Organic-rich shales from Lower Silurian are widely distributed in the Middle Yangtze region, central China. However, the lack of fundamental data for shale gas reservoirs increases the difficulty of ...gas exploration. In this study, 34 core samples were collected to characterize the shale pore structure and conduct a preliminary evaluation of the shale gas reservoir. The TOC (total organic carbon) content of the successively-deposited black shales range from 1.6% to 5.9%, while the total porosity range from 0.5% to 4.2%. The positive correlation between TOC and porosity indicates that TOC is the key factor determining porosity. The major component of the mineral matrix is quartz (content of 21.4%–69.2%), followed by clay minerals (content of 16.7%–44.5%). Field-emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS) results illustrate that organic matter, mixed with clay minerals, can form an organo-clay complex containing many nanopores. Furthermore, larger organic pores are developed in organo-clay complexes with higher clay content than in those with lower clay content.
Correlational analyses between pore volume (or pore surface area) and TOC (or clay content) demonstrate that micropores are associated with organic matter, while mesopores and macropores are probably associated with clay minerals. Many of the clay-related nanopores are organic in nature and are developed in organo-clay complexes containing both organic matter and clay minerals. Overall, the TOC content controls development of nanopores in the shale pore structure, followed by clay content. The DFT-derived PSD indicates that the pore volume is comprised primarily of pores having widths larger than 10 nm, while the surface area is comprised primarily of micropores. When considering the gas in place model and mechanisms of shale gas storage, further shale gas exploration in central China should aim to the deep (>1000 m) and well preserved Longmaxi Shales.
•Numerous organic pores exist in organo-clay complex.•Micropores are related to organic matters.•Mesopores and macropores are probably related to clay matters, especially for illite.•Pore volume in Longmaxi Shale is mainly contributed from pores with width larger than 10 nm.
HZSM-5, Hβ, HY and USY zeolites were applied to the isomerization of glucose. An excellent selectivity (96%) of fructose was achieved, catalyzed by HY zeolite in gamma-butyrolactone/H2O over the ...fixed bed reactor. Moreover, the glucose isomerization could be carried out for over 480 h under the optimal conditions. High density of Lewis acid (0.27 mmol·g−1) over HY facilitates the intramolecular C2 → C1 H-shift reaction over the glucopyranose ring, which is the rate-determining step during Lewis acid-catalyzed steps of the glucose isomerization. Besides, large porous structure of HY zeolite (7.4 Å) facilitates the isomerization of glucose.
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•A method is proposed for glucose isomerization in GBL-H2O over fixed bed reactor.•A selectivity (96%) of fructose is achieved over HY zeolite for over 480 h.•Lewis acid sites and large pores of HY zeolite promote glucose isomerization.•Mixed solid of glucose and fructose could be separated and GBL could be reused.
Great progress has been made in the exploration of tight sandstone gas resources in Kuqa depression. Great progress has been made in Dibei structural belt, which proves the previously unproven ...favorable area for tight sandstone gas. The physical properties, controlling factors, and characteristics of tight sandstone from the Ahe (J1a) Formation in the Dibei gas reservoir are analyzed. The results show that the tight sandstone of the J1a Formation is mainly feldspar lithic sandstone, with low porosity (average 9.1%) and low permeability (average 0.09 mD). Compaction (average compaction rate 61.9%) reduces porosity more than cementation (average cementation rate 14.3%). Secondary dissolution pores (average thin section porosity is 3.4%) dominate. The homogenization temperature has two peaks; the first peak is 85–110 °C, and the other peak is 115–140 °C, indicating that oil and gas experienced two filling stages at 12 Ma and 4.5 Ma, respectively. Eodiagenesis, A substage of mesogenetic diagenesis, and B substage of mesogenetic diagenesis happened in the area. Tight sandstone is developed in the B substage of mesogenetic diagenesis. The main controlling factors of diagenesis are: strong dissolution and structural pore increase; oil and gas charging and overpressure. The reservoir forming mode of the Dibei gas reservoir is: crude oil filling in the Late Neogene (12 Ma); reservoir densification in the late deposition of Kangcun Formation (7 Ma), mature natural gas filling in the early deposition of Kuqa Formation (4.5 Ma), and gas reservoir formed after transformation and adjustment in the deposition period of Quaternary (2 Ma). According to this model, it is predicted that the favorable area of the Dibei gas reservoir is in the southeast of the Yinan 2 well. This study provides guidance for the study of tight sandstone gas in other areas of the Kuqa Depression.
This study is predominantly about the differences in shale pore structure and the controlling factors of shale gas content between Lower Silurian and Lower Cambrian from the upper Yangtze plate, ...which are of great significance to the occurrence mechanism of shale gas. The field emission scanning electron microscopy combined with Particles (Pores) and Cracks Analysis System software, CO2/N2 adsorption and the high-pressure mercury injection porosimetry, and methane adsorption were used to investigate characteristics of overall shale pore structure and organic matter pore, heterogeneity and gas content of the Lower Paleozoic in southern Sichuan Basin and northern Guizhou province from the upper Yangtze plate. Results show that porosity and the development of organic matter pores of the Lower Silurian are better than that of the Lower Cambrian, and there are four main types of pore, including interparticle pore, intraparticle pore, organic matter pore and micro-fracture. The micropores of the Lower Cambrian shale provide major pore volume and specific surface areas. In the Lower Silurian shale, there are mesopores besides micropores. Fractal dimensions representing pore structure complexity and heterogeneity gradually increase with the increase in pore volume and specific surface areas. There is a significant positive linear relationship between total organic carbon content and micropores volume and specific surface areas of the Lower Paleozoic shale, and the correlation of the Lower Silurian is more obvious than that of the Lower Cambrian. The plane porosity of organic matter increases with the increase in total organic carbon when it is less than 5%. The plane porosity of organic matter pores is positively correlated with clay minerals content and negatively correlated with brittle minerals content. The adsorption gas content of Lower Silurian and Lower Cambrian shale are 1.51–3.86 m3/t (average, 2.31 m3/t) and 0.35–2.38 m3/t (average, 1.36 m3/t). Total organic carbon, clay minerals and porosity are the main controlling factors for the differences in shale gas content between Lower Cambrian and Lower Silurian from the upper Yangtze plate. Probability entropy and organic matter plane porosity of the Lower Silurian are higher than those of Lower Cambrian shale, but form factor and roundness is smaller.
The gas-source correlation of highly mature natural gas in marine strata has always been a contentious issue due to the complexities of the petroleum systems, which involve multiple ...source-reservoir-cap assemblages. To shed light on this matter, a study was conducted using data from five typical gas fields and two hot exploration blocks in the northwestern Sichuan Basin. Thirty-seven samples from marine strata were collected, and their natural gas molecular compositions and stable carbon isotopes were examined to investigate the gas genetic types and origins. Based on detailed gas geochemistry information, combined with source rocks and reservoir characteristics, hydrocarbon accumulation history, and tectonic evolution, the formation of natural gas was studied. The results suggest that the natural gases in the area are dominated by hydrocarbon gases with extremely high dryness coefficients and a trace of CO2 and N2. These natural gases can be separated into three groups based on the development of structures and different source rocks, according to the identification of the gas-source correlation. The presence of oil cracking gas in natural gas increases with the amount of fracture development in the gas-bearing area and the amount of input from sapropelic organic matter in the Qiongzhusi Formation (Fm). Conversely, the contribution from mixing sapropelic-humic organic matter in the Middle-Upper Permian increases noticeably. The different geochemical characteristics of natural gas in the northwestern Sichuan Basin are the result of three-factor coupling, involving different source rocks, diversified fracture evolution, and various secondary alterations (thermochemical sulfate reduction alteration, thermal maturity effect, and mixing of gas). The development of fracture determines the contribution proportion of different source rocks, while secondary alteration further transforms the geochemical characteristics of natural gas.
Joint Cramér‐Rao lower bound (JCRLB) is very useful for the performance evaluation of joint state and parameter estimation (JSPE) of non‐linear systems, in which the current measurement only depends ...on the current state. However, in reality, the non‐linear systems with two‐adjacent‐states dependent (TASD) measurements, that is, the current measurement is dependent on the current state as well as the most recent previous state, are also common. First, the recursive JCRLB for the general form of such non‐linear systems with unknown deterministic parameters is developed. Its relationships with the posterior CRLB for systems with TASD measurements and the hybrid CRLB for regular parametric systems are also provided. Then, the recursive JCRLBs for two special forms of parametric systems with TASD measurements, in which the measurement noises are autocorrelated or cross‐correlated with the process noises at one time step apart, are presented, respectively. Illustrative examples in radar target tracking show the effectiveness of the JCRLB for the performance evaluation of parametric TASD systems.
The interpretation of the sedimentary paleogeographic environment of the Lower Permian Shanxi Formation (P1s) coal strata in the southeastern Ordos Basin remains a subject of significant debate. In ...this paper, based on detrital zircon U–Pb source analysis, paleosalinity assessment, the sandstone modal composition, and other methods, we analyzed the P1s source system and constructed a model of the sedimentary evolution. The findings reveal that the primary source of the clastic materials in the study area stems from a mixed-source within the recycling orogenic belt. During the deposition period, the Shanxi Formation developed two predominant material source systems: one in the north, primarily linked to the Paleo-Yinshan Fold Orogenic Belt (YFOB), and the other in the south, originating from the North Qinling Orogenic Belt (NQinOB). These two major source systems converged in the Yichuan–Fuxian area. From the early stages of the Shanxi Formation period (Shan1), there was a regional retreat of the sea in the area. The seawater receded in a southeastward direction, leading to a gradual reduction in the paleosalinity and Sr/Ba-ratio variability during the Shan1 period. The influence of the seawater diminished, transitioning into a deltaic depositional system. This shift towards a terrestrial lakeshore basin reached its full development during the Lower Xiashihezi period. This study concludes that the Shanxi Formation in this area represents the evolution of a deltaic depositional system originating from a shallow sea shelf. This evolution can be divided into three major stages: remnants of the shallow sea shelf, barrier island–lagoon–littoral, and deltaic deposition. Within this framework, the shoreline underwent frequent lateral migration, influencing a broad range of characteristics. In the vertical direction, numerous alternating sets of sandstone bodies and mudstone, shale, and coal beds formed, creating a significant relationship between coal hydrocarbon sources and reservoirs. This study also establishes the stratigraphic-sequence framework of the basin for this period. These results hold great importance for the expansion of natural gas exploration and development efforts.
Adsorption and diffusion are the key factors affecting coalbed methane (CBM) accumulation, resource assessment and production prediction. To study the adsorption and diffusion mechanism of Fukang ...low-rank coal at the microscopic level, samples of Fukang low-rank coal were collected, and the elemental composition, carbon type distribution and functional group type of the Fukang low-rank coal structure were determined by elemental analysis (Ea), Fourier-transform interferometric radiometer (FTIR), X-ray photoelectron spectroscopy (XPS) and 13C nuclear magnetic resonance (13C NMR) experiments to construct a 2D molecular structure of the coal and a 3D macromolecular structure model. The adsorption and diffusion characteristics of methane were researched by giant regular Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods. The results showed that the excess adsorption amount of methane increased and then decreased with the increase in pressure. The diffusion of methane showed two stages with increasing pressure: a sharp decrease in the diffusion coefficient from 0.5 to 5.0 MPa and a slow decrease in the diffusion coefficient from 5.0 to 15.0 MPa. The lower the pressure, the larger the effective radius of the CH4 and C atoms, and the higher the temperature, the more pronounced the diffusion and the larger the effective radius.
The cyclic fructose was converted to furfural via open-ring tautomer over beta zeolite, and the selective splitting of CC bond was proved to be located between C5 and C6 atom.
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...•Insights the mechanism of furfural formation with respect to fructose isomers.•Investigating the furfural formation in view of shape selectivity of zeolites to fructose tautomer.•In situ NMR monitored the cleavage of CC bond of fructose using isotope 13C labeling.
The mechanism for the formation of furfural by dehydration of d-fructose via selective carbon-carbon (CC) bond cleavage was investigated over beta zeolite (Hβ). Several different pore size zeolites were employed to determine the shape selectivity of fructose isomers. Zeolitic pore sizes that smaller than the kinetic diameter of cyclic fructose also produced yield furfural (∼22.5%), while the high yield (66.0%) of hydroxymethylfurfural (HMF) can be achieved over large pore zeolite (USY zeolite), which could accommodate the cyclic fructose. These results indicated that the furfural formation likely began with acyclic fructose. In situ13C NMR and GCMS studies, using labeled 13C-1-fructose as substrate, suggested that the conversion of fructose to furfural involved with splitting of the C5-C6 bond. Furthermore, the C1 compound from the cleavage of CC bond was identified as formaldehyde, inferring that the selective scission of CC bond was ascribe to the retro-aldol reaction. Interestingly, in situ NMR studies implied that the acyclic fructose mainly derived from pyranose forms. In addition, compared with glucose, fructose directly converted to furfural at the higher yield and reaction rate.
Autosomal dominant hypertension with brachydactyly type E syndrome caused by pathogenic variants in the PDE3A gene was first reported in 2015. To date, there are only a few reports of this kind of ...syndrome. Other patients still lack a genetic diagnosis. We present a report linking a de novo PDE3A variant to autosomal dominant hypertension with brachydactyly type E syndrome.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK