Preparation method and application of a nitrogen-rich polyethyleneimine derivative adsorbent material

Abstract

The application discloses a preparation method and application of a nitrogen-rich polyethyleneimine derivative adsorbent material. The nitrogen-rich polyethyleneimine derivative is composed of a high-molecular polyethyleneimine as a base material, a grafting modifier and a neutralizing agent are added, an acrylation reaction is performed to prepare a polyethyleneimine precursor containing a vinyl group, and polymerization is performed to obtain the PAPEI adsorbent material. The polyethyleneimine (PEI) is rich in amino functional groups and has strong capturing capacity for various adsorbents. However, the direct use of the PEI is limited by water solubility. In the application, the PEI is used as a unique matrix to synthesize the nitrogen-rich polyethyleneimine derivative adsorbent for efficient adsorption and removal of pollutants in water, and the use value of the PEI as the adsorbent material is improved.

Description

Technical Field

[0001] This invention belongs to the field of polymer adsorbent technology, specifically relating to a method for preparing and applying a nitrogen-rich polyethyleneimine derivative adsorbent material. Background Technology

[0002] Industrial wastewater poses a serious threat to the ecological environment. Therefore, industrial wastewater treatment has become a pressing social issue. Heavy metal ions in water can accumulate in the human body through the food chain, posing a deadly threat to human health. For example, mercury ions in industrial wastewater are among the most toxic heavy metal pollutants, capable of inducing serious liver and kidney damage. Adsorption is a simple, economical, and effective method for heavy metal removal and has been widely used for the efficient adsorption and removal of pollutants in water. However, traditional adsorbent materials are limited by insufficient adsorption sites and low affinity, still facing problems such as low adsorption efficiency, low adsorption capacity, and poor selectivity in pollutant treatment. Therefore, developing novel adsorbent materials with high affinity and high selectivity for pollutants is of great significance for solving water pollution problems.

[0003] Polyethyleneimine (PEI) is a water-soluble polymer containing numerous amino functional groups, exhibiting excellent binding capacity for many pollutants in water. In recent years, the use of PEI as an adsorbent for pollutant removal in water has been widely reported. However, due to PEI's inherent water solubility, it must be loaded onto other solid media, which not only limits the exposure of PEI active sites but also restricts the affinity of the adsorption sites, resulting in poor selectivity and low adsorption capacity in the prepared PEI composite adsorbents. Therefore, improving the adsorption performance of PEI composite adsorbents is essential. Summary of the Invention

[0004] The purpose of this section is to outline some aspects of embodiments of the present invention and to briefly describe some preferred embodiments. Simplifications or omissions may be made in this section, as well as in the abstract and title of this application, to avoid obscuring the purpose of these documents; however, such simplifications or omissions should not be construed as limiting the scope of the invention.

[0005] In view of the problems existing in the above and / or prior art, the present invention is proposed.

[0006] Therefore, the purpose of this invention is to overcome the shortcomings of the prior art and provide a nitrogen-rich polyethyleneimine derivative adsorbent material.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a nitrogen-rich polyethyleneimine derivative adsorbent material, characterized in that it comprises,

[0008] The nitrogen-rich polyethyleneimine derivative is composed of high-molecular-weight polyethyleneimine as the matrix material, with the addition of grafting modifiers and neutralizing agents. A vinyl-containing polyethyleneimine precursor is prepared by acrylation reaction, and then polymerized to obtain PAPEI adsorbent material.

[0009] As a preferred embodiment of the macromolecular crosslinking agent-toughened hydrogel material of the present invention, wherein the molecular weight of the high molecular weight polyethyleneimine is between 300 and 700,000.

[0010] As a preferred embodiment of the macromolecular crosslinking agent-toughened hydrogel material of the present invention, wherein: the grafting modifier is acryloyl chloride, and the neutralizing agent is one or more of triethylamine, sodium hydroxide, sodium carbonate, etc.

[0011] As a preferred embodiment of the macromolecular crosslinking agent-toughened hydrogel material of the present invention, the reaction temperature is room temperature; the reaction time is 0.5 to 5 days.

[0012] Another objective of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a nitrogen-rich polyethyleneimine derivative adsorbent material, wherein:

[0013] Polyethyleneimine and triethylamine are mixed and dissolved in an aqueous solution to obtain a polyethyleneimine solution;

[0014] Acryloyl chloride was added dropwise to a polyethyleneimine solution, stirred, and stored at room temperature to obtain a mixed solution.

[0015] The above mixed solution was extracted with an extractant to obtain a polyethyleneimine precursor solution containing vinyl groups;

[0016] PAPEEI material is obtained by rotary evaporation and polymerization under heating conditions.

[0017] In a preferred embodiment of the preparation method described in this invention, the room temperature storage time is 6–72 h.

[0018] In a preferred embodiment of the preparation method described in this invention, the extractant is one or more of ethyl acetate, dichloromethane, chloroform, diethyl ether, and ethanol.

[0019] In a preferred embodiment of the preparation method described in this invention, the reaction temperature of the polyethyleneimine solution and the mixed solution is 0°C ice bath, and the temperature of the rotary evaporation is 60°C.

[0020] As a preferred embodiment of the preparation method described in this invention, the nitrogen-rich polyethyleneimine derivative adsorbent has an adsorption capacity of 770–1832 mg / g for mercury ions.

[0021] Another objective of this invention is to overcome the shortcomings of the prior art and provide an application of a nitrogen-rich polyethyleneimine derivative adsorbent in the adsorption of heavy metals and dyes.

[0022] Beneficial effects of this invention:

[0023] (1) In this invention, PEI is used as the main material and acryloyl chloride is used as the grafting modification material. PEI and acryloyl chloride are simply mixed and extracted. While the extractant is removed by rotary evaporation, the precursor solution undergoes bulk polymerization, polymerizing from liquid into a non-water-soluble solid material. PEI is used as the sole matrix to synthesize nitrogen-rich polyethyleneimine derivative adsorbents for the efficient adsorption and removal of Hg(II) in water, significantly improving the adsorption selectivity and adsorption capacity for Hg(II).

[0024] (2) The synthesis route of this invention is simple and the material cost is low;

[0025] (3) The present invention has good adsorption capacity for a variety of organic dyes. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. Wherein:

[0027] Figure 1 The synthetic route of the PAPEI adsorbent in Example 1 of this invention.

[0028] Figure 2 The APEI precursor, PAPEI adsorbent, and PAPEI / Hg in Example 1 of this invention are... 2+ FTIR plot of the composite material.

[0029] Figure 3 The APEI precursor and PAPEI adsorbent in Example 1 of this invention 13 C-NMR spectrum.

[0030] Figure 4 In this embodiment of the invention, the PAPEI adsorbent is used for Hg 2+ Adsorption capacity diagram.

[0031] Figure 5 The figure represents the removal rate of mixed mercury / copper / lead / cadmium ions by the PAPEEI adsorbent in this embodiment of the invention. Detailed Implementation

[0032] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the examples in the specification.

[0033] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0034] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0035] All reagents and raw materials used in this invention were purchased from Aladdin Reagent Co., Ltd.

[0036] Example 1

[0037] 1. Preparation of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material

[0038] First, 2.5 g of polyethyleneimine and 20 ml of triethylamine were dispersed in 50 ml of water. Then, 12 ml of acryloyl chloride was added dropwise to the mixture in an ice bath. The reaction was carried out at room temperature for 12 h. The mixture was then extracted with ethyl acetate to obtain a vinyl-containing polyethyleneimine (APEI) precursor solution. Finally, the APEI precursor self-polymerized to form a PAPEI adsorbent by rotary evaporation, such as... Figure 1 As shown.

[0039] Figure 2 The images show the FTIR spectra of the APEI precursor and PAPEI adsorbent. Figure 2 In the APEI spectrum, 930 and 982 cm⁻¹ -1 The corresponding peak is C=C, proving that the vinyl group was successfully attached to the polyethyleneimine molecular chain to obtain a vinyl-containing polyethyleneimine (APEI) precursor. Figure 2 The absence of C=C in the PAPEI spectrum indicates that APEI was successfully polymerized to obtain the PAPEI adsorbent.

[0040] Figure 3 As an APEI precursor and PAPEI adsorbent 13 C-NMR spectrum. Figure 3 In the NMR spectrum of APEI, 167.4 ppm corresponds to a carbon atom in C=C. In Figure 3In the NMR spectrum of APEI, the signal of the carbon atom in C=C is significantly weakened, proving that APEI was successfully polymerized to obtain PAPEEI adsorbent.

[0041] Figure 2 and Figure 3 This proves that the PAPEEI adsorbent was successfully prepared.

[0042] Example 2

[0043] 1. Preparation of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material

[0044] First, 2.5 g of polyethyleneimine was dispersed in 50 ml of water. Then, 12 ml of acryloyl chloride was added dropwise to the mixture in an ice bath. The reaction was carried out at room temperature for 18 h, and the mixture was extracted with ethyl acetate to obtain a vinyl-containing polyethyleneimine (APEI) precursor solution. Finally, the APEI precursor self-polymerized to form the PAPEEI adsorbent by rotary evaporation.

[0045] Example 3

[0046] 1. Preparation of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material

[0047] First, 2.5 g of polyethyleneimine was dispersed in 50 ml of water, and then 12 ml of acryloyl chloride was added dropwise to the mixture at room temperature. The reaction was allowed to proceed for 24 h at room temperature, followed by extraction with chloroform to obtain a vinyl-containing polyethyleneimine (APEI) precursor solution. Finally, the APEI precursor self-polymerized to form the PAPEEI adsorbent via rotary evaporation.

[0048] Example 4

[0049] 1. Mercury ion removal performance of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material

[0050] The PAPEEI adsorbent prepared in Example 1 was placed in 20 ml of 300 mg / L mercury ions (Hg). 2+ The adsorption capacity of PAPEEI for mercury ions was obtained, as follows: Figure 4 As shown, PAPEI adsorbent has an adsorption capacity for mercury ions as high as 770-1832 mg / g. Figure 1 The N-Hg peak in the PAPEI-Hg composite material appears at 1370 cm⁻¹. -1 This indicates that the capture of mercury ions by the PAPEEI adsorbent is mainly due to the interaction between nitrogen atoms and mercury ions.

[0051] Example 5

[0052] 1. Performance of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material in removing mercury / copper / lead / cadmium ions

[0053] The PAPIEI adsorbent prepared in Example 1 was placed in a mixed ion solution containing 100 mg / L of mercury / copper / lead / cadmium to obtain the removal rate (%) of mercury / copper / lead / cadmium ions by PAPIEI. Figure 5 As shown, the removal rates of mercury / copper / lead / cadmium ions were 89%, 24%, 20%, and 24%, respectively, indicating that PAPEEI has selective adsorption performance for mercury ions.

[0054] Example 6

[0055] 1. Adsorption performance of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material for methylene blue dye

[0056] The PAPEEI adsorbent prepared in Example 2 was placed in a solution containing 100 mg / L methylene blue, and the adsorption capacity of PAPEEI for methylene blue dye reached 813 mg / g.

[0057] Example 7

[0058] 1. Adsorption performance of nitrogen-enriched polyethyleneimine derivative adsorbent (PAPEI) material on Rhodamine B dye

[0059] The PAPEEI adsorbent prepared in Example 3 was placed in a solution containing 400 mg / L of Rhodamine B, and the adsorption capacity of PAPEEI for Rhodamine B dye was found to be close to 1000 mg / g.

[0060] Comparative Example 1

[0061] A polymer adsorbent containing an N-rich aromatic ring structure was used to adsorb Hg from water. 2+ The adsorbent is effective against Hg. 2+ Its adsorption capacity is less than 100 mg / g.

[0062] Comparative Example 2

[0063] Polyacrylic acid hydrogels are used to adsorb Hg in water. 2+ The hydrogel is sensitive to Hg in water. 2+ Its adsorption capacity is less than 35 mg / g.

[0064] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A nitrogen-rich polyethyleneimine derivative adsorbent material, characterized in that: The nitrogen-rich polyethyleneimine derivative is composed of high molecular weight polyethyleneimine as the matrix material, with the addition of grafting modifier and neutralizing agent, and is prepared by acrylation reaction to obtain a vinyl-containing polyethyleneimine precursor, which is then polymerized to obtain PAPEI adsorbent material. The grafting modifier is acryloyl chloride, and the neutralizing agent is one or more of triethylamine, sodium hydroxide, and sodium carbonate.

2. The nitrogen-rich polyethyleneimine derivative adsorbent material as described in claim 1, characterized in that: The molecular weight of the high molecular weight polyethyleneimine is between 300 and 700,000.

3. The nitrogen-rich polyethyleneimine derivative adsorbent material as described in claim 1, characterized in that: The reaction temperature is room temperature; the reaction time is 0.5 to 5 days.

4. A method for preparing a nitrogen-rich polyethyleneimine derivative adsorbent material as described in any one of claims 1 to 3, comprising: Polyethyleneimine and triethylamine are mixed and dissolved in an aqueous solution to obtain a polyethyleneimine solution; Acryloyl chloride was added dropwise to a polyethyleneimine solution, stirred, and stored at room temperature to obtain a mixed solution. The above mixed solution was extracted with an extractant to obtain a polyethyleneimine precursor solution containing vinyl groups; PAPEEI material is obtained by rotary evaporation and polymerization under heating conditions.

5. The preparation method according to claim 4, characterized in that: The room temperature storage time is 6~72 h.

6. The preparation method according to claim 4, characterized in that: The extractant is one or more of ethyl acetate, dichloromethane, chloroform, diethyl ether, and ethanol.

7. The preparation method according to claim 4, characterized in that: The rotary evaporation temperature is 60°C.

8. The application of a nitrogen-rich polyethyleneimine derivative adsorbent as described in any one of claims 1 to 3 in the adsorption of heavy metals and dyes.

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