Catalytic oxidation of methanol to formaldehyde: an example of kinetics with transport phenomena in a packed-bed reactor

In the present work the partial oxidation of methanol to formaldehyde has been studied as an example of strongly exothermic reaction affected by internal diffusion in order to deep the topic of mass and heat transfer in packed-bed catalytic reactors both at particle level, introducing the calculation of the effectiveness factor for complex reactions network, and at reactor level, for what concerns long range gradients of composition and temperature. The aim of the work is to stress the impact of the use of rigorous numerical methods, today possible for the high performances reached by the computers, in the solution of a simultaneous set of many differential equations that are necessary to describe completely the mentioned system. A complete mathematical model of the particle and the reactor is presented and a solution strategy is reported for the chosen reaction by considering a reliable kinetic law and evaluating related parameters from experimental data reported by the literature. Calculation results are reported for both particle internal profiles and reactor simulation. The described approach can easily be extended to many other devices and reactors geometry such as, e.g., the ones used in the field of environmental catalysis.     

Hybrid simulation based optimization approach for supply chain management

In this work, we propose a hybrid simulation optimization approach that addresses the problem of supply chain management. We formulated the problem as a mathematical model which minimizes the summation of production cost, transportation cost, inventory holding and shortage costs, subject to capacity and inventory balance constraints and propose a hybrid approach combining mathematical programming and simulation model to solve this problem. The main objective of this approach is to overcome the computational complexity associated with solving the underlying large-scale mixed integer linear problem and to provide a better representation of supply chain reality. The simulation-based optimization strategy uses an agent-based system to model the supply chain network. Each entity in the supply chain is represented as an agent whose activity is described by a collection of behavioral rules. The overall system is coupled with an optimization algorithm that is designed to address planning and scheduling level decisions.     

Process control applications of an extended Kalman filter algorithm

An efficient new algorithm is described and illustrated on process examples for solution of the extended Kalman filter equations for a continuous dynamic system with discrete measurements. Implicit simultaneous methods, which are powerful in terms of accuracy and efficiency, are utilized for numerical integration. At the internal integration step level, the new algorithm exploits the decoupled nature of the state estimate and error covarience equations along with the symmetry of the error covariance matrix. The error control strategy includes both the state estimates and error covariances.     

Optimization and nonlinear control of a batch crystallization process

Crystallization process has been widely used for separation in many chemical industries due to its capability to provide high purity product. To obtain the desired quality of crystal product, an optimal cooling control strategy is studied in the present work. Within the proposed control strategy, a dynamic optimization is first preformed with the objective to obtain the optimal cooling temperature policy of a batch crystallizer, maximizing the total volume of seeded crystals. Two different optimization problems are formulated and solved by using a sequential optimization approach. Owing to the complex and nonlinear behavior of the batch crystallizer, the nonlinear control strategy which is based on a generic model control (GMC) algorithm is implemented to track the resulting optimal temperature profile. The optimization integrated with nonlinear control strategy is demonstrated on a seeded batch crystallizer for the production of potassium sulfate.     

A systematic approach for synthesizing a low-temperature distillation system

In this paper, by combining a stochastic optimization method with a refrigeration shaft work targeting method, an approach for the synthesis of a heat integrated complex distillation system in a low-temperature process is presented. The synthesis problem is formulated as a mixed-integer nonlinear programming (MINLP) problem, which is solved by simulated annealing algorithm under a random procedure to explore the optimal operating parameters and the distillation sequence structure. The shaft work targeting method is used to evaluate the minimum energy cost of the corresponding separation system during the optimization without any need for a detailed design for the heat exchanger network (HEN) and the refrigeration system (RS). The method presented in the paper can dramatical y reduce the scale and complexity of the problem. A case study of ethylene cold-end separation is used to il ustrate the application of the approach. Compared with the original industrial scheme, the result is encouraging.     

From discretization to regularization of composite discontinuous functions

Discontinuities between distinct regions, described by different equation sets, cause difficulties for PDE/ODE solvers. We present a new algorithm that eliminates integrator discontinuities through regularizing discontinuities. First, the algorithm determines the optimum switch point between two functions spanning adjacent or overlapping domains. The optimum switch point is determined by searching for a “jump point” that minimizes a discontinuity between adjacent/overlapping functions. Then, discontinuity is resolved using an interpolating polynomial that joins the two discontinuous functions.This approach eliminates the need for conventional integrators to either discretize and then link discontinuities through generating interpolating polynomials based on state variables or to reinitialize state variables when discontinuities are detected in an ODE/DAE system. In contrast to conventional approaches that handle discontinuities at the state variable level only, the new approach tackles discontinuity at both state variable and the constitutive equations level. Thus, this approach eliminates errors associated with interpolating polynomials generated at a state variable level for discontinuities occurring in the constitutive equations.Computer memory space requirements for this approach exponentially increase with the dimension of the discontinuous function hence there will be limitations for functions with relatively high dimensions. Memory availability continues to increase with price decreasing so this is not expected to be a major limitation.     

A sweep-heuristic based formulation for the vehicle routing problem with cross-docking

Cross-docking is a warehousing strategy in logistics used by process industries making products with high proportions of distribution costs. It is described as the process of moving goods from suppliers to customers through a cross-dock terminal without a long-term storage in this facility. The vehicle routing problem with cross-docking (VRPCD) consists of fulfilling a set of transportation requests using a fleet of homogeneous vehicles to sequentially accomplish the pickup and delivery tasks. Between those operations, there is a consolidation process of incoming shipments at the cross-dock. This work introduces a monolithic formulation for the VRPCD that determines pickup/delivery routes and schedules simultaneously with the truck scheduling at the terminal. To derive a more efficient formulation, a constraint set mimicking the widely known sweep algorithm was incorporated into the rigorous model. The resulting model based on the sweep heuristic can find near-optimal solutions to large problems at very acceptable CPU times.     

Auslegung und Optimierung von hybriden Trennverfahren

Design and Optimization of Hybrid Separation Processes Hybrid separation processes are defined as the combination of at least two different unit operations in different apparatus which contribute to the separation task. Hybrid processes are used for difficult separations, e.g., close‐boiling mixtures and azeotropes, if a single unit operation, e.g., distillation, membranes, extraction, crystallization or chromatography, is not efficient or even not feasible. Because of the structure of a hybrid process which implies two or more unit operations and recycle streams, the design is not straightforward and therefore subject of today's research. In this work general criteria for such a consistent design method are described and a design approach for hybrid separation processes is presented. It bases on rigorous modeling of the unit operations and simultaneous multivariable optimization. The approach feasibility is demonstrated by the separation of an isomer mixture.     

CFD modelling of inorganic membrane modules for gas mixture separation

This work is aimed at investigating the capability of a computational fluid dynamics (CFD) approach to reliably predict the fluid dynamic and the separation performances of inorganic membranes modules for gas mixture separation.The simulations are based on the numerical solution of the Navier-Stokes equations on the three dimensional domain representing quite closely the selected module geometry. The membrane is modelled as a selective layer, which allows the permeation of different components as a function of the transport mechanism and the driving force.The computational strategy is strictly evaluated by comparing the results with available experimental data. The simulation predictions show fairly good agreement with the measured permeation data and allow to recognise the critical local fluid dynamic features of the separation module.     

油水乳液体系水合分离塔的模拟计算

在水合物法辅助分离乙烯裂解气流程中,水合物分离塔是非常关键的单元操作设备。气体混合物在塔内的分离过程与气体吸收塔类似,但因涉及气-液-液-固4相,所以计算更加复杂。将速率法和平衡级法相结合,提出了油水微乳体系吸收-水合分离塔的模拟计算方法。模拟计算了一典型乙烯裂解气在水合分离塔内的分离状况。为了确定适宜的操作条件,分别考核计算了操作温度和气液比对分离效果及能量消耗的影响。所得结果对水合分离塔的设计、操作条件的确定以及乙烯裂解气分离流程的制定有很重要的意义。计算结果还表明,通过水合物技术在0℃左右可实现氢气、甲烷和C₂以上组分的有效分离,因此可以节约大量制冷功耗。     

A pattern based strategy for using multidimensional sensors in process control

Multidimensional sensors can deliver vast and rich information about the industrial processes operation. At industrial level, they are becoming widely available for supervising tasks. However, their use at control level is not very widespread, since there are no standard methodologies for including the information provided by this type of sensors into existing control systems. This paper describes the traditional approach to include multidimensional information into conventional control systems, and proposes a new structure based on pattern recognition. The latter makes use of artificial neural networks and finite state machines as a framework for designing the control system. The main characteristics and limitations of both approaches are illustrated by the image based control of an experimental fluidization bed.     

考虑中间换热器的能量集成精馏序列合成

针对考虑中间换热器（IHE）的精馏序列合成问题,提出基于随机优化策略的能量集成非清晰精馏序列（IHE-HIDSs）合成方法。通过对精馏序列分离任务合并处引入二元0/1变量表示是否存在IHE,以精馏序列的年总成本（TAC）为优化目标,建立了该合成问题的隐式混合整数非线性规划模型（MINLP）,通过模拟退火和粒子群优化（SA-PSO）混合随机优化算法进行求解。为验证在精馏序列合成中同时考虑IHE的必要性以及所提出合成方法的有效性,对五组分醇类混合物和五组分烷烃类混合物两个算例的精馏序列合成问题进行了研究。结果表明,相比同时考虑热耦合和能量集成的精馏序列,IHE-HIDS具有更低的TAC。此外,所提出的方法可以在合理的计算时间内以高概率获得多个分离序列方案。     

非平衡级法气体混合物吸收-水合双塔分离单元的模拟计算

水合物技术应用于低沸点气体混合物分离的优势在于其可在0℃左右操作,因此可极大地降低制冷所消耗的能量。由于此分离方法尚处在理论研究阶段,还不能实现工业化,因此对操作流程模拟计算的研究很有必要。采用非平衡级法(速率法)对水合塔-吸收塔串联操作流程进行了模拟计算,其中涉及水合物生成动力学模型、水合物分解动力学模型以及混合气体在乳液相的吸收传质动力学模型。探讨了两个串联分离塔操作参数,如温度、压力等,对分离效率的影响,所得结果对水合物技术分离低沸点气体混合物流程的设计有重要意义,同时也可为以后的工业化奠定一定的理论基础。     

Separation network design with mass and energy separating agents

The mathematical model developed in this paper deals with simultaneous synthesis of the integrated separation network, where both mass separating agents (MSAs) and energy separating agents (ESAs) are taken into account. The proposed model formulation is believed to be superior to the available ones. Traditionally, the tasks of optimizing ESA-based and MSA-based processes were either performed individually or studied on a heuristic basis. In this work, both kinds of processes are incorporated into a single comprehensive flowsheet and a novel state-space superstructure with multi-stream mixings is adopted to capture all possible network configurations. By properly addressing the issue of interactions between the MSA and ESA subsystems, lower total annualized cost (TAC) can be obtained by solving the corresponding mixed-integer nonlinear programming (MINLP) model. A benchmark problem already published in the literature has been investigated to demonstrate how better conceptual designs can be generated by our proposed approach.     

DYNAMIC OPTIMAL CONTROL OF BATCH CRYSTALLIZATION PROCESSES

This work applies an on-line optimal control strategy developed by Zhang (2001) to two cooling batch crystallization processes. The algorithm initially finds the optimal crystallizer temperature and subsequently uses a feedback control system in order to achieve the desired final product quality of the crystals expressed in terms of the final crystal size distribution. In both batch processes, it is shown that the on-line optimal control approach provides better final product quality as compared with a simplified optimal cooling policy. The improvement is especially noticeable in the presence of plant/model mismatch or errors in the initial conditions.     

Application of a fuzzy match inference strategy in synthesis of separation systems

Symbolic representation and sequential processing of information in most expert systems have made it difficult to represent continuous variables and to model interactions among different parts of a large process system. This paper proposes a new approach, principally aimed at function oriented engineering design problems. Continuous variables and qualitative information are treated as fuzzy sets. A fuzzy match inference strategy is proposed to assess design schemes with rules in parallel. The fuzzy match inference strategy is then extended to multi-step decision making in the synthesis of multicomponent separation sequences. The new concepts have been implemented in a prototype expert system, where the selection of separation technologies and sequencing of separators are approached in an integrated manner. It is shown from several examples that the inference strategy yields promising results in quantitative evaluation of process synthesis and combinatorial optimization.     

Model based operation of emulsion polymerization reactors with evaporative cooling: Application to vinyl acetate homopolymerization

This work aims at maximizing the productivity of emulsion homopolymerization processes. A dynamic model of emulsion polymerization processes is extended by the inclusion of vaporization from the liquid phases in the reactor to the gaseous phase. The multi-component gas–liquid mass transfer phenomenon is described by the Maxwell–Stefan diffusion equations, which are solved by a special algorithm. A novel operation strategy is developed for running a reactor optimally with respect to batch time. This strategy is applied first to an industrial scale reactor, which is run without using evaporative cooling. Then, based on the extended model, controlled vaporization is included by which additional heat is removed from the reaction system. This makes it possible to extend the restrictions imposed by the limited heat removal of the cooling jacket considerably. Simulation results are presented for the homopolymerization of vinyl acetate in an industrial scale reactor operated in semi-batch mode. The results show that a significant amount of heat can be removed by evaporative cooling thus leading to higher productivity.     

Synthesis and sizing of batch/semicontinuous processes: single product plants

An approach is reported for the preliminary design of single product batch/semicontinuous plants. The methodology consists of two components: a new approximate sizing procedure, which determines the number of units in parallel at each stage as well as the sizes of the batch and semicontinuous units and a set of synthesis rules, which serve to select structural features such as consecutive tasks that should be merged or split and tasks that should be separated by intermediate storage. The sizing procedure can accommodate both new plant design as well as some simple forms of retrofitting applications. The effectiveness of the approach is demonstrated with comparisons to designs obtained using nonlinear programming formulations solved by using a generalized reduced-gradient algorithm.     

Integrated design of diesel hydrotreating processes

This work presents an integrated approach for the design of diesel hydrotreating processes employing a simulated annealing optimisation algorithm. The modelling of reactor, separation and heat recovery system for diesel hydrotreating processes is discussed, and a novel optimisation framework is developed for the design of complex refinery processes. A comparison with conventional approach to process design, i.e. sequential evolution of design, is given to illustrate the ability of proposed approach to obtain overall hydrotreating process designs with minimum total annualised costs. The proposed integrated approach takes into account the trade-offs between capital and operating costs, as well as interactions between the hydrotreater, distillation column, and the associated heat exchanger network.     

Multi-scale catalyst design

Catalyst design has long been sought in catalysis and reaction engineering research. In this work, multi-scale analysis and strategy is explored to take a holistic view toward catalyst design perspective and elucidate impacts of designs at different scales to a catalytic reaction process performance. A few promising design concepts are introduced to break the compromise that often needs to be made in the conventional design approach. In the catalyst bed scale, micro- or mini-structured catalyst designs can be used to potentially eliminate all mass transfer resistance and realize intrinsic catalytic performance. At the particle level, incorporation of membrane separation functions into the catalyst unit enables regulation of mass transfer rate of individual reactant or product molecules that high reaction selectivity is achieved. At the level of intrinsic catalyst structures, three-dimensional (3-D) catalyst design models are outlined here to outweigh limitations or constraints imposed by the conventional way of thinking 2-D catalyst surface. Examples of exceptional catalytic activity or concerted effects are shown by incorporating different materials into nano-composite catalysts and optimizing size and/or shape of a catalyst material at the nano-scale.