Investigations on hydrotreating of fischer tropsch-biowaxes for generation of bio-products from lignocellulosic biomass

Abstract

The present study describes the application of Fischer Tropsch biowaxes as a feedstock in a pilot-scale hydroprocessing unit at operating conditions very similar to industrial size hydrotreating plants of traditional refineries. The project focus on a future coprocessing of biowax/gasoil blends due to produce bio-products derived from lignocellulosic biomass: crack gases, naphtha, kerosene, diesel and a residual product. Hydro-processing plants operating at mild cracking conditions support the production of high amounts in middle distillates at reduced coke formation. Premium bio-diesel and bio-kerosene with excellent cold flow properties are the main objective of the investigations. Various test runs with different hydrotreating catalysts have been conducted due to determine the influence of waxy feedstock on catalyst behavior and product distribution. Depending on the catalyst selected, the fixed bed reactor streamed by hydrogen operates under specified cracking condition defined by the following parameters: reactor temperature, hydrogen pressure and weight hourly space velocity (WHSV). Test runs with selected catalysts - isodewaxing (IDW), hydro-desulphurization (HDS) and the catalytic deparaffination (CDP) catalyst - have been executed at constant process conditions in order to compare the product spectrum and properties of product groups. Highest amounts of bio-diesel and bio-kerosene with excellent cold flow properties can be obtained with the IDW catalyst. This NiW- based catalyst with special additives generates cleaved and reshaped molecular fragments via skeletal isomerisation increasing the isoparaffin content of naphtha and middle distillates. Further investigations with this catalyst type have been executed due to determine the catalyst aging effect in a separate long term test run. The loss of cracking severity during operation of the catalyst can be observed by a steady decline in conversion. Unsaturated hydrocarbons such as olefins and diolefines in the bio-feedstock support the formation of a coke layer on the catalyst surface resulting in reinforced deactivation. As the consequence naphtha and finally the crack gases and the kerosene fraction are shifted to higher molecular fragments increasing the diesel and residue yield. Physicochemical properties of the product groups obtained during the test run vary and especially the cold flow properties from the diesel and kerosene fraction degrade significant. Balancing the conversion decline of the catalyst in operation can be realized by increasing the reactor temperature and the hydrogen pressure, but the effect is time limited.