光催化降解乐果的动力学研究

采用30 W石英紫外灯作为光源,研究了乐果在二氧化钛悬浮体系中光催化降解反应的动力学规律。考察了乐果起始浓度、TiO2用量、溶液pH值及温度对乐果光催化降解速率的影响,结果表明,乐果光催化降解符合表观零级动力学规律。由于速率常数k与乐果起始浓度有关,表明乐果光催化降解反应不是一个简单的零级反应。     

A study on the adsorption of chromium on laterite from Guizhou Province,China

The adsorption behaviors of Cr(VI) on laterite from Guizhou Province were studied in this paper, and the adsorption mechanism was discussed as well. Results showed that different mineral compositions in the laterite would cause differences in the capacity of laterite to absorb Cr(VI). Gibbsite, iron oxide minerals and non-crystalloids are the main contributors to enhancing the capacity of laterite to absorb Cr(VI). The pH of the solution is an important factor affecting the adsorption of Cr(VI) on laterite. Acidic environment (pH=2–5) is favorable to the adsorption of Cr(VI). The amount of adsorbed Cr(VI) decreases with increasing pH of the solution. With increasing initial concentrations of Cr(VI), the amount of adsorbed Cr(VI) increases first, and then decreases. The optimal adsorption concentration of Cr(VI) on laterite is 250 μg/mL. The adsorption of Cr(VI) on laterite is a rapid process, about 80% Cr(VI) will be adsorbed within 2 hours. And the adsorption of Cr(VI) on kaolinite is a slow process.     

塔里木盆地库车坳陷中生界烃源岩生烃动力学参数研究

根据封闭体系黄金管热模拟实验结果,应用Kinetics专用软件,研究了塔里木盆地库车坳陷中生界不同类型烃源岩的生烃特征与动力学参数。库车坳陷侏罗系煤、碳质泥岩、泥岩及三叠系湖相泥岩具有各自的活化能分布和频率因子,揭示出其生烃行为的差异性。利用GOR-IsotopeKinetics软件,推导了库车坳陷侏罗系煤、泥岩和三叠系湖相泥岩3类烃源岩的碳同位素动力学参数。上述参数的获取,为盆地模拟、烃源岩评价、生烃量计算及资源量预测提供了重要的基础地球化学数据。      

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

石煤中钒的氧化动力学初步研究

含钒石煤是我国一种新类型钒矿资源,钒的氧化是石煤提钒的基础。本文对钒的氧化动力学作了初步工作,通过试验数据处理结果表明,采用Ерофеев综合动力学公式:描述石煤中钒的氧化过程:2VO2固+1/2O2=Y2O5固简明可行,较为适宜。 钒氧化反应初期阶段以动力学方式进行:n1=1,属一级反应过程;继之,n2=0.2,反应受扩散制约。测定了由动力学过程转换为扩散过程所需的反应时间及其钒氧化率,计算了这两种过程的速率常数和表观活化能。     

东濮凹陷沙一段源岩的成烃动力学参数特征

运用成烃动力学原理对东濮凹陷沙一段源岩进行研究表明,沙一段源岩中的成烃有机质具有非均质性．沙一段目前正在生烃的活化能范围为90kJ／mol～110kJ／mol之间．对应的成熟生烃门限埋深约在2200m左右。该结果为评价沙一段源岩提供了基于动力学上的证据．同时对推进沙一段的油气勘探具有积极意义。     

丁二酸桥联双核铜Cu(C_3N_2H_4)_2(C_4H_5O_4)_2晶体的超分子结构及形貌特征

用XRD,SEM和TEM研究新型配合物Cu(C3N2H4)2(C4H5O4)2的超分子结构和微观形貌,并对新型晶体的平衡外形进行模拟计算,结果表明:该配合物分子具有丁二酸桥联的双核铜结构,中心铜离子处在2个咪唑和4个丁二酸以单齿配位组成的八面体中心,在ab平面,分子中有十四元大环,环内Cu(1)-Cu(2)原子间距为0.8031nm,C(2)-C(2′)为0.4183nm;在ac平面,沿着[010]方向分子内呈现凹的六边形纳米级孔洞;沿[100]方向分子依靠弱的氢键作用,层状堆积成三维超分子结构。此外,随着丁二酸的碳链沿[001]方向无限延伸,形成以铜离子为交叉中心的带状拓扑构型。SEM观察到晶体表面形成有明显的凹坑,区域呈现层状阶梯,说明晶体在(100)面遵照台阶-扭折模型呈层状生长结晶。TEM微区形貌像显示晶体存在条纹和缺陷结构,整体保持柱状构型,这与模拟的晶体平衡外形呈柱状一致。模拟结果表明晶体最易外显晶面为(100)面,外显比例达41.247%,这与晶体超分子层沿[100]方向通过氢键作用堆积,键作用力较弱密切相关。     

A simulation experimental study on oxidative kinetics of sphalerite under hypergene condition

The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT     

准噶尔盆地陆东-五彩湾石炭系烃源岩特征及生烃动力学研究

准噶尔盆地陆东-五彩湾地区石炭系具有良好的勘探前景,该地区石炭系烃源岩有机质丰度较高,成熟度范围宽,主要处于成熟-高成熟演化阶段,主要由Ⅲ型有机质组成。在对烃源岩样品进行常规评价的基础上,用开放体系进行了热解实验和动力学模拟,对陆东-五彩湾地区的生烃特征进行了研究,尝试了高成熟烃源岩生烃过程研究及Ⅲ型干酪根液态烃排烃时间的估计,并对石炭系地层产烃率进行了计算。结果显示,陆东-五彩湾地区石炭系最早在二叠纪（距今264 Ma左右）开始生烃,后期由于地层抬升,在古近纪早期（距今61 Ma左右）结束生烃。下石炭统产烃率大,液态烃排出时间估计在距今232~196 Ma之间;上石炭统产烃率较小,液态烃排出时间估计在距今196~178 Ma 之间,但天然气生成相对较晚,有利于天然气的保存。天然气可能主要来源于上石炭统烃源岩。     

β-环糊精交联聚合物对氯苯的吸附特性

通过对水中含有微量氯苯的吸附特性研究,考察β-环糊精交联聚合物吸附氯苯的动力学、热力学及连续运行条件下的稳定性和再生性能。实验结果表明:β-环糊精交联聚合物吸附氯苯的过程符合准二级动力学模型,即化学吸附是吸附过程的控制步骤;β-环糊精交联聚合物上的等温吸附符合Langmuir吸附等温模型。在15、25、35℃时最大吸附量分别为23.36、28.17、27.85mg/g;动态模拟实验中,当氯苯质量浓度为10mg/L时,氯苯的去除率大于80%。乙醇作为溶剂可以使吸附饱和的β-环糊精交联聚合物再生。