Thermogravimetric Kinetics Study of Scrap Tires Pyrolysis Using Silica Embedded With NiO and/or MgO Nanocatalysts

In this study, a set of three new silica-based embedded with NiO and/or MgO nanocatalysts (SBNs) have been prepared and tested for the pyrolysis of scrap tires (STs). The intent is to identify and optimize the best nanocatalyst that decreases the operating temperature and speeds up the pyrolysis reaction rate. The influence of the three prepared SBNs nanocatalysts on STs was scrutinized using thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The kinetic triplets were estimated utilizing the isoconversional method of the Ozawa–Flynn–Wall (OFW) corrected model. Experimental TGA and FT-IR results showed a thermal decomposition of all volatile organic additives alongside the polyvinyl compounds at a lower temperature in the presence of these SBNs. However, a competitive decomposition behavior appeared for each SBN nanocatalysts. The kinetic triplets’ findings showed different effective activation energy trends at two different conversion regions (low and high conversions), suggesting different reaction mechanisms confirmed by the reaction kinetic models. Interestingly, NiO-MgO-SBNs showed the highest reaction rate for this thermo-pyrolysis of STs, which could be because of synergetic interaction between NiO and MgO nanoparticles. Moreover, the results of the change in Gibbs free energy of activation (ΔG‡) indicated the promising catalytic activity for those SBNs by promoting the spontaneity of pyrolysis reaction. These proof-of-concept findings could promote the futuristic use of NiO-MgO-SBNs at the industrial level toward sustainable ST pyrolysis.

Pyrolysis Kinetics and Flammability Evaluation of Rigid Polyurethane with Different Isocyanate Content

Polyurethane (PU) is a typical product of the reaction between isocyanate and polyol, whose ratio would greatly influence material properties. In this paper, to investigate the influence of isocyanate on PU thermal stability and flammability, three kinds of rigid polyurethanes (RPUs) with different isocyanate ratio (1.05, 1.1, and 2.0) were manufactured in a laboratory and employed to have a series of TG (thermogravimetry), DSC (differential scanning calorimetry), and cone calorimetry tests. Kissinger’s method was used to calculate the activation energy and judge their stabilities. However, for such a complex degradation which consists of five reactions, it does not make sense by Kissinger method to obtain only two peak active energies. Considering complexity of PU degradation in air, genetic algorithm (GA) was employed to calculate kinetic triplets of five sub-reactions. The effects of isocyanate contents on each sub-reaction stability were obtained and then analyzed. By cone calorimeter testing, we found that great differences in heat release rate data. However, DSC analysis showed a complete opposite changed trend. Such difference is caused by DSC and calorimeter’s sample morphology, the former using grinded polyurethane powders but the latter polyurethane foam block.

Identification of kinetic triplets by results of derivatographic analysis

The method for identification of the triplet of kinetic parameters of a heterogeneous reaction using the data of the derivatographic analysis is proposed. This method is characterized by high accuracy and relative simplicity and it can be effectively realized using MS Excel software.