CN113680333A - Magnetic hyperbranched adsorbent for removing heavy metal ions and preparation method thereof - Google Patents
Magnetic hyperbranched adsorbent for removing heavy metal ions and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of heavy metal pollution treatment, in particular to a magnetic hyperbranched adsorbent for removing heavy metal ions and a preparation method thereof. The application provides a magnetic hyperbranched adsorbent for removing heavy metal ions, which comprises the following raw materials in parts by mass: fe3O420-70 parts of particles, 15-25 parts of oleic acid, 30-80 parts of methanol, 5-15 parts of tetraethyl orthosilicate, 10-15 parts of 3-aminopropyltriethoxysilane, and 40-E of itaconic acid80 parts of triethanolamine, 30-60 parts of triethanolamine, 5-25 parts of succinic acid and 15-30 parts of N, N-dimethylformamide. The magnetic hyperbranched adsorbent provided by the application shows good adsorption performance to heavy metal ions, and has a good recycling effect.
Description
Technical Field
The application relates to the technical field of heavy metal pollution treatment, in particular to a magnetic hyperbranched adsorbent for removing heavy metal ions and a preparation method thereof.
Background
With the development of mineral resources, the phenomenon of heavy metal pollution in water bodies in mining areas is gradually serious, the heavy metal pollution has accumulation and non-biodegradability, and the low-concentration heavy metal can damage the health of people after being transmitted through food chains.
The technology for treating the heavy metal in the water body comprises a chemical precipitation method, an electrolysis method, a chemical adsorption method and the like, wherein the chemical precipitation method and the electrolysis method have the defects of high cost, complex treatment process, poor treatment effect and the like, and the chemical adsorption method has a simple process and high treatment efficiency, so that more and more attention is paid. In recent years, the main adsorption materials used in the chemical adsorption method include bentonite, activated carbon and the like, which are difficult to re-separate from the water body after adsorption is completed and easily cause secondary environmental pollution, so researchers have developed magnetic adsorption materials, such as Fe, which can be rapidly separated from the water body under the action of an external magnetic field3O4And (3) granules. However, magnetic Fe3O4When the nano particles are independently used as an adsorbent, the phenomenon of particle agglomeration is easy to occur, and Fe3O4The nano particles are easy to corrode in a wastewater environment and lose performance, so that the adsorption rate is influenced.
Based on the above analysis, how to align magnetic Fe3O4The treatment of nanoparticles to improve the adsorption performance of the nanoparticles on heavy metal ions is an urgent problem to be solved.
Disclosure of Invention
The embodiment of the application provides a magnetism hyperbranched adsorbent for heavy metal ion gets rid of, and the magnetism hyperbranched adsorbent that this application provided shows good adsorption efficiency to heavy metal ion, and has better reuse effect.
In a first aspect, an embodiment of the present application provides a magnetic hyperbranched adsorbent for removing heavy metal ions, including the following raw materials in parts by mass: fe3O420-70 parts of particles, 15-25 parts of oleic acid, 30-80 parts of methanol, 5-15 parts of tetraethyl orthosilicate, 10-15 parts of 3-aminopropyltriethoxysilane, 40-80 parts of itaconic acid, 30-60 parts of triethanolamine, 5-25 parts of succinic acid and 15-30 parts of N, N-dimethylformamide.
In some embodiments, the hyperbranched adsorbent comprises the following parts by mass of raw materials: fe3O440 parts of particles, 20 parts of oleic acid, 60 parts of methanol, 10 parts of tetraethyl orthosilicate, 12 parts of 3-aminopropyltriethoxysilane, 50 parts of itaconic acid, 40 parts of triethanolamine, 25 parts of succinic acid and 30 parts of N, N-dimethylformamide.
In some embodiments, the hyperbranched adsorbent comprises the following parts by mass of raw materials: fe3O455 parts of particles, 15 parts of oleic acid, 40 parts of methanol, 8 parts of tetraethyl orthosilicate, 15 parts of 3-aminopropyltriethoxysilane, 40 parts of itaconic acid, 30 parts of triethanolamine, 15 parts of succinic acid and 25 parts of N, N-dimethylformamide.
In some embodiments, the hyperbranched adsorbent comprises the following parts by mass of raw materials: fe3O425 parts of particles, 15 parts of oleic acid, 50 parts of methanol, 6 parts of tetraethyl orthosilicate, 10 parts of 3-aminopropyltriethoxysilane, 45 parts of itaconic acid, 35 parts of triethanolamine, 15 parts of succinic acid and 25 parts of N, N-dimethylformamide.
In a second aspect, the present application provides a preparation method of the above magnetic hyperbranched adsorbent for heavy metal ion removal, including the following steps:
step S101, adding Fe3O4Adding the particles and oleic acid into methanol, and performing ultrasonic dispersion to obtain a dispersion liquid;
step S102, adding tetraethyl orthosilicate into the dispersion liquid, and heating to react to obtain Fe3O4@SiO2Particles;
step S103, adding Fe3O4@SiO2Adding 3-aminopropyl triethoxysilane into the particles, heating and reacting to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding itaconic acid and triethanolamine into N, N-dimethylformamide, stirring for dissolving, and heating for reaction to obtain a prepolymer;
step S105, adding succinic acid into the prepolymer obtained in the step S104 for reaction, and after the reaction is finished, concentrating and drying to obtain a hyperbranched polymer;
step S106, for Fe3O4@SiO2-NH2And (4) carrying out ultrasonic dispersion on the particles, then adding the hyperbranched polymer prepared in the step (S105), heating for reaction, and after the reaction is finished, cleaning and drying to obtain the magnetic hyperbranched adsorbent.
In some embodiments, the heating temperature in step S102 is 50-70 ℃.
In some embodiments, the heating temperature in step S103 is 65-80 ℃.
In some embodiments, the heating temperature in step S104 is 115-130 ℃.
In some embodiments, the heating temperature in step S106 is 40-55 ℃.
In a third aspect, the embodiment of the present application provides an application of the above magnetic hyperbranched adsorbent for removing heavy metal ions, where the magnetic hyperbranched adsorbent is used for Pb in water body in a mining area2+、Cd2+And Cu2+Adsorption of heavy metal ions.
The preparation method provided by the application adopts itaconic acid, triethanolamine and succinic acid to react to obtain the hyperbranched polymer with the terminal group of carboxyl, the hyperbranched polymer contains a large amount of carboxyl groups, and the large amount of carboxyl groups can react with Fe3O4@SiO2-NH2The amino group in the material undergoes condensation acylation reaction, so that the hyperbranched polymer is modified in Fe3O4@SiO2-NH2Surface of (2), increasing Fe3O4@SiO2-NH2Stability of (2).
The application provides a contain a large amount of carboxyl groups and acylamino group in the magnetism hyperbranched adsorbent, carboxyl and heavy metal ion complex formation complex, and the carboxyl that produces after the acylamino hydrolyzes also can be complexed with heavy metal ion for this magnetism hyperbranched adsorbent has better adsorption performance, adsorbs the back of accomplishing, utilizes Fe3O4The magnetic property of the adsorbent can quickly separate the adsorbent from the water body.
The beneficial effect that technical scheme that this application provided brought includes:
1. the magnetic hyperbranched adsorbent provided by the application shows good adsorption performance on heavy metal ions and can adsorb Pb2+、Cd2+And Cu2+The saturated adsorption amounts of (A) and (B) were 203.6mg g-1、109.9mg·g-1、93.9mg·g-1The adsorbent has better recycling effect;
2. the magnetic hyperbranched adsorbent provided by the application has magnetism, and is convenient for rapid separation from a water body in a mining area after adsorption is completed;
3. the magnetic hyperbranched adsorbent provided by the application has better stability and is less influenced by interference cations;
4. the magnetic hyperbranched adsorbent provided by the application can effectively relieve the severe situation that heavy metals cause harm to the surrounding water environment of a mining area, and provides a new technology for promoting the application of the functional adsorbent in the field of restoration of the water environment of the mining area.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for preparing a magnetic hyperbranched adsorbent for heavy metal ion removal provided in an embodiment of the present application;
FIG. 2 is a reaction scheme for preparing a magnetic hyperbranched adsorbent according to the present application;
FIG. 3 is a graph showing the results of an isothermal adsorption test of the magnetic hyperbranched adsorbent prepared in example 1 of the present application;
FIG. 4 is a graph showing the measurement results of the reusability of the magnetic hyperbranched adsorbent prepared in example 1 of the present application;
FIG. 5 shows the adsorption of interfering cations to Pb by the magnetic hyperbranched adsorbent prepared in example 1 of the present application2+Schematic diagram of the effect of (c).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a magnetism hyperbranched adsorbent for heavy metal ion gets rid of, and the magnetism hyperbranched adsorbent that this application provided shows good adsorption efficiency to heavy metal ion, and has better reuse effect.
Referring to fig. 1, an embodiment of the present application provides a method for preparing a magnetic hyperbranched adsorbent for heavy metal ion removal, comprising the following steps:
step S101, 20-70 parts by mass of Fe3O4Dispersing the particles and 15-25 parts of oleic acid in 30-80 parts of methanol for ultrasonic dispersion treatment to obtain a dispersion liquid;
step S102, adding 5-15 parts by mass of tetraethyl orthosilicate (TEOS) into the dispersion liquid obtained in step S101, and stirring and reacting at 50-70 ℃ for 10 hours to obtain Fe3O4@SiO2Particles;
step S103, adding Fe in parts by mass to the step S1023O4@SiO2Adding 10-15 parts of 3-Aminopropyltriethoxysilane (APTES) into the particles) Continuously stirring and reacting for 10h at 65-80 ℃, discharging to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding 40-80 parts by mass of itaconic acid and 30-60 parts by mass of triethanolamine into 15-30 parts by mass of N, N-dimethylformamide, stirring and dissolving, transferring the dissolved mixed solution into a three-neck flask connected with a mechanical stirrer and a condenser tube, and adding the N-dimethyl formamide into the three-neck flask2Under the protection condition, heating to 115-130 ℃, and reacting for 4 hours to obtain a prepolymer;
step S105, adding 5-25 parts by mass of succinic acid into the prepolymer obtained in the step S104, continuing to react for 4 hours, after the reaction is finished, evaporating and concentrating the obtained reaction product by using a rotary evaporator, and then drying in vacuum at 120 ℃ to obtain a hyperbranched polymer, which is recorded as HBP-COOH;
step S106, adding Fe3O4@SiO2-NH2Dispersing the particles in distilled water, performing ultrasonic dispersion for 30min, adding the hyperbranched polymer HBP-COOH obtained in the step S105, stirring and reacting for 20h at 40-55 ℃, cleaning with distilled water, performing vacuum drying for 24h at 50 ℃, cooling, and discharging to obtain the magnetic hyperbranched adsorbent.
In the above preparation process, the reaction formula of the magnetic hyperbranched adsorbent prepared in steps S104-S106 is shown in FIG. 2, the substance with the structure of formula (I) represents a prepolymer, the substance with the structure of formula (II) represents a hyperbranched polymer HBP-COOH, the substance with the structure of formula (III) represents a magnetic hyperbranched adsorbent, and the sphere represents Fe3O4@SiO2-NH2Particles.
The following provides a detailed description of the magnetic hyperbranched adsorbent for removing heavy metal ions and the preparation method thereof with reference to the examples.
Example 1:
embodiment 1 of the present application provides a method for preparing a magnetic hyperbranched adsorbent for heavy metal ion removal, comprising the following steps:
step S101, 40 parts by mass of Fe3O4The particles and 20 parts oleic acid were dispersed in 60 parts methanolPerforming ultrasonic dispersion treatment to obtain dispersion liquid;
step S102, adding 10 parts by mass of tetraethyl orthosilicate (TEOS) into the dispersion, and stirring and reacting at 60 ℃ for 10 hours to obtain Fe3O4@SiO2Particles;
step S103, by mass, adding Fe3O4@SiO2Adding 12 parts of 3-Aminopropyltriethoxysilane (APTES) into the particles, continuously stirring at 70 ℃ for reaction for 10 hours, and discharging to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding 50 parts by mass of itaconic acid and 40 parts by mass of triethanolamine into 30 parts by mass of N, N-dimethylformamide, stirring and dissolving, then transferring the dissolved mixed solution into a three-mouth bottle connected with a mechanical stirrer and a condenser tube, and dissolving in N2Under the protection condition, heating to 120 ℃ and reacting for 4h to obtain a prepolymer;
step S105, adding 25 parts by mass of succinic acid into the prepolymer to continue reacting for 4 hours, after the reaction is finished, evaporating and concentrating the obtained reaction product by using a rotary evaporator, and then drying in vacuum at 120 ℃ to obtain a hyperbranched polymer HBP-COOH;
step S106, adding Fe3O4@SiO2-NH2Dispersing the particles in distilled water and performing ultrasonic dispersion for 30 min; and then adding hyperbranched polymer HBP-COOH, stirring and reacting for 20h at 45 ℃, washing with distilled water, vacuum drying for 24h at 50 ℃, cooling, and discharging to obtain the magnetic hyperbranched adsorbent.
The magnetic hyperbranched adsorbent prepared in example 1 was tested for performance by the following specific method:
for one, to Pb2+、Cd2+、Cu2+Isothermal adsorption test of (1):
(1) 0.800g of the magnetic hyperbranched adsorbent prepared in example 1 was divided into eight parts on average, and each 0.100g of the magnetic hyperbranched adsorbent was added to Pb (NO) (0.001 mol/L, 0.002mol/L, 0.003mol/L, 0.005mol/L, 0.008mol/L, 0.01mol/L, 0.02mol/L, 0.03 mol/L) at a concentration of Pb (NO)3)2In solution, each portionPb(NO3)2The volume of the solution is 100mL, the pH value of the solution is adjusted to be 4.5, the solution is placed in a constant temperature oscillator at 55 ℃ for oscillation for 120min, then the magnetic hyperbranched adsorbent is separated by adopting a centrifugal method, and the Pb in the supernatant is measured2+And calculating the relationship between the equilibrium concentration and the adsorption capacity of the solution;
(2) 0.800g of the magnetic hyperbranched adsorbent prepared in example 1 was divided into eight parts on average, and 0.100g of each part of the magnetic hyperbranched adsorbent was added to Cd (NO) (0.001 mol/L, 0.002mol/L, 0.003mol/L, 0.005mol/L, 0.008mol/L, 0.01mol/L, 0.02mol/L, 0.03 mol/L) at concentrations3)2In solution, each Cd (NO)3)2The volume of the solution is 100mL, the pH value of the solution is adjusted to be 4.5, the solution is placed in a constant temperature oscillator at 55 ℃ for oscillation for 120min, then the magnetic hyperbranched adsorbent is separated by adopting a centrifugal method, and Cd in the supernatant is measured2+And calculating the relationship between the equilibrium concentration and the adsorption capacity of the solution;
(3) 0.800g of the magnetic hyperbranched adsorbent prepared in example 1 was divided into eight parts on average, and 0.100g of each part of the magnetic hyperbranched adsorbent was added to Cu (NO) (0.001 mol/L, 0.002mol/L, 0.003mol/L, 0.005mol/L, 0.008mol/L, 0.01mol/L, 0.02mol/L, 0.03 mol/L) at a concentration of Cu (NO)3)2In solution, each part of Cu (NO)3)2The volume of the solution is 100mL, the pH value of the solution is adjusted to be 4.5, the solution is placed in a constant temperature oscillator at 55 ℃ for oscillation for 120min, then the magnetic hyperbranched adsorbent is separated by adopting a centrifugal method, and the Cu in the supernatant is measured2+And calculating the relationship between the equilibrium concentration and the adsorption capacity of the solution;
the results of the isothermal adsorption test are shown in FIG. 3, and it can be seen from FIG. 3 that Pb is accompanied by Pb2+、Cd2+And Cu2+Increase of equilibrium concentration, magnetic hyperbranched adsorbent for Pb2+、Cd2+And Cu2+The adsorption capacity of the magnetic hyperbranched adsorbent shows a trend that the adsorption capacity is increased rapidly and then tends to be gentle, and the magnetic hyperbranched adsorbent has good adsorption capacity for Pb2+、Cd2+And Cu2+The saturated adsorption amounts of (A) and (B) were 203.6mg g-1、109.9mg·g-1、93.9mg·g-1(ii) a In addition, it can be seen from FIG. 3 that the magnetic hyperbranched adsorbent is directed to Pb2+The saturated adsorption capacity of the catalyst is far more than that of Cd2+And Cu2+The saturated adsorption amount of (a), which indicates that the adsorbent is adsorbing Pb2+The adsorption of the lead-zinc ore deposit is more biased and is suitable for removing lead in water around the lead-zinc ore deposit.
Secondly, measuring the repeated use performance: to 100mL of Pb (NO) with a concentration of 200mg/L3)2Adding 0.100g of the magnetic hyperbranched adsorbent prepared in example 1 into the solution, adjusting the pH of the solution to 4.5, placing the solution in a constant temperature oscillator at 55 ℃ for oscillation for 120min, performing magnetic separation on the adsorbent after adsorption, and further using 0.1 mol.L-1Eluting with deionized water to neutrality, and applying the adsorbent to Pb2+The adsorption capacity was calculated, and the above-mentioned method was repeated to obtain adsorption performance of the adsorbent which was reused 15 times, and the results are shown in fig. 4.
As can be seen from FIG. 4, as the number of regeneration cycles of the adsorption-desorption cycle increases, the adsorbent is responsible for Pb2+Shows a tendency of gradually decreasing, and after 10 consecutive cycles, the adsorbent is used for adsorbing Pb2+The removal rate of the adsorbent is still kept above 60%, which shows that the adsorbent has good recycling effect and is a blotting adsorption material with good performance and capable of realizing rapid separation.
Thirdly, interfering the cation to adsorb Pb by the adsorbent2+The influence of (a): four portions of the solution with the volume of 100mL and the concentration of 0.01 mol.L are measured-1Pb (NO) of3)2Solution to each part of Pb (NO)3)20.100g of each of the magnetic hyperbranched adsorbents obtained in example 1 was added to the solutions, and then separately added to Pb (NO)3)2The solution was added in a volume of 100mL and a concentration of 0.01 mol. L-1Interfering cation K of+、Na+、Mg2+、Ca2+Adjusting pH to 4.5, placing in a constant temperature oscillator at 55 deg.C, oscillating for 120min, centrifuging to separate adsorbent, and measuring Pb in supernatant2+And calculating the residual concentration of the adsorbent to Pb2+Is suckedThe results are shown in FIG. 5.
As can be seen from FIG. 5, the adsorbent is for Pb in the presence of interfering cations2+Still maintains the removal effect of more than 50 percent, which shows that the adsorbent has better stability and good Pb resistance2+The adsorptivity of (A) is as follows.
Example 2:
step S101, 55 parts by mass of Fe3O4Dispersing the particles and 15 parts of oleic acid in 40 parts of methanol for ultrasonic dispersion treatment to obtain a dispersion liquid;
step S102, adding 8 parts by mass of tetraethyl orthosilicate (TEOS) into the dispersion, and stirring and reacting at 60 ℃ for 10 hours to obtain Fe3O4@SiO2Particles;
step S103, adding Fe in parts by mass to the step S1023O4@SiO2Adding 15 parts of 3-Aminopropyltriethoxysilane (APTES) into the particles, continuously stirring at 70 ℃ for reaction for 10 hours, and discharging to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding 40 parts by mass of itaconic acid and 30 parts by mass of triethanolamine to 25 parts by mass of N, N-dimethylformamide, stirring and dissolving, and then transferring the dissolved mixed solution to a three-neck flask connected with a mechanical stirrer and a condenser tube, wherein the N is the solution obtained by dissolving itaconic acid and triethanolamine in N2Under the protection condition, heating to 120 ℃ and reacting for 4h to obtain a prepolymer;
step S105, adding 15 parts by mass of succinic acid into the prepolymer to continue reacting for 4 hours, after the reaction is finished, evaporating and concentrating the obtained reaction product by using a rotary evaporator, and then drying in vacuum at 120 ℃ to obtain a hyperbranched polymer HBP-COOH;
step S106, adding Fe3O4@SiO2-NH2Dispersing the particles in distilled water, ultrasonically dispersing for 30min, adding hyperbranched polymer HBP-COOH, stirring at 45 deg.C for 20 hr, washing with distilled water, and vacuum drying at 50 deg.CDrying for 24h, cooling and discharging to obtain the magnetic hyperbranched adsorbent.
Example 3:
embodiment 3 of the present application provides a method for preparing a magnetic hyperbranched adsorbent for removing heavy metal ions, comprising the following steps:
step S101, 25 parts by mass of Fe3O4Dispersing the particles and 15 parts of oleic acid in 50 parts of methanol for ultrasonic dispersion treatment to obtain a dispersion liquid;
step S102, adding 6 parts by mass of tetraethyl orthosilicate (TEOS) into the dispersion, and stirring and reacting at 60 ℃ for 10 hours to obtain Fe3O4@SiO2Particles;
step S103, by mass, adding Fe3O4@SiO2Adding 10 parts of 3-Aminopropyltriethoxysilane (APTES) into the particles, continuously stirring at 70 ℃ for reaction for 10 hours, and discharging to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding 45 parts by mass of itaconic acid and 35 parts by mass of triethanolamine to 25 parts by mass of N, N-dimethylformamide, stirring and dissolving, transferring the dissolved mixed solution to a three-neck flask connected with a mechanical stirrer and a condenser tube, and dissolving in N2Under the protection condition, heating to 120 ℃ and reacting for 4h to obtain a prepolymer;
step S105, adding 15 parts by mass of succinic acid into the prepolymer to continue reacting for 4 hours, after the reaction is finished, evaporating and concentrating the obtained reaction product by using a rotary evaporator, and then drying in vacuum at 120 ℃ to obtain a hyperbranched polymer HBP-COOH;
step S106, adding Fe3O4@SiO2-NH2Dispersing the particles in distilled water, performing ultrasonic dispersion for 30min, adding hyperbranched polymer HBP-COOH, stirring at 45 ℃ for reaction for 20h, washing with distilled water, vacuum drying at 50 ℃ for 24h, cooling, and discharging to obtain the magnetic hyperbranched adsorbent.
Example 4:
embodiment 4 of the present application provides a method for preparing a magnetic hyperbranched adsorbent for removing heavy metal ions, comprising the following steps:
step S101, 60 parts by mass of Fe3O4Dispersing the particles and 18 parts of oleic acid in 65 parts of methanol for ultrasonic dispersion treatment to obtain a dispersion liquid;
step S102, adding 12 parts by mass of tetraethyl orthosilicate (TEOS) into the dispersion, and stirring and reacting at 60 ℃ for 10 hours to obtain Fe3O4@SiO2Particles;
step S103, by mass, adding Fe3O4@SiO2Adding 12 parts of 3-Aminopropyltriethoxysilane (APTES) into the particles, continuously stirring at 70 ℃ for reaction for 10 hours, and discharging to obtain Fe3O4@SiO2-NH2Particles;
step S104, adding 55 parts by mass of itaconic acid and 45 parts by mass of triethanolamine to 20 parts by mass of N, N-dimethylformamide, stirring and dissolving, and then transferring the dissolved mixed solution to a three-neck flask connected with a mechanical stirrer and a condenser tube, wherein the N is the solution obtained by dissolving itaconic acid and triethanolamine in N2Under the protection condition, heating to 120 ℃ and reacting for 4h to obtain a prepolymer;
step S105, adding 16 parts by mass of succinic acid into the prepolymer to continue reacting for 4 hours, after the reaction is finished, evaporating and concentrating the obtained reaction product by using a rotary evaporator, and then drying in vacuum at 120 ℃ to obtain a hyperbranched polymer HBP-COOH;
step S106, adding Fe3O4@SiO2-NH2Dispersing the particles in distilled water, performing ultrasonic dispersion for 30min, adding hyperbranched polymer HBP-COOH, stirring at 45 ℃ for reaction for 20h, washing with distilled water, vacuum drying at 50 ℃ for 24h, cooling, and discharging to obtain the magnetic hyperbranched adsorbent.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
It is noted that, in the present application, relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element. In this application, "plurality" means at least two, e.g., two, three, etc., unless specifically stated otherwise.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. Heavy metal ionThe removed magnetic hyperbranched adsorbent is characterized by comprising the following raw materials in parts by mass: fe3O420-70 parts of particles, 15-25 parts of oleic acid, 30-80 parts of methanol, 5-15 parts of tetraethyl orthosilicate, 10-15 parts of 3-aminopropyltriethoxysilane, 40-80 parts of itaconic acid, 30-60 parts of triethanolamine, 5-25 parts of succinic acid and 15-30 parts of N, N-dimethylformamide.
2. The magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 1, wherein the hyperbranched adsorbent comprises the following raw materials in parts by mass: fe3O440 parts of particles, 20 parts of oleic acid, 60 parts of methanol, 10 parts of tetraethyl orthosilicate, 12 parts of 3-aminopropyltriethoxysilane, 50 parts of itaconic acid, 40 parts of triethanolamine, 25 parts of succinic acid and 30 parts of N, N-dimethylformamide.
3. The magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 1, wherein the hyperbranched adsorbent comprises the following raw materials in parts by mass: fe3O455 parts of particles, 15 parts of oleic acid, 40 parts of methanol, 8 parts of tetraethyl orthosilicate, 15 parts of 3-aminopropyltriethoxysilane, 40 parts of itaconic acid, 30 parts of triethanolamine, 15 parts of succinic acid and 25 parts of N, N-dimethylformamide.
4. The magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 1, wherein the hyperbranched adsorbent comprises the following raw materials in parts by mass: fe3O425 parts of particles, 15 parts of oleic acid, 50 parts of methanol, 6 parts of tetraethyl orthosilicate, 10 parts of 3-aminopropyltriethoxysilane, 45 parts of itaconic acid, 35 parts of triethanolamine, 15 parts of succinic acid and 25 parts of N, N-dimethylformamide.
5. The method for preparing the magnetic hyperbranched adsorbent for heavy metal ion removal according to any one of claims 1 to 4, comprising the steps of:
s101, mixing Fe3O4Granules and oilAdding acid into methanol, and performing ultrasonic dispersion to obtain a dispersion liquid;
s102, adding tetraethyl orthosilicate into the dispersion liquid, and heating to react to obtain Fe3O4@SiO2Particles;
s103, adding into the Fe3O4@SiO2Adding 3-aminopropyl triethoxysilane into the particles, heating and reacting to obtain Fe3O4@SiO2-NH2Particles;
s104, adding itaconic acid and triethanolamine into N, N-dimethylformamide, stirring for dissolving, and heating for reaction to obtain a prepolymer;
s105, adding succinic acid into the prepolymer obtained in the step S104 for reaction, and after the reaction is finished, concentrating and drying to obtain a hyperbranched polymer;
s106, for Fe3O4@SiO2-NH2And (4) carrying out ultrasonic dispersion on the particles, then adding the hyperbranched polymer prepared in the step (S105), heating for reaction, and after the reaction is finished, cleaning and drying to obtain the magnetic hyperbranched adsorbent.
6. The preparation method of the magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 5, wherein in the step S102, the temperature of the heating reaction is 50-70 ℃.
7. The preparation method of the magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 5, wherein in the step S103, the temperature of the heating reaction is 65-80 ℃.
8. The method for preparing the magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 5, wherein the temperature of the heating reaction in step S104 is 115-130 ℃.
9. The method for preparing the magnetic hyperbranched adsorbent for removing heavy metal ions according to claim 5, wherein the temperature of the heating reaction in step S106 is 40-55 ℃.
10. Use of the magnetic hyperbranched adsorbent for heavy metal ion removal prepared by the preparation method of claim 5, wherein the magnetic hyperbranched adsorbent is used for Pb2+、Cd2+And Cu2+Adsorption of (3).
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130037175A1 (en) * | 2011-08-10 | 2013-02-14 | Basf Se | Preparation of itaconic acid homo- or copolymers and amine- or amide- containing alcohols for metal surface treatment |
| CN103446964A (en) * | 2013-08-29 | 2013-12-18 | 西北工业大学 | Preparation method of carboxyl functionalized hyperbranched magnetic mesoporous silica composite microspheres |
| CN106902777A (en) * | 2017-04-21 | 2017-06-30 | 南京师范大学 | A kind of magnetic dissaving polymer or derivatives thereof blood adsorbent for heavy metal and its preparation method and application |
| CN108414655A (en) * | 2018-05-28 | 2018-08-17 | 陕西师范大学 | A kind of magnetism ultrabranching polyamide-amine and the application in organophosphorus pesticide detection |
| CN108620044A (en) * | 2018-05-30 | 2018-10-09 | 广西大学 | Magnetic response graphene oxide/plant fiber sorbing material and its preparation method and application |
| CN109174033A (en) * | 2018-08-27 | 2019-01-11 | 南京师范大学 | A kind of blood lead ion scavenger and its preparation method and application that can pass in and out red blood cell safely |
| CN110756178A (en) * | 2019-10-28 | 2020-02-07 | 王柏君 | Bimetal oxide-hyperbranched polymer adsorbent and preparation method thereof |
| CN112604668A (en) * | 2020-11-27 | 2021-04-06 | 桐乡市创辉科技合伙企业(有限合伙) | Dy-doped Fe3O4Adsorption material of grafted polyamide-amine and preparation method thereof |
| CN113061601A (en) * | 2021-03-17 | 2021-07-02 | 东北农业大学 | Method for preparing immobilized phospholipase C based on multipoint covalent interaction |
-
2021
- 2021-09-09 CN CN202111054377.1A patent/CN113680333A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130037175A1 (en) * | 2011-08-10 | 2013-02-14 | Basf Se | Preparation of itaconic acid homo- or copolymers and amine- or amide- containing alcohols for metal surface treatment |
| CN103446964A (en) * | 2013-08-29 | 2013-12-18 | 西北工业大学 | Preparation method of carboxyl functionalized hyperbranched magnetic mesoporous silica composite microspheres |
| CN106902777A (en) * | 2017-04-21 | 2017-06-30 | 南京师范大学 | A kind of magnetic dissaving polymer or derivatives thereof blood adsorbent for heavy metal and its preparation method and application |
| CN108414655A (en) * | 2018-05-28 | 2018-08-17 | 陕西师范大学 | A kind of magnetism ultrabranching polyamide-amine and the application in organophosphorus pesticide detection |
| CN108620044A (en) * | 2018-05-30 | 2018-10-09 | 广西大学 | Magnetic response graphene oxide/plant fiber sorbing material and its preparation method and application |
| CN109174033A (en) * | 2018-08-27 | 2019-01-11 | 南京师范大学 | A kind of blood lead ion scavenger and its preparation method and application that can pass in and out red blood cell safely |
| CN110756178A (en) * | 2019-10-28 | 2020-02-07 | 王柏君 | Bimetal oxide-hyperbranched polymer adsorbent and preparation method thereof |
| CN112604668A (en) * | 2020-11-27 | 2021-04-06 | 桐乡市创辉科技合伙企业(有限合伙) | Dy-doped Fe3O4Adsorption material of grafted polyamide-amine and preparation method thereof |
| CN113061601A (en) * | 2021-03-17 | 2021-07-02 | 东北农业大学 | Method for preparing immobilized phospholipase C based on multipoint covalent interaction |
Non-Patent Citations (8)
| Title |
|---|
| PENGFEI GUO ET AL.: "Controllable synthesis of terminal carboxyl hyperbranched polyester and their retarding effect on concrete" * |
| TJ. N. ASAAD ET AL.: "Evaluation of Some New HyperbranchedPolyesters as Binding Agents for Heavy Metals" * |
| Y. HARINATH ET AL.: "Development of hyperbranched polymer encapsulated magnetic adsorbent (Fe3O4@SiO2-NH2-PAA) and its application for decontamination of heavy metal ions" * |
| Y. HARINATH ET AL.: "Development of hyperbranched polymer encapsulated magnetic adsorbent (Fe3O4@SiO2–NH2-PAA) and its application for decontamination of heavy metal ions" * |
| 周立: "超支化聚缩水甘油基无机纳米复合材料的制备及应用研究" * |
| 李美兰等: "无磷型绿色端羧基超支化聚酯的制备及其阻垢行为研究" * |
| 蔡松韬: "环糊精修饰的四氧化三铁纳米粒子的合成及其应用" * |
| 龚伟等: "柠檬酸型超支化聚酰胺淋洗剂对重金属污染土壤的修复效果" * |
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