Interestingly, the two articles also address the issue of digital transformation of the oil industry.
How so?
Petroleomics offers detailed molecular characterization of petroleum-related samples by mass spectrometry. This detailed characterization results in massive amounts of data. Effective analysis of this data requires AI-Artificial Intelligence, with all the associated technologies that AI requires.
Excerpts from the two petroleomics articles appear below, along with links to the free full text source of each.
TIP: Google® petroleomics to find more on this fascinating topic.
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Journal of the Japan Petroleum Institute, 63, (3), 133-140 (2020)
Prospect of Petroleomics as a Tool for Changing Refining Technologies (2019)
[Review Paper]
Keita Katano, Yuuki Takahashi, Koichi Sat O, Koji Tsuji, Toshiaki Hayasaka, Tsutomu Nakamura, Yoshiyuki Toyooka, And Kazuhiro Inamura
Japan Petroleum Energy Center (JPEC), Tokyo (Received December 9, 2019)
Japan Petroleum Energy Center (JPEC) and partners have been developing “Petroleomics” as a new refining technology since 2011. Petroleomics can be a technology to achieve the ultimate method based on molecular reaction models with molecular level analyses of heavy oil. After the fundamental stage taking five years, our petroleum informatics database includes more than 25 million chemical structures of heavy oil components constructed with the aid of Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). Subsequently, reaction modeling studies were applied to residue hydrodesulfurization (RDS) and the aggregation model for asphaltenes to sediments, both of which are particularly important subjects in heavy oil upgrading. Our Petroleomics project is now in the application stage to attempt three major investigations:
- a molecular data-base of crude oils including unconventional oils
- total optimization of RDS and residue fluid catalytic cracking (RFCC) operations with reaction modeling, and
- the mechanism of asphaltene aggregation responsible for fouling and plugging in some heavy oil upgrading processes
Further progress in Petroleomics is expected to achieve practical applications in refineries, such as advanced performance diagnosis, operational optimization, and catalyst and process development.
Free full text source: https://www. jstage. jst. go. jp/article/jpi/63/3/63_133/_pdf
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Annual Review of Analytical Chemistry
Annu. Rev. Anal. Chem. 2020. 13:20.1–20.26
Petroleomics: Tools, Challenges, and Developments
Diana Catalina Palacio Lozano,1 Mary J. Thomas,1,2 Hugh E. Jones,1,2 and Mark P. Barrow1
1 Department of Chemistry, University of Warwick, Coventry, United Kingdom; email: M.P.Barrow@warwick.ac.uk
2 Molecular Analytical Sciences Centre for Doctoral Training, University of Warwick, Coventry, United Kingdom
Abstract
The detailed molecular characterization of petroleum-related samples by mass spectrometry, often referred to as petroleomics, continues to present significant analytical challenges. As a result, petroleomics continues to be a driving force for the development of new ultrahigh resolution instrumentation, experimental methods, and data analysis procedures. Recent advances in ionization, resolving power, and mass accuracy, and the use of separation methods, have allowed for record levels of compositional detail to be obtained for petroleum-related samples. To address the growing size and complexity of the data generated, vital software tools for data processing, analysis, and visualization continue to be developed. The insights gained impact upon the fields of energy and environmental science and the petrochemical industry, among others. In addition to advancing the understanding of one of nature’s most complex mixtures, advances in petroleomics methodologies are being adapted for the study of other sample types, resulting in direct benefits to other fields.
1. INTRODUCTION
Crude oil and natural mixtures such as organic matter in soil and water, bio-oils, and lignin are characterized by their extraordinary chemical complexity and molecular diversity. Therefore, their composition at the molecular level cannot be determined by conventional analytical techniques. The comprehensive analysis of complex mixtures is of pivotal importance for the understanding of petroleum refining, exploration, and extraction, and the effects of this human activity on different ecosystems.
In this review, we cover the recent analytical challenges, tools, and developments encountered in the analysis of complex chemical systems.
1.1. Ultrahigh Resolution Mass Spectrometry
Ultrahigh resolution mass spectrometers are indispensable tools for the analysis of complex mixtures, such as petroleum. Their performance characteristics afford detailed compositional profiles, with many thousands of unique molecular assignments obtained from a single spectrum.
To date, the sample introduction system most widely used in petroleomics is direct infusion. Some advantages of this method include minimal sample preparation, rapid analysis, and a wide number of compounds detected in a single experiment. As a consequence of the high complexity of crude oils, it is becoming increasingly common to perform offline or online separations of sample analytes prior to analysis by MS. Some of these systems include gas chromatography (GC), liquid chromatography (LC), supercritical fluid chromatography (SFC), pyrolizer/GC, and trapped ion mobility spectrometry (TIMS), among others (3).
2. PETROLEOMICS TOOLS
2.1. Kendrick Mass Defect
With sufficient resolving power and mass accuracy, it is possible to determine the composition of complex mixtures at the molecular level. The elemental compositions define the compositional space that is the unique, characteristic signature, also called a fingerprint or profile, of the sample (12). An example of the molecular mass distribution of a crude oil can be found in Figure 1.
Use of Kendrick mass defect (KMD) greatly aids complex mixture analysis. The Kendrick mass scale (16) exploits the 14.01565 Da (CH2) alkyl repeat unit to find group members of the same heteroatom class and double bond equivalents (DBE) (17) into homologous series.
Recently, KMD analysis was extended to polymer research (19) by using the exact mass of the repeat unit as the reference mass to calculate defects and further developed with the use of fractional base units (20). This has allowed the visualization of complex mass spectra in resolution-enhancedKMDplots (21). The use of mass defect analysis has been also used in metabolomics (22) and mass remainder analysis (MARA) for an elemental compositional assignment algorithm (23).
2.2. Categorization
Elemental compositions are commonly assigned using the form CcHhNnOoSs, where c, h, n, o and s are the numbers of the respective elements. The compositions are then categorized according to (a) heteroatom class, (b) DBE, and (c) carbon number.
Petroleomics data are typically presented in four main plot types: heteroatomic class contribution, DBE versus carbon number (4) (Figure 2),KMD versus nominal Kendrick mass (16, 18), and van Krevelen plots of H/C versus O/C ratios (24, 25). Van Krevelen plots have been extended to three-dimensional (3D) space, with the third dimension as the relative peak intensity (26), using the third dimension for an additional ratio axis (27), which allows the H/C, O/C, and N/C ratios to be compared simultaneously.
2.3. Complex Organic Mixtures
Petroleomic tools have been utilized in the analysis of crude oil and their fractions (3, 4, 13), dissolved organic matter (DOM) (28–31), biofuels (32, 33), oil sands (34), bitumen (35, 36), and lignin (37, 38), with a wide range of related studies that include environmental applications.
Bio-oils: A sustainable source of energy, biomass-derived fuels can be generated from lignocellulosic materials (42). The fuel produced is a complex mixture of oxygenated and nonoxygenated hydrocarbons. Its properties include low calorific value, high oxygen and water contents, low pH, low stability, and immiscibility with conventional petroleum (32).
Natural organic matter (NOM) and DOM: Products of plant and animal tissue decay that may be found in soil, sediments, and natural water, or as aerosol in the atmosphere (43, 44). NOM consists largely of carbon, hydrogen, and oxygen, and contributions from heteroatoms such as nitrogen, sulfur, and phosphorus are found in minor traces (12).DOM may be defined as the components capable of passing through a 0.45-μm filter pore (43). DOM is predominantly found in oceans but may also be detected in terrestrial sources such as biomass, soil, and plant litter before being transferred to waterways. Assessing the composition of NOM and DOM is a pivotal environmental and ecological concern and can aid the understanding of global carbon and other elemental cycles (43).
Oil sands: A natural mixture of clay, sand, water, and bitumen. Bitumen is highly viscous and immobile in reservoir conditions (45, 46). The production of synthetic oil engenders a high cost and considerable impact on the environment; 2–4 barrels of water are required to produce 1 barrel of oil (47), with the water subsequently stored in expansive on-site tailings ponds (48). One of the major areas of environmental concern is therefore oil sands process-affected water (OSPW), a complex mixture that includes polycyclic aromatic hydrocarbons (PAHs), naphthenic acids (NAs) known to be toxic to aquatic organisms, and trace elements (e.g., metals and metalloids). Short- and long-term sustainable water management practices, such as recycling and remediation, are required while minimizing the effects on human health and the natural environment.
3. ANALYTICAL CHALLENGES
The primary analytical challenges for complex mixtures characterization can be summarized as follows:
- Ionization: As a consequence of chemical complexity, comprehensive characterization requires the use of a combination of ionization methods.
- Resolving power and mass accuracy: Unique assignments can only be attained if compositions with very small mass difference can be separated from one another.
- Isomer separation: MS coupled to prior separation is required to differentiate structural isomers of species with the same elemental composition.
- Data handling and visualization: The growing size and complexity of the data necessitate that software and new visualization tools need to be developed.
4. EXAMPLES OF APPLICATIONS
4.1. Crude Oil
Only the lowest boiling or polar components (104) and average or bulk properties (105, 106) of crude oils can be assessed using conventional analytical techniques (107). Studies of crude oils using UHR MS methods include characterization of whole oils (69) and SARA fractions following prior separation (108–110). Extensive studies of multiple petroleum samples have demonstrated that the profiles obtained using FTICR MS correlate with bulk properties (110). The analysis of crude oils has also included focused investigation into the naphthenic acids (111, 112) and sulfur-containing (113–115) compounds known to cause corrosion in refineries (116, 117). In addition to causing corrosion, sulfur-containing compounds are prone to fouling catalysts used to hydrotreat sour crude oils (116), and removal of sulfur can be particularly problematic when contained within thiophenic structures (118, 119). Recent work has focused on the analysis of polar sulfur compounds and sulfoxides in crude oils, which could lead to developments in catalysts and improvements in desulfurization processes (113). Fragmentation of different crude oil cuts has demonstrated that sulfur is located in a diverse range of structures and may be more difficult to remove in heavier fractions (114).
4.2. Asphaltenes
Asphaltenes are the fraction of crude oil defined as insoluble in n-alkanes such as n-heptane and soluble in aromatic solvents such as toluene. Asphaltenes are known for causing major problems in downstream and upstream processing (120) due to their propensity to flocculate above a critical concentration (120), under extreme conditions (121), or when constituent in an incompatible blend (122), and their subsequent deposition is a major problem in the field. Asphaltenes consist of PAH cores (123), may contain heteroatoms such as N,O, or S, and exist as island or archipelago structures, defined as a single alkyl-substituted PAH core or multiple PAH cores bridged by alkyl chains, respectively (124, 125). Fragmentation methods such as collision-induced dissociation (CID) (126), high-energy collision dissociation (HCD) (127), and infrared multiphoton dissociation (IRMPD) have been used to assess the prevalence of island and archipelago asphaltenes in different petroleum samples (128).
4.4. Oil Sands
High-resolution LC-MS and GC × GC-MS have recently been used to study oil field–produced water, tentatively identifying constituents and assessing the importance of these unknowns as potential toxicity contributors (135). Similarly, monitoring the impact of oil production on the environment by analyzing OSPW presents another important petroleomics application (136). Petroleomics methodologies are regularly used to understand OSPW composition (136–138) and toxicity as it ages (139, 140). Recent research has demonstrated the effectiveness of catalytic processes aimed at reducing the concentration of organic compounds in OSPW, a promising prospect for the remediation of tailings ponds sites (34). The impact of experimental parameters on the observed OSPW profile has also been demonstrated, which may lead to the development of more robust environmental monitoring (40, 47).
5. FUTURE ISSUES
Despite the recent developments in petroleomics and the analysis of other complex mixtures, there remain pertinent and immediate challenges in the field.
Although a plethora of ionization methods are available, offering complementary information by preferentially accessing different compound types, there are undoubtedly fractions of petroleum that currently remain unseen, even with prior separation improving access to the compositional space (109, 148, 149). Where samples are solid or absorbed in situ, for example, asphaltene deposits or biochar, the challenge remains to successfully desorb intact molecules to avoid overcomplicating the resulting spectrum with fragments or adducts and to provide a representative analysis of nonhomogeneous substances (144).
Given that the relative abundance of different compounds cannot be taken to relate directly to their concentration, quantification of individual components remains a major challenge for petroleomics. The use of standards spiked at known concentrations for hyphenated experiments may make possible quantification of known compounds of concern, although quantification of a broader range of components, particularly those with high isomeric diversity (147), presents a greater task (104). The use of hyphenated techniques would also allow the isomeric complexity underlying each molecular composition to be better understood.
With the shift toward petroleum production from unconventional sources continuing, the characterization of ever heavier and more complex samples presents an ongoing challenge. While a record resolving power of 3 million across the full mass range (m/z 260–1,505) has recently been achieved, to resolve the mass split of 0.1 mDa at m/z 1,000, a resolving power of around 10 million will be required (13, 104).
While UHR MS is capable of unrivaled compositional analysis of petroleum samples, assessment of molecular structure remains a challenge. Methods including CID and IRMPD fragmentation can be used on small mass windows, but the inherent complexity of petroleum samples means that multiple compositions and their isomers are fragmented simultaneously.
DISCLOSURE STATEMENT
M.P.B. is a trustee and elected member of the executive committee of the British Mass Spectrometry Society (BMSS).He has also received grants and industrial funding in the field of petroleomics. The other authors are not aware of any affiliations, memberships, funding, or financial holdings that might be perceived as affecting the objectivity of this review.
source: https://www.annualreviews.org/doi/pdf/10.1146/annurev-anchem-091619-091824
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