RESUMEN
Plastic pollution is a critical environmental issue due to the widespread use of plastic materials and their long degradation time. Hydrocracking (HDC) offers a promising solution to manage plastic waste by converting it into valuable products, namely chemicals or fuels. This work aims to investigates the effect of catalyst accessibility and acidity on the HDC reaction of high density polyethylene (HDPE). Therefore, a variety of materials with significant differences in both textural and acidic properties were tested as catalysts. These include H-USY and H-ZSM.5 zeolites with various Si/Al molar ratios (H-USY: Si/Al = 2.9, 15, 30 and 40; H-ZSM-5: Si/Al = 11.5, 40, 500) and mesostructured MCM-41 materials modified with Ga and Al, also with different Si/metal ratios (Si/Al = 16 and 30; Si/Ga = 63 and 82). Thermogravimetric analysis under hydrogen atmosphere was used as a preliminary screening tool to evaluate the potential of the various catalysts for this application in terms of energy requirements. In addition, batch autoclave reactor experiments (T = 300 °C, PH2 = 20 bar, t = 60 min) were conducted to obtain further information on conversion, product yields and product distribution for the most promising systems. The results show that the catalytic performance in HDPE hydrocracking is determined by a balance between the acidity of the catalyst and its structural accessibility. Accordingly, for catalyst series where the structural and textural properties do not vary with the Si/Al ratio, there is a clear correlation of the HDPE degradation temperature and of the HDPE conversion with the Si/metal ratio (which relates to the acidic properties). In contrast, for catalyst series where the structural and textural properties vary with the Si/Al ratio, no consistent trend is observed and the catalytic performance is determined by a balance between the acidic and textural properties. The product distribution was also found to be influenced by the physical and chemical properties of the catalyst. Catalysts with strong acidity and smaller pores were observed to favor the formation of lighter hydrocarbons. In addition to the textural and acidic properties of the catalyst, the role of coke formation should not be neglected to ensure a comprehensive analysis of the catalytic performance.
RESUMEN
Zeolites are widely used in high-temperature oil refining processes such as fluid catalytic cracking (FCC), hydrocracking, and aromatization. Significant energy cost are associated with these processes due to the high temperatures required. The induction heating promoted by magnetic nanoparticles (MNPs) under radio frequency fields could contribute to solving this problem by providing a supplementary amount of heat in a nano-localized way, just at the active centre site where the catalytic process takes place. In this study, the potential of such a complementary route to reducing energetic requirements is evaluated. The catalytic cracking reaction under a hydrogen atmosphere (hydrocracking) applied to the conversion of plastics was taken as an application example. Thus, a commercial zeolite catalyst (H-USY) was impregnated with three different magnetic nanoparticles: nickel (Ni), cobalt (Co), maghemite (γ-Fe2O3), and their combinations and subjected to electromagnetic fields. Temperature increases of approximately 80 °C were measured for H-USY zeolite impregnated with γ-Fe2O3 and Ni-γ-Fe2O3 due to the heat released under the radio frequency fields. The potential of the resulting MNPs derived catalyst for HDPE (high-density polyethylene) conversion was also evaluated by thermogravimetric analysis (TGA) under hydrogen atmosphere. This study is a proof of concept to show that induction heating could be used in combination with traditional resistive heating as an additional energy supplier, thereby providing an interesting alternative in line with a greener technology.
RESUMEN
The ultra-stable Y (H-USY) zeolite is used as catalyst for the conversion of plastic feedstocks into high added value products through catalytic cracking technologies. However, the energy requirements associated with these processes are still high. On the other hand, induction heating by magnetic nanoparticles has been exploited for different applications such as cancer treatment by magnetic hyperthermia, improving of water electrolysis and many other heterogeneous catalytic processes. In this work, the heating efficiency of γ-Fe2O3 nanoparticle impregnated zeolites is investigated in order to determine the potential application of this system in catalytic reactions promoted by acid catalyst centers under inductive heating. The γ-Fe2O3 nanoparticle impregnated zeolite has been investigated by X-ray diffraction, electron microscopy, ammonia temperature program desorption (NH3-TPD), H2 absorption, thermogravimetry and dc and ac-magnetometry. It is observed that the diffusion of the magnetic nanoparticles in the pores of the zeolite is possible due to a combined micro and mesoporous structure and, even when fixed in a solid matrix, they are capable of releasing heat as efficiently as in a colloidal suspension. This opens up the possibility of exploring the application at higher temperatures.
RESUMEN
New micro three-dimensional (3D) scaffolds using biobased unsaturated polyesters (UPs) were prepared by microstereo-thermal-lithography (µSTLG). This advanced processing technique offers indubitable advantages over traditional printing methods. The accuracy and roughness of the 3D structures were evaluated by scanning electron microscopy and infinite focus microscopy, revealing a suitable roughness for cell attachment. UPs were synthesized by bulk polycondensation between biobased aliphatic diacids (succinic, adipic and sebacic acid) and two different glycols (propylene glycol and diethylene glycol) using fumaric acid as the source of double bonds. The chemical structures of the new oligomers were confirmed by proton nuclear magnetic resonance spectra, attenuated total reflectance Fourier transform infrared spectroscopy and matrix assisted laser desorption/ionization-time of flight mass spectrometry. The thermal and mechanical properties of the UPs were evaluated to determine the influence of the diacid/glycol ratio and the type of diacid in the polyester's properties. In addition an extensive thermal characterization of the polyesters is reported. The data presented in this work opens the possibility for the use of biobased polyesters in additive manufacturing technologies as a route to prepare biodegradable tailor made scaffolds that have potential applications in a tissue engineering area.