Extraction and stripping of actinide elements with changes in supply flow rate and nitric acid concentration using centrifugal contactors in single cycle solvent extraction system

Counter current experiments in a single cycle solvent extraction system were carried out with centrifugal contactors to study flow rate reductions in extraction solvent and stripping solution with a dissolver solution of irradiated mixed oxide (MOX) fuel. Uranium and Pu leaked to the raffinate with a 15% decrease in the extraction solvent flow rate, which brought about an accumulation of U and Pu in the co-decontamination section. The discharge of other actinide elements and fission products (FPs) in the raffinate was constant when the extraction solvent reduced by 15%. On the other hand, a 15% decrease in the stripping solution flow rate did not affect the stripping of U and Pu so greatly. The polymerization of Pu was not observed in the counter current experiments, and the time taken to change 2% of Pu(IV) to Pu polymers in the stripping section was evaluated. Simulation results based on these experiments showed that a high HNO₃ concentration in the feed solution was advantageous for Np extraction, because Np oxidation progressed in the extraction section.     

Calculation of vapor-liquid equilibria in aqueous sulfuric acid solutions using the UNIQUAC equation in the whole concentration range

Sulfuric acid has many industrial applications. Its main use can be related to fertilizer manufacture, process with ore, chemical synthesis, liquid effluents treatment and the petroleum refine. A main characteristic of this acid is its behavior depending on concentration. When it is dilute, under molar concentrations of 90%, the solution acts as a strong acid and does not show dehydration power. On the other hand, when it is concentrated, above 90%, its acidic feature is omitted and its dehydration power increases. Due to its importance in chemical process and in view of all works present in the literature, one does not consider both dissociation reactions in the liquid phase and the complex formation reaction in the vapor as one, a thermodynamic model has been developed using Prigogine and Defay Chemical Theory. This model takes into account phase and chemical equilibria, simultaneously, with satisfactory results to calculate vapor-liquid equilibria of H₂O-H₂SO₄ solutions in the whole concentration range and temperatures from 0 to 150 °C.     

Modelling of organic liquid-phase decomposition reactions through gas-phase product analysis: Model systems and peracetic acid

A new method for modelling of liquid-phase decomposition reactions was developed. The method is based on rapid on-line mass spectrometric analysis of liberated products in gas phase. The experimental set-up and the generalized modelling principles were introduced. The approach was demonstrated with first and zero order as well as for complex decomposition kinetics (decomposition of peracetic acid). The interaction of decomposition kinetics and mass-transfer effects was illustrated with theoretical and real reaction conditions. The approach is generally applicable to any liquid-phase decomposition, provided that gaseous products can be quantitatively analyzed.     

Optimal design of axial noble metal distribution for improving dual monolithic catalytic converter performance

In practical applications, monolithic catalytic converters are operated at non-isothermal conditions. In this case, the active metal distribution along the length of the converter may influence its performance. Indeed, better conversions can be achieved by controlling the distribution of the same quantity of active material. In this study, we used a one-dimensional catalyst model to predict the transient thermal and conversion characteristics of a dual monolithic catalytic converter with Platinum/Rhodium (Pt/Rh) catalysts. The optimal design of a longitudinal noble metal distribution of a fixed amount of catalyst is investigated to obtain the best performance of a dual monolithic catalytic converter. A micro-genetic algorithm with considering heat transfer, mass transfer, and chemical reactions in the monolith during the FTP-75 cycle was used. The optimal design for the optimal axial distribution of the catalyst was determined by solving multi-objective optimization problems to minimize both the CO cumulative emissions during the FTP-75 cycle, and the difference between the integral value of a catalyst distribution function over the monolith volume and total catalytic surface area over the total monolith volume.     

Effective approach to cyclic steady state in the catalytic reverse-flow combustion of methane

Computer-based simulations of a reverse-flow reactor should be carried out till the attainment of the so-called cyclic steady state. Usually this state is achieved by the method of direct dynamic simulations. In the paper of Unger et al. (Comput. Chem. Eng. 21 (1997) 5167.) special approaches, making use of various minimization algorithms based most often on Newton algorithms, are proposed. In the present paper one deals with a comparison and an appraisal of these methods, applied to the reverse-flow catalytic combustion of methane that occurs in coal-mine ventilation air.     

Probabilistic monitoring of chemical processes using adaptively weighted factor analysis and its application

As a probabilistic statistical method, factor analysis (FA) has recently been introduced into process monitoring for the probabilistic interpretation and performance enhancement of noisy processes. Generally, FA methods employ the first several factors that are regarded as the dominant motivation of the process for process monitoring; however, fault information has no definite mapping relationship to a certain factor, and useful information might be suppressed by useless factors or submerged under retained factors, leading to poor monitoring performance. Weighted FA (WFA) for process monitoring is proposed to solve the problem of useful information being submerged and to improve the monitoring performance of the GT² statistic. The main idea of WFA is firstly building a conventional FA model and then using the change rate of the GT² statistics (RGT²) to evaluate the importance of each factor. The important factors tend to have larger RGT² values, and the larger weighting values are then adaptively assigned to these factors to highlight useful fault information. Case studies on both a numerical process and the Tennessee Eastman process demonstrate the effectiveness of the WFA method. Monitoring results indicate that the performance of the GT² statistic is improved significantly compared with the conventional FA method.     

Optimization of nonlinear process based on sequential extreme learning machine

In this paper, a new approach to the optimal control with constraints is proposed to achieve a desired end product quality for nonlinear processes based on new kernel extreme learning machine (KELM). The contributions of the paper are as follows: (1) In existing ILC algorithm, the model was built only between manipulated input variables U and output variables Y without considering the state variables. However, the states variables X_state are important in the industrial processes, which are usually constrained. In this paper, the variables are divided into state variables X_state, manipulated input variables U and output Y in the process of modeling. Then ΔU can be obtained by batch-to-batch iterative learning control separately. Kernel algorithm is added to ELM. (2) Constraints of state variables X_state and the input variables U are considered in the current version. PSO is used to solve the optimization problem. (3) Kernel trick is introduced to improve accuracy of ELM modeling. New KELM algorithm is proposed in the current version. The input trajectory for the next batch is accommodated by searching for the optimal value through the error feedback at a minimum cost. The particle swarm optimization algorithm is used to search for the optimal value based on the iterative learning control (ILC). The proposed approach has been shown to be effective and feasible by applying bulk polymerization of the styrene batch process and fused magnesium furnace.     

A new generic approach for the modeling of fluid catalytic cracking (FCC) riser reactor

A new kinetic model for the fluid catalytic cracking (FCC) riser is developed. An elementary reaction scheme, for the FCC, based on cracking of a large number of lumps in the form of narrow boiling pseudocomponents is proposed. The kinetic parameters are estimated using a semi-empirical approach based on normal probability distribution. The correlation proposed for the kinetic parameters’ estimation contains four parameters that depend on the feed characteristics, catalyst activity, and coke forming tendency of the feed. This approach eliminates the need of determining a large number of rate constants required for conventional lumped models. The model seems to be more versatile than existing models and opens up a new dimension for making generic models suitable for the analysis and control studies of FCC units. The model also incorporates catalyst deactivation and two-phase flow in the riser reactor. Predictions of the model compare well with the yield pattern of industrial scale plant data reported in literature.     

对甲酚催化氧化制备对羟基苯甲醛热力学分析

对甲酚催化氧化法合成对羟基苯甲醛因其工艺路线简单,是工业上常用方法之一。为了有效利用资源,对对甲酚催化氧化合成对羟基苯甲醛的反应过程进行了较为详尽的热力学分析,对于开发该反应的催化剂和反应工艺具有重要的指导意义。利用热力学原理,首次建立了该反应的焓变和Gibbs自由能变化与反应温度的关系,并计算了反应在不同温度下的平衡常数。经计算得出,该反应的ΔrHβm㈠(298 K)=-387.901 kJ/mol,ΔrGβm㈠(298 K)=-345.875 kJ/mol;在研究温度范围内,该反应为放热反应,且能自发进行。     

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reported for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO₂ using the principle of micellar catalysis. [CF₃(CF₂)₈COO]₂Co·xH₂O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co²⁺ cations in scCO₂) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water–CO₂ mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 °C. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF₃(CF₂)₈COO]₂Mg·yH₂O/Co(II) acetate is as effective as the [CF₃(CF₂)₈COO]₂Co·xH₂O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO₂ can be easily separated via CO₂ depressurisation and be reused without noticeable deactivation.     

Partial oxidation of toluene to benzaldehyde and benzoic acid over model vanadia/titania catalysts: role of vanadia species

Pure and K-doped vanadia/titania prepared by different methods have been studied in order to elucidate the role of vanadia species (monomeric, polymeric, bulk) in catalytic toluene partial oxidation. The ratio of different vanadia species was controlled by treating the catalysts in diluted HNO₃, which removes bulk vanadia and polymeric vanadia species, but not the monomeric ones, as was shown by FT-Raman spectroscopy and TPR in H₂. Monolayer vanadia species (monomeric and polymeric) are responsible for the catalytic activity and selectivity to benzaldehyde and benzoic acid independently on the catalyst preparation method. Bulk V₂O₅ and TiO₂ are considerably less active. Therefore, an increase of the vanadium concentration in the samples above the monolayer coverage results in a decrease of the specific rate in toluene oxidation due to the partial blockage of active monolayer species by bulk crystalline V₂O₅. Potassium diminishes the catalyst acidity resulting in a decrease of the total rate of toluene oxidation and suppression of deactivation. Deactivation due to coking is probably related to the Brønsted acid sites associated with the bridging oxygen in the polymeric species and bulk V₂O₅. Doping by K diminishes the amount of active monolayer vanadia leading to the formation of non-active K-doped monomeric vanadia species and KVO₃.     

相转移催化氧化合成苯甲酸

研究了季铵盐CTAB催化高锰酸钾氧化氯化苄合成苯甲酸的反应。考察了CTAB用量、高锰酸钾用量、反应温度、反应时间对反应的影响。结果表明,合成苯甲酸的最优条件为:高锰酸钾与氯化苄的摩尔比为2∶1,CTAB的摩尔分数为氯化苄的8%,反应温度90℃,反应时间为3h,苯甲酸的产率可达89%。     

Determination of steel quality based on discriminating textural feature selection

Image data can be acquired from a product surface in real time by image sensor systems in chemical plants. For quality determination based on these image datasets, effective texture classification methodology is essential to handle highly dimensional images and to extract quality-related information from these product surface images.Wavelet texture analysis is useful for reducing the dimension and extracting textural information from images. Although wavelet texture analysis extracts only textural characteristics from images, the extracted features still contain unnecessary information for classification. The texture analysis method can be improved by retaining only class-dependent features and removing common features. In previous works, best basis and local discriminant basis are the most popular techniques for selecting an important basis from the wavelet packet basis. However, feature selection based on wavelet texture analysis has been studied for texture classification. Because previous methods are designed for wavelet coefficients with features for analysis, their performance is poor with wavelet texture analysis.We propose a novel texture classification methodology for quality determination based on feature selection using wavelet texture analysis. The proposed methodology applies the sequential forward floating selection (SFFS) algorithm as a feature selection strategy to select discriminating wavelet signatures using wavelet texture analysis. The proposed methodology is validated through quality determination for industrial steel surfaces. The results show that the proposed method has fewer classification errors with fewer number of features than previous methods.     

Experimental campaign,modeling, and sensitivity analysis for the molecular distillation of petroleum residues 673.15 K+

This research activity proposes a sensitivity analysis of the molecular distillation process by focusing the attention on the response of the overall distillate flow rate under several conditions of distillation temperature and feed flow rate. Specific equations to characterize physicochemical properties of petroleum residues have been formulated by means of ASTM-based experimental campaigns combined with specific optimization techniques.     

Process analysis and optimisation of hybrid processes for the dehydration of ethanol

Promising hybrid processes for ethanol dewatering consist of different combinations of distillation with adsorption and/or vapour permeation. This paper presents an analysis and optimisation of these hybrid processes using non-equilibrium models and an evolutionary algorithm. Four different membrane assisted configurations are compared with a benchmark process consisting of distillation and pressure swing adsorption. In total 12 cases were investigated while assuming different feed and product compositions at different production capacities: three ethanol mass fractions in feed 45, 80, 92 wt.%, two product purities 99.6, 99.95 wt.% and two production capacities 25,000, 250,000 m³/year. The influence of decisive operating and structural variables on important target variables such as total membrane area is demonstrated. Finally, the processes are evaluated regarding operating costs and energy consumption depending on product purity and production capacity. The operating costs of the membrane assisted configurations differ only in a small range of −3% to 6% from those of the benchmark. The energy consumption of the membrane assisted configurations without distillation is up to 30% lower compared to the benchmark. Especially the combination of vapour permeation and adsorption is a promising alternative allowing for producing ethanol with high purities at lower operating pressures compared to the vapour permeation as stand alone process.     

Simulation of a multi-annular photocatalytic reactor for degradation of perchloroethylene in air: Parametric analysis of radiative energy efficiencies

A multi-annular photocatalytic reactor was designed, that shows good effectiveness for perchloroethylene (PCE) removal from contaminated air streams. In a previous work, a rigorous physical and mathematical model of the photocatalytic reactor was developed and experimentally verified. In this work, this mathematical model was used to study the radiative energy efficiency of the multi-annular photoreactor. The total quantum efficiency is defined as the ratio of the number of molecules of PCE reacted to the number of photons emitted by the lamp, and it is expressed as the product of the following factors: the reactor radiation incidence efficiency, the catalyst radiation absorption efficiency, and the overall reaction quantum efficiency. For the employed reactor, the numerical values of each one were 83%, 92%, and <2.5%, respectively. Particularly, the dependence of the overall reaction quantum efficiency upon operating variables such as the PCE feed concentration, gas flow rate, irradiation level and relative air humidity was analyzed. These results are useful to optimize the operating conditions and design parameters of the photocatalytic reactor.     

离子液体相转移催化氧化苯甲醛制备苯甲酸

以N-甲基咪唑、四氟硼酸铵、正丁醇、溴化钠为主要原料合成了1-正丁基-3-甲基咪唑四氟硼酸咪唑盐型离子液体。以该离子液体作相转移催化剂研究了双氧水氧化苯甲醛制备苯甲酸的反应。结果表明,该氧化反应中加入离子液体可起到溶剂及相转移催化剂的作用,当反应5 h时,苯甲醛可达最大转化率88%。反应后离子液体可回收再利用。     

On the modelling of multidisciplinary electrochemical systems with application on the electrochemical conversion of CO2 to formate/formic acid

This paper presents a model-based approach on the analysis of complex multidisciplinary electrochemical processes, with implementation on a reactor for the electrochemical conversion of CO₂ to formate/formic acid. The process is regarded as a system of interacting physical and electrochemical mechanisms. A process model is developed by combining individual mathematical sub-models of the mechanisms, organised at groups of compartments following the physical process structure. This approach results in a generic reconfigurable model that can be used as a part of integrated systems, and to test design modifications. The approach is demonstrated on an electrochemical cell, where CO₂ is converted to formate/formic acid. The model captures the molar transportation under electric field, the two-phase flow effects, and the key electrochemical reactions. The model is calibrated and validated against experimental data obtained from a continuous flow cell. The key parameters affecting the process performance are discussed through scale-up analysis.