CN108047361B - A kind of Properties of Magnetic Chelating Resins, preparation method and its application in combined pollution water body purification - Google Patents

A kind of Properties of Magnetic Chelating Resins, preparation method and its application in combined pollution water body purification Download PDF

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CN108047361B
CN108047361B CN201810006928.9A CN201810006928A CN108047361B CN 108047361 B CN108047361 B CN 108047361B CN 201810006928 A CN201810006928 A CN 201810006928A CN 108047361 B CN108047361 B CN 108047361B
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particle
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properties
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CN108047361A (en
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王未
周庆
朱增银
张满成
祁梦
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Nanjing University
Jiangsu Provincial Academy of Environmental Science
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Jiangsu Provincial Academy of Environmental Science
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Abstract

The present invention is prepared for a kind of novel magnetic high-ratio surface chelating resin, it is mainly obtained by following steps: (1) preparing magnetic nano-particle by coprecipitation, be successively surface modified using oleic acid, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane to it；(2) suspension polymerisation occurs for strict control temperature program, magnetic nano-particle and divinylbenzene and methyl acrylate after making modification；(3) post-crosslinking is carried out to resin to react with group.The Properties of Magnetic Chelating Resins specific saturation magnetization that the present invention developed is high, has both higher specific surface area and group content, can have good removal effect to the combined pollution system that organic matter and heavy metal coexist, have excellent application prospect.

Description

A kind of Properties of Magnetic Chelating Resins, preparation method and its in combined pollution water body purification Application
Technical field
The present invention relates to a kind of Properties of Magnetic Chelating Resins and preparation method thereof and it is compound in purifying organic and heavy metal Application in polluted-water belongs to Properties of Magnetic Chelating Resins and its preparation technical field.
Background technique
Pollutant kind is various in environment water, forms the combined pollution state that multiple pollutant coexists.Wherein, You Jihe The combined pollution of inorganic substances especially poisons the complexing of organic matter and heavy metal, is the important problem that current water process faces. Organic matter and heavy metal can be combined together by coordination, absorption or chemical action, change its form, transportion and transformation and Bio-toxicity often brings higher ecological risk.
Absorption method is the common efficient depth removal technology that organic matter, heavy metal ion etc. poison pollutant.Resin adsorption Agent is widely used in a variety of water because its adsorption capacity is big, high mechanical strength, structure is controllable, is easy to the advantages that desorption and regeneration It handles in engineering.The fast development of magnetic resin and full-mixing type adsorption treatment process in recent years solves usual resins absorption skill Art investment is big, operating cost is high problem, its application range of further expansion.Chelating resin is being directed to because its selectivity is strong It is used widely in heavy metal ion adsorbed removal.But its absorption for organic matter and heavy metal coexisting system, then show slightly Deficiency especially is difficult to effectively remove to organic matter.
CN 201310264731.2 discloses a kind of amido modified magnetic hypercrosslinked polymeric resin material, while having higher Specific surface area and ion exchange capacity, can effectively synchronize removal water body in all kinds of organic pollutants.But this resinoid is with third E pioic acid methyl ester (MA) and divinylbenzene (DVB) are used as monomer, tend to lead because intersolubility is bad both in polymerization process Cause polymerization effect bad；And during trial prepares magnetic material, the magnetic nano-particle amount of introducing is relatively fewer, influences Final separating property, and nanoparticle is easier to dissolve out in use process, influences water quality.
CN 201310330339.3 discloses a kind of weak acid modification high-specific surface area magnetic resin, utilizes oleic acid coated magnetic Nanoparticle can enhance the affinity between magnetic nano-particle and oily phase to a certain extent, improve methyl acrylate (MA) with the polymerization effect of divinylbenzene (DVB).However the improvement of this affinity is limited, so that the magnetism of resin is lower, and And in application process, the acid resistance of resin is not high, and magnetic nano-particle easily dissolves out.
Summary of the invention
Goal of the invention: the technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of magnetic chela Resin and preparation method thereof, solves that magnetic nano-particle and reaction monomers are difficult to effective integration and resin acid resistance is not strong asks Topic, while effectively being purified for organic matter and heavy-metal composite pollution water body using the Properties of Magnetic Chelating Resins.
In order to solve the above-mentioned technical problem, the invention discloses a kind of preparation method of Properties of Magnetic Chelating Resins, including it is following Step:
(a) molar ratio the preparation of magnetic nano-particle: is hydrated three for the six of 1:0.4~1:0.6 under the protection of nitrogen Iron chloride and Iron dichloride tetrahydrate are dissolved in deionized water, are warming up to 75~85 DEG C of 30~60min of reaction, cooling to clean；
(b) surface modification of magnetic nano-particle: under nitrogen protection, magnetic particle prepared by step (a) is added to In the ammonium hydroxide of 0.16~0.18wt%, oleic acid is added after being uniformly mixed, is used after being warming up to 75~85 DEG C of 30~60min of reaction Then it is mixed with acetone and is placed in 25~28wt% ammonium hydroxide by methanol rinse, vinyltriethoxysilane is added in 30 After~50 DEG C of 4~8h of reaction, methacryloxypropyl trimethoxy silane is added in 30~50 DEG C of 4~8h of reaction, cooling After use methanol rinse；The acetone is the solvent of reaction, and dosage guarantees that reaction can be carried out sufficiently, generally magnetic particles 10~35 times of protonatomic mass.
(c) suspension polymerization: reaction monomers mix as oily phase with pore-foaming agent toluene, reaction monomers are diethyl Alkene benzene and methyl acrylate, mass ratio are 1:0.6~1:2, and the mass ratio of reaction monomers and pore-foaming agent is 1:0.5~1:2, to oil Magnetic nano-particle and initiator benzoyl peroxide after step (b) modification is added in phase, the amount of magnetic nano-particle are oil The 10~30% of phase quality, the amount of initiator are the 0.5~1% of oily phase quality；Stirring is warming up to 35~45 DEG C, and reaction 30~ Water phase is added after 60min to continue to stir, water phase is the water-soluble of the sodium chloride of gelatin and 5~25% containing mass fraction 2~5% Liquid, water phase additional amount are 4~8 times of oily phase quality；Then with the speed of 3~8 DEG C/min, temperature is risen into 75~85 DEG C of reactions 1~2h, then 90~95 DEG C of 6~12h of reaction are warming up to, magnetic resin is obtained with methanol rinse after cooling；
(d) groupization is reacted: magnetic resin obtained by previous step is placed in 2~6h of swelling in tetraethylenepentamine solution, tree Rouge and the mass ratio of tetraethylenepentamine are 1:2~1:5, stirred at 125~140 DEG C after swelling and be condensed back reaction 20~ 26h uses methanol rinse after cooling；
(e) magnetic resin obtained by previous step post-crosslinking reaction: is placed in 1~4h of swelling, resin in 1,2- dichloroethanes It is 1:5~1:10 with the mass ratio of 1,2- dichloroethanes, anhydrous ferric chloride is added in swelling later, react 6 in 75~85 DEG C~ 10h, the quality of anhydrous ferric chloride are the 15~25% of magnetic resin quality, after reaction cooling methanol rinse, deionization Water cleaning, drying.
Preferably, above-mentioned steps are not the absolute limitations to preparation sequence, and only most preferred scheme, excellent as other Scheme is selected, preparation step is prepared using the sequence of (a)~(c), (e), (d), and it is unfavorable to cause to result of the invention Influence.
In step (b), the mass ratio of the oleic acid and magnetic nano-particle is 1:1~5:1, preferably 1:1.
In step (b), the vinyltriethoxysilane is previously dissolved in acetone, vinyltriethoxysilane and third The mass ratio of the preferred 1:5~1:10 of the mass ratio of ketone, magnetic nano-particle and vinyltriethoxysilane is 1:2~1:10, It is preferred that 1:2.
In step (b), the methacryloxypropyl trimethoxy silane is previously dissolved in acetone, methacryl Preferred 1:5~the 1:10 of the mass ratio of oxygroup propyl trimethoxy silicane and acetone, magnetic nano-particle and methacryloxy The mass ratio of propyl trimethoxy silicane is 1:2~1:10, preferably 1:2.
Preferably, in step (c), the revolving speed that water phase stirs before being added is not higher than 100rpm, and water phase will stirring speed after being added Degree rises to 200~500rpm.
The Properties of Magnetic Chelating Resins being prepared using any one of the above preparation method is also within the protection scope of the present invention.
Further, which is 400~900m2/ g, functional group content be 3.25~ 6.12mmol/g, specific saturation magnetization are 8.2~22.5emu/g.
Above-mentioned Properties of Magnetic Chelating Resins containing the application in organic matter and heavy-metal composite pollution water body purification also in the present invention Protection scope in.
Further, the organic matter is one of tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen and phenol etc. Or a variety of mixing；The heavy metal is one of Cu, Ni, Pb and Cr etc. or a variety of mixing.
The present invention is first by magnetic nano-particle successively through oleic acid, vinyltriethoxysilane and methacryloxy Propyl trimethoxy silicane carries out surface and is modified, and greatlys improve the affinity between magnetic nano-particle and oily phase, meanwhile, second The addition of alkenyl triethoxysilane and methacryloxypropyl trimethoxy silane significantly improves the antiacid of magnetic resin Performance.
Then using divinylbenzene and methyl acrylate as reaction monomers, pore-foaming agent, initiator and water phase is mixed and is carried out Magnetic resin is prepared in suspension polymerisation, then reacts to form ammonium salt through group, most obtains magnetic chela through post-crosslinking reaction afterwards Resin；Or magnetic resin first passes through post-crosslinking reaction, then reacts to obtain Properties of Magnetic Chelating Resins through group.
The utility model has the advantages that
1, the application successively uses oleic acid, vinyltriethoxysilane, methacryloxypropyl trimethoxy silicon The magnetic nano-particle that alkane prepares coprecipitation is surface modified, the affine energy between enhancing magnetic nano-particle and oily phase Power improves the specific saturation magnetization of resin, and resin is made to be easy to Magnetic Isolation, while improving the Antacid effectiveness of resin.
2, the application uses magnetic nano-particle packaging method, improves and polymer monomer divinylbenzene and acrylic acid first Affinity between ester improves the yield of resin.
3, the Properties of Magnetic Chelating Resins not only functional group content with higher of the application preparation, can be to the weight in water body Metal ion carries out chelating removal, while specific surface area also with higher, can be solved with the organic matter in efficient absorption water body The chelating resin problem ineffective to organic matter removal at present, suitable for the quick of organic matter and heavy-metal composite pollution water body High-efficient purification.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned And/or otherwise advantage will become apparent.
Fig. 1 is the basic structure schematic diagram of Properties of Magnetic Chelating Resins of the present invention.
Fig. 2 is the hysteresis loop figure of Properties of Magnetic Chelating Resins prepared by embodiment 1.
Fig. 3 is the hysteresis loop figure of the bubble of Properties of Magnetic Chelating Resins prepared by embodiment 1 acid after a week.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Embodiment 1
0.1mol Iron(III) chloride hexahydrate and 0.04mol Iron dichloride tetrahydrate are dissolved in 500mL deionized water, in nitrogen It is warming up to 75 DEG C of reaction 30min under the protection of gas, magnetic nano-particle is made, it is cooling to clean；
Obtained 10g magnetic particle is added in the ammonium hydroxide that 200mL concentration is 0.16%, is added after being uniformly mixed 10g oleic acid is modified, and is used methanol rinse after being warming up to 75 DEG C of reaction 30min, is then mixed it with 100g acetone and be placed on 200mL concentration is that 20g is added and is dissolved in the modification of the vinyltriethoxysilane in 100g acetone in 25% ammonium hydroxide, anti-in 30 DEG C After answering 4h, 20g is added and is dissolved in the methacryloxypropyl trimethoxy silane in 100g acetone in 30 DEG C of reaction 4h again Modification uses methanol rinse after cooling；
By the magnetic nano-particle 14.4g and 20g divinylbenzene, 12g methyl acrylate, 16g toluene, 0.24g after modification After benzoyl peroxide mixing, under the revolving speed of 50rpm, 35 DEG C are warming up to, 200mL is added containing mass fraction after reacting 30min The water phase of 5% gelatin and 25% sodium chloride, while mixing speed is risen into 200rpm, it, will be warm then with the speed of 3 DEG C/min Degree rises to 75 DEG C of reaction 1h, then is warming up to 90 DEG C of reaction 6h, obtains magnetic resin with methanol rinse after cooling；
It is subsequently placed in 2 times of resin quality of tetraethylenepentamine solution swelling 2h, stirs and condenses at 130 DEG C after swelling Back flow reaction 20h uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 5 times of resin quality of 1,2- dichloroethanes and is swollen 1h, be added Quality is that 15% anhydrous ferric chloride of resin quality is cleaned simultaneously with methanol rinse, deionized water after reaction in 75 DEG C of reaction 6h It is dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 869m2/ g, functional group content is 3.25mmol/g, than saturation The intensity of magnetization is 22.5emu/g.It takes 0.05g resin to be placed in the combined pollution water body of 100mL organic matter and heavy metal and handles 1h, Wherein organic pollutant is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and through detecting, removal rate is as shown in table 1, magnetism chelating tree The basic structure of rouge is shown in Fig. 1；Prepared Properties of Magnetic Chelating Resins hysteresis loop figure is shown in Fig. 2, it is seen that the ratio saturated magnetization of resin is strong Degree is 22.5emu/g, has very strong magnetism, Magneto separate can be effectively performed；By the Properties of Magnetic Chelating Resins of preparation pH be 2 Hydrochloric acid solution impregnate after a week, its specific saturation magnetization is measured, as a result as shown in figure 3, the specific saturation magnetization of resin Only decline 3.19emu/g than the resin (pH=7) without acid processing, still there is stronger magnetism, therefore the chelating resin has Stronger Antacid effectiveness.
Table 1
Pollutant Tetracycline Ciprofloxacin Carbamazepine Ketoprofen Phenol Cu Ni Pb Cr
Removal rate (%) 92.4 90.5 98.2 97.6 92.1 98.7 97.2 99.6 97.3
Embodiment 2
0.03mol Iron(III) chloride hexahydrate and 0.018mol Iron dichloride tetrahydrate are dissolved in 500mL deionized water, In It is warming up to 85 DEG C of reaction 60min under the protection of nitrogen, magnetic nano-particle is made, it is cooling to clean；
Obtained 3g magnetic particle is added in the ammonium hydroxide that 200mL concentration is 0.18%, is added after being uniformly mixed 15g oleic acid is modified, and is used methanol rinse after being warming up to 85 DEG C of reaction 60min, is then mixed it with 100g acetone and be placed on 200mL concentration is that 30g is added and is dissolved in the modification of the vinyltriethoxysilane in 300g acetone in 28% ammonium hydroxide, anti-in 50 DEG C After answering 8h, 30g is added and is dissolved in the methacryloxypropyl trimethoxy silane in 300g acetone in 50 DEG C of reaction 8h again Modification uses methanol rinse after cooling；
By the magnetic nano-particle 4.8g and 6g divinylbenzene, 10g methyl acrylate, 32g toluene, 0.48g mistake after modification After Benzoyl Oxide mixing, under the revolving speed of 50rpm, 45 DEG C are warming up to, 300mL is added containing mass fraction 2% after reacting 60min Gelatin and 5% sodium chloride water phase, while mixing speed is risen into 500rpm, then with the speed of 8 DEG C/min, by temperature liter To 85 DEG C of reaction 2h, then 95 DEG C of reaction 12h are warming up to, with methanol rinse obtain magnetic resin after cooling；
It is subsequently placed in 5 times of resin quality of tetraethylenepentamine solution swelling 6h, stirs and condenses at 140 DEG C after swelling Back flow reaction 26h uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 10 times of resin quality of 1,2- dichloroethanes and is swollen 4h, be added Quality is that 25% anhydrous ferric chloride of resin quality is cleaned with methanol rinse, deionized water after reaction in 85 DEG C of reaction 10h And it is dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 415m2/ g, functional group content is 6.12mmol/g, than saturation Magnetic intensity is 8.2emu/g.0.05g resin is taken to be placed in the combined pollution water body of 100mL organic matter and heavy metal, wherein handling 1h, organic pollutant are tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；With much money Belonging to is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and through detecting, removal rate is as shown in table 2:
Table 2
Pollutant Tetracycline Ciprofloxacin Carbamazepine Ketoprofen Phenol Cu Ni Pb Cr
Removal rate (%) 87.3 82.6 90.5 88.2 85.3 97.6 98.5 99.1 95.6
Embodiment 3
0.05mol Iron(III) chloride hexahydrate and 0.025mol Iron dichloride tetrahydrate are dissolved in 500mL deionized water, In It is warming up to 80 DEG C of reaction 40min under the protection of nitrogen, magnetic nano-particle is made, it is cooling to clean；
Obtained 5g magnetic particle is added in the ammonium hydroxide that 200mL concentration is 0.17%, is added after being uniformly mixed 10g oleic acid is modified, and is used methanol rinse after being warming up to 80 DEG C of reaction 40min, is then mixed it with 100g acetone and be placed on 200mL concentration is that 20g is added and is dissolved in the modification of the vinyltriethoxysilane in 150g acetone in 25% ammonium hydroxide, anti-in 40 DEG C After answering 6h, 20g is added and is dissolved in the methacryloxypropyl trimethoxy silane in 150g acetone in 40 DEG C of reaction 6h again Modification uses methanol rinse after cooling；
By the magnetic nano-particle 6g and 10g divinylbenzene, 10g methyl acrylate, 20g toluene, 0.4g peroxide after modification After changing benzoyl mixing, under the revolving speed of 50rpm, 40 DEG C are warming up to, 200mL is added containing mass fraction 4% after reacting 45min The water phase of gelatin and 15% sodium chloride, while mixing speed is risen into 300rpm, then with the speed of 5 DEG C/min, by temperature liter To 80 DEG C of reaction 1h, then 92 DEG C of reaction 8h are warming up to, with methanol rinse obtain magnetic resin after cooling；
It is subsequently placed in 4 times of resin quality of tetraethylenepentamine solution swelling 4h, stirs and condenses at 125 DEG C after swelling Back flow reaction for 24 hours, uses methanol rinse after cooling；
Then magnetic resin obtained by previous step is placed in 8 times of resin quality of 1,2- dichloroethanes and is swollen 3h, be added Quality is that 20% anhydrous ferric chloride of resin quality is cleaned simultaneously with methanol rinse, deionized water after reaction in 80 DEG C of reaction 8h It is dry.
Obtained Properties of Magnetic Chelating Resins specific surface area is 657m2/ g, functional group content is 4.97mmol/g, than saturation The intensity of magnetization is 15.7emu/g.It takes 0.05g resin to be placed in the combined pollution water body of 100mL organic matter and heavy metal and handles 1h, Wherein organic pollutant is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and through detecting, removal rate is as shown in table 3:
Table 3
Pollutant Tetracycline Ciprofloxacin Carbamazepine Ketoprofen Phenol Cu Ni Pb Cr
Removal rate (%) 89.5 88.3 95.5 93.3 90.2 97.1 96.7 99.2 95.4
Embodiment 4
Then acquired magnetic resin is placed in the 1,2- of 5 times of resin quality with embodiment 1 by magnetic resin preparation method 1h is swollen in dichloroethanes, addition quality uses first in 75 DEG C of reaction 6h for 15% anhydrous ferric chloride of resin quality after reaction Alcohol rinsing；
It is subsequently placed in 2 times of resin quality of tetraethylenepentamine solution swelling 2h, stirs and condenses at 130 DEG C after swelling Back flow reaction 20h is washed and dried after cooling with methanol rinse, deionized water.
Obtained Properties of Magnetic Chelating Resins specific surface area is 725m2/ g, functional group content is 3.35mmol/g, than saturation The intensity of magnetization is 18.6emu/g.It takes 0.05g resin to be placed in the combined pollution water body of 100mL organic matter and heavy metal and handles 1h, Wherein organic pollutant is tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen, phenol, and concentration is respectively 0.01mmol/L；Weight Metal is respectively Cu, Ni, Pb, Cr, and concentration is respectively 0.02mmol/L, and through detecting, removal rate is as shown in table 4:
Table 4
Pollutant Tetracycline Ciprofloxacin Carbamazepine Ketoprofen Phenol Cu Ni Pb Cr
Removal rate (%) 90.5 88.1 96.5 95.6 90.4 97.6 98.3 98.1 96.7
The present invention provides a kind of Properties of Magnetic Chelating Resins, preparation method and its applications in combined pollution water body purification Thinking and method, there are many method and the approach for implementing the technical solution, and the above is only preferred implementation of the invention Mode, it is noted that for those skilled in the art, without departing from the principle of the present invention, also Several improvements and modifications can be made, these modifications and embellishments should also be considered as the scope of protection of the present invention.It is unknown in the present embodiment The available prior art of true each component part is realized.

Claims (10)

1. a kind of preparation method of Properties of Magnetic Chelating Resins, which comprises the following steps:
(a) preparation of magnetic nano-particle: six trichloride hydrates for being 1:0.4~1:0.6 by molar ratio under the protection of nitrogen Iron and Iron dichloride tetrahydrate are dissolved in deionized water, are warming up to 75~85 DEG C of 30~60min of reaction, cooling to clean；
(b) surface modification of magnetic nano-particle: under nitrogen protection, magnetic particle prepared by step (a) is added to 0.16~ In the ammonium hydroxide of 0.18wt%, oleic acid is added after being uniformly mixed, is floated after being warming up to 75~85 DEG C of 30~60min of reaction with methanol It washes, it is mixed with acetone then and is placed in 25~28wt% ammonium hydroxide, vinyltriethoxysilane is added in 30~50 DEG C After reacting 4~8h, methacryloxypropyl trimethoxy silane is added in 30~50 DEG C of 4~8h of reaction, uses first after cooling Alcohol rinsing；
(c) suspension polymerization: reaction monomers mix as oily phase with pore-foaming agent toluene, reaction monomers are divinylbenzene And methyl acrylate, mass ratio are 1:0.6~1:2, the mass ratio of reaction monomers and pore-foaming agent is 1:0.5~1:2, into oily phase Magnetic nano-particle and initiator benzoyl peroxide after step (b) modification is added, the amount of magnetic nano-particle are oily phase matter The 10~30% of amount, the amount of initiator are the 0.5~1% of oily phase quality；Stirring is warming up to 35~45 DEG C, reacts 30~60min Water phase is added afterwards to continue to stir, water phase is the aqueous solution of the sodium chloride of gelatin and 5~25% containing mass fraction 2~5%, water phase Additional amount is 4~8 times of oily phase quality；Then with the speed of 3~8 DEG C/min, temperature is risen into 75~85 DEG C of 1~2h of reaction, It is warming up to 90~95 DEG C of 6~12h of reaction again, obtains magnetic resin with methanol rinse after cooling；
(d) groupization is reacted: magnetic resin obtained by previous step is placed in tetraethylenepentamine solution 2~6h of swelling, resin with The mass ratio of tetraethylenepentamine is 1:2~1:5, stirs and be condensed back 20~26h of reaction after swelling at 125~140 DEG C, Methanol rinse is used after cooling；
(e) post-crosslinking reaction: magnetic resin obtained by previous step being placed in 1,2- dichloroethanes and is swollen 1~4h, resin and 1, The mass ratio of 2- dichloroethanes is 1:5~1:10, and anhydrous ferric chloride is added in swelling later, in 75~85 DEG C of 6~10h of reaction, nothing The quality of water iron chloride is the 15~25% of magnetic resin quality, after reaction cooling methanol rinse, deionized water cleaning, Drying.
2. a kind of preparation method of Properties of Magnetic Chelating Resins, which comprises the following steps:
(a) preparation of magnetic nano-particle: six trichloride hydrates for being 1:0.4~1:0.6 by molar ratio under the protection of nitrogen Iron and Iron dichloride tetrahydrate are dissolved in deionized water, are warming up to 75~85 DEG C of 30~60min of reaction, cooling to clean；
(b) surface modification of magnetic nano-particle: under nitrogen protection, magnetic particle prepared by step (a) is added to 0.16~ In the ammonium hydroxide of 0.18wt%, oleic acid is added after being uniformly mixed, is floated after being warming up to 75~85 DEG C of 30~60min of reaction with methanol It washes, it is mixed with acetone then and is placed in 25~28wt% ammonium hydroxide, vinyltriethoxysilane is added in 30~50 DEG C After reacting 4~8h, methacryloxypropyl trimethoxy silane is added in 30~50 DEG C of 4~8h of reaction, uses first after cooling Alcohol rinsing；
(c) suspension polymerization: reaction monomers mix as oily phase with pore-foaming agent toluene, reaction monomers are divinylbenzene And methyl acrylate, mass ratio are 1:0.6~1:2, the mass ratio of reaction monomers and pore-foaming agent is 1:0.5~1:2, into oily phase Magnetic nano-particle and initiator benzoyl peroxide after step (b) modification is added, the amount of magnetic nano-particle are oily phase matter The 10~30% of amount, the amount of initiator are the 0.5~1% of oily phase quality；Stirring is warming up to 35~45 DEG C, reacts 30~60min Water phase is added afterwards to continue to stir, water phase is the aqueous solution of the sodium chloride of gelatin and 5~25% containing mass fraction 2~5%, water phase Additional amount is 4~8 times of oily phase quality；Then with the speed of 3~8 DEG C/min, temperature is risen into 75~85 DEG C of 1~2h of reaction, It is warming up to 90~95 DEG C of 6~12h of reaction again, obtains magnetic resin with methanol rinse after cooling；
(e) post-crosslinking reaction: magnetic resin obtained by previous step being placed in 1,2- dichloroethanes and is swollen 1~4h, resin and 1, The mass ratio of 2- dichloroethanes is 1:5~1:10, and anhydrous ferric chloride is added in swelling later, in 75~85 DEG C of 6~10h of reaction, nothing The quality of water iron chloride is the 15~25% of magnetic resin quality, after reaction cooling methanol rinse, deionized water cleaning, Drying；
(d) groupization is reacted: magnetic resin obtained by previous step is placed in tetraethylenepentamine solution 2~6h of swelling, resin with The mass ratio of tetraethylenepentamine is 1:2~1:5, stirs and be condensed back 20~26h of reaction after swelling at 125~140 DEG C, Methanol rinse is used after cooling.
3. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b), The mass ratio of the oleic acid and magnetic nano-particle is 1:1~5:1.
4. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b), The vinyltriethoxysilane is previously dissolved in acetone, the mass ratio of magnetic nano-particle and vinyltriethoxysilane For 1:2~1:10.
5. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (b), The methacryloxypropyl trimethoxy silane is previously dissolved in acetone, magnetic nano-particle and methacryloxy The mass ratio of propyl trimethoxy silicane is 1:2~1:10.
6. a kind of preparation method of Properties of Magnetic Chelating Resins according to claim 1 or 2, which is characterized in that in step (c), The revolving speed that water phase stirs before being added is not higher than 100rpm, and mixing speed is risen to 200~500rpm after water phase addition.
7. the Properties of Magnetic Chelating Resins that any one preparation method is prepared in claim 1~6.
8. Properties of Magnetic Chelating Resins according to claim 7, which is characterized in that Properties of Magnetic Chelating Resins specific surface area be 400~ 900m2/ g, functional group content are 3.25~6.12mmol/g, and specific saturation magnetization is 8.2~22.5emu/g.
9. Properties of Magnetic Chelating Resins described in claim 7 is containing the application in organic matter and heavy-metal composite pollution water body purification.
10. Properties of Magnetic Chelating Resins according to claim 9 is in containing organic matter and heavy-metal composite pollution water body purification Using, which is characterized in that the organic matter is one of tetracycline, Ciprofloxacin, carbamazepine, Ketoprofen and phenol or more The mixing of kind；The heavy metal is one of Cu, Ni, Pb and Cr or a variety of mixing.
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