Patent Application
20240142433
Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57. This application claims the benefit of Brazilian Application No. BR 10 2022 019814 4, filed 30 Sep. 2022, the entire contents of which are hereby incorporated by reference.
The present invention relates to the field of organic geochemistry wherein a method for accessing high molecular mass aromatic hydrocarbons and diamondoids was developed from comprehensive characterization carried out by high resolution spectrometry coupled with the atmospheric pressure photoionization source (APPI FT-ICR MS). Based on the compositional profile of diamondoids and aromatic hydrocarbons, it is possible to quickly and robustly classify oils in relation to their origin and thermal evolution. It is verified that the compositional detail provided by the APPI(+)-FT-ICR MS analysis allowed the development of new molecular proxies, accessed without the need for any preliminary separation technique, in order to become a powerful tool for prospecting the use of oils exploited for specific purposes.
In the last 20 years, mass spectrometry (MS) has undergone great development. One of the highlights was in relation to analyzers, with the advent of mass spectrometry of very high resolution and accuracy (FT-MS, Fourier transform mass spectrometry), initially represented by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) (Marshall, Hendrickson and Jackson, 1998). These new techniques and equipment make it possible to characterize polar compounds extremely quickly and efficiently. Oils of different origins, biodegradation levels (Vaz, et al., 2013) and thermal maturation (Rocha, et al., 2018) have presented very distinct and characteristic profiles. As FT-ICR MS is a comprehensive characterization technique, its results can be used both as an aid to exploration and production, refining and distribution activities (Hughey, et al., 2001; Smith, et al., 2007; Dalmaschio, et al., 2014).
The coupling of FT-ICR MS with atmospheric pressure ionization techniques, such as electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI), made it possible to characterize polar and even non-polar compounds (aromatic hydrocarbons) extremely quickly and efficiently. The success of FT-ICR MS for the study of oil and oil derivatives is due not only to advances in instrumentation (analyzer and ionization techniques) but also to data processing methods. In relation to these, it is necessary to use specific software for processing the spectra, such as Composer. Such software, in addition to assigning molecular formulas for each mass/charge relation (m/z), has a set of graphical tools that allow all compositional information to be displayed in a clearer and more visual way. Graphical tools such as: class diagrams and DBE vs carbon number graphs are routinely the most used (Hsu, Qian and Chen, 1992; Kim, Kramer and Hatcher, 2003). Ternary diagrams, DBE distribution graphs, total carbon, among others can be obtained by using specific software, such as Thanus. Such diagrams and graphs constitute essential tools for interpreting and analyzing data trends.
Despite all the development experienced by petroleomics in recent years, methodological developments are necessary to overcome the challenges that still exist, mainly in the establishment of new parameters for the geochemical evaluation of oils. In recent years, there have been few petroleomics studies applied to organic geochemistry. The few studies focus on the global evaluation of the composition as a function of a geochemical process, that is, biodegradation (Vaz, et al., 2013), thermal evolution (Oldenburg, et al., 2014), lithofacies (Silva, et al., 2020), migration (Poets, et al., 2019) or origin (Rocha, et al., 2018). The need to establish new parameters and in-depth evaluation of results for proper use as a tool for geochemical classifications is evident (Asemani and Rabbani, 2020).
When analyzing the state of the art, documents were found that disclose procedures, methods and techniques normally used for the compositional analysis of oil. Although the documents found do not disclose all the main features of the present invention, it is clear that the matter in question arouses special interest in the scientific community, since the use of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with the atmospheric pressure photoionization (APPI) source has shown considerable potential for the detection, not only of aromatic hydrocarbons, but also for the geochemical/compositional characterization of oil, as noted below.
In US patent document 8,932,863 B2, methods for evaluating a fuel by identifying trace components therein are disclosed. According to that document, a method of evaluating a fuel includes providing a test sample of the fuel. In addition, the method includes analyzing the test sample and identifying a trace compound in the test sample. The method also determines whether the fuel is of biological origin based on the trace compound identified. Said analysis includes ionizing the test sample by an atmospheric pressure photoionization (APPI) source, followed by verification with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS).
Despite the similarity due to the use of the APPI (+) FT-ICR MS source, it is clear that the method is limited to discriminating the raw material for fuel production, being applied with the purpose of differentiating fossil fuels from those of biological origin, such as biodiesel and related materials. Therefore, there is no indication in U.S. Pat. No. 8,932,863 B2 that discloses, not even by logical inference, the method for detecting aromatic hydrocarbons and/or diamondoids with the purpose of detailing the composition of hydrocarbons and using the same for geochemical classification of oils.
Document U.S. Pat. No. 10,725,013 B2 refers to a method for the evaluation of oil samples and their fractions by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), using, among other techniques, the atmospheric pressure photoionization (APPI) as an ionization source.
In document U.S. Pat. No. 10,725,013 B2, again, there is as similarity of using the APPI (+) FT-ICR MS source, but with another purpose. A detailed characterization of the molecular composition of oils and heavy oil fractions is observed by APPI(+)-FT-ICR MS. However, the main object of U.S. Pat. No. 10,725,013 B2 refers to the method that consists of using the molecular composition obtained by APPI(+)-FT-ICR MS to determine oil properties such as: cetane number, pour point, cloud point, aniline point and octane number in the gasoline fraction. These correlations provided information on oil to gas properties without fractionation/distillation, bringing valuable information for production, refining and oil quality markers. Several equations have been proposed for this purpose. However, at no time were aromatic hydrocarbons used to evaluate the thermal evolution of oils, and there was no reference to the geochemical/compositional characterization of oil, not even to the markers proposed by the present invention.
Document WO2020257277A1 refers to a system and method for characterizing oil and its derivatives by combining total sulfur determination and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which may be equipped with atmospheric pressure photoionization (APPI). In addition, such a document states that it is the first time that aromatic compounds have been determined by APPI FT-ICR MS.
In document WO2020257277A1, there is as similarity in the use of the APPI (+) FT-ICR MS source, as well as the evaluation of the aromatic hydrocarbon fraction of the oils. The difference in relation to the present invention lies in the application of the set of data generated, that is, the compounds ionized by this technique. In reference WO2020257277A1, a method for determining the main characteristics of hydrocarbon (saturated and aromatic) and sulfur fractions is proposed. The method, in short, consisted of carrying out a “group-type” analysis using APPI (+) FT-ICR MS data. As a result, the mass fraction of sulfur and aromatic compounds was obtained, useful information to support refining actions. At no time were aromatic hydrocarbons used to evaluate the thermal evolution of oils, a focus of geochemical application, nor the markers proposed in the present invention.
Document CN107643357B refers to a method for the analysis of sterane-based compounds in a geological sample of oil. According to this method, organic materials in a rock core sample are extracted with an organic solvent and the supernatant is analyzed using Fourier transform ion cyclotron resonance mass spectrometry coupled with an atmospheric pressure photoionization source (APPI FT-ICR MS).
Despite the similarity with the use of the APPI (+) FT-ICR MS source and the analysis of steranes, the present invention differs from document CN107643357B by the application of the set of data generated, that is, the compounds ionized by this technique, which in this patent proposed a method for extracting steranes from rock using organic solvent and subsequent analysis directly by APPI(+) FT-ICR MS. Steranes are polycyclic hydrocarbons with the general formula CnH2n-6 (n>3). Although steranes are markers for studies in organic geochemistry, the strategy employed in the method of the present invention was never used.
Document JP2021162365 A presents an analytical method for heavy oil fractions using Fourier transform ion cyclotron resonance mass spectrometry coupled with an atmospheric pressure photoionization source (APPI FT-ICR MS).
Despite the similarity with the use of the APPI (+) FT-ICR MS source, the present invention differs from document JP2021162365 A by the application of the set of data generated, that is, the compounds ionized by this technique, which in this patent proposed a method for analyzing heavy fractions of oil by examining the sulfur content present. JP2021162365 A does not present similarity with the methodological strategy used in the present invention for the use of hydrocarbons in organic geochemistry studies.
The paper by BAE et al. (2010), Identification of about 30 000 Chemical Components in Shale Oils by Electrospray Ionization (ESI) and Atmospheric Pressure Photoionization (APPI) Coupled with 15T Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) and a Comparison to Conventional Oil. Energy Fuels 2010, 24, 2563-2569: DOI:10.1021/ef100060b, refers to the identification of chemical components, including aromatic hydrocarbons, in shale oil using electrospray ionization (ESI) and atmospheric pressure photoionization (APPI) coupled to Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS).
Although there is similarity with the use of the APPI (+) FT-ICR MS source, the present invention differs from the document by BAE et al. by the application of the generated data set, that is, of the compounds ionized by this technique, which in this paper, general characterizations of three oils were carried out by relative abundance, length of the alkyl chain and class unsaturations. This paper at no time discloses the use of aromatic hydrocarbons for the purpose of the present invention, which involves application in organic geochemistry studies.
The paper by PEREIRA, T. M. C. (2013), Aplicaøões da espectrometria de massas de ressonância ciclotrônica de íons por transformada de Fourier (FT-ICR MS) em petroleomica (Applications of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in petroleomics) (Master's thesis in Chemistry—UFES), refers to spectrometry applications of Fourier transform ion cyclotron resonance mass in Petroleomics using various ionization sources, among them, photoionization at atmospheric pressure for the acquisition of data related to the characterization of asphaltenes and oil samples.
In the paper by PEREIRA, T. M. C. (2013), there is as a similarity the use of the APPI source (+) FT-ICR MS. However, the present invention differs from the aforementioned paper by the application of the set of data generated, that is, the compounds ionized by this technique, which in this master's thesis was the use of the method for analyzing asphaltenes and acidic oil fractions. The aforementioned master's thesis at no point discloses the use of aromatic hydrocarbons for application in organic geochemistry studies.
The paper by PURCELL et al. (2009) Stepwise Structural Characterization of Asphaltenes during Deep Hydroconversion Processes Determined by Atmospheric Pressure Photoionization (APPI) Fourier Transform Ion Cyclotron Resonance (FT-ICR) Mass Spectrometry. Energy Fuels 2010, 24, 2257-2265: DOI:10.1021/ef900897a, refers to the structural characterization of asphaltenes during deep hydroconversion process determined by Fourier transform ion cyclotron resonance mass spectrometry coupled with atmospheric pressure photoionization source (APPI FT-ICR MS). According to this document, such techniques provide detailed molecular characterization for, among others, the hydrocarbon asphaltene.
In the paper by PURCELL et al. (2009), despite using the APPI (+) FT-ICR MS source to monitor a conversion in asphaltenes process and detailing the composition of the fractions analyzed in terms of carbon number, DBE and classes, there is no inference regarding the use of any reason for classifying the thermal evolution of oils, a focus of geochemical application, nor of the markers proposed in the present invention.
The paper by ROGERS & MCKENNA (2011), Petroleum Analysis, Anal. Chem. 2011, 83, 4665-4687 (2011), dx.doi.org/10.1021/ac201080e is a literature review of the main techniques used in oil analysis. Among the mentioned techniques, the use of Fourier transform ion cyclotron resonance mass spectrometry coupled with an atmospheric pressure photoionization source for detailed compositional analysis of hydrocarbons and crude oil is mentioned.
This review mentions the use of the APPI (+) FT-ICR MS source for evaluating the composition of oils and distillation products, showing an increase in aromatization and carbon number of the hydrocarbons with increasing distillation cutoff proving Boduszynski's prediction was right. However, at no time was the use of this technique mentioned for geochemical evaluations using hydrocarbons.
From the analysis of the state of the art, it was possible to observe that, despite the similarity in the use of the APPI (+) FT-ICR MS ionization source for the analysis of oil and by-products, in all documents found it was used the same ionization source but with focus on different applications and in different fields, without impairing the inventive nature of the present invention, nor even bringing precepts that, added to technical knowledge and combined with other available data, could directly lead to the present invention. No document shows the analysis of aromatic hydrocarbon compounds applied to geochemical studies, nor even the reference to the compounds used in the present invention for the geochemical classification of oils in relation to thermal evolution.
It is reiterated that the present invention has as its main focus the analysis at the elementary level of hydrocarbon compounds in order to provide a direct method, without the need for prior fractionation, or compound concentration steps, as is traditionally carried out. The method presented herein has several adjustments to the spectra acquisition parameters in the mass spectrometer in order to provide direct access to compounds such as diamondoids (adamantane and diamantane).
Furthermore, an extremely important step is data processing. The strategy used guaranteed access to compounds of great value for geochemical applications. It should be emphasized here that after extensive scrutiny in the literature, there is no report on the analysis of these compounds by direct ionization from oil. The method proposed herein, consisting of several steps, includes oil data acquisition parameters, data processing and establishment of ratios, “proxies”, for geochemical classification of oils in relation to the thermal evolution.
This new method for evaluating aromatic hydrocarbons, in addition to diamondoids, presents the evaluation of other markers such as phenanthrene, naphthalene, and mono- and triaromatic steranes for direct application in organic geochemistry to determine the thermal evolution of oils and condensates.
Therefore, as in the cited references that rely on the APPI method coupled to Fourier transform ion cyclotron resonance mass spectrometry, but employing different strategies for specific objectives, the present invention uses the same technique, although with a purpose and modus operandi different than that previously reported. In this way, the invention preserves the new and inventive character in face of the aforementioned state of the art.
The present invention relates to a method for the direct detection of diamondoids and a plurality of aromatic hydrocarbons by the APPI (+) FT-ICR MS technique, previously accessed by methods that require several laborious steps such as fractionation, extraction, in addition to chromatographic analysis of fractions and extracts. Furthermore, the invention, based on the compositional profile of diamondoids and aromatics, allows the classification of oils in relation to origin and thermal evolution with high speed and robustness. Therefore, the invention contributes to greater economy, since the proposed method employs the direct analysis of crude oil, without prior steps of sample preparation. Finally, the great compositional detail provided by APPI(+)-FT-ICR MS analysis allowed the development of new molecular parameters for geochemical characterization of oils in relation to origin and thermal evolution with great reliability. The new molecular parameters discussed in the present invention, accessed without the need for any preliminary separation technique, can become a powerful tool for prospecting the use of explored oils for specific purposes.
The comprehensive molecular characterization of oils by APPI(+) FT-ICR MS allows obtaining indices for evaluating the thermal evolution of fluids, oil, from oil reservoirs. The thermal evolution is an important geochemical parameter used to describe the history of accumulation and, mainly, to support basin modeling that allows the exploration potential to be leveraged while minimizing risks.
The two indices, proxies, fruits of this invention, will allow qualitatively access to the thermal evolution of oils of different origins. Traditionally, the thermal evolution is established using numerous molecular markers, each accessed by a specific method, which makes the analysis complex. The indices proposed herein proved to be robust and are produced by a direct APPI (+) FT-ICR MS analysis of the crude oil.
In order to complement the present description and obtain a better understanding of the features of the present invention, and in accordance with a preferred embodiment thereof, in annex, a set of figures is presented, where in an exemplified, although not limiting, manner, its preferred embodiment is represented.
The prospecting of markers for geochemical characterization of oil using advanced mass spectrometry techniques, especially Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS, is a current challenge in organic geochemistry of the oil. What is currently routine marker analysis is the application of conventional mass spectrometry to investigate specific molecules that provide information, for example, about the origin and degree of thermal evolution of condensed oils.
Over the last few decades, several biomarkers from the classes of hopanes, steranes and diamondoids have been used with the purpose of geochemically characterizing this type of sample, assisting in the study of oil systems. However, there is still no set of molecular parameters considered absolute and infallible in the geochemical characterization of oil, especially those associated with the thermal maturation thereof.
FT-ICR MS, despite not discriminating specific molecules, is being proposed as an alternative and robust tool for investigating the level of thermal evolution of oils and condensates, through the analysis of diamondoids and aromatic biomarkers, and using a source with APPI ionization (+), which directly ionizes nonpolar ions such as hydrocarbons.
Experimentally, there is no report in the literature (scientific paper or patent) of the identification of diamondoids and aromatic compounds by atmospheric pressure ionization methods coupled with FT-ICR MS. This opens the door for the establishment of new molecular parameters for the geochemical characterization of oils, even for the classification of oils in terms of paleodepositional aspects.
The compositional characterization of oils using petroleomics strategies allows access to thousands of potential markers. The ionization method by photoionization at atmospheric pressure is a method that can access low, medium and higher polarity molecules in oil. It is a method that presents good reproducibility and repeatability and is therefore credible to be used as a standard method for establishing new protocols for the geochemical characterization of oil.
When coupled to FT-ICR MS, it makes it possible to access thousands of chemical constituents, a number greater than any other analytical method. Based on the disclosure, the present invention therefore addresses to the development of a method for direct characterization, without fractionation and chromatographic elution, of aromatic hydrocarbons and diamondoids using the atmospheric pressure photoionization (APPI) ionization technique combined with Fourier transform resonance mass spectrometry ion cyclotronic (FT-ICR MS) and its application in geochemical characterizations of oils.
A wide set of oils was analyzed by APPI (+) FT-ICR MS. The spectra were acquired with a resolving power R=800,000.00.
In
In
In thermal evolution studies, the reasons involving phenanthrene and methylphenantrene are already established in the literature. Through the abietic acid biosynthetic path, tetracyclic diterpenes are transformed into phenanthrenes through retene and simonellite. This biosynthetic path can be followed using the APPI ionization source; however, this source does not effectively ionize ions of the O2 class, the precursor of this path. In this way, the relative abundances of structures from dehydroabiethene to phenanthrene were evaluated, highlighted in red in
Diamondoids
Experimentally, there is no report in the literature that the APPI source can ionize these structures (Oldenburg et al, 2014). For this purpose, fragmentation experiments of these structures were carried out in order to ensure that these structures ionize using APPI (+) FT-ICR MS. For this, the APCI source was used, as it already resembles EI ionization, which has already been widely discussed in the literature de fragment ions of these types of compounds; the ionization involves the mechanism of chemical ionization through the use of corona discharge. For this evaluation, the COP 96 sample was chosen because it presents a high thermal evolution, and an energy of 8 eV was used, with an isolation window of 2 Da. In
In
Validation of Evaluations with Hydropyrolysis Samples
Hydropyrolysis experiments are normally carried out in order to simulate the thermal evolution of source rocks, evaluate the extent of oil and bitumen formation and with the aim of calibrating the thermal history of the sedimentation basin by simulating physical conditions such as temperature and pressure (Mackenzie, et al., 1981; Seifert and Moldowan, 1978, 1980). In the experiment carried out at CENPES Petrobras with Type II-S kerogen samples, aliquots of samples were taken at temperature intervals, starting at 300° C. and ending at 365° C., at which the peak of the oil window was reached. Using ultra-high resolution mass spectrometry, with the APPI (+) ionization source, changes in the compositions of biomarkers and molecular markers of aromatic hydrocarbons were evaluated with the increase in the thermal evolution of hydropyrolysis samples with the aim of validating the main reasons used for samples from the Santos Basin.
In
In
In
The invention proposed here consists of a method for obtaining two new proxies for evaluating thermal evolution. As seen in
Mass spectrometry analyses were carried out using an FT-ICR MS 7T SolariX 2xR equipment (Bruker Daltonics—Bremen, Germany) coupled to the ESI and APPI source. The equipment was calibrated daily with a solution of 0.1 mg·mL−1 of NaTFA calibrant, for positive and negative mode, in the m/z range of 150 to 2000. The average calibration error varied between 0.02 and 0.04 ppm in linear regression mode. 8MW data sets files were acquired via magnitude mode with the detection range of m/z 150-2000. Typically, for each sample, a total of 300 scans were acquired to obtain spectra with excellent signal/noise values. The sodium trifluoroacetate (NaTFA) calibrant used to calibrate the mass spectrometer is from Sigma-Aldrich (Steinheim, Germany).
Routinely, in petroleomics, data processing consists of three steps, as illustrated in
In step e.1—recalibration—the raw spectra obtained by the FT-ICR MS, 7T SolariX 2xR, were recalibrated internally using the DataAnalysis 5.0 SRI software (Version 5.0 Build 203.2.3586 64-bit Copyright© 2017 Bruker Daltonik GmbH).
Step e.2 of data processing consists of assigning molecular formulas based on the recalibrated spectra. To do this, the Composer 64 software (Version 1.5.3 Sierra Analytica, Modesto, USA) is used.
In general, the processing conditions established were similar for all samples. However, the intensity threshold, minimum abundance and minimum abundance parameters varied according to the noise intensity of each spectrum and the used ionization source. These three parameters are used to define a relative abundance limit, so that molecular formulas were only assigned to peaks with an intensity higher than the pre-established limit, that is, 3 times higher than the spectrum noise. In this way, mistaken assignments for low-intensity signals, which could be noise, are avoided.
The composition data obtained in Composer are saved in csv format (separated by commas), which are used as input data in the Thanus software. The visualization can be related not only to the elaboration of different types of graphs but also to the simultaneous visualization of data from different samples, facilitating the interpretation of data and comparison of a set of samples.
Those skilled in the art in the technical field of organic geochemistry will value the knowledge presented herein and will be able to reproduce the invention in the presented embodiments and in other variants, encompassed by the scope of the attached claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2022 019814 4 | Sep 2022 | BR | national |
