CN115400741B - Crosslinked polyacrylonitrile resin, preparation method and application thereof - Google Patents
Crosslinked polyacrylonitrile resin, preparation method and application thereof Download PDFInfo
- Publication number
- CN115400741B CN115400741B CN202211034528.1A CN202211034528A CN115400741B CN 115400741 B CN115400741 B CN 115400741B CN 202211034528 A CN202211034528 A CN 202211034528A CN 115400741 B CN115400741 B CN 115400741B
- Authority
- CN
- China
- Prior art keywords
- acrylonitrile
- crosslinked
- weight
- polyacrylonitrile resin
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006350 polyacrylonitrile resin Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 239000004005 microsphere Substances 0.000 claims abstract description 24
- 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 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- -1 fluorine ions Chemical class 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 13
- 239000004342 Benzoyl peroxide Chemical group 0.000 claims abstract description 12
- 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 12
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 12
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 10
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 10
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000011324 bead Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000001035 drying Methods 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 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
- 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
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 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
- 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
- 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
- 238000004519 manufacturing process 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
- 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
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
- B01J20/265—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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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, 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 spherical beads, and heating to 70-95 ℃ for curing reaction to obtain acrylonitrile skeleton copolymer crosslinked microspheres; 4) And mixing and reacting the acrylonitrile skeleton copolymer crosslinked microsphere 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 higher adsorption rate on fluorine ions.
Description
Technical Field
The invention relates to a crosslinked polyacrylonitrile resin, a preparation method and application thereof.
Background
The main source of fluorine pollution in water environment is fluorine-containing 'three wastes' discharged by industrial production, and relates to the industry mainly comprising aluminum electrolysis, steel, cement, bricks and tiles, ceramics, phosphate fertilizer, glass, semiconductors, pharmacy and the like. The common characteristic of these industries is that fluorine-containing minerals are used as main raw materials or auxiliary raw materials, and fluorine is decomposed from the minerals and enters the environment in the smelting and production processes of the fluorine-containing minerals, so that fluorine pollution is caused.
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 fluoride ions and low adsorption capacity, and limits the industrial application of the conventional ion exchange resin in treating fluoride-containing wastewater.
Therefore, there is a need for a resin having high adsorption capacity and good selectivity for fluoride ions.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a method for preparing a crosslinked polyacrylonitrile resin, which has a good effect of adsorbing fluorine ions. It is another object of the present invention to provide a crosslinked polyacrylonitrile resin prepared according to the above-described preparation method. It is a further object of the present invention to provide a use of the crosslinked polyacrylonitrile resin.
The invention realizes the aim through the following technical scheme.
In one aspect, the invention provides a method for preparing a crosslinked polyacrylonitrile resin, comprising 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 1:50-120;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and C1-C6 alkyl substituted benzene to obtain an organic phase; wherein, the weight ratio of triallyl isocyanurate to acrylonitrile is 0.17-0.5:1; the weight of benzoyl peroxide is 0.8-1.7% of the sum of the weight of acrylonitrile and 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 0.9-2:1;
3) Adding the organic phase into the water phase, stirring to form spherical beads, and 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 1.25-2.8:1;
4) Mixing and reacting the acrylonitrile skeleton copolymer crosslinked microsphere with an aqueous solution of inorganic ferric salt to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microsphere to the iron element is 1:0.41-1.1.
The prepared cross-linked polyacrylonitrile resin has higher adsorption rate of fluoride 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 from 1:50 to 120, preferably from 1:65 to 110, more preferably from 1:70 to 105.
In step 2) of the present invention, the weight ratio of triallyl isocyanurate to acrylonitrile may be from 0.17 to 0.5:1, preferably from 0.19 to 0.4:1, more preferably from 0.2 to 0.35:1. The weight of benzoyl peroxide may be 0.8 to 1.7%, preferably 0.85 to 1.5% of the sum of the weights of acrylonitrile and triallyl isocyanurate. The C1-C6 alkyl-substituted benzene means the number of carbon atoms of the substituted alkyl group. In the present invention, the C1-C6 alkyl-substituted benzene may include toluene, ethylbenzene, cumene, preferably toluene. The ratio of the weight of C1-C6 alkyl-substituted benzene to the sum of the weight of acrylonitrile and triallyl isocyanurate may be from 0.9 to 2:1, preferably from 1.0 to 1.7:1.
In step 3) of the present invention, according to one embodiment of the present invention, an organic phase is added to an aqueous phase, stirred to form uniform-sized beads, slowly heated to 70 to 95 ℃, and cured at the temperature, and toluene is removed after the reaction is finished (toluene may be removed by alcohol extraction, for example, ethanol extraction may be employed, specifically, multiple extractions may be employed with a soxhlet extractor filled with ethanol), to obtain acrylonitrile-skeleton copolymer crosslinked microspheres.
The volume ratio of the aqueous phase to the organic phase may be 1.25 to 2.8:1, preferably 1.3 to 2.5:1. The curing reaction temperature may be 70 to 95 ℃, preferably 75 to 90 ℃. The curing reaction time may be 5 to 13 hours, preferably 7 to 11 hours. This facilitates the formation of crosslinked microspheres of acrylonitrile backbone copolymer.
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 1:0.41 to 1.1, preferably 1:0.5 to 0.9. The inorganic ferric salt is selected from one of ferric nitrate, ferric sulfate or ferric trichloride, preferably ferric trichloride.
The aqueous solution of the inorganic ferric salt can be obtained by mixing the inorganic ferric salt with water, wherein the weight ratio of the iron element in the inorganic ferric salt to the water can be 1:2.5-11, and is preferably 1:3-10. The reaction temperature is 40 to 90 ℃, preferably 40 to 85 ℃, 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.
In the step 4), after the reaction is finished, washing with water and drying to obtain the crosslinked polyacrylonitrile resin. The drying temperature may be 70 to 100 ℃, preferably 75 to 90 ℃. The drying time may be 5 to 20 hours, preferably 9 to 15 hours. Thus being beneficial to the high adsorption rate of the obtained crosslinked polyacrylonitrile resin to fluoride ions.
The invention discovers that the above parameters are controlled within a specific range, which is beneficial to obtaining the crosslinked polyacrylonitrile resin with higher fluorine ion adsorption rate.
According to the preparation method of the present invention, preferably, in the step 2), 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 1:50-120;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and liquid paraffin to obtain an organic phase; wherein, the weight ratio of triallyl isocyanurate to acrylonitrile is 0.17-0.5:1; the weight of benzoyl peroxide is 0.8-1.7% of the sum of the weight of acrylonitrile and 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 0.9-2:1;
3) Adding the organic phase into the water phase, stirring to form spherical beads, and 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 1.25-2.8:1;
4) Mixing and reacting the acrylonitrile skeleton copolymer crosslinked microsphere with an aqueous solution of inorganic ferric salt to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microsphere to the iron element is 1:0.41-1.1.
According to the preparation method of the present invention, preferably, in the step 2), the weight ratio of triallyl isocyanurate to acrylonitrile is 0.19-0.4:1; the weight of benzoyl peroxide is 0.85-1.5% of the sum of the weight of acrylonitrile and triallyl isocyanurate.
According to the preparation method of the present invention, preferably, in the step 3), the curing reaction time is 5 to 13 hours.
According to the preparation method of the present invention, preferably, the inorganic iron salt is ferric trichloride.
According to the preparation method of the present invention, preferably, in step 4), the crosslinked acrylonitrile-skeleton copolymer microsphere is mixed with an aqueous solution of an inorganic iron salt and reacted, and after the reaction is completed, the mixture is washed with water and dried to obtain the crosslinked polyacrylonitrile resin.
According to the preparation method of the present invention, preferably, in the step 4), the reaction temperature is 40 to 90 ℃; the reaction time is 8-20 h.
In another aspect, the present invention also provides a crosslinked polyacrylonitrile resin prepared according to the preparation method described above.
In still another aspect, the present invention also provides a use of the crosslinked polyacrylonitrile resin as described above for removing fluorine ions, wherein the adsorption rate of the crosslinked polyacrylonitrile resin to fluorine ions in a solution is more than 98%. Preferably, the resulting crosslinked polyacrylonitrile resin has an adsorption rate of fluoride ions in the solution of 98.5% or more, more preferably 99% or more.
The cross-linked polyacrylonitrile resin prepared by the preparation method has good effect of adsorbing fluorine ions, and the adsorption rate is more than 98%.
Drawings
FIG. 1 is a polarized light micrograph of the crosslinked acrylonitrile skeleton copolymer microsphere obtained in example 1.
FIG. 2 is a polarized light micrograph of the crosslinked polyacrylonitrile resin obtained in example 1.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited thereto.
The test method is described as follows:
(1) And (3) adsorption rate test: 1g of the prepared crosslinked polyacrylonitrile resin was taken, and the fluorine concentration at 100mL was 10mg/L (C 0 ) Carrying out static adsorption test in the adsorption stock solution with pH value of 4, wherein 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 was calculated as follows:
adsorption rate= (C 0 -C t )/C 0 ×100％。
(2) Iron content in crosslinked polyacrylonitrile resin: determined by ICP-MS.
(3) Photomicrographs: the microscope used was manufactured by Leica and model DFC450C.
Example 1
1) According to the formulation of table 1, hydroxyethylcellulose was added to deionized water and heated to 65 ℃ until the solids were completely dissolved, yielding an aqueous phase.
2) The acrylonitrile, triallyl isocyanurate, benzoyl peroxide and toluene were mixed uniformly to obtain an organic phase.
3) Adding the organic phase into the water phase, stirring to form uniform-sized spherical beads, slowly heating to 80 ℃, curing at 80 ℃ for 8 hours, and removing toluene after the reaction is finished to obtain the acrylonitrile skeleton copolymer crosslinked microspheres.
4) Mixing the acrylonitrile skeleton copolymer crosslinking microsphere with an aqueous solution of ferric trichloride, reacting at 60 ℃ for 12 hours, washing with water after the reaction is finished, and drying at 80 ℃ in vacuum for 12 hours to obtain the crosslinking polyacrylonitrile resin.
The obtained crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluoride ions, and the results are shown in table 2.
Comparative examples 1 to 5
The types and amounts of the raw materials are shown in Table 1, and the rest is the same as in example 1.
The obtained crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluoride ions, and the results are shown in table 2.
TABLE 1
Example 2
1) 3.3g of hydroxyethylcellulose was added to 330mL of deionized water and heated to 65℃until the solids were completely dissolved, giving an aqueous phase.
2) 60g of acrylonitrile, 12.99g of triallyl isocyanurate, 0.73g of benzoyl peroxide and 72.99g of toluene are uniformly mixed to obtain an organic phase.
3) Adding the organic phase into the water phase, stirring to form uniform-sized spherical beads, slowly heating to 80 ℃, curing at 80 ℃ for 8 hours, and removing toluene after the reaction is finished to obtain the acrylonitrile skeleton copolymer crosslinked microspheres.
4) 20g of acrylonitrile skeleton copolymer crosslinked microspheres are mixed with an aqueous solution of ferric trichloride (formed by mixing 40g of ferric trichloride with 100mL of water), reacted at 60 ℃ for 12 hours, washed with water after the reaction is finished, and dried in vacuum at 80 ℃ for 12 hours to obtain the crosslinked polyacrylonitrile resin.
The obtained crosslinked polyacrylonitrile resin was subjected to an adsorption test for fluoride ions, and the results are shown in table 2.
TABLE 2
| Sequence 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 |
| Acrylonitrile-skeleton copolymer Cross-Linked microsphere obtained in example 1 | 17.3 |
The acrylonitrile skeleton copolymer crosslinked microspheres and crosslinked polyacrylonitrile resin obtained in example 1 were subjected to microscopic examination. The results are shown in FIGS. 1 and 2. As shown in the figure, the acrylic 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 into the resin skeleton.
The iron content of the adsorbents obtained in example 1 and example 2 and comparative examples 1 and 2 was measured, and the results are shown in table 3.
TABLE 3 Table 3
| Name of the name | 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 modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (7)
1. The application of the crosslinked polyacrylonitrile resin in removing the fluoride ions is characterized in that the adsorption rate of the crosslinked polyacrylonitrile resin to the fluoride ions in the solution reaches more than 98 percent;
the preparation method of the crosslinked polyacrylonitrile resin 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 1:50-120;
2) Mixing acrylonitrile, triallyl isocyanurate, benzoyl peroxide and C1-C6 alkyl substituted benzene to obtain an organic phase; wherein, the weight ratio of triallyl isocyanurate to acrylonitrile is 0.17-0.5:1; the weight of benzoyl peroxide is 0.8-1.7% of the sum of the weight of acrylonitrile and 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 0.9-2:1;
3) Adding the organic phase into the water phase, stirring to form spherical beads, and 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 1.25-2.8:1;
4) Mixing and reacting the acrylonitrile skeleton copolymer crosslinked microsphere with an aqueous solution of inorganic ferric salt to obtain crosslinked polyacrylonitrile resin; wherein the weight ratio of the acrylonitrile skeleton copolymer crosslinked microsphere to the iron element is 1:0.41-1.1.
2. Use according to claim 1, characterized in that in step 2) the C1-C6 alkyl-substituted benzene is toluene.
3. Use according to any one of claims 1 to 2, characterized in that in step 2) the weight ratio of triallyl isocyanurate to acrylonitrile is 0.19 to 0.4:1; the weight of benzoyl peroxide is 0.85-1.5% of the sum of the weight of acrylonitrile and triallyl isocyanurate.
4. Use according to any one of claims 1 to 2, characterized in that in step 3) the curing reaction time is between 5 and 13 hours.
5. Use according to any one of claims 1 to 2, characterized in that the inorganic iron salt is ferric trichloride.
6. The use according to any one of claims 1 to 2, wherein in step 4), the crosslinked acrylonitrile-framework copolymer microspheres are mixed with an aqueous solution of an inorganic iron salt and reacted, and after the reaction is completed, the mixture is washed with water and dried to obtain the crosslinked polyacrylonitrile resin.
7. Use according to any one of claims 1 to 2, characterized in that in step 4) the reaction temperature is 40 to 90 ℃; the reaction time is 8-20 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034528.1A CN115400741B (en) | 2022-08-26 | 2022-08-26 | Crosslinked polyacrylonitrile resin, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211034528.1A CN115400741B (en) | 2022-08-26 | 2022-08-26 | Crosslinked polyacrylonitrile resin, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115400741A CN115400741A (en) | 2022-11-29 |
| CN115400741B true CN115400741B (en) | 2023-11-24 |
Family
ID=84161469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211034528.1A Active CN115400741B (en) | 2022-08-26 | 2022-08-26 | Crosslinked polyacrylonitrile resin, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115400741B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001047042A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Method for removing fluorine |
| JP2006297382A (en) * | 2005-03-25 | 2006-11-02 | Asahi Kasei Chemicals Corp | Porous molding with high adsorption capacity and its production method |
| CN101579620A (en) * | 2008-05-12 | 2009-11-18 | 旭化成化学株式会社 | Porous former with high adsorption performance and manufacturing method thereof |
| CN102268114A (en) * | 2011-05-24 | 2011-12-07 | 南京大学 | Defluorinating resin with compound functions and preparation method thereof |
| CN109021165A (en) * | 2018-08-29 | 2018-12-18 | 扬州金珠树脂有限公司 | A kind of preparation method of the high cross-linked acrylic acid system ion exchange resin of macroporous type |
| CN109867745A (en) * | 2019-01-04 | 2019-06-11 | 蚌埠市辽源新材料有限公司 | A kind of polyacrylonitrile resin and preparation method thereof |
| CN111135807A (en) * | 2020-02-20 | 2020-05-12 | 刘云晖 | High-mechanical-strength hydrophilic adsorbent for whole blood perfusion and preparation method thereof |
| CN114763393A (en) * | 2021-01-13 | 2022-07-19 | 朗盛德国有限责任公司 | Cation exchangers, method for the production thereof, use thereof and polymers |
-
2022
- 2022-08-26 CN CN202211034528.1A patent/CN115400741B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001047042A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Method for removing fluorine |
| JP2006297382A (en) * | 2005-03-25 | 2006-11-02 | Asahi Kasei Chemicals Corp | Porous molding with high adsorption capacity and its production method |
| CN101579620A (en) * | 2008-05-12 | 2009-11-18 | 旭化成化学株式会社 | Porous former with high adsorption performance and manufacturing method thereof |
| CN102268114A (en) * | 2011-05-24 | 2011-12-07 | 南京大学 | Defluorinating resin with compound functions and preparation method thereof |
| CN109021165A (en) * | 2018-08-29 | 2018-12-18 | 扬州金珠树脂有限公司 | A kind of preparation method of the high cross-linked acrylic acid system ion exchange resin of macroporous type |
| CN109867745A (en) * | 2019-01-04 | 2019-06-11 | 蚌埠市辽源新材料有限公司 | A kind of polyacrylonitrile resin and preparation method thereof |
| CN111135807A (en) * | 2020-02-20 | 2020-05-12 | 刘云晖 | High-mechanical-strength hydrophilic adsorbent for whole blood perfusion and preparation method thereof |
| CN114763393A (en) * | 2021-01-13 | 2022-07-19 | 朗盛德国有限责任公司 | Cation exchangers, method for the production thereof, use thereof and polymers |
Non-Patent Citations (1)
| Title |
|---|
| 钱庭宝等.三烯丙基三聚异氰酸酯交联大孔聚丙烯腈树脂的合成及其孔性能研究.离子交换与吸附.1988,第4卷(第6期),407-412. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115400741A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108246269B (en) | Lithium ion adsorbent and preparation method and application thereof | |
| CN104262521B (en) | The preparation method of styrene divinylbenzene copolymer hydrophobic catalyst carrier | |
| CN109111207B (en) | Porous phosphorus removal ceramsite and preparation method thereof | |
| CN105597668A (en) | Preparation method and application of modified zeolite | |
| CN101559353B (en) | Preparation method of zinc chloride modified red mud | |
| CN107673439A (en) | A kind of sewage disposal medicament | |
| CN104399427A (en) | Preparation method and application of porous silicon dioxide microsphere adsorbent | |
| CN110801814A (en) | Preparation method of magnetic amino walnut shell biochar novel adsorbent | |
| CN110898802A (en) | Sludge-based biochar and preparation method and application thereof, acetic acid modified sludge-based biochar and preparation method and application thereof | |
| CN107973365B (en) | Adsorbent for treating dye-containing wastewater, preparation method and application thereof | |
| CN115400741B (en) | Crosslinked polyacrylonitrile resin, preparation method and application thereof | |
| CN114870823A (en) | Lanthanum-based metal organic framework dephosphorization composite material and preparation method and application thereof | |
| CN105688795B (en) | Anionic dye adsorbent composite material and preparation method and application thereof | |
| CN115260383B (en) | Acrylic acid skeleton adsorption resin and production method and application thereof | |
| CN107935016A (en) | A kind of method that liquid containing ammonium sulfate waste water prepares alpha semi-hydrated gypsum | |
| CN107446096A (en) | Heavy metal ion porous adsorbent and its preparation method and application | |
| CN103962160A (en) | Carbon-based solid acid Fenton carrier as well as preparation method and application thereof | |
| CN110586029A (en) | Salt modified silicate cement phosphorus removal adsorbent, preparation method of adsorbent, regeneration method of adsorbent and application | |
| CN113713722B (en) | Preparation method of EPS-like agarose-based hydrogel and application of EPS-like agarose-based hydrogel in adsorption dephosphorization | |
| CN102872844A (en) | Composite adsorption material for removing gallium ions from natural water and preparation method for adsorption material | |
| CN109482133B (en) | Method for preparing adsorbing material by using waste liquid of Hummers method | |
| CN110064380B (en) | Nitrogen/sulfur co-doped porous cellulose adsorbent and preparation method and application thereof | |
| CN113398897A (en) | Preparation method of magnetic chromium ion chelating agent, obtained product and application | |
| CN113083216A (en) | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application for removing phosphate radical | |
| CN105948294B (en) | A kind of waste acid resource treatment process blocking method based on nano combined carrier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |