Cleaner Fuel Production via Co-Processing of Vacuum Gas Oil with Rapeseed Oil Using a Novel NiW/Acid-Modified Phonolite Catalyst

Clean biofuels are a helpful tool to comply with strict emission standards. The co-processing approach seems to be a compromise solution, allowing the processing of partially bio-based feedstock by utilizing existing units, overcoming the need for high investment in new infrastructures. We performed a model co-processing experiment using vacuum gas oil (VGO) mixed with different contents (0%, 30%, 50%, 70%, 90%, and 100%) of rapeseed oil (RSO), utilizing a nickel–tungsten sulfide catalyst supported on acid-modified phonolite. The experiments were performed using a fixed-bed flow reactor at 420 °C, a hydrogen pressure of 18 MPa, and a weight hourly space velocity (WHSV) of 3 h−1. Surprisingly, the catalyst stayed active despite rising oxygen levels in the feedstock. In the liquid products, the raw diesel (180–360 °C) and jet fuel (120–290 °C) fraction concentrations increased together with increasing RSO share in the feedstock. The sulfur content was lower than 200 ppm for all the products collected using feedstocks with an RSO share of up to 50%. However, for all the products gained from the feedstock with an RSO share of ≥50%, the sulfur level was above the threshold of 200 ppm. The catalyst shifted its functionality from hydrodesulfurization to (hydro)decarboxylation when there was a higher ratio of RSO than VGO content in the feedstock, which seems to be confirmed by gas analysis where increased CO2 content was found after the change to feedstocks containing 50% or more RSO. According to the results, NiW/acid-modified phonolite is a suitable catalyst for the processing of feedstocks with high triglyceride content.

Co-feeding of vacuum gas oil and pinewood-derived hydrogenated pyrolysis oils in a fluid catalytic cracking pilot plant to generate olefins and gasoline

Background: The Waste2Road project exploits new sustainable pathways to generate biogenic fuels from waste materials, deploying existing industrial scale processes. One such pathway is through pyrolysis of wood wastes. Methods: The hereby generated pyrolysis liquids were hydrogenated prior to co-feeding in a fluid catalytic cracking (FCC) pilot plant. So-called stabilized pyrolysis oil (SPO) underwent one mild hydrogenation step (max. 200 °C) whereas the stabilized and deoxygenated pyrolysis oil (SDPO) was produced in two steps, a mild one (maximum 250 °C) prior to a more severe process step (350 °C). These liquids were co-fed with vacuum gas oil (VGO) in an FCC pilot plant under varying riser temperatures (530 and 550 °C). The results of the produced hydrocarbon gases and gasoline were benchmarked to feeding pure VGO. Results: It was proven that co-feeding up to 10 wt% SPO and SDPO is feasible. However, further experiments are recommended for SPO due to operational instabilities originating from pipe clogging. SPO led to an increase in the hydrocarbon gas production from 45.0 to 46.3 wt% at 550 °C and no significant changes at 530 °C. SDPO led to a rise in gasoline yield at both riser temperatures. The highest amount of gasoline was produced when SDPO was co-fed at a 530 °C riser temperature, with values around 44.8 wt%. Co-feeding hydrogenated pyrolysis oils did not lead to a rise in sulfur content in the gasoline fractions. The highest values were around 18 ppm sulfur content. Instead, higher amounts of nitrogen were observed in the gasoline. Conclusions: SPO and SDPO proved to be valuable co-refining options which led to no significant decreases in product quality. Further experiments are encouraged to determine the maximum possible co-feeding rates. As a first step, 20-30 wt% for SPO are recommended, whereas for SDPO 100 wt% could be achievable.

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

The Fischer–Tropsch heavy fraction is a potential feedstock for transport-fuels production through co-processing with fossil fuel fraction. However, there is still the need of developing new and green catalytic materials able to process this feedstock into valuable outputs. The present work studies the co-hydrocracking of the Fisher–Tropsch heavy fraction (FT-res.) with vacuum gas oil (VGO) at different ratios (FT-res. 9:1 VGO, FT-res. 7:3 VGO, and FT-res. 5:5 VGO) using phonolite-based catalysts (5Ni10W/Ph, 5Ni10Mo/Ph, and 5Co10Mo/Ph), paying attention to the overall conversion, yield, and selectivity of the products and properties. The co-processing experiments were carried out in an autoclave reactor at 450 °C, under 50 bars for 1 and 2 h. The phonolite-based catalysts were active in the hydrocracking of FT-res.:VGO mixtures, presenting different yields to gasoline, diesel, and jet fuel fractions, depending on the time of reaction and type of catalyst. Our results enable us to define the most suitable metal transition composition for the phonolite-based support as a hydrocracking catalyst.