CN103588919A - Preparation method of magnetic porous adsorbent by suspension polymerization - Google Patents
Preparation method of magnetic porous adsorbent by suspension polymerization Download PDFInfo
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- CN103588919A CN103588919A CN201310528523.9A CN201310528523A CN103588919A CN 103588919 A CN103588919 A CN 103588919A CN 201310528523 A CN201310528523 A CN 201310528523A CN 103588919 A CN103588919 A CN 103588919A
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- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003463 adsorbent Substances 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002594 sorbent Substances 0.000 claims description 57
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
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- 238000003756 stirring Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
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- 239000002105 nanoparticle Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000000703 high-speed centrifugation Methods 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
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- 230000002194 synthesizing effect Effects 0.000 claims description 2
- PCWZHTGDXLRULT-UHFFFAOYSA-N buta-1,3-dienylbenzene styrene Chemical compound C(=C)C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 PCWZHTGDXLRULT-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 230000003068 static effect Effects 0.000 abstract description 6
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- 239000003999 initiator Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract 2
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- 238000010521 absorption reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 9
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 7
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Abstract
本发明涉及一种通过悬浮聚合制备磁性多孔吸附剂的方法，属于环境功能材料制备技术领域。特指以苯乙烯，二乙烯基苯为功能单体，以偶氮二异丁腈为引发剂，以甲苯和环己醇为致孔剂，采用悬浮聚合法制备获得多孔吸附剂，并利用磺酸化方法在其表面修饰生成磁性材料，最终制备获得磁性多孔吸附剂。获得的吸附剂具有多孔的结构，有利于吸附污染物，而且磁性有利于快速分离。吸附剂应用于在水环境中选择性吸附苯酚类污染物。静态吸附实验用来研究吸附剂的吸附平衡，动力学和热力学性能。结果表明利用本发明获得的磁性多孔吸附剂具有较好的吸附能力，较快的吸附动力学性质。
The invention relates to a method for preparing a magnetic porous adsorbent through suspension polymerization, and belongs to the technical field of preparation of environmental functional materials. Specifically refers to the porous adsorbent prepared by suspension polymerization with styrene and divinylbenzene as the functional monomer, azobisisobutyronitrile as the initiator, and toluene and cyclohexanol as the porogen. The acidification method is used to modify the surface to generate magnetic materials, and finally obtain magnetic porous adsorbents. The obtained adsorbent has a porous structure, which is favorable for the adsorption of pollutants, and the magnetic properties are favorable for rapid separation. Adsorbents are used for the selective adsorption of phenolic pollutants in aqueous environments. Static adsorption experiments are used to study the adsorption equilibrium, kinetics and thermodynamic properties of adsorbents. The results show that the magnetic porous adsorbent obtained by the invention has better adsorption capacity and faster adsorption kinetic properties.
Description
Technical field
The invention belongs to environment functional material preparing technical field, relate to a kind of method of preparing magnetic porous sorbent material by suspension polymerization, and chlorophenol pollutant in selective adsorption Separation of Water environment.
Background technology
Chlorophenol, as 2,4 dichloro phenol (2,4-DCP), 2,4,6-Trichlorophenol (2,4, be 6-TCP) the multiduty starting material in chemical industry, and be widely used in various industrial production, as oil, chemical industry, petrochemical complex, gasification of coal and carbonization, pharmacy, timber, plastics, paper, fiber, rubber, photography, dyestuff, sterilization and pesticide industry.Yet because chlorophenol has higher toxicity, and various different bioprocesss are all had to injury, environment protection tissue (EPA) classifies chlorophenol and derivative thereof as toxic pollutant as.Chlorophenol has niff in tap water, and even in water, the chlorophenol of minute quantity all can cause serious injury for aquatic organism and human health.Chlorophenol can be encroached on the mankind's nervous center, causes pain in various degree, vomiting and other ill symptomses.Most phenolic comp ' ds pollution is considered to the mankind's carcinogens.Therefore, from the aqueous solution, effectively remove the important topic that chlorophenol is field of environment protection.
Various methods and technology can be used for removing the chlorophenol in the aqueous solution, and absorption is a kind of not only economy but also effective method.Recently, porous polymeric sorbent material is produced production, and it is low that these materials generally have density, porous, and the characteristic of easy functionalization, and be widely used in the chlorophenol of removing in the aqueous solution.In preparing the method for porous polymer material, suspension polymerization is proved to be the most simple and efficient method.Suspension polymerization is to be dissolved with the monomer of initiator to suspend in water and carry out the method for radical polymerization with droplet-like.Suspension polymerization is advantage simple to operate not only, and the product purity obtaining is also very high.In addition, the porous polymer microsphere of preparing by suspension polymerization, as a kind of functionalization high polymer material with special surface morphology, has larger specific surface area and the good significant advantages such as absorption property.
In order to solve better the difficulty that reclaims sorbent material from dispersion soln, people focus onto the direction that magnetic Nano material and traditional sorbent material combine.The a series of sorbent material being comprised of magnetic-particle and inorganic materials is produced and studies, for example, and γ-Fe
2o
3with the magnetic Nano material that cerium atom forms, Fe
2o
3nano particle is applied to multilayer carbon nanotube synthesizing magnetic sorbing material.This sorbent material is by the polymer layer pollutent that unbinds, and utilizes the magnetic particle of polymkeric substance inside to realize efficient magnetic response.Magnetic particle has shown the high-performance in sepn process, and this sorbent material is highly susceptible to separation, no longer needs extra centrifugal or filtration.The magnetic porous polymer microballoon of preparing by suspension polymerization not only has higher specific surface area, remarkable absorption property, and can under the effect of external magnetic field, realize simple separated.The magnetic porous sorbent material of preparing by suspension polymerization pollutes process field at water and plays an important role.
Summary of the invention
Technical scheme of the present invention refers to generate styrene-divinylbenzene (St-DVB) porous adsorbent with suspension polymerization preparation, and utilize sulfonated method to generate magneticsubstance in its finishing, finally prepare magnetic porous sorbent material, and be applied to selective adsorption phenol pollutent in water surrounding.
technical scheme
Utilize suspension polymerization to prepare the method for magnetic porous sorbent material, carry out according to the following steps:
(1) porous styroyl-Vinylstyrene (St-DVB) sorbent material is synthetic:
By vinylbenzene (St), Vinylstyrene (DVB), Diisopropyl azodicarboxylate (AIBN) and hexalin are dissolved in toluene solution and form organic phase, and sodium-chlor (NaCl) and Natvosol (HEC) are dissolved in and in deionized water, form water.Wherein control St:DVB:AIBN: hexalin: toluene: the molar mass of NaCl is than being (43-46): (52-55): (1.2-1.6): (60-63): (39-41): (25-27), the ratio of controlling HEC and deionized water is 0.9-1.1:70-75(g/mL).After abundant stirring, two-phase is mixed 15-30 min and is formed emulsion under ultrasonic condition.This emulsion is transferred in the there-necked flask of 250 ml that condenser and nitrogen device are housed, stirred 1-2 h under the protection of nitrogen, temperature is elevated to 70 ℃ from room temperature afterwards.Reaction is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min.Finally, obtain porous St-DVB microballoon, by high speed centrifugation, carry out separation.
(2) utilize the vitriol oil to carry out finishing to porous St-DVB nanoparticle:
Porous St-DVB microballoon and the dense H of gained will be prepared in step (1)
2sO
4in 50 ml flasks, mix, control porous St-DVB microballoon and dense H
2sO
4mass ratio be 2:25, at 50 ℃, with the speed of 600 rmp/min, stir 5-6 h, make yellow viscous liquid, with acetone precipitation and washing, obtain sulfonated polystyrene microballoon.
(3), in the there-necked flask of 250 ml, add the sulfonated polystyrene microballoon of gained in step (2), the FeCl of 1 mol/L
24H
2o solution, wherein sulfonated polystyrene microballoon and FeCl
24H
2the ratio of O solution is 1.5:(65-80) g/ml, stirring at room 24 h, make it carry out sufficient ion-exchange.
(4) products therefrom in step (3) is crossed leakage with sand core funnel, after deionized water wash several, product is transferred in the there-necked flask of 250 ml, the NaOH solution that adds deionized water and 3.75 mol/L, wherein the ratio of step (3) products therefrom, deionized water and NaOH solution is 3:(40-50): (40-50) g/ml/ml, be heated to 60 ℃, under the stirring velocity of 200 rpm/min, in 15-30 min, dropwise add the hydrogen peroxide (H of 30wt%
2o
2) solution, controlling NaOH solution be (40-50) with the volume ratio of superoxol: 20, and then, reactant continues to stir 1.5 h again, and with deionized water wash, to neutrality, redispersion, in dehydrated alcohol, in 60 ℃ vacuum is dried after crossing leakage with sand core funnel.
The polymerization process adopting in above-mentioned technical scheme is suspension polymerization.
Vinylbenzene described in above-mentioned technical scheme and Vinylstyrene, it act as function monomer.
Diisopropyl azodicarboxylate described in above-mentioned technical scheme, it act as initiator.
Toluene described in above-mentioned technical scheme and hexalin, it act as pore-creating agent.
Natvosol described in above-mentioned technical scheme, it act as tensio-active agent.
The vitriol oil described in above-mentioned technical scheme, it act as coating materials.
Hydrogen peroxide described in above-mentioned technical scheme, it makes promising oxygenant.
Technological merit of the present invention: this product is magnetic porous sorbing material, and wherein vesicular structure has increased specific surface area, can effectively increase loading capacity; Inorganic particle layer in shell makes sorbing material physical strength high, and recognition site is difficult for destroyed; The magneticsubstance of modifying adsorbent surface by sulfonated method has good magnetic response performance, can realize sharp separation; Sorbent material has good magnetic and thermostability simultaneously, has significant absorption property.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of magnetic porous St-DVB sorbent material in embodiment 1.From a, can find out, the mean diameter of the microballoon that embodiment 1 obtains is 7 microns, from b, can find out, microsphere surface presents a lot of holes, what in c and d, show is the microballoon after absorption and wash-out, and this microballoon is still keeping the spherical form of rule, and still there is a lot of holes on surface, what e figure showed is the power spectrum of microsphere surface material, therefrom can find out the existence of magnetic substance.
Fig. 2 is the magnetic hysteresis loop of magnetic porous St-DVB sorbent material in embodiment 1.As can be seen from the figure, the magnetic porous St-DVB sorbent material that embodiment 1 obtains is superparamagnetic, and the magnetic saturation intensity of the magnetic porous St-DVB sorbent material obtaining in embodiment 1 is 40 emu/g.
Embodiment
Absorption property analysis test method described in technique scheme is specially:
(1) Static Adsorption test
By 2 of 10 ml different concns, 4-DCP and 2,4,6-TCP solution joins in colorimetric cylinder, adds respectively the magnetic porous St-DVB sorbent material of 10mg, be placed on the standing different time in the water bath with thermostatic control of differing temps, investigate in test soln 2,4-DCP and 2,4, the starting point concentration of 6-TCP, the impact on sorbent material absorption property of temperature of reaction and time of repose; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP and 2,4,6-TCP, and according to result calculate loading capacity (
q e, mg/g):
Wherein
c 0(mg/L) and
c e(mg/L) be respectively absorption front and back 2, the concentration of 4-DCP and 2,4,6-TCP,
w(g) be sorbent material consumption,
v(mL) be test fluid volume.
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
1, a method for magnetic porous sorbent material is prepared in suspension polymerization, and its preparation method carries out according to following step:
(1) porous styroyl-Vinylstyrene (St-DVB) nanoparticle is synthetic:
By 5 ml vinylbenzene (St), 7.5 ml Vinylstyrenes (DVB), 0.25 g Diisopropyl azodicarboxylate (AIBN) and 6.3 ml hexalin are dissolved in 4.2 ml toluene solutions and form organic phase, and 1.5 g sodium-chlor (NaCl) and 0.9 g Natvosol (HEC) are dissolved in 70 ml deionized waters and form water.After abundant stirring, two-phase is mixed 15 min and is formed emulsion under ultrasonic condition.This emulsion is transferred in the there-necked flask of 250 ml that condenser and nitrogen device are housed, stirred 1 h under the protection of nitrogen, temperature is elevated to 70 ℃ from room temperature afterwards.Reaction is sustained reaction 24 h under the high-speed stirring of 800 rpm/min.Finally, obtain porous St-DVB sorbent material, by high speed centrifugation, carry out separation.Prepare gained St-DVB porous adsorbent scanning electron microscope and can spectrogram etc. refer to Fig. 1, as can be seen from the figure sorbent material is the spherical of rule, surface arrangement a large amount of holes.
(2) utilize the vitriol oil to carry out finishing to porous St-DVB nanoparticle:
St-DVB porous adsorbent 2g and the dense H of 25g of gained will be prepared in step (1)
2sO
4in 50 ml flasks, mix, the speed with 600 rmp/min at 50 ℃ stirs 5-6 h,, make yellow viscous liquid, with acetone precipitation and washing, obtain sulfonated polystyrene microballoon.
(3), in the there-necked flask of 250 ml, add the sulfonated polystyrene microballoon of gained in 1.5 g steps (2), the FeCl of 1 mol/L of 65 ml
24H
2o solution, stirring at room 24 h, make it carry out sufficient ion-exchange.
(4) products therefrom in step (3) is crossed leakage with sand core funnel, after deionized water wash several, product is transferred in the there-necked flask of 250 ml, adding 40 ml deionized waters and 40 ml concentration is the NaOH solution of 3.75 mol/L, be heated to 60 ℃, under the stirring velocity of 200 rpm/min, in 15 min, dropwise add 20 mL(30wt%) hydrogen peroxide (H
2o
2) solution, then, reactant continues to stir 1.5 h again, and with deionized water wash, to neutral, redispersion is in dehydrated alcohol, dry in 60 ℃ of vacuum after crossing leakage with sand core funnel.Prepare gained magnetic porous St-DVB sorbent material magnetic hysteresis loop as shown in Figure 2, as can be seen from the figure, sorbent material is superparamagnetic, has stronger magnetic saturation intensity.
2, absorption property analytical test:
(1) Static Adsorption test 1
10 ml concentration are respectively to 10,30,50,80,100,150,2 of 200,300 and 400 mg/L, 4-DCP and 2,4,6-TCP solution joins in colorimetric cylinder, adds respectively the magnetic porous St-DVB sorbent material of 10mg, be placed on standing 12h in 25 ℃ of waters bath with thermostatic control, investigate in test soln 2,4-DCP and 2, the impact of the starting point concentration of 4,6-TCP on sorbent material absorption property; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP and 2,4,6-TCP, according to formula calculation result.
Result shows: magnetic porous St-DVB sorbent material in the time of 25 ℃ to 2, the saturated adsorption capacity of 4-DCP is 38 mg/g, magnetic porous St-DVB sorbent material in the time of 25 ℃ to 2,4, the saturated adsorption capacity of 6-TCP is 50 mg/g, and magnetic porous St-DVB sorbent material is to 2,4, the loading capacity of 6-TCP is apparently higher than 2,4-DCP.
(2) Static Adsorption test 2
By 10 ml concentration, be 2 of 100 mg/L, 4-DCP and 2,4,6-TCP solution joins in colorimetric cylinder, adds respectively the magnetic porous St-DVB sorbent material of 10mg, standing 10 min of difference in 25 ℃ of waters bath with thermostatic control, 30 min, 1 h, 2 h, 4 h and 8 h, investigate the impact of reaction times on sorbent material absorption property; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP and 2,4,6-TCP, according to formula calculation result.
Result shows: magnetic porous St-DVB sorbent material is 250 min to the adsorption saturation time of 2,4-DCP, and magnetic porous St-DVB sorbent material is to 2, the adsorption saturation time of 4,6-TCP is 130 min, and magnetic porous St-DVB sorbent material is in absorption 2, during 4,6-TCP, can reach quickly balance.
embodiment 2:
1, a method for magnetic porous sorbent material is prepared in suspension polymerization, and its preparation method carries out according to following step:
(1) porous styroyl-Vinylstyrene (St-DVB) nanoparticle is synthetic:
By 5 .3ml vinylbenzene (St), 7.8 ml Vinylstyrenes (DVB), 0.2 g Diisopropyl azodicarboxylate (AIBN) and 6.5 ml hexalin are dissolved in 4.3 ml toluene solutions and form organic phase, and 1.57 g sodium-chlor (NaCl) and 1.1g Natvosol (HEC) are dissolved in 75 ml deionized waters and form water.After abundant stirring, two-phase is mixed 30 min and is formed emulsion under ultrasonic condition.This emulsion is transferred in the there-necked flask of 250 ml that condenser and nitrogen device are housed, stirred 2 h under the protection of nitrogen, temperature is elevated to 70 ℃ from room temperature afterwards.Reaction is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min.Finally, obtain porous St-DVB sorbent material, by high speed centrifugation, carry out separation.
(2) utilize the vitriol oil to carry out finishing to porous St-DVB nanoparticle:
St-DVB porous adsorbent 2 g and the dense H of 25 g of gained will be prepared in step (1)
2sO
4in 50 ml flasks, mix, at 50 ℃, with the speed stirring reaction 5-6 h of 600 rmp/min, make yellow viscous liquid, with acetone precipitation and washing, obtain sulfonated polystyrene microballoon.
(3), in the there-necked flask of 250 ml, add the sulfonated polystyrene microballoon of gained in 1.5 g steps (2), the FeCl of 1 mol/L of 80 ml
24H
2o solution, stirring at room 24 h, make it carry out sufficient ion-exchange.
(4) products therefrom in step (3) is crossed leakage with sand core funnel, after deionized water wash several, product is transferred in the there-necked flask of 250 ml, adding 50 ml deionized waters and 50 ml concentration is the NaOH solution of 3.75 mol/L, be heated to 60 ℃, under the stirring velocity of 200 rpm/min, in 30 min, dropwise add 20 mL(30wt%) hydrogen peroxide (H
2o
2) solution, then, reactant continues to stir 1.5 h again, and with deionized water wash, to neutral, redispersion is in dehydrated alcohol, dry in 60 ℃ of vacuum after crossing leakage with sand core funnel.
2, absorption property analytical test:
(1) Static Adsorption test 1
By 10 ml concentration, be 2 of 50 mg/L, 4-DCP solution joins in colorimetric cylinder, adds respectively the magnetic porous St-DVB sorbent material of 10mg, respectively at 15 ℃, standing 12h in 25 ℃ and 35 ℃ of waters bath with thermostatic control, investigates the impact of differential responses temperature on sorbent material absorption property; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and not 2 of absorption, the concentration ultraviolet spectral analysis of 4-DCP, according to formula calculation result.Result substitution Gibbs free energy formula calculates.
Result shows: by Gibbs free energy formula, the value of trying to achieve Δ Ho is 0.0058, Δ
sthe value of o is that Δ G corresponding under 0.023, three differing temps is respectively-6.699 ,-6.931 and-7.164.Δ Ho>0 explanation adsorption process is absorbed heat, Δ
g<0 shows that sorbent material is spontaneous to the absorption of 2,4-DCP.
(1) Static Adsorption test 2
By 10 ml concentration, be 2,4 of 150 mg/L, 6-TCP solution joins in colorimetric cylinder, add respectively the magnetic porous St-DVB sorbent material of 10mg, respectively at 15 ℃, standing 12h in 25 ℃ and 35 ℃ of waters bath with thermostatic control, investigates the impact of differential responses temperature on sorbent material absorption property; After saturated adsorption, sorbent material is collected with Nd-Fe-B permanent magnet, and not 2,4 of absorption, the concentration ultraviolet spectral analysis of 6-TCP, according to formula calculation result.Result substitution Gibbs free energy (Gibbs free energy) formula calculates.
Result shows: by Gibbs free energy formula, the value of trying to achieve Δ Ho is 0.0075, and the value of Δ So is that Δ G corresponding under 0.029, three differing temps is respectively-8.373 ,-8.664 and-8.955.Δ Ho>0 explanation adsorption process is absorbed heat, and Δ G<0 shows that sorbent material is spontaneous to the absorption of 2,4,6-TCP.
Claims (6)
1. a method of preparing magnetic porous sorbent material by suspension polymerization, according to following step, carry out: with suspension polymerization preparation, generate styrene-divinylbenzene porous nano particle, and utilize sulfonated method to generate magneticsubstance in its finishing, finally prepare magnetic porous sorbent material.
2. a kind of method of preparing magnetic porous sorbent material by suspension polymerization according to claim 1, is characterized in that, the preparation process of the magnetic porous sorbent material of described synthesizing styrene-Vinylstyrene (St-DVB) is as follows:
(1) porous styroyl-Vinylstyrene (St-DVB) sorbent material is synthetic:
By vinylbenzene (St), Vinylstyrene (DVB), Diisopropyl azodicarboxylate (AIBN) and hexalin are dissolved in toluene solution and form organic phase, and sodium-chlor (NaCl) and Natvosol (HEC) are dissolved in and in deionized water, form water; After abundant stirring, two-phase is mixed 15-30 min and is formed emulsion under ultrasonic condition; This emulsion is transferred in the there-necked flask of 250 ml that condenser and nitrogen device are housed, stirred 1-2 h under the protection of nitrogen, temperature is elevated to 70 ℃ from room temperature afterwards; Reaction is sustained reaction 24 h under the high-speed stirring condition of 800 rpm/min; Finally, obtain porous St-DVB microballoon, by high speed centrifugation, carry out separation;
(2) utilize the vitriol oil to carry out finishing to porous St-DVB nanoparticle:
Porous St-DVB microballoon and the dense H of gained will be prepared in step (1)
2sO
4in 50 ml flasks, mix, the speed with 600 rmp/min at 50 ℃ stirs 5-6 h, makes yellow viscous liquid, with acetone precipitation and washing, obtains sulfonated polystyrene microballoon;
(3), in the there-necked flask of 250 ml, add the sulfonated polystyrene microballoon of gained in step (2), the FeCl of 1 mol/L
24H
2o solution, stirring at room 24 h, make it carry out sufficient ion-exchange;
(4) products therefrom in step (3) is crossed leakage with sand core funnel, after deionized water wash several, product is transferred in the there-necked flask of 250 ml, the NaOH solution that adds deionized water and 3.75 mol/L, be heated to 60 ℃, under the stirring velocity of 200 rpm/min, in 15-30 min, dropwise add the hydrogen peroxide (H of 30wt%
2o
2) solution, then, reactant continues to stir 1.5 h again, and with deionized water wash, to neutral, redispersion is in dehydrated alcohol, dry in 60 ℃ of vacuum after crossing leakage with sand core funnel.
3. the method for magnetic porous sorbent material is prepared in suspension polymerization according to claim 2, it is characterized in that wherein in step (1), controlling St:DVB:AIBN: the molar mass of hexalin: toluene: NaCl is than being (43-46): (52-55): (1.2-1.6): (60-63): (39-41): (25-27); The ratio of controlling HEC and deionized water is (0.9-1.1): (70-75) g/mL.
4. the method for magnetic porous sorbent material is prepared in suspension polymerization according to claim 2, it is characterized in that wherein in step (2), controlling porous St-DVB microballoon and dense H
2sO
4mass ratio be 2:25.
5. the method for magnetic porous sorbent material is prepared in suspension polymerization according to claim 2, it is characterized in that the wherein middle sulfonated polystyrene microballoon of step (3) and FeCl
24H
2the ratio of O solution is 1.5:(65-80) g/ml.
6. the method for magnetic porous sorbent material is prepared in suspension polymerization according to claim 2, it is characterized in that wherein the ratio of middle step (3) products therefrom of step (3), deionized water and NaOH solution is 3:(40-50): (40-50) g/ml/ml; The volume ratio of controlling NaOH solution and superoxol is (40-50): 20.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226274A (en) * | 2014-07-08 | 2014-12-24 | 兰州大学 | Adsorbing agent for removing petroleum type pollutants in environmental water sample and preparation method of adsorbing agent |
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| CN106693928A (en) * | 2016-12-30 | 2017-05-24 | 仇颖超 | Method for preparing super oil absorption material from magnetic porous polydivinylbenzene |
| CN107973872A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | Nano ferriferrous oxide adulterates the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier |
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| CN115286741A (en) * | 2022-09-01 | 2022-11-04 | 江苏大学 | A method for preparing magnetic mesoporous sulfonated crescent-shaped adsorbent by emulsion interfacial polymerization and its lead ion adsorption application |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159351A (en) * | 1996-03-12 | 1997-09-17 | 西安电力树脂厂 | Medicine magnetic response carrier and production method thereof |
| US5977016A (en) * | 1996-06-22 | 1999-11-02 | Mhb Filtration Gmbh & Co. Kg | Process for producing granulated activated carbon |
| CN1390861A (en) * | 2002-06-26 | 2003-01-15 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its preparing process by combination of reverse-phase emulsion polymerization with suspension polymerization |
| CN1718619A (en) * | 2005-08-08 | 2006-01-11 | 北京师范大学 | Magnetic composite microsphere with inorganic/organic core-shell structure and preparation method thereof |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthetic method of ultra-high cross-linked adsorption resin containing composite function of sulfonic acid group |
| CN101183589A (en) * | 2007-10-25 | 2008-05-21 | 上海交通大学 | Preparation method of magnetic microspheres with surface functional groups |
| CN102407116A (en) * | 2011-10-13 | 2012-04-11 | 西北工业大学 | Large-pore high-specific-surface magnetic visible-light-driven photocatalyst Fe3O4/TiO2Preparation method of (1) |
| CN102964539A (en) * | 2012-10-19 | 2013-03-13 | 南京林业大学 | Preparation method of porous magnetic polystyrene microspheres |
-
2013
- 2013-10-31 CN CN201310528523.9A patent/CN103588919A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159351A (en) * | 1996-03-12 | 1997-09-17 | 西安电力树脂厂 | Medicine magnetic response carrier and production method thereof |
| US5977016A (en) * | 1996-06-22 | 1999-11-02 | Mhb Filtration Gmbh & Co. Kg | Process for producing granulated activated carbon |
| CN1390861A (en) * | 2002-06-26 | 2003-01-15 | 天津大学 | Magnetic composite microsphere of molecular blot polymer and its preparing process by combination of reverse-phase emulsion polymerization with suspension polymerization |
| CN1718619A (en) * | 2005-08-08 | 2006-01-11 | 北京师范大学 | Magnetic composite microsphere with inorganic/organic core-shell structure and preparation method thereof |
| CN1772774A (en) * | 2005-11-08 | 2006-05-17 | 南京大学 | Synthetic method of ultra-high cross-linked adsorption resin containing composite function of sulfonic acid group |
| CN101183589A (en) * | 2007-10-25 | 2008-05-21 | 上海交通大学 | Preparation method of magnetic microspheres with surface functional groups |
| CN102407116A (en) * | 2011-10-13 | 2012-04-11 | 西北工业大学 | Large-pore high-specific-surface magnetic visible-light-driven photocatalyst Fe3O4/TiO2Preparation method of (1) |
| CN102964539A (en) * | 2012-10-19 | 2013-03-13 | 南京林业大学 | Preparation method of porous magnetic polystyrene microspheres |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226274A (en) * | 2014-07-08 | 2014-12-24 | 兰州大学 | Adsorbing agent for removing petroleum type pollutants in environmental water sample and preparation method of adsorbing agent |
| WO2017005090A1 (en) * | 2015-07-09 | 2017-01-12 | 于杰 | Micro-nano medical adsorbent resin powder material |
| CN106693928A (en) * | 2016-12-30 | 2017-05-24 | 仇颖超 | Method for preparing super oil absorption material from magnetic porous polydivinylbenzene |
| CN107973872A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | Nano ferriferrous oxide adulterates the preparation method of styrene diethylene benzene copoly mer hydrophobic catalyst carrier |
| CN109060979A (en) * | 2018-08-02 | 2018-12-21 | 成都中医药大学 | A kind of measuring method of (methylenedioxy) benzyl ethylene toxin |
| CN115286741A (en) * | 2022-09-01 | 2022-11-04 | 江苏大学 | A method for preparing magnetic mesoporous sulfonated crescent-shaped adsorbent by emulsion interfacial polymerization and its lead ion adsorption application |
| CN116440877A (en) * | 2023-05-22 | 2023-07-18 | 福州大学 | Trace metal ion adsorbent in NMP system |
| CN116440877B (en) * | 2023-05-22 | 2024-10-29 | 福州大学 | Trace metal ion adsorbent in NMP system |
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