阅读说明：本技术 一种铁基金属催化材料及其制备方法与应用 (Iron-based metal catalytic material and preparation method and application thereof ) 是由 卢德力 陈哲 杨琦东 许钰萌 严春阳 杨洋 韩生 于 2021-08-10 设计创作，主要内容包括：本发明涉及一种铁基金属催化材料及其制备方法与应用,催化材料的制备方法包括以下步骤：1)将氯化铁或含有氯化铁的混合金属盐酸盐在有氧环境下进行煅烧,得到煅烧产物；2)将步骤1)中的煅烧产物洗涤后干燥,即得到铁基金属催化材料；应用时,催化材料作为催化剂,在高级氧化体系中对废水中的有机污染物进行降解。与现有技术相比,本发明中的铁基金属催化材料制备简单,成本低廉,反应条件温和,催化活性高,且在双氧水、过氧一硫酸盐、过氧二硫酸盐等多种不同的高级氧化体系中均具有较高的活性,并在对废水中的有机污染物进行降解的过程中有较高含量的单线态氧产生,促进了对有机污染物的降解。(The invention relates to an iron-based metal catalytic material and a preparation method and application thereof, wherein the preparation method of the catalytic material comprises the following steps: 1) calcining ferric chloride or mixed metal hydrochloride containing the ferric chloride in an aerobic environment to obtain a calcined product; 2) washing and drying the calcined product in the step 1) to obtain the iron-based metal catalytic material; when in use, the catalytic material is used as a catalyst to degrade organic pollutants in wastewater in an advanced oxidation system. Compared with the prior art, the iron-based metal catalytic material has the advantages of simple preparation, low cost, mild reaction conditions and high catalytic activity, has higher activity in various different advanced oxidation systems such as hydrogen peroxide, peroxymonosulfate, peroxydisulfate and the like, generates higher content of singlet oxygen in the process of degrading organic pollutants in wastewater, and promotes the degradation of the organic pollutants.)

1. A preparation method of an iron-based metal catalytic material is characterized by comprising the following steps:

1) calcining ferric chloride or mixed metal hydrochloride containing the ferric chloride in an aerobic environment to obtain a calcined product;

2) and (2) washing and drying the calcined product in the step 1) to obtain the iron-based metal catalytic material.

2. The method of claim 1, wherein the mixed metal hydrochloride in step 1) comprises ferric chloride and other metal hydrochlorides, and the mole percentage of the other metal hydrochlorides in the mixed metal hydrochlorides is 0-20%.

3. The method as claimed in claim 2, wherein the other metal hydrochloride is one of manganese chloride, cobalt chloride and nickel chloride.

4. The method of claim 2, wherein the mixed metal hydrochloride is prepared by: grinding and mixing ferric chloride and other metal hydrochlorides uniformly.

5. The method as claimed in claim 1, wherein the temperature of the step 1) is 200-300 ℃ and the time is 2-3 h.

6. The method of claim 1, wherein the step 2) comprises washing with methanol; in the drying process, the temperature is 35-45 ℃ and the time is 10-14 h.

7. An iron-based metallic catalytic material, characterized in that it is prepared by a method according to any one of claims 1 to 6.

8. Use of an iron-based metallic catalytic material as defined in claim 7 as a catalyst for the degradation of organic pollutants in waste water in advanced oxidation systems.

9. The use of an iron-based metallic catalytic material as claimed in claim 8, wherein said advanced oxidation system comprises one or more of hydrogen peroxide, peroxymonosulfate or peroxydisulfate.

10. The use of an iron-based metallic catalytic material as claimed in claim 8, wherein the catalytic material is added to the wastewater in an amount of 0.08-0.12 mg/mL.

Technical Field

The invention belongs to the technical field of organic pollutant-containing wastewater treatment, and relates to an iron-based metal catalytic material, and a preparation method and application thereof.

Background

With the development of society and economy, the problem of water pollution is increasingly prominent. The waste water has wide sources, various types and great harm, wherein the waste water containing organic pollutants such as dyes, personal care products, medicaments, endocrine disruptors, heterocyclic aromatic hydrocarbons and the like greatly destroys the water environment, has the characteristics of high chroma, high chemical oxygen demand, difficult degradation, large water volume and the like, and can seriously endanger the ecological environment and biological individuals when being treated improperly or discharged randomly.

For wastewater treatment, common methods include physical methods, biological methods, chemical methods, and the like. The physical method mainly comprises membrane separation, adsorption, extraction and other methods, and the method can only realize the enrichment of harmful substances and separate the harmful substances from a water phase, but cannot destroy and decompose the harmful substances, so that secondary pollution is easily caused, and the method is generally used as an auxiliary means in combination with other methods. The biological method mainly means introducing microorganisms or plants, removing harmful substances in water by means of metabolism, and comprises the action modes of biological flocculation, biological adsorption, biological degradation and the like, has the advantages of low cost, economy and environmental protection, but also has the defects of long strain culture time, easy poisoning, high selectivity on the types of the harmful substances and the like. The Advanced Oxidation Processes (AOPs) are also called deep Oxidation technologies including fenton Oxidation, photocatalytic Oxidation, sonochemical Oxidation, electrochemical Oxidation and the like, and are an effective solution for refractory wastewater. The method generates active oxygen under specific conditions to degrade macromolecular refractory organic pollutants, has the advantages of high activity, high universality and the like, can realize the decomposition and even complete mineralization of most refractory organic pollutants, and has excellent application and development prospects.

However, the existing advanced oxidation system has the disadvantages of high catalyst cost, low catalytic activity and the like, and further application of the catalyst is limited.

Disclosure of Invention

The invention aims to provide an iron-based metal catalytic material, and a preparation method and application thereof. The catalytic material prepared by the invention can be used for different advanced oxidation systems such as hydrogen peroxide, peroxymonosulfate, peroxydisulfate and the like, and can be used for performing visible light synergetic catalytic degradation on organic pollutants in wastewater.

The purpose of the invention can be realized by the following technical scheme:

a method for preparing an iron-based metal catalytic material, comprising the steps of:

1) calcining ferric chloride or mixed metal hydrochloride containing the ferric chloride in an aerobic environment to obtain a calcined product;

2) and (2) washing and drying the calcined product in the step 1) to obtain the iron-based metal catalytic material.

Further, in step 1), the mixed metal hydrochloride includes ferric chloride and other metal hydrochlorides, and the molar percentage of the other metal hydrochlorides in the mixed metal hydrochloride is 0-20% (value is not 0).

Further, the other metal hydrochloride is one of manganese chloride, cobalt chloride or nickel chloride, that is, the iron-based metal catalytic material is a single-metal iron-based metal catalytic material or a double-metal iron-based metal catalytic material. The chloride of the adjacent transition element is selected to realize partial substitution of the iron element in the material on the premise of not introducing other elements, thereby changing the generation rate of the material to active oxygen substances.

Further, the preparation process of the mixed metal hydrochloride comprises the following steps: grinding and mixing ferric chloride and other metal hydrochlorides uniformly.

Further, in the step 1), the temperature is 200-300 ℃ and the time is 2-3h in the calcining process. The muffle furnace heating rate is preferably 5-20 ℃/min. Aerobic thermal cracking is achieved by calcination in an aerobic environment.

Further, in the step 2), methanol is adopted for washing; in the drying process, the temperature is 35-45 ℃ and the time is 10-14 h.

An iron-based metal catalytic material is prepared by the method.

The application of an iron-based metal catalytic material as a catalyst for degrading organic pollutants (such as tetracycline) in wastewater in an advanced oxidation system.

Further, the advanced oxidation system contains hydrogen peroxide (H)₂O₂) Peroxomonosulfate (2 KHSO)₅·KHSO₄·K₂SO₄PMS for short or peroxodisulfate (Na)₂S₂O₈PDS for short), the catalytic material can achieve effective activation of different systems with singlet oxygen production in all three systems.

Furthermore, the adding amount of the catalytic material in the wastewater is 0.08-0.12 mg/mL.

Compared with the prior art, the invention has the following characteristics:

1) the iron-based metal catalytic material is simple to prepare, low in cost, mild in reaction condition and high in catalytic activity, and has high activity in various advanced oxidation systems such as hydrogen peroxide, peroxymonosulfate, peroxydisulfate and the like;

2) the iron-based metal catalytic material is applied to an advanced oxidation system, and is different from a traditional pure hydroxyl radical and sulfate radical system, and high-content singlet oxygen is generated in the process of degrading organic pollutants in wastewater, so that the degradation of the organic pollutants is promoted.

Drawings

FIG. 1 is a graph showing the degradation effect of the iron-based metal catalytic material in the PDS system according to the examples and the comparative examples;

FIG. 2 is a graph showing the degradation effect of the iron-based metal catalytic material in the PMS system according to the example and the comparative example;

FIG. 3 shows the example and comparative example of the Fe-based metal catalyst material in H₂O₂Degradation effect in the system.

Detailed Description

The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

The invention provides a preparation method of an iron-based metal catalytic material, which comprises the following steps:

1) calcining ferric chloride or mixed metal hydrochloride containing the ferric chloride in an aerobic environment to obtain a calcined product;

2) and (2) washing and drying the calcined product in the step 1) to obtain the iron-based metal catalytic material.

In the step 1), the mixed metal hydrochloride comprises ferric chloride and other metal hydrochlorides, and the mole percentage content of the other metal hydrochlorides in the mixed metal hydrochloride is 0-20% (the value is not 0). The other metal hydrochloride is one of manganese chloride, cobalt chloride or nickel chloride. The preparation process of the mixed metal hydrochloride comprises the following steps: grinding and mixing ferric chloride and other metal hydrochlorides uniformly. In the calcining process, the temperature is 200-300 ℃, and the time is 2-3 h.

In the step 2), methanol is adopted for washing; in the drying process, the temperature is 35-45 ℃ and the time is 10-14 h.

The invention also provides an iron-based metal catalytic material which is prepared by the method.

The invention also provides application of the iron-based metal catalytic material, and the catalytic material is used as a catalyst to degrade organic pollutants in wastewater in an advanced oxidation system. The advanced oxidation system contains one or more of hydrogen peroxide, peroxymonosulfate or peroxydisulfate. The addition amount of the catalytic material in the wastewater is 0.08-0.12 mg/mL.

Example (b):

1) preparation of iron-based metal catalytic material

In four groups of 2.703g FeCl respectively₃·6H₂251mg of MnCl is added into O₂、540.6mg FeCl₃·6H₂O、476mg CoCl₂·6H₂O or 475mg NiCl₂·6H₂And O, grinding, uniformly mixing, placing in a crucible, transferring into a muffle furnace, calcining for 2.5h at 250 ℃, washing the obtained product with methanol, and drying in vacuum for 12h at 40 ℃ to obtain a dark powder product, namely the iron-based metal catalytic material.

2) Application of wastewater containing organic pollutants in degradation

0.5mg of each of the four groups of products prepared in the step 1) is respectively added into 5mL of wastewater containing organic pollutants, wherein the organic pollutants are tetracycline hydrochloride, the concentration of the tetracycline hydrochloride is 20mg/L, 1mM of sodium peroxodisulfate or potassium peroxomonosulfate composite salt or hydrogen peroxide exists in the system, the light source is visible light of a 300W xenon lamp (attached with an optical filter), samples are taken after 5min of degradation reaction, and the samples are sent to high performance liquid chromatography for analysis, and the results are shown in a figure 1, a figure 2 and a figure 3.

Comparative example:

the trapping experiment was carried out on the basis of step 2) of the example, i.e.the system was supplemented with 5mM tryptophan (C)₁₁H₁₂N₂O₂Abbreviated Trp), the analysis time of the samples for the degradation reaction was extended to 10min, and the results are shown in fig. 1, fig. 2 and fig. 3.

As can be seen from fig. 1, 2, and 3:

when the material only contains iron, the material has better performance in a system of sodium peroxodisulfate and potassium peroxomonosulfate composite salt; when the material is doped with other metals such as manganese, cobalt or nickel besides iron, the material has excellent performance in three systems of sodium peroxydisulfate, potassium peroxymonosulfate composite salt and hydrogen peroxide, and the activity of the material is generally higher than that of the material only containing iron, so that the introduction of manganese, cobalt or nickel elements to replace part of iron elements can greatly improve the activity of the material.

In the capture experiment of the comparative example, the introduced tryptophan can effectively capture singlet oxygen in the reaction system and prevent the singlet oxygen from oxidizing and degrading organic pollutants in the reaction system. The degradation efficiency of the sodium peroxydisulfate, potassium peroxymonosulfate composite salt and hydrogen peroxide is obviously reduced after tryptophan is introduced, and the phenomenon also proves that singlet oxygen exists in the reaction system and the singlet oxygen has great contribution to the degradation of organic pollutants in the reaction system.

The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.