CN108057427B - Solid magnetic heavy metal ion separation material and preparation method thereof - Google Patents

Solid magnetic heavy metal ion separation material and preparation method thereof Download PDF

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CN108057427B
CN108057427B CN201711343185.6A CN201711343185A CN108057427B CN 108057427 B CN108057427 B CN 108057427B CN 201711343185 A CN201711343185 A CN 201711343185A CN 108057427 B CN108057427 B CN 108057427B
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heavy metal
ferroferric oxide
metal ion
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separation material
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CN108057427A (en
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刘立华
胡博强
赵露
薛建荣
唐安平
周智华
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Hunan University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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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    • 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
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention relates to a solid magnetic heavy metal ion separation material and a preparation method thereof. Firstly, epichlorohydrin and triethylene tetramine are subjected to polymerization reaction in the presence of ferroferric oxide microspheres to generate linear macromolecular chains, and the linear macromolecular chains are adsorbed in situ and wound on the surfaces of the ferroferric oxide microspheres; then, further crosslinking the polymer chains by glutaraldehyde in toluene so as to stably coat the ferroferric oxide microspheres on the surfaces; in the aqueous solution, iminodiacetic acid groups are connected to a polymer chain net on the surface of the ferroferric oxide microspheres through dialdehyde substances, so that the surface of the ferroferric oxide microspheres is coated with a layer of rich-N (CH)2COO—)2、—NH2The polymer chain net with active groups such as-NH-and-OH greatly improves the trapping and adsorbing capacity of heavy metals, has excellent magnetic separation performance, is simple in subsequent separation, can realize continuous operation of adsorption and separation, and is convenient for industrial application and popularization.

Description

Solid magnetic heavy metal ion separation material and preparation method thereof
Technical Field
The invention relates to the field of heavy metal wastewater treatment, in particular to a solid magnetic heavy metal ion separation material and a preparation method thereof.
Background
Toxic heavy metal contaminated water has become a global major environmental problem. Fertilizer production, pesticide manufacturing, leather production, mineral mining, selection, smelting and processing, material surface finishing, battery manufacturing and the like all generate a large amount of wastewater containing heavy metals, and the safety of water environment and the health of people are seriously threatened. In order to deal with the increasing threat of heavy metal pollution, various heavy metal wastewater treatment methods such as a traditional chemical precipitation method, a chelating flocculation method, a coagulation/flocculation method, a ferrite method, an ion exchange method, a reinforced ultrafiltration method, an ion flotation method, electrodialysis, electrodeposition, an adsorption method and the like have been developed. Among them, the adsorption method is widely regarded as being particularly suitable for the advanced treatment of low-concentration wastewater or wastewater because of its simple operation, high treatment efficiency and low cost. The effect of the adsorption method for treating the heavy metal wastewater mainly depends on the performance of the adsorption material. The developed adsorbing materials have some disadvantages, for example, natural adsorbing materials are limited by the structure of the natural adsorbing materials, the adsorbing capacity is generally not large, and a large amount of solid waste containing heavy metals is easy to generate; the synthetic adsorption material, such as the carbonaceous adsorption material, has a small adsorption capacity, while the synthetic resin, the synthetic porous material and the synthetic nano material have complex preparation processes and high manufacturing cost; the biological adsorption material has the problems of poor selectivity and adaptability to heavy metals, difficulty in breeding strains and the like. Therefore, an adsorbing material with large adsorption capacity, good regeneration performance, long service life, lower cost and good separation performance is lacked at present. The development of novel efficient adsorbing materials with excellent adsorption performance, low cost and easy separation is an important task in front of the vast environment protection workers.
The research and development of the novel efficient adsorbing material need to start from the aspects of the structure, surface active groups, elution regeneration performance, separation performance after adsorption and the like of the adsorbing material, and the defects of the existing adsorbing material in certain performances are overcome and improved. It is known that ethylenediaminetetraacetic acid and its sodium salt (EDTA) are chelating agents having a strong chelating ability for a wide variety of metal ions, and that the chelating action is such that the carboxyl and N atoms readily form stable five-membered rings with the metal ions, e.g. by grafting the structure or part of the structure of EDTA onto the adsorbent material, e.g. iminodiacetate (-N (CH)2COO—)2) The resulting adsorbent material will also exhibit similar properties to EDTA for a variety of substratesThe metal ions have better chelating capacity, thereby improving the adsorption capacity to heavy metals. Magnetic separation is a separation mode which is convenient to operate and continuous operation, and is increasingly widely applied in the separation process.
Disclosure of Invention
Aiming at the defects of the prior adsorbing material in the treatment of heavy metal wastewater and the iminodiacetic acid ion (-N (CH)2COO—)2) The invention provides a solid magnetic heavy metal ion separation material with excellent heavy metal adsorption and trapping capacity and separation performance, which is black solid powder and has the structure that iminodiacetic acid groups (N (CH) with strong chelating capacity to various heavy metal ions are wound, coated and modified on the surface of a magnetic ferroferric oxide microsphere2COO—)2) A cage structure formed by the polymer chain of (a); the method is characterized in that: (1) wrapping magnetic ferroferric oxide particles with a polymer chain with multiple active groups, and then adding-N (CH)2COO—)2Modifying the polymer chain to form a cage-shaped structure material with magnetic particles as an inner core and rich chelating groups distributed on the outer surface; (2) the synthesized adsorbing material not only has good chelating and trapping performance on heavy metals, but also can conveniently separate the adsorbing material from the treated water through magnetic field attraction, thereby realizing the continuity of the adsorption and separation process, improving the adsorption and separation effect and efficiency and facilitating large-scale industrial popularization and application.
The second purpose of the invention is to provide a preparation method of the solid magnetic heavy metal ion separation material, which comprises the following steps:
(1) adding ferroferric oxide microspheres and a polar organic solvent into a reactor according to the mass-volume ratio of the ferroferric oxide microspheres to the polar organic solvent of 1: 40-50 g/ml, then adding polyethylene polyamine according to the mass ratio of the polyethylene polyamine to the ferroferric oxide microspheres of 1.5-3.0: 1, stirring for 2-3 h by an ultrasonic-assisted machine, then heating to 50-60 ℃, slowly dropwise adding epoxy chloropropane according to the mass ratio of the epoxy chloropropane to the polyethylene polyamine of 1.0-1.1: 1, after dropwise adding, continuing to react for 2-3 h, cooling to room temperature, and then separating solid substances by magnet attraction;
(2) transferring the solid matter obtained in the step (1) into a reactor, adding toluene according to the mass-volume ratio of the ferroferric oxide microspheres to the toluene of 1: 40-50 g/ml, stirring for 2-3 h by using an ultrasonic-assisted machine, measuring glutaraldehyde according to the mass ratio of the glutaraldehyde to the polyethylene polyamine of 1: 8-10, preparing a chloroform solution with the mass percentage concentration of 5-10%, slowly adding the chloroform solution into the reactor, and crosslinking for 3-4 h at the temperature of 60-80 ℃; cooling to room temperature, separating with a magnet and a solvent, and washing with ethanol and distilled water for 3-5 times;
(3) transferring the solid substance obtained in the step (2) into a reactor, adding distilled water with the mass 35-50 times of that of the solid substance, then weighing sodium iminodiacetate according to the mass ratio of the sodium iminodiacetate to the polyethylene polyamine of 2.0-4.0: 1.0, adding the sodium iminodiacetate into the reactor, and stirring for dissolving; then weighing the dialdehyde substances according to the mass ratio of 1.0-1.5: 1.0 of the dialdehyde substances to the sodium iminodiacetate substances to prepare aqueous solution with the mass percentage concentration of 10-20%, slowly dripping the aqueous solution into the reaction liquid, and reacting for 2-4 h at the temperature of 50-80 ℃; and cooling to room temperature, adsorbing with a magnet, separating from the solution, washing with distilled water for 3-5 times, and drying to obtain the solid magnetic heavy metal ion separation material.
Further, the diameter of the ferroferric oxide microspheres is 200-500 nm.
Further, the polar organic solvent is absolute ethyl alcohol or tetrahydrofuran.
Further, the polyethylene polyamine is triethylene tetramine or tetraethylene pentamine.
Further, the dialdehyde substance is glyoxal or glutaraldehyde.
Further, the reactor is preferably a three-necked flask, more preferably a three-necked flask with a reflux condenser tube, a constant pressure dropping funnel and a mechanical stirring device.
Further, the drying is vacuum drying, and the temperature is 50-70 ℃.
Furthermore, the epichlorohydrin, toluene, glutaraldehyde, chloroform, ethanol and sodium iminodiacetate used were all analytically pure.
The invention relates to a solid magnetic heavy metal ion separation material and a preparation method thereof. Firstly, generating linear macromolecular chain in-situ adsorption and winding on the surface of ferroferric oxide microspheres by the polymerization reaction of epichlorohydrin and triethylene tetramine in the presence of the ferroferric oxide microspheres; separating the ferroferric oxide microspheres from a reaction solution by using magnetic adsorption, dispersing the ferroferric oxide microspheres in nonpolar methylbenzene, adding glutaraldehyde to further crosslink a polymer chain wound on the surfaces of the ferroferric oxide microspheres, and thus stably coating the ferroferric oxide microspheres on the surfaces; then in the aqueous solution, taking sodium iminodiacetate as a raw material, and leading iminodiacetic acid group (-N (CH) to pass through dialdehyde substances2COO—)2) Is connected to the polymer chain net on the surface of the ferroferric oxide microsphere, so that the surface of the ferroferric oxide microsphere is coated with a layer of rich-N (CH)2COO—)2、—NH2and-NH-and-OH and other active groups, greatly improves the trapping and adsorbing capacity of heavy metals. Meanwhile, as ferroferric oxide is wrapped in the polymer chain network, the ferroferric oxide magnetic separation material also has excellent magnetic separation performance. Therefore, the method not only solves the problems of insufficient surface active groups of the ferroferric oxide microspheres and poor heavy metal adsorption capacity, but also solves the problems of complicated separation and incapability of continuous operation after the adsorption material adsorbs heavy metals, can realize continuous operation of adsorption and separation, and is convenient for industrial application and popularization.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, ferroferric oxide microspheres are dispersed in a polar organic solvent, and then under the existence of the ferroferric oxide microspheres, polyethylene polyamine and epichlorohydrin are reacted to generate linear macromolecules which are wound and wrapped on the surfaces of the ferroferric oxide microspheres in situ, so that the uniformity and the stability of the wrapping are improved; then the macromolecular chains wound and coated on the particle surface are further crosslinked to form a macromolecular chain network through glutaraldehyde, so thatThe coating layer can be stably coated on the surface of the ferroferric oxide microsphere, so that the stability of the adsorption material is improved. Meanwhile, polyethylene polyamine and epoxy chloropropane are subjected to polymerization reaction to generate a polymer chain, active groups such as hydroxyl, amino, imino and the like are effectively modified on the surface of the ferroferric oxide microsphere, and the active groups are convenient to further convert into iminodiacetic acid group (-N (CH) with strong chelating capacity to heavy metal2COO—)2)。
(2) The method of the invention adopts ferroferric oxide microspheres which are wound and adsorb high molecular chains to be dispersed in toluene, and then glutaraldehyde is added for crosslinking, thereby reducing the falling of the water-soluble high molecular chains from the surfaces of the microspheres, ensuring the amount of the coated high molecular chains and further ensuring the number of active groups.
(3) The method disclosed by the invention adopts the magnet to adsorb and separate substances which are beneficial to separation of nonmagnetic substances, so that the obtained intermediate and product are substances with high molecular chains wrapping the ferroferric oxide microspheres, the interference of nonmagnetic substances is reduced, and the wrapping layers on the surfaces of the ferroferric oxide microspheres are more uniform.
(4) The product particles of the invention take magnetic ferroferric oxide microspheres as cores, and the surfaces of the product particles are made of iminodiacetic acid groups (-N (CH) containing rich active groups2COO—)2) The product has excellent capability of chelating and trapping heavy metals and excellent magnetic separation performance, greatly improves the trapping and adsorbing capability of heavy metals, effectively solves the problems that an adsorbing material is complicated to separate after adsorbing heavy metals and cannot be continuously operated, and can realize high-efficiency removal and continuous operation of adsorption and separation of heavy metals, so that compared with other adsorbing materials, the solid magnetic heavy metal ion separating material has higher industrial application value and is convenient for industrial popularization and application.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the present invention;
FIG. 2 is a structural view of the solid magnetic heavy metal ion separation material of the present invention;
FIG. 3 is an infrared spectrum of the solid magnetic heavy metal ion separation material obtained in example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the solid magnetic heavy metal ion separation material obtained in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the attached drawing figures.
Example 1
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 435nm and 100mL of absolute ethyl alcohol are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, 4.10g of triethylene tetramine with the mass percentage concentration of 95.0% is added, and the mechanical stirring is assisted by ultrasonic waves for 3 hours. Heating to 60 ℃, slowly dripping 2.4mL of epoxy chloropropane with the mass percentage concentration of 99.0%, continuing to react for 3h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL toluene, mechanically stirring for 3h under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.36mL glutaraldehyde through the dropping funnel, and reacting for 3h at 70 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 5 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL distilled water, adding 11.95g sodium iminodiacetate, and stirring for dissolving; weighing 5.88g of glyoxal and adding distilled water to prepare 10 mass percent aqueous solution, slowly dripping the aqueous solution into the reaction solution through a dropping funnel, and reacting for 4 hours at 70 ℃; cooling to room temperature, separating with magnet, washing with distilled water for 5 times, and oven drying at 60 deg.C in vacuum drying oven to constant weight to obtain solid magnetic heavy metal ion separation material 3.23 g.
Example 2
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 340nm and 90mL of absolute ethyl alcohol are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, 4.50g of triethylene tetramine with the mass percentage concentration of 95.0% is added, and the mechanical stirring is assisted by ultrasonic waves for 2.5 hours. Raising the temperature to 55 ℃, slowly dripping 2.6mL of epoxy chloropropane with the mass percentage concentration of 99.0%, continuing to react for 2.5h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 90mL of toluene, mechanically stirring for 2h under the assistance of ultrasonic waves, slowly dropwise adding a 7.0 mass percent chloroform solution prepared from 0.33mL of glutaraldehyde through the dropping funnel, and reacting for 3h at 80 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 4 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80mL of distilled water, adding 16.34g of sodium iminodiacetate, and stirring for dissolving; weighing 6.43g of glyoxal and adding distilled water to prepare an aqueous solution with the mass percentage concentration of 15%, slowly dripping the aqueous solution into the reaction solution through a dropping funnel, and reacting for 2 hours at 80 ℃; cooling to room temperature, separating with magnet, washing with distilled water for 4 times, and oven drying at 70 deg.C in vacuum drying oven to constant weight to obtain solid magnetic heavy metal ion separation material 3.14 g.
Example 3
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 218nm and 80mL of absolute ethyl alcohol are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then 5.00g of triethylene tetramine with the mass percentage concentration of 95.0% is added, and the mechanical stirring is assisted by ultrasonic waves for 3 hours. Heating to 50 ℃, slowly dripping 2.97mL of epoxy chloropropane with the mass percentage concentration of 99.0%, continuing to react for 3h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL toluene, mechanically stirring for 3h under the assistance of ultrasonic waves, slowly dropwise adding a 10.0 mass percent chloroform solution prepared from 0.41mL glutaraldehyde through the dropping funnel, and reacting for 3h at 80 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 5 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 70mL distilled water, adding 12.11g sodium iminodiacetate, and stirring for dissolving; weighing 5.56g of glyoxal and adding distilled water to prepare an aqueous solution with the mass percentage concentration of 20%, slowly dropwise adding the aqueous solution into the reaction solution through a dropping funnel, and reacting for 3.5 hours at 60 ℃; cooling to room temperature, separating with magnet, washing with distilled water for 3 times, and oven drying at 60 deg.C in vacuum drying oven to constant weight to obtain solid magnetic heavy metal ion separation material 2.98 g.
Example 4
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 275nm and 100mL of absolute ethyl alcohol are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then 3.00g of triethylene tetramine with the mass percentage concentration of 95.0% is added, and the mechanical stirring is assisted by ultrasonic waves for 2 hours. Heating to 60 ℃, slowly dripping 1.62mL of epichlorohydrin with the mass percentage concentration of 99.0%, continuing to react for 2h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 90mL of toluene, mechanically stirring for 2h under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.24mL of glutaraldehyde through the dropping funnel, and reacting for 4h at 60 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 3 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80mL of distilled water, adding 14.53g of sodium iminodiacetate, and stirring for dissolving; weighing 4.76g of glyoxal and adding distilled water to prepare an aqueous solution with the mass percentage concentration of 10%, slowly dropwise adding the aqueous solution into the reaction solution through a dropping funnel, and reacting for 4 hours at 50 ℃; cooling to room temperature, separating with magnet, washing with distilled water for 5 times, and oven drying at 50 deg.C in vacuum drying oven to constant weight to obtain solid magnetic heavy metal ion separation material 3.04 g.
Example 5
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 435nm and 95mL of tetrahydrofuran are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then 6.00g of tetraethylenepentamine with the mass percentage concentration of 99.8% is added, and the mechanical stirring is assisted by ultrasonic waves for 3 hours. Heating to 60 ℃, slowly dripping 2.63mL of epoxy chloropropane with the mass percentage concentration of 99.0%, continuing to react for 3h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL toluene, mechanically stirring for 2.5h under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.42mL glutaraldehyde through the dropping funnel, and reacting for 3.5h at 70 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 5 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL distilled water, adding 19.63g sodium iminodiacetate, and stirring for dissolving; weighing 12.21g of glutaraldehyde and adding distilled water to prepare an aqueous solution with the mass percentage concentration of 20%, slowly dripping the aqueous solution into the reaction solution through a dropping funnel, and reacting for 3.5 hours at 70 ℃; cooling to room temperature, separating with magnetic adsorption and solution, washing with distilled water for 5 times, and oven drying in vacuum drying oven at 60 deg.C to constant weight to obtain solid magnetic heavy metal ion separation material 3.34 g.
Example 6
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 435nm and 80mL of tetrahydrofuran are added into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, 5.00g of tetraethylenepentamine with the mass percentage concentration of 99.8% is added, and the mechanical stirring is assisted by ultrasonic waves for 2.5 hours. Raising the temperature to 55 ℃, slowly dripping 2.30mL of epoxy chloropropane with the mass percentage concentration of 99.0%, continuing to react for 2.5h after finishing dripping, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid matter obtained by the separation in the step (1) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80mL of toluene, mechanically stirring for 3h under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.39mL of glutaraldehyde through the dropping funnel, and reacting for 3h at 80 ℃; cooled to room temperature, separated from the solvent by magnetic adsorption, and then washed 4 times with ethanol and distilled water, respectively.
(3) Transferring the solid substance obtained in the step (2) into a 250mL three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100mL distilled water, adding 14.03g sodium iminodiacetate, and stirring for dissolving; weighing 7.93g of glutaraldehyde and adding distilled water to prepare an aqueous solution with the mass percentage concentration of 10%, slowly dripping the aqueous solution into the reaction solution through a dropping funnel, and reacting for 4.0 hours at 50 ℃; cooling to room temperature, separating with magnet, washing with distilled water for 4 times, and drying in vacuum drying oven at 60 deg.C to constant weight to obtain solid magnetic heavy metal ion separation material 3.45 g.
The process flow diagram of the method of the invention is shown in fig. 1, and the structure of the resulting material is shown in fig. 2. The infrared spectrum characterization and transmission electron microscope scanning were performed on the materials obtained in examples 1 to 6, and the obtained results were substantially consistent. The material obtained in example 1 (denoted as Fe)3O4@ PM-IDA), infrared spectroscopy and transmission electron microscopy analysis results are shown in FIGS. 3 and 4.
FIG. 3 shows the following absorption peaks in the IR spectrum: fe3O43403.2cm in-1Stretching vibration peak for associated-OH, corresponding to 1628.7cm-1An absorption peak of bound water molecules, 1387.5cm-1Adsorption of-CH in organic molecules for preparative processes2Asymmetric stretching vibration peak of-1056.1 cm-1The stretching vibration peak of C-O-C in the organic molecules adsorbed in the preparation process is 628.8 and 574.9cm-1Is Fe3O4Characteristic absorption peak of middle Fe-O. With Fe3O4In comparison, when in Fe3O4After the surface is coated with the organic polymer chain network and the chelating group, the infrared spectrum is obviously changed at 2927.4 and 2865.1 cm-1Is in the form of-CH2Symmetric and asymmetric stretching vibration peaks of-corresponding to 1353.7cm-1Where its bending vibration peak occurs; at 1670.1cm-1Is imino diacetic acid radical-COO—At 1408.7 cm-1A symmetric stretching vibration peak of the group appears; at 1082.3 and 1042.2cm-1The weak peak of (a) is the stretching vibration peak of the C-N, C-O bond; fe3O4The characteristic absorption peak of the medium Fe-O is slightly shifted. The results show that the polymer chain network and the chelating group-N (CH) have been successfully synthesized2COO—)2Modification to magnetic Fe3O4The surface of the microsphere. FIG. 4 shows the results of transmission electron microscopy analysis in Fe3O4Coated with a thin layer of material further demonstrates the success of the polymer chain network and chelating groups-N (CH)2COO—)2Modification to Fe3O4On the microspheres.
Example 7
Samples obtained in examples 1 to 6 and ferroferric oxide microspheres with the average particle size of 435nm are taken as adsorbing materials and are respectively marked as 1#、2#、3#、4#、5#、6#And 7#Separately preparing a solution containing Cu2+、Ni2+、Cd2+And Pb2+The mass volume concentration of the simulated heavy metal water sample is 100 mg/L. Adsorption test conditions: (1) measuring adsorption capacity, respectively taking 50mL of simulated heavy metal water sample, placing in a100 mL conical flask, respectively weighing 25mg of adsorption material, adding into the conical flask, placing on a constant temperature shaking table, oscillating at 293K for 2h, and adsorbing with magnet to obtain solid particlesSeparating from the solution, measuring the concentration of the adsorbed heavy metal ions in the solution on an AA100 type atomic absorption spectrometer (PE company, USA), and calculating the adsorption capacity of the adsorption material; (2) measuring adsorption time, namely sampling and measuring the ion concentration at intervals of 5min according to the test method, and determining the time for reaching saturated adsorption; (3) and (3) heavy metal desorption and recovery, namely adsorbing the adsorption material with saturated adsorption by using a magnet to separate solid particles from the solution, washing the solid matters adsorbed by the magnet by using deionized water to remove the metal ions which are not adsorbed, then adding the solid matters into 0.01mol/L hydrochloric acid, oscillating the solid matters on a shaking table for 1h, adsorbing the solid particles from the solution by using the magnet, washing the solid particles by using the deionized water, measuring the amount of the eluted heavy metals, and calculating the recovery rate of the heavy metals, wherein the results are shown in Table 1.
TABLE 1 adsorption Properties of the products of the invention on heavy metal ions
Figure BDA0001508851100000081
As can be seen from Table 1, the product of the invention is on free Cu2+、Ni2+、Cd2+And Pb2+The plasma has good adsorption effect, high adsorption rate, short adsorption equilibrium time and far greater adsorption capacity than the ferroferric oxide microspheres (7) without modified chelating groups#) And has excellent elution regeneration performance. This is because the surface of the prepared solid magnetic heavy metal ion separation material is rich in-N (CH) after coating and modification2COO—)2、—NH2and-NH-and-OH, and the like, thereby greatly improving the chelating adsorption capacity of heavy metals. The product particle core of the invention is the magnetic ferroferric oxide microspheres, so the product particle core also has excellent magnetic separation performance, and after adsorption, only by using a magnet for attraction, the adsorption solution is quickly clarified without filtration or centrifugal separation.
According to the above test method, considering the loss of the adsorption material in the test process, the scale is enlarged by 100 times, i.e. firstly 2.5 g of sample is taken for test, the test scale is gradually reduced, and the adsorption material regenerated by elution is reused for adsorption of heavy metal ionsTo be attached to Cd2+The regeneration and recycling were examined, and the results of 5 recycling were shown in Table 2.
TABLE 2 Recycling of the product of the invention (for Cd)2+Adsorption of (2) as an example
Figure BDA0001508851100000082
The results in Table 2 show that the elution regeneration has little effect on the adsorption capacity, the time for reaching saturation adsorption in 5 elution cycles is basically unchanged, and the recovery rate is reduced but not much. Therefore, the solid magnetic heavy metal ion separation material has the advantages of good heavy metal recovery, regeneration of the adsorption material, recycling, long service life and the like.
The above are only preferred embodiments of the present invention, and those skilled in the art can make various modifications and changes to the process conditions for preparation according to the above concept of the present invention, and such modifications and changes are also within the spirit of the present invention.

Claims (8)

1. A preparation method of a solid magnetic heavy metal ion separation material is black solid powder, and the structure of the material is that iminodiacetic acid groups with strong chelating ability to various heavy metal ions, namely-N (CH), are wound and coated and modified on the surface of a magnetic ferroferric oxide microsphere2COO—)2The cage-like structure of (2), comprising the steps of:
(1) adding ferroferric oxide microspheres and a polar organic solvent into a reactor according to the mass-volume ratio of the ferroferric oxide microspheres to the polar organic solvent of 1: 40-50 g/ml, then adding polyethylene polyamine according to the mass ratio of the polyethylene polyamine to the ferroferric oxide microspheres of 1.5-3.0: 1, stirring for 2-3 h by an ultrasonic-assisted machine, then heating to 50-60 ℃, slowly dropwise adding epoxy chloropropane according to the mass ratio of the epoxy chloropropane to the polyethylene polyamine of 1.0-1.1: 1, after dropwise adding, continuing to react for 2-3 h, cooling to room temperature, and then separating solid substances by magnet attraction;
(2) transferring the solid matter obtained in the step (1) into a reactor, adding toluene according to the mass-volume ratio of the ferroferric oxide microspheres to the toluene of 1: 40-50 g/ml, stirring for 2-3 h by using an ultrasonic-assisted machine, measuring glutaraldehyde according to the mass ratio of the glutaraldehyde to the polyethylene polyamine of 1: 8-10, preparing a chloroform solution with the mass percentage concentration of 5-10%, slowly adding the chloroform solution into the reactor, and crosslinking for 3-4 h at the temperature of 60-80 ℃; cooling to room temperature, separating with a magnet and a solvent, and washing with ethanol and distilled water for 3-5 times;
(3) transferring the solid substance obtained in the step (2) into a reactor, adding distilled water with the mass 35-50 times of that of the solid substance, then weighing sodium iminodiacetate according to the mass ratio of the sodium iminodiacetate to the polyethylene polyamine of 2.0-4.0: 1.0, adding the sodium iminodiacetate into the reactor, and stirring for dissolving; then weighing the dialdehyde substances according to the mass ratio of 1.0-1.5: 1.0 of the dialdehyde substances to the sodium iminodiacetate substances to prepare aqueous solution with the mass percentage concentration of 10-20%, slowly dripping the aqueous solution into the reaction liquid, and reacting for 2-4 h at the temperature of 50-80 ℃; and cooling to room temperature, adsorbing with a magnet, separating from the solution, washing with distilled water for 3-5 times, and drying to obtain the solid magnetic heavy metal ion separation material.
2. The method for preparing the solid magnetic heavy metal ion separation material as claimed in claim 1, wherein the diameter of the ferroferric oxide microspheres is 200-500 nm.
3. The method for preparing a solid magnetic heavy metal ion separation material according to claim 1, wherein the polar organic solvent is absolute ethanol or tetrahydrofuran.
4. The method for preparing a solid magnetic heavy metal ion separation material according to claim 1, wherein the polyethylene polyamine is triethylene tetramine or tetraethylene pentamine.
5. The method for preparing a solid magnetic heavy metal ion separation material according to claim 1, wherein the dialdehyde substance is glyoxal or glutaraldehyde.
6. The method for preparing a solid magnetic heavy metal ion separation material according to claim 1, wherein the reactor is a three-necked flask.
7. The preparation method of the solid magnetic heavy metal ion separation material according to claim 1, wherein the drying is vacuum drying at a temperature of 50-70 ℃.
8. The method for preparing the solid magnetic heavy metal ion separation material according to claim 1, wherein the epichlorohydrin, the toluene, the glutaraldehyde, the chloroform, the ethanol and the sodium iminodiacetate are analytically pure.
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