The dynamic catalysis of Ga/ZSM-5 catalysts for propane-CO_(2) coupling conversion to aromatics and syngas

Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owing to the quick evolution of the metallic active sites and the complex reaction processes including direct propane aromatization,CO_(2) hydrogenation,reverse water-gas shift reaction,and propane-CO_(2) coupling aromatization.Herein,Ga/ZSM-5 catalysts were constructed to study the dynamic evolution of the metallic active sites and the role of CO_(2) during the propane and CO_(2) coupling reaction.After optimizing the reaction conditions,a notable propane conversion rate of 97.9%and an impressive aromatics selectivity of 80.6%in hydrocarbons can be achieved at the conditions of 550℃and CO_(2)/C_(3)H_(8) of 4.^(13)CO_(2)isotope experiments illustrate that C-atoms of CO_(2) can enter into CO(86.5%)and aromatics(10.8%)during the propane-CO_(2) coupling reaction process.In situ XANES and FTIR spectroscopies at 550℃and H_(2)/C_(3)H_(8) atmosphere reveal that GaO_(x) species can be gradually dispersed into[GaH_(2)]^(+)/[GaH]^(2+)on the Bronsted acid sites of ZSM-5 zeolite during H_(2) and/or C_(3)H_(8) treatment,which are the real active sites for propane-CO_(2) coupling conversion.In situ CO_(2)-FTIR experiments demonstrate that the[GaH_(2)]^(+)/[GaH]^(2+)species can react with CO_(2) and accelerate the propane and CO_(2) coupling process.This work not only presents a cost-effective avenue for CO_(2) utilization,but also contributes to the active site design for improved alkane and CO_(2) activation in coupling reaction system.

用于GaN基HEMT栅极金属TiN的ICP刻蚀工艺

GaN基高电子迁移率晶体管(HEMT)在射频(RF)通信及新能源汽车领域有着巨大的应用潜力。TiN材料因其良好的热稳定性、化学稳定性及工艺兼容性,可用作GaN基HEMT的栅极材料。采用ULVAC公司生产的NE-550型电感耦合等离子体(ICP)刻蚀设备对TiN材料进行了干法刻蚀工艺的研究。采用光刻胶作为刻蚀掩膜,Cl_(2)和BCl_(3)混合气体作为工艺气体,通过调整工艺参数,研究了ICP源功率、射频(RF)偏压功率、腔体压力、气体体积流量以及载台温度对TiN刻蚀速率和侧壁角度的影响。最后通过优化工艺参数,得到了TiN刻蚀速率为333 nm/min,底部平整且侧壁角度为81°的栅极结构。

基于GRA-GASA-SVM的煤层瓦斯含量预测方法研究

为提升煤层瓦斯含量预测精度,提出一种采用遗传模拟退火算法混合优化支持向量机(SVM)参数的瓦斯含量预测模型(GRA-GASA-SVM模型)。该模型将GA和SA整合为遗传模拟退火算法协同优化SVM的参数,以解决传统网格寻优算法取值范围无法确定和单一智能算法优化程度有限等问题。利用灰色关联分析(GRA)压缩数据集维度,建立瓦斯含量预测参数体系并作为GASA-SVM的输入数据集。结果表明:SVM模型、GA-SVM模型和GASA-SVM模型10折交叉验证瓦斯含量预测总平均相对误差分别为15.98%、13.55%和10.58%。相比SVM模型和GA-SVM模型,GASA-SVM模型预测稳定性更优、预测精准度更高且对新样本泛化能力更强。

Unconventional Natural Gas Accumulations in Stacked Deposits:A Discussion of Upper Paleozoic Coal-Bearing Strata in the East Margin of the Ordos Basin, China

The Upper Paleozoic(Carboniferous to Permian) succession in the east margin of the Ordos Basin in the North China Craton has a potential to contain significant hydrocarbon resources, though attention have been mainly attracted for its successful development of coalbed methane(CBM). To improve the previous resource estimates and evaluate the hydrocarbon play possibilities, this study incorporated new discoveries of hydrocarbon units and their stratigraphic relation with source rocks, hydrocarbon migration and trapping configurations. Continuous hydrocarbon accumulation units were identified within the Upper Paleozoic, including the Taiyuan, Shanxi and Xiashihezi formations with great tight gas potential, and the Taiyuan and Shanxi formations also containing shale gas and CBM. Different strata combinations are identified with coal deposition and favour for continuous gas accumulations, including the tidal flat, deltaic and fluvial systems distributed in most of the study areas. Methane was not only generated from the thick coal seams in the Taiyuan and Shanxi formations, but also from shale and dark mudstones. The coal, shale and tight sandstones are proved of remarkable gas content and hydrocarbon indications, and the gas saturation of tight sandstones decreases upward. The stacked deposit combinations vary isochronally in different areas, while the coal seams were developed stably showing good gas sources. Two key stages control the hydrocarbon enrichment, the continuous subsidence from coal forming to Late Triassic and the anomalous paleo-geothermal event happened in Early Cretaceous, as indicated by the fluid inclusions evidence. Extensive areas show good hydrocarbon development potential presently, and more works should be focused on the evaluation and selection of good reservoir combinations.

Regional gas drainage techniques in Chinese coal mines

China's rapid economic development has increased the demand for coal.These results in Chinese coal mines being extended to deeper levels.The eastern Chinese,more economical developed,regions have a long history of coal mining and many coal mines have now started deep mining at a depth from 800 to 1500 m.This increase in mining depth,geostresses,pressures,and gas content of the coal seam complicates geologic construction conditions.Lower permeability and softer coal contribute to increasing numbers of coal and gas outburst,and gas explosion,disasters.A search on effective methods of preventing gas disasters has been provided funds from the Chinese government since 1998.The National Engineering Research Center of Coal Gas Control and the Huainan and Huaibei Mining Group have conducted theoretical and experimental research on a regional gas extraction technology.The results included two important findings.First,grouped coal seams allow adoption of a method where a first,key protective layer is mined to protect upper and lower coal seams by increasing permeability from 400 to 3000 times.Desorption of gas and gas extraction in the protected coal seam of up to 60%,or more,may be achieved in this way.Second,a single seam may be protected by using a dense network of extraction boreholes consisting of cross and along-bed holes.Combined with this is increased use of water that increases extraction of coal seam gas by up to 50%.Engineering practice showed that regional gas drainage technology eliminates regional coal and gas outburst and also enables mining under low gas conditions.These research results have been adopted into the national safety codes of production technology.This paper systematically introduces the principles of the technology,the engineering methods and techniques,and the parameters of regional gas drainage.Engineering applications are discussed.

Experiment of gas diffusion and its diffusion mechanism in coal

In coal,the gas mainly exists in a free or an adsorption state.When the coal containing gas is damaged,gas desorption and diffusion will occur which can result in gas disaster.This research on gas desorption and diffusion provides a theoretical basis for gas disaster mechanism and prevention.The influence of pressure and temperature on gas diffusion is studied by the experiment.And the mechanism of pressure and temperature on gas diffusion is also analysed.The research results indicate that gas diffusion capacity increases with increasing temperature under the same pressure for the same coal sample.This is mainly because the temperature increases,gas molecular hot motion is severer,kinetic energy of gas molecular increases,and gas desorption quickens,therefore gas diffusion capacity changes stronger.Under other unchanged conditions,the greater gas adsorption balance pressure,the more gas adsorption content,and the higher the initial gas concentration.When gas diffusion begins,the greater the gas concentration gradient,the faster the gas diffusion speeds.

Geological and Geochemical Characteristics and Exploration Prospect of Coal-Derived Tight Sandstone Gas in China： Case Study of the Ordos, Sichuan, and Tarim Basins

This work extensively investigated global tight sandstone gas, and geologically and geochemically analyzed the tight sandstone gas in China＇s Ordos, Sichuan, and Tarim basins. We compared typical tight sandstone gas in China with that in North America. We proposed six conditions for the formation of China＇s tight sandstone gas, and illustrated the geological characteristics of tight sandstone gas. In China, gas-bearing tight sandstones were mainly deposited in continental lake deltas and marine-terrigenous facies basin environments, associated with coal-measure strata, and were mostly buried deeper than 2000 in under a formation pressure of 20-30 MPa, with pressure coefficients varying from overpressure to negative pressure. In other countries, tight gas bearing sandstones were dominantly deposited in marine to marine-terrigenous facies environments, occurred in coal-measure strata, and were mostly buried shallower than 2000 m in low-pressure systems. We systematically analyzed tight sandstone gas in the Ordos, Sichuan, and Tarim basins in terms of chemical compositions, geochemical characteristics of carbon isotopes, origins, and sources. Tight sandstone gas in China usually has a hydrocarbon content of 〉95%, with CH4 content 〉90%, and a generally higher dry coefficient. In the three above-mentioned large tight sandstone gas regions,δ13C1 and δJ3C2 mainly ranges from -42%o to -28%o and from -28%o to -21%o, respectively. Type III coal-measure source rocks that closely coexist with tight reservoirs are developed extensively in these gas regions. The organic petrology of source rocks and the carbon isotope compositions of gas indicate that tight sandstone gas in China is dominantly coal-derived gas generated by coal-measure strata. Our analysis of carbon isotope series shows that local isotope reversals are mainly caused by the mixing of gases of different maturities and that were generated at different stages. With increasing maturity, the reversal tendency becomes more apparent. Moreover, natural gas with medium-low maturity （e.g., Xujiahe Formation natural gas in the Sichuan Basin） presents an apparent reversal at a low-maturity stage, a normal series at a medium -maturity stage, and a reversal tendency again at a high-maturity stage. Finally, we proposed four conditions for preferred tight sandstone gas ＂sweep spots,＂ and illustrated the recoverable reserves, proven reserves, production, and exploration prospects of tight sandstone gas. The geological and geochemical characteristics, origins, sources, and exploration potential of tight sandstone gas in China from our research will be instructive for the future evaluation, prediction, and exploration of tight sandstone gas in China and abroad.

How moisture loss affects coal porosity and permeability during gas recovery in wet reservoirs?

Moisture in coal seams changes gas adsorption capacity, induces coal deformation, and affects coal porosity. However, fewer studies have investigated the dynamic process of moisture loss. In this study, a fully coupled multi-physical model for coal deformation, gas flow and moisture loss was implemented. It validated the coal-gas-moisture interactions of the decay of gas adsorption capacity and the coal shrinkage.Subsequently, the proposed model was applied to a simulation of coal seam gas recovery from wet reservoir and solved using the finite method in COMSOL Multiphysics 3.5. Analyses of the component factors and the sensitive parameters of moisture loss on coal porosity and permeability were comprehensively studied at last. The results reveal that moisture loss enhances coal porosity and permeability. The decay of gas adsorption capacity decreases coal permeability while the coal shrinkage promotes it. The decrease of the adsorption decay coefficient and the increase of the initial density of saturated water vapor and water evaporation constant can enhance the permeability of wet coal seams.

Upper Paleozoic coal measures and unconventional natural gas systems of the Ordos Basin,China

Upper Paleozoic coal measures in the Ordos Basin consist of dark mudstone and coal beds and are important source rocks for gas generation. Gas accumulations include coal-bed methane （CBM）, tight gas and conventional gas in different structural areas. CBM accumulations are mainly distributed in the marginal area of the Ordos Basin, and are estimated at 3.5 × 1012 m3. Tight gas accumulations exist in the middle part of the Yishan Slope area, previously regarded as the basin-centered gas system and now considered as stratigraphic lithologic gas reservoirs. This paper reviews the characteristics of tight gas accumulations： poor physical properties （porosity 〈 8%, permeability 〈 0.85 × 10 3 μm2）, abnormal pressure and the absence of well-defined gas water contacts. CBM is a self-generation and self- reservoir, while gas derived from coal measures migrates only for a short distance to accumulate in a tight reservoir and is termed near-generation and near-reservoir. Both CBM and tight gas systems require source rocks with a strong gas generation ability that extends together over wide area. However, the producing area of the two systems may be significantly different.

Effects of coal damage on permeability and gas drainage performance

Coal permeability is a measure of the ability for fluids to flow through coal structures. It is one of the most important parameters affecting the gas drainage performance in underground coal mines. Despite the extensive research conducted on coal permeability, few studies have considered the effect of coal damage on permeability. This has resulted in unreliable permeability evaluation and prediction. The aim of this study is to investigate the effect of coal damage on permeability and gas drainage performance. The Cui-Bustin permeability model was improved by taking into account the impact of coal damage on permeability. The key damage coefficient of the improved permeability model is determined based on the published permeability data. A finite-element numerical simulation was then developed based on the improved permeability model to investigate the damage areas and the permeability distribution around roadway. Results showed that the tensile failure occurs mainly on the upper and lower sides of the roadway while the shear failure symmetrically occurs on the left and right sides. With the increase in the friction angle value, the damage area becomes small. A good agreement was obtained between the results of the improved permeability model(c = 3) and the published permeability data. This indicated a more accurate permeability prediction by the improved permeability model. It is expected that the findings of this study could provide guidance for in-seam gas drainage borehole design and sealing, in order to enhance the gas drainage performance and reduce gas emissions into underground roadways.

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.

Hydraulic drill hole reaming technology with large flow and draining of coal mine gas

This paper takes Zhaozhuang mine in Shanxi province as an example to study the technology of hydraulic reaming drill hole for improving the gas extraction.The influence of the physical properties of coal seam on the hydraulic reaming drill holes and the draining of coal mine gas were analyzed and discussed for different coal structure areas,and the following conclusions were made.Hydraulic drill hole reaming has had a positive impact in Zhaozhuang Mine,and can improve the efficiency of gas extraction to different degrees.The water jet pressure used in hydraulic drill hole reaming mainly depends on the structure of the coal.When the coal seam basically becomes integrated,the critical water jet pressure increases,the discharge becomes relatively easy to achieve,the blocking effect on the gas extraction decreases,and the gas extraction significantly increases after the reaming process.When the coal seam is broken,the critical water jet pressure decreases,the discharge becomes difficult to achieve,the blocking effect on the gas extraction becomes obvious,and the gas extraction changes slightly after reaming.

Distribution Characteristics and Accumulation Model for the Coal-formed Gas Generated from Permo-Carboniferous Coal Measures in Bohai Bay Basin, China: A Review

Coal-formed gas generated from the Permo-Carboniferous coal measures has become one of the most important targets for deep hydrocarbon exploration in the Bohai Bay Basin,offshore eastern China.However,the proven gas reserves from this source rock remain low to date,and the distribution characteristics and accumulation model for the coal-formed gas are not clear.Here we review the coal-formed gas deposits formed from the Permo-Carboniferous coal measures in the Bohai Bay Basin.The accumulations are scattered,and dominated by middle-small sized gas fields,of which the proven reserves ranging from 0.002 to 149.4×108 m3 with an average of 44.30×108 m3 and a mid-point of 8.16×108 m3.The commercially valuable gas fields are mainly found in the central and southern parts of the basin.Vertically,the coal-formed gas is accumulated at multiple stratigraphic levels from Paleogene to Archaeozoic,among which the Paleogene and PermoCarboniferous are the main reservoir strata.According to the transporting pathway,filling mechanism and the relationship between source rocks and reservoir,the coal-formed gas accumulation model can be defined into three types:"Upward migrated,fault transported gas"accumulation model,"Laterally migrated,sandbody transported gas"accumulation model,and"Downward migrated,sub-source,fracture transported gas"accumulation model.Source rock distribution,thermal evolution and hydrocarbon generation capacity are the fundamental controlling factors for the macro distribution and enrichment of the coal-formed gas.The fault activity and the configuration of fault and caprock control the vertical enrichment pattern.

Spatial context in the calculation of gas emissions for underground coal mines

The prediction of gas emissions arising from underground coal mining has been the subject of extensive research for several decades, however calculation techniques remain empirically based and are hence limited to the origin of calculation in both application and resolution. Quantification and management of risk associated with sudden gas release during mining(outbursts) and accumulation of noxious or combustible gases within the mining environment is reliant on such predictions, and unexplained variation correctly requires conservative management practices in response to risk. Over 2500 gas core samples from two southern Sydney basin mines producing metallurgical coal from the Bulli seam have been analysed in various geospatial context including relationships to hydrological features and geological structures. The results suggest variability and limitations associated with the present traditional approaches to gas emission prediction and design of gas management practices may be addressed using predictions derived from improved spatial datasets, and analysis techniques incorporating fundamental physical and energy related principles.

Law of gas production during coal heating oxidation

Coal spontaneous combustion is a great threat to mine safety,and gas is the key index to describe coal spontaneous combustion.Taking the coal samples of different kinds of coal as research object,the temperature programmed oxidation experiment was carried out,and the gases produced by coal samples at different temperatures were collected and analyzed by gas chromatography.This research studied the variation characteristics of gas species and gas concentrations in different coal samples during heating oxidation.The experimental results show that different coal samples produce different kinds of gases in the process of heating and oxidation.The order of gas production is CO,C2H6,C2H4,C3H8,and the relationship between gas production and temperature is approximately exponential.With the increase of coal metamorphic degree,the turning point temperature of sharp rise in coal sample gas production rate become higher,the oxidation ability of coal sample decreases,and the quantity of gas production decreases during the same time period.

Assessment of gas and dust explosion in coal mines by means of fuzzy fault tree analysis

During the past decade, coal dust and gas explosions have been the most two serious types of disasters in China, threatening the lives of miners and causing significant losses in terms of national property. In this paper, an evaluation model of coal dust and gas explosions was constructed based on a fuzzy fault tree by taking the Xingli Coal Mine as a research site to identify the risk factors of coal dust and gas explosions.Furthermore, the hazards associated with such explosions were evaluated for this particular coal mine.After completing an on-site investigation, the fuzzy probabilities of basic events were obtained through expert scoring, and these expert opinions were then aggregated as trapezoidal fuzzy numbers to calculate the degrees of importance of all basic events. Finally, these degrees of importance were sorted. According to the resulting order, the basic events with higher probabilities were determined to identify key hazards in the daily safety management of this particular coal mine. Moreover, effective measures for preventing gas and coal dust explosions were derived. The fuzzy fault tree analysis method is of high significance in the analysis of accidental coal mine explosions and provides theoretical guidance for improving the efficiency of coal mine safety management in a scientific and feasible manner.

Desulfurization kinetics of ZnO sorbent loaded on semi-coke support for hot coal gas

Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.

Strength criterion effect of the translator and destabilization model of gas-bearing coal seam

Coal seam destabilization inflicts damage to equipment, causes property loss and personnel casualties,and severely threatens mining safety and efficient production. To further understand this destabilization based on the basic theory of Lippmann seam destabilization, a mathematical model was introduced for gas pressure distribution by considering intermediate principal stress and support resistance.Subsequently, we established a translation model suitable for the entire roadway coal seam with rocky roof and floor by applying the unified form of yield criterion in the state of plane strain. We also obtained the analytic expressions of coal seam stress distribution on both sides of the roadway and the widths of plastic and disturbance zones. Afterward, we analyzed several typical cases with different material yield criteria, obtained the plastic zone widths of the coal seam under different gas pressures, and assessed the effects of support resistance, roadway size, and coal strength on coal seam destabilization. Results showed that: the results obtained on the basis of Wilson and Mohr–Coulomb criteria are considerably conservative, and the use of Druker–Prager criteria to evaluate the rockburst-induced coal seam destabilization is safer than the use of the two other criteria; coal seam stability is correlated with gas pressure;and high-pressure gas accelerates the coal seam destabilization.

Spatial-temporal evolution of gas migration pathways in coal during shear loading

Custom designed and built meso shear test equipment was used to examine the shear crack propagation in gassy coal under different gas pressures.The spatial-temporal evolution of gas migration pathways in the coal during shear loading was also researched.The results show that gas pressure can hasten crack growth at the shear fracture surface,can reduce the shear strength of gassy coal,and can accelerate the shear failure process.Shear failure in gassy coal exhibits five stages:the pre-crack stage;the stable crack growth stage;the unsteady crack growth stage;the fracture stage;and,finally,the friction crack stage.The shear breaking creates two kinds of crack,shear cracks and tensile cracks.Cracks first appear in the shear plane at both ends and then extend toward the center until a shear fracture surface forms.The direction of shear crack propagation diverges from the predetermined shear plane by an angle of about 5°-10°.