CN112538129B - Preparation method of graphene composite ion exchange resin for membraneless electrodeionization system - Google Patents
Preparation method of graphene composite ion exchange resin for membraneless electrodeionization system Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F212/36—Divinylbenzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
Abstract
The invention belongs to the field of ion exchange resin preparation, and relates to a preparation method of graphene composite ion exchange resin for a membraneless electrodeionization system. According to the invention, the graphene composite copolymerization white ball and the sulfonating agent are mixed for reaction at 60-150 ℃, the temperature is reduced to 30-50 ℃ after the reaction is completed, and the ion exchange resin prepared through post-treatment is suitable for wastewater treatment and high purity water preparation of a membraneless electrodeionization system, and compared with the conventional resin, the graphene composite copolymerization white ball and sulfonating agent have the advantages that the exchange capacity and the conductivity are greatly improved, the membraneless electrodeionization performance is improved, and the regeneration voltage and the energy consumption of the membraneless electrodeionization system are reduced.
Description
Technical Field
The invention belongs to the field of ion exchange resin preparation, and relates to a preparation method of graphene composite ion exchange resin for a membraneless electrodeionization system.
Background
The membrane-free electrodeionization method is a novel water treatment method, and the method is divided into two stages of treatment and regeneration, wherein the treatment is similar to a common ion exchange process, after the ion exchange resin fails, high-voltage direct current is applied to the two ends of the resin for regeneration, and hydrogen ions and hydroxyl ions generated by electrolysis and water splitting regenerate the failed ion exchange resin. Compared with the traditional ion exchange method, the method does not need to use acid-base medicament, and can realize in-situ electric regeneration of the ion exchange resin; compared with the traditional electrodeionization technology, the method does not need to use an ion exchange membrane, and has the advantages of simple device structure, difficult polarization scaling, convenient disassembly and assembly and the like. The film-free electrodeionization has wide application prospect in the field of wastewater treatment and high purity water preparation.
The ion exchange resin is a core material of the membraneless electrodeionization system, and has great influence on the quality of effluent water, energy consumption, water recovery rate and the like of membraneless electrodeionization. The ideal resin should have excellent adsorption performance, electric regeneration performance, exchange capacity and electric conductivity. However, since adsorption and regeneration are a pair of contradictions, adsorption capacity is strong, regeneration is difficult, regeneration is easy, adsorption capacity is weak, and on the other hand, conductivity and exchange capacity are also a pair of contradictions, conductivity is strong, exchange capacity is small, and exchange capacity is large, conductivity is weak, and therefore it is almost impossible to find an ideal resin satisfying the above conditions in a general negative-positive resin.
Chinese patent application publication No. CN111097555A discloses a strong-alkaline graphene composite ion exchange resin material and a preparation method thereof, wherein the prepared alkaline graphene composite ion exchange resin material is uniformly dispersed in a polymer matrix in a covalent bond form and has good thermal stability and swelling resistance, but the prepared alkaline anion exchange resin cannot be used for treating cations such as heavy metals.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides a preparation method of graphene composite ion exchange resin, which can prepare graphene composite ion exchange resin with large exchange capacity and excellent conductivity for a membraneless electrodeionization system.
The aim of the invention can be achieved by the following technical scheme: the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system comprises the steps of mixing and reacting graphene composite copolymerization white balls with a sulfonating agent at 60-150 ℃, cooling to 30-50 ℃ after the reaction is completed, and performing aftertreatment.
The sulfonation reaction can load a functional group-sulfonic acid group on the resin, the sulfonic acid group can effectively adsorb cations such as heavy metals, and the sulfonic acid group is easy to dissociate H in the solution + Thus strongly acidic, and after dissociation of the resin, the bulk contains negatively charged groups, e.g. SO 3- Can adsorb other cations in the binding solution, and the adsorption capacity is greatly improved after a large amount of sulfonic acid groups are loaded.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the mass ratio of the graphene composite copolymerization white ball to the sulfonating agent in the mixing reaction is (1-1.5): (3-5). The proportion relation of the graphene composite copolymerization white ball and the sulfonating agent directly influences the content of graphene and functional groups on the resin, the proportion is too high, the content of graphene is high, but the content of functional groups is low; if the ratio is too low, the functional group content is high, but the graphene content is low.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the sulfonating agent is sulfuric acid solution with the solute mass fraction of 30-99%. When the sulfuric acid concentration is too low, the supported sulfonic acid groups are less, resulting in insufficient adsorption capacity.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the particle size of the graphene composite copolymerization white ball is 0.4-0.8mm. The particle size is mainly determined by the micropores in the resin, the more the micropores are, the larger the particle size is, the faster the resin exchange speed is, the regeneration is easier, but the conductivity is reduced; the smaller the number of micropores, the smaller the particle diameter, the slower the resin exchange speed, and the less easily the regeneration, but the conductivity is increased. When the particle size is 0.4-0.8mm, the regeneration capability and conductivity of the graphene composite copolymerization white ball reach the highest cost performance, thereby meeting the requirement of the regeneration capability and having excellent conductivity.
In the above preparation method of the graphene composite ion exchange resin for a membraneless electrodeionization system, the preparation method of the graphene composite copolymerization white ball comprises the following steps:
(1) Weighing 5-15 parts of graphene, 100-120 parts of styrene, 100-150 parts of divinylbenzene, 50-150 parts of dispersing agent, 3-8 parts of initiator, 10-30 parts of catalyst and 150-300 parts of pore-forming agent;
(2) Adding 20-60% of graphene into styrene for ultrasonic treatment, adding the rest graphene, and then carrying out ultrasonic treatment to obtain graphene/styrene suspension;
(3) And sequentially adding 10-50 parts of the graphene/styrene suspension, divinylbenzene, a dispersing agent, an initiator, a catalyst and a pore-forming agent into pure water at 40-60 ℃ to uniformly stir to form a mixed solution, heating the mixed solution to 60-120 ℃, preserving heat for suspension polymerization reaction, cooling to 30-50 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain the graphene composite copolymerization white ball.
According to the invention, the conductivity and the exchange capacity of the resin are greatly increased by adding the graphene, the graphene is uniformly dispersed into the suspension by utilizing ultrasonic oscillation, and the dispersibility of the graphene is further improved by a two-step graphene adding method.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the dispersing agent is one or two of polyvinyl alcohol and sodium chloride.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the initiator is one or two of benzoyl peroxide and lauroyl peroxide.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the catalyst is one or two of zinc chloride and nickel chloride. The zinc chloride and the nickel chloride are used as catalysts to accelerate the reaction speed, promote the occurrence of polymerization reaction and functional group reaction, and improve the adsorption and regeneration performance of the ion exchange resin.
In the preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system, the pore-forming agent is one or two of toluene, ethylbenzene and propylbenzene. The pore-forming agent can increase the specific surface area of the resin, so that the functional group point position is increased, and the resin exchange capacity is improved.
Compared with the prior art, the invention has the following beneficial effects: the graphene composite ion exchange resin prepared by utilizing the sulfonation reaction is suitable for wastewater treatment and high purity water preparation of a membraneless electrodeionization system, greatly improves the exchange capacity and the conductivity of the resin compared with the conventional resin, improves the membraneless electrodeionization performance, and is beneficial to reducing the regeneration voltage and the energy consumption of the membraneless electrodeionization system.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
(1) Firstly adding 5 parts of graphene into 120 parts of styrene, carrying out ultrasonic oscillation for 2 hours, then adding 4 parts of graphene, and carrying out ultrasonic oscillation for 1 hour to obtain a suspension. Adding 30 parts of graphene/styrene suspension, 120 parts of divinylbenzene, 120 parts of polyvinyl alcohol, 5 parts of benzoyl peroxide, 20 parts of zinc chloride and 200 parts of toluene into pure water at 50 ℃ and uniformly stirring to form a mixed solution, heating the mixed solution to 80 ℃, preserving heat for suspension polymerization reaction, cooling to 40 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymerization white balls with the particle size of 0.5mm;
(2) Mixing the graphene composite copolymerization white ball and a sulfonating agent according to a ratio of 1:4, mixing and reacting at 80 ℃, wherein the sulfonating agent is sulfuric acid with the mass fraction of 99%, cooling to 30 ℃ after the reaction is finished, and diluting with dilute sulfuric acid and washing with water to be neutral to obtain the graphene composite ion exchange resin.
Example 2:
(1) Firstly adding 2 parts of graphene into 120 parts of styrene, carrying out ultrasonic oscillation for 2 hours, then adding 3 parts of graphene, and carrying out ultrasonic oscillation for 1-2 hours to obtain a suspension. Adding 10 parts of graphene/styrene suspension, 100 parts of divinylbenzene, 50 parts of sodium chloride, 3 parts of lauroyl peroxide, 10 parts of nickel chloride and 150 parts of ethylbenzene into pure water at 40 ℃ and uniformly stirring to form a mixed solution, heating the mixed solution to 60 ℃, preserving heat for suspension polymerization reaction, cooling to 30 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymer white balls with the particle size of 0.4 mm;
(2) Mixing the graphene composite copolymerization white ball and a sulfonating agent according to a ratio of 1:2, mixing and reacting at 60 ℃, wherein the sulfonating agent is sulfuric acid with the mass fraction of 30%, cooling to 30 ℃ after the reaction is finished, and diluting with dilute sulfuric acid and washing with water to be neutral to obtain the graphene composite ion exchange resin.
Example 3:
(1) Firstly, adding 5 parts of graphene into 120 parts of styrene, carrying out ultrasonic oscillation for 2 hours, then adding 8 parts of graphene, and carrying out ultrasonic oscillation for 2 hours to obtain a suspension. Adding 50 parts of graphene/styrene suspension, 150 parts of divinylbenzene, 150 parts of polyvinyl alcohol, 8 parts of benzoyl peroxide, 30 parts of zinc chloride and 300 parts of toluene into pure water at 60 ℃ and uniformly stirring to form a mixed solution, heating the mixed solution to 120 ℃, preserving heat for suspension polymerization reaction, cooling to 50 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymer white balls with the particle size of 0.8 mm;
(2) Mixing the graphene composite copolymerization white ball and a sulfonating agent according to a ratio of 1: and 5, mixing and reacting at 150 ℃, wherein the sulfonating agent is sulfuric acid with the mass fraction of 60%, cooling to 50 ℃ after the reaction is finished, and diluting with dilute sulfuric acid and washing with water to be neutral to obtain the graphene composite ion exchange resin.
Example 4:
(1) Firstly adding 3 parts of graphene into 110 parts of styrene, carrying out ultrasonic oscillation for 1 hour, then adding 4 parts of graphene, and carrying out ultrasonic oscillation for 2 hours to obtain a suspension. Adding 20 parts of graphene/styrene suspension, 120 parts of divinylbenzene, 60 parts of polyvinyl alcohol, 7 parts of benzoyl peroxide and 20 parts of zinc chloride 180 parts of toluene into pure water at 55 ℃ and uniformly stirring to form a mixed solution, heating the mixed solution to 100 ℃, preserving heat for suspension polymerization reaction, cooling to 45 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymerization white balls with the particle size of 0.5mm;
(2) Mixing the graphene composite copolymerization white ball and a sulfonating agent according to a ratio of 1:6, mixing and reacting at 80 ℃, wherein the sulfonating agent is sulfuric acid with the mass fraction of 60%, cooling to 35 ℃ after the reaction is finished, and diluting with dilute sulfuric acid and washing with water to be neutral to obtain the graphene composite ion exchange resin.
Example 5:
(1) Firstly adding 5 parts of graphene into 120 parts of styrene, carrying out ultrasonic oscillation for 1 hour, then adding 3 parts of graphene, and carrying out ultrasonic oscillation for 1 hour to obtain a suspension. Adding 12 parts of graphene/styrene suspension, 100 parts of divinylbenzene, 60 parts of polyvinyl alcohol, 5 parts of benzoyl peroxide, 28 parts of zinc chloride and 155 parts of toluene into pure water at 45 ℃ to uniformly stir to form a mixed solution, heating the mixed solution to 65 ℃, preserving heat for suspension polymerization reaction, cooling to 42 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymer white balls with the particle size of 0.6 mm;
(2) Mixing the graphene composite copolymerization white ball and a sulfonating agent according to a ratio of 1: and (3) mixing and reacting at 70 ℃ with a sulfonating agent which is sulfuric acid with the mass fraction of 60%, cooling to 40 ℃ after the reaction is finished, and diluting with dilute sulfuric acid and washing with water to be neutral to obtain the graphene composite ion exchange resin.
Comparative example 1:
according to the method in Chinese patent application (CN: CN 111097555A), dichloroethane, trimethylamine hydrochloride and sodium hydroxide solution are added into the graphene composite copolymer white ball to react for 6 hours at 30 ℃.
Comparative example 2:
the difference from example 1 is only that the graphene composite copolymerized white spheres were not mixed and reacted with the sulfonating agent in the preparation of the composite ion exchange resin of comparative example 2, but added with the conventional amination agent to be mixed and reacted.
Comparative example 3:
the only difference from example 1 is that this comparative example does not add graphene.
Capacity change and conductivity performance tests were performed on the graphene composite ion exchange resins prepared in examples 1 to 5 and comparative examples 1 to 3.
Table 1: performance test of graphene composite ion exchange resin prepared by the methods described in examples 1-5 and comparative examples 1-3
| Examples | Cation exchange capacity (eq/L) | Conductivity (S/m) |
| Example 1 | 3.1 | 1.9 |
| Example 2 | 1.5 | 1.5 |
| Example 3 | 2.2 | 2.1 |
| Example 4 | 2.9 | 1.3 |
| Example 5 | 1.3 | 1.8 |
| Comparative example 1 | 0 | 1.0 |
| Comparative example 2 | 0 | 0.1 |
| Comparative example 3 | 0.2 | 0.2 |
In conclusion, the graphene composite ion exchange resin prepared by utilizing the sulfonation reaction is suitable for wastewater treatment and high-purity water preparation of a membraneless electrodeionization system, the exchange capacity and the conductivity of the graphene composite ion exchange resin are greatly improved, the membraneless electrodeionization performance is improved, and the regeneration voltage and the energy consumption can be reduced.
The point values in the technical scope of the present invention are not exhaustive, and the new technical solutions formed by equivalent substitution of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the present invention; meanwhile, in all the listed or unrecited embodiments of the present invention, each parameter in the same embodiment represents only one example of the technical scheme (i.e. a feasibility scheme), and no strict coordination and limitation relation exists between each parameter, wherein each parameter can be replaced with each other without violating axiom and the requirement of the present invention, except what is specifically stated.
The technical means disclosed by the scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, and such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (1)
1. The preparation method of the graphene composite ion exchange resin for the membraneless electrodeionization system is characterized in that the graphene composite ion exchange resin is prepared by mixing and reacting graphene composite copolymerization white balls with a sulfonating agent at 80 ℃, cooling to 30 ℃ after the reaction is completed, and then post-treating;
the mass ratio of the graphene composite copolymerization white ball to the sulfonating agent in the mixing reaction is 1:4, a step of;
the particle size of the graphene composite copolymerization white ball is 0.5mm;
the sulfonating agent is sulfuric acid solution with 99% of solute mass fraction;
the preparation method of the graphene composite copolymerization white ball comprises the following steps:
(1) Weighing 9 parts of graphene, 120 parts of styrene, 120 parts of divinylbenzene, 120 parts of dispersing agent, 5 parts of initiator, 20 parts of catalyst and 200 parts of pore-forming agent;
(2) Adding 56% of graphene into styrene for ultrasonic treatment, adding the rest of graphene, and then carrying out ultrasonic treatment to obtain graphene/styrene suspension;
(3) Sequentially adding 30 parts of graphene/styrene suspension, divinylbenzene, a dispersing agent, an initiator, a catalyst and a pore-forming agent into pure water at 50 ℃ to uniformly stir to form a mixed solution, heating the mixed solution to 80 ℃, preserving heat to perform suspension polymerization reaction, cooling to 40 ℃ after the heat preservation is finished, and washing, filtering and drying to obtain graphene composite copolymerization white balls;
the catalyst is zinc chloride;
the dispersing agent is polyvinyl alcohol;
the initiator is benzoyl peroxide;
the pore-forming agent is toluene.
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| CN202011375812.6A CN112538129B (en) | 2020-11-30 | 2020-11-30 | Preparation method of graphene composite ion exchange resin for membraneless electrodeionization system |
| AU2021103256A AU2021103256A4 (en) | 2020-11-30 | 2021-06-10 | Preparation method of graphene-composited ion exchange resin for membrane-free electrodeionization system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647545A (en) * | 2017-10-11 | 2019-04-19 | 中国石油化工股份有限公司 | Strong basicity composite Nano inorganic oxide-graphene-ion exchange resin material |
| CN111097555A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Strong-alkaline graphene composite ion exchange resin material and preparation method thereof |
| CN111111792A (en) * | 2020-01-07 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Strong acid cation exchange resin for adsorbing iron and preparation method and application thereof |
| CN111655630A (en) * | 2017-12-30 | 2020-09-11 | 印度理工学院马德拉斯(Iit马德拉斯) | Integrated CDI electrode |
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| US10971722B2 (en) * | 2018-03-02 | 2021-04-06 | Global Graphene Group, Inc. | Method of manufacturing conducting elastomer composite-encapsulated particles of anode active materials for lithium batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647545A (en) * | 2017-10-11 | 2019-04-19 | 中国石油化工股份有限公司 | Strong basicity composite Nano inorganic oxide-graphene-ion exchange resin material |
| CN111655630A (en) * | 2017-12-30 | 2020-09-11 | 印度理工学院马德拉斯(Iit马德拉斯) | Integrated CDI electrode |
| CN111097555A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Strong-alkaline graphene composite ion exchange resin material and preparation method thereof |
| CN111111792A (en) * | 2020-01-07 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Strong acid cation exchange resin for adsorbing iron and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| 复合离子交换树脂催化环氧乙烷水合制乙二醇的性能研究;李亚男等;《化学反应工程与工艺》;20150225(第01期);第8-14页 * |
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