Assessing the potential for CO2 adsorption in a subbituminous coal,Huntly Coalfield,New Zealand,using small angle scattering techniques

Small angle scattering techniques (SAXS and SANS) have been used to investigate the microstructural properties of the subbituminous coals (R_max 0.42–0.45%) from the Huntly Coalfield, New Zealand. Samples were collected from the two thick (> 5 m) coal seams in the coalfield and have been analysed for methane and carbon dioxide sorption capacity, petrography, pore size distribution, specific surface area and porosity.Specific surface area (SSA) available for carbon dioxide adsorption, extrapolated to a probe size of 4 Å, ranged from 1.25 × 10⁶ cm^? 1 to 4.26 × 10⁶ cm^? 1 with total porosity varying from 16% to 25%. Porosity was found to be predominantly composed of microporosity, which contributed the majority of the available SSA. Although considerable variation was seen between samples, the results fit well with published rank trends.Gas holding capacity at the reservoir pressure (approximately 4 MPa) ranged from 2.63 to 4.18 m³/t for methane on a dry, ash-free basis (daf) and from 22.00 to 23.72 m³/t daf for carbon dioxide. The resulting ratio of CO₂:CH₄ ranged from 5.7 to 8.6, with an average of 6.7:1.Holding capacities for both methane and carbon dioxide on a dry ash free basis (daf) were found to be correlated with sample microporosity. However, holding capacities for the two gases on an as analysed (aa) basis (that is including mineral matter and moisture), showed no such correlation. Carbon dioxide (aa) does show a negative correlation with both specific surface area and microporosity. As the coals have low inorganic matter content, the reversal is thought to be related to moisture which is likely concentrated in the pore size range 12.5–125 Å. Methane holding capacity, both daf and aa, correlates with macroporosity, thus suggesting that the holding capacity of micropores is diminished by the presence of moisture in the pores.     

Modeling of coal bed methane (CBM) production and CO2 sequestration in coal seams

A mathematical model was developed to predict the coal bed methane (CBM) production and carbon dioxide (CO₂) sequestration in a coal seam accounting for the coal seam properties. The model predictions showed that, for a CBM production and dewatering process, the pressure could be reduced from 15.17 MPa to 1.56 MPa and the gas saturation increased up to 50% in 30 years for a 5.4 × 10⁵ m² of coal formation. For the CO₂ sequestration process, the model prediction showed that the CO₂ injection rate was first reduced and then slightly recovered over 3 to 13 years of injection, which was also evidenced by the actual in seam data. The model predictions indicated that the sweeping of the water in front of the CO₂ flood in the cleat porosity could be important on the loss of injectivity. Further model predictions suggested that the injection rate of CO₂ could be about 11 × 10³ m³ per day; the injected CO₂ would reach the production well, which was separated from the injection well by 826 m, in about 30 years. During this period, about 160 × 10⁶ m³ of CO₂ could be stored within a 21.4 × 10⁵ m² of coal seam with a thickness of 3 m.     

Atomistic simulation of the structure and elastic properties of pyrite (FeS2) as a function of pressure

Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS₂. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS₂ marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.     

CO2地质封存中储层流体压力演化规律的解析模型

为使解析模型可以更加科学准确地描述储层中多相流体的迁移机制与压力演化规律,提高解析计算与分析的精度。首先将储层中的流场划分为3个区域,然后根据渗流体积守恒方程反演储层中两相流体混合渗流区的各相流体饱和度,进而将总流度直接引入到达西公式中得到了一个适用于两相流的广义达西公式,据此推导出了一个更为精确的表征储层流体压力演化规律的解析模型。最后,通过案例分析,将该解析模型的计算结果与既有文献的显式积分解及TOUGH2/ECO2N的数值解进行对比,验证了该模型的可靠性及相比于既有文献的显式积分解在计算精度方面的优越性。此外,计算结果也表明,该解析模型虽然是在稳态流的假定条件下得到的,但对于实际储层流体压力演化的全过程均具有很强的表征能力,这主要归因于该模型可科学准确地确定饱和度,因此,可以在工程中推广应用。     

煤的吸附常数与最高试验压力关系的研究

研究煤的吸附性能时,意外地发现同一试验条件下获得煤的L angmuir等温吸附常数并非常数,是一变值,其变化是由试验采用的最高试验压力不同而引起。通过对中国主要煤田不同变质程度煤的等温吸附试验数据处理,证明煤的L angmuir等温吸附常V_L,p_L与最高试验压力分别呈正线性相关,并具有普遍性。为了确保煤的吸附常数之间的可比性以及对已有资料的正确利用,建立了将不同最高试验压力的等温吸附试验结果统一到同一最高试验压力的方法。     

Thermo‐hydro‐mechanical modeling with Langmuir's adsorption isotherm of the CO2 injection in coal

In this paper, we used a theoretical model for the variation of Eulerian porosity, which takes into account the adsorption process known to be the main mechanism of production or sequestration of gas in many reservoir of coal. This process is classically modeled using Langmuir's isotherm. After implementation in Code_Aster, a fully coupled thermo‐hydro‐mechanical analysis code for structures calculations, we used numerical simulations to investigate the influence of coal's hydro‐mechanical properties (Biot's coefficient, bulk modulus), Langmuir's adsorption parameters, and the initial liquid pressure in rock mass during CO₂ injection in coal. These simulations showed that the increase in the values of Langmuir's parameters and Biot's coefficient promotes a reduction in porosity because of the adsorption process when the gas pressure increases. Low values of bulk modulus increase the positive effect (i.e., increase) of hydro‐mechanical coupling on the porosity evolution. The presence of high initial liquid pressure in the rock mass prevents the progression of injected gas pressure when CO₂ dissolution in water is taken into account. Copyright © 2014 John Wiley & Sons, Ltd.     

沁水盆地南部中高阶煤高压甲烷吸附行为

煤层气吸附作用是发生在煤基质内表面的物理过程,而煤岩复杂孔裂隙网络为高压甲烷吸附提供了丰富的空间。开展沁水盆地南部高阶煤30℃高压甲烷等温吸附实验,结合煤岩煤质参数与孔隙特征参数,通过改进的D-R模型分析了煤岩性质、孔隙特征与吸附参数的相关性。煤岩性质对最大吸附能力和吸附热参数的影响是多因素叠加的综合效应,而最大吸附能力与微孔体积,吸附体积校正参数与大中孔比表面积呈较好的正相关性,表明甲烷分子在煤基质内表面会根据孔径尺度大小呈现不同的吸附方式。据此提出高压甲烷在煤基质微孔中呈紧密堆积状态而在大中孔中呈多层分子堆叠状态的新认识,为进一步研究煤层气吸附机理提供了新的思路。     

Physical properties of selected block Argonne Premium bituminous coal related to CO2, CH4, and N2 adsorption

CO₂, CH₄, and N₂ adsorption and gas-induced swelling were quantified for block Blind Canyon, Pittsburgh #8 and Pocahontas Argonne Premium coals that were dried and structurally relaxed at 75 °C in vacuum. Strain measurements were made perpendicular and parallel to the bedding plane on ~ 7 × 7 × 7 mm³ coal blocks and gravimetric sorption measurements were obtained simultaneously on companion coal blocks exposed to the same gaseous environment. The adsorption amount and strain were determined after equilibration at P  ≤ 1.8 MPa. There is a strong non-linear correlation between strain and the quantity of gas adsorbed and the results for all gases and coals studied follow a common pattern. The dependence of the coal matrix shrinkage/swelling coefficient (C_gc) on the type and quantity of gas adsorbed is seen by plotting the ratio between the strain and the adsorbate concentration against the adsorbate concentration. In general, C_gc increases with increasing adsorbate concentration over the range of ~ 0.1 to 1.4 mmol/g. Results from the dried block coals are compared to CO₂ experiments using native coals with an inherent level of moisture as received. The amount of CO₂ adsorbed using native coals (assuming no displacement of H₂O by CO₂) is significantly less than the dried coals. The gas-induced strain (S) and adsorption amount (M) were measured as a function of time following step changes in CO₂, CH₄, and N₂ pressure from vacuum to 1.8 MPa. An empirical diffusion equation was applied to the kinetic data to obtain the exponent (n) for time dependence for each experiment. The data for all coals were pooled and the exponent (n) evaluated using an ANOVA statistical analysis method. Values for (n) near 0.5 were found to be independent on the coal, the gas or type of measurement (e.g., parallel strain, perpendicular strain, and gas uptake). These data support the use of a Fickian diffusion model framework for kinetic analysis. The kinetic constant k was determined using a unipore diffusion model for each experiment and the data were pooled for ANOVA analysis. For dry coal, statistically significant differences for k were found for the gases (CO₂ > N₂ > CH₄) and coals (Pocahontas >Blind Canyon > Pittsburgh #8) but not for the method of the kinetic measurement (e.g., strain or gas uptake). For Blind Canyon and Pittsburgh #8 coal, the rate of CO₂ adsorption and gas-induced strain for dry coal was significantly greater than that of the corresponding native coal. For Pocahontas coal the rates of CO₂ adsorption and gas-induced strain for dry and native coal were indistinguishable and may be related to its low native moisture and minimal amount of created porosity upon drying.     

In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature

The structure of deuterated portlandite, Ca(OD)₂, has been investigated using time-of-flight neutron diffraction at pressures up to ∼4.5 GPa and temperatures up to ∼823 K. Rietveld analysis of the data reveals that with increasing pressure, unit-cell parameter c decreases at a rate about 4.5 times larger than that for a, which is largely due to rapid contraction of the interlayer spacing in this pressure range. Fitting of the determined cell volumes to the third-order Birch–Murnaghan equation of state yields a bulk modulus (K ₀) of 32.2 ± 1.0 GPa and its first derivative (K ₀′) of 4.4 ± 0.6. Moreover, on compression, hydrogen-mediated interatomic interactions within the interlayer become strengthened, as reflected by decreases in interlayer D···O and D···D distances with increasing pressure. Correspondingly, D–D, the distance between the three equivalent sites over which D is disordered, increases, suggesting a pressure-induced hydrogen disorder. This behavior is similar to that reported in brucite at elevated pressure. On heating at ∼2.1 GPa, cell parameter c increases more rapidly than a, as expected. However, because of the pressure effect, the thermal expansion coefficients, particularly along c, are much smaller than those at ambient pressure. With increasing temperature, the three partially occupied D sites become further apart, and the D-mediated interactions, mainly the interlayer D···D repulsion, become weakened.     

Isothermal compression behavior of (Mg,Fe)O using neon as a pressure medium

We present isothermal volume compression behavior of two polycrystalline (Mg,Fe)O samples with FeO = 39 and 78 mol% up to ~90 GPa at 300 K using synchrotron X-ray diffraction and neon as a pressure-transmitting medium. For the iron-rich (Mg_0.22Fe_0.78)O sample, a structural transition from the B1 structure to a rhombohedral structure was observed at 41.6 GPa, with no further indication of changes in structural or compression behavior changes up to 93 GPa. In contrast, a change in the compression behavior of (Mg_0.61Fe_0.39)O was observed during compression at P ≥ 71 GPa and is indicative of a spin crossover occurring in the Fe²⁺ component of (Mg_0.61Fe_0.39)O. The low-spin state exhibited a volume collapse of ~3.5%, which is a larger value than what was observed for a similar composition in a laser-heated NaCl medium. Upon decompression, the volume of the high-spin state was recovered at approximately 65 GPa. We therefore bracket the spin crossover at 65 ≤ P (GPa) ≤ 77 at 300 K (Mg_0.61Fe_0.39)O. We observed no deviation from the B1 structure in (Mg_0.61Fe_0.39)O throughout the pressure range investigated.     

Determination of acoustic phonon dispersion curves in layer silicates by inelastic neutron scattering and computer simulation techniques

Inelastic neutron scattering and computer modelling techniques have been used to study acoustic phonons in several layer silicate minerals. Experimental measurements have been made on four layer silicate minerals; namely samples of muscovite, Fe-bearing muscovite, margarite and chlorite. The longitudinal acoustic modes propagating along the [0, 0, ξ] direction of muscovite and Fe-bearing muscovite were found to be the same, within experimental error. The longitudinal and transverse acoustic modes propagating along [0, 0, ξ] of muscovite have been calculated using computer simulation techniques based on lattice dynamics. The experimental and calculated longitudinal modes of muscovite are in excellent agreement, thereby demonstrating the complementary nature of both techniques. The shape of both experimental and calculated dispersion curves was found to be approximately sinusoidal, indicating that interatomic forces act principally between nearest-neighbour atoms.     

Armalcolite stability as a function of pressure and oxygen fugacity

The stability of synthetic armalcolite of composition (Fe_0.5Mg_0.5Ti₂O₅ was studied as a function of total pressure up to 15 kbar and 1200°C and also as a function of oxygen fugacity (?O₂) at 1200°C and 1 atm total pressure. The high pressure experiments were carried out in a piston-cylinder apparatus using silver-palladium containers. At 1200°C, armalcolite is stable as a single phase at 10 kbar. With increasing pressure, it breaks down ($\text{dT}\text{dP}\text{= 20°C/}\text{kbar}$), to rutile, a more magnesian armalcolite, and ilmenite solid solution. At 14 kbar, this three-phase assemblage gives way ($\text{dT}\text{dP}\text{= 30°C/}\text{kbar}$) to a two-phase assemblage of rutile plus ilmenite solid solution.A zirconian-armalcolite was synthesized and analyzed; 4 wt % ZrO₂ appears to saturate armalcolite at 1200°C and 1 atm. The breakdown of Zr-armalcolite occurs at pressures of 1–2 kbar less than those required for the breakdown of Zr-free armalcolite. The zirconium partitions approximately equally between rutile and ilmenite phases.The stability of armalcolite as a function of ?O₂ was determined thermogravimetrically at 1200°C and 1 atm by weighing sintered pellets in a controlled atmosphere furnace. Armalcolite, (Fe_0.5Mg_0.5)-Ti₂O₅, is stable over a range ?O₂ from about 10^?9.5to 10^?10.5 atm. Below this range to at least 10^?12.8 atm, ilmenite plus a reduced armalcolite are formed. These products were observed optically and by Mössbauer spectroscopy, and no metallic iron was detected; therefore, some of the titanium must have been reduced to Ti³⁺. This reduction may provide yet another mechanism to explain the common association of ilmenite rims around lunar armalcolites.     

Development of detection and monitoring techniques of CO2 leakage from seafloor in sub-seabed CO2 storage

Carbon dioxide capture and storage (CCS) in sub-seabed geological formations is currently being studied as a potential option to mitigate the accumulation of anthropogenic CO₂ in the atmosphere. To investigate the validity of CO₂ storage in the sub-seafloor, development of techniques to detect and monitor CO₂ leaked from the seafloor is vital. Seafloor-based acoustic tomography is a technique that can be used to observe emissions of liquid CO₂ or CO₂ gas bubbles from the seafloor. By deploying a number of acoustic tomography units in a seabed area used for CCS, CO₂ leakage from the seafloor can be monitored. In addition, an in situ pH/pCO₂ sensor can take rapid and high-precision measurements in seawater, and is, therefore, able to detect pH and pCO₂ changes due to the leaked CO₂. The pH sensor uses a solid-state pH electrode and reference electrode instead of a glass electrode, and is sealed within a gas permeable membrane filled with an inner solution. Thus, by installing a pH/pCO₂ sensor onto an autonomous underwater vehicle (AUV), an automated observation technology is realized that can detect and monitor CO₂ leakage from the seafloor. Furthermore, by towing a multi-layer monitoring system (a number of pH/pCO₂ sensors and transponders) behind the AUV, the dispersion of leaked CO₂ in a CCS area can also be observed. Finally, an automatic elevator can observe the time-series dispersion of leaked CO₂. The seafloor-mounted automatic elevator consists of a buoy equipped with pH/pCO₂ and depth sensors, and uses an Eulerian method to collect spatially continuous data as it ascends and descends.Hence, CO₂ leakage from the seafloor is detected and monitored as follows. Step 1: monitor CO₂ leakage by seafloor-based acoustic tomography. Step 2: conduct mapping survey of the leakage point by using the pH/pCO₂ sensor installed in the AUV. Step 3: observe the impacted area by using a remotely operated underwater vehicle or the automatic elevator, or by towing the multi-layer monitoring system.     

Dynamics of fluid and heat flow in a CO2-based injection-production geothermal system

CO2 is now considered as a novel heat transmission fluid to extract geothermal energy. It can be used for both energy exploitation and CO2 geological sequestration. Here, a 3-D, “two-spot” pattern well model is developed to analyze the mechanism of CO2-water displacement and heat extraction. To obtain a deeper understanding of CO2-geothermal system under some more realistic conditions, heterogeneity of reservoir’s hydrological properties is taken into account. Due to the fortissimo mobility of CO2, as long as the existence of highly permeable zone between the two wells, it is more likely to flow through the highly permeable zone to reach the production well, even though the flow path is longer. The preferential flow shortens circulation time and reduces heat-exchange area, probably leading to early thermal breakthrough, which makes the production fluid temperature decrease rapidly. The analyses of flow dynamics of CO2-water fluid and heat may be useful for future design of a CO2-based geothermal development system.     

Modeling of the solubility of a one-component H2O or CO2 fluid in silicate liquids

The modeling of the solubility of water and carbon dioxide in silicate liquids (flash problem) is performed by assuming mechanical, thermal, and chemical equilibrium between the liquid magma and the gas phase. The liquid phase is treated as a mixture of ten silicate components + H₂O or CO₂, and the gas phase as a pure H₂O or CO₂. A general model for the solubility of a volatile component in a liquid is adopted. This requires the definition of a mixing equation for the excess Gibbs free energy of the liquid phase and an appropriate reference state for the dissolved volatile. To constrain the model parameters and identify the most appropriate form of the solubility equations for each dissolved volatile, a large number of experimental solubility determinations (640 for H₂O and 263 for CO₂) have been used. These determinations cover a large region of the P-T-composition space of interest. The resultant water and carbon dioxide solubility models differ in that the water model is regular and isometric, and the carbon dioxide model is regular and non-isometric. This difference is consistent with the different speciation modalities of the two volatiles in the silicate liquids, producing a composition-independent partial molar volume of dissolved water and a composition-dependent partial molar volume of dissolved carbon dioxide. The H₂O solubility model may be applied to natural magmas of virtually any composition in the P-T range 0.1 MPa–1 GPa and > 1000 K, whereas the CO₂ solubility model may be applied to several GPa pressures. The general consistency of the water solubility data and their relatively large number as compared to the calibrated model parameters (11) contrast with the large inconsistencies of the carbon dioxide solubility determinations and their low number with respect to the CO₂ model parameters (22). As a result, most of the solubility data in the database are reproduced within 10% of approximation in the case of water, and 30% in the case of carbon dioxide. When compared with the experimental data, the H₂O and CO₂ solubility models correctly predict many features of the saturation surface in the P-T-composition space, including the change from retrograde to prograde H₂O solubility in albitic liquids with increasing pressure, the so-called alkali effect, the increasing CO₂ solubility with increasing degree of silica undersaturation, the Henrian behavior of CO₂ in most silicate liquids up to about 30–50 MPa, and the proportionality between the fugacity in the gas phase, or the saturation activity in the liquid phase, and the square of the mole fraction of the dissolved volatile found in some unrelated silicate liquid compositions. Received: 21 August 1995 / Accepted: 8 July 1996     

A review of fluid flow and heat transfer in the CO2-EGS

Carbon dioxide enhanced geothermal system (CO2-EGS) now is an emerging research field that is attracting an increasing research interest with broad application prospects based on its low-carbon, economical and renewable features. The fluid flow and heat transfer is the core of CO2-EGS research. In this paper, further research focus is pointed out after summarizing the latest research progress in this field based on the explanation and the advantages of CO2-EGS development process in the hope of providing reference for researchers engaged in this field.     

Solubility of crude oil in methane as a function of pressure and temperature

The solubility of a 44° API (0.806 sp. gr.) whole crude oil has been measured in methane with water present at temperatures of 50 to 250°C and pressures of 740 to 14,852 psi, as have the solubilities of two high molecular weight petroleum distillation fractions at temperatures of 50 to 250°C and pressures of 4482 to 25,266 psi. Both increases in pressure and temperature increase the solubility of crude oil and petroleum distillation fractions in methane, the effect of pressure being greater than that of temperature. Unexpectedly high solubility levels (0.5–1.5 grams of oil per liter of methane—at laboratory temperature and pressure) were measured at moderate conditions (50–200°C and 5076–14504 psi). Similar results were found for the petroleum distillation fractions, one of which was the highest molecular weight material of petroleum (material boiling above 266°C at 6 microns pressure). Unexpectedly mild conditions (100°C and 15,200 psi; 200°C and 7513 psi) resulted in cosolubility of crude oil and methane. Under these conditions, samples of the gas-rich phase gave solubility values of 4 to 5 g/l, or greater.Qualitative analyses of the crude-oil solute samples showed that at low pressure and temperature equilibration conditions, the solute condensate would be enriched in C₅–C₁₅ range hydrocarbons and in saturated hydrocarbons in the C₁₅₊ fraction. With increases in temperature and especially pressure, these tendencies were reversed, and the solute condensate became identical to the starting crude oil.The data of this study, compared to that of previous studies, shows that methane, with water present, has a much greater carrying capacity for crude oil than in dry systems. The presence of water also drastically lowers the temperature and pressure conditions required for cosolubility.The data of this and/or previous studies demonstrate that the addition of carbon dioxide, ethane, propane, or butane to methane also has a strong positive effect on crude oil solubility, as does the presence of fine grained rocks.The n-paraffin distributions (as well as the overall composition) of the solute condensates are controlled by the temperature and pressure of solution and exsolution, as well as by the composition of the original starting material. It appears quite possible that primary migration by gaseous solution could ‘strip’ a source rock of crude-oil like components leaving behind a bitumen totally unlike the migrated crude oil. The data of this study demonstrate previous criticisms of primary petroleum migration by gas solution are invalid; that primary migration by gaseous solution cannot occur because methane cannot dissolve sufficient volumes of crude oil or cannot dissolve the highest molecular weight components of petroleum (tars and asphaltenes).     

Development of a CO2 emission factor in Korea from sub-bituminous coal by the classification method

While the Intergovernmental Panel on Climate Change classifies coal as anthracite, bituminous coal, and sub-bituminous coal, Korea only distinguishes coal as anthracite and bituminous coal while sub-bituminous coal is considered bituminous coal. As a result, Korea conducted research in the CO₂ emission factors of anthracite and bituminous coal, but largely ignored sub-bituminous coal. Therefore, the purpose of this research is to develop the CO₂ emission factor of sub-bituminous coal by classifying sub-bituminous coal from resources of bituminous coal activities collected in Korea between 2007 and 2011. The 2007–2011 average carbon content of sub-bituminous coal was analyzed to be 69.63 ± 3.11 %, the average hydrogen content 4.97 ± 0.37 %, the inherent moisture 12.60 ± 4.33 %, the total moisture 21.91 ± 5.45 %, and the dry-based gross calorific value was analyzed to be 5,914 ± 391 kcal/kg; using these analyzed values, the as-received net calorific value was found to be 20.75 ± 7.59 TJ/Gg and the CO₂ emission factor was found to be 96,241 ± 4,064 kg/TJ. In addition, the 62.7 million ton amount for the 2009 greenhouse gas emission from sub-bituminous coal as estimated with the analyzed value of this study is an amount that is equivalent to 11.1 % of the 2009 total greenhouse gas emission amount of 564.7 million tons, and this amount is larger than the 9.3 % for the industrial processes sector, 3.3 % for the agricultural sector and 2.5 % for the waste sector. Therefore, it is important to reflect the realities of Korea when estimating the greenhouse gas emission from such sub-bituminous coals.