CN101053828A - 一种吸附单环硝基芳香化合物树脂的再生方法 - Google Patents
一种吸附单环硝基芳香化合物树脂的再生方法 Download PDFInfo
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Abstract
本发明公开了一种吸附单环硝基芳香化合物树脂的再生方法。其步骤包括:(A)将吸附有单环硝基芳香化合物的树脂置入反应容器溶液中,该溶液的pH值控制为6.5~8,温度为20~30℃;(B)投加对硝基苯类物质具有降解能力的微生物;(C)控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过24h~72h,将树脂装柱回用。微生物对单环硝基芳香化合物的高效降解,有效提高了处理设施的处理负荷,实现了有毒难降解有机物的高效集约化处理;生物降解脱附的反应条件温和,设备要求简单,避免了有机溶剂的使用,减少了复杂化工设备的建设与维护,从而降低了基建成本与运营成本;单环硝基芳香化合物得到彻底生物降解,实现了污染物的无害化处理。
Description
技术领域
本发明涉及一种吸附树脂的再生方法,更具体地说是一种吸附单环硝基芳香化合物树脂的再生方法。
背景技术
单环硝基芳香化合物是一类用途广泛的化工原料,因此也产生了量大面广的含有该种化合物的化工废水。该类物质所具有的特殊硝基与苯环结构,导致其对微生物具有较强的活性抑制作用,具有“致癌、致畸、致突变”作用,从而被列为环境优先控制污染物。近年来生物技术的发展,人们通过生物筛选或基因技术获得对硝基苯类物质具有良好降解能力的高效菌种,开始针对单环硝基芳香化合物废水进行生物处理。
传统的处理含硝基苯类物质的方法主要有微电解、活性碳吸附、树脂吸附等方法。微电解不仅会产生大量的电解泥渣,变水体污染为固体废弃物污染,造成污染转移和二次污染,而且硝基苯还原所产生的苯胺本身也是一种环境污染物,仍然需要进一步的后续处理;而活性碳吸附则存在脱附困难,吸附能力下降快,活性碳消耗大,且仍需要对吸附硝基苯的报废活性碳进行后处理。
树脂吸附法处理含有单环硝基芳香化合物的工业废水,具有操作简单、分离效果好的优点,被广泛应用于含单环硝基芳香化合物废水的治理。但是,吸附饱和的树脂通常使用价格较高有机溶剂来进行脱附再生,脱附过程中产生的含有单环硝基芳香化合物的有机脱附液,需要进行一系列的精馏提纯等操作单元,都提高了处理成本,而且在整个处理过程中污染物质没有被彻底降解,仍然存在环境风险,这些问题严重制约了树脂吸附法在含单环硝基芳香化合物废水处理领域的应用范围。
发明内容
1.发明要解决的技术问题
本发明的目的是提供一种吸附单环硝基芳香化合物树脂的再生方法,针对以往处理吸附有单环硝基芳香化合物的树脂需要采用价格较高的有机溶剂进行脱附,脱附液需要后续处理,本发明利用部分微生物对单环硝基芳香化合物的降解作用,将树脂所吸附的单环硝基芳香化合物进行降解脱附,实现树脂的生物再生和单环硝基芳香化合物的无害化处理。
2.本发明的技术方案如下:
一种吸附单环硝基芳香化合物树脂的再生方法,其步骤包括:
(A)将吸附有单环硝基芳香化合物的树脂置入反应容器溶液中,该溶液的pH值控制为6.5~8,温度为20~30℃;
(B)投加对硝基苯类物质具有降解能力的微生物;
(C)控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过24h~72h,将树脂装柱回用。
单环硝基芳香化合物包括硝基苯、三硝基甲苯、二硝基甲苯、2,4,6-三硝基苯酚、4-硝基苯甲酸。对硝基苯类物质具有降解能力的微生物包括硝基苯降解菌(吉氏杆菌、屎拟杆菌、产气夹膜杆菌、棒状杆菌、门多萨氏菌、肺炎克雷伯氏菌、葡萄球菌、链球菌、恶臭假单胞菌),三硝基甲苯降解菌(芽孢杆菌、克鲁丝假丝酵母、柠檬杆菌、橡树假丝酵母、无名假丝酵母、脱硫菌、肠杆菌、埃希氏杆菌、伯杰汉逊酵母、亚膜汉逊酵母、白地霉菌、白腐真菌、假单胞菌、克氏杆菌),二硝基甲苯降解菌(假单胞菌、脱硫弧菌),2,4,6-三硝基苯酚降解菌(红球菌、假单胞菌、韦荣氏球菌),4-硝基苯甲酸降解菌(假单胞菌、丛毛单胞菌、埃希氏菌、脱硫弧菌、梭菌、产甲烷菌)。
这些菌种的筛选方法如下:菌种来自生产硝基苯(硝基甲苯、硝基苯甲酸、三硝基甲苯等)的化工厂排水管道的污泥,选择培养基(0.3%K2HPO4,0.3%KH2PO4,0.5%NaCl,0.05%MgSO4),分别将硝基苯(三硝基甲苯、硝基甲苯、硝基苯甲酸)按一定量加入作为微生物生长的唯一碳源和能量来源。将浓缩后的活性污泥加入装有玻璃珠的三角摇瓶,匀速摇动将其打碎搅匀,稀释划平板分离,放置于30℃恒温箱内培养数天,观察菌落生长情况,把形成的耐受力强的单菌落挑斜面保存。反复划线纯化,把长出的不同形态的单菌落在分别挑斜面,得到原始纯菌种。
对以上菌种的鉴别参考了东秀珠、蔡妙英等编著的《常见细菌系统鉴定手册》(科学出版社出版,2001年,ISBN 7-03-008460-8,中国版本图书馆CIP数据核字(2001)第06567号);《伯杰氏细菌鉴定手册》(bergey’s manual ofdeterminative bacteriology);《伯杰氏系统细菌手册》(bergey’s manual ofsystematic bacteriology);国际系统细菌学杂志(international journal ofsystematic bacteriology)。
步骤(A)树脂是具有苯乙烯骨架的中国产的NDA-99树脂,NDA-88树脂、NDA-150树脂、NDA-1800树脂、NDA-16、CHA-101树脂、CHA-111树脂、H-103树脂、JX-101树脂或者是美国Amerlite XAD-2树脂、XAD-4树脂、XAD-7树脂、XAD-8树脂,或者是日本Dision HP系列吸附树脂。
步骤(B)中按照废水体积的5%~20%投加菌悬液,每毫升菌悬液含菌数为1010~1018。这个比例关系影响不大,微生物的菌悬液浓度低了,降解时间长些,浓度高了,降解时间尽量短些,只要浓度不是高到成糊状就可以了。一般而言,时间可以控制在24h~72h。
3.有益效果
本发明公开了一种吸附单环硝基芳香化合物树脂的再生方法。本发明利用高效菌种对单环硝基芳香化合物的降解作用,将树脂所吸附的单环硝基芳香化合物进行降解脱附,实现树脂的生物再生和单环硝基芳香化合物的无害化处理。专用菌种对单环硝基芳香化合物的高效降解,有效提高了处理设施的处理负荷,实现了有毒难降解有机物的高效集约化处理;生物降解脱附的反应条件温和,设备要求简单,避免了有机溶剂的使用,减少了复杂化工设备的建设与维护,从而降低了基建成本与运营成本;单环硝基芳香化合物得到彻底生物降解,不产生二次污染,实现了污染物的无害化处理。
具体实施方式
以下通过实施例进一步说明本发明。
实施例1
将100L的吸附有硝基苯的树脂NDA-150装入生物反应器中,补充营养物质,调节混合溶液pH为6.5~8,温度为20~30℃,投加对硝基苯具有降解能力的枯草芽苞杆菌(投加的量为溶液体积的5%~20%,每毫升菌悬液含菌数为1010~1018),控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过48h的反应,树脂所吸附的硝基苯被完全降解脱附,树脂恢复吸附分离能力后装柱回用。
硝基苯培养优化条件(营养物质):FeSO4=0.5g/L;MgSO4=0.2g/L;NaCl=3g/L;NaH2PO4.12H2O=3.84g/L;KH2PO4=1g/L。
实施例2
将50L的吸附有三硝基甲苯的树脂XAD-7装入生物反应器中,加入蒸馏水,控制pH值为6~8,温度为20~30℃,投加对三硝基甲苯具有降解能力的埃希氏杆菌(投加的量为溶液体积的5%~10%,每毫升菌悬液含菌数为1010~1018),控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过24h的反应,树脂所吸附的三硝基甲苯被完全降解脱附,树脂恢复吸附分离能力后装柱回用。
实施例3
将5m3的吸附有二硝基甲苯的树脂NDA-99装入生物反应器中,投加溶液(0.3%K2HPO4,0.3%KH2PO4,0.5%NaCl,0.05%MgSO4)中,控制pH为6~8,温度为10~20℃,投加对二硝基甲苯具有降解能力的脱硫弧菌(投加的量为溶液体积的10%~20%,每毫升菌悬液含菌数为1010~1018),控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过72h的反应,树脂所吸附的二硝基甲苯被完全降解脱附,树脂恢复吸附分离能力后装柱回用。
实施例4
将100mL的吸附有2,4,6-三硝基苯酚降解菌的树脂NDA-88装入生物反应器中,控制溶液pH为6~8,温度为20~30℃,投加对2,4,6-三硝基苯酚降解菌具有降解能力的韦荣氏球菌(投加的量为溶液体积的5%~10%,每毫升菌悬液含菌数为1010~1018),控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过48h的反应,树脂所吸附的2,4,6-三硝基苯酚降解菌被完全降解脱附,树脂恢复吸附分离能力后装柱回用。
实施例5
将100L的吸附有4-硝基苯甲酸的树脂NDA-16装入生物反应器中,投加含有0.5%NaCl,0.05%MgSO4的溶液,调节pH为6~8,温度为20~30℃,投加对4-硝基苯甲酸具有降解能力的丛毛单胞菌(投加的量为溶液体积的10%~15%,每毫升菌悬液含菌数为1010~1018),控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过48h的反应,树脂所吸附的4-硝基苯甲酸被完全降解脱附,树脂恢复吸附分离能力后装柱回用。
Claims (6)
1.一种吸附单环硝基芳香化合物树脂的再生方法,其步骤包括:
(A)将吸附有单环硝基芳香化合物的树脂置入反应容器溶液中,该溶液的pH值控制为4~9,温度为10~40℃;
(B)投加对硝基苯类物质具有降解能力的微生物;
(C)控制溶解氧浓度在2mg/L以上,搅拌保持树脂与微生物的充分接触,经过24h~72h,将树脂装柱回用。
2.根据权利要求1所述的一种吸附单环硝基芳香化合物树脂的再生方法,其特征在于步骤(B)中微生物包括硝基苯降解菌、三硝基甲苯降解菌、二硝基甲苯降解菌、2,4,6-三硝基苯酚降解菌、4-硝基苯甲酸降解菌。
3.根据权利要求2所述的一种吸附单环硝基芳香化合物树脂的再生方法,其特征在于步骤(B)中硝基苯降解菌为吉氏杆菌、屎拟杆菌、产气夹膜杆菌、棒状杆菌、门多萨氏菌、肺炎克雷伯氏菌、葡萄球菌、链球菌、恶臭假单胞菌),三硝基甲苯降解菌为芽孢杆菌、克鲁丝假丝酵母、柠檬杆菌、橡树假丝酵母、无名假丝酵母、脱硫菌、肠杆菌、埃希氏杆菌、伯杰汉逊酵母、亚膜汉逊酵母、白地霉菌、白腐真菌、假单胞菌、克氏杆菌,二硝基甲苯降解菌为假单胞菌、脱硫弧菌,2,4,6-三硝基苯酚降解菌为红球菌、假单胞菌、韦荣氏球菌,4-硝基苯甲酸降解菌为假单胞菌、丛毛单胞菌、埃希氏菌、脱硫弧菌、梭菌、产甲烷菌。
4.根据权利要求1~3中任一项所述的一种吸附单环硝基芳香化合物树脂的再生方法,其特征在于步骤(B)中按照废水体积的5%~20%投加菌悬液,每毫升菌悬液含菌数为1010~1018。
5.根据权利要求1~3中任一项所述的一种吸附单环硝基芳香化合物树脂的再生方法,其特征在于步骤(A)中树脂是具有苯乙烯骨架的NDA-99树脂、NDA-88树脂、NDA-150树脂、NDA-1800树脂、NDA-16、CHA-101树脂、CHA-111树脂、H-103树脂、JX-101树脂或者是XAD-2树脂、XAD-4树脂、XAD-7树脂、XAD-8树脂,或者是Dision HP系列吸附树脂。
6.根据权利要求1~3中任一项所述的一种吸附单环硝基芳香化合物树脂的再生方法,其特征在于步骤(A)中的溶液的pH值控制为6~8,温度为20~30℃。
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CN103288283A (zh) * | 2013-06-14 | 2013-09-11 | 陕西蓝深特种树脂有限公司 | 一种dnt生产废水回收及处理系统和方法 |
CN108126764A (zh) * | 2017-12-07 | 2018-06-08 | 燕山大学 | 一种吸附剂的生物再生方法 |
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CN103288283A (zh) * | 2013-06-14 | 2013-09-11 | 陕西蓝深特种树脂有限公司 | 一种dnt生产废水回收及处理系统和方法 |
CN108126764A (zh) * | 2017-12-07 | 2018-06-08 | 燕山大学 | 一种吸附剂的生物再生方法 |
CN108126764B (zh) * | 2017-12-07 | 2021-01-08 | 燕山大学 | 一种吸附剂的生物再生方法 |
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