Modeling flotation separation in a semi-batch process

A model for a semi-batch flotation separation process has been developed, based on available microprocess probabilities, and compared to experimental data obtained using a WEMCO laboratory flotation cell. In general, the model predicts the correct experimental trends. In many cases, the model also predicts removal efficiency very well. Parametric studies reveal that the model predictions are sensitive to a stability parameter, the turbulent energy density in the flotation cell, the contact angle between the solid particle and fluid, and the ratio of initial-to-critical film thickness.     

Kinetic study of the deep hydrodesulfurization of dibenzothiophene over molybdenum carbide supported on a carbon black composite: Existence of two types of active sites

Hydrodesulfurization (HDS) is part of the hydrotreating process, which is an ensemble of several reactions (HDN, HDO, HDS, etc.) taking place simultaneously at the industrial scale. Only sulfur is currently submitted to drastic Europeans specifications and conventional commercial catalysts cannot reach the specifications at low cost. This paper presents the behavior of a potential substitute catalyst tested for the deep HDS of a model molecule such as the dibenzothiophene (DBT). The substitute is molybdenum carbide supported on a mesoporous carbon black composite of surface area 240 m² g⁻¹. A global kinetic study of the deep HDS of DBT (300 ppm S) was performed at 623 K and 5.0 MPa and a global kinetic model was proposed as well as global rate constants were calculated to obtain theoretical plots of concentration versus contact time to compare with the experimental data. The kinetic model and global kinetic orders were confirmed as an acceptable correlation was found between calculated and experimental data. Furthermore, the determination of the global kinetic orders indicated that two types of active sites must be present on the surface in order to explain the observed results.     

~(131)I-Lym-2单克隆抗体实验研究

不同浓度的~(131)I-Lym-2 MoAb与ARH-77和CEM细胞进行结合试验,结果表明:随浓度增大,结合值均升高;实验组裸鼠模型9只获得动力学数据。实验组和对照组注射~(131)I-Lym-2 MoAb后144h解剖,进行生物学分布(％D/g)测定,实验组肿瘤为16.88±12.64,肌肉为0.72±0.56。结果表明,~(131)I-131-Lym-2MoAb对临床B细胞淋巴瘤的放射免疫分析、显像有良好的效果。     

General rate equations and their applications for cyclic reaction networks: multi-cycle systems

The network reduction technique and the Bodenstein approximation of quasi-stationary behavior of reaction intermediates were systematically applied to derive general yield ratio and rate equations for multi-cycle reaction networks in homogeneous catalysis. Dual-cycle reaction networks connected by a linear pathway, multi-cycle networks stemming from the same intermediate, and single-cycle with arbitrary number of pathways between two intermediates were considered. The general yield ratio and rate equations derived in this study are applicable for most enzymatic reactions and for homogeneous catalytic reactions. Examples of homogeneous catalysis were used to illustrate the application of the general yield ratio and rate equations for network elucidation.     

Design and characterisation of a close-concentric annular reactor for kinetic studies at high temperatures

A novel annular reactor for kinetic studies at high temperature and flow conditions has been designed to keep eccentricity tolerances below 10%. In a previous work, we have shown that it is very important to keep such low eccentricity values in order to collect reliable kinetic data from this type of reactors. As proposed in this study, a modified reactor with the use of a spacer could guarantee an annular duct with low levels of eccentricity. Manufacturing tolerances or deformation effects giving rise to eccentricity can be significantly minimised when using this apparatus. The reactor has been both experimentally and theoretically characterised. Carbon monoxide oxidation was used as a model reaction under mass-transfer limited conditions revealing an eccentricity of ∼5%. With such small eccentricity levels, a concentric annular form can be assumed in the reactor analysis. Simple 1D or 2D models can therefore be inexpensively used in the evaluation of the kinetic data. Also, prior to the design of the annular reactor, a numerical investigation was carried out to clarify the effects of eccentricity, physical properties of the carrier gas and the annular aspect ratio on mass-transfer limitations. Contrary to expectations, a considerable increase in the fuel mass-diffusivity by carrier gas substitution did not change the mass-transfer rates for cases when eccentricity and aspect ratios were high.     

A new approach for sequential experimental design for model discrimination

Model discrimination procedures are useful tools for selection of the best mathematical models to be used to represent a specific chemical process. The present paper presents and discusses a new sequential discrimination procedure, which makes use of model probabilities and concentrates the efforts on models with higher probabilities. Model probabilities are determined based on simple statistical arguments. Four numerical examples illustrate the application of the proposed discrimination procedure. The obtained results indicate that the new procedure is able to discriminate kinetic models with fewer experiments when compared to other procedures and also indicates when model discrimination is not possible and, thus, when the sequential design must be halted. Furthermore, the speed of the proposed discrimination procedure can be controlled by tuning a design parameter which reflects the analyst's mood (confidence) towards the discrimination problem and allows for increase or decrease of the number of experiments required for model discrimination during the sequential procedure.     

膨胀石墨对各种油类的吸附动力学

通过对吸附率(有效吸附系数)Ks和饱和吸附量msat的测量,描述了粘度为0.001 Pa·s～0.850 Pa·s的各种油类在膨胀石墨柱中的吸附动力学,发现吸附率Ks对油类粘度有很强的相关性.吸入膨胀石墨柱中的饱和吸附量msat几乎恒定在50kg/kg,该值略低于由膨胀石墨块直接浸渍在油中测得的吸附容量,这是由于所吸附的油沿膨胀石墨柱高度存在重力梯度.     

An approximate method for solving gas-solid non-catalytic reactions

A simple treatment for obtaining the solution of single isothermal gas-solid non-catalytic reactions is presented. The model is formulated under a local volumetric approach and permits to incorporate non-linear chemical kinetics and the change in porous structure during conversion. The methodology developed in this work is based on the quantize method for decoupling the solid and gas equations and on perturbation and matching techniques for approximating the gas conservation equation. With this strategy, the calculation of gas concentration and solid conversion at any time and position are reduced to the solution of two coupled algebraic equations. The model compares favourably with the exact (numerical) solution for a variety of cases. This procedure provides an effective and general tool for obtaining the solution of gas-solid reactions with minor calculations.     

A Practical Method to Derive Sample Temperature during Nonisothermal Coupled Thermogravimetry Analysis and Differential Scanning Calorimetry Experiments

Nonisothermal thermogravimetry differential scanning calorimetry (TG‐DSC) mounting is intensively used for the determination of kinetic parameters and reaction heat along the chemical transformation of a solid. Nevertheless, when tests are performed with heating rates as high as those encountered in industrial processes, e.g., several tens of K min^–1, there is great uncertainty in the knowledge of the exact sample temperature. In this work, a method to derive a simple mathematical expression is proposed and fully described in order to calculate the real sample temperature throughout a temperature‐ramped test on a commercial apparatus. The furnace temperature and the heat flow signals were used, together with the crucible specific heat and the heating rate. A number of validation tests were performed to derive similar reaction rates for a reference. First‐order kinetic reactions were presented and reconciled over a large range of heating rates from 3 to 50 K min^–1.