铵在中砂上的3种吸附形态研究     

付佳妮  刘菲  陈坚  徐基胜  梁静 《矿物学报》2011,31(4):757-764

通过动力学和等温吸附实验,研究了不同初始氨氮浓度下水溶铵、交换铵和固定铵在中砂上的吸附规律。结果表明,吸附平衡时各种形态铵含量随初始氨氮浓度增加而增大。3种形态铵吸附行为符合准二级动力学方程。吸附速率常数K大小顺序为：固定铵〉交换铵〉水溶铵,初始速率：固定铵〈交换铵〈水溶铵。随着初始氨氮浓度的增加,水溶铵占总铵的比重由40%上升到65%,其吸附的主要限制步骤为颗粒间扩散。交换铵对总铵的贡献率维持在25%左右,吸附饱和后有所降低,初始氨氮浓度为交换铵吸附的主要限制步骤。固定铵达到饱和时,吸附量只有26.18 mg/kg,对总铵的贡献率由33%下降到9%。  相似文献   

The Impact of Aqueous Medium on Gas Yields and Kinetic Behaviors of Hydrogen Isotope Fractionation during Organic Matter Thermal Degradation     

LU Shuangfang  WANG Min  XUE Haitao  LI Jijun  CHEN Fangwen  XU Qingxia 《《地质学报》英文版》2011,85(6):1466-1477

In order to recognize the impact of aqueous medium on gas yields and the kinetic behaviors of hydrogen isotope fractionation during organic matter thermal degradation, the gold tube apparatus was used to conduct thermal simulation experiments by mixing the nC18 with the water of different properties and proportions. The yields of natural gas components, the relation among hydrogen isotope composition of each component and the experimental temperatures vs. heating rates have been obtained, and the results indicate that under the higher temperature conditions, the hydrous experiment has obvious impact on gas yields, such as when more water is added, higher amounts of hydrocarbon gas and H2 are yielded, and the existence of water obviously prolongs the temperature interval with the existence of heavy hydrocarbon gas. It also shows that the hydrogen isotope of hydrocarbon gas generated by the hydrous experiment is obviously lighter than that generated by the anhydrous experiment, and with the increasing amount of added water, the δD value of hydrocarbon gas gradually decreases. Compared with gas yields, the variation of δD value is more sensitive to aqueous medium in the thermal simulation experiment. However, compared with the amount of the added water, the aqueous medium property has smaller impact on the gas yields, which still shows the inherit effect on hydrogen isotope composition of aqueous medium. Through the model simulation and the isotope fractionation behavior analysis, it is validated that the hydrogen isotope fractionation process can be well described by the chemical kinetic model. The difference of reaction fraction of normal methane and D-containing methane is large, corresponding to the same activation energy. The content of normal methane is obviously higher in the part with lower activation energy, while the content of D-containing methane is higher in the part with higher activation energy. Therefore, it will result in larger hydrogen isotope fractionation amplitude, and the δD values will be more sensitive to the variation of maturity. Meanwhile, the average activation energy of methane generation from nC18 in the hydrous experiment is higher than that in the anhydrous experiment, and the greater amount of added water, the larger the average activation energy of methane generation reaction. This has laid foundation for its exploratory application in the study of gas reservoir forming history and the gas-source correlation, which indicates the research and application prospects in this orientation.  相似文献   

Water Role and Its Influence on Hydrogen Isotopic Composition of Natural Gas during Gas Generation     

LI Jijun  LU Shuangfang  WU Wei  XUE Haitao  XU Qingxi  GENG Jie  YU Yinghua 《《地质学报》英文版》2011,85(5):1203-1210

In order to discuss the role and influence of water during the generation of natural gas, the participation mechanism of water during the evolution of organic matter and its influences were summarized. In addition, we carried out an anhydrous cracking experiment of oil extracted from the Feixianguan Formation source rock in a closed system, which led to the establishment of the kinetic models for describing carbon and hydrogen isotopic fractionation during gas generation from organic matter. The models were calibrated and then applied to the northeastern Sichuan Basin. By combining a series of gas generation experiments from octadecane pyrolysis without water or with distilled water in varying mass proportions, several results were proved: (1) the hydrogen isotopic composition of natural gas becomes lighter with the participation of formation water; (2) we can quantitatively study the hydrogen isotopic fractionation with the kinetic model for describing carbon isotopic fractionation; (3) more abundant and reliable geological information can be obtained through the combined application of carbon and hydrogen isotopic indices.  相似文献   

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

Wang Min  Lu Shuang-fangXue Hai-tao 《Marine and Petroleum Geology》2011,28(9):1714-1726

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.  相似文献   

多孔介质中石油挥发过程研究     

马艳飞  郑西来  冯雪冬  李永霞 《中国海洋大学学报(自然科学版)》2011,41(9):53-58

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%。  相似文献   

New modeling paradigms for the sorption of hydrophobic organic chemicals to heterogeneous carbonaceous matter in soils, sediments, and rocks   总被引：4，自引：0，他引：4  

Richelle M. Allen-King  Peter Grathwohl  William P. Ball   《Advances in water resources》2002,25(8-12)

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The Reaction Kinetics between CO2-bearing Fluid and Olivines/Hawaiian Picrites     

WANG Zhengrong  QIU Lin  ZHANG Shuang  KARATO Shun-ichiro  Kevin JOHNSON  Jay AGUE  Michael ORISTAGLIO  Edward BOLTON  David BERCOVICI 《《地质学报》英文版》2013,87(Z1):967-968

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

姚占力  高世扬 《盐湖研究》1995,3(4):44-49

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。  相似文献   

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

Jack C. Parker  Ronald W. Falta 《Advances in water resources》2008

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.  相似文献   

川东北飞仙关组鲕滩气藏天然气运聚效率   总被引：3，自引：1，他引：2  

李吉君  卢双舫  薛海涛  胡国艺  谢增业  徐庆霞 《地球科学》2008,33(4):565-571

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.   相似文献