RESUMEN
Propane dehydrogenation reaction (PDH) is an extremely attractive way to produce propylene; however, the catalysts often lead to byproduct formation and suffer from deactivation. This research focuses on the development of efficient Pt/Sn-based shaped catalysts by utilizing Mg-modified mesoporous silica, sepiolite (natural SiMgO x mesoporous clay), and sepiolite/bentonite/alumina as supports with the aim of achieving superior stability and selectivity for industrial propylene production by PDH. The catalysts were prepared by sequential impregnation of the supports with the corresponding solutions of tin chloride and platinum chloride, by obtaining a nominal loading of 0.7 wt % of Sn and 0.5 wt % of Pt. A range of analytical techniques were used to characterize the catalysts, including X-ray diffraction, nitrogen physisorption isotherms, Hg intrusion porosimetry, thermogravimetric analyses, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. The basicity of the catalysts was assessed using carbon dioxide temperature-programmed desorption (CO2-TPD). The results confirm that the support material plays a critical role in catalyst performance; in particular, the presence of weak basic sites, due to magnesium addition, improved selectivity to propylene and reduced coke formation. Catalytic pellets of Sn-Pt supported on macroporous sepiolite or sepiolite and bentonite-modified mesoporous alumina performed comparably with propane conversion very close to thermodynamic equilibrium and selectivity to propylene above 95%. The latter support led to improved stability and was regenerated at milder temperatures, making it suitable for industrial applications.
RESUMEN
The propylene production processes currently used in the petrochemical industry (fluid catalytic cracking and steam cracking of naphtha and light diesel) are unable to meet the increase of propylene demand for industrial applications. For this reason, alternative processes for propylene production have been investigated, and among the others, the propane dehydrogenation (PDH) process, allowing the production of propylene as a main product, has been industrially implemented (e.g., Catofin and Oleflex processes). The main drawback of such processes is closely linked to the high temperature required to reach a sustainable propane conversion that affects catalyst stability due to coke formation on the catalyst surface. Accordingly, the periodic regeneration of the catalytic bed is required. In this work, the performance in the PDH reaction of different Sn-Pt catalysts, prepared starting by alumina- and hydrotalcite-based supports, is investigated in terms of propane conversion and selectivity to propylene in order to identify a more stable catalyst than the commercial ones. The experimental tests evidenced that the best performance was obtained using the catalyst prepared on commercial pellets of hydrotalcite PURALOX MG70. This catalyst has shown, under pressure conditions of 1 and 5 bar (in order to evaluate the potential future application in integrated membrane reactors), propane conversion values close to the thermodynamic equilibrium ones in all of the investigated temperature ranges (500-600 °C) and the selectivity was always higher than 95%. So, this catalyst was also tested in a stability run, performed at 500 °C and 5 bar: the results highlighted the loss of only 12% in the propane conversion with no changes in the selectivity to propylene. Properly designed experimental tests have also been performed in order to evaluate the kinetic parameters, and the developed mathematical model has been optimized to effectively describe the system behavior and the catalyst deactivation.
RESUMEN
Plasma science has attracted the interest of researchers in various disciplines since the 1990s. This continuously evolving field has spawned investigations into several applications, including industrial sterilization, pollution control, polymer science, food safety and biomedicine. nonthermal plasma (NTP) can promote the occurrence of chemical reactions in a lower operating temperature range, condition in which, in a conventional process, a catalyst is generally not active. The aim, when using NTP, is to selectively transfer electrical energy to the electrons, generating free radicals through collisions and promoting the desired chemical changes without spending energy in heating the system. Therefore, NTP can be used in various fields, such as NOx removal from exhaust gases, soot removal from diesel engine exhaust, volatile organic compound (VOC) decomposition, industrial applications, such as ammonia production or methanation reaction (Sabatier reaction). The combination of NTP technology with catalysts is a promising option to improve selectivity and efficiency in some chemical processes. In this review, recent advances in selected nonthermal plasma assisted solid-gas processes are introduced, and the attention was mainly focused on the use of the dielectric barrier discharge (DBD) reactors.