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[固相萃取-气相色谱法测定甲醇制烯烃汽油副产物及甲醇制汽油产物中的含氧化合物]

[Determination of oxygenates in methanol-to-olefin gasoline byproducts and methanol-to-gasoline product with solid phase extraction-gas chromatography].

作者信息

Tian Wenqing, Li Jiwen, Wang Chuan

机构信息

SINOPEC Shanghai Research Institute of Petrochemical Technology, National Key Laboratory of Green Chemical and Industrial Catalysis, Shanghai 201208, China.

出版信息

Se Pu. 2017 Nov 8;35(11):1204-1209. doi: 10.3724/SP.J.1123.2017.07022.

Abstract

Silica solid phase extraction (SPE) column was used for sample pretreatment to enrich the target analytes and simplify background. Due to its high efficiency, reliability and simplicity, the technique has been widely used in many fields. The byproduct gasoline of methanol-to-olefin (MTO) and the product of methanol-to-gasoline (MTG) mainly consist of hydrocarbons along with small amounts of oxygenates. Trace amounts of oxygenates are hard to identify because of their complex hydrocarbon components. With the SPE technique, the samples were separated into two major classes, oxygenates and hydrocarbons. Oxygenates were then determined with gas chromatography-mass spectrometry (GC-MS). The elution conditions of the silica solid phase extraction column were optimized with the standard sample. Under the optimized elution conditions, the hydrocarbons were first eluted from the SPE column with 5 mL dichloromethane, the oxygenates were then eluted with 3 mL acetonitrile. The recoveries of standard samples were tested before and after pretreatment. The standard recoveries were 87.7%-95.3%. The oxygenates except methanol and ethanol were then quantified by gas chromatography-flame ionization detection (GC-FID) and internal standard method. Methanol and ethanol were then quantified by extracting characteristic ion chromatograms and external standard method. The results show that the oxygenates of MTO byproduct gasoline and MTG product mainly consist of ketones and aldehydes. The method improves the sensitivities of the target compounds and reduces the interference of the background.

摘要

硅胶固相萃取(SPE)柱用于样品预处理,以富集目标分析物并简化背景。由于其高效、可靠和简便,该技术已在许多领域广泛应用。甲醇制烯烃(MTO)的副产汽油和甲醇制汽油(MTG)的产物主要由烃类以及少量含氧化合物组成。由于其复杂的烃类成分,痕量含氧化合物难以鉴定。采用SPE技术,将样品分为含氧化合物和烃类两大类别。然后用气相色谱 - 质谱联用仪(GC - MS)测定含氧化合物。用标准样品对硅胶固相萃取柱的洗脱条件进行了优化。在优化的洗脱条件下,先用5 mL二氯甲烷从SPE柱上洗脱烃类,然后用3 mL乙腈洗脱含氧化合物。对预处理前后标准样品的回收率进行了测试。标准回收率为87.7% - 95.3%。然后用气相色谱 - 火焰离子化检测(GC - FID)和内标法对除甲醇和乙醇之外的含氧化合物进行定量。甲醇和乙醇则通过提取特征离子色谱图和外标法进行定量。结果表明,MTO副产汽油和MTG产物中的含氧化合物主要由酮类和醛类组成。该方法提高了目标化合物的灵敏度并减少了背景干扰。

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