are 0.08 mol/L and 0.02 mol/L respectively, and the molar concentration ratio is 4:1) of dissolved 1.601 g of chromium nitrate nonahydrate and 0.297 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres H with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material H and the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material H is the same as that in example 4.

[ example 9 ]

50 ml of deionized water solution (molar concentrations are 0.02 mol/L and 0.08 mol/L respectively, and the molar concentration ratio is 1:4) of dissolved 0.400 g of chromium nitrate nonahydrate and 4.943 g of ammonium molybdate tetrahydrate is poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres I with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of the ternary composite microsphere I and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microsphere was allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and the mixture is washed with water, and is further washed with water to be neutral after being transformed by adding sodium hydroxide, so that the ternary composite ion exchange resin material I is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material I is soaked in 200 ml of methanol and washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material I.

[ example 10 ]

50 ml of deionized water solution (molar concentrations are 0.04 mol/l and 0.06 mol/l respectively, and the molar concentration ratio is 2:3) of dissolved 0.800 g of chromium nitrate nonahydrate and 3.708 g of ammonium molybdate tetrahydrate is poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres J with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material J and the strong-alkaline ternary composite nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material J is the same as that in example 9.

[ example 11 ]

50 ml of deionized water solution (molar concentrations are 0.05 mol/L and 0.05 mol/L respectively, and the molar concentration ratio is 1:1) of dissolved 0.744 g of chromium nitrate nonahydrate and 3.090 g of ammonium molybdate tetrahydrate is poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres K with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material K and the strong-alkaline ternary complex nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material K is the same as that in example 9.

[ example 12 ]

50 ml of deionized water solution (molar concentrations are 0.06 mol/L and 0.04 mol/L respectively, and the molar concentration ratio is 3:2) of dissolved 1.200 g of chromium nitrate nonahydrate and 2.472 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres L with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material L and the strongly basic ternary complex nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material L is the same as that in example 9.

[ example 13 ]

50 ml of deionized water solution (molar concentrations are 0.08 mol/L and 0.02 mol/L respectively, and the molar concentration ratio is 4:1) of dissolved 1.601 g of chromium nitrate nonahydrate and 1.236 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the ternary composite microspheres M with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material M and the strongly basic ternary complex nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material M was the same as in example 9.

[ example 14 ]

50 ml of deionized water solution (molar concentrations are 0.02 mol/l and 0.08 mol/l respectively, and the molar concentration ratio is 1:4) of 0.297 g of zinc nitrate hexahydrate and 4.943 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed with deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres N with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of ternary composite microsphere N and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microsphere was allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water to be neutral, so that the ternary composite ion exchange resin material N is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material N is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano zinc oxide/molybdenum oxide-graphene-ion exchange resin material N.

[ example 15 ]

50 ml of deionized water solution (molar concentrations are 0.04 mol/L and 0.06 mol/L respectively, and the molar concentration ratio is 2:3) of 0.595 g of zinc nitrate hexahydrate and 3.708 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres O with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material O and the strongly basic ternary complex nano zinc oxide/molybdenum oxide-graphene-ion exchange resin material O is the same as that in example 14.

[ example 16 ]

50 ml of deionized water solution (molar concentrations are 0.05 mol/L and 0.05 mol/L respectively, and the molar concentration ratio is 1:1) of dissolved 0.744 g of zinc nitrate hexahydrate and 3.090 g of ammonium molybdate tetrahydrate is poured into 2.5 g of multilayer graphene, the mixture is stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, the hydrothermal kettle is kept at 160 ℃ for 24 hours, the hydrothermal kettle is cooled to room temperature, washed by deionized water and poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and the mixture is stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres P with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material P and the strongly basic ternary complex nano zinc oxide/molybdenum oxide-graphene-ion exchange resin material P is the same as that in example 14.

[ example 17 ]

50 ml of deionized water solution (molar concentrations are 0.06 mol/L and 0.04 mol/L respectively, and the molar concentration ratio is 3:2) of 0.892 g of zinc nitrate hexahydrate and 2.472 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres Q with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material Q and the strongly basic ternary complex nano zinc oxide/molybdenum oxide-graphene-ion exchange resin material Q is the same as that in example 14.

[ example 18 ]

50 ml of deionized water solution (molar concentrations are 0.08 mol/L and 0.02 mol/L respectively and the molar concentration ratio is 4:1) of dissolved 1.190 g of zinc nitrate hexahydrate and 1.236 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, the mixture is stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour and is kept at 160 ℃ for 24 hours, the mixture is cooled to room temperature, washed by deionized water and poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and the mixture is stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres R with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material R and the strongly basic ternary complex nano zinc oxide/molybdenum oxide-graphene-ion exchange resin material R is the same as that in example 14.

[ example 19 ]

50 ml of deionized water solution (the molar concentrations are 0.02 mol/L, 0.04 mol/L and 0.04 mol/L respectively and the molar concentration ratio is 1:2:2) of 0.400 g of chromium nitrate nonahydrate, 0.595 g of zinc nitrate hexahydrate and 2.472 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace for 24 hours at 160 ℃ after being subjected to ultrasonic oscillation for 1 hour, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and stirred for 2 hours at 60 ℃ for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres S with the particle size of 0.35-0.60 mm.

In a 250 ml three-necked flask, 30 g of the ternary composite microspheres S and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃ and the ternary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, so that the ternary composite ion exchange resin material S is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material S is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline ternary composite nano chromium oxide/zinc oxide/molybdenum oxide-graphene-ion exchange resin material S.

[ example 20 ]

50 ml of deionized water solution (molar concentrations are 0.04 mol/l, 0.02 mol/l and 0.04 mol/l respectively, and the molar concentration ratio is 2:1:2) of 0.800 g of chromium nitrate nonahydrate, 0.297 g of zinc nitrate hexahydrate and 2.472 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace for 24 hours at 160 ℃ after being subjected to ultrasonic oscillation for 1 hour, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and stirred for 2 hours at 60 ℃ for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres T with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material T and the strongly basic ternary complex nano chromium oxide/zinc oxide/molybdenum oxide-graphene-ion exchange resin material T was the same as in example 19.

[ example 21 ]

50 ml of deionized water solution (the molar concentrations are 0.04 mol/L, 0.04 mol/L and 0.02 mol/L respectively and the molar concentration ratio is 2:2:1) of 0.800 g of chromium nitrate nonahydrate, 0.595 g of zinc nitrate hexahydrate and 1.236 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace for 24 hours at 160 ℃ after being subjected to ultrasonic oscillation for 1 hour, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, 80.6 g of p-chloromethyl styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator are added, and stirred for 2 hours at 60 ℃ for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres U with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary complex ion exchange resin material U and the strongly basic ternary complex nano chromium oxide/zinc oxide/molybdenum oxide-graphene-ion exchange resin material U was the same as in example 19.

[ example 22 ]

50 ml of deionized water solution (molar concentrations are respectively 0.033 mol/l, 0.033 mol/l and 0.033 mol/l, and the molar concentration ratio is 1:1:1) of 0.491 g of zinc nitrate hexahydrate and 2.039 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace for 24 hours at 160 ℃ after being subjected to ultrasonic oscillation for 1 hour, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene and 0.1 g of divinylbenzene peroxide initiator are added, and stirred for 2 hours at 60 ℃ for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres V with the particle size of 0.35-0.60 mm.

The subsequent preparation process of the ternary composite ion exchange resin material V and the strongly basic ternary composite nano chromium oxide/zinc oxide/molybdenum oxide-graphene-ion exchange resin material V was the same as in example 19.

[ example 23 ]

50 ml of deionized water solution (the molar concentrations are 0.02 mol/L and 0.08 mol/L respectively, and the molar concentration ratio is 1:4) of 0.400 g of chromium nitrate nonahydrate and 1.190 g of zinc nitrate hexahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 85.7 g of 4- (3-chloropropyl) styrene, 3.5 g of divinylbenzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the ternary composite microspheres D2 with the particle size of 0.35-0.60 mm.

In a 250 ml three-necked flask, 30 g of the ternary composite microsphere D2 and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃ and the ternary composite microsphere was allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, and then the ternary composite ion exchange resin material D2 is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material D2 was soaked in 200 ml of methanol and washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano chromium oxide/zinc oxide-graphene-ion exchange resin material D2.

[ example 24 ]

50 ml of deionized water solution (molar concentrations are 0.02 mol/L and 0.08 mol/L respectively, and the molar concentration ratio is 1:4) of dissolved 0.400 g of chromium nitrate nonahydrate and 4.943 g of ammonium molybdate tetrahydrate are poured into 2.5 g of multilayer graphene, stirred and poured into a hydrothermal kettle, the hydrothermal kettle is placed in a hydrothermal furnace after being subjected to ultrasonic oscillation for 1 hour, kept at 160 ℃ for 24 hours, cooled to room temperature, washed by deionized water, poured into a 250 ml three-neck flask, added with 80.6 g of p-chloromethyl styrene, 3.8 g of dipropenyl benzene and 0.1 g of benzoyl peroxide initiator, and stirred at 60 ℃ for 2 hours for prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the ternary composite microspheres I2 with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of ternary complex microspheres I2 and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary complex microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, so that the ternary composite ion exchange resin material I2 is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material I2 was soaked in 200 ml of methanol and washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano chromium oxide/molybdenum oxide-graphene-ion exchange resin material I2.

[ example 25 ]

Preparing 50 ml of deionized water solution (the molar concentration is 0.1 mol/L) from 1.487 g of zinc nitrate hexahydrate, soaking the solution into 2.5 g of multilayer graphene powder, stirring the solution and pouring the solution into a hydrothermal kettle, ultrasonically oscillating the solution for 1 hour, keeping the temperature of the hydrothermal kettle at 160 ℃ for 24 hours, cooling the solution to room temperature, and washing the solution with deionized water to obtain a nano zinc oxide-graphene binary composite sample. In a 250 ml three-necked flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene and 0.1 g of azobisisobutyronitrile initiator were charged, and they were stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the ternary composite microspheres B2 with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of ternary composite microspheres B2 and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the ternary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, and the ternary composite ion exchange resin material B2 is obtained.

The post-treatment process is as follows: 50 ml of the ternary composite ion exchange resin material B2 was soaked in 200 ml of methanol and washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline ternary composite nano zinc oxide-graphene-ion exchange resin material B2.

[ example 26 ]

The water content and the basic group content of the strongly basic ternary complex ion exchange resin materials A to V, D2, I2 and B2 obtained in the examples 1 to 25 were evaluated, and the results are shown in Table 1.

Comparative example 1

In a 250 ml three-necked flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene, 2.5 g of multilayer graphene and 0.1 g of benzoyl peroxide initiator were added, and stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the binary composite microspheres W with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of binary composite microspheres W and 50 ml of dichloroethane were added, the water bath temperature was adjusted to 30 ℃, and the binary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, so that the binary composite ion exchange resin material W is obtained.

The post-treatment process is as follows: 50 ml of the binary composite ion exchange resin material W is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline binary composite graphene-ion exchange resin material W.

Similarly [ example 26 ], the water content and the basic group content of the ion exchange resin material W were evaluated, and the results are shown in Table 1.

Comparative example 2

In a 250 ml three-necked flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene, 2.5 g of monolayer graphene and 0.1 g of benzoyl peroxide initiator were added, and stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, filtering, drying in an oven at 80 ℃, sieving, and collecting the binary composite microspheres W2 with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of binary composite microspheres W2 and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃, and the binary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water until the mixture is neutral, so that the binary composite ion exchange resin material W2 is obtained.

The post-treatment process is as follows: 50 ml of the binary composite ion exchange resin material W2 was soaked in 200 ml of methanol and washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline binary composite graphene-ion exchange resin material W2.

Similarly [ example 26 ], the water content and the basic group content of the ion exchange resin material W2 were evaluated, and the results are shown in Table 1.

Comparative example 3

Preparing 50 ml of deionized water solution (the molar concentration is 0.1 mol/L) from 1.190 g of cobalt chloride hexahydrate, soaking the solution into 2.5 g of multilayer graphene powder, stirring the solution and pouring the solution into a hydrothermal kettle, ultrasonically oscillating the solution for 1 hour, keeping the temperature of the hydrothermal kettle at 160 ℃ for 24 hours, cooling the solution to room temperature, and washing the solution by using deionized water to obtain a nano cobalt oxide-graphene binary composite sample. In a 250 ml three-neck flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene, 2.5 g of a nano cobalt oxide-graphene binary composite sample and 0.1 g of benzoyl peroxide initiator were added, and stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the binary composite microspheres X with the particle size of 0.35-0.60 mm.

In a 250 ml three-neck flask, 30 g of binary composite microspheres X and 50 ml of dichloroethane were added, the water bath temperature was adjusted to 30 ℃, and the binary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water to be neutral, so that the binary composite ion exchange resin material X is obtained.

The post-treatment process is as follows: 50 ml of the binary composite ion exchange resin material X is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strongly alkaline ternary composite nano cobalt oxide-graphene-ion exchange resin material X.

Similarly [ example 26 ], the water content and the basic group content of the ion exchange resin material X were evaluated, and the results are shown in Table 1.

Comparative example 4

0.877 g of tin tetrachloride pentahydrate is prepared into 50 ml of deionized water solution (the molar concentration is 0.1 mol/L), the deionized water solution is soaked into 2.5 g of multilayer graphene powder, the mixture is stirred and poured into a hydrothermal kettle, ultrasonic oscillation is carried out for 1 hour, the mixture is kept for 24 hours at 160 ℃ in a hydrothermal furnace, the mixture is cooled to room temperature and washed by deionized water, and the nano tin oxide-graphene binary composite sample is obtained. In a 250 ml three-neck flask, 80.6 g of p-chloromethylstyrene, 3.5 g of divinylbenzene, 2.5 g of nano iron oxide-graphene binary composite sample and 0.1 g of benzoyl peroxide initiator were added, and stirred at 60 ℃ for 2 hours to perform prepolymerization. A solution of 1.5 g polyvinyl alcohol in 150 ml of deionized water was added. Adjusting the stirring speed, gradually raising the temperature to 80 ℃ at the same time, and reacting for 5 hours; then the temperature is raised to 90 ℃ for reaction for 5 hours, and finally the temperature is raised to 98 ℃ for reaction for 6 hours. After the reaction is finished, pouring out the upper layer liquid, washing with hot water, then filtering, putting into an oven for drying at 80 ℃, sieving, and collecting the binary composite microspheres Y with the particle size of 0.35-0.60 mm.

In a 250 ml three-necked flask, 30 g of the binary composite microspheres Y and 50 ml of dichloroethane were added, the temperature of the water bath was adjusted to 30 ℃ and the binary composite microspheres were allowed to swell at that temperature for 2 hours. Then 27 g of trimethylamine hydrochloride and 130 ml of 20% sodium hydroxide solution were added and the mixture was reacted at about 30 ℃ for about 8 hours. After the reaction is finished, water is gradually added to dilute until the specific gravity is equal to 1.0, and then the mixture is washed with water, and after sodium hydroxide is added for transformation, the mixture is further washed with water to be neutral, so that the binary composite ion exchange resin material Y is obtained.

The post-treatment process is as follows: 50 ml of the binary composite ion exchange resin material Y is soaked in 200 ml of methanol and then washed with 700 ml of deionized water. Then loading the resin into a glass column with a sand core, washing the resin by deionized water, wherein the flow rate of the deionized water is 5 ml/min, and the treatment time is 30 min; the resin was washed with 0.75 mol/l HCl solution at a flow rate of 2 ml/min for a treatment time of 90 minutes; then washing the resin by deionized water until the eluate is neutral; the resin was washed with 0.3 mol/l NaOH solution at a flow rate of 1.7 ml/min for a treatment time of 200 min; and then washing the resin with deionized water until the eluate is neutral, and airing the water at room temperature of 25 ℃ to obtain the strong-alkaline ternary composite nano tin oxide-graphene-ion exchange resin material Y.

Similarly [ example 26 ], the water content and the basic group content of the ion exchange resin material Y were evaluated, and the results are shown in Table 1.

TABLE 1

Claims

1. The strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material is characterized by comprising the following components in parts by weight:

(a) 70-85 parts of a polymerized monomer;

(b) 3-15 parts of a comonomer;

(c) 0.1-10 parts of graphene;

(d) 0.1-1 part of a nano inorganic oxide component;

(e) 0.1-10 parts of an initiator;

the graphene is selected from at least one of single-layer graphene or multi-layer graphene;

the nano inorganic oxide component is selected from at least one of nano zinc oxide, nano chromium oxide and nano molybdenum oxide;

the initiator is selected from at least one of benzoyl peroxide, azobisisobutyronitrile, lauroyl peroxide and cumene hydroperoxide;

the preparation method of the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material comprises the following steps:

(1) preparing a nano inorganic oxide soluble precursor salt into an aqueous solution A with the molar concentration of 0.01-5 mol/L; wherein the soluble precursor salt of the nano inorganic oxide is selected from at least one of soluble precursor salts corresponding to nano zinc oxide, nano chromium oxide and nano molybdenum oxide;

(2) dipping the solution A into graphene, performing ultrasonic oscillation for 1-6 hours at normal temperature, adding a precipitator into a high-pressure reactor, sealing and preserving heat for 2-24 hours at the temperature of 100-500 ℃, then slowly cooling, and washing to room temperature to obtain a nano inorganic oxide-graphene binary material B; wherein the precipitant is selected from at least one of deionized water, ammonia water, urea, sodium hydroxide or potassium hydroxide;

(5) pre-polymerizing the solution D at 40-60 ℃ for 0.5-2.5 hours; stirring and mixing the solution D and the solution C, heating to 55-85 ℃, reacting for 3-10 hours, then heating to 80-95 ℃, reacting for 3-10 hours, and curing and forming; after the reaction is finished, pouring out the upper layer liquid, washing, filtering, drying and sieving, and collecting the ternary composite nano inorganic oxide-graphene-ion exchange resin microspheres with the particle size range of 0.35-0.60 mm;

(6) adding a swelling agent accounting for 100-200% of the weight of the composite microspheres, an amination reagent accounting for 50-150% of the weight of the composite microspheres and an alkali accounting for 50-150% of the weight of the composite microspheres into the ternary composite microspheres, and reacting for 3-20 hours at 25-40 ℃; after the reaction is finished, washing with water, adding alkali for transformation, and washing with water to be neutral to obtain the strong-alkaline ternary composite nano inorganic oxide-graphene-ion exchange resin material.

2. The preparation method of the strongly basic ternary complex type nano inorganic oxide-graphene-ion exchange resin material of claim 1, which comprises the following steps:

3. The method for preparing the strongly basic ternary complex nano inorganic oxide-graphene-ion exchange resin material according to claim 2, wherein the swelling agent is at least one selected from dichloromethane, 1, 2-dichloroethane, chloroform, N-dimethylformamide, dimethylsulfoxide and tetrahydrofuran.

4. The preparation method of the strongly basic ternary complex nano inorganic oxide-graphene-ion exchange resin material according to claim 2, characterized in that the amination reagent is selected from at least one of trimethylamine salt, triethylamine salt, diethylamine salt or tributylamine salt; the alkali is at least one of sodium hydroxide, potassium hydroxide or sodium bicarbonate.

5. The method for preparing the strong alkaline ternary complex type nano inorganic oxide-graphene-ion exchange resin material according to claim 2, wherein the precipitant is at least one selected from water and sodium hydroxide.

6. The preparation method of the strongly basic ternary complex nano inorganic oxide-graphene-ion exchange resin material according to claim 2, characterized in that the polymerization auxiliary agent is selected from at least one of polyvinyl alcohol or gelatin; the swelling agent is at least one of dichloromethane or tetrahydrofuran; the amination reagent is selected from at least one of trimethylamine salt or triethylamine salt.