Kinetic simulation of hydrocarbon generation from lacustrine type I kerogen from the Songliao Basin: Model comparison and geological application

Eight lacustrine Type I kerogen samples from the Songliao Basin were pyrolyzed using the Rock-Eval equipment, and parallel first-order reaction models including the model with a single frequency factor and a discrete distribution of activation energies (SFF model) and the model with multiple frequency factors and a discrete distribution of activation energies (MFF model) were adopted to analyze kinetic characteristics of hydrocarbon generation of the Type I kerogen samples. The results show that the MFF and SFF models can satisfactory simulate hydrocarbon generation under laboratory conditions and the Type I kerogen shows relatively concentrated activation energy distributions (activation energies of MFF model range from 190 kJ/mol to 250 kJ/mol, activation energies of SFF model range from 220 kJ/mol to 240 kJ/mol), which indicates a homogeneous chemical bond structure of the Type I kerogen. The hydrocarbon generated curves from Type I kerogen were calculated by using the two models with a linear heating rate (3.3 K/Ma). It indicates that the hydrocarbon generation potentials (reaction fractions) are underestimated by using the SFF model during the kerogen thermal degradation for the components with chemical bond of lower and higher activation energies, while this problem can be avoided by using the MFF model. The calculated temperatures for 50% transformation ratio (TR) of all samples differ by as much as 20 °C. For the SFF model, the hydrocarbon generation curve obtained by using the weighted averaged kinetic parameters and the SFF model almost includes every curve calculated by using its own kinetic parameters. While the curve obtained by using the weighted averaged kinetic parameters and the MFF model cannot include every curve for all samples, it lies at the position of the averaged curve of all samples. The application of the MFF model in Songliao Basin shows that if TR 10% is taken as the onset of hydrocarbon generation, the threshold depth of hydrocarbon generation is about 1700 m, which is consistent with other geochemical parameters, such as S₁/TOC, S₁/(S₁ + S₂) and HC/TOC.     

多孔介质中石油挥发过程研究

根据齐鲁石化地区石油污染特点,模拟天然条件下,多孔介质中石油的挥发过程,通过差减法确定石油挥发量与时间的关系。结果表明,Elovich模型和零级动力学方程分别能很好描述多孔介质中汽油和柴油挥发动力学曲线,且汽油在粗砂中的挥发速率系数较在亚黏土中大,而柴油在亚黏土中的挥发速率系数是在粗砂中的2.0~2.5倍。采用线性方程和二项式分别表达多孔介质中汽油和柴油挥发速率系数随含油率增加而增加的趋势。汽油在亚黏土中较在粗砂中的挥发率低,但挥发率一般均在90%以上;经过10 d挥发后,柴油在亚黏土中挥发率为7.2%~37.8%,在粗砂中的挥发率为5.0%~14.0%。     

盐卤硼酸盐化学XXVLi2O—B2O3—H2O过饱和溶液20℃结晶动力学研究

Ｌｉ２Ｏ·３Ｂ２Ｏ３—Ｈ２Ｏ及Ｌｉ２Ｏ·４Ｂ２Ｏ３—Ｈ２Ｏ）过饱和溶液２０℃结晶过程均只有一个阶段。前者结晶析出Ｌｉ２Ｂ４Ｏ７·３Ｈ２Ｏ，后者结晶析出ＬｉＢ５Ｏ８·５Ｈ２Ｏ。本文探讨了这两种固相的结晶机理并拟合出结晶动力学方程，结果表明两个结晶过程均受控于单核表面反应。     

强震前的“加速矩释放”（AMR）现象：对一个有争议的地震前兆的回溯性震例研究

近年来,国际上对于强震前的加速矩释放（AMR）现象是否可作为一种可靠的、带有普遍性的地震前兆现象争议较大.本文以2008年3月21日新疆于田M_S7.3地震为例,试图从前兆存在的客观性和与地震发生的物理相关性两方面考察本次地震前的AMR现象.用“破裂时间分析”方程中的幂指数m作为描述震前加速矩释放“程度”的参量,在时间-空间-地震序列截止震级组成的三维参数空间（T,R,M_c）内考察AMR现象存在的客观性.考虑了多种因素对m（T, R, M_c）分布图像可能的影响,其中,余震是否删除和M_c对计算影响不大,但M_L6.0以上“干扰”事件的影响则较大.结果表明,于田地震前的确存在AMR现象,但得到的m（T, R, M_c）分布图像较为复杂,可观测到两个明显的AMR集中分布区.此外,在以实际震中为圆心的多个圆形区域内,使用固定时间窗向实际发震时刻滑动逼近,可观测到m值逐渐减小,即加速特征逐渐明显的过程.对震前矩释放程度m值的时-空扫描结果显示,出现AMR现象的空间区域与震中位置似有较好的对应,但其时-空演化图像与滑动时-空窗的选取有关.这表明,本次M_S7.3地震前的确存在AMR现象,并与其孕震过程在物理上相关.但本文仅是一个震例的研究,无法给出具有统计显著性的结论,此外,用AMR来约束地震发生的时间看来是困难的.     

Comparison of alternative upscaled model formulations for simulating DNAPL source dissolution and biodecay

This paper compares the performance of analytical and numerical approaches for modeling DNAPL dissolution with biodecay. A solution derived from a 1-D advective transport formulation (“Parker” model) is shown to agree very closely with high resolution numerical solutions. A simple lumped source mass balance solution in which with decay is assumed proportional to DNAPL mass (“Falta1” model) over- or underpredicts aqueous phase biodecay depending on the magnitude of the exponential factor governing the relationship between dissolution rate and DNAPL mass. A modification of the Falta model that assumes decay proportional to the source exit concentration is capable of accurately simulating source behavior with strong aqueous phase biodecay if model parameters are appropriately selected or calibrated (“Falta2” model). However, parameters in the lumped models exhibit complex interdependencies that cannot be quantified without consideration of transport processes within the source zone. Combining the Falta2 solution with relationships derived from the Parker model was found to resolve these limitations and track the numerical model results. A method is presented to generalize the analytical solutions to enable simulation of partial mass removal with changes in source parameters over time due to various remedial actions. The algorithm is verified by comparison with numerical simulation results. An example application is presented that demonstrates the interactions of partial mass removal, enhanced biodecay, enhanced mass transfer and source zone flow reduction applied at various time periods on contaminant flux reduction. Increasing errors that arise in numerical solutions with coarse discretization and high decay rates are shown to be controlled by using an adjusted decay coefficient derived from the Parker analytical solution.     

川东北飞仙关组鲕滩气藏天然气运聚效率

设计进行了封闭体系下原油裂解成气的模拟实验, 建立并标定了原油裂解成气及其碳同位素分馏的化学动力学模型, 以罗家寨气田罗家7井为例分别进行了地质应用.生烃动力学研究发现, 飞仙关组古油藏具备“高效气源灶”的特点, 原油在中晚侏罗世172~151Ma约20Ma时期内裂解殆尽, 且原油裂解气的生成与其运聚成藏作用具有良好的时空匹配关系, 由此可促成飞仙关组气藏天然气的高效运聚.碳同位素分馏动力学研究证实甲烷成藏参与率达87%.利用生烃动力学与碳同位素分馏动力学结合的方法对天然气的运聚效率进行探讨是一个新的有效途径.      

Combustion Kinetics of Athabasca Bitumen from 1D Combustion Tube Experiments

There are two basic requirements for heavy-oil recovery processes: first, mobilize the bitumen, and second, have a drive mechanism deliver the mobilized bitumen to a production wellbore. In situ combustion has the potential to be an important heavy-oil recovery method. Before design of in situ combustion recovery processes can start, it is necessary as a first step to understand the kinetics of various complex chemical reactions and determine kinetic constants associated with the reactions. Even with modern reservoir simulation capabilities, this is a significant challenge. In this research, an Athabasca bitumen combustion tube experiment, conducted by the ISC Research Group at the University of Calgary, was history matched by using a reservoir thermal simulator to determine a set of kinetic parameters as well as the transport parameters for the system. The main results of the history match was a match of air injection rate, bitumen and gas production volumes, average product gas compositions, temperature profiles along the tube through time, and pressure. Gridding sensitivities were examined to determine if the derived kinetic and transport parameters were dependent on gridblock size. The results revealed that the grid was refined enough to sufficiently capture thermal, mass transfer, and reaction length scales. After this single match was achieved, the same constants were used to successfully predict several other combustion tube experiments. The results suggest that the fuel (coke) for high-temperature oxidation (HTO) originates mainly from low-temperature oxidation (LTO) and not from thermal cracking. This implies that the major control on HTO is upstream oxygen transfer into the LTO region. If LTO does not occur, then a relatively small amount of coke is deposited in the matrix due to thermal cracking and this may be insufficient to start or sustain HTO.     

Adsorption kinetics, isotherm, and thermodynamic studies of adsorption of pollutant from aqueous solutions onto humic acid

In the present study,humic acid was used as an adsorbent for the investigation of the adsorption kinetics,isotherms,and thermo-dynamic parameters of hexavalent chromium from aqueous solution at varying pH,temperatures,and concentrations.Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to three well-known iso-therm models:Langmuir,Freundlich,and Redlich-Peterson.The results showed that the Langmuir and Redlich-Peterson models appear to fit the adsorption better than did the Freundlich adsorption model for the adsorption of chromium onto humic acid.The equilibrium constants were used to calculate thermodynamic parameters such as the change of free energy,enthalpy,and entropy.The derived adsorption constants (logaL) and their temperature dependencies from Langmuir isotherm have been used to calculate the corresponding thermodynamic quantities such as the free energy of adsorption,heat,and entropy of adsorption.The thermo-dynamic data indicate that Cr (VI) adsorption onto humic acid is entropically driven and characterized by physical adsorption.     

Comments on “Two-dimensional concentration distribution for mixing-controlled bioreactive transport in steady-state” by O.A. Cirpka and A.J. Valocchi

In this comment we present a re-analysis of the analytical solution presented by Cirpka and Valocchi for steady-state concentrations of dissolved bioreactive compounds and bacterial biomass in porous media. We discuss the validity range of the analytical solution. In particular, the criterion used to determine the sustainability of biomass is revisited. This re-analysis shows that the ω$\omega$ criterion used by Cirpka and Valocchi is only a necessary but not a sufficient criterion to determine the bioreactive zones. As a consequence, the analytical solution does not provide the exact distribution of compounds throughout the domain, but can serve as upper or lower boundaries for species concentrations at a given location. These conclusions are supported by the simulation results obtained from an established reactive transport model.