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Hydrodeoxygenation (HDO) of pyrolysis oil fractions was studied to better understand the HDO of whole pyrolysis oil and to assess the possibility to use individual upgrading routes for these fractions. By mixing pyrolysis oil and water in a 2 : 1 weight ratio, two fractions were obtained: an oil fraction (OFWA) containing 32 wt% of the organics from the whole oil and an aqueous fraction water addition (AFWA) with the remaining organics. These fractions (and also the whole pyrolysis oil as the reference) were treated under HDO conditions at different temperatures (220, 270 and 310 C), a constant total pressure of 190 bar, and using 5 wt% Ru/C catalyst. An oil product phase was obtained from all the feedstocks; even from AFWA, 29 wt% oil yield was obtained. Quality parameters (such as coking tendency and H/C) for the resulting HDO oils differed considerably, with the quality of the oil from AFWA being the highest. These HDO oils were evaluated by co-processing with an excess of fossil feeds in catalytic cracking and hydrodesulfurisation (HDS) lab-scale units. All co-processing experiments were successfully conducted without operational problems. Despite the quality differences of the (pure) HDO oils, the product yields upon catalytic cracking of their blends with Long Residue were similar. During co-processing of HDO oils and straight run gas oil in a HDS unit, competition between HDS and HDO reactions was observed without permanent catalyst deactivation. The resulting molecular weight distribution of the co-processed HDO/fossil oil was similar to when hydrotreating only fossil oil and independent of the origin of the HDO oil.

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A system to remove in situ char/ash from hot pyrolysis vapors has been developed and tested at the University of Twente. The system consists of a continuous fluidized bed reactor (0.7 kg/h) with immersed filters (wire mesh, pore size 5 µm) for extracting pyrolysis vapors. Integration of the filter system in the fluidized bed should overcome operational problems related to the increase in pressure drop across the filter in time and a decrease in oil yield as typically observed in downstream pyrolysis vapor filtration and lead to process intensification. In this study the effect of in situ hot pyrolysis vapor filtration has been studied with respect to process stability, product yields, and product quality. Oil obtained via a more conventional cyclone system placed in parallel to the filter system served as reference for the quality and yields of the filtered oil. Good process stability concerning temperature and pressure drop across the hot gas vapor filter was achieved during a 2 h run, even when using a reused filter. Particles (char/sand) were retained inside the filter pores located at the outside surface of the filter, while the inside of the filter remained clean apart from some deposits formed on the metal wire and small 1 µm particles which slipped through the filter. Mass balance closures higher than 94 wt % were obtained. Comparable yields (cyclone + filtered oil) were obtained as in the experiments carried out with only the cyclones. The filtered oil contained significantly less solids, alkali metals, and ash compared to cyclone oil. For the alkali metals, only a considerable amount of potassium (K) was still present in filtered pyrolysis oil, which most likely entered the filtered oil via the vapor phase. There were no significant differences in the elemental composition of the oil produced via the filter line and cyclone line. The molecular weight of the filtered oil obtained with nondried feed was always marginally lower compared to the cyclone oil. Results of the aging tests show that the reactivity of pyrolysis oil can already originate from the highly reactive components in pyrolysis oil itself and does not need the presence of char/ash. To show the intrinsically high reactivity of solids-free pyrolysis oil vapors, an external filter section (1 µm pore size) was placed additionally and in series with the filter inside the fluidized bed. The results show that char is formed from the reactive pyrolysis vapors.

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