Application of a complexing agent-based nanoparticle material in treatment of halogen wastewater

Abstract

The present application relates to a kind of for processing complexing agent based nanometer material (CA@RF NPs) containing bromine / iodine wastewater.The preparation of ammonia catalysis sol-gel method is carried out, by adding different complexing agents in the precursor resorcinol compound, and the halogen substitution is carried out using its rich aromatic group.This innovation greatly shortens the halogen adsorption time, and improves the adsorption amount of halogen.Complexing agent based nanoparticle material realizes 90% or more of solid bromine efficiency in 3 hours, shows excellent adsorption performance, and can efficiently remove halogen pollutants in wastewater.The material has the characteristics of high efficiency, economy and environmental protection, as a new type of halogen wastewater treatment technology, can reduce the influence of halogen-containing wastewater on environment and human health, and has important application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of wastewater treatment, in particular to the application of complexant-based nanoparticles in treating halogen (Br2 / I2) containing wastewater. TECHNICAL BACKGROUND

[0002] Halogen wastewater is a common type of wastewater generated in industrial production and other activities, which contains elemental, anionic, inorganic halogen species and organic halogen species, etc. These wastewaters pose potential threats to the environment and human health. The bromine / iodine elements in halogen elements have strong toxicity and volatility, and the high reactivity of bromine / iodine makes more bromine / iodine by-products exist in water, which seriously threatens the safety of drinking water. In addition, with the development of energy storage battery technology, the widespread application of various Zn-Br2 / Zn-I2 batteries will cause more halogen waste liquid. Therefore, effective treatment methods are needed to reduce the impact of bromine / iodine containing wastewater on the environment and human health.

[0003] Traditional treatment methods include chemical precipitation, adsorption and ion exchange technologies, however, these methods have problems such as poor water stability, low treatment efficiency, high treatment cost and generation of large amounts of chemical waste. Therefore, it is very important to find a new type of treatment technology that is efficient, economical and environmentally friendly. SUMMARY

[0004] The present application provides the application of a complexant-based nanomaterial in treating halogen wastewater, which has the ability to efficiently remove halogen pollutants, and has good water stability, regenerability and environmental friendliness, and can achieve more efficient and safer removal of Br2 / I2 in water.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] The application of a complexant-based nanomaterial in treating halogen-containing wastewater, wherein 0.5mg-40mg / mL of the complexant-based nanomaterial (CA@RF NPs) is added to 0.001mol / L-0.2mol / L halogen-containing wastewater and left for 3h, and the removal rate of halogen is greater than 90%.

[0007] The complexant-based nanomaterial is composed of the following components: (1) a nanoscale carrier; (2) a complexing agent. The preparation route is as follows:

[0008] 1) Stir and mix the water and alcohol solution in a volume ratio of 5:1, then add a certain amount of ammonia water and mix uniformly, add a benzene-diol compound, and stir uniformly in a 50℃ water bath. Then add an aldehyde solution and stir and mix uniformly in a 50℃ water bath.

[0009] 2) Add the complexing agent and stir for 6-24h in a 50℃ water bath.

[0010] 3) Centrifuge the reaction system solution (15000 r / min, 3 min), and wash the obtained nanomaterial three times to obtain the complexing agent-based nanoparticles.

[0011] Preferably, the concentration of the phenolic compound in the mixed solution is 2-18 g / L.

[0012] Preferably, the volume ratio of the ammonia water to the mixed solution is 0.001-0.02.

[0013] Preferably, the volume ratio of the aldehyde solution to the mixed solution is 0.001-0.018.

[0014] Preferably, the concentration ratio of the complexing agent to the mixed solution is 0.02-2.5 mol / L.

[0015] Advantages of the present application:

[0016] The present application introduces a complexing agent to prepare a complexing agent-based nanomaterial (CA@RF NPs) for treating bromine / iodine-containing wastewater, and the material is prepared by an ammonia-catalyzed sol-gel method. The complexing agent is added to a precursor phenolic compound and an aldehyde solution, and halogen substitution is performed by the rich aromatic groups contained in the complexing agent. The introduction of the complexing agent greatly shortens the time for halogen removal treatment, and increases the adsorption amount of the material to halogen. The high adsorption efficiency can achieve the removal of halogen pollutants in wastewater in a short time. The rich phenolic hydroxyl groups make the material have good water dispersibility and stability, and it is easy to recycle and treat. In the preparation process, a large amount of chemical reagents do not need to be added, the generation of chemical waste is reduced, the environment is friendly, and the material has high market prospect and economic benefit. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 SEM image of CA@RF NPs.

[0018] Figure 2 Photo comparison of static removal of Br2 by CA@RF NPs.

[0019] Figure 3 Stability photo of brominated CA@RF NPs.

[0020] Figure 4 Bromine removal rate of CA@RF NPs in 3 h. DETAILED DESCRIPTION

[0021] The following examples further illustrate the present application, but it should be understood that the present application is not limited to these examples. Modifications and substitutions can be made to the methods, steps, or conditions of the present application without departing from the spirit and scope of the present application.

[0022] Example 1

[0023] Preparation of complexant-based nanoparticles:

[0024] Obtained by the extended method. First, 0.2 mL of ammonia water (28 wt%) was added to a mixture of 16 mL of anhydrous ethanol and 40 mL of deionized water, and stirred uniformly. Then, 0.2 g of resorcinol was added to form a uniform solution. Then, 280 μL of formaldehyde solution was added and mixed uniformly. Finally, 2.7 g of 1-ethyl-1-methylpiperidine bromide salt was added, and the mixture was stirred at 50°C for 6 h to synthesize the complexant-based nanoparticles (AC@RF NPs). The obtained solid particles were washed three times at a centrifuge speed of 15000 r / min for 3 min. The obtained solid particles were dried in a drying oven at 70°C for 12 h.

[0025] The SEM image of the prepared complexant-based nanoparticles is shown in Figure 1 , which presents a uniform spherical morphology. The addition of the complexant does not change the morphology of the material.

[0026] Example 2

[0027] 10 mg of complexant-based nanoparticles were added to bromine water with different concentrations of 0.001 mol / L-0.1 mol / L, and the Bt2 adsorption was observed.

[0028] The complexant-based nanoparticles in this example contain abundant aromatic groups, which are beneficial to halogen substitution reaction. At the same time, the addition of the complexant greatly shortens the halogen adsorption time. Taking bromine water with a concentration of 0.005 mol / L as an example, after 3 h of standing, the bromine water liquid faded almost transparent, and the KI-starch test was colorless. This proves the excellent Br2 removal capacity of the complexant-based nanoparticles. Figure 2 In high concentration bromine water (0.05 mol / L), the bromine removal rate was 95% in 3 h, which can realize short-time and efficient bromine removal. Figure 4

[0029] Example 3

[0030] In this example, the system in which the complexant-based nanoparticles completely adsorbed bromine and the color completely faded was heated in a water bath. As shown in Figure 3 , there was no obvious change in the test system before and after heating. The KI-test paper was colorless, i.e., no Br2 leakage was detected, indicating that this Br2 removal is not a reversible adsorption process, and the brominated complexant-based nanoparticles after Br2 adsorption have excellent stability.

[0031] Example 4 ​

[0032] Preparation of complexant-based nanoparticles:

[0033] The complexant-based nanoparticles were obtained by the extended Method. First, 1 mL of aqueous ammonia (28 wt%) was added to a mixture of 20 mL of anhydrous ethanol and 30 mL of deionized water, and stirred until uniform. Then, 1.5 g of hydroquinone was added and stirred to form a uniform solution. To this, 320 μL of formaldehyde solution was added and mixed well. Finally, 4.5 g of 1-butyl-1-methylpiperidine bromide salt was added, and the mixture was stirred at 50 °C for 12 h to synthesize the complexant-based nanoparticles. The obtained solid particles were washed three times by centrifugation at 15000 r / min for 3 min. The obtained solid particles were dried in a drying oven at 70 °C for 12 h.

Claims

1. The application of a complexing agent-based nanoparticle material in the treatment of halogen-containing wastewater, characterized in that... Adding 0.5 mg to 40 mg / mL of complexing agent-based nanomaterials to 0.001 mol / L to 0.2 mol / L halogen-containing wastewater and allowing it to stand for 3 hours resulted in a halogen removal rate greater than 90%. The preparation route of the complexing agent-based nanoparticle material is as follows: 1) Mix water and alcohol solution in a volume ratio of 5:1 until homogeneous, add an appropriate amount of ammonia and mix until homogeneous, then add hydroquinone compound and stir until homogeneous in a 50°C water bath. 2) Add the aldehyde solution and stir until well mixed in a 50°C water bath; 3) Add complexing agents of different concentrations, and then stir in a 50℃ water bath for 6-24 hours; 4) Centrifuge the reaction system solution at 15000 r / min for 3 min, and wash the resulting solid three times to obtain complexing agent-based nanoparticles; The complexing agent is one of 1-ethyl-1-methylpiperidine bromide, 1-butyl-1-methylpiperidine bromide, 1-hexyl-1-methylpiperidine bromide, decaalkyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and octadecyltrimethylammonium bromide.

2. The application of a complexing agent-based nanoparticle material according to claim 1 in the treatment of halogen-containing wastewater, characterized in that... The hydroquinone compound is one of resorcinol, hydroquinone, and catechol, and the concentration of the hydroquinone compound in the mixed solution is 2-18 g / L.

3. The application of a complexing agent-based nanoparticle material according to claim 1 in the treatment of halogen-containing wastewater, characterized in that... The volume ratio of ammonia to the mixed solution is 0.001-0.

02.

4. The application of a complexing agent-based nanoparticle material according to claim 1 in the treatment of halogen-containing wastewater, characterized in that... The volume ratio of aldehyde solution to mixed solution is 0.001-0.

018.

5. The application of a complexing agent-based nanoparticle material according to claim 1 in the treatment of halogen-containing wastewater, characterized in that... The concentration ratio of the complexing agent to the mixed solution is 0.02-2.5 mol / L.

6. The application of a complexing agent-based nanoparticle material according to claim 1 in the treatment of halogen-containing wastewater, characterized in that... The sources of halogen wastewater include, but are not limited to, industrial wastewater and wastewater discharged from sewage treatment plants.

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