Nanopore Structure of Different Rank Coals and Its Quantitative Characterization

2021 ◽  
Vol 21 (1) ◽  
pp. 22-42
Author(s):  
Xiangchun Li ◽  
Zhongbei Li ◽  
Fan Zhang ◽  
Qi Zhang ◽  
Baisheng Nie ◽  
...  

Based on gas adsorption theory, high-pressure mercury intrusion (HPMI), low-temperature liquid nitrogen gas adsorption (LT-N2GA), CO2 adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and small-angle X-ray scattering (SAXS) techniques were used to analyze the pore structures of six coal samples with different metamorphisms in terms of pore volume, specific surface area (SSA), pore size distribution (PSD) and pore shape. Combined with the gas adsorption constant a, the influence and mechanism of the pore structure of different coal ranks on gas adsorption capacity were analyzed. The results show that there are obvious differences in the pore structure of coals with different ranks, which leads to different adsorption capacities. To a large extent, the pore shapes observed by SEM are consistent with the LT-N2GA isotherm analysis. The pore morphology of coal samples with different ranks is very different, indicating the heterogeneity among the coal surfaces. Adsorption analysis revealed that mesopore size distributions are multimodal and that the pore volume is mainly composed of mesopores of 2–15 nm. The adsorption capacity of the coal body micropores depends on the 0.6–0.9 nm and 1.5–2.0 nm aperture sections. The influence of coal rank on gas desorption and diffusion is mainly related to the difference in pore structure. The medium metamorphic coal sample spectra show that the number of peaks in the high-wavenumber segment is small and that it is greater in the high metamorphic coal. The absorption intensity of the C–H stretching vibration peak of naphthenic or aliphatic hydrocarbons varies significantly among the coal samples. Over a small range of angles, as the scattering angle increases, the scattering intensity of each coal sample gradually decreases, and as the degree of metamorphism increases, the scattering intensity gradually increases. That is, the degree of metamorphism of coal samples is directly proportional to the scattering intensity. The influence of coal rank on gas adsorption capacity is mainly related to the difference in pore structure. The gas adsorption capacity shows an asymmetric U-shaped relationship with coal rank. For higher rank coals (Vdaf < 15%), the gas adsorption consistently decreases significantly with increasing Vdaf. In the middle and low rank coal stages (Vdaf > 15%), it increases slowly with the increase of Vdaf. We believe that the results of this study will provide a theoretical basis and practical reference value for effectively evaluating coal-rock gas storage capacity, revealing the law of CBM enrichment and the development and utilization of CBM resources.

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.


Geofluids ◽  
2018 ◽  
Vol 2018 ◽  
pp. 1-11 ◽  
Author(s):  
Run Chen ◽  
Yong Qin ◽  
Pengfei Zhang ◽  
Youyang Wang

The pore structure and gas adsorption are two key issues that affect the coal bed methane recovery process significantly. To change pore structure and gas adsorption, 5 coals with different ranks were treated by CS2 for 3 h using a Soxhlet extractor under ultrasonic oscillation conditions; the evolutions of pore structure and methane adsorption were examined using a high-pressure mercury intrusion porosimeter (MIP) with an AutoPore IV 9310 series mercury instrument. The results show that the cumulative pore volume and specific surface area (SSA) were increased after CS2 treatment, and the incremental micropore volume and SSA were increased and decreased before and after Ro,max=1.3%, respectively; the incremental big pore (greater than 10 nm in diameter) volumes were increased and SSA was decreased for all coals, and pore connectivity was improved. Methane adsorption capacity on coal before and after Ro,max=1.3% also was increased and decreased, respectively. There is a positive correlation between the changes in the micropore SSA and the Langmuir volume. It confirms that the changes in pore structure and methane adsorption capacity due to CS2 treatment are controlled by the rank, and the change in methane adsorption is impacted by the change of micropore SSA and suggests that the changes in pore structure are better for gas migration; the alteration in methane adsorption capacity is worse and better for methane recovery before and after Ro,max=1.3%. A conceptual mechanism of pore structure is proposed to explain methane adsorption capacity on CS2 treated coal around the Ro,max=1.3%.


2021 ◽  
Author(s):  
Barkat Ullah ◽  
Yuanping Cheng ◽  
Liang Wang ◽  
Weihua Yang ◽  
Izhar Mithal Jiskani ◽  
...  

Abstract Accurate and quantitative investigation of the physical structure and fractal geometry of coal has important theoretical and practical significance for coal bed methane and the prevention of dynamic disasters such as coal and gas outbursts. This study investigates the pore structure and fractural characteristics of soft and hard coals using nitrogen and carbon dioxide (N2/CO2) adsorption. Coal samples from Pingdingshan Mine in Henan province of China were collected and pulverized to the required size (0.2-0.25mm). N2/CO2 adsorption tests were performed to evaluate the pore size distribution (PSD), specific surface area (SSA), and pore volume (PV). The pore structure was characterized based on fractural theory. The results unveiled that the strength of coal has a significant influence on pore structure and fracture dimensions. The obvious N2-adsorption isotherms of the coals were verified as Type IV (A) and Type II. The shape of the hysteresis loops indicates the presence of slit-shaped pores. There are significant differences in SSA and PV between both coals. The soft coal showed larger SSA and PV than hard coal that shows consistency with adsorption capacity. The fractal dimensions of soft coal are respectively larger than that of hard coal. The greater the value of D1 (complexity of pore surface) of soft coal is, the larger the pore surface roughness and gas adsorption capacity is. The results enable us to conclude that the characterization of pores and fractures of soft and hard coals is different, tending to different adsorption/desorption characteristics and outburst sensitivity. In this regard, results provide a reference for formulating corresponding coal and gas outburst prevention and control measures.


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.


2021 ◽  
Vol 2021 ◽  
pp. 1-10
Author(s):  
Xun Zhao ◽  
Tao Feng ◽  
Ping Wang ◽  
Ze Liao

In order to grasp the effect of soft and hard coal pore structure on gas adsorption characteristics, based on fractal geometry theory, low-temperature nitrogen adsorption and constant temperature adsorption test methods are used to test the pore structure characteristics of soft coal and its influence on gas adsorption characteristics. We used box dimension algorithm to measure the fractal dimension and distribution of coal sample microstructure. The research results show that the initial nitrogen adsorption capacity of soft coal is greater than that of hard coal, and the adsorption hysteresis loop of soft coal is more obvious than that of hard coal. And the adsorption curve rises faster in the high relative pressure section. The specific surface area and pore volume of soft coal are larger than those of hard coal. The number of pores is much larger than that of hard coal. In particular, the superposition of the adsorption force field in the micropores and the diffusion in the mesopores enhance the adsorption potential of soft coal. Introducing the concept of adsorption residence time, it is concluded that more adsorption sites on the surface of soft coal make the adsorption and residence time of gas on the surface of soft coal longer. Fractal characteristics of the soft coal surface are more obvious. The saturated adsorption capacity of soft coal and the rate of reaching saturation adsorption are both greater than those of hard coal. The research results of this manuscript will provide a theoretical basis for in-depth analysis of the adsorption/desorption mechanism of coalbed methane in soft coal seams and the formulation of practical coalbed methane control measures.


BioResources ◽  
2021 ◽  
Vol 16 (3) ◽  
pp. 6074-6082
Author(s):  
Weikai Wang ◽  
Minghan Li ◽  
Jiabin Cai

In order to study the effects of a messmate heartwood extraction process on its cell wall pore structure and its drying ability, its nanopore structure was explored after via gas adsorption technology. Specifically, the messmate heartwood particles were extracted with methanol, and then the cell wall pore structure of the original and extracted samples were evaluated by N2 and CO2 sorption and pycnometer methods, respectively. Overall, compared with the original samples, the cell wall porosity, micropore volume, mesopore volume, BET specific surface area, and specific surface area of the micropores of the extracted messmate heartwoods increased by 2.55%, 0.007 cm3/g, 0.0014 cm3/g, 0.24 m2·g-1, and 21.9 m2·g-1, respectively. The cell wall pore volume measured via the gas adsorption method was smaller than the measurement from the pycnometer method. The results indicated that the presence of extractives made the messmate cell wall have a decreased pore volume and porosity, which may be one of the reasons messmate wood is difficult to dry. Messmate extractives primarily were present in the micropores of the cell wall in the range of 0.4 nm to 0.7 nm. However, gas sorption technology could not detect all the pores in the cell wall of the messmate heartwood sample.


2018 ◽  
Vol 78 (10) ◽  
pp. 2096-2103 ◽  
Author(s):  
Wenhao Yu ◽  
Chao Xu ◽  
Chai Yin ◽  
Shitao Yu ◽  
Weizhi Sun ◽  
...  

Abstract A series of post-crosslinked resins were synthesized from macroporous chloromethylated styrene-divinylbenzene copolymer by controlling post-crosslinked reaction conditions. Adsorption study towards aniline showed that the three resins, ST-DVB-WH5, ST-DVB-WH6, and ST-DVB-WH7, prepared at different temperatures, and which had nearly identical static adsorption capacity, displayed great disparity in kinetic behavior. The rate constant of ST-DVB-WH7 by the pseudo-first-order model was 1.50 and 1.19 times higher than that of ST-DVB-WH5 and ST-DVB-ST-DVB-WH6. Further analysis of the diffusion model showed that the three resins exhibited different diffusion rates due to the difference in oxygen content and pore structure of each resin. The results showed that the adsorption capacity was mainly decided by the pore volume within 1.14 and 3.42 nm and the adsorption rate was mainly decided by the oxygen content of the resin. In addition, as the best synthetic resin for aniline adsorption, the equilibrium adsorption capacity of ST-DVB-WH7 was 1.57 times and 1.44 times higher than that of H-103 and NKA-II, respectively.


2021 ◽  
pp. 014459872110310
Author(s):  
Ming Yang ◽  
Gaini Jia ◽  
Jianliang Gao ◽  
Jiajia Liu ◽  
Xuebo Zhang ◽  
...  

To deeply study the variation characteristics of the gas content in the process of gas adsorption for coal samples under different gas pressures and confining pressures, low-field nuclear magnetic resonance technology was used to carry out experimental research on the gas adsorption of coal. The relationship between the T2 spectrum amplitude integral and the gas quantity was analyzed. The results show the following: (1) When the samples were inflated for 11 h at each gas pressure point (0.31, 0.74, 1.11, and 1.46 MPa), after ∼5 h of adsorption, the amount of adsorbed gas exceeded 85.0% of the total adsorption capacity; additionally, as the adsorption time increased, the amount of adsorbed gas gradually tended to stabilize. When the gas pressure was >1 MPa, the amount of adsorbed gas exceeded 90.0% of the total adsorption capacity; Higher the pressure of aerated gas, greater the gas pressure gradient or concentration gradient on the surface of the coal sample and the greater the driving force for gas molecules to seep or diffuse into the coal sample. (2) When the samples were inflated for 11 h at each confining pressure point (3, 4, 5, and 7 MPa), the adsorbed gas increased by ∼85.0% of the total adsorbed gas in the first 5 h. When the pressure was <5 MPa, the amount of adsorbed gas exceeded 85.0% of the total amount of adsorption; that is, the increase in adsorbed gas was the largest at ∼5 h in the adsorption process for the columnar coal sample under different confining pressures, and the increase was ∼5.0% from 7–11 h. When the large pores in the coal sample closed, the amount of gas that seeped into the deep part of the coal sample within the same aeration time was reduced.


2018 ◽  
Vol 140 (5) ◽  
Author(s):  
Shuwen Zhang ◽  
Xuefu Xian ◽  
Junping Zhou ◽  
Guojun Liu ◽  
Yaowen Guo ◽  
...  

In order to study the effects of particle size on the determination of pore structure in shale, the outcrop of Ordovician Wufeng (WF) and Silurian Longmaxi shale (LMX) samples from Sichuan basin were chosen and crushed into various particle sizes. Then, pore structure was analyzed by using low-pressure gas adsorption (LPGA) tests. The results show that the pore of shales is mainly composed of slit-type pores and open pores. The specific surface areas of shale are mainly contributed by micropores, while the largest proportion of the total pore volume in shale is contributed by mesopores. With the decreasing of particle size, the specific surface area of both samples is decreased, while average pore diameter and the total pore volume are increased gradually. The influences of particle size on the pore structure parameters are more significant for micropore and macropore, as the particle sizes decrease from 2.36 mm to 0.075 mm, the volume of micropores in Longmaxi shale increases from 0.283 cm3/100 g to 0.501 cm3/100 g with an increment almost 40%, while the volume of macropores decreases from 0.732 cm3/100 g to 0.260 cm3/100 g with a decrement about 50%. This study identified the fractal dimensions at relative pressures of 0–0.50 and 0.50–0.995 as D1 and D2, respectively. D1 increases with the decrease of particle size of shale, while D2 shows an opposite tendency in both shale samples.


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