海相碳酸盐岩干酪根热解成气过程及其碳同位素演化特征

应用高压封闭体系,对海相碳酸盐岩干酪根进行了热裂解模拟实验,并从气态烃、非气态烃产率及碳同位素演化特征等方面,探讨了海相碳酸盐岩烃源岩干酪根作为气源的生气机理。在模拟实验基础上,结合专用Kinetics软件求取碳酸盐岩烃源岩干酪根裂解产气动力学参数(活化能和指前因子),并将模拟实验结果外推至地质条件下,探讨其动力学模型的实际应用。结果表明,在该地质条件下,甲烷在EasyRo为0.9%时进入主生气期(转化率为10%),2.9%时主生气期结束(转化率为90%)。乙烷至戊烷在EasyRo为1.1%时进入主生气期(转化率10%),2.7%时主生气期结束(转化率90%)。该研究成果为我国海相碳酸盐岩裂解气的判识、资源评价提供了可靠的实验依据。     

Kinetic control of staurolite–Al2SiO5 mineral assemblages: Implications for Barrovian and Buchan metamorphism

The distribution and textural features of staurolite–Al₂SiO₅ mineral assemblages do not agree with predictions of current equilibrium phase diagrams. In contrast to abundant examples of Barrovian staurolite–kyanite–sillimanite sequences and Buchan‐type staurolite–andalusite–sillimanite sequences, there are few examples of staurolite–sillimanite sequences with neither kyanite nor andalusite anywhere in the sequence, despite the wide (~2.5 kbar) pressure interval in which they are predicted. Textural features of staurolite–kyanite or staurolite–andalusite mineral assemblages commonly imply no reaction relationship between the two minerals, at odds with the predicted first development (in a prograde sense) of kyanite or andalusite at the expense of staurolite in current phase diagrams. In a number of prograde sequences, the incoming of staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is coincident or nearly so, rather than kyanite or andalusite developing upgrade of a significant staurolite zone as predicted. The width of zones of coexisting staurolite and either kyanite, in Barrovian sequences, or andalusite, in Buchan‐type sequences, is much wider than predicted in equilibrium phase diagrams, and staurolite commonly persists upgrade until its demise in the sillimanite zone. We argue that disequilibrium processes provide the best explanation for these mismatches. We suggest that kyanite (or andalusite) may develop independently and approximately contemporaneously with staurolite by metastable chlorite‐consuming reactions that occur at lower P–T conditions than the thermodynamically predicted staurolite‐to‐kyanite/andalusite reaction, a process that involves only modest overstepping (<15°C) of the stable chlorite‐to‐staurolite reaction and which is favoured, in the case of kyanite, by advantageous nucleation kinetics. If so, the pressure difference between Barrovian kyanite‐bearing sequences and Buchan andalusite‐bearing sequences could be ~1 kbar or less, in better agreement with the natural record. The unusual width of coexistence of staurolite and Al₂SiO₅ minerals, in particular kyanite and andalusite, can be accounted for by a combination of lack of thermodynamic driving force for conversion of staurolite to kyanite or andalusite, sluggish dissolution of staurolite, and possibly the absence of a fluid phase to catalyse reaction. This study represents an example of how kinetic controls on metamorphic mineral assemblage development have to be considered in regional as well as contact metamorphism.     

水-岩化学作用等效裂纹扩展细观力学模型

从化学腐蚀下岩石细观结构的变化出发,研究水化学溶液对岩石中裂纹的腐蚀作用。运用地球化学矿物-水反应的溶解动力学,考查水-岩反应化学溶液中不同时间段离子浓度的变化,从理论上探讨化学腐蚀下等效裂纹扩展的定量化分析方法。通过质量守恒定律计算出裂纹在迹长及隙宽方向的变化,将水化腐蚀等效成有效裂纹长度,建立了水-岩化学作用下等效裂纹扩展的计算公式并计算应力强度因子。通过对砂岩的研究结果表明,水-岩化学作用对岩石裂纹的扩展有显著影响,并且具有时间效应。同时,水化学溶液的离子浓度及pH值大小对裂纹的扩展存在影响,其中pH值的变化对岩石的断裂力学效应更加显著。当溶液的酸性越强或碱性越强,腐蚀越大,裂纹扩展越快;pH值为中性时,腐蚀作用得到较大缓解,裂纹发展缓慢。为定量研究裂隙岩体在水岩化学作用下的细观机理提供了一种新的思路。     

水化学作用对砂岩抗剪强度特性影响效应研究

开展了不同水化学溶液侵蚀条件下砂岩的抗剪强度试验,分析了水化学作用对砂岩微细观结构的影响效应,探讨了砂岩的水化学损伤机制。在此基础上,分析了水化学作用对砂岩抗剪强度的影响规律。通过引入岩石水化学损伤度,定量表达了砂岩抗剪强度参数随水化学损伤的演化过程,并采用化学动力学方法,模拟在给定水化学环境条件下重庆砂岩损伤度随时间演化过程,进而预测其抗剪强度参数演化规律。所得结果为定量化研究水化学作用对岩石物理力学特性的影响效应及预测与水化学作用相关的岩土工程的安全性和稳定性提供了良好的借鉴作用。     

负载镧的EGDE交联壳聚糖微球对氟离子的吸附平衡与吸附动力学

采用负载镧的乙二醇二缩水甘油醚(EGDE)交联壳聚糖微球对含氟水进行吸附处理.该吸附剂的适宜工作条件为:温度30～50℃,pH值7.0,吸附时间30 min.用吸附等温线描述了F-在吸附剂上的吸附平衡,并用动力学模型研究了其吸附动力学机制.结果表明:吸附剂对F-的吸附平衡符合Langmuir吸附等温线和Freundlich吸附等温线,饱和吸附容量为25.7mg·g-1;该吸附剂对F-的吸附既包含化学吸附又包含物理吸附过程,以单分子层的化学吸附为主;吸附动力学符合拟二级动力学方程,吸附过程受化学吸附机理的控制,颗粒内扩散和液膜形成的边界层是其限速步骤.     

Electrochemical properties of electrodes with different shapes and diffusion kinetic analysis of microbial fuel cells on ocean floor

Microbial fuel cell(MFC) on the ocean floor is a kind of novel energy-harvesting device that can be developed to drive small instruments to work continuously.The shape of electrode has a great effect on the performance of the MFC.In this paper,several shapes of electrode and cell structure were designed,and their performance in MFC were compared in pairs:Mesh(cell-1) vs.flat plate(cell-2),branch(cell-3) vs.cylinder(cell-4),and forest(cell-5) vs.disk(cell-6) FC.Our results showed that the maximum power densities were 16.50,14.20,19.30,15.00,14.64,and 9.95 mWm-2 for cell-1,2,3,4,5 and 6 respectively.And the corre-sponding diffusion-limited currents were 7.16,2.80,18.86,10.50,18.00,and 6.900 mA.The mesh and branch anodes showed higher power densities and much higher diffusion-limited currents than the flat plate and the cylinder anodes respectively due to the low diffusion hindrance with the former anodes.The forest cathode improved by 47% of the power density and by 161% of diffusion-limited current than the disk cathode due to the former’s extended solid/liquid/gas three-phase boundary.These results indicated that the shape of electrode is a major parameter that determining the diffusion-limited current of an MFC,and the differences in the elec-trode shape lead to the differences in cell performance.These results would be useful for MFC structure design in practical applica-tions.     

Kinetic study of alkaline protease 894 for the hydrolysis of the pearl oyster Pinctada martensii

A new enzyme (alkaline protease 894) obtained from the marine extremophile Flavobacterium yellowsea (YS-80-122) has exhibited strong substrate-binding and catalytic activity, even at low temperature, but the characteristics of the hydrolysis with this enzyme are still unclear. The pearl oyster Pinctada martensii was used in this study as the raw material to illustrate the kinetic properties of protease 894. After investigating the intrinsic relationship between the degree of hydrolysis and several factors, including initial reaction pH, temperature, substrate concentration, enzyme concentration, and hydrolysis time, the kinetics model was established. This study showed that the optimal conditions for the enzymatic hydrolysis were an initial reaction pH of 5.0, temperature of 30°C, substrate concentration of 10% (w/v), enzyme concentration of 2 500 U/g, and hydrolysis time of 160 min. The kinetic characteristics of the protease for the hydrolysis of P. martensii were obtained. The inactivation constant was found to be 15.16/min, and the average relative error between the derived kinetics model and the actual measurement was only 3.04%, which indicated a high degree of fitness. Therefore, this study provides a basis for the investigation of the concrete kinetic characteristics of the new protease, which has potential applications in the food industry.     

海相碳酸盐岩烃源岩热解动力学研究:全岩和干酪根的对比

我国海相碳酸盐岩地层分布广泛,厚度巨大,经历的地质历史较长,特点是有机质丰度低,多处于高过成熟阶段.碳酸盐岩烃源岩评价对我国的油气资源评价与勘探至关重要.用生烃动力学方法来研究碳酸盐岩生油气过程是一个值得探索的研究方向.本文通过生烃动力学热模拟实验,求取了碳酸盐岩全岩和其干酪根不同烃类组分(甲烷、 C2～ C5气态烃)的生成动力学参数并进行对比.结果表明,在生烃动力学热解实验中,全岩和其干酪根具有相似的动力学参数,采用烃源岩应该比干酪根更符合实际,但是干酪根样品可以测得更为详细的实验数据,因此可以根据样品的情况,选择合理且易行的实验条件.在此基础上,以本文得到的参数作为参照指标,用动力学方法外推到地质实际中,可准确地提出适合我国的碳酸盐岩生烃定量模型,能为碳酸盐岩的资源评估等方面给出定量数值,从而为有效烃源岩的定量评价提供一种新的方法和途径.     

化学溶液侵蚀下灰岩的力学及化学溶解特性研究

针对龙门石窟灰岩水溶液侵蚀破坏现象,考虑石窟区的泉水、石窟渗水和雨水的化学成分,配置不同的化学溶液,研究不同化学溶液作用下龙门石窟灰岩的力学损伤特性及化学溶解行为。通过不同化学溶液侵蚀不同时间下灰岩的力学试验及分析,获得不同化学溶液侵蚀下龙门石窟灰岩强度损伤特性,建立化学溶液作用下灰岩单轴抗压强度随时间的侵蚀损伤方程。通过不同化学溶液侵蚀不同时间下灰岩溶解动力学试验及分析,研究灰岩在不同化学溶液中的溶解特性,建立化学溶液作用下灰岩侵蚀溶解动力学方程。试验分析研究表明,由于水化学溶液的溶解作用,化学溶液侵蚀下灰岩强度均有所下降。盐效应、同离子效应对灰岩溶解速率和强度的影响较大。盐效应提高灰岩溶解速率,同离子效应降低灰岩溶解速率。盐的种类和浓度均相同时,酸性越强,溶解速率越大;盐的种类和pH值相同时,盐浓度升高,灰岩溶解速率增大。研究结果将为石质文物及岩石工程的长期保护提供重要的理论基础,具有广泛的实际工程应用价值和应用前景。