Ľudovít Jelemenský

Kinetic study of wood chips decomposition by TGA

Pyrolysis of a wood chips mixture and main wood compounds such as hemicellulose, cellulose and lignin was investigated by thermogravimetry. The investigation was carried out in inert nitrogen atmosphere with temperatures ranging from 20°C to 900°C for four heating rates: 2 K min−1, 5 K min−1, 10 K min−1, and 15 K min−1. Hemicellulose, cellulose, and lignin were used as the main compounds of biomass. TGA and DTG temperature dependencies were evaluated. Decomposition processes proceed in three main stages: water evaporation, and active and passive pyrolysis. The decomposition of hemicellulose and cellulose takes place in the temperature range of 200–380°C and 250–380°C, while lignin decomposition seems to be ranging from 180°C up to 900°C. The isoconversional method was used to determine kinetic parameters such as activation energy and pre-exponential factor mainly in the stage of active pyrolysis and partially in the passive stage. It was found that, at the end of the decomposition process, the value of activation energy decreases. Reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. Obtained kinetic parameters were used to calculate simulated decompositions at different heating rates. Experimental data compared with the simulation ones were in good accordance at all heating rates. From the pyrolysis of hemicellulose, cellulose, and lignin it is clear that the decomposition process of wood is dependent on the composition and concentration of the main compounds.

Impact of mathematical model selection on prediction of steady state and dynamic behaviour of a reactive distillation column

The objective of this paper was to compare the prediction of the equilibrium (EQ) and nonequilibrium (NEQ) models during safety analysis of a reactive distillation column focusing on the identification of hazardous situations or particular operability problems. The safety and operability analyses are based on application of the HAZOP procedure integrated with a mathematical model with the aim to determine the column response to deviations from normal operation conditions or during a nonstandard procedure, e.g. the start-up of the reactive distillation column. A significant part of the safety and operability problems analysis is the identification of multiple steady states and their stability. A reactive distillation column can in general exhibit multiple steady states which reduce the column operability and controllability during perturbations of the manipulated variables and particularly during the start-up and shut down procedures. The EQ and NEQ models were compared focusing on prediction of the multiple steady states phenomenon and of the consequences which can result from this phenomenon.

Kinetic study of pyrolysis of waste water treatment plant sludge

Activated sewage sludge samples obtained from two different waste water treatment plants were investigated by thermogravimetric analysis. Due to a very high content of water in the sludge samples, these had to be dried at 160°C in an electrical oven in order to remove all adsorbed water. To ensure pyrolysis conditions, nitrogen atmosphere was applied. The pyrolysis decomposition process was carried out in the temperature range from ambient temperature to 900°C at three different heating rates: 2 K min−1, 5 K min−1, 10 K min−1. TGA and DTG curves of the decomposition processes were obtained. Temperature of onset decomposition, final temperature of decomposition, maximum decomposition rate, and decomposition temperature were determined by thermogravimetric analysis for both sludge samples used. The main decomposition process takes place at temperatures in the range from 230°C to 500°C. Above this temperature, there are only small changes in the mass loss which are often attributed to the decomposition of carbonates present in the sewage sludge samples. To determine the apparent kinetic parameters such as the activation energy and the preexponential factor, the so called Friedman isoconversional method was used. Because of the requirements of this method, initial and final parts of the decomposition process, where crossings of the decomposition lines occurred, were cut off. Obtained dependencies of the apparent activation energies and preexponential factors as a function of conversion were used backwards to calculate the modeled decomposition process of sewage sludge and the experimental data were in good accordance with the data obtained by simulation.

CFD-based atmospheric dispersion modeling in real urban environments

The process of CFD model application for atmospheric dispersion modeling is presented. Increasing the CPU power opens new possibilities of the CFD approach application for consequence analysis in real complex urban environments. As successful CFD simulation is directly dependent on the quality and complexity of the computational mesh, a new methodology of transferring the Geographic Information System (GIS) data to the computational mesh can be utilized. A user software for importing and manipulation with the GIS data and their subsequent transfer to an instructional file for the generation of the computational mesh was prepared and tested. The introduced methodology is relatively simple and it requires only a small amount of input data. The process of creating a computational mesh is very straightforward and fast, which enables the application of CFD modeling in urban environments in all fields of engineering applications in safety analysis. Several recommendations concerning proper definition of boundary conditions for atmospheric dispersion modeling were summarized. The presented approach was tested on a realistic case study of liquefied chlorine release in a real town. Results obtained by the CFD approach were compared with those obtained by a simpler but standard integral model.

Catalytic gasification of pyrolytic oil from tire pyrolysis process

The present work deals with thermo-catalytic decomposition of pyrolytic oil from the scrap tire pyrolysis process. Such oil can be used as a model tar in an experimental study of tar removal from pyrolysis or gasification process gas. Several experiments under different conditions were carried out in order to determine conditions of the gasification and pyrolysis processes. Influence of the oil to steam ratio, temperature, and of the presence of dolomite catalyst was studied. Addition of water steam has positive effect on the hydrogen content in the outgoing process gas as well as on the conversion of the injected oil. The catalytic gasification experiment in a quasi steady state produced process gas with the composition: 61 mole % of H2, 6.4 mole % of CO, and 11.7 mole % of CH4. At temperatures lower than 800°C, the amount of process gas decreased resulting also in a decrease of the oil conversion. A comparison of gasification experiments using fresh calcined dolomite with experiments proceeding with regenerated dolomite was done under the same conditions. There was a decrease in the process gas volumetric flow when regenerated catalyst was used.

Utilization of parallel computing in chemical engineering

Abstract The main objective of the presented work was to explore the possibilities of parallel computing utilization in chemical engineering. Parallel computers and principles of parallel computing are in brief described in Introduction. The next part exposes the possibilities of parallel programming in Matlab and C# programming language environment. The next three parts provide case studies of parallel computing in chemical engineering. Each example of the benefits of HPC involves a comparison with its serial equivalents.

Ammonia synthesis fundamentals for a model-based HAZOP study

Abstract Hazard and operability (HAZOP) analysis is a highly disciplined process hazard analysis (PHA) technique based on the exploration of the effects of process variables deviations. Inconveniences of a conventional HAZOP study are its time-consuming character and high cost. The principal objective of this paper is to present a new methodology for hazard identification of a selected chemical production process. Model-based HAZOP study is a very robust tool for predicting a systems response to deviations from design or operation conditions. An approach based on the mathematical modelling of a process can help to identify sources of hazard that could be overlooked by conventional PHA techniques. A case study focused on the multiple steady states phenomenon in an ammonia synthesis reactor is presented. The process simulation was performed using the Aspen HYSYS v8.4 process modelling environment. Nonlinear behaviour of the investigated fixed-bed reactor system was confirmed by an accident in an industrial ammonia synthesis reactor. The analysed system exhibited the feed temperature and pressure dependence of various operation parameters. This fact indicates the presence of multiple steady states. From the safety analysis point of view, switching between steady states can lead to process hazards.

Kinetics of thermal degradation of wood biomass

Pyrolysis kinetics of a hardwood representative, beech (Fagus sylvatica), was investigated by two different kinetic approaches: model-free isoconversional method and model-fitting method. The model-free isoconversional method was used for the determination of apparent kinetic parameters, i.e. the activation energy and pre-exponential factor. The model fitting method was used for the optimization of kinetic parameters of the reaction pathways of three selected reaction mechanisms: one-step, two-step, and three-step one. In both approaches, thermo-gravimetric data were used at five heating rates: 2°C min−1, 5°C min−1, 10°C min−1, 15°C min−1 and 20°C min−1. As the most suitable mechanism, the three-step mechanism containing the intermediate degradation step was chosen. This selection was supported by experimental results from the 13C NMR analysis of solid residues prepared at the key temperatures within the range of 230–500°C. The progress of mass fraction values of each component in this mechanism was simulated. Conclusions from the simulation were confronted with experimental results from the 13C NMR.

Impact of Mass Transfer on Modelling and Simulation of Reactive Distillation Columns

1.1 Reactive distillation In chemical process industries, chemical reaction and purification of the desired products by distillation are usually carried out sequentially. In many cases, the performance of this classic chemical process structure can be significantly improved by an integration of reaction and distillation in a single multifunctional process unit. This integration concept is called ‘reactive distillation’ (RD); when heterogeneous catalysts are applied, the term ‘catalytic distillation’ is often used. As to the advantages of this integration, chemical equilibrium limitations can be overcome, higher selectivity achieved, by-product formation reduced, heat of the reaction can be used for distillation in-situ, hot spots and run-away effect can be avoided, and azeotropic or closely boiling mixtures can be separated more easily than in a non-RD process. Some of these advantages are realised using a reaction to improve the separation; others are realised using separation to improve the reaction (Sundmacher & Kienle, 2002). Technological advantages as well as financial benefit resulting from this integration are important. Simplification or elimination of the separation system can lead to significant capital savings, increased conversion and total efficiency, which then result in reduced operating costs (Taylor & Krishna, 2000).

Fault propagation behavior study of CSTR in HAZOP

This paper discusses the role of process modeling in safety analysis. Process modeling is applied in the fault propagation behavior study of CSTR chemical production. For that purpose, HAZOP methodology and continuation analysis were used. The proposed hazard identification methodology involves analysis of steady-state multiplicity and safe operating conditions as well as those which can shift process units from one steady state to another. All presented case studies are also supported by system dynamic simulations, essential to detect oscillatory thermal instability. In this paper, N-oxide alkylpyridines production process was chosen to identify potential hazard and operational problems. Presented dynamic simulations represent an analysis of the system response to step changes in the key operating parameters. The effect of deviations of three key parameters on the reactor safe operation was investigated. The proposed numerical algorithms represent a mathematical engine of the simulation module within an automated model-based HAZOP analysis tool.