CN112246231A - Magnetic polyaspartic acid adsorbent and preparation method thereof - Google Patents
Magnetic polyaspartic acid adsorbent and preparation method thereof Download PDFInfo
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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
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- 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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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a magnetic polyaspartic acid adsorbent and a preparation method thereof, wherein the magnetic polyaspartic acid adsorbent comprises the following components: 1) preparing polysuccinimide; 2) polysuccinimide, 4-aminoethyl pyridine and aminated Fe3O4Reacting the nano particles with an alkali solution, extracting and drying to obtain a magnetic polyaspartic acid adsorbent; the adsorbent contains carboxyl, tertiary amine, amide, primary amine and other groups, provides a plurality of heavy metal adsorption sites, and is compatible with Cd (II), Cu (II) and Cr (II)(VI) capable of forming stable complexes; and grafted with superparamagnetic Fe3O4The material can be separated from the absorbed aqueous solution for recovery and reuse, has good reproducibility, and has wide application prospect in green water treatment agents.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a magnetic polyaspartic acid adsorbent and a preparation method thereof.
Background
Polyaspartic Acid (PASP) is a polymer of amino acids, the amino and carboxyl groups naturally present in aspartic acid molecules in shells of mollusks and snails form amide bonds after condensation, which form a macromolecular main chain, and the other carboxyl group is distributed on two sides of the main chain. The peptide bond on the structural main chain of the polyaspartic acid is easy to break under the action of microorganisms, fungi and the like, and the final degradation products are ammonia, carbon dioxide and water which are harmless to the environment, so the polyaspartic acid is an environment-friendly chemical with good biodegradability. The polyaspartic acid macromolecule has rich amide groups and carboxyl functional groups, is one of the currently accepted green water treatment agents, and has immeasurable application prospect as the environmental protection consciousness of people is enhanced along with the proposal of sustainable development strategy in China.
However, the unit structure of PASP is single, the chelating ability with metal is limited, the mechanical strength is low, and the PASP is easy to dissolve in an acid solution, so that the modification of PASP is an effective way for improving the application of PASP in the field of water treatment. Chen et al (Synthesis of modified polymeric acid and evaluation of surface area and dispersion capacity: desalinization, 2015,358:42) use the amino group on the serine as the nucleophilic group to carry out ring-opening modification on Polysuccinimide (PSI) to obtain a graft copolymer (Ser-PASP), which improves the chelating ability to calcium salts of different anions; the hydrozyyangsheng (hydrozylated polyaspartic acid synthesized in water system and its antisludging performance. polymer material science and engineering, 2008,24(11),44-46.) in water system, ethanolamine and Polysuccinimide (PSI) are reacted to synthesize hydroxyl modified PASP, which can raise the antisludging capacity of calcium phosphate. The two modification modes improve the ions (mainly Ca (II)) which are commonly used for hardening water in a circulating water system by PASP]The scale inhibition performance of the composite material is good, but no application research is carried out on the chelation of other heavy metal ions. CN 110385109A discloses GO- (o-MWCNTs) -CoFe hybrid of PASP modified graphene oxide-carbon nano tube and magnetic particles2O4Improves the surface adsorption sites of the magnetic GO- (o-MWCNTs) hybrid, and is beneficial to the adsorption sites of various heavy metal ions [ such as Cd (II), Cu (II) and Ni (II) in sewage)]Adsorption of (2) CoFe2O4Magnetic nanoparticles are loaded on the surface of GO- (o-MWCNTs), aiming at separating the adsorbent material from the adsorbed aqueous solution, but the defect that the binding site of the polyaspartic acid and the metal is single is not solved.
Disclosure of Invention
The invention aims to provide a magnetic polyaspartic acid adsorbent, which is prepared by introducing diversified polar groupsClusters, increasing the chelating sites of the adsorbent with the metal; and grafting Fe having magnetism3O4Particles are used to separate the adsorbent material from the adsorbed water solution for cyclic utilization.
The invention also aims to provide a preparation method of the magnetic polyaspartic acid adsorbent.
The reaction process and the preparation method of the magnetic polyaspartic acid adsorbent are as follows:
1. preparation of Polysuccinimide (PSI)
Adding maleic anhydride and deionized water into a three-neck flask provided with a constant-pressure dropping funnel, heating to 70-90 ℃, fully reacting for 0.5-1 h, then dropping 25% ammonia water into a maleic anhydride aqueous solution, performing amination hydrolysis reaction for 2-5 h, and removing the solvent through reduced pressure distillation to obtain white flaky crystals; heating to 180-200 ℃ to melt the wafer, stirring to perform a condensation reaction, gradually changing the color of the liquid in the reaction to red, performing a polycondensation reaction for 1-4 hours to change the melt into a brownish red sticky substance, and cooling to room temperature to obtain Polysuccinimide (PSI).
In the reaction, 200-400 mL of deionized water and 30-40 mL of 25% ammonia water are needed for 1mol of maleic anhydride.
2. Preparation of magnetic polyaspartic acid adsorbent (Py-PASP-Fe)3O4)
According to the literature [ Ding, Y.L., et al, Mater. Sci. Eng. C.48,487-498(2015)]The method can obtain powdered magnetic Fe3O4Nanoparticles, again as described in the literature [ Makhluf, S.B., et al Small 4,1453-]Method for preparing powdered magnetic Fe3O4The surface of the nano particles is modified to introduce amino to obtain aminated Fe3O4Nanoparticles. Amination of Fe3O4The nano particles are dispersed in N, N-dimethylformamide by ultrasonic for standby.
Weighing PSI and 4-aminoethyl pyridine according to a proportion, putting the PSI and the 4-aminoethyl pyridine into a three-neck flask, adding N, N-dimethylformamide with a volume twice that of the PSI and the 4-aminoethyl pyridine for dissolution, heating to 80-140 ℃, stirring for reaction for 1-2 hours, and adding the aminated Fe3O4With mechanical stirring, followed byKeeping the temperature for reaction for 1-3 h, cooling to 50-60 ℃, adding a certain amount of 5mol/L NaOH aqueous solution, adjusting the pH of the solution to 8-10, stirring and hydrolyzing for 0.5-1 h, and finishing the reaction. Adding equal volume of anhydrous ethanol into the reaction bottle for extraction, repeating for 3 times, taking the lower layer liquid, and distilling under reduced pressure to obtain Py-PASP-Fe3O4。
The above reaction, PSI, 4-aminoethyl pyridine, amination Fe3O4The feeding mass ratio of the raw materials is 100: 12-40: 5-11.
Reaction of the above, Fe3O4The suspension of N, N-dimethylformamide means that every 3g of aminated Fe3O4The nano particles are dispersed in 500-800 mLN, N-dimethylformamide to prepare a suspension.
The invention has the following advantages and beneficial effects:
(1) the magnetic polyaspartic acid adsorbent prepared by the invention contains carboxyl, tertiary amine, amide, primary amine and other groups, provides adsorption sites of multiple heavy metals, and can form a stable complex with Cd (II), Cu (II) and Cr (VI).
(2) The magnetic polyaspartic acid adsorbent prepared by the invention is grafted with superparamagnetic Fe3O4So that the material can be separated from the adsorbed aqueous solution for recovery and reuse, and has good reproducibility.
(3) In addition, the material has simple preparation method and is beneficial to large-scale production.
Drawings
FIG. 1 shows a magnetic hysteresis loop of a magnetic polyaspartic acid adsorbent.
FIG. 2 shows the effect of the magnetic poly-aspartic acid adsorbent prepared in example 1 on the static saturation adsorption capacity Q of Cd (II), Cr (VI) and Cu (II) under different acidity of solution.
FIG. 3 is a graph showing the change of the static saturation adsorption amount Q of Cd (II), Cr (VI), Cu (II) with time of the magnetic polyaspartic acid adsorbent prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The test of the invention comprises the following steps:
analysis of saturation magnetization: and (3) measuring the saturation magnetization intensity of the sample by adopting a low-temperature comprehensive physical property measurement system PPMS Dynacool, controlling the measurement temperature to be 280 ℃, controlling the measurement frequency to be 12Hz, and controlling the measurement range to be-20000 Oe.
And (3) testing the static saturated adsorption quantity of the metal ions: weighing 20mg of sample, placing the sample in a conical flask with a plug, adding 10mL of HAc-NaAc buffer solution (pH is 2-6), soaking for 12h, adding 10mL of 2mmol/L metal salt solution respectively, and shaking at constant temperature of 45 ℃ for a certain time. Separating the adsorbent under the action of external magnetic field, and measuring the residual ion concentration of the solution by using an inductively coupled plasma emission spectrometer. The static saturated adsorption amount Q is calculated by the following formula (I):
in the formula, C0Is the initial concentration (mg/L) of the solution, CtThe concentration of the solution at adsorption equilibrium (mg/L), V is the volume of the solution to be measured (L), and m is the mass of the adsorbent (g).
The optimal pH values of the Cu (II), Cd (II) and Cr (VI) adsorbed by the magnetic polyaspartic acid adsorbent are 5.1, 3.8 and 5.5 respectively, see the attached figure 2; the adsorption equilibrium is reached when the magnetic polyaspartic acid adsorbent adsorbs Cu (II), Cd (II) and Cr (VI) solutions for 100 min, 180 min and 250min respectively, and refer to the attached figure 3.
And (3) testing the reproducibility: the metal ion solution (20mL, 100mg/L) was adsorbed with an adsorbent (20mg) at 25 ℃ and pH 4.0, and shaken at constant temperature for a desired static saturation adsorption time. After adsorption is finished, separating the adsorbent saturated in adsorption by using an external magnetic field, washing the adsorbent by using deionized water to remove unadsorbed metal ions, and then washing the adsorbent by using 20mL of 0.6mol/L HNO3And desorbing in the solution. The desorption was carried out at 25 ℃ for 20min with shaking at a frequency of 120 r/min. After desorption is finished, the mixture is separated out by using an external magnetic fieldThe adsorbent was thoroughly washed with deionized water to pH 4.0 and then reused in the next adsorption process. The final metal ion concentration was measured by inductively coupled plasma emission spectrometer and subjected to 5 cycles of adsorption-desorption treatment.
The corresponding static saturation adsorption amounts of the three examples in the solution with the optimum pH value for metal ion adsorption are shown in Table 1, and the pH values of Cu (II), Cd (II), Cr (VI) solutions are 5.1, 3.8 and 5.5 respectively.
Example 1
(1) Preparation of Polysuccinimide (PSI)
Adding 68.52g of maleic anhydride and 210mL of deionized water into a three-neck flask with a constant-pressure dropping funnel, heating to 80 ℃, fully reacting for 0.5h, dropping 22mL of ammonia water with the mass fraction of 25% into the maleic anhydride aqueous solution, performing amination hydrolysis reaction for 3.5h, and removing the solvent through reduced pressure distillation to obtain white flaky crystals; heating to 200 deg.C to melt the wafer, stirring to make condensation reaction, making the liquid color gradually turn red, performing polycondensation reaction for 3 hr to obtain brown red viscous substance, and cooling to room temperature to obtain Polysuccinimide (PSI).
(2) Preparation of magnetic polyaspartic acid adsorbent (Py-PASP-Fe)3O4)
According to the literature [ Ding, Y.L., et al, Mater. Sci. Eng. C.48,487-498(2015)]The method can obtain powdered magnetic Fe3O4Nanoparticles, again as described in the literature [ Makhluf, S.B., et al Small 4,1453-]Method for preparing powdered magnetic Fe3O4The surface of the nano particles is modified to introduce amino to obtain aminated Fe3O4Nanoparticles (amino content 18.25 mmol/g). Amination of 10g Fe3O4The nano particles are dispersed in 2LN, N-dimethylformamide by ultrasonic for standby.
Weighing 21.11g of PSI and 7.96g of 4-aminoethyl pyridine according to a proportion, putting the PSI and the 4-aminoethyl pyridine into a three-neck flask, adding N, N-dimethylformamide with the volume twice that of the PSI and the 4-aminoethyl pyridine for dissolving, heating to 85 ℃, stirring for reacting for 1 hour, and adding 474g of the aminated Fe3O4The suspension of the N, N-dimethylformamide is continuously reacted for 1 hour under the condition of mechanical stirring, the temperature is reduced to 50 ℃, and then the mixture is addedAdding 5mol/L NaOH aqueous solution, adjusting the pH of the solution to 9.6, stirring and hydrolyzing for 1h, and finishing the reaction. Adding equal volume of anhydrous ethanol into the reaction bottle, stirring for 1min, pouring into a separating funnel, standing for layering, wherein the upper layer is light yellow, and the lower layer is blood red. Pouring out the lower layer, adding equal volume of anhydrous ethanol, repeating for 3 times, and drying in a vacuum drying oven for 72h to obtain Py-PASP-Fe3O4。
Example 2
The difference from example 1 is that step (2) includes PSI, 4-aminoethylpyridine and aminated Fe3O4The feeding mass of the suspension is 17.55g, 6.63g and 295g respectively; 5mol/L NaOH aqueous solution was added to adjust the pH of the solution to 8.1.
Example 3
The difference from example 1 is that step (2) includes PSI, 4-aminoethylpyridine and aminated Fe3O4The feeding mass of the suspension is 18.21g, 2.38g and 204g respectively; 5mol/L NaOH aqueous solution was added to adjust the pH of the solution to 8.3.
Example 4
The difference from example 1 is that step (2) includes PSI, 4-aminoethylpyridine and aminated Fe3O4The feeding mass of the suspension is 15.65g, 3.93g and 265g respectively; 5mol/L NaOH aqueous solution was added to adjust the pH of the solution to 9.2.
Example 5
Example 1 differs in step (2) PSI, 4-aminoethylpyridine, aminated Fe3O4The feeding mass of the suspension is 17.92g, 2.25g and 301g respectively; 5mol/L NaOH aqueous solution was added to adjust the pH of the solution to 9.8.
TABLE 1
Examples 1 to 3 adding magnetic Fe in different proportions3O4The experiment of the nano particles and the static saturated adsorption capacity shows that the proportion of the magnetic particles has little influence on the adsorption capacity of the metal by the adsorbent, compared with the examples 2, 4 and 5 which have the advantages thatThe higher the pyridine proportion is, the stronger the adsorption capacity of the adsorbent to metal is, and the higher the static saturated adsorption capacity is. Under different solution acidity, the optimal adsorption quantity pH values of the adsorbent to three metals are respectively as follows: cd (II)3.7, Cr (VI)4.8, Cu (II)5.6, see FIG. 2; under the optimal pH value of the adsorption quantity, the static saturated adsorption time of the adsorbent to three metals is respectively as follows: cd (II)165min, Cr (VI)215min and Cu (II)215min, and the results are shown in FIG. 3.
Claims (2)
1. A magnetic polyaspartic acid adsorbent and a preparation method thereof are characterized by comprising the following steps:
(1) preparation of polysuccinimide
Dripping ammonia water into the aqueous solution of maleic anhydride for hydrolysis, and drying to obtain flaky crystals; preparing polysuccinimide from the flaky crystal through a melt condensation reaction;
(2) preparation of magnetic polyaspartic acid adsorbent
Polysuccinimide is put into a solvent, and then the polysuccinimide, 4-aminoethyl pyridine and aminated Fe are respectively added3O4Reacting the nano particles with an alkali solution, extracting and drying to obtain the magnetic polyaspartic acid adsorbent.
2. The magnetic polyaspartic acid adsorbent of claim 1, wherein the magnetic polyaspartic acid adsorbent comprises:
200-400 mL of deionized water and 30-40 mL of 25% ammonia water are needed for 1mol of maleic anhydride in the step (1);
the solvent in the step (2) is N, N-dimethylformamide;
the alkali solution in the step (2) is a 5mol/LNaOH aqueous solution;
the step (2) comprises polysuccinimide, 4-aminoethyl pyridine and aminated Fe3O4The feeding mass ratio of the raw materials is 100: 12-40: 5-11;
the reaction temperature of the polysuccinimide obtained in the step (2) and the 4-aminoethyl group is 80-140 ℃, and the reaction time is 1-2 h;
the polysuccinimide of the step (2) is aminated with Fe3O4The reaction temperature is 50-60 ℃, and the reaction time is 0.5-1 h;
the reaction temperature of the polysuccinimide obtained in the step (2) and the alkali solution is 80-140 ℃, and the reaction time is 1-3 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216336A (en) * | 2008-09-15 | 2011-10-12 | 纳米化学解决方案有限公司 | Method of making graft copolymers from sodium poly (aspartate) and the resulting graft copolymer |
| CN103920466A (en) * | 2014-05-05 | 2014-07-16 | 湖南大学 | Preparation method and application of modified ramie fiber adsorbent |
| WO2015076370A1 (en) * | 2013-11-25 | 2015-05-28 | 株式会社クラレ | Biopolymer-adsorbing composition and water treatment method using same |
| CN111081953A (en) * | 2019-11-20 | 2020-04-28 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for efficiently capturing metal ions, diaphragm and application of diaphragm |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216336A (en) * | 2008-09-15 | 2011-10-12 | 纳米化学解决方案有限公司 | Method of making graft copolymers from sodium poly (aspartate) and the resulting graft copolymer |
| WO2015076370A1 (en) * | 2013-11-25 | 2015-05-28 | 株式会社クラレ | Biopolymer-adsorbing composition and water treatment method using same |
| CN103920466A (en) * | 2014-05-05 | 2014-07-16 | 湖南大学 | Preparation method and application of modified ramie fiber adsorbent |
| CN111081953A (en) * | 2019-11-20 | 2020-04-28 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for efficiently capturing metal ions, diaphragm and application of diaphragm |
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