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CN114949720B - A method and system for treating antibiotic residue - Google Patents

A method and system for treating antibiotic residue Download PDF

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CN114949720B
CN114949720B CN202210648383.8A CN202210648383A CN114949720B CN 114949720 B CN114949720 B CN 114949720B CN 202210648383 A CN202210648383 A CN 202210648383A CN 114949720 B CN114949720 B CN 114949720B
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CN114949720A (en
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王建龙
初里冰
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Tsinghua University
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    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/15Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to particle radiation, e.g. electron beam radiation
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/26Organic substances containing nitrogen or phosphorus
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/28Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses

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Abstract

The embodiment of the invention provides a method and a system for preparing antibiotic residues, wherein calcium peroxide is dissolved in antibiotic residues with higher water content, and generated calcium ions can replace hydrogen ions of acidic proteins under the acidic condition of the antibiotic residues to form insoluble protein-calcium precipitates, so that the proteins are coagulated, the competition of the proteins and antibiotics on hydroxyl free radicals generated by irradiation is eliminated, the number of hydroxyl free radicals reacted with the antibiotics in an irradiation system is obviously increased, and the pollution of antibiotics in the antibiotic residues is thoroughly eliminated. According to the embodiment of the invention, under the synergistic interaction of electron beam irradiation and calcium peroxide, the antibiotics in the antibiotic residues can be completely degraded, so that the concentration of the antibiotics can not be detected by liquid chromatography, namely the antibiotic removal rate can reach 100%. In the method provided by the embodiment of the invention, electron beam irradiation is performed at normal temperature, so that large-scale industrial application is easy to realize.

Description

一种抗生素菌渣处理方法、系统A method and system for treating antibiotic residue

技术领域technical field

本发明实施例涉及固体废弃物处理领域,尤其涉及一种抗生素菌渣处理方法、系统。The embodiments of the present invention relate to the field of solid waste treatment, in particular to a method and system for treating antibiotic residues.

背景技术Background technique

头孢类抗生素是目前使用最为广泛的广谱抗生素之一,头孢菌素C(CPC)是头孢类抗生素的主要原料药。CPC是以顶头孢霉菌为发酵菌种,以玉米浆、花生饼粉、糊精、蛋氨酸、豆油、无机盐等为培养基通过好氧发酵产生。发酵过程完成后,在发酵液中加入硫酸酸化使菌丝体和蛋白沉淀,上清液经过陶瓷膜过滤除去大分子蛋白物质,再经过树脂吸附纯化、浓缩等工艺得到最终原料药产品。硫酸酸化的沉淀物以及陶瓷膜分离的浓液即为抗生素菌渣废弃物,其主要成分为残留的菌丝体,培养基和抗生素。Cephalosporin antibiotics are currently one of the most widely used broad-spectrum antibiotics, and cephalosporin C (CPC) is the main raw material drug of cephalosporin antibiotics. CPC is produced by aerobic fermentation using Cephalosporium acremonium as the fermentation strain and using corn steep liquor, peanut cake powder, dextrin, methionine, soybean oil, inorganic salts, etc. as the medium. After the fermentation process is completed, sulfuric acid is added to the fermentation broth to acidify the mycelia and protein to precipitate, and the supernatant is filtered through a ceramic membrane to remove macromolecular protein substances, and then undergoes processes such as resin adsorption purification and concentration to obtain the final raw material drug product. The precipitate acidified by sulfuric acid and the concentrate separated by the ceramic membrane are antibiotic residue waste, and its main components are residual mycelium, culture medium and antibiotics.

抗生素菌渣营养丰富,富含多糖、蛋白质、多种氨基酸和微量元素等,蛋白含量可达30%以上。残留的抗生素是抗生素菌渣中的污染源,若能将其从抗生素菌渣中去除,有望将抗生素菌渣从危险废物中脱除,无害化的抗生素菌渣可制成肥料变为资源再利用,进而解决抗生素菌渣处理处置难题。Antibiotic bacteria residue is rich in nutrition, rich in polysaccharides, proteins, various amino acids and trace elements, etc., and the protein content can reach more than 30%. Residual antibiotics are the source of pollution in antibiotic residues. If they can be removed from antibiotic residues, it is expected that antibiotic residues will be removed from hazardous waste. Harmless antibiotic residues can be made into fertilizers and reused as resources, thereby solving the problem of antibiotic residues treatment and disposal.

抗生素菌渣为粘稠的固液混合物,通常的紫外、光催化等处理方法难以穿透进入到菌渣内部反应,抗生素的去除率不高。Antibiotic residue is a viscous solid-liquid mixture, and the usual treatment methods such as ultraviolet light and photocatalysis are difficult to penetrate and react inside the residue, and the removal rate of antibiotics is not high.

因此,目前亟需一种高去除率的抗生素菌渣处理方法。Therefore, there is an urgent need for a high-removal antibiotic residue treatment method.

发明内容Contents of the invention

本发明实施例提供一种抗生素菌渣处理方法、系统,以对抗生素菌渣中的抗生素进行降解,使抗生素菌渣中的抗生素浓度降至液相色谱无法检出。The embodiments of the present invention provide a method and system for treating antibiotic residues, so as to degrade antibiotics in antibiotic residues, so that the concentration of antibiotics in antibiotic residues can be reduced to undetectable by liquid chromatography.

本发明实施例第一方面提供了一种抗生素菌渣方法,所述方法包括:The first aspect of the embodiments of the present invention provides a method for antibiotic scum, said method comprising:

将抗生素菌渣与过氧化钙混合,得到混合物;Mix antibiotic scum with calcium peroxide to obtain a mixture;

利用电子束对所述混合物进行辐照,以降解所述抗生素菌渣中的抗生素;irradiating the mixture with an electron beam to degrade the antibiotics in the antibiotic residue;

其中,所述过氧化钙溶解产生钙离子,在所述抗生素菌渣的酸性条件下,所述钙离子置换酸性蛋白质的氢离子,形成不溶的蛋白质-钙沉淀,使蛋白质凝结,消除蛋白质对电子束辐照产生的羟基自由基的竞争作用,使处理体系中与抗生素反应的羟基自由基数量增加,强化电子束辐照降解抗生素菌渣中的抗生素。Wherein, the calcium peroxide dissolves to generate calcium ions, and under the acidic condition of the antibiotic residue, the calcium ion replaces the hydrogen ion of the acidic protein to form an insoluble protein-calcium precipitate, coagulates the protein, eliminates the competition effect of the protein on the hydroxyl radicals produced by electron beam irradiation, increases the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthens electron beam irradiation to degrade antibiotics in antibiotic residues.

可选地,所述将抗生素菌渣与过氧化钙混合,得到混合物,包括:Optionally, the antibiotic scum is mixed with calcium peroxide to obtain a mixture, including:

向所述抗生素菌渣中投加过氧化钙,将所述抗生素菌渣与所述过氧化钙混匀,得到混合物;Adding calcium peroxide to the antibiotic residue, mixing the antibiotic residue with the calcium peroxide to obtain a mixture;

利用电子束对所述混合物进行辐照,包括:The mixture is irradiated with an electron beam, comprising:

将所述混合物送至电子加速器的辐照室,利用电子束对所述混合物进行辐照。The mixture is sent to an irradiation chamber of an electron accelerator, and the mixture is irradiated with an electron beam.

可选地,所述抗生素菌渣为抗生素生产过程中产生的含有残留抗生素的头孢发酵菌渣,所述抗生素为头孢菌素C。Optionally, the antibiotic residue is cephalosporin fermentation residue containing residual antibiotic produced during antibiotic production, and the antibiotic is cephalosporin C.

可选地,所述头孢发酵菌渣中残留的头孢菌素C含量为200~1000mg/kg,所述头孢发酵菌渣的含水率为85%-95%。Optionally, the residual cephalosporin C content in the cephalosporin fermentation residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation residue is 85%-95%.

可选地,所述电子束的辐照吸收剂量为40kGy~75kGy。Optionally, the radiation absorbed dose of the electron beam is 40kGy-75kGy.

可选地,所述过氧化钙的投加量为0.04mM~0.1mM。Optionally, the dosage of the calcium peroxide is 0.04mM-0.1mM.

本发明实施例第二方面提供了一种抗生素菌渣系统,所述系统用于实现上述第一方面任一项所述的抗生素菌渣处理方法,所述系统包括:The second aspect of the embodiment of the present invention provides an antibiotic residue system, which is used to implement the antibiotic residue treatment method described in any one of the above first aspects, the system comprising:

反应器,用于盛放抗生素菌渣,以对所述抗生素菌渣进行处理;The reactor is used to hold the antibiotic residue for processing the antibiotic residue;

过氧化钙投加装置,用于向所述反应器中投加过氧化钙;Calcium peroxide dosing device, used to add calcium peroxide to the reactor;

搅拌装置,用于将所述抗生素菌渣与所述过氧化钙混匀,得到混合物;A stirring device for mixing the antibiotic residue and the calcium peroxide to obtain a mixture;

电子加速器,用于产生电子束对所述混合物进行辐照,以降解所述抗生素菌渣中的抗生素;An electron accelerator for generating an electron beam to irradiate the mixture to degrade the antibiotic in the antibiotic residue;

其中,所述过氧化钙溶解产生钙离子,在所述抗生素菌渣的酸性条件下,所述钙离子置换酸性蛋白质的氢离子,形成不溶的蛋白质-钙沉淀,使蛋白质凝结,消除蛋白质对电子束辐照产生的羟基自由基的竞争作用,使处理体系中与抗生素反应的羟基自由基数量增加,强化电子束辐照降解抗生素菌渣中的抗生素。Wherein, the calcium peroxide dissolves to generate calcium ions, and under the acidic condition of the antibiotic residue, the calcium ion replaces the hydrogen ion of the acidic protein to form an insoluble protein-calcium precipitate, coagulates the protein, eliminates the competition effect of the protein on the hydroxyl radicals produced by electron beam irradiation, increases the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthens electron beam irradiation to degrade antibiotics in antibiotic residues.

可选地,所述抗生素菌渣为抗生素生产过程中产生的含有残留抗生素的头孢发酵菌渣,所述抗生素为头孢菌素C,所述头孢发酵菌渣中残留的头孢菌素C含量为200~1000mg/kg,所述头孢发酵菌渣的含水率为85%-95%。Optionally, the antibiotic residue is cephalosporin fermentation residue containing residual antibiotics produced in the antibiotic production process, the antibiotic is cephalosporin C, the residual cephalosporin C content in the cephalosporin fermentation residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation residue is 85%-95%.

可选地,所述电子束的辐照吸收剂量为40kGy~75kGy。Optionally, the radiation absorbed dose of the electron beam is 40kGy-75kGy.

可选地,所述过氧化钙的投加量为0.04mM~0.1mM。Optionally, the dosage of the calcium peroxide is 0.04mM-0.1mM.

本发明实施例提供的抗生素菌渣方法中,电子束的辐射作用和抗生素菌渣的酸性环境(pH值通常在4.0左右)有利于过氧化钙原位分解产生过氧化氢,过氧化氢与辐照产生的eaq-和·H反应促进·OH产生;同时,过氧化钙溶解产生的钙离子在抗生素菌渣较强的酸性条件下,能置换酸性蛋白质的氢离子,形成不溶性的蛋白质-钙沉淀,使蛋白质凝结,进而消除其与抗生素对辐照产生羟基自由基的竞争作用,使辐照体系中与抗生素反应的羟基自由基数量显著增加,进而彻底消除抗生素菌渣中的抗生素污染。In the antibiotic slag method that the embodiment of the present invention provides, the radiation effect of the electron beam and the acidic environment (pH value is usually about 4.0) of the antibiotic slag are conducive to the in-situ decomposition of calcium peroxide to produce hydrogen peroxide, and the e produced by hydrogen peroxide and irradiationaqThe - and H reaction promotes the production of OH; at the same time, the calcium ions produced by the dissolution of calcium peroxide can replace the hydrogen ions of the acidic protein under the strong acidic conditions of the antibiotic slag, forming insoluble protein-calcium precipitates to coagulate the protein, thereby eliminating its competition with the antibiotics for the hydroxyl radicals produced by irradiation, and significantly increasing the number of hydroxyl radicals reacting with the antibiotics in the irradiation system, thereby completely eliminating antibiotic pollution in the antibiotic slag.

本发明实施例中,在电子束辐照与过氧化钙的协同互促作用下,可以实现完全降解抗生素菌渣中的抗生素,使抗生素浓度降至液相色谱无法检出,即抗生素去除率可达100%。本发明实施例提供的方法中,电子束辐照在常温进行,易于实现大规模工业应用。可见,本发明实施提供的方法高效、方便、适用面广,可应用于抗生素菌渣处理,在有害固体废弃物处理领域具有广阔的应用前景。In the embodiment of the present invention, under the synergistic interaction between electron beam irradiation and calcium peroxide, the antibiotics in the antibiotic residue can be completely degraded, and the concentration of antibiotics can be reduced to undetectable by liquid chromatography, that is, the removal rate of antibiotics can reach 100%. In the method provided by the embodiment of the present invention, electron beam irradiation is carried out at normal temperature, which is easy to realize large-scale industrial application. It can be seen that the method provided by the implementation of the present invention is efficient, convenient, and widely applicable, can be applied to the treatment of antibiotic bacteria residues, and has broad application prospects in the field of hazardous solid waste treatment.

附图说明Description of drawings

为了更清楚地说明本发明实施例的技术方案,下面将对本发明实施例的描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings used in the description of the embodiments of the present invention. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without paying creative labor.

图1是本发明实施例的一种抗生素菌渣方法的流程图;Fig. 1 is the flowchart of a kind of antibiotic bacterium residue method of the embodiment of the present invention;

图2是本发明实施例的另一种抗生素菌渣方法的流程图;Fig. 2 is the flowchart of another kind of antibiotic slag method of the embodiment of the present invention;

图3是本发明实施例的一种抗生素菌渣系统的示意图。Fig. 3 is a schematic diagram of an antibiotic residue system according to an embodiment of the present invention.

具体实施方式Detailed ways

为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图和具体实施方式对本发明作进一步详细的说明。In order to make the above objects, features and advantages of the present invention more comprehensible, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

电子束辐照技术是利用电子加速器产生的电子束对污染物进行处理。电子束为密集的高速电子流,具有极高的能量密度。高能电子束可以深入到菌渣内部,通过康普顿效应直接破坏抗生素的分子结构;同时,电子束可激发水分子电离,产生·OH、eaq-、·H等活性粒子(如式1所示,括号内数值为每种活性粒子的辐射化学产率),抗生素可与这些活性粒子发生氧化-还原反应而被降解。Electron beam irradiation technology uses electron beams generated by electron accelerators to treat pollutants. The electron beam is a dense high-speed electron flow with extremely high energy density. The high-energy electron beam can penetrate deep into the bacterial residue and directly destroy the molecular structure of the antibiotic through the Compton effect; at the same time, the electron beam can excite the ionization of water molecules to generate active particles such as OH, e aq -, H, etc. (as shown in formula 1, the values in brackets are the radiation chemical yield of each active particle), and the antibiotic can be degraded by oxidation-reduction reaction with these active particles.

在电子束辐照对抗生素菌渣的处理过程中,当吸收剂量为40kGy时,抗生素的去除率可达90%以上。但是继续增加剂量,抗生素去除率的提高幅度不大,无法达到理想去除率。During the treatment of antibiotic residues by electron beam irradiation, when the absorbed dose is 40kGy, the removal rate of antibiotics can reach more than 90%. But continue to increase the dose, the increase in the removal rate of antibiotics is not large, and the ideal removal rate cannot be achieved.

相关技术中,通常采用的方法是,利用氧化剂强化电子束辐照降解菌渣中的抗生素,以产生更多强氧化性的·OH,促进氧化-还原反应,进而促进抗生素的降解,但是,这种方法依然无法达到将抗生素浓度降至液相色谱无法检出的效果,也就无法达到理想的去除率。In related technologies, the commonly used method is to use oxidants to strengthen electron beam irradiation to degrade antibiotics in bacterial residues to generate more strong oxidizing OH, promote oxidation-reduction reactions, and then promote the degradation of antibiotics. However, this method still cannot achieve the effect of reducing the concentration of antibiotics to a level that cannot be detected by liquid chromatography, and cannot achieve an ideal removal rate.

因此,发明人对抗生素菌渣处理方法进行了探索,发明人发现,抗生素菌渣溶液中存在的蛋白质、多糖等物质与抗生素竞争辐照产生的自由基,从而限制了抗生素的进一步降解。抗生素的浓度越低,这些物质的竞争作用越强,对抗生素降解的影响越大。其中,蛋白质的辐照竞争作用最强,为彻底消除抗生素污染,需要抑制蛋白质的辐照竞争作用。Therefore, the inventor explored the treatment method of antibiotic residue, and the inventor found that the protein, polysaccharide and other substances present in the antibiotic residue solution competed with the antibiotic for the free radicals generated by irradiation, thus limiting the further degradation of the antibiotic. The lower the concentration of antibiotics, the stronger the competition of these substances and the greater the impact on antibiotic degradation. Among them, the irradiation competition of protein is the strongest. In order to completely eliminate the antibiotic pollution, it is necessary to inhibit the irradiation competition of protein.

基于上述探索发现,提出本申请的发明构思:用过氧化钙强化电子束辐照降解菌渣中的抗生素,其中,所述过氧化钙在含水量较高的抗生素菌渣中溶解产生钙离子,在抗生素菌渣的酸性条件下,钙离子置换酸性蛋白质的氢离子,形成不溶的蛋白质-钙沉淀,使蛋白质凝结,消除蛋白质对电子束辐照产生的羟基自由基的竞争作用,使处理体系中与抗生素反应的羟基自由基数量增加,强化电子束辐照降解抗生素菌渣中的抗生素。Based on the above findings, the inventive concept of the present application is proposed: use calcium peroxide to strengthen electron beam irradiation to degrade antibiotics in bacterial residues, wherein the calcium peroxide dissolves in antibiotic residues with higher water content to generate calcium ions, and under the acidic conditions of antibiotic residues, calcium ions replace hydrogen ions of acidic proteins to form insoluble protein-calcium precipitates to coagulate proteins, eliminate the competition of proteins to hydroxyl radicals produced by electron beam irradiation, increase the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthen electron beam irradiation to degrade antibiotic residues. antibiotics in.

基于上述发明构思,本发明第一方面提出了一种抗生素菌渣处理方法,下面结合附图1对本发明提出的一种抗生素菌渣处理方法进行说明,该方法包括以下步骤:Based on above-mentioned inventive concept, the first aspect of the present invention proposes a kind of antibiotic scum treatment method, below in conjunction with accompanying drawing 1 a kind of antibiotic scum treatment method that the present invention proposes is illustrated, and this method comprises the following steps:

S101,将抗生素菌渣与过氧化钙混合,得到混合物。S101, mixing antibiotic residues with calcium peroxide to obtain a mixture.

本发明实施例中,可以采用相关技术中任意可行的方法对抗生素菌渣与过氧化钙进行混合,本发明实施例对此不作具体限制。In the embodiment of the present invention, any feasible method in the related art can be used to mix the antibiotic residue and calcium peroxide, which is not specifically limited in the embodiment of the present invention.

S102,利用电子束对所述混合物进行辐照,以降解所述抗生素菌渣中的抗生素。S102. Using electron beams to irradiate the mixture to degrade the antibiotics in the antibiotic residues.

本发明实施例中,可以采用相关技术中任意可行的方法利用电子束对混合物进行辐照,本发明实施例对此不作具体限制。In the embodiment of the present invention, any feasible method in the related art may be used to irradiate the mixture with electron beams, which is not specifically limited in the embodiment of the present invention.

本发明实施例中,过氧化钙在含水量较高的抗生素菌渣中溶解,产生钙离子,在所述抗生素菌渣的酸性条件下,所述钙离子置换酸性蛋白质的氢离子,形成不溶的蛋白质-钙沉淀,使蛋白质凝结,消除蛋白质对电子束辐照产生的羟基自由基的竞争作用,使处理体系中与抗生素反应的羟基自由基数量增加,强化电子束辐照降解抗生素菌渣中的抗生素。In the embodiment of the present invention, calcium peroxide is dissolved in the antibiotic slag with high water content to generate calcium ions. Under the acidic conditions of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble protein-calcium precipitates, coagulate the protein, eliminate the competition effect of the protein on the hydroxyl radicals produced by electron beam irradiation, increase the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthen the electron beam irradiation to degrade the antibiotics in the antibiotic slag.

本发明实施例中,电子束的辐射作用和所述抗生素菌渣的酸性环境使得过氧化钙原位分解产生过氧化氢,过氧化氢与电子束辐照产生的eaq-和·H反应促进·OH产生,可以通过促进氧化-还原反应进一步强化电子束辐照降解抗生素菌渣中的抗生素。In the embodiment of the present invention, the radiation effect of the electron beam and the acidic environment of the antibiotic slag cause calcium peroxide to decompose in situ to generate hydrogen peroxide, and the reaction between hydrogen peroxide and e aq- and H produced by electron beam irradiation promotes the generation of OH, and the degradation of antibiotics in the antibiotic slag by electron beam irradiation can be further strengthened by promoting the oxidation-reduction reaction.

基于上述发明构思,本发明还提出了另一种抗生素菌渣处理方法,下面结合附图2对本发明提出的另一种抗生素菌渣处理方法进行说明,该方法包括以下步骤:Based on above-mentioned inventive concept, the present invention also proposes another kind of antibiotic scum treatment method, below in conjunction with accompanying drawing 2 another kind of antibiotic scum treatment method that the present invention proposes is illustrated, and this method comprises the following steps:

S201,向所述抗生素菌渣中投加过氧化钙,将所述抗生素菌渣与所述过氧化钙混匀,得到混合物。S201, adding calcium peroxide to the antibiotic residue, and mixing the antibiotic residue with the calcium peroxide to obtain a mixture.

本发明实施例中,所述过氧化钙可以选用粉末状固体,以便与抗生素菌渣混合均匀,并加快反应速率。In the embodiment of the present invention, the calcium peroxide may be powdery solid, so as to be evenly mixed with the antibiotic residue and to speed up the reaction rate.

本发明实施例中,所述抗生素菌渣为抗生素生产过程中产生的含有残留抗生素的头孢发酵菌渣,所述抗生素为头孢菌素C。In the embodiment of the present invention, the antibiotic residue is cephalosporin fermentation residue containing residual antibiotic produced during the antibiotic production process, and the antibiotic is cephalosporin C.

本发明实施例中,所述头孢发酵菌渣中残留的头孢菌素C含量为200~1000mg/kg,所述头孢发酵菌渣的含水率为85%-95%。In the embodiment of the present invention, the residual cephalosporin C content in the cephalosporin fermentation residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation residue is 85%-95%.

本发明实施例中,所述过氧化钙的投加量为0.04mM~0.1mM。In the embodiment of the present invention, the dosage of the calcium peroxide is 0.04mM-0.1mM.

优选地,考虑到去除效果和成本,所述过氧化钙的投加量为0.06mM。Preferably, considering the removal effect and cost, the dosage of calcium peroxide is 0.06mM.

S202,将所述混合物送至电子加速器的辐照室,利用电子束对所述混合物进行辐照。S202, sending the mixture to an irradiation chamber of an electron accelerator, and irradiating the mixture with an electron beam.

本发明实施例中,可以将混合物置于电子加速器的束下传输系统用传送带送至电子加速器的辐照室进行辐照。In the embodiment of the present invention, the mixture can be placed in the electron accelerator's under-beam transport system and transported to the electron accelerator's irradiation chamber by a conveyor belt for irradiation.

本发明实施例中,所述电子束的辐照吸收剂量为40kGy~75kGy。In the embodiment of the present invention, the radiation absorbed dose of the electron beam is 40kGy-75kGy.

具体地,本发明实施例中,可以通过控制束流强度和传输速度得到不同的辐照吸收剂量。Specifically, in the embodiment of the present invention, different radiation absorbed doses can be obtained by controlling the beam intensity and transmission speed.

优选地,所述电子束的辐照吸收剂量为50kGy。Preferably, the radiation absorbed dose of the electron beam is 50kGy.

本发明实施例中,在电子束辐照与过氧化钙的协同互促作用下,可以实现完全降解抗生素菌渣中的抗生素,使抗生素浓度降至液相色谱无法检出。本发明实施例提供的方法中,电子束辐照在常温进行,易于实现大规模工业应用。In the embodiment of the present invention, under the synergistic interaction between electron beam irradiation and calcium peroxide, the antibiotics in the antibiotic residues can be completely degraded, and the concentration of antibiotics can be reduced to undetectable by liquid chromatography. In the method provided by the embodiment of the present invention, electron beam irradiation is carried out at normal temperature, which is easy to realize large-scale industrial application.

基于上述发明构思,本发明第二方面提出了一种抗生素菌渣处理系统,系统用于实现本发明实施例第一方面任一项所述的抗生素菌渣处理方法,下面结合附图3对本发明提出的另一种抗生素菌渣处理系统进行说明,所述系统包括:Based on the above-mentioned inventive concept, the second aspect of the present invention proposes a system for treating antibiotic scum, which is used to implement the method for treating antibiotic slag described in any one of the first aspects of the embodiments of the present invention. Below in conjunction with accompanying drawing 3, another antibiotic slag processing system proposed by the present invention will be described. The system includes:

反应器,用于盛放抗生素菌渣,以对所述抗生素菌渣进行处理;The reactor is used to hold the antibiotic residue for processing the antibiotic residue;

过氧化钙投加装置,用于向所述反应器中投加过氧化钙;Calcium peroxide dosing device, used to add calcium peroxide to the reactor;

搅拌装置(图中未示出),用于将所述抗生素菌渣与所述过氧化钙混匀,得到混合物;A stirring device (not shown in the figure), used to mix the antibiotic residue and the calcium peroxide to obtain a mixture;

电子加速器,用于产生电子束对所述混合物进行辐照,以降解所述抗生素菌渣中的抗生素;An electron accelerator for generating an electron beam to irradiate the mixture to degrade the antibiotic in the antibiotic residue;

其中,所述过氧化钙在含水量较高的抗生素菌渣中溶解,产生钙离子,在所述抗生素菌渣的酸性条件下,所述钙离子置换酸性蛋白质的氢离子,形成不溶的蛋白质-钙沉淀,使蛋白质凝结,消除蛋白质对电子束辐照产生的羟基自由基的竞争作用,使处理体系中与抗生素反应的羟基自由基数量增加,强化电子束辐照降解抗生素菌渣中的抗生素。Wherein, the calcium peroxide is dissolved in the antibiotic slag with high water content to generate calcium ions, and under the acidic condition of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble protein-calcium precipitates, coagulate the protein, eliminate the competition effect of the protein on the hydroxyl radicals produced by electron beam irradiation, increase the number of hydroxyl radicals reacting with the antibiotics in the treatment system, and strengthen the electron beam irradiation to degrade the antibiotics in the antibiotic slag.

本发明实施例中,所述抗生素菌渣为抗生素生产过程中产生的含有残留抗生素的头孢发酵菌渣,所述抗生素为头孢菌素C,所述头孢发酵菌渣中残留的头孢菌素C含量为200~1000mg/kg,所述头孢发酵菌渣的含水率为85%-95%。In the embodiment of the present invention, the antibiotic residue is cephalosporin fermentation residue containing residual antibiotics produced in the antibiotic production process, the antibiotic is cephalosporin C, the residual cephalosporin C content in the cephalosporin fermentation residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation residue is 85%-95%.

本发明实施例中,所述过氧化钙的投加量为0.04mM~0.1mM。In the embodiment of the present invention, the dosage of the calcium peroxide is 0.04mM-0.1mM.

本发明实施例中,所述电子束的辐照吸收剂量为40kGy~75kGy。In the embodiment of the present invention, the radiation absorbed dose of the electron beam is 40kGy-75kGy.

为使本领域技术人员更好地理解本发明,以下通过多个具体的实施例来说明本发明提供的抗生素菌渣处理方法。In order to enable those skilled in the art to better understand the present invention, the method for treating antibiotic scum provided by the present invention will be described below through a number of specific examples.

实施例1Example 1

头孢发酵菌渣取自我国西部某抗生素生产企业,其含水率为91%,C/N比值为4.9,pH值为4.0,挥发性悬浮固体(VSS)/总悬浮固体(TSS)比值为92%,残留CPC的浓度为290±12mg/kg。过氧化钙为市售分析纯。过氧化氢为市售分析纯。The cephalosporin fermentation residue is taken from an antibiotic production enterprise in the west of my country. Its water content is 91%, the C/N ratio is 4.9, the pH value is 4.0, the volatile suspended solids (VSS)/total suspended solids (TSS) ratio is 92%, and the concentration of residual CPC is 290 ± 12mg/kg. Calcium peroxide was of analytical grade commercially available. Hydrogen peroxide was commercially available of analytical grade.

取50g左右头孢发酵菌渣混合液,分别加入过氧化钙0.01mM、0.02mM、0.04mM、0.06mM,搅拌均匀后放入样品袋中,用传送带送至电子加速器的辐照室进行辐照。不加过氧化钙的菌渣样品同时辐照进行对比。同时,为比较过氧化钙由于钙离子的存在相比于过氧化氢辐照强化作用的优势,取50g左右头孢发酵菌渣混合液,分别加入过氧化氢0.02mM、0.04mM,搅拌均匀后放入样品袋中,用传送带送至电子加速器的辐照室同时进行辐照。对比过氧化钙和过氧化氢相同投加剂量下CPC的辐照去除效果。Take about 50g of the cephalosporin fermentation residue mixture, add calcium peroxide 0.01mM, 0.02mM, 0.04mM, 0.06mM respectively, stir evenly, put it into a sample bag, and send it to the irradiation room of the electron accelerator by a conveyor belt for irradiation. The bacteria residue samples without calcium peroxide were irradiated at the same time for comparison. At the same time, in order to compare the advantages of calcium peroxide due to the presence of calcium ions compared with hydrogen peroxide irradiation enhancement, about 50 g of cephalosporin fermented slag mixture was taken, and hydrogen peroxide 0.02 mM and 0.04 mM were added respectively, stirred evenly, put into a sample bag, and sent to the irradiation room of the electron accelerator by a conveyor belt for irradiation at the same time. The irradiation removal effect of CPC under the same dosage of calcium peroxide and hydrogen peroxide was compared.

通过控制束流强度和传输速度得到不同的辐照吸收剂量30kGy、40kGy,50kGy,75kGy。检测辐照前后菌渣中CPC浓度。Different absorbed radiation doses of 30kGy, 40kGy, 50kGy, and 75kGy are obtained by controlling the beam intensity and transmission speed. The concentration of CPC in the bacterial residue before and after irradiation was detected.

菌渣中残留的CPC先用磷酸盐缓冲溶液(PBS)提取,再采用高效液相色谱检测。The residual CPC in the bacterial residue was first extracted with phosphate buffered saline (PBS), and then detected by high performance liquid chromatography.

其中,CPC提取方法为:取5mg左右菌渣放于50mL聚丙烯离心管中,加入20mL0.1mol/LPBS缓冲液(pH 5.0),涡旋振荡1min,超声辅助提取30min。以6000rpm离心10min,取上清液,用0.22μm滤膜过滤至进样小瓶中备用。Among them, the CPC extraction method is as follows: take about 5 mg of bacterial residue and put it in a 50 mL polypropylene centrifuge tube, add 20 mL of 0.1 mol/LPBS buffer solution (pH 5.0), vortex for 1 min, and ultrasonically assist extraction for 30 min. Centrifuge at 6000rpm for 10min, take the supernatant, and filter it with a 0.22μm filter membrane into a sample injection vial for later use.

其中,所用液相色谱仪为美国安捷伦公司的高效液相色谱仪(Agilent1200),色谱柱为XDB-C18反相柱,柱温:30℃。检测器为紫外检测器,检测波长:260nm;流动相为0.1%甲酸水溶液和乙腈,混合比例为90:10。Wherein, the liquid chromatograph used is a high-performance liquid chromatograph (Agilent 1200) from Agilent Corporation of the United States, the chromatographic column is an XDB-C18 reverse-phase column, and the column temperature is 30°C. The detector is an ultraviolet detector, and the detection wavelength is 260nm; the mobile phase is 0.1% formic acid aqueous solution and acetonitrile, and the mixing ratio is 90:10.

不同辐照吸收剂量以及过氧化钙、过氧化氢投加量条件下,菌渣中检测出的CPC浓度列在表1。可以看出,单独采用电子束辐照,吸收剂量从30kGy提高到40kGy,CPC的去除效率从76.7%显著提高到92.0%;继续提高剂量到50kGy和75kGy,CPC的浓度降至12.5mg/kg和8.5mg/kg,去除率提高幅度不大,为95.7%和97.1%。过氧化钙本身对菌渣中CPC的氧化降解能力较弱,在其用量为0.01mM~0.06mM时,CPC的去除率仅为1.6%~10.4%。The concentration of CPC detected in the bacterial residue is listed in Table 1 under the conditions of different absorbed radiation doses, calcium peroxide and hydrogen peroxide dosages. It can be seen that with electron beam irradiation alone, the absorbed dose increases from 30kGy to 40kGy, and the removal efficiency of CPC increases significantly from 76.7% to 92.0%. If the dose is continued to increase to 50kGy and 75kGy, the concentration of CPC drops to 12.5mg/kg and 8.5mg/kg, and the removal rate increases slightly, to 95.7% and 97.1%. Calcium peroxide itself has a weak ability to oxidize and degrade CPC in bacterial residues. When its dosage is 0.01mM-0.06mM, the removal rate of CPC is only 1.6%-10.4%.

过氧化钙可显著促进电子束辐照对菌渣中CPC的降解效率。相同辐照吸收剂量下,CPC的去除率随过氧化钙投加量的增加而增加。在辐照吸收剂量为40kGy,过氧化钙投加量从0.01mM、0.02mM、0.04mM提高到0.06mM时,CPC去除率从97.0%、98.7%、99.6%提高到100%。在辐照吸收剂量为50kGy,过氧化钙投加量从0.01mM、0.02mM提高到0.04mM时,CPC去除率从99.0%、99.6%提高到100%。吸收剂量为40kGy,过氧化钙投加量为0.06mM以及吸收剂量为50kGy,过氧化钙投加量为0.04和0.06时,菌渣中的CPC浓度可降至液相色谱无法检出。Calcium peroxide can significantly promote the degradation efficiency of CPC in fungal residue by electron beam irradiation. Under the same absorbed radiation dose, the removal rate of CPC increased with the increase of calcium peroxide dosage. When the absorbed radiation dose was 40kGy, and the dosage of calcium peroxide increased from 0.01mM, 0.02mM, 0.04mM to 0.06mM, the removal rate of CPC increased from 97.0%, 98.7%, 99.6% to 100%. When the absorbed radiation dose is 50kGy, and the dosage of calcium peroxide increases from 0.01mM, 0.02mM to 0.04mM, the removal rate of CPC increases from 99.0%, 99.6% to 100%. When the absorbed dose is 40kGy, the dosage of calcium peroxide is 0.06mM and the absorbed dosage is 50kGy, and the dosage of calcium peroxide is 0.04 and 0.06, the concentration of CPC in the bacterial residue can be reduced to be undetectable by liquid chromatography.

过氧化氢对辐照降解CPC的促进作用显著低于过氧化钙,而且CPC的浓度越低,其强化促进作用越不明显。在过氧化氢投加量为0.02mM和0.04mM,辐照吸收剂量为75kGy时,菌渣中CPC残留浓度为8.0mg/kg和7.5mg/kg,基本接近单独辐照时的CPC的残留浓度8.5mg/kg。电子束辐照与过氧化氢协同无法将头孢发酵菌渣中的抗生素CPC降至液相色谱无法检出。The promoting effect of hydrogen peroxide on the degradation of CPC by irradiation was significantly lower than that of calcium peroxide, and the lower the concentration of CPC, the less obvious its enhancing effect was. When the dosage of hydrogen peroxide is 0.02mM and 0.04mM, and the absorbed radiation dose is 75kGy, the residual concentration of CPC in the fungus residue is 8.0mg/kg and 7.5mg/kg, which is basically close to the residual concentration of CPC of 8.5mg/kg when irradiated alone. The combination of electron beam irradiation and hydrogen peroxide could not reduce the antibiotic CPC in cephalosporin fermentation residue to undetectable by liquid chromatography.

表1实施例1不同实验条件下处理后抗生素菌渣中的CPC含量(mg/kg,ND表示未检出)The CPC content (mg/kg, ND represents not detected) in the antibiotic bacterium slag after table 1 embodiment 1 handles under different experimental conditions

实施例2Example 2

头孢发酵菌渣取自我国西部某抗生素生产企业,其含水率为89%,C/N比值为4.5,pH值为3.8,挥发性悬浮固体(VSS)/总悬浮固体(TSS)比值为90%,残留CPC的浓度为917±25mg/kg。过氧化钙为市售分析纯。过氧化氢为市售分析纯。The cephalosporin fermentation residue is taken from an antibiotic production enterprise in the west of my country. Its water content is 89%, the C/N ratio is 4.5, the pH value is 3.8, the volatile suspended solids (VSS)/total suspended solids (TSS) ratio is 90%, and the concentration of residual CPC is 917±25mg/kg. Calcium peroxide was of analytical grade commercially available. Hydrogen peroxide was commercially available of analytical grade.

取50g左右菌渣混合液,分别加入过氧化钙0.02mM、0.04mM、0.06mM、0.1mM,以及分别加入过氧化氢0.04mM、0.1mM,搅拌均匀后放入样品袋中,用传送带送至电子加速器的辐照室进行辐照。单独菌渣样品同时辐照进行对比。通过控制束流强度和传输速度得到不同的辐照吸收剂量30kGy、40kGy,50kGy,75kGy。检测辐照前后菌渣中CPC浓度。Take about 50g of the bacterial residue mixture, add calcium peroxide 0.02mM, 0.04mM, 0.06mM, 0.1mM respectively, and add hydrogen peroxide 0.04mM, 0.1mM respectively, stir evenly, put it into a sample bag, and send it to the irradiation room of the electron accelerator by a conveyor belt for irradiation. Separate fungal residue samples were irradiated at the same time for comparison. Different absorbed radiation doses of 30kGy, 40kGy, 50kGy, and 75kGy are obtained by controlling the beam intensity and transmission speed. The concentration of CPC in the bacterial residue before and after irradiation was detected.

菌渣中残留的CPC先用PBS缓冲溶液提取,再采用液相色谱检测。CPC的提取和检测方法与实施例1相同。The residual CPC in the bacterial residue was first extracted with PBS buffer solution, and then detected by liquid chromatography. The extraction and detection method of CPC are the same as in Example 1.

不同辐照吸收剂量以及过氧化钙和过氧化氢投加量条件下,头孢菌素菌渣中检测出的CPC浓度列在表2。可以看出,单独采用电子束辐照,随着辐照吸收剂量的增加,CPC的降解效率先急剧增加,然后趋于平缓。吸收剂量为30kGy、40kGy、50kGy和75kGy时,CPC去除率为81.8%、93.5%、97.7%和98.5%。过氧化钙本身对菌渣中CPC的氧化降解能力较弱,在其用量为0.2mM~0.1mM时,CPC的去除率为4.3%~10.5%。The CPC concentrations detected in cephalosporin residues under different absorbed radiation doses and calcium peroxide and hydrogen peroxide dosages are listed in Table 2. It can be seen that with electron beam irradiation alone, the degradation efficiency of CPC increases sharply at first and then tends to be flat with the increase of radiation absorbed dose. When the absorbed dose was 30kGy, 40kGy, 50kGy and 75kGy, the removal rate of CPC was 81.8%, 93.5%, 97.7% and 98.5%. Calcium peroxide itself has a weak ability to oxidize and degrade CPC in bacterial residues. When its dosage is 0.2mM-0.1mM, the removal rate of CPC is 4.3%-10.5%.

如表2所示,随着过氧化钙投加量的增加,电子束辐照过程中CPC的降解效率随之增加。在辐照吸收剂量为50kGy,过氧化钙投加量从0.02mM、0.04mM提高到0.06mM时,CPC去除率从99.6%、99.9%提高到100%,CPC浓度可降至液相色谱无法检出。当过氧化钙投加量为0.1mM时,吸收剂量为40kGy时头孢发酵菌渣中的CPC即可降至液相色谱无法检出。As shown in Table 2, as the dosage of calcium peroxide increases, the degradation efficiency of CPC increases during electron beam irradiation. When the absorbed radiation dose is 50kGy, and the dosage of calcium peroxide increases from 0.02mM, 0.04mM to 0.06mM, the removal rate of CPC increases from 99.6%, 99.9% to 100%, and the concentration of CPC can be reduced to undetectable by liquid chromatography. When the dosage of calcium peroxide is 0.1mM, the CPC in cephalosporin fermentation residue can be reduced to undetectable by liquid chromatography when the absorbed dose is 40kGy.

过氧化氢对辐照降解CPC的促进作用显著低于过氧化钙,而且CPC的浓度越低,其强化促进作用越不明显。在过氧化氢投加量为0.04mM和0.1mM,辐照吸收剂量为75kGy时,CPC仍可检出,其残留浓度12.0mg/kg和11.0mg/kg基本接近单独辐照时CPC残留浓度13.6mg/kg。电子束辐照与过氧化氢协同无法将头孢发酵菌渣中的抗生素CPC降至液相色谱无法检出。The promoting effect of hydrogen peroxide on the degradation of CPC by irradiation was significantly lower than that of calcium peroxide, and the lower the concentration of CPC, the less obvious its enhancing effect was. When the dosage of hydrogen peroxide is 0.04mM and 0.1mM, and the absorbed dose of radiation is 75kGy, CPC can still be detected, and its residual concentration of 12.0mg/kg and 11.0mg/kg is basically close to the residual concentration of CPC of 13.6mg/kg when irradiated alone. The combination of electron beam irradiation and hydrogen peroxide could not reduce the antibiotic CPC in cephalosporin fermentation residue to undetectable by liquid chromatography.

表2实施例2不同实验条件下处理后抗生素菌渣中的CPC含量(mg/kg,ND表示未检出)CPC content (mg/kg, ND represents not detected) in the antibiotic bacterium slag after table 2 embodiment 2 handles under different experimental conditions

此实施例仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求的保护范围为准。This embodiment is only a preferred specific implementation of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be covered within the scope of protection of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

尽管已描述了本发明实施例的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例做出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明实施例范围的所有变更和修改。Having described preferred embodiments of embodiments of the present invention, additional changes and modifications can be made to these embodiments by those skilled in the art once the basic inventive concept is appreciated. Therefore, the appended claims are intended to be interpreted to cover the preferred embodiment and all changes and modifications which fall within the scope of the embodiments of the present invention.

最后,还需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者终端设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者终端设备所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者终端设备中还存在另外的相同要素。Finally, it should also be noted that in this document, relational terms such as first and second etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article or end-equipment comprising a set of elements includes not only those elements but also other elements not expressly listed or which are inherent to such a process, method, article or end-equipment. Without further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article or terminal device comprising said element.

以上对本发明所提供的一种抗生素菌渣方法、装置、服务器及存储介质,进行了详细介绍,本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想;同时,对于本领域的一般技术人员,依据本发明的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本发明的限制。The method, device, server and storage medium of an antibiotic bacteria residue provided by the present invention have been introduced in detail above. In this paper, specific examples are used to illustrate the principle and implementation of the present invention. The description of the above examples is only used to help understand the method of the present invention and its core idea. At the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation and scope of application. In summary, the content of this specification should not be understood as a limitation of the present invention.

Claims (7)

1. A method for treating antibiotic residues, the method comprising:
mixing the antibiotic residues with calcium peroxide to obtain a mixture;
irradiating the mixture by using an electron beam to degrade antibiotics in the antibiotic residues;
under the acidic condition of the antibiotic bacterial residues, the calcium ions replace hydrogen ions of acidic proteins to form insoluble protein-calcium precipitates, so that proteins are coagulated, the competitive action of the proteins on hydroxyl free radicals generated by electron beam irradiation is eliminated, the number of hydroxyl free radicals reacting with antibiotics in a treatment system is increased, and the degradation of antibiotics in the antibiotic bacterial residues by electron beam irradiation is enhanced;
the antibiotic residues are cephalosporin fermentation residues containing residual antibiotics generated in the production process of the antibiotics, and the antibiotics are cephalosporin C;
the addition amount of the calcium peroxide is 0.04 mM-0.1 mM.
2. The method for treating antibiotic residues according to claim 1, wherein the mixing of the antibiotic residues with calcium peroxide to obtain a mixture comprises:
adding calcium peroxide into the antibiotic residues, and uniformly mixing the antibiotic residues and the calcium peroxide to obtain a mixture;
irradiating the mixture with an electron beam, comprising:
the mixture is sent to an irradiation chamber of an electron accelerator, and is irradiated by an electron beam.
3. The antibiotic residue treatment method according to claim 1, wherein the content of residual cephalosporin C in the cephalosporin fermentation residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation residue is 85% -95%.
4. The antibiotic slag treatment method according to claim 1, wherein the irradiation absorbed dose of the electron beam is 40kGy to 75kGy.
5. An antibiotic slag treatment system for implementing the antibiotic slag treatment method of any one of claims 1-4, the system comprising:
the reactor is used for containing antibiotic residues so as to treat the antibiotic residues; the antibiotic residues are cephalosporin fermentation residues containing residual antibiotics generated in the production process of the antibiotics, and the antibiotics are cephalosporin C;
the calcium peroxide adding device is used for adding calcium peroxide into the reactor; the adding amount of the calcium peroxide is 0.04 mM-0.1 mM;
the stirring device is used for uniformly mixing the antibiotic residues with the calcium peroxide to obtain a mixture;
an electron accelerator for generating electron beams to irradiate the mixture so as to degrade antibiotics in the antibiotic residues;
under the acidic condition of the antibiotic bacterial residues, the calcium ions replace hydrogen ions of acidic proteins to form insoluble protein-calcium precipitates, so that proteins are coagulated, the competitive action of the proteins on hydroxyl free radicals generated by electron beam irradiation is eliminated, the number of hydroxyl free radicals reacting with antibiotics in a treatment system is increased, and the degradation of antibiotics in the antibiotic bacterial residues by electron beam irradiation is enhanced.
6. The antibiotic dregs treatment system according to claim 5, wherein the content of residual cephalosporin C in the cephalosporin fermentation dregs is 200-1000 mg/kg, and the water content of the cephalosporin fermentation dregs is 85% -95%.
7. The antibiotic slag treatment system of claim 5, wherein the radiation absorbed dose of the electron beam is between 40kGy and 75kGy.
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