Effects of Pore Structure and Wettability on Methane Adsorption Capacity of Mud Rock: Insights from the Organic Matter/Clay Minerals Mixtures

Author(s):  
P. Luo ◽  
N.N. Zhong ◽  
Z.P Guo
Fuel ◽  
2019 ◽  
Vol 251 ◽  
pp. 551-561 ◽  
Author(s):  
Peng Luo ◽  
Ningning Zhong ◽  
Imran Khan ◽  
Xiaomei Wang ◽  
Huajin Wang ◽  
...  

Energies ◽  
2020 ◽  
Vol 13 (7) ◽  
pp. 1690
Author(s):  
Yong Han ◽  
Yanming Zhu ◽  
Yu Liu ◽  
Yang Wang ◽  
Han Zhang ◽  
...  

This study focuses on the nanostructure of shale samples with type III kerogen and its effect on methane adsorption capacity. The composition, pore size distribution, and methane adsorption capacities of 12 shale samples were analyzed by using the high-pressure mercury injection experiment, low-temperature N2/CO2 adsorption experiments, and the isothermal methane adsorption experiment. The results show that the total organic carbon (TOC) content of the 12 shale samples ranges from 0.70% to ~35.84%. In shales with type III kerogen, clay minerals and organic matter tend to be deposited simultaneously. When the TOC content is higher than 10%, the clay minerals in these shale samples contribute more than 70% of the total inorganic matter. The CO2 adsorption experimental results show that micropores in shales with type III kerogen are mainly formed in organic matter. However, mesopores and macropores are significantly affected by the contents of clay minerals and quartz. The methane isothermal capacity experimental results show that the Langmuir volume, indicating the maximum methane adsorption capacity, of all the shale samples is between 0.78 cm3/g and 9.26 cm3/g. Moreover, methane is mainly adsorbed in micropores and developed in organic matter, whereas the influence of mesopores and macropores on the methane adsorption capacity of shale with type III kerogen is small. At different stages, the influencing factors of methane adsorption capacity are different. When the TOC content is <1.4% or >4.5%, the methane adsorption capacity is positively correlated with the TOC content. When the TOC content is in the range of 1.4–4.5%, clay minerals have obviously positive effects on the methane adsorption capacity.


Geofluids ◽  
2021 ◽  
Vol 2021 ◽  
pp. 1-12
Author(s):  
Xianglu Tang ◽  
Wei Wu ◽  
Guanghai Zhong ◽  
Zhenxue Jiang ◽  
Shijie He ◽  
...  

Adsorbed gas is an important component of shale gas. The methane adsorption capacity of shale determines the composition of shale gas. In this study, the methane adsorption capacity of marine, transitional, and lacustrine shales in the Sichuan Basin was analyzed through its isothermal adsorption, mineral composition, water content, etc. The results show that the methane adsorption capacity of marine (Qiongzhusi Formation and Longmaxi Formation), transitional (Longtan Formation), and lacustrine (Xujiahe Formation and Ziliujing Formation) shales is significantly different. The Longtan Formation has the strongest methane adsorption capacity. This is primarily related to its high organic matter and organic matter type III content. The methane adsorption capacity of the lacustrine shale was the weakest. This is primarily related to the low thermal evolution degree and the high content of water-bearing clay minerals. Smectite has the highest methane adsorption capacity of the clay minerals, due to its crystal structure. The water content has a significant effect on methane adsorption largely because water molecules occupy the adsorption site. Additionally, the temperature and pressure in a specific range significantly affect methane adsorption capacity.


Author(s):  
Wen Liu ◽  
Qiuchen Xu ◽  
Haizhou Wang ◽  
Peng Liu ◽  
Ruiliang Guo ◽  
...  

AbstractQuantitative characterization of pore structure and analysis of influencing factors of methane adsorption are important segments in shale gas reservoir and resources evaluation and have not been systematically carried out in marine–continental shale series. A series of integrated methods, including total organic carbon (TOC) contents, Rock-Eval pyrolysis, mineral composition analysis, pore structure measurement, high-pressure CH4 adsorption analysis and FE-SEM observation, were conducted on 12 transitional shale samples of well WBC-1 in the southern North China Basin (SNCB). The results indicate that TOC contents of the transitional shales range from 1.03 to 8.06% with an average of 2.39%. The transitional shale consists chiefly of quartz, white mica and clay minerals. Interparticle pore, intraparticle pore, dissolution pore and microfracture were observed in the FE-SEM images. The specific surface area (SSA) of BET for the samples ranges from 3.3612 to 12.1217 m2/g (average: 6.9320 m2/g), whereas the DR SSA for the samples ranges from 12.9844 to 35.4267 m2/g (average: 19.67 m2/g). The Langmuir volume (VL) ranges from 2.05 to 4.75 cm3/g (average = 2.43 cm3/g). There is unobvious correction between BET and DR SSA with TOC contents, which means inorganic pores are the main component of pore space in the transitional shale from the SNCB. The relationship of SSA and pore volume shows that micropore has a greater impact on the CH4 adsorption capacity than mesopore–macropore in the transitional shale. Different from shales in other petroliferous basin, clay minerals are the primary factor affecting adsorption capacity of CH4 for transitional shale in this study. The pore structure of the transitional shale for this study is characterized by higher fractal dimension and more heterogeneous pore structure compared to shale in other petroliferous basin. This study provides an example and new revelation for the influencing factors of pore structure and methane adsorption capacity of marine–continental transitional shale.


Author(s):  
Shangbin Chen ◽  
Chu Zhang ◽  
Xueyuan Li ◽  
Yingkun Zhang ◽  
Xiaoqi Wang

AbstractIn shale reservoirs, the organic pores with various structures formed during the thermal evolution of organic matter are the main storage site for adsorbed methane. However, in the process of thermal evolution, the adsorption characteristics of methane in multi type and multi-scale organic matter pores have not been sufficiently studied. In this study, the molecular simulation method was used to study the adsorption characteristics of methane based on the geological conditions of Longmaxi Formation shale reservoir in Sichuan Basin, China. The results show that the characteristics of pore structure will affect the methane adsorption characteristics. The adsorption capacity of slit-pores for methane is much higher than that of cylindrical pores. The groove space inside the pore will change the density distribution of methane molecules in the pore, greatly improve the adsorption capacity of the pore, and increase the pressure sensitivity of the adsorption process. Although the variation of methane adsorption characteristics of different shapes is not consistent with pore size, all pores have the strongest methane adsorption capacity when the pore size is about 2 nm. In addition, the changes of temperature and pressure during the thermal evolution are also important factors to control the methane adsorption characteristics. The pore adsorption capacity first increases and then decreases with the increase of pressure, and increases with the increase of temperature. In the early stage of thermal evolution, pore adsorption capacity is strong and pressure sensitivity is weak; while in the late stage, it is on the contrary.


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 ◽  
Vol 9 ◽  
Author(s):  
Shouxu Pan ◽  
Ming Zha ◽  
Changhai Gao ◽  
Jiangxiu Qu ◽  
Xiujian Ding

In order to examine the pore structure and reveal the fractal geometric nature of shales, a series of laboratory experiments were conducted on lacustrine shale samples cored from the Kongdian Formation. Based on the low temperature nitrogen adsorption, fluorescent thin section and field emission scanning electronic microscope, a comprehensive pore structure classification and evaluation were conducted on shale samples. Fractal dimensions D1 and D2 (with relative pressure of 0–0.45 and 0.45–1.00, respectively) were obtained from the nitrogen adsorption data using the fractal Frenkel-Halsey-Hill (FHH) method. With additional means of X-ray diffraction analysis, total organic carbon content analysis and thermal maturity analysis, the relationships between pore structure parameters, fractal dimensions, TOC content and mineral composition are presented and discussed in this paper. The results show that interparticle pores and microfractures are predominant, whereas organic matter pores are rarely found. The pore morphology is primarily featured with wide-open ends and slit-shaped structures. In terms of pore scale, mesopores and macropores are predominant. The value of fractal dimension D1 representing small pores ranges from 2.0173 to 2.4642 with an average of 2.1735. The value of D2 which represents large pores ranges from 2.3616 to 2.5981 with an average of 2.4960. These low numbers are an indication of few pore types and relatively low heterogeneity. In addition, smaller D1 values reveal that large pores have more complicated spatial structures than smaller ones. The results of correlation analysis show that: 1) D2 is correlated positively with specific surface area but negatively with average pore diameter; 2) D1 and D2 literally show no obvious relationship with mineral composition, TOC content or vitrinite reflectance (Ro); 3) both total Barrett-Joyner-Halenda (BJH) volume and specific surface area show a positive relationship with dolomite content and a negative relationship with felsic minerals content. These results demonstrate that the pore types are relatively few and dominated by mesopores, and the content of brittle minerals such as dolomite and felsic minerals control the pore structure development whilst organic matter and clay minerals have less influence due to low thermal maturity and abundance of clay minerals.


2021 ◽  
Vol 43 (7) ◽  
pp. 537-546
Author(s):  
Heejong Son ◽  
Sangki Choi ◽  
Byungryul An ◽  
Hyejin Lee ◽  
Hoon-Sik Yoom

Objectives : The purpose of this study was to evaluate the effect of increasing the number of regeneration of granular activated carbon (GAC) on the adsorption capacity of natural organic matter (NOM), and to suggest the technical process options associated the limit number of regeneration and the efficient use of regenerated GAC.Methods : The physicochemical properties of virgin and thermally regenerated GAC were analyzed. To evaluate the NOM adsorption capacity of virgin- and regenerated-GAC, five laboratory-scale columns packed with virgin- and regenerated-GAC were used for treating effluent from pilot-scale drinking water treatment facility. The NOM concentration in the influent and the effluent treated by each column was analyzed by LC-OCD (liquid chromatography-organic carbon detector) to evaluate the adsorption capacity of each NOM fractions (humic substances (HS), building blocks (BB), low molecular weight organics (LMWs)).Results and Discussion : Due to the change in the pore structure of GAC by thermal regeneration, the volume of micropores (< 2 nm) decreased, while the volume of mesopores (> 2 nm) increased. The volume ratio of micropore in virgin-GAC was about 60%, but it gradually decreased as the number of regenerations increased, resulting that the volume ratio of micropore in the 5th-regenerated (5th-Re) GAC decreased to 23%. On the other hand, the volume ratio of mesopore increased in proportion to the number of regenerations from 40% of the virgin GAC to 77% of the 5th-Re-GAC. The DOC adsorption capacities of the regenerated GACs were higher than that of virgin GAC, and the DOC adsorption capacity increased as the number of regenerations increased. As a result of comparing the adsorption capacity of virgin- and regenerated-GAC by NOM fractions, the adsorption capacity of high molecular weight NOM, such as HS, increased by 1.5 to 1.7 times as the number of regenerations increased. In contrast, the adsorption capacity of low molecular weight NOM, such as BB and LMWs, decreased by 78% and 48% as the number of regeneration increased. The limit number of regeneration was evaluated based on that the adsorption capacity (qe) of each NOM fractions keep over than 70% relative to its virgin GAC. As a result, the adsorption capacity for low molecular weight NOM was greatly reduced in GAC regenerated over than 3rd time, so that the 2nd-Re-GAC was valid to keep 70% removal of whole NOM fractions. Low adsorption of low molecular weight NOM (BB and LMWs) by 3rd-Re-GAC could be complemented by using together with virgin-GAC, and low adsorption of high molecular NOMs (HS) could be compensated as well.Conclusions : Due to the change in the pore structure of GAC by thermal regeneration, the DOC adsorption capacity was higher in regenerated GAC than its virgin-GAC, and the adsorption capacity of DOC and high molecular weight NOM (HS) was enhanced as the number of regenerations increased. On the other hand, the pore volume of micropore was reduced by regenerations, and in more than 3rd times regenerations, the adsorption capacity of low molecular weight NOMs (BB and LMWs) was reduced by less than 70% compared to its virgin GAC, so that 2nd-Re-GAC was suggested for suitable GAC. When using a mixture of virgin- and 3rd-Re-GAC, low adsorption of low molecular weight NOM (BB and LMWs) by 3rd-Re-GAC could be complemented by using together with virgin-GAC, and low adsorption of high molecular NOMs (HS) could be compensated as well.


2019 ◽  
Vol 7 (4) ◽  
pp. T843-T856
Author(s):  
Xinghua Wang ◽  
Arash Dahi Taleghani ◽  
Wenlong Ding

Characteristics of shale pore structures may play an important role in natural gas accumulation and consequently estimating the original gas in place. To determine the pore structure characteristics of Niutitang marine shale in the Sangzhi block, we carried out [Formula: see text] adsorption-desorption (LP-[Formula: see text]GA), [Formula: see text] adsorption (LP-[Formula: see text]GA), and methane isothermal adsorption on shale samples to reveal the pore size distribution (PSD) and its impact on the adsorption capacity. Results indicate that the Niutitang Shale is in stages of maturity and overmaturity with good organic matter, and they also indicate well-developed interparticle, intraparticle, and organic pores. Quartz and clay are found to be the main minerals, and the high illite content means that the Niutitang Shale is experiencing the later stage of clay mineral transformation. Various-sized shale pores are well-developed, and most of them are narrow and slit-like. For pores with diameters of 2–300 nm measured with LP-[Formula: see text]GA, mesopores (2–50 nm) contribute most of the total specific surface area (SSA) and total pore volume (TPV) in comparison to macropores (50–300 nm). For micropores ([Formula: see text]) tested by LP-[Formula: see text]GA, the PSD appears to be multimodal; shale pores of 0.50–0.90 nm diameter contribute most of the SSA and TPV. [Formula: see text]-SSA and [Formula: see text]-SSA indicate positive correlations with their corresponding TPV. The total organic matter (TOC) has good correlation with the SSA and TPV of micropores. The Langmuir volume positively correlates with the total SSA. Additionally, the TOC content has a good correlation with the Langmuir volume, which is consistent with the observation of well-developed fossils of diatoms and organic pores. As an important source of organic matter, more diatoms mean more organic matter, larger TOC values and quartz content, larger SSA and TPV of micropores, and, of course, stronger shale adsorption capacity. The results provide important guidance for the exploration and development of shale gas existing in the Sangzhi block.


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