Coalification temperatures are often considered to be approximately 100-170 ℃ for bituminous coal and 170-275 ℃ for anthracite. However, our micropetrographic observations, solid state ^27Al magic-angle spinning nuc...Coalification temperatures are often considered to be approximately 100-170 ℃ for bituminous coal and 170-275 ℃ for anthracite. However, our micropetrographic observations, solid state ^27Al magic-angle spinning nuclear magnetic resonance measurements, interpretation of δ^13C values for whewellite in pelosiderite concretions from Carboniferous sediments, and assessment of whewellite thermal stability show that coalification temperatures can be significantly lower. Also the temperatures of coal alteration may be substantially lower than is stated. Ordinarily, high- temperature alteration is reported, but microthermometric measurements of fluids temperatures and micropetrographic observations show that the coal alteration can take place at low temperatures. For this reason, coals from the Kladno- Rakovnik Basin, part of Late Paleozoic continental basins of the Czech Republic, were analyzed. Regarding coalification, micropetrographic characterizations of unaltered coals, the presence of thermally unstable Al complexes in the coal organic mass documented using ^27Al MAS NMR method, and proven occurrence of whewellite in pelosiderite concretions suggest a lower coalification temperature, max. -70 ℃. Regarding coal alteration, micropetrographic observations revealed （a） the weaker intensity of fluorescence of liptinite, （b） mylonitic structures and microbreccia with carbonate fluid penetration, and （c） high oxygen content in coals （37-38 wt.%）. These phenomena are typical for thermal and oxidative alteration of coal. As the temperature of carbonate fluids inferred from fluid inclusion analysis was evaluated as -100-113 ℃, the temperature of coal alteration was suggested as -113℃; the alteration was caused by hot hydrothermal fluids.展开更多
Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase...Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase bilinearly with the number of carbon atoms in the molecule. It was found that in a high density stationary phase, the longer alkyl side chains of compounds in question are subject to cyclization as a result of the resistance force of this phase affecting molecules during their thermal and diffusion motion. Consequently, common conventional aromatic-aliphatic molecules become new molecules with quasi-alicyclic rings. In comparison with the conventionally conceived molecules, the resulting aromatic–quasi-alicyclic molecules are characterized by rather different, possibly even completely different non-covalent interactions between the molecules, which then affect the retention characteristics. Moreover, cyclization facilitates the mixing of n-alkyl arenes and n-alkyl phenols with high-molecular stationary phases, because the thermodynamic condition for mixing is better fulfilled.展开更多
For geochemical purposes, complex aluminum compounds in coal organic matter in different types of coal were identified by solid state nuclear magnetic resonance measurements of <sup>27</sup>Al. Low ash sam...For geochemical purposes, complex aluminum compounds in coal organic matter in different types of coal were identified by solid state nuclear magnetic resonance measurements of <sup>27</sup>Al. Low ash samples of anthracites, bituminous coals and altered coals from the Czech Republic, Russia, Ukraine, China and Australia were tested;further, low ash lignite and xylite from the Czech Republic and gagatite from Poland were analyzed. In acquired <sup>27</sup>Al MAS NMR spectra, two significant peaks at chemical shifts were recorded, at 3.5 - 4 and 13.5 - 15 ppm. It was found that the significant peak at chemical shift at 3.5 - 4 ppm in spectra of bituminous coals, lignite, gagatite and a thermally weakly altered coal corresponds to that obtained for triaquo-hydroxo-diphenoxido-Aluminum(III) complex. The existence of triaquo-triphenoxido-Aluminum(III) complex in the spec- tra of anthracites, some bituminous coals and another thermally altered coal can be approved by the chemical shift at 13.5 - 15 ppm. These findings indicate that at least two different Al complexes were identified in coal organic matter. Further it was found that these complexes are concentrated in vitrinite fraction (alicyclic-aromatic part of coal), notably in collotelinite (gelified and homogenous vitrinite constituent). Ways of Al complexes formation in coal are suggested and their thermal stability is discussed.展开更多
Gas chromatographic measurements of the retention times of alkyl naphthalenes on packed columns with polar and non-polar stationary phases have proven that the logarithm of the relative retention time increases bi-lin...Gas chromatographic measurements of the retention times of alkyl naphthalenes on packed columns with polar and non-polar stationary phases have proven that the logarithm of the relative retention time increases bi-linearly (not linearly) with the number of carbon atoms in a molecule. This is caused by a strong inclination of alkyl side chains toward intramolecular cyclization. A FTIR spectral analysis has shown that longer alkyl side chains of alkyl naphthalenes are cyclized through an interaction between the terminal CH3 group and the aromatic ring. Conventional aromatic-aliphatic molecules thus become new molecules with quasi-alicyclic rings. This, however, alters the effect of non-covalent van der Waals attractive forces both inside and outside the molecules, which is reflected in an exponential increase of the retention times of alkyl naphthalenes with a side chain longer than propyl and in the bi-linearity of the logarithmic dependence of the relative retention times on the number of carbons in the molecule.展开更多
文摘Coalification temperatures are often considered to be approximately 100-170 ℃ for bituminous coal and 170-275 ℃ for anthracite. However, our micropetrographic observations, solid state ^27Al magic-angle spinning nuclear magnetic resonance measurements, interpretation of δ^13C values for whewellite in pelosiderite concretions from Carboniferous sediments, and assessment of whewellite thermal stability show that coalification temperatures can be significantly lower. Also the temperatures of coal alteration may be substantially lower than is stated. Ordinarily, high- temperature alteration is reported, but microthermometric measurements of fluids temperatures and micropetrographic observations show that the coal alteration can take place at low temperatures. For this reason, coals from the Kladno- Rakovnik Basin, part of Late Paleozoic continental basins of the Czech Republic, were analyzed. Regarding coalification, micropetrographic characterizations of unaltered coals, the presence of thermally unstable Al complexes in the coal organic mass documented using ^27Al MAS NMR method, and proven occurrence of whewellite in pelosiderite concretions suggest a lower coalification temperature, max. -70 ℃. Regarding coal alteration, micropetrographic observations revealed （a） the weaker intensity of fluorescence of liptinite, （b） mylonitic structures and microbreccia with carbonate fluid penetration, and （c） high oxygen content in coals （37-38 wt.%）. These phenomena are typical for thermal and oxidative alteration of coal. As the temperature of carbonate fluids inferred from fluid inclusion analysis was evaluated as -100-113 ℃, the temperature of coal alteration was suggested as -113℃; the alteration was caused by hot hydrothermal fluids.
文摘Gas chromatographic measurements of the relative retention times of alkyl-substituted arenes and phenols on capillary columns at temperatures of 125 – 140°C have shown that logarithms of retention times increase bilinearly with the number of carbon atoms in the molecule. It was found that in a high density stationary phase, the longer alkyl side chains of compounds in question are subject to cyclization as a result of the resistance force of this phase affecting molecules during their thermal and diffusion motion. Consequently, common conventional aromatic-aliphatic molecules become new molecules with quasi-alicyclic rings. In comparison with the conventionally conceived molecules, the resulting aromatic–quasi-alicyclic molecules are characterized by rather different, possibly even completely different non-covalent interactions between the molecules, which then affect the retention characteristics. Moreover, cyclization facilitates the mixing of n-alkyl arenes and n-alkyl phenols with high-molecular stationary phases, because the thermodynamic condition for mixing is better fulfilled.
文摘For geochemical purposes, complex aluminum compounds in coal organic matter in different types of coal were identified by solid state nuclear magnetic resonance measurements of <sup>27</sup>Al. Low ash samples of anthracites, bituminous coals and altered coals from the Czech Republic, Russia, Ukraine, China and Australia were tested;further, low ash lignite and xylite from the Czech Republic and gagatite from Poland were analyzed. In acquired <sup>27</sup>Al MAS NMR spectra, two significant peaks at chemical shifts were recorded, at 3.5 - 4 and 13.5 - 15 ppm. It was found that the significant peak at chemical shift at 3.5 - 4 ppm in spectra of bituminous coals, lignite, gagatite and a thermally weakly altered coal corresponds to that obtained for triaquo-hydroxo-diphenoxido-Aluminum(III) complex. The existence of triaquo-triphenoxido-Aluminum(III) complex in the spec- tra of anthracites, some bituminous coals and another thermally altered coal can be approved by the chemical shift at 13.5 - 15 ppm. These findings indicate that at least two different Al complexes were identified in coal organic matter. Further it was found that these complexes are concentrated in vitrinite fraction (alicyclic-aromatic part of coal), notably in collotelinite (gelified and homogenous vitrinite constituent). Ways of Al complexes formation in coal are suggested and their thermal stability is discussed.
基金This work was carried out thanks to the support of the long-term project for the conceptual development of the research organization No.67985891.
文摘Gas chromatographic measurements of the retention times of alkyl naphthalenes on packed columns with polar and non-polar stationary phases have proven that the logarithm of the relative retention time increases bi-linearly (not linearly) with the number of carbon atoms in a molecule. This is caused by a strong inclination of alkyl side chains toward intramolecular cyclization. A FTIR spectral analysis has shown that longer alkyl side chains of alkyl naphthalenes are cyclized through an interaction between the terminal CH3 group and the aromatic ring. Conventional aromatic-aliphatic molecules thus become new molecules with quasi-alicyclic rings. This, however, alters the effect of non-covalent van der Waals attractive forces both inside and outside the molecules, which is reflected in an exponential increase of the retention times of alkyl naphthalenes with a side chain longer than propyl and in the bi-linearity of the logarithmic dependence of the relative retention times on the number of carbons in the molecule.
