CN112723682A - 一种喹诺酮类抗生素生产废水集成处理方法 - Google Patents
一种喹诺酮类抗生素生产废水集成处理方法 Download PDFInfo
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Abstract
本发明提供一种喹诺酮类抗生素生产废水集成处理方法。喹诺酮类抗生素合成过程中,会产生大量的生产废水,废水中既有母核化合物的残留物和降解物,又有大量未提取完全的生成物以及精馏未完全回收的溶剂残留,废水的生物降解性差,有鉴于此,本发明提出一种喹诺酮类抗生素生产废水集成处理方法,废水经过铁镁碳微电解,微电解的废水加入双氧水与铁镁碳材料溶出的Fe2+形成Fenton试剂进行氧化后,以氢氧化钠调节废水的PH值至中性,加入聚丙烯酰胺助凝,进行泥水分离后利用多效蒸发去除废水中的无机盐,蒸发除盐后的废水,经过厌氧生物、A/O好氧生物处理和Fenton试剂氧化等工段处理后,废水能满足合成制药工业废水排放指标要求。
Description
技术领域
本发明属于环保技术领域,具体涉及一种喹诺酮类抗生素生产废水集成处理方法。
背景技术
喹诺酮类抗生素常用的主要有诺氟沙星(NorfloxAcin)又名腐哌酸,盐酸环丙沙星(CiprofloxAcin hydrochlorid)别名环丙腐哌酸、左氧氟沙星(LerofloxAcin)别名左氧沙星等三大类,均由化学合成方法生产。具有抗菌谱广,抗菌作用强等特点。合成喹诺酮类抗生素母核化合物主要有三大类荼啶羧酸类(NAPHthyridinic Acids)、吡啶并嘧啶羧酸类(Pyridopymidinic Acids)和喹啉羧酸类(QuiAnolinic Acids)均为多环芳香类化合物,喹诺酮类抗生素合成过程中产生大量的生产废水,废水中既有母核化合物未完全反应的残留物及其降解物,又有未完全提取的生成物和溶剂精馏回收中未完全回收的溶剂和高沸点化合物,废水生物降解性差,无法直接进行生物处理。同时,酸碱反应生成的大量的盐类,是典型的高盐废水,目前尚未有完善的处理工艺方法。
有鉴于此,特提出本发明。
发明内容
本发明针对喹诺酮类抗生素化学合成过程中产生的废水,废水难以直接进行生物处理,目前尚未有成熟的处理工艺的技术不足,提供一种喹诺酮类抗生素生产废水的集成处理方法。废水经铁镁碳微电解和Fenton试剂氧化及多效蒸发除盐等预处理工艺,其可生化性得以提高,经预处理的废水采用生物处理和Fenton氧化深度处理,废水能满足合成制药工业废水的排放要求。
为解决上述技术问题,本发明采用以下技术方案。
一种喹诺酮类抗生素生产废水的集成处理方法,包括如下步骤:
1.以氢氧化钠和硫酸调节废水的PH为3-5;
2. 调节PH值后的废水进入铁镁碳微电解系统进行微电解,铁镁碳的质量比为(1-2):(0.05-1):1,铁镁碳微电解系统中铁镁碳的填充比例30-50%(体积比),废水在铁镁碳微电解系统中停留时间 2-4小时。
3.经过铁镁碳微电解系统处理后的废水加入双氧水(质量分数27.5%),双氧水与废水COD的质量比(0.1-0.3):1,搅拌反应2-4小时,加入氢氧化钠调节废水的PH值6-9,加入聚丙烯酰胺溶液絮凝沉淀进行泥水分离。
4.经过铁镁碳微电解和Fenton试剂氧化预处理的废水,采用三体三效的蒸发系统进行蒸发,废水经过蒸发浓缩后,形成过饱和盐溶液,冷却结晶离心分离除盐。
5.经过预处理后的废水进入厌氧生物处理系统,厌氧采用UASB厌氧生物反应器,UASB厌氧生物反应器的容积负荷1.5-3.0kg/(m3·d),经过厌氧生物处理后的废水,采用A/O好氧生物处理工艺,A段的停留时间根据废水中总氮的量进行增减,O段的停留时间为120-190小时。
6.经过厌氧和A/O好氧生物处理,废水中仍存在一定量的生物不可降解的有机物,为满足排放要求,采用Fenton试剂氧化进行深度处理。废水以硫酸调节PH为3-5,采用双氧水(质量分数27.5%)与硫酸亚铁的摩尔比3:(0.5-1)的Fenton试剂,反应时间3-4小时,反应结束后,以氢氧化钠调整废水的PH值6-9,加入聚丙烯酰胺助凝,进行重力式泥水分离,废水实现达标排放。
本发明的有益效果:化学合成喹诺酮类抗生素生产废水,合成过程中会产生大量的多环芳烃类有机物,生物降解性差,无法直接生物处理。采用铁镁碳微电解废水,能使废水中多环芳烃有机物开环断链,大分子有机物降解为小分子有机物,生化性能得以高。同时,添少量金属镁的铁碳形成铁镁碳,作为内电解材料,具有内电解电流大和电解效果好的特点。且少量的金属镁的添加,降低铁镁碳材料中铁的腐蚀强度,铁镁碳材料应用周期得到延长,表面不易硬化板结,使用更加方便。
铁镁碳微电解过程中,还溶出一部分Fe2+,Fe2+与双氧水形成Fenton体系,Fenton的强氧化性进一步降解多环芳烃类有机物,使其开环或断裂,甚至将部分小分子有机物矿化生成二氧化碳和水,废水的可生化性得到进一步提高。
喹诺酮类抗生素化学合成过程由于酸碱的加入形成一定量的盐,废水中的盐分可达5%以上,属于典型的高盐废水,抑制生物处理的进行。采用三体三效蒸发器,对废水进行蒸发,浓缩除盐,经过蒸发浓缩除盐后的废水其含盐量低于0.5%。
喹诺酮类抗生素合成生产废水经过以上步骤预处理,生物可降解得到提高,同时盐分含量控制在0.5%以下,为后续的生化和物化处理创造有利条件。
附图说明
图1为本发明的工艺流程图。
具体实施方式
下面结合具体实施例对本发明作进一步说明,应理解以下实施例仅用于说明本发明,而非限制本发明的范围,该领域的技术熟练人员可以根据上述发明内容做出一些非本质的改进和调整。
喹诺酮类抗生素主要由化学合成法生产,合成过程中产生大量的生产废水,具有高盐、有机物浓度高、难以生物降解等点。其中PH5.35、废水COD 68660mg/L,盐92203mg/L、Cl-54480mg/L,因此盐份主要以氯化钠为主。以下结合附图对本发明做进一步的描述。
如图1所示,一种喹诺酮类抗生素生产废水集成处理方法,包括如下步骤:
1.废水经过硫酸调整PH值3.2;
2.经过PH值调节的废水进入铁镁碳微电解系统进行微电解,铁镁碳材料中铁镁碳的质量比为1.5:0.08:1,铁镁碳微电解系统铁镁碳材料填充比例40%(体积比),废水在铁镁碳微电解系统的停留时间3.5小时,经过铁镁碳微电解预处理的废水,其各项指标如表1。
3.经过铁镁碳微电解处理过废水加入双氧水(质量分数27.5%)与废水COD质量比为0.15:1,搅拌反应3小时,加入氢氧化钠,调整废水的PH为7.5,加入聚丙烯酰胺溶液絮凝沉淀,进行泥水分离。经过Fenton试剂氧化和絮凝沉淀预处理后废水各项指标如表1。
4.经过铁镁碳微电解和Fenton试剂氧化预处理后的废水采用三体三效的蒸发系统进行蒸发浓缩,形成饱和溶液后,冷却盐分结晶,离心分离除盐,经过三体三效蒸发浓缩除盐后废水的各项指标如表1。
5.经过预处理的废水进入厌氧生物处理系统,厌氧采用UASB厌氧生物反应器,UASB厌氧生物反应器COD容积负荷2.0kg/(m3·d)。经过厌氧生物处理的废水,采用A/O好氧生物处理,其中A段根据废水总氮量增减停留时间,O段的停留时间144小时。经过厌氧-好氧生物处理后,废水的各项指标如表1。
6.经过厌氧和A/O好氧生物处理的废水,采用Fenton试剂进行深度处理,以硫酸调整PH 3.2,双氧水(质量分数27.5%)与硫酸亚铁的摩尔比3:1反应3.5小时,反应结束后,以氢氧化钠调节废水的PH值7.0,加入聚丙烯酰胺助凝进行重力式泥水分离,实现废水的达标排放。
本发明提出的喹诺酮类抗生素生产废水集成处理方法,废水经过铁镁碳微电解Fenton试剂预处理后废水中的多环芳烃类有机物,开环变直链化合物,大分子化合物降解成小分子化合物,废水的生物降解性能得以提高。利用多效蒸发除盐预处理后,废水中盐分大部分得以去除。经过预处理的废水采用厌氧-好氧A/O生物处理工艺,废水中大部分有机污染物得以去除,经过生物处理后的废水采用Fenton试剂氧化深度处理,进一步去除废水中的污染物,经过上述工艺处理的废水能满足合成制药工业废水排放要求。
表1 各工段的去除率
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (8)
1.一种喹诺酮类抗生素生产废水集成处理方法,其特征在于:
(1)喹诺酮类抗生素生产废水经过硫酸或氢氧化钠调节PH值;
(2)调整PH值后的废水进入铁镁碳微电解系统进行微电解;
(3)经过微电解的废水加入双氧水与铁镁碳材料溶出的Fe2+形成Fenton试剂进行氧化;
(4)经过氧化后的废水以氢氧化钠调节废水的PH值至中性,加入聚丙烯酰胺助凝,进行泥水分离;
(5)泥水分离废水进入蒸发系统进行除盐;
(6)除盐后的废水经过厌氧生物处理,A/O好氧生物处理和Fenton试剂深度氧化处理,经过深度氧化处理后的废水实现达标排放。
2.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(1)中喹诺酮类抗生素生产废水经过硫酸或氢氧化钠调节废水的PH值为3-5。
3.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(2)中铁镁碳微电解系统中铁镁碳的质量比为(1-2):(0.05-0.1):1,铁镁碳微电解系统中铁镁碳的填充比为30-50%,废水在铁镁碳微电解系统的停留时间为 2-4小时。
4.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(3)中加入双氧水形成Fenton试剂进行氧化其特征在于,铁镁碳微电解系统的出水加入双氧水,其中,双氧水与废水COD的质量比为(0.1-0.3):1,搅拌反应2-4小时。
5.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(4)中加入氢氧化钠调节废水PH值6-9,加入聚丙烯酰胺溶液絮凝沉淀,进行泥水分离。
6.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(5)中废水进入蒸发系统进行除盐是将废水进入三体三效蒸发装置进行蒸发浓缩,废水蒸发过程中形成过饱和盐溶液,冷却结晶,离心分离除盐。
7.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(6)中厌氧生物处理采用UASB厌氧生物反应器,UASB厌氧生物反应器的容积负荷1.5-3.0kg/(m3·d),经过厌氧生物处理后的废水利用A/O好氧工艺进行生物处理,其中A段的停留时间,根据废水中总氮的含量进行增减,O段的停留时间为120-190小时。
8.根据权利要求1所述的喹诺酮类抗生素生产废水集成处理方法,其特征在于:所述步骤(6)中Fenton试剂深度氧化处理时,废水以硫酸调节PH值3-3.5,采用双氧水与硫酸亚铁的摩尔比为3:(0.5-1)的Fenton试剂,Fenton试剂深度氧化处理的时间为3-4小时,反应结束后,以氢氧化钠调整废水的PH值6-9,加入聚丙烯酰胺助凝,进行重力式泥水分离。
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