Reciclagem química de Polietileno utilizando Sílica Mesoporosa tipo SBA-15 avalizada por Termogravimetriae Espectrometria de Massas

The chemical recycling of polyolefins has been the focus of increasing attention owing potential application as a fuel and as source chemicals. The use of plastic waste contributes to the solution of pollution problems.The use of catalysts can enhance the thermal degradation of synthetic polymers, which may be avaliated by Themogravimetry (TG) and mass spectrometry (MS) combined techniques. This work aims to propose alternatives to the chemistry recycling of low-density polyethylene (LDPE) on mesoporous silica type SBA-15 and AlSBA-15.The mesoporous materials type SBA-15 and AlSBA-15 were synthesized through the hydrothermal method starting from TEOS, pseudobohemite, cloridric acid HCl and water. As structure template was used Pluronic P123. The syntheses were accomplished during the period of three days. The best calcination conditions for removal of the organic template (P123) were optimized by thermal analysis (TG/DTG) and through analyses of Xray diffraction (XRD), infrared spectroscopy (FT-IR), nitrogen adsorption and scanning electron microscopy (SEM) was verified that as much the hydrothermal synthesis method as the calcination by TG were promising for the production of mesoporous materials with high degree of hexagonal ordination. The general analysis of the method of Analog Scan was performed at 10oC/min to 500 oC to avoid deterioration of capillary with very high temperatures. Thus, with the results, we observed signs mass/charge more evident and, using the MID method, was obtained curve of evolution of these signals. The addition of catalysis produced a decrease in temperature of polymer degradation proportional to the acidity of the catalyst. The results showed that the mesoporous materials contributed to the formation of compounds of lower molecular weight and higher value in the process of catalytic degradation of LDPE, representing an alternative to chemical recycling of solid waste

True liquid crystal templating of SBA-15 with reduced microporosity

Mesoporous silica SBA-15 was synthesised by the true liquid crystal templating method, yielding a material with reduced microporosity compared with that produced by the more conventional liquid crystal templating route. Further advancements allow the generation of metal nanoparticle-doped SBA-15 materials with well-defined metal particle sizes, which posses potential as catalytic systems. © 2013 Elsevier Inc. All rights reserved.

New insights in the deactivation of sulfonic modified SBA-15 catalysts for biodiesel production from low-grade oleaginous feedstock

Arenesulfonic-acid functionalized SBA-15 materials have been used in the production of biodiesel from low grade oleaginous feedstock. These materials display an outstanding catalytic activity, being able to promote the transformation of crude palm oil with methanol into fatty acid methyl esters with high yield (85%) under mild reaction conditions. However, high sensitivity of the catalyst against poisoning by different substances has also been detected. Thus, alkaline metal cations, such as sodium or potassium exert a negative influence on the catalytic activity of these materials, being necessary amounts around 500 ppm of sodium in the reaction media to decrease the catalytic activity of these materials to a half of its initial value in just two reaction runs. The deactivation of arenesulfonic acid functionalized SBA-15 materials seems to occur in this case by ion exchange of the acid protons at the sulfonic groups. Organic unsaponifiable compounds like lecithin or retinol also induce a negative influence in the catalytic activity of these sulfonic acid-based materials, though not so intense as in the case of alkaline metals. The deactivating mechanism associated to the influence of the organic compounds seems to be linked to the adsorption of such substances onto the catalytic acid sites as well as on the silica surface. The accumulation of lecithin in the surface of catalyst, observed by means of thermogravimetric analysis, suggest the creation of a strong interaction, probably by ion pair, between this compound and the sulfonic acid group.

Support enhanced α-pinene isomerization over HPW/SBA-15

A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while 1H NMR gave information about the integrity of the as-recycled template. The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O2 and thereby the oxidation rate of the template burning. © 2013 Elsevier Inc. All rights reserved.

Preparação, caracterização e aplicação de derivados do ácido 12- tungstofosfórico suportado em SBA-15

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2016.

UHMWPE/SBA-15 nanocomposites synthesized by in situ polymerization

Different nanocomposites have been attained by in situ polymerization based on ultra-high molecular weight polyethylene (UHMWPE) and mesoporous SBA-15, this silica being used for immobilization of the FI catalyst bis [N-(3-tert-butylsalicylidene)-2,3,4,5,6-pentafluoroanilinato] titanium (IV) dichloride and as filler as well. Two distinct approaches have been selected for supporting the FI catalyst on the SBA-15 prior polymerization. A study on polymerization activity of this catalyst has been performed under homogenous conditions and upon heterogenization. A study of the effect of presence of mesoporous particles and of the immobilization method is also carried out. Moreover, the thermal characterization, phase transitions and mechanical response of some pristine UHMWPEs and UHMWPE/SBA-15 materials have been carried out. Relationships with variations on molar mass, impregnation method of catalyst and final SBA-15 content have been established.