Constraints on Characteristics and Distribution of Gas Hydrate and Free Gas Using Broad-Band Processing of Three-Dimensional Seismic Data

Gas hydrate drilling expeditions in the Pearl River Mouth Basin,South China Sea,have identified concentrated gas hydrates with variable thickness.Moreover,free gas and the coexistence of gas hydrate and free gas have been confirmed by logging,coring,and production tests in the foraminifera-rich silty sediments with complex bottom-simulating reflectors(BSRs).The broad-band processing is conducted on conventional three-dimensional(3D)seismic data to improve the image and detection accuracy of gas hydratebearing layers and delineate the saturation and thickness of gas hydrate-and free gas-bearing sediments.Several geophysical attributes extracted along the base of the gas hydrate stability zone are used to demonstrate the variable distribution and the controlling factors for the differential enrichment of gas hydrate.The inverted gas hydrate saturation at the production zone is over 40% with a thickness of 90 m,showing the interbedded distribution with different boundaries between gas hydrate-and free gas-bearing layers.However,the gas hydrate saturation value at the adjacent canyon is 70%,with 30-m-thick patches and linear features.The lithological and fault controls on gas hydrate and free gas distributions are demonstrated by tracing each gas hydrate-bearing layer.Moreover,the BSR depths based on broad-band reprocessed 3D seismic data not only exhibit variations due to small-scale topographic changes caused by seafloor sedimentation and erosion but also show the upward shift of BSR and the blocky distribution of the coexistence of gas hydrate and free gas in the Pearl River Mouth Basin.

Adsorbed and free gas occurrence characteristics and controlling factors of deep shales in the southern Sichuan Basin,China

Deep shale gas(3500-4500 m)will be the important succeeding field for the growth of shale gas production in China.Under the condition of high temperature and high pressure in deep shale gas reservoirs,its gas occurrence characteristics are markedly different from those of medium and shallow layers.To elucidate the gas occurrence characteristics and controlling factors of deep shales in the Wufeng-Longmaxi Formation,methane adsorption,low-temperature N2,and cO2 adsorption experi-ments were conducted.The results show that in deep shales,the mesopores provide approximately 75%of the total specific surface area(SA)and 90%of the total pore volume(PV).Based on two hypotheses and comparing the theoretical and actual adsorption capacity,it is speculated that methane is adsorbed in deep shale in the form of micropore filling,and free gas is mainly stored in the mesopores.Correlation analysis demonstrated that ToC is the key material constraint for the adsorption capacity of deep shale,and micropore SSA is the key spatial constraint.Other minerals and mesopore parameters have limited effect on the amount of adsorbed gas.Moreover,the free gas content ranges from 2.72 m^(3)/t to 6.20 m^(3)/t,with an average value of 4.60 m^(3)/t,and the free gas content ratio is approximately 58%,suggesting that the deep shale gas reservoirs are dominated by free gas.This ratio may also increase to approximately 70%when considering the formation temperature effect on adsorbed gas.Gas density,porosity,and gas saturation are the main controlling factors of free gas content,resulting in significantly larger free gas content in deep shale than in shallower formations.

Performance of free gases during the recovery enhancement of shale gas by CO_(2) injection:a case study on the depleted Wufeng–Longmaxi shale in northeastern Sichuan Basin,China

In this work, a novel thermal–hydraulic–mechanical (THM) coupling model is developed, where the real geological parameters of the reservoir properties are embedded. Accordingly, nine schemes of CO_(2) injection well (IW) and CH_(4) production well (PW) are established, aiming to explore the behavior of free gases after CO_(2) is injected into the depleted Wufeng–Longmaxi shale. The results indicate the free CH4 or CO2 content in the shale fractures/matrix is invariably heterogeneous. The CO_(2) involvement facilitates the ratio of free CH_(4)/CO_(2) in the matrix to that in the fractures declines and tends to be stable with time. Different combinations of IW–PWs induce a difference in the ratio of the free CH4 to the free CO_(2), in the ratio of the free CH_(4)/CO_(2) in the matrix to that in the fractures, in the content of the recovered free CH_(4), and in the content of the trapped free CO_(2). Basically, when the IW locates at the bottom Wufeng–Longmaxi shale, a farther IW–PWs distance allows more CO2 in the free phase to be trapped;furthermore, no matter where the IW is, a shorter IW–PWs distance benefits by getting more CH_(4) in the free phase recovered from the depleted Wufeng–Longmaxi shale. Hopefully, this work is helpful in gaining knowledge about the shale-based CO_(2) injection technique.

Coal-rock gas:Concept,connotation and classification criteria

In recent years,great breakthroughs have been made in the exploration and development of natural gas in deep coal-rock reservoirs in Junggar,Ordos and other basins in China.In view of the inconsistency between the industrial and academic circles on this new type of unconventional natural gas,this paper defines the concept of"coal-rock gas"on the basis of previous studies,and systematically analyzes its characteristics of occurrence state,transport and storage form,differential accumulation,and development law.Coal-rock gas,geologically unlike coalbed methane in the traditional sense,occurs in both free and adsorbed states,with free state in abundance.It is generated and stored in the same set of rocks through short distance migration,occasionally with the accumulation from other sources.Moreover,coal rock develops cleat fractures,and the free gas accumulates differentially.The coal-rock gas reservoirs deeper than 2000 m are high in pressure,temperature,gas content,gas saturation,and free-gas content.In terms of development,similar to shale gas and tight gas,coal-rock gas can be exploited by natural formation energy after the reservoirs connectivity is improved artificially,that is,the adsorbed gas is desorbed due to pressure drop after the high-potential free gas is recovered,so that the free gas and adsorbed gas are produced in succession for a long term without water drainage for pressure drop.According to buried depth,coal rank,pressure coefficient,reserves scale,reserves abundance and gas well production,the classification criteria and reserves/resources estimation method of coal-rock gas are presented.It is preliminarily estimated that the coal-rock gas in place deeper than 2000 m in China exceeds 30×10^(12)m^(3),indicating an important strategic resource for the country.The Ordos,Sichuan,Junggar and Bohai Bay basins are favorable areas for large-scale enrichment of coal-rock gas.The paper summarizes the technical and management challenges and points out the research directions,laying a foundation for the management,exploration,and development of coal-rock gas in China.

Non-resistivity-based saturation evaluation methods in shale gas reservoirs

Free gas saturation is a key parameter for calculating shale gas reserves.The complex conductivity mechanism of shale reservoirs restricts the application of Archie's formula and its extended form for the evaluation of free gas saturation.Instead,a number of non-resistivity-based saturation evaluation methods suitable for shale gas reservoirs have been established,including core calibration(TOC method,clay content method),gas porosity cutoff,excavation effect and four-pore modeling.These methods,together with adsorbed phase porosity correction,are used to calculate the free gas saturation.These methods are applied to shale reservoirs of the Upper Ordovician Wufeng Formation and the Lower Silurian Longmaxi Formation in the Sichuan Basin,southwestern China to test their applicability and accuracy.The results,when compared with measured data from core samples,show that the TOC-based core calibration is more accurate in evaluating free gas saturation in the entire shale gas interval,which is of great significance to the calculation of shale gas reserves.

De Haas-van Alphen Effect of Free Electron Gas Revisited

The free electron gas in a uniform magnetic field at low temperature is restudied. The grand partition function previously obtained by Landau＇s quantitative calculation contains three parts, which are all approximate. An improved calculation is presented, in which two of the three parts are obtained in exact forms. A simple remedy for Landau and Lifshitz＇s qualitative calculation in the textbook is also given, which turns the qualitative result into the same one as obtained by the improved quantitative calculation. The chemical potential is solved approximately and the thermodynamic quantities are caiculated explicitly in both a weak field and a strong field. The thermodynamic quantities in a strong field obtained here contain both non-oscillating and oscillating corrections to the corresponding results derived from Landau＇s grand partition function. In particular, Landau＇s grand partition function is not sufficiently accurate to yield our nonzero results for the specific heat and the entropy. An error in the Laplace-transform method for the problem is corrected. The results previously obtained by this method are also improved.

New method for prediction of shale gas content in continental shale formation using well logs

Shale needs to contain a sufficient amount of gas to make it viable for exploitation. The continental heterogeneous shale formation in the Yan-chang （YC） area is investigated by firstly measuring the shale gas content in a laboratory and then investigating use of a theoretical prediction model. Key factors controlling the shale gas content are determined, and a prediction model for free gas content is established according to the equation of gas state and a new petrophysical volume model. Application of the Langmuir volume constant and pressure constant obtained from results of adsorption isotherms is found to be limited because these constants are greatly affected by experimental temperature and pressures. Therefore, using measurements of adsorption isotherms and thermodynamic theory, the influence of temperature, total organic carbon （TOC）, and mineralogy on Langmuir volume constants and pressure constants are investigated in detail. A prediction model for the Langmuir pressure constant with a correction of temperatures is then established, and a prediction model for the Langmuir volume constant with correction of temperature, TOC, and quartz contents is also proposed. Using these corrected Langmuir constants, application of the Langmuir model determined using experimental adsorption isotherms is extrapolated to reservoir temperature, pressure, and lithological conditions, and a method for the prediction of shale gas content using well logs is established. Finally, this method is successfully applied to predict the shale gas content of the continental shale formation in the YC area, and practical application is shown to deliver good results with high precision.

AVO Character Research of Natural Gas Hydrates in the East China Sea

Natural gas hydrates are considered as strategic resources with commercial potential in the 21st century. Obvious BSR characteristics will be shown on seismic profiles, if there exist natural gas hydrates. The AVO method is one of the methods which can be used to identify and forecast lithologic characteristics and fluid properties by using the relationship between Amplitude and Offset. AVO anomaly is one of the significant signs to check out whether or not there is free gas below the BSR, so it can be used to detect natural gas hydrates from the seismic profile. Considering the geological and geophysical characteristics of the Okinawa Trough and making use of the techniques mentioned above, we can conclude that the conditions there are favorable for the formation and concentration of natural gas hydrates. By analyzing the data collected from the study area, one can discover many different anomalous phenomena on the seismic profile which are related to the existence of natural gas hydrates. Preliminary estimation of the natural gas hydrates in the Okinawa Trough shows that the trough is rich in natural gas hydrates and may become a potential important resources exploration area.

A system consisted of flame ionization detector and sulfur chemiluminescence detector for interference free determination of total sulfur in natural gas

A new detection system consisted of a flame ionization detector（FID） and a sulfur chemiluminescence detector（SCD） was developed for sensitive and interference free determination of total sulfur in natural gas by non-separation gas chromatography. In this system, sulfur containing compounds and hydrocarbons were firstly burned in the FID using oxygen rich flame and converted to SO_2, CO_2 and H_2O, respectively. The products from FID were transported into the SCD with hydrogen rich atmosphere wherein only SO_2 could be reduced to SO and reacted with O_3 to produce characteristic chemiluminescence. Therefore, the chemiluminescence of CO found in conventional SCD were eliminated because CO_2 could not be reduced to CO under these conditions. The experimental parameters were systematically investigated. Limit of detection obtained by the proposed system is better than 0.5 mmol/mol for total sulfur and superior to those previously reported. The proposed method not only retains the advantages of the conventional SCD but also provides several unique advantages including no hydrocarbon interference, better stability, and easier calculation. The utility of this technique was demonstrated by the determination of total sulfur in real samples and two certified reference materials（GBW 06332 and GBW（E） 061320）.

Numerical modeling of the dynamic variation in multiphase CH_(4) during CO_(2) enhanced gas recovery from depleted shale reservoirs

Regarding CO_(2)enhanced shale gas recovery,this work focuses on changes in the multiphase(free/adsorbed)CH_(4)in the process of CO_(2)enhanced shale gas recovery,by utilizing a rigorous numerical model with real geological parameters.This work studies nine injection well(IW)and CH_(4)production well(PW)combinations of CO_(2)to determine the influence of IW and PW locations on the dynamic interaction of multiphase CH_(4)during 10000 d of CO_(2)injection.The results indicate that the content of both the adsorbed CH_(4)and free CH_(4)is strongly variable before(and during)the CO_(2)-CH_(4)displacement.In addition,during the simulation process,the proportion of the adsorbed CH_(4)among all extracted CH_(4)phases dynamically increases first and then tends to stabilize at 70%-80%.Moreover,the IW-PWs combinations signifi-cantly affect the outcomes of CO_(2)enhanced shale gas recovery-for both the proportion of adsorbed/free CH_(4)and the recovery efficiency.A longer IW-PW distance enables more adsorbed CH_(4)to be recovered but results in a lower efficiency of shale gas recovery.Basically,a shorter IW-PWs distance helps recover CH_(4)via CO_(2)injection if the IW targets the bottom layer of the Wufeng-Longmaxi shale formation.This numerical work expands the knowl-edge of CO_(2)enhanced gas recovery from depleted shale reservoirs.

Ultraslow electron-phonon scattering and polaron formation in magnetite

The comprehensive analysis of AC electrical conductivity in magnetite was performed in order to find relations between the formation of polarons,phonons and conduction by a virtual free electron gas.The analysis performed here for the first time shows experimental data for the behavior of electrons for magnetite with the scattering time shifted to the GHz region.According to our study,the DC electrical conductivity can be described by the virtual free electron gas model,and high frequency conductivity can be described by the combination of the Drude model for disordered materials and Jonscher's universal power law.The observed peak at the imaginary part of AC conductivity was related to the scattering time of the electron-phonon coupling.This interaction between electrons and thermally formed phonons results in the formation of large polarons,and these are responsible for high frequency conductivity in magnetite.