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Alan G Marshall - One of the best experts on this subject based on the ideXlab platform.
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advances in asphaltene petroleomics part 4 compositional trends of solubility subfractions reveal that polyfunctional oxygen containing compounds drive asphaltene chemistry
Energy & Fuels, 2020Co-Authors: Martha L Chaconpatino, Donald F Smith, Alan G Marshall, Christopher L Hendrickson, Ryan P RodgersAbstract:Asphaltenes have traditionally been conceived as highly aromatic, alkyl-deficient compounds enriched in pericondensed aromatic “island” motifs. This structural definition evolved into the general notion that aromatic core-dominated interactions (π-stacking) drive asphaltene aggregation, and Heteroatom-based intermolecular forces have no significant effect on the overall solubility and aggregation behavior. However, the exclusion of Heteroatoms in asphaltene chemistry is inconsistent with the Boduszynski continuum and known asphaltene properties, such as increased Heteroatom Content relative to maltenes, interfacial activity, and strong adsorption to polar stationary phases. Thus, to determine whether or not Heteroatoms are involved in solubility, we have separated asphaltene fractions enriched in single-core (island) or multicore motifs (archipelago) according to their partitioning in n-heptane by two fractionation methods. In the first separation procedure, the acetone fraction from Wyoming deposit n-heptane asphaltenes (island-enriched) was adsorbed on polytetrafluoroethylene powder and Soxhlet extracted with n-heptane. Subfractions were collected after one day, one week, one month, and three months of extraction, and the residue, n-heptane insoluble material, was recovered with a mixture of toluene and dichloromethane. In the second method, the acetone fraction from Athabasca bitumen n-heptane asphaltenes (archipelago-enriched) was fractionated by differential precipitation in mixtures of n-heptane and toluene. The molecular composition of the asphaltene subfractions was accessed by positive-ion atmospheric pressure photoionization coupled to 9.4 T Fourier transform ion cyclotron resonance mass spectrometry and structures were determined by infrared multiphoton dissociation. The compositional trends for Heteroatom Content, double bond equivalents, and alkyl substitution suggest that the Boduszynski continuum can be extended to asphaltenes. In particular, the compositional range of polyoxygenated asphaltene compounds shifts toward lower aromaticity, whereas oxygen-depleted species are more aromatic. Moreover, the results demonstrate that polyoxygenated species (e.g., O₃ and S₂O₃ classes) are pivotal in asphaltene solubility, as they concentrate in the most polarizable and insoluble asphaltene subfractions. Therefore, the results support the existence of atypical asphaltene species with remarkably low aromaticity that reside in the most insoluble asphaltene subfractions because of their high Heteroatom Content. Such asphaltene compounds preferentially ionize as protonated molecules rather than radical cations and overlap the compositional range of interfacially active species, consistent with their tendency to participate in hydrogen bonding. Collectively, the results highlight the need for an asphaltene molecular model based on the existence of polyfunctional species capable of interacting with neighboring asphaltene molecules through several intermolecular forces, including London dispersion forces between aliphatic moieties, π-stacking of aromatic cores, hydrogen bonding between nitrogen and oxygen-containing functionalities, and acid/base interactions between carboxylic acids and pyridine rings.
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heavy petroleum composition 5 compositional and structural continuum of petroleum revealed
Energy & Fuels, 2013Co-Authors: David C Podgorski, Alan G Marshall, Amy M Mckenna, Yuri E Corilo, Leonard Nyadong, Vladislav V Lobodin, Benjamin J Bythell, Winston K Robbins, Ryan P RodgersAbstract:Twenty-five years ago, Boduszynski et al. conducted a comprehensive study of heavy oil composition and concluded that crude oil composition increases gradually and continuously with regard to aromaticity, molecular weight, and Heteroatom Content from the light distillates to non-distillables (the Boduszynski continuum model). Previous exhaustive characterization of heavy vacuum gas oil by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provided compositional data that strongly supports the continuum model. However, when the molecular formulas obtained by FT-ICR MS for the distillates and asphaltenes from the same parent crude oil are plotted as double bond equivalents (DBE) versus carbon number, a gap appears between the compositional space of “asphaltenes” and “maltenes”, in contradiction to the Boduszynski–Altgelt model. Here, a heavy distillate cut (atmospheric equivalent boiling point of 523–593 °C) is fractionated according to the number of aromatic rings by HPLC-2. The C7-dea...
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heavy petroleum composition 2 progression of the boduszynski model to the limit of distillation by ultrahigh resolution ft icr mass spectrometry
Energy & Fuels, 2010Co-Authors: Amy M Mckenna, Ryan P Rodgers, Gregory T Blakney, Feng Xian, Paul Burchell Glaser, Alan G MarshallAbstract:Heavy petroleum fractions are structurally and compositionally complex mixtures that defy characterization by many traditional analytical techniques. Here, we present the detailed characterization of a Middle Eastern heavy crude oil distillation series, in further support of the Boduszynski model, which proposes that petroleum is a continuum with regard to composition, molecular weight, aromaticity, and Heteroatom Content as a function of the boiling point. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolving power and mass accuracy and thereby allows for elemental assignment for each of the tens of thousands of peaks in a single crude oil sample. Part 1 of our five-part series established the validity of the Boduszynski model for the heavy vacuum gas oil (HVGO) distillation series. Here, we extend our analysis to fractions from a Middle Eastern heavy crude with cut temperatures including and beyond the middle distillate range. Collectively, the detailed com...
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effect of thermal treatment on acidic organic species from athabasca bitumen heavy vacuum gas oil analyzed by negative ion electrospray fourier transform ion cyclotron resonance ft icr mass spectrometry
Energy & Fuels, 2009Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Alan G MarshallAbstract:We examine suspected molecular transformations of thermally treated Athabasca bitumen heavy vacuum gas oil (HVGO) by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Liquid products from HVGOs treated under an inert N2 atmosphere at temperatures of 300, 325, 350, and 400 °C were each characterized by class (Heteroatom Content), type (double-bond equivalents = number of rings plus double bonds to carbon), and carbon number distribution. In addition, the inert N2 sweep gas of the autoclave was collected, condensed, and analyzed. The total acid number (TAN) of the HVGO liquid products decreases with an increasing treatment temperature (from 4.13 at 300 °C to 1.46 at 400 °C), indicative of potential carboxylic acid decomposition. The highly abundant O2 class contains species with DBE = 3; however, no compositional changes occur with increased treatment temperature. A bimodal DBE distribution is observed for the S1O2 class, suggesting two po...
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characterization of acidic species in athabasca bitumen and bitumen heavy vacuum gas oil by negative ion esi ft icr ms with and without acid ion exchange resin prefractionation
Energy & Fuels, 2008Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Tanner Schaub, Alan G MarshallAbstract:Because acids in petroleum materials are known to corrode processing equipment, highly acidic oils are sold at a discount [on the basis of their total acid number (TAN)]. Here, we identify the acidic species in raw Canadian bitumen (Athabasca oil sands) and its distilled heavy vacuum gas oil (HVGO) as well as acid-only and acid-free fractions isolated by use of an ion-exchange resin (acid−IER) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT−ICR MS) mass spectrometry. The ultrahigh mass resolving power ( m/Δ m 50% > 400 000) and high mass accuracy (better than 500 ppb) of FT−ICR MS, along with Kendrick mass sorting, enable the assignment of a unique elemental composition to each peak in the mass spectrum. Acidic species are characterized by class (N n O o S s Heteroatom Content), type [number of rings plus double bonds to carbon or double-bond equivalent (DBE)], and carbon number distribution. We conclude that the analytical capability of FT−ICR MS and the selecti...
Ryan P Rodgers - One of the best experts on this subject based on the ideXlab platform.
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advances in asphaltene petroleomics part 4 compositional trends of solubility subfractions reveal that polyfunctional oxygen containing compounds drive asphaltene chemistry
Energy & Fuels, 2020Co-Authors: Martha L Chaconpatino, Donald F Smith, Alan G Marshall, Christopher L Hendrickson, Ryan P RodgersAbstract:Asphaltenes have traditionally been conceived as highly aromatic, alkyl-deficient compounds enriched in pericondensed aromatic “island” motifs. This structural definition evolved into the general notion that aromatic core-dominated interactions (π-stacking) drive asphaltene aggregation, and Heteroatom-based intermolecular forces have no significant effect on the overall solubility and aggregation behavior. However, the exclusion of Heteroatoms in asphaltene chemistry is inconsistent with the Boduszynski continuum and known asphaltene properties, such as increased Heteroatom Content relative to maltenes, interfacial activity, and strong adsorption to polar stationary phases. Thus, to determine whether or not Heteroatoms are involved in solubility, we have separated asphaltene fractions enriched in single-core (island) or multicore motifs (archipelago) according to their partitioning in n-heptane by two fractionation methods. In the first separation procedure, the acetone fraction from Wyoming deposit n-heptane asphaltenes (island-enriched) was adsorbed on polytetrafluoroethylene powder and Soxhlet extracted with n-heptane. Subfractions were collected after one day, one week, one month, and three months of extraction, and the residue, n-heptane insoluble material, was recovered with a mixture of toluene and dichloromethane. In the second method, the acetone fraction from Athabasca bitumen n-heptane asphaltenes (archipelago-enriched) was fractionated by differential precipitation in mixtures of n-heptane and toluene. The molecular composition of the asphaltene subfractions was accessed by positive-ion atmospheric pressure photoionization coupled to 9.4 T Fourier transform ion cyclotron resonance mass spectrometry and structures were determined by infrared multiphoton dissociation. The compositional trends for Heteroatom Content, double bond equivalents, and alkyl substitution suggest that the Boduszynski continuum can be extended to asphaltenes. In particular, the compositional range of polyoxygenated asphaltene compounds shifts toward lower aromaticity, whereas oxygen-depleted species are more aromatic. Moreover, the results demonstrate that polyoxygenated species (e.g., O₃ and S₂O₃ classes) are pivotal in asphaltene solubility, as they concentrate in the most polarizable and insoluble asphaltene subfractions. Therefore, the results support the existence of atypical asphaltene species with remarkably low aromaticity that reside in the most insoluble asphaltene subfractions because of their high Heteroatom Content. Such asphaltene compounds preferentially ionize as protonated molecules rather than radical cations and overlap the compositional range of interfacially active species, consistent with their tendency to participate in hydrogen bonding. Collectively, the results highlight the need for an asphaltene molecular model based on the existence of polyfunctional species capable of interacting with neighboring asphaltene molecules through several intermolecular forces, including London dispersion forces between aliphatic moieties, π-stacking of aromatic cores, hydrogen bonding between nitrogen and oxygen-containing functionalities, and acid/base interactions between carboxylic acids and pyridine rings.
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heavy petroleum composition 5 compositional and structural continuum of petroleum revealed
Energy & Fuels, 2013Co-Authors: David C Podgorski, Alan G Marshall, Amy M Mckenna, Yuri E Corilo, Leonard Nyadong, Vladislav V Lobodin, Benjamin J Bythell, Winston K Robbins, Ryan P RodgersAbstract:Twenty-five years ago, Boduszynski et al. conducted a comprehensive study of heavy oil composition and concluded that crude oil composition increases gradually and continuously with regard to aromaticity, molecular weight, and Heteroatom Content from the light distillates to non-distillables (the Boduszynski continuum model). Previous exhaustive characterization of heavy vacuum gas oil by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provided compositional data that strongly supports the continuum model. However, when the molecular formulas obtained by FT-ICR MS for the distillates and asphaltenes from the same parent crude oil are plotted as double bond equivalents (DBE) versus carbon number, a gap appears between the compositional space of “asphaltenes” and “maltenes”, in contradiction to the Boduszynski–Altgelt model. Here, a heavy distillate cut (atmospheric equivalent boiling point of 523–593 °C) is fractionated according to the number of aromatic rings by HPLC-2. The C7-dea...
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heavy petroleum composition 2 progression of the boduszynski model to the limit of distillation by ultrahigh resolution ft icr mass spectrometry
Energy & Fuels, 2010Co-Authors: Amy M Mckenna, Ryan P Rodgers, Gregory T Blakney, Feng Xian, Paul Burchell Glaser, Alan G MarshallAbstract:Heavy petroleum fractions are structurally and compositionally complex mixtures that defy characterization by many traditional analytical techniques. Here, we present the detailed characterization of a Middle Eastern heavy crude oil distillation series, in further support of the Boduszynski model, which proposes that petroleum is a continuum with regard to composition, molecular weight, aromaticity, and Heteroatom Content as a function of the boiling point. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides ultrahigh resolving power and mass accuracy and thereby allows for elemental assignment for each of the tens of thousands of peaks in a single crude oil sample. Part 1 of our five-part series established the validity of the Boduszynski model for the heavy vacuum gas oil (HVGO) distillation series. Here, we extend our analysis to fractions from a Middle Eastern heavy crude with cut temperatures including and beyond the middle distillate range. Collectively, the detailed com...
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effect of thermal treatment on acidic organic species from athabasca bitumen heavy vacuum gas oil analyzed by negative ion electrospray fourier transform ion cyclotron resonance ft icr mass spectrometry
Energy & Fuels, 2009Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Alan G MarshallAbstract:We examine suspected molecular transformations of thermally treated Athabasca bitumen heavy vacuum gas oil (HVGO) by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Liquid products from HVGOs treated under an inert N2 atmosphere at temperatures of 300, 325, 350, and 400 °C were each characterized by class (Heteroatom Content), type (double-bond equivalents = number of rings plus double bonds to carbon), and carbon number distribution. In addition, the inert N2 sweep gas of the autoclave was collected, condensed, and analyzed. The total acid number (TAN) of the HVGO liquid products decreases with an increasing treatment temperature (from 4.13 at 300 °C to 1.46 at 400 °C), indicative of potential carboxylic acid decomposition. The highly abundant O2 class contains species with DBE = 3; however, no compositional changes occur with increased treatment temperature. A bimodal DBE distribution is observed for the S1O2 class, suggesting two po...
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characterization of acidic species in athabasca bitumen and bitumen heavy vacuum gas oil by negative ion esi ft icr ms with and without acid ion exchange resin prefractionation
Energy & Fuels, 2008Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Tanner Schaub, Alan G MarshallAbstract:Because acids in petroleum materials are known to corrode processing equipment, highly acidic oils are sold at a discount [on the basis of their total acid number (TAN)]. Here, we identify the acidic species in raw Canadian bitumen (Athabasca oil sands) and its distilled heavy vacuum gas oil (HVGO) as well as acid-only and acid-free fractions isolated by use of an ion-exchange resin (acid−IER) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT−ICR MS) mass spectrometry. The ultrahigh mass resolving power ( m/Δ m 50% > 400 000) and high mass accuracy (better than 500 ppb) of FT−ICR MS, along with Kendrick mass sorting, enable the assignment of a unique elemental composition to each peak in the mass spectrum. Acidic species are characterized by class (N n O o S s Heteroatom Content), type [number of rings plus double bonds to carbon or double-bond equivalent (DBE)], and carbon number distribution. We conclude that the analytical capability of FT−ICR MS and the selecti...
Donald F Smith - One of the best experts on this subject based on the ideXlab platform.
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advances in asphaltene petroleomics part 4 compositional trends of solubility subfractions reveal that polyfunctional oxygen containing compounds drive asphaltene chemistry
Energy & Fuels, 2020Co-Authors: Martha L Chaconpatino, Donald F Smith, Alan G Marshall, Christopher L Hendrickson, Ryan P RodgersAbstract:Asphaltenes have traditionally been conceived as highly aromatic, alkyl-deficient compounds enriched in pericondensed aromatic “island” motifs. This structural definition evolved into the general notion that aromatic core-dominated interactions (π-stacking) drive asphaltene aggregation, and Heteroatom-based intermolecular forces have no significant effect on the overall solubility and aggregation behavior. However, the exclusion of Heteroatoms in asphaltene chemistry is inconsistent with the Boduszynski continuum and known asphaltene properties, such as increased Heteroatom Content relative to maltenes, interfacial activity, and strong adsorption to polar stationary phases. Thus, to determine whether or not Heteroatoms are involved in solubility, we have separated asphaltene fractions enriched in single-core (island) or multicore motifs (archipelago) according to their partitioning in n-heptane by two fractionation methods. In the first separation procedure, the acetone fraction from Wyoming deposit n-heptane asphaltenes (island-enriched) was adsorbed on polytetrafluoroethylene powder and Soxhlet extracted with n-heptane. Subfractions were collected after one day, one week, one month, and three months of extraction, and the residue, n-heptane insoluble material, was recovered with a mixture of toluene and dichloromethane. In the second method, the acetone fraction from Athabasca bitumen n-heptane asphaltenes (archipelago-enriched) was fractionated by differential precipitation in mixtures of n-heptane and toluene. The molecular composition of the asphaltene subfractions was accessed by positive-ion atmospheric pressure photoionization coupled to 9.4 T Fourier transform ion cyclotron resonance mass spectrometry and structures were determined by infrared multiphoton dissociation. The compositional trends for Heteroatom Content, double bond equivalents, and alkyl substitution suggest that the Boduszynski continuum can be extended to asphaltenes. In particular, the compositional range of polyoxygenated asphaltene compounds shifts toward lower aromaticity, whereas oxygen-depleted species are more aromatic. Moreover, the results demonstrate that polyoxygenated species (e.g., O₃ and S₂O₃ classes) are pivotal in asphaltene solubility, as they concentrate in the most polarizable and insoluble asphaltene subfractions. Therefore, the results support the existence of atypical asphaltene species with remarkably low aromaticity that reside in the most insoluble asphaltene subfractions because of their high Heteroatom Content. Such asphaltene compounds preferentially ionize as protonated molecules rather than radical cations and overlap the compositional range of interfacially active species, consistent with their tendency to participate in hydrogen bonding. Collectively, the results highlight the need for an asphaltene molecular model based on the existence of polyfunctional species capable of interacting with neighboring asphaltene molecules through several intermolecular forces, including London dispersion forces between aliphatic moieties, π-stacking of aromatic cores, hydrogen bonding between nitrogen and oxygen-containing functionalities, and acid/base interactions between carboxylic acids and pyridine rings.
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effect of thermal treatment on acidic organic species from athabasca bitumen heavy vacuum gas oil analyzed by negative ion electrospray fourier transform ion cyclotron resonance ft icr mass spectrometry
Energy & Fuels, 2009Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Alan G MarshallAbstract:We examine suspected molecular transformations of thermally treated Athabasca bitumen heavy vacuum gas oil (HVGO) by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Liquid products from HVGOs treated under an inert N2 atmosphere at temperatures of 300, 325, 350, and 400 °C were each characterized by class (Heteroatom Content), type (double-bond equivalents = number of rings plus double bonds to carbon), and carbon number distribution. In addition, the inert N2 sweep gas of the autoclave was collected, condensed, and analyzed. The total acid number (TAN) of the HVGO liquid products decreases with an increasing treatment temperature (from 4.13 at 300 °C to 1.46 at 400 °C), indicative of potential carboxylic acid decomposition. The highly abundant O2 class contains species with DBE = 3; however, no compositional changes occur with increased treatment temperature. A bimodal DBE distribution is observed for the S1O2 class, suggesting two po...
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characterization of acidic species in athabasca bitumen and bitumen heavy vacuum gas oil by negative ion esi ft icr ms with and without acid ion exchange resin prefractionation
Energy & Fuels, 2008Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Tanner Schaub, Alan G MarshallAbstract:Because acids in petroleum materials are known to corrode processing equipment, highly acidic oils are sold at a discount [on the basis of their total acid number (TAN)]. Here, we identify the acidic species in raw Canadian bitumen (Athabasca oil sands) and its distilled heavy vacuum gas oil (HVGO) as well as acid-only and acid-free fractions isolated by use of an ion-exchange resin (acid−IER) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT−ICR MS) mass spectrometry. The ultrahigh mass resolving power ( m/Δ m 50% > 400 000) and high mass accuracy (better than 500 ppb) of FT−ICR MS, along with Kendrick mass sorting, enable the assignment of a unique elemental composition to each peak in the mass spectrum. Acidic species are characterized by class (N n O o S s Heteroatom Content), type [number of rings plus double bonds to carbon or double-bond equivalent (DBE)], and carbon number distribution. We conclude that the analytical capability of FT−ICR MS and the selecti...
Tanner Schaub - One of the best experts on this subject based on the ideXlab platform.
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hydrothermal liquefaction oil and hydrotreated product from pine feedstock characterized by heteronuclear two dimensional nmr spectroscopy and ft icr mass spectrometry
Fuel, 2014Co-Authors: Nilusha Sudasinghe, John R Cort, Richard T Hallen, Mariefel V Olarte, Andrew J Schmidt, Tanner SchaubAbstract:Hydrothermal liquefaction (HTL) crude oil and hydrotreated product from pine tree farm waste (forest product residual, FPR) have been analyzed by direct infusion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) in both positive- and negative-ionization modes and high-resolution twodimensional heteronuclear 1H-13C NMR spectroscopy. FT-ICR MS resolves thousands of compounds in complex oils and provides unparalleled compositional details for individual molecules for identification of compound class (Heteroatom Content), type (number of rings plus double bonds to carbon or double bond equivalents (DBE) and carbon number (degree of alkylation). Heteronuclear 1H-13C NMR spectroscopy provides one-bond and multiple-bond correlations between pairs of 1H and 13C chemical shifts that are characteristic of different organic functional groups. Taken together this information provides a picture of the chemical composition of these oils. Pyrolysis crude oil product from pine wood was characterized for comparison. Generally, pyrolysis oil is comprised of a more diverse distribution of Heteroatom classes with higher oxygen number relative to HTL oil as shown by both positive- and negative-ion ESI FT-ICR MS. A total of 300 N1, 594 O1 and 267 O2 compounds were observed as products of hydrotreatment. The relative abundance of N1O1, N1O2, N1O3, N2, N2O1, N2O2more » and O3 compounds are reduced to different degrees after hydrotreatment and other higher Heteroatom containing species (O4-O10, N1O4, N1O5 and N2O3) are completely removed by hydrotreatment.« less
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characterization of acidic species in athabasca bitumen and bitumen heavy vacuum gas oil by negative ion esi ft icr ms with and without acid ion exchange resin prefractionation
Energy & Fuels, 2008Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Tanner Schaub, Alan G MarshallAbstract:Because acids in petroleum materials are known to corrode processing equipment, highly acidic oils are sold at a discount [on the basis of their total acid number (TAN)]. Here, we identify the acidic species in raw Canadian bitumen (Athabasca oil sands) and its distilled heavy vacuum gas oil (HVGO) as well as acid-only and acid-free fractions isolated by use of an ion-exchange resin (acid−IER) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT−ICR MS) mass spectrometry. The ultrahigh mass resolving power ( m/Δ m 50% > 400 000) and high mass accuracy (better than 500 ppb) of FT−ICR MS, along with Kendrick mass sorting, enable the assignment of a unique elemental composition to each peak in the mass spectrum. Acidic species are characterized by class (N n O o S s Heteroatom Content), type [number of rings plus double bonds to carbon or double-bond equivalent (DBE)], and carbon number distribution. We conclude that the analytical capability of FT−ICR MS and the selecti...
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heat exchanger deposits in an inverted steam assisted gravity drainage operation part 2 organic acid analysis by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry
Energy & Fuels, 2007Co-Authors: Tanner Schaub, Ryan P Rodgers, David W Jennings, Sunghwan Kim, Alan G MarshallAbstract:As a complement to the bulk analyses presented in part 1 (Jennings, D. W.; Shaikh, A. Energy Fuels 2007, 21, 176-184), we report detailed compositional analysis of the organic acids from heat-exchanger deposits and produced water from an inverted steam-assisted gravity drainage (SAGD) bitumen production process. The current analyses were performed by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry [(-) ESI FT-ICR MS] and reveal distributions of molecular weight, Heteroatom Content, aromaticity, and carbon number for several thousand organic acids in each sample. High mass accuracy combined with Kendrick mass defect analysis allows for assignment of a unique elemental composition, C c -H h N n ,O o S s , to each mass spectral peak. Three-dimensional mass spectral images generated from the molecular formulas reveal compositional differences that may be rationalized on the basis of sample processing. In particular, we report lower overall Heteroatom Content, higher average carbon number, and lower aromaticity for early stage deposits and the produced bitumen compared to later stage samples that show increased water solubility. Little was previously known about those species other than the presence of organic acid/acid salt functionality. Moreover, we report the first in vacuo isolation and tandem mass spectrometry of individual components of petroleum mixtures. Tandem mass spectrometry by infrared multiphoton dissociation of trapped ions indicates dicarboxylic acid structures for predominant C c H h O 4 and dicarboxylic acid structures with thiophenic sulfur for predominant C c H h SO 4 species. In this manner, we provide a highly detailed landscape for the organic acid Content of inverted SAGD heat-exchanger deposits, to further illuminate the nature of fouling in those systems.
Alem Teclemariam - One of the best experts on this subject based on the ideXlab platform.
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effect of thermal treatment on acidic organic species from athabasca bitumen heavy vacuum gas oil analyzed by negative ion electrospray fourier transform ion cyclotron resonance ft icr mass spectrometry
Energy & Fuels, 2009Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Alan G MarshallAbstract:We examine suspected molecular transformations of thermally treated Athabasca bitumen heavy vacuum gas oil (HVGO) by ultrahigh-resolution negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Liquid products from HVGOs treated under an inert N2 atmosphere at temperatures of 300, 325, 350, and 400 °C were each characterized by class (Heteroatom Content), type (double-bond equivalents = number of rings plus double bonds to carbon), and carbon number distribution. In addition, the inert N2 sweep gas of the autoclave was collected, condensed, and analyzed. The total acid number (TAN) of the HVGO liquid products decreases with an increasing treatment temperature (from 4.13 at 300 °C to 1.46 at 400 °C), indicative of potential carboxylic acid decomposition. The highly abundant O2 class contains species with DBE = 3; however, no compositional changes occur with increased treatment temperature. A bimodal DBE distribution is observed for the S1O2 class, suggesting two po...
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characterization of acidic species in athabasca bitumen and bitumen heavy vacuum gas oil by negative ion esi ft icr ms with and without acid ion exchange resin prefractionation
Energy & Fuels, 2008Co-Authors: Donald F Smith, Ryan P Rodgers, Parviz Rahimi, Alem Teclemariam, Tanner Schaub, Alan G MarshallAbstract:Because acids in petroleum materials are known to corrode processing equipment, highly acidic oils are sold at a discount [on the basis of their total acid number (TAN)]. Here, we identify the acidic species in raw Canadian bitumen (Athabasca oil sands) and its distilled heavy vacuum gas oil (HVGO) as well as acid-only and acid-free fractions isolated by use of an ion-exchange resin (acid−IER) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance (ESI FT−ICR MS) mass spectrometry. The ultrahigh mass resolving power ( m/Δ m 50% > 400 000) and high mass accuracy (better than 500 ppb) of FT−ICR MS, along with Kendrick mass sorting, enable the assignment of a unique elemental composition to each peak in the mass spectrum. Acidic species are characterized by class (N n O o S s Heteroatom Content), type [number of rings plus double bonds to carbon or double-bond equivalent (DBE)], and carbon number distribution. We conclude that the analytical capability of FT−ICR MS and the selecti...