• Energy Research

The pyrolysis kinetics of beech wood was analyzed using model-free and model-fitting methods. Experimental measurements of the pyrolysis process were conducted in two thermogravimetric analyzers (TGA), a TG 209/2/F from Netzsch and a TGA Q500 from TA Instruments, which were found to have a similar precision in the establishment of the present heating rate. Two experimental procedures were employed: (i) introducing samples which were pre-dried externally before the experiments were executed and (ii) internal (in situ) drying of the samples in the TGA via a special temperature program below 150 degrees C which preceded the pyrolysis process. The kinetic parameters were derived (i) using several model-free methods, namely Kissinger method, iso-conversional methods, a simplified Distributed Activation Energy Model (sDAEM) and, (ii) using a model-fitting method via a five-step reaction model which calculates the differential thermogravimetric (DTG) curves at different heating rates; the calculated DTG curves were further analyzed by Kissinger's method to obtain overall kinetic data. The kinetic parameters were found to be different in the two experimental procedures. Also, they turned out different when the assumed end temperature of the pyrolysis process was varied. This is because the pyrolysis of slowly charring solid residues becomes more important with increasing temperature and finally overruns the release of volatiles from the wood samples. For the same experimental procedure and for sufficiently low end temperatures, corresponding to a degree of conversion less than 85%, model-free and model-fitting methods resulted in similar kinetic parameters. The authors express their gratitude to the BIOLAB experimental facility, to the “Programa de movilidad de investigadores en centros de investigación extranjeros (Modalidad A)” from the Carlos III University of Madrid (Spain) and to the Institute of Combustion Technology at DLR for the financial support conceded to Antonio Soria-Verdugo for a research stay at the German Aerospace Center DLR (Stuttgart, Germany) during the summer of 2018. Funding by the Helmholtz Association of German Research Centers in the research fields energy, fuels and gasification, especially in the Program “Energy Efficiency, Materials and Resources“, is acknowledged by the Institute for Technical Chemistry at KIT, Karlsruhe, and by the Institute of Combustion Technology at DLR Stuttgart. Publicado

Abstract Particle-resolved simulations have been performed to study the pyrolysis process of a high-density polyethylene (HDPE) particle in an inert hot nitrogen flow. The simulations resolve the velocity and temperature boundary layers around the particle, as well as the gradients of temperature and concentration within the particle. The objective of this work is to gain an in-depth understanding of the effect of particle morphology-specifically, the particle size and shape-on the interplay between heat transfer and pyrolysis progress, as well as to assess the applicable particle size when using the Lagrangian concept for simulating plastic pyrolysis. In all simulation cases, the pyrolysis reaction is initiated at the external surface of the particle, where the particle is heated the fastest. The reaction front propagates inward toward the core of the particle until it is fully pyrolyzed. For particle diameters larger than 4 mm, distinct temperature gradients within the particle can be detected, leading to a temperature difference of more than 10 K between the core and the external surface of the plastic particle. In this case, the Lagrangian simulations yield a considerably slower conversion compared with the particle-resolved simulations. Moreover, the cylindrical particle in longitudinal flow has been found to be pyrolyzed more slowly compared with the spherical and shell-shaped particles, which is attributed to the enhanced heat transfer conditions for the cylindrical particle. The results reveal the importance of considering particle morphology when modeling plastic pyrolysis. In addition, the Lagrangian approach, which assumes particle homogeneity, is only applicable for particle diameters smaller than 2 mm when modeling plastic pyrolysis.

Pyrolysis of plastic waste is a key technology for closing the anthropogenic carbon cycle. The energy demand (ED) of this endothermic process is a crucial factor to evaluate its benefits compared to established recycling pathways. The pyrolysis ED can be determined experimentally. However, this is elaborate and limited in transferability. Existing models cover virgin plastics or hydrocarbon thermoplastic mixtures on a laboratory scale. Here, a model for calculating the ED of thermoplastic mixtures based on the superposition of virgin polymer data is developed. The material data, such as heat capacity, phase transition enthalpy, and reaction enthalpy, are determined using differential scanning calorimetry. Pilot-scale experiments are performed in a 1 kg/h screw reactor. These experimental data are compared to model calculations. The feedstock-specific ED for pyrolysis is plastic-type independent. It amounts to approximately 4−6% of the feedstocks’ net calorific value. The validation shows excellent accordance for virgin plastics and hydrocarbon plastics mixtures. The modeled ED of mixtures including heteroatoms is systematically underestimated, which indicates changes in the degradation mechanism. The model allows for resolving several phenomena contributing to the pyrolysis ED. The simple calculation of the ED with in-depth information on occurring phenomena enables more reliable process design, optimization, and evaluation.

Combustion tests and gaseous emissions of olive mill solid wastes pellets (olive pomace (OP), and olive pits (OPi)) were carried out in an updraft counter-current fixed bed reactor. Along the combustion chamber axis and under a constant primary air flow rate, the bed temperatures and the mass loss rate were measured as functions of time. Moreover, the gas mixture components such as O2, organic carbon (Corg), CO, CO2, H2O, H2, SO2, and NOx (NO + NO2) were analyzed and measured. The reaction front positions were determined as well as the ignition rate and the reaction front velocity. We have found that the exhaust gases are emitted in acceptable concentrations compared to the combustion of standard wood pellets reported in the literature (EN 303-5). It is shown that the bed temperature increased from the ambient value to a maximum value ranging from 750 to 1000 °C as previously reported in the literature. The results demonstrate the promise of using olive mill solid waste pellets as an alternative biofuel for heat and/or electricity production.

This research investigates the flight behavior of refuse-derived fuel (RDF) in a drop shaft using Computer Vision to obtain statistical data on the aerodynamic properties of the particles. Methods to determine 3D geometry models of complex-shaped particles by photogrammetry and to obtain time resolved particle positions and velocities are described. Furthermore, an approach to obtain the frequency distribution of drag and lift coefficients from photogrammetric analysis and drop shaft experiments is presented. The image evaluation is based on algorithms of the open-source libraries OpenCV, COLMAP as well as MeshLab and Open3D. The precision of the system is validated employing model particles with known geometry. The 3D particle models overestimate the particle surface area by 4.58 %, the position detection works with a mean deviation of 2.73 %. The average sink rate is calculated with an accuracy of 4.87 % and the drag coefficient with an accuracy of 2.08 %. Finally, the frequency distribution of four RDF fractions, namely, textiles, cardboard, 3D plastic particles and 2D plastic foils are presented.

Abstract Nanostructured materials are widely used to improve the properties of consumer products such as tires, cosmetics, light weight equipment etc. Due to their complex composition these products are hardly recycled and thermal treatment is preferred. In this study we investigated the thermal stability and material balance of nanostructured metal oxides in flames, in a pilot scale combustion plant and an industrial hazardous waste incinerator. We studied the size distribution of nanostructured metal oxides (CeO2, TiO2, SiO2) in a flame reactor and in a heated reaction tube. In the premixed ethylene/air flame, nano-structured CeO2 partly evaporates forming a new particle mode. This is probably due to chemical reactions in the flame. In addition sintering of agglomerates takes place in the flame. In the electrically heated reaction tube however only sintering of the agglomerated nanomaterials is observed. Ceria has a low background in waste incinerators and is therefore a suitable tracer for investigating the fate of nanostructured materials. Low concentrations of Ceria were introduced by a two-phase nozzle into the post-combustion zone of a waste incinerator. By the incineration of coal dust in a burning chamber the Ceria nanoparticles are mainly found in the size range of the fly ash (1 – 10 µm) because of agglomeration. With gas as a fuel less agglomeration was observed and the Ceria nanoparticles were in the particle size range below 1 µm.

AbstractCatalytic pyrolysis of post‐industrial and post‐consumer waste is studied in an auger‐type reactor at pilot scale by applying two different zeolites and an amorphous silica‐alumina catalyst in‐situ at 400–550 °C. Contrary to thermal pyrolysis, of polyolefin‐rich waste, high gaseous pyrolysis product yields of approx. 85 wt % are achieved with C2–C4 olefin contents of up to 67 wt %. After deactivation by coke deposition catalyst regeneration is proved feasible for maintaining the gaseous product yield and composition. Waste feedstocks with significant nitrogen and halogen heteroatom content are not suitable for in‐situ catalytic pyrolysis.