Heterogeneous extractive batch distillation of chloroform-methanol-water: Feasibility and experiments

A novel heterogeneous extractive distillation process is considered for separating the azeotropic mixture chloroform-methanol in a batch rectifying column, including for the first time an experimental validation of the process. Heterogeneous heavy entrainer water is selected inducing an unstable ternary heteroazeotrope and a saddle binary heteroazeotrope with chloroform (ternary diagram class 2.1-2b). Unlike the well-known heterogeneous azeotropic distillation process and thanks to continuous water feeding at the column top, the saddle binary heteroazeotrope chloroform-water is obtained at the column top, condensed and further split into the liquid-liquid decanter where the chloroform-rich phase is drawn as distillate. First, feasibility analysis is carried out by using a simplified differential model in the extractive section for determining the proper range of the entrainer flowrate and the reflux ratio. The operating conditions and reflux policy are validated by rigorous simulation with ProSim Batch Column^® where technical features of a bench scale distillation column have been described. Six reproducible experiments are run in the bench scale column matching the simulated operating conditions with two sequentially increasing reflux ratio values. Simulation and experiments agree well. With an average molar purity higher than 99%, more than 85% of recovery yield was obtained for chloroform and methanol.     

Comparison of numerical simulations and experiments in conical gas-solid spouted bed

Flowbehavior of gas and particles in conical spouted beds is experimentally studied and simulated using the twofluid gas-solid model with the kinetic theory of granular flow. The bed pressure drop and fountain height are measured in a conical spouted bed of 100mmI.D. at different gas velocities. The simulation results are compared with measurements of bed pressure drop and fountain height. The comparison shows that the drag coefficient model used in cylindrical beds under-predicted bed pressure drop and fountain height in conical spouted beds due to the partial weight of particles supported by the inclined side walls. It is found that the numerical results using the drag coefficient model proposed based on the conical spouted bed in this study are in good agreement with experimental data. The present study provides a useful basis for further works on the CFD simulation of conical spouted bed.     

Comparison of continuous homogenous azeotropic and pressure-swing distillation for a minimum azeotropic system ethyl acetate/n-hexane separation

Continuous homogenous azeotropic distillation (CHAD) and pressure-swing distillation (PSD) are explored to separate a minimum-boiling azeotropic system of ethyl acetate and n-hexane. The CHAD process with acetone as the entrainer and the PSD process with the pressures of 0.1 MPa and 0.6 MPa in two columns are designed and simulated by Aspen Plus. The operating conditions of the two processes are optimized via a sequential modular approach to obtain the minimum total annual cost (TAC). The computational results show that the partially heat integrated pressure-swing distillation (HIPSD) has reduced in the energy cost and TAC by 40.79% and 35.94%, respectively, than the conventional PSD, and has more greatly reduced the energy cost and TAC by 62.61% and 49.26% respectively compared with the CHAD process. The comparison of CHAD process and partially HIPSD process illustrates that the partially HIPSD has more advantages in averting the product pollution, energy saving, and economy.     

Operation and control of batch extractive distillation for the separation of mixtures with minimum-boiling azeotrope

Batch distillation is commonly used in the fine chemicals, specialty polymer, biochemical, pharmaceutical, and food industries. For separating mixtures with minimum-boiling azeotrope, a heavy entrainer is frequently added to the top section of the batch column to aid in the separation. This process is called batch extractive distillation. Most of the papers in open literature have only studied the first operating step of the batch extractive distillation which is the recovery of the light component without mentioning the later steps for the recovery of the other component and entrainer. In this paper, two real chemical systems, one separating acetone and methanol using water as entrainer and the other separating isopropyl alcohol (IPA) and water using dimethyl sulfoxide (DMSO) as entrainer, are studied for the feasible operation of the complete batch distillation sequence. The operating variables, including the pre-load amount with the mixture, continuous feed rate of the entrainer, and reflux ratio at each operating step are determined in the operating sequence. The constant reflux ratio and constant entrainer feed rate operating policy and another policy to allow these two operating variables to be varied will be compared in order to further improve the batch operation. All dynamic simulations that are performed directly mimic industrial situations from an empty column using a rigorous dynamic simulator, Aspen Dynamics™.     

基于Excel、Matlab&CAD求解馏出液组成恒定的间歇精馏

介绍了使用Excel对非理想溶液保持馏出液组成恒定的间歇精馏的计算方法.该方法具有简便、准确和可靠等优点.使用CAD结合Matlab代替传统图解法中的繁琐、精度差的操作.通过上述两种方法的对比得出结论,逐板计算法的结果比图解法准确性高,更加可靠.     

Reburning and burnout simulations of natural gas for heavy oil combustion

Reburning and burnout simulations were carried out through PLUG code of CHEMKIN-III using a reduced mechanism, in order to determine preliminary experimental parameters for achieving maximum NO_x reduction to implement the reburning technology for heavy oil combustion in pilot scale equipments in Brazil. Gas compositions at the entrance of the reburning zone were estimated by the AComb program. Simulations were performed for eight conditions in the usual range of operational parameters for natural gas reburning. The maximum NO reduction (ca. 50%) was reached with 10 and 17.5% of power via natural gas and 1.5 and 3.0% O₂ excess, respectively, at 1273 K. The model predicts 250 ppm of NO, 50 ppm of CO and air mass flows in the range of about 50-130 kg/h for burnout.     

Development, analysis and validation of population models for continuous and batch crystallizers

This contribution deals with the derivation of mathematical models for continuous and batch crystallizers based on the population balance approach. Detailed kinetic expressions for primary nucleation, crystal growth and attrition are incorporated into the models. The proper mathematical formulation of these phenomena as well as their incorporation into the population balance are discussed. Subsequently, system theoretical properties (e.g. the differential index of the resulting differential-algebraic equation system) of the derived models are analysed. Finally, the models for the continuous and the batch crystallizer are validated by comparison to measurements of temperature, supersaturation and particle size distribution.     

A combined method for the design and optimization of intensified distillation systems

The sequential design method (SDM) is a recently introduced distillation column design method based on the correspondence between the simple column and the alternative sequences design parameters. It can be defined as a method that combines the alternatives generation step with the design procedure. The Multi-Objective Differential Evolution (MODE) algorithm instead, is based on the minimization or maximization of a defined objective function; it is a strong method that allows the evaluation of a large number of alternatives.The SDM is characterized by a poor control of the error propagation among the sequences, the MODE algorithm by a high computational time. It was obtained that a proper combination of the methods allows the compensation of the drawbacks of the stand-alone procedures. For the case study considered, when the MODE algorithm is initialized with the SDM, a 39% reduction of the computational time was observed. If the combination between the methods is realised at the beginning of the design procedure, the reduction of the computational time was of about 28%. The time reduction was due to a narrower initialization of the MODE algorithm with the parameters obtained applying the SDM. Moreover, when some overestimated design values where used to initialize the MODE algorithm, it is still possible to identify a configuration very close to the optimum.     

Design of batch operations: Systematic methodology for generation and analysis of sustainable alternatives

The objective of this paper is to present a new methodology that is able to generate, screen and identify sustainable alternatives to continuous chemical processes as well as processes operating in the batch mode. The methodology generates the sustainable (design) alternatives by locating the operational, environmental, economical and safety related problems inherent in the process (batch or continuous). Alternatives that are more sustainable, compared to a reference, are generated and evaluated by addressing one or more of the identified problems. A decomposition technique as well as a set of batch indicators for batch operations has been developed and added to the methodology so that a wide range of processes that operate in continuous mode, in semi-continuous and/or in batch modes can be improved. The principal calculation steps of the methodology for applications to continuous and batch processes are described, highlighting the main differences between them. Through two case studies, the application of the methodology, to obtain sustainable design alternatives for batch plants, is highlighted.     

Scale-up and design of a continuous microwave treatment system for the processing of oil-contaminated drill cuttings

A continuous microwave treatment system has been developed for the remediation of contaminated drill cuttings at pilot scale. Using the mechanisms of oil removal as a basis, a design was produced using electromagnetic simulations to find the optimum microwave applicator geometry which yielded the most favourable power density distribution. Bulk materials handling and process engineering principles were systematically integrated with the electromagnetic design to produce a system capable of treating 500 kg/h of material. The effects of the key design parameters are simulated, and a number of the simulations are verified with experimental data. It is shown that the environmental discharge threshold of 1% oil can be achieved in continuous operation, and the sensitivity of the system to changing feedstock properties is also highlighted. The parity between the simulations and experimental results in this paper highlights the necessity of electromagnetic modelling in the design and scale-up microwave processing equipment.     

Design of process and control scheme for cyclohexanol production from cyclohexene using reactive distillation

Cyclohexanol is a commonly used organic compound. Currently, the most promising industrial process for synthesizing cyclohexanol, by cyclohexene hydration, suffers from a low conversion rate and difficult separation. In this paper, a three-column process for catalytic distillation applicable in the hydration of cyclohexene to cyclohexanol was established to solve these. Simulation with Aspen Plus shows that the process has good advantages, the conversion of cyclohexene reached 99.3%, and the product purity was ≥99.2%. The stable operation of the distillation system requires a good control scheme. The design of the control scheme is very important. However, at present, the reactive distillation process for cyclohexene hydration is under investigation experimentally and by steady-state simulation. Therefore, three different plant-wide control schemes were established (CS1, CS2, CS3) and the position of temperature sensitive stage was selected by using sensitivity analysis method and singular value decomposition method. The Tyreus-Luyben empirical tuning method was used to tune the controller parameters. Finally, Aspen Dynamics simulation software was used to evaluate the performance of the three control schemes. By introducing ΔF ±20% and x_ENE ±5%, comparison the changes in product purity and yield of the three different control schemes. By comparison, we can see that the control scheme CS3 has the best performance.     

Biotechnology group meeting. Biochemistry and genetics for increasing productivities of industrial fermentation

Biosorption of heavy metals by microbial cells has been recognized as a potential alternative to existing technologies for removing heavy metals from industrial waste waters. Many aquatic microorganisms, such as algae, can take up dissolved metals from their surroundings to their cells. In this study, the adsorption of lead(II) ions was investigated in a single-staged batch reactor. Chlorella vulgaris, a green alga, was used as the sorbent. The sorption phenomenon was expressed by the Freundlich adsorption isotherm and this expression was used for the calculation of residual or adsorbed metal ion concentration at equilibrium (C_eq or C_x,eq) at a given ‘volume of waste water containing heavy metal ion/quantity of alga (V₀/X₀)’ ratio in a single-staged batch reactor. Experimental C_eq and C_x,eq values were compared to calculated ones. Applications in waste water treatment for lead(II) removal have been suggested.     

反应精馏合成醋酸正丁酯的模拟和优化

利用Aspen Plus模拟了合成醋酸正丁酯的反应精馏过程,并分析各工艺参数对产品纯度和再沸器热负荷影响。通过优化得出最佳工艺参数为:理论塔板数为16;精馏段、反应段和提馏段塔板数分别为5、7和4;醋酸和正丁醇的进料塔板数分别为5和7;酸醇进料比为1:1;回流比为1。在此条件下产品醋酸正丁酯的纯度达99.55%;乙酸的转化率达99.71%,再沸器的能耗较低。     

工业锅炉脱硫再生耦合技术的应用

阐述了脱硫再生耦合装置系统的流程、原理和特点，对实际应用中技术指标进行了测试和分析。总结了主要运行经验，找出了本装置稳定运行的最佳工况。     

Use of coupling agents for increasing passivants and cohesion ability of consolidant on limestone

Deterioration of monuments constructed of limestone could be potentially arrested by applying a combination of coupling agents with consolidants, which can prevent acid attack and mechanical weakening. Two different coupling agents including N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane (AE-APMDMS) and diethyl phosphatoethyl triethoxysilane(DEPETES) were used to link calcite. Calcite was impregnated with these coupling agents and studied by FTIR, TG-DSC and contact angle measurement. According to these techniques, new bands, a two stage decomposition pattern appeared and a slight increase in surface hydrophobicity for AE-APMDMS and DEPETES that indicated interactions between the coupling agents and calcite. The Scotch Tape test and compressive strength test showed that the cohesion between consolidant and limestone powder improved, while the ability of consolidation decreased, which were resulted by coupling agents. Resist acid test on limestone powder coated with the coupling agents resulted in a decreased deterioration rate. Limestone treated with combined consolidant plus AE-APMDMS or DEPETES showed a significant decrease in capillarity water absorption.     

Recursive data-based prediction and control of product quality for a PMMA batch process

In many batch processes, frequent process/feedstock disturbances and unavailability of direct on-line quality measurements make it very difficult to achieve tight control of product quality. Motivated by this, we present a simple data-based method in which measurements of other process variables are related to end product quality using a historical data base. The developed correlation model is used to make on-line predictions of end quality, which can serve as a basis for adjusting the batch condition/time so that desired product quality may be achieved. This strategy is applied to a methyl methacrylate (MMA) polymerization process. Important end quality variables, the weight average molecular weight and the polydispersity, are predicted recursively based on the measurements of reactor cooling rate. Subsequently, a shrinking-horizon model predictive control approach is used to manipulate the reaction temperature. The results in this study show promise for the proposed inferential control method.     

A two-stage approach for the synthesis of inter-plant water networks involving continuous and batch units

This paper presents a mathematical optimization model for inter-plant water network (IPWN) synthesis, where process units operate in mixed continuous and batch modes. The current developed model consists of a two-stage approach, and is dedicated to the special case where there are more continuous than batch units. In the first stage, all batch units are treated as continuous units by using auxiliary water storage tanks, and a continuously operated IPWN is synthesized to minimize the fresh water consumption. Subject to the determined IPWN flow rates, the water storage policy for the batch units is determined in the second stage to minimize the total storage capacity. Alternatively, the formulations of both stages can be combined and solved simultaneously to minimize the IPWN cost. Two modified literature examples are used to illustrate the proposed approach.     

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.     

燃煤机组脱硫废水零排放物料-能-水耦合机制及优化

湿法脱硫排出的废水是燃煤机组废水中最难处理的末端废水之一。热法固化是实现脱硫废水零排放的必然途径。通过构建整个燃煤机组厂级尺度热力系统虚拟仿真模型,从能量流、物料流、水平衡及其之间的相互影响机制的角度对比分析了目前三种主流不同脱硫工艺路线的优劣。在此基础上,提出了基于吸附式热泵和多效蒸馏浓缩,废热用于干燥的新型脱硫工艺,新工艺所需的高温烟气量最小,仅为旁路直喷式的1/5,为目前主流浓缩干燥方案的1/3,在回收水分的同时,极大降低高温烟气的消耗量,降低对主机安全性的影响。相关研究可以为燃煤机组脱硫废水零排放及深度节水提供新的解决思路。