甲醇分解系统复杂反应动力学研究

采用固定床直流积分反应器,在常压下、国产C301型铜基催化剂上,对甲醇分解反应本征动力学进行了测定,测定时的温度及浓度范围与合成甲醇工业操作条件相似。根据测定数据,应用改进高斯一牛顿法对动力学模型参数进行估值,得到了双响应动力学方程。     

速差动力学分析法同时测定铁、锌、铜

将化学计量学方法引入速差动力学分析方法中,在不预知动力学模型参数(速率常数)的情况下,用人工神经网络(ANN)依据铁、锌、铜的EGTA配合物与PAR置换反应的速度差异,对其三组分混合体系进行了同时测定.并对人工神经网络和偏最小二乘法对多波长、多时间点的三维量测模型的解析能力进行了比较,结果表明前者总体上优于后者.混合体系中铁、锌、铜测定的相对标准偏差分别为1.63%,3.29%和4.41%.本法还被用于饲料添加剂中微量元素的测定.     

快速测定酶法动力学拆分中转化率和ee值的新方法

在动力学拆分反应中 ,转化率和对映体过量值( ee值 )是经常需要测量的两个重要参数 .传统的测定转化率的方法包括色谱法、分光光度法和滴定法等 .而测定 ee值主要应用手性色谱柱、手性毛细管电泳、核磁以及旋光法等 .在动力学拆分过程中 ,需要对反应进程进行监测 ,而应用传统的方法进行监测需要同时测定两个量 (转化率和 ee值 ) ,工作量较大 ,且使用手性色谱柱进行监测成本也较高 ,不适合大量实验数据的常规分析 .为此 ,需要发展一种快速、灵活、经济的测量方法 ,用以实验前期筛选条件时的常规分析 .基于此思路 ,我们借助于自己编制的计算机…     

RP/HPLC测定吡虫啉血药浓度及其大鼠灌胃药代动力学评价

建立了大鼠血浆中吡虫啉的反相高效液相色谱(RP/HPLC)分析方法,并用于吡虫啉在大鼠体内的代谢动力学行为及特征研究。血浆样品经甲醇萃取,反相HPLC法测定血浆中的吡虫啉浓度。色谱柱为Agilent ZORBAX C18柱(4. 6 mm×250 mm,5μm),流动相为甲醇-水(30∶70),进样量20μL,检测波长245nm,流速1. 0 m L/min。在最佳条件下,吡虫啉的线性范围为0. 5～100 mg·L-1(r2=0. 999 8),检出限为10μg·L-1,平均加标回收率为74. 7%。大鼠单剂量灌胃给予68. 1 mg·kg-1吡虫啉,分别测定给药后不同时间下血浆中吡虫啉的浓度,并计算代谢动力学参数。灌胃给药后吡虫啉的Cmax为23. 557 mg/L,tmax为7. 333h,t1/2α为4. 472 h,AUC(0-t)为276. 727 mg·h/L。代谢动力学结果显示,吡虫啉在大鼠体内呈二隔室模型分布,以一级药代动力学方式消除。该方法简便可靠,能够满足血浆中吡虫啉测定及药代动力学研究的要求。     

最小二乘法计算苯、噻吩和正辛烷在NaY上程序升温脱附活化能

采用程序升温脱附(TPD)技术测定了苯、噻吩和正辛烷在NaY上以不同升温速率升温时的TPD谱图. 利用TPD谱图的峰形和其微分曲线判断了程序升温脱附过程中的脱附级数. 提出了一种利用最小二乘法计算吸附剂/催化剂的脱附活化能及其动力学参数的方法. 以这些TPD谱图为基础, 分别采用传统TPD计算模型、最小二乘法以及一阶微分曲线法计算了苯、噻吩和正辛烷在NaY上的脱附活化能和动力学参数. 结果表明, 最小二乘法对在不同线性升温速率时的程序升温脱附活化能的计算结果是一致的.     

烷基苯类化合物气相色谱保留指数与分子结构的相关性研究

利用分子力学和量子化学方法计算出烷基苯类化合物的分子结构描述参数,用逐步回归法建立烷基苯类化合物在不同极性色谱柱上的QSRR模型。烷基苯类化合物在不同极性色谱柱上的气相色谱保留指数与其分子结构描述参数之间具有较好的线性关系。建立了在不同极性色谱柱上的烷基苯类化合物的色谱保留QSRR模型,并预测烷基苯类化合物的色谱保留值,结果具有较好的稳定性和准确性。     

二水草酸亚铁热分解反应动力学

用原位XRD技术和热重法分析了二水草酸亚铁的热分解过程, 并进行了动力学研究. 通过结合主曲线法和统计方法判定了热分解过程的动力学模型函数, 并求算了动力学参数. 在静态自产气氛下, 二水草酸亚铁脱水反应遵循随机成核与核增长模型, 草酸亚铁热分解生成氧化铁遵循相界面控制动力学模型. 结果表明, 该方法可以准确、可靠地判定非等温热分解反应的动力学模型函数,并求算动力学参数.     

液相色谱双保留机理动力学过程研究

本文根据质量平衡原理建立了反相色谱双保留机理的质量平衡模型, 导出了色谱流出曲线的一阶矩和二、三阶中心矩, 获得了双保留机理色谱容量因子和塔片高度的表达式. 讨论了各种色谱动力学参数对柱效和峰形的影响, 对改善色谱峰对称度和提高柱效的措施作了理论说明。     

基于遗传算法的费托合成反应动力学模型参数优化

详细动力学模型是费托合成反应技术从实验室走向工业化过程中最关键的基础研究项目之一。目前对动力学模型的参数估算仍然停留在传统的LM算法上,LM算法属于无约束方法,在计算中容易因参数越界而使计算失败,计算结果强烈依赖于初值,且容易陷于局部最优,运用遗传算法来解决费托合成反应详细动力学模型的参数优化问题,是一种全新的尝试,通过系统的实验我们获得了比较满意的参数估算结果,证明该算法用于解决动力学模型参数优化是非常有效的。     

Pd/C催化松脂分子间氢转移反应的集总动力学

以Pd/C为催化剂,在改进的动力学实验装置上研究了松脂分子间氢转移反应的集总动力学.在消除内、外扩散影响的条件下,在线跟踪反应产物并用气相色谱法测定反应体系组成随时间的变化,构造了Pd/C催化剂上松脂分子间氢转移集总反应网络,建立了包含单萜烯、枞酸型树脂酸、海松酸型树脂酸、对伞花烃、氢化单萜烯、脱氢枞酸、氢化枞酸型树脂酸和氢化海松酸型树脂酸等复杂反应体系的集总动力学模型,并估算了模型参数.松脂单萜烯和树脂酸的反应级数分别为1和2,并得到了松脂分子间氢转移中各反应过程的活化能.结果表明,所建动力学模型与实验数据吻合良好,并能预测反应在533 K下的集总组分浓度分布.Pd/C催化松脂分子间氢转移反应以脱氢反应为主,树脂酸的氢转移速率大于单萜烯的氢转移速率.     

A finite element model of loading and unloading of an asperity contact with adhesion and plasticity

An elastic-plastic microcontact with adhesion was studied using a finite element model. This model differs from the existing models, in that it includes the effect of adhesion on the deformation and stresses field, making it applicable to a wide range of material properties. It shows two distinct separation modes, brittle separation and ductile separation. To the best of our knowledge this is the first time that a finite element model has predicted ductile separation in an adhesive contact. Three key parameters affecting the contact and separation modes are also discussed. Further work is expected to fully reveal the effect of these parameters on the separation modes.     

Understanding of peak deterioration in hyphenated speciation systems due to gas-liquid separation in the hydride generation interface.

In hyphenated speciation systems with a hydride generation interface one of the processes influencing peak deterioration is gas-liquid separation. A mathematical model was developed to calculate attenuation, signal tailing and resolution loss of HPLC peaks due to gas-liquid separation. It was shown experimentally--using an HPLC-hydride generation-atomic fluorescence spectrometry system for arsenic speciation--that the mathematical model predicts peak deterioration well. This allowed us to study the parameters influencing the deterioration, viz. gas-liquid separation parameters (gas-liquid separator head space volume and purge gas volume flow-rate) and HPLC peak parameters [width (ratio) and resolution] theoretically, simulating HPLC peaks with gaussian functions.     

模拟退火神经网络用于药物液相色谱梯度分离条件的优化

模拟退火神经网络用于药物液相色谱梯度分离条件的优化。使用均匀设计法以乙腈在线性梯度展开时的初始浓度和线性梯度的斜率为优化参数,对六种药物混合体系进行优化。采用退火神经网络方法建立了有效的分离条件预测模型。对神经网络模型所预测的最佳分离条件进行试验,分离结果满意。模拟退火神经网络可有效地用于药物液相色谱分离条件的优化。     

化学计量学方法用于多环芳烃液相色谱分离条件优化

本文报道化学计量学方法用于多环芳烃(PAHs)液相色谱分离条件的优化.使用均匀实验设计法,以乙腈在线性梯度展开时的初始浓度和线性梯度的斜率为优化参数,对16种多环芳烃混合体系进行液相色谱分离条件优化,采用遗传算法和退火神经网络方法建立了有效的分离条件预测模型.对模型所预测的最佳分离条件进行试验,分离结果满意.     

Optimal design of batch and simulated moving bed chromatographic separation processes

Preparative chromatography, especially simulated moving bed (SMB) chromatography, is a key technology for the separation of fine chemicals on a production scale. Most of the design methods for batch and SMB processes proposed in the open literature deal with the optimisation of the operating conditions for a given chromatographic unit only. Therefore, a comparison of the process economy may lead to incorrect results. In this contribution, an effective strategy for the optimal choice of all process parameters (operation and design parameters) is proposed. The main idea of this strategy is to apply a detailed and experimentally validated process model and to reduce the number of influencing parameters by introducing and optimising dimensionless process parameters. It is shown that there is an infinite choice of design and operating parameters to achieve maximum productivity or minimum separation costs and not at the maximum pressure drop only. The detailed design of the chromatographic unit and the selection of the operating conditions can be adjusted by considering the availability of columns and packing materials. As the model system, the separation of a racemic mixture (EMD53986) on Chiralpak AD was investigated. After complete optimisation of a batch and a SMB unit, a real comparison of the process economy can be achieved. Finally, the influences of two different objective functions, productivity and specific separation cost, are analysed.     

A model of separation of wastewater containing vat dyes

Mechanism of fluid separation with capillary-porous polymeric membranes was studied and a mathematical model of separation by ultrafiltration of vat-dye-containing wastewater from finishing shops of textile plants was suggested. The model takes into account the effect of physical parameters on the mechanism and kinetics of the cross-membrane transfer of ingredients, in which a gel layer is formed.     

Business-objective-directed, constraint-based multivariate optimization of high-performance liquid chromatography operational parameters

The goal of a separation can be defined in terms of business needs. One goal often used is to provide the required separation in minimum time, but many other goals are also possible. These include maximizing resolution within an analysis-time limit, or minimizing the overall cost. The remaining requirements of the separation can be applied as constraints in the optimization of the goal. We will present a flexible, business-objective-based approach for optimizing the operational parameters of high performance liquid chromatography (HPLC) methods. After selecting the stationary phase and the mobile-phase components, several isocratic experiments are required to build a retention model. Multivariate optimization is performed, within the model, to find the best combination of the parameters being varied so that the result satisfies the goal to the fullest extent possible within the constraints. Interdependencies of parameters can be revealed by plotting the loci of optimal variable values or the function being optimized against a constraint. We demonstrate the concepts with a model separation originally requiring a 54 min analysis time. Multivariate optimization reduces the predicted analysis time to as short as 8 min, depending on the goals and constraints specified.     

Retention parameters of aromatic polar species via reversed-phase liquid chromatography with application to coal liquefaction products

High performance liquid chromatography in the reversedphase mode was used for the analysis of coal liquefaction materials. The chromatographic system used was optimized for separation of the more polar, heteroatom-containing components. A model study of a wide variety of compounds was undertaken in which capacity factors were correlated to a set of structural parameters in order to gain insight into the retention mechanism. Reversed-phase separation of a model mixture as well as separation of boiling fractions of hydrotreated and nonhydrotreated process recycle solvents are compared.