对氟苯甲酸乙酯油溶性示踪剂的制备与溶解性能研究

Preparation and Solubility Property of Ethyl 4-Fluorobenzoate as Oil Soluble Tracer

孟科全 温守国 王跃宽 陈维余 尹瑞娟 江 涛

MENG Kequan WEN Shouguo WANG Yuekuan CHEN Weiyu YIN Ruijuan JIANG Tao

针对油田用油溶性示踪剂种类少的情况， 根据含氟有机化合物性质稳定、 检测灵敏度高的特点， 通过氯化亚砜法和浓硫酸催化法两种方法合成对氟苯甲酸乙酯 （EB-F）， 用核磁共振氢谱和质谱对产物结构进行了表征，根据高效液相色谱测得的色谱峰面积计算得到 EB-F在水和煤油中的溶解度， 通过 EB-F标准曲线的建立获得气质联用仪测定 EB-F浓度的检测下限。结果表明， 氯化亚砜法和浓硫酸催化法的产品收率约为 86%， 浓硫酸催化法操作简便、 成本低， 对环境污染小， 更适合工业化生产。EB-F 在油中易溶， 在水中微溶， 在煤油和水中的溶解度分别为 90 和 0.051 g/L， 油水分配比为 338。用气质联用仪可以对 EB-F 乙腈溶液进行痕量检 测， 标准曲线的线性范围为 0.1×10-3～ 50×10-3 mg/L， R2为 0.9984， 相对标准偏差 RSD为 4.1%， 最低检测限为 1.5×10-6mg/L。图3参 12

Aiming at the fact that there were few species of oil soluble tracer used in oilfield and according to the properties of organofluorine compound with stability and high sensitivity， ethyl 4-fluorobenzoate（EB-F）was synthesized by thionyl chloride method and concentrated sulfuric acid catalysis method. The structure of the product was characterized by 1H NMR and mass spectrometry. The solubility of EB-F in water and kerosene was researched through chromatographic peak area which detected by HPLC. And the detection limit of EB-F concentration by GC-MS instrument was determined by the establishment of standard curve. The results showed that the product yield of thionyl chloride method and concentrated sulfuric acid catalysis method was about 86%. Compared with thionyl chloride method， concentrated sulfuric acid catalysis method was easier to operate， had lower cost and less pollution to environment， and was more suitable for industrial production. EB-F was soluble in oil and slightly soluble in water. The solubility in kerosene and water was 90 and 0.051 g/L respectively， and the oil-water partition ratio was 338. Trace amount of EB-F acetonitrile solution could be detected by GC-MS with 0.1×10-3—50×10-3 mg/L linear range of standard curve， 0.9984 R2， 4.1% RSD， and 1.5×10-6mg/L minimum detection limit

10.19346/j.cnki.1000-4092.2018.01.030