CN115400741A - Cross-linked polyacrylonitrile resin and its preparation method and use - Google Patents
Cross-linked polyacrylonitrile resin and its preparation method and use Download PDFInfo
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- CN115400741A CN115400741A CN202211034528.1A CN202211034528A CN115400741A CN 115400741 A CN115400741 A CN 115400741A CN 202211034528 A CN202211034528 A CN 202211034528A CN 115400741 A CN115400741 A CN 115400741A
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- acrylonitrile
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- triallyl isocyanurate
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- 229920006350 polyacrylonitrile resin Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000004005 microsphere Substances 0.000 claims abstract description 27
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- -1 fluorine ions Chemical class 0.000 claims abstract description 17
- 239000012071 phase Substances 0.000 claims abstract description 16
- 239000004342 Benzoyl peroxide Chemical group 0.000 claims abstract description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 12
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 12
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 7
- 239000011324 bead Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims 2
- 230000000052 comparative effect Effects 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 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 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004075 alteration 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Chemical & Material Sciences (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a crosslinked polyacrylonitrile resin and a preparation method and application thereof. The preparation method comprises the following steps: 1) Mixing hydroxyethyl cellulose with water to obtain a water phase; 2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and C1-C6 alkyl substituted benzene to obtain an organic phase; 3) Adding the organic phase into the water phase, stirring to form beads, heating to 70-95 ℃ for curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; 4) And (3) mixing and reacting the acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of inorganic ferric salt to obtain the crosslinked polyacrylonitrile resin. The cross-linked polyacrylonitrile resin obtained by the invention can be used for removing fluorine ions, and has high adsorption rate to the fluorine ions.
Description
Technical Field
The invention relates to a cross-linked polyacrylonitrile resin and a preparation method and application thereof.
Background
The main source of fluorine pollution in water environment is fluorine-containing 'three wastes' discharged from industrial production, and relates to the industries of aluminum electrolysis, steel, cement, brick and tile, ceramics, phosphate fertilizer, glass, semiconductors, pharmacy and the like. The common characteristic of these industries is that the fluorine-containing minerals are used as main or auxiliary raw materials, and during the smelting and production processes, fluorine is decomposed from the minerals and enters the environment, resulting in fluorine pollution.
Ion exchange is one of the mainstream methods for treating fluorine-containing wastewater. The ion exchange resin has the advantages of high separation efficiency, good selectivity, simple operation and the like, and is commonly used for separating and extracting trace elements. However, the conventional ion exchange resin has poor selectivity to fluorine ions and low adsorption capacity, and limits the industrial application of the conventional ion exchange resin in treating fluorine-containing wastewater.
Therefore, a resin having high selectivity to fluorine ions and high adsorption capacity and having adsorption performance is demanded.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a cross-linked polyacrylonitrile resin, wherein the prepared cross-linked polyacrylonitrile resin has a good adsorption effect on fluorine ions. Another object of the present invention is to provide a crosslinked polyacrylonitrile resin prepared according to the above preparation method. It is still another object of the present invention to provide a use of the crosslinked polyacrylonitrile resin.
The invention achieves the above purpose through the following technical scheme.
In one aspect, the invention provides a preparation method of a crosslinked polyacrylonitrile resin, which comprises the following steps:
1) Mixing hydroxyethyl cellulose with water to obtain a water phase; wherein the weight ratio of the hydroxyethyl cellulose to the water is 1;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and C1-C6 alkyl substituted benzene to obtain an organic phase; wherein the weight ratio of the triallyl isocyanurate to the acrylonitrile is 0.17-0.5; the weight of the benzoyl peroxide is 0.8 to 1.7 percent of the sum of the weight of the acrylonitrile and the triallyl isocyanurate; the ratio of the weight of the C1-C6 alkyl substituted benzene to the sum of the weight of the acrylonitrile and the weight of the triallyl isocyanurate is 0.9-2;
3) Adding the organic phase into the water phase, stirring to form beads, heating to 70-95 ℃ for curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; wherein the volume ratio of the water phase to the organic phase is 1.25-2.8;
4) Mixing acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of an inorganic ferric salt, and reacting to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microspheres to the iron element is 1.41-1.1.
The prepared cross-linked polyacrylonitrile resin has high adsorption rate to fluorine ions.
In step 1) of the present invention, the dissolution may be promoted by heating, and the heating temperature may be 45 to 70 ℃, preferably 55 to 65 ℃. The weight ratio of hydroxyethyl cellulose to water may be 1.
In step 2) of the present invention, the weight ratio of triallyl isocyanurate to acrylonitrile may be 0.17 to 0.5, preferably 0.19 to 0.4, and more preferably 0.2 to 0.35. The amount of benzoyl peroxide may be between 0.8 and 1.7%, preferably between 0.85 and 1.5% of the sum of the amounts of acrylonitrile and triallyl isocyanurate. C1-C6 in the C1-C6 alkyl-substituted benzene means the number of carbon atoms in the substituted alkyl group. In the present invention, the C1-C6 alkyl-substituted benzene may include toluene, ethylbenzene, cumene, and preferably toluene. The ratio of the weight of the C1-C6 alkyl substituted benzene to the sum of the weights of acrylonitrile and triallyl isocyanurate may be from 0.9 to 2, preferably from 1.0 to 1.7.
In step 3) of the present invention, according to an embodiment of the present invention, adding the organic phase into the aqueous phase, stirring to form uniform-sized beads, slowly heating to 70-95 ℃, curing at the temperature, and removing toluene after the reaction (the toluene can be removed by alcohol extraction, for example, ethanol extraction can be used, and specifically, a soxhlet extractor filled with ethanol can be used for multiple extractions) to obtain the acrylonitrile skeleton copolymer crosslinked microspheres.
The volume ratio of the aqueous phase to the organic phase may be from 1.25 to 2.8, preferably from 1.3 to 2.5. The curing reaction temperature may be 70 to 95 ℃ and preferably 75 to 90 ℃. The curing reaction time may be 5 to 13 hours, preferably 7 to 11 hours. This facilitates the formation of acrylonitrile skeleton copolymer crosslinked microspheres.
In step 4) of the present invention, the weight ratio of the acrylonitrile skeleton copolymer crosslinked microspheres to the iron element in the inorganic iron salt may be 1. The inorganic ferric salt is selected from one of ferric nitrate, ferric sulfate or ferric trichloride, and is preferably ferric trichloride.
The aqueous solution of the inorganic iron salt can be obtained by mixing the inorganic iron salt and water, wherein the weight ratio of the iron element in the inorganic iron salt to the water can be 1. The reaction temperature is 40 to 90 ℃, preferably 40 to 85 ℃, and more preferably 60 to 85 ℃. The reaction time is 8 to 20 hours, preferably 10 to 18 hours. The water used in this step may be deionized water.
And 4), washing and drying after the reaction is finished to obtain the crosslinked polyacrylonitrile resin. The drying temperature may be 70 to 100 deg.C, preferably 75 to 90 deg.C. The drying time may be 5 to 20 hours, preferably 9 to 15 hours. Thus being beneficial to leading the obtained crosslinking polyacrylonitrile resin to have higher adsorption rate to the fluorinion.
The invention finds that the parameters are controlled within a specific range, so that the crosslinked polyacrylonitrile resin with high fluorine ion adsorption rate can be obtained.
According to the preparation method of the invention, in step 2), preferably, the C1-C6 alkyl substituted benzene is toluene.
The invention also provides a preparation method of the crosslinked polyacrylonitrile resin, which comprises the following steps:
1) Mixing hydroxyethyl cellulose with water to obtain a water phase; wherein the weight ratio of the hydroxyethyl cellulose to the water is 1;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and liquid paraffin to obtain an organic phase; wherein the weight ratio of the triallyl isocyanurate to the acrylonitrile is 0.17-0.5; the weight of the benzoyl peroxide is 0.8 to 1.7 percent of the sum of the weight of the acrylonitrile and the weight of the triallyl isocyanurate; the ratio of the weight of the liquid paraffin to the sum of the weight of the acrylonitrile and the weight of the triallyl isocyanurate is 0.9-2;
3) Adding the organic phase into the water phase, stirring to form beads, heating to 70-95 ℃ for curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; wherein the volume ratio of the water phase to the organic phase is 1.25-2.8;
4) Mixing acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of an inorganic ferric salt, and reacting to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microspheres to the iron element is 1.41-1.1.
According to the preparation method of the present invention, preferably, in the step 2), the weight ratio of triallyl isocyanurate to acrylonitrile is 0.19-0.4; the weight of the benzoyl peroxide is 0.85-1.5% of the sum of the weight of the acrylonitrile and the triallyl isocyanurate.
According to the preparation method of the invention, in the step 3), the curing reaction time is preferably 5-13 h.
According to the preparation method of the present invention, preferably, the inorganic iron salt is ferric chloride.
According to the preparation method of the invention, preferably, in the step 4), the acrylonitrile skeleton copolymer crosslinked microspheres and the aqueous solution of the inorganic ferric salt are mixed and reacted, and after the reaction is finished, the mixture is washed and dried to obtain the crosslinked polyacrylonitrile resin.
According to the preparation method of the invention, preferably, in the step 4), the reaction temperature is 40-90 ℃; the reaction time is 8-20 h.
In another aspect, the invention also provides the crosslinked polyacrylonitrile resin prepared according to the preparation method.
In another aspect, the invention further provides the use of the crosslinked polyacrylonitrile resin in removing fluorine ions, wherein the adsorption rate of the crosslinked polyacrylonitrile resin on the fluorine ions in the solution is more than 98%. Preferably, the adsorption rate of the obtained crosslinked polyacrylonitrile resin to fluorine ions in a solution is more than 98.5%, and more preferably more than 99%.
The cross-linked polyacrylonitrile resin prepared by the preparation method has good adsorption effect on fluorine ions, and the adsorption rate is more than 98%.
Drawings
FIG. 1 is a photomicrograph of a polarized light microscope showing crosslinked microspheres of acrylonitrile-based copolymer obtained in example 1.
FIG. 2 is a polarization microscope photograph of the crosslinked polyacrylonitrile resin obtained in example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
The test method is described below:
(1) And (3) testing the adsorption rate: 1g of the prepared crosslinked polyacrylonitrile resin was taken and the fluorine concentration at 100mL was 10mg/L (C) 0 ) The adsorption stock solution with the pH value of 4 is subjected to a static adsorption test, the adsorption temperature is room temperature, the adsorption time is 8h, and the concentration of fluorine ions in the adsorption tail solution is C t . The adsorption rate is calculated as follows:
adsorption rate = (C) 0 -C t )/C 0 ×100％。
(2) The iron content in the crosslinked polyacrylonitrile resin is as follows: measured by ICP-MS.
(3) Photomicrographs: the microscope used was manufactured by Leica, model DFC450C.
Example 1
1) According to the formulation of table 1, hydroxyethyl cellulose was added to deionized water and heated to 65 ℃ until all the solids dissolved, resulting in an aqueous phase.
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and toluene uniformly to obtain an organic phase.
3) And adding the organic phase into the water phase, stirring to form uniform-sized balls, slowly heating to 80 ℃, carrying out curing reaction for 8 hours at 80 ℃, and removing toluene after the reaction is finished to obtain the acrylonitrile skeleton copolymer crosslinked microspheres.
4) Mixing acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of ferric trichloride, reacting for 12 hours at 60 ℃, washing with water after the reaction is finished, and drying for 12 hours in vacuum at 80 ℃ to obtain the crosslinked polyacrylonitrile resin.
The resulting crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluorine ions, and the results are shown in table 2.
Comparative examples 1 to 5
The kinds and amounts of the raw materials are shown in Table 1, and the rest is the same as example 1.
The obtained crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluorine ions, and the results are shown in table 2.
TABLE 1
Example 2
1) 3.3g of hydroxyethyl cellulose was added to 330mL of deionized water and heated to 65 ℃ until all the solids were dissolved, yielding an aqueous phase.
2) 60g of acrylonitrile, 12.99g of triallyl isocyanurate, 0.73g of benzoyl peroxide and 72.99g of toluene were uniformly mixed to obtain an organic phase.
3) And adding the organic phase into the water phase, stirring to form uniform-sized balls, slowly heating to 80 ℃, carrying out curing reaction for 8 hours at 80 ℃, and removing toluene after the reaction is finished to obtain the acrylonitrile skeleton copolymer crosslinked microspheres.
4) Mixing 20g of acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of ferric trichloride (formed by mixing 40g of ferric trichloride with 100mL of water), reacting at 60 ℃ for 12h, washing with water after the reaction is finished, and drying in vacuum at 80 ℃ for 12h to obtain the crosslinked polyacrylonitrile resin.
The resulting crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluorine ions, and the results are shown in table 2.
TABLE 2
| Serial number | Adsorption Rate% |
| Example 1 | 99.8 |
| Example 2 | 98.6 |
| Comparative example 1 | 90.3 |
| Comparative example 2 | 94.6 |
| Comparative example 3 | 92.4 |
| Comparative example 4 | 95.7 |
| Comparative example 5 | 96.1 |
| Crosslinked microspheres of acrylonitrile skeleton copolymer obtained in example 1 | 17.3 |
The acrylonitrile skeleton copolymer crosslinked microspheres and the crosslinked polyacrylonitrile resin obtained in example 1 were subjected to a microscopic test. The results are shown in FIGS. 1 and 2. As shown in the figure, the acrylic acid skeleton copolymer crosslinked microsphere has transparent light rings under a polarizing microscope, the transparent light rings on the surface of the resin after iron loading disappear, and the sphere is opaque, which indicates that iron ions are loaded in the resin skeleton.
The iron content of the adsorbents obtained in example 1 and example 2 and comparative example 1 and comparative example 2 was measured, and the results are shown in table 3.
TABLE 3
| Name (R) | Iron content% |
| Example 1 | 19.6 |
| Example 2 | 17.5 |
| Comparative example 1 | 11.6 |
| Comparative example 2 | 14.7 |
The present invention is not limited to the above-described embodiments, and any variations, modifications, and alterations that may occur to those skilled in the art may fall within the scope of the present invention without departing from the spirit of the present invention.
Claims (10)
1. The preparation method of the crosslinked polyacrylonitrile resin is characterized by comprising the following steps of:
1) Mixing hydroxyethyl cellulose with water to obtain a water phase; wherein the weight ratio of the hydroxyethyl cellulose to the water is 1;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and C1-C6 alkyl substituted benzene to obtain an organic phase; wherein the weight ratio of the triallyl isocyanurate to the acrylonitrile is 0.17-0.5; the weight of the benzoyl peroxide is 0.8 to 1.7 percent of the sum of the weight of the acrylonitrile and the triallyl isocyanurate; the ratio of the weight of the C1-C6 alkyl substituted benzene to the sum of the weight of the acrylonitrile and the triallyl isocyanurate is 0.9-2;
3) Adding the organic phase into the water phase, stirring to form balls, heating to 70-95 ℃, and carrying out curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; wherein the volume ratio of the water phase to the organic phase is 1.25-2.8;
4) Mixing acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of an inorganic ferric salt, and reacting to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microspheres to the iron element is 1.41-1.1.
2. The method according to claim 1, wherein the C1-C6 alkyl-substituted benzene in step 2) is toluene.
3. The preparation method of the crosslinked polyacrylonitrile resin is characterized by comprising the following steps of:
1) Mixing hydroxyethyl cellulose with water to obtain a water phase; wherein the weight ratio of the hydroxyethyl cellulose to the water is 1;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and liquid paraffin to obtain an organic phase; wherein the weight ratio of the triallyl isocyanurate to the acrylonitrile is 0.17-0.5; the weight of the benzoyl peroxide is 0.8 to 1.7 percent of the sum of the weight of the acrylonitrile and the weight of the triallyl isocyanurate; the ratio of the weight of the liquid paraffin to the sum of the weights of the acrylonitrile and the triallyl isocyanurate is 0.9-2;
3) Adding the organic phase into the water phase, stirring to form beads, heating to 70-95 ℃ for curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; wherein the volume ratio of the water phase to the organic phase is 1.25-2.8;
4) Mixing acrylonitrile skeleton copolymer crosslinked microspheres with an aqueous solution of an inorganic ferric salt and reacting to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microspheres to the iron element is 1.41-1.1.
4. The production method according to any one of claims 1 to 3, wherein in the step 2), the weight ratio of triallyl isocyanurate to acrylonitrile is 0.19 to 0.4; the weight of the benzoyl peroxide is 0.85-1.5% of the sum of the weight of the acrylonitrile and the triallyl isocyanurate.
5. The method according to any one of claims 1 to 3, wherein in step 3), the curing reaction time is 5 to 13 hours.
6. The method according to any one of claims 1 to 3, wherein the inorganic iron salt is ferric chloride.
7. The preparation method according to any one of claims 1 to 3, wherein in the step 4), the acrylonitrile skeleton copolymer crosslinked microspheres are mixed with an aqueous solution of an inorganic ferric salt for reaction, and after the reaction is finished, the mixture is washed with water and dried to obtain the crosslinked polyacrylonitrile resin.
8. The method according to any one of claims 1 to 3, wherein the reaction temperature in step 4) is 40 to 90 ℃; the reaction time is 8-20 h.
9. The crosslinked polyacrylonitrile resin prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the polyacrylonitrile cross-linked resin according to claim 9 in removing fluorine ions, wherein the adsorption rate of the polyacrylonitrile cross-linked resin to fluorine ions in a solution is more than 98%.
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