Bifurcation analysis of the conversion degrees in systems based on the cascade of tank reactors

The scope of the paper is the analysis of the possibility of increasing conversion in different types of systems based on continuous stirred tank reactors. A numerical model of the cascade with constant direction of material flow is tested, a model of changes of direction flow and a relaxation model. The analysis is conducted by means of parametric continuation method and numerical simulation, with the designation of bifurcation diagrams and time series. An essential impact of the relaxation method on the increase of the conversion degree is indicated.     

Towards multiscale modelling in product engineering

A concept of multiscale modelling of product manufacturing based on integration of three modelling methods currently applied at different scales of length and time: process system modelling, computational fluid dynamics and computational chemistry was presented. Major features of the three key types of modelling in the chemical and process industries were briefly described. The first applications and mutual benefits of joint use of two of the three approaches were presented along with the perspectives for the full integration of all three methods. The crucial role of a universal interface, such as the CAPE-OPEN standard, was emphasized.     

Application of recurrent neural networks in batch reactors: Part I. NARMA modelling of the dynamic behaviour of the heat transfer fluid temperature

This paper is focused on the development of nonlinear models, using artificial neural networks, able to provide appropriate predictions when acting as process simulators. The dynamic behaviour of the heat transfer fluid temperature in a jacketed chemical reactor has been selected as a case study. Different structures of NARMA (Non-linear ARMA) models have been studied. The experimental results have allowed to carry out a comparison between the different neural approaches and a first-principles model. The best neural results are obtained using a parallel model structure based on a recurrent neural network architecture, which guarantees better dynamic approximations than currently employed neural models. The results suggest that parallel models built up with recurrent networks can be seen as an alternative to phenomenological models for simulating the dynamic behaviour of the heating/cooling circuits which change from batch installation to installation.     

Current challenges in the design and control of multiscale systems

Multiscale modelling is a new emerging field in process systems engineering. Although the idea of linking events occurring across time and length scales is not new, the numerical solution of these models is challenging because of computational limitations and the difficulty in coupling modelling methods with different characteristics. Although an extensive set of tools are currently available to improve the performance of processes described using continuum models, most of these tools are not suitable to design and control a multiscale process. This work presents the approaches that are currently available to perform multiscale modelling and identifies the key challenges that need to be addressed to improve the performance of macroscopic processes by controlling events occurring at the atomistic, molecular and nanoscopic levels.     

Modelling of unsteady-state hydrodynamics in periodically operated trickle-bed reactors:Influence of the liquid-phase physical properties

Process intensification using periodic operation of trickle bed reactors (TBRs) is still a long way from replacing conventional steady-state operation in industrial use, despite the numerous benefits described in the literature. Complex interactions between hydrodynamics, mass transfer and reaction phenomena make the design of periodically operated TBRs an almost insurmountable challenge. The development of hydrodynamic models able to provide reliable quantitative predictions of flow behaviour and possessing a sound physical basis, is an essential prerequisite for obtaining the necessary insights into this complexity. In this work, the two-phase pressure drop and dynamic liquid hold-up during max/min and on/off periodical operation were predicted using a model based on the relative permeability concept. In order to demonstrate the utility of this approach, a systematic investigation of the quantitative influence of the liquid-phase physical properties was carried out. The results obtained show that the modelling of the hydrodynamics in periodically operated TBRs using the relative permeability concept is feasible. By selecting suitable permeability parameters, unsteady-state hydrodynamics for different periodic operating modes can be predicted successfully.     

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.     

A network theory for the structured modelling of chemical processes

A structuring methodology for dynamic models of chemical engineering processes is presented. The main ideas of the methodology were outlined in a previous publication for the class of well-mixed systems. In this contribution, the methodology is extended to spatially distributed systems and to particulate processes. Furthermore, the structuring principle is used to make a conceptual link between the macroscopic world of process simulation and the microscopic world of molecular simulation. It is shown that a uniform structuring principle can be applied to the modularisation of most classes of chemical engineering models. The structuring principle can be used as a theoretical framework for the implementation of modular families of chemical engineering models in modern computer aided modelling tools.     

Dynamic modelling of an industrial R2R FCC unit

The aim of this study is to obtain a model that can simulate the performance of an industrial fluid catalytic cracking (FCC) unit in steady and dynamic state, and which will subsequently be used in studies of control and real time optimisation. In this paper, a dynamic model for a R2R type FCC unit is presented. The model includes the riser, the stripper/disengager, the regeneration system and the catalyst transport lines. Mass, energy and pressure balances are performed for each of these sections.Simulation results for steady state are presented and compared qualitatively to those obtained from previous FCC models. The dynamic behaviour of the system is explored through two perturbations in open loop, one on the fresh feed flow rate and one on the air flow rate to the first regenerator. The results illustrate the consistency of the model and are in agreement with what has been observed in studies available in the open literature.     

Mathematical modelling of low-temperature hydrogen production with in situ CO2 capture

Theoretical analysis of a process for low-temperature hydrogen production through steam methane reforming (SMR), based on the concept of adsorption-enhanced reaction, is presented. In the proposed process, mobile (pneumatically conveyed) adsorbent particles are passed through a stationary SMR catalyst monolith. Adsorbent regeneration is carried out in an external unit, thus decoupling the reaction and adsorbent regeneration steps, and allowing continuous operation. Heat for reaction is also supplied via the regeneration unit (via the thermal capacitance of the adsorbent), and thus effective energy integration is possible between the reactor and regenerator units. A mathematical model accounting for non-isothermal reaction and adsorption, mass transfer limited adsorption kinetics and non-linear (Langmuirian) adsorption equilibria, has been developed. The performance of the adsorptive reactor in terms of conversion enhancement is presented in this paper. Simulation results indicate considerable conversion enhancement through the use of a flowing adsorbent medium. The importance of the correct selection of operating parameters, i.e., adsorbent mass flow rate and temperature, on the process feasibility is also highlighted.     

The continuous self stirred tank reactor: measurement of the cracking kinetics of biomass pyrolysis vapours

The continuous self stirred tank reactor is a well known suitable device for studying the kinetics of high-temperature gas phase reactions. Temperature and composition are uniform at any point of the reactor, and for a given residence time, it is easy to calculate the values of kinetic constants from a very simple mathematical model. The aim of the present paper is to report the first experimental results obtained on the thermal cracking of vapours produced by the pyrolysis of biomass. The experiments are carried out between 836 and 1303 K and under mean residence times ranging from 0.3 to 0.5 s. The calculated activation energy and preexponential factor are in good agreement with those obtained by other authors operating in more usual devices, but needing the solving of more sophisticated models.     

Effect of the mode of heat withdrawal on the asymmetry of temperature profiles in reverse-flow reactors. Catalytic combustion of methane as a test case

Results of simulations are presented concerning a reverse-flow reactor for the catalytic combustion of methane that occurs in coal-mine ventilation air. Two variants of heat withdrawal are analysed. The simulations show that a relation exists between the method for heat withdrawal and the asymmetry in the profiles of the catalyst temperature over half-cycles of flow reversal. Too strong asymmetry impairs the efficient utilization of the heat produced. The results reveal that the recovery of heat by hot gas withdrawal from the central part of the reactor, and then, the introduction of the gas into a boiler wherein it is cooled to about 333 K (60 °C) guarantee more favourable symmetry of the half-cycle profiles and much better utilization conditions than the direct withdrawal of heat from the mid-section of the reactor (central cooling).     

Process systems modelling and applications in granulation: A review

Granulation is one of the fundamental operations in particulate processing and has a very ancient history and widespread use. Much fundamental particle science has occurred in the last two decades to help understand the underlying phenomena. Yet, until recently the development of granulation systems was mostly based on popular practice. The use of process systems approaches to the integrated understanding of these operations is providing improved insight into the complex nature of the processes.Improved mathematical representations, new solution techniques and the application of the models to industrial processes are yielding better designs, improved optimisation and tighter control of these systems. The parallel development of advanced instrumentation and the use of inferential approaches provide real-time access to system parameters necessary for improvements in operation. The use of advanced models to help develop real-time plant diagnostic systems provides further evidence of the utility of process system approaches to granulation processes. This paper highlights some of those aspects of granulation.     

Multi-feed attainable region construction using the Shrink-Wrap algorithm

An implementation of the Infinite DimEnsionAl State-space (IDEAS) based Shrink-Wrap algorithm for attainable region (AR) construction is developed, which identifies the multi-feed AR in reduced dimension (ARrd). The proof of the validity of the method is based on the stoichiometric characteristics of the reaction system and the properties of well-connected reactor networks, which allow the establishment of necessary and sufficient conditions for a point in mass fraction space to be in the multi-feed AR. The two-feed AR for methane steam reforming at isothermal and isobaric conditions is identified in the three-dimensional mass fraction space, and it is shown that for feeds consisting of pure methane and pure water, the equilibrium curves define the boundaries of the projections of the two-feed AR.     

Mathematical modelling of temperature induced moisture migration in bulk powders

This paper reviews the importance of temperature gradient induced moisture diffusion in powder beds. Redistribution of moisture by this mechanism is important for a wide variety of products, especially those which are crystalline in nature. Moisture transfer in these products can result in very high local water activity and lead to microbial spoilage and caking problems. A conceptual model was developed for heat and moisture transfer due to the application of thermal gradients across a one-dimensional powder bed. The validity of the key assumptions in the model formulation were demonstrated and a mathematical model was derived and solved numerically. The model was validated against experimental data collected using crystalline lactose powders as a working example.     

Adsorptive reactor technology for VOC abatement

The use of the monolith as an adsorptive reactor (M_AR) is proposed as a viable and novel alternative for VOC disposal. The M_AR combines adsorptive separation and catalytic combustion of the VOC in a single reactor unit and is thought to make effective utilisation of energy due to efficient heat integration. Theoretical studies on the feasibility and application of the adsorptive reactor concept for VOC oxidation is presented in this paper. Thus unlike previous work, present studies focus on an exothermic reaction system and the ability of the M_AR to control thermal runaway. A two dimensional mathematical model accounting for non isothermal adsorption and reaction, mass transfer limited adsorption kinetics and non linear (Tóth) adsorption equilibria, has been developed. The process is operated cyclically in two steps: adsorption and desorption/reaction. The VOC is fed into the reactor in the adsorption step and captured to produce a pure carrier gas effluent. Concentration and thermal swing is induced in the second step by means of an air feed. The most outstanding feature of the M_AR is its ability to prevent thermal runaway whilst maintaining a high VOC conversion. Simulation results indicate that the careful selection of step times for adsorption and desorption, feed temperatures and inlet velocities lead to stability and energy requirements which outperform equivalent conventional designs. The M_AR is thermally more stable due to the controlled release of the reactant from the adsorbed phase into the reaction zone, and also the heat integration of endothermic desorption and exothermic reaction.     

Rate-based analysis of reactive distillation sequences with different degrees of integration

In this work, reactive distillation sequences with different degrees of integration are investigated with the aim to identify the optimal configuration. Such integration includes the combination of both unit operations, reaction and distillation, as well as the combination of distillation columns within one unit. For rapid determination of required design parameters, a special two-step approach based on the decomposition method is developed.As a test system, the transesterification of carbonates is chosen, and three promising configurations with increasing integration degree are identified. These configurations comprise two different combinations of single non-reactive and reactive distillation columns as well as a highly integrated reactive dividing wall column. Their analysis shows that the unit integration leads to significant savings in energy consumption and production costs.     

A model predictive formulation for control of open-loop unstable cascade systems

Cascade control is commonly used in the operation of chemical processes to reject disturbances that have a rapid effect on a secondary measured state, before the primary measured variable is affected. In this paper, we develop a state estimation-based model predictive control approach that has the same general philosophy of cascade control (taking advantage of secondary measurements to aid disturbance rejection), with the additional advantage of the constraint handling capability of model predictive control (MPC). State estimation is achieved by using a Kalman filter and appending modeled disturbances as augmented states to the original system model. The example application is an open-loop unstable jacketed exothermic chemical reactor, where the jacket temperature is used as a secondary measurement in order to infer disturbances in jacket feed temperature and/or reactor feed flow rate. The MPC-based cascade strategy yields significantly better performance than classical cascade control when operating close to constraints on the jacket flow rate.     

A dynamic model of the fuel processor for a residential PEM fuel cell energy system

A dynamic numerical model describing an experimental methane fuel processor for a residential PEMFC energy system is presented. In contrast to previous simulation studies of steam reforming of methane, this model includes the various energetic couplings due to spatial proximity and constructive layout of the components. Thus, all significant energy flows inside the system are taken into account, including those caused by unintended conduction and radiation. Steady-state simulations were carried out to investigate the effect of a constructional modification in the reformer, which clearly reveal the significant influence of thermal couplings on the reformer efficiency. Furthermore, dynamic simulations were performed for the start-up procedure of the fuel processor and compared to experimental data. The results demonstrate that the dynamic model is a useful tool for further investigations of unsteady operating conditions and for optimisation with respect to both construction and system operation.