scholarly journals Evolution characteristics and model of nanopore structure and adsorption capacity in organic-rich shale during artificial thermal maturation: A pyrolysis study of the Mesoproterozoic Xiamaling marine shale with type II kerogen from Zhangjiakou, Hebei, China

2018 ◽  
Vol 37 (1) ◽  
pp. 493-518 ◽  
Author(s):  
Liangwei Xu ◽  
Yang Wang ◽  
Luofu Liu ◽  
Lei Chen ◽  
Ji Chen

Thermal maturity has a considerable impact on hydrocarbon generation, mineral conversion, nanopore structure, and adsorption capacity evolution of shale, but that impact on organic-rich marine shales containing type II kerogen has been rarely subjected to explicit and quantitative characterization. This study aims to obtain information regarding the effects of thermal maturation on organic matter, mineral content, pore structure, and adsorption capacity evolution of marine shale. Mesoproterozoic Xiamaling immaturity marine oil shale with type II kerogen in Zhangjiakou of Hebei, China, was chosen for anhydrous pyrolysis to simulate the maturation process. With increasing simulation temperature, hydrocarbon generation and mineral transformation promote the formation, development, and evolution of pores in the shale. The original and simulated samples consist of closed microspores and one-end closed pores of the slit throat, all-opened wedge-shaped capillaries, and fractured or lamellar pores, which are related to the plate particles of clay. The increase in maturity can promote the formation and development of pores in the shale. Heating can also promote the accumulation, formation, and development of pores, leading to a large pore volume and surface area. The temperature increase can promote the development of pore volume and surface area of 1–10 and 40-nm diameter pores. The formation and development of pore volume and surface area of 1–10 nm diameter pores are more substantial than that of 40-nm diameter pores. The pore structure evolution of the sample can be divided into pore adjustment (T < 350°C, EqRo < 0.86%), development (350°C < T < 650°C, 0.86% < EqRo < 3.28%), and conversion or destruction stages (T > 650°C, EqRo > 3.28%). Along with the increase in maturity, the methane adsorption content decreases in the initial simulation stage, increases in the middle simulation stage, and reaches the maximum value at 650°C, after which it gradually decreases. A general evolution model is proposed by combining the nanopore structure and the adsorption capacity evolution characteristics of the oil shale.

2017 ◽  
Vol 36 (3-4) ◽  
pp. 904-918 ◽  
Author(s):  
Deyong Guo ◽  
Xiaojie Guo

In this paper, scanning electron microscopy, low-temperature N2 adsorption and CH4 isothermal adsorption experiments were performed on 11 coal samples with Ro,max between 0.98 and 3.07%. The pore structure characteristics of coals (specific surface area, total volume distribution) were studied to assess the gas adsorption capacity. The results indicate that there is significant heterogeneity on coal surface, containing numerous channel-like pores, bottle-shaped pores and wedge-shaped pores. Both Langmuir volume (VL) and Langmuir pressure (PL) show a stage change trend with the increase of coalification degree. For different coalification stages, there exist different factors influencing the VL and PL values. For low-rank coals (Ro,max < 1.1%), the increase of VL values and decrease of PL values are mainly due to the abundant primary pore and fracture within coal. For middle-rank coals (1.1% < Ro,max < 2.1%), the moisture content, vitrinite content and total pore volume are all the factors influencing VL, and the reduction of PL is mainly attributed to the decrease of moisture content and inertinite content. Meanwhile, this result is also closely related to the pore shape. For high-rank coals (Ro,max > 2.1%), VL values gradually increase and reach the maximum. When the coal has evolved into anthracite, liquid hydrocarbon within pore begins pyrolysis and gradually disappears, and a large number of macropores are converted into micropores, leading to the increase of specific surface area and total pore volume, corresponding to the increase of VL. In addition, the increase of vitrinite content within coal also contributes to the increase of VL. PL, reaches the minimum, indicating that the adsorption rate reaches the largest at the low pressure stage. The result is mainly controlled by the specific surface area and total pore volume of coal samples. This research results will provide a clearer insight into the relationship between adsorption parameters and coal rank, moisture content, maceral composition and pore structure, and it is of great significance for better assessing the gas adsorption capacity.


Author(s):  
Youwei Zheng ◽  
Deliang Fu ◽  
Jianqiang Qin ◽  
Xianrong Liu ◽  
Bing Tian ◽  
...  

AbstractThe nano-scale pore structure of shale is closely related to the self-generated and self-accumulated shale oil and gas. The Bohai Bay Basin is a crucial oil-bearing basin in eastern China, and the Paleogene Shahejie Formation is the most important source rock section in this area. In order to study the internal relationship between hydrocarbon generation evolution and pore structure characteristics of source rocks, we conducted hydrocarbon generation simulation tests with a closed gold tube system, and heated up original rocks from Shahejie Formation in Laizhou Bay Sag, southern Bohai Bay Basin, from 290 °C to 440°C at different heating rates. Besides, we carried out low-temperature N2 adsorption experiments on sample residues, and measured their pore structure characteristic parameters. The results show that with the increase of simulated temperature, the specific surface area and pore volume of nano-pores below 10 nm (which are mainly organic pores) decrease first and then increase, while those of nano-pores above 10 nm increase all the way. The evolution trend of total specific surface area and pore volume is mainly controlled by pores below 10 nm which are mainly organic pores, especially micropores below 2 nm. There are two main factors affecting the development of inorganic pores: (1) Dissolution of organic acids produced by pyrolysis of organic matter in hydrocarbon-generation evolution; (2) Deformation of crystal structure of mineral components under the combined action of temperature and pressure. The experimental results at different heating rates demonstrate that rapid settlement under geological conditions is not conducive to the development of nano-pores, especially micro-pores composed of organic pores.


Minerals ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 298
Author(s):  
Chenlong Ding ◽  
Jinxian He ◽  
Hongchen Wu ◽  
Xiaoli Zhang

Ordos Basin is an important continental shale gas exploration site in China. The micropore structure of the shale reservoir is of great importance for shale gas evaluation. The Taiyuan Formation of the lower Permian is the main exploration interval for this area. To examine the nanometer pore structures in the Taiyuan Formation shale reservoirs in the Lin-Xing area, Northern Shaanxi, the microscopic pore structure characteristics were analyzed via nitrogen adsorption experiments. The pore structure parameters, such as specific surface area, pore volume, and aperture distribution, of shale were calculated; the significance of the pore structure for shale gas storage was analyzed; and the main controlling factors of pore development were assessed. The results indicated the surface area and hole volume of the shale sample to be 0.141–2.188 m2/g and 0.001398–0.008718 cm3/g, respectively. According to the IUPAC (International Union of Pure and Applied Chemistry) classification, mesopores and macropores were dominant in the pore structure, with the presence of a certain number of micropores. The adsorption curves were similar to the standard IV (a)-type isotherm line, and the hysteresis loop type was mainly similar to H3 and H4 types, indicating that most pores are dominated by open type pores, such as parallel plate-shaped pores and wedge-shaped slit pores. The micropores and mesopores provide the vast majority of the specific surface area, functioning as the main area for the adsorption of gas in the shale. The mesopores and macropores provide the vast majority of the pore volume, functioning as the main storage areas for the gas in the shale. Total organic carbon had no notable linear correlation with the total pore volume and the specific surface area. Vitrinite reflectance (Ro) had no notable correlation with the specific surface area, but did have a low “U” curve correlation with the total pore volume. There was no relationship between the quartz content and specific surface area and total pore volume. In addition, there was no notable correlation between the clay mineral content and total specific surface area and total pore volume.


2021 ◽  
Vol 15 (2) ◽  
pp. 131-144
Author(s):  
Chunjiang Jin ◽  
Huimin Chen ◽  
Luyuan Wang ◽  
Xingxing Cheng ◽  
Donghai An ◽  
...  

In this study, aspen wood sawdust was used as the raw material, and Fe(NO3)3 and CO2 were used as activators. Activated carbon powder (ACP) was produced by the one-step physicochemical activation method in an open vacuum tube furnace. The effects of different mass ratios of Fe(NO3)3 and aspen wood sawdust on the pore structure of ACP were examined under single-variable experimental conditions. The mass ratio was 0–0.4. The detailed characteristics of ACP were examined by nitrogen adsorption, scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The adsorption capacity of ACP was established by simulating volatile organic compounds (VOCs) using ethyl acetate. The results showed that ACP has a good nanostructure with a large pore volume, specific surface area, and surface functional groups. The pore volume and specific surface area of Fe-AC-0.3 were 0.26 cm3/g and 455.36 m2/g, respectively. The activator played an important role in the formation of the pore structure and morphology of ACP. When the mass ratio was 0–0.3, the porosity increased linearly, but when it was higher than 0.3, the porosity decreased. For example, the pore volume and specific surface area of Fe-AC-0.4 reached 0.24 cm3/g and 430.87 m2/g, respectively. ACP presented good VOC adsorption performance. The Fe-AC-0.3 sample, which contained the most micropore structures, presented the best adsorption capacity for ethyl acetate at 712.58 mg/g. Under the action of the specific reaction products nitrogen dioxide (NO2) and oxygen, the surface of modified ACP samples showed different rich C/O/N surface functional groups, including C-H, C=C, C=O, C-O-C, and C-N.


2016 ◽  
Vol 75 (2) ◽  
pp. 350-357
Author(s):  
Graham Dawson ◽  
Wei Chen ◽  
Luhua Lu ◽  
Kai Dai

The adsorption properties of two nanomorphologies of trititanate, nanotubes (TiNT) and plates (TiNP), prepared by the hydrothermal reaction of concentrated NaOH with different phases of TiO2, were examined. It was found that the capacity for both morphologies towards methylene blue (MB), an ideal pollutant, was extremely high, with the TiNP having a capacity of 130 mg/g, higher than the TiNT, whose capacity was 120 mg/g at 10 mg/L MB concentration. At capacity, the well-dispersed powders deposit on the floor of the reaction vessel. The two morphologies had very different structural and adsorption properties. TiNT with high surface area and pore volume exhibited exothermic monolayer adsorption of MB. TiNP with low surface area and pore volume yielded a higher adsorption capacity through endothermic multilayer adsorption governed by pore diffusion. TiNP exhibited a higher negative surface charge of −23 mV, compared to −12 mV for TiNT. The adsorption process appears to be an electrostatic interaction, with the cationic dye attracted more strongly to the nanoplates, resulting in a higher adsorption capacity and different adsorption modes. We believe this simple, low cost production of high capacity nanostructured adsorbent material has potential uses in wastewater treatment.


2018 ◽  
Vol 6 (4) ◽  
pp. T819-T833 ◽  
Author(s):  
Yang Gu ◽  
Wenlong Ding ◽  
Min Yin ◽  
Ruyue Wang ◽  
Baocheng Jiao ◽  
...  

The marine shale in South China has great gas exploration potential, and exploration in the Sichuan Basin has been successful, but the degree of exploration remains low in the Guizhou Province. We used organic geochemical analyses (total organic carbon content and kerogen type), scanning electron microscopy (SEM), field emission SEM, nuclear magnetic resonance (NMR), X-ray diffraction analysis, and low-temperature [Formula: see text] and [Formula: see text] adsorption experimental methods to study the micropore types and pore structures and their effects on the methane adsorption capacity of organic-rich shales found in the Fenggang block in northern Guizhou Province. The results indicate that the microscopic surface porosity of the lower Cambrian Niutitang Formation ranges from 2.88% to 5.34%, with an average value of 3.86%. Based on nitrogen adsorption methods, the range of the average pore size distribution is 4.6–9.491 nm, with an average value of 6.68 nm. All of the samples exhibit significant unimodal distributions. The main pore size is less than 10 nm, and these pores account for most of the mesopore volume, which is generally consistent with the NMR results. The methane adsorption capacity of the shale samples gradually increases in the range of 0–8 MPa at 30°C and reaches a maximum at approximately 10 MPa. Positive correlations were found between the gas content and specific surface area, total pore volume, and micropore volume. These strong correlations indicate that the Niutitang Shale has a high specific surface area, a high pore volume, and narrow-diameter pores, demonstrating that it has a high gas adsorption capacity. The results of this study provide valuable information regarding the adsorption characteristics of marine shales and the factors that affect those characteristics.


2019 ◽  
Vol 944 ◽  
pp. 1192-1198
Author(s):  
Rong Wang ◽  
Zhi Xiang Lin ◽  
Yang Zhao ◽  
Xiao Dong Xu ◽  
Yan Xi Deng

An Al-supported cage-like mesoporous silica type MCM-41 has been prepared using a simple one-step synthetic procedure using oil shale residue and CTAB(Hexadecyl trimethyl Ammonium Bromide) as the template. The effects of temperature on the porosity, structure and surface area of Al-MCM-41 mesoporous materials were characterized by X-ray powder diffraction, N2adsorption desorption, scanning electron micrographs (SEM), transmission electron microscopy (TEM) techniques and Fourier transform infrared spectroscopy (FT-IR). The results indicated that temperature was a key to the characteristics of Al-MCM-41 materials, and when the temperature up to 333 K, Al-MCM-41 exhibited excellent characteristics with high degree of order, high surface area and pore volume. The one-step hydrothermal synthesized MCM-41 mesoporous material possessed high BET surface area, high pore size and high pore volume. They are respectively 835.1 m2/g, 32.6 Å and 1.22 cm3/g under the condition of the Si : Al =78:1, pH =10, crystallization temperature was 333K, crystallization time was 48h and calcination at 823 K for 5 h in air. All the results indicated the possibility of using oil shale residue as silicon and aluminum source to produce Al-MCM-41, and gave us a new way to recycle a solid waste. As well as this made it impossible to large-scale production of Al-MCM-41. Keywords: Al-MCM-41 mesoporous materials, oil shale residue, one-step synthesis


2020 ◽  
Vol 38 (5) ◽  
pp. 1484-1514 ◽  
Author(s):  
Rongfang Qin ◽  
Anmin Wang ◽  
Daiyong Cao ◽  
Yingchun Wei ◽  
Liqi Ding ◽  
...  

The physical properties of thick coal seams show strong vertical heterogeneity; thus, an accurate characterization of their pore structure is essential for coalbed methane (CBM) exploration and production. A total of 18 coal samples, collected from a thick coal seam in the Yili Basin of NW China, were tested by a series of laboratory experiments to investigate the peat mire evolution and pore structure characteristics. The results show that the No. 4 coal seam has undergone multiple stages of evolution in the peatification stage, and was divided into four water-transgression/water-regression cycles according to the regular cyclic changes of the vitrinite/inertinite ratio, structure preservation index, gelification index, vegetation index, trace element ratios, and stable carbon isotopes of organic matter. The changes of pore structure characteristics with the changes of coal deposition cycles are also analyzed. It is concluded that pore structure characteristics of the four cycles are quite different. In each water-transgression cycle, the vitrinite gradually increased and the inertinite gradually decreased, resulting in a decrease of the porosity, pore volume, specific surface area, and fractal dimension. While in each water-regression cycle, the vitrinite gradually decreased and the inertinite gradually increased, leading to an increase of the porosity, pore volume, specific surface area, and fractal dimension. A strong relationship exists between the porosity, pore volume, specific surface area, fractal dimension, and submacerals, with fusinite and semifusinite which contained more pores having a positive correlation, desmocollinite and corpovitrinite which contained few pores having a negative correlation.


2014 ◽  
Vol 2014 ◽  
pp. 1-13
Author(s):  
Xiaoshi Li ◽  
Yiwen Ju ◽  
Quanlin Hou ◽  
Zhuo Li ◽  
Mingming Wei ◽  
...  

The enrichment of coalbed methane (CBM) and the outburst of gas in a coal mine are closely related to the nanopore structure of coal. The evolutionary characteristics of 12 coal nanopore structures under different natural deformational mechanisms (brittle and ductile deformation) are studied using a scanning electron microscope (SEM) and low-temperature nitrogen adsorption. The results indicate that there are mainly submicropores (2~5 nm) and supermicropores (<2 nm) in ductile deformed coal and mesopores (10~100 nm) and micropores (5~10 nm) in brittle deformed coal. The cumulative pore volume (V) and surface area (S) in brittle deformed coal are smaller than those in ductile deformed coal which indicates more adsorption space for gas. The coal with the smaller pores exhibits a large surface area, and coal with the larger pores exhibits a large volume for a given pore volume. We also found that the relationship betweenSandVturns from a positive correlation to a negative correlation whenS>4 m2/g, with pore sizes <5 nm in ductile deformed coal. The nanopore structure (<100 nm) and its distribution could be affected by macromolecular structure in two ways. Interconversion will occur among the different size nanopores especially in ductile deformed coal.


Author(s):  
Sergio Acevedo ◽  
Liliana Giraldo ◽  
Juan Carlos Moreno-Piraján

Abstract Activated carbons are obtained by chemical activation of African Palm shells (Elaeis guineensis) with different impregnating agents, i. e. magnesium chloride (MgCl2) and calcium chloride (CaCl2) aqueous solutions at different concentrations (3, 5 and 7 % w/v) and temperatures (between 773 and 1073 K), in order to assess their influence on the development of the porosity. The activated carbons prepared are characterized in terms of both textural and chemical properties. The activated carbons have a surface area and a pore volume ranging between 19 and 501 m2.g−1 and 0.03–0.29 cm3.g−1, respectively. Based on the obtained results, the samples with higher surface area and pore volume (i. e. those impregnated with MgCl2 and CaCl2 solutions and thermally treated at 1073 K) are selected to evaluate the adsorption capacity and affinity for CO2. CO2 adsorption capacity varies between 1.78 and 2.95 mmolCO2.g−1 at 273 K and low pressure, and the activated carbon impregnated with the solution of MgCl2 3% and activated at 1073 K (i. e. ACMg3-1073) showed the best performances. Finally, the kinetic results show that adsorption rate for sample ACMg3-1073 is enhanced by its micro-mesoporous nature, being the access routes to the micropores larger.


Sign in / Sign up

Export Citation Format

Share Document