CN111024474A - 针对含硫地区油气化探样品芳烃类物质测定的前处理方法 - Google Patents
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Abstract
本发明属于实验测试领域，公开了一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法，包括：铜粉使用前，进行净化；取利用国标方法得到的上清液，至比色管中，加入净化好的铜粉，摇匀震荡，静置；再次加入净化好的铜粉，摇匀震荡，静置；采用离心过滤或有机滤膜过滤，消除铜粉对比色皿的沾着。本发明通过二次铜粉除硫，可以将饱和的单质硫正己烷溶液中的硫全部除去，且不引进其它的紫外与荧光污染，不影响芳烃类物质的测定；测得的数据客观：通过消除干扰物质单质硫，所得的紫外与荧光数据能真实反映调查地区的芳烃类物质含量；本发明便于推广：成本低，易于操作，便于推广，对现行国标进行补充。
Description
技术领域
本发明属于实验测试领域，尤其涉及一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法。
背景技术
油气地球样品中的芳烃类物质目前根据《油气地球化学勘探试样测定方法》 (GB/T 29173-2012)中的规定，利用荧光分光光度计与紫外分光光度计进行测定。
国标中规定了样品的前处理方法：称取20.0g粒径为0.176mm的试样，置于60mL具塞三角烧瓶中，加入30mL石油醚，摇匀，放入振荡器中振荡20min。放置12h以上，再振荡20min，放置1h，澄清。将清液转入20mL具塞试管中，加入0.5g无水硫酸钠待测。
在实际工作中发现样品中存在单质硫的存在，含量范围从1.49 mg/kg—705mg/kg，通过对单质硫的干扰试验得出当样品中单质硫含量高于0.15 mg/kg时，引起紫外吸光度的增强，影响了芳烃及其衍生物总量的检测；当样品中单质硫含量高于15mg/kg时，引起荧光的猝灭，影响了稠环芳烃的检测。
国标方法中仅提出如果荧光强度低可能是由于浓度因素造成的荧光猝灭，需稀释后测定，对其它并未提及。自然界中地表土壤单质硫含量大小不一，为了客观地反应地区芳烃类物质的含量，为油气地质背景调查提供准确的数据资料，本发明提出一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法。
综上所述，现有技术存在的问题是：
现有技术采用的前处理方法均是利用正己烷对样品中的芳烃类物质进行萃取，在荧光与紫外仪器上利用特征波长进行检测，然而由于单质硫的8个硫原子组成的空间结构特性，尽管是无机物，仍可以部分溶解在正己烷溶剂中，被萃取出来和待测组分仪器被检测；
由于单质硫的硫原子采取sp3杂化态，与激发态的稠环芳烃分子不断碰撞引起了荧光测定的动态猝灭；单质硫低间隙能使其在芳烃的特征吸收谱带中均有强吸收，引起了紫外吸收加强，对测试结果产生干扰；现有的方法 GB/T29173-2012中并未采用除硫的方法，而是直接测定。
由于单质硫的化学性质与物理性质，与单质硫化学反应很多，但本领域的检测方法采用正己烷作为溶剂，沸点67℃，剧烈的化学反应均不能使用。如何在常温下，利用常见的试剂或物质进行有效的除去单质硫，并且不能引进新的荧光与紫外污染是本发明的技术难点。
发明内容
针对现有技术存在的问题，本发明提供了一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法。
本发明是这样实现的，一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法，所述针对含硫地区油气化探样品芳烃类物质测定的前处理方法，包括以下步骤：
铜粉的净化：分析纯，使用前进行净化；
第一次除硫：取利用国标方法得到的上清液，至比色管中，加入净化好的铜粉，摇匀震荡，静置；
第二次除硫：再次加入净化好的铜粉，摇匀震荡，静置；
过滤：采用离心机过滤或者采用有机滤膜过滤，消除铜粉对比色皿的沾着。
进一步，铜粉的净化为：采用色谱纯的正己烷与乙酸乙酯交替浸泡，时间为10—20min，净化三次，利用荧光分光光度计与紫外分光光度计检测净化效果。
进一步，第一次除硫具体包括：取利用国标方法得到的上清液10ml，至 25ml比色管中，加入净化好的铜粉1.0g，摇匀震荡1min～2min，静置24h。
进一步，第二次除硫具体包括：再次加入净化好的铜粉0.5g，摇匀震荡，静置10min。
进一步，过滤中，采用0.45um有机滤膜过滤。
本发明的优点及积极效果为：
目前在油气资源区域调查工作中，科技工作者均按照《GB/T 29173-2012油气地球化学勘探试样测定方法》进行样品的分析工作，荧光与紫外法均以检测特征波长下的强度值来获取稠环芳烃以及芳烃与衍生物总量信息，长期以来，此法为研究局部地质背景异常提供大量的芳烃类物质的数据资料。在实践工作中也发现利用芳烃类的数据进行异常点的圈定时，效果不如酸解烃指标理想，甚至有时出现与其相悖的结论。
究其原因，主要是样品中硫的干扰，而硫广泛分布于煤矿、油气田地区，利用本专利技术排除硫的干扰，真实客观地反映调查地区的芳烃类物质含量，补充现行的国标方法，维持标准方法指标的统一性；对油源对比、估计生油岩和原油的成熟度，确定沉积环境及研究石油的运移规律，油气藏勘探等研究有着十分重要的意义。对于其它的土壤中有机检测也有重要的借鉴意义。
本发明的具体的效果列举如下：
1、通过正己烷与乙酸乙酯交替浸泡，消除铜粉的紫外荧光污染，达到可以利用本发明除硫的用途，见表1。
2、利用本发明可以在常温条件下，铜粉用量1.0g以上，在12h以上可以将实际样品中的单质硫100％除去(见表2和图2)，消除单质硫对荧光紫外法检测的影响，保证了样品中目标物检测的客观性，所得的紫外与荧光数据能真实反映调查地区的芳烃类物质含量，对国标GB/T29173-2012进行补充。见表3、表4。
3、本发明采用市售分析纯铜粉，成本低，易于操作，效果好，便于推广。
附图说明
图1是本发明实施例提供的针对含硫地区油气化探样品芳烃类物质测定的前处理方法流程图。
图2是本发明实施例提供的处理时间对除硫效果的影响图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
下面结合附图对本发明的应用原理作详细描述。
图1是本发明实施例提供的针对含硫地区油气化探样品芳烃类物质测定的前处理方法，包括：
S101:铜粉的净化：采用市售的分析纯与色谱纯的铜粉均可进行使用，经试验发现分析纯的效果优于色谱纯的，在使用前，需净化。净化方法为，采用色谱纯的正己烷与乙酸乙酯交替浸泡，时间为20min，净化三次，利用荧光分光光度计与紫外分光光度计检测净化效果。
S102:第一次除硫：取利用国标方法得到的上清液10ml，至25ml比色管中，加入净化好的铜粉1.0g，摇匀震荡1min～2min，静置24h；
S103:第二次除硫：再次加入净化好的铜粉0.5g，摇匀震荡，静置10min；
S104:过滤：采用离心机过滤或者0.45um有机滤膜过滤均可，已消除铜粉对比色皿的沾着，影响透光率。
本发明实施例提供的铜粉经三次净化后效果，如表1。
表1铜粉经三次净化后效果
本发明实施例提供的铜粉纯度与用量对除硫效果的影响，如表2。
表2铜粉纯度与用量对除硫效果的影响
本发明实施后对实际样品除硫效果比较(硫含量变化，荧光与紫外强度值变化)如表3、4。
表3样品未处理前荧光与紫外强度值
表4样品经本发明处理后荧光与紫外强度值
“-”表示未检出
本发明除通过二次铜粉除硫，可以将饱和的单质硫正己烷溶液中的硫全部除去，且不引进其它的紫外与荧光污染，不影响芳烃类物质的测定；利用本发明处理的样品，测得的数据客观：通过消除干扰物质单质硫，所得的紫外与荧光数据能真实反映调查地区的芳烃类物质含量；本发明便于推广：本方法成本低，易于操作，便于推广，对现行国标进行补充。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种针对含硫地区油气化探样品芳烃类物质测定的前处理方法，其特征在于，所述针对含硫地区油气化探样品芳烃类物质测定的前处理方法，包括以下步骤：
步骤1，将铜粉进行净化；
步骤2，第一次除硫，操作人员取利用国标方法得到的上清液，转移至比色管中，加入上述净化好的铜粉，摇匀震荡，静置；
步骤3，第二次除硫，再次在上清液中加入净化好的铜粉，摇匀震荡，静置；
步骤4，过滤，采用离心机或者采用有机滤膜对上清液进行过滤，消除铜粉对比色皿的沾着。
2.如权利要求1所述的针对含硫地区油气化探样品芳烃类物质测定的前处理方法，其特征在于，
铜粉的净化方法为：采用色谱纯的正己烷与乙酸乙酯交替浸泡，时间为20min，净化三次，利用荧光分光光度计与紫外分光光度计检测净化效果。
3.如权利要求1所述的针对含硫地区油气化探样品芳烃类物质测定的前处理方法，其特征在于，
第一次除硫具体包括：取利用国标方法得到的上清液10ml，至25ml比色管中，加入净化好的铜粉1.0g，摇匀震荡1min～2min，静置24h。
4.如权利要求1所述的针对含硫地区油气化探样品芳烃类物质测定的前处理方法，其特征在于，
第二次除硫具体包括：再次加入净化好的铜粉0.5g，摇匀震荡，静置10min。
5.如权利要求1所述的针对含硫地区油气化探样品芳烃类物质测定的前处理方法，其特征在于，过滤中，采用0.45um有机滤膜过滤。
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