Geological characteristics and exploration breakthroughs of coal rock gas in Carboniferous Benxi Formation,Ordos Basin,NW China

To explore the geological characteristics and exploration potential of the Carboniferous Benxi Formation coal rock gas in the Ordos Basin,this paper presents a systematic research on the coal rock distribution,coal rock reservoirs,coal rock quality,and coal rock gas features,resources and enrichment.Coal rock gas is a high-quality resource distinct from coalbed methane,and it has unique features in terms of burial depth,gas source,reservoir,gas content,and carbon isotopic composition.The Benxi Formation coal rocks cover an area of 16×104km^(2),with thicknesses ranging from 2 m to 25 m,primarily consisting of bright and semi-bright coals with primitive structures and low volatile and ash contents,indicating a good coal quality.The medium-to-high rank coal rocks have the total organic carbon(TOC)content ranging from 33.49%to 86.11%,averaging75.16%.They have a high degree of thermal evolution(Roof 1.2%-2.8%),and a high gas-generating capacity.They also have high stable carbon isotopic values(δ13C1of-37.6‰to-16‰;δ13C2of-21.7‰to-14.3‰).Deep coal rocks develop matrix pores such as gas bubble pores,organic pores,and inorganic mineral pores,which,together with cleats and fractures,form good reservoir spaces.The coal rock reservoirs exhibit the porosity of 0.54%-10.67%(averaging 5.42%)and the permeability of(0.001-14.600)×10^(-3)μm^(2)(averaging 2.32×10^(-3)μm^(2)).Vertically,there are five types of coal rock gas accumulation and dissipation combinations,among which the coal rock-mudstone gas accumulation combination and the coal rock-limestone gas accumulation combination are the most important,with good sealing conditions and high peak values of total hydrocarbon in gas logging.A model of coal rock gas accumulation has been constructed,which includes widespread distribution of medium-to-high rank coal rocks continually generating gas,matrix pores and cleats/fractures in coal rocks acting as large-scale reservoir spaces,tight cap rocks providing sealing,source-reservoir integration,and five types of efficient enrichment patterns(lateral pinchout complex,lenses,low-amplitude structures,nose-like structures,and lithologically self-sealing).According to the geological characteristics of coal rock gas,the Benxi Formation is divided into 8 plays,and the estimated coal rock gas resources with a buried depth of more than 2000 m are more than 12.33×10^(12)m^(3).The above understandings guide the deployment of risk exploration.Two wells drilled accordingly obtained an industrial gas flow,driving the further deployment of exploratory and appraisal wells.Substantial breakthroughs have been achieved,with the possible reserves over a trillion cubic meters and the proved reserves over a hundred billion cubic meters,which is of great significance for the reserves increase and efficient development of natural gas in China.

New advances in coal structure model

Although human beings have come to understand and utilize coal for a very long history, no theoretical breakthrough in the study of coal structure has been made, which still needs continuous efforts of coal chemical workers. Based on the viewpoint of ‘vague/clear', the species classification and accurate analysis on coal were conducted by using the natural clustering all-component separation method. A more systematic and detailed coal embedded structure model theory which is suitable for coal of all ranks was developed from the previous one and a more complete theoretical system about the component and structure of coal was constructed. The whole establishment process of the theory was summarized and some of the main support data and analysis test results, including TEM, AFM, FTIR, GC/MS, MALDI/TOF/MS, DART/MSD, fractal analysis and so on were provided. The coal embedded structure theory fully considers both the identity and the particularity of all-rank coal, reflects the coal component and structure in the full range of coal rank, solves the systematic cognitive problem of coal component and structure on macro and micro level, and provides a valuable and meaningful theoretical approach for the coal processing and conversion technology.

The inner circulation mechanism in sinking column formation in North China coal field ——A case study in Fengfeng mining areas

Sinking columns are one of the most hazardous geological structures in north Chine typed coal fields. To understand the sinking column formation, to judge if the columns are hazardous or not, the inner circle mechanism of groundwater in forming sinking columns in the relatively isolated areas was proposed according to the investigation on formation or distribution of sinking columns in some north China typed coal fields, such as Fengfeng, Xiangtai, Huaibei, Yangquan and so on. The heat generated by magma energized groundwater circulation and developed limestone karst in the relatively isolated areas. The CaCO3 solution accelerated by geothermal abnormality, the effect of high content of CO2 on dissolution and saturation of CaCO3 were discussed. Compared the forming conditions of the sinking columns developed in other coal mining areas in north China coal field, the paper deduced that the above factors collude karst development and sinking column formation, the columns in current geothermal areas are permeable and those in high coal rank areas or in paleo abnormally geothermal areas. The paper suggested that the sinking columns in the current abnormally geothermal areas were permeable, but those in the areas with high coal rank were not on contract.

Effects of coal rank on physicochemical properties of coal and on methane adsorption

For the thorough research on coal metamorphism impact on gas adsorption capacity, this paper collected and summarized parameters of experimental adsorption isotherms, coal maceral, proximate analysis and ultimate analysis obtained from National Engineering Research Center of Coal Gas Control and related literatures at home and abroad, systematically discussed the coal rank effect on its physicochemical properties and methane adsorption capacity, in which the coal rank was shown in Vitrinite reflectance, furthermore, obtained the Semi-quantitative relationship between physicochemical properties of coal and methane adsorption capacity.

Effects of Coal Rank and High Organic Sulfur on the Structure and Optical Properties of Coal-based Graphene Quantum Dots

Coal-based graphene quantum dots(GQDs) were successfully produced via a one-step chemical synthesis from six different coal ranks, from which two superhigh organic sulfur(SHOS) coals were selected as natural S-doped carbon sources for the preparation of S-doped GQDs. The effects of coal properties on coal-based GQDs were analyzed by means of high-resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), ultraviolet-visible(UV-Vis) absorption spectroscopy, and fluorescence emission spectra. It was shown that all coal samples can be used to prepare GQDs, which emit bluegreen and blue fluorescence under ultraviolet light. Anthracite-based GQDs have a hexagonal crystal structure without defects, the largest size, and densely arranged carbon rings in their lamellae; the highrank bituminous coal-based GQDs are relatively reduced in size, with their hexagonal crystal structure being only faintly visible; the low-rank bituminous coal-based GQDs are the smallest, with sparse lattice fringes and visible internal defects. As the metamorphism of raw coals increases, the yield decreases and the fluorescence quantum yield(QY) initially increases and then decreases. Additionally, the surface of GQDs that were prepared using high-rank SHOS coal(high-rank bituminous coal) preserves rich sulfur content even after strong oxidation, which effectively adjusts the bandgap and improves the fluorescence QY. Thus, high-rank bituminous coal with SHOS content can be used as a natural S-doped carbon source to prepare S-doped GQDs, extending the clean utilization of low-grade coal.

Effects of coal rank, Fe_3O_4 amounts and activation temperature on the preparation and characteristics of magnetic activated carbon

Coal-based Magnetic Activated Carbons （CMAC＇s） were prepared from three representative coal samples of various ranks： Baorigele lignite from Inner Mongolia; Datong bitumite from Shanxi province; and Taixi anthracite from Ningxia Hui Auto- nomous Region. Fe3O4 was used as a magnetic additive. A nitrogen-adsorption analyzer was used to determine the specific surface area and pore structure of the resulting activated carbons. The adsorption capacity was assessed by the adsorption of iodine and methylene blue. X-ray diffraction was used to measure the evolution behavior of Fe304 during the preparation process. Magnetic properties were characterized with a vibrating-sample magnetometer. The effect of the activation temperature on the performance of CMAC＇s was also studied. The results show that, compared to Baorigele lignite and Taixi anthracite, the Datong bitumite is more appropriate for the preparation of CMAC＇s with a high specific surface area, an advanced pore structure and suitable magnetic properties. Fe304 can effectively enhance the magnetic properties and control the pore structure by increasing the ratio of meso- pores. An addition of 6.0% Fe304 and an activation temperature of 880 ℃ produced a CMAC having a specific surface area, an iodine adsorption, a methylene blue adsorption and a specific saturation magnetization of 1152.0 m2/g, 1216.7 mg/g, 229.5 mg/g and 4.623 emu/g, respectively. The coal used to prepare this specimen was Datong bitumite.

Hydrogen Bonds in Coal——The Influence of Coal Rank and the Recognition of a New Hydrogen Bond in Coal

By means of in situ diffuse reflectance FTIR, the IR spectra of 6 coals with different ranks were obtained from room temperature to 230 ℃. A new curve fitting method was used to recognize the different hydrogen bonds in the coals, and the influence of coal ranks on the distribution of hydrogen bonds(HBs) in the coals and their thermal stability were discussed. The results show that there is another new HB(around 2514 cm -1 ) between the -SH in mercaptans or thiophenols and the nitrogen in the pyridine like compounds in the coals, and the evidence for that was provided. The controversial band of the HB between hydroxyl and the nitrogen of the pyridine like compounds was determined in the range of 3028-2984 cm -1 , and the result is consistent with but more specific than that of Painter et al .. It was found that the stability of different HBs in the coals is influenced by both coal rank and temperature. For some HBs, the higher the coal rank, the higher the stability of them. Within the temperature range of our research, the stability of the HB between the hydroxyl and the π bond increases to some extent for some coals at temperatures higher than 110 or 140 ℃.

Physical simulation of hydrodynamic conditions in high rank coalbed methane reservoir formation

In order to select highly productive and enriched areas of high rank coalbed methane reservoirs, based on hydrologic geology as one of the main factors controlling coalbed methane （CBM） reservoir formations, the effect of hydrodynamic forces controlling CBM reservoir formations was studied by a physical simulation experiment in which we used CBM reservoir simulation facilities. The hydrodynamic conditions of high coal rank reservoirs in the Qinshui basin were analyzed. Our experiment shows the following results： under strong hydrodynamic alternating action, 6C~ of coalbed methane reservoir changed from the start at -2.95% ~ -3.66%, and the lightening process occurred in phases; the CI-I4 volume reduced from 96.35% to 12.42%; the CO2 vo- lume decreased from 0.75% in sample 1 to 0.68% in sample 2, then rose to 1.13% in sample 3; the N2 volume changed from 2.9% in sample 1 to 86.45% in sample 3. On one hand, these changes show the complexity of CBM reservoir formation; on the other hand, they indicate that strong hydrodynamic actions have an unfavorable impact on CBM reservoir formation. It was found that the gas volume and hydrodynamic intensity were negatively correlated and low hydrodynamic flow conditions might result in highly productive and enriched areas of high rank CBM.

Influence of heating rate on reactivity and surface chemistry of chars derived from pyrolysis of two Chinese low rank coals

A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.

Crossing point temperature of coal

A further understanding of the self-heating of coal was obtained by investigating the crossing point temperature（CPT） of different ranks of coal.The tests were carried out using a self-designed experimental system for coal self-heating.50 g（±0.01 g） of coal particles ranging from 0.18 mm to 0.38 mm in size were put into a pure copper reaction vessel attached to the center of a temperature programmed enclosure.The temperature program increased the temperature at a rate of 0.8℃/min.Dry air was permitted to flow into the coal reaction vessel at different rates.The surrounding temperature and the coal temperature were monitored by a temperature logger.The results indicate that CPT is affected by coal rank,moisture,sulfur, and the experimental conditions.Higher ranked coals show higher CPT values.A high moisture content causes a delay phenomenon during the self-heating of the coal.Drying at 40℃decreases the effects of moisture.The reactivity of sulfur components in the coal is low under dry and low-temperature conditions. These components form a film that covers the coal surface and slightly inhibits the self-heating of the coal. The flow rate of dry air,and the heating rate of the surroundings,also affect the self-heating of the coal.The most appropriate experimental conditions for coal samples of a given weight and particle size were determined through contrastive analysis.Based on this analysis we propose that CPTs be determined under the same,or nearly the same conditions,for evaluation of the spontaneous combustion of coal.

Effect of the benzene ring of the dispersant on the rheological characteristics of coal-water slurry:Experiments and theoretical calculations

In this study,low-rank coal-water slurry(LCWS)was prepared using polyoxyethylene dodecylphenol ether(PDPE)and polyoxyethylene lauryl ether(PLE),respectively.A combination of experiments and simulations was used to investigate the pulping properties and microscopic mechanism of the LCWS samples prepared using the two agents,so as to explore the influence of benzene ring on the performance of dispersant.The results of the LCWS preparation experiments revealed that the pulp-forming performance of PDPE exceeded that of PLE.When LCWS concentration is 62%,64%,and 66%,the apparent viscosity corresponding to PDPE is 247.80,504.17,and 653.10 mPa·s,and the apparent viscosity corresponding to PLE is 548.10,1470.61,and 1549.98 mPa·s,respectively.The C_(1000)(When the apparent viscosity is 1000 mPa·s,the corresponding concentration of LCWS is defined as C_(1000))values of PDPE and PLE are 67.60%and 62.95%,respectively.In addition to the van der Waals forces and hydrogen bonds between the PDPE and/or PLE molecules and coal,the benzene rings of PDPE presentπ-πstacking effect with the aromatic rings of coal.That could facilitate and strengthen the adsorption of PDPE on coal,which would be conducive to further improving the dispersion of coal particles.The two dispersants have no significant difference in effect on the pyrolysis of LCWS.The simulation results indicated that the times for PDPE and PLE molecules to reach flat adsorption state on coal are approximately 290 and 565 ps,respectively.The self-diffusion coefficient(D)of the PDPE and PLE on coal is 3.16 x 10^(-6)and6.57×10^(-6)m~2/s,respectively,and their interaction energies with coal are 785.71 and 648.60 kcal/mol,respectively.The results of the simulation calculations demonstrated that PDPE adsorbed on coal easier than PLE,and its binding is more stable than that of PLE owing to theπ-πstacking effect,which is conducive to uniform dispersion of coal in solution.The simulation results confirmed the experimental results.

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.

Mechanism of oxidation of low rank coal by nitric acid

The pretreatment of low rank coal with nitric acid oxidation can promote its bio-liquefaction. However, the detailed mechanism of which remains an unresolved problem. In the present work, the characteristics of Fushun coal before and after oxidation by nitric acid were investigated combined with elemental composition, pore volume and pore size, Zeta potential, FT-IR, and 13C solid NMR spectrum analysis. The results show that the inorganic substance inlaid in coal are dissolved by ni- tric acid, which results in the decrease of coal ash content and increase of pore volume and pore size. Furthermore, there exist obvious chemical reactions between nitric acid and the functional groups of coal including aromatic ring carboxylation, side chain alkyl of aromatic ring oxidation and aromatic ring nitration. Among these reactions, some led to the increase in content of carboxyl, aliphatic carbon connected with O and humic acid carbon, while others caused the reduction of aromaticity, methyl carbon, substituted aryl carbon and side chain.

Coal reservoir characteristics and their controlling factors in the eastern Ordos basin in China

In the eastern Ordos basin, due to the diversity of the tectonic setting, coal rank, gas content and permeability, coal reservoirs have differing characteristics. In this paper, based on coal reservoir geometry, gas content, adsorption capacity, pores and fissures developments and permeability data, the coalbed methane(CBM) reservoir characteristics and their controlling factors in the eastern Ordos basin is discussed. The results show that, due to undergoing different paleo-temperatures in the geological history,coal rank has a higher trend from the north part to the south and from the shallow part to the inward basin, which determines CBM distribution and recoverability. In the north, although having large coal thickness and high permeability, Zhungeer-Xingxian coal rank is low, and gas content is small. In the central part, with medium rank, higher gas content and relatively high permeability, and the Wubao-Liulin area is the most favorable area in the eastern Ordos basin. In the southern part, medium and high metamorphism coal occurs, and although having the highest gas content, the permeability in the Hancheng area is low due to the development of sheared coal.

Characteristics of oxygen consumption of coal at programmed temperatures

Oxygen consumption is an important index of coal oxidation.In order to explore the coal-oxygen reaction,we developed an experimental system of coal spontaneous combustion and tested oxygen consumption of differently ranked coals at programmed temperatures.The size of coal samples ranged from 0.18~0.42 mm and the system heat-rate was 0.8℃/min.The results show that, for high ranked coals,oxygen consumption rises with coal temperature as a piecewise non-linear process.The critical coal temperature is about 50℃.Below this temperature,oxygen consumption decreases with rising coal temperatures and reached a minimum at 50℃,approximately.Subsequently,it begins to increase and the rate of growth clearly increased with temperature.For low ranked coals,this characteristic is inconspicuous or even non-existent.The difference in oxygen consumption at the same temperatures varies for differently ranked coals.The results show the difference in oxygen consumption of the coals tested in our study reached 78.6%at 100℃.Based on the theory of coal-oxygen reaction,these phenomena were analyzed from the point of view of physical and chemical characteristics,as well as the appearance of the coal-oxygen complex.From theoretical analyses and our experiments,we conclude that the oxygen consumption at programmed temperatures reflects the oxidation ability of coals perfectly.

Cation exchange for mercury and cadmium of xanthated,sulfonated,activated and non-treated subbituminous coal,commercial activated carbon and commercial synthetic resin:effect of pre-oxidation on xanthation of subbituminous coal

A subbituminous coal was oxidized with air at 150℃on a fixed bed for 4 h and xanthated with carbondisulfide in a basic solution,at 30 or 5-10℃.This xanthated coal was evaluated for the removal of Hg^(2+)and Cd^(2+)from 7,000 mg/L aqueous solutions;metal concentrations were detemmined by atomic absorption spectrometry.The ionexchange of the xanthated coal was compared against those of the original subbituminous coal,a sulfonated subbituminouscoal,activated carbon,commercial activated carbon,and commercial synthetic resin.The commercial synthetic resinshowed the highest exchange capacity(concentration factor 98%)followed by the xanthated coal(concentration factor 96%).The retention of cadmium on the sulfonated subbituminous coal was lower(exchange capacity 0.56 meq/g)thanthat of xanthated coals(1.85±0.09 meq/g).Our xanthated coal showed a better Cd^(2+)removal(8l%o against 15%)than anon preoxidized 40-h-xanthated coal,which shows that oxidation of coal increased the amount of oxygenated groups whichenhanced xanthation.

Resistivity response to the porosity and permeability of low rank coal

Laojunmiao coal samples from the eastern Junggar basin were studied to understand the relationship between coal resistivity and the physical parameters of coal reservoirs under high temperatures and pressures.Specifically,we analysed the relationship of coal resistivity to porosity and permeability via heating and pressurization experiments.The results indicated that coal resistivity decreases exponentially with increasing pressure.Increasing the temperature decreases the resistivity.The sensitivity of coal resistivity to the confining pressure is worse when the temperature is higher.The resistivity of dry coal samples was linearly related to φ~m.Increasing the temperature decreased the cementation exponent(m).Increasing the confining pressure exponentially decreases the porosity.Decreasing the pressure increases the resistivity and porosity for a constant temperature.Increasing the temperature yields a quadratic relationship between the resistivity and permeability for a constant confining pressure.Based on the Archie formula,we obtained the coupling relationship between coal resistivity and permeability for Laojunmiao coal samples at different temperatures and confining pressures.

Blended coals for improved coal water slurries

Three coal samples of different ranks were used to study the effect of coal blending on the preparation of Coal Water Slurry (CWS). The results show that by taking advantage of two kinds of coal, the coal concentration in slurry made from hard-to-pulp coal can be effectively improved and increased by 3%–5% generally. DLT coal (DaLiuTa coal mine) is very poor in slurryability and the stability and rheology of the resulting slurry are not very good. When the amount of easily slurried coal is more than 30%, all properties of the CWS improve and the CWS meets the requirements for use as fuel. Coalification, porosity, surface oxygenic functional groups, zeta potential and grindability have a great effect on the performance of blended coal CWS. This leads to some differences in performance between the slurry made from a single coal and slurry made from blended coal.

Estimation of correction coefficients for measured coal bed methane contents

Improving the accuracy and precision of coal bed methane(CBM) estimates requires correction of older data from older coal exploration surveys to newer standards.Three methods,the depth gradient method,the contour aerial weight method,and the well-point aerial weight method,were used to estimate the correction coefficient required to predict CBM gas content from coal exploration data.The data from the Nos.3 and 15 coal seams provided the coal exploration data while the CBM exploration stages within the X1 well block located in the southern part of the Qinshui Basin provided the data obtained using newer standards.The results show the correction coefficients obtained from the two aerial weight methods are similar in value but lower than the one obtained from the depth gradient method.The three methods provide similar results for the Nos.3 and 15 seams in that the correction factor is lower for the former seam.The results from the depth gradient method taken together with the coal seam burial depth and the coal rank suggest that variations in the correction factor increase linearly along with coal seam burial depth and coal rank.The correlation obtained can be applied to exploration and the evaluation of coal bed gas resources located in coalfields.

Investigation of polycyclic aromatic hydrocarbons from coal gasification

The hazardous organic pollutants generated from coal gasification, such as polycyclic aromatic hydrocarbons(PAHs), are highly mutagenic and carcinogenic. More researchers have paid particular attention to them. Using air and steam as gasification medium, the experiments of three kinds of coals were carried out in a bench scale atmospheric fluidized bed gasifier. The contents of the 16 PAHs specified by US EPA in raw coal, slag, bag house coke, cyclone coke and gas were measured by HPLC to study the contents of PAHs in raw coal and the effects of the inherent characters of coals on the formation and release of PAHs in coal gasification. The experimental results showed that the distributions of PAHs in the gasified products are similar to raw coals and the total\|PAHs content in coal gasification is higher than in raw coal(except Coal C). The total\|PAHs contents increase and then decrease with the rise of fixed carbon and sulfur of coal while there has an opposite variation when volatile matters content increase. The quantities of PAHs reduce with the increase of ash content or the drop of heating value during coal gasification.