CN111804287B - Fluorenone type chelate resin and preparation method and application thereof - Google Patents

Abstract

。同时，本发明还公开了该螯合树脂的制备方法及应用。本发明的鳌合树脂可实现对Cu(Ⅱ)、Ni(Ⅱ)、Pb(Ⅱ)等金属离子进行富集回收，有效解决了含重金属离子废水的深度处理问题。The invention relates to a fluorenone-type chelating resin. The chelating resin uses 4,5-diazafluorene-9-ketone as a ligand and is prepared by reacting with the side groups of chloromethylated polystyrene microspheres. , its structural formula is as follows:

. Meanwhile, the invention also discloses the preparation method and application of the chelating resin. The chelating resin of the invention can realize the enrichment and recovery of metal ions such as Cu(II), Ni(II), Pb(II), etc., and effectively solve the problem of advanced treatment of wastewater containing heavy metal ions.

Description

A kind of fluorenone type chelating resin and its preparation method and application

technical field

The invention relates to the field of chelating resin materials, in particular to a fluorenone-type chelating resin and a preparation method and application thereof.

Background technique

Heavy metal ion wastewater is one of the industrial wastewaters with the most serious environmental pollution and the greatest harm to human beings. Most of the metal ions and their compounds are easily adsorbed by suspended particles in the water and deposited in the sediment layer on the bottom of the water, polluting the water body for a long time. Certain heavy metals can accumulate, accumulate in fish and other aquatic organisms and in crop tissues and participate in the biosphere cycle, thereby threatening human life and health. Therefore, wastewater containing heavy metals must be treated before being discharged. In the current society, the pollution of water environment is becoming more and more serious. How to efficiently remove heavy metal ions in wastewater is a research hotspot. Heavy metal wastewater is usually treated by chemical or physicochemical methods, such as neutralization, chemical precipitation, electrolysis, reverse osmosis, adsorption, redox and ion exchange. Adsorption is considered to be one of the most attractive technologies for treating heavy metal ions in wastewater due to its advantages of high efficiency, low cost, easy operation, and no secondary pollution.

Chelating resin is a polymer solid chelating agent, which is a cross-linked polymer containing chelating groups and insoluble in water and other solvents. It can selectively chelate specific metal ions from an aqueous solution containing metal ions. Bonds and covalent bonds form cyclic complexes. Compared with organic small molecule chelating agents, polymer chelating resins not only have the chelating effect of functional groups, but also can produce polymer effects, such as the high adsorption characteristics caused by the concentration of chelating groups and the solid phase extraction process. It has the characteristics of separability and reusability. In addition, chelating resin has the advantages of high selectivity, good physical and chemical stability, simple operation, and the wastewater after treatment meets the national discharge standard, so it is widely used. In recent years, domestic and foreign polymer chemists have been very active in the research of new polymer chelating resins, heavy metal recovery and environmental protection, and have made great contributions to the treatment of heavy metal ion wastewater.

The precursor of chelating resin can be cross-linked polystyrene, cross-linked polyacrylonitrile or cross-linked polyacrylic acid, etc., all of which are prepared by conventional macromolecule suspension polymerization, with mature preparation technology, easy functionalization, mechanical High strength and good chemical stability. The disadvantage is that they all have one thing in common, that is, divinylbenzene is basically used as a cross-linking agent, which has the disadvantage of poor hydrophilic performance.

Patent No. CN 104959130 A "chelating adsorption functional resin, its preparation method and application" discloses a kind of macroporous chloromethylated cross-linked polystyrene microsphere as the parent body and methylpiperazine as the compound. It is a chelating adsorption functional resin modified by the benzyl group on the chlorine ball, which can remove heavy metal ions in sewage, is easy to separate and recover, and can be recycled. However, the binding amount of salicylic hydroxamic acid on the chelating resin is 0.38~0.43 g/g, the adsorption effect of Cu ²⁺ , Cd ²⁺ , Ni ²⁺ , Pd ²⁺ plasma is not ideal, and the adsorption capacity is low , the equilibrium static adsorption capacity of 60 mg/L metal ion solution is between 8 and 30 mg/g, and the equilibrium static adsorption capacity of 1000 mg/L metal ion solution is between 20 and 44 mg/g.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a fluorenone-type chelating resin with high adsorption capacity for heavy metals.

Another technical problem to be solved by the present invention is to provide a preparation method of the fluorenone type chelating resin.

The third technical problem to be solved by the present invention is to provide the application of the fluorenone type chelating resin.

In order to solve the above problems, a fluorenone-type chelating resin according to the present invention is characterized in that: the chelating resin uses 4,5-diazafluoren-9-one as a ligand, and is mixed with chloromethyl The side group reaction of the polystyrene microspheres is obtained, and its structural formula is as follows:

。

.

The reaction percentage of the fluorenone with the side groups of the chloromethylated polystyrene microspheres is 74%.

The preparation method of a kind of fluorenone type chelating resin as above, comprises the following steps:

(1) Add a solvent to the container of the macroporous chlorine balls after vacuum drying, stir and swell for 12~15 h to obtain reaction solution A; the mass volume ratio of the macroporous chlorine balls to the solvent is 1 g: 40~50 mL;

(2) The reaction solution A is heated to 60-90 °C, triphenylphosphine is added, and the reaction is performed at a constant temperature of 60-90 °C for 16-19 h to obtain a quaternary phosphonium product; the macroporous chlorine ball and the triphenylphosphine are The mass ratio of phosphine is 1g: 1.15~1.2g;

(3) Described quaternary phosphonium product is redissolved in described solvent after dehydrated alcohol washing, vacuum drying, obtains reaction solution B; The mass volume ratio of described quaternary phosphonium product and described solvent is 1 g: 40～50 mL;

(4) Add 4,5-diazafluoren-9-one to the reaction solution B, and stir and react at 60-90 ° C for 15-18 h to obtain a reaction product, which is washed with anhydrous ethanol and vacuum-dried, The fluorenone type chelating resin is obtained; the mass ratio of the macroporous chlorine sphere to the 4,5-diazafluoren-9-one is 1 g: 1.05-1.1 g.

The process route is as follows:

The macroporous chlorine ball in the described step (1) is macroporous chloromethylated divinylbenzene cross-linked polystyrene beads (CPS), the degree of cross-linking is 6%, the chlorine content is 18-20%, and the chloromethylated The branch rate is 70~75%, the pore size of the chlorine ball is 25~30 nm, and the particle size is 0.4~1.0mm.

The solvent in the step (1) and the step (3) all refer to a solution in which toluene and dioxane are mixed in a volume ratio of 1:1.

The conditions for vacuum drying in the step (3) and the step (4) refer to a temperature of 60° C., a pressure of 20KPa, and a time of 6 h.

The application of the above-mentioned fluorenone-type chelating resin in the treatment of heavy metal ion-containing wastewater is characterized in that: after the fluorenone-type chelating resin is packed in an adsorption column, the concentration of 100mg/L of heavy metal ions containing The wastewater is subjected to adsorption treatment; the heavy metal ions in the wastewater refer to one or more of Cu(II), Ni(II) and Pb(II).

Compared with the prior art, the present invention has the following advantages:

1. The present invention uses macroporous chloromethylated polystyrene beads (chlorine balls, CPS) as the matrix resin and fluorenone as the ligand. Both N atoms have strong coordination ability, and the most important thing is that 4,5-diazafluoren-9-one has an active carbonyl group at the 9-position, which can be brought to a variety of derivatives, which can be It is easy to bond it to the chlorine sphere and modify the benzyl group on the chlorine sphere to obtain a new type of chelating resin with pyridine as the functional group.

Figure 1 shows the infrared spectra of the chloromethylated polystyrene microspheres, the quaternary phosphonium product and the fluorenone-type chelating resin. It can be seen from the figure that in the spectrum of chloromethylated polystyrene microspheres, in addition to the characteristic absorption peak of polystyrene, the strong absorption peak at 678 cm ^-1 is C- in -CH ₂ Cl Stretching vibration of the Cl bond; 1267 cm ^-1 is the in-plane bending vibration of the CH bond on the 1, 4-disubstituted benzene ring strengthened after the 4-position of the benzene ring is substituted by -CH ₂ Cl, and the in-plane bending vibration of the CH bond at 826 cm ^-1 The absorption is the out-of-plane bending vibration of the CH bond on the benzene ring after binary substitution. In the spectrum of the fluorenone-type chelating resin, two new peaks appear: the absorption at 1635 cm ^-1 is the C=C stretching vibration peak of the fluorenone-type chelating resin. The absorption at 1045 cm ^-1 is the in-plane bending vibration of the CH bond on the 1,4-disubstituted benzene ring which is strengthened after the 4-position of the benzene ring is substituted by C=C. Infrared spectrum analysis shows that 4,5-diazafluoren-9-one has been successfully bonded to the side group of chloromethyl polystyrene, and the fluorenone type chelating resin is prepared.

Elemental analysis is carried out on the chloromethylated polystyrene microspheres and the described fluorenone-type chelating resin, and the element contents of the chloromethylated polystyrene microspheres and the described fluorenone-type chelating resin are shown in Table 1, shown in Table 2.

Table 1 Elemental analysis of chloromethylated polystyrene

Elemental analysis of the fluorenone-type chelating resins described in Table 2

As can be seen from Tables 1-2, the content of N in the fluorenone-type chelating resin is about 74% of the theoretical value, indicating that 4,5-diazafluoren-9-one and chloromethyl polyphenylene The reaction ratio of the vinyl pendant groups is about 74%.

2. The chelating resin of the present invention has the advantages of simple preparation process, easy control of the preparation process, easy synthesis, readily available raw materials and low cost, which is beneficial to industrialized production.

3. The chelating resin of the present invention has a good selection of chelating properties for metal ions such as Cu(II), Ni(II), Pb(II), the chelating rate is fast, the chelating amount is large, and it is very effective for heavy metal ions. High coordination and complexing ability, its adsorption capacity of Cu(II) can reach 162 mg/g, therefore, the chelating resin prepared by the present invention is packed in the adsorption column, and the enrichment and recovery of various heavy metals can be realized, Effectively solve the problem of advanced treatment of wastewater containing heavy metal ions.

【Adsorption capacity test】

1000 mg/L Cu(II), Pb(II) and Ni(II) solutions were prepared and diluted to different concentrations. Take 50 mg of the fluorenone-type chelating resin prepared in Example 1 of the present invention and add it to 100 mL of solutions of Cu(II), Pb(II) and Ni(II) with different concentrations, and put them into a constant temperature culture shaker. After shaking at room temperature for 24 h, the absorbance change of the solution was measured to observe the adsorption effect. The measurement results are shown in Figure 2. The maximum adsorption capacities of the fluorenone-type chelate resin for Cu(II), Pb(II), and Ni(II) were 162 mg/g, 105 mg/g, and 79 mg/g, respectively. g.

Take 1 g of the fluorenone-type chelating resin prepared in Example 1 of the present invention and add it to 100 mL, 200 mg/L of Cu(II), Pb(II), and Ni(II) solutions, and use hydrochloric acid to adjust the concentration of the solution. The initial pH values were 1, 2, 3, 4, 5, and 6, and they were placed in a constant temperature incubation shaker for 30-60 min at room temperature, and then the absorbance changes of the solution were measured to observe the adsorption effect. The measurement results are shown in Figure 3. Since Cu(II), Pb(II) and Ni(II) will form hydroxide precipitation under alkaline conditions, the pH value on the adsorption effect was observed under the condition of pH<7. influences. It can be seen from Figure 3 that when pH<4, the adsorption capacity increases with the increase of pH value, but when pH>5, the adsorption capacity of the adsorbent tends to be stable. Therefore, it can be seen from Figure 3 that the optimum adsorption pH of the fluorenone-type chelating resin is 5.

【Columnar Experiment】

1 g of the fluorenone-type chelating resin prepared in Example 1 of the present invention was loaded into a glass column with a height of 50 cm and a diameter of 1.0 cm. At 25 °C, 500 mL of single metal ion solutions of Cu(II), Ni(II) and Pb(II) with an initial concentration of 150 mg/L were allowed to flow down the column at a flow rate of 1.0 mL/min. Use a microcomputer high-range copper (lead, nickel) ion concentration analyzer to measure the outlet metal ion concentration. The loaded resin was eluted and regenerated with 0.2 M HCl after adsorption, and then the resin was carefully washed with distilled water until pH neutral and ready for reuse. The adsorption-desorption cycle of metal ions was repeated 5 times. The measurement results of the outlet metal ion concentration are shown in Table 3. During the adsorption process of the fixed bed column, the removal of Cu(II), Ni(II) and Pb(II) by the fluorenone-type chelate resin prepared in Example 1 of the present invention The effect is also very good. The adsorption data showed that at a flow rate of 1.0 mL/min and at 25 °C, the final concentrations of Cu(II), Ni(II) and Pb(II) metal ion solutions were all lower than 1.0 mg/L each time, which was in line with the national heavy metal wastewater discharge. Standard (GB8978-1996).

Table 3 Columnar experiment outlet metal ion concentration (mg/L)

4. The chelating resin of the present invention is easy to use, easy to separate and recycle, easy to desorb, regenerate and reuse, and the chelating resin can be recycled for 10 times, and the adsorption performance is basically unchanged.

【Recycling Experiment】

Take 50 mg of the fluorenone-type chelating resin prepared in Example 1 of the present invention and add it to 20 mL, 50 mg/L of Cu(II), Pb(II) and Ni(II) solution, and put it at room temperature. After being placed in a constant temperature incubation shaker for 30-60 min, the absorbance change of the solution was measured to observe the adsorption effect. The saturated adsorbent with the target pollutants was packed in a chromatography column, rinsed with 0.1M hydrochloric acid for 5 h, and then washed with deionized water for the next round of adsorption. A total of 5 times were reused, and the experimental results are shown in Figure 4. It can be seen from Figure 4 that the adsorption capacity of the fluorenone-type chelate resin to Cu(II), Pb(II) and Ni(II) decreased slightly after repeated use for 5 times. After 5 cycles, the adsorption of Cu(II), Pb(II) and Ni(II) by fluorenone chelate resin can still reach 92%, 90% and 89% of the first adsorption, respectively. It is proved that the fluorenone-type chelating resin has high stability, is a durable resin for adsorbing single metal ions, and can be used repeatedly.

Description of drawings

The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

Fig. 1 is the infrared spectrogram of chloromethylated polystyrene microspheres, quaternary phosphonium products and fluorenone type chelating resin in the present invention.

Figure 2 shows the maximum adsorption capacity of Cu(II), Ni(II) and Pb(II) by the fluorenone-type chelating resin of the present invention.

Figure 3 shows the effect of pH on the adsorption of Cu(II), Ni(II) and Pb(II) by the fluorenone-type chelating resin of the present invention.

Figure 4 shows the repeated use performance of the fluorenone-type chelating resin for adsorbing Cu(II), Ni(II) and Pb(II).

Detailed ways

A fluorenone-type chelating resin, the chelating resin uses 4,5-diazafluoren-9-one as a ligand, and is prepared by reacting with the side groups of chloromethylated polystyrene microspheres. The structure is as follows:

。

.

Among them, the reaction percentage of fluorenone with the side groups of chloromethylated polystyrene microspheres is 74%.

Embodiment 1 A preparation method of fluorenone-type chelating resin, comprising the following steps:

(1) Add 40 mL of solvent to the container where 1 g of vacuum-dried macroporous chlorine balls are placed, and stir and swell for 12 h to obtain reaction solution A;

(2) The reaction solution A was heated to 60 °C, 1.15 g of triphenylphosphine was added, and the reaction was carried out at a constant temperature of 60 °C for 16 h to obtain a quaternary phosphonium product;

(3) 1 g of the quaternary phosphonium product was washed with absolute ethanol, dried under vacuum at 60°C and 20KPa for 6 h, and redissolved in 40 mL of solvent to obtain reaction solution B;

(4) 1.05 g of 4,5-diazafluoren-9-one was added to the reaction solution B, and the reaction was stirred at 60 °C for 15 h to obtain the reaction product. Under vacuum drying conditions for 6 h, the fluorenone-type chelating resin was obtained.

Embodiment 2 A preparation method of fluorenone-type chelating resin, comprising the following steps:

(1) Add 50 mL of solvent to the container where 1 g of vacuum-dried macroporous chlorine balls are placed, and stir and swell for 13 h to obtain reaction solution A;

(2) The reaction solution A was heated to 70 °C, 1.2 g of triphenylphosphine was added, and the reaction was carried out at a constant temperature of 70 °C for 17 h to obtain a quaternary phosphonium product;

(3) 1 g of the quaternary phosphonium product was washed with anhydrous ethanol, dried under vacuum at 60°C and 20KPa for 6 h, and redissolved in 50 mL of solvent to obtain reaction solution B;

(4) 1.1 g of 4,5-diazafluoren-9-one was added to the reaction solution B, and the reaction was stirred at 70 °C for 16 h to obtain the reaction product. Under vacuum drying conditions for 6 h, the fluorenone-type chelating resin was obtained.

Embodiment 3 A preparation method of fluorenone-type chelating resin, comprising the following steps:

(1) Add 45 mL of solvent to the container where 1 g of vacuum-dried macroporous chlorine balls are placed, and stir and swell for 14 h to obtain reaction solution A;

(2) The reaction solution A was heated to 80 °C, 1.18 g of triphenylphosphine was added, and the reaction was carried out at a constant temperature of 80 °C for 18 h to obtain a quaternary phosphonium product;

(3) 1 g of the quaternary phosphonium product was washed with anhydrous ethanol, dried under vacuum at 60 ° C and 20 KPa for 6 h, and redissolved in 45 mL of solvent to obtain reaction solution B;

(4) 1.08 g of 4,5-diazafluoren-9-one was added to the reaction solution B, and the reaction was stirred at 80 °C for 17 h to obtain the reaction product. Under vacuum drying conditions for 6 h, the fluorenone-type chelating resin was obtained.

Embodiment 4 A preparation method of fluorenone-type chelating resin, comprising the following steps:

(1) Add 40 mL of solvent to the container where 1 g of vacuum-dried macroporous chlorine balls are placed, and stir and swell for 15 h to obtain reaction solution A;

(2) The reaction solution A was heated to 90°C, 1.15 g of triphenylphosphine was added, and the reaction was performed at a constant temperature of 90°C for 19 h to obtain a quaternary phosphonium product;

(3) 1 g of the quaternary phosphonium product was washed with anhydrous ethanol, dried under vacuum at 60°C and 20KPa for 6 h, and redissolved in 40 mL of solvent to obtain reaction solution B;

(4) 1.05 g of 4,5-diazafluoren-9-one was added to the reaction solution B, and the reaction was stirred at 90 °C for 18 h to obtain the reaction product. Under vacuum drying conditions for 6 h, the fluorenone-type chelating resin was obtained.

In the above-mentioned embodiments 1~4, the macroporous chlorine balls are macroporous chloromethylated divinylbenzene cross-linked polystyrene beads (CPS), the degree of cross-linking is 6%, the chlorine content is 18~20%, and the chloroform The graft ratio of the base is 70~75%, the pore size of the chlorine ball is 25~30 nm, and the particle size is 0.4~1.0 mm.

The solvent refers to a solution in which toluene and dioxane are uniformly mixed in a volume ratio of 1:1.

The vessel has an electric stirrer, a condenser tube and a feeding port.

The application of the fluorenone-type chelating resin prepared in the above-mentioned examples 1 to 4 in the treatment of wastewater containing heavy metal ions: after the fluorenone-type chelating resin is packed in the adsorption column, the concentration of the fluorenone-type chelating resin is 100mg/L. The wastewater is treated by adsorption; the heavy metal ions in the wastewater refer to one or more of Cu(II), Ni(II) and Pb(II).

Claims (7)

1. A fluorenone type chelate resin characterized in that: the chelating resin is prepared by taking 4, 5-diazafluorene-9-ketone as a ligand and reacting with a side group of chloromethylated polystyrene microspheres, and has the following structural formula:

。

2. the chelating resin of claim 1, wherein the fluorenone is: the percentage of reaction of the 4, 5-diazafluoren-9-one with the pendant groups of the chloromethylated polystyrene microspheres was 74%.

3. The method for preparing the fluorenone-type chelate resin according to claim 1, comprising the steps of:

adding a solvent into a container for placing vacuum-dried macroporous chlorine balls, and stirring and swelling for 12-15 hours to obtain a reaction liquid A; the mass volume ratio of the macroporous chlorine spheres to the solvent is 1 g: 40-50 mL;

heating the reaction liquid A to 60-90 ℃, adding triphenylphosphine, and reacting at the constant temperature of 60-90 ℃ for 16-19 h to obtain a quaternary phosphonium product; the mass ratio of the macroporous chlorine spheres to the triphenylphosphine is 1 g: 1.15-1.2 g;

washing the quaternary phosphonium product with absolute ethyl alcohol, drying in vacuum, and dissolving in the solvent again to obtain a reaction solution B; the mass-to-volume ratio of the quaternary phosphonium product to the solvent is 1 g: 40-50 mL;

adding 4, 5-diazafluorene-9-one into the reaction liquid B, stirring and reacting for 15-18 h at 60-90 ℃ to obtain a reaction product, washing the reaction product with absolute ethyl alcohol, and drying in vacuum to obtain fluorenone type chelate resin; the mass ratio of the macroporous chlorine spheres to the 4, 5-diazafluoren-9-one is 1 g: 1.05-1.1 g.

4. The method for preparing a fluorenone-type chelate resin according to claim 3, wherein: the macroporous chlorine balls in the step are macroporous chloromethylated divinylbenzene crosslinked polystyrene beads, the crosslinking degree is 6%, the chlorine content is 18-20%, the chloromethyl grafting rate is 70-75%, the pore diameter of the chlorine balls is 25-30 nm, and the particle size is 0.4-1.0 mm.

5. The method for preparing a fluorenone-type chelate resin according to claim 3, wherein: the solvent in the step I and the step III refers to the solvent formed by mixing toluene and dioxane in a ratio of 1: 1 volume ratio of the mixture to the solution.

6. The method for preparing a fluorenone-type chelate resin according to claim 3, wherein: the vacuum drying conditions in the third step and the fourth step are that the temperature is 60 ℃, the pressure is 20KPa, and the time is 6 h.

7. The use of the fluorenone-type chelate resin of claim 1 for treating heavy metal ion-containing wastewater, wherein: after fluorenone type chelating resin is filled in an adsorption column, carrying out adsorption treatment on the wastewater containing heavy metal ions and having the concentration of 100 mg/L; the heavy metal ions in the wastewater refer to one or more of Cu (II), Ni (II) and Pb (II).

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