Inverse methods and kinetic models of hydrocarbon generation: III. Case histories for autoclave product analysis

From a determination of the transformation matrix for three pyrolysis product experimental data sets, an examination is given of both the applicability of the laboratory experimental data to the modeling of oil cracking in a sedimentary basin, and of the appropriateness of an inverse model. The results of the laboratory experimental data sets, which were done under different thermodynamic conditions and using different sources, show that the transformation matrix varies over each data set and also with time. Therefore, it is necessary to check the data sets before applying them to a basin for hydrocarbon modeling. The laboratory experimental data taken at lower temperature and over longer times appear more pertinent for the construction of an oil-cracking kinetic model suitable for geologic conditions.     

High pressure metamorphism in the nappes of the Valle dell'Orco traverse (Western Alps collisional belt) *

Abstract A detailed field and petrological study of rocks from nappes cut by the Valle dell'Orco (Italian Western Alps), in particular the Sesia–Lanzo composite unit, has revealed geological and metamorphic histories which started in pre-alpine times and lasted up to the alpine subduction-collisional processes. During these processes the nappes sustained an early high P–low T stage and a later low P greenschist facies stage, but followed partly distinctive P–T–time trajectories. This paper discusses the kinematic evolution and the thermal history of the alpine belt from the early subduction/underthrust to the later exhumation stage. The metamorphic crystallization is often governed by incomplete and/or local equilibrium, and the pervasive syn-metamorphic deformation and the composition of the syn-metamorphic fluid phase (if present) have exerted an effective local control on reaction kinetics.     

Kinetics of phosphate adsorption by iron oxyhydroxides in aqueous systems

The rate of uptake of phosphate onto synthetic Fe(III)- and Fe(II)-derived oxyhydroxides has been studied using reaction conditions similar to those encountered in natural waters. Kinetic analyses were carried out on the adsorption profiles and both first-order and second-order conditional rate constants were obtained. The temperature dependence of some of the rate constants was investigated and corresponding apparent activation energies calculated. Similar experiments and analyses were undertaken using Fe from natural sources and in general the conditional rate constants obtained in seawater were in agreement with the synthetic ones. The results of this study are of value when comparing the time scales of adsorption processes in natural waters with the time scales of mixing and advection.     

A Comparative Study of Pollutant Removal Stability in Hybrid Wetland Columns

This study investigated the effects of two alternative substrates(wood mulch and zeolite) on the performance of three laboratory-scale hybrid wetland systems that had identical system components and configurations.Each system consisted of a vertical flow(VF) wetland column,followed by a horizontal flow(HF) column and a vertical flow column.The substrates employed were wood mulch,gravel and zeolite,and Phragmites australis were planted in each column.The systems received synthetic wastewater,with pollutant loadings in the range of 8.5-38.0 g/(m2·d) total nitrogen(TN) and 4.0-46.4 g/(m2·d) biological oxygen demand(BOD5).Wood mulch and zeolite substrates showed higher efficiencies in terms of removing nitrogenous compounds and biodegradable organics.The supply of organic carbon from the organic mulch substrates enhanced denitrification,while adsorption of influent ammoniacal nitrogen(NH4-N) in zeolite played a major role in the removal of nitrogenous species in the wetland columns.Overall,the average percentage removals of TN and BOD5 reached >66% and >96% respectively,indicating stable performances by the hybrid wetland systems under the experimental loading ranges.Mathematical models were developed,based on the combination of Monod kinetics and continuously-stirred tank reactor(CSTR) flow patterns to describe the degradation of nitrogenous compounds.Predictions by the models closely matched the experimental data,indicating the validity and potential application of Monod kinetics in the modelling and design of treatment wetlands.     

Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia

The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H₂O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ～70 °C overstepping was required for the growth of Al₂SiO₅ from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.     

吐哈盆地低熟气评价的化学动力学方法及其应用

针对目前尚无公认的有效方法评价低熟气生成量的难题,本文从低熟气的（低温）热成因机理出发,认为被广泛、成功应用于成熟的热成因天然气生成量评价的化学动力学理论仍然应该是评价低熟气生成量的有效方法。在此基础上,建立并标定了吐哈盆地代表性泥岩、煤岩干酪根成气的化学动力学模型,与可能部分成为低熟气先质的非烃、沥青质的化学动力学模型一起,构成了评价低熟气生成量的方法。标定结果表明,盆地内有机质成气的平均活化能低于其成油的活化能,而且成气过程中低活化能组分的含量也高于成油过程。这可能正是吐哈盆地的有机质在大量生油之前的低成熟阶段,能开始规模性地生成低熟气、从而导致工业性的低熟气聚集的内因所在。应用表明,吐哈盆地低熟气的总生成量可观,达到632．15×10^11 m^3,而且生气强度较高,最高达到100×10^8m^3／km^2以上。吐哈盆地低熟气资源量约为3．16×10^11～12．62×10^11 m^3。可见,盆地内低熟气具有可观的勘探潜力。本文所建立的方法应该可被推广应用到其他含低熟气盆地的低熟气的评价当中。     

爱沙尼亚干酪根催化降解生烃过程及动力学研究

以爱沙尼亚油页岩干酪根为对象,利用热模拟实验方法和化工催化原理,考察了不同介质对干酪根热解生烃过程的影响,从热解生烃量、生烃组成特征及生烃动力学等方面进行了探讨。结果表明:膏岩对干酪根的生烃具有明显催化作用,碳酸盐岩对干酪根的生烃具有一定反催化作用,各种盐类对干酪根的生烃量影响较小。干酪根热解动力学研究表明,生烃动力学参数表观活化能E与视频率因子A两者之间不是独立变化的,而是具有一定的关系,即:E与lnA之间服从直线关系(R=0.99),这些认识对于深入探讨爱沙尼亚油页岩干酪根的化学结构、建立热解动力学模型具有一定的参考价值。     

Calibration method affects the measured δ2H and δ18O in soil water by direct H2Oliquid–H2Ovapour equilibration with laser spectroscopy

The direct H₂O_liquid–H₂O_vapour equilibration method utilizing laser spectroscopy (DVE-LS) is a way to measure soil pore water stable isotopes. Various equilibration times and calibration methods have been used in DVE-LS. Yet little is known about their effects on the accuracy of the obtained isotope values. The objective of this study was to evaluate how equilibration time and calibration methods affect the accuracy of DVE-LS. We did both spiking and field soil experiments. For the spiking experiment, we applied DVE-LS to four soils of different textures, each of which was subjected to five water contents and six equilibration times. For the field soil experiment, we applied three calibration methods for DVE-LS to two field soil profiles, and the results were compared with cryogenic vacuum distillation (CVD)-LS. Results showed that DVE-LS demonstrated higher δ²H and δ¹⁸O as equilibration time increased, but 12 to 24 hr could be used as optimal equilibration time. For field soil samples, DVE-LS with liquid waters as standards led to significantly higher δ²H and δ¹⁸O than CVD-LS, with root mean square error (RMSE) of 8.06‰ for δ²H and 0.98‰ for δ¹⁸O. Calibration with soil texture reduced RMSE to 3.53‰ and 0.72‰ for δ²H and δ¹⁸O, respectively. Further, calibration with both soil texture and water content decreased RMSE to 3.10‰ for δ²H and 0.73‰ for δ¹⁸O. Our findings conclude that the calibration method applied may affect the measured soil water isotope values from DVE-LS.     

碳酸氢钠冷却结晶动力学

碳酸氢钠(NaHCO_3)俗称小苏打,其产品质量取决于颗粒的大小,晶体的形貌和样品的纯度等诸多因素。本论文基于连续稳态MSMPR结晶器原理,研究了不同停留时间下,碳酸氢钠从碳酸钠溶液中冷却结晶过程动力学。利用实验数据建立了NaHCO_3的结晶动力学操作模型。实验和计算结果表明,随停留时间的增加,NaHCO_3过饱和度降低,晶体生长速率和成核速率均减小,相应的平均粒径增加,细颗粒含量减小;适当延长停留时间是制取高品质小苏打产品的有效途径。冷却结晶过程可有效增加小苏打产量,小苏打收率维持在55%左右。此外,一定Na_2CO_3存在下冷却结晶碳酸氢钠晶体形态由细长的针状变为规整的片状。     

东营凹陷民丰地区天然气生成机理与化学动力学研究

民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30～40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。