Oxalic Acid as a Hydrogen Donor for the Hydrodesulfurization of Gas Oil and Deoxygenation of Rapeseed Oil Using Phonolite-Based Catalysts

Abstract

The use of renewable local raw materials to produce fuels is an important step toward optimal environmentally friendly energy consumption. In addition, the use of these sources together with fossil fuels paves the way to an easier transition from fossil to renewable fuels. The use of simple organic acids as hydrogen donors is another alternative way to produce fuel. The present work reports the use of oxalic acid as a hydrogen donor for the catalytic hydrodesulfurization of atmospheric gas oil and the deoxygenation of rapeseed oil at 350 °C. For this process, one commercial NiW/SiO2–Al2O3 solid and two NiW/modified phonolite catalysts were used, namely Ni (5%) W (10%)/phonolite treated with HCl, and Ni (5%) W (10%)/phonolite treated with oxalic acid. The fresh phonolite catalysts were characterized by Hg porosimetry and N2 physisorption, ammonia temperature programmed desorption (NH3-TPD), X-ray diffraction (XRD), and X-ray fluorescence (XRF). The sulfided metal phonolite catalysts were characterized by XRD and XRF. Hydrodesulfurization led to a decrease in sulfur content from 1 to 0.5 wt% for the phonolite catalysts and to 0.8 wt% when the commercial catalyst was used. Deoxygenation led to the production of 15 and 65 wt% paraffin for phonolite and commercial solids, respectively. The results demonstrate the potential of using oxalic acid as a hydrogen donor in hydrotreating reactions.

Mesityl Oxide Reduction by Using Acid-Modified Phonolite Supported NiW, NiMo, and CoMo Catalysts

“…Because the raw phonolite material had very poor textural properties, an acid treatment of this raw material was performed. An increase in the total porosity and number of weak acid sites on the surface of the solid was found [14,17] resulting in an increase in the pore volume and specific surface area. These changes in the support used to produce the new catalysts are described in previous publications [14,17].…”

“…An increase in the total porosity and number of weak acid sites on the surface of the solid was found [14,17] resulting in an increase in the pore volume and specific surface area. These changes in the support used to produce the new catalysts are described in previous publications [14,17]. The acid treatment led to the removing of mainly Al and Na with the consequent increase of the creation of new pores in the solid.…”

“…In this work, the aim was to gain more knowledge about the MSO reduction by using metal sulfide catalysts. In addition, we used a catalyst based on the modification of a mineral source of phonolite (Ph) which is located near to the refinery in the Northwest of Czech Republic with the aim of obtaining a cost-effective catalyst similar to the commercial metal sulfide catalysts based on the use of a support with high contents of SiO 2 -Al 2 O 3 [13][14][15]. A previous experience by using a NiW-supported catalyst on oxalic acid modified Ph for the production of MIBK led to continue with the research of the MSO reduction [16].…”

Hydrocracking of Heavy Fischer–Tropsch Wax Distillation Residues and Its Blends with Vacuum Gas Oil Using Phonolite-Based Catalysts

“…The brief characteristics of utilized support material and synthesized catalysts is presented in Table 6. Further analysis of the prepared catalysts, including scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), hydrogen temperature-programmed reduction (H 2 -TPR), and ammonia and CO 2 temperature-programmed desorption (NH 3 -TPD, CO 2 -TPD), can be found in previous works from the authors [31,32].…”

Phonolite Material as Catalyst Support for the Hydrotreatment of Gas Oil and Vegetable Oil Type Feedstocks

“…Nevertheless, our previous studies indicated that this igneous rock is also suitable as a catalyst support or metal-adsorbent (Ca, Mg, K, P and Na), increasing its specific surface (from 5 to 167 m 2 /g) after an acid treatment [ 21 ]. In this way, the following studies were focused on the characterisation, and use of Ni-W Ph for the deoxygenation of animal fats and vegetable oils, obtaining a high rate of oxygen compounds decrease [ 22 , 23 ]. In line with these promising results, the subsequent studies focused on synthesising Co-Mo, Ni-Mo and Ni-W Ph catalysts for biofuels and platform chemicals production.…”