Structural analysis of coal through RICO reaction: detailed analysis of heavy fractions

Murata, Satoru; Tani, Yasufumi; Hiro, Masataka; Kidena, Koh; Artok, Levent; Nomura, Masakatsu; Miyake, Mikio

doi:10.1016/s0016-2361(01)00093-x

Cited by 75 publications

(45 citation statements)

References 25 publications

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“…Nitrogen-containing and partially aromatic compounds may also form spontaneously in humic compounds at low temperature (Thorn and Mikita, 1992;Kraus et al, 2004;Hsu and Hatcher, 2005) or may have a catalytic origin (Jokic et al, 2004). Several studies report the occurrence of nitrogen-containing aromatic systems in brown coals (Imuta and Ouchi, 1973;Chaffee and Johns, 1983;Chaffee et al, 1984;Murata et al, 2001;Kashimura et al, 2004). We expect that these nitrogen species were produced by aromatization of inherited or neoformed condensed polycyclic compounds (e.g., terpenoids, steroids, hopanoids, alkaloids; Hayatsu et al, 1987) and could secondarily react with organic nitrogen and/or ammonia, nitrogen oxides and nitrates.…”

Section: Increase Of N-c 3 Substituting For Carbon In Condensed Partmentioning

confidence: 99%

Organic nitrogen chemistry during low-grade metamorphism

Boudou

Schimmelmann

Ader

et al. 2008

Geochimica et Cosmochimica Acta

129

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-Most of the organic nitrogen (N org ) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil N org within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of N org and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of N org a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of N org speciation, transformation and elimination before and during metamorphism and advocates the use of XRay Photoelectron Spectroscopy (XPS) to monitor changes in N org speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset N org is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much N org is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for N org elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate N org along a progressing reaction front, without causing nitrogen isotope fractionation in the residual N org in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core N org chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized π-electron systems (nitrogen atoms substituting for "graphitic" carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.

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Section: Increase Of N-c 3 Substituting For Carbon In Condensed Partmentioning

confidence: 99%

Organic nitrogen chemistry during low-grade metamorphism

Boudou

Schimmelmann

Ader

et al. 2008

Geochimica et Cosmochimica Acta

129

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“…also reported in the products from coal oxidation. 52 As demonstrated in Figure 10, the species with DBE at 5, 8, 11, and 14 in the O 4 class may be alkyldihydroxyarenoic acids with ARs from 1 to 4, while species with DBE at 6, 9, and 12 are most likely to be alkylarenedicarboxylic acids with 1−3 ARs. As illustrated in Figure 11, the ranges of DBE and CNs for the O 5 class species in E 1 −E 4 almost center from 2 to 13 and from 7 to 25, respectively.…”

Section: O 3 Classmentioning

confidence: 99%

Characterization of Oxygen-Containing Species in Methanolysis Products of the Extraction Residue from Xianfeng Lignite with Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

et al. 2014

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Methanolysis of an extraction residue (ER) from Xianfeng lignite was carried out to obtain extracts 1−4 (E 1 −E 4 ). The molecular compositions (MCs) of oxygen-containing species (OCSs) in E 1 −E 4 were characterized using negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). In addition, solid-state 13 C nuclear magnetic resonance and X-ray photoelectron spectrometry were used to analyze the carbon types and oxygen functional groups (OFGs) in the ER. The results show that the carbon skeleton structures in the ER are dominated by aliphatic (50.2%) and aromatic (44.9%) carbons. Methylene and methoxy carbons are the most abundant among the aliphatic carbons. Each aromatic cluster contains three rings on average with two substituent groups on each ring. The OFGs in the ER include hydroxy, ether, carbonyl, and carboxyl groups, among which the hydroxy group is the most abundant. The ESI FT-ICR MS analysis shows that the molecular mass distributions of E 1 −E 4 range from 150 to 500 u. The O n (n = 1−6) class species are the predominant OCSs in E 1 −E 4 , with 0−14 double bond equivalent (DBE) values and 9−34 carbon numbers (CNs). The most abundant O n class species in E 1 −E 4 are O 2 , O 2 , O 2 −O 3 , and O 3 , respectively. The OCSs in E 4 contain low abundances of O 1 and O 2 class species but relatively high abundances of O 4 −O 6 class species. In addition, the O n class species in E 4 have narrower ranges of DBE values and CNs than those in E 1 −E 3 . A series of acidic species with different DBE values and CNs are assigned to alkanoic acids, alkanedioic acids, alkanetricarboxylic acids, alkylarenols, alkylarenediols, alkylarenetriols, and alkylarenoic acids. With high resolving power and mass accuracy, ESI FT-ICR MS is an effective technique for characterizing MC of the soluble portion from lignites, which will facilitate producing important chemicals from lignites.

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“…The results showed that coal has a wide structural diversity, which cannot be adequately elucidated by any conventional molecular structure representation that meets the requirement for structural completeness in the traditional sense of the natural product chemistry [21]. Nomura et al improved the validity of the RICO technique [23] and applied it to determine the aliphatic bridges and functional groups in various coal samples [24][25][26][27][28] and petroleum fractions [29][30][31]. RICO has been one of the most effective approaches for the coal structure investigation [32][33][34][35][36][37][38][39][40][41][42][43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Ruthenium Ion-Catalyzed Oxidation for Petroleum Molecule Structural Features: A Review

Shi

Wang

Zhou

et al. 2015

Structure and Modeling of Complex Petroleum Mixtures

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Ruthenium ion-catalyzed oxidation (RICO) is an oxidative degradation approach for the structural investigation of petroleum fractions. It is based on the selective oxidation and near quantitative removal of aromatic carbon from aromatic petroleum fractions, while leaving the structural integrity of aliphatic units intact. RICO method has played a highly useful role in the investigation of the molecular structures of heavy petroleum. It distinguishes alkyl groups attached to aromatic rings, alkyl bridges between aromatic rings, the nature of aromatic condensation, etc. The application of RICO to petroleum chemistry was promoted by Strausz and coworkers for the study of asphaltene and other high molecular weight petroleum fractions. Structural details on asphaltenes and their ramifications were revealed by the RICO-based studies, and a hypothetical molecular model was proposed for the petroleum asphaltenes. The structural information obtained from the model is valuable for understanding such complex molecular systems. Another application of the RICO technique in the petroleum industry is the characterization of biomarkers in heavy petroleum fractions and kerogen, which were connected to the condensed core structures by chemical bonds. Generally, only the oxidation of aromatic carbon to carbon dioxide and carbonyl functionalities in RICO is considered; however, other reactions may also take place. Since they occur parallel to the oxidation of aromatic carbon, misinterpretation of the relevant experimental results may result. Recent research based on ultrahigh-resolution mass spectrometry has provided new evidence for the side reactions, which leads to a more informative interpretation of the RICO results. This paper reviews the RICO-related studies on petroleum fractions. The interpretation of RICO experimental results is also discussed.

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Structural analysis of coal through RICO reaction: detailed analysis of heavy fractions

Cited by 75 publications

References 25 publications

Organic nitrogen chemistry during low-grade metamorphism

Organic nitrogen chemistry during low-grade metamorphism

Characterization of Oxygen-Containing Species in Methanolysis Products of the Extraction Residue from Xianfeng Lignite with Negative-Ion Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Ruthenium Ion-Catalyzed Oxidation for Petroleum Molecule Structural Features: A Review

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