AU2021103256A4 - Preparation method of graphene-composited ion exchange resin for membrane-free electrodeionization system - Google Patents
Preparation method of graphene-composited ion exchange resin for membrane-free electrodeionization system Download PDFInfo
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- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 32
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000009296 electrodeionization Methods 0.000 title claims abstract description 22
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910021389 graphene Inorganic materials 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000003361 porogen Substances 0.000 claims description 7
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000012498 ultrapure water Substances 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- 230000010355 oscillation Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- 230000008094 contradictory effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QQGISFDJEJMKIL-JAIQZWGSSA-N (5z)-5-[[3-(hydroxymethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical group C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1CO QQGISFDJEJMKIL-JAIQZWGSSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
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Abstract
OF THE DISCLOSURE
The present disclosure belongs to the field of preparation methods of ion exchange resins, and
relates to a preparation method of a graphene-composited ion exchange resin for a membrane-free
electrodeionization system. The ion exchange resin is prepared by mixing a graphene-composited
polystyrene-divinylbenzene copolymer and a sulfonating agent for reaction at 60-150°C, cooling to
30-50°C, and conducting post-treatment. The ion exchange resin is suitable for wastewater
treatment and high-purity water preparation in membrane-free electrodeionization systems. The
present disclosure has a greatly-improved exchange capacity and conductivity compared with
conventional resins, and improves the performance of membrane-free electrodeionization, thereby
reducing the regeneration voltage and energy consumption of the membrane-free
electrodeionizationsystem.
Description
[01] The present disclosure belongs to the field of preparation of ion exchange resins, and relates to a preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system.
[02] The membrane-free electrodeionization method is a novel water treatment method and involves treatment and regeneration. The treatment is conducted like an ordinary ion exchange process. High-voltage direct current is applied to both ends of the resin for regeneration when the ion exchange resin fails. The hydrogen ions and hydroxide ions generated by electrolysis and water splitting regenerate the failed ion exchange resin. Compared with the traditional ion exchange methods, this method does not require acid and alkali chemicals, and can realize in-situ electric regeneration of ion exchange resin. Compared with the traditional electrodeionization technology, this method does not require ion exchange membranes, and has the advantages of simple device structure, less chance of polarization and fouling, and convenient disassembly and assembly. Membrane-free electrodeionization has broad use prospects in wastewater treatment and high-purity water preparation.
[03] Ion exchange resin is a core material of the membrane-free electrodeionization system, and has a great impact on the effluent quality, energy consumption, and water recovery rate thereof. An ideal resin is required to have excellent adsorption performance, electrical regeneration performance, exchange capacity and electrical conductivity. However, adsorption and regeneration are contradictory. A stronger adsorption capacity means more difficult regeneration. On the other hand, conductivity and exchange capacity are also contradictory. A stronger conductivity means a lower exchange capacity. Therefore, it is almost impossible to find out an ideal resin from ordinary anion and cation resins that can meet the above requirements.
[04] Chinese patent application document (publication number: CN111097555A) discloses a strong-alkaline graphene-composited ion exchange resin material and a preparation method thereof. The prepared alkaline graphene-composited ion exchange resin material is uniformly dispersed in the form of covalent bonds in a polymer matrix, and has desirable thermal stability and swelling resistance. However, the present disclosure prepares an alkaline anion exchange resin that cannot be used to treat cations of heavy metals and the like.
[05] Described herein is a preparation method of a graphene-composited ion exchange resin. The method can prepare a graphene-composited ion exchange resin with large exchange capacity and excellent conductivity for use in a membrane-free electrodeionization system.
[06] Preferred embodiments of the present invention seek to provide a preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system includes mixing a graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent for reaction at 60-150°C, cooling to 30-50°C, and conducting post-treatment.
[07] The sulfonation can load functional groups, sulfonic acid groups, on the resin. The sulfonic acid groups can effectively adsorb heavy metals and other cations, and the sulfonic acid groups are easily dissociated into H' in the solution to be strongly acidic. After the resin is dissociated, the negatively charged groups contained in the resin, such as S03-, can adsorb and bind other cations in the solution. When a large number of sulfonic acid groups are loaded, the resin has a greatly improved adsorption capacity.
[08] In the above preparation method, the graphene-composited polystyrene-divinylbenzene copolymer and the sulfonating agent may have a mass ratio of (1-1.5):(3-5). The ratio of the graphene-composited polystyrene-divinylbenzene copolymer and the sulfonating agent directly affects the content of graphene and functional groups on the resin. An excessively high ratio causes a high graphene content and a low content of functional groups; and an excessively low ratio causes a high content of functional groups and a low graphene content.
[09] In the above preparation method, the sulfonating agent may be a sulfuric acid solution with a solute mass fraction of 30-99%. When the concentration of sulfuric acid is too low, there are fewer sulfonic acid groups loaded, which leads to an insufficient adsorption capacity.
[10] In the above preparation method, the graphene-composited polystyrene-divinylbenzene copolymer may have a particle size of 0.4-0.8 mm. The particle size is mainly determined by the micropores in the resin. More micropores mean a larger the particle size, faster resin exchange rate, easier regeneration, and decreased conductivity; vice versa. The regeneration ability and conductivity of the graphene-composited polystyrene-divinylbenzene copolymer reach the highest cost performance when the particle size is 0.4-0.8 mm, thus not only meeting the requirements of regeneration ability, but also having an excellent conductivity.
[11] In the above preparation method, a preparation method of the graphene-composited polystyrene-divinylbenzene copolymer may include:
[12] (1) weighing 5-15 parts by weight of graphene, 100-120 parts by weight of styrene, 100 150 parts by weight of divinylbenzene, 50-150 parts by weight of a dispersant, 3-8 parts by weight of an initiator, 10-30 parts by weight of a catalyst, and 150-300 parts by weight of a porogen;
[13] (2) adding 20-60% of the graphene into the styrene for ultrasonic treatment, and adding the remaining graphene to continue ultrasonic treatment to obtain a graphene/styrene suspension; and
[14] (3) adding 10-50 parts by weight of the graphene/styrene suspension, the divinylbenzene, the dispersant, the initiator, the catalyst, and the porogen sequentially into 40-60°C pure water and stirring uniformly to form a mixed solution, heating the mixed solution to 60-120°C and conducting heat preservation to conduct suspension polymerization, cooling to 30-50°C, washing, filtering and heat-drying to obtain the graphene-composited polystyrene-divinylbenzene copolymer.
[15] The present disclosure greatly increases the conductivity and exchange capacity of the resin by adding graphene, uniformly disperses graphene into the suspension using ultrasonic oscillation, and further improves the dispersibility of graphene by adding graphene in two steps.
[16] In the above preparation method, the dispersant may be one or two selected from the group consisting of polyvinyl alcohol and sodium chloride.
[17] In the above preparation method, the initiator may be one or two selected from the group consisting of benzoyl peroxide and lauroyl peroxide.
[18] In the above preparation method, the catalyst may be one or two selected from the group consisting of zinc chloride and nickel chloride. The zinc chloride and nickel chloride as catalysts can accelerate the reaction, promote the occurrence of polymerization and functional grouping reactions, and improve the adsorption and regeneration performance of ion exchange resins.
[19] In the above preparation method, the porogen may be one or two selected from the group consisting of toluene, ethylbenzene, and propylbenzene. The porogen can increase the specific surface area of the resin, thereby increasing the sites of functional groups and increasing the exchange capacity of the resin.
[20] Compared with the prior art, the present disclosure has the following beneficial effects: the graphene-composited ion exchange resin prepared by sulfonation is suitable for wastewater treatment and high-purity water preparation in a membrane-free electrodeionization system. The present disclosure has a greatly-improved exchange capacity and conductivity than conventional resins, and improves the performance of membrane-free electrodeionization, so as to help to reduce the regeneration voltage and energy consumption of the membrane-free electrodeionization system.
[21] The technical solutions of the present disclosure are described in further detail below with reference to the specific examples, but the present disclosure is not limited thereto.
[22] Example 1
[23] (1) 5 parts by weight of graphene was added to 120 parts by weight of styrene and ultrasonic oscillation was conducted for 2 hours, and another 4 parts by weight of graphene was added and ultrasonic oscillation was continued for 1 hour to obtain a suspension; 30 parts by weight of graphene/styrene suspension, 120 parts by weight of divinylbenzene, 120 parts by weight of polyvinyl alcohol, 5 parts by weight of benzoyl peroxide, 20 parts by weight of zinc chloride, and
200 parts by weight of toluene was added into pure water at 50°C and stirred evenly to form a mixed solution; the mixed solution was heated to 80°C and held the temperature to conduct suspension polymerization, cooled to 40°C, washed, filtered and dried to obtain a graphene composited polystyrene-divinylbenzene copolymer with a particle size of 0.5 mm; and
[24] (2) the graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent were mixed to react at 80°C with a mass ratio of 1:4, where the sulfonating agent was sulfuric acid with a mass fraction of 99%; cooled to 30°C, diluted with dilute sulfuric acid and washed with water to neutral, so as to obtain a graphene-composited ion exchange resin.
[25] Example 2
[26] (1) 2 parts by weight of graphene was added to 120 parts by weight of styrene and ultrasonic oscillation was conducted for 2 hours, and another 3 parts by weight of graphene was added and ultrasonic oscillation was continued for 1-2 hours to obtain a suspension;10 parts by weight of graphene/styrene suspension, 100 parts by weight of divinylbenzene, 50 parts by weight of sodium chloride, 3 parts by weight of lauroyl peroxide, 10 parts by weight of nickel chloride, and 150 parts by weight of ethylbenzene was added into pure water at 40°C and stirred evenly to form a mixed solution; the mixed solution was heated to 60°C and held the temperature to conduct suspension polymerization; cooled to 30°C, washed, filtered and dried to obtain a graphene composited polystyrene-divinylbenzene copolymer with a particle size of 0.4 mm;
[27] (2) the graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent were mixed to react at 60°C with a mass ratio of 1:2, where the sulfonating agent was sulfuric acid with a mass fraction of 30%; cooled to 30°C, diluted with dilute sulfuric acid and washed with water to neutral, so as to obtain a graphene-composited ion exchange resin.
[28] Example 3
[29] (1) 5 parts by weight of graphene was added to 120 parts by weight of styrene and ultrasonic oscillation was conducted for 2 hours, and another 8 parts by weight of graphene was added and ultrasonic oscillation was continued for 2 hours to obtain a suspension;50 parts by weight of graphene/styrene suspension, 150 parts by weight of divinylbenzene, 150 parts by weight of polyvinyl alcohol, 8 parts by weight of benzoyl peroxide, 30 parts by weight of zinc chloride, and 300 parts by weight of toluene was added into pure water at 60°C and stirred evenly to form a mixed solution; the mixed solution was heated to 120°C and held the temperature to conduct suspension polymerization, cooled to 50°C, washed, filtered and dried to obtain a graphene composited polystyrene-divinylbenzene copolymer with a particle size of 0.8 mm; and
[30] (2) the graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent were mixed to react at 150°C with a mass ratio of 1:5, where the sulfonating agent was sulfuric acid with a mass fraction of 60%; cooled to 50°C, diluted with dilute sulfuric acid and washed with water to neutral, so as to obtain the graphene-composited ion exchange resin.
[31] Example 4
[32] (1) 3 parts by weight of graphene was added to 110 parts by weight of styrene and ultrasonic oscillation was conducted for 1 hour, and another 4 parts by weight of graphene was added and ultrasonic oscillation was continued for 2 hours to obtain a suspension;20 parts by weight of graphene/styrene suspension, 120 parts by weight of divinylbenzene, 60 parts by weight of polyvinyl alcohol, 7 parts by weight of benzoyl peroxide, 20 parts by weight of zinc chloride, and 180 parts by weight of toluene was added into pure water at 55°C and stirred evenly to form a mixed solution; the mixed solution was heated to 100°C and held the temperature to conduct suspension polymerization, cooled to 45°C, washed, filtered and dried to obtain a graphene composited polystyrene-divinylbenzene copolymer with a particle size of 0.5 mm; and
[33] (2) the graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent were mixed to react at 80°C with a mass ratio of 1:6, where the sulfonating agent was sulfuric acid with a mass fraction of 60%; cooled to 35°C, diluted with dilute sulfuric acid and washed with water to neutral, so as to obtain a graphene-composited ion exchange resin.
[34] Example 5
[35] (1) 5 parts by weight of graphene was added to 120 parts by weight of styrene and ultrasonic oscillation was conducted for 1 hour, and another 3 parts by weight of graphene was added and ultrasonic oscillation was continued for 1 hour to obtain a suspension;12 parts by weight of graphene/styrene suspension, 100 parts by weight of divinylbenzene, 60 parts by weight of polyvinyl alcohol, 5 parts by weight of benzoyl peroxide, 28 parts by weight of zinc chloride, and 155 parts by weight of toluene was added into pure water at 45°C and stirred evenly to form a mixed solution; the mixed solution was heated to 65°C and held the temperature to conduct suspension polymerization, cooled to 42°C, washed, filtered and dried to obtain a graphene composited polystyrene-divinylbenzene copolymer with a particle size of 0.6 mm; and
[36] (2) the graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent were mixed to react at 70°C with a mass ratio of 1:1, where the sulfonating agent was sulfuric acid with a mass fraction of 60%; cooled to 40°C, diluted with dilute sulfuric acid and washed with water to neutral, so as to obtain a graphene-composited ion exchange resin.
[37] Comparative Example 1
[38] According to the method in Chinese patent application document (CN111097555A), dichloroethane, trimethylamine hydrochloride and sodium hydroxide solution were added to the graphene-composited polystyrene-divinylbenzene copolymer and reacted at 30°C for 6 hours.
[39] Comparative Example 2
[40] The only difference from Example 1 was that the graphene-composited polystyrene divinylbenzene copolymer was mixed with a conventional aminating agent instead of the sulfonating agent.
[41] Comparative Example 3
[42] The only difference from Example 1 was that graphene was not added.
[43] The graphene-composited ion exchange resins prepared by the methods described in Examples 1-5 and Comparative Examples 1-3 was tested for capacity exchange and conductivity.
[44] Table 1 shows a performance test of graphene-composited ion exchange resins prepared by the methods described in Examples 1-5 and Comparative Examples 1-3.
[45] Example 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
[46] In summary, the graphene-composited ion exchange resin prepared by the present disclosure through sulfonation is suitable for wastewater treatment and high-purity water preparation in membrane-free electrodeionization systems. The present disclosure greatly improves the exchange capacity and conductivity, improved the membrane-free electrodeionization performance, and can reduce regeneration voltage and energy consumption.
[47] The examples that are not exhaustive in the technical scope of the present disclosure, and the new technical solutions formed by the equivalent replacement of single or multiple technical features in the technical solutions of the examples shall fall within the protection scope of the present disclosure. Meanwhile, in all the listed or unlisted examples of the solution of the present disclosure, each parameter in the same examples only represents an example of its technical solution (that is, a feasible solution). In addition, there is no strict cooperation and limitation relationship between the various parameters and the various parameters can be replaced with each other if they do not violate the axioms and the requirements of the present disclosure, unless otherwise stated.
[48] The technical means disclosed in the solution of the present disclosure are not limited to the technical means disclosed in the above technical means, but also include technical solutions composed of any combination of the above technical features. The descriptions above are preferred implementations of the present disclosure. It should be noted that for a person of ordinary skill in the art, various improvements and modifications can be made without departing from the principles of the present disclosure. These improvements and modifications should also be regarded as falling into the protection scope of the present disclosure.
[49] The specific examples described herein are merely intended to illustrate the spirit of the present disclosure. A person skilled in the art can make various modifications or supplements to the specific examples described or replace them in a similar manner, but it may not depart from the spirit of the present disclosure or the scope defined by the appended claims.
[50] The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.
[51] Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
Claims (5)
1. A preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system, comprising mixing a graphene-composited polystyrene-divinylbenzene copolymer and a sulfonating agent for reaction at 60-150°C, cooling to 30-50°C, and conducting post-treatment.
2. The preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system according to claim 1, wherein the graphene-composited polystyrene divinylbenzene copolymer and the sulfonating agent has a mass ratio of (1-1.5):(3-5).
3. The preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system according to claim 1 or 2, wherein the sulfonating agent is a sulfuric acid solution with a solute mass fraction of 3 0 - 9 9 %.
4. The preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system according to claim 1 or 2, wherein the graphene-composited polystyrene-divinylbenzene copolymer has a particle size of 0.4-0.8 mm.
5. The preparation method of a graphene-composited ion exchange resin for a membrane-free electrodeionization system according to claim 4, wherein a preparation method of the graphene composited polystyrene-divinylbenzene copolymer comprises: (1) weighing 5-15 parts by weight of graphene, 100-120 parts by weight of styrene, 100-150 parts by weight of divinylbenzene, 50-150 parts by weight of a dispersant, 3-8 parts by weight of an initiator, 10-30 parts by weight of a catalyst, and 150-300 parts by weight of a porogen; (2) adding 20-60% of the graphene into the styrene for ultrasonic treatment, and adding the remaining graphene to continue ultrasonic treatment to obtain a graphene/styrene suspension; and 6. (3) adding 10-50 parts by weight of the graphene/styrene suspension, the divinylbenzene, the dispersant, the initiator, the catalyst, and the porogen sequentially into 40-60°C pure water and stirring uniformly to form a mixed solution, heating the mixed solution to 60-120°C and conducting heat preservation to conduct suspension polymerization, cooling to 30-50°C, washing, filtering and heat-drying to obtain the graphene-composited polystyrene-divinylbenzene copolymer; wherein the dispersant is one or more selected from the group consisting of polyvinyl alcohol and sodium chloride; wherein the initiator is one or more selected from the group consisting of benzoyl peroxide and lauroyl peroxide; wherein the catalyst is one or more selected from the group consisting of zine chloride and nickel chloride; wherein the porogen is one or more selected from the group consisting of toluene, ethylbenzene, and propylbenzene.
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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 |
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