CN116655867A - Granular ion sieve and preparation method and application thereof - Google Patents
Granular ion sieve and preparation method and application thereof Download PDFInfo
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- CN116655867A CN116655867A CN202310661018.5A CN202310661018A CN116655867A CN 116655867 A CN116655867 A CN 116655867A CN 202310661018 A CN202310661018 A CN 202310661018A CN 116655867 A CN116655867 A CN 116655867A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000012071 phase Substances 0.000 claims abstract description 62
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 19
- 239000008346 aqueous phase Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims description 71
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 15
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 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 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 8
- 239000003361 porogen Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- 150000005673 monoalkenes Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 27
- 238000005406 washing Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000004342 Benzoyl peroxide Substances 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 230000003179 granulation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002148 Gellan gum Polymers 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000216 gellan gum Substances 0.000 description 1
- 235000010492 gellan gum Nutrition 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a granular ion sieve, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Dissolving the polymerized monomer in an organic solventThe solvent is used for obtaining an oil phase, the oil phase is mixed with the ion sieve powder, and the pre-polymerization reaction and the slurrying are carried out under the stirring to obtain a prepolymer; (2) And (3) mixing the prepolymer obtained in the step (1) with an aqueous phase containing a high molecular dispersing agent, and carrying out suspension polymerization reaction to obtain the granular ion sieve. The method of simultaneously carrying out the prepolymerization and the slurrying can thoroughly mix the ion sieve powder with the polymerized monomer, is not easy to diffuse into the water phase in the polymerization process, and improves the process stability and the product performance ， The ball forming rate of the prepared granular ion sieve is more than 70% in the qualified grain size range 。
Description
Technical Field
The invention belongs to the technical field of resin materials, and particularly relates to a granular ion sieve, a preparation method and application thereof.
Background
The ion sieve is a nanoscale powder adsorbent which is widely researched and used, and has the advantages of high adsorption quantity, high adsorption rate and good selective adsorption. The manganese ion sieve precursor has a cubic crystal structure, lithium ions are replaced by hydrogen ions after acid activation, the part of sites have specific adsorption capacity for the lithium ions, the theoretical adsorption capacity is changed according to different lithium contents in the precursor, the maximum adsorption capacity can reach 44mg/g, and the adsorption can reach equilibrium in a few hours. However, the ionic sieve is difficult to be industrially applied, the powdery ionic sieve is easy to be blocked when being directly used, and the ionic sieve can be practically used only by forming micron or millimeter-sized pellets through granulation, but the adsorption performance of the ionic sieve can be greatly reduced in the granulation process, and the mass transfer is further influenced by serious deformation in the repeated use process, and even the mass transfer is fallen off.
Most of granulation is realized by bonding, most typically polyvinyl chloride, is obtained by uniformly mixing an ion sieve, an adhesive and an organic solvent, dispersing the mixture in a water phase to form balls, wherein the adsorption equilibrium time of the obtained adsorbent exceeds two days, and the adsorbent is seriously fallen off when being repeatedly used; recently, polymer granulation has been reported ("Lithium ion recovery from brine using granulatedpolyacrylamide-MnO) 2 ion-sieve ", xiao J, et al Chemical Engineering Journal, 2015) to obtain the adsorbent by mixing powder and monomer and polymerizing, the performance of the adsorbent is improved compared with that of the adhesive method. However, at present, hydrophilic monomers such as acrylamide are used for polymerization granulation, and the hydrophilic monomers are synthesized through reverse suspension polymerization, because ion sieve powder is relatively hydrophilic, the traditional suspension polymerization can cause serious diffusion and incapability of solid carrying in a water phase, and the problem of the reverse suspension polymerization mainly comprises three points: when hydrophilic polymer is used in water phase, volume change occurs along with pH change, so that the adsorbent is seriously deformed to influence mass transfer; secondly, the hydrophilic polymers reported at present cannot obtain a high cross-linked structure, have limited strength and cannot withstand too high pressure and higher temperature; thirdly, the hydrophilic material is seriously swelled and fallen off in water treatment, and the repeated use performance is poor.
CN105195070a discloses a preparation method of molecular sieve microsphere: mixing aluminum gel with molecular sieve powder to obtain slurry, heating the slurry to 65-90 ℃, and adding gellan gum into the slurry; adding the slurry into an oil phase at 80-100 ℃ for high-speed stirring, cooling, adding a cationic solution, and continuously stirring to obtain gel microspheres; and washing, drying and roasting the gel microspheres to obtain the molecular sieve microspheres. The method has the advantages of high molding speed, no pollution in the preparation process, low production cost and the like, and has simple operation steps, thereby being easy to realize industrial production; the product has good wear resistance and fluidization performance, and the particle size can meet the requirements of various reactors. However, the swelling phenomenon easily occurs in the use process, and the application in water treatment is difficult to meet.
CN115364783a discloses a hierarchical lithium ion sieve microsphere, and the preparation method of the hierarchical lithium ion sieve microsphere comprises the following steps: ti is mixed with 3 C 2 MXene, hydrogen peroxide solution and sodium hydroxide solution are uniformly stirred, and hydrothermal reaction is carried out to obtain sodium titanate; placing sodium titanate into hydrochloric acid solution for reaction, washing and drying after the reaction is finished to obtain nanobelts, then uniformly mixing the nanobelts and lithium hydroxide solution by ultrasonic, performing secondary hydrothermal reaction, washing and drying after the reaction is finished to obtain Li 4 Ti 5 O 12 The method comprises the steps of carrying out a first treatment on the surface of the Li is mixed with 4 Ti 5 O 12 Calcining to obtain a lithium ion sieve precursor; the lithium ion sieve precursor is placed in hydrochloric acid solution and then dried to obtain the lithium ion sieve microsphere with the hierarchical structure, but the lithium ion sieve microsphere is easy to diffuse in water.
Because the ion sieve in the prior art has the problems of easy swelling, easy loss in the water treatment process, easy diffusion in water and the like. Therefore, development of a granular ion sieve which is not easy to swell and has excellent adsorption performance and a preparation method which is not easy to lose in the water treatment process and spread to the water phase in the polymerization process are the problems to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a granular ion sieve, a preparation method and application thereof, wherein the preparation method is characterized in that oil phases are singly prepolymerized, the control time is used for avoiding the oil phases from singly and violently polymerizing, the oil phases are not easy to diffuse to water phases in the polymerization process, the particle diameter of the obtained granular ion sieve is uniform, no adhesion exists, the synthesis process is stable and repeatable, and the adsorption performance and the reuse performance of lithium adsorption are high.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of preparing a particulate ion sieve, the method comprising the steps of:
(1) Dissolving a polymerization monomer in an organic solvent to obtain an oil phase, mixing the oil phase with ion sieve powder, and carrying out prepolymerization reaction and slurrying under stirring to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1) with an aqueous phase containing a high molecular dispersing agent, and carrying out suspension polymerization reaction to obtain the granular ion sieve.
Preferably, the polymeric monomer comprises a mono-olefin monomer and/or a crosslinking monomer.
Preferably, the polymeric monomer comprises any one or a combination of at least two of styrene, styrene-based modifying monomers, crosslinking monomers or methacrylate-based monomers.
Preferably, the ionic sieve powder and the polymerized monomer are thoroughly mixed by a method of simultaneously carrying out prepolymerization and slurrying, so that the ionic sieve powder is not easy to diffuse into a water phase in the suspension polymerization reaction process, and the process stability and the product performance are improved.
Preferably, the styrenic modifying monomer comprises chloromethyl styrene.
Preferably, the crosslinking monomer comprises divinylbenzene.
Preferably, the methacrylate monomer comprises methyl methacrylate and/or ethylene glycol methacrylate.
Preferably, the mass of the polymerized monomer is from 0% to 100%, and the mass of the crosslinking monomer may be, for example, 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, and specific point values between the above point values, and the present invention is not intended to be exhaustive of the specific point values included in the range for reasons of brevity and conciseness.
Preferably, the oil phase of step (1) further comprises an initiator and a porogen.
Preferably, the initiator is an oil-soluble initiator.
Preferably, the initiator comprises dibenzoyl peroxide.
Preferably, the initiator is used in an amount of 0.5 to 3% by mass of the polymerized monomer, for example, 0.5%, 0.7%, 0.9%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3% and the specific point values between the above point values, are limited in space and, for the sake of brevity, the invention is not exhaustive of the specific point values comprised in the stated ranges.
Preferably, the porogen is an oil-soluble inert material.
Preferably, the porogen comprises liquid wax and/or white oil.
Preferably, the porogen is used in an amount of 1-100% by mass of the polymerized monomer, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100% and specific point values between the above point values, are limited in length and for brevity the invention is not intended to be exhaustive of the specific point values included in the ranges.
Preferably, the organic solvent is an aliphatic short-chain ester or a long-chain alcohol.
Preferably, the organic solvent comprises any one or a combination of at least two of ethyl acetate, isooctyl alcohol, butyl acetate or toluene.
Preferably, the organic solvent is used in an amount of 1 to 100% by mass of the polymerized monomer, and may be, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, and specific point values between the above point values, but are limited to the space and, for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the polarity of the oil phase is enhanced after the use of an organic solvent in place of the aromatic hydrocarbon solvents used in conventional styrene polymerizations, helping to retain the ion sieve powder.
Preferably, the amount of the ionic sieve powder in the step (1) is 1-50% of the mass of the polymerized monomer, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
Preferably, the ion sieve powder comprises a manganese ion sieve.
Preferably, the particle size of the ion sieve powder is < 1 μm, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 0.99 μm, and specific point values between the above point values, are not exhaustive of the specific point values included in the range for reasons of brevity and conciseness.
Preferably, the stirring speed in step (1) is 200-600r/min, for example, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min, 600r/min, and specific point values among the above point values are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the stirring in step (1) is electromagnetic stirring.
Preferably, the reaction temperature of the prepolymerization reaction in step (1) is 65-80 ℃, for example 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃,78 ℃,80 ℃ and specific values between the above mentioned values, which are limited in space and for the sake of brevity, the invention is not exhaustive.
Preferably, the reaction time of the prepolymerization reaction in the step (1) is 30-90min, for example, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min, 90min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the oil phase is pre-polymerized separately for a controlled time to avoid too fast an oil phase polymerization.
Preferably, the volume ratio of the oil phase to the water phase is 1: (2-6), for example, can be 1:2, 1:2.5, 1:3. 1:3.5, 1:4. 1:4.5, 1:5. 1:5.5, 1:6, and specific point values between the above point values, are limited in space and for brevity, the present invention is not intended to exhaustively enumerate the specific point values included in the range.
Preferably, the polymeric dispersant comprises polyvinyl alcohol.
Preferably, the concentration by mass of the polymeric dispersant in the aqueous phase of step (2) is between 0.5 and 3%, for example, it may be between 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, and the specific values between the above values are limited in space and for the sake of brevity, the invention is not intended to be exhaustive of the specific values comprised in the range.
Preferably, the polymeric dispersant may act as a surfactant to stabilize droplets of oil phase formation.
Preferably, the aqueous phase of step (2) further comprises an inorganic salt.
Preferably, the mass concentration of the inorganic salt in the aqueous phase of step (2) is 2-10%, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, and the specific values between the above values are limited in length and for simplicity, the invention is not intended to be exhaustive list of the specific values comprised in the range.
Preferably, the inorganic salt comprises sodium chloride.
Preferably, the inorganic salt may reduce dissolution of the polymerized monomer in the aqueous phase, and may also adjust the density of the aqueous phase.
Preferably, the suspension polymerization reaction of step (2) is carried out under stirring conditions, more preferably under electromagnetic stirring conditions.
Preferably, the stirring speed is 100-400r/min, for example, 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, and specific point values among the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, the reaction temperature of the suspension polymerization reaction in step (2) is 75-90 ℃, for example, 75 ℃,78 ℃,80 ℃, 82 ℃,85 ℃, 88 ℃, 90 ℃, and specific values between the above values, and the present invention is not exhaustive of the specific values included in the range for reasons of space and for reasons of brevity.
Preferably, the suspension polymerization reaction in step (2) has a reaction time of 5 to 10 hours, for example, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, and specific point values among the above point values, and the present invention is not exhaustive of the specific point values included in the range for reasons of brevity and conciseness.
Preferably, the prepolymer is poured into an aqueous phase and dispersed at a suitable stirring speed, and the particle size of the ion sieve can be effectively controlled by adjusting the speed of electromagnetic stirring.
Preferably, the preparation method further comprises a post-treatment.
Preferably, the post-treatment comprises washing, natural drying, rope lifting and sieving.
Preferably, the washing includes washing with hot water and ethanol.
Preferably, the time of natural drying is 4-10h, for example, it may be 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, and specific point values among the above point values, limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the soxhlet is washed with petroleum ether in a soxhlet extractor.
Preferably, the time of the cable is 5-8h, for example, may be 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, and specific point values among the above point values, which are limited in length and for brevity, the present invention is not exhaustive.
Preferably, the screening is in a two-layer screen.
Preferably, the preparation method specifically comprises the following steps:
(1) Mixing a polymerization monomer initiator, a pore-forming agent and an organic solvent to obtain an oil phase, mixing the oil phase with ion sieve powder, and carrying out prepolymerization reaction and slurrying under stirring to obtain a prepolymer;
the polymerization monomer comprises a mono-olefin monomer and/or a crosslinking monomer, the initiator is an oil-soluble initiator, the pore-forming agent is an oil-soluble inert substance, the organic solvent is aliphatic short-chain lipid or long-chain alcohol, the particle size of the ion sieve powder is less than 1 mu m, the reaction temperature of the prepolymerization reaction is 65-80 ℃, and the reaction time is 30-90min;
(2) Mixing the prepolymer obtained in the step (1) with water containing a high molecular dispersing agent and inorganic salt, and carrying out suspension polymerization reaction to obtain the granular ion sieve;
the volume ratio of the oil phase to the water phase is 1: (2-6); the mass concentration of the high molecular dispersing agent in the water phase is 0.5-3%; the mass concentration of the inorganic salt in the water phase is 2-10%; the reaction temperature of the suspension polymerization reaction is 78-90 ℃ and the reaction time is 5-10h.
In a second aspect, the present invention provides a particulate ion sieve prepared by the preparation method of the first aspect.
Preferably, the particle size of the particulate ion sieve is 300-1000 μm, for example 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, 1000 μm, and specific point values between the above point values, are limited in length and for brevity the invention is not exhaustive list of the specific point values comprised in the range.
Preferably, the particulate ion sieve has a moisture content of 50 to 65wt%, such as 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 65wt%, and specific point values between the above point values, for the sake of brevity and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
In a third aspect, the present invention provides the use of a particulate ion sieve as described in the second aspect in an adsorbent.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the granular ion sieve, the synthesized granular ion sieve has good black non-adhesion spheres, controllable particle size and high strength; the granular ion sieve obtained by forward suspension polymerization is not easy to fall off in repeated use, the prepolymerization process is stable, the serious diffusion of the ion sieve into a water phase does not occur, the ion sieve powder and the polymerized monomer can be thoroughly mixed by a method of simultaneous prepolymerization and slurrying, the process stability and the product performance are improved in the polymerization process, the balling rate of the prepared granular ion sieve is more than 70% in the particle size range of 250-850 mu m, the water content is 53.34-62.46wt%, the saturated adsorption amount is 10.3-16.3mg/g, the adsorption equilibrium time is 10-14h, the saturated adsorption amount is 9.8-15.2mg/g after repeating 10 times, and the saturated adsorption equilibrium time is 10-14h.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The experimental materials used in the examples and comparative examples of the present invention are as follows:
(1) Manganese ion screen (same preparation method as literature, "Synthesis of granulated H 4 Mn 5 O 12 /chitosan with improved stability by a novel cross-linking strategy for lithium adsorption from aqueous solutions"，Ding W,et al.[J].Chemical Engineering Journal,2021,426:131689.)；
(2) Titanium ion sieves (preparation method is the same as literature, "Synthesis ofPolyporous Ion-Sieve and ItsApplication for Selective Recovery ofLithium from Geothermal Water", lin H, et al [ J ]. ACS Applied Materials & Interfaces,2019,11 (29));
(3) Polyvinyl alcohol, brand 1788, vendor aratin;
example 1
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 78 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide, 10g of ethyl acetate and 10g of liquid wax, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 200r/min to obtain a sol with the particle size of about 500 mu m, reacting at 78 ℃ for 8 hours to obtain a product, washing with hot water until no foam exists, washing with ethanol to remove excessive moisture, naturally drying for 6 hours, carrying out rope extraction with petroleum ether to obtain a granular ion sieve, and sieving with a gauze with 450 mu m and 550 mu m to obtain a final product.
Example 2
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 2g of polyvinyl alcohol are dissolved in 200mL of water, stirred in a 500mL three-neck flask, and heated to 78 ℃ to obtain a water phase; respectively weighing 15g of styrene, 15g of divinylbenzene, 0.2g of benzoyl peroxide and 15g of butyl acetate, uniformly mixing to obtain an oil phase, adding 15g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 70min to obtain a prepolymer, adding the prepolymer into the water phase, regulating stirring speed to 300r/min to obtain sol with the particle size of about 400 mu m, reacting for 8 hours at 85 ℃, obtaining a product, washing with hot water until no foam exists, washing with ethanol for removing excessive water, naturally drying for 6 hours, extracting with petroleum ether rope for 6 hours to obtain a granular ion sieve, and sieving with a 350 mu m gauze and a 450 mu m gauze to obtain a final product.
Example 3
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 0.5g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 78 ℃ to obtain a water phase; 15g of divinylbenzene, 0.15g of benzoyl peroxide and 5g of ethyl acetate are respectively weighed, uniformly mixed to obtain an oil phase, then 7.5g of titanium ion sieve is added, under the electromagnetic stirring of 500r/min, the water bath is heated to 78 ℃ for reaction for 30min to obtain a prepolymer, the prepolymer is added into an aqueous phase, the stirring speed is regulated to 400r/min to obtain sol with the particle size of about 800 mu m, and the reaction is carried out for 8 hours at 85 ℃. Washing the obtained product with hot water until no foam exists, washing off excessive water with ethanol, naturally drying for 6 hours, extracting with petroleum ether for 6 hours to obtain a granular ion sieve, and sieving with 750 μm and 850 μm gauze to obtain the final product.
Example 4
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 78 ℃ to obtain a water phase; respectively weighing 15g of chloromethyl styrene, 5g of divinylbenzene, 0.2g of benzoyl peroxide and 10g of isooctanol, uniformly mixing to obtain an oil phase, adding 10g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 400r/min to obtain a sol with the particle size of about 300 mu m, reacting at 80 ℃ for 8 hours to obtain a product, washing the product with hot water until no foam exists, washing excessive water with ethanol, naturally drying for 6 hours, extracting with petroleum ether rope to obtain a granular ion sieve, and sieving with 250 mu m and 350 mu m gauze to obtain a final product.
Example 5
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 78 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide and 20g of ethyl acetate, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 200r/min to obtain sol with the particle size of about 500 mu m, reacting at 78 ℃ for 8 hours to obtain only random polymer with very poor spherical shape, wherein the amount of an organic solvent used exceeds a preferred range, and the polymer is excessively swelled after being molded and cannot be solidified into balls.
Example 6
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 78 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide, 10g of ethyl acetate and 10g of liquid wax, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 200r/min to obtain sol with particle size of about 500 mu m, reacting at 95 ℃ for 8 hours to obtain a banded hard polymer, wherein the reaction temperature of suspension polymerization exceeds a preferred range, and the polymer is subjected to viscous flow state transition at high temperature and is seriously adhered under stirring.
Example 7
The preparation method of the granular ion sieve comprises the following steps:
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 85 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide, 10g of ethyl acetate and 10g of liquid wax, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, heating to 78 ℃ in a water bath under electromagnetic stirring of 500r/min, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 200r/min to obtain a sol with the particle size of about 500 mu m, reacting for 6 hours at 85 ℃, washing the obtained product with hot water until no foam exists, washing the excessive moisture with ethanol, naturally drying for 6 hours, carrying out rope extraction with petroleum ether to obtain a granular ion sieve, and sieving with a gauze of 450 mu m and 550 mu m to obtain the final product.
Comparative example 1
A process for preparing a granular ion sieve differs from example 1 in that slurrying and prepolymerization are carried out separately.
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 85 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide, 10g of ethyl acetate and 10g of liquid wax, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, pulping for 1 hour under electromagnetic stirring of 500r/min, heating to 78 ℃ in a water bath, reacting for 90min to obtain a prepolymer, adding the prepolymer into an aqueous phase, regulating stirring speed to 200r/min to obtain sol with the particle size of about 500 mu m, reacting for 6 hours at 85 ℃, washing the obtained product with hot water until no foam exists, washing excessive moisture with ethanol, naturally drying for 6 hours, and extracting with petroleum ether for 6 hours to obtain a part of granular ion sieve and white balls, wherein the load is far lower than that of the product obtained by pulping and prepolymerization.
Comparative example 2
A process for preparing a granular ion sieve differs from example 1 in that no prepolymerization, slurry and suspension polymerization are carried out simultaneously.
5g of sodium chloride and 1g of polyvinyl alcohol are dissolved in 100mL of water, stirred in a 250mL three-neck flask, and heated to 85 ℃ to obtain a water phase; respectively weighing 10g of styrene, 2g of divinylbenzene, 0.12g of benzoyl peroxide, 10g of ethyl acetate and 10g of liquid wax, uniformly mixing to obtain an oil phase, adding 6g of manganese ion sieve, adding the oil phase into the water phase together, regulating stirring speed to 200r/min to obtain sol with the particle size of about 500 mu m, reacting at 85 ℃ for 6 hours to obtain a product, washing the product with hot water until no foam exists, washing the excessive water with ethanol, completely unloading white balls of the product, and completely losing the ion sieve powder in washing.
The granular ion sieves provided in examples 1-7 and comparative examples 1-2 were tested for performance by the following procedure:
(1) Particle size: measuring by using a laser particle size analyzer, adding a certain amount of granular ion sieve into water, stirring, and measuring the refraction of the water to determine the particle size;
(2) Water content: the measurement was performed using a moisture meter. Selecting about 1g of granular ion sieve, placing the granular ion sieve in a moisture tester, and selecting a program of 3 minutes at 160 ℃ for quick measurement;
(3) Balling rate: the product is weighed after sieving, the moisture is measured to determine the dry weight m, and the total mass of the polymerized monomer and the ion sieve powder is m during feeding 0 ，m 0 And/m is the balling rate;
(4) Saturated adsorption amount: selecting 0.5g/L, 1g/L, 1.5g/L, 2g/L and other concentrations of lithium hydroxide solution as simulation solution, placing a granular ion sieve with dry weight of m into a conical flask, adding the simulation solution with volume of V, performing static adsorption in a constant-temperature shaking table, and measuring the adsorbed solution and the initial simulation solution by ICP to determine the lithium concentration of c respectivelyAnd c 0 Saturated adsorption amount is (c-c) 0 )*V/m；
(5) Adsorption equilibration time: a certain amount of 500ppm lithium hydroxide solution is prepared, a granular ion sieve is placed into the solution, static adsorption is carried out in a constant temperature shaking table, sampling is carried out every half an hour, ICP is used for measuring to determine the lithium concentration, and the time is adsorption equilibrium time until the lithium concentration is not changed any more.
TABLE 1
As can be seen from the data in Table 1, the granular ion sieves synthesized by the method provided by the invention have the advantages that compared with comparative examples 1-2, the granular ion sieves synthesized by the method provided by examples 1-4 and 7 have black non-blocking spheres, controllable particle sizes (250-850 μm), water content of more than 50%, ball forming rate of more than 70% after sieving, and example 3 only uses divinylbenzene as a polymerization monomer, so that the ion sieves with hundred percent crosslinking degree and high temperature and pressure resistance are obtained.
TABLE 2
As can be seen from the data in Table 2, the saturated adsorption amounts of the granular ion sieves synthesized in examples 1-4 and 7 are higher than those in comparative examples 1-2, the adsorption equilibrium time is longer, and the saturated adsorption amounts and the saturated adsorption equilibrium time after repeating 10 times are also significantly improved than those in comparative examples 1-2.
The applicant states that the present invention has been described by way of the above examples to illustrate a particulate ion sieve of the present invention and a method of making and using it, but the present invention is not limited to, i.e. it is not meant that the present invention must be practiced in dependence upon, the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method of preparing a granular ion sieve, the method comprising the steps of:
(1) Dissolving a polymerization monomer in an organic solvent to obtain an oil phase, mixing the oil phase with ion sieve powder, and carrying out prepolymerization reaction and slurrying under stirring to obtain a prepolymer;
(2) And (3) mixing the prepolymer obtained in the step (1) with an aqueous phase containing a high molecular dispersing agent, and carrying out suspension polymerization reaction to obtain the granular ion sieve.
2. The method of claim 1, wherein the polymerized monomer of step (1) comprises mono alkenyl monomer and/or crosslinking monomer;
preferably, the polymeric monomer comprises any one or a combination of at least two of styrene, styrene-based modified monomers, crosslinking monomers or methacrylate-based monomers;
preferably, the styrenic modifying monomer comprises chloromethyl styrene;
preferably, the crosslinking monomer comprises divinylbenzene;
preferably, the methacrylate monomer comprises methyl methacrylate and/or ethylene glycol methacrylate;
preferably, the mass of the polymerized monomer is 100% and the mass of the crosslinking monomer is 0 to 100%.
3. The method of claim 1 or 2, wherein the oil phase of step (1) further comprises an initiator and a porogen;
preferably, the initiator is an oil-soluble initiator;
preferably, the initiator comprises dibenzoyl peroxide;
preferably, the initiator is used in an amount of 0.5 to 3% by mass of the polymerized monomer;
preferably, the porogen is an oil-soluble inert substance;
preferably, the porogen comprises liquid wax and/or white oil;
preferably, the porogen is used in an amount of 1 to 100% by mass of the polymerized monomer.
4. A method of preparation according to any one of claims 1 to 3 wherein the organic solvent is an aliphatic short chain lipid or long chain alcohol;
preferably, the organic solvent comprises any one or a combination of at least two of ethyl acetate, isooctyl alcohol, butyl acetate or toluene;
preferably, the organic solvent is used in an amount of 1 to 100% by mass of the polymerized monomer;
preferably, the dosage of the ion sieve powder in the step (1) is 1-50% of the mass of the polymerized monomer;
preferably, the ion sieve powder comprises a manganese ion sieve;
preferably, the particle size of the ion sieve powder is less than 1 μm;
preferably, the reaction temperature of the prepolymerization reaction in the step (1) is 65-80 ℃;
preferably, the reaction time of the prepolymerization reaction in the step (1) is 30-90min.
5. The method according to any one of claims 1 to 4, wherein the volume ratio of the oil phase to the water phase is 1: (2-6).
6. The method according to any one of claims 1 to 5, wherein the polymeric dispersant comprises polyvinyl alcohol;
preferably, the mass concentration of the high molecular dispersing agent in the water phase in the step (2) is 0.5-3%;
preferably, the aqueous phase of step (2) further comprises an inorganic salt;
preferably, the inorganic salt comprises sodium chloride;
preferably, the mass concentration of the inorganic salt in the aqueous phase of step (2) is 2-10%;
preferably, the reaction temperature of the suspension polymerization reaction in the step (2) is 75-90 ℃;
preferably, the suspension polymerization reaction in step (2) takes 5 to 10 hours.
7. The preparation method according to claim 1, characterized in that it comprises the following steps:
(1) Mixing a polymerization monomer initiator, a pore-forming agent and an organic solvent to obtain an oil phase, mixing the oil phase with ion sieve powder, and carrying out prepolymerization reaction and slurrying under stirring to obtain a prepolymer;
the polymerization monomer comprises a mono-olefin monomer and/or a crosslinking monomer, the initiator is an oil-soluble initiator, the pore-forming agent is an oil-soluble inert substance, the organic solvent is aliphatic short-chain lipid or long-chain alcohol, the particle size of the ion sieve powder is less than 1 mu m, the reaction temperature of the prepolymerization reaction is 65-80 ℃, and the reaction time is 30-90min;
(2) Mixing the prepolymer obtained in the step (1) with water containing a high molecular dispersing agent and inorganic salt, and carrying out suspension polymerization reaction to obtain the granular ion sieve;
the volume ratio of the oil phase to the water phase is 1: (2-6); the mass concentration of the high molecular dispersing agent in the water phase is 0.5-3%; the mass concentration of the inorganic salt in the water phase is 2-10%; the reaction temperature of the suspension polymerization reaction is 78-90 ℃ and the reaction time is 5-10h.
8. A granular ion sieve, characterized in that it is produced by the production process according to any one of claims 1 to 7.
9. The particulate ion sieve of claim 8, wherein the particulate ion sieve has a particle size of 300-1000 μm;
preferably, the particulate ion sieve has a moisture content of 50 to 65wt%.
10. Use of a particulate ion sieve according to claim 8 or 9 in an adsorbent.
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