CN113713775A - Schiff base modified nano magnetic composite adsorption material and preparation method thereof - Google Patents
Schiff base modified nano magnetic composite adsorption material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 29
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 24
- 239000002262 Schiff base Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- 238000006243 chemical reaction Methods 0.000 claims description 69
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- 235000019441 ethanol Nutrition 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- 239000000696 magnetic material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B01J20/28009—Magnetic properties
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- 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
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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Abstract
The invention discloses a Schiff base modified nano magnetic composite adsorbing material and a preparation method thereof. The invention has selective adsorbability on heavy metal ions in water, and has the advantages of large adsorption capacity, recyclability, no need of secondary treatment, environmental protection, no pollution and the like.
Description
Technical Field
The invention belongs to the technical field of adsorption and removal of heavy metal ions in water and purification of water pollution, and particularly relates to a Schiff base modified nano magnetic composite adsorption material and a preparation method thereof.
Background
The adsorption of heavy metal ions from water using adsorbents is considered to be the simplest and most suitable method, and various adsorption materials such as activated carbon, mineral adsorbents, high molecular polymer adsorbents, organic biomass adsorbents, etc. have been developed. However, most of the adsorbing materials generally have the problems of poor adsorption selectivity, low adsorption capacity, secondary treatment, secondary pollution and the like, and particularly after adsorption is completed, the adsorbing materials and the wastewater are difficult to realize quick and effective separation, so that the application value of the adsorbing materials is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the Schiff base modified nano magnetic composite adsorption material and the preparation method thereof, which have selective adsorption on heavy metal ions in a water body, and have the advantages of large adsorption capacity, recyclability, no need of secondary treatment, environmental protection, no pollution and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a Schiff base modified nano magnetic composite adsorption material takes a magnetic material as a core, an inorganic wrapping material as a shell, and a core-shell structure surface modified adsorption material containing one or more imino or azomethine (-RC-N-) active groups in a molecular structure.
A preparation method of a Schiff base modified nano magnetic composite adsorption material comprises the following steps;
step 1, magnetic inorganic coating composite material (Fe)3O4@SiO2) Preparing;
preparation of Fe by embedding3O4@SiO2Taking nano Fe3O4Dispersing the particles in an alcohol-water system, and fully dispersing the dispersed nano Fe3O4Transferring the dispersion liquid into a reaction kettle, mechanically stirring at a constant speed, adjusting the pH value to about 10 by using ammonia water, preparing an inorganic coating material solution dissolved by ethanol, adding the inorganic coating material solution into the reaction kettle in a dropwise manner, stirring and reacting for 10 hours, changing the reaction system from black to light gray, stopping the reaction, performing suction filtration, and alternately washing by using distilled water and ethanol to obtain Fe coated with gray surface3O4@SiO2Particles;
mixing Fe3O4@SiO2Adding into anhydrous toluene, ultra-dispersing, and transferring toIn the reaction kettle, mechanically stirring, adding amino (-NH)2) Heating and refluxing the modified reagent in oil bath, naturally cooling, stopping the reaction, washing and separating by using ethanol to obtain the amino modified magnetic composite material (Fe)3O4@SiO2-NH2)；
Step 3, diamino modified magnetic composite material (Fe)3O4@SiO2-N2H4) Preparing;
taking Fe3O4@SiO2-NH2Adding into a reaction kettle filled with methanol, stirring, introducing nitrogen, slowly and uniformly dripping a Michelal addition reaction reagent into the reaction kettle, stirring again, heating and stirring, continuously dripping a mixed solution of Ethylenediamine (EDA) and methanol into the reaction kettle slowly and uniformly, stirring again, heating to finish the reaction, carrying out vacuum filtration, washing with absolute ethyl alcohol, and drying in vacuum to obtain Fe3O4@SiO2-N2H4Particles;
mixing Fe3O4@SiO2-N2H4Dispersing the particles in ethanol, transferring the solution to a reaction kettle, introducing nitrogen, dropwise adding 10mL of aldehyde group (-COH) containing modified reagent, heating for reaction, naturally cooling to room temperature, performing suction filtration, alternately washing with ethanol and deionized water, and performing vacuum drying to obtain the Schiff base modified nano magnetic composite adsorbing material Fe3O4@SiO2-S2。
In the step 1, nano Fe3O4Dispersing the particles in an alcohol-water system with the volume ratio of 10:1, fully dispersing for about 30min, and keeping the water bath temperature of the reaction kettle at 20 ℃.
The step 2 is heated and refluxed for 18 hours at 110 ℃ in an oil bath.
Stirring at 0 ℃ in the step 3, introducing nitrogen, slowly and uniformly dropping Michelal addition reaction reagent into the reaction kettle, completing dropping for 1h, stirring for 30min at 0 ℃, then heating to 50 ℃, stirring for 12h, continuously and uniformly dropping mixed solution of Ethylenediamine (EDA) and methanol into the reaction kettle, completing dropping for 2h, stirring for 0.5h again at 0 ℃, then heating to 50 ℃, stirring for 12h, finishing reaction, performing vacuum filtration, washing for 3 times by using absolute ethyl alcohol, and performing vacuum drying on particles for 6h at 80 ℃.
In the step 4, Fe3O4@SiO2-N2H4Dispersing the particles in ethanol for 30min, transferring to a reaction kettle, introducing nitrogen, dropwise adding 10mL of aldehyde group (-COH) containing modified reagent (after dropwise adding for about 20 min), heating to 75 deg.C, reacting for 2h, naturally cooling to room temperature, vacuum-filtering, alternately washing with ethanol and deionized water, and vacuum-drying at 80 deg.C for 6 h.
The black nano Fe in the step 13O4The size of the particles is between 10 and 200 nanometers;
the step 2 contains amino (-NH)2) The reagent comprises: one or two of 3-Aminopropyltrimethoxysilane (APTMS) and 3-Aminopropyltriethoxysilane (APTES);
the Michelal addition reaction reagent in the step 3 comprises: one or two of Methyl Acrylate (MA) and Ethyl Acrylate (EA).
The aldehyde group (-COH) containing modification reagent in the step 4 comprises: one or two of Benzaldehyde (BE) and Salicylaldehyde (SA).
The invention has the beneficial effects that:
the adsorption material is a nano magnetic composite adsorption material, and has wide application in the technical fields of adsorption and removal of heavy metal ions in water, purification of water pollution and the like. The prepared adsorbing material has the advantages of being recyclable, strong in selective adsorption, large in adsorption capacity and environment-friendly.
Description of the drawings:
FIG. 1 is an IR spectrum of the material of example 1 of the present invention.
FIG. 2 is a hysteresis loop chart of the material of example 1 of the present invention.
FIG. 3 shows the adsorption capacity of the adsorbent of inventive example 1 for various heavy metal ions (all at a mass concentration of 800 mg/L).
FIG. 4 shows a suction device according to example 1 of the present inventionThe auxiliary material is used for Hg in different water bodies2+The adsorption capacity of (c).
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the adsorbing material comprises the following steps: taking 5g of nano Fe3O4Dispersing the particles in a mixed solution of 100mL of ethanol and 10mL of deionized water, fully dispersing for about 30min by ultrasonic treatment, and then dispersing the nano Fe3O4The dispersion was transferred to a 250mL reaction vessel and mechanically stirred at a constant speed. Ammonia water is dripped to adjust the pH value to about 10, and the water bath temperature of the reaction kettle is kept at 20 ℃. Preparing a mixed solution of 12g of Tetraethoxysilane (TEOS) dissolved in 50mL of ethanol, dripping the mixed solution into a reaction kettle through a dropping funnel, uniformly stirring and reacting for 10 hours, changing the reaction system from black to light gray, performing suction filtration, and alternately washing with distilled water and ethanol to obtain Fe with the gray surface coated3O4@SiO2And (3) granules.
Fe to be prepared3O4@SiO2Adding into 100mL of anhydrous toluene, transferring into a 250mL reaction kettle after ultra-dispersion, mechanically stirring, adding 10mL of 3-Aminopropyltriethoxysilane (APTES), oil-bathing at 110 ℃ for heating reflux reaction for 18h, naturally cooling, stopping reaction, washing with ethanol, and separating to obtain the amino-modified magnetic composite material Fe3O4@SiO2-NH2And (3) granules.
Fe to be prepared3O4@SiO2-NH2The mixture was charged into a 250mL reaction vessel containing 80mL of methanol, stirred at 0 ℃ and purged with nitrogen. Slowly dripping 30mL of Methyl Acrylate (MA) into the reaction kettle at a constant speed for 1h, stirring for 30min at 0 ℃, then heating to 50 ℃, and stirring for 10 h. And (3) continuously dropwise adding a mixed solution of 40mL of Ethylenediamine (EDA) and 30mL of methanol into the reaction kettle at a constant speed slowly, dropwise adding the mixed solution for 2h, stirring the mixed solution for 0.5h at the temperature of 0 ℃, then heating the mixed solution to 40 ℃, and stirring the mixed solution for 24h to finish the reaction. Vacuum filtering, washing with anhydrous ethanol for 3 times, vacuum drying at 80 deg.C for 6 hr to obtain diamino modified magnetic composite material Fe3O4@SiO2-N2H4And (3) granules.
Fe to be prepared3O4@SiO2-N2H4Dispersing the particles in 50mL of ethanol for 30min, transferring the solution to a 100mL reaction kettle, introducing nitrogen, dropwise adding 10mL of Salicylaldehyde (SA), after about 20min of dropwise adding, heating to 75 ℃, reacting for 2h, naturally cooling to room temperature, performing suction filtration, alternately washing with ethanol and deionized water, and performing vacuum drying at 80 ℃ for 6h to obtain the Schiff base modified nano magnetic composite adsorbing material Fe3O4@SiO2-S2And (3) granules.
Example 2
The preparation method of the adsorbing material comprises the following steps: taking 100g of nano Fe3O4Dispersing the particles in a mixed solution of 1000mL of ethanol and 100mL of deionized water, fully dispersing for about 60min by mechanical rapid stirring, and then dispersing the nano Fe3O4The dispersion was transferred to a 2.50L reactor and mechanically stirred at a constant speed. Ammonia water is dripped to adjust the pH value to about 10, and the water bath temperature of the reaction kettle is kept at 20 ℃. Preparing a mixed solution of 500mL of ethanol dissolved with 120g of tetraethyl orthosilicate (TEOS), dripping the mixed solution into a reaction kettle through a dropping funnel, stirring at a constant speed for reaction for 10 hours, filtering the reaction system after the reaction system is changed from black to light gray, and washing the reaction system alternately with distilled water and ethanol to obtain Fe with the gray surface coated3O4@SiO2And (3) granules.
Fe to be prepared3O4@SiO2Adding the mixture into 800mL of anhydrous toluene, transferring the mixture into a 2.50L reaction kettle, mechanically and quickly stirring and dispersing the mixture for 30min, then dropwise adding 100mL of 3-Aminopropyltrimethoxysilane (APTMS), carrying out oil bath heating reflux reaction at 110 ℃ for 24h, naturally cooling the mixture, stopping the reaction, washing and separating the mixture by using ethanol to obtain the amino modified magnetic composite material Fe3O4@SiO2-NH2。
Fe to be prepared3O4@SiO2-NH2The mixture was charged into a 2.50L reactor containing 500mL of methanol, stirred at 0 ℃ and purged with nitrogen. 200mL of Methyl Acrylate (MA) is slowly dripped into the reaction kettle at a constant speed for 1 hour, the mixture is stirred for 1 hour at the temperature of 0 ℃, and then the mixture is heated to 50 ℃ and stirred for 10 hours. Continuously dropwise adding 300mL of ethylenediamine (E) into the reaction kettle slowly at a constant speedDA) and 300mL of methanol, dripping for 2h, stirring for 0.5h at 0 ℃, then heating to 40 ℃, stirring for 24h, and finishing the reaction. Vacuum filtering, washing with anhydrous ethanol for 3 times, vacuum drying at 80 deg.C for 6 hr to obtain diamino modified magnetic composite material Fe3O4@SiO2-N2H4And (3) granules.
Fe to be prepared3O4@SiO2-N2H4Dispersing the particles in 500mL of ethanol for 30min, transferring to a 2.5L reaction kettle, introducing nitrogen, dropwise adding 100mL of Salicylaldehyde (SA), after dropwise adding for about 30min, heating to 75 ℃, reacting for 3h, naturally cooling to room temperature, performing suction filtration, alternately washing with ethanol and deionized water, and performing vacuum drying at 80 ℃ for 6h to obtain Fe3O4@SiO2-S2And (3) granules.
Example 3
The preparation method of the adsorbing material comprises the following steps: taking 100mg of nano Fe3O4Dispersing the particles in a mixed solution of 50mL of ethanol and 5mL of deionized water, performing ultra-dispersion for about 30min, and then dispersing the nano Fe3O4The dispersion was transferred to a 100mL three-necked flask and mechanically stirred at a constant speed. Ammonia water is added dropwise to adjust the pH value to about 10, and the water bath temperature of the three-neck flask is kept at 10 ℃. Preparing a mixed solution of 10mL of ethanol and 2mL of methyl orthosilicate (TMOS), dripping the mixed solution into a three-neck flask through a dropping funnel, stirring at a constant speed for reaction for 12 hours, filtering and washing alternately by using distilled water and ethanol after a reaction system is changed from black to light gray to obtain Fe with a gray surface coating3O4@SiO2And (3) granules.
Fe to be prepared3O4@SiO2Adding into 50mL of anhydrous toluene, transferring into a 100mL reaction kettle, super-dispersing for 30min, dropwise adding 10mL of 3-Aminopropyltrimethoxysilane (APTMS), carrying out oil bath heating reflux reaction at 110 ℃ for 12h, naturally cooling, stopping reaction, washing with ethanol, and separating to obtain the amino-modified magnetic composite material Fe3O4@SiO2-NH2。
Fe to be prepared3O4@SiO2-NH21 containing 30mL of methanol was addedA00 mL three-necked flask was stirred at 0 ℃ and charged with nitrogen. And slowly dripping 10mL of Ethyl Acrylate (EA) into the reaction kettle at a constant speed for 1h, stirring for 1h at 0 ℃, then heating to 60 ℃, and stirring for 6 h. And (3) continuously dropwise adding a mixed solution of 15mL of Ethylenediamine (EDA) and 10mL of methanol into the reaction kettle at a constant speed slowly, completing dropwise addition for 1h, stirring for 0.5h at the temperature of 0 ℃, then heating to 50 ℃, stirring for 10h, and finishing the reaction. Vacuum filtering, washing with anhydrous ethanol for 3 times, vacuum drying at 80 deg.C for 6 hr to obtain diamino modified magnetic composite material Fe3O4@SiO2-N2H4And (3) granules.
Fe to be prepared3O4@SiO2-N2H4Dispersing the particles in 50mL of ethanol for 30min, transferring the solution to a 100mL three-neck flask, introducing nitrogen, dropwise adding 15mL of Benzaldehyde (BE), after dropwise adding for about 30min, heating to 75 ℃, reacting for 2h, naturally cooling to room temperature, performing suction filtration, alternately washing with ethanol and deionized water, and performing vacuum drying at 80 ℃ for 6h to obtain Fe3O4@SiO2-S2。
The nano magnetic material is black nano Fe3O4The particles and the inorganic coating material are Tetraethoxysilane (TEOS) or methyl orthosilicate (TMOS), and the functional modification material comprises: containing amino groups (-NH)2) Reagents, Michelal addition reaction reagents, ester exchange reaction reagents and modifying reagents containing aldehyde groups (-COH).
As can be seen from FIG. 1, 560cm-1Is a characteristic absorption peak of Fe-O, 1030cm-1Antisymmetric absorption peak at Si-O-Si, 756cm-1The absorption peak is the symmetrical absorption peak of Si-O-Si. Fe3O4@SiO2-NH21132cm in the spectrum-1Is a characteristic absorption peak of C-N, 1558cm-1Is a characteristic absorption peak of N-H, indicating-NH2Successful access, Fe3O4@SiO2-S2Absence of-NH in the spectrum2And at 1633cm-1And an imino (C ═ N) strong characteristic absorption peak appears, which indicates that the Schiff base grafting modification is successfully carried out on the nano particles.
As can be seen from FIG. 2, Fe3O4、Fe3O4@SiO2-NH2And Fe3O4@SiO2-S2Saturation magnetization M ofs72.9, 55.7 and 45.9emu/g respectively, all have good superparamagnetism. Fe3O4Has the highest saturation magnetism, Fe3O4@SiO2-S2Because the surface is SiO coated2After the coating, the density of magnetic particles per unit particle becomes low, the magnetic saturation intensity is reduced, and the magnetic Fe is increased with the degree of surface modification3O4The surface thickness of the particles is increased, the density of magnetic particles in unit particles is lower, and the magnetic saturation intensity is lower.
As can be seen from FIG. 3, Fe3O4@SiO2-S2For Hg2+Has better adsorbability than other heavy metal ions, respectively than Pb2+、Cu2+、Co2+、Ni2+、Mn2+、Al3+1.9, 23, 3.28, 3.04, 5.65, and 5.38 times higher. Pd2+、Cd2+、Pt2+、Hg2+、Ag+Etc. also belong to soft acids, and the adsorbing materials containing Schiff base groups also have good adsorption performance for the soft acids. However, Pb2+、Cu2+、Co2 +、Ni2+、Mn2+、Al3+But the affinity of the boundary acid or the hard acid to N ═ C is not as good as Hg2+。
As can be seen from fig. 4, the desorption rate of the adsorbent after the 1 st cycle was 99.03%, and the desorption rate after the 3 rd cycle was 96.48%, and the desorption rate tended to decrease as the number of cycles increased; after 5 times of adsorption-desorption, the desorption rate of the adsorbent is still kept above 89%, which shows that the prepared magnetic nano adsorption material has good recycling property. The main reason why the nitric acid solution containing thiourea desorbs the adsorbent is protonation of functional groups (-CH ═ NH) under acidic conditions+H) to make a large number of adsorption sites on the surface of the adsorbent material covered with H3O+Occupation of Hg2+The adsorption sites are reduced, and the purpose of elution and desorption is achieved; secondly, thiourea will also be involvedAnd the same adsorbent to Hg2+The adsorption competition of (2) and the strengthening of the desorption process.
Claims (10)
1. The Schiff base modified nanometer magnetic composite adsorbing material is characterized in that a magnetic material is used as a core, an inorganic wrapping material is used as a shell, and the surface of the adsorbing material modified by the core-shell structure contains one or more imino groups or azomethine (-RC-N-) active groups in the molecular structure.
2. A preparation method of a Schiff base modified nano magnetic composite adsorption material is characterized by comprising the following steps;
step 1, magnetic inorganic coating composite material (Fe)3O4@SiO2) Preparing;
preparation of Fe by embedding3O4@SiO2Taking nano Fe3O4Dispersing the particles in an alcohol-water system, and fully dispersing the dispersed nano Fe3O4Transferring the dispersion liquid into a reaction kettle, mechanically stirring at a constant speed, adjusting the pH value to about 10 by using ammonia water, preparing an inorganic coating material solution dissolved by ethanol, adding the inorganic coating material solution into the reaction kettle in a dropwise manner, stirring and reacting for 10 hours, changing the reaction system from black to light gray, stopping the reaction, performing suction filtration, and alternately washing by using distilled water and ethanol to obtain Fe coated with gray surface3O4@SiO2Particles;
step 2, amino-modified magnetic composite material (Fe)3O4@SiO2-NH2) Preparing;
mixing Fe3O4@SiO2Adding into anhydrous toluene, ultra-dispersing, transferring into reaction kettle, mechanically stirring, adding amino (-NH)2) Heating and refluxing the modified reagent in oil bath, naturally cooling, stopping the reaction, washing and separating by using ethanol to obtain the amino modified magnetic composite material (Fe)3O4@SiO2-NH2)；
Step 3, diamino modified magnetic composite material (Fe)3O4@SiO2-N2H4) Preparing;
taking Fe3O4@SiO2-NH2Adding into a reaction kettle filled with methanol, stirring, introducing nitrogen, slowly and uniformly dripping a Michelal addition reaction reagent into the reaction kettle, stirring again, heating and stirring, continuously dripping a mixed solution of Ethylenediamine (EDA) and methanol into the reaction kettle slowly and uniformly, stirring again, heating to finish the reaction, carrying out vacuum filtration, washing with absolute ethyl alcohol, and drying in vacuum to obtain Fe3O4@SiO2-N2H4Particles;
step 4, Schiff base modified magnetic nano composite adsorbing material (Fe)3O4@SiO2-S2) Preparing;
mixing Fe3O4@SiO2-N2H4Dispersing the particles in ethanol, transferring the solution to a reaction kettle, introducing nitrogen, dropwise adding 10mL of aldehyde group (-COH) containing modified reagent, heating for reaction, naturally cooling to room temperature, performing suction filtration, alternately washing with ethanol and deionized water, and performing vacuum drying to obtain the Schiff base modified nano magnetic composite adsorbing material Fe3O4@SiO2-S2。
3. The preparation method of the Schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein in the step 1, nano Fe3O4Dispersing the particles in an alcohol-water system with the volume ratio of 10:1, fully dispersing for about 30min, and keeping the water bath temperature of the reaction kettle at 20 ℃.
4. The preparation method of the Schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein the reaction is performed in step 2 by heating and refluxing in an oil bath at 110 ℃ for 18 h.
5. The preparation method of the Schiff base modified nano magnetic composite adsorbing material according to claim 2, wherein in the step 3, the mixture is stirred at 0 ℃, nitrogen is introduced, Michelal addition reaction reagent is slowly dripped into the reaction kettle at a constant speed for 1 hour, the mixture is stirred at 0 ℃ for 30min, then the mixture is heated to 50 ℃ and stirred for 12 hours, a mixed solution of Ethylenediamine (EDA) and methanol is slowly dripped into the reaction kettle at a constant speed, the mixture is dripped for 2 hours, the mixture is stirred at 0 ℃ for 0.5 hour, then the mixture is heated to 50 ℃ and stirred for 12 hours, the reaction is finished, the pressure is reduced, the filtration is carried out, the particles are washed for 3 times by using absolute ethyl alcohol, and then the particles are dried in vacuum at 80 ℃ for 6 hours.
6. The preparation method of the Schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein in the step 4, Fe is added3O4@SiO2-N2H4Dispersing the particles in ethanol for 30min, transferring to a reaction kettle, introducing nitrogen, dropwise adding 10mL of aldehyde group (-COH) containing modified reagent (after dropwise adding for about 20 min), heating to 75 deg.C, reacting for 2h, naturally cooling to room temperature, vacuum-filtering, alternately washing with ethanol and deionized water, and vacuum-drying at 80 deg.C for 6 h.
7. The preparation method of the Schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein the black nano-Fe in the step 13O4The size of the particles is between 10 and 200 nanometers.
8. The preparation method of the Schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein the amino (-NH) is contained in the step 22) The reagent comprises: one or two of 3-Aminopropyltrimethoxysilane (APTMS) and 3-Aminopropyltriethoxysilane (APTES).
9. The method for preparing the schiff base modified nano-magnetic composite adsorbing material according to claim 2, wherein the Micheal addition reaction reagent in the step 3 comprises: one or two of Methyl Acrylate (MA) and Ethyl Acrylate (EA).
10. The preparation method of the schiff base modified nano-magnetic composite adsorbing material as claimed in claim 2, wherein the aldehyde group (-COH) containing modifying reagent in the step 4 comprises: one or two of Benzaldehyde (BE) and Salicylaldehyde (SA).
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