Multi-scale pore fractal characteristics of differently ranked coal and its impact on gas adsorption

Well-developed pores and cracks in coal reservoirs are the main venues for gas storage and migration.To investigate the multi-scale pore fractal characteristics,six coal samples of different rankings were studied using high-pressure mercury injection(HPMI),low-pressure nitrogen adsorption(LPGA-N2),and scanning electron microscopy(SEM)test methods.Based on the Frankel,Halsey and Hill(FHH)fractal theory,the Menger sponge model,Pores and Cracks Analysis System(PCAS),pore volume complexity(D_(v)),coal surface irregularity(Ds)and pore distribution heterogeneity(D_(p))were studied and evaluated,respectively.The effect of three fractal dimensions on the gas adsorption ability was also analyzed with high-pressure isothermal gas adsorption experiments.Results show that pore structures within these coal samples have obvious fractal characteristics.A noticeable segmentation effect appears in the Dv1and Dv2fitting process,with the boundary size ranging from 36.00 to 182.95 nm,which helps differentiate diffusion pores and seepage fractures.The D values show an asymmetric U-shaped trend as the coal metamorphism increases,demonstrating that coalification greatly affects the pore fractal dimensions.The three fractal dimensions can characterize the difference in coal microstructure and reflect their influence on gas adsorption ability.Langmuir volume(V_(L))has an evident and positive correlation with Dsvalues,whereas Langmuir pressure(P_(L))is mainly affected by the combined action of Dvand Dp.This study will provide valuable knowledge for the appraisal of coal seam gas reservoirs of differently ranked coals.

A Modified Peng-Robinson Equation State for Prediction of Gas Adsorption Isotherm

This research proposes a modified two-dimensional Peng-Robinson equation model to predict adsorption isotherm in adsorbate-adsorbent systems. The parameters of the proposed model are calculated by using the optimization of experimental data for the different single gas adsorption systems at various temperatures. The experimental adsorption equilibrium data of adsorbate-adsorbent systems was compared with the calculated results in our proposed model and the two-dimensional Hill-deBoer equation model. The proposed model as indicated in the results shows a better prediction of the experimental results compared with two others.

An improved theoretical procedure for the pore-size analysis of activated carbon by gas adsorption

Amorphous carbon materials play a vital role in adsorbed natural gas(ANG) storage. One of the key issues in the more prevalent use of ANG is the limited adsorption capacity, which is primarily determined by the porosity and surface characteristics of porous materials. To identify suitable adsorbents, we need a reliable computational tool for pore characterization and, subsequently, quantitative prediction of the adsorption behavior. Within the framework of adsorption integral equation(AIE), the pore-size distribution(PSD) is sensitive to the adopted theoretical models and numerical algorithms through isotherm fitting. In recent years, the classical density functional theory(DFT) has emerged as a common choice to describe adsorption isotherms for AIE kernel construction. However,rarely considered is the accuracy of the mean-field approximation(MFA) commonly used in commercial software. In this work, we calibrate four versions of DFT methods with grand canonical Monte Carlo(GCMC) molecular simulation for the adsorption of CH_4 and CO_2 gas in slit pores at 298 K with the pore width varying from 0.65 to 5.00 nm and pressure from 0.2 to 2.0 MPa. It is found that a weighted-density approximation proposed by Yu(WDA-Yu) is more accurate than MFA and other non-local DFT methods. In combination with the trapezoid discretization of AIE, the WDA-Yu method provides a faithful representation of experimental data, with the accuracy and stability improved by 90.0% and 91.2%, respectively, in comparison with the corresponding results from MFA for fitting CO_2 isotherms. In particular, those distributions in the feature pore width range(FPWR)are proved more representative for the pore-size analysis. The new theoretical procedure for pore characterization has also been tested with the methane adsorption capacity in seven activated carbon samples.

Synthesis, Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4？-DPA)]·(DMF)}_n

The reaction of Cd（NO_3）_2·4H_2O with 4,4？-dipyridylacetylene（4,4？-DPA） and 2-nitroterephthalic acid（2-NO_2-H_2BDC） in DMF/H_2O mixed solvent has afforded a compound {[Cd（2-NO_2-BDC）（4,4？-DPA）]·（DMF）}_n（1）. Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488（3）, b = 14.6689（3）, c = 13.1615（3） ？, β = 111.809（3）o, V = 2177.63（9） ？~3, Z = 4, C_（23）H_（18）N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^（-1）, F（000） = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s（I）. In compound 1, the Cd（Ⅱ） ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2（COO）_2 units, which are further connected by the 4,4？-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.

Gas adsorption in shaped zeolitic imidazolate framework-8

Zeolitic imidazolate framework-8(ZIF-8) was prepared through a solve-thermal reaction method and then shaped using different additives. The in fluence of the shaping conditions on the microstructure of the shaped samples was characterized by the XRD, BET, and SEM techniques. The results demonstrate that the compressive strength of the various shaped tablets is greatly increased and capable of meeting the industrial requirements compared to the unshaped ZIF-8 and that the loss rate of speci fic surface areas was maintained at 10% after the addition of 10%(by mass) binder and 10%(by mass) solvent. The adsorption isotherms of CO2, CH4, C3H8, and C3H6 on powdery ZIF-8and the shaped tablets(T-shaped ZIF-8, C-shaped ZIF-8, and N-shaped ZIF-8) were determined through volumetric measurements under different pressures and temperatures(298.2, 323.2, and 348.2 K). The adsorption capacities of the gases on both the ZIF-8 powder and the shaped tablets follow the order C3H6 N C3H8N CO2 N CH4. Furthermore,the results show that the adsorption capacities of the gases on the shaped tablets are lower by approximately 10%–20% than those on the powdery ZIF-8. In fact, the adsorption equilibrium isotherms for CO2, CH4, C3H8, and C3H6 on both powdery and shaped ZIF-8 can be well described by the Langmuir equation.

Synthesis,gas adsorption and reliable pore size estimation of zeolitic imidazolate framework-7 using CO_2 and water adsorption

Reliable estimation of the pore size distribution(PSD) in porous materials such as metal–organic frameworks(MOFs) and zeolitic imidazolate frameworks(ZIFs) is crucial for accurately assessing adsorption capacity and corresponding selectivity. In this study, the so-called zeolitic imidazolate framework-7(ZIF-7) is successfully synthesized via relatively fast and convenient microwave technique. The morphology and structure of the obtained MOF were characterized by XRD, SEM and N_2 and CO_2adsorption/desorption isotherms at 77 K and0 °C respectively. Then, to determine the PSD of the fabricated MOF, carbon dioxide isotherms are experimentally measured at various temperatures up to atmospheric pressure. Afterward, the experimental CO_2 isotherms data are utilized in two recently proposed in-house algorithms of SHN1 and SHN2 to extract the true PSD of manufactured ZIF-7. The obtained results revealed that median pore diameter of the fabricated ZIF-7 is estimated around 0.404 nm and 0.370 nm by using CO_2 isotherms at 273 K and 298 K respectively. These values are in good agreement with the real pore diameter of 0.42 nm. Moreover, experimental data of water adsorption isotherms over four different MOFs, borrowed from literature, are employed to illustrate further effectiveness of the above algorithms on successful determination of the corresponding pore size distributions. All predicted PSDs are proved to be in good agreement with those obtained from independent methods such as topology and morphology studies.

EFFECT OF YELLOW LOESS ON ODOROUS GAS ADSORPTION AND ECOTOXICITY TEST USING DAPHNIA MAGNA

To minimize damage caused by harmful substances released from artificial construc-tion materials,there has been increasing interest in eco-friendly houses constructed with natural materials.Among natural materials,yellow loess is South Korea’s most representative eco-friendly construction material,with high purification performance for indoor use.However,there has been no objective assessment of yellow loess’s performance at purifying indoor air.In this study,internal pores were found in yellow loess that were of a lamellar crystal structure consisting of bonds of silica and alumina plates,and there was a high negative charge on the loess surface;these might have contributed to the excellent performance of yellow loess in adsorbing odorous gas.There was also an exposure test using Daphnia magna to determine the eco-friendliness of yellow loess compared with that of cement mortar.Results showed the survival of Daphnia magna was longer in the indoor environment of a test chamber with higher concentration of ammonia wherein yellow loess was placed.EC50(median effective concentration,the concentration that caused death of 50%of bio-specimens)value of 19 ml of ammonia(0.1%solution),which was three times more than EC50 value of 6 ml of ammonia of the same area of cement mortar.

Real-time pore structure evolution difference between deep and shallow coal during gas adsorption:A study based on synchrotron radiation small-angle X-ray scattering

Coal seam CO_(2) sequestration is an important option to address global warming.A better knowledge on coal pore structure evolution during gas adsorption can provide guidance for coal seams CO_(2) seques-tration.However,few investigations on the pore structure evolution differences between the deep and shallow coal were conducted during gas adsorption.In this study,based on the real-time synchrotron radiation small-angle X-ray scattering(SAXS)observation,the average pore diameter and pore surface fractal dimension evolution differences between deep and shallow coal were investigated from the as-pects of coal compositions and stress history.Two types of coal deformation(inner-swelling and outer-swelling)coexist during gas adsorption.Coal compositions have significant impact on the dominance of deformation type.The dominance of inner-swelling in deep coal is induced by the higher ash contents,and there is the decrease of average pore diameter during gas adsorption.The impact of stress-history(burial depth)on adsorption-induced deformation is more prominent than that of gas adsorption ca-pacity.In deep coal,the surface fractal dimension evolution presents a negative correlation with the evolution of pore diameters.In shallow coal,the surface fractal dimension evolution presents a Langmuir-type correlation with the adsorption time.

Massive Preparation of Coumarone-indene Resin-based Hyper-crosslinked Polymers for Gas Adsorption

Hyper-crosslinked polymers （HCPs） are promising materials for gas capture and storage because of their low cost and easy preparation. In this work, we report the massive preparation of coumarone-indene resin-based hyper-crosslinked polymers via one-step Friedel-Crafts alkylation. Low-cost coumarone-indene resin serves as the new building block and chloroform is employed as both solvent and external crosslinker. A maximum surface area of 966 m2·g-1 is achieved, which is comparable with that of previously-reported coal tar-based porous organic polymers. Most importantly, a large number of heteroatoms including inherent oxygen atoms and introduced chlorine atoms in obtianed HCPs further enhance the interaction between specific sorbate molecule and adsorbent. Therefore, optimal structural and chemical property endow the new coumarone-indene resin-based HCPs with decent gas storage capacity （14.60 wt% at 273 K and 0.1 MPa for CO2; 1.18 wt% at 77.3 K and 0.1 MPa for H2）. These results demonstrate that new HCPs are potential candidates for applications in CO2 and H2 capture.

Tetra-armed conjugated microporous polymers for gas adsorption and photocatalytic hydrogen evolution

Two novel tetra-armed conjugated microporous polymers with different geometries have been designed and synthesized via Suzuki-Miyaura cross coupling polycondensation. Both polymers are stable in various organic solvents tested and are thermally stable. The pyrene-containing polymer of PrPy with the rigid pyrene unit shows a higher Brunauer-Emmet-Teller specific surface area of 1219m2g-1 than the tetraphenylethylene-containing polymer of PrTPE （770m2g 1）, which leads to a high CO2 uptake ability of 3.89mmolg I at 1.13bar/273K and a H2 uptake ability of 1.69wt% at 1.13bar/77K. The photocatalytic hydrogen production experiments revealed that PrPy also shows a better photocatalytic performance than PrTPE due to the higher conjugation degree and planar structure, the broader UV-visible （UV-Vis） absorption, the lower photoluminescence lifetime, and the higher specific surface area.

A Novel Co(Ⅱ)-organic Framework with Multiple Active Sites for Selective Gas Adsorption

A novel metal-organic framework[Co(BTTA)(H_(2)O)_(2)]_(n)(FJI-H_(2)4)has been prepared from H_(2)BTTA ligand and CoCl_(2),and its structure was determined by single-crystal X-ray diffraction,thermogravimetric analysis,and Fourier transform infrared spectroscopy.It has relatively narrow pores and high density of open metal ions and free Lewis base sites.Gas adsorption tests demonstrate that FJI-H_(2)4 has moderate CO_(2)(34.0 cm^(3)·g^(–1))and C_(2)H_(2)(53.0 cm^(3)·g^(–1))adsorption capacity,but displays high selectivity of CO_(2)/N_(2)(87)and C_(2)H_(2)/CH_(4)(66)under ambient conditions(298 K,1 atm),which may be attributed to its relatively narrow pores and polar environment.This work will provide a potential strategy for preparing practical porous metal-organic frameworks for gas adsorption and purification.

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.

Achieving a stable COF with the combination of“flat”and“twist”large-size rigid synthons for selective gas adsorption and separation

A new type of covalent organic framework(COF)was achieved using combination of structrally rigid and conformationally othorganal building blocks.The N-2-aryl-substituted triazole derivative(NAT-CHO)was prepared with co-planar conformation among the three aromatic rings as the“flat”building block.The 4,4,4,4-(ethene-1,1,2,2-tetrayl)tetraaniline)(ETTA)was applied as the“twist”building block.A 2 D sheet of network was obtained through imine formation.The resulting NAT-COF gave excellent thermal and chemical stability,survived aqueous solutions from p H 5 to 13.With large-size building blocks,the porous framework NAT-COF gave efficient gas adsorption with excellent selectivity of C3 propane over C1 me-thane,suggesting its potential application for selective gas capture and separation.

Effect of Fluorination on the Crystal Structure,Stability and Gas Adsorption Property in Zinc (Ⅱ) Metal-organic Frameworks

Three zinc(Ⅱ) metal-organic frameworks (x F-MAC-3) have been synthesized by using Zn(Ⅱ) salts,3,5-dimethyl-1H-1,2,4-triazole (Hdmtrz) and different fluorination degree carboxylate ligands,which are analogic structures and can be described as (6,6)-connected pcu-b net.We find that the fluorine atoms have structural regulation effect on x F-MAC-3,which can not only enlarge the torsion angle φ of carboxylate ligands but also elevate the space group of structures.Besides,the CO_(2)-273 K uptake increased from 23.21 cm^(3)·g^(-1) (MAC-3) to36.13 cm^(3)·g^(-1) (4F-MAC-3) and H_(2)-77 K uptake increased from 24.33 cm^(3)·g^(-1) (MAC-3) to 59.79 cm^(3)·g^(-1)(4F-MAC-3),which means fluorination can enhance the gas adsorption uptake of x F-MAC-3 analogues.Furthermore,the results of fluorination in x F-MAC-3 analogues offer a potential way to study the ligand pre-functionalization effect on the structures and properties of MOFs analogues.

Determination of gas adsorption capacity in organic-rich marine shale: a case study of Wufeng-Lower Longmaxi Shale in the southeast Sichuan Basin

Determination of gas adsorption capacity under geological conditions is essential in evaluating shale gas resource potential.A quantitative determination of gas adsorption capacity was proposed through 1)investigating controlling geological factors(including both internal ones and external ones)of gas adsorption capacity in organic-rich marine shale with geochemical analysis,XRD diffraction,field-emission scanning electron microscopy,and methane sorption isotherms;2)defining the relationship between gas adsorption capacity and single controlling factor;3)establishing a comprehensive determination model with the consideration of all these controlling factors.The primary controlling factors of the sorption capacity for the studied O3wLower S1l shale are TOC,illite and quartz,temperature,pressure,Ro,and moisture(water saturation).Specifically,TOC,thermal maturity,illite,and pressure are positively correlated with sorption capacity,whereas,quartz and temperature contribute negatively to the sorption capacity.We present the quantitative model along with application examples from the Wufeng-Lower Longmaxi Shale in the southeast Sichuan Basin,west China,to demonstrate the approach in shale gas evaluation.The result shows that the comprehensive determination model provides a good and unbiased estimate of gas adsorption capacities with a high correlation coefficient(0.96)and bell-shaped residues centered at zero.

Porous Organic Frameworks-derived Porous Carbons with Outstanding Gas Adsorption Performance

A series of porous carbon materials was synthesized via high temperature pyrolysis from well-defined and thermally stable precursors, namely porous organic frameworks（POFs）, in inert atmosphere. The porous carbon materials showed enhanced gas adsorption capacities together with increased heat of adsorption and stronger affinity between the frameworks and the gases as compared to the precursor materials. To exemplify, sample C-POF-TBBP-1000 with a high BET surface area of 1290 m^2/g can adsorb 2.8 mmol/g CH4（273 K, 101.325 kPa）, 5.4 mmol/g CO2（273 K, 101.325 kPa） and 2.2% H2（mass fraction, 77 K, 101.325 kPa）, thereby surpassing most other porous adsorbent materials reported till date. The study highlights the potential of porous carbons derived from novel porous organic framework structures for gas adsorption applications.

Numerical simulation of influence of Langmuir adsorption constant on gas drainage radius of drilling in coal seam

To determine reasonable distance of gas pre-drainage drillings in coal seams, a solid–gas coupling model that takes gas adsorption effect into account was constructed. In view of different adsorption constants,the paper conducted the numerical simulation of pre-drainage gas in drillings along coal seam, studied the relationship of adsorption constants and permeability, gas pressure, and effective drainage radius of coal seams, and applied the approach to the layout of pre-drainage gas drillings in coal seams. The results show that the permeability of coal seams is on the gradual increase with time, which is divided into three sections according to the increase rate: the drainage time 0–30 d is the sharp increase section;30–220 d is the gradual increase section; and the time above 200 d is the stable section. The permeability of coal seams is in negative linear and positive exponent relation with volume adsorption constant VLand pressure adsorption constant PL, respectively. The effective drainage radius is in negative linear relation with VLand in positive exponent relation with PL. Compared with the former design scheme, the engineering quantity of drilling could be reduced by 25%.

Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach

To characterize the pore features of outburst coal samples and investigate whether outburst coal has some unique features or not, one of the authors, working as the member of the State Coal Mine Safety Committee of China, sampled nine outburst coal samples(coal powder and block) from outburst disaster sites in underground coal mines in China, and then analyzed the pore and surface features of these samples using low temperature nitrogen adsorption tests. Test data show that outburst powder and block coal samples have similar properties in both pore size distribution and surface area. With increasing coal rank, the proportion of micropores increases, which results in a higher surface area. The Jiulishan samples are rich in micropores, and other tested samples contain mainly mesopores, macropores and fewer micropores. Both the unclosed hysteresis loop and force closed desorption phenomena are observed in all tested samples. The former can be attributed to the instability of the meniscus condensation in pores,interconnected pore features of coal and the potential existence of ink-bottle pores, and the latter can be attributed to the non-rigid structure of coal and the gas affinity of coal.

Molecular Simulations of FCC Dry Gas Components Adsorption in Zeolite Y

Adsorption of FCC dry gas components, hydrogen(H_2), nitrogen(N_2), methane(CH_4), ethane(C_2H_6) and ethylene(C_2H_4) in zeolite Y was studied by performing the Grant Canonical Monte Carlo(GCMC) simulations at 298K and 823K and under a pressure range up to 10 MPa. Simulation results were analyzed using the Langmuir model, which presented fitting of dry gas components adsorption to be suggested as the monolayer adsorption. C_2H_4 presented most single adsorption amount, which reached 7.63 mol/kg at 298K under a pressure of 200kPa. Thermodynamic parameters of the Gibbs free energy change, enthalpy change and entropy change were analyzed based on adsorption equilibrium constant obtained from the GCMC simulations. The results suggested that it was more favorable for C_2H_4 to be adsorbed in zeolite Y. Adsorption molecules were in ordered arrangement in the zeolite, and C_2H_4 exhibited a more orderly arrangement than other components. Additionally, a competition in the adsorption of a mixture of dry gas components was found, and supercages were the priority adsorption space. The competition was favorable to CH_4 and C_2H_6, and the competitive power was affected by temperature.

Adsorption Regularity and Characteristics of sp^3-Hybridized Gas Molecules on Anatase TiO_2(101) Surface

We report the anatase titanium dioxide （101） surface adsorption of sp3-hybridized gas molecules, including NH3, 1-12 0 and CH4, using first-principles plane-wave ultrasoft pseudopotential based on the density functional theory. The results show that it is much easier for a surface with oxygen vacancies to adsorb gas molecules than it is for a surface without oxygen vacancies. The main factor affecting adsorption stability and energy is the polarizability of molecules, and adsorption is induced by surface oxygen vacancies of the negatively charged center. The analyses of state densities and charge population show that charge transfer occurs at the molecule surface upon adsorption and that the number of transferred charge reduces in the order of N, 0 and C. Moreover, the adsorption method is chemical adsorption, and adsorption stability decreases in the order of NH3, tt2 0 and CH4. Analyses of absorption and reflectance spectra reveal that after absorbed CH4 and H2 O, compared with the surface with oxygen vacancy, the optical properties of materials surface, including its absorption coefficients and reflectivity index, have slight changes, however, absorption coefficient and reflectivity would greatly increase after NH3 adsorption. These findings illustrate that anatase titanium dioxide （101） surface is extremely sensitive to NH3.