"This dissertation documents a study on parameter estimation methods for comprehensive pyrolysis modeling. There are four parts to this work, which are (1) evaluating effects of applying different kinetic models to pyrolysis modeling of fiberglass reinforced polymer composites; (2); evaluation of pyrolysis parameters for fiberglass reinforced polymer composites based on multi-objective optimization; (3) parameter estimation for comprehensive pyrolysis modeling: guidance and critical observations; and (4) engineering guide for estimating material pyrolysis properties for fire modeling. In the first section (Section 1), evaluation work is conducted to determine the effects of applying different kinetic models (KMs), developed based on thermal analysis using TGA data, when used in typical 1D pyrolysis models of fiberglass reinforced polymer (FRP) composites. The study shows that that increasing complexity of KMs to be used in pyrolysis modeling is unnecessary for the FRP samples investigated. Additionally, the findings from this research indicates that the basic assumption of considering thermal decomposition of each computational cell in comprehensive pyrolysis modeling as equivalent to that in a TGA experiment becomes inapplicable at depth and higher heating rates. The second part of this dissertation (Section 2) reports the results from a study conducted to investigate the ability of global, multi-objective and multi-variable optimization methods to estimate material parameters for comprehensive pyrolysis models. The research materials are two fiberglass reinforced polymer (FRP) composites that share the same fiberglass mats but with two different resin systems. One resin system is composed of a single component and the other system is composed of two components (resin and fire retardant additive). The results show that for a well-configured parameter estimation exercise using the optimization method described above, (1) estimated results are within ± 100% of the measurements in general; (2) increasing complexity of the kinetic modeling for a single component system has insignificant effect on estimated values; (3) increasing complexity of the kinetic modeling for a multiple component system with each element having different thermal characteristics has positive effect on estimated values; and (4) parameter estimation using an optimization method with appropriate level of complexity in kinetic model and optimization targets can find estimations that can be considered as effective material property values. The third part of this dissertation (Section 3) proposes a process for conducting parameter estimation for comprehensive pyrolysis models. The work describes the underlying concepts considered in the proposed process and gives discussions of its limitations. Additionally, example cases of parameter estimation exercise are shown to illustrate the application of the parameter estimation process. There are four materials considered in the example cases – thermoplastics (PMMA), corrugated cardboard, fiberglass reinforced polymer composites and plywood. In the last part (Section 4), the actual Guide, a standardized procedure for obtaining material parameters for input into a wide range of pyrolysis models is presented. This is a step-by-step process that provides a brief description of modeling approaches and assumptions; a typical mathematical formulation to identify model parameters in the equations; and methods of estimating the model parameters either by independent measurements or optimization in pair with the model. In the Guide, example cases are given to show how the process can be applied to different types of real-world materials. "

This research investigates the decomposition and burning behaviours of polyurethane foams experimentally and compares the experimental results obtained with the numerical results from the pyrolysis model of Fire Dynamics Simulator, Version 5 (FDS 5). Based on the comparison of model and experimental heat release rates, the accuracy of the pyrolysis model is quantified. In total, this research tested seven polyurethane foams consisting of three non-fire retardant (NFR) and four fire retardant (FR) foams. According to the simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) experiments, the decomposition behaviour of polyurethane foams under nitrogen environment is represented by two pyrolysis reactions. The first reaction consists of foam decomposition into melts and gases while the second reaction consists of the decomposition of the remaining melts into gases. The kinetic properties which govern the rate of decomposition are the activation energy (E), pre-exponential factor (A), reaction order (n) and heat of reaction (Δhr). Using graphical techniques, E, A and n of the first and second reactions are determined from the thermogravimetric analysis (TGA) results. Through analysing the differential scanning calorimetry (DSC) results, Δhr is determined from the changes in heat flow and sample mass. The thermophysical properties govern the heat transfer through material and these are the thermal conductivity (λ) and specific heat (cp) which are measured experimentally at ambient temperature through the Hot Disk method. Through the Sample Feeding Vertical Cone, the decomposition and melting behaviours of polyurethane foams in a vertical orientation are investigated and the foams tested can be categorised into those which produce melts only after ignition and those which produce melts and char after ignition. The 1-dimensional burning behaviour of foams is obtained from the cone calorimeter experiments. The NFR foams show a change from plateau burning behaviour at low heat flux to two stage burning behaviour at high heat flux while the FR foams consistently show two stage burning behaviour. The combustion property governs the amount of heat released when fuel combusts and this is the effective heat of combustion (Δhc,eff) which is determined from the heat released and mass consumed in the cone experiment. The 1-dimensional burning behaviour is simulated using the pyrolysis model of FDS 5 and two different modelling approaches are considered. The direct method uses the material properties determined experimentally as FDS 5 inputs while the refined method uses the genetic algorithm of Gpyro to refine the kinetic properties which are later used as FDS 5 inputs. The heat release rate of the model and experiment are compared through linear regression analysis which quantifies the accuracy of both methods. The accuracy is defined as the percentage of data points within the boundary of acceptance which is bounded by 25 % of the greatest experimental heat release rate. This assessment method places greater emphasis on the accuracy of developed burning phases and lesser emphasis on the accuracy of initial growth and final decay. The accuracy of the direct method is found to be 56 % while the refined method with estimated kinetic properties achieves a higher accuracy of 75 %. The 2-dimensional burning behaviours are investigated in the foam slab experiments for two different slab thicknesses, 120 and 100 mm. The opposed-flow spread of 120 mm slab is more intense and rapid while for the 100 mm slab, the flame spread is less intense and slow. FDS 5 is used to simulate the experimental results but when the material properties either developed experimentally or refined by Gpyro are used as inputs, the model fails to produce flame spread. This is because FDS 5 does not yet have the features which address the dynamics of foam melting and the reactive nature of the flame. In order to produce flame spread in the model, E of the reactions have been reduced to increase the decomposition rate.

"Material property estimation method is developed with 1-D heat conduction model and bounding exercise for Fire Dynamics Simulator (FDS) analysis. The purpose of this study is to develop an unsophisticated tool to convert small scale cone calorimeter data into input data that can be used in computational fluid dynamics (CFD) models to predict flame spread. Specific interests of input data for FDS in this study include thermal conductivity, specific heat, pre exponential factor, activation energy, heat of vaporization. The tool consists of two objects; 1-D model and bounding exercise. Main structure of the model is based on one of the thermal boundary conditions in the FDS, named as “Pyrolysis Model, Thermally-Thick Solid”, in which pyrolysis flux occurs on the surface of the object under radiant heat flux. This boundary condition is adopted because it has the best characteristics in the dynamics of modeling which are subject to our interests. The structure of the model is simple and concise. For engineering point of view, a practical model ought to have such simplicity that saves time and effort. Pyrolysis model in FDS meets this requirement. It is also a part of reason that this study is to develop a computational model which converts a set of data from the cone calorimeter test to a set of input data for FDS. A pyrolysis term on a surface of an object in this boundary condition will be playing an important role regarding a surface temperature and a mass loss rate of the object. Bounding exercise is introduced to guide proper outcome out of the modeling. Prediction of the material properties from the simulation is confirmed by the experimental data in terms of surface temperature history and mass loss rate under the bounding exercise procedure. For the cone calorimeter, thirteen different materials are tested. Test materials vary with their material composition such as thermoplastics, fiber reinforced plastics (FRP), and a wood. Throughout the modeling fed by a set of the cone calorimeter test data, estimated material properties are provided. So called “Bounding Exercise” is introduced here to draw the estimated material properties. Bounding exercise is a tool in order to guide the material property estimation procedure. Three sets of properties (Upper, Standard and Lower) are derived from the boundary exercise as recommended material properties. From the modeling results, PMMA shows the best agreement regarding the estimated material properties compared with already known results from the references. Wood indicates, however, somewhat different results, in which the mass loss rate takes a peak around the ignition and decreases sharply. This burning behavior can not be predicted using the “Pyrolysis Model”. The model in this study does not account so called “Charring Behavior” that a charring layer toward a surface or difference between a charred density in a charring layer and a normal density in a virgin layer of a wood. These factors result in a discrepancy of the estimated material properties with the reference data. Unlike PMMA and wood, FRP materials show a unique ignition characteristic. Mass loss rate history from some FRP materials indicate more a thermoplastic burning behavior and other materials tend to char. In addition there are few known material property data for theses materials and it is difficult to verify the results from this study with pre-existing data. Some plastic samples also indicate difficulties of the modeling. Because some samples melt and disfigure during the test, one dimensional heat transfer boundary condition is no longer applicable. Each bounding exercise results are fully examined and analyze in Chapter 6. Some of limitations contain model’s structural limitation, in which the model is too simple for certain cases, as well as limitations of bounding exercise. Finally, recommendations are made for future work including upgraded model accountable for the pyrolysis of charring material and FRP materials, data comparison with FDS results, and improved bounding exercise method."

The present work focuses on the study of biomass gasification process for generating hydrogen rich synthetic gas with oxy-steam as reactants using experiments and modeling studies. Utilization of the syngas as a fuel in general applications like fuel cells, Fischer-Tropsch FT) process and production of various chemicals like DME, etc. are being considered to meet the demand for clean energy. This study comprises of experiments using an open top down draft reactor with oxygen and steam as reactants in the co-current configuration. Apart from the standard gasification performance evaluation; parametric study using equivalence ratio, steam-to-biomass ratio as major variables towards generation of syngas is addressed towards controlling H2/CO ratio. The gasification process is modeled as a packed bed reactor to predict the exit gas composition, propagation rate, bed temperature as a function of input reactants, temperature and mass flux with variation in thermo-physical properties of biomass. These results are compared with the present experiments as well as those in literature. Experiments are conducted using modified open top downdraft configuration reactor with lock hoppers and provision for oxy-steam injection, and the exit gas is connected to the cooling and cleaning system. The fully instrumented system is used to measure bed temperatures, steam and exit gas temperature, pressures at various locations, flow rates of fuel, reactants and product gas along with the gas composition. Preliminary investigations focused on using air as the reactant and towards establishing the packed bed performance by comparing with the experimental results from the literature and extended the study to O2-N2 mixtures. The study focuses on determining the propagation rate of the flame front in the packed bed reactor for various operating conditions. O2 is varied between 20-100% (vol.) in a mixture of O2-N2 to study the effect of O2 fraction on flame propagation rate and biomass conversion. With the increase in O2 fraction, the propagation rates are found to be very high and reaching over 10 mm/s, resulting in incomplete pyrolysis and poor biomass conversion. The flame propagation rate is found to vary with oxygen volume fraction as XO22.5, and stable operation is achieved with O2 fraction below 30%. Towards introducing H2O as a reactant for enhancing the hydrogen content in the syngas and also to reduce the propagation rates at higher ER, wet biomass is used. Stable operating conditions are achieved using wet biomass with moisture-to-biomass (H2O:Biomass) ratio between 0.6 to 1.1 (mass basis) and H2 yield up to 63 g/kg of dry biomass amounting to 33% volume fraction in the syngas. Identifying the limitation on the hydrogen yield and the criticality of achieving high quality gas; oxy-steam mixture is introduced as reactants with dry biomass as fuel. An electric boiler along with a superheater is used to generate superheated steam upto 700 K and pressure in the range of 0.4 MPa. Steam-to-biomass ratio (SBR) and ER is varied with towards generating hydrogen rich syngas with sustained continuous operation of oxy-steam gasification of dry biomass. The results are analysed with the variation of SBR for flame propagation rates, calorific value of product syngas, energy efficiency, H2 yield per kg of biomass and H2/CO ratio. Hydrogen yield of 104 g per kg of dry casuarina wood is achieved amounting to 50.5% volume fraction in dry syngas through oxy-steam gasification process compared to air gasification hydrogen yield of about 40 g per kg of fuel and 20% volume fraction. First and second law analysis for energy and exergy efficiency evaluation has been performed on the experimental results and compared with air gasification. Individual components of the energy input and output are analysed and discussed. H2 yield is found to increase with SBR with the reduction in energy density of syngas and also energy efficiency. Highest energy efficiency of 80.3% has been achieved at SBR of 0.75 (on molar basis) with H2 yield of 66 g/kg of biomass and LHV of 8.9 MJ/Nm3; whereas H2 yield of 104 g/kg of biomass is achieved at SBR of 2.7 with the lower efficiency of 65.6% and LHV of 7.4 MJ/Nm3. The energy density of the syngas achieved in the present study is roughly double compared to the LHV of typical product gas with air gasification. Elemental mass balance technique has been employed to identify carbon boundary at an SBR of 1.5. Controlling parameters for arriving at the desired H2/CO ratio in the product syngas have been identified. Optimum process parameters (ER and SBR) has been identified through experimental studies for sustained continuous oxy-steam gasification process, maximizing H2 yield, controlling the H2/CO ratio, high energy efficiency and high energy density in the product syngas. Increase in ER with SBR is required to compensate the reduction in O2 fraction in oxy-steam mixture and to maintain the desired bed temperature in the combustion zone. In the range of SBR of 0.75 to 2.7, ER requirement increases from 0.18 to 0.3. The sustained continuous operation is possible upto SBR of 1.5, till the carbon boundary is reached. Operating at high SBR is required for high H2 yield but sustained highest H2 yield is obtained as SBR of 1.5. H2/CO ratio in the syngas increases from 1.5 to 4 with the SBR and depending on the requirement of the downstream process (eg., FT synthesis), suitable SBR and ER combination is suggested. To obtain high energy density in syngas and high energy efficiency, operations at lower SBR is recommended. The modeling study is the extension of the work carried by Dasappa (1999) by incorporating wood pyrolysis model into the single particle and volatile combustion for the packed bed of particles. The packed bed reactor model comprises of array of single particles stacked in a vertical bed that deals with the detailed reaction rates along with the porous char spheres and thermo-physical phenomenon governed by the mass, species and energy conservation equations. Towards validating the pyrolysis and single particle conversion process, separate analysis and parametric study addressing the effects of thermo-physical parameters like particle size, density and thermal conductivity under varying conditions have been studied and compared with the available results from literature. It has been found that the devolatilisation time of particle (tc) follows closely the relationship with the particle diameter (d), thermal conductivity (k), density () and temperature (T) as: The complete combustion of a single particle flaming pyrolysis and char combustion has been studied and validated with the experimental results. For the reactor modeling, energy, mass and species conservation equations in the axial flow direction formulate the governing equations coupled to the detailed single particle analysis. Gas phase reactions involving combustion of volatiles and water gas shift reaction are solved in the packed bed. The model results are compared with the experimental results from wood gasification system with respect to the propagation rate, conversion times, exit gas composition and other bed parameters like conversion, peak bed temperatures, etc. The propagation rates compare well with experimental data over a range of oxygen concentration in the O2- N2 mixture, with a peak at 10 mm/s for 100 % O2. In the case of oxy-steam gasification of dry biomass, the results clearly suggest that the char conversion is an important component contributing to the bed movement and hence the overall effective propagation rate is an important parameter for co-current reactors. This is further analyzed using the carbon boundary points based on elemental balance technique. The model predictions for the exit gas composition from the oxy-steam gasification matches well with the experimental results over a wide range of equivalence ratio and steam to biomass ratio. The output gas composition and propagation rates are found to be a direct consequence of input mass flux and O2 fraction in oxy-steam mixture. The present study comprehensively addresses the oxy-steam gasification towards generating hydrogen rich syngas using experimental and model studies. The study also arrives at the parameters for design consideration towards operating an oxy-steam biomass gasification system. The following flow chart provides the overall aspects that are covered in the thesis chapter wise.