Component fractionation of temporal evolution in adsorption-desorption for binary gas mixtures on coals from Haishiwan Coal Mine

Adsorption-desorption experiments on CO2-CH4 gas mixtures with varying compositions have been conducted to study the fractionation characteristics of CO2-CH4 on Haishiwan coal samples. These were carried out at constant temperature but different equilibrium pressure conditions. Based on these experimental results, the temporal evolution of component fractionation in the field was investigated. The results show that the CO2 concentration in the adsorbed phase is always greater than that in the original gas mixture during the desorption process, while CH4 shows the opposite characteristics. This has confirmed that CO2 , with a greater adsorption ability has a predominant position in the competition with CH4 under different pressures. Where gas drainage is employed, the ratio of CO2 to CH4 varies with time and space in floor roadways used for gas drainage, and in the ventilation air in Nos.1 and 2 coal seams, which is consistent with laboratory results.

Desorption of Cl^(-) from Mg-Al layered double hydroxide intercalated with Cl^(-) using CO_(2) gas and water

Mg-Al layered double hydroxide intercalated with CO_(3)^(2-)(CO_(3)·Mg-Al LDH) is effective for treating HCl exhaust gas.HCl reacts with CO_(3)^(2-) in CO_(3)·Mg-Al LDH, resulting in the formation of Cl·Mg-Al LDH.We propose that CO_(2) can be used for the desorption of Cl^(-)from Cl·Mg-Al LDH to regenerate CO_(3)·Mg-Al LDH.Herein,we studied the desorption of a from CI-Mg-Al LDH by adding water to Cl·Mg-Al LDH and blowing CO_(2) into it.We also analyzed the effects of temperature and water addition speed on the desorption of CI^(-)from Cl·Mg-Al LDH.Our results show that the added water adhered to CI·Mg-Al LDH and that CO_(2) in the gaseous phase was dissolved in this adhered water,thus generating CO_(3)^(2-).Therefore,anion exchange occurred between CO_(3)^(2-) and Cl^(-)in the Cl·Mg-Al LDH,thus desorbing Cl^(-).

Research advances in enhanced coal seam gas extraction by controllable shock wave fracturing

With the continuous increase of mining in depth,the gas extraction faces the challenges of low permeability,great ground stress,high temperature and large gas pressure in coal seam.The controllable shock wave(CSW),as a new method for enhancing permeability of coal seam to improve gas extraction,features in the advantages of high efficiency,eco-friendly,and low cost.In order to better utilize the CSW into gas extraction in coal mine,the mechanism and feasibility of CSW enhanced extraction need to be studied.In this paper,the basic principles,the experimental tests,the mathematical models,and the on-site tests of CSW fracturing coal seams are reviewed,thereby its future research directions are provided.Based on the different media between electrodes,the CSW can be divided into three categories:hydraulic effect,wire explosion and excitation of energetic materials by detonating wire.During the process of propagation and attenuation of the high-energy shock wave in coal,the shock wave and bubble pulsation work together to produce an enhanced permeability effect on the coal seam.The stronger the strength of the CSW is,the more cracks created in the coal is,and the greater the length,width and area of the cracks being.The repeated shock on the coal seam is conducive to the formation of complex network fracture system as well as the reduction of coal seam strength,but excessive shock frequency will also damage the coal structure,resulting in the limited effect of the enhanced gas extraction.Under the influence of ground stress,the crack propagation in coal seam will be restrained.The difference of horizontal principal stress has a significant impact on the shape,propagation direction and connectivity of the CSW induced cracks.The permeability enhancement effect of CSW is affected by the breakage degree of coal seam.The shock wave is absorbed by the broken coal,which may hinder the propagation of CSW,resulting in a poor effect of permeability enhancement.When arranging two adjacent boreholes for CSW permeability enhancement test,the spacing of boreholes should not be too close,which may lead to negative pressure mutual pulling in the early stage of drainage.At present,the accurate method for effectively predicting the CSW permeability enhanced range should be further investigated.

Method for rapid on-site identification of VOCs

Rapid on-site identification of volatile organic compounds （VOCs） in ambient air is an important first step in remediation efforts. This study describes modification of a commercially available, portable GC/MS system and development of an analysis protocol for rapid （〈 3 min） sampling and identification of VOCs typically found at contaminated sites at the low ppbv level.

Time-dependent categorization of volatile aroma compound formation in stewed Chinese spicy beef using electron nose profile coupled with thermal desorption GC–MS detection

In the present study,flavor profiles of Chinese spiced beef in the cooking process were comparatively analyzed by electronic nose,gas chromatography–mass spectrometry(GC–MS)with a thermal desorption system(TDS),and solid-phase microextraction(SPME).A total of 82 volatile compounds were identified,and 3-methyl-butanal,pentanal,hexanal,-xylene,heptanal,limonene,terpinene,octanal,linalool,4-terpinenol,-terpineol,and(E)-anethole were identified as the characteristic flavor compounds in Chinese spiced beef.Variation in the content of volatile components produced by different cooking processes was observed.In general,a cooking time of 4 h resulted in optimal flavor quality and stability.Results indicated that the electronic nose could profile and rapidly distinguish variation among different cooking time.The volatile profiling by TDS-GC–MS and responses from the electronic nose,in combination with multivariate statistical analysis,are a promising tool for control the cooking process of spiced beef.

Rapid decompression and desorption induced energetic failure in coal

In this study, laboratory experiments are conducted to investigate the rapid decompression and desorption induced energetic failure in coal using a shock tube apparatus. Coal specimens are recovered from Colorado at a depth of 610 m. The coal specimens are saturated with the strong sorbing gas CO2 for a certain period and then the rupture disc is suddenly broken on top of the shock tube to generate a shock wave propagating upwards and a rarefaction wave propagating downwards through the specimen.This rapid decompression and desorption has the potential to cause energetic fragmentation in coal.Three types of behaviors in coal after rapid decompression are found, i.e. degassing without fragmentation, horizontal fragmentation, and vertical fragmentation. We speculate that the characteristics of fracture network（e.g. aperture, spacing, orientation and stiffness） and gas desorption play a role in this dynamic event as coal can be considered as a dual porosity, dual permeability, dual stiffness sorbing medium. This study has important implications in understanding energetic failure process in underground coal mines such as coal gas outbursts.

Impact of clay stabilizer on the methane desorption kinetics and isotherms of Longmaxi Shale,China

Knowing methane desorption characteristics is essential to define the contribution of adsorbed gas to gas well production.To evaluate the synthetic effect of a clay stabilizer solution on methane desorption kinetics and isotherms pertaining to Longmaxi shale,an experimental setup was designed based on the volumetric method.The objective was to conduct experiments on methane adsorption and desorption kinetics and isotherms before and after clay stabilizer treatments.The experimental data were a good fit for both the intraparticle diffusion model and the Freundlich isotherm model.We analyzed the effect of the clay stabilizer on desorption kinetics and isotherms.Results show that clay stabilizer can obviously improve the diffusion rate constant and reduce the methane adsorption amount.Moreover,we analyzed the desorption efficiency before and after treatment as well as the adsorbed methane content.The results show that a higher desorption efficiency after treatment can be observed when the pressure is higher than 6.84 MPa.Meanwhile,the adsorbed methane content before and after treatment all increase when the pressure decreases,and clay stabilizer can obviously promote the adsorbed methane to free gas when the pressure is lower than 19 MPa.This can also be applied to the optimization formulation of slickwater and the design of gas well production.

Research on Reliability of Desorption Indexes of Drilling Cuttings(K_(1)andΔh_(2)):A Case-Based on Pingdingshan Mining Region,China

To accurately predict the risk of coal and gas outburst and evaluate the reliability of desorption indexes of drilling cuttings(K_(1) andΔh_(2))in No.16 coal seam of Pingmei No.12 coal mine,two sets of coal samples were selected from the target coal seams for proximate analyses,methane adsorption/desorption tests,and desorption indexes of drilling cuttings tests.The results indicated that the desorption volume in the initial stage of desorption is large,and increases slowly in the later stage.The methane desorption volume of PMD1 and PMD2 coal samples accounts for 15.14%-18.09%and 15.72%-18.17%respectively in the first 1 min,and 43.92%-48.55%and 41.87%-52.25%respectively in the first 10 min in the 120 min desorption tests.Both K_(1) andΔh_(2) present power function relationships with methane pressure.Similarly,the power function relationships also can be found between the initial desorption characteristics(Q1 and Q4-5)and the methane pressure.Finally,the average relative error between the measured value and the calculated value of Q1 based on K_(1) is less than that of Q4-5 based onΔh_(2),which indicates that K_(1) is a more reliable index thanΔh_(2) to predict the risk of coal and gas outburst in the No.16 coal seam of Pingmei No.12 coal mine.

Isothermal Adsorption and Desorption Properties of Marine Shales on Longmaxi Shale in South China

The investigation of adsorption and desorption properties of shale are important for estimating reserves and exploitation. The shale samples used in this paper were from the marine shale on Longmaxi shale in Sichuan and Hubei province, China. A series of analyses, such as organic carbon content test, vitrinite reflectance test, rock pyrolysis, X-ray diffraction, and N2/CO2 adsorption were performed. Gravimetric method with magnetic suspension balance was used to conduct isothermal adsorption and desorption experiments. The Langmuir, Freundlich, Langmuir-Freundlich, D-R, semi-pore, and Tothequations were used to fit the isothermal adsorption and desorption curves. And adsorption potential theory was used to explain the adsorption and desorption process. According to the results, the shale samples have a high level of organic carbon content with the same organic matter type II1 and high degree of maturation. The volume of adsorption increases rapidly and slows down to stable with the pressure increasing. Desorption is the inverse process of adsorption and 10 MPa - 0.5 MPa is the main period of shale gas desorption. The fitting results show that three-parameter isotherm equations are better than the two-parameter ones. The adsorption temperature has a great influence on adsorption volume, little effect on potential energy. Adsorption potential varies under different TOC to affect adsorption properties. Moreover, a large adsorption potential means that the gas molecule is easy to adsorb but difficult to desorb.

In-situ gas contents of a multi-section coal seam in Sydney basin for coal and gas outburst management

The gas content is crucial for evaluating coal and gas outburst potential in underground coal mining. This study focuses on investigating the in-situ coal seam gas content and gas sorption capacity in a representative coal seam with multiple sections (A1, A2, and A3) in the Sydney basin, where the CO_(2) composition exceeds 90%. The fast direct desorption method and associated devices were described in detail and employed to measure the in-situ gas components (Q_(1), Q_(2), and Q_(3)) of the coal seam. The results show that in-situ total gas content (Q_(T)) ranges from 9.48 m^(3)/t for the A2 section to 14.80 m^(3)/t for the A3 section, surpassing the Level 2 outburst threshold limit value, thereby necessitating gas drainage measures. Among the gas components, Q_(2) demonstrates the highest contribution to Q_(T), ranging between 55% and 70%. Furthermore, high-pressure isothermal gas sorption experiments were conducted on coal samples from each seam section to explore their gas sorption capacity. The Langmuir model accurately characterizes CO_(2) sorption behavior, with ft coefcients (R^(2)) greater than 0.99. Strong positive correlations are observed between in-situ gas content and Langmuir volume, as well as between residual gas content (Q_(3)) and sorption hysteresis. Notably, the A3 seam section is proved to have a higher outburst propensity due to its higher Q_(1) and Q_(2) gas contents, lower sorption hysteresis, and reduced coal toughness f value. The insights derived from the study can contribute to the development of efective gas management strategies and enhance the safety and efciency of coal mining operations.

Accumulation and exploration enlightenment of shallow normal-pressure shale gas in southeastern Sichuan Basin, SW China

Based on the drilling, logging, experimental and testing data of Well PD1, a shallow normal-pressure shale gas well in the Laochangping anticline in southeastern Sichuan Basin, the shallow shale gas reservoirs of the Ordovician Wufeng Formation to Silurian Longmaxi Formation (Wufeng-Longmaxi) were investigated in terms of geological characteristics, occurrence mechanism, and adsorption-desorption characteristics, to reveal the enrichment laws and high-yield mechanism of shallow normal-pressure shale gas in complex structure areas. First, the shallow shale gas reservoirs are similar to the medium-deep shale gas reservoirs in static indicators such as high-quality shale thickness, geochemistry, physical properties and mineral composition, but the former is geologically characterized by low formation pressure coefficient, low gas content, high proportion of adsorbed gas, low in-situ stress, and big difference between principal stresses. Second, shallow shales in the complex structure areas have the gas occurrence characteristics including low total gas content (1.1-4.8 m3/t), high adsorbed gas content (2.5-2.8 m3/t), low sensitive desorption pressure (1.7-2.5 MPa), and good self-sealing. Third, the adsorbed gas enrichment of shales is mainly controlled by organic matter abundance, formation temperature and formation pressure: the higher the organic matter abundance and formation pressure, the lower the formation temperature and the higher the adsorption capacity, which is more beneficial for the adsorbed gas occurrence. Fourth, the shallow normal-pressure shale gas corresponds to low sensitive desorption pressure. The adsorbed gas can be rapidly desorbed and recovered when the flowing pressure is reduced below the sensitive desorption pressure. Fifth, the exploration breakthrough of Well PD1 demonstrates that the shallow complex structure areas with adsorbed gas in dominance can form large-scale shale reservoirs, and confirms the good exploration potential of shallow normal-pressure shale gas in the margin of the Sichuan Basin.

A Quantitative Evaluation of Shale Gas Content in Different Occurrence States of the Longmaxi Formation: A New Insight from Well JY-A in the Fuling Shale Gas Field,Sichuan Basin

Comprehensive quantitative evaluation of shale gas content and the controlling factors in different occurrence states is of great significance for accurately assessing gas-bearing capacity and providing effective well-production strategies. A total of 122 core samples from well JY-A in the Fuling shale gas field were studied to reveal the characteristics of S_1 l shale,15 of which were selected to further predict the shale gas content in different occurrence states, which are dependent on geological factors in the thermal evolution process. Geological parameters were researched by a number of laboratory programs, and the factors influential in controlling shale gas content were extracted by both PCA and GRA methods and prediction models were confirmed by the BE method using SPSS software. Results reveal that the adsorbed gas content is mainly controlled by TOC, Ro, SSA, PD and pyrite content, and the free gas content is mainly controlled by S_2, quartz content, gas saturation and formation pressure for S_1 l in well JY-A. Three methods, including the on-site gas desorption method, the empirical formula method, and the multiple regression analysis method were used in combination to evaluate the shale gas capacity of well JY-A, all of which show that the overall shale gas content of well JY-A is in the range of 2.0–5.0 m^3/t and that the free gas ratio is about 50%, lower than that of well JY-1. Cause analysis further confirms the tectonics and preservation conditions of S_1 l in the geological processes, especially the influence of eastern boundary faults on well JY-A, as the fundamental reasons for the differences in shale gas enrichment in the Jiaoshiba area.

Discussion on determination of gas content of coal and uncertainties of measurement

Gas content of coal is mostly determined using a direct method, particularly in coal mining where mine safety is of paramount importance. Direct method consists of measuring directly the volume of gas desorbed from coal in several steps, from solid then crushed coal. In mixed gas conditions the composition of the desorbed gas is also measured to account for contribution of various coal seam gas in the mix. The determination of gas content using the direct method is associated with errors of measurement of volume of gas but also the errors associated with measurement of composition of the desorbed gas. These errors lead to uncertainties in reporting the gas content and composition of in-situ seam gas. This paper discusses the current direct method practised in Australia and potential errors and uncertainty associated with this method. Generic methods of estimate of uncertainties are also developed and are to be included in reporting gas content of coal. A method of direct measurement of remaining gas in coal following the completion of standard gas content testing is also presented. The new method would allow the determination of volume of almost all gas in coal and therefore the value of total gas content. This method is being considered to be integrated into a new standard for gas content testing.

A rapid and accurate direct measurement method of underground coal seam gas content based on dynamic diffusion theory

Coal seam gas content is frequently measured in quantity during underground coal mining operation and coalbed methane(CBM)exploration as a significant basic parameter.Due to the calculation error of lost gas and residual gas in the direct method,the efficiency and accuracy of the current methods are not inadequate to the large area multi-point measurement of coal seam gas content.This paper firstly deduces a simplified theoretical dynamic model for calculating lost gas based on gas dynamic diffusion theory.Secondly,the effects of various factors on gas dynamic diffusion from coal particle are experimentally studied.And sampling procedure of representative coal particle is improved.Thirdly,a new estimation method of residual gas content based on excess adsorption and competitive adsorption theory is proposed.The results showed that the maximum error of calculating the losing gas content by using the new simplified model is only 4%.Considering the influence of particle size on gas diffusion law,the particle size of the collected coal sample is below 0.25 mm,which improves the measurement speed and reflects the safety representativeness of the sample.The determination time of gas content reduced from 36 to 3 h/piece.Moreover,the absolute error is 0.15–0.50 m^3/t,and the relative error is within 5%.A new engineering method for determining the coal seam gas content is developed according to the above research.

Investigation of shale gas microflow with the Lattice Boltzmann method

In contrast to conventional gas-bearing rocks, gas shale has extremely low permeability due to its nano- scale pore networks. Organic matter which is dispersed in the shale matrix makes gas flow characteristics more complex. The traditional Darcy＇s law is unable to estimate matrix permeability due to the particular flow mechanisms of shale gas. Transport mechanisms and influence factors are studied to describe gas transport in extremely tight shale. Then Lattice Boltzmann simulation is used to establish a way to estimate the matrix permeability numerically. The results show that net desorption, diffu- sion, and slip flow are very sensitive to the pore scale. Pore pressure also plays an important role in mass fluxes of gas. Temperature variations only cause small changes in mass fluxes. The Lattice Boltzmann method can be used to study the flow field in the micropore spaces and then provides numerical solutions even in complex pore structure models. Understanding the transport characteristics and establishing a way to estimate potential gas flow is very important to guide shale gas t＇eserve estimation and recovery schemes.

Current research into the use of supercritical CO2 technology in shale gas exploitation

The use of supercritical CO2 for shale gas extraction is a promising new technology.This paper explores current research into this process,looking at analysis of the mechanism of CH4 displacement in nanoporous shale,the positive and negative effects accompanying its use for sequestration as well as organic extraction,the migration of elements and the swelling process,and the macro and micro control mechanisms involved in permeability enhancement in reservoirs.Fruitful directions for future research are also considered through comparison with hydraulic fracturing.The research findings indicate that ScCO2 fluid replacement can be used to increase gas production and seal up greenhouse gases as an effective,clean and safe method of shale gas exploitation.It is particularly effective for promoting the desorption of CH4 in shale reservoirs that have developed fine neck-wide body pores,and the subtle structural changes effected by ScCO2 fluid in sensitive minerals in reservoirs with a high brittle mineral content also have a positive effect on permeability and storage capacity.The adsorption process has been characterized as consisting of three stages:short-term shrinkage,slow swelling,and stability;an expansion equation has been proposed for CO2/CH4 that incorporates competitive adsorption,collision desorption,and impingement re-adsorption.ScCO2 fracturing has been found to be more effective than hydraulic fracturing for dense reservoirs and more effective at linking up pore-micro-fissure-fracture systems.

Undesorbable residual gas in coal seams and its influence on gas drainage

The definition of ‘‘residual gas" can be found in different scenarios, such as the ‘‘fast" and ‘‘slow" desorption methods of measuring gas content and the sorption hysteresis test and gas management of coal mines, however, its meaning varies a lot in different contexts. The main aim of this paper is to discuss the existence of truly undesorbable residual gas in coal seam conditions and its impacts on sorption model and gas drainage efficiency. We believe the undesorbable residual gas does exist due to the observation of the extended slow desorption test and the sorption hysteresis test. The origin of undesorbable residual gas may be because of the inaccessible(closed or semi-closed) pores. Some gas molecules produced during coalification are stored in these inaccessible pores, since the coal is relatively intact in the coal seam condition, these gas molecules cannot escape during natural desorption and then create the undesorbable residual gas. Based on the existing adsorption models, we propose the improved desorption versions by taking into consideration the role of residual gas. By numerically simulating a gas drainage case, the gas contents after different drainage times are studied to understand the influence of residual gas content on gas drainage. The results indicate that the influence starts to be obvious even when the total gas content is at a high level, and the impact becomes more and more apparent with increasing drainage time. Our study shows that the existence of residual gas will impede the gas drainage and the total amount of recoverable coal seam methane may be less than expected.

Temperature influence on macro-mechanics parameter of intact coal sample containing original gas from Baijiao Coal Mine in China

Investigation of temperature effect on mechanical parameters of coal is very important for understanding the mechanical response of coal bed at high temperature.It is especially benefcial for mitigating the thermal-induced disasters occurred in those coal mines suffering from heat hazard.In this work,coal samples,obtained from the No.2442 working face of Baijiao Coal Mine,were subjected to uniaxial compression ranging from 20 to 40℃ with an interval of 5℃.The apparatus used was designed to obtain deformation of a stressed sample,as well as the emission of gases desorbing from coal matrix.The adsorbed gas desorption caused by heating is measured during the entire testing.It is evident that the concentrations of releasing gas(containing methane,carbon dioxide and ethane)slightly rise with increasing temperature.Gas movement observed is closely related to the deformation of coal sample.Both uniaxial compressive strength and elastic modulus of coal samples tend to reduce with temperature.It reveals that increasing temperature can not only result in thermal expansion of coal,but also lead to desorption of preexisting gas in coal which can in turns harden coal due to shrinks of the coal matrix.Even though desorption of adsorbed gas can contribute to the hardening effect for the heated coal,by comparison to the results,it could be inferred that the softening of coal resulted from thermal expansion still predominates changes in mechanical characters of coal sample with temperature at the range from20 to 40℃.

Research progress on isotopic fractionation in the process of shale gas/coalbed methane migration

The research progress of isotopic fractionation in the process of shale gas/coalbed methane migration has been reviewed from three aspects: characteristics and influencing factors, mechanism and quantitative characterization model, and geological application. It is found that the isotopic fractionation during the complete production of shale gas/coalbed methane shows a four-stage characteristic of “stable-lighter-heavier-lighter again”, which is related to the complex gas migration modes in the pores of shale/coal. The gas migration mechanisms in shale/coal include seepage, diffusion, and adsorption/desorption. Among them, seepage driven by pressure difference does not induce isotopic fractionation, while diffusion and adsorption/desorption lead to significant isotope fractionation. The existing characterization models of isotopic fractionation include diffusion fractionation model, diffusion-adsorption/desorption coupled model, and multi-scale and multi-mechanism coupled model. Results of model calculations show that the isotopic fractionation during natural gas migration is mainly controlled by pore structure, adsorption capacity, and initial/boundary conditions of the reservoir rock. So far, the isotope fractionation model has been successfully used to evaluate critical parameters, such as gas-in-place content and ratio of adsorbed/free gas in shale/coal etc. Furthermore, it has shown promising application potential in production status identification and decline trend prediction of gas well. Future research should focus on:(1) the co-evolution of carbon and hydrogen isotopes of different components during natural gas migration,(2) the characterization of isotopic fractionation during the whole process of gas generation-expulsion-migration-accumulation-dispersion, and(3) quantitative characterization of isotopic fractionation during natural gas migration in complex pore-fracture systems and its application.

Seepage Mechanism and Transient Pressure Analysis of Shale Gas

The current research of nonlinear seepage theory of shale-gas reservoir is still in its infancy. According to the characteristics of shale gas in adsorption-desorption, diffusion, slippage and seepage during accumulation, migration and production, a mathematical model of unstable seepage in dual-porosity sealed shale-gas reservoir was developed while considering Knudsen diffusion, slip-flow effect and Langmuir desorption effect. By solving the model utilizing the Stehfest numerical inversion and computer programming in Laplace space, several typical curves of bottomhole pressure were obtained. In this paper, we discussed the effects of several parameters on the pressure dynamics, i.e. storativity ratio, Langmuir volume, Langmuir pressure, adsorption-desorption, tangential momentum accommodation coefficient, flow coefficient, boundary. The results show that the desorbed gas extends the time for fluid to flow from matrix system to fracture system;the changes of Langmuir volume and Langmuir pressure associated with desorption and adsorption effect are the internal causes of the storativity ratio change;when the tangential momentum accommodation coefficient decreases, the time for pressure wave to spread to the border reduces;interporosity flow coefficient determines the occurrence time of the transition stage;boundary range restricts the time for pressure wave to spread to the border.