CN111592678A - Preparation method and application of porous magnetic ion exchange resin - Google Patents
Preparation method and application of porous magnetic ion exchange resin Download PDFInfo
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- CN111592678A CN111592678A CN202010334071.0A CN202010334071A CN111592678A CN 111592678 A CN111592678 A CN 111592678A CN 202010334071 A CN202010334071 A CN 202010334071A CN 111592678 A CN111592678 A CN 111592678A
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- ion exchange
- exchange resin
- magnetic ion
- porous magnetic
- ferroferric oxide
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- 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 59
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 59
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 15
- 229960002089 ferrous chloride Drugs 0.000 claims description 15
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000006249 magnetic particle Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- OATFZMZHCHJBGR-UHFFFAOYSA-N ethenoxyperoxysilane Chemical compound C(=C)OOO[SiH3] OATFZMZHCHJBGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- PGOKWMKLPIIFNA-UHFFFAOYSA-N oxalic acid prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C(=O)O)(=O)O.C(C=C)(=O)O PGOKWMKLPIIFNA-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract description 6
- 238000007885 magnetic separation Methods 0.000 abstract description 5
- 102000004310 Ion Channels Human genes 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 30
- 238000001179 sorption measurement Methods 0.000 description 15
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001044 red dye Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/18—Chlorine
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
The invention discloses a preparation method and application of porous magnetic ion exchange resin, relating to the synthesis technology of environment functional materials, and the method comprises the following steps: preparing ferroferric oxide by using a coprecipitation method under an anaerobic condition and using weak base to adjust the pH value; modifying ferroferric oxide by using a silane coupling agent to activate chemical bonds of the ferroferric oxide; taking p-chlorostyrene as a monomer and benzoyl peroxide as an initiator, adding a proper amount of a cross-linking agent and a pore-forming agent, and ultrasonically dispersing modified ferroferric oxide in a solution to obtain an oil phase A; adding a certain amount of composite dispersant and stabilizer into deionized water to serve as a water phase B; and transferring the oil phase A and the water phase B into a reactor to prepare the magnetic ion exchange resin. The ion exchange resin prepared by the method has a core-shell structure coated with magnetic substances, has a plurality of exchangeable ion channels, is easy for magnetic separation, has low cost, and has good application prospect in removing organic matters in industrial wastewater.
Description
Technical Field
The invention relates to an environment functional material synthesis technology, in particular to a preparation method and application of porous magnetic ion exchange resin.
Background
Currently, adsorption technology is considered to be one of the most efficient and economical methods in industrial wastewater treatment. The method for removing the pollutants from the water environment by utilizing the adsorption reaction between the adsorbent and the pollutants is simple to operate, safe in process and good in pollutant removal effect. The efficiency of the sorbent to remove the contaminants is determined by the structure of the sorbent and the nature of the contaminants.
The activated carbon has large porosity and specific surface area and rich surface chemical groups, can remove pollutants through double actions of chemical adsorption and physical adsorption, and is an important adsorption material in the wastewater treatment process. Conventionally, activated carbon has a certain adsorption effect on most pollutants, but the stability is poor, most of the activated carbon is adsorbed on the surface of small molecular ions or groups, and the activated carbon is easy to fall off and causes secondary pollution easily in the using process. Activated carbon also lacks selective adsorption of contaminants and has difficulties in the application of specific adsorption techniques due to the complex functional groups on the surface of biomass.
Ion exchange resin is a new material with a good application prospect which is developed recently, and is a high molecular adsorbent. The ion on the resin can exchange with the ion in the water in equal quantity, and can effectively remove the organic pollutant in the wastewater. Compared with activated carbon, the resin has the advantages of small general surface area and low effective active functional group, but has the advantages of stable chemical property, strong unit adsorption capacity, high selectivity, easy regeneration and the like. Just because of the difference of the resin structure, the resin can be modified and designed according to the application field to prepare the selective high-efficiency adsorbent.
Disclosure of Invention
The invention aims at the problems and provides a preparation method and application of porous magnetic ion exchange resin.
According to an aspect of the present invention, there is provided a method for preparing a porous magnetic ion exchange resin, comprising the steps of:
step 1, weighing a certain amount of ferrous chloride and ferric chloride, dispersing the ferrous chloride and the ferric chloride in deionized water, heating and stirring the mixture under an oxygen-free condition, dropwise adding weak base into the mixture to adjust the pH value, crystallizing the mixture at a constant temperature, and performing coprecipitation to obtain ferroferric oxide;
step 2, dispersing the prepared magnetic particles in absolute ethyl alcohol, adding a certain amount of silane coupling agent, and heating and stirring for reaction;
step 3, taking p-chlorostyrene as a monomer and benzoyl peroxide as an initiator, adding a proper amount of a cross-linking agent and a pore-forming agent, and ultrasonically dispersing modified ferroferric oxide particles in a solution to obtain an oil phase A;
step 4, adding a certain amount of polyvinyl alcohol/polyvinylpyrrolidone dispersing agent and sodium chloride stabilizing agent into deionized water to obtain a water phase B;
and 5, simultaneously transferring the oil phase A and the water phase B obtained in the step into a reactor, and fully polymerizing the mixed solution under the condition of heating and stirring to obtain the magnetic ion exchange resin.
Further, in the step 1, the mass ratio of the ferrous chloride to the ferric chloride is 1: (0-2); adjusting the pH value to 8-12; the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
Further, in the step 2, the silane coupling agent is one or a combination of vinyltrimethoxysilane, vinyltrioxysilane and vinylmethyldimethoxysilane; the concentration of the silane coupling agent is 1-5% (w/w); the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
Further, in the step 3, the crosslinking agent is one of divinylbenzene, triallyl isocyanurate and ethanedioic acid diacrylate or a combination thereof; the pore-forming agent is one or the combination of normal heptane, toluene and xylene; the mass ratio of the monomer, the initiator, the cross-linking agent, the pore-forming agent and the modified ferroferric oxide is 10: (0-0.5): (0-2): (0-5): (0-2).
Furthermore, in the step 4, the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 1: (0-2); the mass ratio of the deionized water to the dispersant to the stabilizer is 100: (0-2): (0-5).
Furthermore, in the step 5, the mass ratio of the oil phase to the water phase is 1 (5-20); the polymerization reaction temperature is 60-95 ℃; the reaction time is 1-5 h.
Furthermore, in all the steps, the oxygen-free condition is one or more of nitrogen, argon and helium.
According to another aspect of the invention, the porous magnetic ion exchange resin prepared by the preparation method of the porous magnetic ion exchange resin is applied to removal of one or more organic matters in industrial wastewater.
The invention has the advantages that:
according to the preparation method of the porous magnetic ion exchange resin, the inorganic magnetic substance is grafted and coated on the surface of the resin by using a unique silane coupling agent in a suspension polymerization mode to obtain a magnetic function, and agglomeration or depression of the resin in the polymerization process is limited under the assistance of auxiliary agents such as a cross-linking agent, a dispersing agent, a pore-forming agent and the like, so that a cross-linked stable net-shaped structure is formed. The resin has a porous core-shell structure, has strong adsorption capacity and is easy for magnetic separation, and can be applied to treatment of organic pollutants in industrial wastewater.
The method and the process are optimized, the prepared ion exchange resin has a core-shell structure coated with magnetic substances, and the resin has a plurality of exchangeable ion channels, is easy for magnetic separation, has low cost and has good application prospect in removing organic matters in industrial wastewater.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below with reference to the drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of a magnetic ion exchange resin according to example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of a magnetic ion exchange resin according to example 1 of the present invention;
FIG. 3 is a hysteresis loop diagram of the magnetic ion exchange resin of example 1 of the present invention.
FIG. 4 is a graph showing the adsorption behavior of the magnetic ion exchange resin of example 1 in the presence of reactive bright red dye.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A preparation method of porous magnetic ion exchange resin comprises the following steps:
step 1, weighing a certain amount of ferrous chloride and ferric chloride, dispersing the ferrous chloride and the ferric chloride in deionized water, heating and stirring the mixture under an oxygen-free condition, dropwise adding weak base into the mixture to adjust the pH value, crystallizing the mixture at a constant temperature, and performing coprecipitation to obtain ferroferric oxide;
step 2, dispersing the prepared magnetic particles in absolute ethyl alcohol, adding a certain amount of silane coupling agent, and heating and stirring for reaction;
step 3, taking p-chlorostyrene as a monomer and benzoyl peroxide as an initiator, adding a proper amount of a cross-linking agent and a pore-forming agent, and ultrasonically dispersing modified ferroferric oxide particles in a solution to obtain an oil phase A;
step 4, adding a certain amount of polyvinyl alcohol/polyvinylpyrrolidone dispersing agent and sodium chloride stabilizing agent into deionized water to obtain a water phase B;
and 5, simultaneously transferring the oil phase A and the water phase B obtained in the step into a reactor, and fully polymerizing the mixed solution under the condition of heating and stirring to obtain the magnetic ion exchange resin.
In the step 1, the mass ratio of the ferrous chloride to the ferric chloride is 1: (0-2); adjusting the pH value to 8-12; the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
In the step 2, the silane coupling agent is one or the combination of vinyltrimethoxysilane, vinyltrioxysilane and vinylmethyldimethoxysilane; the concentration of the silane coupling agent is 1-5% (w/w); the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
In the step 3, the cross-linking agent is one or a combination of divinylbenzene, triallyl isocyanurate and ethanedioic acid diacrylate; the pore-forming agent is one or the combination of normal heptane, toluene and xylene; the mass ratio of the monomer, the initiator, the cross-linking agent, the pore-forming agent and the modified ferroferric oxide is 10: (0-0.5): (0-2): (0-5): (0-2).
In the step 4, the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 1: (0-2); the mass ratio of the deionized water to the dispersant to the stabilizer is 100: (0-2): (0-5).
In the step 5, the mass ratio of the oil phase to the water phase is 1 (5-20); the polymerization reaction temperature is 60-95 ℃; the reaction time is 1-5 h.
In all the steps, the adopted oxygen-free condition is one or more of nitrogen, argon and helium.
According to another aspect of the invention, the porous magnetic ion exchange resin prepared by the preparation method of the porous magnetic ion exchange resin is applied to removal of one or more organic matters in industrial wastewater.
According to the preparation method of the porous magnetic ion exchange resin, the inorganic magnetic substance is grafted and coated on the surface of the resin by using a unique silane coupling agent in a suspension polymerization mode to obtain a magnetic function, and agglomeration or depression of the resin in the polymerization process is limited under the assistance of auxiliary agents such as a cross-linking agent, a dispersing agent, a pore-forming agent and the like, so that a cross-linked stable net-shaped structure is formed. The resin has a porous core-shell structure, has strong adsorption capacity and is easy for magnetic separation, and can be applied to treatment of organic pollutants in industrial wastewater.
The method and the process are optimized, the prepared ion exchange resin has a core-shell structure coated with magnetic substances, the resin has a porous structure, the specific surface area is large, the particle size distribution is small and uniform, a plurality of exchangeable ion channels are provided, the magnetic separation is easy, the cost is low, and the application prospect for removing organic matters in industrial wastewater is good.
Example 1 (the main variable in this example is the dispersant)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, and adding into the deionized water2Heating to 60 ℃ under protection, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing magnetic particles in absolute ethyl alcohol, adding 1 wt% of vinyl methyl dimethoxy silane coupling agent, and reacting in N2Stirring and reacting for 2 hours at 40 ℃ under protection to obtain the modified ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of triallyl isocyanurate and 6.0 g of n-heptane, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.8 g of polyvinyl alcohol/0.8 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
And simultaneously transferring the oil phase A and the water phase B into a reactor, heating to 80 ℃ under stirring for reaction for 2 h, and then heating to 90 ℃ for reaction for 2 h to obtain the magnetic ion exchange resin.
FIG. 1 is a scanning electron microscope image of the porous magnetic ion exchange resin of the present invention, the resin has no obvious pits, the particle size is 40-50 μm, and the surface has large sizeMeasuring micropores, and exchanging ion channels are more. FIG. 2 is an X-ray diffraction pattern of the magnetic ion exchange resin, and the crystallinity of ferroferric oxide in the obtained resin is good, which is consistent with the result of its standard card (No. 19-0029), and a broad peak package appears at 20 degrees, corresponding to the diffraction peak of the polymer. FIG. 3 is a hysteresis chart of a magnetic ion exchange resin showing ferromagnetism and having a saturation magnetization of 11.6 emu g-1. FIG. 4 shows that magnetic ion exchange resin is used for adsorption in the aqueous solution of reactive bright red dye, and after 24 hours, the adsorption amount reaches 177.6 mg/mg, and about 89% of the reactive bright red dye is removed.
Example 2 (the main variable in this example is the crosslinker)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, and adding into the deionized water2Heating to 60 ℃ under protection, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing magnetic particles in absolute ethyl alcohol, adding 1 wt% of vinyl methyl dimethoxy silane coupling agent, and reacting in N2Stirring and reacting for 2 hours at 40 ℃ under protection to obtain the modified ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of divinylbenzene and 6.0 g of n-heptane, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.8 g of polyvinyl alcohol/0.8 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
And simultaneously transferring the oil phase A and the water phase B into a reactor, heating to 80 ℃ under stirring for reaction for 2 h, and then heating to 90 ℃ for reaction for 2 h to obtain the magnetic ion exchange resin.
Example 3 (the main variable in this example is the pore former)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, and adding into the deionized water2Heating to 60 ℃ under protection, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing magnetic particles in absolute ethyl alcohol, adding 1 wt% of vinyl methyl dimethoxy silane coupling agent, and reacting in N2Stirring and reacting for 2 h at 40 ℃ under protection to obtain the modified materialNeutral ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of triallyl isocyanurate and 6.0 g of xylene, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.4 g of polyvinyl alcohol/0.4 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
And simultaneously transferring the oil phase A and the water phase B into a reactor, heating to 80 ℃ under stirring for reaction for 2 h, and then heating to 90 ℃ for reaction for 2 h to obtain the magnetic ion exchange resin.
Example 4 (the main variable in this example is the silane coupling agent)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, and adding into the deionized water2Heating to 60 ℃ under protection, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing magnetic particles in absolute ethanol, adding 1 wt% of vinyl trimethoxy silane coupling agent in N2Stirring and reacting for 2 hours at 40 ℃ under protection to obtain the modified ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of triallyl isocyanurate and 6.0 g of n-heptane, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.4 g of polyvinyl alcohol/0.4 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
And simultaneously transferring the oil phase A and the water phase B into a reactor, heating to 80 ℃ under stirring for reaction for 2 h, and then heating to 90 ℃ for reaction for 2 h to obtain the magnetic ion exchange resin.
Example 5 (the main variables in this example are coupling time and inert gas)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, heating to 60 ℃ under the protection of argon gas, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing the magnetic particles in absolute ethyl alcohol, adding 1 wt% of vinyl methyl dimethoxy silane coupling agent, and stirring and reacting for 1 h at 40 ℃ under the protection of argon to obtain the modified ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of triallyl isocyanurate and 6.0 g of n-heptane, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.4 g of polyvinyl alcohol/0.4 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
And simultaneously transferring the oil phase A and the water phase B into a reactor, heating to 80 ℃ under stirring for reaction for 2 h, and then heating to 90 ℃ for reaction for 2 h to obtain the magnetic ion exchange resin.
Example 6 (the main variables in this example are the polymerization temperature and time)
Weighing a certain amount of ferrous chloride and ferric chloride, dispersing in deionized water, and adding into the deionized water2Heating to 60 ℃ under protection, stirring, dropwise adding weak base to adjust the pH to be =10, and crystallizing at constant temperature for 1 h to obtain ferroferric oxide; dispersing magnetic particles in absolute ethyl alcohol, adding 1 wt% of vinyl methyl dimethoxy silane coupling agent, and reacting in N2Stirring and reacting for 2 hours at 40 ℃ under protection to obtain the modified ferroferric oxide.
Taking 10 g of p-chlorostyrene, 0.2 g of benzoyl peroxide, 2.0 g of triallyl isocyanurate and 6.0 g of n-heptane, and then ultrasonically dispersing 2.0 g of modified ferroferric oxide particles in the solution to obtain an oil phase A; 0.4 g of polyvinyl alcohol/0.4 g of polyvinylpyrrolidone and 4.0 g of sodium chloride were added to 100 mL of deionized water, and dissolved by heating to obtain an aqueous phase B.
Transferring the oil phase A and the water phase B into a reactor simultaneously, heating to 80 ℃ under stirring for reaction for 2 h, then heating to 90 ℃ for reaction for 2 h, and finally heating to 95 ℃ for reaction for 0.5 h to obtain the magnetic ion exchange resin.
In conclusion, the ion exchange resin obtained by the preparation method of the embodiment of the invention has the magnetic function of a core-shell structure, and the research and optimization of the polymerization process, the magnetic ion exchange resin has a stable cross-linked network structure, large specific surface area, small and uniform particle size distribution and strong adsorption capacity, so that the ion exchange resin can be applied to the treatment of organic pollutants in industrial wastewater.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The preparation method of the porous magnetic ion exchange resin is characterized by comprising the following steps
The method comprises the following steps:
step 1, weighing a certain amount of ferrous chloride and ferric chloride, dispersing the ferrous chloride and the ferric chloride in deionized water, heating and stirring the mixture under an oxygen-free condition, dropwise adding weak base into the mixture to adjust the pH value, crystallizing the mixture at a constant temperature, and performing coprecipitation to obtain ferroferric oxide;
step 2, dispersing the prepared magnetic particles in absolute ethyl alcohol, adding a certain amount of silane coupling agent, and heating and stirring for reaction;
step 3, taking p-chlorostyrene as a monomer and benzoyl peroxide as an initiator, adding a proper amount of a cross-linking agent and a pore-forming agent, and ultrasonically dispersing modified ferroferric oxide particles in a solution to obtain an oil phase A;
step 4, adding a certain amount of polyvinyl alcohol/polyvinylpyrrolidone dispersing agent and sodium chloride stabilizing agent into deionized water to obtain a water phase B;
and 5, simultaneously transferring the oil phase A and the water phase B obtained in the step into a reactor, and fully polymerizing the mixed solution under the condition of heating and stirring to obtain the magnetic ion exchange resin.
2. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in the step 1, the mass ratio of ferrous chloride to ferric chloride is 1: (0-2); adjusting the pH value to 8-12; the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
3. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in the step 2, the silane coupling agent is one or the combination of vinyltrimethoxysilane, vinyltrioxysilane and vinylmethyldimethoxysilane; the concentration of the silane coupling agent is 1-5% (w/w); the reaction temperature is 40-80 ℃; the reaction time is 1-5 h.
4. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in the step 3, the crosslinking agent is one or the combination of divinyl benzene, triallyl isocyanurate and ethanedioic acid diacrylate; the pore-forming agent is one or the combination of normal heptane, toluene and xylene; the mass ratio of the monomer, the initiator, the cross-linking agent, the pore-forming agent and the modified ferroferric oxide is 10: (0-0.5): (0-2): (0-5): (0-2).
5. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in the step 4, the mass ratio of the polyvinyl alcohol to the polyvinylpyrrolidone is 1: (0-2); the mass ratio of the deionized water to the dispersant to the stabilizer is 100: (0-2): (0-5).
6. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in the step 5, the mass ratio of the oil phase to the water phase is 1 (5-20); the polymerization reaction temperature is 60-95 ℃; the reaction time is 1-5 h.
7. The method for preparing the porous magnetic ion exchange resin according to claim 1, wherein the porous magnetic ion exchange resin is prepared by a method comprising a step of adding a solvent to the porous magnetic ion exchange resin
Characterized in that in all the steps, the adopted oxygen-free condition is one or more of nitrogen, argon and helium.
8. A process for preparing the porous magnetic ion exchange resin as claimed in any one of claims 1 to 7
The porous magnetic ion exchange resin prepared by the method is applied to removing one or more organic matters in industrial wastewater.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112403450A (en) * | 2020-09-08 | 2021-02-26 | 苏州市相城环保技术有限公司 | Preparation method of magnetic farmland heavy metal adsorbent |
| CN113231034A (en) * | 2021-04-21 | 2021-08-10 | 华南师范大学 | DGT binding phase and preparation method and application thereof |
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| CN103467645A (en) * | 2013-08-30 | 2013-12-25 | 南京大学 | Organic pollution resistance ion exchange resin, and preparation method and application of resin |
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| CN103467645A (en) * | 2013-08-30 | 2013-12-25 | 南京大学 | Organic pollution resistance ion exchange resin, and preparation method and application of resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112403450A (en) * | 2020-09-08 | 2021-02-26 | 苏州市相城环保技术有限公司 | Preparation method of magnetic farmland heavy metal adsorbent |
| CN113231034A (en) * | 2021-04-21 | 2021-08-10 | 华南师范大学 | DGT binding phase and preparation method and application thereof |
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