CN117491536B - 一种prc-apmp工艺制浆废水的微生物毒性物质鉴定方法 - Google Patents
一种prc-apmp工艺制浆废水的微生物毒性物质鉴定方法 Download PDFInfo
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Abstract
本发明公开了一种PRC‑APMP工艺制浆废水的微生物毒性物质鉴定方法,属于废水处理技术领域。本发明以PRC‑APMP工艺制浆废水为萃取对象,采用不同萃取体系进行全质化萃取并测定分析,对分析结果先进行布尔差值计算并排除可生物降解的物质,然后采用发光细菌法来鉴定PRC‑APMP工艺制浆废水中的微生物毒性物质。本发明方法检测物质完全,采用能实现不同用途的两种或三种萃取剂同时处理桉木高得率浆废水,不漏组分,同时对比方便,不需要复杂的检索过程,工作量小,可以定位桉木制浆废水的微生物毒性物质,鉴定效果好。
Description
技术领域
本发明属于废水处理技术领域,更具体地说,涉及一种PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法。
背景技术
国内外对桉木高得率浆废水的组分研究较少,对桉木本身及浸出液含有的成分研究相对较多,脱毒机理的研究未见报道。湖北工大谢益民教授团队认为制浆废液中含有单宁及多酚类物质、木素和碳水化合物的降解产物等是影响废水生化性能的重要原因。澳大利亚Gilles等人及河海大学魏尧等发现桉木中含有较多的多酚类化合物,桉树砍伐残体浸出液中富含溶解性有机碳、单宁酸。Gilles等分析了三种常见澳洲桉树精油的化学成分及抗菌特性,鉴定出胡椒酮、肉桂酸、桉树脑等24种化合物,为桉木毒性分析提供了一定的基础。印度Tyagi等在气相中观察到蓝桉油明显较高的抗菌活性。林化所清洁制浆团队对桉木高得率浆废水毒性开展了系统研究,探讨了鱼毒试验中对花鲢幼鱼毒害性,完成了对该种废水的厌氧和好氧生物处理研究,初步探索了预处理脱毒手段。但桉木废水中微生物毒性物质的鉴定仍缺乏简单实用的方法。
桉木原料中天然含有的多酚类物质在制浆过程中溶出和转化后进入废水,这些抗菌活性成分对微生物有较强的抑制作用,宏观表现为废水生化降解困难,通过锁定这些微生物毒性物质,深入研究其分子结构和特征基团,构建准确的模型化合物,详细研究不同的处理策略对毒性物质的降解脱毒效能和作用机制,有望精准破解此类废水生物降解困难的难题。
发明内容
针对现有技术存在的上述问题,本发明所要解决的技术问题在于提供一种PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,具有检测物质完全,不漏组分,同时对比方便,不需要复杂的检索过程,工作量小,可以定位桉木废水的微生物毒性物质,鉴定效果好的优点。
为了解决上述技术问题,本发明所采用的技术方案如下:
一种PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,以PRC-APMP工艺制浆废水为萃取对象,采用不同萃取体系进行全质化萃取并测定分析,对分析结果先进行布尔差值计算并排除可生物降解的物质,然后采用发光细菌法来鉴定PRC-APMP工艺制浆废水中的微生物毒性物质。
作为优选,所述PRC-APMP工艺制浆废水的制备过程为:将桉木原料和杨木原料分别采用PRC-APMP工艺进行制浆,收集各段产生的废水,制成综合废水,分别为桉木制浆废水和杨木制浆废水。
作为优选,所述桉木原料采用巨尾桉或尾巨桉其中一种,杨木原料采用107速生杨或毛白杨其中的一种。
作为优选,所述PRC-APMP工艺制浆中氢氧化钠用量为50 kg/(t·pulp),双氧水用量为70 kg/(t·pulp),硅酸钠用量为20 kg/(t·pulp),DTPA 用量为5 kg/(t·pulp)。
作为优选,所述萃取体系为乙醚、二氯甲烷和苯-醇萃取体系。
作为优选,所述萃取体系的测定分析为采用三重四极杆气-质进行测定分析。
作为优选,所述萃取体系的测定具体过程为:将PRC-APMP工艺制浆废水取三份,采用乙醚、二氯甲烷的一种或两种,萃取前两份废水中溶解于有机相的物质,多次萃取,合并萃取液并加入无水硫酸钠吸干有机相水分,旋转蒸发至1mL左右进行测定;第三份制浆废水进行室温蒸干,加入苯-醇溶液,充分溶解,溶液经过滤后进行测定。
作为优选,所述苯-醇溶液中,苯和甲醇按体积比1:1混合。
作为优选,所述过滤采用0.22μm有机滤膜进行过滤处理。
作为优选,所述布尔差值计算的具体步骤为:
(1)将桉木制浆废水和杨木制浆废水分别在乙醚萃取体系中进行有机物的萃取,其中,桉木制浆废水的有机物列表记为表1乙醚,杨木制浆废水的有机物列表记为表1’乙醚,将表1乙醚中的有机物相对含量定义为1ai,表1’乙醚中的有机物相对含量定义为1bi,则对于乙醚萃取体系,总潜在微生物毒性物质为T’1j=1ai not 1bi,即1ai与1bi做布尔差集计算,得到待鉴定的微生物毒性物质T1k;
(2)对于二氯甲烷萃取体系,采用与步骤(1)相同的方法,得到T2k;
(3)对于苯醇萃取体系,采用与步骤(1)相同的方法,得到T3k;
(4)则桉木制浆废水中的微生物毒性物质为T=T1k+T2k+T3k,对桉木制浆废水微生物毒性物质得到初步鉴定结果;其中j=1~m,i=1~n,k=1~l,m、n、l为物质的序号。
所述的PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,具体包括以下步骤:
(1)将桉木原料和杨木原料分别采用PRC-APMP工艺制浆,收集各段产生的废水,制成综合废水,分别为桉木制浆废水和杨木制浆废水;
(2)将桉木制浆废水和杨木制浆废水各取三份,采用乙醚、二氯甲烷的一种或两种,萃取前两份废水中溶解于有机相的物质,多次萃取,合并萃取液并加入无水硫酸钠吸干有机相水分,旋转蒸发至1mL左右进行GC-MS测定;第三份废水进行室温蒸干,加入苯-醇溶液充分溶解,溶液经过滤后进行GC-MS测定;
(3)经过GC-MS分析,得到总离子流图谱,通过对各离子流峰进行质谱图库检索,确定各有机物的名称和相对含量;将桉木制浆废水和杨木制浆废水分别做表,乙醚萃取体系中,桉木制浆废水的有机物列表记为表1乙醚,杨木制浆废水的有机物列表记为表1’乙醚,将表1乙醚中的有机物数据定义为1ai,表1’中的数据定义为1bi,则对于乙醚萃取体系,总潜在微生物毒性物质为T’1j=1ai not 1bi,即1ai与1bi做布尔差值计算,得到待鉴定的微生物毒性物质T1k,同样,对于其他的萃取体系,做同样的处理,得到T2k和T3k,则桉木制浆废水中的微生物毒性物质为T=T1k+T2k+T3k,对桉木制浆废水微生物毒性物质得到初步鉴定结果;其中i=1~m,i=1~n,k=1~l,m、n、l为物质的序号;
(4)根据步骤(3)鉴定出的桉木制浆废水微生物毒性物质的相对含量,配制模拟废水,做发光细菌法实验,以发光抑制率为综合生物毒性分级评价标准,判定模拟废水是否与桉木制浆废水具有近似的生物毒性,完成对PRC-APMP工艺制浆废水中微生物毒性物质的鉴定。
相比于现有技术,本发明的有益效果为:
1)本发明采用能实现不同用途的两种或三种萃取剂同时处理桉木高得率浆废水,摒弃单一采用某种有机溶剂萃取桉木废水带来的只能萃取溶于有机相或者只是溶于水相、污染物质片面的缺点,采用多种具有不同极性、能互为补充的溶剂进行全质化萃取,涵盖的物质更完整,可以将废水中的物质完整萃取出来,涵盖了有机相和水相,不漏组分;
2)同属阔叶木的杨木其高得率浆废水生物处理容易,可生化性好,因此本发明采用杨木废水做对比,创新运用布尔运算,锚定微生物毒性物质;
3)本发明方法检测物质完全,不漏组分,同时对比方便,不需要复杂的检索过程,工作量小,可以定位桉木废水的微生物毒性物质,鉴定效果好。
附图说明
图1为实施例1的乙醚萃取桉木废水总离子流谱图;
图2为实施例1的乙醚萃取杨木废水总离子流谱图;
图3为实施例1的二氯甲烷萃取桉木废水总离子流谱图;
图4为实施例1的二氯甲烷萃取杨木废水总离子流谱图;
图5为实施例1的苯醇萃取桉木废水总离子流谱图;
图6为实施例1的苯醇萃取杨木废水总离子流谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面结合具体实施例对本发明进一步进行描述。以下实施例中如无特殊说明,所用的技术手段均为本领域技术人员所熟知的常规手段。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例中测定方法和综合生物毒性分级标准均参照以下内容:
《发光菌国际法ISO11348-3-2007》;
杨俊杰,刘瑞浩,杨子彦等.工业废水水质综合评价研究——基于理化指标和生物毒性分析[J].环境保护科学,2022,48(03):76-80.;
《DB23T 2750—2020水质 生物毒性的测定 发光细菌快速测定法》。
实施例1
(1)桉木废水和杨木废水的制浆与取水
选取广西巨尾桉和107速生杨为原料,采用P-RC APMP工艺制浆,为便于比较,两个树种的加药量相同,氢氧化钠用量为50 kg/(t·pulp),双氧水用量为70 kg/(t·pulp),硅酸钠用量为20 kg/(t·pulp),DTPA 用量为5 kg/(t·pulp)。收集各工段废水,根据各工段的发生量(挤压废水0.78 m3/(t浆),浸渍废水0.83 m3/(t浆),洗浆废水6.69 m3/(t浆))配制成综合废水,分别简记为桉木制浆废水和杨木制浆废水。
(2)废水中有机物的萃取
a.乙醚萃取
取500 mL废水,加入50 mL乙醚萃取,将萃取液移至具塞三角烧瓶中,重复上述步骤 3~4次,加入少量无水硫酸钠于萃取液中干燥过夜。将干燥后的萃取液使用旋转蒸发器浓缩至2 mL,进行GC-MS分析。
b.二氯甲烷萃取
各取水样200ml,分别用浓度为6N的硫酸和浓度为6N的氢氧化钠调节pH至12和2,先取pH为2的水样,用色谱纯二氯甲烷萃取三次,将三次萃取的有机相合并,再取pH为12的水样,重复操作,合并两种pH值水样萃取所得的有机相,加入无水硫酸钠去除水分,在室温下蒸发至1mL,进行GC-MS分析。
c.苯醇萃取
取水样100mL置于干净的表面皿在洁净的环境中室温蒸发至无液体,加入苯和甲醇按体积比1:1混合的苯-醇溶液,充分溶解,溶液经0.22μm有机滤膜过滤后进行GC-MS测定。
(3) 检测条件
色谱柱:HP-5ms石英毛细管柱,柱长30 m,柱内径 0.25 mm;分流比10:1,进样量1µL;色谱分离条件:柱温 40℃(保持5 min)→280℃(10℃/min升温速率,保持10min);进样口温度:280℃;利用氦气作为载体气体(流速为1.0 mL/min),质谱检测器:EI源,电子能量:70eV,源温230℃,扫描范围为50~550 amu,扫描时间1 s/scan。
(4) 微生物毒性物质鉴定
分别对桉木废水和杨木废水进行GC-MS分析,所得的总离子流图谱如图1~图6所示,排除可生物降解的物质,确定各有机物的名称和相对含量,得到最终结果。具体见表1~表3。
对乙醚萃取体系中,桉木废水的组分减去杨木废水中与桉木废水重合的组分,桉木序号1抗氧剂BHT,在杨木废水序号3也有抗氧剂BHT,因此经过差值运算,此组分扣除,桉木序号2肉豆蔻酸异丙酯,与杨木废水序号5相同,予以扣除,以此类推,得到布尔差值运算的结果,排除可生物降解的物质,确定各有机物的名称和相对含量,列于下表1中。
表1:乙醚萃取桉木废水微生物毒性物质运算表
对二氯甲烷萃取体系中,桉木废水的组分减去杨木废水中与桉木废水重合的组分,采用与乙醚萃取体系中相同的方法,得到布尔差值运算的结果,排除可生物降解的物质,确定各有机物的名称和相对含量,列于下表2中。
表2:二氯甲烷萃取桉木废水微生物毒性物质运算表
对苯醇萃取体系中,桉木废水的组分减去杨木废水中与桉木废水重合的组分,采用与乙醚萃取体系中相同的方法,得到布尔差值运算的结果,排除可生物降解的物质,确定各有机物的名称和相对含量,列于下表3中。
表3:苯醇萃取桉木废水微生物毒性物质运算表
将表1中的数据定义为1ai(i=1-n,n为物质的序号),表1’中的数据定义为1bi(i=1-n,n为物质的序号),则对于该萃取体系,总潜在微生物毒性物质为T’1j=1ai not 1bi,1ai与1bi做布尔差值运算,排除可生物降解的物质,得到待鉴定的微生物毒性物质T1k,列于表1。同样,对于二氯甲烷和苯醇体系,做同样的处理,得到T2k和T3k,分别列于表2和表3。则桉木废水中的微生物毒性物质为T=T1k+T2k+T3k,即:羽扇烯酮、alpha-香树精、白桦脂醛、丁香醛、松柏醇、去氧胆酸、beta-香树精、白桦脂醛、3,4,5-三羟基苯甲酸。
选择前述鉴定出的物质,根据这些物质在桉木制浆废水中的相对含量,羽扇烯酮、alpha-香树精、白桦脂醛、丁香醛、松柏醇、去氧胆酸、beta-香树精、白桦脂醛、3,4,5-三羟基苯甲酸含量分别为187mg/L、125mg/L、62mg/L、26mg/L、119mg/L、54mg/L、131mg/L、61mg/L、47mg/L,配成模拟废水,做发光细菌法实验,结果见表4。发光抑制率是表示废水综合毒性的宏观指标,根据中国科学院南京土壤所推荐的水质毒性分级标准,通过发光细菌的相对发光抑制率可以将某类废水定义为相同毒性级别的废水,通过微观有机物成分分析和组分配制的废水得到宏观的验证。从表4可以看出,该模拟废水的综合毒性可以评判为低毒,与原有废水的综合毒性基本相当,因此模拟废水可用,前述鉴定的微生物毒性物质具有可信性。
表4:模拟废水毒性评价表
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,其特征在于,以PRC-APMP工艺制浆废水为萃取对象,采用不同萃取体系进行全质化萃取并测定分析,对分析结果先进行布尔差值计算并排除可生物降解的物质,然后采用发光细菌法来鉴定PRC-APMP工艺制浆废水中的微生物毒性物质;
其中,所述PRC-APMP工艺制浆废水的制备过程为:将桉木原料和杨木原料分别采用PRC-APMP工艺进行制浆,收集各段产生的废水,制成综合废水,分别为桉木制浆废水和杨木制浆废水;
所述萃取体系为乙醚、二氯甲烷和苯-醇萃取体系;
所述萃取体系的测定分析为采用三重四极杆气-质进行测定分析;
所述萃取体系的测定具体过程为:将PRC-APMP工艺制浆废水取三份,采用乙醚、二氯甲烷的一种或两种,萃取前两份废水中溶解于有机相的物质,多次萃取,合并萃取液并加入无水硫酸钠吸干有机相水分,旋转蒸发至1mL左右进行测定;第三份制浆废水进行室温蒸干,加入苯-醇溶液,充分溶解,溶液经过滤后进行测定;
所述布尔差值计算的具体步骤为:
(1)将桉木制浆废水和杨木制浆废水分别在乙醚萃取体系中进行有机物的萃取,其中,桉木制浆废水的有机物列表记为表1乙醚,杨木制浆废水的有机物列表记为表1’乙醚,将表1乙醚中的有机物相对含量定义为1ai,表1’乙醚中的有机物相对含量定义为1bi,则对于乙醚萃取体系,总潜在微生物毒性物质为T’1j=1ai not 1bi,即1ai与1bi做布尔差值计算,得到待鉴定的微生物毒性物质T1k;
(2)对于二氯甲烷萃取体系,采用与步骤(1)相同的方法,得到T2k;
(3)对于苯醇萃取体系,采用与步骤(1)相同的方法,得到T3k;
(4)则桉木制浆废水中的微生物毒性物质为T=T1k+T2k+T3k,对桉木制浆废水微生物毒性物质得到初步鉴定结果;其中j=1~m,i=1~n,k=1~l,m、n、l为物质的序号。
2.根据权利要求1所述的PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,其特征在于,所述苯-醇溶液中,苯和甲醇按体积比1:1混合。
3.根据权利要求1所述的PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,其特征在于,所述过滤采用0.22μm有机滤膜进行过滤处理。
4.根据权利要求1所述的PRC-APMP工艺制浆废水的微生物毒性物质鉴定方法,其特征在于,具体包括以下步骤:
(1)将桉木原料和杨木原料分别采用PRC-APMP工艺制浆,收集各段产生的废水,制成综合废水,分别为桉木制浆废水和杨木制浆废水;
(2)将桉木制浆废水和杨木制浆废水各取三份,采用乙醚、二氯甲烷的一种或两种,萃取前两份废水中溶解于有机相的物质,多次萃取,合并萃取液并加入无水硫酸钠吸干有机相水分,旋转蒸发至1mL左右进行GC-MS测定;第三份废水进行室温蒸干,加入苯-醇溶液充分溶解,溶液经过滤后进行GC-MS测定;
(3)经过GC-MS分析,得到总离子流图谱,通过对各离子流峰进行质谱图库检索,确定各有机物的名称和相对含量;将桉木制浆废水和杨木制浆废水分别做表,乙醚萃取体系中,桉木制浆废水的有机物列表记为表1乙醚,杨木制浆废水的有机物列表记为表1’乙醚,将表1乙醚中的有机物数据定义为1ai,表1’中的数据定义为1bi,则对于乙醚萃取体系,总潜在微生物毒性物质为T’1j=1ai not 1bi,即1ai与1bi做布尔差值计算,得到待鉴定的微生物毒性物质T1k,同样,对于其他的萃取体系,做同样的处理,得到T2k和T3k,则桉木制浆废水中的微生物毒性物质为T=T1k+T2k+T3k,对桉木制浆废水微生物毒性物质得到初步鉴定结果;其中i=1~m,i=1~n,k=1~l,m、n、l为物质的序号;
(4)根据步骤(3)鉴定出的桉木制浆废水微生物毒性物质的相对含量,配制模拟废水,做发光细菌法实验,以发光抑制率为综合生物毒性分级评价标准,判定模拟废水是否与桉木制浆废水具有近似的生物毒性,完成对PRC-APMP工艺制浆废水中微生物毒性物质的鉴定。
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