WO2024022299A1 - 一种负载锰生物炭催化剂及其制备方法与应用 - Google Patents

一种负载锰生物炭催化剂及其制备方法与应用 Download PDF

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Publication number
WO2024022299A1
WO2024022299A1 PCT/CN2023/108945 CN2023108945W WO2024022299A1 WO 2024022299 A1 WO2024022299 A1 WO 2024022299A1 CN 2023108945 W CN2023108945 W CN 2023108945W WO 2024022299 A1 WO2024022299 A1 WO 2024022299A1
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Prior art keywords
manganese
biochar
loaded
antibiotics
concentrated liquid
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PCT/CN2023/108945
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English (en)
French (fr)
Inventor
王华伟
张晨
张华伟
王亚楠
宫兆国
孙英杰
付友先
孙治国
刘克琼
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Qingdao Jieyuan Environment Co Ltd
Qingdao Xiaojianxi Leachate Treatment Co Ltd
Qingdao University of Technology
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Qingdao Jieyuan Environment Co Ltd
Qingdao Xiaojianxi Leachate Treatment Co Ltd
Qingdao University of Technology
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Application filed by Qingdao Jieyuan Environment Co Ltd, Qingdao Xiaojianxi Leachate Treatment Co Ltd, Qingdao University of Technology filed Critical Qingdao Jieyuan Environment Co Ltd
Priority to AU2023314163A priority Critical patent/AU2023314163B2/en
Publication of WO2024022299A1 publication Critical patent/WO2024022299A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate

Definitions

  • the invention relates to the fields of pollutant treatment and chemical materials. Specifically, it discloses a manganese-loaded biochar catalyst and its preparation method and application.
  • Antibiotics are widely used around the world as powerful drugs for the treatment of infectious diseases. Antibiotics enter the environment through the excretion of organisms' feces and urine, the discarding of expired or residual antibiotics in containers, and the discharge of antibiotics lost during the drug production process into water bodies. There are varying degrees of antibiotic pollution in water bodies, soil, sediments and other environments.
  • Landfills are important places for the disposal of discarded pharmaceuticals.
  • Leachate will be produced during the long-term landfilling process of domestic waste.
  • my country's landfill leachate treatment technology is mainly "pretreatment + biological treatment + advanced treatment", especially the advanced treatment technology based on nanofiltration/reverse osmosis (NF/RO), such as “pretreatment + MBR + NF + RO” “The process is widely used in leachate treatment plants. This process can meet the effluent quality requirements of leachate, but membrane separation such as nanofiltration/reverse osmosis The system will produce 30% to 45% concentrated liquid. The system will not only intercept refractory organic matter, heavy metals, salts, etc., but also lead to a large accumulation of antibiotics.
  • NF/RO nanofiltration/reverse osmosis
  • the ozone catalytic oxidation process has been widely used in the treatment of sewage and wastewater. It has the advantages of simplicity, speed, and convenience.
  • the separate treatment process faces shortcomings such as low ozone utilization rate and high cost.
  • Catalysts based on carbon-based materials have been widely used in their treatment processes, but they also face problems such as high production costs and poor wastewater treatment efficiency.
  • the purpose of the present invention is to provide a preparation method and application of manganese-loaded biochar materials.
  • the present invention provides a method for preparing a manganese-loaded biochar catalyst, which includes the following steps:
  • the biochar is polystyrene carbon balls.
  • the present invention provides a manganese-loaded biochar catalyst prepared by the preparation method.
  • the present invention provides a method for utilizing the loaded manganese biochar to catalyze ozone treatment of antibiotics in concentrated liquid, including the following steps:
  • ozone is introduced into the wastewater to perform ozone catalytic oxidation of the antibiotics.
  • the biochar particles selected in the present invention have a large specific surface area and good adsorption performance.
  • the manganese metal-loaded biochar material prepared by the present invention is completely loaded on the surface of the sphere. After catalytic oxidation, the sphere can be reused through high-temperature burning, which reduces the processing cost.
  • the manganese-loaded biochar material provided by the present invention can effectively degrade target pollutants and organic matter in actual concentrated liquid wastewater by catalyzing ozone.
  • Figure 1 is an electron microscope (SEM) image of polystyrene-based carbon sphere particles before and after loading manganese prepared in Example 1 of the present invention.
  • (a) is the prepared biochar;
  • (d) is the manganese-loaded biochar;
  • (b) and (e) are the electron microscope images of the biochar surface scale at 10 ⁇ m before and after loading manganese;
  • (c) and (f) ) is the electron microscope image of the biochar surface scale at 1 ⁇ m before and after loading manganese;
  • Figure 2 is the full XPS scanning spectrum of the surface of biochar particles before and after loading manganese prepared in Example 1 of the present invention
  • Figure 3 is an EDS spectrum of surface elements of biochar particles before and after loading manganese prepared in Example 1 of the present invention.
  • the present invention provides a method for preparing a manganese-loaded biochar catalyst, which includes the following steps:
  • the biochar is polystyrene carbon balls.
  • the number of loadings was two, making the biochar surface coverage almost 100%.
  • the concentration of KMnO 4 is 0.2-0.5moL/L, and the concentration of (NH 4 ) 2 C 2 O 4 is 0.1-0.5moL/L.
  • the concentration of KMnO 4 is 0.2-0.4moL/L, and the concentration of (NH 4 ) 2 C 2 O 4 is 0.1-0.4moL/L.
  • the concentration of KMnO 4 is 0.2-0.3moL/L, and the concentration of (NH 4 ) 2 C 2 O 4 is 0.1-0.3moL/L.
  • the polystyrene carbon spheres have an average specific surface area of 1000 m 2 /g, an average pore diameter of 1.8 nm, and a diameter of 700 ⁇ m.
  • magnetic stirring is performed during the reaction, and the rotation speed is 400-600 rpm/min.
  • the reaction temperature is 150-200°C and the reaction time is 20-30h.
  • the present invention provides a manganese-loaded biochar catalyst prepared by the preparation method.
  • the supported manganese biochar catalyst shows excellent performance in catalyzing ozone treatment of antibiotics in wastewater.
  • the present invention provides a method for utilizing the loaded manganese biochar to catalyze ozone treatment of antibiotics in concentrated liquid, including the following steps:
  • the wastewater Ozone is introduced into the medium to perform ozone catalytic oxidation of antibiotics.
  • the ozone flow rate is 20-100 mg/min, and the pH value of the wastewater is adjusted to 3-11.
  • the dosage of the supported manganese biochar catalyst is 0.5-4g per liter.
  • the step of reusing the manganese-loaded biochar material is also included.
  • the specific method is: burning the recovered manganese-loaded biochar material at high temperature.
  • the high-temperature burning temperature is 250-350°C and the time is 1.5-2.5 hours. After high-temperature burning, trace amounts of organic matter and impurities on the surface of manganese-loaded biochar can be removed.
  • the antibiotic is roxithromycin or tetracycline.
  • the preparation method of supported manganese biochar catalyst includes the following steps:
  • the solid product is taken and loaded twice using the above method to prepare a supported manganese biochar catalyst.
  • Figure 1 is an electron microscope (SEM) image of polystyrene-based carbon sphere particles before and after loading manganese prepared in Example 1 of the present invention.
  • (a) is the prepared biochar;
  • (d) is the manganese-loaded biochar;
  • (b) and (e) are the electron microscope images of the biochar surface scale at 10 ⁇ m before and after loading manganese;
  • (c) and (f) ) is before loading manganese, The electron microscope image of the biochar surface scale at 1 ⁇ m; it should be noted that from (a) and (d) in Figure 1, it can be seen that after the biochar particles are loaded with manganese-based materials, the diameter of the sphere becomes larger, and the surface is completely loaded and covered. The rate is close to 100%. It can be seen from (b), (c), (e), and (f) in Figure 1 that the surface before loading of biochar has a small pore structure, and the surface after loading presents a square grain structure of uneven sizes.
  • Figure 2 is the XPS scanning full spectrum of the surface of biochar particles before and after loading manganese prepared in Example 1 of the present invention; it should be noted that, as can be seen from Figure 2, when the photoelectron kinetic energy is about 51ev and 640ev, the manganese-based material after radiation loading When biochar is produced, photoelectrons are absorbed by the manganese element on the surface of the material, showing the 2p and 3s characteristic peaks of manganese element.
  • Figure 3 is an EDS spectrum of surface elements of biochar particles before and after loading manganese prepared in Example 1 of the present invention. It should be noted that, as can be seen from Figure 3, when the manganese-based material biochar is loaded with photoelectron kinetic energy 4.14kev radiation, the photoelectrons are absorbed by the manganese element on the surface of the material, showing a characteristic peak of manganese element.
  • the concentrated liquid treated in this example was taken from a landfill leachate treatment plant in Qingdao City.
  • the treatment method includes the following steps:
  • test results are shown in Table 1. It should be noted that the pretreatment of water samples, solid phase extraction, and anti- The operations designed in the detection method of antibiotics are routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the operations designed in the pretreatment of water samples, solid phase extraction, and antibiotic detection methods are all routine operations in this field unless otherwise specified.
  • the concentrated liquid processed in this embodiment is the same as in Example 1, and the processing method includes the following steps:
  • test results are shown in Table 1. It should be noted that the pretreatment of water samples, solid phase extraction, and anti- The operations designed in the detection method of antibiotics are routine operations in this field unless otherwise specified.

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Abstract

本发明公开了一种负载锰生物炭材料的制备方法与应用，制备方法，包括如下步骤：将生物炭、KMnO4、(NH4)2C2O4和水混合，将混合物在150-250℃，反应20-30h，在生物炭表面负载锰元素，并重复负载一次；所述生物炭为聚苯乙烯碳球。本发明制备的负载锰金属的生物炭材料，球体表面负载完全，催化氧化后球体通过高温灼烧，能够实现重复利用，降低了处理成本。本发明提供的负载锰生物炭材料，通过催化臭氧，可有效降解实际浓缩液废水中的目标污染物和有机物。

Description

一种负载锰生物炭催化剂及其制备方法与应用
本发明要求于2022年7月26日提交中国专利局、申请号为202210883512.1、发明名称为“一种负载锰生物炭催化剂及其制备方法与应用”的中国专利申请的优先权，其全部内容通过引用结合在本发明中。
技术领域
本发明涉及污染物处理与化学材料领域，具体地说，公开了一种负载锰生物炭催化剂及其制备方法与应用。
背景技术
这里的陈述仅提供与本发明相关的背景技术，而不必然地构成现有技术。
抗生素作为治疗感染性疾病的强效药物，已在世界范围内广泛使用。抗生素通过生物体粪便与尿液排泄、过期或残留容器中抗生素丢弃、药物生产过程损失的抗生素排入水体等途径进入环境，水体、土壤和沉积物等环境中均存在不同程度的抗生素污染。
垃圾填埋场是废弃药品的重要归转场所，生活垃圾长期填埋过程中会产生渗滤液。目前，我国垃圾渗滤液处理工艺主要为“预处理+生物处理+深度处理”，特别是纳滤/反渗透(NF/RO)为基础的深度处理工艺，如“预处理+MBR+NF+RO”工艺广泛用于渗滤液处理厂。该工艺能够满足渗滤液的出水水质要求，但纳滤/反渗透等膜分 离系统会产生30％～45％的浓缩液，系统不仅会截留难降解有机物、重金属、盐分等，也会导致抗生素的大量累积。
近年来，臭氧催化氧化工艺广泛运用于污废水的处理，具有简单、快捷、方便等优点，但单独处理工艺面临臭氧利用率低、成本高等缺陷。以碳基材料为基础的催化剂已被广泛运用其处理工艺中，但同样面临制作成本高、废水处理效率差等问题。
发明内容
针对现有技术存在的不足，本发明的目的是提供一种负载锰生物炭材料的制备方法与应用。
为了实现上述目的，本发明是通过如下的技术方案来实现：
第一方面，本发明提供一种负载锰生物炭催化剂的制备方法，包括如下步骤：
将生物炭、KMnO4、(NH4)2C2O4和水混合，将混合物在150-250℃，反应20-30h，在生物炭表面负载锰元素，并重复负载一次；
所述生物炭为聚苯乙烯碳球。
第二方面，本发明提供一种负载锰生物炭催化剂，由所述制备方法制备而成。
第三方面，本发明提供利用所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，包括如下步骤：
向含有抗生素的废水中投加所述负载锰生物炭催化剂后，向废水中通入臭氧，对抗生素进行臭氧催化氧化。
上述本发明的一种或多种实施例取得的有益效果如下：
本发明所选用的生物炭颗粒，比表面积大，吸附性能好。
本发明制备的负载锰金属的生物炭材料，球体表面负载完全，催化氧化后球体通过高温灼烧，能够实现重复利用，降低了处理成本。
本发明提供的负载锰生物炭材料，通过催化臭氧，可有效降解实际浓缩液废水中的目标污染物和有机物。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明实施例1中制备的负载锰前、后聚苯乙烯基碳球颗粒的电子显微镜(SEM)图。
其中(a)为所制备的生物炭；(d)为负载锰生物炭；(b)、(e)为负载锰前、后生物炭表面标尺在10μm处的电镜图；(c)、(f)为负载锰前、后生物炭表面标尺在1μm处的电镜图；
图2为本发明实施例1中制备的负载锰前、后生物炭颗粒表面XPS扫描全谱图；
图3为本发明实施例1中制备的负载锰前、后生物碳颗粒表面元素EDS能谱图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
第一方面，本发明提供一种负载锰生物炭催化剂的制备方法，包括如下步骤：
将生物炭、KMnO4、(NH4)2C2O4和水混合，将混合物在150-250℃，反应20-30h，在生物炭表面负载锰元素，并重复负载一次；
所述生物炭为聚苯乙烯碳球。
负载次数为两次，使得生物炭表面覆盖率几乎达到100％。
在一些实施例中，混合物中，KMnO4的浓度为0.2-0.5moL/L，(NH4)2C2O4的浓度为0.1-0.5moL/L。
优选的，混合物中，KMnO4的浓度为0.2-0.4moL/L，(NH4)2C2O4的浓度为0.1-0.4moL/L。
进一步优选的，混合物中，KMnO4的浓度为0.2-0.3moL/L，(NH4)2C2O4的浓度为0.1-0.3moL/L。
在一些实施例中，所述聚苯乙烯碳球的平均比表面积为1000m2/g，平均孔径为1.8nm，直径为700μm。
在一些实施例中，反应过程中磁力搅拌，转速为400-600rpm/min。
优选的，反应温度为150-200℃，反应时间为20-30h。
第二方面，本发明提供一种负载锰生物炭催化剂，由所述制备方法制备而成。该负载锰生物炭催化剂，在催化臭氧处理废水中抗生素时表现出优异的性能。
第三方面，本发明提供利用所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，包括如下步骤：
向含有抗生素的废水中投加所述负载锰生物炭催化剂后，向废水 中通入臭氧，对抗生素进行臭氧催化氧化。
在一些实施例中，臭氧流量为20-100mg/min，调节废水pH值为3-11。
优选的，负载锰生物炭催化剂的投加量为每升投加0.5-4g。
在一些实施例中，还包括将负载锰生物炭材料重复利用的步骤，具体方法为：将回收的负载锰生物炭材料高温灼烧，即可。
优选的，高温灼烧的温度为250-350℃，时间为1.5-2.5h。经过高温灼烧，可去除负载锰生物炭表面微量的有机物和杂质。
在一些实施例中，所述抗生素为罗红霉素或四环素。
下面结合各个实施例对本发明作进一步说明。
实施例1
负载锰生物炭催化剂的制备方法，包括如下步骤：
将2g聚苯乙烯基碳球、0.02moLKMnO4，0.01moL(NH4)2C2O4和70mL纯水投加至烧杯中，进行磁力搅拌，搅拌转速为500rpm/min，时间为0.5h，得混合物。将混合物倒入聚氯乙烯材质的反应釜中，在180℃，反应24h；
固液分离，取固体产物，采用上述的方法进行二次负载，制得负载锰生物炭催化剂。
图1为本发明实施例1中制备的负载锰前、后聚苯乙烯基碳球颗粒的电子显微镜(SEM)图。
其中(a)为所制备的生物炭；(d)为负载锰生物炭；(b)、(e)为负载锰前、后生物炭表面标尺在10μm处的电镜图；(c)、(f)为负载锰前、 后生物炭表面标尺在1μm处的电镜图；需要说明的是，由图1中(a)、(d)可知，生物炭颗粒负载锰基材料后，球体直径变大，且表面负载完全，覆盖率接近100％，由图1中(b)、(c)、(e)、(f)可知，生物炭负载前表面为小孔结构，负载后表面呈现大小不均的方块晶粒结构。
图2为本发明实施例1中制备的负载锰前、后生物炭颗粒表面XPS扫描全谱图；需要说明的是，由图2可知，当光电子动能为51ev、640ev左右辐射负载后锰基材料生物炭时，光电子被材料表面锰元素所吸收，表现出锰元素2p、3s特征峰。
图3为本发明实施例1中制备的负载锰前、后生物碳颗粒表面元素EDS能谱图。需要说明的是，由图3可知，当光电子动能为4.14kev辐射负载后锰基材料生物炭时，光电子被材料表面锰元素所吸收，表现出锰元特征峰。
本实施例所处理的浓缩液取自于青岛市某垃圾渗滤液处理厂，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，原始pH值为7.2条件下调节臭氧投量为80mg/min，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗 生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例2
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，原始pH值为7.2条件下调节臭氧投量为20g/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例3
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，原始pH值为7.2条件下调节臭氧投量为40g/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪 (LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例4
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，原始pH值为7.2条件下调节臭氧投量为80g/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例5
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，原始pH值为7.2条件下调节臭氧投量为100g/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例6
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为3，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例7
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为5，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例8
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为9，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例9
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为11，臭氧投量为 80mg/min，实施例1制备的负载锰生物炭投加量为2g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例10
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为3，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为0.5g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例11
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为3，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为1g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
实施例12
本实施例所处理的浓缩液同实施例1，处理方法包括以下步骤：
(1)取浓缩液1L置于反应器中，调节pH为3，臭氧投量为80mg/min，实施例1制备的负载锰生物炭投加量为4g/L，反应时间为0.5h。
(2)待反应结束后，将反应器置于50℃水浴锅内去除水体剩余臭氧。
(3)水样经0.45μm玻璃纤维膜过滤。
(4)对水样进行预处理、固相萃取，然后用色谱-质谱联用仪(LCMS-8050)检测罗红霉素与四环素浓度。
检测结果见表1，需要说明的是，水样的预处理、固相萃取、抗 生素的检测方法中设计到的操作如无特殊说明皆为本领域常规操作。
从以上实施例可以看出：添加实施例1制备的负载锰生物炭后，极大提高了臭氧对浓缩液中红霉素与四环素的氧化性能，罗红霉素去除率达到了87％，四环素的去除率达到了98％，在优化条件下，相比于单独臭氧处理工艺其去除率分别提升了47％、22％。
表1
表2

以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种负载锰生物炭催化剂的制备方法，其特征在于：包括如下步骤：
    将生物炭、KMnO4、(NH4)2C2O4和水混合，将混合物在150-250℃，反应20-30h，在生物炭表面负载锰元素，并重复负载一次；
    所述生物炭为聚苯乙烯碳球。
  2. 根据权利要求1所述的负载锰生物炭催化剂的制备方法，其特征在于：混合物中，KMnO4的浓度为0.2-0.5moL/L，(NH4)2C2O4的浓度为0.1-0.5moL/L；
    优选的，混合物中，KMnO4的浓度为0.2-0.4moL/L，(NH4)2C2O4的浓度为0.1-0.4moL/L；
    进一步优选的，混合物中，KMnO4的浓度为0.2-0.3moL/L，(NH4)2C2O4的浓度为0.1-0.3moL/L。
  3. 根据权利要求1所述的负载锰生物炭催化剂的制备方法，其特征在于：所述聚苯乙烯碳球的平均比表面积为1000m2/g，平均孔径为1.8nm，直径为700μm。
  4. 根据权利要求1所述的负载锰生物炭催化剂的制备方法，其特征在于：反应过程中磁力搅拌，转速为400-600rpm/min；
    优选的，反应温度为150-200℃，反应时间为20-30h。
  5. 一种负载锰生物炭催化剂，其特征在于：由权利要求1-4任一所述制备方法制备而成。
  6. 利用权利要求5所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，其特征在于：包括如下步骤：
    向含有抗生素的废水中投加所述负载锰生物炭催化剂后，向废水中通入臭氧，对抗生素进行臭氧催化氧化。
  7. 根据权利要求6所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，其特征在于：臭氧流量为20-100mg/min，调节废水pH值为3-11；
    优选的，负载锰生物炭催化剂的投加量为每升投加0.5-4g。
  8. 根据权利要求6所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，其特征在于：还包括将负载锰生物炭材料重复利用的步骤，具体方法为：将回收的负载锰生物炭材料高温灼烧，即可。
  9. 根据权利要求8所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，其特征在于：高温灼烧的温度为250-350℃，时间为1.5-2.5h。
  10. 根据权利要求6所述负载锰生物炭催化臭氧处理浓缩液中抗生素的方法，其特征在于：所述抗生素为罗红霉素或四环素。
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