Science and technology of novel processes for deep desulfurization of oil refinery streams

Oil refinery related catalysis, particularly hydrodesulfurization (HDS) processes, is viewed as a mature technology and it is often stated that break-throughs are not to be expected. Although this could be a justified compliment to those who developed this area, at the same time it could also stifle potential new ideas.

The applicability and perspectives of various desulfurization technologies are evaluated taking into account the requirements of the produced fuels. The progress achieved during recent years in catalysis-based HDS technologies (synthesis of improved catalysts, advanced reactor design, combination of distillation and HDS) and in ‘non-HDS’ processes of sulfur removal (alkylation, extraction, precipitation, oxidation, and adsorption) is illustrated through a number of examples.

The discussed technologies of sulfur removal from the refinery streams lead to a wealth of research topics. Only an integrated approach (catalyst selection, reactor design, process configuration) will lead to novel, efficient desulfurization processes producing fuels with zero sulfur emissions.

Ni–W catalysts supported on commercial γ-alumina and silica displayed similar activity in dibenzothiophene hydrodesulfurization (DBT HDS), while the activity of the Ni–W/SiO₂catalyst in toluene hydrogenation (HYD) was 6 times higher compared with Ni–W/Al₂O₃. The dearomatization performance of Ni–W/SiO₂ catalyst was tested over a wide range of operation conditions with naphtha and middle distillates. 90% saturation of aromatics in FCC naphtha (340 °C, LHSV of 1 h⁻¹) and 50% in Light cyclic oil (LCO) (360 °C, LHSV of 1 h⁻¹) was achieved at 5.4 MPa. In a two stage process with the same Ni–W/SiO₂ and intermediate separation of hydrogen sulphide 90% saturation of aromatics in LCO was achieved at 320 °C and total LHSV of 0.5 h⁻¹. At equal conditions, Ni–W/Al₂O₃ catalyst yielded 1.5–4 times lower total aromatics saturation.

The present work focuses on the influence of calcium addition in gasification. The inorganic–organic element interaction as well as the detailed inorganic–inorganic elements interaction has been studied. The effect of calcium addition as calcium sugar/molasses solutions to straw significantly affected the ash chemistry and the ash sintering tendency but much less the char reactivity. Thermo balance test are made and high-temperature X-ray diffraction measurements are performed, the experimental results indicate that with calcium addition major inorganic–inorganic reactions take place very late in the char conversion process. Comprehensive global equilibrium calculations predicted important characteristics of the inorganic ash residue. Equilibrium calculations predict the formation of liquid salt if sufficient amounts of Ca are added and according to experiments as well as calculations calcium binds silicon primarily as calcium silicates and less as potassium calcium silicates.