CN113769793A - Method for regulating and controlling particle size of macroporous anion exchange resin microspheres - Google Patents

Method for regulating and controlling particle size of macroporous anion exchange resin microspheres Download PDF

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Publication number
CN113769793A
CN113769793A CN202111137934.6A CN202111137934A CN113769793A CN 113769793 A CN113769793 A CN 113769793A CN 202111137934 A CN202111137934 A CN 202111137934A CN 113769793 A CN113769793 A CN 113769793A
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China
Prior art keywords
divinylbenzene
crosslinked styrene
anion exchange
exchange resin
controlling
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CN202111137934.6A
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Chinese (zh)
Inventor
陈新德
徐文萍
陈雪芳
姚时苗
张海荣
薛兆能
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Anhui Wandong Resin Technology Co ltd
Guangzhou Institute of Energy Conversion of CAS
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Anhui Wandong Resin Technology Co ltd
Guangzhou Institute of Energy Conversion of CAS
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Priority to CN202111137934.6A priority Critical patent/CN113769793A/en
Publication of CN113769793A publication Critical patent/CN113769793A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00Ion-exchange processes in general; Apparatus therefor
    • B01J47/016Modification or after-treatment of ion-exchangers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12Macromolecular compounds

Abstract

The invention discloses a method for regulating and controlling the particle size of macroporous anion exchange resin microspheres, which relates to the technical field of functional polymer materials.

Description

Method for regulating and controlling particle size of macroporous anion exchange resin microspheres
The technical field is as follows:
the invention relates to the technical field of functional polymer materials, in particular to a method for regulating and controlling the particle size of macroporous anion exchange resin microspheres.
Background art:
at present, the application of the adsorption resin is spread over a plurality of fields, and a unique adsorption separation technology is formed. Due to the structural diversity, the adsorbent resins can be selected or designed according to the actual application, and therefore, a plurality of special varieties with targeted applications are developed.
The macroporous anion exchange resin is a three-dimensional reticular polymer material with anion groups, and is widely applied to the fields of wastewater treatment, wet metallurgy and the like. However, the particle size of the macroporous anion exchange resin has a large impact on performance. The smaller and more uniform the particle diameter, the better the adsorption performance of the resin. However, the particle size is too small, the resistance to fluid is too great during use, filtration is difficult, and the particles are easily lost. The particle size is very difficult for the production of the adsorption resin, and the existing adsorption resin generally has wider particle size distribution. Therefore, the key in the resin preparation technology is to regulate and control the particle size of the macroporous anion exchange resin microspheres.
The invention content is as follows:
the invention aims to solve the technical problem of providing a method for regulating and controlling the particle size of macroporous anion exchange resin microspheres, which is a preparation method of macroporous anion exchange resin with adjustable particle size, wherein crosslinked styrene-divinylbenzene microspheres with different particle sizes are obtained by regulating and controlling the type and the using amount of dispersing agents in the preparation process of the crosslinked styrene-divinylbenzene microspheres, and are subjected to chloromethylation and amination on the basis. The macroporous anion exchange resin has the outstanding advantages of adjustable and controllable microsphere particle size, pore structure and pore size distribution, good wear resistance and the like, and can be applied to the fields of wet metallurgy, wastewater treatment, organic matter separation and purification and the like.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a method for regulating and controlling the particle size of macroporous anion exchange resin microspheres comprises the following steps:
(1) preparing a crosslinked styrene-divinylbenzene microsphere matrix: adding a dispersing agent and sodium salt into water, starting stirring, raising the temperature to completely dissolve the dispersing agent, then cooling, and dropwise adding a methylene blue aqueous solution to obtain a water phase; pouring a mixed oil phase consisting of a monomer, a cross-linking agent, a pore-forming agent and an initiator into the water phase, starting stirring after the nitrogen introduction is finished, heating for reaction, stopping stirring, and alternately washing with hot water and ethanol until the liquid is clear to obtain the styrene-divinylbenzene copolymer white ball;
(2) chloromethylation of crosslinked styrene-divinylbenzene: swelling the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in a chloromethyl ether aqueous solution, adding anhydrous ferric chloride, dropwise adding sulfuric acid while stirring, controlling the reaction temperature, carrying out heat preservation reaction, and carrying out solid-liquid separation to obtain chloromethyl crosslinked styrene-divinylbenzene microspheres as solids;
(3) amination of chloromethyl crosslinked styrene-divinylbenzene: swelling the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2) in dimethylamine, starting stirring, controlling the reaction temperature, carrying out heat preservation reaction, and carrying out solid-liquid separation to obtain the macroporous anion exchange resin microspheres as solids.
The dispersing agent in the step (1) is any one of polyvinyl alcohol, gelatin and hydroxyethyl cellulose.
In the step (1), the monomer is styrene, the cross-linking agent is divinylbenzene, the pore-forming agent is isobutanol, and the initiator is benzoyl peroxide.
In the step (1), the dosage of the cross-linking agent is 0.06-0.3 times of the mass of the monomer, the dosage of the pore-foaming agent is 0.5-1.2 times of the sum of the mass of the monomer and the cross-linking agent, the dosage of the initiator is 0.3-1% of the mass of the monomer, the volume ratio of water to oil is 1-3: 1, the dosage of the dispersing agent is 0.5-1.5% of the mass of the water phase, and the dosage of the sodium salt is 0.05-0.1% of the mass of the water phase.
The consumption of the anhydrous ferric chloride in the step (2) is 20-50% of the mass of the crosslinked styrene-divinylbenzene.
And (3) controlling the reaction temperature in the step (2) to be 30-45 ℃ and keeping the reaction time at 10 h.
And (4) controlling the reaction temperature in the step (3) to be 48-53 ℃, and keeping the temperature for 12 hours.
The macroporous anion exchange resin microspheres prepared in the step (3) have the particle size range of 0.25-2.0 mm and the BET total specific surface area of 20-360 m2The total exchange capacity is 1.0-4.8 mmol/g.
The invention has the beneficial effects that:
(1) the preparation process of the crosslinked styrene-divinylbenzene microsphere is regulated and controlled by changing the type and the using amount of the dispersing agent, so that the obtained crosslinked styrene-divinylbenzene microsphere matrix has the advantages of high mechanical strength, controllable and adjustable particle size macropores and the like, and the macroporous anion exchange resin synthesized on the basis also has controllable and adjustable microsphere particle size and better mechanical strength.
(2) The macroporous anion exchange resin prepared by the invention has the particle size range of 0.25-2.0 mm and the BET total specific surface area of 20-360 m2The total exchange capacity is 1.0-4.8 mmol/g.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
(1) Preparation of crosslinked styrene-divinylbenzene microsphere matrix
In a 500mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser were charged 200g of water, 1.2g of gelatin, 0.1mL of a 1 wt% methylene blue solution and 0.15g of sodium chloride, and heated until the gelatin was dissolved. An oil phase comprising 60g of styrene, 6g of divinylbenzene, 0.5g of benzoyl peroxide and 60g of isobutanol is added, mechanical stirring is started and the stirring speed is adjusted to 170 rpm. Slowly heating to 75 ℃ for reaction for 1h, and then heating to 85 ℃ for reaction for 5 h. And (4) finishing the reaction, carrying out solid-liquid separation on the system, and washing for multiple times to obtain a solid product. And then removing the residual impurities in pore-foaming agent and resin pore channels by Soxhlet extraction to obtain the crosslinked polystyrene-divinylbenzene microsphere matrix.
(2) Chloromethylation of crosslinked styrene-divinylbenzene
Swelling 50g of the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in 200g of chloromethyl ether aqueous solution, adding 10g of anhydrous ferric chloride, dynamically swelling for 2h, slowly dropwise adding a certain amount of concentrated sulfuric acid, controlling the reaction temperature to be 45 ℃, carrying out heat preservation reaction at 45 ℃ for 10h, carrying out solid-liquid separation after the reaction is finished, and recovering the solution.
(3) Amination of chloromethyl crosslinked styrene-divinylbenzene
And (3) draining the surface water of the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2), adding liquid caustic soda with the mass concentration of 32%, adding 220g of dimethylamine solution, starting stirring, keeping the temperature to 48 ℃ for amination for 12h, carrying out solid-liquid separation after the amination is finished, and recovering the solution to obtain the macroporous anion exchange resin microspheres.
The prepared macroporous anion exchange resin has the particle size of 1.0-1.8 mm and the BET specific surface area of 340.5m2The total exchange capacity was 2.0 mmol/g.
Example 2
(1) Preparation of crosslinked styrene-divinylbenzene microsphere matrix
In a 500mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser were charged 210g of water, 1.08g of hydroxyethyl cellulose, 0.1mL of a 1 wt% methylene blue solution and 0.13g of sodium chloride, and heated until the hydroxyethyl cellulose was dissolved. An oil phase comprising 40g of styrene, 20g of divinylbenzene, 0.4g of benzoyl peroxide and 50g of isobutanol is added, mechanical stirring is started and the stirring speed is adjusted to 180 rpm. Slowly heating to 95 ℃ and reacting for 8 h. And (4) finishing the reaction, carrying out solid-liquid separation on the system, and washing for multiple times to obtain a solid product. And then removing the residual impurities in pore-foaming agent and resin pore channels by Soxhlet extraction to obtain the crosslinked polystyrene-divinylbenzene microsphere matrix.
(2) Chloromethylation of crosslinked styrene-divinylbenzene
Swelling 50g of the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in 200g of chloromethyl ether aqueous solution, adding 10g of anhydrous ferric chloride, dynamically swelling for 2h, slowly dropwise adding a certain amount of concentrated sulfuric acid, controlling the reaction temperature to be 45 ℃, carrying out heat preservation reaction at 45 ℃ for 10h, carrying out solid-liquid separation after the reaction is finished, and recovering the solution.
(3) Amination of chloromethyl crosslinked styrene-divinylbenzene
And (3) draining the surface water of the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2), adding liquid caustic soda with the mass concentration of 32%, adding 220g of dimethylamine solution, starting stirring, keeping the temperature to 48 ℃ for amination for 12h, carrying out solid-liquid separation after the amination is finished, and recovering the solution to obtain the macroporous anion exchange resin microspheres.
The prepared macroporous anion exchange resin has the particle size of 0.8-1.5 mm and the BET specific surface area of 165.2m2The total exchange capacity of the catalyst is 2.6 mmol/g.
Example 3
(1) Preparation of crosslinked styrene-divinylbenzene microsphere matrix
In a 500mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, 200g of water, 1.0g of polyvinyl alcohol, 0.2g of gelatin, 0.1mL of a 1 wt% methylene blue solution and 0.16g of sodium chloride were placed, and the flask was heated until the polyvinyl alcohol and the gelatin were dissolved. An oil phase comprising 60g of styrene, 10g of divinylbenzene, 0.7g of benzoyl peroxide and 40g of isobutanol is added, mechanical stirring is started and the stirring speed is adjusted to 200 rpm. Slowly heating to 90 ℃ and reacting for 8 h. And (4) finishing the reaction, carrying out solid-liquid separation on the system, and washing for multiple times to obtain a solid product. And then removing the residual impurities in pore-foaming agent and resin pore channels by Soxhlet extraction to obtain the crosslinked polystyrene-divinylbenzene microsphere matrix.
(2) Chloromethylation of crosslinked styrene-divinylbenzene
Swelling 50g of the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in 200g of chloromethyl ether aqueous solution, adding 10g of anhydrous ferric chloride, dynamically swelling for 2h, slowly dropwise adding a certain amount of concentrated sulfuric acid, controlling the reaction temperature to be 45 ℃, carrying out heat preservation reaction at 45 ℃ for 10h, carrying out solid-liquid separation after the reaction is finished, and recovering the solution. (3) Amination of chloromethyl crosslinked styrene-divinylbenzene
And (3) draining the surface water of the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2), adding liquid caustic soda with the mass concentration of 32%, adding 220g of dimethylamine solution, starting stirring, keeping the temperature to 48 ℃ for amination for 12h, carrying out solid-liquid separation after the amination is finished, and recovering the solution to obtain the macroporous anion exchange resin microspheres.
The prepared macroporous anion exchange resin has the particle size of 0.5-1.5 mm and the BET specific surface area of 83m2The total exchange capacity of the catalyst is 3.8 mmol/g.
Example 4
(1) Preparation of crosslinked styrene-divinylbenzene microsphere matrix
A500 mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was charged with 210g of water, 1.0g of hydroxyethyl cellulose, 0.2g of gelatin, 0.1mL of a 1 wt% methylene blue solution and 0.17g of sodium chloride, and heated until the hydroxyethyl cellulose and the gelatin were dissolved. An oil phase comprising 55g of styrene, 5g of divinylbenzene, 0.35g of benzoyl peroxide and 30g of isobutanol is added, mechanical stirring is started and the stirring speed is adjusted to 200 rpm. Slowly heating to 90 ℃ and reacting for 8 h. And (4) finishing the reaction, carrying out solid-liquid separation on the system, and washing for multiple times to obtain a solid product. And then removing the residual impurities in pore-foaming agent and resin pore channels by Soxhlet extraction to obtain the crosslinked polystyrene-divinylbenzene microsphere matrix.
(2) Chloromethylation of crosslinked styrene-divinylbenzene
Swelling 50g of the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in 200g of chloromethyl ether aqueous solution, adding 10g of anhydrous ferric chloride, dynamically swelling for 2h, slowly dropwise adding a certain amount of concentrated sulfuric acid, controlling the reaction temperature to be 45 ℃, carrying out heat preservation reaction at 45 ℃ for 10h, carrying out solid-liquid separation after the reaction is finished, and recovering the solution.
(3) Amination of chloromethyl crosslinked styrene-divinylbenzene
And (3) draining the surface water of the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2), adding liquid caustic soda with the mass concentration of 32%, adding 220g of dimethylamine solution, starting stirring, keeping the temperature to 48 ℃ for amination for 12h, carrying out solid-liquid separation after the amination is finished, and recovering the solution to obtain the macroporous anion exchange resin microspheres.
The prepared macroporous anion exchange resin has the particle size of 1.2-2.0 mm and the BET specific surface area of 53m2The total exchange capacity of the catalyst is 4.5 mmol/g.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. A method for regulating and controlling the particle size of macroporous anion exchange resin microspheres is characterized by comprising the following steps:
(1) preparing a crosslinked styrene-divinylbenzene microsphere matrix: adding a dispersing agent and sodium salt into water, starting stirring, raising the temperature to completely dissolve the dispersing agent, then cooling, and dropwise adding a methylene blue aqueous solution to obtain a water phase; pouring a mixed oil phase consisting of a monomer, a cross-linking agent, a pore-forming agent and an initiator into the water phase, starting stirring after the nitrogen introduction is finished, heating for reaction, stopping stirring, and alternately washing with hot water and ethanol until the liquid is clear to obtain the styrene-divinylbenzene copolymer white ball;
(2) chloromethylation of crosslinked styrene-divinylbenzene: swelling the crosslinked styrene-divinylbenzene microspheres obtained in the step (1) in a chloromethyl ether aqueous solution, adding anhydrous ferric chloride, dropwise adding sulfuric acid while stirring, controlling the reaction temperature, carrying out heat preservation reaction, and carrying out solid-liquid separation to obtain chloromethyl crosslinked styrene-divinylbenzene microspheres as solids;
(3) amination of chloromethyl crosslinked styrene-divinylbenzene: swelling the chloromethyl crosslinked styrene-divinylbenzene microspheres prepared in the step (2) in dimethylamine, starting stirring, controlling the reaction temperature, carrying out heat preservation reaction, and carrying out solid-liquid separation to obtain the macroporous anion exchange resin microspheres as solids.
2. The method of claim 1, wherein: the dispersing agent in the step (1) is any one of polyvinyl alcohol, gelatin and hydroxyethyl cellulose.
3. The method of claim 1, wherein: in the step (1), the monomer is styrene, the cross-linking agent is divinylbenzene, the pore-forming agent is isobutanol, and the initiator is benzoyl peroxide.
4. The method of claim 1, wherein: in the step (1), the dosage of the cross-linking agent is 0.06-0.3 times of the mass of the monomer, the dosage of the pore-foaming agent is 0.5-1.2 times of the sum of the mass of the monomer and the cross-linking agent, the dosage of the initiator is 0.3-1% of the mass of the monomer, the volume ratio of water to oil is 1-3: 1, the dosage of the dispersing agent is 0.5-1.5% of the mass of the water phase, and the dosage of the sodium salt is 0.05-0.1% of the mass of the water phase.
5. The method of claim 1, wherein: the consumption of the anhydrous ferric chloride in the step (2) is 20-50% of the mass of the crosslinked styrene-divinylbenzene.
6. The method of claim 1, wherein: and (3) controlling the reaction temperature in the step (2) to be 30-45 ℃ and keeping the reaction time at 10 h.
7. The method of claim 1, wherein: and (4) controlling the reaction temperature in the step (3) to be 48-53 ℃, and keeping the temperature for 12 hours.
8. The method of claim 1, wherein: the macroporous anion exchange resin microspheres prepared in the step (3) have the particle size range of 0.25-2.0 mm and the BET total specific surface area of 20-360 m2The total exchange capacity is 1.0-4.8 mmol/g.
CN202111137934.6A 2021-09-27 2021-09-27 Method for regulating and controlling particle size of macroporous anion exchange resin microspheres Pending CN113769793A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114054088A (en) * 2022-01-17 2022-02-18 富海(东营)新材料科技有限公司 Catalyst and application of catalyst in bisphenol S synthesis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114054088A (en) * 2022-01-17 2022-02-18 富海(东营)新材料科技有限公司 Catalyst and application of catalyst in bisphenol S synthesis

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