阅读说明：本技术 一种复合负载型三维催化粒子及其制备方法 (Composite supported three-dimensional catalytic particle and preparation method thereof ) 是由 郭萧 王永平 于 2019-08-28 设计创作，主要内容包括：本发明公开一种复合负载型三维粒子及其制备方法,包括：将Fe(NO<Sub>3</Sub>)<Sub>3</Sub>、无水乙醇、无水SnCl<Sub>4</Sub>和SbCl<Sub>3</Sub>混合,得到溶液A；向水、无水乙醇的混合液中加入乙酸,使溶液的pH＝4.5,得到溶液B；将溶液B加到溶液A中,使得混合液中Fe摩尔浓度为0.5mol/L,得到含Fe、Sn、Sb的凝胶；将GAC粒子浸没在所述含Fe、Sn、Sb的凝胶中,摇床反应使GAC包裹所述含Fe、Sn、Sb的凝胶,之后取出包裹所述含Fe、Sn、Sb的凝胶的GAC粒子,烘干后,于惰性气氛下,450℃烧制2h后,即得所述复合负载型三维粒子。该复合负载型三维粒子催化效果更好,COD去除率和处理效果的稳定性均有明显提升,对于三维电极反应器处理有机污染物有着重要的意义。(The invention discloses a composite load type three-dimensional particle and a preparation method thereof, wherein the preparation method comprises the following steps: mixing Fe (NO) 3 ) 3 Anhydrous ethanol, anhydrous SnCl 4 And SbCl 3 Mixing to obtain a solution A; adding acetic acid to a mixed solution of water and absolute ethyl alcohol to adjust the pH of the solution to 4.5 to obtain a solution B; adding the solution B into the solution A to ensure that the molar concentration of Fe in the mixed solution is 0.5mol/L, and obtaining gel containing Fe, Sn and Sb; immersing the GAC particles in the gel containing Fe, Sn and Sb, carrying out table shaking reaction to enable the GAC to wrap the gel containing Fe, Sn and Sb, taking out the GAC particles wrapping the gel containing Fe, Sn and Sb, drying, and firing at 450 ℃ for 2h in an inert atmosphere to obtain the composite supported three-dimensional particles. The composite load type three-dimensional particle has better catalytic effect, stable COD removal rate and treatment effectThe performance is obviously improved, and the method has important significance for treating organic pollutants by using a three-dimensional electrode reactor.)

1. A preparation method of composite supported three-dimensional particles is characterized by comprising the following steps:

(1) mixing Fe (NO)₃)₃Anhydrous ethanol, anhydrous SnCl₄And SbCl₃Mixing to obtain a solution A; adding acetic acid to a mixed solution of water and absolute ethyl alcohol to adjust the pH of the solution to 4.5 to obtain a solution B; adding the solution B into the solution A to ensure that the molar concentration of Fe in the mixed solution is 0.5mol/L, and obtaining gel containing Fe, Sn and Sb;

(2) immersing the GAC particles in the gel containing Fe, Sn and Sb, carrying out table shaking reaction to enable the GAC to wrap the gel containing Fe, Sn and Sb, taking out the GAC particles wrapping the gel containing Fe, Sn and Sb, drying, and firing at 450 ℃ for 2h in an inert atmosphere to obtain the composite supported three-dimensional particles.

2. The method of claim 1, wherein the GAC particles of step (2) are subjected to a pretreatment comprising: the GAC particles were washed with deionized water and dried at 105 ℃ for 12 h.

3. The production method according to claim 1, wherein in the step (1), the molar ratio of the Sn element to the Fe element is 0.01.

4. The production method according to claim 1, wherein in the step (1), the molar ratio of the Sn element to the Sb element is 10.

5. The production method according to claim 1, wherein in the step (1), the volume ratio of water to absolute ethyl alcohol in the solution B is 1: 3.

6. The method according to claim 1, wherein in the step (2), the drying is performed at 100 ℃.

7. The preparation method according to claim 1, wherein in the step (2), the drying time is 12 hours.

8. The method according to claim 1, wherein in the step (2), the inert gas is nitrogen or argon.

9. The production method according to claim 1, wherein in the step (2), the temperature is raised to the firing temperature at a rate of 5 ℃/min at the time of firing.

10. The composite supported three-dimensional particle prepared by the preparation method of any one of claims 1 to 9.

Technical Field

The invention belongs to the field of environment-friendly materials and wastewater treatment, and particularly relates to a composite supported three-dimensional catalytic particle and a preparation method thereof.

Background

In order to achieve more stringent discharge standards, it is necessary to subject the wastewater to advanced treatment. The following three methods are mainly used for advanced treatment: membrane separation, biological, advanced oxidation. The main principle of membrane treatment technology is physical entrapment and transfer of contaminants, and not efficient mineralization. When wastewater with poor biodegradability and containing a large amount of inorganic salts and heavy metal ions is treated by a biological method, the growth of microorganisms is adversely affected. The advanced oxidation method is mainly a method for generating hydroxyl free radicals with strong oxidation capacity to oxidize organic pollutants in the wastewater into carbon dioxide, water or other minerals.

Wherein, the hydroxyl free radical generated in the electrolytic process by the electrochemical oxidation method is not selectively oxidized and decomposed into organic pollutants, and the degradation rate is high. Other oxidation products (active chlorine, S) are also indirectly generated₂O₈、H₂O₂Etc.) to further promote complete degradation of the organic matter. The traditional two-dimensional electrochemical catalysis has the defects of low current efficiency, small electrode area and the like. The three-dimensional electrocatalysis is that on the basis of two-dimensional electrocatalysis, electrode particles are added between main electrodes to form a three-dimensional electrochemical system, so that the degradation efficiency of pollutants is improved. In the three-dimensional electrocatalysis technology, the selection and preparation of electrode particles are a very key factor influencing the electrocatalysis efficiency.

Disclosure of Invention

In order to further improve the catalytic performance of the supported catalyst GAC particles, the invention prepares a composite catalyst on the basis of the catalyst loaded with Fe and Sn/Sb, and the composite catalyst is loaded on the GAC particles. The precursor of Fe and Sn/Sb is simultaneously dissolved together to prepare a gel containing Fe, Sn and Sb, and then the gel is loaded on GAC particles through a series of methods to form composite catalytic particles GAC-Fe-Sn/Sb, so that the catalytic effect is better, the COD removal rate and the stability of the treatment effect are obviously improved, and the method has important significance for treating organic pollutants by using a three-dimensional electrode reactor.

The purpose of the invention is realized by the following technical scheme.

A preparation method of composite supported three-dimensional particles comprises the following steps:

(1) mixing Fe (NO)₃)₃Anhydrous ethanol, anhydrous SnCl₄And SbCl₃Mixing to obtain a solution A; adding acetic acid to a mixed solution of water and absolute ethyl alcohol to adjust the pH of the solution to 4.5 to obtain a solution B; adding the solution B into the solution A to ensure that the molar concentration of Fe in the mixed solution is 0.5mol/L, and obtaining gel containing Fe, Sn and Sb;

(2) immersing the GAC particles in the gel containing Fe, Sn and Sb, carrying out table shaking reaction to enable the GAC to wrap the gel containing Fe, Sn and Sb, taking out the GAC particles wrapping the gel containing Fe, Sn and Sb, drying, and firing at 450 ℃ for 2h in an inert atmosphere to obtain the composite supported three-dimensional particles. The composite supported three-dimensional particle is marked as GAC-Fe-Sn/Sb.

The GAC particles of step (2) are pretreated, the pretreatment comprising: the GAC particles were washed with deionized water and dried at 105 ℃ for 12 h.

In the step (1), the molar ratio of the Sn element to the Fe element is 0.01.

In the step (1), the molar ratio of the Sn element to the Sb element is 10.

In the step (1), the volume ratio of water to absolute ethyl alcohol in the solution B is 1: 3.

In the step (2), the time of the shaking table reaction is 2 hours.

In the step (2), the drying is drying at 100 ℃.

In the step (2), the drying time is 12 h.

In the step (2), the inert gas is nitrogen or argon.

In the step (2), the temperature is raised to the firing temperature at a rate of 5 ℃/min during firing.

In the step (2), the firing is performed in a muffle furnace.

The invention also provides the composite supported three-dimensional particles prepared by the method.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

according to the invention, the composite load type three-dimensional particles can be prepared by mixing the solution containing Fe and Sn/Sb precursors together to form gel, then immersing the GAC particles in the gel, fully reacting by using a shaker, drying, and roasting by using a muffle furnace. The composite supported three-dimensional particles are used for degrading wastewater containing organic pollutants, and the catalytic performance of the GAC particles loaded with Fe-Sn/Sb is researched by analyzing the pollutant degradation effect.

The composite catalyst is prepared on the basis of the catalyst loaded with Fe and Sn/Sb, and is loaded on GAC particles. The precursor of Fe and Sn/Sb are dissolved together at the same time to prepare a gel containing Fe, Sn and Sb, and then the gel is loaded on the GAC particles through a series of methods to form the composite catalytic particles GAC-Fe-Sn/Sb. Compared with the GAC particles which load Fe or Sn/Sb independently, the catalytic effect is better, the COD removal rate and the stability of the treatment effect are obviously improved, and the method has important significance for treating organic pollutants by using a three-dimensional electrode reactor.

Drawings

FIG. 1 is a graph showing the comparison of COD removal rate of treated wastewater of the present composite supported catalytic particle GAC-Fe-Sn/Sb with respect to the single supported particles GAC-Fe and GAC-Sn/Sb.

Detailed Description

(1) Mixing Fe (NO)₃)₃Anhydrous ethanol, anhydrous SnCl₄And SbCl₃Mixing to obtain a solution A; adding acetic acid to a mixed solution of water and absolute ethyl alcohol to adjust the pH of the solution to 4.5 to obtain a solution B; adding the solution B into the solution A to ensure that the molar concentration of Fe in the mixed solution is 0.5mol/L, and obtaining gel containing Fe, Sn and Sb;

(2) immersing the GAC particles in the gel containing Fe, Sn and Sb, carrying out table shaking reaction to enable the GAC to wrap the gel containing Fe, Sn and Sb, taking out the GAC particles wrapping the gel containing Fe, Sn and Sb, drying, and firing at 450 ℃ for 2h in an inert atmosphere to obtain the composite supported three-dimensional particles. The composite supported three-dimensional particle is marked as GAC-Fe-Sn/Sb.

The GAC particles of step (2) are pretreated, the pretreatment comprising: the GAC particles were washed with deionized water and dried at 105 ℃ for 12 h.

In the step (1), the molar ratio of the Sn element to the Fe element is 0.01.

In the step (1), the molar ratio of the Sn element to the Sb element is 10.

In the step (1), the volume ratio of water to absolute ethyl alcohol in the solution B is 1: 3.

In the step (2), the time of the shaking table reaction is 2 hours.

In the step (2), the drying is drying at 100 ℃.

In the step (2), the drying time is 12 h.

In the step (2), the inert gas is nitrogen or argon.

In the step (2), the temperature is raised to the firing temperature at a rate of 5 ℃/min during firing.

In the step (2), the firing is performed in a muffle furnace.

The GAC particles loaded with Fe-Sn/Sb prepared by the method and single loaded particles GAC-Fe and GAC-Sn/Sb respectively treat COD in wastewater, and the removal rate is shown in figure 1.