Development of a Novel Mass Spectrometric ... - Jacobs University

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Introduction Petroleomics is a field of chemical analysis concerned about the characterization of all of the components of petroleum along with their interaction and reactivity. Acquisition of this knowledge allows to differentiate petroleum samples or distillates and can guide production and refining processes. Such molecular level information on the types of chemical classes and presence of certain functional groups are required by petroleum chemists. For example they can reduce refining byproducts and waste, prevent pipe failures and predict production problems. This need to obtain such detailed compositional information pushed the rapid development of mass spectrometry technology. In 1960s the coupling of gas chromatography to mass spectrometry was achieved. Although the growth continued until 1990, mass spectrometry was limited to low-boiling nonpolar species. After that GC/MS and LC/MS and tandem MS yielded impressive content information of many petroleum distillates such as gasoline, diesel and gas oil. However little was known about other polar species of heavy crude oils and heavy petroleum distillate. Fenn suggested most polar species could be ionized by ESI (Fenn received Noble Prize for ESI). The advent of ESI-FT ICR-MS facilitated the analysis of polar fractions within complex crude oils. However little is known about the compositional knowledge of saturates/olefins. Their tendency to fragment and undergo gas phase reactions leaves them difficult to explore. To this end, even at the expense of the mentioned MS limitations, it is still the cornerstone of the emerging field of petroleomics. Industrial laboratories and research groups have moved from physical (crude oil assays of viscosity, density, etc.) or bulk chemical characterization (% of S content, acid number, etc.) of petroleum into detailed characterization of petroleum compositions. 42 The careful choice of base oil components and their concentration leads to enhancing performance of lubricants. 88 Nowadays interest is even shifted into heavier petroleum fractions as the lighter ones (low sulfur) are depleted. 74,100 High energy demand and rising energy prices have led to mold the attention towards higher-boiling point fractions like vacuum gas oils (VGOs) and vacuum residues (VRs) of crude oil. 13,101 These mixtures should undergo desulfurisation by 23
Introduction catalytic processing to reduce their sulfur content. 102 Optimisation of catalytic operations demands a structural information about components containing S like PASH. 103 However while polar hydrocarbon constituents of petroleum (10%) are readily detected under ESI FT-ICR MS conditions, nonpolar components (90%) are especially problematic and challenging. Recent studies, reviewed in the ‘Use of mass spectrometry for hydrocarbon analyses’ section, have shown a great promise in achieving an efficient and rational analysis of such hydrocarbon mixtures. So far molecular mass distribution, elemental composition assignment and compositional sorting are elaborated for polar fractions within crude oil by virtue of high resolution FT ICR. Up to thousands of different chemical elemental compositions can be resolved in a single mass spectrum. 41,104,105 The resulting compositional information may then be displayed in Kendrick plots for rapid visual comparisons between samples. To this end, energy research will last for the next two decades. Until alternative sustainable energy sources are developed, fossil fuels will remain the major source of energy. The advancements in petroleomics will guide how energy will be processed in the future. 1.3.10 Kendrick plot The advantages of high resolution analysis of crude oil extracts by ESI-FT MS provided access to complex mixture data which were further interpreted in an illustrative and informative way. Elemental composition of ionic species up to ~400 Da can be unambiguously assigned with the virtue of high mass accuracy machines (FT-ICR-MS). 42 However the successfully assigned elemental compositions for higher-mass ions require data reduction based on the Kendrick mass scale. The method was originally introduced by Kendrick in 1963. 106 For ultrahigh-resolution measurements, it is useful to convert the measured mass to the Kendrick mass which allows sorting compounds into homologous series according to alkylation degree, classes (type of heteroatoms), and types (rings plus double bonds). For example, the IUPAC mass of CH 2 , 14.0157 Da, becomes a 24
Page 1 and 2: Development of a Novel Mass Spectro
Page 3 and 4: Declaration of Authorship I ,Nadim
Page 5 and 6: This work has been carried out unde
Page 7 and 8: Contents Contents Declaration of Au
Page 9 and 10: List of Figures List of Figures Fig
Page 11 and 12: List of Figures Figure 3-39 MS 2 fr
Page 13 and 14: List of Tables List of Tables Table
Page 15 and 16: Abbreviations Abbreviations APCI AP
Page 17 and 18: Abbreviations UV VGOs VOCs VRs ultr
Page 19 and 20: Introduction Analytical chemistry h
Page 21 and 22: Introduction 1.2 Presence and Fate
Page 23 and 24: Introduction aliphatic hydrocarbons
Page 25 and 26: Introduction Figure 1-1 Examples of
Page 27 and 28: Introduction Figure 1-2 Range of io
Page 29 and 30: Introduction fractions. 42 Another
Page 31 and 32: Introduction 1.3.5 APLI Other crude
Page 33 and 34: Introduction products). Other molec
Page 35 and 36: Introduction Other studies performe
Page 37 and 38: Introduction APLI-FT ICR-MS Crude o
Page 39: Introduction spectrometry in as muc
Page 43 and 44: Introduction Figure 1-6 Kendrick ma
Page 45 and 46: Introduction including determinatio
Page 47 and 48: Introduction 1.5 Scope and Signific
Page 49 and 50: Experimental e) Other model mixture
Page 51 and 52: Experimental 2.2.2 Preparation of O
Page 53 and 54: Experimental 2.4 Graphical Presenta
Page 55 and 56: Results and Discussion experiment.
Page 57 and 58: Results and Discussion Intens. [%]
Page 59 and 60: Results and Discussion common featu
Page 61 and 62: Results and Discussion 3.2 APCI-TOF
Page 63 and 64: Results and Discussion These compou
Page 67 and 68: Results and Discussion Ions were pr
Page 71 and 72: Results and Discussion procedure ba
Page 75 and 76: Results and Discussion to produce m
Page 77 and 78: Results and Discussion 519.5863 519
Page 79 and 80: Results and Discussion Higher mass
Page 87 and 88: Results and Discussion isolated fro
Page 91 and 92:
Results and Discussion Intens. [%]
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Results and Discussion 3.4.5 Tandem
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Page 97 and 98:
Results and Discussion injected int
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Page 101 and 102:
Results and Discussion 3.4.8 Quanti
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Results and Discussion Int. x 10000
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Results and Discussion Table 3.6 Qu
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Results and Discussion assessment o
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Results and Discussion hydrocarbons
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Page 115 and 116:
Page 117 and 118:
Results and Discussion of n-alkanes
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Results and Discussion flow (in I2)
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Results and Discussion Other intere
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Results and Discussion Figure 3-80
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Results and Discussion KMD 2.4 2.2
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Results and Discussion KMD 1.1 1 Le
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Results and Discussion 3.6.4 Asphal
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Conclusions In conclusion we could
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References References 1. Fay, R. M.
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References 23. Colavecchia, M. V.,
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References 47. Dzidic, I., Petersen
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References Hydroconversion Processe
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References 91. Golovlev, V. V., All
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Appendix Light shredder waste Meas.
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419.4592 C 30 H 59 419.4611 4.6 421
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Liqui Moly car motor oil Meas. m/z
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345.3511 C 25 H 45 345.3516 1.5 349
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