V. J. Fernandes

Thermogravimetric investigations during the synthesis of silica-based MCM-41

MCM-41 material was synthesized starting from hydrogel containing colloidal fumed silica, sodium silicate, cetyltetramethylammonium bromide(CTMABr) as surfactant, and distilled water as solvent. These reactants were mixed to obtain a gel with the following composition: 4SiO2:1Na2O:1CTMABr:200H2O. The hydrogel with pH=14 was hydrothermally treated at100°C, for 4 days. Each day, the pH was measured, and then adjusted to 9.5–10 by using 30%acetic acid solution. Thermogravimetry was the main technique, which was used to monitor the participation of the surfactant on the MCM-41 nanophase, being possible to determine the temperature ranges relative to water desorption as well as the surfactant decomposition and silanol condensation.

Thermogravimetric kinetics of polyethelyne degredation over silicoaluminophosphate

Abstract In the current work, we investigated the Thermogravimetric kinetics of degradation of high-density polyethylene (HDPE) alone, and mixed with silicoaluminophosphate catalyst (SAPO-37/HDPE). To estimate the kinetic parameters of the polymer degradation, the Vyazovkin model-free kinetic method was applied. The activation energy ( E ) was calculated as a function of conversion ( α ) and temperature ( T ), providing an estimate of the time required for the degradation process at a given temperature. The products due to thermal and catalytic cracking of polyethylene were analyzed by gas chromatography/mass spectrometry (GC/MS). The SAPO-37 showed good catalytic activity, decreasing the activation energy for the process.

Thermal Analysis Applied to Solid Catalysts Acidity, Activity and Regeneration

The use of catalysts in numerous important processes is widespread throughout the chemical and petroleum-processing industries. Thermal analytical techniques can be used to evaluate important properties and processes associated with solid catalysts. This paper presents examples carried out in our laboratory of the general application of TG and DSC to the acidity, activity and regeneration of solid catalysts.

Catalytic degradation of polyethylene evaluated by TG

HZSM-5 zeolite was screened as catalyst for high density polyethylene degradation at 450‡C, under nitrogen static atmosphere. Two different samples were studied in this condition: HDPE alone and mixed with HZSM-5. The reactor was connected on line to an HP 5890-II gas Chromatograph. Sample degradation was investigated using a Perkin-Elmer Delta 7 Thermobalance, from room temperature to 800‡C, with heating rates of 5.0, 10.0 and 20.0‡C min−1. From TG curves, the activation energies, calculated using an integral kinetic method, decreased 60.6% in the presence of the zeolite.

Acid properties of SiMCM-41 mesoporous molecular sieve

The SiMCM-41 mesoporous molecular sieve was synthesised by the hydrothermal method. The physicochemical characterisation by infrared spectroscopy, X-ray diffraction and thermogravimetry, showed that the material presents a well-defined structure. In this study, the determination of the total acidity and relative strength of the acid sites of the SiMCM-41,was performed by desorption of adsorbed n-butylamine combined with thermogravimetric measurements. The total acidity, determined by means of the amount of amine desorbed normalised by mass of solid, was equivalent to 0.927 mmol g–1, in the temperature range from 96 to 235°C. By using the Flynn and Wall integral kinetic model, at 5, 10 and 20°C min–1 heating rates, it was determined that the activation energy to desorb n-butylamine was 90.7 kJ mol–1, in the same temperature range, evidencing that SiMCM-41 presents only weak acid sites on its surface.

Kinetic Parameters of Polyethylene Degradation by the Natural Zeolite Chabazite

High-density polyethylene (PE) was subjected to thermal degradation alone and in the presence of an ammonium-exchanged zeolite chabazite (CHA/PE). The processes were carried out in a reactor connected online to a gas chromatograph/mass spectrometer in order to analyse the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature up to 800°C, under a dynamic nitrogen atmosphere, with multiple heating rates. From the TG curves, the activation energy relating to the degradation process was calculated by using the Flynn and Wall multiple heating rate kinetic model for pure PE and for CHA/PE. The exchanged chabazite exhibited good selectivity for the catalytic degradation of PE to low molecular mass hydrocarbons.

Determination of Ca/NaY zeolite acidity by TG and DSC

The acid properties of the Ca/NaY zeolite were investigated by means ofn-butylamine desorption and thermal decomposition, using both thermogravimetry (TG) and differential scanning calorimetry (DSC). The total acidity of the zeolite was calculated from the TG data, while DSC was used with the Borchardt-Daniels kinetic model to determine the relative acid strength of the catalyst, given in J per acid site. The enthalpies of these processes are proportional to the acid site strength in each specific temperature range.

Kinetic Parameters of Polymer Degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800°C, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

Catalytic distillation of an atmospheric petroleum resid using HZSM-5 and HY zeolites

ABSTRACT This work presents a study of the reactive distillation of atmospheric petroleum residue (ATR) containing 10% in mass of HY or HZSM-5 zeolites. The process aims the upgrade of ATR in order to obtain valuable products. The fundamental characteristic of the process is the immediate separation under thermal conditions and subsequent reaction of the products generated by the zeolite catalysts, favoring the displacement of the equilibrium towards the desired reactions. Such reactions occurred in the heterogeneous form, adding the HY or HZSM-5 zeolites to the ATR charge, and heating the mixtures at temperatures in the range of 50 to 500°C. The heating promotes intense heat exchange, solid-liquid reactions, obtaining the desired products. In the reactive distillation process, in presence of the acid sites of the zeolites, the short contact time of the hydrocarbons thermally cracked at low pressures favored secondary cracking reactions, increasing the selectivity to lower weigh molecular hydrocarbons, in the range of liquid gases, naphta, gasoline, jet fuel, diesel and lubricants. The obtained results proved that catalytic or reactive distillation is a promising technology for waste recovery that is surplus to the atmospheric and vacuum distillation processes for the refineries.

Characterization and Acidic Properties of AlMCM-41 Prepared by Conventional and Post-Synthesis Alumination

The catalysts analysed in the current work are variations of MCM-41. The properties of these highly ordered mesoporous aluminosilicates were adjusted by an isomorphous substitution of Si by a trivalent cation, in this case Al3+, generating catalysts of the AlMCM-41 type. The materials were synthesized with a silicon/aluminium ratio of 40, through two methods of impregnation of the metal: conventional and post-synthesis alumination. With the aim of determining the density of the acid sites of the Al40MCM-41 prepared by post-synthesis and conventional alumination, studies of the adsorption of n-butylamine probe molecule were carried out. Further, the studied material was characterized by thermogravimetry measurements, providing the profile of decomposition of the samples, which allowed calculation of the densities of the acid sites. The model-free kinetic algorithms were applied in order to determinate conversion and apparent activation energy. Comparison of energy-dispersive X-ray fluorescence and X-ray photoelectron spectroscopy measurements indicated that the post-synthesis method was more favourable based on the metal positioning, ‘anchored’ in the surface of the catalyst. The textural properties of the calcined Al40MCM-41 prepared by post-synthesis and conventional alumination were characterized by X-ray diffraction, N2 isothermal adsorption measurements (Brunauer–Emmett–Teller and Barrett–Joyner–Halenda), transmission electron microscopy, and X-ray photoelectron spectroscopy.