Characterization of Deasphalted Crude Oils Using Gas Chromatography–Atmospheric Pressure Laser Ionization–Trapped Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry
Characterization of Deasphalted Crude Oils Using Gas Chromatography–Atmospheric Pressure Laser Ionization–Trapped Ion Mobility Spectrometry–Time-of-Flight Mass Spectrometry
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DOI：
10.1021/acs.energyfuels.1c01724
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发表时间：
2021-09
期刊：
影响因子：
5.3
通讯作者：
C. A. Olanrewaju;Cesar E. Ramirez;F. Fernandez-Lima
中科院分区：
文献类型：
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作者：
C. A. Olanrewaju;Cesar E. Ramirez;F. Fernandez-Lima
在目前的工作中，一种新的工作流程的基础上互补的气相分离应用于脱沥青轻（Macondo和Calvert），中（杜里）和重（圣阿尔多）原油的表征。将气相色谱（GC）、大气压激光电离（APLI）和离子迁移谱-质谱（TIMS-MS）联用，实现了多环芳烃（PAHs）及类似物的有效分离和归属。GC-APLI-TIMS-TOF MS的分析能力是基于使用GC和TIMS（R= 50-90，Sr = 0.18 V/ms）气相分离来分离异构体含量，随后是TOF MS分析仪的高质量分辨率和质量准确度（<2 ppm）。以前报道的PAH类已知化合物（130种化合物）的保留时间（RT），碰撞截面（CCS），和质荷比（m/z）的基础上唯一分配显示签名模式和独特的诊断率代表的热成熟度，岩性，和微生物的贡献，每个石油地层。GC-APLI-TIMS-TOF MS的无监督T-Rex 4D分析首次生成了PAH和类似未知组分的详尽列表（1008500），每个组分的特征在于RT，CCS，m/z值，化学式和每个重复分析的峰面积（即，共12个，每种原油3×）。对多环芳烃和类似的未知化合物的检查提供了每种原油的唯一标识符列表（指定化合物的2-4%）以及所有原油共有的分子成分（指定化合物的约50%）。GC-APLI-TIMS-TOF MS的分析能力使用无监督主成分分析（PCA）进行说明，其中四种油可以很容易地分离为两个主成分，占总方差的70%。
In the present work, a novel workflow based on complementary gas-phase separations is applied to the characterization of deasphalted light (Macondo and Calvert), medium (Duri), and heavy (San Ardo) crude oils. The coupling of gas chromatography (GC), atmospheric pressure laser ionization (APLI), and trapped ion mobility spectrometry–mass spectrometry (TIMS–MS) resulted in the effective separation and candidate assignment of polycyclic aromatic hydrocarbons (PAHs) and similar compounds. The analytical power of GC–APLI–TIMS–TOF MS is based on the separation of the isomeric content using the GC and TIMS (R= 50–90 withSr= 0.18 V/ms) gas-phase separations, followed by the high mass resolution and mass accuracy (<2 ppm) of the TOF MS analyzer. Previously reported PAH-like known compounds (130 compounds) uniquely assigned on the basis of their retention time (RT), collisional cross section (CCS), and mass-to-charge ratio (m/z) showed signature patterns and distinctive diagnostic ratios representative of the thermal maturity, lithology, and microbial contribution to each oil formation. The unsupervised T-Rex 4D analysis of GC–APLI–TIMS–TOF MS generated for the first time an exhaustive list of PAHs and similar unknown components (∼8500), with each component characterized by a RT, CCS,m/zvalue, and chemical formula and peak areas for each replica analysis (i.e., 12 total, 3× per crude oil). The inspection of the PAHs and similar unknown compounds provided a list of unique identifiers for each crude oil (2–4% of the assigned compounds) as well as molecular components common to all crude oils (∼50% of the assigned compounds). The analytical power of GC–APLI–TIMS–TOF MS is illustrated using unsupervised principal component analysis (PCA), where the four oils can be easily separated in two principal components that account for 70% of the total variance.