Innate sulfur components in high boiling petroleum samples were used as an internal standard for the estimation of the sample’s composition through atmospheric pressure photo ionization (APPI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). The first step was recording a representative mass spectrum for the aromatic components through the use of a time-of-flight mass spectrometer (TOF MS) to tune the FT-ICR MS parameters. The molecular weight and number of sulfur atoms per species identified in the high-resolution measurement, their mass spectrometric abundance, and the total sulfur content were combined to calculate the mass fraction of each (and by sum all) aromatic sulfur species present. Aromatic hydrocarbon (HC) compound quantification was based on an equimolar response compared to the aromatic sulfur species. Nitrogen species were treated analogously to the sulfur compounds by distributing the total nitrogen content. The mass balance of all aromatic compounds yields the mass fraction of saturated compounds (saturates), which is not directly accessible through the APPI process. The validity and biases of this approach were evaluated on a series of vacuum distilled fractions with narrow boiling ranges using comprehensive two-dimensional gas chromatography (GCxGC) as a reference technique. There are clear biases of the presented mass spectrometric approach compared to the GCxGC analysis, especially the underestimation of monoaromatic compounds and the overestimation of diaromatic sulfur compounds (benzothiophenes); however, the results agree surprisingly well for saturated compounds and, overall, for the aromatic hydrocarbon- and sulfur-containing compound families. The saturates fraction results also matched reasonably with gravimetrically determined saturates contents, and the isolated fractions were further characterized using field desorption/field ionization TOF MS. The inclusion of saturated compound carbon number distribution, in combination with FT-ICR MS data, yields a more complete compositional description of the studied vacuum gas oil samples. The method was also applied to two typical boiling range vacuum gas oil samples (derived from a Norwegian and an Arabian crude oil) to provide an insight into the usefulness and limitations of high-resolution mass spectrometry in a semiquantitative context, which is deemed important for many oil and gas industry applications.

中文翻译：

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固有硫化合物作为通过APPI FT-ICR MS测定真空粗柴油成分的内标

高沸点石油样品中的先天硫成分用作内标，用于通过大气压光电离（APPI）傅里叶变换离子回旋共振质谱（FT-ICR MS）估算样品的成分。第一步是通过使用飞行时间质谱仪（TOF MS）记录FT-ICR MS参数来记录芳族组分的代表性质谱。在高分辨率测量中确定的每个物种的硫原子的分子量和数量，其质谱丰度和总硫含量被组合起来，以计算每种存在的芳族硫物种的质量分数（总和）。芳烃（HC）化合物的定量基于与芳族硫物质相比的等摩尔响应。通过分布总氮含量，类似于硫化合物处理氮物种。所有芳族化合物的质量平衡都会产生饱和化合物（饱和物）的质量分数，而这不能通过APPI工艺直接获得。使用全面的二维气相色谱（GCxGC）作为参考技术，对一系列沸程较窄的真空蒸馏馏分评估了该方法的有效性和偏倚。与GCxGC分析相比，提出的质谱方法存在明显的偏差，尤其是单芳族化合物的低估和二芳族硫化合物（苯并噻吩）的高估。但是，对于饱和化合物，结果出乎意料地一致，总的来说，用于芳族含烃和含硫化合物家族。饱和物馏分的结果也与重量测定的饱和物含量合理匹配，并且分离的馏分使用场解吸/场电离TOF MS进行了进一步表征。包含饱和化合物碳原子数分布，结合FT-ICR MS数据，可以更完整地描述所研究的真空瓦斯油样品的组成。该方法还应用于两个典型的沸程真空瓦斯油样品（源自挪威和阿拉伯原油），以提供对半定量背景下高分辨率质谱法的有用性和局限性的认识，这对于石油和天然气行业的许多应用。饱和物馏分的结果也与重量测定的饱和物含量合理匹配，并且分离的馏分使用场解吸/场电离TOF MS进行了进一步表征。包含饱和化合物碳原子数分布，结合FT-ICR MS数据，可以更完整地描述所研究的真空瓦斯油样品的组成。该方法还应用于两个典型的沸程真空瓦斯油样品（来自挪威和阿拉伯原油），以提供对半定量背景下高分辨率质谱法的有用性和局限性的认识，这对石油和天然气行业的许多应用。饱和物馏分的结果也与重量测定的饱和物含量合理匹配，并且分离的馏分使用场解吸/场电离TOF MS进行了进一步表征。包含饱和化合物碳原子数分布，结合FT-ICR MS数据，可以更完整地描述所研究的真空瓦斯油样品的组成。该方法还应用于两个典型的沸程真空瓦斯油样品（源自挪威和阿拉伯原油），以提供对半定量背景下高分辨率质谱法的有用性和局限性的认识，这对于石油和天然气行业的许多应用。分离的馏分使用场解吸/场电离TOF MS进行进一步表征。包含饱和化合物碳原子数分布，结合FT-ICR MS数据，可以更完整地描述所研究的真空瓦斯油样品的组成。该方法还应用于两个典型的沸程真空瓦斯油样品（源自挪威和阿拉伯原油），以提供对半定量背景下高分辨率质谱法的有用性和局限性的认识，这对于石油和天然气行业的许多应用。分离的馏分用场解吸/场电离TOF MS进一步表征。结合饱和化合物碳数分布以及FT-ICR MS数据，可以更完整地描述所研究的真空瓦斯油样品的组成。该方法还应用于两个典型的沸程真空瓦斯油样品（源自挪威和阿拉伯原油），以提供对半定量背景下高分辨率质谱法的有用性和局限性的认识，这对于石油和天然气行业的许多应用。