CN108031439B - Magnetic solid chelating adsorption material and preparation method thereof - Google Patents
Magnetic solid chelating adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a magnetic solid chelating adsorption material and a preparation method thereof. Firstly, polymerizing epichlorohydrin and triethylene tetramine into a linear macromolecular chain in the presence of ferroferric oxide microspheres, and carrying out in-situ adsorption and winding on the surfaces of the ferroferric oxide microspheres; then dispersing the mixture in toluene, adding glutaraldehyde to further crosslink the polymer chains, thereby stably coating the polymer chains on the surface of the ferroferric oxide microspheres; and then in an aqueous solution, reacting carbon disulfide with active amino or imino on a polymer chain under the catalysis of sodium hydroxide to modify dithioformic acid group on the surface of ferroferric oxide so as to generate the magnetic solid chelating adsorption material. According to the invention, active groups such as dithioformic acid group, amino group, imino group and hydroxyl group are effectively modified on the surface of the ferroferric oxide microsphere, so that the trapping and adsorbing capacity of heavy metals is greatly improved, the magnetic separation performance is excellent, the subsequent separation is convenient, the continuous operation of adsorption and separation can be realized, and the industrial application and popularization are facilitated.
Description
Technical Field
The invention relates to the field of heavy metal wastewater treatment, in particular to a magnetic solid chelating adsorption material and a preparation method thereof.
Background
Due to the rapid development of industry and urbanization, excessive release of heavy metals to the environment has caused a major environmental problem on a global scale. Unlike most organic pollutants which can be degraded into harmless substances, heavy metals cannot be biodegraded and can be finally accumulated to a human body through a food chain to finally generate cumulative poisoning, so that the health of people is seriously harmed. Metal plating, mineral mining, tanning, chlor-alkali industries, radiator manufacturing, smelting, alloy and battery manufacturing, etc. all produce large amounts of waste water containing various heavy metals, such as cadmium, chromium, arsenic, copper, mercury, nickel, antimony, lead, manganese, zinc, etc. The heavy metals not only seriously harm the health of human bodies, but also cause huge economic loss, and become a great problem for restricting the development of the economy and the society of the international society and China and improving the livelihood of the people. Although various heavy metal wastewater treatment methods such as chemical precipitation, ferrite, ion exchange, flotation, membrane separation, electrochemical methods, adsorption, etc. have been developed, these methods have some disadvantages and shortcomings, and thus, there is still a lack of a generally applicable method. In comparison, the adsorption method is simple and efficient to operate, relatively low in cost, and highly adaptable to use environment, and is particularly suitable for the deep treatment of low-concentration wastewater or wastewater, so that the adsorption method receives increasingly wide attention in the field of heavy metal wastewater treatment, and becomes a very important heavy metal wastewater treatment method.
The adsorption method requires that the adsorption material not only has high adsorption capacity and long cycle service life for heavy metals, but also has good separation performance so as to facilitate continuous operation and industrial popularization and application, the adsorption capacity of the adsorption material mainly depends on the specific surface area and surface active groups of the adsorption material, and the porous material also comprises the pore structure, the pore size, the distribution and the like of the porous material, and the separation performance mainly depends on the granularity and the density of the adsorption material, and whether the material is easy to crush, refine, swell and solvate in the using process so as to be difficult to separate from a solvent—) Various heavy metal ions, e.g. Cd2+、Cu2+、Hg2+、Ni2+、Pb2+、Mn2+And Zn2+Etc. all have good effectsChelating ability. 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 dithioformic acid group (-CSS)—) The invention provides a magnetic solid chelating adsorption material with excellent heavy metal adsorption and trapping capacity and separation performance, and aims to provide a black solid chelating adsorption material which is wound on the surface of a magnetic ferroferric oxide microsphere, coated and modified with dithioformate groups (CSS) with strong chelating capacity to various heavy metal ions—) A cage structure formed by the polymer chain of (a); the method is characterized in that: (1) winding and wrapping a polymer chain with various active groups on magnetic ferroferric oxide particles, and then modifying dithioformic acid groups on 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 synthetic material not only has good chelating and trapping performance on heavy metals, but also can lead the adsorbing material to be conveniently separated from the treated water through a magnetic field, thereby realizing the continuity of the adsorption and separation process, improving the adsorption and separation effect and efficiency and being convenient for large-scale industrial application.
The invention also aims to provide a preparation method of the magnetic solid chelating adsorption material, which comprises the following steps:
(1) adding the ferroferric oxide microspheres and the 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, and mechanically stirring for 2-3 hours under the assistance of ultrasonic waves; 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, continuously reacting for 2-3 h after dropwise adding is finished, cooling to room temperature, and adsorbing and separating solid substances by using a magnet;
(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 2-4 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 40-50 times that of the solid substance, then weighing sodium hydroxide and adding the sodium hydroxide into the reactor according to the mass ratio of the sodium hydroxide, the carbon disulfide and the polyethylene polyamine of 2.2-3.9: 2.0-3.0: 1.0, measuring the carbon disulfide after dissolving and slowly dripping into the reactor, and continuing to react for 3-5 hours after the carbon disulfide is completely added; and then heating to 50-65 ℃ for reaction for 30-60 min, cooling to room temperature, adsorbing with a magnet to separate from the solution, washing with distilled water for 3-5 times, and drying to obtain the magnetic solid chelating adsorption 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 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 40-50 ℃.
Furthermore, the epichlorohydrin, toluene, glutaraldehyde, chloroform, ethanol, sodium hydroxide and carbon disulfide used were all analytically pure.
The invention relates to a magnetic solid chelating adsorption material and a preparation method thereof, and the magnetic solid chelating adsorption material is prepared by the steps of dispersing ferroferric oxide microspheres in a polar organic solvent containing polyethylene polyamine by ultrasonic waves, adding epichlorohydrin and triethylene tetramine to generate linear macromolecular chain adsorption, winding the linear macromolecular chain adsorption on the surfaces of the ferroferric oxide microspheres, separating the linear macromolecular chain adsorption from a reaction solution by using magnet adsorption, dispersing the linear macromolecular chain adsorption and the reaction solution in nonpolar toluene, adding glutaraldehyde to further crosslink the macromolecular chain wound on the surfaces of the ferroferric oxide microspheres, and stably coating the macromolecular chain on the surfaces of the ferroferric oxide microspheres; and then in the presence of sodium hydroxide, reacting carbon disulfide with active amino or imino on a polymer chain to modify dithioformic acid groups with strong chelating capacity to various heavy metal ions on the surface of ferroferric oxide to generate the magnetic solid chelating adsorption material. The magnetic ferroferric oxide microsphere can effectively and stably coat a polymer chain containing active groups such as amino, imino, hydroxyl and the like on the surface of the magnetic ferroferric oxide microsphere to form a cage-shaped structure, and a dithioformic acid group with strong chelation on various heavy metal ions is modified on the surface of the ferroferric oxide microsphere through further reaction, so that the surface of the ferroferric oxide microsphere contains rich chelation and coordination groups, the trapping and adsorbing capacity on the heavy metals is greatly improved, and meanwhile, the ferroferric oxide is coated in a polymer chain net, so that the ferroferric oxide microsphere 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) the method comprises the steps of dispersing ferroferric oxide microspheres in a polar organic solvent, reacting polyethylene polyamine with epichlorohydrin in the presence of the ferroferric oxide microspheres to generate linear macromolecules, winding and wrapping the linear macromolecules on the surfaces of the ferroferric oxide microspheres in situ, further crosslinking polymer chains wound and wrapped on the surfaces of particles through glutaraldehyde to form a polymer chain network, and stably wrapping a wrapping layer on the surfaces of the ferroferric oxide microspheres, so that the stability of an adsorption material is obviously improved. Meanwhile, polyethylene polyamine and epoxy chloropropane are subjected to polymerization reaction to generate a polymer chain, and active groups such as hydroxyl, amino, imino and the like are effectively modified on the surface of the ferroferric oxide microsphere, so that the active groups can be further converted into dithioformic acid groups with strong chelating capacity for heavy metals.
(2) After the ferroferric oxide microspheres wound and adsorbed with polymer chains are dispersed in toluene, glutaraldehyde is added for crosslinking, so that the falling of the water-soluble polymer chains from the surfaces of the microspheres is reduced, and the amount of the coated polymer chains is ensured, thereby 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 of ferroferric oxide microspheres wrapped by polymer chains, the interference of nonmagnetic substances is reduced, and the surface wrapping layers of the ferroferric oxide microspheres are more uniform.
(4) The product particles of the invention are in a cage-like structure with magnetic ferroferric oxide microspheres as cores and polymer chain nets containing abundant active groups of dithioformic acid, hydroxyl, amino and imino on the surfaces, so that the product has excellent capability of chelating and trapping heavy metals and excellent magnetic separation performance, the trapping and adsorption capability of the heavy metals is greatly improved, the problems that the adsorption material is complicated to separate and cannot be continuously operated after adsorbing the heavy metals are effectively solved, the continuous operation of efficient removal and adsorption separation of the heavy metals can be realized, and the invention is convenient for industrial popularization and application.
Drawings
FIG. 1 is a block diagram of a process for preparing the present invention;
FIG. 2 is a structural diagram of the magnetic solid chelate adsorbent of the present invention;
FIG. 3 is an infrared spectrum of the magnetic solid chelate adsorbent obtained in example 1 of the present invention;
FIG. 4 is a transmission electron microscope image of the magnetic solid chelate adsorbent 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) Adding 2.0g of ferroferric oxide microspheres with the average particle size of 430nm and 100m L of absolute ethyl alcohol into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then adding 4.00g of 95.0 mass percent triethylene tetramine, ultrasonically assisting the mechanical stirring for 3h, heating to 60 ℃, slowly dropwise adding 2.4m L mass percent of 99.0 mass percent of epoxy chloropropane, after the dropwise adding is finished, continuing to react for 3h, cooling to room temperature, and then adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100m L of toluene, mechanically stirring for 3 hours under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.36m L of glutaraldehyde through the dropping funnel, reacting for 3 hours at 70 ℃ after dropwise adding, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 5 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 110m L of distilled water, adding 3.24g of solid NaOH, stirring and dissolving, slowly adding 4.2m L of carbon disulfide dropwise at room temperature, continuing stirring for 4 hours after adding, then heating to 60 ℃, continuing to react for 50 minutes, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 5 times, and drying in a vacuum drying oven at 40 ℃ to constant weight to obtain 2.67g of the magnetic solid chelate adsorption material.
Example 2
(1) Adding 2.0g of ferroferric oxide microspheres with the average particle size of 340nm and 90m L of absolute ethyl alcohol into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then adding 4.50g of 95.0 mass percent triethylene tetramine, carrying out ultrasonic-assisted mechanical stirring for 2.5h, heating to 55 ℃, slowly dropwise adding 2.6m L mass percent of 99.0 mass percent of epoxy chloropropane, after dropwise adding, continuing to react for 2.5h, cooling to room temperature, and adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 90m L toluene, mechanically stirring for 2h under the assistance of ultrasonic waves, slowly dropwise adding a 7.0 mass percent chloroform solution prepared from 0.33m L glutaraldehyde through the dropping funnel, reacting at 80 ℃ for 3h after dropwise adding, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 4 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100m L of distilled water, adding 3.08g of solid NaOH, stirring and dissolving, slowly adding 4.0m L of carbon disulfide dropwise at room temperature, continuing stirring for 3 hours after adding, then heating to 65 ℃, continuing to react for 30 minutes, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 4 times, and drying in a vacuum drying oven at 50 ℃ to constant weight to obtain 2.79g of the magnetic solid chelate adsorption material.
Example 3
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 218nm and 80m L of absolute ethyl alcohol are added into a 250m L 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, the mechanical stirring is assisted by ultrasonic waves for 3h, the temperature is raised to 50 ℃, 2.97m L of epoxy chloropropane with the mass percentage concentration of 99.0% is slowly dripped, the reaction is continued for 3h after the dripping is finished, the reaction is cooled to the room temperature, and solid substances are separated by magnet adsorption.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100m L toluene, mechanically stirring for 3h under the assistance of ultrasonic waves, slowly dropwise adding 10.0% by mass of chloroform solution prepared from 0.41m L glutaraldehyde through the dropping funnel, reacting at 80 ℃ for 3h after dropwise adding, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 5 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 90m L of distilled water, adding 4.10g of solid NaOH, stirring and dissolving, slowly adding 5.3m L of carbon disulfide dropwise at room temperature, continuing stirring for 5 hours after adding, then heating to 50 ℃, continuing to react for 60 minutes, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 5 times, and drying in a vacuum drying oven at 40 ℃ to constant weight to obtain 2.61g of the magnetic solid chelate adsorption material.
Example 4
(1) Adding 2.0g of ferroferric oxide microspheres with the average particle size of 275nm and 100m L of absolute ethyl alcohol into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then adding 3.00g of 95.0 mass percent triethylene tetramine, carrying out ultrasonic-assisted mechanical stirring for 2h, heating to 60 ℃, slowly dropwise adding 1.62m L mass percent of 99.0 mass percent of epoxy chloropropane, continuing to react for 2h after the dropwise adding is finished, cooling to room temperature, and then adsorbing and separating solid substances by using a magnet.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 90m L toluene, mechanically stirring for 2h under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.24m L glutaraldehyde through the dropping funnel, reacting for 4h at 60 ℃, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 3 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80m L of distilled water, adding 1.81g of solid NaOH, stirring and dissolving, slowly adding 2.53m L of carbon disulfide dropwise at room temperature, continuing stirring for 3 hours after adding, then heating to 60 ℃, continuing to react for 40 minutes, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 3 times, and drying in a vacuum drying oven at 50 ℃ to constant weight to obtain 2.37g of the magnetic solid chelate adsorption material.
Example 5
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 435nm and 95m L of tetrahydrofuran are taken and added into a 250m L 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 percent is added, the mechanical stirring is assisted by ultrasonic waves for 3h, the temperature is raised to 60 ℃, 2.63m L of epichlorohydrin with the mass percentage concentration of 99.0 percent is slowly dripped, the reaction is continued for 3h after the dripping is finished, the reaction is cooled to the room temperature, and then solid substances are adsorbed and separated by a magnet.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100m L of toluene, mechanically stirring for 2.5 hours under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.42m L of glutaraldehyde through the dropping funnel, reacting at 70 ℃ for 3.5 hours after dropwise adding, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 5 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 100m L of distilled water, adding 4.94g of solid NaOH, stirring and dissolving, slowly adding 4.51m L of carbon disulfide dropwise at room temperature, continuing stirring for 5 hours after adding, then heating to 50 ℃, continuing to react for 40 minutes, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 5 times, and drying in a vacuum drying oven at 45 ℃ to constant weight to obtain 2.89g of the magnetic solid chelate adsorption material.
Example 6
(1) 2.0g of ferroferric oxide microspheres with the average particle size of 435nm and 80m of L tetrahydrofuran are taken and added into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, then 5.00g of tetraethylenepentamine with the mass percentage concentration of 99.8% is added, the mechanical stirring is assisted by ultrasonic waves for 2.5h, the temperature is raised to 55 ℃, 2.30m L of epichlorohydrin with the mass percentage concentration of 99.0% is slowly dripped, the reaction is continued for 2.5h after the dripping is finished, the reaction is cooled to the room temperature, and solid substances are adsorbed and separated by a magnet.
(2) Transferring the solid substance separated in the step (1) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80m L of toluene, mechanically stirring for 3 hours under the assistance of ultrasonic waves, slowly dropwise adding a 5.0 mass percent chloroform solution prepared from 0.39m L of glutaraldehyde through the dropping funnel, reacting for 3 hours at 80 ℃ after dropwise adding, cooling to room temperature, separating with a solvent by magnet adsorption, and washing with ethanol and distilled water for 4 times respectively.
(3) Transferring the solid matter obtained in the step (2) into a 250m L three-necked bottle with a dropping funnel, a reflux condenser tube and mechanical stirring, adding 80m L of distilled water, adding 3.80g of solid NaOH, stirring and dissolving, slowly adding 3.4m L of carbon disulfide dropwise at room temperature, continuing stirring for 3h after adding, then heating to 50 ℃, continuing to react for 60min, cooling to room temperature, separating with a magnet to separate from the solution, washing with distilled water for 5 times, and drying in a vacuum drying oven at 50 ℃ to constant weight to obtain 2.67g of the magnetic solid chelate adsorption material.
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-CS2) For example, the results of IR spectroscopy and transmission electron microscopy 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 2923.8 and 2825.7cm-1Is in the form of-CH2Symmetric and asymmetric stretching vibration peaks of-corresponding to 1349.8cm-1Where its bending vibration peak occurs; at 1447.9cm-1Being aminodithioformic acid groups (N-CSS)—) Middle C-N stretching vibration absorption peak, 972.4cm-1is-CSS—C ═ S and C — S stretching vibration peaks; at 1038.2cm-1The weak peak of (a) is a stretching vibration peak of the 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-CSS have been successfully synthesized—Modification 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 proves that the polymer chain network and the chelating group-CSS have been successfully formed—Modification to Fe3O4On the microspheres.
Example 7
The samples obtained in examples 1 to 6 were used as adsorbents and were each designated as 1#、2#、3#、4#、5#And 6#Separately preparing Cr-containing3+、Zn2+、Cd2+And Pb2+The method comprises the following steps of (1) measuring adsorption capacity, respectively taking 50m L simulated heavy metal water samples to be placed in 100m L erlenmeyer flasks, weighing 25mg of the prepared adsorption material and 25mg of magnetic ferroferric oxide, placing the adsorption material and the magnetic ferroferric oxide on a constant-temperature shaking bed, oscillating for 2 hours at 25 ℃, separating solid particles from solution by using magnet adsorption, measuring the concentration of adsorbed heavy metal ions by taking the solution on an AA100 type atomic absorption spectrometer (American PE company), calculating the adsorption capacity of the adsorption material, (2) measuring adsorption time, sampling and measuring the ion concentration by taking 5min as a time interval according to the test method, determining the time for reaching saturated adsorption, (3) desorbing and recovering the heavy metal, separating the adsorbed saturated adsorption material from the solution by using the magnet, washing the unadsorbed metal ions by using deionized water, then adding the heavy metal ions into 0.01 mol/L hydrochloric acid, oscillating for 1 hour on the shaking bed, separating the solid particles from the solution by using the magnet adsorption, measuring the washing amount of the heavy metal ions, and calculating the recovery rate of the heavy metal, wherein the heavy metal is shown in the table 1.
TABLE 1 adsorption Properties of the products of the invention on heavy metal ions
As can be seen from Table 1, the product of the present invention is directed to free Cr3+、Zn2+、Cd2+And Pb2+The plasma has higher adsorption capacity, high adsorption rate, short adsorption equilibrium time, far greater adsorption capacity than that of the ferroferric oxide microspheres without modified chelating groups, and excellent elution regeneration performance. This is because the surface of the magnetic solid chelate adsorption material contains abundant active groups such as dithioformate, amino, imino, hydroxyl, etc., and thus, the chelate adsorption capacity for heavy metal ions is greatly improved. In addition, the product particle core is the magnetic ferroferric oxide microspheres, so the product particle has excellent magnetic separation performance, and the adsorption solution is quickly clarified by only using a magnet after adsorption 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, namely, 2.5g of sample is firstly taken for test, the test scale is gradually reduced, and the adsorption material regenerated by elution is reused for adsorption of heavy metal ions so as to adsorb Pb2+The regeneration and recycling were examined, and the results of 5 recycling were shown in Table 2.
TABLE 2 Recycling of the products according to the invention (for Pb)2+Adsorption of (2) as an example
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 magnetic solid chelating adsorption material has the advantages of good heavy metal recovery, adsorption material regeneration, 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. The magnetic solid chelating adsorption material is characterized by being black solid powder, and the structure of the magnetic solid chelating adsorption material is that dithioformic acid groups with strong chelating capacity for various heavy metal ions, namely CSS, are wound and coated and modified on the surface of a magnetic ferroferric oxide microsphere—A cage structure formed by the polymer chain of (a);
the preparation method of the magnetic solid chelating adsorption material 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 2-4 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 matters obtained in the step (2) into a reactor, adding distilled water with the mass 40-50 times that of the solid matters, then weighing sodium hydroxide and adding the sodium hydroxide into the reactor according to the mass ratio of the sodium hydroxide, the carbon disulfide and the polyethylene polyamine of 2.2-3.9: 2.0-3.0: 1.0, measuring the carbon disulfide after dissolving and slowly dripping into the reactor, and continuing to react for 3-5 hours after the carbon disulfide is completely added; and then heating to 50-65 ℃ for reaction for 30-60 min, cooling to room temperature, adsorbing with a magnet to separate from the solution, washing with distilled water for 3-5 times, and drying to obtain the magnetic solid chelating adsorption material.
2. The method for preparing the magnetic solid chelate adsorption material according to claim 1, 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 2-4 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 matters obtained in the step (2) into a reactor, adding distilled water with the mass 40-50 times that of the solid matters, then weighing sodium hydroxide and adding the sodium hydroxide into the reactor according to the mass ratio of the sodium hydroxide, the carbon disulfide and the polyethylene polyamine of 2.2-3.9: 2.0-3.0: 1.0, measuring the carbon disulfide after dissolving and slowly dripping into the reactor, and continuing to react for 3-5 hours after the carbon disulfide is completely added; and then heating to 50-65 ℃ for reaction for 30-60 min, cooling to room temperature, adsorbing with a magnet to separate from the solution, washing with distilled water for 3-5 times, and drying to obtain the magnetic solid chelating adsorption material.
3. The method for preparing the magnetic solid chelating adsorption material as claimed in claim 2, wherein the diameter of the magnetic ferroferric oxide microspheres is 200-500 nm.
4. The method for preparing a magnetic solid chelate adsorption material according to claim 2, wherein the polar organic solvent is absolute ethanol or tetrahydrofuran.
5. The method for preparing a magnetic solid chelate adsorption material according to claim 2, wherein the polyethylene polyamine is triethylene tetramine or tetraethylene pentamine.
6. The method for preparing the magnetic solid chelate adsorption material according to claim 2, wherein the reactor is a three-necked flask.
7. The preparation method of the magnetic solid chelating adsorption material according to claim 2, characterized in that the drying is vacuum drying at 40-50 ℃.
8. The method for preparing the magnetic solid chelating adsorption material of claim 2, wherein the epichlorohydrin, the toluene, the glutaraldehyde, the chloroform, the ethanol, the sodium hydroxide and the carbon disulfide are analytically pure.
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| CN110115983B (en) * | 2019-05-20 | 2022-03-22 | 湖南科技大学 | Solid cyclodextrin-based chelating and decolorizing adsorption material and preparation method thereof |
| CN110115982B (en) * | 2019-05-20 | 2022-03-25 | 湖南科技大学 | Magnetic cyclodextrin-based chelating and decolorizing adsorption material and preparation method thereof |
| CN110115984B (en) * | 2019-05-20 | 2022-03-22 | 湖南科技大学 | Magnetic cyclodextrin-based cross-linked polymer adsorption material and preparation method thereof |
| CN112844297A (en) * | 2021-01-15 | 2021-05-28 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Preparation method of magnetic heavy metal ion chelating agent and obtained product |
| CN112808239A (en) * | 2021-01-15 | 2021-05-18 | 山东省地质矿产勘查开发局八〇一水文地质工程地质大队 | Method for treating heavy metal ions in water body |
| CN113786820B (en) * | 2021-10-11 | 2023-11-17 | 中科南京绿色制造产业创新研究院 | Functionalized ferroferric oxide particles and preparation method and application thereof |
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