Physics and Analysis Division, IFP Energies Nouvelles-Lyon, F-69360 Solaize, France.
J Chromatogr A. 2011 Dec 23;1218(51):9269-78. doi: 10.1016/j.chroma.2011.10.047. Epub 2011 Oct 24.
A method for the speciation of silicon compounds in petroleum products was developed using gas chromatography coupled to mass spectrometry (GC-MS). Prior to analysis, several precautions about storage and conservation were applied for all samples. In spiked gasoline samples, limits of detection between 24 and 69 μg kg(-1) for cyclic siloxanes (D(4)-D(6)) and between 1 and 7 μg kg(-1) for other species were obtained. In this study, cyclic siloxanes (D(n)) and one ethoxysilane were quantified for the first time in petroleum products by a specific method based on response factor calculation to an internal standard. This method was applied to four samples of naphthas and gasolines obtained from a steam cracking process. Cyclic siloxanes were predominant in four investigated samples with concentrations ranging between 101 and 2204 μg kg(-1). Cyclic siloxane content decreased with an increase in their degree of polymerization. During a steam cracking process, silicon concentrations determined by GC-MS SIM (single ion monitoring) significantly increase. This trend was confirmed by ICP-OES (inductively coupled plasma optical emission spectroscopy) measurements but a difference on the total silicon content was observed, certainly highlighting the presence of unknown silicon species. GC-MS SIM method gives access to the chemical nature of the silicon species, which is crucial for the understanding of hydrotreatment catalyst poisoning in the oil and gas industry.
建立了一种利用气相色谱-质谱联用（GC-MS）对石油产品中硅化合物进行形态分析的方法。在分析之前，对所有样品都采取了一些关于储存和保存的预防措施。在加标汽油样品中，环状硅氧烷（D(4)-D(6)）的检测限为 24-69μgkg(-1)，其他物质的检测限为 1-7μgkg(-1)。在这项研究中，首次通过基于内标物响应因子计算的特定方法，对石油产品中的环状硅氧烷（D(n））和一种乙氧基硅烷进行定量分析。该方法应用于从蒸汽裂化过程中获得的四个石脑油和汽油样品中。在四个研究样品中，环状硅氧烷的浓度范围为 101-2204μgkg(-1)，处于主导地位。环状硅氧烷的浓度随着聚合度的增加而降低。在蒸汽裂化过程中，通过 GC-MS SIM（单离子监测）测定的硅浓度显著增加。这一趋势通过 ICP-OES（电感耦合等离子体光学发射光谱）测量得到了证实，但总硅含量存在差异，这肯定表明存在未知的硅物种。GC-MS SIM 方法可以获得硅物种的化学性质，这对于理解油气工业中加氢处理催化剂中毒非常重要。
