[go: up one dir, main page]

CN114949720A - A kind of antibiotic bacteria residue treatment method and system - Google Patents

A kind of antibiotic bacteria residue treatment method and system Download PDF

Info

Publication number
CN114949720A
CN114949720A CN202210648383.8A CN202210648383A CN114949720A CN 114949720 A CN114949720 A CN 114949720A CN 202210648383 A CN202210648383 A CN 202210648383A CN 114949720 A CN114949720 A CN 114949720A
Authority
CN
China
Prior art keywords
antibiotic
residues
electron beam
residue
calcium peroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210648383.8A
Other languages
Chinese (zh)
Other versions
CN114949720B (en
Inventor
王建龙
初里冰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN202210648383.8A priority Critical patent/CN114949720B/en
Publication of CN114949720A publication Critical patent/CN114949720A/en
Application granted granted Critical
Publication of CN114949720B publication Critical patent/CN114949720B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

本发明实施例提供了一种抗生素菌渣方法、系统,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,产生的钙离子在抗生素菌渣较强的酸性条件下,可以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。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。

Figure 202210648383

The embodiment of the present invention provides a method and system for antibiotic slag. In the embodiment of the present invention, calcium peroxide is dissolved in the antibiotic slag with a high water content, and the generated calcium ions are in a strong acidic condition of the antibiotic slag. , can replace the hydrogen ions of acidic proteins, form insoluble protein-calcium precipitation, coagulate the protein, and then eliminate its competition with antibiotics to generate hydroxyl radicals from irradiation, so that the number of hydroxyl radicals reacting with antibiotics in the irradiation system is reduced. Significant increase, and then completely eliminate the antibiotic contamination in the antibiotic residue. In the embodiment of the present invention, under the synergistic interaction between electron beam irradiation and calcium peroxide, the antibiotics in the antibiotic slag can be completely degraded, so that the antibiotic concentration can be reduced to a level that cannot be detected by liquid chromatography, that is, the antibiotic removal rate can be up to 100%. In the method provided by the embodiment of the present invention, the electron beam irradiation is performed at normal temperature, which is easy to realize large-scale industrial application.

Figure 202210648383

Description

一种抗生素菌渣处理方法、系统A kind of antibiotic bacteria residue treatment method and system

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。Embodiments of the present invention relate to the field of solid waste treatment, and in particular, to a method and system for treating bacterial residues of antibiotics.

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 API of cephalosporin antibiotics. CPC is produced by aerobic fermentation using Cephalosporium acremonium as the fermenting strain and using corn steep liquor, peanut flour, dextrin, methionine, soybean oil, inorganic salts, etc. as the medium. After the fermentation process is completed, sulfuric acid is added to the fermentation broth for acidification to precipitate mycelium and protein, the supernatant is filtered through a ceramic membrane to remove macromolecular protein substances, and then the final raw material drug product is obtained through resin adsorption purification, concentration and other processes. The sulfuric acid-acidified precipitate and the concentrated solution separated by the ceramic membrane are the antibiotic slag 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 slag is rich in nutrients, rich in polysaccharide, protein, 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, antibiotic residues are expected to be removed from hazardous wastes. The harmless antibiotic residues can be made into fertilizers and turned into resources for reuse. , and then solve the problem of treatment and disposal of antibiotic residues.

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 bacterial residue is a viscous solid-liquid mixture, and it is difficult to penetrate into the internal reaction of bacterial residue by common treatment methods such as ultraviolet and photocatalysis, 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 bacterial residue treatment method.

发明内容SUMMARY 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 slag, so as to degrade the antibiotic in the antibiotic slag, so that the concentration of the antibiotic in the antibiotic slag is reduced to a level that cannot be detected 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:A first aspect of the embodiments of the present invention provides a method for antibiotic slag, the method comprising:

将抗生素菌渣与过氧化钙混合,得到混合物;The antibiotic bacterial residue is mixed 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;The mixture is irradiated with an electron beam to degrade the antibiotics in the antibiotic slag;

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 produce calcium ions, and under the acidic conditions of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble protein-calcium precipitation, so that the protein coagulates and eliminates the electron pair of the protein. The competition of hydroxyl radicals generated by beam irradiation increases the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthens the degradation of antibiotics in antibiotic slag by electron beam irradiation.

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 bacterial residue 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;Add calcium peroxide to the antibiotic bacterial residue, and mix the antibiotic bacterial 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, including:

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 a cephalosporin fermentation residue containing residual antibiotics produced in the antibiotic production process, 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 bacteria residue is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation bacteria 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 0.04 mM to 0.1 mM.

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:A second aspect of the embodiment of the present invention provides an antibiotic bacterial residue system, the system is used to realize the antibiotic bacterial residue treatment method according to any one of the above-mentioned first aspect, and 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;a reactor for holding antibiotic bacterial residues, to process the antibiotic bacterial residues;

过氧化钙投加装置,用于向所述反应器中投加过氧化钙;A calcium peroxide dosing device for adding 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 bacterial residue with 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 electron beams to irradiate the mixture to degrade the antibiotics in the antibiotic slag;

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 produce calcium ions, and under the acidic conditions of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble protein-calcium precipitation, so that the protein coagulates and eliminates the electron pair of the protein. The competition of hydroxyl radicals generated by beam irradiation increases the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthens the degradation of antibiotics in antibiotic slag by electron beam irradiation.

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 slag is a cephalosporin fermentation slag containing residual antibiotics produced in the antibiotic production process, the antibiotic is cephalosporin C, and the residual cephalosporin C content in the cephalosporin fermentation slag is 200. ~1000mg/kg, the moisture content of the cephalosporin fermentation bacteria 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 0.04 mM to 0.1 mM.

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 bacterial residue method provided by the embodiment of the present invention, the radiation effect of electron beams and the acidic environment of the antibiotic bacterial residue (the pH value is usually about 4.0) are conducive to the in-situ decomposition of calcium peroxide to generate hydrogen peroxide. The reaction of the generated e aq - and ·H promotes the production of ·OH; at the same time, the calcium ions generated by the dissolution of calcium peroxide can replace the hydrogen ions of acidic proteins under the strong acidic conditions of the antibiotic slag to form insoluble protein-calcium Precipitation makes the protein coagulate, and then eliminates its competitive effect with antibiotics to generate hydroxyl radicals on irradiation, significantly increases the number of hydroxyl radicals reacting with antibiotics in the irradiation system, and completely eliminates antibiotic pollution in 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 slag can be completely degraded, so that the antibiotic concentration can be reduced to a level that cannot be detected by liquid chromatography, that is, the antibiotic removal rate can be up to 100%. In the method provided by the embodiment of the present invention, the electron beam irradiation is performed 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 bacterial 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 illustrate the technical solutions of the embodiments of the present invention more clearly, the following briefly introduces the drawings that are used in the description of the embodiments of the present invention. Obviously, the 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 from these drawings without 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 flow chart of a kind of antibiotic bacterial 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 flow chart of another kind of antibiotic bacterial residue 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。3 is a schematic diagram of an antibiotic bacterial 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 clearly understood, the present invention will be described in further detail below with reference to 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. An electron beam is a dense stream of high-speed electrons with extremely high energy density. The high-energy electron beam can penetrate deep into the slag and directly destroy the molecular structure of the antibiotic through the Compton effect; at the same time, the electron beam can stimulate the ionization of water molecules to generate active particles such as OH, e aq -, and H (as shown in formula 1). shown, the values in parentheses are the radiation chemical yields of each active particle), antibiotics can be degraded by oxidation-reduction reaction with these active particles.

Figure BDA0003686878270000041
Figure BDA0003686878270000041

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 continuing to increase the dosage, the improvement of the antibiotic removal rate 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 the related art, the commonly used method is to use an oxidant to strengthen the electron beam irradiation to degrade the antibiotics in the bacterial residue, so as to generate more strongly oxidizing OH, promote the oxidation-reduction reaction, and then promote the degradation of the antibiotics. This method still cannot achieve the effect of reducing the antibiotic concentration to undetectable by liquid chromatography, and thus cannot achieve the 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 inventors explored the treatment method of antibiotic slag, and found that the proteins, polysaccharides and other substances present in the antibiotic slag solution compete with the antibiotics for free radicals generated by irradiation, thereby limiting the further degradation of the antibiotics. The lower the concentration of antibiotics, the stronger the competition between these substances and the greater the impact on the degradation of antibiotics. Among them, the irradiation competition of proteins is the strongest. In order to completely eliminate antibiotic pollution, it is necessary to inhibit the irradiation competition of proteins.

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-mentioned exploration and discovery, the inventive concept of the present application is proposed: strengthen the electron beam irradiation with calcium peroxide to degrade the antibiotics in the bacterial residue, wherein, the calcium peroxide dissolves in the antibiotic bacterial residue with higher water content to produce calcium ions, Under the acidic conditions of antibiotic slag, calcium ions replace the hydrogen ions of acidic proteins, forming insoluble protein-calcium precipitates, coagulating the proteins, eliminating the competitive effect of proteins on hydroxyl radicals generated by electron beam irradiation, and making the treatment system The number of hydroxyl radicals reacting with antibiotics increased, and the electron beam irradiation was enhanced to degrade the antibiotics in the antibiotic slag.

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 the above-mentioned inventive concept, the first aspect of the present invention proposes a method for treating bacterial residues of antibiotics. The method for treating bacterial residues of antibiotics proposed by the present invention will be described below in conjunction with accompanying drawing 1, and the 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 bacterial residue and 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 may be used to mix the antibiotic bacterial 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, irradiating the mixture with electron beams 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 an electron beam, 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, and under the acidic conditions of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble Protein-calcium precipitation makes protein coagulate, eliminates the competitive effect of protein on hydroxyl radicals generated by electron beam irradiation, increases the number of hydroxyl radicals reacting with antibiotics in the treatment system, and strengthens electron beam irradiation to degrade antibiotic bacteria residues. antibiotic.

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 make the calcium peroxide decompose in situ to generate hydrogen peroxide, and the reaction between the hydrogen peroxide and the e aq - and ·H generated by the electron beam irradiation promotes the OH production can further enhance the degradation of antibiotics in antibiotic slag by electron beam irradiation by promoting 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 the above-mentioned inventive concept, the present invention also proposes another method for treating bacterial residues of antibiotics. Below in conjunction with accompanying drawing 2, another method for treating bacterial residues of antibiotics proposed by the present invention will be described, and the 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 bacteria residue, and mixing the antibiotic bacteria 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 can be selected as a powdered solid, so as to be evenly mixed with the antibiotic slag 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 slag is cephalosporin fermentation slag containing residual antibiotics produced in 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 0.04 mM to 0.1 mM.

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 the 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, the mixture is sent to an irradiation chamber of an electron accelerator, and the mixture is irradiated 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 under-beam transmission system of the electron accelerator and sent to the irradiation chamber of the electron accelerator by means of 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 absorption 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 absorbed doses of radiation 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 50 kGy.

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 slag can be completely degraded, and the antibiotic concentration can be reduced to be undetectable by liquid chromatography. In the method provided by the embodiment of the present invention, the electron beam irradiation is performed 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 inventive concept, the second aspect of the present invention proposes an antibiotic bacterial residue treatment system, which is used to realize the antibiotic bacterial residue treatment method described in any one of the first aspect of the embodiments of the present invention. Another proposed antibiotic bacteria residue treatment system is described, and 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;a reactor for holding antibiotic bacterial residues, to process the antibiotic bacterial residues;

过氧化钙投加装置,用于向所述反应器中投加过氧化钙;A calcium peroxide dosing device for adding 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), for mixing the antibiotic bacterial residue with 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 electron beams to irradiate the mixture to degrade the antibiotics in the antibiotic slag;

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 higher water content to generate calcium ions, and under the acidic conditions of the antibiotic slag, the calcium ions replace the hydrogen ions of the acidic protein to form insoluble protein- Calcium precipitation makes protein coagulate, eliminates the competitive effect of protein on hydroxyl radicals generated 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 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 slag is cephalosporin fermentation slag containing residual antibiotics produced in the antibiotic production process, the antibiotic is cephalosporin C, and the residual cephalosporin C content in the cephalosporin fermentation slag It is 200-1000 mg/kg, and the moisture content of the cephalosporin fermentation bacteria 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 0.04 mM to 0.1 mM.

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 absorption 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 for those skilled in the art to better understand the present invention, the method for treating antibiotic bacterial residues provided by the present invention will be described below through a plurality of specific embodiments.

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。Cephalosporin fermentation residue was taken from an antibiotic production enterprise in western my country. Its moisture content was 91%, the C/N ratio was 4.9, the pH value was 4.0, and the volatile suspended solids (VSS)/total suspended solids (TSS) ratio was 92%. , the concentration of residual CPC was 290±12mg/kg. Calcium peroxide was commercially available of analytical grade. Hydrogen peroxide was of commercially available 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 cephalosporin fermentation bacteria 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 with a conveyor belt for irradiation. The bacterial 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 to the strengthening effect of hydrogen peroxide irradiation, about 50 g of cephalosporin fermentation bacteria residue mixture was taken, and 0.02 mM and 0.04 mM hydrogen peroxide were added respectively, stirred evenly, and then placed into the sample bag and transported to the irradiation chamber of the electron accelerator with a conveyor belt for simultaneous irradiation. The irradiation removal effects of CPC under the same dosage of calcium peroxide and hydrogen peroxide were 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 radiation absorbed doses of 30kGy, 40kGy, 50kGy and 75kGy were 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 solution (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 was as follows: about 5 mg of bacterial residue was placed in a 50 mL polypropylene centrifuge tube, 20 mL of 0.1 mol/L PBS buffer (pH 5.0) was added, vortexed for 1 min, and ultrasonic-assisted extraction was performed for 30 min. Centrifuge at 6000 rpm for 10 min, take the supernatant and filter it with a 0.22 μm filter 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 was a high performance liquid chromatograph (Agilent1200) from Agilent, USA, the chromatographic column was an XDB-C18 reversed-phase column, and the column temperature was 30°C. The detector is an ultraviolet detector, and the detection wavelength is 260 nm; 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 CPC concentrations detected in the bacterial residue under different irradiation absorbed doses and dosages of calcium peroxide and hydrogen peroxide are listed in Table 1. It can be seen that with electron beam irradiation alone, the absorbed dose increased from 30kGy to 40kGy, and the removal efficiency of CPC increased significantly from 76.7% to 92.0%; continuing to increase the dose to 50kGy and 75kGy, the concentration of CPC decreased to 12.5mg/kg and 8.5mg/kg, the removal rate was not much improved, 95.7% and 97.1%. The oxidative degradation ability of calcium peroxide itself to CPC in bacterial residue is weak, and the removal rate of CPC is only 1.6%-10.4% when its dosage is 0.01mM-0.06mM.

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 bacterial residues by electron beam irradiation. Under the same radiation absorbed dose, the removal rate of CPC increased with the increase of calcium peroxide dosage. When the absorbed dose of irradiation was 40kGy and the dosage of calcium peroxide increased from 0.01mM, 0.02mM, 0.04mM to 0.06mM, the CPC removal rate increased from 97.0%, 98.7%, 99.6% to 100%. When the absorbed dose of irradiation was 50kGy and the dosage of calcium peroxide increased from 0.01mM and 0.02mM to 0.04mM, the CPC removal rate increased from 99.0% and 99.6% to 100%. When the absorbed dose was 40kGy, the dosage of calcium peroxide was 0.06mM, and the absorbed dose was 50kGy, the dosage of calcium peroxide was 0.04 and 0.06, the CPC concentration in the bacterial residue could not be detected 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 promotion effect of hydrogen peroxide on irradiation degradation of CPC was significantly lower than that of calcium peroxide, and the lower the concentration of CPC, the less obvious the promotion effect was. When the dosage of hydrogen peroxide was 0.02 mM and 0.04 mM, and the absorbed dose of irradiation was 75 kGy, the residual concentration of CPC in the bacterial residue was 8.0 mg/kg and 7.5 mg/kg, which was basically close to the residual concentration of CPC when irradiated alone. 8.5mg/kg. The combination of electron beam irradiation and hydrogen peroxide could not reduce the antibiotic CPC in cephalosporin fermentation residue to be 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)Table 1 Example 1 CPC content (mg/kg, ND means not detected) in the antibiotic slag after treatment under different experimental conditions

Figure BDA0003686878270000091
Figure BDA0003686878270000091

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。Cephalosporin fermentation residue was taken from an antibiotic production enterprise in western my country. Its moisture content was 89%, the C/N ratio was 4.5, the pH value was 3.8, and the volatile suspended solids (VSS)/total suspended solids (TSS) ratio was 90%. , the concentration of residual CPC was 917±25mg/kg. Calcium peroxide was commercially available of analytical grade. Hydrogen peroxide was of commercially available 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 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 the sample bag, and send it to the Irradiation is carried out in the irradiation chamber of the electron accelerator. Individual bacterial residue samples were irradiated at the same time for comparison. Different radiation absorbed doses of 30kGy, 40kGy, 50kGy and 75kGy were 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 methods of CPC are the same as those 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 the cephalosporin residues under different irradiation absorbed doses and dosages of calcium peroxide and hydrogen peroxide 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 level off with the increase of the absorbed dose of irradiation. When the absorbed doses were 30kGy, 40kGy, 50kGy and 75kGy, the CPC removal rates were 81.8%, 93.5%, 97.7% and 98.5%. The oxidative degradation ability of calcium peroxide itself to CPC in bacterial residue is weak, and the removal rate of CPC is 4.3%-10.5% when its dosage is 0.2mM-0.1mM.

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, the degradation efficiency of CPC during electron beam irradiation increased with the increase of calcium peroxide dosage. When the absorbed dose of irradiation was 50kGy and the dosage of calcium peroxide increased from 0.02mM and 0.04mM to 0.06mM, the CPC removal rate increased from 99.6% and 99.9% to 100%, and the CPC concentration could be reduced to a level that could not be detected by liquid chromatography. out. When the dosage of calcium peroxide is 0.1 mM, and the absorbed dose is 40 kGy, the CPC in the cephalosporin fermentation 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0.04mM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 promotion effect of hydrogen peroxide on irradiation degradation of CPC was significantly lower than that of calcium peroxide, and the lower the concentration of CPC, the less obvious the promotion effect was. When the dosage of hydrogen peroxide is 0.04mM and 0.1mM, and the absorbed dose of irradiation is 75kGy, CPC can still be detected, and its residual concentration of 12.0mg/kg and 11.0mg/kg is basically close to the CPC residual concentration of 13.6 when irradiated alone mg/kg. The combination of electron beam irradiation and hydrogen peroxide could not reduce the antibiotic CPC in cephalosporin fermentation residue to be 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)The CPC content (mg/kg, ND means not detected) in the antibiotic slag after treatment under the different experimental conditions of table 2 embodiment 2

Figure BDA0003686878270000101
Figure BDA0003686878270000101

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 embodiment of the present invention, but the protection scope of the present invention is not limited to this. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention. , all should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to 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。Although preferred embodiments of the embodiments of the present invention have been described, additional changes and modifications to these embodiments may be made by those skilled in the art once the basic inventive concepts are known. Therefore, the appended claims are intended to be construed to include the preferred embodiments as well as all changes and modifications that 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 are used only to distinguish one entity or operation from another, and do not necessarily require or imply these entities or there is any such actual relationship or sequence between operations. Moreover, the terms "comprising", "comprising" or any other variation thereof are intended to encompass non-exclusive inclusion, such that a process, method, article or terminal device comprising a list of elements includes not only those elements, but also a non-exclusive list of elements. other elements, or also include elements inherent to such a process, method, article or terminal equipment. Without further limitation, an element defined by the phrase "comprises a..." does not preclude 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 for antibiotic bacteria residues provided by the present invention have been described above in detail. In this paper, specific examples are used to illustrate the principles and implementations of the present invention. In order to help understand the method of the present invention and its core idea; at the same time, for those skilled in the art, according to the idea of the present invention, there will be changes in the specific implementation and application scope. In summary, this specification The contents should not be construed as limiting the present invention.

Claims (10)

1. An antibiotic fungi residue treatment method is characterized by comprising the following steps:
mixing antibiotic fungi residues with calcium peroxide to obtain a mixture;
irradiating the mixture by using an electron beam to degrade antibiotics in the antibiotic fungi residues;
the calcium peroxide is dissolved to generate calcium ions, the calcium ions replace hydrogen ions of acidic protein under the acidic condition of the antibiotic bacteria residues to form insoluble protein-calcium precipitate, the protein is coagulated, the competition effect of the protein on hydroxyl free radicals generated by electron beam irradiation is eliminated, the number of the hydroxyl free radicals reacted with the antibiotic in a treatment system is increased, and the antibiotic in the antibiotic bacteria residues is degraded by the electron beam irradiation.
2. The method of antibiotic pomace treatment according to claim 1, characterized in that said mixing of antibiotic pomace with calcium peroxide results in a mixture comprising:
adding calcium peroxide into the antibiotic fungi residues, and uniformly mixing the antibiotic fungi residues and the calcium peroxide to obtain a mixture;
irradiating the mixture with an electron beam comprising:
and sending the mixture to an irradiation chamber of an electron accelerator, and irradiating the mixture by using an electron beam.
3. The method for treating the antibiotic residues according to claim 1, wherein the antibiotic residues are cephalosporin fermentation residues containing residual antibiotics generated in the antibiotic production process, and the antibiotics are cephalosporin C.
4. The antibiotic bacteria residue treatment method as claimed in claim 3, wherein the content of residual cephalosporin C in the cephalosporin fermentation bacteria residue is 200-1000 mg/kg, and the water content of the cephalosporin fermentation bacteria residue is 85-95%.
5. The method for treating antibiotic fungi residues according to claim 1, wherein the radiation absorbed dose of the electron beam is 40-75 kGy.
6. The method of treating antibiotic residues according to claim 1, wherein the calcium peroxide is added in an amount of 0.04mM to 0.1 mM.
7. An antibiotic-bacteria-residue treatment system for implementing the antibiotic-bacteria-residue treatment method according to any one of claims 1 to 6, the system comprising:
the reactor is used for containing antibiotic fungi residues so as to treat the antibiotic fungi residues;
the calcium peroxide feeding device is used for feeding calcium peroxide into the reactor;
the stirring device is used for uniformly mixing the antibiotic fungi residues and the calcium peroxide to obtain a mixture;
the electron accelerator is used for generating electron beams to irradiate the mixture so as to degrade antibiotics in the antibiotic fungi residues;
the calcium peroxide is dissolved to generate calcium ions, the calcium ions replace hydrogen ions of acidic protein under the acidic condition of the antibiotic bacteria residues to form insoluble protein-calcium precipitate, the protein is coagulated, the competition effect of the protein on hydroxyl free radicals generated by electron beam irradiation is eliminated, the number of the hydroxyl free radicals reacted with the antibiotic in a treatment system is increased, and the antibiotic in the antibiotic bacteria residues is degraded by the electron beam irradiation.
8. The antibiotic fungi residue processing system of claim 7, wherein the antibiotic fungi residue is cephalosporin fermentation fungi residue containing residual antibiotic generated in the antibiotic production process, the antibiotic is cephalosporin C, the content of the residual cephalosporin C in the cephalosporin fermentation fungi residue is 200-1000 mg/kg, and the water content of the cephalosporin fermentation fungi residue is 85-95%.
9. The antibiotic mushroom dreg processing system according to claim 7, wherein the radiation absorbed dose of the electron beam is 40kGy to 75 kGy.
10. The antibiotic bagasse processing system according to claim 7, wherein the calcium peroxide is added in an amount of 0.04mM to 0.1 mM.
CN202210648383.8A 2022-06-09 2022-06-09 A method and system for treating antibiotic residue Active CN114949720B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210648383.8A CN114949720B (en) 2022-06-09 2022-06-09 A method and system for treating antibiotic residue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210648383.8A CN114949720B (en) 2022-06-09 2022-06-09 A method and system for treating antibiotic residue

Publications (2)

Publication Number Publication Date
CN114949720A true CN114949720A (en) 2022-08-30
CN114949720B CN114949720B (en) 2023-07-21

Family

ID=82962238

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210648383.8A Active CN114949720B (en) 2022-06-09 2022-06-09 A method and system for treating antibiotic residue

Country Status (1)

Country Link
CN (1) CN114949720B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116213434A (en) * 2023-03-31 2023-06-06 中广核达胜加速器技术有限公司 A kind of processing method of erythromycin thiocyanate bacteria residue

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080035580A1 (en) * 2004-09-27 2008-02-14 De Rijk Jan Methods and Compositions for Treatment of Water
US7662294B1 (en) * 2004-02-02 2010-02-16 Cox Jr Henry Wilmore Method for reducing organic contamination
CN108500034A (en) * 2018-03-27 2018-09-07 中广核达胜加速器技术有限公司 A kind of antibiotic bacterium residues processing technique
CN109354365A (en) * 2018-11-20 2019-02-19 同济大学 A method for synergistic removal of refractory drugs in sludge and promoting solubilization and reduction of sludge by UV/calcium peroxide
CN112408685A (en) * 2020-11-25 2021-02-26 上海化工研究院有限公司 Method for removing residual antibiotics in antibiotic dreg slurry

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7662294B1 (en) * 2004-02-02 2010-02-16 Cox Jr Henry Wilmore Method for reducing organic contamination
US20080035580A1 (en) * 2004-09-27 2008-02-14 De Rijk Jan Methods and Compositions for Treatment of Water
CN108500034A (en) * 2018-03-27 2018-09-07 中广核达胜加速器技术有限公司 A kind of antibiotic bacterium residues processing technique
CN109354365A (en) * 2018-11-20 2019-02-19 同济大学 A method for synergistic removal of refractory drugs in sludge and promoting solubilization and reduction of sludge by UV/calcium peroxide
CN112408685A (en) * 2020-11-25 2021-02-26 上海化工研究院有限公司 Method for removing residual antibiotics in antibiotic dreg slurry

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116213434A (en) * 2023-03-31 2023-06-06 中广核达胜加速器技术有限公司 A kind of processing method of erythromycin thiocyanate bacteria residue

Also Published As

Publication number Publication date
CN114949720B (en) 2023-07-21

Similar Documents

Publication Publication Date Title
JP7128547B2 (en) A method for removing antibiotic resistance genes by ionizing radiation
CN103539234B (en) Integrated processing method of fracturing flow-back fluid
CN106348381A (en) Novel treatment process of antibiotic wastewater electron beams
CN113354490B (en) Method for improving aerobic composting effect of cephalosporin fermentation bacteria residues by using electron beam irradiation
CN101993162A (en) Method for treating reverse osmosis concentrated water
CN103495428A (en) Preparation method of carbon nano-tube based Fenton-like catalyst for advanced oxidation system
CN110540283A (en) A method for strengthening the removal of sulfamethoxazole from water
CN114949720B (en) A method and system for treating antibiotic residue
CN109019746A (en) The method of active carbon mediation aqueous electron deoxidization, degradation PFASs
CN106145386A (en) A kind of industrial sewage treating agent
CN109354365A (en) A method for synergistic removal of refractory drugs in sludge and promoting solubilization and reduction of sludge by UV/calcium peroxide
CN108642092A (en) A method of strengthening antibiotic anaerobic degradation
CN108726625A (en) The method for going mental antidepressant in water removal using E-beam irradiation degradation
CN105217845A (en) A kind of deep treatment method of percolate from garbage filling field biological treatment tail water
CN109354109A (en) Method for removing antidepressant psychotropic drugs from water by ionizing radiation degradation
CN106348542B (en) A kind of processing method of the pharmacy waste water of the antibiotic containing high concentration
CN107619072B (en) Curing agent for treating high-COD and high-salinity wastewater and using method
CN105923947A (en) Sludge treatment agent and method for treating sludge by using sludge treatment agent
CN101402476A (en) Irradiation treatment method for vinyl cyanide wastewater
CN116002893A (en) Pesticide wastewater treatment method
KR20160014144A (en) Method for treatment of microwave-assisted solubilization efficiency for waste activated sludge by addition of food wastewater
CN102701429A (en) Technology for removing pentachlorophenol in water by using fixed horseradish peroxidase
CN114262722B (en) A method for resource utilization of kitchen waste
CN106882914B (en) Methods for improving the dewatering performance of excess sludge in urban sewage treatment plants
CN109621888B (en) Method for degrading antibiotics in water body by virtue of synergistic irradiation of titanium dioxide and silicon dioxide

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant